Ocean Dumping of Chemical Munitions: Environmental Effects in Arctic Seas
7
MEDEA
Ocean Dumping of Chemical Munitions:
Environmental Effects in Arctic Seas
7
MEDEA
The interaction* between cnvironmcni and national security arcell articulated. In some cases, tlie coupling is apparent. For example, release of hazardous materials under specific circumstances canerious and quamifiably adverse effect on ecosystems with both direct and indirect consequences lor the integrity of llic environment and tor human health. In other cases, associated, for example, with subtle consequences of genetic engineering or with active acoustic sensing of the ocean and atmosphere, wc are just beginning to learn about tho issues. Our understanding of relevant basic science may be rudimentary and further work must he done if we are to provide responsible guidance for policy.
This report, investigating potential environmental consequences of Cold War disposal of chemical munitions in ihe Russian Arctic, was producedubgroup of MEDEA scientists at the direction of ihe National Intelligence Council. It piovides an excellent example of where well-founded conclusions on an important issue can be drawn from careful analysis despite gaps in data and less than perfect knowledge of detail; it may be viewedrototypical case forclalionship between environment and national security. The study points up the need for broadly based disciplinary expertise in addressing the complex linkages that characterise such issues. Illear example of the important and complementary roles academic and government scientists can bring lo bearopic of mutual interest.
Tbe report identities several longer term studies which would lead to improved understanding of lire potential impact on oceanic ecosystems of the disposal of munitions and toxic chemicals at sea. Such studies would be of interestroad range of disposal sites, not simply limited to the Arctic. It is my hope lhat ibe scientific conclusions reached here, wlien viewed by others, will lead to enlightened management of munitions disposed in the ocean.
I am indebted to the dedicated scientists both inside and outside government who generously contributed their time and talent lo this important effort. MEDEA was pleased to contribute its expertise and guidance to the study Wc look forward to working wiih government agencies in the future lo address similar such topics of national and international interest at the intersection of concerns for environmental integrity and national security.
On belialf ofould likecknowledge the extraordinary efforts and leadership provided by Olis Brown, who chaired the study, and byawker. Without them, this projeci could not have been carried lo its successful conclusion.
MEDEA carried oui this assessment of ttw potential for significant adverse impact on the arctic environment arising from past dumping of chemical warfare munitions in arctic seas at the request of the National Intelligence Council. The assessment primarily was concerned with determining Ihe potential for environmental effects of sufficient magnitude us to pose some concernroadly. national security.
The present report describes the studyas carried out and the findings and recommendations which were developed.
The study was carried outollaboration between an ocean science subgroup of MEDEAumber of collaborators who brought specialised scientific and technical knowledge to the process.
The views reflected herein arc those of MEDEA and specifically the following members who participated in this study:
Mark R. Abbott Dr. Peter O. Brewer
Dr. Otis B. Brown. Chair Dr.awker
Dr. Robert A. Holman Dr. Walter H. Munk Dr. John Orcult
Dr. Ned A. Ostcnso Dr. Robert A. Shuchman Dr. Norbert Untersteiner
Dr. Kail K. Turckian Dr. Wilford F. Weeks
State University
Monterey Bay Aquarium Research Institute
University of Miami
The MITRE Corporation
Oregon State University
Scnpps Institution of Occanogruphy
Scripps Institution of Oceanography
Consultant
Environmental Research Institute of Michigan University of Washington Yale University
University of Alaska/Consultant
the course of theirignificant amount of effort was provided by the following individuals who researched much of tbe information and contributed in major ways to drafting sections of this report:
George O. BizzigOtti
Dr. Robert Edson
Mr. Robert B. Ccrstein
Dr. Jackie Grebmeier
Dr. Richard D. Mavis
Dr. Thomas K. McEntcc, Jr.
Dr. Wade H. Smith
Dr. Fred Tannis
Dr. Barron L. Weand
Systems Office of Naval Research Mitretek Systems University of Tennessee
Mitretek Systems Mitretek Systems Mitietek Systems:
Environmental Research Institute of Michigan Mitretek Systems
The environment in which it was possible io conduct Urn vtudy was created by the National Intelligence Councilpecifically by BG John R. Landry (Rett. National Intelligence Officer for General Purpose Forces.reat number ot source* ol information and llic effort* of numerous individuals were made available
A number of individuals inihcU.S. Government provided background information and lent then nine banmi discussions and review* as this study was beingey include the following:
Robert Edson Doug Demaster Edwin Gicr
William Fceny Tim Smith
Vidar Wcspastel Robert Warrington Dr. Yu-Chu Yang
ot Naval Rccarch
National Oceanic and Atmospheric Administration
U.S. Army. Edgewood Research Development
and Engineering Center
National Ground Intelligence Center
National Oceanic and Atmospheric Administration
National Oceanic and Atmospheric Administration
National Intelligence Council
U.S. Army, Edgewood Research Development
and Engineering Center
with many of its predecessors, this MEDEA eflort wa* made possibleesult of the ellorts of Dr Linda Zall. Central Intelligence Agency, Director of MEDEA Funding was provided through rhc Intelligence Community's Em ironmcmal Intelligence and Applications Program. Mi. Bo Tumasz. Program Manager.
Thereumber of MEDEA members, not listed a*ho nevertheless contributed ideas and comment* and thereby substantially improved the result Their eftoru ire gratefully acknowledged.
The MITRE Corporation provided technical and production support to the conduct of the study and to the preparation ofolume- Of special note wcic die dedicated efforts of Ms. laync Lyons, who acted as the technical coordinator. Ms. Kalhie Barnes coordinated production, including dealing with the large number ol figures. Ms. Helen Duval selflcssly edited this undertaking. Administrative support was provided by Ms. Robhin Bradley.e Howard. Ms. Sabtina Lowe and Mr Kob Sullivan, all of whose efforts are gratefully acknowledged. Many of MEDEA's efforts, especially this one. have been greatly facilitated by thefforts of Mr. Gary Hollis. MITRE.
We wish lo acknowledge the bnvironmenlul Research Insiitute of Michigan for its speedy translationook only recently published in Russian.
MF.DEA would like to warmly acknowledge Ihcl has received trom the many individuals and organizations whose dedicated efforts have been so instrumental to whatever success is achieved here
tabicb*SSpfis:;
UST OF
UST OF
EXECUTIVE
Problem
Historical
The Arctic Radioactive
Steps in the
CHAPTER 2CW DUMPING IN THE ARCTIC
Total
Ocean Dump Sites in Arctic
Dates of
Weapon
CHAPTER 3ENVIRONMENTAL
Barents
Kara
White
Primary Production and Energy Transfer Through the Food
Threatened and Endangered
Indigenous
Other Activities in the Study
Munitions Disposal25
CHAPTER 4SEAWATER
Characteristics of the Marine Environment Affecting Persistence of Chemical
Warfare
Chemistry of
Chemistry of
Chemistry of
Chemistry of
The Chemistry of Arsenic in the
Effects of Pressure on Hydrolysis
Summary of Significant Chemical
CHAPTER 5RELEASE SCENARIOS
Agent Release from Individual
Spatial Distributions at Dump
Agent Release
CW Agent Release
CHAPTER 6TOXICITY
Toxicity of Tabun and its Breakdown
Toxicity of Sarin and its Breakdown
Toxicity of Mustard and iLs Breakdown
Toxicity of Lewisite and its Breakdown
CHAPTER 7PHYSICAL
Tlic Conceptual
Agent Release and
Spatial and Temporal
Toxic Levels from an Impulsive (Acute)
Steady State (Chronic) Release of CW
vcls at the Dump
Potential foi Accumulation of Contaminants in the
Summary of
CHAPTER 8IMPACT ON
of Released Contaminants to Bioaccumulale in the Food
Ecological Effects at Deep Disposal
Ecological Effects al Shallow Disposal
Economicon Oil and Gas Exploration and Exploitation
Threatuman Health and
Cumulative
i in
UST OF FIGURES CHAPTER 1
FigureIllustraiion of Ocean Dump1
FigureDumping Grounds in the Baltic
Figuie 1Dumping Grounds in Japanese-4
FigureSea
Figure 1Waters-8
Figure
CHAPTER 2
FigureAreas Associated with Potential CW
Dumping
CHAPTER 3
Kigureof ihe Barents Sea
FigureSurface Currents in the Barents
KigureProfiles of Temperature. Salinity, and Densityt)
in Arctic and Atlanlic Water Masses in the Barents
FigureComponents of the Pelagic Fond Weh in ihe Barents
KigureComponenls of the Bentho-Pelagic Food Web in the
Barents
Figureof Benthic Biomass in the Barents
Kigureof Ihe Kara
FigureCirculation of the Kara
Figureand Temperature Profiles in the Ease Novaya Zcmlya
Trough in September (A) and the Following Winter
FigureIce Conditions in the Kara
Figureof Benthic Biomass in the Kara
Figureof the White
Kigureor Lipids from Phyloplankton toCapelin in the
Barents Sea
CHAPTER 5
FigureIllustraiion of Ocean Dump
FigureMunitions Related
FigureIllustration of the Dtslribulion of Release
Figureof Agenls Released at Various
g Mass of Mustard Remaining
FigureRale of Dissolved Mustard from Two
FigureSpalial Density of Agents at ihe Dump
VIIAFTHK 7
Illustration of the "Size" of the Problem
7-2
.if Chemical Reaction Quantities
>
of Agent Release Model*
7-4
Ocean Environment and Coordinate System
7-5
of Tabun (OA) and Sarin (GB)
7-6
<GA(/Sarin (GB) Hydrolysis for Various Release Rales Hydrolysisg of Lewisiteeleasedg Day'
7-7
7-8
g of Lewisite (L) Releasedg Day 1
7-9
and Hydrolysisg of Mustard (H)
and Hydrolysis Near the End of Life
oln Height Above the Scafloor
Illustration of Acutely Released CW Agent
of Agent Mass Containedox of Volume xL^U
of Constant Concentration on the Scafloor for Tabun (GA)
Volume* for Three Concentrations of Tabun (GA)
Volumes for Releaseg of Three Agcnis
men non less Plume Function vs.oordinate
Appearanceoxic Plume
<H) Concentration on the Scafloor Along ihe Plume
g Munition Charge
Plume Concentrations of Tabun (GA)
t Current
7 21
of Tabun (GA)i Current
Plume tor Tahun (GAl/Sarin (GB)g day')
Plume for Tabun (GAVSann (GB)1 kg day )
Plume lor Tabun (GAJ/Sann (GB)g day1)
Plume for Tahun (GAVSarin (GB)
1g day')
(Seafloor) Area for Tabun fOAVSarin (GB)
t Current
(Seafloor) Area for Tabun (OAVSarin (GB)
t Current
Volumeor Tabun (GAl/Sarin (GB)
a Currentl
Volumeor Tahun (GAVSarin (GB)
a Currentt
ol Arsenicewisite (L) Plume
ki Current)
of Direct Toxicity al EPEC for All Munitions
Volume* by Site for tbe Initial Five
Release
Area* for the Initial Five Percent Release
Volumes for Steadyive Years
Volume* tor Steadyifty Years
Areas for Steady Slateive Years
Areas for Steady Stateifty Years
of Arsenic vs. Area (Uniform Distribution)
II Ol TS
8
l
Maximumfhe Hi)fonts and Kara Seas That Could Be Containmated With Arsenic From Lewisite at theg kg' Biological Benchmark Coricentruiion Maximum Size of Area in the While Sea That Could Bc Contaminated Wnh Arsenic From Lewisite at theg kg1 Biological Benchmark Concentrationcto- Norwegian Cod Congregation in the" Barents Sea
Region* of Haddock Congregation in tbe Barents Sea Fishing Intensil) tnenli Sea
K 14
8
V
CHAPTER 10
Contaminated Volumesree Concentrations vs. Quanily
9-6
23
Flow
CW Munitions Related Incidents
Schematic Illustration ofistribution of Release Events
5
Dm
USTOFTABLES
CHAPTER I
CHAPTER 2
CHAPTER 3
Dumping in the Baltic Sea
Summary Table. Dumping of Chemical Warfare
Agents al Sea
Chemical Agent Quantities Dumped in Russian Arctic Seas (in tons)
Quantity of CW Agents in Individual Munitions
Characteristics of Explosives Disposal Sites in the Study Region
1-5
chapters
TabkQuestions Related lo Release
TableContaminated VWuma in Hypothetical
TabicDistribution ol Release
TableMaximum Lifetimes of Musiard (H) in
TableRelease Modelse
Tabicof Agents and Densities at Each Dump
Density of Leaking3
CHAPTER 6
TableConcentration Thresholds for Toxic
TableValues for Tabun (GA) in Laboratory
TableValues for
'TabicValues for
TableValues for
TableValues for Satin (GB)boratory
Tableto Death of Aquatic Species at Various Concentrations
of Sarin8
TaNcValues forAcid. mono.
TableValues for Mcihylphosphonie
Tableof Fluoride lo Aquatic
Tabicof Lewisite lo Freshwater
TableValues for Arsenic in AquaticI:
CHAPTER 7
hysical
TableQuestions Related to Physical
TabicGuide to Chapter 7
Tableto Specific Concentrationsg of
Tableof Seafloor/Sea Surface Concentrations
Radii and Associated Timesg of Tabun
TableInstantaneous Volumes and Associated
TableVolumes. Areas, and Timesg Releases Into a
TableExtent ol Contamination from Simultaneous Release
of All Munitions Dumped to Arctic
CHAPTER H
CHAPTER 9
Summary of Potential Rnvironmcnlal, Health. Safety, and Rconomic Effects Imm ihe Presence of Chemical Munitions in the Barents. Kara, imd White Seas
Area of Arsenic-Contaminated Sediment at Two Biological Benchmark Concern rations at the Ifccp Disposal Sites Sediment Arsenic Concentrations That Would Result if All Contamination is Retained Within the Boundaries of the Deep Disposal Sites
Potential Arsenic Sediment Concentrations at Disposal Siten the Pechora Sea Region
Arsenic Cancer Risk of Some Regulated or Background Sceruitos Cancer Risk of Consumption of Fish Contaminated With Arsenic
Hydrolysis Hroducls From VX
LDh Values for VX and2 in Laboratory Animals Twenty-Four Houralues for VX in Aquatic Species Estimated Benchmark Toxic Concentrationsas Estimated Terminal Velocities of Sinking Munitions Estimated Penetration Depths for Postulated Munitions Bundle*
3
1
0
tvi
SIMARY
STATEMENT
The objective of this study was touantitative assessment of the potential for significant adverse impact on the arctic environment arising from the dumping of chemical warfare (CW) munitions in arctic seas by the USSR during the Cold War.
task included estimating-the potential for significant effects on the arctic ecosystem and related human factors. It did not include conducting an assessment of ilte compliance of ocean dumping of CW munitions. law or international convention, nor did it compare the risks associated with various possible disposal methods.
This study was primarily concerned with determining the potentialignificant environmental effect, that is, one large enough to be of some concern. national security, possibly through impact on economically important arctic fish stocks or on human health and safety.
RANGE OFEFFECTS
Beforeiscussion of the specific problem posed by USSR dumping in arctic seas. It will be useful io set the stage by reviewing the variety of possible environmental effects. In general CW agents have the potential to affect the ocean environment in various ways, some relatively benign, some very serious.
agents arc basically immobile and relatively non-toxic in seawater once released from munitions:
Other agents have very short persistence in seawater
and. therefore, presumablyimited threat to the environment;
Some agents or their chemical reaction products may have the potential for biomagnificalion. resulting in increasing concentration within organisms as they pass upward through the food chain;
The toxicity of some CW agents is so high lhat one cannotriori, their causing effects over very large areas, as ocean circulation acts to transport toxic plumes across the arctic seas;
CW agents can add to an existing burden of anthropogenic contamination of the seas causedide variety of toxicrom industrial wasles. and thus can contributeumulative effect;
Still other agents may remain contained in dumped munitions on thefloor with their casings as vet uncorroded and their agents uiireleascd.
Once CW agents are released into the sea. accounting for the resulting environmental effects is complicated by their complex and poorly understood toxicity to marine organisms and by (heir transport by ocean currents while the complex processes of chemical reaction and dilution, through turbulent mixing, take place.
No comprehensive scientific study of the entire chain of physical, chemical, toxicological, and biological processes is known to have been conducted. Nevertheless, several reports, primarily those concerned with the Baltic Sea. have concluded thai these compounds pose little or no environmental threat, largely because of the chemical degradation of CW agents in seawater. The exception frequently noted is the threat to fishermen who may come into direct contact with agents inadvertently collected in Ihcir trawls.
The logical Now of the present assessment is shown in the Haute below.
APPROACH
Most of what is known about arctic dumping of chemical munitions comes from anecdotalresent assessment is basedynthesis of the best available estimates. Tbe resultant picture of CW dumping is combined with resultsetailed analysis of the seawater chemistry and the toxicity of CW agents in computations of the spatial exteni of toxic concentrations produced by the actions of ocean currents and turbulent mixing. Once the extent of toxicity governed by physical ocean processes is estimated, the resulting impact on the arctic marine environment is assessed.
Flow of the Sludy
^EXECUTIVES!
CONTEXT OF OCEAN DUMPING
Beginning before World War II and continuing through the Cold War. ocean dumping of chemical weaponsairly common international practice. Many nations, including the United Slates, other Western countries, and the USSR used this method of disposal of CW slocks.
compiled by. Army7ovements beginningft and ending on
In the, an ad hoc committee of the National Academy of Sciences (NASj was appointed in response lo an Army request to evaluate the hazards involved in the planned ocean disposal of suiplus chemical warfare slocks. The committee
the years immediately following the war. there was extensive ocean dumping by the Allied powers in the Baltic Sea and in Japanese waters. Large ammunition depots were discovered in Germany, containing mustard gas gienadcs and mustard gas. sneezing gas, and tear gas bombs.
6n0 tons of chemical munitions including mustard gas. sneezing gas, and tear gas. were dumped in the Baltic Sea, fifteen miles off the Danish island of Bornholm.epth of.ons of chemical munitions, predominantly mustard gas, were dumped in tbe Gotland basins off the coast of Sweden and possibly In other areas of the Baltic. Numerous reports and papers in medical journals have appeared providing statistics on accidents to fishermen engaged in trawling in the areas of the Baltic dump sites. Studies of the Baltic Sea CW problem continue to be conducted by ihe Helsinki Commission.
Details of dumping operations in Japanese waters were not widely known2 when,esult of numerous accidents with disposed CW reported in, the Japanese Prime Ministerational inquiry to investigate Ihe status of the chemical weapons disposed of in.
Surviving records. Army post-World War II dumping track the movements of CW agents, identify the ports of departure for ocean dumping and, in some cases, specify the location of ihe dump sites. The quantities dumped are given, in most cases,umber of barge loads or by the name of the ship. It appears that mosl or. dumping involved CW munitions that had been scaled in concrete and steelistory of (he transport of chemical weapons report by noting that "continuing inaction will not reduce the hazards of eventual disposal of the chemicals and munitions intended for disposal in9 Operation CHASE and, in some instances, will increase them."
The commit tec made several specificconcerning the surplus chemical warfare munitions:
For cluster bombs containing the agcnl Sarinisassembly at their storage site and chemical destruction of the withdrawn Sarin.
For bulk containers of agent Mustardncineration.
For concrdc and steel "coffins" containing Sarin-filled rockets, further studyechnical group including experts on demolition lo consider whether ihereraciically feasible way to dispose of the coffins on an Anny establishment. In the event that the proposed study provided no feasible alternative method, ihe NAS committee recommended ocean dumping of the coffins. This is in facl what occurred.
This NAS study also noted that the effects on the ocean environment from ocean dumping of Sarin should be minimal because the agent would be dispersed only near the seafloor and hydrolysis would limil its active lifetime.
nother NAS Commilicc was asked to review methods for disposal of. Army's stockpile of CW agents. The Commitice nolcd that ocean dumping was not consistent with current national and international law and "attempting either to modify Ihe
ESS
1 jws or lo seek an exception does not seem justified at this lime" No detailed technical evaluation of the ocean dumping option was made.
In contrast lo the well-characteri/ed campaigns of chemical weapons dumping in the Baltic Sea, Japanese waters, and off the United States coasts, reports of such dumping by the USSR in the arctic seas have never been confirmed officially. The major source of infoimation on Arctic dumping has been Lev Federov' who recently has written books on the subject of CW weapons and their disposal. Additionally, the open press has described alleged incidents in which obsolete Soviet chemical weapons, as well as captured World War-ll-cra German chemical munitions, were dumped in the northern and eastern seas surrounding Russia. Any study, including the present one. conducted in the absence of actual records of this dumping must contain substantial uncertainty, especially regarding site locations and total quantities dumped.
CW PRODUCTION AND INVENTORY
Mustard production by the Soviet Union15 was estimated to have0 tons'. Production of low-purity mustard began prior0 and, while reliable estimates of this phase of mustard production arc not available, it is likely that up0 tons were produced. Lewisiteroduction during World Warlightly0 tons. Consequently, combined production of mustard and Lewisite may haveons
There arc descriptions of the capture of German production facilities for Tabun (GA) by the Soviet Army at the end of World War II. Allied data indicated that the German facility had0 tons of Tabun. For purposes of this assessment, it has been assumed lhat no more0 tons of Tabun were dumped in arctic seas. This estimate is possibly too high, if one considers the German production only.
Sarin was apparently not produced successfully by the Soviets until theerman Sarin production facility was under construction at the end of World War II and the Soviet Army captured the equipment for its production, including pilot quantities and transported everything to the Soviet Union. It is not known if stocks of German Sarin weapons were captured by the Soviet Army. For the present study, the assumption was made that no moreons of Sarin was dumped in the arctic seas.
This assessment does not require precise dates of the dumping since our primary concern is to estimate environmental effects once an agent was released, not to predict when"thai release would, or did. occur. Based on Federov's analysis, wc assume thai the dumping of mustard and Lewisite took place in; the Tabun was also dumped in; and that in. Sarin as well as additional Tabun was dumped.
CW DUMPS IN ARCTIC SEAS
Identification of dump sites for this assessment was based upon delineation of restricted or hazardous areas on Soviet and later Russian-navigation maps for the arctic seas of interest. Based on this, and other, information, it is highly probable that dumping of munitions containing the CW agents Tabun. Sarin, mustard, and Lewisite were dumped in thousand metric ton quantities in the White. Kara, and Barents Seas.
The tive sites identified in this assessment are shown on the map below.
Restricted Areas Associated with Potential CW Dumping Activities
1
EXEGl.TlNjte:V{
is estimatedaximum of0 tons of mustard and Lewisite were dumped into the White Seaaximum0 tons were dumped into the Barents and Kara Seasaximum0 tons of Tabunon* of Sarin was estimated io have been dumped in the White. Barents, and Kara Seas. These quantities refer to CW agents only and not the weaponi/cd quantities, which woulc wete two reported deaths resultingustard disposal mishap. As recently1 incidents of
fishermen finding CW munitions or agents were reported. Reports to the Helsinki Commission on Dumped Chemical Munitions state that, as recently as
n examination of Baltic dump sites showed ihe presence of both intact and completely corroded munitions remaining on the seafloor.
CW AGENT RELEA SE
A compilation of medical records and incident reports involving fishermen who recovered CW munitions in the Baltic Sea and Japanese waters since the end of World War II indicates lhal CW munitions dumped in the sea will remain intact for long periods if left undisturbed. The Baltic experience slums clearly that if fishing, especially bottom trawling, occurs at the dump sites, munitions on the seafloor can be disturbed, leading to harm and sometimes death.6hereotalatients suffering from mustard gas exposure in the Balticotalere treated as ambulatory patients andere admitted to the hospital. In7here
Unlike the Baltic, there are no reports of fishermen encountering chemical weapons from arctic seas. This difference could be because ihe "Hazardous Dump Site" warnings on Russian charts has limited the scope of trawling activities at these sites, leaving (he munitionsie undisturbed on the seafloor for decades. Another contributing factor is that, with the exception of the Barents Sea. the arctic areas have historically been less heavily fished because the presence of pack ice limits access during most of the year.
Also, even when there has been widespread and continued disturbance of dump sites, as in the Bailie, il appears that large numbers of munitions continue to remain intact. If this were not the case. CW agents, primarily lumps of muslard. would not continue to bc
Human Encounters with Dumped Chemical Weapons
recovered decades later, because the agent would have dissolved.'
Lacking detailed information of ihc condition of the dump sites, it is possible tolausible hypothetical picture based on what is known about other dump sites, shipwrecks, and the physics of ocean systems. The first step, following dumping, willlow corrosion of the steelrtillery shell or bomb casings. This is likely toorous mass, or sludge, of iron oxides, until finally, the integrity of the casing is breached and the agent is released into the sea. At this point, conversion of lite CW agent along various chemical pathways will begin, as will transport in the local ocean current and dilution through mixing, in the near-bottom turbulent boundary layer generated by the current.
CHEMISTRY OF CW AGENTS IN SEAWATER
Chemical transformations that the CW agents Tabun. Sann. mustard, and Lewisite are likely to undergo in the marine environment are critical issues along the path to assessing their impact on the environment.
The chemistry of CW agents in the marine environment is dominated by hydrolysis, tlie reaction of the agents with water. For each toxic agent, hydrolysis results in characteristic reaction products. Some of these are basically inert biologically and others arc as toxic as the original agent. These products are described below.
Tabun is fairly soluble in water and hydrolyzeseriod of daysalf life of forty hours. The principal toxic breakdown producttable cyanide compound, HCN.
Sarin is miscible, that is. it mixes in all proportions with water, lt also hydrolyzeseriod of days,alf-life of sixteen hours. Hydrolysis products arc all very much less toxic than Sarin and can be assumed to be essentially inert.
Dissolved mustard hydroly/cs relatively rapidly,alf life of five hours. However, the appearance of mustard in the marine environment is controlled by the rate at which it dissolves, which is much slower than the rate of hydrolysis. The expected lifetimes of mustard lumps corresponding to typical munitions quantities are eight monthsgn an artillery shell, eighteen months0 kg lump, and thirty-nine monthsgomb.
Lewisite is soluble in water and hydroly/es very rapidly, in seconds. The initial hydrolysis products of Lewisite are as toxic as lewisite and persist infor months or longer. Tlie major toxic Lewisite reaction productschlorocthcnyl) arsonous acid and inorganic forms of arsenic. Their long persistence will result in redistribution by transport and mixing.
TOXICITY TO MARINE SPECIES
There are few measurements on the toxicity of CW agents to marine species. However, therereat deal of information on toxicity to other organisms. The synthesis of this information provides all entry into the estimations of effects on marine oiganisms. The results show dial, of the short-lived compounds, agents. Or hydrolysis products, Tabun and Sarin are the most toxic. Of the long-lived compounds, organicydrolysis product of Lewisite, is the most toxic.
The primary source ot aquatic information used in this study was the AQUIRE database [Aguatic Toxicity Information Rctnevall, which is supported by. Environmental Protection Agency, The AQUIRE lexicological dala summary is designed for usetand-alone reference database origh-quality data source for risk assessment tools. Test organisms are limited to those that ate exclusively aquatic. The system presently contains data on morehemicals,eferences and approximately sixty effectsoxicity tests.
Where available, measuredalues (the concentration of the agent in water, which resulted in the death ofercent of the exposed marine organisms during the specified time interval) were the most useful measure in assessing the toxic effects. Where LC^ values were unavailable, reported LDW values (the lethal dose of the agenl. which resulted in the dealh ofercent of the exposed organisms during the specified time interval) were used.
ol mu-flanl <uJ utberadarctvd qukntiuilicly in Ihn xuiy.
ES-6
For the purpose ofoxic threshold for the chemicals of concern, ihe lowest reported LCW was identified and one-tenth of this value was chosenoncenlration at which marine organisms would not experience acute toxicity. This value is identified as the Estimated No Effects Concentrationhe EN EC multiplied by tenheevel) was established as the Estimated Probable Effects Concentrationshe ENEC multiplied by one hundred was established as ihe Estimated Lethal Effects Concentrations (ELEC).
For simplicity, and because data does not exist loore fine grained analysis, these levels (ENEC.re taken to apply equally to nil marine species. Data loore fine-grained analysis does noi exist and this assumption consililuies one major source of uncertainty in this study.
EXTENT OF CONTAMINATION: SINGLE MUNITIONS
For the four types of CW agents considered, estimates were computed showing that Ihe contaminationeaking, single CW munition willocal one, that is. confined to small ocean areas having dimensions on the order of hundreds of meters or less. This conclusion is valid at all concentrations of environmental concern. There is essentially no possibilily of dispersing loxie levels of these agents throughout the entire arctic via ocean circulation.
The mosl plausible form of release of agents, other than mustard, is through pinholes in the casings formed by corrosion. It is expected lhat once pinholes develop, agents will leak into the sea. This process may lasi days, even weeks or months. Once released, the agents will cause toxic plumes lhat have their maximum extent on the seafloor
For release from single munitions, these plumes at ENEC will have dimensions on ihe orderewmeters or less along Iheew tens of meters across ihe curreni.ew melers thick above the seafloor. Plume dimensions aiPEC will be much smaller. The volume of seawaler contaminated at ENEC that is contained inlume will be no greaieiew thousand cubic melers and may he much less.
Plumes will persist while the CW agent is releasing from ihe munition, the slower the release, the longer the period. However, it also follows that the slower ihe release rale, the smaller the plume. The maximum volumes of contamination can occur only for release rales lhat wouldypical artillery shellay or less.
Because of iis high viscosity and low solubility, the dispersal of mustard occurs differently. Following an abrupt and complete disintegrationunition casing by corrosion, ihe appearance of dissolved mustard agent in ihe sea is determined primarily by ihe exposed surface areahe shape of tin: lump offter ihe last of the mustard is dissolved, the remaining agent in solution hydrolyzes rapidly and within twenty-five to fifty hours can be regarded as being completely eliminated from the environmenl. However, dissolutionlow process, wiih estimates indicatingg lumps remain for monthsg lumps for several years.
Moreover, musiard, once if is released from the munition and dissolved, can generate concentrations at loxic levels only in ihe immediate vicinity of the disintegrated munition,lume only tens of centimeters in length and several centimeters thick. This is an upper bound. Thus, any adverse environmental effect can result only from direct contact with musiard exposed on the seafloor.
EXTENT OF CONTAMINATION: ENTIRE DUMP SITES
The exienl of loxic waters at any given lime at Uie dump sites were found to be limitedmall fraction of the area of the dump site itself and to heightsew melers above the seafloor. In the worst case scenario, the entire area of the dump site would be contaminated lo levels of EPEC and would remain so for years.
At ihe shallow dump site.. in the southern Barenls Sea. Ihere may bc sufficienl munitions to extend arsenic contamination upward throughout ihe water column. At die deeper sites toxic levels cannot extend upward toward the surface and into regions where increased light levels would support more biological activity.
The figure above shows an estimate of ihe fractional area of the seafloor thai could be contaminated lo an
ENEC level at the various sites. The area fiaction is referenced to ihe seafloor area of ihe regional sea in which the site is located. In this worst case cslimaic, ii was assumed that all of ihe munitions release iheir CW agem over five years, an unrcalistically short period, asBaltic experience shows. It is seen that in all cases, the contaminated areas arc less than the areas of the dump sues and are very small fractions of the total areas of the seas in which the dump sites are locaied. Ihe fractional areas of the various sites are indicated for reference.
Because of the small sizes of ihe toxic plumes generated by individual munitions and the rcmoic locations of the dump siics, there is very litile possibility that loxic concentrations could be transported to nearby shores where they might more directly affcci human activities. There is even less likelihood of transport lo distant shores that would pose international concerns.
'Note tOgimlhiiMC vafc in mil figuor-
EXKfcl 'TIVE SIIARV
ARCTIC ENVIRONMENT
All of Iht! dump sites ate located in relatively shallow coniincntal waters- The Barents Sea has severaln deep antong shallow banksarge shallow area lesseep called the Pechora Sea. Most of the Kara Sea is lesseep, with deeper areas adjacent lo Novaya Zcmlya and troughs ott'the northern portion of the shelf. The White Seaentral basinepthn and is connected io ihe Barents Seahallow inlet of.
A pelagic (within ihe water column) food web is dominant in the walers deeperentho-pelagic (seafloor and water column) food web is dominant in shallower waters. The benthic (seafloor) community is an important component of the food web of tlic bentho-pelugic system and is much less important in the pelagic system. The figure below depicls the major components of ihe benlho-pclagic food web.
Barents Sea fish and shrimp populations are exploitedarge and important commercial fishery. Commercial fish landings from the Kara and White Seas are small in comparison. The Barents, White, and Kara Seas arc areas of active exploration for oil and gas resources.
POTENTIAL THREATS TO THE ARCTIC ENVIRONMENT DUE TO PAST DUMPING
The regional marine systems can potentially be affectedariety of activities past and present. These include ihe testing of nuclear weapons in the atmosphere on Novaya Zcmlya, the disposal of solid and liquid radioactive material, the exploration and production of oil and gas resources, the over-exploitation of commercial Fish stocks, and the disruption of benthic communities from using bottom trawls in the presence of dumped chemical weapons-
The main threats to marine ecosystems from the release of CW agents at die disposal sites are the direct toxicity of released agents and their breakdown products, bioaccumulation in the food web and long-term contamination of sediments from the arsenic contained in Lewisite.
Potential threats to human health and safety include the consumption of fish contaminated with arsenic, the capture of munitions and mustard lumps in trawl nets by tlie conunercial fishery and the exposure of crews to agents during oil and gas resource exploration and development; activities.
Potential economic threats are the loss of commercial fish markets because of arsenic contamination and increased costs of exploring for and developing offshore oil and gas resources.
Effects from chemical munitions would be cumulative with the adverse effects caused by other activities in the regional marine environments.
THE LIKELIHOODAJOR ECOS YSTEM CATASTROPHE
This sludy found no evidence that the past dumping has ledajor catastrophe to the regional ecosystems or the arctic environment,hole, nor is there any evidenceotential future threat of this magnitude.
The maximum area of the seafloor that could be affected by acutely toxic plumes would be no larger than the area of the disposal site and could be much less. In the absence of upwclling. toxic plumes would be present onlyew meters of the bottom. The worst-case effect would be the loss of benthic biomass and productivily in the disposal site area for uporty-year period.
Tlie figure on the following page shows the distribution of benthic biomass in the Barents Sea in units. High values typically found in continental margins would be; or greater. 'Inc dump sites are seen to be located in areas of relatively low biomass.
At the four deeper siles. the effect of losing this productivity on the ecosystem in the vicinity of the disposal site would be small because of the small contribution of the benthic community to the predominantly pelagic food web.
Effects on marine mammals would be small because the siles arc loo deep for walnis. which feed on benthic organisms, and are probably unattractive feeding areas for seals, because of the low benthic biomass present. Whale species that normally exploit mid-water food sources would not be likely to enter water very near the bottom.
It is unlikely that toxic levels at the shallow southern Barents disposal site.. would reach high enough levels to result in catastrophic effects. Effects on the size of ibe bini, walrus, and seal populations on
the northern and western shores of Kolguev Island could bc moderate to large because the loss of the benihic produciiviiy within the site area could significantly reduce the carrying capacity of the marine region supporting these populations. Effects on the larger Pechora Sea region would be small because the benthic area affected is small relative to the shallow production area withinsobath. The area of toxicity is also very small at this scale and could onlymall portion of the slocks of pelagic organisms that arc widely distributed in Ihe region.
Some fish in the vicinity of the shallow disposal siie are likely to have increased body burdens of arsenic. Sale Of fish harvested from this area could be banned in Finland and the United Kingdom if their arsenic concentration increases as the result of degradation of Lewisite. At present, these two European countries arc the only countries that have standards for the maximum arsenic conccntraiion allowed in commercial fish products. Sale of fish oils would probably not be affected because the refining process greatly reduces the comeni of contaminants.
OF IMPORTANT MARINE SPECIES
It is improbable that any dominant regional species would be so significantly affected as to imperil its viability.
The major vertebrate and invertehralc populations are distributed over regions very much larger than the disposal sites. The contribution of benthicat deep disposal siles to pelagic stocks is small. The loss of carrying capacity at the shallow site is small compared to ihe very large regions that support the major stocks of invertebrates, fish, marine mammals, and birds.
While this study was conducted on the basis of the live identified CW disposal sites, there is sufficieni diversity in their ocean environments to provide some confidence that the major results are relatively insensitive to details of site location. It is important to appreciate that while this assessment finds little possibility of major catastrophes to ecosystems or species, ocean dumping or highly toxic CW agents will certainly harm, even kill, numbers of individual organisms within the areas of the dump sites.
ECONOMIC EFFECTS
Any economic effects on the commercial fishery in the Barents, Kara, or White Seas are likely lo be small to moderate. Effects of contamination on ihe size of commercial fish stocks would be very small, as discussed above. Bottom trawling is currentlyarvesting method extensively used at the deep disposal sites and fishing is currently strongly discouraged in all disposal sites.
HUMAN HEALTH ANO SA FF.TY
Human health and safety concerns could potentially involve exposure of people engaged in off-shore activities, (fishing and oil/gasonsumption of contaminated fish or shellfish, and the possibility Of toxic concentrations being washed ashore by ocean currents.
It is highly unlikely that human health or safety could be impacted by toxic concentrations being carried ashore by ocean currents. Estimates of the extent of such concentrations show them to be limited to the immediate vicinity of die dump site.
Commercial fishing and offshore drilling and pipe laying crews could be directly exposed to chemical agents if these activities are carried out in the disposal sites.
Munitions still containing agents or solid lumps of mustard could bc captured in trawl nets fished on ihe bottom. Boat crews would be at great risk of injury or death when Ihe nets arc brought on board, which has occurred for many years in the Baltic Sea and the Sea of Japan. Drilling crews could be exposedhemical agenl that contaminates drilling mud or drill strings, which arc materials and items lhat return to the drilling platform when drilling operations arc carried out. Pipe laying crews could be exposed lo agents brought to ihe surface and to agents on equipment used for pipeline construction. All of these are "point problems" specific to dump siies.
The region nearn the southern Barents Sea is an area of intense commercial fishing. Inorganic
ESI2
increased risk from consuming fish contaminated wiih arsenic atpm of total arsenic (ten times Ihe likely natural concentration) is in the range of one0 to one. This is at the upper end of the range of increased risk usually acceptable to tegulatory agencies concerned with human health. This estimate is conservative because it is based on Ihc assumption thatercent of the fish consumedeventy-year lifetime is contaminated atpm.
The risk to indigenous peoples consuming large quantilics offish contaminated with arsenic atpmignificant portion of their diet could be moderate. Given this level of consumption, the increased risk would be in the range of oneo onehe upper end of Uiis rangeonservative estimate because it is based on consuming contaminated fish al all mealseventy-year lifetime.
CUMULATIVE EFFECTS
A variety of past and current activities in the Barents, Kara, and White Seas have adversely affected the marine environment. Any adverse environmental or economic effects resulting from the presence of chemical munitions would add to these effects.
The White Sea receives industrial and domestic wastewater effluents fiom human activities. The open press0 spill of thousands of Ions of rocket fuel into Dvina Bay from the Russian military base at Severodvinsk. This spill may have been the cause of an apparently large kill of invertebrates, fish, and sealsarge area of the Bay. Acid deposition, caused by atmospheric transport of emissions from the burning of fossil fuels in Europe, is occurring in ihe region. Acidification of regional soils mayonsequence of this deposition and may be causing the release of some metals from the soils into runoff damaged by bottom trawling. Although the magnitude of the damage is not known, the claim of damage has been disputed.
ENDANGERED SPECIES
The following animals are known io be or could be in the region and are considered threatened or endangered: tbe polar bear, the Atlantic walrus, the gray seal, Ihc narwhal, ihc bowhead whale, the beluga whale, ihe harbor porpoise, and Dall's porpoise. These species are unlikely to be affected at tbe deep disposal sites. Data on the occurrence of these species ai the shallow site was not found during our study, but there may he some risk lo endangered species at this location.
The Atlantic walrus lias die greatest potential to be affected at ihe shallow Soulhcm Barents site. This species feeds predominantly on benthic organisms and could be exposed to toxic plumes and contaminated sediments. The site is in the historic range of this species, although no daia on its existence al the site was found. The potential for effects on this species is likely to be small because the current occupied range of this species is large compared lo the contaminated area.
BIOACCUMULATION AND LONG TERM EFFECTS
Most chemical agents and breakdown products would not bioaccumulate in the food web. Arsenicodesi potential to bioaccumulate in the trophic levels most closely associated with arsenic-contaminated sediments. Some increase would occur in higher trophic levels, Biomagnification io high concentrations would not occur. Significant effects on the ecosystem
due lo arsenic bioaccumulation are nol likely. The potential exists, however, for economic effects on the commercial fishery, as discussed above.
Arsenic in Lewisite is released from munitions in organic forms. It is likely that these compounds would continue to undergo reactions lo inorganic forms and enter the natural cycle of arsenic in the physical and biological environment of (he region. The transport processes for arsenic in ilte marine environment arc nol well understood.
An area of sediment affected atpm was estimated for sevcial quantities of Lewisite in order to bound the issue. This is the concentration lhat is likely to have significant effects on benthic organisms. For Lewisite quantities at Barents, and Kara Sea sites rangingons0 tons, the area affected would0 km'. For lewisite quantities al the White Sea site ranging0 tons, the area affected would0 km'. The likely effect of arsenic in sediments atpm would be to reduce benthic biomass and species diversity permanenily.
Kcosystcm effects at the deep disposal sites would he small because of ihe small coupling between the benthic community and the dominant pelagic community in ihe food web occurring in the deeper waters o( ihe region.
Effects al ihe shallow disposal site wouldeduction in carrying capacity of the Kolguev Island region and some contamination of the food web by arsenic, as discussed above. The existing area ism' and is contaminated with arsenic in the Pechora Sea off ihe southern coast of Novaya Zcmlya.arge area is contaminated al the disposal site, the total contaminated area could bc nearlyercent of the Pechora Sea region withinsobath. Permanent loss of some benthic productivityegion of this size couldodest effect on the carrying capacity of the Pechora Sea region.
SIGNIFICANT UNCERTAINTIES
While there arc many uncertainties that could alter deiails of the analysis in this assessment, there arcmall number that could significantly alter the overall findings.
Toial quantities of CW munitions dumped into arctic seas could he less, even significantly less, than indicated here, with correspondingly reduced likelihood for environmental impact.
All the evaluations of biological impact conducted in this study were based on applying the three benchmark concentrations uniformly to all marine species. This must remain as one of the most important sources of uncertainly, one lhat would be difficult to remove.
If bollom trawling does occur at the arctic CW dump siies. release of agents could bc significantly accelerated and direct und acute harm to individuals and to fish catches is possible.
There are several additional uncertainties important to the analysis of environmental effects. These include the following: the rate of agent release from munitions, transport and fate of arsenic in Lewisite, the number and type of munitions present al each site, and knowledge of (he physical and biological conditions at each siic and its vicinity.
The raie of release of agentsorroded munition is important to determining wheiher acute toxicity is an issueite. At slow but plausible release rales, essentially no toxic plume would be produced. In this siiuation, there would bc no effects from acute toxicily. Additional analysis of corrosion processes could provide some additional insight as could observations of dump sites.
More detailed modeling of arsenic transport could provide some better definition of the area affected al each site. How far the arsenic in Lewisite and its breakdown products are transported before depositing in the sediments determines the concentration of arsenic contamination.
If third generation CW materials, suchas. have been dumped into arctic seas, one could noi easily exclude ihe possibility of environmemal impactery much wider basis than found here. No anecdotal evidenceas dumping in ihe Arctic has been found. However, ihe very long half-lifefive years)as, and its high toxicily .suggestore careful examination of this question mighi bc warranted.
CONCLUSIONS AND RECOMMENDATIONS
This siiiily has foundery small likelihood thai ihe pasl dumping of chemical weapons in arctic seas would causeidespread impart on (he arctic environment thai il would he of concern toational security, however broadly dial is mlerprcied However, local advene impacts ma> bc ptesent but thein this dimension of ihe assessment are large.
The most important information gaps involve Ihe location and condition of the dump sues, the types and amounts of munitions dumped, and when they were dumped. In addition, no reports similar io the various European studies of the Ballic tracking reports of fishermen encountering CW munitions were found.
It is our recommendation that. Government nol approach this information gap solelyonventional intelligence problem. Rather, it should bc viewed largelycientific problem, one where (he intelligence and ihe scientific communities could collaborate.
Russian cooperation should be solicitedhare information refunding past ocean dumping in. and Russian walers. Both countries could carry out an occanographic survey of one of the dump sites considered in this assessment, including collection of water, sediment, biological samples, and underwater photography of the condition ol the munitions. Inow-level ongoing effort might be put in place to monitor local fishing- conditions and. especially, lo collect any information regarding encounters with chemical weapons debris in fish catches. These efforts should draw heavily upon the Ballic experience beginningomprehensive review of existing studies and site surveys of the various BahK CW dump sues
Advantage should be taken of an) tercndipilous opportunity thjt arises in connectionlanned occanographic cruise in orderollect sediment, water samples, und even underwater photographs from one of ihe dump sites.
PROBLEM STATEMENT
The objective of this study was iouantitative assessment ot' the potential for significant adverse environmental impact on arctic ecosystems arising from chemical warfare (CW) munitions dumped in arctic seas. While there have been several assessments of environmental impact associated with CW ocean dumping, there has been no quantitative evaluation of the amounts of CW agents that could be released into the sea. the level and duration of produced toxins, the effects on specific marine species, human health and safety, or economic factors.
It is important to appreciate that what was intended here was to understand the magnitude of any effects on arctic ecosystems and related human factors. It was not to conduct an assessment of compliance. law or international convention of ocean dumping of CW munitions. Further, to the extentull understanding cannot be reached because of unknown factors, the test to he applied will be lhat of "significantor diis study, this was taken to mean an elicit large enough to have national security significance, perhaps through economic impact on the commercial fish market or to human health and safety. The four toxic agents (TA) examined in this study are Tabunarinustardnd Lewisite1
L2 HISTORICAL CONTEXT
Immediately after World War II. Allied Forces needed to dispose of German and Japanese chemical weapon stockpiles. It was decided then that the simplest and safest method for disposal was to dump the captured stocks into marked disposal areas in the marine environment referred to as dumping grounds. Because official records either no longer exist or never existed, details on the dumping locations, quantities, and types of chemical munitions are often sketchy.
Accidents, mostly involving fisherman snaring chemical weapons wiih nets, have raised concerns regarding these dumping grounds (seehese accidents have resultedariety of injuries and provide insight lo life spans of the chemical agents dumped in seawatcr.
Chemical Munitions Dump Sites in the Baltic Sea
At the end of World War II. large ammunition depots were discovered in Germany containing mustard gas grenades and mustard gas. irritants (Clark I. Clark II. andnd tear gas bombs.6n0 tons of chemical
eters in the Boniholm basin, fifteenmiles off die Danish Island of Bornholm. etails the official dumping grounds in the Bornholm Basin.ons of chemical munitions, predominantly mustard gas and irritants, were dumped in the Gotland basins off the coast of Sweden.
Unofficial dumping look place as well, according to eyewitnesses who reported dumping activities north of the Gotlandsacompilationofwhat is known to have been dumped officially and unofficially in die Baltic Sea.
i
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Tbeohikl. N.uhl. -ChemicalAgcmhe Bull*emooi Journal of. Cunvnibe ie. tm ironmeniof the Thinl Inncnvuical SdciiUnc SymftMum.ay IW. HunhufC2
Chemical Munitions Dumping in Japanese Witters
details of dumping operations in japanese waters were nol widely known2 when ihe japanese prime ministerational inquiry lo investigate ihe status of the chemical weapons disposed of in. numerous accidents inrompted ihe inquiry and some details are now known."
after the war, the elimination of chemical weapons was conducted by. occupation forces. as with the german weapons, it was determined that the safest method was lo dump them in the sea in officially marked areas (see.. mandated dial the dumping areas be at least ten nautical miles from the japanese shore and at depths of at. the dumping operations were carried out by japanese workers in chartered disposal ships. il is believed that prior lo ihe close of the war, the japanese imperial army buried chemical munitions on land and dumped chemical weapons into the sea in unmarked disposal sites. although no records of official burial sites were noted, there were reports of numerous accidenis occurring away from ihe official dumping sites.'
Ocean Dumping of CW Agents by the United States
the uniied stales used ocean dumpingeihod for disposal of cw agenis untilhen the practice was discontinued.ummarizes ocean dumping for which records are available,
it appears unlikelyompletely accurate record of united stales dumping activities can be reconstructed.illiam r. brankowiiz of. army office of the program manager for chemical munitions (demilitarization and binary) (provisional)
h.thc Joum suflcrtkp: ot detente agency.ie desmieiio* of ihehe japt*icte
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'
istory. chemical weapons movements6r. Brankowiiz stated lhat "had all of [the Army records) been preserved, [they! would have madeomplete record of all operations. Unfortunately, this was apparently not then testimonyongressional subcommittee, the Departmem of Stale testified that the Department of Defense had not been able to provide records as to where ii had dumped chemicalhe United Slates Government is doublful lhal il would be able to account completely for all of CW agent dumping following World War II.
In addition, theie do nol appear to he any surviving records concerning pre-war activities.
Those records lhal do survive identify the ports of departure for ocean dumping: however, locating exactly where the actual dumping occurred is sometimes difficult. The quantities dumped are given in many casesumber of barge loads, or the name of ihe ship. In several cases, the movements of CW agents into the port prior to dumping can bc found; however, the quantities are given as ihe number of rail cars. Such records do nol account for material loaded
6,
"Brnnkcttiii.Atixitat Hvofumi Minriunr/ Wtivn- Ci-np"<Hl<>n. OfTie* of the Prurnmi Mieujei lor Ocmkal Mimiuani (Denutiinrluel Binary)buidevn Ituniqi Ground. MD.II..
isposal of Umtmctabir CVnwuf AfwurMw. neailnj. before Hie Subeo.nm.iiee on OcwnogrMth, ol Die Committee an Merchant MarineFiihcriet. Houte ofinety nmerial..
al CW agent storageaken by barge from Edgcwood Arsenal.
'Ihe United Stales dumped Lewisiteewisite was loaded on ships and batges at Aim and Adak. Alaska: Concord. CA: Colls Neck, NJ; Bdgcwood Arsenal. MD; Sunny Point. NC; and Charlesion. SC. Of particular significance were ihe following events:
Innons" of Lewisiteons of mustard were shipped to Charleston, where there remained some musiard, phosgene, and Tabun lhat had arrived by ship from Europe. This inaleriul was dumped loose from barges.
Inhe Army conducted Operation Geranium, duringons of Lewisite'* were loaded aboard ihe S. S. Joshuaorld War II merchant hulk, in Charleston.
Inons of Lewisite andons ofere dumped from barges loaded at Sunny Point.
Inilliam Ralston was loaded in Concoidons of Lewisiteombs containingnd scutlled at sea. Inons of Lewisiteons of musiard" were loadedarge in Concord for dumping in
The available documents were nol always precise in identifying where these dumps occurred. For example, "Atlantic Ocean. Dump Sile 'Raker" was the dcstinaiion of6 dumping campaign. However,umber of cases there are slrong indications as lo specific dumping locations. The material loaded al Sunny Point8 was dumped in ihe "Atlantic Ocean Off Southecords from the Naval operation CHASE in ihendicatedhip of surplus ammunition, loaded in Charleston, was sunktatute miles .southeast ofhe Operation Geranium ship was0 miles offitetatute miles easi. northeast of Cape Canaveral. Florida was used for ocean dumping of CW agents loaded at Sunny Point" In contrast, records indicate that. William Ralslon and Ihe barge loaded al Concord were sunk'W. approximatelylalutc miles west ofSanurthcr investigation of Naval records might provide more precise locations for al! the Lcwisile dumping events desenbed above.
Although ocean dumping had been widely used for Ihe disposal of CW agents and munitions for many years, American public atlcniion focused on ihe issue in the. An ad hoc committee of the Nationul Academy of Sciences (NAS) was appointed in response to an Army requesl to evaluate the hazards involved in the execution of planned ocean disposal of .surplus CW siockshe committee began its report by noting lhal "continuing inaction will nol reduce the hazards of eventual disposal of Ihe chemicals and munitions intended for disposal in9 Operation CHASE, and in some instances will increasehe committee then made several specific recommendations concerning ihe surplus chemical warfare munitions:
For cluster bombs containing agent Sarin, disassembly at their siorage sile and chemical destruction of the withdrawn Sarin.
For bulk containers of agent musiard, incineration,
For concrete and sieel "coffins" containing Sarin-filled rockets, further studyechnica) group including experts on demolition io consider whether thereractically feasible way lo dispose of the coffins on an Army establishment. In the event thai the proposed study could provide no feasible alternative mclhod. Ihe NAS committee
*f= fMlinuo. of ihe Jciunlof CW uftnto. owed mi ibr number ot milol nwnliion* thipptd to Ihe pon.jpwiivcm* Of nwniiMiiit per rail or. awl lypkal.. mustard by weigh! inK* jgeni h( we^to
h? Tijehl in buli. mtilairrni
"Aciwi wriEhi of CWrakubittl ftom toummg dumped tutiu W> fl mnnkinn:Reference 12
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ocean dumping of the coffins. This is in lad wtuu occurred.
The commitItx concludeduggestion outside us terms ol reference lhal "Ihe Department of Defense adopt basically ihe MM approach io CW agents and munitions thai the Alomic Energy Commission has adopted toward radioactive waste products from nuclear reactors. It should he assumed that all such agents and munitions will requite eventual disposal and thai dumping al sea should lie avoided."
he United Slatese Convention on the Prevention or Murine Pollution by Dumping of Wastes and Other Mailer, which explicitly prohibits the dumping of materials -produced ftw biological or chemicalilier signatories of ihe convention include nations such a* France. Italy, Japan, the Union of Soviet Socialistndmied Kingdom which formerly or currently stockpile chemical weapons. Alsohe Marine Protection. Research, and Sanctuaries Act was enacted, which prohibits the oceanhemical warfare agents from the United State*
nother NAS Committee was asked to review methods for disposal of. Army'* stockpile of CW agents. The Committee noted lhat ocean dumping was not consilient wilh eurrem national and international law and "attempting cuhcr to modify the laws or to seek nn exception doe* noi seem justified at tinso detailed technical evaluation of the ocean dumping option was made.
Accidents Related to CW Ocean Dump Sites
Accidents have been reported in both the Baltic Sea and along the const of Japan. No reported accidents due to CW' dumping were found in references. disposal activities other than accidents reported during the dumping operations in ihe. Moat reports in Germany and Japan were from fishermen who inadvertently had vrurcd chemical weapons casings with their net* In nun* instances, the fishermen were unaware ot the danger of the chemical agents and severe injuries resulted. Accidents were also reported during the CW disposal process and during ihe decontamination of exposed vessels.
Il is io bc noted that because Denmark pays fishermen for the discovery of contaminated catches, there is extensive statistical daia on ihe findings of chemical agenls in Ihe Ballic Sea by Danishhe statistical data exists6n ihe time6he annual reported incidents range from live to fortycighl.here was an increaseiscoveries. The reasons for this increase arc not entirely clear although shifts in fishing grounds and heightened awareness of the problem among Danish fishermen are probable causes. German fishermen receive no incentive lo report findings of chemical agents and therefore, there are fewer reports about finds by German fiShcrmcn in the Baltic Sea.
Most accident* base involved ihe dredging up of mustard gas. which over time typically forms an outer crustolatile, viscous liquid cure. In liquid form, mustard gas penetrates ordinary textiles and leatherewlthough oilskins, rubber and plastic offer limited protection.*'
General injuries resulting from contact with chemical weapons include lesions accompanied by rashes, blistering and. in extreme cases, pathological death of tissue. Eyes are also commonly affected through the development of lesions. Increased leat flow, sensitivity lo light and swelling of the tissues."
altic Sea Accidents
hows the distribution of musiard gas injuries by year in ihe Ballic Sea.6hereotalatients reported suffering from mustard yas cxrx>*iirc in ihe Balticotalere treated as ambulatory patients andere admitted lo the hospital In7here were two reported deaths resultingustard disposal mishap. The study ran only
1 'Krterrmr 2
apanese Accidents
ln Japan, thereeported incidents, resultingnjuries andasualties (see' These incidents include accidents attributed to both unofficial land and sea disposal as well as official sea disposal.
There was no distinction made in the reported accident statistics between land and sea incidents. It was noted that many of the accident site have occurred on land and arc attributed to unofficial disposal of chemical weapons by the Japanese Imperial Army, probably during the later stages of World War II.
apanese Waters Accidents"
RdciTOM
1,3 APPROACH
This study estimates the environmental impact of chemical munitions disposed in the Russian arctic. As such, there are many imponderables, not the least of which concerns the quality and diversity of information. Most of what is known comes from anecdotal sources. This study is based on the best
Each agent released into the sea is transported by ocean currents and. possibly, by general ocean circulation, while the processes of chemical reaction and dilution take place. The processes of transport, dilution, and chemical persistence were evaluated in light of the biological toxicity of each agent. Once the volumetric and aerial extent of toxicity is estimated, the ecosystem impact is evaluated over this domain. It is at this point
which were synthesized from allwc provide estimates of environmental impact for
concerning sueh disposal and then modulated byquantities known to have been into2 International Convention on
Chemical THE ARCTIC RADIOACTIVE PROBLEM
toxic agents challenge the environment in varying ways:
Some agents are basically immobile and relatively non-toxic in seawater once released from munitions;
Other agents have very short persistence in seawater and, therefore, are of limited concern;
Some compounds may have the potential for bio-magification. resulting in their concentrations increasing as they pass upward through the food chain:
Toxic levels for some CW agents are so low tliat one cannotriori, their effects over very large scales, such as the entire arctic, as ocean currents transport toxic plumes:
CW agents add to an already existing burden of anthropogenic contamination of the seaside variety of toxic compoundsrom industrial wastes) and contributeumulative effect at the ecosystem level not obvious when considering only direct toxicity on individual species:
Finally, oilier agents may still be contained in dumped munitions and could pose future environmental or health risks as their casings corrode and agents are released into the environment
It should be noted lhal ihis study is complementary lo work done for ihe Arctic Nuclear Waste Program (ANWAP) in which the transport of radioactive materials in ihe arctic isnowledge of basic arctic processes, circulation, and transport mechanisms, population dynamics and dietary habits of local inhabitants can be applied from ANWAP lo this investigation. However, chemical contaminants differ significantly from radionuclide contaminants making direct application of ANWAP results meaningless wiih respect io the chemical munitions assessment. Differences between chemical and radionuclide contaminants include differentays to years versus years to millenniums; different physical, particle reactivity and solubility; and different toxicitycute versus chronic.
The ANWAP was initiated3esult of Congressional concern over the disposal of nuclear materials by the former Soviet Union into the arctic marine environment. The program is pan of the larger DoL> Cooperative Threat Reduction (CTR) Program. Specific management of ANWAP is conducted by the Ocean, Atmosphere and Space Modeling and Prediction Division of the Office of Naval Research.
ANWAP is specifically aimed at addressing the following questions:
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wiitftme AmtiMirfcir Waiu Au.-imw.if rVi,nimffice Ol. Edtotrv Julie Moqiiin tod Looif Codiinoci.
1-9
i is (he magnitude and location of the radioactive waste that has entered into the arctic marine environment;
How is radioactive contamination transported ahout the arctic basin and what are the present levels in areas away from the various con lamination sources;
is the risk to the environment and toTiuman healthcsull of this ladioactive contamination.
The program is comprised of approximately eighty different projects conducting various types of research: field surveys, laboratory experiments, modeling studies, and archival data analysis. The investigators include contractors. academic institutions, government laboratories and agencies, and foreign institutions. Of particular emphasis is an attempt to include Russian institutions in this research program. To date approximately ten percent of the funds have gone to Russian institutions for research or Ingislical support. Additionally, ANWAP has strong linkages and collaborations with both national and international organizations concerned with arctic environmental contamination. These collaborations include the International Arctic Seas Assessment (IASA) Piogram and the Arctic Bnvironmcnial Protection StrategyArctic Monitoring and Assessment Program.
The major conclusion from the research to date is That the largest signals for region-wide radionuclide contamination in Ihc arctic marine environment appear to arise from the following:
Atmospheric testing of nuclearractice that has been discontinued:
Nuclear fuel re-processing wastes carried into the arctic from re-processing facilities in Western Europe: and
Accidents such as Chernobyl.
The order listed above represents the relative magnitude of the contribution to the contamination from each source. Because the signals from one and two have decreased with time, region-wide concentrations of radionuclides in the water column and in surface sediments appear to have decreased significantly from their peak levels. Overall. ievels"of radionuclide activity in the Arctic and Pacific regions are low. The Ycnlscy and Ob Rivers appear io liave hadodest impact on radionuclide levels in the Kara Sea and the Arctic Ocean region. However, local siles of elevated radionuclide concent ration arising from dumping and weapons testing have been identified in ihe Kara Sea region.
While initial results are encouraging, there remain significanl scienlilic issues specific to the arctic that must be addressed. They include sediment and sea icelee ling contaminant transport, data from winter periods, and watershed and river transport of contaminants. Additionally, quantification of the terrestrial source term and its impact on the marine environment is just beginning. The final result of this research will be in the formormal, integrated risk assessment. This assessment is scheduled for completion in the summer
IJi STEPS IN THE ANALYSIS
The steps taken in this study (see) and described fully in subsequent chapters trace CW agents fiom iheir entry into the sea through to an assessment of their biological impact.
BACKGROUND
To assess ihe environmental impaci of Soviet CW clumping, estimates of chemical agents, their dumping locations, and quantities were chosenompilation of all available sources. Sources include Russian navigation charts, maps prepared by the Murmansk Marine Biological Institute, Ihe Defense Mapping Agency, and the writings of Lev Federov.
CONCLUSIONS
Based on Federov's estimates of Russian CW possession, the following toxic agents were chosen: mustardewisiteabunnd Sarinepresentative dumping locations and quantities were selected for each of the toxic agents. An estimate0 tons of mustard and Lewisite were dumped into the White Seaotal0 tons were dumped into the Barents and Karaotal0 tons of Tabunons of Sarin are ihe estimates used for dumping in ihe While, Barcnls. and Kara Seas.
The analysis does nol require precise dates of the dumping. Using Federov's assumptions, the dumping of musiardwisite look place in. Tabuu was also dumped in. In, additional Tabun was dumped wiili Sarin.
INTRODUCTION
This chapter addresses the problem of establishing the quantities and types of toxic agents or CW munitions that may have been dumped in arctic seas by the USSR during the Cold War years. The estimates presented here, along with dates of the dumping and locations of dump sites are basedompilation of all the material available. Il is nol possible to state confidence limits on these estimates, but they are believed to represent total quantities.
Reporting on occurrences of dumping of chemical agents and weapons in the Russian arctic seas is ambiguous and incomplete. In contrast lo fairly well-documented campaigns of chemical weapons dumping in the Ballic Sea by the Allies inollowing the end of World War II. reports of such dumping in the aietic regions have never hcen confirmed officially. The open press has described alleged incidents in which obsolete Soviet chemical weapons and World War ll-era German chemical munitions were dumped in ihe northern and far eastern seas surrounding Russia.
For the purpose of assessiug ihe environmcnial impact of chemical agents and munitions in the arctic regions, the agents, dumping locations, and quantities listed in
ave been selected.
2.2 TOTAL QUANTITIES
Reports in the open press on the dumping of Tabun in the arctic seas are scarce and only anecdotal. The Soviet Army captured the German production facilities for Tahun al the end of World War II. Allied data indicated thai the German facility had0 tons ofor purposes of the study, it is assumed that no more0 tons of Tabun were dumped in arctic seas. This estimate is possibly toy high, if only Germany is responsible lor all Tabun produced.
Sarin was not produced successfully by the Soviets until the. Jt is generally acceptederman Sarin production facility was under construction al the end of World War German equipment for its production, including pilot quantities, was captured by the Soviet Army and transported to the Soviet Union after World War II. If is not known if stocks of German Sarin weapons weie caplured by the Soviet Army. For the present sludy, the assumption will be made that no moteons of Sarin were dumped in the Russian arctic seas.
Mustard production by the Soviet Union15 has been estimated by Federov io have0eginninglie Soviets produced low-punly muslard and. while reliable estimates of this phase of mustard production are not available, it is reasonable to assume lhat up0 ions were produced. Lewisite production during World War II slightly0 tons. Thus, combined production of mustard and Lewisite may haveonshese quantities all refer to the CW agents, not weaponized quantities.
5 open-press report from Moscow indicated0 tons of mustard and Lewisite were dumped in ihe White Sea duringacking any oilier quantitative leporting. this value has been sclcclcd lo represent the level of dumping in the White Sea in the present sludy. The0 tons of muslard and Lewisite, remains as the total quantity dumped in cilher or both ihe Barents and Kara Seas.
There are allegations thai Soviets also dumped their chemical weapons agents in tlie seas adjoining its former boundaries, including the Baltic Sea, the Black Sea. tlie Sea of Okhotsk and the Sea ofhese areas are outside the scope of the present study and will noi be considered. Finally, there is no evidence or even suggestions that any quantities of the later generation chemical agents. Soman (GDI or VX. have been dumped into the Russian arctic seas.
2J OCEAN DUMP SITES IN ARCTIC-WATERS
Allhough there are no confirmed ocean dumping sites for Russian or Soviet CW munitions apart from the Baltic Sea. there is, pervasive anecdotal evidence that extensive dumping of CW munitions in arctic seas did occur. The identification of specific sites for the present study is based upon (he restricted areas on Russian navigation maps for the arctic seas of interest: dumping areas shown on maps prepared by Genady G. Malishov of the Murmansk Marine Biological Institute (MMBI) of the Russian Academy of Sciences (in cooperation with ihe Norwegian Polar Research Instilule and the Inslilutc of Occanology of Ihc Polish Academy ofnd the writings of Levhese selected sites are representative of the types of <iccanographic scenarios lhal comprise ihe Russian arctic seas. Locations selected for the present sludy arc shown in.
'r'tJCKiv. LA. Thr VmktGrtdiunvbKd IruniRuMiM It)Brixidcasi lnfoOTiulw Service
Manual of Mauary Cl-nn'Mry. UVaww I. CfitmHtyVbrtnt* Agtmi. Drvnebcr Milluiivnluc; Beffia7 Translated frwn German. rxeoniwm of Comiw.ee. National Bureau ofmiinitc for Applied Technology. NTIS no.MA pp.
- .ii.I.
InfcifM.ecembertft2 GMTnd (IV-5.
WmpiM. (miipl. Ncu.tgun IViIib Research Imiirmc. Qslii. Will, adopted fiom Russian OftgiWl prrpaiwl b) Cieaiity Ciurmansknlcfxal Iflsmuic. Academy of Sciences of USSR.
irrtyafttanv}xintiiiitfe it' Ooeanokigy, Pel ids Academy of Sconces. Sopor. Mumunsk Marine OKtlorictJ Inuiiotr. Roiwin Academy of Sciences. Murmansk: adapted from Russian original prepared hy Genudy O. Mansho.
Fcdennplty"eal chenusiry andhe (untie' Soviel CW proprain Allhuufh he nescr noted on llic CW piOKimi. he itim ihe Savin (fonnnUKiiuian scieniific conununily.redible vie* of tbe past practice* within die Soviet CW propram.
'
Fcdcrov provides numerous indications ol organized dumping adivilies. The following are representative samples:"
r USSR Marshal R. Malinovsky's decree onurvey of storage facilities with captured munitions of German. Italian. Romanian, and Japanese armies was conducted. Munitions consisted primarily of air bombs, artillery shells, land-mines, and toxic agents (TA) ineveral thousand shells were found which did not meet safety standards. Inecision was made to submerge these supplies in the sea. Marshal Malinovsky suggested three areas for submerging: areas of the White. Barents, and Baltic Seas.
Destruction of chemical weapons, including burying and submerging, has been carried out during all times throughout the existence of the Soviet Army.
[Destruction or disposal techniques include) submerging of chemical munitions and containers with TA of Soviet production and captured foreign products in the Baltic, Barents, White, Kara, and Black Seas and in the Sea of Okhotsk and Japan; and probably in other seas. The total number of large ocean areas is estimated al twelve, although there arc hundreds of smaller sites, including submerging of TA in rivers and swamps.
Excerptseport by V. Danilov-Danilyan (Minister of Environmental Protection and Natural Resources of the Russianhe Ministry is involved in collection, analysis and summarizing of data related to the problem of chemical weapons submerging in the territorial waters of Russia. Wc came to the conclusion lhal the Baltic. Barents, Kara, Okhotsk, Black, and Japan Seas have been subjected lo (his type of anthropogenic impact for more thanears.'
Loading of this hazardous cargo was implemented at the following shipping centers; ai Pechenga Stationestination Port Liinahamari (Murmanskaya Oblasl') by truck for submerging in the Barents and Kara Seas, known: at Severodvinsk Navy Port (Arkhangel'skaya Oblasl') for submerging in tbe White and Barents Seas; knownL]
Barents Sea
According to the maps prepared by Matishov. two sites in Ihe Barents Sea were candidate locations for CW munitions dumping: one site is located off the wesi coast Of Novaya Zeinlyahe second is north of Kolguev IslandE55'. These are shown on Russian navigation maps as.
ff Novaya Zemlya is depictedircleiameterm, this corresponds to an area of aboutater depths in this area range.
ff Kolguev Island is also circular,iameter9 km and an area ofm'. Water depths are remarkably shallow, ranging from onlyo
I.nd ilV.5.
ands: Ato.uja. Mapinwnrjle uf NiiviuoUon and Qicanopaphy uf ,he Mmiiuveleave
of uic ussr nm>
cBarew* Seu: from Cap, Orior-Tetikiy u,ara Srraiiiap. Omcionile of Navt$*ion and Oceanography ol ihe Ministry of Oefcmc or ihe USSRI.
Although there were eyewitness accounts of submersions of CW in an area near Spitsbergen, maps and navigation charts do not show any restrictions in this area. It seems doubtful that any organized dumping would have occurred, given that no dumped CW munitions have been revealed to date.
Kara Sea
In the Kara Sea. an explosives and military materials dumping area is shown in the Matishov maps. It is located at the northern end of Novaya Zemlya, off Cape Zhclanyia. in the region boundedIt encompasses an area of0his region is depictedussian nautical map as. Water depths in this area rangeith ihe typical depth.elated map. this area is designatedumping location for explosives and military materials" Giemical weapons weren the border of tbe Barents and Karan area near Novaya Zemlya close to Cape Zhelniel)""
A second area. Area, is locatedNI9'off the eastern coast of Novaya Zemlya,s circular,iameterm which corresponds to an area of abouthe depth of this area is.
While Sea
In ihe While Sea, sites of submerging are well known. "They can be found on navigation maps where these sites arc referred to as 'explosive materialswo sites of toxic agents submerging are indicated under this code on the White Sea navigation map to the Norih-Easi from Soiovctsk Islands (so-called areas.otal ofreas are indicated on this map as restricted for8
Both sites were identifiedefense Mapping Agencyautions thai magnetic anomalies may be encountered. On the other hand, in
, anchoring, bottom fishing, and submarine works ore prohibited, which is more suggesiive of hazards from dumped munitions and chemical weapons.s locatedlmm rectangle, having an area ofepths in this area range.
There have been reports on official comments, provided by Gen. S. Petrov (Stanislavonfirming "small burial sites" of chemical weapons in ihe White Sea."
2.4 DATES OF DUMPING
Official acknowledgment of past Soviet practices of chemical weapons dumping is nonexistent. According to ihe provisions of2 Convention on Chemical Weapons, ihe Soviets were not required to declare chemical weapons previously destroyed, thai is. buriedr submerged
There weie four major phases of Soviet chemical weapons destruction, as follows:*
first and most comprehensive phase of dumpiug wai6t thatarge quantity of musiard gas from Par Eastern supplies was submerged in the Sea of Japan. The quantily was estimated to0 ions, although it is unclear if lhal quantity is the net weight of ihe mustard or the weight with ihe munitions included.
second phase of chemical weapons destruction was6uring this phase, ihe Soviets began dumping second generation weapons. Also at this time, ihe Soviets changed their military strategy and emptied Air Force warehouses of artillery, Zarinc. and other toxic agents. These toxic agents, along with their munitions, were earmarked for dumping into ihe northern seas.
io.
-E. Tikkwien. M_. Kiirmtn a,tone of rte Emimwuent anJ Envinmnt-Mlfiemmieaalut
rt* AMi AwuiaAi. Antic Onire. llnnvitity Ol Laptwl...
"Reference I. HV*I.leiurc 14
'ffjuMn* flrfeie Morr (Whlu Seal Pakuifaumi ZJazhfimtn, Mip. Dclcnse Mapenng AgeniyW.yI.JIV.3.
The third phase, in, saw the destruction, probably through submersion, of chemical munitions filled with first generation toxic agents. There were also reports of land burial sites.
The fourth and final phase was in. By this lime, munitions with first generation toxic agents had almost disappeared. Supplies of persistent toxic agents were left at two Chemical Forces bases in Kambarka and Corny, where they had been stored in containers for the pasi few decades.
It is not important for our purposes to identify dates with very much precision, bin generally, the following general dates seem reasonable:
2.5 WEAPON TYPES
Musiard. Lewisite and their combinations were loadedariety of air bombs, artillery shells, rocket artillery shells, andhere arc anecdotal reports on the disposal at sea of air bombs, artillery shells, mines, and containers containing toxic agents without specifying quantities of specific weapons or agent
was no determination between agent weight and the gross weight of the filled munitions. For purposes of establishing quantities of CW agents contained in these munitions, the estimates inan be used.
: Dumping of mustard and Lewisite;
: Dumping uf additional mustard and Lewisite, as well as Tabun;
of Tabun and Sarin.
'Reference5
BACKGROUND
Most of (he Barents Sea shelf is in severaln deep among shallow banks. The soulhcaslcrn portion of Ihe shelf, called Ihe Pechora Sea,n or less in depth. The southern portion of the shelf is dominated by warm Atlantic water, which flows onto the shelf from the west. The northern portion is dominated by cold arclie water flowing in from the arctic basin to ihe north. The waler masses meet and mix at the Polarelagic community is dominant in the deeper pans of die Barentscniho-pclagic community is dominant in the shallow areas. The benlhic community is more important in the bentho-pelagic system than in the pelagic system. Barents Sea fish and shrimp populations are exploitedarge and important commercial fishery, which exists primarily in the waters south of the
Polar Front.
of the Kara Sea is lesseep. Deeper areasasin adjacent io Novaya Zeinlya. whicheep, and iroughs on the northern portion of the shelf, which arc upeep. Biological productivity in the Kaia Sea is less than in the Barents Sea. Commercial fish landings are small compared to the Barents Sea fishery.
The While Seaasin conneclcd io the Barents Seahallow inlet The deep central basmeep. The inlet connection io the Barents Sea is abouteep. Three water layers exist. The deep layer occupies depthsnd has little mixing with the intermediate and surface layers. Comnvercial fish landings are very small compared lo the Barents Sea fishery.
Four of Ihe live designated disposal sites are located inr deeper. The filth site is inn deep. At all sites, bottom salinity is greater thanads per thousandottom water temperature is lessl the deep sites and aboutat the shallow site.
regional marine systems arc affected by other activities past and ongoing. These include testing of nuclear weapons, disposal of solid and liquid radioactive material, and exploration and production of oil and gas resources.
CONCLUSIONS
' The Barents. Kara, and White Seas arc arctic marine ecosystems each with distinct characteristics.
fish and shrimp populations in the Barents Sea support important coiiunercial fisheries. Commercial fishing in the Kara and While Seas is less important.
SEA
arctic seas potentially affected by the dumpingBarents Seaarge, continental shelf system off
chemical munitions are located in coast of northern Norway and northwest Russia
Scandinavia and northwestern Russia.he boundaries are the Norwegian
ihe Barents Sea. Kara Sea. and White Sea. Eachlo the west, the Arctic Ocean to the north, and
distinct oceanographic and ecologicalZcmlya and the Kara Sea to the cast. The
This chapter summarizes the importantsoutheastern portion of the Barents Sea is also
and ecological features of each of these areas,as the Pechoraon the five dump silcs identified in
Chapter 2.
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3-2
Physical Characteristics
The bathymetry, Ihe inieraciion ol" Atlantic and Arctic water masses, and the volume of inflow freshwater are important determinants for the physical characteristics of the Barents Sea. The volume of the Barents Sea ismV
I Pn/li,.nitlK
.1 i
The majority of the Barents Sea shelfeep. The bathymetry of this area is characterized by deep basins and shallow banks. The larger southeastern portion of the shelf is shallower with depths less
Sandy sills and muds cover most of the Barents Sea bottom in areas deeper, with the muds occurring predominantly in the basins deeper. The sediments of the shallow Pechora Sea and other shallow areas are primarily sand and sandyith many areas of rocky or siouyecause of the small amount of freshwater inflow, the sedimentation rate is very' low and is estimated toears.1
Brown mudsrown tint to the sediments is characteristic of the sediments of the northern portion of the shelf. This is due to ferric and manganic hydroxides, which exist as concretions and, in some places,hin pavement.*"
The volume of freshwater flowing into the Barents Sea is small compared lo the volume of shelf water. The main source is the Pechora River, which flows into the shallow Pechora Sea.
Because of the low volume of freshwater inflow, currents and water masses in the Barents Sea are determined mainly by inflow and mixing of Atlantic and coastal waters from the Norwegian Sea from the west with arctic water from the Arctic Ocean from the
from the Norwegian Sea flow onio the shelf between the Norwegian coast and Bear Island. This walcr, flowing from west to east, covers much of the southern part of the shelf. Water from the Arctic Ocean flows onto ihe shelf from tbe north and east. Cunents in arctic water are westward or soulhweslwanl. The two waier masses meet and mix at the Polar From.
Vertical stability of the shelf water masses may vary during the year. Atlantic and Arctic water may be homogeneous in the winter (seen the summer, arctic water siratifics near the surface because salinity decreases duece melting and the temperature increases due to solar warming of the surface layer. Coastal and Atlantic waters, which are ice-free during the winter, also stratify near the surface in the warm period because of some freshwater input from Norwegian and Russian coastal streams and solar warming of the surface layer.
Formation of dense bottom water in the fall is important to the hydrographic structure of the shelformation of dense bottom waterwo-step process. First, water density increases as surface water cools in ihe fall. Cooling slows as the water temperature nears the freezing point. The second step begins with ice formation. Surface water density increases rapidly because of the increase in salinity resulting from rejection of brine to the water from the
1 -feaare. erf ins Phyiical Ouun.^Mftiic Conditions ot tfict-AwS- IS.
cinWo' of ihe Ba'etai onrfeas Map ebonhe Geolupwl Society of America. Boulder. CO
lhehe USSR InutsciciwcYork. NY
.ht Encyclopedia ofOcemvgrapkv ReinhoU Pobluhinj Carpariban. New Yoik. NY.
ifi. IkeSea (MootTiamUicd from the Pottih hy. Departmenttbe Interior and the National Science rwmdaton Clear inghouw lor Fcdenl Scientific and TechnKal lofcernativo. Scnigficld. VA 'Reinrncc S.
5 'Geoehrmraryoncretion* ia thefaniw.
Formation of Dew* Bottom Water in theeep Sea Select*.
nd DC5umerical Study of Dense Wace* FornuUon and Traninanhallow. Sloping ContinentalVI7
IttJcitfttC i
forming ice. This dense water then sinks to the bottom and flows along slopes and into depressions. In water less than about ten meters deep, formation of dense bottom water can cause convective mixing of the whole water column and rcsuspension ol" bottom sediments. The dense bottom water layer flowing away from the source may be only ten metersew tens of meters thick. Because of the density difference, there is little mixing of the-bottom water layer-and overlying water.
Formation of dense bottom water has been documented on the shallow bank adjacent to the west coast of Novaya Zemlya and may occur also in other shallow areas, such as the hanks cast of Svalbard."The dense water formed over the shallow bank west of Novaya Zemlya sinks to the bottom and flows downslope along the bottom into the basins to the west and northwest. It also flows to the northeast along the hank slope and into the St. Anna Trough between Novaya Zemlya and Franz Josef Land.
Temperature and Salinity
The Atlantic and Arctic water masses have different salinity and temperature characteristics (seerctic wateremperature0alinity of5 ppt. Atlantic wateremperature ofalinity of aboutpt. In the summer for each water mass, the top fifty meters have higher temperatures and lower salinity than the deeper water.
Cover
The warm Atlantic water of the southwestern portion of the Barents Sea remains ice-free all year (seehe maximum extent of ice cover in winter in the central and eastern Barents Sea can vary considerably from year to year. In most years, the entire shelf is free of ice in the summer.
iological Characteristics
The Barents Seaiologically productive shelf ecosystem with two main types of ecologicaln the deep central and western parts of the sea, where depthsxcept on banks, the community iselagice mho- pelagic community occurs In the areas lesseep. The sea is an important nursery and feeding ground for commercially important fish stocks, which arc exploited by an international commercial fishery in the western areaussian fishery east of
.
elagic Community
The pelagic communityimple food webew dominant species at each trophic level (seeost biological activity takes place in Ihe water column. The benthic community is less important in the food web.
Plankton. The base of the food web is the phytoplankion, which produce organic matter by photosynthesis. Diatoms and colonial algae are the dominant phytoplankion types. Calanoid copepods (Calanus finmarchicus and C. glacialis) and krill (Thysanoessare ihe dominant herbivores feeding on the
Planktivores. Capelin (Mallotusierring (Ctupea hurengus) and polar cod (Boreogttdus saidn) arc the main planktivorous fish feeding on the zooplankton.
"Ret'eeenee 2.
-SaviOHV^IN. UirtW lieniictun*.An Otnw* <if CartW8 pp. Trondheim. tionoy.
5 "Pelagic fuh ond ihe fcnlogical Impact of (hehrng InduiiiY in the Boreal*B. 'Relcreikc It.
floH-Mmnn Gnuing by Catmtuinmorcllicn and C. tnvrwhmm in ihe Rcjic* of Ire Fvlir from, Barmu. Sen. Mmiat- It.
ande and EM.anil Repim) Variation in ihe Coptpiidin ihe CewraJ Bmb Sea Durinj
Spin* and EiilyKnndYUlJft'.'BZ
.XVa/in? Raie*ht CopctudtgtucMiisn the Arctic Wnier* otmsJH.
The entire life cycle of the capelin stock takes place in the Barentsapelin adults are most abundant in the arctic water mass of the northern part of the shelf. Adults migrate in late winter to the spawning grounds in the shallow coastal waters on the southern shelf off Norway and Russia. Hatched larvae float east and north with the coastal and Atlantic water currents to the nursery areas of the central shelf.
The Barents Sea is the nursery area for the herring stock. Spawning occurs in the Norwegian Sea along the coast of nonhcm Norway. Eggs and larvae are transported to (he Barents Sea in the Norwegian Coastal Current. Herring remain primarily in the Atlantic water mass in the southern Barents Sea for two to four years before migrating to the spawning areas in the Norwegian Sea.*
The biology of the polar cod is not wellhe species occurs throughout ihe Barents Sea but mainly in the eastern and northeastern pail of the shelf. Spawning takes place in ihe Pechora Sea and, possibly, cast of Svalbard during winter or early spring. Polar cod are found near the bottom, but apparently feed mainly on pelagic organisms.
redators. The Aicto-Norwegian Cod (Gadusarine mammals and sea birds are important consumers ofhe life cycle of the Arcto-Norwcgian cod is similar to the herring. The main spawning grounds are in the Norwegian Sea off northern Norway near Eofoion. Eggs and larvae arc carried into the Barents Sea by the Norwegian coastal curreni and Atlanticatvac are pelagic for live toonths and then settle to the bottom for further development. Adults remain mostly in the Atlantic water of ihe shelf."
Capelin and herring are an important source of food for fish-eating sea birds. In the spring during ice melt, thick-billed murres Wria lomvia) are abundant along Ihe ice edge and on packn August and September, fulmars and kittiwakes constitute the vast majority of birds on ihe central and northern shelf. The disiribution of these birds is generally correlated with the distribution of capelin and polarhich remain mostly in the arctic water mass.
Marine mammals arc important consumers of fish. Seals are found along the ice edge, on pack ice, and along the shore" Harp seals can foiage al deplhs as gieat*
hales. The numbers and distribution of whales in the region are nol well known. Minke and humpback whales as well as white-sided and whiie-beaked dolphins arc known to beeluga whales are found in the Pechora Sea region as far west as the White Sea and along the west coasi of Novayadditional species also are known to occur."
Both baleen and toothed whales are known to occur in the Barents Sea. Baleen whales filler large volumes of water to obtain plankton and small fish for food. Toothed whales exploit the regional fish and squid stocks.
entho-Pelagic Community
The bentho-pelagic
of the Barents Sea is illustrated in. Much of ihe organic mailer produced in ihc phytoplankton sinks to the bottom without being consumed by zixiplanklon and is available to benthic organisms. Fish, sea birds and marine mammals are important components of the food web in this community. Birds feed on both fish and the benthic organisms. Walrus feed on benthic organisms. Polar bears Iced on marine mammals.""
Walrus occur in Ihc shallow Pechora Sea region, along the Novaya Zemlya coast and on Franz Josef Land andlthough walrus hunting is no longer allowed, populations arc much reduced from prehunling numbers.
enthic Community
The biomass of the benthic community varies greatly over ihe shelf area (seeiomass in water deepers generally low. usually lessiih large areas less thanuch greater biomass: occurs in shallow areas, such as banks and ihc Pechora Sea region. Small areas of very high biomass greaterccur in the northern Pechora Sea and along the west coast of Novaya Zemlya.
and juveniles of ihc various species/
Mosl of the finfish harvest takes place in the warm water of ihe Atlantic water mass and in ihe vicinity of the Polar From. Capelin arc harvested using purse seines. Both midwater and bottom trawling are used extensively for other species. Polar cod are harvested primarily in the eastern Barents Sea and the shallow area of the Pechora Sea legion.
33
The northern shrimp (Pandalus borea/is) is also harvested commercially.*'
KARA SEA
The Kara Seahallow shelf system bounded by Novaya Zemlya and Fran/nd on Ihc west, the Arctic Ocean on tlie north, and tlie Russian land mass and Scvcmaya Zemlya on the casl (seche sea receives large freshwater inflows seasonally from the Ob and Yeniscy Rivers, which arc among the largest riveis in the world.
m3
5T in tviiPii on
* Physical Characteristics
The Kara Sea is characterized by shallow areas and deep troughs and by the large volume of freshwater inflow. Its volume ism'.*
Most of the Kara Sea shelf is lesslarge areas shallower thanseeeep areas ate the East Novaya Zemlya Trough and the Si. Anna and Vbroninhe St. Anna and Voronin Troughsaximum depth ofnd open into ihc arctic basin."
Silty Clay or mud are the dominant sediments in the Kara Seaerrigenous silt of glacial marine type is tbund in the deeper areas. In ihe southwestern portion of theyclonic or counterclockwise surface circulation pattern favors the accumulation of mud at shallow- depths. The sediments are brown in color indicating ihe presence of manganese and ironarge number of ferromangancsc concretions arc characteristic of the Kara Sea.**
Sands and silty sands predominate in the shallow shelf area near the mouths of the Ob and Yenisey Rivers in tlie southeastern portion of the basin. Ihis portion of the basin is characterized by submerged teiraces which trend northcasl-soulhwest. The terraces mark the iransgrcssive and regressive stages of multiple glaciaiions. Hard rock bonom is encountered in many places on the margins of these terraces. The absence of sedimentary cover is indicativeenerally slow rate of sedimentation, or scouring, by strong currents.
ydrography
The Kara Sea is greatly influenced by the large seasonal inflow of freshwater from the Ob and Yenisey Rivers. Mosi discharge occurs between May and October with peak flow in June. Some flow also continues during theiver water remains in the central and eastern portions of ihc shelf, although
The general surface circulation in the Kara Sea is shown inhe large seasonal freshwater inflow from the Ob and Yenisey Rivers flows lo the northeast across the shallow portion of ihe shelf. This inflowtrongly stratified water column in the surface layer. Ocean water enters the Kara Sea through the straits at the south end of Novaya Zemlya and from the Barents Sea and Arctic Ocean on theounterclockwise gyre is present in tlie western portion of the shelf over Ihe Gasl Novaya Zemlyawo-way water exchange takes place with the Barents Sea through tlie Kara Strait al the .south end of Novaya Zemlya.
Two-directional flow occurs at depths in the St. Annatlantic water flows southward onio the shelf along the wesiem side of ihe trough while the water flow is northward into ihe arctic basin on ihe east side of the trough. Some of the southward flowing water enters the Fast Novaya Zemlya Trough.
ater Temperature and Sahmly
In the Easi Novaya Zemlya Trough, waier temperature in depths belows constant all year alC. The surface temperature is warmer
J_A-Sediment biWrrtnilion in Deep Arras ofil>em Kara. In Herman. Y.fririoe
aikfSpringer.Wring. New Yort. NY.
"Referent* 3.
"Reference St.
"Reierence S.
"RvfeniiBW 4.
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.Hydrograptuc StrMUit and variability of the Kan Sea: Implication* for PollaUuttu-Sra AVunxnW0
-Han/lick. D. and K.nd Atlantic Water in ihe Karaournal of Groph/slati ffcnwiA SSfOlia'HMW.
M.
NV1 RONMEISTtfPTIO N
ihe summer (seeBottom water temperature in the Si. Anna Trough is about'C"
Surface salinities are low near the mouth of the Ob and Yenisey River and in the near shore region lo the northeast in the direction of ihe current flow.AI The East Novaya Zemlya Trough accumulates high salinity waicr of5 ppt (see" Rapid cooling and ice formation in the shallow water along the east coast of Novaya Zemlya creates brine that drains into the trough."
The water column is slrongly stratified in ihe topn warm weather periods due to solar warming and salinity reduction from freshwater inflow.
ce Cover
The generalized sea ice characteristics of the Kara Sea are shown in* The entire sea is usually covered with ice in winter except for polynyas in the easiem portion of the sea thai form over many years. Fast ice lasts into July in many areas. The entire sea is usually free of sea ice by early August. The persistent mass of ice off Novaya Zemlya. which sometimes lasts all summer, results from ihe cyclonic gyre in ihe surface water of this region. The icebergs sometimes observed along the east coast of Novaya Zemlya are thought lo originate by calving from glaciers that terminate in bays on the northern portion of the island.
Biological Characteristics
Benthic organism biomass is low in much of the Kara Sea (sec. Biomass in tlie areas of brown mud are generally less thanr. Biomass in the troughs is less'v* (Noic: While pelagic biomass is normally given in units of mass per unil volume of seawater, benthic biomass is given in mass per unit area of the seabed.)
Fish biomass is much less than in the productive Barents Sea. Typical species are polar cod. navaga, eclpouts. polar dab andery small populations occur in ihe areas of brown muds/'
Beluga whales Occur throughout the Kara Sea. Walrus occur only along the coast of Novaya Zemlya and in the southern portion of the sea between Ihe Kara Straits and the Yamalolar bears occur on Novaya Zemlya."
Commercial Fisheries
The commercial fishery is limited in the Kara Sea because of the small biomass offish. The largest catch is polar cod by trawl and seine in the southern portion of Ihc region."
3.4 WHITE SEA
The While Sea is an enclosed, fjord-like marine SySiem in northwestern Russia connected to the Barents Sea (see.
is dominated by diatoms and peridineaiis. The mam ztwplankton species is Calanus finmart'hicus, which is less dominant in biomass than in the Barents Sea. Zooplankton biomassm- is typical of tlie Russian arctic shelf seas to the east, but much less than ihe biomass of greaterin the Barents Sea."
IWcrencceference 61
"rV-lnv. Vui I'm. "HyJiviiuiWucutosiciil Rejime ot Uw Kara. Laptev,iDcnanechnical Memneandurn APL-UW TMI-%.
Applied Pliysx* Uburai.iry. llJnvcmr, of WaAiitguin. Scanle, WA.
"Reference 61
-Re Icence i.
"Reference J.
SI).
"Referciicv
"Reference X
i: generalized ice conditions in ihe kara sea"
The While Seaasin separated at its entrance to the Barents Seaillepth ofseehe deep central basinaximum depth greatern. The shallow southern Ortega Bay is less thaneep. Dvina Bay slopes downward towaid the central basin. Depths in this hay are mostly less. The central basin occupies much of Kandalaksha Bay with shallow edges lesseep.
Pebbles, gravel, and sand are the dominant sediments in the shallows along the coast and in Strait Gorlo. which is the passage between the White Sea and the Barents Sea. Fine-grained sediments (muddy sand, sand, and mud) occur on the slopes of the central basin of the White Sea. The central basin is covered by very line-grained, brown clay-likehe sedimentation rate for the central basin ismears and aboutmears in the near-shore areas."
WaterSalinity
Three water masses exist in the Whiteurface layer approximatelyeep forms in the summeresult of ice melting, freshwater inflow, and surface heating from increased insolation. In this layer, the salinity is less thanpt and the temperature is greater thanC. An intermediate layer also forms in the summer with salinity ofoptemperature oftoThis layer occupies depths fromoeep layer, which forms in the winter,alinity greater thanptemperature less. This water occupies depths greaterransition layer often occurs between each of the three water layers. In the winter, the top two summer water masses arc the only ones involved in convcctivc mixing.
The main sources of freshwater enter the White Sea in Dvina Bay from the Dvina River and in Onega Bay from the Onega River.
The White Sea is usually completely covered with ice in the winter and free of ice in the waim months.
Biological Characteristics
Phytoplankion are mainly diatoms andhe diatoms include the genus Chaerataceros. Pcridincans include Ccratium fusus and Peridinium conicum.
The zooplankton community comprises two groups corresponding io the layered structure of the water mass.'! One group, comprising boreal and cosmopolitan species, lives in the upper summer-formed layers, primarily in the upper. These species include Evatbie nort/mitnni. Fritillaria borealis and Amnio longiremis. The other group, comprising arctic and arcto-borcal species, lives in Ihe cold water of the deep layer, primarilyepth of. The species include Calanus gutciatis. Oikop/eura vanhofferi, Metridia longa and Clitme limttcina.
Three distinct benlhic communities have been identified that correspond roughly with the thrcc-laycied water mass structure of ihe sea. Types of organisms present arc also influenced by scilimenihe PortUmdia arciica community is ihe dominant type on pelile silts in the cold water of the deep waterenlhic organises in ihe deep basin are primarily deposit feeders, while those in shallower walcrs arc primarily suspension feeders."
-ReferenceReference* "Reference S. "Reference V
tenerowi1 Factor, Dtiwwnwxe WMu Sea "Reference*
Ye GH. -Some VenicaJ Diariburion Pattern*Zooplanklun of Ihe WhileDeiemiiried bv dv Recurrcr*
eculluiiie* of Compouiice. and ItainhulleBe/Benlhle Fauna Ininlelw5ne|r'
BenHne Fauna aod Ftoia PP. Shinhov Iniiitixe ofcademy of Science* nf ihe USSR, Mciicow.
lEWikosmkntai. description
species present include herring, navaga, smell, While Sea cod. dab. and whiiefish. Arctic cod and capelin also enter the White Sea at limes* Three populations of White Sea herring (Clupea harengus marisalbi) live in the Whitehis species feed intensively on large and small zooplankton.
Seals are common in the White Sea. The Beluga whale also occurs.*"
ommercial Fishery
Fish stocks of ihe White Sea are exploitedmall Russian commercial fishery. Navaga and While Sea herring account for most of the landings. Oliver species harvested include smelts, cod. and dab.""
PRIMARY PRODUCTION AND ENERGY TRANSFER THROUGH THE FOOD WEB
Arctic ecosystems must be adapted to surviveold environment lhat receives solar energy forortion of the year. Production of organic matter by phytoplankion (primary production) begins with the return of significant solar radiation in the spring. As the ice melts and moves northward during the spring and summer, an intense bloom of phytoplankion with high rates of primary production occurs in the vicinity of the ice edge. In the pelagic community, /ooplankton graze on most of the bloom, leaving little to settle to the bottom as food for benthic organisms. In ihe shallower areas, much of the primary' production sinks to the bottom without being grazed, becoming available to benthic organisms.
Because energy from the sun needed io produce organic mailer by photosynthesis is available for only pan of the year, the biological communities have evolved with mechanisms lo caplure the food produced in ihe Short period of primary production. The biological communities store the energy for later use during the period of low insolation. Much of Ihe energy is stored in lipid compounds oropepods glazing on phytoplankion grow continuously during the bloom period, increasing their lipid conteni during this time fromercent toercent during the two to three month period of Ihe spring bloom. Krill Increase their lipid conteni over five months fromercent toercent. The energy captured and stored by zooplankton is passed up (lie food web to capelin. which increases its lipid content fromercent tohe energy finally reaches the top carnivores, such as marine mammals, sea birds, and polar bears. Marine mammals and polar bears store much of the fat so dial the eneigy is available during the long period of low lighl, cold temperatures, and ice cover when food is scaice. The bsnsfer of energy stored in lipids from phyloplankton to capelin is shown inhe dependence on energy storage in lipids makes arctic ecosystems particularly vulnerable to bioaccumulation of contaminants that are preferentially stored in fats, such as chlorinated hydrocarbons.
3.6 THREATENED AND ENDANGERED SPECIES
Many of the mammal species of the study region are threatened. endangered, or greatly reduced in numbers. Hunting of many of ihe species continued into.
The polar bear, Atlantic walrus, gray seal, narwhale. and bowltead whale are listed in ihe Red Book of Russia, which is ihe list of protected species in4 Red List of Threatened Animals of the International Union for the Conservation of Nature lists die following regional animals and their
"Reference 4.
"NKymart. Ve5 -AihImIi Ol Hie Population Dynamic, of (he While Sea riming"B tlir Feeding of the White Sea llerrtng.orr**u, wit-m, -Reference-Reference
S. CCE.Trophichi ihe. Aret* Food Weh" po- Hjrnci. M.ibsonrophk ttekaUwihlp. in ihe Mnfai*Aberdeen Unitr-nhyScotland
'ai1(vnr^,'iioui IteutacUan of the Eomstemi in the Barton andKola Scientific Crnier, Ru>um Acadcmv
olpeiiiv
jthr Fnm; hnejtsmd tAnhipelate aod Stwtfi. Kola Scientific Center.
Academy ot Science! Piesx Apaciiy.
x:-ggVIIM)NMgfj^AU UKStRIP^N
for the Russian Federation: polar heareluga whale, narwhal, harbour porpoise, and Dall's porpoise (insufficiently known).
Whales are protected under ihe International Convention for ihe Regulation of Whaling. Regional species protected under. Endangered Species Act ate tlie blue whale, bowhead whale, humpback whale; and*
3.7 INDIGENOUS PEOPLES
Indigenous groups inhabit the sludy region andortion of their food from the marine waters that could be contaminated with arsenic. These groups are potentially at risk of exposure to arsenic-contaminated fish, shellfish, and marine mammals if these food sourcesubstantial portion of their did.
Two principal groups of indigenous people populate the study area. 'Ihc Lapps, also known as the Sami, occupy the European section extending from northern Norway through the extreme northwestern section of the Russian Arctic into the Kola Peninsula. Ihe Nencls and Khanty are found in ihc central and eastern portion of the study area on the land masses bordering the southern and eastern coasts of the Kara Sea.
The Sami arc of four regional and cultural types. These include the forest, field (mountain,ea. and Kola Peninsula Sami. The sea Sami live along the arctic coast of Norway. In winter they hunt and in the summer they fish on the sea. The Sami of ihc Kola Peninsula arc the original inhabitants of the region. Their population has remained roughly the same, slightly. They live mostly by fishing and by herding reindeer.
The Nenets and Khanty were primarily nomadic reindeer herdsman who migrated up and down the Yamal Peninsula seeking seasonal pastures for their herds, ln the, these nomadic people were forced onto collective farms and the state established boarding schools for the children of both the nomadic families and the settled villagers. The children retained little knowledge of their parents' subsistence economy.
When the collective farms ofere transformed into the Soviet farms of, the Nenets and the Khanty became hired workers in the state-run reindeer breeding enterprises. More recently, the economy of the region has begun to stabilize and sustainable fishing and hunting enterprises were established alongside the reindeer breeding industry. However, the discovery of huge gas deposits on the Yamal Peninstila-and-the-tmpending development-of these resources are new factors affecting the Nenets and Khanty peoples.
The breakup of ihe former Soviet Union has been accompanied by increased liberalization in political life, growing independence among scholars and the press, and the advent of new social movements. This shift has fostered the creation of special social and political organizations of native peoples. These organizations are helping lo curb the threats to their culture and their tradiiional means ofivelihood."
3.8 OTHER ACTIVITIES IN THE STUDY REGION
Other pasl and ongoing activities affect the marine ecosystems of the study region. These include disposal of nuclear wastes, testing of nuclear weapons and exploration and production of oil and gas resources.
uclear Waste Disposal
Both liquid low level nuclear wastes and high level wastes (including reactor vessels with spent nuclear fuel) have been dumped in Eurasian arcticumping has taken place9 with ihe latest known dumping to have occurred
Liquid waste with the highest radioactive concentration has been dumped in ihree dumping fields in ihc central portion of the Barents Sea. The first dumping field is off the west coast of Novaya Zemlya in an area ranging fromorth latitude andtocasi longitude. Further to the west, the second area extends fromtonorth and rangesasL The third high level waste
. 1W.hiter* andKeirOetrHeater,ofNonhno t'aiaiia University Frew cTXew England. Hanover. Nll.
TunslaKd by Mnreia Lcvounn.
'TUfcrence-W
mi CS. UnityThr International Arctic Sea* AwmrH Project: Progress Rcpon' IAEA Untteim "ill
disposal area* byrea centeredorthast
Disposal of low level nuclear wastes has occurred in dumping areas off the Barents Sea coast of the Kola Peninsula.
Solid radioactive waste has hern dumped in several locationshe Barents and Kara Seas Solid wastes includeeactor parts, generators, cooling pumps. looU. and equipment. In some instances the material was stored on ship* or barges that were sunk. Aside from the known disposal areas in the Barents Sea. several dumping areas have been identified in the Kara Sea.
Both the Northern Meet and the civil fleet of nuclear icebreakers have dumped material in eight different bays on the east coast of Novnyu Zemlya and in the Kara Sea, in both the Novaya Zemlya and Sr. Anna's Troughs. Sinkings arc known to have occurred in Tcchemya Bay and in the southeast Barents Sea near Kolgucv Island. An accidental sinking occurred9esultire aboard the nuclear powered submarine Komsomolcts. Ihc submarine sank at the western entrance to the Barents Sea about halfway between Svalhard and Hear Island.
Testing of Sucltar Hrcuxmi
Several hundred nuclear tens, both above and below ground, are known to have occurred on Novaya Zemlya. The principal testing areas were located along the central west coast of the island. Also, nuclear devices were tested near Cuba Chcmaya, in Point Cemyi. in the extreme southwest portion of theAtmospheric fallout, runoff and river borne contaminants, in addition to direct release into the oceans, have contributed radioactive pollutants to the northern ocean areas
Oil and Gas Resource Exploration and Exploitation
Exploration and exploitation programs for petroleum resources arc currently underway in both ihe Barents and Karaeophysical investigations in the Norwegian sector uf the Barents Sea begancreage was offered and awarded to several companies in the Norwegian fifth round of concessionsourteen concession rounds have resulted in steady growth in the leased acreage. Diilling activity has been maintainedow but stable level with fifty wildcat wells having been drilled over the period. There have been several important discoveries of natural gas but only minor oil discoveries. 'Ihc Hammcrfcst Basin liesorthast and is the principal area of interest in the Norwegian sector of the Barents Sea.
The Russian sector of the Barents Sea and the Kara Sea has been explored more extensively, first by Russian oil interests and then by these same interests in partnership with foreign entities. The onshore oil and gas fields of the Timan-Pechoia basin border the Pechora Sea. Investigations in the Pechora Sea carried out duringstablished the probabilityajor sedimentary basin lay offshore. Numerous offshore prospects have been identified. Some of ihcsc arc cither ready for drilling or have been tlie object of some initial drilling. The Prirazlomnoya oil fieldecent significant discovery in this region.
Exploration surveys in the Russian sector of the Barents Sea indentified about twenty-five prospective structures. About twenty-five wells have been drilled and some very significant finds, primarily of gas, have been made. These extendand from the west coast of Novaya Zemlya southwestward toward ihe city of Murmansk on the Kola Peninsula.
"Setcre-iKc I
"Voir. AtiBareni* Sea Geology. Petroleum Resmrcei.
The Russian sector of the Barents Sea may be divided into two hydrocarbon provinces. The southeast region is characterized by promising shows of oil, whereas the central and southwestern portions of the region appear to contain significant gas reserves.
Natural gas deposits beneath the eastern portion of the Kara Sea arc considered to bc the seaward extension of thegas province on the Yamal Peninsula.
3.9 MUNITIONS DISPOSAL SITES
As described in Chapterive munitions disposal sites have been identified. Two sites are in the Barents
Sea. two are in the Kara Sea and one is in the White Sea. Hour of the sites are located in water deeper. The site near Kolguev Island in the Pechora Sea region is located in shallow water.
Characteristics of the disposal sites are given in. Bathymetry of each site is shown in,o data that had been gathered from
Characteristics of these sites are inferred from information in. Sediment and bottom water temperature data aie available for disposaln the St. Anna Trough.1"
ikmis
M
BACKGROUND
This chapter describes the chemical transformations that CW agents Tabun, Sarin, mustard and Lewisite are likely to undergo in the marine environment.
Temperature, pH, ion concentrations, and pressure are characteristics of the marine environment that potentially affect die persistence of CW agents.
- The chemistry of CW agents in the marine environment is dominated by hydrolysis, the reaction of the agents with water. Major products of the hydrolysis reactions are identified,
All agents and their hydrolysis products have estimated logvalues of less than three.
Some of the important characteristics of these agents are.
CWg L1
Tabun (GA) hr
Sarin IGB) hr
Mustard <H) hr
lewisite fL) >
CONCLUSIONS
key features of the chemistry of the CW agents in the marine environment are as follows:
Tabun is fairly soluble in water and hydrolyzcseriod of days;
Sarin is miscible (mixes in all propoitions) with water and also hydrolyreseriod of days;
Dissolved mustard hydrolyzcs relatively rapidly. However, the persistence of mustard in the marine cnvironmenl is controlled by the rate at which it dissolves;
Lewisite is soluble in water and hydrolyzes very rapidly. The initial hydrolysis products of Lewisite are also very toxic and persist in seawater for months or longer. Ultimately, the Lewisite hydrolysis products are convened to arsenic.
INTRODUCTION
This chapter describes the chemical transformations that CW agents are likely to undergo in the marine environment Chemical structures of the four CW agents covered in this study are provided in, along with their common names. Chemical Abstracts Service (CAS) names, molecular formulas, molecular weights, and CAS registry numbers.
The key questions addressed in this chapter arc summarized in, followedompilation of those characteristics of the marine environment that affect the persistence of CW agents. Information will be provided for each of these agents on the following:
Manufacture of the agent;
Hydrolysis reactions and rates;
Oxidation reactions;
Photolysis reactions: and
Thermolysis reactions.
After the individual agents (Tabun. Sarin, mustard and Lewisite) arcrief survey of the
t 4.
of arsenic in the environment followsiscussion of the effects of pressure on hydrolysis tates concludes this chapter.
4.2 CHARACTERISTICS OF THE MARINE ENVIRONMENT AFFECTING PERSISTENCE OF CHEMICAL WARFARE AGENTS
The chemistry related to the environmental fate and transport of chemical warfare agents at the floor of the ocean is an important component of this study. However, few measurements of chemical properties and reaction rates of the compounds of interest for this study are made under the conditions found at the ocean floor in the study area. Nevertheless, existing measurements have been extrapolated to those conditions according to well-established chemical principles. The characteristics of the ocean environment that potentially affect the rates at which reactions occur include the following:
Temperature. In the areas where CW munitions were dumped, the temperatures at the bottom of the sea range from 3'C in pans of the Barents SeaC at the bottom of the East Novaya Zemlya Trough. All reaction rales have been adjusted to 0JC as representative of the conditions in the various study areas.
pH. The rales of hydrolysis reactions by hydroxide anion are dependent on the hydroxide concentration, and thus on pH. All reaction rates were adjusted to.
Concentration of metal ions. Magnesium and calcium ions and their complexes are known lo catalyze the hydrolysis of Sarin. The range of salinity found in the study area (see Chapterndicate thai the ionic concentrations should be typical ofnd
Concentration of chloride ion. Chloride inhibits the hydrolvsis of mustard. In seawater.5 moleL
Ioniche dependence of the inhibition of mustard hydrolysis by chloride also depends on ionic strength. In
Pressure. In ihe sludy area, munitions were dumped al depths ranging from. The pressures al such depths range fromotmospheres.
( HEMISTRY OFTABIW
(rtneral Information
Tnhun was discoveredy G. Shrader ofarben in Germany1 and was first manufactured' labun was used by the Iraqis during the Iran-Iraq war' Puiv Tubun or GAolorless liquidruityhe
industrial productrownish color and an odor reminiscent of bitter almonds from the formation of hydrogen cyanide. The industrial product generallyhlorobcn/cnc (vide infra)olvent nnd stabilizer. The physical properties of Tabun arc given in. In the absenceeasured solubility value utor information on the temperature dependence of solubility, the value ofill be used for the solubility of
labun ai OX.
: Physical Properties af Tabun KiA)'
point
point
C
mm Hp
Ci
c cm
solubility (no tcmrxiatuie provided)
Y
1-
log Kinr
44
1 t
Manufacturing Processes
The manufacturing processes for Tabun generally involve the reaction of phosphorous oxychloride with dimethylamine, sodium cyanide, and cthanol. as in tbe original Schrader process:1
CH, O
II
CHjfcNH -
cht CN
The rnder of addition is not critical One variant of the process adds ethanol followed by dimethylamine followed by cyanide. Another adds dimethylamine first, then todium cyanide and ethanol separately in thathird variant reaction uses phosphorous uxhkwidc as the starting material and cyanogen chloride rather than cyanide
OL
CI#
CH,^ H,CH,
tt
m)-ch.cHj
i wrapm at ow fur-,cmarj,. p
T'litlr S mncta MiliOfseiUj Hnhn
Kpuiiramfnai Uhtumumtdnk luw lartB MB oonWu.
pMOT. B. 'rhruiii- ii. U. Htfrt italnaay. M. WW. pNmdI
O SB TMV
aawd. P. II.Santa)
I.fan In IVM.MIr uk
W1
Hydrolysis
At. Tabun is hydrolyzed by hydroxidecyanide anion andas initial producls:
H.CH3
CHT OH
At. Tabun is hydrolyzeder, producing the same initial products:
CH, O
H^CH,+ Vc^CH,
Atabun is hydrolyzed by acid. The acidic reaction produces protonated dimethylamine and monoethyl phosphorocyanate:
^
Under the conditions found in the oceanoth the neutral and basic reactions occur, producing cyanide as the first hydrolysis product. The monoethyl dimethylphosphoramidate subsequently hydrolyzes to ethanol and diroelhylphosphoramidic acid, which in turn slowly hydrolyzes to dimethylamine and phosphoric acid:
The compounds produced during the hydrolysis reaction in Ihe marine environment are listed in. Of these products, cyanide and dimethylamine arc known lo have significant toxicity (see
The rate constant for the hydrolysis of Tabun has been measuredariety of pH and temperatures; these values are reported in. From this data, an activation1 kcal mole1 was calculated for the basic hydrolysis ofhus, atndthe rate constant for the basic process is calculated using the Anlienius expression" ashr'. Nois available for the neutral Tabun hydrolysisroup. Army researchers has also measured the half-life of Tabun in seawater at several different temperatures; these values are reported inlong with the corresponding rate constants.
Two approaches were used to estimate the rate of the neutral reaction under sealloor conditions.normal" solution, ion-dipolc reactionequal to approximatelycalanale constantr' from the value9 hr1 (measuredC andr4 hr' from the value7 hr" (measured atandhese two rate constants should reflect the pll-iiidependcnl rale of the neutral reaction. Based on this calculation, it is apparent that atnd OX' the neutral reaction will dominate the
observed rate of reaction, and that Tahun hydrolysis should occurate
r'. Alternatively, one can use the Anhenius expression to extrapolate the seawater datar'. equivalentalf life,ours. Ihe latter value will be used as the hydrolysis rate constant for Tabun in seawaterNo information is available on the rate at-which Tabun dissolves in water. Therefore, given the fairly high solubility of Tabun. it will be assumed for purposes of this study that the rate of dissolution is limited only by the physical mixing of Tabun with water.
4X4 Photolysis
Tabun and its hydrolysis products exhibit no significant phototransformations in sunlight."
Tabun and its hydrolysis products arc thermally stable at temperatures less than
of Chlorobenzene
Tahun, as an industrial product, generally contains five to twenty percent cliloroben/cne (CAS registryolventtabilizer. Itolorless liquidot unpleasant odor usedhemical intermediate and solvent. Chlorobenzene is unreactive toward water and decomposes only at high temperatures. 'Ihe physical properties of chlorobenzene are given in.
: Physical Properties of Chlorobenzene"
Mi'lLmu poitu
point
i cm'
solubility'1
CHEMISTRY OF General Information
. primipu, ofchanhat bwKi Academic Ptcm Nn.. ito. -Relererecahtc J.
^Refcrtree, coiiplundcci.hcu-nc "OKd
QGKOW DATABANK. Sorbin ResearchomreaL Quebec.4 "Reference, 2Si.
Sarin or GB was discovered in Germany9 by G. Shrader. Thirty tons of II were produced in pilot plants beginning inwo large industrial plants for full scale Sarin production were under construction at the conclusion of World War II. Sarinolorless and odorless liquid. The rate of dissolution of Sarin is limited only bv the physical mixing with water because water and Sarin arc miscible. The physical properties of Sarin arc given in.
: Physical Properties of Sarin (CB)'K
Meitimr point
point
)
mm Hg
m'
solubility
log
Manufacturing Processes1'
manufacturing routes to dichtor. The "DM PIP' process proceeds'1 from phosphorous trichloride and methanol through several intermediates:
H.OH CI
0
II
ch,
CH, CrhO-
HCI,-*
PCIj+atalyst+ O,
ii
i
I
CM,
II
H,
The HTM Pyro reactionybrid of the two previous reactions
O O
II IICH
H,
umber of similar reaction schemes that have been used to manufacture dichlor. Dichlor is convened to methylphosphonyldifluoridc (difluor) using either hydrofluoric acid or sodium fluoride:
.
0
ii
I
HFor NaF
Finally, ilifluor reactsropanolive Sarin. This is Ihe same reaction lhal occurs during delivery of Sarin binary munitions:
The HF byproduct can he used to convert dichlorilluor in situ;ixture of dichlor and difluor is mixedropanol in the manufacturing process.
Hydrolysis
Sarin undergoes hydrolysis by acidic, neutral, and basic mechanisms, all of which produce fluoride and Isopropyl methylphosphonate as the initial products. Under the conditions found in the oceanoth the neutral and basic reactions will occur. The neutral reaction is as follows:
HFUcHCH,
The basic reaction produces the same products by wayifferent mechanism. The compounds produced during the basic hydrolysis reaction arc given in. Of these products, only fluoride is known to have significant toxicity, as discussed in Chapterydrolysis reaction rate constants for Sarin for the basicand the neutral reactions,unction of temperature, are listed inf).
*Rclefence. cninpoundcicnce. compound3
. hi.Mmuirt ft.irf flnue* Ifsl. CRC6
: Sarin (GB) Hydrolysis Products
Compound
f LJ
log*-'
Producedg GB, g
ins HF)
01
cthvlcthvl ester
acid
'*
The E, values6 kcalcal mole1en: calculated from the bask: rule constants. Other observed rate constants for Sarin hydrolysis at various umpaabic and pH values aie given in
Observed Sarin (GB) Hydrolysis Rate Constants
T
seawater.eported constant pH. the half-life of Sarin at any temperatureC can be estimated using the following expression:"
K
. Mtiftrll.Kindle Sndy of the COppMH) CMatt-cuhxed Hydrolytr. ot hufnpH Methvlphc^ncdaor-Jaie. Clem,
JMUi
nil A.The Subiltiy ot Sarin and Somanfcloie Aqueous Solution* and a* Caraiyilc Effect ot Aeeialevinw..
Hoc-idont. C. andhcrfciin.-Hansen. "Saceen^eineor iu^iopyl meAylpho^fcttoriuoridalc (Sarin)njclel (or enayme mhittuonAr. Trot. Ohm8
J7.
"Deinrk. M. M.Bttuv-vnl (hcrnM-il Afenis in
In seawater, CV' and Mg" significantly catalyze Sarin hydrolysis. Alin seawatcr. the measured half-life of Sarinorrespondingale constant for hydrolysisr'. Finally, if the initial concentration of Sarin1 mole. the quantity of acidic reaction products wilfbe sufficient lo oveiwhelm ihe buffering capacity of seawater" and autocatalysis will occur, increasing the rate of hydrolysis.
i
"3*
44M Photolysis
Sarin and its hydrolysis products exhibit no significant photooajisfoniiation* in Thermolysis
Sarin and its hydrolysis products are thermally stable at temperatures lessC*
4.5 CHEMISTRY OF General Information
Mustardas first used on the night7 by the Germans against the British near Ypres in Belgium" Subsequent documented uses of mustard include use by the Italians during the invasion or Ethiopiand by both sides in the Iran-Iraqrgc quantities were prepared by both the Allies and the Axis during World War II, although no CW agents arc known to have been used inhen pure, mustardolorless and odorless liquid. Agent grade material is typically yellow to dark brownweet odor reminiscent of freshly cut hay and ittronghysical properties of mustard are given in
hysical Properties of MuUard
I4'C
point
C
mm Hp.
I'O Cj
cm"
i
f'O"
7 sL-
soliihility
p L
Inn K.
Ion
Manufacturing Processes
There are several methods used to manufacture mustard. The original preparation of muslard involved (he intermediate ihiodiglycolrepared from sodium sulfide and ethylene oxide (which is in mm prepared from ethylene):
'IMfl*
'IktocKal*. IIS -RrtWmwlfp IN. IIS
Mml
'KrimM. compound
*tvun Emmtofeia tj Mm mat mnmmfcta aVM S. pp.
n> ottrmw inattcODl. "Cm DKfaorechylwlphioe (Mimw) Oh) in StauKlny nnd lIvcMyuiDMWI<*clh;lMilcc.luer. Mnln3Mim-iioi Snull Amnion.
ecrJ, OH Rmenbim.wufcnn*McGraw-Hill Boot Conwy Nn* York.
HjCrVOH
TOG Ihcn reads wilh hydrogen chloride or other chlorinating agents:
HO-CHCI H^CHrCI
This preparation is more complicated and lime-consuming in comparison with direct methods. Direct synthesis is the fastest, most econoiuical method of prodtidion. There are two direct synthesis methods, the Guthrie method:
H^-CI
and the LcvUistein method:
I,
The Levinstein method also produces die CWnd other higher analogues of mustard.
The former Soviet Unionariation on the Levinstein process developed by V. S. Zaykov. In the Zaykov process, propylene was used to replace all or part of the ethylene,ixture of mustard,hloropropanel, and various mixed analogues whichower freezing temperature than pureThe reactivity of Zaykov mustard should be entirely analogous to the reactivity of mustard.
Hydrolysis
The first step in the hydrolysis of mustarducleophilic attack of theeighboring group oncarbon lo form an intermediate sulfonium ion: u
k, CHa Cl"
H,CH1-CI^F^ I
CH*
This is considered to be an SnI reaction witheighboringssistance. The reactant and ihe ion pair are in equilibrium, so lhat the observed reaction rate will decrease with increasing chloride concentration. Water attacks the sulfonium ion at one of the ring carbons, opening the ring to give hemimustard and hydrogen chloride:
rfeO | CH,CH*-a CH,
Clvx/eatI" ftiuini* Hlnaii, EcologyS.Ttrolalcd from Russian by Forcivn Broadcaw InfonnaiKin Service-.
P. IJ.lnencHyiayl.tni and Diiplseeraem Rea.inni uf fl.Sulfide (Mniiaidndiloto-frSullide (MuUanlum
Hemimustard isesicant, ft then reactsimilar fashion with water to give thiodiglycol and an additional molecule of hydrogen chloride:
CI
CH*
The cyclic intermediate formed from hemimustard also reacts via an internal displacement tohioxane and an additional molecule of hydrogen chloride:
^-OH^CH,
CH* CI
-OH
/
CHjCHj
hemimustard hydrolysis reactionatio of thiodiglycol to thioxanche amounts of TIX) and thioxanc produced by mustard hydrolysis are given in
usiard (H) Hydrolysis Products
Compound
Producedg II, B
rate constant atofhr1 for mustard has been established and, for hemimustardemimustardelatively short-lived hydrolysis intermediate. Ihe kinetics of hydrolysis have been determined at different temperatures and are presented inhe activation enthalpy,5 kcalas been determined for mustard hydrolysis."
Another consideration is that aqueous chloride ions affect the equilibrium between mustard and the intermediate sulfonium ion. One approach to calculating the magnitude of this effect is to use the experimental value for the reaction ratend correct for the chloride ion present in seawater. The effect of chloride is to slow the observed rate of mustard hydrolysisactor equal to:
Us:
k
'ITAjotfiiiO P. A. andThe Identification otallard Hvdroly.nicWfeSS^rktnlHon. Alberta.vailable throush DTIC.. Thii rapwr altoirhiantvinylirno)cUiiinol as products in the aqocou. nnaw froma high concc nuitioniHijji lemjwlixeOtCt Tbnc wb-nance* likely ante from the high concentration and lempcitfuil oied by Uie Canadians and Kt likely ui repaienl minor pathways under the ceodiuoni at ihefloor of rhe ttudy area
"Recently. inveWiiiahinueuWned rhe validity of the rare conitanu inndecause they -ere caleubwdiojlereaction rather than consecutive fir*-order reactions Seck rtetntwivrrorpii ofeAfomeUiyl'Ihenmxltim.S Ho-evee. wing accepted value,cal mote'l and iheate contfanf(Oil*value of9fC much t. lbie.alue olan-
'Yang.* al. "On the activation energy for the hydnilysit ol*iride.
aries with the ionic strength according to the Bronstcd-Bjetrum rate equationimiting value ofole1 at zero ionic strength:*
hich uses the constant from the Dcbye-Huckcl equation:'"
=
liOekTTH
OX, the value of theerm is calculatedhe charges (zu* andarend -I. and the ionic strength of seawater.hichalueor seawater at OX. If the hydrolysis rate constant in freshwater8nd5 mole L1 thisydrolysis rate constant2n scawalcr."
ydrolysis Rale Constants of Mustard (H) at Various Temperatures
min*'
It"
fciencc
-Cwellan. G. W_ Unocal ChtMur,:Adduon-We,(ey:J.
"Note boweva,he ionic tircngih olbove (helcvLiKii*(be Debye HucM law arc lypicaMv observed The uue -slue of ihe raie cuiiWuk may he wmcwhai higher due ioifeviaimnt
- BrooUleld.. S. Woodward,nt. "The Kinetic* oflichfciMdiclhyltulpriideJfcwm
irn Greatarch
"Tlie accuracy of ihe raie eonnn.it in reieeeneeove horn quetiktned became ol ihe cipcnmenul leclinniue used hyewrirw. w. fi.
LinwW. R_ P. -Ruroinn* of ihe Chlonne Atoms of Muslard Gai in AqueomO
"Mahler. H. J. HMinagcl. Cnemi'iotoXIII. fhMytsrW-diaiMialfid, lick. Chun
"Men. R.aller. -Rale of libenlion c* Aodulfide and in Arttlognnt it. RelMinn In Ihe "Acid" Theory ol Skin
Yewaikin.
I
A group. Army researchers has also measured ihc half-life of mustard in seawater at several different temperatures: these values are reported in5 along with the corresponding rate constants. An alternative approach lo calculating the magnitude of the chloride effcel is to use the experimental value for the reaction rate in seawater and extrapolate that rate toThe extrapolated reaction rate,0 min', is in agreement with ihe value previously calculated. The rate constant2 min" will be used as the mustanl hydrolysis rate in subsequent chapters of this study.
alf-lives of Mustard (H) in Seawater"
T'C
tw (min)
calculated (min1)
the relative rapidity of ihc hydrolysis reaction, mustard has been found lo persist in soil or even in water for periods of* In such incidents of long-term persistence, the common thread is the presence of bulk muslard. While the hydrolysis of dissolved mustard is relatively fast, ihe dissolution of mustard docs not occurikely sequence for the fate of bulk muslard introduced into quiescent water would be the following:
Mustard that initially dissolves from the droplet is hydrolyzed lo TDG.
At the interface where little water is present, the intermediate sulfonium ion forms and then reacts wiih another molecule of mustard (rather than with water) tohloroethyl)thio|cthane (Q)ichloroeihane:
LI
+ CI-CH,CH;-Cl
Inyproduct of several methods of mustard agent manufacturing, including the Levinstein process used by the United States. Thus, under long term storage conditions of muslard. significant additional amountsan accumulate in ihe container.
Note that the presenceertain levelas considered desirable because itowerful vesicant in its own right and depresses Ihc freezing point of mustard. The solubility
"Munlum, dnpoied of in me Balne Sc. niter World Wu IIeleasedthai han hew,i ihe wriaee.il ha* inured fi<hennenreeenUyorgetwn. ft.emiwn. Muaant gat octieftiu- n* MivnlMfan. VgrA,. "Mimiimqi Aiposed nl inific Ocejn wd lap^ww eoasul -aicrt uliei World War II have relaxed rnuMard IhM hoi been hitsijhi lit ihe lurface. where il ha. injuredeeenllyuraia. H.m-dfnm rfte dt-irutneo htmraltetimrtMm tax)Stockholm Iniemanonal Pekc Rcicajch Inuiuxc, Taylor anil Francii:p.
Due lo lack ol appreciableoncentrated 'ITXi layer builds up at the mustard droplet water interface. The TDG at the interface also reacts with the intermediate sulfonium ion to form stable sulfonium salts of the
CrhChVOH
K,CH,-OHO-CHrClfc^CHiCHrS-CHjCHr*-CHiCIMH
In time, non-reactive sulfonium salts such as these and higher homologucsrom the analogous reactions of Q) build up at the interface between the mustard droplet and the bulk aqueous phase. The sulfonium saltshicker boundary layer.
Dissolution of mustard slows because the driving force for diffusion of mustard into the bulk aqueous phase decreases. Similarly, diffusion of water into tbe mustard droplet slows, which lowers die observed rate of hydrolysis. However, if the water is sub)ect to disturbance, sucheavy rain, or is rapidly flowing, it is less likely that mustard droplets would persist for significant periods.
Brookficld, et al. first established the rate (a) at which musiard dissolves in quiescent waterunction of temperature:3'
More recently, Dcrnek et al. measured the rate of mustard dissolutionm cnv! sec"5 knotpstein, et al. estimatedne ton block of mustard would require five yearsylinder of solid mustard with surface aream' is placed5 knot current, mustard concentration
drops within one foothus, in order to perform environmental fate assessments of mustard, both the hydrolysis and dissolution rate must be considered.
Mustard and its hydrolysis products exhibit no significant phototransformations in sunlight"
iil..
'C Piullifu. The Rale uf Diiuriiiiioiinion^hytnlpnidrliullcd aod Nsuinl
aturn Oat Rca.tr/Client Brlrain.CtJirftci
J9.
"Reference IT.
l altauta of rn# Chtmtcat Suvn- atnn Wittni*s. P. IL. ttiiUonmruiaf Condition RrporlDtrp WtocrOienpAiwM.NRl. Report JSSl.Rcrtuiclir.1n..
Mustard and its hydrolysis products are thermally stable at temperatures lessC-H
II MINI RY
Oxidative Degradation
Mustardumber of its hydrolysis products arc oxidized in air at significant rates, giving the sulfoxide and sulfone analogs. These reactions occur more readily under alkalinehe sulfoxide and sulfone analogs of mustard arc toxic, but undergo hydrolysis to less toxic products. Il is unlikely, however, lhal the oxidation reactions will compete with hydrolysis to any significant extent in the marine environment. Therefoie. these oxidation products will not he considered in subsequent chapters of this study.
4.6 CHEMISTRY OF General Information
lewisite was first prepared by Americans toward the end of World War I. but was never used because of Ihe armistice. During World War II, both the American and German armies had considerable slocks of Lewisitel may have been used by ihe Iraqis in addition to musiardndustrially-produced Lewisitetrong penetrating geranium odor; the puie compound is odorless. Physical properties of Lewisite are given in
Processes
is manufactured from acetylene and arsenic irichloride using cuprous chloride as catalyst:
This procedureixture of vis- and trans- isomers of Lewisite, plus small amounts of bis<2-
HC=sCI,I-CH-CH-AsCL
"RefoeM (9
. "Relereere 3.
"Reieicnc*p.anleu ixhenmc noted
'CICH^CHPCI,an cibmaieri valueing referencen liactneni descriptioni -err avulaDtc fiv ar-enx
ars.t:ljW Rariffltadidw liiraaih
ational Laboratory reportS: The estimate of arsenic atil-walcr diMribuUun coefficiciil i* batedMoi>lant efecneoial tisnifcr coefficient for vegetative pnniont ol rood eiop* and teedpbnn.
ehlorovinyl)chloroarsine.hlomvinyl)arsine. and arsenic trichloride. These minor constituents arc less toxic than Lewisite and produce analogous products when they react. Therefore, they will not be considered in subsequent chapters of this study.
Hydrolysis
The hydrolysis of lewisite proceeds according to the following scheme:
2-chlorovinylarsonous acid
CI-CH.CH-Asl.OH), H=CH-As=0 Lewisite oxide
^
Tlie hydrolysis product mixtureeported" The initial hydrolysis reaction is rapid relative lo formation ofhloro-vinylarsenous acid/Lewisite oxide equilibrium mixture. Lewisite is more rapidlyd thanhe literatureeport that states that "complete hydrolysis of the chlorine attached to the arsenic occursew minuteshereasercent hydrolyzes rapidly, the rest morefercent of Lewisite hydrolyzes within two minutes, the rate is at least fifty limes tlie rate for mustard atIf we take the rate of hydrolysis of mustard8 min', then ihc rate of Lewisiteught to be at4 min' based on the literature report; the reaction rate is likely more rapid.
Ihc immediate hydrolysishloro-vinylarsenous acid and lewisite oxide, arc alsohere is no appreciable difference in toxicity between Lewisite andhlorovinyl-arsenous acid/Lewisite oxide equilibrium mixture. Given the rapidity of hydrolysis it is possible that these species arc responsible in vivo for the effects of lewisite. 'Ihe vesicant properties of the mixture arc reported to remain unchanged after storage for ten weeks in seawater."
Over time, the hydrolysis products will be transformed into both other organic and inorganic forms of arsenic. Waters and Williams observed that cold alkalihlorovinylarsonous acid into arsonous acid, acetylene, and chloride:*
C=CH+ As|OH),
"Winers,I. II. Williams. 'Ilydral,-e*nroe Vcmcjmhan
-CfcnmtnJ Atumtn HI:hiirjc ol Km lib. G.
C, this reaction shows no detectable acetylene product afterours allight amount of product after twenty-four hours atnd substantial amounts of product after two hours atn approximate extrapolation toandndicates that the reaction should occurime scale of months in seawater. This time scale is roughly consistent with the observation in referencef continued vesicant properties after len weeks. The arscnous acid produced will subsequently undergo the expected transformations of arsenic in the environment (videhe products of Lewisite hydrolysis are given in
No information is available on lite rate at which Lewisite dissolves in. Army scientist has indicated that like mustard, the hydrolysis of lewisite is limited by the rate ofowever, given that Lewisite hydrolyzes much more rapidly than musiard. it is unclear whether of nol the rate of dissolution will affect rhe release of Lewisite. Therefore, il will be assumed for purposes of this study lhal the rate of dissolution is limited only by the physical mixing of Lewisite with water.
lewisite docs not oxidize significantly. However, the oxide produced by hydrolysis can be slowly oxidizedhlorovinylarsonic acid:
0 II
[fJl
lewisite and its hydrolysis products exhibit no significant phototransformations in sunlight.1"
The hydrolyiii miirnreircatci rtu* two reietnt in
stimated value4 wing referenceo fragment description* were available for ranK.tu an estimated value4 ujinp referenceo fragment description* were available foe anenie. "Dr. V. C. Yang. Edge wood Research. Development, and RngiBeenn" Cenier. pergonalReference
Lewisite and its hydrolysis products arc thermally stable at temperatures less than
4.7 THE CHEMISTRY OF ARSENIC IN THE ENVIRONMENT
The arsenic from lewisite is hydroly/.ed and converted to arsonous acid, as discussed above. Once this occurs, the arsenic from Lewisite will be indistinguishable from and undergo the characteristic environmental reactions of ubiquitous environmental arsenic acid. The arscnous acidn thexidation state will bc oxidized to arsenaten thexidation date according to the reduction potential of the environment. The ionization of arsenate ions is controlled by the pH of the water. In natural waters, Ihe predominant species areAsOY-sO; in sediment.nd HbAsCh predominate."
Dissolved arsenic enters the biological arsenic cycle and is transformed into less toxic methylated derivatives or into volatile arsincs. Dimcthylarsine is produced in meilianobucterium species via an anaerobic biomcthylarion pathway:*
CHj-As-CHi H
t'
ii
HO-As-OH OH
aerobic conditions, the biomethylation pathway continues to trimethyl arsinc
Crb
The methylated arsines are then excreted from the organism. Marine algae, marine invertebrates, and fishortion of the arsenate within the cells as complex organic compounds including dimethylarsenosugars. arseno-lipids, and arsenobelaine."
CI*,
CH,
OH OH
0=As-r < H?CHCHrR
k
OHOH
-lim.no. Naiof tbe Chemical andof Arsenical Compound* mHeavilyPuriT The Fait and Speciaiton of Arsenical Compounds in Aquaticerauncvn.'nui. Set lltatOi. Pan. "McBridc. B.l "Anaeiohic and Aerobic Alleviation ofn Brmkmxn. F. e. and J. M. Beltama. fab..ACSSympS.
S. and W. T. Fmnltenberger. "Environmental BiiKberniiery of Anenic."CamI Ift
EVW/^Kft'HKMJSTRV
EFFECTS OF PRESSURE ON HYDROLYSIS RATES
nk- Inlc,'
Munitions disposed of at depths ofn water will experienceotmospheres of pressure. High pressure can influence the rates of chemical reactions according to the expiession:
PAV'
HT
y't
where ft is the rates pressure. AV is the volume of activation for thes the gas constant,s absoluten the absence uf any measurements of volumes of activation for the hydrolysis reactions described above, estimates of die contributions of bond0 rnL mole') and0 mL mole') and0 mL mole') will behe rate determining step of Sarin hydrolysis has been reported to be bieakdown of tbe pentacoordinate reaction intermediate resulting from addition of water or hydroxide to the Sarin phosphorusolume of activation ofL mole" can bc assumed. Tor other phosphonatc hydrolyses. formation ofond is ratehus, for (lie hydrolysis ofolume of activationL mole' can bc assumed. For mustard hydrolysis, bond cleavage plus ionization occur in the rate determining step,olume of activation ofL mole'. Alim pressure, volumes of activationL mole"l. mole'- values3espectively. The range of activation volumes for reactions in aqueous solvents runsL mole'1L mole These values givevalues5hese calculations indicate that it is likely that pressures at depths upill affect the rates of hydrolysisercent or less; it is very unlikely that the effect will exceedercetu. The effect of pressure on reaction rates is small compared to the uncertainties involved in extrapolating rate constants to low temperatures, as well as to seawater ionic strength and pH. Thus, pressure effects can be safely ignored in subsequent analyses of this report.
4.9 UNCERTAINTIES
The environmental fate of the CW agents and breakdown products covered by this study depends on the rates of the chemical transformations described previously in this chapter. Uncertainties in the rates of chemical and physical processes result in uncertainties in the environmental fate and, consequently, in uncertainties in the environmental effects of ocean dumping. Quantitative data from the peer-reviewed literature are available for only some of the chemical and physical processes discussed in this chapter. The remaining values are estimated, adding uncertainly to this.
The available data in the literature for the following rales ate either qualitative or semi-quantitative:
Hydrolysis rate of Lewisite;
Dissolution rate of Lewisite:
Hydrolysis rateshlorovinylarsonoushlorovinylarsunous oxide, and Lewisite polymer.
Rates alhlorovinylarsonous acidhlorovinylarsonous oxide and Lewisite polymer and the rates of the reverse reactions: and
Oxidation ratehlorovinylarsonous acid.
This study is limited by using only rough estimates of these parameters. Quantitative measurements wouldore precise estimate of the fate of Lewisite in the marine environment. In addition, no information is available in the literature for the dissolution rate of Tabun at OC. However, this studylausible assumption for this parameter; it appears unlikelyuantitative measurement would improve the estimate of the environmental fate of Tabun.
nd M. fVilunyi. Snu* Appli/tH*m> fifth*uae Milhod tti tat CO& ulcaiiM Of KtailiOn ttlcnUWi. fapttioll, Ol Solmiun.
FarotkrtTJ.
T.eNtttc. -Atli-alMn andtne. InReference It.
l al "NoclwiphlLc aod Pmtolytic Catalyst* of Pbo&phonaicIsotope h'ffectt and Acunitinci. Am. Chtm..
There arc no quantitative measurements for the following.
Hydrolysis rate of Tahun ai OX in seawatcr; ot
Hydrolysis rate of mustardn scawatcr
For these parameters, available information allows extrapolation fn nn rcponed conditions to conditions in the study area according to well established chemical principles. Furthermore, these extrapolations are confirmed using independent data from limited circulation, non-peer reviewed documents. Again, it appears unlikely that quantitative measurements of these parameter wouldihe estimates of the environmental falc of Tabun and mustard.
Finally, there are several parameters for which only csrimatcs arc available. These include log /V- for all compounds (excepl chlonihcn/cnc) covered in this study and the aqueous solubilities of the following substances:
monoethyl ester ofacid;
dimcthylphovptHirarnidic acid, ami
I -methylethyl ester of mcthylphusphonic acid.
Estimating the environmental (ate of the compounds covered by this study docs no) require very precise values of these parameters. The available estimates for log K- and aqueous .solubility arc sufficiently reliable fot purposes of this sludy.
SUMMARY OF SIGNIFICANT CHEMICAL PROPERTIES
The chemistry of CW agents in the marine environment is dominated by hydrolysis, the reaction of the agents with Mater. The key features of the chemistry of the CW agents in the marine environment
Tabun is fairly soluble in water and hydr0ly7.eseriod of days.
Sarin is nttscible (mixes in all proportions) with water and also hydrolyzesenod of days.
Divsotxcd mustard hydrolyzes rclatnely rapidly However, the persistence of mustard in the marine environment is controlled b> the rate at which it dissolves: dissolution is much slower than hydrolysis, requiring months for kilogram sized quantities
Lewisite is soluble in water and hydrolyzes very rapidly. Tie initial hydrolysis products of Lewisite are also very toxic and persist in scawatcr for months or longer Ultimately, the Lewisite hydrolysis products arc convened to arsenic.
The following key physical properties of agents and hydrolysis products thai relateheir emm-nmental fate and transport arc summarized in8
solubility is used in calculating the amount of an agent that is released from dumped munitions and in determining the environmental fateubstance.
- Hydrolysis rule constantdetermines the rate at which aa agent reacts with and thus is removed from water.
(twt of an agenl in seawater is the time required lot the concentration of ihc agentecrease byercent; this is another measure of the rate at which tlie agent is removed Irom water and is calculated directly from
Estimated log of the octanol-watcr partitioneasure ofulfuric' partitions between water and oclanol. Octanola surrogate for animal fat; log A'. is used in ihe analysis of ihc accumulation of the substance in tissues ol living organisms.
The rate of dissolution (al. which governs the persistence of muslard in the environment.
Tatmn: ftmenvlchr^horamrdrx^nidic aad elhyl
2
ummary of Tabun (GA) Chemistry In Seawater
ch,
hr 1
0
t-fl
Wtir
cn
est
Abstracts Service
2
6
8
6
Common Name(s) ol (CAS) tome ot Molecular CAS Registry
Hydrolysis Weight Numper
Hydrogen cyanide
gram alcohol
Dinwhyiphosphoramidic acid, cihunoip monoethyl ester
Dimrrthylphosphoram'dic acid
DimeTtiyta-nne
aod Prwspncnc
6 7
' Chlorotwnnne isydrproduct, but is present0erman-produced GA
Chemical Smicture
hcn d
ch,chro-ni
on
hop!
ch3ch-oh
>*
ch:!ihch: hjpo.
a-
Solubility. Estimated QL-' logKow
0 04
miscibte
9
0
-i
ummary of Sarin (GB) Chemistry in Seawater
Meihylphosphonofluoridic acid,methylelnyl)8
Solubility,iscible
II
F-PO-CHCH) CH.CH,
1
Abstracts Service
Common Name(s) of (CAS) Name ofRegistry
Hytirolysis Product
CtfnOsP 0 -
Hydrogen Ruoride Hydrofluoric acid HF
aod.
ethylethyl) ester
Isopropyl Alcohol
CHsOjP 5
Chemical Structure HF
0
II
j-CHCH, CH,CH, HO-CKCH, CHi
O
II
JH
I
CH,
Solubility, Estimated
"very"
very"
llio
litii!
ummary ot Lewisite (L) Chemistry In Seawater
OhS3roetfiefryl)afSOtrOus dlcfiknide 3
CiHjAsCh.2
Solubility. QKn, (estimate)
Abstracts Service
Common Name(s) ol (CAS) Name of Hydrolysis Molecular Molecular CASEstimated
Hydrolysis Weight Number Chemical Structure gl' log Kg.
CI
chloroethenyl)arsonoos CjHiAsCfO? 3 1
I
ci
s
Cl
AstOHh
LeNVtsite oxide dUoroetnerryl)oxoarsine CjH2AsCI0 1 20 4
r*)roetherryl)arsontc4 acid
=AtDM
BACKGROUND
of agents fiom individual munitions containing Tabun. Sarin, or Lewisite was modeled as cither of the following two types:
Impulsive release of the entire chargeatter of minutes):
Steady state release with rates in the range oneo one kg day'.
over many weeks. Rates of production of dissolved mustardypical artillery shell are estimated to be on the order1 kg per day foT one hundred days.
is assumed that less than five percent of all munitions dumped will begin to release agents immediately following dumping.
After dumping andery long period il is possible lhatmall number of very thin walled bombs will release CW agent and that artillery shells may take many decades to corrode sufficiently to begin release.
CW munitions were disposed of at sea in five areas whose sizes range fromm:0 km-.
highest density of munitions is expected to be in the White Sea where there are as many0 munitions per km'.
The primary release periods that are times over which all ihc munitions at any site could be expected to undergo corrosive disintegration arc assumed to be in the range of five to fifty years, and this was treated paramctrically.
Estimates of the number of munitions per square kilometer range fromith separations between munitions that are leaking ranging from hundreds of metersew kilometers. Tens of meters is possibleew cases.
CONCLUSIONS
each primary release period and each site, four release scenarios were developed, as follows:
scenarios governing the release of Tabun. Sarin, and Lewisite:
Oneteady slate model and
One using an impulsive model;
One scenario for mustard using the calculations of dissolution; and
One scenario governing the five percent of munitions expected to release immediately upon dumping.
there are significant uncertainties, these release scenarios and associated models are consistent with known facts. It is not expected that deviations from these scenarios and models will lead to significantly different environmental assessments.
S.I INTRODUCTION
'Ihis chapter address ihe problem of determining how CW agents are released into the sea. The departure point is established by tlie results of Chapterhich identified the dump sites, the CW agents dumped, and the total quantities; and by Chapterhich established the physical properties of the agents and have of the dumped munitions is shown schematically in.
The challenge in litis chapter is to use the little information available and attempt to bound some of the important characteristics of these dump sites. Tlie key questions to be addressed in this Chapter are summarized in.
chematic Illustration of Ocean Dump Sites
. RELEASE SWJNARIOSp^
principle, these questions could be answered it one knew the probability distribution for release of an agent atingle, given munition and the distribution of types of munitions that were dumped at each site. In practice wc know neither quantity, nor type of munition.
Even if full knowledge of the materials used in the manufacture of each munition type were available, the authors have little confidenceimited investigation of corrosion processes would leaduantitative picture of agent release in which one had any reasonable confidence. However, while very little is known with certainty about how chemical munitions behave on the scafloor. we hypothesize the following scenario: Immediately after dumping there is.ransient period when munitions with cracks and other defects immediately begin to teak CW agents. Subsequently there could be some protracted period, governed by corrosion processes, over which little or no release is seen. Finally, with pinholes developing followed by corrosive disintegration, CW agents are introduced into the local environment.
All of this is assuming that the munitions arc undisturbed. As the Baltic experience shows however, when trawling occurs over the dump sites, even the viscous mustard, which is probably solid, will be released from munitions. Presumably, this happens because battering and scraping by the trawl removes the thin pansadly corroded casing.
The other key distribution is the spatial distribution of munitions on the scafloor. In principle spatial distribution is ascertainable since one might hope tourvey wiih unmanned vehicles and combine this with deck log records from the ships that did the supposed dumping. However, there have been no such surveys, and to our knowledge no deck logs exist.
Given this degree of ignorance about both distributions, the only recourse was to use existing
f jnti Iii hrtiinrl itv ftrnKli*rn-in kjiinr* ntinkur- ilt'*r
klUL.;* lUfU IV Ul'UIIU lln. Nin/ILIII IIII*ik* IIIOIITLVl ll
allows useful conclusions to be drawn.
Lest it be imagined that release scenarios could somehow turn out to be irrelevant, it is worthwhile to calibrate one's intuition by examining the total volumes of seawater that could be contaminated by the total quantities of CW agents thought to have been dumped (seesing the maximum concentrations at which no biological effects are expected (ENEC) and the total quantities.hows the maximum volumes of w'atcr that it would be possible to contaminate tin the unrealistic case in which all the agenl is instantaneously released and dispersed over ihcsc volumes before hydrolysis can act).
These volumes are very large indeed, the0 km', represents approximatelyercent of the total volume of the Kara Sea. It is the release scenario, distributing tlie release over lime, that will reduce ihe volume of water that can be contaminatediven toxic level.
5.2 AGENT RELEASE FROM INDIUNITIONS
Dump Sites and Total Release limes
shells would lake approximately five, and perhaps len limes as long to corrode to the point of agem release. Il is our impression thai artillery shells could bc madeore corrosion-resistant steel than bombs, but it may also bc that corrosion around the seals is Ihe primary mechanism of release.
Dcspiic the uncertainties, ii is inluilivc to expect artillery shells to remain intact much longer than thinner walled bombs. It is our view lhat the Baltic experience, could be almost entirely the rcsuli of leakage from bombs and lhal ihere could he very large quantities of inlaci artillery shells in situ.
If release of CW agents from scaled munitions occursesult of corrosive processes attacking Ihe casing walls, as opposed lo the seals on Ihe filling port, and
ombines the available information from the Dultic and ihe Japanese experiencesingle graph (sec references in
indicating enough harm to have been entered as medical leports.
While drawing any solid conclusions from this data is somewhat risky, we can construct some relatively clear consistent hypotheses.
There maysmall" initial release immediately following dumping, possibly due to munitions having material defects or munitions damaged by the dumping.
Thea foreriod are reports by Danish fishermen of "findings" and do not necessarily indicate any medical problems. It can be presumed that such "findings" occurred in previous years as well
W Munitions Related Incidents
o
iliE
a a
oi eo en
<o
oiaiototacianooioi
ELEASES* IWUlO**
mayenod following this post-dumping release during which very feu munitions are opened: prcsumnMy. ihis ishen corrosion is acting on ihe casing.
Trawling can he expectedatter ihe munitions sufficiently to open them and release agenis.
The corrosive disiniegiotion of munitions appears io lake place over decades, perhaps many decades. There is no data strongly indicating that extensive corrosive disintegration, especially of artillery shells, has occurred as yet.
Musiard, when released, stays relatively intact on the seafloor for weeks or months. This is evident from ihe recovery of musiard lumps.
This data, primarily involving ihe near-solid musiard. doe* not shed any light on the possibility of corrosion causing pinholes in the casing through which rhe CW agent leaks al very low rates. One must expect that this process docs occur and may be the primary means for release of highly soluble agent* We are led to hypothesize, then, lhat the distribution of release events could be a* shown schematically in.
The distribution contains three periods, rhe initial transient, the extended period during which corrosion attacks the casings, and the primary release period during which agents arc released from munitions as they develop pinholes. Releaseingle munition may take days, weeks or even months, but thes thought or as lasting years,ew decades. Of course, wc do not expccl lhal this "boxcar" distribution best represents reality, which probably would be modeled betteruylcigh distribution. Il is reasonable lo expect that niter limein which corrosion decays casings ami which lasts decades, there willrimary release extendingears during which there willomewhat constant rate of individual munitions beginning to release agents. This is summarized in.
Although there is no reason to suppose that forty years represents the nunimum release penod, we will take it as such, simply for lack ol evidence Hi ihe contrary -od because doing so will provide an upper bound on
: Schematic Illustration of tht Distribution ofents
C
a
1
E
Disintegration Fteriod T,
Initial release
(decades)
possible harm to the environment since spreading releases out over longer periods leads to lower agent concentrations and reduced toxicity.
Release from Individual Munitions
One point to be consmViedthe total quantity of agent that could have beeniven individual munition.ontains the best mforrnaUon available to the aulbots at the lime of writing. As staled above, artillery shell casings arc expected to be thicker than the bomb casings More specifically, bomb casings are expected toom in thickness while artillery shells are expected to beom in thickness Consequently, bomb casings arc expected to undergo corrosive disintegration much more rapidly than the shells. As stated in Chapterhe bulk Of CW agents thought to have been released were in the form of artillery shells, followed by bombs. Not listed above arc bulk storage canisters, thought to have been an Insignificant factor in this problem since almost all the captured or manufactured CW agent is thought lo have beenhe agents dumped at any particular site are unknown mixtures of these types, but mixtures certainly dominated by artillery shells.
Wc assume that the release of mustardingle munition, because of its high viscosity aod km dissolutionbrupt. Thai is. the effect of pinhole leaks is negligible and nothing of interest happens until the casing is essentially completely corroded. This is at least consistent with reports from tbe Baltic describing lumps of musiard. with no mention of fragments of casing.
The question of pinhole leaks needs to be discussed briefly in order lo argue that there are two bounds that constrain this probkm. On the one hand, if the release rate is so slow that dilution and hydrolysis effectively reduce agent concentrations to harmless levels essentially as fast as it is released, then that rate, or any slower rate, will produce no biological harm. Later we will quantify this. On the other hand, if the release is so rapid that it happensime short compared to all the other time scales in the probkm. see Chapterhen it might just as well be an inviantancous release In any case, the release can proceed only as long as the agent remains in the munition, ln this way. whik wc know no more about the growth of pinhole leaks than before, some useful bounds may be possible.
imple calculation of leleased massunction of time for various release rates Q.
hells couldelease rate of as greatg per day for tens ofime much greater lhan the time required toteady state condition. However, much greater rules, saygould only be supported for times that become comparable with the time required toteady st.irc and thus need to be addressed differently.
Because Tabun and Sarin arc highly soluble in water and Lewisite mayigh dissolution rate, the wide vanety of the rates and times illustrated inre apphcahk to these agents.
Mustard howescr.cry different story. It is very viscous al 0'C In fact, it is not solid because il was mixed with other compounds in ordci to hrwer its
100
( i
; Illustration of Agents Released at Various Rates
poini so (hat it could bc used in cold weather military operations. In addition, the dissolution rateO1s so low that this process might well dominate all others.
Musiard releases into one of two scenarios: dissolutionphere, and dissolutionhin cylinderhe rate of production of dissolved mustardphere immersed in seawater.issolution rate ofand an initial radius ofis given by.
here the lifetime of the sphere, is given by
The fraction of mass remaining in the dissolving sphere is given by:
For Ihe pancake the radiusand heightq is still given byut with the maximum lifetime defined by.
Z"
In ihe second case, it is assumed lhat dissolution occurs at die top and sides of the pancake but not on the bottom, where il rests on the seafloor.'
rovides expected lifetimes for several masses of mustard for these two models.
Ii is not difficult to believe that many, if not all. of the mustard globs found by fishermen in the Ballic could have come from bombs, nol only because their casings are thinner and corrode faster than artillery sbclls, but because the life of the mustard once released is much longer, making il more likely for them io be found. The fraction of mass remaining intactg mass is shown in. which
TVrwioiablt whiletbe lad of now beneath would quicklyto laturawii and no rurthci dnutfuimu.
5-7
also graphs.g mass of mustard in two shapes. The sphereadius3 cm and the pancakeadiusm as wellery small height6 cm.
phere is the solid having the minimum surface area for given volume and the pancake shown is very thin, we regard these estimates as bounding the realistic dissolution of mustard releasedisintegrating munition.hows this quantity. Q. for the two shapes.
Several conclusions can bc made:
Mustard released from munitions in kilogram quantities will be introduced into ihe sea as dissolved ageill at very low rates, on ihe orderkg day';
This rale will remain approximately constant over long periods, perhaps as long as several thousand hours:
PaRiW
A simple approximation lo what happensonstanteriod equal io two "hair-lives" with an effective rulen the cases of the sphere and the pancake, as seen ins eouulX5ours respectively. For Ihe sphere, thispproximately equal8 kg per dayays and for ihes approximately equalg per day lorays. These approximations arc shown as dotted lines in.
With the approximations discussed above it becomes plausible to consider lhal one release model is applicable to all fouionstant rale ofor some lime t. Another release model that needs lo be considered, if only to bound ihe eventual estimation of toxicity extent,ingle, sudden release or an impulsive release of all the agent in Ihe munition. 'Ihis model will not be applicable to mustard. Wc will bc able to model only the temporal behaviorelease of the CW agents shown in.
SJ SPA TIA I.VMP SITES
Since Ihcrc is no hard information about how munitions were dumped or abouthe sites, it will bc necessary to make some assumptions that are consistent with what little is known, which is largely the Baltic experience. We reasonably suppose lhat dumping of munitionship in arciic seas at some time inthould result in the following:
intention io remain within the area designated.
Dumping pallets or crates of munitions while dnfting with the current in calm seas or at low speed, with occasional corrections to remain within the site;
ship loads to each dump site;
Navigationtar sights,n laternd DR ofom; and
Human factors.
One might expect ihere toomewhat random scattering ol munitions across the dump site and even outside of it, possiblyreater concentration toward the center.
We also plausibly assume lhat the larger dump sites are largeeason, namely the intention to dump more munitions there. That is, lacking any other information, ihc physical area of the dump site is significant as an indication of the quantities dumped. However, in order to avoid the results being dominated by the uncertain area of tlie very largen the Karaew adjustments will be made to increase Ihc quantities assigned to the smaller sites. Taking the results ofnd the foregoing, we assumed the prescription in.
In. the total quantities given byL have been equally divided between II and L. The third column, giving the density of agent per square kilometer, is numerically equal to the number of munitions per square kilometer if the typical munition is assumed tog of agent. These same spatial density values are shown graphically in.
5.4 AGENT RELEASE MODELS
In, wc argued that it was plausible to assume that however long the period from dumping to the beginning of significant release.the primary releaseould last years, pertiaps decades and that, lacking other guidance, we would assume that the occurrence of leaking munitions would be uniformly distributed over this period. Given these assumptions, and the estimates in, it is possible to estimate the number of leaking munitionsite. This will be donequaling five, len, twenty, and forty years.
In Chaptere argue that Ihc plumes created by leaking munitions could be separate from one another. Ihus allowing the contaminated seafloor areas and water volumes io be computed simply by multiplication of the number by the area or volume contaminatedingle munition. The mean spacing between all of the munitions (againg munitions) is simply the reciprocal of the square root of the number per unit area. Similarly, with an estimate of the total number of leaking muniiions, il is
ki iis( iaakios
stimated Spatial Density of Agents at the Dump Siles
I MOM
esnity
m"2)
iodo
r
123
to estimate their number per unit area and then iheir mean separation.
ives estimates of ihc mean spacing of all monitions and the density of leaking munitions per day.s.s the km' per day of leaking munitions and wc later decide toime of five daysingle munition to empty itself, thuseakage rate ofhen the mean number of munitions leaking per knr in any five day interval is 5X.
Ihe largest number in this table ismhe fact that it is so small means that evenotal ic lease penod of five years, there will be lesseaking muniiions per square kilometer even if the release timeingle munition
is. say, twenty days. This wmildean spacing greater thanetween leaking munitions. If, by contrast, the release period is fifty years, the mean spacing between leaking munitions, again emptying in twenty days, would become.
Wc have learned something about the constraints imposed by the expected length of the primary release penodile of muniiions and by the size of the dump sites. The rrmjoi conclusions of this section are as follows:
The muniiionsean density on the scafloor at the sites rangingew hundred io tens of thousands per square kilometer with the maximum still being less than one munition per'.
This assumes .ill inanitionsg of CW agent and since many munitions, like the bombs,reat deal more, the actual density will be smaller
Ifinwy release pericd to
of five lo forty years, and the timeg munition to release all of itsA) days, then the mean number of leaking munitions per square kilometer at ihc site is givens the appropriate number in. This, is expected to be on the order of severul hundred or less,
large quantity of CW munitions thought to have been dumped in the White Sea, coupled with the relatively small area of that dump. lead to
ELEASE SCEW KIOS
: Estimated Density of Leaking Munitions
Site' (tr/km'day") Ifl/km'day') (Wkm'day') km') Total Leaking aking Leaking leaking) r r r r
Seam*)
lO'
L^SxlO1
5<)
GA-LlxlO1
GB--0
00
Sea8 km1)
r
l0'
lO
GH-II
Seam')
H-2xl0'
L=2xl0'
10
xlO'
GB-jI^xIO1
Seam')
l0'
2 I
1
IV
GB-^O
Sea2 km')
xl(r
l(r
l(r
t
conclusion that the mean density of munitions at this mic must he greater than at any other site.
The most important uncertainty concerns thef the total quantities of munitions across the dump sites in the Barents and Kara Seas. If, torarge quantity of munitions were dumpedmall shallow site in the Barents Sea. then its small size would necessarily leadigh density of munitions. Wc have taken this smalls an indicator that this did not occur, but thishaky assumption.
5.5 CW AGENT REUCA SE MODELS
Based on the foregoing we have developed three release models, each of whichuantity ofelease rateingle munition and the primary release period over which the entire sire releases all of its agent.
Scenario I: Tahun. Sarin and Lewisite Constant Release
The munitions in quantities given inre distributed uniformly over the dump sites;
The lime to initial release fromercent of the individual munitions is uniformly distributed in timehich is treated paramctrically as being in the range of five to 6fty years.
For these values of T. the densities of munitions leaking per km'rc as given in.
the agenl from an individual munition happensonstanteriod which will be taken lo be approximately one tohundred days which grsesgg day'
Scenarioalmn. Sarin and Lewisite Instantaneous Release
IThe munitions inrc uniformly distributed over the entire dump site;
The time delay to release fromercent of Ihe individual munitions is uniformly distributed in limehich is treated paRimetrically as being in the range of five to fifty years.
Tlie spatial density of munitions which have disintegrated and begun to dissolve at the site is given by.
Release of dissolved agent from an individual munition can he neglected until complete disintegration of the casing when mustard is deposited on the seafloor. DissolutionnustjrJ ageni being introduced into the seaateg day'ime on the order of
ays.
munitions arc uniformly districted over the clinic dump site;
* Five percent of the individual munitions arc released immediately.
Scenariommediate Releaserf All Agents
scenarios
UNCERTAINTIES
In view of ihe quantitative results contained in the previous section, and the shaky foundation of fact on which they were based, it is important to review what has been accounted for in these release scenarios, what has not. and how much the latter could affect the results.
What has been accounted for?
Total quantities of agents thought to have been dumped
The types of agents dumped;
" The locations of rhe dump sites;
Ijfgc dump sites are largeeason, namely lhal more munitions were dumped there;
Empirical data showing that munition* remain on ihe sc.illtior in relatively intact form for long periods, with corrosive disintegration happening over decades; and
The physical propertiesmpulsive release or slow dissolution, of the various agents.
What has not been accounted for and how much doc* il mailer?
Even if the total quantities of agent inre correct, the hieakdown by site is highly uncertain and was. guided roughly by ihe aieas of the sites;
accurate accounting for corrosion, except to the extent that it exists;
The actual distribution of munitions on the seafloor at ihe dump sites;
The"waiiingpcriod"T1 lor ihe release to begin was not addressed in this chapter, but il has been inhen it is necessary to draw conclusions about ecosystem impact; and
Ihe temporal distribution of release, especially the total lime T.
It is possible to view these uncertainties as implying that so little is known lhal there is no objective way to proceed. However, we do place some credibility in the total quantities of dumped munitions and in Ihe identification of the dumpn addition, there can be little doubt lhal the munitions were scattered across large areas of the seafloor when dumped, if only because of navigational errors, Finally, the Ballic experience certainly suggests lhat munitions on the seafloor will remain intact for long periods, otherwise, even the slow dissolution rate of mustard would have caused all the agent to have disappeared by now. The bounds developed here, falling backarametric treatmentew unknown quantities, would seem to credibly hound ihe problem of release scenarios.
BACKGROUND
Ail available toxicity data regarding ihe chemical warfare agents of primary concern and ihe expecicd degradaiion products in the marine environment were gathered and summarized.
This information was used to compare the toxicities of the different agents and theit degradation products and to decide which chemicals mayoxic threat to Ihe environment.
For each of those chemicals dial are potentially toxic, an estimated no effects concentration [ENECJ was derived, usually as one-tenth of the lowest LC^ value for marine organisms.
In addition, to define areas affected by these chemicals, estimated probable effects concentrationsnd estimated lethal effects concentrations [ELEC) were designated as ten and one hundred times the ENEC concentrations, respectively.
Because of the sparscness of studies uf long-term, non-lethal effects at low concentration, the bi-levels established here are considered more reliable at ELEC and EPEC levels than ENEC.
For simplicity and because data docs not exist for those agents ioore true ground analysis, ihese levels [ENEC,rc taken io apply equally to all marine species.
CONCLUSIONS
Tabun (GA) and Sarin (GB) are of approximately equal toxicity. They were both assigned an ENECS Musiard (H) is orders of magnitude less toxic with an ENECg 1'. Lewisite has intermediate toxicity with an ENEC ofg 1'.
Cyanidereakdown product of Tabun and was assigned an ENECg 1'. Dimelhylamine isreakdown product of Tabun with an ENECg Chloroben/eneomponent of Ihe Tabun formulation, present up lo twenty percent. Chloroben/ene was assigned an ENEC
Most of Ihe breakdown products of Sarin have toxicities six orders of magnitude less titan Sarin. Fluoride is the only exception to this and it was assigned an ENEC
Mustard breakdown products are thiodyglycul, with an ENECg I"hioxanc with an ENEC0
lewisite hydrolyzcshlorovinylarsonous acid, which was assigned an ENEC ofg I'. ihe same as the parent compound Lewisite. Inorganic arsenic is ihe ullimalc degradation product of Lewisite, with an ENEC of
OBJECTIVES
This chapter addresses the problem of determining the toxicity in the marine environment. The available toxicity information was used to compare the toxicities of the different agents and their degradation products and io decide which chemicals mayoxic threat to the environment For each of those chemicals that are potentially toxic, an estimated no effects concentration [ENEC] was derived, as described below, to be used in ihe interpretation of the results of modeling their transport and breakdown.resents the ENEC values derived in this chapter.
Also discussed below are dose-response experiments for acute toxicity that represent the most commonly available information. This type of experiment provides the range of the amounts of chemical intake per kg body weight (dose) or the amounts of chemical per volume of water (concentration) that result in the death of the animal. The data from this type of experiment on laboratory animals and aquatic species is the basis for the assessment of the toxicities of each chemical of concern.
6.2 DATA SOURCES
Toxicity information on chemical warfare agent hydrolysis products was retrieved by searching the CAS database, which covers the literaturehis was supplemented with other conventional reference materials. Toxicity information for the agents themselves was obtained from conventional reference materials. The primary source of aquatic information used in this report was the AQUIRE database [Aquatic Toxicity Informationhich is supported by. Environmental Protection Agencyhe AQUIRE loxioological data summary is designed for usetand-alone reference database origh-quality data source for risk assessment tools. The majority or reported lest results0 and current publications arc continually and systematically acquired and reviewed. Test organisms are limited to those lhat are exclusively aquatic. The system presently contains data on moreeferences, and approximatelyffectsoxicity lests.
6.3 APPROACH
There are many variablesoxicity study that affect the relevance of the results to the assessment being made. In particular, the species used in the study, the endnoint of the sludy, and the length of time of exposure are important considerations. The general
approach used lo apply available toxicity information to the assessment of toxic effects in the marine environment was as follows.
Focus on acute toxicity. The assessment of potential environmental effects of chemical release would be based ideally on studies of all possible effects of the chemicals of concern on all of the specific species found in the affected ecosystem. The reality of the available information, however, is lhat studies of non-lethal, long-term (chronic) endpoints in species other lhan laboratory animals are rare or non-exisient. Available information on the chemicals of concern in this analysis is limited to studies of laboratory animals and selected aquatic species with acuteeath, as the endpoint. For many of the chemicals of concern, especially the chemical agents themselves, acute toxicity is the primary concern, since they are acutely toxic, degrade over the course of hours, and would not be expected lo produce chronic effects in eithei the laboratory or the environment.
The reported LCW values' were the mosi useful measure in assessing the toxic effects of these chemicals in seawater. Thel values' for aqualic and laboratory species were also considered in order to compare toxicities wherevalues were limited or not available. The values of LCM vary with the organism tested, reflecting die variation in sensitivity of different speciesifferent chemicals. They also vary inversely wilh the length of exposure, wiih longer exposure times resulting in lower LCW values. For the purpose ofoxic threshold for chemicals of concern, generally the lowest reported LCy, was identified and one-tenth of this value was chosenoncentration at which marine organisms would not experience acute toxicity. This value is identified as the estimated no effects concentrationor Ihe purpose of defining volumes of sea lhal would experience loxic effects of these chemicals, the ENEC was multiplied by ten to yield estimated probable effects concentrations [EPEC] and by one hundred to yield estimated lethal effects concentrationsalues of EPEC and El .EC are shown inlong with ihe ENEC values.
Use data from marine species. No data was found for arctic species or for the temperature of ihe study region, toxicity data from marine organisms was used preferentially, when available. However, for many chemicals of concern, information was only available for freshwater organisms.
Identify substances with little potential for acute marine toxicity. The maximum amounts of the degradation products per kilogram of the chemical agems were calculated from the stoichiometric relationships in Chapterrom these amounts and assumed release scenarios for rhe agents, maximum concentrations can be calculated. Acrual concentrations will be substantially less lhan those calculated in this way because the breakdown reactions arc not instantaneous and because the primary breakdown products are subject to further degradation and dilution. However, if the maximum potential concentrationubstance based on Ihe assumed release scenario for ihe agent can be showne significantly less than ils ENEC value, then the substance can he assumed lo be of no concern wiih respect to acute marine toxicity.
OF TABUN ANDPRODUCTS
Tabunotent inhibitor of cholineslerase. which is the mechanism of its toxicity. The LDW values for various laboratory animals are shown in. It is similar to Sarin in its toxicity io mice, with an LDW for intraperitoneal injectiong kg1 compared2 mgor Sarin. Tabun is about one-lhird as toxic as Sarin in guinea pigs,2 pg kg'g kg1 forrinking water criteria for Tabun has been established at
1'. compared3 pg I' for Sarin.'
'Lethalhe cctfceentttic* nt the subukKe Out resulted In the deathercent of the cipcoedduntigcified lime interval
'lahnl Oow SO. thef die meoWix Out re wiled in the deathrevent or the espvoed uqjanittn* during the specified time iiaerwl
'USInterimCTraicTcaicdcfical CnwirafoeChenwal WjrfiieCompound!"Memueundum MCHB-DC-C. IIS.i-.ilUi
nd Preveemvt Medicine,
No information on the aquatic toxicity of Tabun is available in the AQUIRE database. Because the toxicity of Tabun, as shown by the abovevalues and drinking water criteria, is similar to that of Sarin, the ENEC forg I', which is derived below on the basis of aquatic toxicity measures, was adopted for Tabun.
No toxicity information is available for the monoethyl ester of dimethylphosphoramidic acid or dimclhylphosphoramidic acid, which are the primary hydrolysis products of Tabun. The lack of Ihe cyanide-phosphate bond in these hydrolysis products lenders them much less reactive, however and. thus, they are significantly less toxic than Tabun. Larssonirst-order loss of toxicity of Tabun during its hydrolysis, with no apparent indication of toxicity due lo the buildup of Ihe hydrolysishe absence of toxicity data for these hydrolysisindicates they will not exert marine toxicity.
Dimethylamine. which is the hydrolysis product of dimclhylphosphoramidic acid,ow toxicity compared to the ENEC of Tabun.alues for daphnia and rainbow irout are shown in. The LCW values rangeg I"hich is three to five orders of magnitude less toxic than tlie ENEC of Tabun.ultipliero the lowest0o estimate the concentration at which acute marine toxicity will be negligible, yields an ENEC valueg I" for dimethylamine.
OXK IIY ass ess Mi: VI
isydrolysis product of Tabun. LCW values for cyanide for several aquatic species are shown in. lt is more toxic than ihc other hydrolysis products of Tabun. yet less loxic than Tabun by two orders of magnitude. Because of its relatively higher toxicity compared to other hydrolysis products, and its persistence, an ENEC was derived tog 1', one-tenth of the lowest reported LCW.
Chlorobenzeneomponent of Tabun that can be present in the mixlure at five to twenty percent. Its toxicity is much lower than Tabun as shown by thevalues in. The most sensitive saltwater species is the sheepshead minnow and an ENECg I" was derived as one-tenth of the LCUI for this species.
'Kcfacnoc h.
6.5 TOXICITY OF SARIN AND ITS BREAKDOWN PRODUCTS
Sarinotent inhibitor of cholinesterase, which is the mechanism of its toxicity. Thevalues for various laboratory animals are shown in. It is similar to Tabun in its toxicity to mice, with anfor intraperitoneal injection2 mg kg" compared0 mg kgfor Tabun. Sarin is about three times as toxic as Tabun in guinea pigs,ubcutaneous LDWg kg'2 pg kg' forrinking water criteria for Sarin has been established3 pg IV
0 Amhi^mifrQmlkyCriierh^'Cu<pntiotiJBenientiCriteriaandSumluili.Division.OfficeWaici Regulation* ml Stdrddih..
h.
aquatic toxicity of Sarin has been studied in three freshwater species: fathead minnows, sunfish andime-to-death ofercent of the test species at several concentrations was measured as shown in.1he lowest concentration studied.ercent of the test groups died,ays for minnows, sunfish and goldlish. respectively,C Extrapolation of the concentration data to lower concentrations suggests thatercent of the most sensitive species, the fathead minnow, would survive forayspm, which is one-tenth the lowest concentration studied. Since the half-life of Sarin in seawater is estimated to be aboutours, (see
Chapteroncentrationg I' would persist formall fraction of theay survival time.gas chosen as the ENEC for Sarin.
An earlier report by Weiss'5alues from data atC for both Tabun and Sann for sunfish, fathead minnows, and goldfish. These calculations showed the toxicity of these two compounds to be within the same order of magnitude, with Satin being the more toxic. No data were given for lower temperatures approaching that of scawatcr in the study region. Thus, the data from the later report" atwere used to derive the ENEC values for both Sarin and Tabun.
em:ftuJbeatrr. IW..Uiecihyl.Mcifuoaalfonaicn iheTreilinnnl1 A.
'Wcim.. Hon* imj. 'Thr Kcipontc ot Some Methwoici Fiih lo Impropyt Mclhylpho-^lKmofliKiridaie (Sarin)l
TO
The Reipobc ol Some Fretmiwr Fiih loG Aecnis InedKilResearch Krrpon8 Army Chemical Outer, Abcrflecn.eference II.
The hydrolysis products of Sarin are less toxic than the parent compound hy orders of magnitude. No aquatic toxicity data was found for methylphosphonic acid.methylethyl) ester. This primary hydrolysis product of Sarin hasalues in drinking water of rats and mice, as shown in. in the rangemo effects concentrationm I' foror mediylphosphonic acid,values are available for aquatic species and are shown in, They are in Ihe range8 gm I1 for freshwater protozoa.
mfor66 gmor minnows and sunfish.8 gm I'for algae. Isopropanol is also only toxic in the concentration range of grams per liter. While no aquatic toxicity data arc availahlc, the oral LDW in ratsm kg"m kg' is fatal in humans. From these values, compared to the toxicity of Sarin, it can be readily concluded that these hydrolysis products will present lessoxicity threat to the environment than Sarin by six orders uf magnitude and that their areas of influence will be less than that of Sarinimilar factor.
'Rclrtpme 1)
atxmalit*Erafaoiiewand DCPD iPhaie iii-litpay LilKin Bionrtxs.TTp.
nv
: IJJM Values for Methylphosphonic Acid, mono,ethyleihyl) ester"
Substance
Drinking Water
sphonic Acid,mcthylelhyl) ester
Effects at
g/l
: LDM Values for Methylphosphonic Acid11
Substance
Acid
hr.
minnow -Piincp hales pro me las
hr.
minnow -Pimcphalcs promelas
hr.
minnow -Pimcphalcs promelas
hr.
-
1-cpomis
maci'iKThiniv
hr.
Jav
Selcnastrum capricornutum
day
The toxicity of fluoride is also several0 mg 1'. Because of the persistence of
magnitude less than that of Sarin.n Ihe environment, an ENEC was chosen as
alues for several aquatic species. Themg i', one-tenth of the lowest LC^ reported for
sensitive species. Scud,angeWmost sensitive species.
'Reference IS.
T. WJt MiDer. ami AR.EnvOimnwnul File ant) Effect* of Tribotyl Phutehut xalftifphcmie
oxicity of Fluoride to Aquatic Species"
I1)
Fluoride
Grandidierella sp.
day test
angasi
day lest
mussel -Pcrna pcma
0
day3
oyskT
Saccosuca
commercialus
dav test
crabTylodiplax hlephariskios
day test3
Therapon jarbua
day test3
mullet Mugil ccpbalus
day test3
TOXICITY OF MUSTARD AND ITS BREAKDOWN PRODUCTS
Mustardesicant and alkylating agent, producing cytotoxic action on the hematopoietic tissues, which arc especially sensitive. 'Ihc rale of detoxification in the human body is vety slow and repealed exposuresumulative effect. Mustard has been found touman carcinogen by the International Agency for Research on Cancer. The oralor mangrinking water criteria for mustard has been established6 pg IV Mustard is lipid soluble and can he absorbed into all organs. Skin penetration is rapid without skin irritation. Swelling and reddening of the skin occursatency period4 hours. Although the dissolution of mustard into water is slow, dissolved mustard hydrolyzesaximum half-life5 hours. Hydrolysis products include thiodiglycolhioxane.
No information was found in the AQUIRE database for mustard.tudy by Buswell elf lime-to-death for bluegill sunfishery large increase in toxicity with increasing concentration. No deaths were observedoncentrationg I" during thirty days of exposure.g Itwenty-two out of thirty sunfish diedhirty-day test.g I', all individuals died in about thirteen days. Similar results were found for red-eared sunfish and black bullheads. While these data arc not amenableonventionalalculation, the intermediate doseg I' can be taken as an approximation of anultiplier. to estimate the concentration at which acute aquatic toxicity will be negligible,alueg I' for the mustard ENEC.
"ReferenceReference
He EffraoS Crnam Chrmiail Wirfoir AgmB in Whinqmuic Orta/iiim Report OSROl Ihe National Dcfeinr Kcwarch Ctenmlucc Office of ScEnufk RerKarch and Development
Y assessment .Jfc '
aluegor an ENEC for TlXi. The solubility of mustard'g I'. If this concentration of mustard were stoichiomctrically converted to TlXi. the result wouldoncentrationecause this maximum possible concentration of TDG is an order of magnitude less than the water flea LC.,j. the murine toxicity of TDG,roduct of hydrolysis of released mustard, will not be of concern.
No data on the environmental effectsydrolysis product of mustard, was found. However, this compoundreliminary remediation goal value for drinking water, set byf. EPA. ofecause this concentration is intended lo be protective of human health, it may be also assumed to be the ENEC for this compound. Assuming that mustard was released at lis maximum solubility' atstoichiometric hydrolysis
Lewisite has been establishedg 1The immediate hydrolysis products.hlorovinyl)arson-ous acidchlorovinyl)arsonOus oxide, are also vesicants. Ultimately the degradation of one mass unit of Lewisite can result in the productionnits of inorganic arsenic. In addition to lewisite itself, toxicity concerns have focused on these three products.
No information was found in the AQUIRE database for Lewisite. However, others" repotted on the effects of Lewisite on several freshwater fish species, as shown inhe golden shiner was found to be the most sensitive of ihe species tested, with Iwo out ofercent) of the test organisms deadewisite concentrationg I'. One-tenth of this value.g I', is chosen as the ENEC. The solubility ofgC, is three orders of magnitude greater than ihc ENEC value.
^Rtference i.
"Itawohbii.MSioli-tiioi6 Salu'mfv Tottniival Report 7SW. US. Army Medical Bioenpnrerinc Research and De>etopmeni Laboraimy.
No informationound on the aquatic toxicity of the hydrolysiscfuonninyliarroous acidchtoovinyl>ur*oaou* oxide. These compounds have been reponcd to show intravenous and ocular toxicity similar tohe rapid hydrolysis of Lewisite and the similar toxicity of these hydrolysis products makes il likely that the hydrolysis products are rhe active formwisile. An ENEC equal lo lhat of Lewisite was assignedhlorvinylarsonous acid.
'Ihe toxicity of inorganic arsenic toward several aquatic species is shown inhe lowest
Ialve is for the marine Calaooid copepod Acartiaour da> expoMiie indicated inf WFulnp.ier, to estimate the concentnuion al which direct aquatic toxicity will be negligible,alue ufor ihe inorganic arsenic ENEC. Note that evaluation of ihis limit should consider that one mass unil of lewisite can ultimately result innits of arsenic.
rl .- Ummvr. ^rr-" aIk^Jmd anontl sauul
BACKGROUND
A methodology was developed lo quantify the etlecis of advection. mixing or dilution, and hydrolysisgents that bave been released into the sea from .ingle munitions and to extrapolate this in order lo estimate the extent ot toxicity at typical arctic dump sites.
For the four types of CW agents considered, convincing results were reached showing that the coniumination ol Ihe seaingle leaking CW munition willocalthai is, one confined lo an area with dimensions on ihe orderilometer or less.
Release of AgCitb fiomjjinglc Munitions. RcauilS Released agents will be confined lo volumes on the order ofx Lvrc ihe horizontal and vertical mixing distances measuredydrolysis time scale. These dimensions will he on the order of lens of mcterv
Mustard, however it is released, can leadai most, concentrations a: or above minimum toxic level* only in Ihe immediate vicinity of ihe disintegrated munition,lume only ccr.nmcters in length and several cemimelersihKk. This is an upper bound However, ihe slow dissolution rate, which limits the physical extent. .iKti results in (his small region of toxicity persisting for long periods
Agents released very rapidlygractured munitions, will produce toxic concentrations over water volumes and seafloor areas as fallows;
Volumes(hr)
Tabun 11
Sarin II
Lewisite
The agents released slowly form plumes thai will have dimensions on the orderew hundred meters along Iheew lens of melers across ihe current, ami less than ten meters thick above ihe seafloor. These sizes are upper bounds and could be much leu.
Plume si/cs generatedlow releaseelease of Tabung/day. whichlumeoncentration of "no biological effects"olumend an area on thef lessm'.
CONCIMSIOSS
The extent of toxic contamination al the dump sites is limitedraction of the area of the dumplf and to heights above (he sealloorew tens of meters although probably much less. Sufficient munitions were probably dumped lo extend the overall duration of lite contamination for decades once significant release begins, which may itself lake many decades.
As an example of Ihe low end of toxic extent, the largest dump,Karaay have had as much0 tons of mustard dumped. This quantity of agent. If it were releaseden year period, would lead to coniaminaiionery large number of small areas within the site totaling lessm' in area, with each individual plume lasting approximately three lo four monUis. This is an upper bound since the lolal period over which release occurs is probably approximately thirtyifty years not ten.
However, the more toxic and soluble agents, also piobably dumped in kiloton quantities, could produce much more extensive contamination at rhe dump sites, though mil confined io tbe site area. For example, the quantity of agents possibly dumped atouldrrr ai ENEC if released uniformlyeriod of five yean. Similarly, the toxic contamination at the shallow Barents Sea, could approach fifty percent of the *ne areaive year primary release period However, the Baltic Sea experience suggests rather strongly lhat corrosion of munitions takes place over long periods, some munitions releasing agent very soon alter dumping and some remaining intact after fitly years
7.1 INTRODUCTION
Thu chapter addresses ihe problem of determining ihe spatialleniporal changes in ibe concentration of CW agents once they are released into Ihet impoitant io ai*pit(uue thai it is necessary lo obtain numerical estimates of Ihe spalial extent of contamination at specific concentrations in order lo evaluate ecosystem effects. These effects will hinge on bounding the spatial extent of toxic levels and then duration. However. Ihe overriding driver in this entire study is that CW agents appear to have been disposed of in arctic seas in quantitiesg. Thus, in the absence of quantitative estimates of the extent of toxic concentration, there would be no confidence that ecosystem effects could be usefully bounded. The primary objective of this chapter is to estimate (he volume of seawater and the associated seafloor areas Thai could be contaminated at tliei and EPEC concentrations for each CW agent.
The job of Urn chapter primarily willthe spatial aod temporal scalesi inetermining
which of them dominate in given circumstances
inimum, the important physical effects include the hydrolysis of agents into toxic and non-loxic products (seche transport of agents and the hydrolysis products by ocean currents; and ihc dilution,esult of mixing hy eddy diffusion in the benthic boundary layer. Effects for possible future consideration include ihe scavenging ol agenl* by particulates or scavenging al the scaflour.
In this approach, the first step was io develop estimates of the extent of contamination producedinglehe dimensions of toxicnd then to combine these estimates with ihe results provided inn release scenarios. Having done that, the overall extent olconutnimilion produced by the five dump sites emerged. This data was used to answer the seven key questions, listed in. These unsweis were used lo assess Ihe impact on arctic ecosystems (sec
Answering Question I, establishes tlie fundamental limits on the time scales of (he problem. Answeringstablishes space and time boundaries which limit the extent of the toxic levels. This concept is illustrated schematically in, where "space" denotes the contaminated volume of Ihe plume or the associated area of the contaminated scafloor. and time tbe period over which ihc plume persists
The departure point for investigations into ihc effects of physical processes is defined by the conclusions of Chapters, andhe environmental descriptions provided inupply the basic framework lot the modeling lo be carried out here, while Ihe toxic levels provided instablishes ihe bounds on (he concentrations dtat are relevant to considerations of an ccosyslem impact in Chapter 8.
Pet the reader's convenience.uide io the remainder of the material in this chapter
7.2 THE CONCEPTUAL MODEL
The key to ihc utility of this chapter will reside in capturing the essential elements of the real problemodel thai is tractable and in obtaining answers lhat are illuminating The most important area in which considerable approximation will heM MM ihc ircatmcnt of mixingimple eddy diffusion model will be used to parameterize the process. In addition, the chemical model will assume independence of hydrolysis from the process of eddy diffusion, an approximation which requires lhat Ihe time scales of hydrolysis are much slower than those of turbulent mixing in the benthic boundary layer In Ihe case of CW agents having hydrolysis half-lives of many hours (see Chapterhisery good approximation since it can be expected that mixing through small scale eddy diffusion in the benthic boundary layerrocess in which spatial scale* are centimeters with time scales in seconds.
Recalling Chapterhe hydrolysis of ihe agents labun. Sarin and dissolved mustard was modeled as simple reactions producing non-toxic products lhal arc of no further concern here. On Ihe other hand, ihe model for Lewisite showed it hydrolyzingariety of toxic arsenical compounds with subsequent reactions simply redistributing arsenic into stable, inorganic, toxic compounds. For purposes of this chapter, the chemical model will be assumed to be one of the following three types:
(Al CWA
(B) CWA
-tflSTP
account for two products in reaction B.llustrates the behavior of the second reactionypothetical hydrolysis rate,half-life ofr)
<C) USTP
NTPSTP
+ CjSTP
whereis the mass fraction determined by the stoichiometry of Ihe reactions the hydrolysis rale constant. The abbreviations stand for Chemical Warfare Agenttable Toxic Productsnstable Toxic Products (USTP) and Stable Non-Toxic Productseaction (A) applies to Sarin and mustard. Reaction (B) applies to Tabun with STP being hydrocynanic acideaction (C) appliesewisite where the products are organic and inorganic arscnicals.
The coupled equations governing the quantities ofnd product Mp in reactionre* MA andwith modifications
CW Agent Injection Model
If the physical processes of hydrolysis, mixing, and advection are slow compared to the rate of agent release, the appropriate model is the impulsivehile if the physical processes are rapid compared to the release, then the appropriate modelteady state oneonstant releasehe relevant physic* obtained from these two events bound the problem. Ihe dcgiee to which either situation fits the actual release process depends on two lime scales, the durationignificant release of CW agent, and the time for physical processes to produce dispersal and hydrolysis of the agent.
The two types of behavior expected from agents leleased into water are depicted schematically in. along with their simplest mathematical models.
: Illustration of Chemical Reaction Quantities
CW Agentoxicducl
k
? /s
Products
Toxic Product
Figurellustration of Agent Release Models
seen in Chapterhe siluaiion for musiard is somewhat special and must bc considered separately toseful picture. Il will be argued laterseful model is oneonstant injection of dissolved mustard for an extended life, followedswitching off when ihe lump of mustard is completely dissolved.
Physical Model
A wide variety of physical processes act to redistribute in space and time the CW agents lhal arc released into Ihe sea.ufficiently detailedodel of this redistribution should account for changes in momentum, density, temperature, and chemical composition at spatial scales corresponding to those of mixing in the benthic boundaryentimeters. In addition lo this variety of small-scale piocesses. various circulation processes act to redistribute momentum and density over larger scales. Developmentodel accounting for the coupled hydrodynamical and chemical processes governing ihe evolution of CW agents and their reaction products in the benthic boundary layer and having the necessary spatial resolution lies well beyond the scope of this study.
A full treatment of the problem at hand mighl begin wiih the Ilow fields defined throughout the water column over Ihe region of interest: and hydrodynamic equations, incorporating the effects of stress at Ihe seafloor interface. This stress leads to turbulenceenlhic boundary layer and to mixing, Of course, in order to know the flow fields one must begin cither with assumptions about the size of tbe ocean region lhat is relevant and introduce the flow fields from the outsideorth Atlantic current flowing into the Barents, tidal flows,reneral circulation model including wind driven and tidal effects. Even with Ihe flow fields identified, the closure problem must be addressed since turbulence is normally treated statistically.
Even if one wanted to proceed with ihe latter approach, one would he faced with ihe problem thai mixing in the benthic boundary' layer is empirically thought to bc a
process whose spatial scales are on Ihe order of centimetersull numerical solution of ocean circulation at centimeter resolution remains impractical. In fact,egional model of circulation in the Barents Sea taking the flow fields as input from the outside, would have resolutions far too coarse to address our problem.
Another plausible approach Is to rely on thraveraging of turbulent effects over sufficiently large spatial scales toescription in terms of eddy diffusion, analogous to Pick's law for molecular diffusion, yet not aveiaging over scales so large that they arc comparable with those of hydrolysis or advectivc processes. The separation of scales necessary to justify'odel would seem to be plausible in the CW problem so long as we do not ask detailed questions about the line grained behavior of agents within the benthic boundary layer. In addition, as will be seen later, (his approach producesarameterization which requires that the flow and the eddy diffusivity be introduced by relying on experiment and physical intuition and docs notclf-consistenl description of the governing physics.
The needimple model suggests lhat we must first attempt to determineocal description will Suffice, that is. requiring treatment of ocean scales only on the orderew tens of kilometers and times on the order of hundreds of hours or less. If so. we would be done; if not. Ihcn large scale circulation, and possibly other effects, would need to be considered.
inimum, wc should account for the process already identified, hydrolysis, as well as for the local ocean current and the turbulent mixing of agentsince the time scales of hydrolysis are exponentially shorter than the half-life of radioactive decay of even the mostsotopes, the CW agent problem may not require the full treatment of arctic circulation and may turn out toocal problem.
Before proceeding to deal with some level of complexity it will be worthwhile to summarize the expected behavior of agents released into the sea.
From Chaptere expect that labun. Sarin, and Lewisite can be released either at very slow rates for limes on the order of many hydrolysis half-lives or very abruptly in kilogram quantities.
From Chapterc expect agents Tabun. Sarin, and mustard, with half-lives measuredours respectively, to effectively vanish from the oceanime scale on the orderew tens of half-lives.
By thoe simple arguments we are led lo expectproblem may be local, and thai "local" willshorterew hundred boutsundredhis is.i> ohsjxHhcsjs. although ncomforting io see it emerge from aso that the interplay of the processesunderstood.
The coordinate system and general depiction of the local environment to be used is shown schematically in.
With the coarse-grained view of thehi--li. effects of mixing are describediffusion-like process containingroportionalily constant, the eddy diffusivily. which must be prescribed based on empirical knowledge. With this assumption, tbe nue of change of concentration (coarse grained user suitable spatial scales) is given by ihc usual advectrve-di IIus ion equation.
--.
( where the diffusrviucs in the horizontal and vertical directions are K* and Kv respectively, and thes assumed to bc inhorizontal)j) is the source function developed innd summarized in.
Ii is imponant io apprcciaic thai while mathematicalhe current, v, and the eddy diffusivily. K. appear to bc independent parameters, theyhe underlying physics of turbulent mixing. However, since the flows arc not known in out problem the diflusivities cannot be estimated and both must he trealed paramedically, guided by an empirical knowledge of the upper limits on ocean currents due to circulation or tides, and by measurements of diffusivily.
This can produce no understanding of the physics of tufbulcnt mixing, but it can produce an estimate of mean conccmraiionunction of space and time, which is the objective. Il is not intended lhal calculations based on this equation should be regarded a* an analysis of ocean circulation or of benttuc boundary layers, only thai solutions, with suitable values of the parameters, adequately describe the
averaged behavior of ihe concentration of CW agents. Discussion of ihe use of "diffusion" models of turbulent mixing are given in references one through*
In addition lo this equation, we musl address whai happens at thehe seafloor and ihe sea surface. Consistent with our intention to first address le-localoth boundaries-will-be takcn-as plane, as suggested by. In the local environment changes in bathymetry will be ignored, accenting only for the mean waier deplh ai the dump sites. Moreover, at least initially, il will bc assumed thai there is no flux across either IwuiKlary. lhat is.
- {
Later il may turn out to be important to address volume or boundary scavenging. This would be needed in the case of the stable arsenical reaction products for example. In the case of boundary scavenging the condition on the normal gradient at the seafloor would be modified toK(t) on the righl side of. where vhpeed associated wiih deposition (note, vB would be negative indicating deposition into the seafloor).
73 AGENT RELEASE AND HYDROLYSIS
This section discusses the evolution of total mass of agent in the ocean and the concentration averaged over large plane surfaces. The reason for this initial focus is pragmatic. By dealing with Ihese integrated quantities.ill need to be solved in one or two dimensions only, thus extracting useful results with minimum complexity.
Total Mass of CW Agent in thetotal mass of agent in the ocean. M. is given- )
Integratingver the volume using Green's ihcorem io obtain surface integrals from integrating the diffusivily terms and applying the boundary condition of vanishing flux across the boundaries, one obtains,
M/ -
where Hv is ihe volume integral of the source - .> d*
The modificalions to include die chemical reactions discussed inre straightforward.
esults for Tabun and Sarin
Using ihe hydrolysis rates fromith modifications to account for HCN and using an impulsive source inesults in ihe solutions illustrated in.
A sudden releaseg of Tabun would resultecrease by six orders of magnitude,g. inours and for Sarinours. Of course, overeriod of time, turbulent mixing would bc expected to dominate the behavior of the concentration. Wc have therefore learned that for ihe non-persistent agents. Tabun and Sarin in particular, there is an ouier bound on the direct loxiciiy problem of some hundreds of hours. Moreover, this hound docs not depend on any knowledge of ocean parameters such as diffusivitics, or processes such as upwelling. tidal currents, and large scale circulation. However,ound dtws not apply lo stable loxic reaction products, such as HCN, as can be seen in.
There is no reason why corrosion of the munitions could not cause highly soluble agents like Tabun and Sarin lo be leaked into the sea at very slow rales as
Akiiim Rnerjyhe lhip"iimMaui tiitpascdatla the Deep Sea.No 11
-Monin. AS.umtaeal. Cambridge. MA. MIT
nrfwlV* DfgUuan'I*icldcl PuMuJiiag Company. Bowb MA. Ch 5.
he MiwiUiiivcisily Prcw..Voit.
I CR. Tvrtiulcni intrusion iiomin CampletHoi Hf. FhtdWiX.
1i
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E-03-
develop. Since we lacked detailed knowledge of the complex corrosionarameiric analysis was necessary to determine what would occur. The simplest model forrocessteady release with an abrupt start and cessation. That is. for time,therwise. The results of using this model for the cases of Tabun and Sarin arc shown inor two durations.oursg1 kg day1).
In all four cases, tlie total quantity of agentg. The time at which the release ends,ours respectively, are clearly seen as the points at which there is no further increase of agent in the water. The total mass of agent Tabun Is reduced to one gram in lessours. For Sarin, the time to one gram remaining is lessours. For perspective, we note that it will be shown laterate appreciably less thang day' will result in plumes of essentially negligible dimensions.
SUMMARY OF RESULTS FOR TABUN AND SARIN
Regardless of transport and mixing processes, an impulsive or acute release of Tabun will hydrolyze kilogram quantities down to gram quantities in less thanours. This time period represents the upper bound on the temporal scale of toxicity of Tabunudden release into cold seawater and not one that is sensitive to other uncertainties.
The situation for Sarin is similar except the upper bound isours.
Either agent could be released at very slow rates through pinhole leaks in munitions casings. The time scale ofelease would be governed by the release time constant.
VSH
i'ROC KSNF'S
E.OO
: Tabun (GAVSarin (GB, Hydrolysis for Various Release Rales
Results for Uwisile
Since the reaction products ot Lewisite hydrolysis include stable and nearly stable toxic compounds, we cannot expect to find so convenient jn upper bound on the time scale ot the problem, at least not until wc include the effects ot mixing. For present purposes it will suffice lo examine the hydrolysis of lewisite and confirm what is to beapid conversion into arscnicals.
In Chaptert was shown that tlie hydrolysis of Lewisite takes place in two stages. The first stageery tapid reaction resulting in thechloroclhenyl)arsonous acid, proceedingime scale of seconds and producingramsg ot Lewisite. The second reaction, resulting in inorganic arsenic, takes placeime scale of months and producesrams of arsenicg of Lewisiic. As argued in ChapterhlorocthcnyI karsooous acid is at least four time* more toxic than inorganic arsenic and with its long half-lifeery serious environmental concern.
hows the results of this modelwnsitc being releasedonstant rateg day' forapcriod of twenty-fourotal massg. The half-lifechlortKthenyl)arsonous ucid is estimated to be two months for purposes of this illustration. The most important conclusion is that over the period encompassing the limes ot interest in our modeling, the predominant toxic agent presentchloiocthenyl)arsonous acid, not Lewisite and not inorganic arsenic.
Although there is nothing very significant about twenty-four hours,elease rale is probably much higher than corrosive disintegrationhell casing would produce. On the other hand, the basic conclusions would be unchanged a* long as the release occurredhort time scale compared lo the second stage reaction of two months This is illustrated in. which shows the same calculations as inxcept that its release rale has been reducedactor of ten and the duration extended by the sanvc factor.
Over the time scales in which wc expect to be interested (minuies io lens of hours) it willchloroethenyl)ursonous acid that will be present in quantity, not Lewisite.
: Hydrolysisg of Lewisite {Lt Releasedg Day'
SUMMARY OF RESULTS FOR LEWISITE
Once released, hydrolysis will rapidly convert Lewisite agem io highly toxic quasichloroethcnyl)arsonous acid.
For purposes of this assessment, the direct effects of Lewisite can be ignored since It will exist in the environment for mereime scale much shorter than those associated with advection and mixing
_ much less biological processes. This, in turn, means lhat the agent will exist only in the immediate vicinity of leaking munitions.
The major toxic reactionchlorocthcnyl)arsonous acid and inorganic arsenic, appear in respective quantities of approximately eighty percent and thirty percent of the mass of Lewisite. They persist in the environment for long periods and arc redistributed by advection and mixing.
For the time scales of interest in the ocean problem, the predominant toxic substance willchlorocthenyl)arsoiious acid, which will persist for several months before it is converted to inorganic arsenic. which has lower toxicity.
Should corrosive disintegration of die munition result in release through small pinholes, release of Ixwisite into the ocean could occur on time scales of days, even weeks or months. Inase, conversionchlon>elhenyl)arsonous acid and then to inorganic arsenic would occurale determined by the release rate. The total quantities present at any time would be determined by both hydrolysis of organic arsenic and the release rates.
Results for Muslard
Because of its very slow dissolution rate and its low solubility, the appearance of mustard agent in seawater is governed by its dissolution rate, while its disappearance is governed by its hydrolysis rate.
Since dissolution depends upon the surface area exposed to scawatcr and also to its shape, there cannotingle definitive answer to the fateiven amount of mustard once it has been released from its casing by corrosion. However, as wc saw in Chaptere can bound the problem by considering two plausiblepherical clumphin pancake. The former is an upper boundphere is Ihe shape having least surface areaiven volume. As the Baltic experience shows, mustard not specifically modified for cold weather operations tends to solidify in cold scawatcr. However, since there arc reasons to believe that the Soviet military requirements included consideration of cold weather operations, it is likely that the mustard dumped in ihe arctic seas might well resemble highly viscous fluids. Therefore, it seems reasonable and informative to continue to consider dissolution of both spherical and pancake shapes.
hows the results of both shapes for the initial releaseg of mustard. The lifetimes of the shapesours for the sphereours for the pancake. For contrast with the sphere and to work toward what seemed physically plausibleinimum bound, this model has the pancake spread very thin, beingm in diameter andm thick.
The sphere dissolves more slowly than the pancake, andonger lifetime. Since it has the same initialower level of dissolved mustard is injected into the sea until times near the end of the life of Ibe pancake. Mustard in solution, as represented by the dotted curves rises steadilynitially, to peak near the respective lifetimes. Although it cannot be seen on this figure because of the scale, mustard persistshort period after muslard has dissolved until hydrolysis can eliminate it. This can be seen more readily in0 which shows the same calculations on an expanded scale.
1
Time rni)
SUMMARY OF RESULTS FOR MUSTARD
Following abrupt and complete disintegrationunition casing hy corrosion, ihc appearance of dissolved musiard ageni in ihe sea is delcrmincd primarily by the shape of ihe clump of musiard. wiih ihe total lifetimeg quantity beingays.
Mustard clumps originating in bombs containing on the order of MX)could persist for periods up to several years before being completely dissolved (seche rule of introduciion of dissolved musiard into the seu would be larger for such large clumps according lo the ratio of surface areas, which is approximately equal to mass".
After ihe last of the miismrd charge is dissolved, the remaining agent in solution hydrolyzes rapidly and within live to ten hydrolysis lifetimes that is, approximately twenty-five lo fitly hours and can be regarded as completely eliminated from the environment.
Because of ihe relatively slow dissolution rate and rapid hydrolysis rate, the amount of mustard ageni in the waler is very low. with ihc maximum being less than ten grams from theg quantity.
SPATIAL AND TEMPORAL SCALES
This section addresses the physical processes of advection and mixing. In order to extract the important results easily.illne-dimensional problem. However, rather lhan artificially abstracting the three-dimensional problemingle dimension, spatial iniegrations will bc introduced obtaining "averaged" conccn (rations whichransport equation having one spatial dimension. This approach will not allow us to obtain estimate* for the spatial and temporal changes in concentration or for boundaries on loxic levels. Il will allow us to obtain estimates of the major spatial and temporal scales governing the problem.
Specifically, by integrating over two spuria! dimensions and then examining the concentration in one spatial and one lime dimension, il will be possible io understand the general character of more general four-dimensional solutions Ihe quantity of most interest is obtained by integratingnd y.
where the integrals are liken over the entire plane. For ccfflvcrucnce. wc will refer lo quantities as "averaged" concentration, although ihe factor of inverse area required to produce in average is missing and the units are mass/length. In fact. Ibis quantity is mass density, the mass ol agent per unit length in the vertical direction. When integrated over the remaining spalial coordinate this quantity yields the total mass treated in.
When introduced in. and using Green's theorem to rewrite the urea integralivergence, one obtains for the following:
Cw-/dl
where the line integral is around die boundaries oflane and therefore vanishes. Ihc rcsuli becomes:
d c/
v yit,
- JJC. x. Dd&dy
The function S, is ihc integralver VJ The quantityobeys the spatial boundary conditions associated with those of the concentration,ormal flux vinishcs at the boundaries. In the leiiuindcr of this section.ill he solved for twoteady state evem and an impulsive event.
Steady Slate Events
)) and setting dC/din any of these equations, the equationternly state event will be obtained.
The equation for vertical mass density, together wiih the boundary conditions,to.H)
is:
t)
lobe:
and can be solved by first moving the sourcend laterhe solution for t>
dnoM c.
'osh
where
WLJ
andTheas Hk dimensions of length and represents the vertical mixing distance, which is the square of the vertical dilfussivily measuredydrolysis lime scale.
The solutionenotedis found toHVL,)
Now scttiog=e have (only the firsi solui ions interesting now),
oshinh
The mosi interesting resuli thai isoiiublc from2 is ihe ratio ol ihc concentration at the seand theII This is found lo bc:
eafloor)/Cwosh (H'LV)
The valuesn relation to several values of KH arc shown in. The water depth ofs the shallowest depth at any of the dump sues. Provided thatthere will be effectively no agent present at or near rhe sea surface, in water depths greater lhan or equal ton otherheew extends above the seafloor in appreciable quantities onlyeightew vertical mixing lengths. Moreover, in such circumstances one may ignore the sea surface boundary condition and treat ihe problemalf-space, thus simplifying (mine icsiilts
Vertical dilfusiviiies are not very well-established, however, there arc some relevant published values cited as highn the Ycrmak's' may bc taken as an upper bound for our purposes.
In any case, it is clear fromhal unless Kv is greaterV. there will not be appreciable quantities near the sea surface. This is illustrated in1 whichz)unction of
KOO.SSCS
above the scafloorteady injectionram second'gn the minimum water depth of.
The situation for Lewisite is quite different. The hydrolysis rate for the agent itself is so rapid that there could be no appreciable vertical mixing. Ofteady slate solution itself would nuke no sense for Ihe Lewisite agent. On the other hand, the principal reaction product.hloroethenyharsonous acid,alf-life of approximately two months, certainly couldteady state if slowly released. Since for this compound Lv equals approximately. it would mix upward through the eniiie water column even at significant waterng before mixing could occur in Ihe vertical over several factors of Lv, we expeci to find lhat mixing in the horizontal would have resulted in quantities diminished to well below safely ihiesholds.
ln this section we have considered the linear mass density produced by integrating overlane. If one were to consider the corresponding integration over the other paiiS of spatial coordinates,) andquations analogous toould be obtained and solutions would contain the horizontal counterpart to the verticals before, the parameterhas the dimension of length and represents the horizontal mixing distance, which is the square of the horizontal diffussivity measuredydrolysis time scale.
There are several important conclusions that can he drawn even from this simple analysis as follows:
TOXIC LEVELS FROM AN IMPULSIVE (ACUTE! RELEASE
In order loimple understanding of some of the general properties of the solutions, only an integrated quanlily. linear mass density, has been examined thus far. However, before biological impacts can be assessed, ii will be necessary to have actual concentraiions andequires addressing the three-dimensional problem and solving. This will be done genetically for the two classes of sources being considered, impulsive and steady state, followed by numerical calculation* for the various CW agents
Ot-Htric Rnulit
For an impulsivehe total mass of agent infected. The solution which isalf-spaceith the boundary condition of zero flux across the scafloor, is found to be:
This solution, when intcgraied over any two of the spatial coordinates, reproduces the results ofnd. when integrated over all three spatialives the total mas* of agent remaining in the-.
For simplicity here, the previous results, showing at water depths of interest thai there is no appreciable concentraUon reaching the sea surface, have been used to eliminate ihe upper boundary condition, justifying the applicability of this half-space solution.
HYSICAL PKOCIiSSESp^^
is clear that ihis solutionulse, singular. moving alongxis aiiih iis amplitude decreasing away fiom ihe peak aiccording lo ihe Gaussian functions. The role of the various constants can be appreciated more easily by introducing the following scaled dimcnsionless coordinates.
icHr
e e
and the concentration becomes:
Ai ihesc coordinates, the peak atidih in all three dimensions: and an amplitude factor of mass (Q) per the natural volume (L'.iLv)ydrolysis decay rate of uniiy. In rewriting
wiih C, being the total mass remaining, divided by the volume defined by the naturalxLHxLv and with F, involving only non-dimensional coordinates and the non-dimensional parameter
' -V )e
i the factor
hen expressed in terms ofand with the scaled speedist Is the same for all values of diffusivily and hydrolysis rales. The contours of constant conceniration arc seen io bc circles, centered atchematic illustration of ilte general appearance ofloud of CW ageni is shown inhichrowing cloud moving with the current v.
The magnitude of the spatial distribution of concentration in ihree dimensions can be seen byube of size Ixlxl in these scaled coordinates, lhal is, overhoordinates. Tbe result is the mass Mi(t) containedox having the natural volume
)
where erl'C) is the usual error function,0s
Ihe release can be adequately modeled as an impulsiveelta function in time. Since we are still considering releaseingle munition, the spatial distribution of the source will againelta function. An impulsive releasefuzzy ball" of contamination, moving with the current and becoming less toxic with lime due to the twin effects of hydrolysis and dilution. As noted in. the
Mior three boxof constant concentration, in any plane, for an
L!hLv,Lv,iLv. The conclusion to be impulsive source arc circles in scaled coordinates and
is that al times of interest,lmost all Of the remaining mass from an impulsive injection of CW agent will be containedox whose dimensions are several multiples of the mixing lengths.
Acuie Release of Specific CW Agents
If the release rate is much faster than the other relevant processes of hydrolysis, diffusion, and advection, then circles or ellipses inoordinates. According tohe shape of the three-dimensional) is an oblate spheroid bisected by the seafloor
The radius of the iso-concenlration contours inlane can be written as
RJC'Qe' rw]
where Ci is defined by0s the fixed concentration of interest. The maximum height or the semi-minor axis of the truncated oblate spheroidpecific concentration surface teaches above the seafloor is
h(i) =
4 shows the radii of concentration on the seafloorunction of time for the caseudden releaseg of Tabun.
The maximum radius and associate times for these three cases are tabulated inor convenience.
The general shape of these curves can be understood as primarily the result of dilution through the turbulent mixing process being modeled hereoarse grained sense. Initially, the point source has no radius at any finite concentration, so an increases all that can happen. However, as dilution proceeds, abetted by some hydrolysis, concentrations drop. The half-life of Tabun is forty hours by whichoncentrationor exumple. has vanished entirely in approximately thirteen hours, thus showing thai the effects seen are primarily due to dilution. This conclusion is not general however, since if enough agent is injected initially, some will survive at any given concentration until the passage of time allows hydrolysis to become effective.
For the values of vertical and horizontal dilfusivities used1he maximum height above the scafloor at ihe three conccnlralions in5 is. by) orhis is consistent with the results in, where ihe solution for linear
adius af Constant Concentration on the Seafloor for Tabua (GA)
i Ml nil
: 1
mass densities incorporating ihe sea surface boundary condition was used to argue that this boundary condition was irrelevant. The additional quantities of interest are the enclosednd the area on (he seafloorf the oblate spheroid.
5 shows the associated volume of the oblate spheroid defined by the same three levels of concentration for the case of an acute relea.seg of Tabun
For the case of releaseg of Tabuningle munition, these curvesetric that is rather close to what is needed to assess biological implications, the volume of water affected. The effects of the current in transporting this contaminated volume are not accounted for inn the sensehis volume "sweeps out" water along the direction of the currentistance vt in time t.
Before further discussing this phenomenon, it will bc useful lo summarize the instantaneous volumes for all three agents lhat can lead to an impulsive release of Tahun. Sarin, and arsenic from Lewisite.6 shows the corresponding curves for all three agents at the concentrations corresponding to non-toxic and loxic levels. In the caseg of Lewisite, the initial mass of arsenicrams and the toxicity levels shown arc those associalcd wiih arsenic.
'Ihc maximum volumes, areas on the seafloor. and associated times are summarized in.
nstantaneous Volumes for Three Concentrations of Tabun (GA)
Cauf- UDI naL
oi roi
. 6pi ml. _
1
]
1 1
ft i
10 ICC
<w)
si s
nstantaneous Volumes for Releaseg of Three Agents
tax
' *' -x
c- 0id1 m
!
!
c.
b. c. aai
l
]
|
Tin* (Itr)
on tlie lotal volumes and areas is simply linear. That is, for twice thet, the toxic water is transpoited twice the distance in the same lime hence both scafloor area and swept-oul volume are doubled. The dependence on oiheror example, is not so simple.
In addition to these areas and times, wc need to account for ihc advection of the mass of toxic water. This is accounted for inut Ihe areas and volumes discussed above were instanlancous. If we arc entitled to argue lhat the important quantity for assessing biological effects is the total volume of water swept outpecified conceniration, then the relevant volume is that of cones, bisected by their inteisection witheafloor. increasing in radius from zero,aximum and then decreasing again to zero.
volume can easily be shown asvAt. whereis the maximum radius reached, and Ai is the elapsed time from initial release until the radius at the specified concentration vanishes. Likewise, there is an area swept-out on the seafloor shown byvAt. These volumes and areas, which are now integrated quantities that do not change with time, are given inlong with the elapsed time. Tlie volumes and areas arc not contaminated over this entire period; elapsed lime is the total event time, These areas and volumes are seen to be significantly larger lhan their instantaneous counterparts, as would be expected since over ihe total elapsed times,t current will sweep the contamination up to several kilometers.
Since the effects of the currcnl are lo transport the ioxic region downstream only (in this model we have assumed that diffusivities can be specified independently of thehe effects of the current
Generic Results
Based on the one dimensional results in, we expect lo obtain plume solutions for the steady suite>he steady stale (half space) solution loor this source can be shown as:
4l, p
where the scaled radials given by
s given bytill meaning scaled speed. The plume character of this solution can be seen by examining the case. The result can be written as
. Note lhal furIhe exponential decayL-o. indicating ihehchavioj of (he plume. Increasing currents (a) cause ihc length of ihe plumej) to be extended in the downstream direction.
Since>ecays exponentiallyncreasing in ihc positive direction wiih the current, but lets rapidly than it doesncreasing negatively against the current. This, with ihe increasing transverse width already shows the characlcnsiicslume, and as wiih the time dependent solution, itlume closely confined lo Ihe region near the seafloor.
Introducing the same scaled dimension less coordinate* as hetorc.2 can be written as
The. has the dimensions of mass and is the mas* injected in the hydrolysisnd the factor.is jusi the "natural" volume encountered previously Hence the factor multiplying MMitp) is again mass per natural volume, and
For illustration, as inhe plume function Fi Is shownunctionfor several values of o. whereo uvoidingularity onxis The asymmetry due lo the curreni is evident, with mixingarge effect against the current and much less with il.
While specific results for the CW agents or interest will be given in ihc following sections, it should be noted here that rhe scale factors on horizontal distances ate on tbe order of lens of meters, and the scale factors on time of ibe order. Foralf-life of ten hourst currentpproximately. In terms of the real problems at hand.
Iimension/ess Plume Function vs.oordinate
I0 -E
might be on ihc orderm andighturrent on the ordert (secighturrent on the orderl. What is seen here is that al fixed concentration,ixed. the peak of the plume moves away from ihe source and the larger the scaled current, ihe further ihc peak moves away. The general appearance oflume of CW agent is depicted schematically"iih some exaggeration of ihe vertical scale.
If ihe release rate is much slower than the other operating processes hydrolysis, diffusion, and advection. then the release can be regarded as being constantong enough period lo establish steady state conditions.
It can be shown that xp, the approximate on-axis length of the plume on the)iven concentration, is given by
--- (nAayK^)
Likewise,istance from the source of x. the plumes given by
n(xyx0>
)
The maximuman be shown to occurat which point the plume width, >v, is
78 are valid only for XeLn o. It should be observed that for smallmall a, xi is linear in Q. It also should be noted that to the first order, the plume length is independent or both ihc current and die hydrolysis rate. This iseflection of the "fact ihe plume is dominated by diffusion and not by hydrolysis., wc have ihc pure diffusionoJ.
By approximating the area on the seafloor as an ellipse, it can be estimated using the approximations in7iving
i.Hxn/err
imilar vein, the height of the plume at fixed concentration can be appioximaled as
The volume of ihe plumeixed concentration, using an ellipsoidal approximation to its shape, is given by
) X,3 )AZ,
with die volume of the plume behaving approximately
as
v
In the sections to follow, numerical results will be shown for the various agents, but we can see here thai the volume of water contaminatedpecified concentration is more sensitive to releasehan to the current v.
The Case of Muslard
lecause oi tne slow dissolution rate or mustard, it is clearteady stale release is the only reasonable approximation.9 shows that following complete disintegration of the casingunition containing mustard, dissolutiong mass would take on the orderays orours and not greaterays orours. Since the other lime scales in the problem operate on the order of hours, it is clear that the approximate modelteady stute process over the lifetime determined by the mass of mustard available, whichg in our usual model.
g mass completely dissolvingours would have an average release raleg day'. The concentrations of the plume alongxis in the direction of the current on the seafloorased
uslard (H) Concentration on the Seafloor Along the Plumeg Munition Charge
on4 arc shown inhe expected release rate are examined in addition to greater rates.
The ENEC level is highlighted in this figure, from which it is clear that the dissolution tate of mustard is SO low that evenistance of one meter downstream, the maximum concentration will be two orders of magnitude below this safe level. In Chaptere estimated release ratesg clumps of mustard, finding that the largest instantaneous value wouldg day' Isect this release rate, muslard concentrations just reach the non-toxic level atm from ihe source. Since the sourceancakem in diameter, levels at or above thethreshold are confinedew centimeters thick. This conclusion is an upper bound since it was basedelease rateery thin pancake, possible only for rather low viscosity mustard, ln somewhat purer form, mustardolid whose shape would lead to even lower rates and shorter distances.
Thereautionary note that must he applied to these results for mustard. The spatial dimensions of the plumes arc sufficiently small lhat the Ireaimeni using the advectivediftussion model is itself suspect. That is not to sayore detailed treatment of turbulent mixing would lead to large plume dimensions, only that the details here should not be taken too seriously.
Tabun and Sarin
The only way thai the highly soluble agents Tabun and Sarin couldteady stale releaseingle munilion would be from pinhole leaks that would allow release to be extendederiod of days.0 shows the resulting concentration of the plume on the seafloor along ihe currentunction of distance from the leaking munition (x) parameterized by the release rate.
ingle munitiong of agent and with perhaps one hour needed toteady state, the steady stale model estimates thai the maximum release rate wouldew kgt the level. the plume for this release rale isn length along the seafloor. In this regime the plume length is linear with C. so the length at the toxicI for Tabun, is approximatelyn length.
Tlie results for Sarin are essentially identical, with the
rclcvani toxic levels being the same and the half-lives differing only slightly.
In addition to the behavior on the seafloor along the plume axist is illuminating to examine the concentration in the transverse direction1t several positions downstream, all located on the scafloor. It will be observed that. the concentration is the same as in
One conclusion that can be drawn from these figures is that if the release rate of Tabunarin is lessghe extent of the plume at the concentration corresponding to the "just safe" level will be less than one meter at the seafloor. Plausibly we could take this, or if necessary, one order of magnitude1 kg day'. tohreshold for being ignorable. especially since the width and thickness of the plume will be an order of magnitude less.
24 show the contours on the seafloor of the plume corresponding to no effects, probable effects, and lethal levels for release ralesggndg day', respectively.
kt. These results apply
In all cases the currentqually to Tabun and Sarin.
5 shows the same situation asxcept that ihe currentl rathert.
It should be noted thai the plume dimensions, particularly its length, correspond quite closely with the approximate results obtained earlier in, for example.hichlume length for25 of.
Beyond these individual depictions of plume characteristics, it was necessary to know the volumes of water and associated scafloor areas contained within plumes generated by various release rates.6 shows, for both Tabun and Sarin, the area of the seafloor under the plumeunction of the release rate ranging fromay' to approximatelyg day '. at three concentrations andurrentt.7 shows the area for Tabun and Sarinurrentl.
As noted previously, whenthe plume dimensions become independent of the hydrolysis rate.
oncentration of Tabun >GA)t Current
longitudinal axis, meters
means that the plume is formed by advection and mixingime thai is relatively short compared to the time scale of hydrolysis. Inircumstance, the hydrolysis rate has nothing lo do with the plume size.
The associated plume volumes are depicted inpplying to both Tabun and Sarin,urrent of
nd in9urrentt.
Plume Results for Lewisite
As argued earlier, the key issue for Lewisite is organic arsenic and that remains true eventeady state release.0 shows an organic arsenic concentration along the lengthlume which
lume (Seafloor) Area for Tabun (GA)/Sarin (GB)l Current
across the seafloor for various release rales of Lewisite. The estimated no-effects level2 mg L" is highlighted.
The major conclusion to he drawn from this figure is that the release of Lewisiteingle munition, at rates lessg day', will result in toxic levels al distances measured in tens of meters or less. Furthermore, release rates lower thangill produce toxic plumes on Ihc orderew meters or less.
For release rates relevant io munitions containingg of Lewisite and persisting long enoughteady state solution, an upper bound on the release rate would beghis rate wouldhort-lived plumeolume at the no-cffecis level of* andcafloor area ofJ. We can regard these as being upper bounds on the sizes of an arsenic plume, but it is important io note thai their lifetimes will be short, that is, approximately one hour in the caseg munition. However, it is easy lo imagine that in the course of corrosive development of leaks, that there first would be the appearance of pinholes allowing only much smaller rates, resulting in much smaller toxic volumes and areas.
7.7 TOXIC LEVELS AT THE DUMP SITES
There were two ways to proceed from this point, one potentially offering more generality than the other, although because of our state of iguorance about the dump sites they could end up being the same.
The first approach would have been totatistical source distribution functioniving the probability that at location) thereeaking munition) for each dump site and, recognizing that the solutions already) are Green's functions, convolve the two and compute expectationhe mean concentration.
The second approach, the path taken, was to recognize
lhal because the estimated mean separation between leaking munitions will be generally larger than the sues of the plumes or the toxicity fields generatedudden release, an "independence" approximation will be very good This will be especially true foe total dump site lifetimes greater than the expected lifetime of twenty years Further, we will assume that the munition* arc distnbuted uniformly across the sile With these assumptions, the total volume of contaminated water was obtained simply by multiplying ihc size of the contaminated volume fromsingle munition by the mean number of munition* leaking over the interval, which is determined by the time it takes tounition.
Under the assumptions of uniform distribution and indepcnilence, these two approaches yield the same result The convolution in the first approach becomes the sum of leaking munitions whose concentrations do not overlap at any relevant levels.
Toxicity from Rapid (Impulsive) Release of Agent
As we have learned, an abrupt or impulsive release of CW agent could possibly apply to Tabun. Sarin or Lewisite, but not to Mustard where the slow dissolution rate forces considerationlume description.ummarizes the total areas and volumes that can be contaminated at the ENEC and EPEC levels for these three agents.
To obtain the real extent of toxicity, we now need lo combine these results with ihe conclusions othich provided the density of munition* on the seafloor. Since there is so much uncertainly aboul the duraiion of the primary release period, five, ten, twenty, forty years, or perhaps longer, as well as the spatial distribution of munitions, il will he useful simply to compute the maximum areas and volumes using all the agent thought to have been dumped. As
PHYSIC
oncentrations of Arsenicwistie (X)1 kt current)
been shown, the maximum volumes thai can be contaminated by the agentingle munition would ariseingle impulsive release.
Taking the results fromnd the volumes and areas from, we have the results in. It should be appreciated that these areas and volumes areith the toxic levels indicated extending over time given in. These values are simply the sums over all the areas and volumes taken independently, whether they resultingle, massive, simultaneous release from all munitions or the addition of the individual areas and volumes disregarding tbe times.
The magnitude of these values can be appreciated by realizing that the largest, Tabun, is comparable to ihc Kara Sea in both area and volume. These volumes and areas are those "swept out" by the loxic water moving with the current. However, these volumes cannot he realistically produced and we must introduce the primary release period in order to obtain somethingealistic picture.
1 shows the volume estimateunction of the total release period for both ENEC and EPEC levels. Il should be understood that these volumes are maintained over the entire release period, whereas those inerehat is. if we thought that the release period was at least ten years, then the maximum volume that could be contaminated by Tabun at the EPEC level would be no greaterm- and this volume would persist for at least ten years.
The results in1 have nothing to do with the spatial distribution of the munitions, except lo assume lhal they are spread sparsely to result in independent areas and volumes of toxicity. For release periods greater llian five years, thisood assumption.
With this as background, we can complete the analysis for impulsive release by introducing the assumptionniform spatial distribution over the sites and the munitions quantities assigned to the sites in Chapter2 shows the volumes by site for the initial release of five percent of the munitions and3 shows the areas. It was assumed here lhat this initial releaseingle event, whereas in reality, with munitions being dumped from ships
arriving over months if not years, even this "initial" live perceni event would he spread out in time. If this were taken into account, the volumes and areas would he reduced, perhaps by factors as great as two orders of magnitude.
The sites producing the most contamination aren the Kara Sea,n the White Sea. and, the shallow site in the southern Barents Sea. With the assumptioningle release of live percent of the munitions, these volumes and areas are very large The total volume of the Kara Sea. for example, ism' with an area ofm
Il is important to appreciate that the volume and area shown are "tmeased on an impulsive release from five percent of the muniiions dumped. This is in contrast to die sicady state problem discussed below, where the result will be contaminated areas and volumes existing over periods of years, even decades.
Steady State Release
The first issue to be confronted is tlie release rale Q, since, as we have seen in, contaminated volumes and areas are quite sensitive toIn, il was shown that the contaminated area and volume were proportional to Qw and 0'- respectively. Since what we want to do is to obtainunds on the contaminated areas and volumes, it will be sufficient lo use asalues is consilient with both plausitMlity and wiih the use of the steady state solution. This will he taken io beg da> tor Tabun. Sarin, and Lewisite1 Wj day' lor mustard. Il should be understoodhis is not necessarily ihe most likely rare-which may be two orders of magnitude smaller in many cases- itigh rate, possibly near the maximum. At this rate wcuration for eachg munition of one day except fot mustard, whichurationays.
ontaminated Volumes by Site for ihe Initial Five Percent Release
: Contaminated Areas for the Initial Fire Percent Release
llic plume volumes and associated scafloor areas previously estimated and the spatial and temporal distribution assumptions of Chaptere can arrive at estimates for the areas and volumes associated with enure dump sites. These are given in45 where they arc referred to with respect to the volumes and areas of the relevant:
In all cases, the volumes are usually very much lessm' It is important to appreciate that since, in this model, the initiationelease is assumed to be uniformly distributed over time T, taken loears orears, the volumes indicated are preseni for these entire periods. Of course, the munitions that arc actually releasing will vary from one time to another. It is only ihc number that is being held constant.
The associated areas on the seafloor arc given in6
Ihc most important conclusion to be drawn from the estimates given for contain iruicd areas and volumes is that bothery small function of the areas or volumes of the seas in which the sites arc located.
Moreover, the contaminated areas arcsmall fraction of the site areas. Both conclusions are true evenotal release penod of five years, which is uruealisUcally short.
7.H POTENTIAL FORION OF CONTAMINANTS IN THE SEDIMENTS
After release to the water column, chemical agents, additives, and breakdown products can remain in solution or suspension, where they may undergo additional breakdown reactions and continue to be diluted in the regional waters. Some contaminants may be carried lo ihe sedimcnl where persistent contaminants could increase greatly in concentration over background amounts.
Arsenic in Lewisite is the only contaminant likely to be carried to the sediments in significant quantity and to remain fur long periods.
8 shows the areas overiven quantity of arsenic would need to be distributed in
1 Li II
7 PHYSICALsi s
toiven coiKeniraiion. The range of naturally occurring background levels is highlighted.
These value*niform distribution in areaepthm. If, as we mentioned earlier, mixing through bioturbationepth ofm is plausible over long periods, then these values would be divided by ten.
Fate of Chemical Agents and Organic Breakdown Products
The reactions of chemical agent* in the marine environment have been discussed in Chapterlthough the long-term reactions of these compounds are not well known, it is likely that most of the organic products will continue to undergo breakdown reaction! in the water or In the sediments. Most of these compounds would probably not be long-lived in the environment.
The short-lived contaminants arc not likely to be earned to the sediments, as indicated by their very low or negative ocional-water partition coefficientsee81 inhemicals with log Kw greater than lour have the greatest affinity for adsorption in sediments or onto suspended matter that can sink to the bottom.
Tbe estimated log K_ for Lewisite is two to three, which is greater than most of the other compounds, but still less than the lower end of the range of greatest adsorption. It is unlikely that lewisite would be carried to sediments in significant concentrations because the very large hydrolysis rate discussed earlier in this chapter would not allow it lo persist for sufficient time for this process to be effective.
Only rough estimate* of log K_ for thr organic breakdown products of Lewisite are available from the phosphorus analogues. The relatively low estimates arc consistcni with the expected degree of disassociation nt thef the marine waters of ihe
study area. This disassociation makes it likely that these compounds would stay in solution in preference lo sorption to sediments.
For Tabun. no measurement or estimate ofould he found lor two of the organic breakdown products. These acids are significantly disassociated in seawater atnd arc likely to have low toxicity. Accumulation in sediments at concentrations that could produce toxic effects is unlikely In any case, we have shown that significant Tabun concentrations must be restricted to the site itself.
Arsenic
Arsenic in Lewisite is released from munitions in organic forms. Since organic arsenic compounds are readily oxidized in aerobicuch as in the study region, it is likely that these compounds would continue to undergo reactions to inorganic forms and enter the natural cycle ot arsenic in the physical and biological environment of the region. Significant quantities of arsenic are likely lo remain in sediments
Adsorption of arsenic into sediments and copiedpltution may be important controlling factors In the fate of arsenic in thersenic may be sorbed onto clays, aluminum hydroxide, iron oxides, and organic material Coprecipitation or sorption with hydrous oxides of iron is an important process. The4 for arsenicodest affinity forediments Oxyanions of both arsenic and arscnous acid can coprecipitaie with hydrous iron and manganese oxides. Ihc rate of adsorption decreases widi increasing salinity. Ihe formation of fcrroimingancse concretions in the Barents and Kara Seas" could indicate that this mechanism would operate in the study region.
The prevalent form of inorganic arsenic in seawatcr ishe inorganic form is probably the predominant form in marine sediments, although the method of extraction for measurement can change the
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Cyanide
()tkc produced. Tabun can exisl in several different forms in the aquatic environment. The primary loxic agent of concern is free cyanide, which consists of HCN and the cyanide ion in equilibrium:
HCN N
Cyanideydrolysis product of Tahun. Cyanide would likely remain as free cyanide in the form of HCN. Ii is likely thai the faic of this acid primarily will bc governed by btodegradalion and volatilization, if bni io Ihc surface.
The pK. for HCNCN is far more loxic to aquatic species than the cyanide ion. presumablyan more easily penetrate the gills. Except under extreme conditions of. HCN would be the dominant form in aqueous solutions In marine waters, which are well-buffered by the carhonaic systemH near eight, probablyerceni of the free cyanide would cxisi as HCN
Although it is well-known lhat free cyanide can be chemically oxidized to cyanalcata on ihe chemical oxidation of cyanide in natural aquatic systems is not available."
No data was found on the absorption of free cyanide to suspended particulates or bottom sediments in natural systems, but it has been dcmonstraled thai ihe cyanide ton is not strongly adsorbed or retained int is unlikely that cyanide would strongly partition io the sediment* in aquatic systems. Furthermore, insolublekeljrrcipiMU-aters because of the low metal concentrations
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IS
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encounieted. Because of its high solubility in water, hydrogen cyanide is not strongly adsorbed to sediments or suspended material."
Most of the research on the fate of cyanide-containing compounds is based on investigations of industrial wastewaters containing cyanide in concentrations in the mgange and usually in association with other contaminants, such as metals. Sonic of the mechanisms that have been shown to affect cyanide concentrations are biodegradalion. volatilization, chemical oxidation, photolysis, and precipitation. However, very linle information is available about the fate of cyanide compounds in natural waters.
There are many inorganic cyanide complexes that can form with the transition metals and this formation serves to remove cyanide from aquatic systems. These complexes have the following general formula:
[M-
These complex ions are variable in their stability. Ihc copper complexes arc moderately stable. The iron complexes are very stable and can serve to reduce the availability of free cyanide. The high stability of the ferric hydroxides, however, keeps the ferric ion activity so low lhal the extent of iron complexation is limited. Overall, it is probable that meials in seawater would form complexes with dominant anions such as hydroxide, chloride, sulfate, and carbonates and thai cyanide would be present in concentrations too low to permit significant complex formation.'*
If cyanide complexes form, ihereotential for later release of cyanide. Hot example, although iron-cyanide complexes are not toxic, ultraviolet or visible light can liberate the cyanide ion."
Hydrogen cyanide is volatile,apor pressureon atVolatilization, particularly in turbulent waters, mayignificant means of removing free cyanide from aqueous systems. In deep marine environments and during periods of ice cover, this mechanism would bc unimportant. In shallow systems, circulation could bring water in contact with the atmosphere and volatilization could occur.
Cyanides at low concentrations are biodegraded by almost allaking this an important process in the aquatic fate of this contaminant. Under aerobic conditions, cyanide salts in the soil arc degraded microbially to nitrites or they form metallicnder anaerobic conditions, cyanides denitrify to nitrogen compounds. Cyanides do not seem to persisi in aquatic environments. In small, cold lakes treatedgcute toxicity was negligible within forty days. In warm, shallow ponds, toxicity disappeared wilhin four days."
Chlorobenzene
Chloroben7cnc can bc releasedixture with Tabun. Chlorobenzene is resistant lo hydrolysis and could bc persistent in the marineI is likely that chlorobenzene would noi accumulate in sediments in significanl amounts.
Chlorobenzenehichow io modes! affinity for adsorption onto sediment and particulate matter. The adsorption. for chlorobenzene is in ihc range of. This coefficienteasure of the affinity to sorb onto organicalues in this range indicate there is little affinity for adsorption onto sediment."
Chlorobenzeneapor pressure8 Torr alwhich indicates il will partition to the airurfacen quiescent water, the evaporative half-life of chlorobenzene has been estimated to be ninen agitated waters, such as
while capping in ihe ocean, ihe rale would bc higher In deep walers. chlorobenzene would not have ihe opportunity to volatilize, bin in shullow areas this could be an important mechanism by which die substance is lost from the aquatic system.
Photolysis potentially can reduce chloiobenzene concentrations. Chlorobenzenepm in river water pholodegradcd lo phenol and chlorophenol when exposed to artificial sunlight.*
The half-life of chlorobenzene in sediments has been reported asl this rate, overercent of the compound would bc degraded within one year. The temperaiure regime for this estimate was not repented. Biodegradation of chlorobenzene in aquatic systems is likely io bc slow."
7.9 SUMMARY OF RESULTS
At the beginning of this chapter seven key questions were posed. These questions were developed inay that their answers would serve as the departure poinl for the assessment of the ecosystem effects to be carried out in Chapterhe most succinct way to summarize the substantial quantity of material in this chapter is lo provide answers to these questions.
ollowing releaseingle munition, how does the total quantity of the remaining CW agent change with time due to chemical reactions?
The total quantity of agent present in the ocean decreasesesult of chemical reactionshe rales of which have been establishedn some cases the reaction products are relatively non-toxic, in others they arc less toxic than the CW ageni, bul long-lived.
In the cases of mustard and Sarin, all the hydrolysis products are very much less loxic than the agent and aflcr approximately len hydrolysis half-lives essentially no toxic material remains.
In the case of Tabun, after approximately ten half-lives essentially all the agent has been hydrolyzed into relatively non-ioxic compounds except for ihc stable loxic compound HCN (hydrogen cyanide) of whichs producedg of ageni.
In ihe casewisite. there isery rapid hydrolysis, occurring on ihc order of seconds, producing organic arsenic, which has substantial toxicity. Subsequently, very much slower reactions, occurring on the orderew months, convert this organic arsenic to loxic. inorganic forms.
The values for ten hydrolysis half-lives of tliese agents are:
half-lives
Musiard ours
Lewisite seconds (to organic arsenic,
months to% stable
HCNhours
udden release ofCW agent, what is the spatial extent of toxic contamination and how does It change with time?
It is expected thai sudden release could occur onlyunition were fractured upon impacting the seafloor following dumping, or upon being impactedishing (bottom) trawl.udden release of all the agentcloud" of contaminated water will be produced. This cloud grows in size because of mixing via eddy diffusion and is transported downstream by the local ocean curreni. Meanwhile, the process of hydrolysis continues to alter its chemical composition.
HYSICALsl s
mixing upward in (he hcnlhic boundary layer Is much slower than mixing horizontally, this cloud has an oblate spheroidal shape For sudden releaseg of an agent, ihc radius on ihc seafloor of this cloud at the ENEC level can grow lo urns of metersew lens of hours. Us thickness or height above the seafloor will be lessactor ofSubsequently, tbe conilnned effects of mixing and hydrolysis then rapidly reduce the volume of toxic contamination to zero
At one hydrolysis half-life, when the quantity has been reduced byercent, approximatelyercent of Uie remaining agent is containedox having the dimensionsv. where these lengths are the horizontal and vertical mixing distances.
Ihe instantaneous radius of this cloud of contamination is proportional to the first power of the quantity of agent released, and to Lh1.
loud of contain malum is transported downstream by tbe current, it "sweepsolume of seawater thai is much larger than the volume of ihc cloud itself. For the agents considered, this volume could be as large as' at an EPEC levell curreni. By contrast, ihc instantaneous volume of the cloud would be no larger than0 in' al EPEC.
hm is the spatial extent ofthe toxic plume lhat ii expected lo formWlowly released into the oceanong period oflime?
The size of the toxic plume formed by the slow release of an agent depends on the release rate Q. the iwo eddy diffusiviiicsKv. the specifiednd the local ocean curreni v. The maximum dimensionlume is its down-current length along the seafloor. which is given approximatelyhe thickness of the plume is very much less, both because of the action ol the current and because ihe vertical eddy dirrUsrvity is much smaller.
probablyactor of ten or more, than the horizontal diffusivily.
The volume of water containedlume of specified toxic concentration and the associated area of the seafloor beneath the plume, are important measures of ihe potential lor causing significant biological effects. The volumelume is pniporuotial lo C"nd its area on ihc seafloork-v'Cw.
Plume volumes at ihc ENEC levelate of release of Tabun or Sarin that wouldg munition in twenty-four hours would beorresponding seafloor areaThe thickness of such plumes will lypically beew meters as would be expected from the volume/area ratio in the foregoing example.
Because of its very low dissolution rate, plumes grncraied by musiard base dimensions on rhe orderew tern of tenumeters, or Ics* Because ihc EN FX" and FPEC values of organic arsenic are levs lhan those for Tabun or Sarin. The volumes of the plumes al the same release raic are less by C' These dimensions are, in fact, so small thai ihe physical model used in this study is probably not applicable.
The most important result concerning the sizes of loxic plumes ^cncMled by single munitions is that their maximum dimensions arc on ihc order of lens or hundreds of meters, not kilomeiets much less lenshundreds of kilometers.
o what degree are ihe answers loensitive to details of the local ocean environment?
Hydrolysis rates do depend on temperature and pH. However, temperature at the bottom of arctic seas is very stable as is the pH. In any case, the appiopnaic temperature and pll were used ino develop values for ihe hydrolysis rales used in this chapter. There is. therefore, essentially no sensitivity to the answer to Question I
The dimensions of the cloud of conlamimilion produced by sudden releaseW agenl do depend on the diffusivities with its radius proportional to LH and to Ihe logarithm of other parameters and its height (thickness) additionally proportional tooreover, the extent of the region swept out by the downstream transport of the cloud by the local ocean current clearly depends on the magnitude of rhai current. There is some substantial sensitivity to these parameters, but the values for the extent of toxic cementations developed arc upper bounds based on maximum expected values for diffusivitics and cases were worked out for several values of local ocean current.
Tlie same statements us in ihe foregoing paragraph also apply lo the estimates of the extern of toxic plumes. The results curried forward into estimates of dump site contamination and intore believed to be plausible upper bounds based on parametric analysts guided by an empirical understanding ot ihc important physical quantinc.
hat is the potential for the transport of toxic concentrations by ocean currents over great distances?
There is essentially nn possibility that contaminationingle munition due lo any of the agents considered in this chapter could be transported at toxic levels over basin-wide distances, or even across regional scales.
For the short-lived compounds such as Tahun or Sarin, the process of hydrolysis sets an upper limit on the duration that is relevant, approximately ten hydrolysis half-lives. Even neglecting the very considerable effects of dilution (mixing) over suchew tens or hundreds of hours is insufficient to involve general ocean circulation resulting in arctic-wide transport
When the effects of lurbulenl mixing arc included, the effective spatial scales for the short-lived compounds arc reducedew tens,ew hundreds, of meters. The concentrations of the long-livedrsenic, are also diluted by mixing. Moreover, they are expected to accumulate on suspended particulates and be carried lo the sediments wheie stable long-term burial results. Given the quantities of Lewisite that were probably dumped, the sizes of .scafloor areas that could be contaminated by arsenic at levels significantly above natural background do not appreciable exceed site dimensions.
ii. What is the total extern, including water volumes and affected areas of the seafloor, of toxic concentrations producedump site?
The best estimate thai can be developed based on available information shows thai at any of the dump sites considered here, the size of the seafloor area that can be contaminated at tlie ENEC level is much less than the area of the site.
If all of the dumped muniiions arc assumed lo release their agentseriod of five years, the largest area found was form che White Sea where the area contaminated at ENEC wasery small fraction of the site area foe Tabun and still less for Ihe other agents In no case did the estimated size approach much less exceed the site area, and still les* were ihc contaminated volumes ot areas comparable with those of the regional seas.
The well-documented Hultic Sea experience suggests rather strongly lhat corrosion of CW munitions takes place over long periods, with some munitions releasing agents very soon after dumping and Mime remaining intact after fifty years. Thus it is plausible, though not conclusive, lhat tbe sire of the area contaminated at ENEC willery small fraction of the total site area. The area contaminated at FPfcC or ELEC will be smaller by orders of magnitude. The area of the plume generatedingle munition is proportional toeduction ofor EPEC.or ELEC. relative to ENEC.
Since the exient of toxic concemrations at ENEC or greater is confinedew meters of the seafloor by the low vertical eddy diffusivity in the benthic boundary layer, the volumes of contaminated scawatcrmall fraction of the site area multipliedew meters
l'RGCKSSKS-.
methodology used did not permit estimating the lime delay after the dumping until corrosive disintegration leads to the formation of toxic concentrations at the sites. Parametric analysis was used to bound the consequences of release once begun and to account lor ihc possibilitymall fraction, live percent, of the munitions might fracture and release agents immediately upon dumping.
7. What is the sensitivity of the answer to Question ft* to uncertainties in the analysis?
There is significant sensitivity to uncertainues in Ihe quantities of munitions that were dumped and to Ihe condition of the munitions at ihc dump site wiih the passage of time. If there are reasons to think that agents not consideredas for example, had been dumped in arctic seas, the conclusions of this assessment would not apply.
There is less sensitivity to uncertainties in the description of the local ocean environment in ihc sense that upper bounds were obtained for the extent of toxic concentrations based on upper bounds for expected eddy diffusivitics. This study sheds little light on Ihe question of determining when toxic concentrations can be expected to appear at Ihc dump sites. The uncertainly in this remains significant.
As long as it can be safely assumed that there arc no additional dump sites located in very shallow waters, particularly in the southern Barents Sea where biological productivity is high, there is little sensitivity to dump site location.
Thereonsiderable sensitivity of contaminated volume lo ihe toxicity being consideredhehe volumeoxic plume is proportional toand there could be ordcr-of-magnitudc uncertainty in Ihe levelspecific degree of biological effect, especially across all marine species.
CONCWSIONS
Sources of Environmental Effects from Chemical Mii nil inns: The main potential sources of environmental effect from chemical munitions present at the dump sites are acute toxicity of released agents and associated breakdown products, adverse effects from bioaccumulalion of contaminants in the food web. and the long-term effects of permanently contaminating sediments with arsenic contained in Lewisite. Plumes of contaminants al toxic concentrations could be produced by Lewisite. Tabun. and Sarin. Mustard would not produce toxic plumes, but would be present for decades on the bottom as viscous liquid. Toxic plumes would aeffect ihe entire area of ihe disposal site for as long as it takes to cmply ihc muniiions that arc prcscnl at the site. Arsenic could settle in large quanlilics of sediments at adverse concentrations and could affect an area Up
times the disposal site.
PotcntiaLfor Released Contaminants to Bioaccumulate in the Food Web: Most chemical agents and their breakdown products have no or very low potential to bioaccumulate in ihe food web. Arsenicow to moderate potential to bioaccumulate in organisms most closely associated with arsenic-contaminated sediments. At the deep disposal sites, bioaccumulalion of arsenic in higher trophic levels would be very small because of the small contribution of the benthos to the pelagic food web. At the shallow disposal site, some bioaccumulalion would occur in higher trophic levels because the benthos are more important in the food web at this site.
Potential EffectsPisposal She*enthic and demerscl organisms would be lost or reduced in number by toxic plumes and contamination of sediments by arsenic. Loss of bemhicand dcmcrscl organisms wouldmall effect on the ecosystems of the deep disposal site regions because the contribution of the benthos is small io the predominantly pelagic food web of ihe deep waicrs of the region Marine mammals, which include endangered species, arc at low risk at the deep disposal sites. Depths arc at the limit or are too great for bottom feeding by seals and walrus. Whales arc unlikely lo come in contact with the bottom ot enter ihe water near the bottom containing toxic plumes.
Potential Effects at Shallow Disposal Site: Benthic and demeisel organisms would be lost or reduced in number by toxic plumes and contamination of sediments ny arsenic. Effects on the seal and bird populations of ihc Kolgucv Island region would he moderate to large because the loss of carrying capacity from the site is large relative lo the marine area supporting these populations. Theof bird and mammal populations on the island could decline to match the resources available. Ecosystem effects on the Pechora Sea region would be moderate to small. This would depend mainly on the sue of the area affected delctcriously by arsenic in sediments. This would add to an existing large area of contamination.
Some bioaccumulalion of arsenic could occur at higher trophic levels because of the importance of the benthos in the food web of the region and the accessibility of contaminated sediments to seals and walrus.
Potential Effects on Human Healrh and Safety: The risk of increased cancer to consumers eating fish contaminated with arsenic from the siles is near the upper limit of the risk deemed acceptable. regulatory agencies. Indigenous people eating large quantities of contaminated fish couldmall to moderate increased risk. Fishing boal crews would be at risk of injury or death from capturing mustard lumps or munitions containing agent in trawl nets fished on the bottom. Oil and gas workers arcmall risk of injury or death during activities that could bring an agent lo the surface or could contaminate drilling or pipelaying equipment.
Potential Economic Effects: Commercial fish stocks nearn the Pechora Sea could have increased body burdens of arsenic, especially the dcmcrscl species, which could exceed arsenic standards for Finlandpm) and the United Kingdom (one ppm) and some other non-European countries. Economic effects would be small because stocks can be sold in countries without standards, although there could be someffect while new markets are found. Economic effects could be greater if otiicr countries or consumers become concerned about arsenic contamination in fish from the region.
gas resources within.ould not he exploited if drilling could not he carriedwithin the site boundaries. If operations can take place within sites, exploration and exploitationbe significantly increased if munitions must be cleared from an area before undertaking activities.
8.1 INTRODUCTION
The data ptcscnicd in Ihc previous chapters shows that the chemical warfare munitions and agents at disposal sites in the Barents, Kara, and White Seashreat to the arctic marine ecosystems, to the regional economy based on exploitation of these ecosystems, and to human health and safety. These threats include the following:
Acute toxicity to marine organisms of agents and breakdown products released into the water.
Chronic toxicity on marine organisms of long-lived contaminants in the sediments,
Bioaccumulation or biomagnification of released contaminants in the food web.
Human health effects from consuming marine organisms that have accumulated released contaminants.
Threat to human safety if muniiions are caught in commercial fishing nets or encountered during oil and gas resource development activities,
Regional economic effects if commercial fish stocks are reduced in size, if sales of commercially important species are affected by contamination with released agents or breakdown products, or if additional large areas are closed to fishing and oil and gas resource development activities.
This chapter assesses the possible magnitude of the environmental, human health and safety, and economic effects that could result from the above environmental threats. The results of the analyses presented in ihe previous chapters provide much of the input for estimating ihe likely effects. The starting point for the assessment is the description of the regional ecosystemshe types, quantities, and distribution of munitions and chemical agents in the disposal sitesndstablish the magnitude of the chemical threat that could be present at the sites.escribes how these chemical agents would react and spread in the environment when released from the munitions; and on the amount of bottom area and water volume affected at contaminant concentrations injurious to aquatic organisms are estimatedhis information is the basis for estimating the magnitude of the effect on biological communities in ihc site regions. The data inn chemical properties of the agents and iheir breakdown products is used to determine if these contaminants can bioaccumulate or biomagnify in the food web to harmful concentrationshapter it establishes Ihe environmental concentrations of agents and breakdown products that can be harmful.
Other activities besides the disposal of chemical munitions have also affected the regional environment. Effects from chemical munitions disposal would add to the environmental impacts resulting from these other past, current, and future activities. Environmental effects from these other activities include the following:
Possible over-cxploitalion of the commercial fish stocks and damage to benthic habitats by the large commercial fishery in Ihc Barents Sea.
Release of contaminants and damage to benthic habitats from exploration and exploitation of regional oil and gas resources.
Release of radioactive contaminants from testing of nuclear weapons in the atmosphere and the disposal of nuclear wastes,
Emissions and effluents from mining activities on the Kola Peninsula.
Long-range transport of contaminants into the region from elsewhere in Europe and Russia.
Details of the assessment of the threats to the enviionment, human health and safely, and the region economy are given in.ummary of the main findings of this assessment.
TableSummary of Potential Environmental. Health, Safety, and Economic Effects' Prom the Presence of Chemical Muniiions in the Barents. Kara, and White Seas
Effects
Disposal Sites
Disposal
for bioaccumulalion ot contaminants In the food web
or estimated log k_ values negativey small tor mootJ fjreakcewn products None are lively to Dtoaccurrulate. CMcoCoozono couUow but not skjnrficant bicaccumutabon Arsen* would have low lenoency towardsbut would notin rugher trophic levels. Arsenic increaserophic levels cjosety associated with contaminated sediments
Toxicity Effects
Presence of
viscous mustard
coukl ripest mustard,siies may be too deep or unattractive toi feeding. Sites loo deep tor walrus feeding Whales have low potential torttom
andseals at nsfc because bottom wrtun drvog range Risk may be low because ot low encounter rate orearned avoKlance of lumps Whales have tow potential for contacting bottom at site Humpback whale coukl contact bottom with jaw if certain feeding boiavor used. Ettect would likely be blistering or lesions.
plumes ot Lewisite, OA nnd GB
biomass eliminated or reduced over entire site for period of release of agent from all munitions. Effect of productivity loss small lo dominant pelagic ecosystem present at deep water sites. Risk of mortality or injury small to marine mammals because sites unattractive as feeding areas. Whales unlikely to enter toxic plume near bottom
Recovery Slow, requiring ten to pemaps twenty years to regain biomass and diversity-
in'v Island Region
Benthic biomass eliminated or reduced overslto for period of release ot agent from all muniiions. Effecl ot productivity loss moderate to large because of reduced carrying capacity for island seal and bird populations supported by resources in site vicinity. Risk ol mortality or injury to seals and walrus greatest for five-year release penod Oecajse forty percent of sie bottom area covered by tone plumes on any day. Orvy an percent covered on any day for lorry-year reease penod.
Roccrvery Slow, requiring ten totwenty years to regain biomass and diversityMe area island ww and bro pcx, jiat-ons would rocovor as region carrying capacty is
Sea Region
Benthic biomass eliminated or reduced over entire site for period ofol agenl from all munitions. Effect of lost productivitym' site smsb onm' region shallowerrcto-Norwegian cod and haddock stocks could be affected ki vicinity of site, but slocks are very large and widespread in regon. Polar cod spawning of pelagic eggs occurs over region large in relation to areae. Maroe mammals distributed over area veryefabon to site area
Recovery- Slow. reoA*nna ten to pe-tvaps twentyo regaai biomass and diversity in site area Small loss ot carrying capacity regained tor region.
Table Summary of Potential Environmental, Health, Safety, and Economic Effects From the Presence of Chemical Munitions in Ihe Barents, Kara, and White Seas /continued)
Potential Effects
Disposal Sites
Dis
arsenic
contamination of sediment i
seme COkW permanently contaminate up0 km* at Mas in Barents and Kara Seas0 km' at White Sea site at Biological benchmark concentration otg kg' which ts likely to causo oltects on benthic community. Contaminating maximum aroo very unlikely. Benthic end dnmomnt organism biomass and cWorsity could be greatly reduced in contaminated region. Low e'leel on region because of small conlnhuton ol benttiic community to pelagic fooo weft. Arsenic wouldissues ot benmc and demersal organisms Low potential to* trans'erring arsenc to higher troohc levels.
Island Region
Arsenic could permanently contaminate an area up to tour or five nmesm* site at biological benchmark concentration olghich is likely to cause effects on benlhic community. Contaminating maximum area very unlikely, iin:l offei-ls: Be-itMir ;nd demersal organism biomass and divers-ly could be greatlyontaminated region. Loss ot carrying capacity myn largest area could nave large erectsland btt) and sealr_mulai-On Arsenic wouWissues of benthc ana demersal organisms Moderate potential tor transferring arsenicigher trophic levels because ol Importance ol benthos in food web. Possibltily ol transferring arsenic rt phytoplankion lipid compounds il arsenic is mixed to surface during spnng btoom period. Transport in ice: Potential thai arsenic could be incorporated into ice and transported away from area
Sea
area0 km' area in the sea Biokicical effe. ol0 contaminated range ol live tc nma ahailowe capacity ol reg affected if larg at site Contan veryenvHsa area McxMra! Iransterr ir; ar levels because
DC'itliOS 'I loc
toi arsenc mc dsn stocks. m<
minated added to already contaminated
is: Upper pound total
*m' for two
ireas would be In ten percent ol region. Carrying on could begin to be
ist area contaminatedmaximum area
rt Arsenic would ues of benthic andotential lor ienic to higher trophic oi mpotanceeb. Some potential ease in commercial
inly demersal species.
ol effects
stocks such as cod. haddock, and whales not present ounng ce-cover penod Potential sSgltty greater Ounng warm penod because migratory stocks preseni and BiologicA productivity high nea' water surface. Small interaction ot benthic community and near-bottom water with surface walers
to ice-assr-oated species, such as seals, walois. and polar bears, greatest durng ice formation and ce men when ice is present over and near see. Risk to migratory species greatest when present rjurlng warm penod. PosscrWy of transferringds greatestintense btoompring and summer when tx>*Cs>cai proouctfviTy is greatest
; Summary of Potential Environmental, Health, Safety, and Economic Effects From the Pretence of Chemical Munitions in ihe Barents, Kara, and While Seas Icontinuedj
Effects
Disposal Shea
Disposal
threat to commercial fishery
possibility ole of peagc slocks orissues not likely lo be affected because of small contribution ol benthos to rood web. Bottom trawling, notarvest method at sites.
sates: Stock size not likelye efidCteO significantly, although some potential if targe area affected by arsenic, incoased arsenic in tissues of demersal fish and shellfish species, and possibly some pelagic species, in vicinity of contamination. Finnish and United Klngoom standards likely to be exceeded in demersal speaos and possibly in some pelagic species. Temporary economic effect if sales aio banned in Finland and United Kingdom while sales ate shifted lo other maikota Large economic effect possible It other nations ban sales or consumers develop negative altitude toward regional ten products because ol concern over arsenic contamination.
Fan oil: No effect likely because running process likely to leduce arsenic
concentration less than regulatory concern.
Closure of fishing area:currently discouraged in site area
Presence Of munitions wouW result in continuation of current situation
on oil and gas exploration and exploitation activities
activities withn sic Current ould access resourcesew km of boundano* Most resources underouM not be reachedould potentially be exploited by dtf actional drf*ng Activities withm site Costs increased If survey fo* munitions or munitions clearing required. Costs potentially high for munition clearing.
activities within site: Current directorial d'W technologies could access
Activities withn ste Costs increased it survey for munitions or munitions clearing rec ji*ed Costs potenaaSy high foronrinrj
to human health and safety
of araonic-coninminaied lish: Risk of cancer small for consumption al high end. range. Risk is do' o'fi range of regulatory concern set. agencies responsible lor human health. Risk lo indigenous people who consume largo quantities ol fish is small lo moderate. Upper end of risk range within lower end of range of regulatory concern sot. agencies respons*ie fo* human heanh.
Consumers ol fish oil: Insignificant risk ol cancer because rehning process likely lo reduce arsenic contaminationmounts
Fishing boat crews Could be exposed to tf|ury and death if munbons or mustard lumps are captured in trawl nets fished on the bottom No reports of ncicems from stjdy region wereiterature rev-ewed-Oil and pas resource expkyalion and expkjilaeonws coukl be eiposeC to agon' corlamr>.atng equipment ma' comes in contact with bottom or enters tone pkjmes near bonom Crews coukl also be exposed to agents brought to the drflkng platform tn dnaVig muds or circulated to tne waters surface.
ANALYTICAL APPROACH
The potential sources of impacts on ihe biological communities' and ecosystems uf the study region arc the acute toxicity of the released agents and breakdown products, the permanent contamination of sediments with arsenic, and possible bioaccumulation of contaminants in Ihe food web. Described below are the considerations important in determining the kinds and magnitude of effects that can be caused by these sources or impact.
Ihe type of food web presentisposal site is also important in determining how released agents can affect the biological community. This issue is considered when determining whether the disposal sites must be analyzed separately or can be grouped for analysis.
of Disposal Sitesafysis
escribes the structure and function of the biological communities and ecosystems in the study region. In deep water areas, the biological productivity and energy flow take place primarily in the water column. The contribution of the benthic community to the biological activity in the water column is small. Thus there should be relatively little exchange of materials between the upper ocean ecosystem and materials near tbe seafloor. In shallow water, the benthic communityuch more important component of the biological system.
When wc examine the characteristics of the disposal sites as given in Chaptere see that four sitesn the White Sea,n the Barents Sea, andn the Kara Sea) are in water deepernd are similar in temperature, salinity and stratification. These sites arc grouped together for analysis because they are likely to have pelagic food webs that arc similar.n the southeastern Barents Sea. however, is in much sliallower water (about0 m) and is likely toentho-pelagic food web. This sile is analyzed separately.
ihe Potential forBioaccumulate or Biomagnify InWeb
alues arc used to estimate the bioaccumulation potential of the chemical agents and breakdown products discussed in Chapterhese values aie given in8
Bioaccumulation of contaminants is the net accumulationubstance by an organismesult of uptake from all environmental sources. Environmental contaminants can accumulate in the tissues of organisms or bioaccumulate throughout the food web at concentrations that are many times greater than in the water or sediments to which the organisms arc exposed. Organisms can be adversely affected if the accumulated concentration is great enough.
Of particular concern in bioaccumulation is the special process of biomagnilication of concentration through the food web. Hydrophobic chemicals, such as DDT and other chlorinated organic compounds, are particularly prone lo exhibit this phenomenon. Biomagnilication occurs when an absorbed or ingested contaminant is not metabolized or excreted but, instead, is stored preferentially in fatty tissue. It accumulates and is passed on lo the next level in ihc food web.esult. Ihc quantity of the contaminant in the body increases dramatically at each level. This process affects organisms at the top of the food web, such as polar hears and sea birds, even though the contaminants arc present at very low, non-toxic concentrations in the water. It results in accumulated amounts lhat arc orders of magnitude greater than the amounts found in the water or sediments lltal serve as the source of tbe contamination.
The potential lo bioaccumulate and biomagnify has been measured experimentally for many chemicals and can be estimated from chemical properties using several methods. For organic chemicals, the octanol-waier partition coefficientcan be used as an indicator of bioaccumulation potential. Values of K. for the agents of interest are tabulated in Chapter8
is determined experimentally byhemical of interestwo-phase system consisting of water and thecianol. This alcoholood surrogate for lipids, such as fish fatty tissue. After ihe mixture is shaken, the amount of the chemical dissolved in the water and alcohol phases is measured. Kow is defined as the ratio of the amount of chemical in the alcohol phase to that in the water phase. The result is often reported as the logarithm of the ratio.
Ihe greater the logvalue, the greater Is the atiinJtyhemical for lipids and the greater is the potentialhemical to bioaccumulate or biomagnity in the food web. Chemicals with loginange bioaccumulate to the greatest degree and are of greatest concern.1
Analyzing the Acute Toxicity Effects of Mustard *
Mustard exposed by ihc corrosion of munitions would existolid or viscous liquid on the bottom. In. the analysis shows that ihe rate of dissolution of this mass is so slow that no toxic concentration of mustard would be produced in the water surrounding the mustard lump. Individual mustard lumpsg, once exposed to water, would last fot many months, takingays to dissolve completely. Because the munitionsite would constantly be corroding through, muslard lumps are likely to be presentite for the many years that il takes for complete disintegration of all munitions. It is assumed in this analysis that muslard is present at the site for the entire period of agent release.
The effects of muslard in ihc environment would result from contact of organisms with the lumps. The magnitude of the elfecl wouldunction of the probability of such contact and ihe injury or death that results.
Analyzing Acute Toxiciry Effects of Lewisite. Tabun, and Sarin
In. we can see that it is possible for munitions leaking Lewisite. Tabun. and Sarin to release agent or breakdown products into the surrounding water al concentrations potentially toxic lo marine organisms. The resulting downcurrent plume would remain on the bottom and mix verticallyewew tens of mcicrs. The size of this plume is dependent on the rate of leakage. Toxicity could be confined lo withinew centimetersetereaking munition al the low, but plausible, leakage rates analyzed. At the high release rates0ghe toxic plume couldewew tens of meters along the bottom. Because the plumes produced stay on and near the bottom, the main effects would be on benthic organisms covered by the plume and on mobile species, such as marine mammals and tish schools, thai could swim into the plume near die bottom.
The ecosystem effect of toxicity io benthic organisms is determined by the loss of biomass and productivity and" by tlie importance of ihe benthiecommunityiofood web at that location. This effect would be partly determined by Ihe size of the area affected and the length of time the effect remains.
At the high release ratesog day', il is likely lhat the benthic communities would be reduced in biomass or eliminated over much of the site because of the likely random nature of release from individual munitions over time and the slow recovery rate of arctic benthic communities. As muniiions randomly release their contents over the five to fifty year periods analyzed in Chapterach plume wouldmall area of benthic communityeriod of one day lo perhapsr so days. This same botiom area would soon be affected once again by the plume from another nearby munition when its contents were released. The return period of effect on an area of bottom could varyew daysew months depending on the length of the period over which all munitions leleascd their contents and the number of munitions presentite. Because the recovery rate for benthic communities in arctic waters mayecade or longer, the overall effect within the site is that the entire bottom area would he affected for the entire release period. Benthic recovery rate is discussed in more detail in later sections of this chapter.
For mobile organisms, such as marine mammals, the potential lo be exposed to harm isunction of ihc probability of swimming into an area of toxicity near the bottom. This probability would he determined by the area of bottom covered and volume of water at harmful concentrations thai exists on any day during Ihe period of release. The area of boltom covered calculated inas been used in this analysis.
Lewisite breakdown products are arsenicals. Since inorganic forms of arsenic have toxicity, these
'Bsird.Annhftj WH. HeCinwi ami Camonv. New Yort. NY
s. impact
products could have continued toxicity as ihey are transformed in the marine environment. As discussed below, the first toxic breakdown products of Lewisite are organic compounds and arc about as toxic as Lewisite. Inorganic arsenic compounds shown inre toxiconcentration about one-third that of Lewisite. Therefore, any toxicity from inorganic arsenic, if it occurs, would be encompassed within Ihc plume dimensions of lewisite breakdown product.
Chlorobcnzcne is an additive in German-produced Tabun and would be released with Tabun. The acute toxicity of chlorobenzene is three orders of magnitude less titan Tabun, so it is likely that chlorobcnzcne would not be released in toxic concentrations.
Cyanidereakdown product of Tabun. Cyanide is three to four times less toxic than Tabun. Therefore, any toxicity from cyanide would be encompassed within the plume dimensions of released Tahun.
Fluoride and dimethylamine arc breakdown products of Tabun and Sarin. Their toxicity is two orders of magnitude less than Tabun and Sann. Any toxic concentrations from these substances would be encompassed within the plumes of Tabun and Sarin.
Analyzing Contamination of Sediments with Arsenic
Arsenic released from munitions in Lewisite would be distributed in the manne environment by currents and other natural transport phenomena. It is anticipated that much of it would be carried to the sediments eventually. How much the sediment concentration increases beyond its natural background concentration would depend on how widely the arsenic is dispersed and diluted before settling into the sediments. The concentration of arsenic in ihe sediment is important because it determines the ecological effect. Benchmark concentrations of sediment arsenic concentrations are used to determine how large an area could be contaminated at biologically harmful concentrations.
The Barents and Kara Seas arc not likely to be widely contaminated by anthropogenic sources of arsenic and. thus they should have sediment arsenic concentrations in the range of naturally occurring values for marineean arsenic concentration ofg kg' has been measured at uncontaminated sites. coastal and estuarinc locations andg kg" for similar siteshus, tthe natural background sediment concentration of arsenic in the Barents and Kara Seas is estimated to beg kg'.'
No measurement of arsenic in White Sea sediments has been found in the litcnilurc. The White Sea receives effluents from human activities and may be contaminated with arsenic. For purposes of this study, the estimate of arsenic concentration in the sediments of the deep basin in tlie While Sea isg kg'.
Benchmark concentrations for arsenic in sediment that cause no biological effect and the median value that has been demonstrated to cause biological effects have been determined by Long andhe lower value, called effects range-low. is the sediment concentration al the low end of the range in which biological effects were observed. This value was estimated to heg kg'. The higher value, called effects range-median, is the sediment concentration median for reported values associated with biological effects. This value was estimated to beg kg'. The benchmark values selected for analysis of biological effects at CW disposal sites aregndghich are rounded approximations of the Long and Morgan values.
The distance that arsenic, released from Lewisite, travels before settling in the sediments cannot be estimated with precision. This issue is important, however, because transport distance detennincs dilution and spatial distribution of the arsenic before deposition and adsorption occurs.
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Bounds on ihc area cocuami ruled al ihc biological bcnchmaik sedimeni concentrations can be estimated. These hounds arc calculated by determining how Large an area the quantity of arsenic potentially presentisposal sue must he spread oser and mixedm deep inio the sedimenis lo incieaso ihe total arsenic concentrationhe hciiehnwk cone em rations. This assumes jhat the background concentrations for arsenic presented above areepth ofm was usedeasonable depth for mixing by organisms lhal live in the sedimenislso shows the sediment concentration of arsenicunction of areaange of arsenie quantities released, butixing depth ofm.
Arsenic docs not biomagnify in the foodost likely because animals conven arsenic to oiganoarscnic compounds thai can be excreted. However, arsenic docs bioaccumulaie in marine organisms ai concentrations greater lhan in the water surrounding the organism. The log of the bioconccnrraimn factor for arsenic in fishioconcenirniion factor is the ratio of the concentrationhemical mcasuied in the tissue of an organism to the coneenlraiion in ihc surrounding waier. High concentrations of arsenic have been measured in organisms from enviionmeiiis wiih abnormally high levels of arsenic in the sediment oruch as areas polluted by mining wastes or industrial wastewater discharges. Conccnlralions are often greater in inolliisks and cnistaccans lhan in fid) :|
POTENTIAL OP RELEASED
CONTAMINANTS TO BIOACCUMULATE IN THE FOOD WEB
Measured and estimated values lor logfor agents and breakdown product* are listed in Chapter8I. The logvalues for most of the compounds arc very kn* or negative. Therefore, many of these contaminants are not likely lo exhibit any tendency to bioaccumulate in the food web. In contrast, the estimated logvalue for Lewisite is near the lower end of the range ol" greatest concern for bioaccumulation given in. Since Lewisiie is short-lived and therefore is unlikely to bc released to the environment in any significant quantity, it is unlikely that it would bioaccumulaie to any significant extent.
Chlorobenzene. an additive to Tubun.valuc4ioconcentraiion factorIt is likely that some bioaccumulation of chlorobenzene could occur ai ihc lowest trophic levels. However, it is also likely, given the log K- value, that ihereow potential to btoaceumulaic at higher irophic levels.
8.4 ECOLOGICAL EFFECTS AT DEEP DISPOSAL SITES
The deep disposal sites are analyzed together. As discussed in. these sites have similar physical characteristics and the biological community is hkely toelagic food web. so the environmental effects from agent rekase are likely lo be similar al ihe sites.
As can be seen in Chaptergents teleased from leaking munitions would slay near or on ihc bottom and the arsenic iclcased from Lewisite would eventually end upong-term contaminant in the sediments. Therefore, the acute and chronic toxicity would be exerted mainly on benthic communities and on any mobile organisms that swim near the bottom or feed on benlhic organisms.
The ecological effects at the deep disposal sites should bc small because of ihe small amount of benthic area affected and ihc small contribution (biological coupling) of the benthic cormnumly to the pelagic food
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likely lo be present. However, in other marine ecosystems, resting or larval stages of various organisms may spend part of Iheir existence in the bottom sediments. These forms later return io ihc upper ocean cither when conditions improve or as ihe organisms maiure. This wouldathway between the benthic and upper ocean communities. It is nol known if such processes arc significant ai the deep disposal sites, but the evidence suggests lhat this is not the case.
Effects of Mustard
Mustard may be presentiscous form on the scafloor somewhere on the site for many years. Benthic organisms would be killed when exposed lo or contact with mustard. The exposed surface area of mustard is small and therefore, tlie number of benthic organisms killed by contact with muslard wouldery small loss to the food web and unlikely to have measurable effects.
Marine mammals could be injured or killed by ingesting or coming into contact wiih Ihc muslard subslance, however, this nsk is likely to be very low. Injury or deatheals from ingesting or coming into contact with muslard while feeding on the bottom is possible, but is likely to be small al the deep disposal sites because benthic feeding species arc not attracted lo the deep locations for feeding. The depth of the sites is within the diving range of the harp seal which is able lo dive to depths. They feed on benthic fishes andearded seals feed on benthichis species occurs on ice over waters of depthsr less, so the siles would be at the limit of their diving range. The low benthic biomass at ihe Kara Sea siles (less thanill likely make these areas unattractive for feeding by seals thai forage on benthic organisms. Sitet the northern end of Novaya Zemlya may be too deep for seal feeding if ihe munitions are in the deeper sections of the siic. Benthic biomass at the White Sea siie is not known, but may be low because of the muddy sediments present. Siten the Barents
Sea has grealer biomasslian tbe other sites and could be used by seals during the period when ice conditions arc favorable for seals to be present.
Walrus arc found in the vicinity of the Kara and Barents Sea sites, lt is an endangered species that feeds predominantly on mollusks and other benthic organisms. The sites, however, are too deep for walrus foraging because they are limitediving depth of about1 No walrus live in the White Sea.
Whales would not ingesl mustard because there are no bottom-feeding whales in Ihe study region. Most whales inhabiting, the disposal sites, feed in the water column and wouldery low probability of contacting the bottom. Humpback whales, however, may come in contacl wiih the bottom during certain feeding behaviors" and wouldlight possibility of coining inio contacl with muslard if this behavior occurs in the study region. The expected effects include lesions from the vesicant action of the muslard, most likely in the jaw region. While it is unlikely that this effect would be significant within the humpback whale population in the region, any effect on these whales is of concern because of iheir status as an endangered species.
Toxic Effects of Lewisite, Tabun, and Sarin
Benthic and demersal organisms would be eliminated or significantly reduced in numbers or species diversity over the area of the disposal site for the cnlire period of agent release from the munitions preseni at the site. The effect is independent of the period of release because of the slow recovery rate of arctic benthic organisms, as discussed in.
'Ihc effect of the loss of benthic organisms and productivity on higher trophic levels in ihc region of the sites would likely be small. The food web and energy flow of ihc deep water areas is located predominantly in the near-surface waters. The organic matter produced by the phytoplankton when light is
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available is consumed heavily by zooplankion and other nekton within the surface water layers. Fecal material produced by these grazers may sink to the scafloor where il will be available to the benthic community. The higher trophic levels of fish, birds, and mammals that feed on the upper ocean are found predominantly in the near-surface water where the food is availabkv In this system, benthic biomass is low and the benthic community contributes only small or modest amounts to the pelagic food web because of tlie small biomass of organisms available and the depth of the water.
Risk of mortality or injury to marine mammals would be small. The risk of injury to seals would largely be based on the probability of swimminglume of agentarmful concentration near the bottom; the more area covered at any time, the greater is the possibility of encounteringlume. The area of bottom covered at any time during the release period has been estimated in. As would be expected, the amount of area covered and volume affected is greatestive-year release period and leastifty-year release period (see4. For seals, the depth of the sites and the likely small quantity of biomass present, as discussed above for mustard, makes these areas unattractive feeding locations. There would he no risk to walruses because the sites arc loo deep for feeding. Whales would only be affected if they enter the toxic plume near the bottom, which is unlikely because no bottom-feeding whales inhabit the region of interest.
There is some uncertainty in the above analysis because it is possibleisposal area to he locatedabitat importantarticular species orarticular life stage of an organism. No detailed data are available on the biological communities of the disposal sites. However, the data reviewed for this study docs not suggest that the disposal sites are located in any areas of special significance.
Recoveiy of benthic and demersal communities would occur when toxic plumes ate no longer present. Data on the rate of recovery of benthic and demersal communities at deep arctic locations was not found. Benthic organisms may grow slowly, have long individual life spans, and low turnover rates.'ruMany organisms brood their young rather than release pelagicispersal of brooded youngite would be slow. Pelagic larvae would colonizclHe site much faster. It is likely lhat the rate of regeneration would be slow, perhapseriod of one or two decades to recover to the original biomass and diversity.
Ixmg.Tenn Effects of Arsenic-Contaminated Sediments
ersistent contaminant from Lewisite, would be added permanently to the sediments and be available for uptake by marine organisms. Because arsenic is potentially toxic, there could be chronic toxic effects from its long-term presence in the sediments of the regional environment.
Marine organisms can be exposed to arsenic in sediments in several ways. These include absorption of dissolved arsenic from the water or sediments through the skin nnd gills, eating other organisms containing aisenic in their tissue or gut, ingcsling contaminated sedimentsood source or incidentally while feeding on benthic organisms, and filtering contaminated particles from the water.
Arsenic is biologically available primarily in the inorganic dissolvedrganic arsenic breakdown products of Lewisite will ultimately be converted to inorganic forms and enter into tbe natural aisenic cycle. Marine phyioplankton and macrualgae readily take up the inorganic formnd convert it to water-soluble and lipid-typc compounds, primarily ribosides. Animals convert arsenic compounds into low-toxicity organic forms, primarilyhe organic arsenics arc readily excreted by animals.
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factors determine whether arsenic in sediments could have adverse effects on regional marine ecosystems. These include the concentration of arsenic in the sediment, the total area affected by concentrations that could have adverse atTects. the bioavailability of the arsenic, and the potential of arsenic to bioaccumulate or biornagnify in the food web.
stimate of'Arsenic Contamination of Sediments at Biological Benchmark Concentrations
In. arsenic sediment concentrations ofgndg kg' were selected as biological benchmarks for analyzing the possible effects of arsenic on benthic populations.
hows the area of sediment that could be contaminated at these biological benchmark concentrations by different quantities of arsenic that could be presentisposal site. These areas were calculated by the method discussed in.8 also shows the sediment concentration of arsenicunction of areaange of arsenic quantities released. This area calculationniform distribution of arsenic mixed into sedimentepthm. To match the data inhe mixing depths must be reduced by an order
The quantities of Lewisite inre bounding values. Ihc highest value0 tons disposedite is highly unlikely. It could only occur if all muniiions dumped in the Kara or White Seas
disposed of at only oneighly unlikely scenario.
I^irge areas could be affected if large quantities of Lewisite arc presentite.how the size of die area that would be contaminated atg kg1 by the largest quantity of Lewisite given in.
hows the concentration that would result if all the arsenic remained in the sediments within the disposal site boundary. Very high concentrations would occur at the small circular sites in the Barents and Kara Seas. Sediment arsenic would increaseittle in the site in the St. Anna Trough because the site is so large. Increases at the White Sea site would be modest because less Lewisite is likely to have been disposed there than at the odier sites.
value is from Chapterther value* urc one-half and one-tenth of greatest value.mdeep.
'Increase tog kg' from background ofg kg' in ihe Raienis and Kara Seas andg kg* in the White Sea.
'Increase tog kg" from background ofg kg' in the Barents and Kara Sea andg kg' in ihe While Sea.
in parentheses is Ihe approximate length of the sides if area is square.
cosystem Effects
The potential exists lhal large areas of sediments could be contaminated al theg kg" benchmark for arsenic, which could produce effects on benthic organisms. The main effect would he to reduce or eliminate benthic organism biomass and reduce species diversity. Demersal organisms could also experience some loxic effects because of their close association with the sediments and reduction or loss of benthosood source. Contamination couldreater effect on early life stages, such as eggs and larvae, than on adults.
The ecosystem effects of sediment contamination is likely to be small in the White Sea and Ihc Kara Sea because of the very low biomass of benihos in the vicinity of the disposal sites and ihc likely small coupling of ihc benlhic community with ihe predominantly pelagic system, as discussed above for acute toxicity.
Siten the Barents Sea may have greater benthic biomasshan the other sites and is adjacent to shallow areas of high benlhic biomass between the sile and Novaya Zemlya. The nearby productive area could bc affected if arsenic from the site were spread to the east. Although current direction at ihe site has not been measured, it is likely that bottom currents would be to the north andt is likely that this is also the main flow direction at the bottom. Bottom water is formed during aThis water would flow downvlopc lo ihe northwest and toward ihe deep West Novaya Zemlya Trough and the Central Basin. Ii is unlikely dial any significant quantity of arsenic would he transported to the east.
otential for Bioaccumulation of Arsenic in Higher Trophic Ltftb
It is highly probable that the marine organisms associated wiih ihc areas of increased arsenic concentration in sediments contaminated by released Lewisite would have greater quantities ol arsenic in their tissues. This increase would he greatest in benlhic organisms, which arc directly and constantly exposed lo ihe contaminated sediments, and in demersal species, which are exposed to ihesc sediments and feed on contaminated benthic organisms. At ihe deep disposal sites, transfer of arsenic from benthic organisms to pelagic organisms is likely lo he very small because of ihc small contribution of the benihos lo the food web in these deep waters and the fact that arsenic does not hiomagnily in the food web. as discussed in.
The production of hpid-solublc arsenic compounds by phytoplankion inctcases the risk of bioaccumulation at higher levels in the food web. Phytoplankionarge quantity of lipids during Ihe spring and summer period of intense growth and these lipids are passed up the food web. as described in Chapterrsenic in this formigh potential to affect higher trophic levels.
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S. IMPACT-ON K(
risk ofin phytoplanktoo lipids iv low al ihe deep dinposal sites To be availablehyutplankuio. ihe arsenic must be mixed into ihe surfaceof water. As shown in Chapterhe plumes released from munitions on the bottom remain near the bottom. No strong mechanisms exist to mix the water column to the depths of the site. Also, the water column is stratified strongly in theuring the bloom period because melting ice lowers salinity and increasing insolation warms the water. It is highly unlikely thai significant quantities of arsenic could be mixed into the productive surface waters and he available lor phytoplankton uptake.
Seasonality oj Ecosystem Effects
The risks to the ecosystem of ihe regions of the sites vary somewhat over the year These risks would he reduced during the winter period of ice cover and increased during the warm month* when the ice cover is gone.
During Ihc cold period of kc cover, ihe risk* would be reduced for migratory species that leave the shelf regions. These include important commercial fish stocks such as Arcio- Norwegian cod. hemng. and haddock. Whales also are nol present during this penod. The potential for arsenic to be incorporated into phytoplankton lipid compounds would be very low during (his period because of greatly reduced solar insolation and low primary production.
The nsk is slightly greater during the warm period. Phytoplankton grow rapidly near (he surface. Migratory stocks of fish are present in large numbers and whales are present. Based on the bloom of phytoplankton productivity, thereigh rale of flow of material and energy in the surface waters. However, the interaction of the hcnihic community and ihewater with Ihe surface waters is generally small, as discussed in.
8.S ECOI.fHilC'M. EFFECTS AT SHAIJAW DISPOSAL SITE
Disposal Siteocated near Kolgucv Island in the southeastern Barents Sea.ifferent physicalcological-situation-than--the-deep disposal sites considered above. As can be seen in. this area of ihe Barents Sea, called the Pechora Sea, is shallow wiih water lesseep. Water depths in Siterco.
escribes the bent ho-pelagic food web lhat occurs in the shallow portions of the sludy region. The food web ai Sites likely to be of this type, although data specific to the structure of the biological communities in the Pechora Sea region was not found in the English language literature collected for this study. In the betriho-pclagic food web. much of the organic matter produced by the phytoplankton in the water columnhe bottom and is available as food to the benthic community. Because of this food source, the biomass of benthic organisms is greater in ihese shallow areas than in the deep waters, as can be seen in. In ihese shallow waters, the benthic biomass is also within the diving depths of the walrus and several species of sculs thai feed on benthic organisms
Sites close to Kolgucv Island, which is reported to have large populations of seals and seaIhese populations foiagc in ihe marine waters near their roosting and liauloul areas and are supported by the biological productivity of thesehe disposal site waters arc within the foraging range of birds and seals on the northern and western shores of ihe island.
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The Pechora Sea also supports an important commercial fishery, as described in. The benlhic community is important to this fishery, and bottom trawls are used extensivelyseihod of harvest.
It is clear, then, that the benthic community in shallow waters is an important component of the food web and is closely coupled to the productivity uf the overlying water column. In this situation, the potential threat posed by released agent that primarily affects the bottom community, as described in Chapterould bc great,
Effects of Mustard
As discussed for the deep water sites, it is possible for mustard to be presentiscous form on the sea floor somewhere on the disposal site for many years.g quantity of mustard exposed to seawater at the site would dissolve in less lhan one year (seeew mustard would constantly bc exposed as shells corroded at different rates, as discussed In. Benlhic organisms in contact with the mustard would be killed. However, the area occupied by exposed mustard at any one lime would be small compared to the area of the disposal sile. Theiefore. the number of benthic organisms killed by mustard wouldery small loss Io ihe food web and unlikely to have measurable effects.
Unlike the deep water sites, ingestion of or contact with mustard in the shallow water sitesore likely potential source of injury or death to seals feeding on theap produced byhows Kolguev Island waters as having abundant occunences of ringed, bearded, and Greenland seals. Although most seals feed predominantly on fish and oilier pelagic organisms in the walcr column, some hoitoin feeding takeshe bearded seal feeds primarily on bottomenlhic biomass ul the site is likely to be in ihe rangehe attractiveness of ihe disposal site for seal feeding is not known but is likely to be typical of the region.
Ihe magnitude of the musuud risk to seals is difficult to estimate, bui ts likely to be low even in these shallow water sites. This conclusion is based on several considerations. The number of mustard lumps exposed al any time should be small so lhat the rale of encounter is low. If seals are using sight during foraging, it is possible that they would avoid lumps alter the first encounter lhat results in an inilalion or injury. Also, no mention of unusual seal mortalities or injuries in this region were found in any of the fcnglish language literature reviewed during this assessment This suggests lhal no mortality or injury fiom mustard lumps occursthat it occurstw rate not noticed as unusual. Il is also possible that no mustard is preseni.
Ihc disposal site is within the range ol thehich feeds on benlhic organisms in water up ioeep.': Mollusksominant food organism of walrus" andajor component of Ihe benthic biomass in the region of the disposalo data was found to determine if walrus populations are present on nearby Kolguev Island, and the map of Malishov* does not show walrus preseni. Il i* possible, however, lhat wall us are preseni during the period when ice is advancing or retreating over ihe area As with seals ihc risk of injur, in death to walrus is difficult to estimate but is likely to be low for reasons similar to those for seals. Because of Ihc endangered status of walrus, any potential for effects would be of mjiiic concern.
S. IMI'ACTONKCONiSII MS
is possible for whale* lo be present in this disposal sue region. The main threat is contact with mustard when foraging near the bottom Ingestion of mustard ishreat because there arc no booom-fecding whales in the siudy region. The shallow Pechora Sea region is in the range of die belugahich occurs in lurgehis species feeds primarily on lish andnd is nol likely to come in contact wiih die bottom. Minke whales are common in ihc deeper waters lo the north and west" hut no data was found on ihcir occurrence in disposal site waters. This speciesaleen whale feeding on pelagic organisms and would not come in contact with the bottom. Humpback whales, which may come in contact with Ihc bottom during certain feedingo nol occur in ihe disposal sitet is likely lhal the threat ol injury to whales from cootactine musiard is very low.
Toxic Effects of lewisite. Tabun, and Sarin
As discussed in Chapterewisite. Tabun. and Sann released from leaking munition* would stay near or oo ihc bottom, and the arsenic released from Lewisite would eventually end upong-teim contaminant insediments Therefore, the acute and chronic toxicity would he exerted mainly on benthic communities and on any mobile organisms that swim near the bottom or feed on benlhic organisms. The importance of the benthic community in the food web of ihc disposal site region was discussed ut the beginning of.
The magnitude of the ecological effect at the disposal site would be largely determined by ihe amount of benlhic produciiviiy lost due to the toxicity of the agent plumes and the long-letm effects on productivity and species diversity due to arsenic contamination of the sedimenis. This issue must bc analyzed at two regional scales One scale is ihe region of Kolguev Island and the populations of birds and seals found there. The other region is iruf of the Pechora Sea. defined as the area withinepth contour.
At the greater agent release rales considered in Chapterhe benlhic organisms and demersal species would be eliminated or significantly reduced in numbers or in species diversity over the entire disposal site area for the period of agent release from all the munitions preseni (seche loss of this important benthic productivity ut the base of the food web would affect higher tiophic levels by reducing the carrying capacity of the region. Carrying capacity is the quantity of organisms al all irophic levels thut can bc sustainedegion by the biological production tint is available to support ihcm.
The effect oi the loss oi carrying capacity would be one of scale. The greatest effect would bc on the populations of birds and marine mammals on Kolguev Island near the sile because these populations are mostly supported by the marine environment and the disposal sitearge traction of the total area There would be less effect on ihe larger Pechora Sea region ecosystem because of its sue relative to the disposal sile. Mure details on these two regions follow.
- Kolguev Island Region
At this disposal site, the kiss or reduction of benthic biomass and productivity and demersal species wouldoderate lo large elfcci because the area of ihc sile is large compared to ihe area of the Kolguev Islandikely effect wouldeduction in the size of resident seal and marine bird populations on the northern and western shoies of Kolguev Island. These populations are supported by the biological productivity of the adjaccni marine ecosystems, which includes the disposal siteignificant loss of food resources in ihcir region of foraging reduces the carrying capacity for these populations.maller carrying capacity, population sizes would decline
it
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evel dial could be sustained by this reduced biological produclivily.
The magnitude of ihc effect in ihe Kolguev island region cannot be eslimuted easily with (he data available.s likely lhat the loss would be in proportion to the reduction in productivity in the area used by the populations most affected. This productivity is determined by both the local area and the much larger region of the Pechora Sea and the Barents Sea The loss ofikely to be less than die proportion of bottom area in ihc disposal site to the larger area supporting Ihe Kolguev Island populations Those species feeding directly on benthic and demersal organisms, such as bearded seals, would be afTecicdreater extent than species feeding on primarily pelagic species.
No data are available on ihe effect of the chemical agents on marine mammals, nxatiiinaiion of the plume characteristics analyzed inndicatesarge pan of tlie plume volume would be between the ENEC and EPEC levels (seciscussion of these toxicityt is possible, then, that injury rather than death would he the most likely effect. It is also possible thai veals and walrus could learn to avoid Ihe disposal site area because of irritation or injuries received and because ihe reduction ot elimination ol load sources mates the area unattractive for foraging
For maniK mammals, tlie probability of encountering toxic plumes at ihe disposal sue wouldunction of the area of the site near llic bottom covered by plumes on any day. This area is dependent on the agent release period, as shown in4f all the agenl is releasedive-year period, approximatelyercent of (he disposal site area is covered with plumes al the ENKC on any day.ifty-year release period, six percent of the area is covered by toxic plumes.
'echora Sea Region
The ecosystem effect on the larger Pechora Sea region would be small. The area of the disposalm', is modest compared to them' area of the Pechora Sea region. The likely hcnihic hi amass: at the Siteedium amount for the Barents Sea. but less than the high biomassm'found in the northern portiiMi of Ihe Pechora Sea region (seeoss or reduction of benthic biomass in the disposal site could be small when considering the total regional productivity of benthic communities.
the eflovt* on moiould he small. These populations are distributed over an area large in comparison to the dispersal site area
The distribution offish in the Pechora Sea legion is not well documented but data are available on Arcto-Norwegian aid. haddock, and polarhe first two species arc important components of the regional commercial fishery The polar cod spawns in the region, but is less important to the fishery.
Immature Arcto-Norwegian cod exist in large numbers in the fall and winter in tbe Pechora Sea region (see) Spawning takes place in the Norwegian Sea and tod arc widely distributed in the Barenis Sea. They feed predominantly on pelagic species. The loss of productivity of (he disposal site area could possibly affect the abundance of cod locally but is unlikely to have an cllcct on the large Barents Sea stock. Any effect would he indistinguishable from (he large year-to-year varialions in stock size that occur naturally.
Adult haddock occur in the Pechora Sea region in the summer and fall (icepawning takes place in the Norwegian Sea. Adult haddock feed predominantly on benthic and demersal species*The loss in the disposal site area for feeding by haddock could resultmall reduction of the stock size that
0
lMPACT.TENlS_
be .supported in the Pechora Sea region. The effect on the larger Barents Sea stock probably would be very small.
The polar cod spawns off tlie west coast of Novaya Zemlya in ihc fall and under the ice in the Pechora Sea region in January andggs are pelagic. Eggs and larvae lhat enler ihc contaminated water near the bottom in the disposal site would likely be killed. Tlie effect of this egg and larvae mortality on the regional stock is difficult to estimate, because the factors affecting stock size are not well known for this species. However, the effect is estimated to be small.
ecovery of Benthic and Demersal Communities
Toxic effects on benthic and demersal communities would not he permanent. The benthic habitat affected would noi be alteied permanently and recovery would occur once Ihc toxic plume is no longer present. Currents would bring pelagic larvae of benthic organisms lo the site from the surrounding bonom areas. Demersal species from nearby areas would move into the disposal area.
Long-Term Effects of Arsenic-Contaminated Sediments
Arsenicersistent contaminant from Lewisite thai would remain permanently in ihe sediments and be available for uptake by marine organisms. Because arsenic is potentially toxic, there could be chronic toxic effects from its long-term presence in the
or ibe deep disposal sites. This issueoncern at the shallow disposal site because the benthic community is important in the food web of the regional ecosystem.
Mosl of the Pechora Sea sediments are at natural background arsenicarge area of arsenic contamination exists in the northern Pechora Sea off the south coast of Novaya Zemlya (seeInc contaminated area estimated lo he greater thane kg' ise source of the arsenic is not known."
stimate of Arsenic Contamination of Sediments at Biological Benchmark Concentrations
was not found on ihe rate of recovery of benthic and demersal communities at shallow arctic shelf locations, such as the disposal site. It is likely that the rate would be slow, perhapsecade or two to recover to ihe original biomass and diversity. Several factors are important to the rate of recovery. Benthic organisms may grow slowly and have long individual lifespans and low turnoverany organisms brood their young rather than release pelagicispersal of brooded youngite would be slow. Pelagic larvae would colonire the site much faster. Recovery rate of demersal species would be dependent on the recovery of the henlhic community on which Ihcy Iced. As the benthic productivity is restored, the carrying capacity of ihc area would return to the previous level. Populations of birds and seals on Kolguev Island would return to previous sizes.
hows ihc area lhat could be contaminated at the biological benchmark arsenic concentrations and the concentrations lhat would result if all of the arsenic were spread only over the area of the disposal site.hows Ihe area contaminated at Ihegenchmark concentration if the largest quantity of Lewisite is present at the site. The areas were calculated as described in.8 also shows the sediment concentration of aisenicunction of areaange of arsenic quantities released. This area calculationniform distribution of arsenic mixed into sedimentepthm. To match the data inhe mixing depths must be reduced by an order of magnitude.
IT. "Relcicncc lit.Relererve 2.
<iie:itesr value is from Chapterihcr values arc one-half and onc-icnth of grcaicsieep
-Increase iog kg' from background ofg kg'.
'Increase tog kg' from background ofg kg'.
'Number in parentheses is the approximate length of the sides if urea is square.
'Sediment arsenic concentration thai would result if Ihe eniire quantity of arsenic released
remained wiih Ihe boundary of the disposal site and mixed into sedimentsepth
Include* background eonccniraiions ofg kg".
quantities of lewisite given are bounding values. The highest value0 tons is highly unlikely. It could only occur if all vesicant munitions dumped were filled with lewisite and they all were disposed of at Siteighly unlikely scenario.
cosystem Effects
As can be seen from, arsenic has the poteniial to contaminate large areas of sediments at theg kg1 benchmark. It is possible that the main effect would be to reduce or eliminate benthic organism biomass and species diversity. Demersal organisms could also experience some toxic effects because of their close association with the sediments and reduction or loss of benthosood source. Contamination couldreater effect on early life stages- such as eggs and larvae, than on adults.
The maximum area affected at theg kg' biological benchmark would be on the order of four times the size of the disposal site (seeince some effects could still occur in the concentration range betweeng kg andg kg', deleterious effects could take place over perhaps live times the area of the disposal site. If small quantities of arsenic were released, however, the deleterious zone would be only ihc size of the disposal site or less.
The likely effect in the deleterious zone would be to reduce the biomass of benthic and demersal organisms present. The diversity of species could also be reduced or changed because the effect of arsenic is likely to vary for different species.
Reduction or loss of benthic biomass would reduce the carrying capacity significantly in the Kolguev Island region, for similar reasons detailed above for toxicignificant loss of productivity over an area five times ihe size of the disposal site would probably resultarge effect on ihc population of seals and birds on Kolguev Island. The loss due to arsenic contamination would be very long term, lasting as long as the arsenic contamination remained in the biologically active zone of the topm of sediment. Since sediment deposition rates in the Barents Seamears, some effect could remain0 years.
The ecosystem effect on the larger Pechora Sea region could be small to moderate if the contamination0his area would be added tom! region already contaminated in the northern Pechora Sea. It is noted that no data arc available from this region to determine if benthic biomass and diversity has actually been affected. The total of the
K.MMKMS
areasew peiceni of (he area of Pechora scawalers withinsobath
8-SJ.3al Highrr Truphit Uvcli
Arsenic in sediments of the disposal site and surrounding area would he readily available for interaction with the food web of the region because of the importance of benthic organisms in this community. The risk ol bioaccumulalion of arsenic in higher trophic levels is modest, however, because arsenic docs not biomagnify in the food ueb and may not bioaccumulate much beyond the lowest trophic levels, a" discussed in. Bearded seals and walrus would be mosi exposed to arsenic contamination by feeding on benthic organisms, which can include ingesting contaminated sediments during feeding.
Arsenic in tissues of benthic organisms would increase significantly in ihc area of contamination, as observed in other arsenic-contaminated aquatic environments. The biomass al the site may be dominated by organisms thai filler ihe overlying water to obtain then-food (filler feeders) Fewer organisms may he present that directly ingest contaminated sediments or bottom organicilter feeders would have somewhat less exposure lo arsenic because they primarily would be ingesting material suspended in the water. However, rcsuspension of arsenic-con laminated material from the bottom inio the water may be frequent. Turbulence from strong surface winds can resuspend sediments during the icc-frcc period if strong density stratification in the surface water layer is not present. Sinking dense water formed when brine is rejected during ice formation can also impinge on the bottom with enough velocity to resuspend sediments
Ihe potential for body burden of arsenic in demersal fish and invertebrates would also increase significantly in the contaminated area. Demersal invertebrates, such as crabs and shrimp, lecd directly on benthic organisms, sediments, and organic matter. Demersal fish feed on benthic organisms or Other fish and invertebrates living on or near the bottom. Demersal fish, such as the flatfishes and skates, are common in thc.region and may be aliccied."
Walrus would he directly exposed lo arsenic through consumption of contaminated bcnlhic organisms and by incidentally ingesting contaminated sediments while feeding. If walrus occur in the region, they would experience some increase in arsenic body burden
Polar bears are not shown to be present on Kolguev Island, but arc shown to be present on Novayaears could have some access to the contaminated area near the disposal site during winter ice cover and spring kv melt but the exposure is likely lo be brief. Ringed seals, which feed mainly on fish, are the principal food source of polar bears, and this species is present in the Kolguev Island region in laigc numbers. The polar hear would only be exposed to arsenic indirectly thiough the food wen from eating contaminated seals. Because of the low bioaccumulalion of arsenic, polar bears would have low potential to increase their body burden of arsenic. Any bear exposure to arsenic could add to stress caused by high concentrations of chlorinated hydrocarbons that may exist currently."
It is possible lhat some food web transfer of arsenic could occur by incorporation into lipids in phytoplankton For this to occur, soluble inorganic arsenic would have lo be mixed into the surface phone layer while primary production is occurring. It is
JS
Vtapalc IWi{wikifit Horativ'i IX .Mo
possible iliat some arsenic could reach the surface layers during strong winds thai mix the entire water column and then could be available for phytoplankion uptake. The water column is likely lo stratify during ice melt, which is the period of greatest primary production. No data are available from Ihe sile or ils environs to determine the potential for water column mixing and arsenic transport to (he surface, so no estimate can be made of ihc magnitude of this arsenic transler mechanism. If il occurs at the site, arsenic-could be transferredigher irophic levels much more efficiently than by other mechanisms.
otential for Transport of Arsenic in Ice
Because the disposal site is shallow, it is possible dun arsenic could bc incorporated into ice during freezing. This can occur if sediments ate icsuspended while ice is forming over ihe contaminated area and by incorporation into anchor, slush, and frazil ice lhat forms in contaminated areas. Arsenic could then bc carried to other areas as ice moves in the region.
Rcsuspcnsion of sediments into Ihe water occurs in two ways. One is turbulence induced by strong winds that blow over the site while ice is forming. In the Bering Sea, wind turbulence has been measured to depths of. The second mechanism is by the rejection of brine during ice formation. The heavy water produced sinks and impinges ihc bottom. In shallow water, the impingement velocity can sometimes be great enough to resuspcud sediments.
Sediments can also bc incorporated into an overlying ice cover by two other mechanisms (hat can occur if the total waier column is less thannce the entire water column becomes slightly supercuolcd, small frazil ice crystals can nucleate throughout the column. Once formed they gradually float to ihc surface where they become incorporated in the overlying ice sheet. During their rise they scavenge any suspended particles that arce found in the water column.omewhat related process, supercooled water swept down from ihe ocean surface can feed the growth of ice crystals that nucleate on materialshe seafloor. Once ihese anchor ice crystal masses become large, their buoyancy is sufficient to lift materials direclly off the seafloor, ultimately transporting them to the overlying ice cover. Once incorporated in the ice masses al ihe sea surface, the potential exists for the sediment to be transported outside of the local region.
No data are available to determine if incorporation of sediments inlo ice occurs in the region of tlic disposal site, nor can an estimate be made of (he magnitude of transport if it occurs. However, ihc potential exists for these mechanisms to operate in the region.
Seasonality of Ecosystem Effects
The risk to components of the regional ecosystem would vary over ihc year. Risk to ice-associated species such as polar bears, walrus, and possibly seals could bc grealesl when ice is present because these species would be present in and adjacent to the disposal site. Risk to migratory species of birds, whales, and fish stocks would be much greater during the warm months when these populaiions are present in the Pechora Sea region. The potential to incorporate arsenic into phytoplankion lipids would be greatesl during the .spring and summer periods of the greatest primary production in surface waters.
8.6 ECONOMIC EFFECTS
Commercial fishing is an important economic activity in the Barents and While Seas, 'lherc are several threats to the commercial fishery from the presence of chemical munitions in the region. These include changing or reducing the size of the commercially important stocks, contaminating fish products rendering them unable to be sold in the marketplace, and closing areas to commercial fishing b; cause of the presence of munitions or the contamination of the area by agents or breakdown products.
rCnmtidi, K. Mf Dcwjiull mrf E.Sediment Eiponlee Haltingraual PMynya. Arei* Aliska. USA' An'k and Atamf
I.audi. and WFIW.raifejnn ol foiiauMt Oy Airtfc Sm Ice" Thr JVciierv/ifir Taufl EmimwmviUfc
MPACT ON ECOSYM IV
or Reduction of Fish Stocks
Commercial fish stocks in the regions of ihe deep sites arc pelagic species Such as capelin and Areto-Norwegian cod. It is likely that these stocks would not change or be reduced in size because of munitions at the sites. Contamination would be confined to benthic and demersal organisms as discussed in. Because benthic communities in contribute little to the food web. pelagic fish stocks are not likely to he altered significantly at the deep siles. In the region of shallow site,mall effect is likely on the commercially important species Arcio-Norwegian cod and haddock (see
of Fish Flesh byand Breakdown Products
Other than Arsenic
Concentrations of arsenic in commercially important fish in the Barents Sea are probably low althoughew measurements were found. Values in Barents Sea codpm lor musclepm in liver. Values for cod taken off Norway and in Oslofjord were reportedpm for muscle andpm for liver.
mostly on organisms in. on. or near the bottom are likely ioreater increase in arsenic in their bodies than pelagic species, which reside and feed mostly in the water column. Arsenic concentrations inemersal fish, were reported to he considerably greater than inelagic fish, for specimens taken in Norwegian waters."1
eep Disposal Sites
agents and their breakdown products could contaminate commercial fish slocks by bioaccumulalion or bioconccn(ration in the food web. prevailing or affecting the sale of fish flesh in the commercial market. As discussed in, the hinconccntralion potential of the chemical agents and their breakdown products is low. These contaminants are not likely to be present in commercial fish flesh in significant quantities.
Contamination of Fish Flesh by Arsenic
The analyses inndicates that the arsenic concentration in sediments in and near the disposal sites would increase from the release of arsenic lo the water. Tlie amount of arsenic in fish will increase in their tissue, and because arsenicuman carcinogen, the amount of arsenic in commercial list) products (flesh and oils) is of concern.
An arsenic standard in fish and lislteiy products, rangingopm. has been establishedumber ofn Europe, Finland and the United Kingdom have established limitspmpm. respectively.
At the deep disposal sites, contamination of commercial species with arsenic is not likely toignificani problem. Arsenic could increase in demersal fish, which interact with the arsenic-contaminated sediments and benthic organisms. These species, however, are not likely to be harvcsicd in significant numbers in the trawl fishery because bottom trawling is not used in the deep areas. Some transfer of arsenic to pelagic species could occur by transfer through the food web. The amount is likely to be small because of ihc small contribution of the bcnlhic community to the predominantly pelagic food web in these areas.
hallow Disposal Site
The shallow waters of ihe Pechora Sea region are fished extensively (seercto-Norwcgian cod and haddock constitute (he large majority of (he catch. Polar cod, plaice, and halibut are also harvested."
8.
. Cohntben. S. Fifk.iViriscn. Chemical fa/luiMnm ArAmn KtovtUdfS NlNA-fopiffMNorway.
wil Stfh.Anlien Otrrvitw ofCur/tnt
h; IMI'AflON IXOSVSIKMS
arsenic concentrations arc likely in commercial fish species near Site. The increase is likely lo be greatest in demersal species, such as haddock, plaice, and halibut. Some arsenic would be passed to Ihe pelagic fish, such as Ihc cods. The area with significantly increased arsenic concentrations could he several times the size oi the disposal site if large quantities ol'munitions containing lewisite were dumped there.
Pishing is discouraged within the disposal site, according to postings on Russian navigation chart. It is possible that contaminated fish could move outside the marked areas and be caught because trawling takes place in the vicinity of the site. Demersal, as well as pelagic species, are potential catches because of bottom trawling. It is likely that ihe area of arsenic-contaminated scdimcnls near the southern coast of Novaya Zemlya is also contributinghe amount of arsenic in commercial species in the legion.
It is difficult to quantify the increase in arsenic amounts lhat is likely lo occur in commercial species near the disposal site. However, it is probable that the body burdens in demersal species within the contaminated zone would exceedpm limit for arsenic established by the United Kingdom and it is likely that the Finnish limit ofpm could also be exceeded in many individual fish. It is possible that pelagic species that remain and feed in and near the contaminated area could also exceed both limits.
The economic effect of fish contaminated with arsenic would likely be insignificant under current conditions. Information was not found on the market distribution of fish caught in the Kolguev Island and Pechora Sea region, so it is not known if any of ihe caich could be barred from Finland and United Kingdom markets. If lhat occurs, the catch could be shifted to other European or world markets that do not have arsenic standards for fish. There could be some temporary economic effects while new markets are developed.
The economic effect could be large if, in the future, other national governments become concerned about arsenic contamination of fish from the icgion and impose bans on sales. Sales could also be reduced if consumers develop negative attitudes toward fish from the region because of die possibility of arsenic contamination.
Contamination of Commercial Fish Oils
Commercial fish oils could become contaminated with arsenic if prepared from species contaminated by aisenic in the shallow Pechora Sea. It is likely, however, lhat refining processes used in fish oil manufacturing can greatly reduce contaminant concentrations. For example, refining of menhaden oil reduces arsenic concentrations4 ppm to lessefining crude fish oil reduced DDT and PCB concentrations by two orders of magnitude* It is unlikely that there couldignificanl economic effeci on fish oil products.
Closure of Fishing Areas
Commercial fishing activities could he affected if areas were to be closed to fishing because either fish stocks are contaminated with hazardous materials or chemical munitions could be captured by fishing nets. Loss of fishing areas could substantially reduce the quantities of catch and increase fishing pressure on the remaining area.
The waters over ihe deep disposal areas are not currently closed to fishing. Because these areas are not currently productive for bottom trawling, the commercial fishery would experience no change in limiting the area for bottom trawling.
It is not likely that pelagic fish stocks in and near ihc deep sites would experience significant contamination from arsenic released to sediments at these sites. Il is unlikely that the waters in and around the disposal sites would be closed to fishing for health reasons.
Fishing i* currently discouraged in disposal Site IM according to pollings on Russian navigation chart. Chemical muniiions. if present on ihc scaOour. could cause the area in and around ihe disposal site to remain closed to fishing in thek- closure would need to continue at least until it could be determined that all agents had been released from the munitions. The lengdi of this period cannot be estimated wiih certainty becauseack of information on corrosion rates in arctic waters. Experience with mustard disposed in the Baltic Sea" and the Sea of Japan" indicates mustard munitions can last for many decades in cold marine environments.
8.7 EFFECTS ON OIL AND GAS
EXPLORATION AND EXPWITATION ACTIVITIES
The Barents and Kara Seas arc anas of active oil and gas exploration and oil production (seche presence of chemical munitions could increase COW or present the development of oil and gas resources if exploration and exploitation activities were to lake place in the disposal siles.
If resources were discovered in ihc disposal.. ii is possible that they could not he exploited il drilling could not be carried out from wilhin tlie site boundaries because of iheir extent. The use of directional drilling technology from locations outside ihe site boundaries could reachew kilometers inio the site area limiting access lo other portions of the siles. Access ios possible if conditions are appropriate for directional drilling because they are smaller.
If il were determined thai operations could lake place within the disposal sites, resource exploration and development costs would potentially be increased, (rinding muniiions and ensuring thai the area of interest is cleat would drive up costs Activities thai could result in contact with agents include some seismic techniques, exploratory drilling, developing production infrastructure, and pipclaying Costs in locale the presence of munitions could be small compared to ihe costs of operating in the regional environment. Costs to clear munitions before exploration ot exploitation activities take place could be potentially large.
8.8 THREAT TO HUMAN HEALTH AND SAFETY
Human health and safely is potentially al risk in several ways from (he presence of chemical munitions in the aictic marine environment. Viscous pieces of raw muslard or munitions containing chemical agent could be ensnared in the trawling nets of commercial fishing boats. There are similar threats to oil and gas exploration crews when they conduct activities thai coukl contact munitions on the bottom. Consumers of commercial fish products could ingest arsenic Indigenous peoples could be exposed to contaminated fish and mammals in their traditional diets or love traJidonal subsistence food sources because of contamination or reduced populations
Consumers of Fish
Consumption of arscnic-conuminated fish from the siudy region could potentially affect the health of consumers. Consuming arsenic in drinking water has been shown to be associated with skin cancerarge epidemiologicaln the butls of this study, inorganic arsenic has been classifieduman carcinogen by. Environmental Protection Agency.arcinogens are substances proven to be carcinogenic in humans
Consumers of fish products in those countries that currentlyiandard for maximum arsenic concentration in fish and fish products are protected against potential adverse health effects ofonsumers in other countries, including the Untied States, would he exposed lo arsenic -contaminated products because the arsenic content of fish products is
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nol regulated. The potential cancer risk lo these consumers is estimated below using the methods of human health risk assessment.
The slope factor" for calculation of cancer riskaily averaged lifetime dose of inorganic arsenic5 mghows the calculated cancer risk resulting from applying this slope factor in
ingestion or ingestion rates lhal have been deemed acceptable by organizations concerned with human health. The estimated normal intake of arsenic in food, for example, isg per day.'" which correspondsancer risk5 xThe World Health Organization hasolerable daily intake of arsenicg kg' body weighthich correspondsaily intakeerg per adultancer risk.. Food and Drug Administration hasolerancepm of arsenic in food. This concentrationcenarioaily intakeer adultms of such food is ingested. This corresponds to the highest regulated risk inf.
hows Ihc lifetime cancer risk from consuming fishopm of inorganic arsenic. Ihc concentrationpm is well within the naturally occurring concentration of arsenic in marine fish and shellfish. The concentration of total arsenic in fish, especially demersal species, could increase topm in Ihe areas of aisenic-contaminated sediments. The variables in addition to concentration thai affect
consumed per day and the fraction of total fish consumption that is contaminated. Consumption of forty grams per day ish percentile of fish consumption in Ihe Unitedhe consumptionrams per dayounds) is the maximum possible daily consumptionubsistence fisherman eating three meals of fish per day ofounds of fish per meal.
The lifetime cancer risk due lo consumption of fish containing total arsenicpm ranges' forh. consumption IOor the subsistence scenario. The risk forh. consumption is well within the range of
thipeieutiiic at lieu iiAiBiikv. ft* larucr Hie *lvpcvalue.yrc-alrr llie poitiKy.
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regulated or background scenarios shown in. The subsistence scenario risk is close to the risk Horn consuming food containing. Food and Drug Administration tolerance staudaid. It only half of the fish consumed arc conlaminalcd, the cancer risk is also halved. At the higher concentration ofpm. the risks are higher by an order of magnitude.
The risk values inre piobably overesiimates because the slope factor used in the calculations is for inorganic arsenic. Approximatelyercent of the arsenic in fish would be in an organic form" lhat is notrganic arsenic is not converted to inorganic forms by humans and is excreted unchanged inf only one percent of the total arsenic consumed in the calculations used is in ihc inorganic form, the risks would be reduced by two oiders of magnitude from those given in the table.
In addition, the slope factor used in the calculations assumes that the daily intake rate used in the calculation continuesifetime. If subsistence fishermen spend lesseventy-year lifetimerams of fish per day. ihe risk would be reduced proportionately. Similarly, if the subsistence food souicc was fish for only half of tlie year and meat, such as reindeer, was consumed during the other half of Ihe year, the cancer risk due to arsenic would be reduced by one-half.
If the risk calculated above is reduced by two oiders of magnitude because arsenic consumed is mostly organic in form, the increased risk to consumers eating fish quantities al ihc high end of ihe range for the United Stales is likely to be small lo modest The increased risk from consuming fish contaminated with arsenic atpm of total arsenic (len times the likely natural concentration) is In Ihe range of one0 to one. This is at the upper end of the range of increased risk usually acceptable to regulatory agencies concerned wiih human henlth. This estimate could be conservative because it is based on the assumption thai fifty io one hundred percent of the fish consumedcveniy-ycar lifetime is contaminated atpm.
A moderate risk exists for indigenous peoples consuming fish contaminated with arsenic atpmignificant portion of their diel. Increased risk is in ihe range of oneo onehe high end of ihis range is at the lower limit of risk considered of regulatory concern. regulatory agencies concerned with human health. The upper end of this rangeonservative estimate because il is based on consuming contaminated fish at al) mealseventy-year lifetime.
nd ICLowac; It*tuKC-lmiy. aod BirtogicalI0:TS-IIS
of Commercial Fish Oils
Exposure off fish oil products lo significant arsenic concentrations is likely to bc low. Refining of fish oils to produce the finished product for sale can reduce the concentration of metals by iwo orders ofaking il unlikely lhal consumers could receive significant doses of arsenic from these products.
and Safely of Fishing Boat Crews
Munitions containing agems or viscous pieces of raw musiaid can be captured during bottom trawling by commercial fishing boats, exposing boat crews to injury and dcaih when the nel is brought on board. Recovery of chemical munitions and injury and death of fishing boat crew members has been documented innd the Baltic Sea."*
No reports of chemical munitions caplured during commercial fishing operaiions in the siudy region have been foundearch of news sources, government reports, or technical literature. Several explanations exist thai could account for this. Munitions could have been dumped only in deep areas where bottom trawling is nol used. If munitions were dumped in shallow waters, the siles used could be in areas closed to fishing or are in areas with bottom characteristics thai are unsuitable for ihe use of boltom irawling gear. Ii is also possible that no chemical munitions have been dumped in regional waters and thai the reports reported inre not accurals
If chemical munitions are preseni in regional waters, fishing boat crews could bc exposed to injury or death in the future, under some conditions. Bottom trawling could be used al deep locations if changes in gear technology make this fishing method productive and profitable. Opening shallow areas currently closed to fishing would expose any munitions or agent still present.
Health and Safety of Oil anil Gas Resource Exploration and Exploitation Crews
The presence of chemical munitions could threaten the safely of crews involved in oil and gas exploration and exploitation activities within disposal sites although this risk is probably low. Any acliviiics lhal contacl Ihc bottom couldcontamimue equipmenl with an ageni. Seismic surveying crews are also at risk when using certain techniques. Drilling crews could bc exposed if agent contaminates drilling muds or drill strings, which are brought to the drilling platform. Crews installing production infrastructure are at risk from coniaminatcd conslruction equipmenl. Pipclaying crews installing gathering systems and trunk lines could be exposed to agent released to the water or contaminating equipment during trenching and pipclaying operations.
8.9 CUMULATIVE IMPACTS
A variety of past and current activities in the Barents. Kara, and White Seas have affected the marineny advetse environmental or economic cffecls resulting from Ihe presence of chemical munitions would add to these effects.
White Sea
Little data on the effects of past and current human activities on the White Sea was found in the English-language publications reviewed for this study. Some things, however, were identified as occurring in the region.
The White Sea is receiving some effluents from industrial activities associated with mining on the Kola Peninsula. These effects are occurring primarily in Kandalaksha Bay. Acid deposition, caused by atmospheric transport of emissions from the burning of
fossil fuels in Europe, is occurring in the region. Acidification of regional soils mayonsequence of (his deposition and may be causing die release of some metals from the soils into runoff into thepill0 of "thousands of tons" of rocket fuel into Dvina Bay from the Russian military base al Severodvinsk caused an enormous kilt of invertebrates, fish, and sealsarge area of Ihc bay. Fishing was'suspended by the local government during this period."
If munitions filled with Lewisite were dumped into the White Sea al disposal Site. the long-term effect would be an area of permanent arsenic contamination in the sediment of the deep basin. The size of this area would depend on die quantity of Lewisite disposed at the site but could bc several times the size of the disposal area.
Barents Sea
A variety of activities have affected the Barents Sea ecosystem. These include nuclear weapons testing in the atmosphere on Novaya Zemlya and in the offshore waters, disposal of liquid and solid radioactive materials, oil and gas exploration and production, and possible over-exploitation of the fishery. Large areas of benthic habitat may be damaged by bottom trawling in the shallow central and southern areas of (he Barents Sea allltough the magnitude of the damage is not known."
Benlhic productivity could be lost at une or both Barents Sea disposal sites from the toxicity of leaking chemical agents and breakdown pioducts and by deposition of arsenic in the sediments if munitions containing Lewisite were disposed of at these sites. The effect of toxic agent plumes on ihe benthos would be temporary but cnild lastecade or several decades. Any toss of pruductiviiy (torn contamination of sediments by arsenic would bc permanent in the lime scale of human activities.
Benthic productivity losses from munition disposal would be additive with ihc other activities that could temporarily and permanently affect benthic habilal and productivity. Large areas may have been damaged by bottom trawling. The magnitude of this damage is nol stated, but loss of some productivity would be likely. Oil and gas exploration and produclion activities have been modest to date, bin the potential exists for extensive activities in the future. Benthic systems would be affected by disposal of drilling muds and cuttings, discharge of produced waters, and installation uf gathering and trunk pipeline systems from areas of produclion.
Kara Sea
Little data on the c'fecis ol pasi and current human activities oa the Kara Sea was found in ihc English-language publications reviewed for this study. Disposal of radioactive material in fjords and hays on the cast coast of Novaya Zemlya and testing of nuclear weapons in the atmosphere on Novaya Zemlya may bc the main activities thai could affect the marine ecosystem. Arsenic contamination of sediment at the deep disposal stirs would he an additional effect in ihc near-shore region of Novaya Zemlya.
This chapter considers mo topics thai have been defeired in previous chapters, the highly toxic, third generation. CWas and the potential concern over munitions dumped from ships being buried in the sediments.
wasn isomer referred toas was developed later by the USSR.
Chemistrygents in thr Ocean Environment
hypothetical question concerning the environmental impact should some nation contemplate future arctic scan disposal of this agent. Also, one might wish lo consider ihe consequencesossible mistake having been made in the past resulting in ocean dumping or limited quanutiesgcnt
9J
In prior chapters of this study, it has been assumed that the dumped munitions lie on the seafloor. exposed to corrosion and damage by trawling. However, burial of CW munitions could perhaps occur, citheresult of impacting the sea floor at sufficient speed to directly bury in soft sediments oresult of sedimentation over Ihc years as ihe munitions lie on the seafloor.
V AGENTS
gents arc the most recently developed ol" ihe conventional nerve agents. They were discovered indepcndcntls by Ranaji Goshcm. ofnd Lars-Erik Tanunelin. of ihe Swedish Institute of Defense Research,hortly thereafter, ihc US. Armyyslematic investigation of this class of compounds at Kdgewood Arsenal andesult, VX
ethylpropylre members of the phosphorylthiocholine class Of compounds
VX was produced and stockpiled by the Unitedas was produced and stockpiled by the Soviet Union. VX is colorless and odorless Both VXas have the formulaand molecularhe Chemical Abstracts Service registry number for VXas the registry number.
One group gives hydrolysis rate conslanls lor VXercent)r'ercent) in distilled waterCJ Rate constantsr1 atr' aiave also been measuredCRale constants have beea measured atynthetic seawater solution ai several temperaturesC;r1C.
The rale constantunction of temperature atn seawater obeyed the following expression:
allahan. Bur. "Thrnd Murium'mi orVipluuKiilrxilaKt ui Dilute AiiucuutlIS7-ir.>
n hrX* with this expression, the nic constant it calculated as
r'. Thi* conespoodsalf-lifeears in seawatcr under conditions of this sludy;
VX is thus extremely long-lived in the ocean. For purposes of this sludy. the valueears will he used for the halt-lifeas.
The first step in the basic hydrolysis of VX is the attack of hydroxide on the phosphorous to form anwhich then enn decompose in one of two ways. In the first mode, the anion of diisopropy-laminocthancthiol is expelled to give the ethyl ester of methylphosphonic acid:
g
ch.
This reaction accounts foro SCLperccnt of VX hydrolysis. The remainder of VX. roughlyercent, hydrolyxcx via displacementhiophosphonate anionarbon atom.
The amounts of Uk compounds produced during the hydrolysis reaction are given in. The logvalue for VX* Of these products, only2 is known to have significant toxicity.2 is very long-lived: under comparableC. pH2 undergoesimes more slowly than VX. If the same is true under the conditions of this study.2 wouldalf-life of overyears.
This reaction accounts foroercent of VX hvdrolv&ii in distilledn the second, erboxide is expelled to give
The hydrolysis chemistry of theas is expected to he similar. Compounds produced during hydrolysis of theas are likely to include:
Methylphosphonothioicietliylamino)eihyl] ester (the analog of
H*CH,-lC
propanol
Meihylphosphoniccthylpropyl ester
iethylamino)eihancthiol
Meihylphosphonic acid
Toxicityas and Their Breakdown Products
X, values of VX and its major toxic breakdown product,, for various laboratory animals arc shown in. Comparison with the data inhows that VX is roughly twice as toxic in rabbits, and five limes as toxic in guinea pigs, as Sarin.
The major breakdown product.s roughly half as loxic as ihe parent compound VX. when compared ing kg' for2 comparedg kg' for VX. Thus, the degradation of VXalf-lifeears, will reduce the toxicity lo ihe marine environment byactor of two.
The acquatic toxicity of-VX-is-illustraied in
The most sensitive species, striped bass, has an LCg I'. Consistent with the methodology used for other agents,ulliplcro this number yields an ENEChile thisold lugher than the ENEC for Tabun and Sarin,esser loxicity, the use of thisenchmark for marine toxicity should consider two significant facts regarding VX. One is the fact that available data indicates that VX isold more toxic to mammalian species than Sarin or Tabun. Two is the fact that VX undergoes relatively slow hydrolysis,alf-lifeears,ompound lhat is only half as toxic to mammals and orders of magnitude more persistent than the parent compound.
Thisery different situation from the release of the other agents analyzed, whose more rapid hydrolysis reduces toxicity by several orders of magnitude.
wenty-Four, Values for VX in Aquatic Species'
Species
Crab
Perch
Bass
I1
. Rolirbuugh. -OiiJiilw<itCfttv* Si* II2IIH|:
"Gordon. IJ. Jfld L.7 TVeihvt.PvridMUum MMhaanulfooJte iP2S> In Ihc
aadry uf VX aadGO mihr Cai'ut tiland Pu Ana Miaetrxl Arsttul
XTENSIONS
which will place much more stringent limits a% seen below. Moreover, the principal hydrolysis product. EAtable and even more toxic than ihc agent. However,as and2 have small values. indicating link likelihood for adsorption onto particulates.
In advance of doing any estimates of dispersal, one has
extent
primarily by dilutionesult of tbe turbulent mixing processes generated by the prevailing currents. To gam some appreciation for the limits of toxicityas.hows the total volume (in km') of seawatcr that could be coniaminaied at the three benchmark concentrationsunction of the quantity (in kg) of agent.
No toxicity data are availableav It can be plausibly assumed from its structural homology to VX that the mechanism and potency of the toxicityas and its bicakdown pnxluets arc similar to VX, and that an ENECgould be appropriateas as well, 'llic remaining two benchmark levels. EPEC and ELEC. can be obtained in the same fashionfor ihe four agents previously considered (multiplication by factors of,hy Thus, the benchmark levels thai would be used in an of toxicity is analysis of the extentas marine toxicity, such as that carried out for other ugents in Chapterre given in.
should be appreciated that ihe values inre forV.Ras.bu> its major breakdown product.oxicity higher ihan the agentactor of two. However, with Ihe hair lifeas being more Ihan fivehe rale ol production of2 would be sufficiently low thai, lo first order, diiect toxicity will be driven by Ihc concentration of ihe agent.
Dispersal by Ocean Processes
as is released from munitions inio the sea. dilution through turbulent mixing, transport by ocean currents, and hydrolysis all will lake place, as seen in Chapterowever, in Ihc caseas. the combinationeiy long half-life and high toxicity suggest that wc must reexamine the previous conclusion that dispersalocal problem.
The first and most obvious conclusion to be drawn about dispersalas released into ihc ocean environment is thai hydrolysis lo benign compounds will notseful upper bound on ihc relevant tune scales. The half-lifeean means that after eighteen yean, approximatelyercent of the initial mass of agent will remain in ihe ocean. Such times arc comparable with those of general arctic circulation and suggest that the proMcm might be pan-arctic, this suggestion" ignores dilution iluough turbulent
It is only when quantities nn the order of kilotons arc considered that warer volumes approaching the volume of ihc While Sea. or an appreciable fraction of the Kara Sea. can be contammaled at ihe lowest coocentralHxi of interest. ENEC. Thus, their is no possibility that the cntue Arctic Ocean, or even ihe entirety of ihe Barents or Kara Seas, could become toxic to marine life even if al some futureas were dumped in kiloton quantitiesere were any reason to have concern over dumpingas in quantities greater ihan KKI.OOO metric ions in ihe White Sea. (hen gieatei than Hi percent of the water volume could reach ihc ENEC lor very long periods of time before hydrolysis or flushing into ihe Barents reduced the concennation.
Of course this docs not rule out contamination of volumes sufficiently large to pose significant environmentaluantityonsas could contaminate upm' of awwater If diluted to the level of significant biological effects. EPEC. In the southern Barents and Pechora Seas,ean water depth of less, this would encompass an area greaterm. There would certainly be significant direct biological effects from such contamination and because of the persistenceas. an unpad on the regional ecosystem could not easily be ruled out.
The forcgoiiig simplified view, while containing an important bound, ignores two important dimensions of ihe issue, one of which can be addressed in a
: Contaminated Volumes at Three Concentrations vs. Quantityas
fashion using the methods of Chapterhe linear extent of loxichy in plumes subjected lo transport by ocean currents will establish the spatial extern of slowly released agent. However, this spatially averaged view encompassed by the advective-diffusion equation docs not consider "pockets'" of higher concentration trapped in turbulent eddies which, because of the very long hydrolysis half-life, have the potential to be transported long distances before being smoothed by mixing and molecular diffusion. Addiessing this second concern lies beyond the scope of this study.
As we found in Chapterontamination generated by leaking munitions has concentrations lhat vary wiih two length scales, one in the horizontal and one in the vertical. These two key length scales are U = . and U =. where
nd K. are the horizontal and vertical dilTusiviiies that parameterize ihe average effects of turbulent mixing. Because of the long half-lifeas, these lengths.. are significantly longer than in the case of Tabun. This already suggests that the spatial scales ol"as problem would be much greater than ihe ones encountered previously in this study.
(1)
It was shown inhat Ihc spatially averaged concetitration, parameterized by the adveciive-diffusion equation. Ihe lengthlume atenerated by release of agents given approximately by:
x,-C <QV4(i sJrOC)
elease rateg day, ihe lengthlume of Sarin at ENEC was shown lo he approximately. Thus, ihe corresponding plume lengthas released al the same rale would bc largeractor of ten. the ratio of concentrations,as. At the release rateg day' the plume length at the ENEC would. Of course these dimensions only bound the ENEC region whereas most of the massong-lived compoundas is actually located outside Uie plume at much reduced concentrations. With the larger plume dimensionsas. relative to ihc other agents considered, and the long half-life, the extrapolation to the extent Of conlamiiialionite containing many munitions may not he done as simply as what has been done previously. Here, too, it is not at all clear that the "local view" adopted throughout this study isimple estimate of the contaminated sile volumes obtained, assuming thai leaking munitions were widely separated and subjected to the same uniform ocean current, is certainly suspect.
Since there is no reason to believeas has been dumped in arctic seas and because some elements of the methodology developed here for other agents is suspect when appliedas. it would nol be useful lo speculate on potential environmental effects. However, while ii is clear that while pan-arctic contamination resulting from dumpingas in kiloton quantities is unlikely, extensive regional effects could occuriner grained analysis than that conducted here would be needed to quantify ihe environmental impact.
9.2 BURIAL OF DUMPED MUNITIONS
It has been assumed in this study that most munitions dumped at the disposal sites did not significantly penetrate into the sedimenis upon impact and were not burled subsequently by natural sedimentation. In this section, this assumption is revisited based on an assessment of the likely sediment characteristics al the disposal sites, on estimates of the impaci velocity on the seafloor of palletized munitions during dumping and on natural rales of sedimentation in the Sludy region.
Packing at Time of Disposal
No information is available on how munitions were packed when they were disposed of in the Barents. Kara, and White Seas. It is highly likely, however, thai most munitions were packaged in groups on pallets, since this methodommon way of packing munitions for case of handling during storage, transport, and deployment to points of use. Ii is likely lhal very few munitions were disposed of as individual rounds, since handling of individual rounds would have been unsafe and very difficult logistically. given the volume of munitions lhat seem to have been disposed. (Seeherefore, since there are no reports of the disposal of chemical weapons in arctic seas by sinking loaded ships, and since dumping of individual rounds is impracticalarge scale, il will bc assumed here that Ihc preferred method was the dropping of palletized munitions overboard.
Velocity of Dumped Munitions
Palletized munitions dumped into the water at ihe disposal sites would acceleraieerminal sinking velocity well before reaching the bottom. The terminal velocity would be determined by Ihe mass and shape of the sinking object, with its resulting buoyancy and the drag resistance exerted on the object by seawater. Depending on the nature of the sediments and the terminal velocity of the objects, the munitions could become buried in ihe sediments upon impact.
The forces acting on an object immersed in an incompressible fluid arc the weight |W| of the object, the buoyant forcef lite fluid and the drag forceof the fluid on ihc object. At the terminal velocity (u)inking object, die sum of the forces acting in the downward direction will be balanced by the buoyancy and drag forces. In its simplest. +where= (unil weight of thevolume of the. where C. is the dimensionless drag ciwfficient, p, is the density of the fluid at specifieds the terminal velocity,s the frontal area of the sinking object-Graphical forms of analytical or quasi-analytical solutions for (lie drag coefficient of certain shapes can be found in various engineeringandhe drag coefficient is normally plotted against the
1 thtma Minddtdfr^Vwfc. NY
yg. ^EXThNSIONj^;
Sea .sediments in the deep basin are coveredhallow, very fine-grained, brown, clayey mud aboutm thick. Bedrock is exposed in some places. Ihc thinness of this layer means that munition pallets could not sink deeply into the sediments, even if the low impact velocity and firmness of ihe sediments did not prevent it.
Sediment al disposal sites in the Barents Sea is probably fairly firm because of the sand content.est of Novaya Zemlya is likely to be silty sand or sandy silt, which couldand content ofoercent. Sediment al disposuln ihe Barents Sea off Kolguev Island is sand or sandy silt, which would he very firm.
Sediment at disposaln the Kara Sea at the northern end of Novaya Zemlya is greaterercent sand and gravel, ranging up toercent near the southern end of the disposalhese sediments would be fairly firm.
Sediment at disposaln ihc liasl Novaya Zemlya Trough is silty. It is possible that pallets couldittle way into these sediments upon impact, but it is unlikely tliat they would be completely covered.
Munition Burial
Terminal velocities at the low end of Ihe range estimated inepresent the postulated munitions bundles or reclangular prisms with relatively high dragot streamlined, low drag coefficients were used to conservatively bound the velocity calculation. These coefficients in
resui
Overall, however, these velocities are relatively slow and the kinetic energy on impact would be equivalenton automobile crash test ofndph.
While the specific characteristics of the sediments at the disposal sites are not known. Ihe dominant sedimentation processes and high content of coarse terrigenous material suggests rather compact sediments at the disposal sites. This implies lhat ihe low eneigy impacts have limited potential for impact burial of the muniiions bundles.rovides estimated penetration depths for the postulated munitions bundles. The basic principle is that the energy of impact will be dissipated by the cohesive material on the ocean floor.'" The equation governing the energy transformation is given below: Another factor is that the sedimentation tales in the
where
V
Il ultimata I
A P
velocity
bearing capacity of sediment (based on dimensionless bearing capacity coefficients as described in reference) area (fmnlal area of falling object) specific weight of') penetration depth
A ami JH4 "ScJlmc*eep Area* ol ihe Northern Kara Seaerman. v.anx*ceanography of >ht Arctic Sea.New York. NY.
"Schenek. Hilhcn.S.o thttmChopracGraw-Hill. New York. NY.
study legion are variable but. generally, are very slow. For Ihc Barents Sea, Ihe rate is reported to bemn ihe central part of the White Sea, the location of, the rate of accumulation of the very fine grained, brown, clayey mudmears. On ihe western margin of ihe Kara Sea. in the Novaya Zemlya Trough, the sedimentation rale is cited asomThese rates are much too slow to buiy munitions pallets or single munitions on the sediment surface during the period of corrosion and subsequent iclcase of agent, which is likely to be on the order of twenty to fifty years.
. The FiKiiiirtMitoRcirfwMogclcr H..nviiwnwnuoi.
York. NY.
TO. FFNIMNC.S
objective of this study was toredible assessment of the potential for significant adverse impact on the environment arising from CW munitions dumped in arctic seas. In the view of theredible assessment required addressing all of ihe zcroth order processes involving agent release, seawater chemistry, physics of ocean dispersal, biological interactions, and the like. The intent was to quantify the magnitude of the effects of these processes on ecosystems. Moreover, given die nature of. Government request for this study, the intent was not to conduct an assessment of compliance. law or internaiional convention regarding ocean dumping of CW munitions.
Since we arc dealing with chemical munitions developed for military operations, il is obvious that once dumped into the sea. any CW agent leaking out is likely to have some level of adverse impact on the environment. The issue for this assessment was to quantify this impact to the degree possible and to determine its significance. The test for significance was laken to mean an effect large enough io have some potential importance for national security perhaps, for example, through impact on fish stocks, on human health and safely, on exploitation of natural resources, or on international relations.
To this point, the assessment has proceeded according to the logic in
Each chapter in this flow contains several levels of summary material which are not reproduced here. In the next section the primary results obtained throughout this lengthy analysis are recast in terms of answersumber of key questions that bear directly on the purposes for which this assessment was
i-ond lifted
10U FINDINGS
As mentioned above, the findings of this assessment are put forth as the answerscries of key questions.
s it probable lhat large quantities of CW munitions were dumped by the USSR in the arctic seas?
Yes. highly probable. Ocean dumping of CW muniiionsairly common internaiional practice during the Cold War era. All information available strongly suggests that ilie USSR extensively dumped CW munitionsariety of ocean areas, including antic waters.
In ihe linal years of World War II, chemical muniiions certainly were dumped at sea by Germany and Japan. In Ihc years immediately following [he war. i( is well-documenied lhal there was extensive ocean dumping by the Allied powers in the Baltic and in Japanese waters. Thereonsiderable, though poorly documented, history thioughoul the subsequent Cold War years of dumping of CW munitions at sea by-several nations, including the United States.
At the end of World War II. large ammunition depots were discovered in Germany containing mustard gas gienadcs and mustard gas. sneezing gas and tear gas bombs.6nX)ons of chemical munitions were dumpedepth ofn the Horn holm Basins, fifteen miles olfthc Danish island.) tons of chemical munitions, predominantly mustard gas and sneezing gas, were dumped in the Gotland basins off the coast of Sweden.
Details of dumping operations in Japanese waters were nol widely known2 when the Japanese Prime Ministerational inquiry to investigate the status of the chemical weapons disposed of in. Numerous accidents inndrompted the inquiry.
Open source reporting on the dumping of chemical agents and weapons in the arctic seas by ihc USSR during the Cold War years is ambiguous and incomplete. The major source has been Russian scientists, especially Lev Fcdcrov who has written several recent books on the subjects of CW weapons and their disposal. The open press has described alleged incidents in which obsolete Soviet chemical weapons, as well as German chemical munitions captured afier World War II. were dumped in the northern and far eastern seas surrounding Russia. In contrast to well-characterized campaigns of chemical weapons dumping in the Baltic Sea by the Allies in, reports of such dumping in the arclic regions by the USSR have never been confirmed officially.
Nol surprisingly, compiling and accurately documenting statistics on USSR dumping activities in the arctic seat would be difficult and would require the cooperation of ihc Russian government. However, the accumulation of sources reporting specific* of ocean dumping and the continuity with what had become common international practice during the Cold War, is eoovincing lhal such dumping did occur. Moreover, it extended over many years, and may have involved large quantitiesariety of CW agents.
s it known where and when this dumping may have occurred, what agents may have been dumped and in what quantities?
Little is known wiih any certainly. However, ir is highly probable lhal thousands of melric tons of munitions containing the CW agents lahun. Sarin, mustard, and Iswtxite were dumped in the While. Kara, and Barents Seas. Other agents may have been dumped as well, but evennown and it is very likely that, if such dumping occurred, the quantities were much smaller.
Identification of site* for this assessment was based upon the following:
Delineation of restricted or hazardous areas on Soviet and Russian navigation charts for the arctic seas of interest;
Dumping ureas .shown on maps prepated bynlishov of Ihe Murmansk Marine Biological lnsiilule iMMBI) of ihc Russian Academy of Sciences, in cooperation with the Norwegian Polar Research Institute and the Institute of Occannlogy of the Polish Academy of Sciences;
Recent writings of Russian scientists: and
Defense Mapping Agency maps.
The Barents Sea has two candidate locations for CW munitions dumping: one sile is west of Novaya Zemlya localedHO0'; ihe
second is north ol' Kolguev IslandN35'
In the Kara Sea. eight explosive anddumping areas arc identified atend of Novaya Zemlya. offin the region bounded byencompassing an area of
Two closely related dump sites have been identified in the While Sea. northeast of the Solovctsk Islands. Both sites are identified in DMA charts and inE. Many activities arc prohibited al these siles, including anchoring, bottom fishing, and undersea work, suggesting that there arc real hazards from dumped munitions.
5 open press report from Moscow indicated0 tons of mustard and Lewisite weie dumped in the White Sea during. Lacking any other quantitative reporting, this value has been used to represent the level of dumping in the White -Sea in the present sludy.
However, combined production of mustard and Lewisite in the Soviet Union15 is estimated to haveons. The0 Ions of mustard and Lcwisilc. is taken as the total quantity dumped in the Barents and Kara Seas, jointly or severally.
Reports in the open press on the dumping of Tabun in the arctic seas arc scarce and only anecdotal. There are descriptions of tlie capture of German production facilities for labun by ihc Soviet Army ai the end of World War II. Allied data indicated that the German facility had0 tons of Tabun. For purposes of this assessment, it was assumed that no more0 tons of Tabun were dumped in arctic seas. This is possibly loo high, if one lakes into accounl the German production only. It was taken as an upper hound for purposes of this study.
Sarin apparently was not produced successfully by the Soviets until ihe. It is generally understooderman production facility was under construction at the end of World War II and that the German equipment for its production, including pilot quaniitics, was caplured by the Soviet Army and transported to the Soviet Union after World War II. It is not known if stocks of German Sarin weapons were captured by the Soviet Army. For the present study, the assumption was made that no moreons of Sarin were dumped in ihe Russian arctic seas.
hat is the condition of the dump sites; how long alter dumping would the CW agents be contained in the muniiions?
Tliere is no information concerning the current eondiiioo of the probable antic CW dump sites, nor is there information concerning their past condition. There is only anecdotal and inferential support for the view that the period may be very long, even decades, over which chemical munitions could remain intact on the seafloor before corrosion of ihe casings allows the agents to be released into the sea. We cannot exclude the possibilityaige fraction of the munitions dumped in arctic seas could remain intact today, with any consequent impact on the ecosystems yet to occur.
2ompilation ol both medical records involving actual harm to fishermen, anecdotal Baltic data involving fishermen recovering CW weapons, and various incidents from Japan. It presumed that the greater numbers of yearly data points intudy than inludy are because the laiter involve incidents serious enough to have generated medical reports whereas the former only involve recovery of weapons debris.
The Ballic experience shows conclusively that if fishing, especially trawling, occurs at the dump sites, munitions on Ihe scafloor can be disturbed leading to harm lo fishermen and sometimes death.6hereotalatients suffering from mustard gas exposure in the Ballicotalere treated as ambulatory patients andere admitted to the hospital. In7here were Iwo reported deaths resultinguslard disposal
W Munitions Related Incidents
As recentlyncidcnls of fishermen recovering CW munitions debris were reported, though none apparently resulted in injury.
The Baltic experience clearly suggests that some munitions remain intact on the seafloor after fifty years. There is no evidence to suggestajor release of agents fmm the CW munitions dumped into arctic seas has already occurred. The coirosive disintegration period,is defined as the elapsed time after dumping and before corrosion begins to release agents from large numbers of munitions. The primary release period, T, is the lime period during which most of the munitions at any she could be expected to undergo corrosive disintegration. This release period was treated paramedical ly in this assessment,ounded by five and fifty years, as shown in
There is no information that exists to indicate what T, is, except for discovery of munitions on the seafloor of the Baltic after fifty years. Unlike the Baltic, there arc no widespread reports of fishermen in arctic seas encountering chemical weapons. This could bc because ol" ihe "Hazardous Dump Site" warnings on chaits have limited the scope of trawling activities at these sites and the munitions have laid undisturbed for decades. This study sheds no further light on the periodreferring only to Ihc empirical Baltic experience for insight.
nce CW agents begin to leak Into the sea, are any chemical reactions lhat may occur understood well enough to support reliable estimates of the quantity of toxic compounds that could be produced?
Yes- An understanding of the chemicalthat CW agents are likely to undergo are critical lo assessing their impact on the envimnnient. The chemistry of CW agents in the marine environment is dominated by hydrolysis, the reaction of the agents wiih wttier. The important reaction products have been identified and the rale constants determined.
The key features of the chemistry of CW agents in the murine environment are as follows:
HI. FINDINGS
is fairly soluble in water and hydrolyzesalf-life of forty hours. The principal toxic breakdown producttable cyanide compound. HCN;
Sarin is miscible, that is. it mixes in all proportions with water and hydrolyzesalf-life of sixteen hours into relativelyreaction products:
Dissolved mustard hydrolyzes relatively rapidly,alf-life of five hours. However, the persistence of muslard in the marine environment is controlled by the rate at which it dissolves. Dissolution is much slower than hydrolysis, allowing clumps of exposed mustard to persist in the sea for months, for kilogram quantities, or years for hundred kilogram quantities.
Lewisite is soluble in water and hydrolyzes veryn seconds. The initial hydrolysis products Of Lewisite are also very toxic and persist in seawater for months or longer.
The major toxic Lewisite reactionchlorocthenyl) arsonous acid and inorganic arsenic, appear in quantities of approximately
BO percent andercent, respectively, of Ihc mass of Lewisite. The half-lifechlorocthenyl) arsonous acid is several months, whereas the inorganic arscnicals arc stable.
hat is the toxicity of the CW agents and products to organisms in (he marine environment?
There is Hale information /tearing directly on the toxicity of the CW agents to marine species. However, therereat deal of information on toxicity to other organisms, which has been synthesized lo pwtluce estimates for three benchmark levels. Tliese levels are to be applied lo all marine organisms equally. Of the non-persistent agents. Tabun and Sarin are the most toxic. Of the persistent compoutuls, organicchlomvinyl)arsenOusydivlysis product of Lewisite, is the mosi toxic.
defined as die concentrationubstance which results in the death ofercent of the exposed organisms during the specified time interval, was die most useful measure in assessing the toxic effects of these chemicals in seawater. Tlie reported lethal dose fiftyalues, which
arc ihc dosesubsiance resultingeiceni uf the exposedihc specified lime interval, were alsoestimaie toxicitieswere
limited or not available. The values ofvary with ihe organism tested, reflecting ihe variation in scnsiliviiy of different species to different chemicals.
For the purpose ofoxic threshold for the compounds of concern, onc-tenih ol tbe lowest'. was selected as rhe concentration at which marine organisms would not experience acute toxicity. This value is identified as the estimated no effe'tifoncentratum or ENEC and is lo be understood as the highest concerAration which is unlikely to ptt*lucc observable biological effects. For the purpose of defining volumes lhat would show toxic effects of these chemicals, the ENEC was multiplied by len lo yield estimated pmbahle effects cimccnirallims. EPEC. and by one hundied to yield estimated lethal effects concentrations, ELEC.
Because of the sparsencss of studies of long-term non-lethal effects at low concentration, the benchmark levels established here arc considered more reliable at ELEC and EPEC levels than ai ENEC levels. Ikx simplicity and because data did not exist on those agents toetter analysis, these levels are taken io apply equally to all mannc species.
Tabun and Sarin arc ol approximately equal toxicity. They were both assigned an ENECg I'. mustard is orders of magnitude less toxic, wiih an ENECg I' and Lewisite has intermediate toxicity with an ENEC of
Cyanide and dimethylamine are breakdown products of Tahun and were assigned ENECg I'espectively.omponent of the Tahun lormulation. is present up toercent. Chleroberu'ene was assigned an ENEC
Most of the breakdown products of Sarin have toxicities six orders of magnitude less than Sarin. Fluoride is the only exception lo ihis and was assigned an ENfcCg I'.
Mustaid breakdown products are thiodyglycol, with an ENECMdMM with an ENEC0 pg I'.
LewiMicchJc*ovinyliarscnous acid, which was assigned an INK" of. the same ai the parent compound, lewisiic Inotganic arsenic is the ultimate degradation product of Lewisite, with an ENEC ofg I'.
nce CW agents leak oulingle munition, what Is Ihe extent of toxic concent rut inn, how long can this persist and how does il differ fori Mm- CW agents?
for the four types of CW agents considered estimates nerr made that show that contamination by leaking single CW munitions Millocal one. that is. one confined to small arras having dimensions OH the order of hundreds of melers or less. This conclusion was foundalid at all concentrations of any environmenutl concern. There is little possibility that ocean circulation could disperse toxic levels throughout the entire arctic, or even over the extent of Ihe regional sea. This does not mean tluit the extent of toxic contamination fnjm an enure dump site is limited tomall area (see Question
The rate of appearance of dissolved mustard is determined primarily by the sutfacc of the mass of mustard following the abrupt and complete corrosionunition casing. The total lifetimeg quantity is approximately ISOays, although quantities on the orderg, from homhs could persist up to Ihrce years after being completely exposed.
After the last of ihe mustard is dissolved, ihe remaining agent in solution hydroly/es rapidly and. within five in ten hydrolysis lifetimes or approximately twenty-five lo fifty hours, it can beeing completely eliminated from ihc environment.
Moreover, mustard, once il is released, can lead to concent rat ions ai loxic levels only in the immediate
HI. IIMllM.SAMIkHIONS
of ihe disintegrated munition,lume only tens of centimeter* in length and several centimeters thick. This is an upper bound.
The most plausible form of rclcusc of agents other than mustard is through pinholes formed by corrosion It is expected that once pinholes develop, the leaking of agent into the sea willrocess lasting days, even week* or months Once released, agents will cause toxic plumes that have their maximum extent on the seafloor. These plumes will have dimensions on the orderew hundred meters or less in the direction of theew tens of meters acioss ihe currentew meters thick. The volumes of contaminated scawatcr contained inlume can be expected to be no greaterew thousand cubic mcicrs and may be much less.
Plumes will persist for the lime period that CW agent is releasing from the munition, the slower the release the longer the period.ver, it also follows thai the slower ihe release, the smaller the plume. The maximum volumes olew thousand cubic meters, can occur only for release rates that wouldypical artillery shellay.
What is the extent and duration of toxic contamination over Hie ocean areas surrounding the arctic dump sites?
TTir- extent of taxtc contaminatiim af the dump sites will be tinuied to asmall fro* tioa of the area iff the dump sile itself andolume upew meters above the seafloor. In the worst case, lessractionercent of Ihe total area of the dump sile could be contaminated to ENEC levels and remain so for years However, this rould occur imly if all the muniiionspecific agent located at the site were to release an agentew year period. This periinl is viewed as being unrealixtieally short, possibly by an order of magnitude. At the shallow dump site in the southern Barents Seahere are xufficieni munitions estimated to have been dum/>ed to extend the cmuaminatiim of anentc throughout much of ihe water ,olumn.
If nil of the CW agentiven type dumped at the various sites were to be releasedingle five-year period, il was estimated that the volumes of water that could be contaminated to ihe ENEC level would bef ihe volumes of the seas in which ihe siles are located. Kor example, forn ihc White Sea. tlie volume of Kawaiet thai could be contaminated lo ENECive-year release of Tabun would bef the volume of the While Sea. The volumes at ENEC for ihc other thtee agents would be significantlyor the same five-year release period, the scafloor areas contaminated lo ENEC by dumped Tabun would bef the areas of (he associated seas, and significantly less for the other agents. For Tabun uln the White Sea, the scafloor area directly contaminated by loxic plumes could be as great ashirtieth of the site area. When, alter dumping, tbe five year period occurs is of no consequence to these conclusions With the assumptionelease it uniformly distnhutcd inelease over fifty veais raihcr than five years would reduce the foregoing valuesactor of fifty.
hat are the major potential threats to the arctic environment and to humans posed by the dumping or chemical weapons in arctic was?
The main threats to the marine ecosystems frwii tlie ivlease of chemical agents at the disposal sites occur from immediatecute toxicity of released agenl and associated breakdown products; long lent effects such at bioatxumulaiiim in the food neb: and the long-term contamination of sediments with arsenic contained in Lewisite.
Potential threats to human health and safety are Ihc consumption of fish contaminated with arsenic, the snaring of munitions and mustard lumps in irawling nets, and (he exposure of crews to agents during ml nnd gas drilling or during exploitation of seafloor mineral resources.
Economic threats could include the loss of commercial fish markets because of arsenic contamination and increased coos in exploring and
developing offshore oil and gas resources.
Effects from chemical munilions would be cumulative wiih ihe adverse effects caused by other activities in the regional marine environments, including industrial pollution.
What is the likelihood that there could be a
entire arctic ecosystem?
There is almost no possibilityajor catastrophe to the regional ecosystems, much less the entire attic environment, could occur as result of the release of chemical agents at the disposal sites. This conclusion should nol obscure the fact lhat sufficient CW agents were apparently dumped at the airtic sitesffect individual organisms, even in large numbers (see.
The maximum bottom area thai could be affected by acutely toxic plumes would bc much less than the area of the disposal site. The plumes would be present onlyew meters of the bottom. The worst-case effect would be the loss of benthic biomass and productivity in the disposal site areaeriod that couldewecovery period of perhaps ten to twenty years would take place because of the slow growth and long-lived nature of benlhic organisms in very cold arctic waters. Moreover, the sites are not located where biomass concentration is the greatest, so even if the extent of toxicity were to be much greater than our estimatesalamitous effect on the total biomass would be unlikely.
At the deeper sites, the effect of losing ihis produciiviiy on the local ecosystem would be small because of the limited contribution of the benthic community lo the predominantly pelagic food web waters deeper. Effects on marine mammals would be small. Walrus and seals, which can dive to those depths, would find ihe low benthic biomass to provide unattractive feeding areas. It is importantemember that tlw benchmark levels used in this study to define regions of toxicity are based on exposure times sufficiently long to enable mobilehe walrus, lo move out of ihc contaminated area.
Cataslrophic effects of direct toxicity are also highly unlikely at the shallow disposal site,n the southern Barents Sea. Ihc size of bird, walrus, and seal populations on the northern and western shores of Kolguev Island could be moderately and possibly significantly aiYectcd. Ihc loss of benthic productivityile area would reduce the carrying capacity of the marine region supporting these populations. However, effects on die larger Pechora Sea region would be small because the benthic area affected is small relative to the entire shallow water area of high biological productivity.
is the likelihood that dominantb* affectedevel that wouldviability of populations?
Thereery low likelihood that dominant regional stocks could be affected so as to imperil stock viability.
Because toxic concentrations are confined to the near-boitom region, benthic and demersal organisms would be Ihe main communities affected. However,mall portion of these communities would be affected and large unaffected areas would be availableource for recovery of larvae and juveniles. The major vertebrate and invertebrate populations arc distributed over regions very much larger than the disposal sites. The contribution of benthic communities al deep disposal sites to pelagic stocks is small. The loss of carrying capacity at ihc shallow site is small compared to the very large regions thai support the major stocks of invertebrates, fish, marine mammals, and birds but could be large for populations of seals and birds on Kolguev Island.
there be significant economic effects onfishery or on the developmentoil and gas resources?
Economic effects on the commercial fishery are likely to be small to nutderate.
III. HMJIMiS VMI Kl (iitvs
discussed above. Ihe effects of contamination on ihc viability of commercial fish slocks would be very small Moicovct. bollom trawling is currentlyarvest nwibod used at the deep disposal mm and fishing has been -uungly discouraged al ihc shallow disposal site. Some fish in the vicinity of the shallow disposal site ate likely lo see increased body burdens of arsenic.esult, the sale of fish harvested from this area couldbe-banned in Finland and Ihe United Kingdom, which ate the only countries in Ihe region thai have standards for the maximum arsenic concentration allowed in commercial fish products If othet countries become concerned about arsenic contamination and ban sales, the economic effect could be large. Sale of fish oils would not he affected because ihc refining process greatly reduces the conteni of contaminanis
The effecis on offshore oil and gas resource development would bc small if ihe munitions arc present only al the identified disposal sites. Presence of munitions would not prevenl. seismic profiling andof the resource wouldpoint" problem. Resources under ihe disposal sites could lie reached by directional drilling if drilling could not be earned out within ihc disposal sile. Pipelines required to gamer and bring ihc resource io shore could be routed around the disposal sites.
an human henllh and safety be adversely affected by direct contact wiih contaminanis released at (he disposal silcs?
y little chance lhal their could he significant and direct human contact with toxic coniomutatiun due to CW agents at locutums remote from the dumpt beaches where contamination was carried ashore by currents Commercial fishing and offshore drilling and pipe laying crews could be directly exposed to contact with chemical agents if these activities are carried out within the disposal sues.
Munitions with agents or solid lumps of musiard would likely bc capiured in trawling nets if bottom trawling occurs at these sites. Boat crews, ihen, would be at significant risk of injury or death when the nets arc brought on board, as had occurred for many years in the Baltic Sea and Japanese tin However, there is essentially no chance lhal dissolved agents or reaction products could be carried io remote shores in concentrations sufficient to directly affect humans having contact with thrsea: This conclusion isa consequence of the effects of turbulent mixing in diluting agents tu harmless concentrations over distances much less than the distances from dump siteseaches, us well as ihc effects of hydrolysis in reducing agents to compounds of much lower toxicity over limes much shorter than the time lo advect compounds io remote shores.
Drilling crews could be exposedhemical agents lhat contaminate drilling mud or drill sirings. which are materials and ilems that return io the drilling platform when drilling operations ure carried out. Pipe laying crews could be exposed lo agents brought to ihe waier surface on equipment used for pipeline construction. However, both of these arc "point problems' that would occur only in connection with activities on rhe seafloor ai the dump sites, if tins, indeed weic permitted.
an human health and safety be adversely affected by contaminants from the disposal silcs entering Ihc food web?
Fish in rhe vicinity of the shallow disposal site In the southern Harems Sen would likely have arsenic concentrations greater than naturally occurring background umounis for fish in ihe Harems Sea. although the polentuil effecis lomld be low The region "here this site is located ii an area of intense commercial fishing. Inorganic arsenicnnen carcinogen in humans However, up toenent of arsenic in fish tissue are in organic forms, which are not known to be carcinogenic.
The increased risk from consuming fish contaminated aipm of total arsenic (ten limes the natural concentration in fish) is in the ranee of oneo one. This is al ihe
upper end of Ihc range of increased risk usually acceptable. rcgulaiory agencies concerned with human health. This estimate could be conservative because it is based on the assumption thatercent of the fish consumedeventy year lifetime is contaminated atpm.
The risk to indigenous peoples consuming fish contaminated with arsenic atpmignificant portion of their diet could bc moderate. Increased risk is in Ihe range of oneo onehe upper end of this rangeonservative estimate because il is based on consuming contaminated fish at all mealseventy-year lifetime.
hat are the other activities affecting Ihe regional marine ecosystems lhat are cumulative with the effects of chemical agents and munitions?he likelihood that toxicity of chemical agents, even if insufficient to affect ecosystems or populations, could be the critical additional .stress on lop of existingcontamination and would produce large scale effects?
A variety of past and current activities in the Barents, Kara, and White Seas Itave adversely affected the marine environment. Any environmental or economic effects resulting front the presence of chemical munitions would certainly add to these effects. However, there is insufficient information concerning the. baseline burden of anthropogenic coiiiainiimiioii to allow quantifying the cumulative effects of contamination due to chemical warfare agents at the arctic dump sites.
The While Sea receives industrial and domesiic wastewater effluents from humanpill0 of thousands of tons of rocket fuel into Dvina Day from the Russian military base at Severodvinsk caused an enormous kill of invertebrates, fish, and sealsarge area of the bay. Acid deposition, caused by atmospheric transport of emissions from the burning of fossil fuels in Furopc. is also occurring in ihc region. Acidification of regional soils mayonsequence of this deposition and may be causing the release of some soil metals into runoff into the sea.
A vancty of activities have affected the Barents Sea ecosystem. These include nuclear weapons testing in the atmosphere on Novaya Zemlya and in Ihc offshore waters, disposal of liquid and solid radioactive materials, oil and gas exploration and produclion, and possible over-exploilation of theery large pioporlion of the area of benthic habiiat in the shallow central and southern areas of the Barents Sea may be damaged by bottom trawling, although the magnitude of the damage is not known. This claim of damage has been dispuicd.
In the Kara Sea, disposal of radioactive material in fjords and bays on the east coast of Novaya Zemlya and testing of nuclear weapons in Ihe atmosphere on Novaya Zemlya could have affected the marine ecosystem.
The main effect of chemical agent release would he Ihc loss of benthic productivity from toxic plumes and high arsenic concentrations in sediments. These effects would likely be additive lo other benthic disturbances roughly in proportion to ihe area affected. However, ii seems unlikely that the effects caused by the release of chemical agents alone would cause large-scale regional effects when added lo Uie effects of other human activities
IS. What would be the first indicationsarge-scale effect on the ecosystem or species populations?
Release of chemical agents at the disposal sites is highly unlikely to produce large-scale effects on populations or ecosystems of the region. However, first indications of suih an effect, would be high mortality or significant decreases hi fish populations that could not be readily explained by natural processes ar known detrimental human activity. Chemical agent effects on fish stocks may be difficult to distinguish from the large fluctuations in population size that occur naturally. Ofcientific sampling program to monitor water quality, sediment contamination.
Ml. FINDINGSIONS
fish catches, if carried amustained manner, would offer the first opportunities toeveloping problem.
hat is Ihe likelihood thai endangered species could be affected? Which endangered species are most susceptible? Could the numbers affected be large enough to affect the viability of populations?
the following animals known to live or capable of living in the region are cimsidered by russian souives lo be threatened or endangered: the polar bear, tlie atlantic walrus: the gray seal, the narwhal, the bowhead whale, the beluga whale, ihe harbor porpoise, and doll's porpoise. there is little data availablendicate the size of the populations or their degree of fragility ol or near any of ihe aivtic cw disposal siles.cientific assessment of the poteiaial damage from cw agents is difficult if not impossible. however, ii seems unlikely lliat these specks would be affected al the deep disposal sites, although there may be some risk of appreciable adveise effects at ihe shallow disposal silt:
At the four deeper sites, the near-bottom confinement of high concentrations of CW agents willignificant isolation of these endangered species front effects due to direct toxicity. On this basis, it would be expected that adverse consequences at the population level would not be significant unless these populations areighly fragile condition.
The Atlantic walrus has the greatest potential of any endangered species to be affected at the shallow site. This species feeds predominantly on benthic organisms and, thus, could be exposed lo toxic plumes and contaminated sediments. The site is in the historic range of this species, although data on its occurrence at this site was not found. The potential for effects on this species is likely to be small because the current occupied range of this species is large compared to the contaminated area. There is some risk to the Other marine mammals in entering the toxic plumes near the bottom while feeding in the water column.
agents or breakdown productsin the food weh? If so, what areon the ecosystem?
most chemical agents and breakdown products would not bioaccumulate in the food web. arsenicodest potential to bioaccumulate in the trophic levels most closely associated with arsenic-comammated sediments. some increase-would occur tn higher trophic levels. biamognificaiion resulting in high concentrations in high livphiv levels would not occur. signi/kanl effects on the ecosystem due lo arsenic bioaccumulalion are not likely. the potential exists, however, for economic effects on the commercial fishery, as discussed above.
large an area of the seafloor couldcontaminated b> thein lewisite and what are theecosystem effects?
arsenic in lewisite is released from munitions in organic forms. these compounds would continue to undergo reactions to inorganic forms iuul enter the naiural cycle of arsenic in the physical and biological environment of the region. the transport and fate processes for arsenic in the marine environment are noi well understood. however, ihere is sufficient arsenic in the lewisite dumped at the arctic silesllow contamination well above natural background levels over areas somewhat greater than those of the dump sites themselves.
The area of sediment affected atg kg1 of arsenic was estimated for several quantities of Lewisite in order to bound the problem. This is the concentration likely to have significant effects on benthic organisms. For Lewisite quantities at Barents and Kara Sea sites rangingons0 tons, the area affected wouldor Lewisite quantities at the White Sea site ranging0 tons, the area affected wouldhe likely effect of arsenic in sediments atgould be to reduce permanently benthic biomass and species diversity.
Ecosystem effects at the deep disposal sites would he small because of the small contribution of the benthic community to the dominant pelagic food web occurring in the deep waters ol the region.
Effects ai the shallow disposal site wouldeduction in carrying capacity of the Kolguev Island region and some contamination of the food web with arsenic, as discussed abuse The area at the site would add to an existing area ofm: contaminated with anenic in Ihe Pechora Sea off die southern coast of Novaya Zemlyaarge area is contaminated at Ibe disposal site, the total comaminaicd area could reachercent of the Pechora Sea region shallowern. Permanent loss of some bcnihic productivityegion of this size couldodest eff'eel on the carrying capacity of the Pechora Sea region.
It. Air there uncertainties lhat could significantly affect the answers to ihe foregoing questions and. if so. how might they he rrmored?
While there tire manv uncertainties that could alter details in this assessment, there aremall number that could significantly alter the lap-level findings. Tiiey include the following;
Total quantities of CW muniiions dumped inio arctic sea, could he.than hulicated here, with correspondingly reduced likelihood for impact.
hin! generation CW materials, suchgent, have been dumped mto arctic seas, tine could not easily exclude the possibility of emirtmmenial impactery much wider basis llum found here. Ii is nol believed thai dis/x'Sal of thirtl generation munitions has occurred.
The benchnmrk levels of toxicity developed in this study and applied uniformly lo all marine organisms contain significant uncertainty, both in the numbers ihemsehes and their universal applicabiluy- Only the use of what are believed to be highly ctmservattve levels for ENEC prevents this factor fntm driving the uncertainly equation.s believed thru there is little cltance that biological effects could be worse than portrayed here, but could lie very much less.
If bottom trawling does occur at the arctic CW dump siles. then die release oftuld be significantly accelerated Direct acute harm to individuals and to fish catches is possible.
There are several uncertainties important lo the analysis of environmental effects. These include the rate ol agent release from munitions, the transport and fate of arsenic in Lewisite, the number and type of munitions presenl at each site, and knowledge of the physical conditions and biological components and processes at each site and its vicinity.
The rate of release of an agenlorroded munition determines whether acuie toxicity is an issueile. At slow but plausible release rales, no toxic plume would be produced In ihis situation, there would be nom acute toxicity. Additional analysis of corrosion processes could provide some additional insight.
Tlie distance that arsenic is transported, before depositing in die sediments, determine* ihc concentration of arsenic contamination as docs the rale of hioiurbation. which mixes the aisenic into ihe top of ihe sediment column. More detailed modeling of arsenic transport could provide better definition of the area affected at each site, as would measured data.
Data specific lo the disposal sites and vicinity are needed in order to analyze sile-spccific effects. This daia includes the benthic community structure and biomass. the main components of the food web, ihe occurrence of endangered species, ihe trophic relations in the food web, the current speed and direction, and the sensitivity of species to the agent and breakdown product toxicity. Without site-specific data, conclusions were drawn based on general data for the large region or other areas in the arctic with environments that could be similar
MI KKC YH'ND.Vt IONS
CONCLUSIONS ANO RECOMMENOA TJONS
This study has foundery small likelihood that the past dumping of chemical weapons in arctic seas would causearge or widespread impact on the arctic environment that it would be of concern. national security, however broadly that is
conventional intelligence ptoblcm. Rather, it should be viewed largelycientific problem, one where the intelligence and Ihc scientific communities could collaborate.
Russian cooperation should he solicited toregarding past ocean dumping inSlates and Russian waters. Both However, local adverse impacts-mayout an oceanographic survey of one of the
but the uncertainties in this dimension of the assessment are large. The assessment carried out in this study is believed to bc conservative in the sense that any adverse environmental effects lhat may bc encountered are unlikely to bc larger than the estimates developed here.
The most important information gaps involve the location and condition of the dump sites, the types and amounts of munitions dumped, when they were dumped, and the toxicity of CW agents and reaction productsarine species. In addition, no reports were found similar to the various European studies of the Baltic tracking reports of fishermen encountering CW munitions.
It is our recommendation that. Government not approach this information gap solelyump sites considered in this assessment. That survey would include collection of water, sediment, biological samples, and underwater photography of the condition of the munitions. Advantage should be taken of any serendipitous opportunity thai arises in connectionlanned occanographic cruise in order to collect sediment, water samples, and even underwater photographs from one of the dump sites.
Inow-level ongoing effort might be put in place to monitor local fishing conditions and, especially, to collect any information regarding encounters with chemical weapons debris in fish catches. These efYoits should draw heavily from tlic Baltic experience, beginningomprehensive review of existing studies and site surveys of the various Baltic CW dump sites.
Original document.
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