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SE 9307/97
KEM Eseoti
No 2/98
received
JUN 2 9 m
O&T I
Arsenic in the aquatic environment
- speciation and biological effects
Exemption Substances Project

Lars Landner
Swedish Environmental Group
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Arsenic in the aquatic environment
- speciation and biological effects
ISSN: 0284-1185
Order No. 360 599
Printed by: Printgraf, Stockholm, March 1998
Publisher: Swedish National Chemicals Inspectorate©
Order address: P.O. Box 1384, S-171 27 Solna, Sweden
Telefax 46 8-735 52 29, e-mail infogruppen@kemi.se
Preface
This report is a contribution to EC Commission's undertaking to
review existing EC provisions on the substances for which Sweden
has been granted transitional provisions*. The provisions imply that
Sweden may maintain more stringent regulations on four substances
until the end of 1998. The report is one in a series providing further
facts to the Commission and Member states in the review process,
and is produced within the Exemption Substances Project at the
National Chemicals Inspectorate. Exempted substances are arsenic
and organotin compounds (Directive 89/677/EEC),
pentachlorophenol (91/171/EEC), cadmium (91/33 8/EEC), and
fertilizers with regard to their cadmium content (76/116/EEC).
The present report deals with speciation and biological effects of
arsenic in three types of aquatic environments - marin water,
estaurin or brackish-water and freshwater. The similarity between
arsenate and phosphate and the interference in phosphorylation
reactions is discussed. It is clear that in Scandinavian inland waters
the concentration of phosphorus is on average lower than in most
inland waters in continental Europe. However, in most inland waters
phosphorus is the limiting actor for phytoplancton development and
eutrofication, which means that there is a clear risk for detrimental
effects in the great majority of inland waters, also eutrophic waters.
The author alone is responsible for the contents of the report.
Solna,
Lars Gustafsson, Project Manager
Exemption Substances Project
*Act concerning the conditions of accession and the adjustments to
the Treaties on which the Union is founded (OJ 94/C241/08)
Table of Contents
SUMMARY 1
SAMMANFATTNING 6
I. INTRODUCTION 11
II. SPECIATION OF ARSENIC IN THE AQUATIC
ENVIRONMENT 13
1. Marine Environment 13
1.1 Inorganic arsenic species 13
1.2 Organic arsenic species 16
1.3 Biotransformation of arsenic - metabolic cycle 21
1.4 Sinks, mobilization and bioavailability of arsenic
species 28
1.5 Uptake in organisms and bioaccumulation 30
1.6 Natural factors affecting speciation and
bioavailability 30
2. Estuarine or Brackish Water Environment 32

2.1 Arsenic levels and speciation in water and
sediments 32
2.2 Arsenic levels and speciation in biota 39
2.3 Biotransformation of arsenic 41
species 43
bioavailability 51
3. Freshwater Environment (Lakes and Rivers) 53

3.1 Arsenic speciation in water and sediments 53
3.2 Arsenic levels and speciation in biota 57
3.3 Biotransformation of arsenic 58
species 60
bioavailability 67
4. Water Quality Characteristics in inland European

Water Bodies of Relevance for Arsenic
Speciation 68
III. EFFECTS OF VARIOUS ARSENIC SPECIES IN
THE AQUATIC ENVIRONMENT 71
1. Marine Environment 71
1.1 Effects on microorganisms 71
1.2 Effects on macroalgae and other plants 76
1.3 Effects on invertebrates 76
1.4 Effects on marine fish 77
1.5 Effects at the ecosystem level 78
1.6 Arsenic criteria for protection of marine life 80
2. Estaurine or Brackish Water Environment 81

2.2 Effects on macroalgae and other plants 82
2.4 Effects on estuarine fish 86
3. Freshwater Environment (Lakes and Rivers) 87

3.2 Effects on aquatic plants 90
3.4 Effects on freshwater fish 92
3.6 Arsenic criteria for protection of freshwater
aquatic life 93
4. Mechanisms of Toxicity - Interaction with

Phosphorus 94
IV. LITERATURE REFERENCES 96

SUMMARY
1. Predominant Arsenic Species in Aquatic

Environments
Arsenate is the predominant form of arsenic in marine waters, because it
is the thermo-dynamically most stable form in oxic waters. In addition to
arsenate, three other arsenic species are commonly encountered in
dissolved form in marine as well as brackish water: the reduced
incorganic form, arsenite, and two methylated species, methylarsonic
acid (MAA) and dimethylarsinic acid (DMAA). Other, more complex
organic forms of arsenic may be present as well, but their concentrations
in water are low, and they are not generally detected using conventional
analytical methods.
In reducing environments, such as anoxic water or sediments, arsenite is

the more stable inorganic arsenic species, but it is also found in aerobic
systems. However, the oxidation of arsenite to arsenate, in the presence
of oxygen, is usually rapid.
The rate of uptake of arsenate into autotrophs (phytoplankton, periphyton

and macroalgae) in the marine environment is relatively high. The
uptake is followed by a rapid transformation of arsenate to low-
molecular, methylated arsenic species, such as MAA and DMAA, which
are excreted back to the water phase, or - mainly - to complex organic
arsenic species, arseno-sugars (dimethylarsinylribosides and
trimethylarsonioribosides), which are stored inside the aquatic plants.
The arsenosugars are then transformed in several steps to arsenocholine
and arsenobetaine. Arsenobetaine is the predominant arsenic compound
found in marine animals, including fish.
The biogeochemistry of arsenic has been thoroughly studied and

described in the marine environment, and most of our present knowledge
about the metabolic transformations of arsenic in aquatic ecosystems has
been obtained from marine studies. However, also in estuarine or
brackish-water ecosystems, many similar studies have been conducted
and it is now well established that the principle pattern of arsenic
turnover is similar in these aquatic environments. Due to the usually
higher aquatic productivity of estuaries and land-locked seas, as
compared to the open ocean, the production and release by algae of
arsenite and DMAA is often much higher than in the open sea.
1
While arsenic speciation has been thoroughly studied in marine
ecosystems, and is also relatively well investigated in brackish-water
ecosystems, much less data on the exact speciation and transformation of
arsenic are available from freshwater ecosystems. In lakes and rivers, it
appears that pH and the content of humic substances, as well as the
existence of hydrous iron, manganese and aluminium oxides, play a
relatively more important role for the form of occurrence and bioavail
ability of arsenic. For example, in acid lakes with a high content of
humic material, arsenic will form stable complexes with humic acid,
which tend to increase the mobility of arsenic, but without increasing its
bioavailability.
Biomethylation of arsenic by freshwater organisms has been

experimentally proven, but the exact nature and the chemical structure of
the organic arsenic compounds present in the living cells of freshwater
organisms still have to be revealed. However, at least traces of the
comparatively non-toxic compound arsenobetaine have been positively
identified in freshwater fish. It has also been demonstrated that the
arsenic compounds that predominate in freshwater fish are trimethylated,
i.e. they have the same number of methyl groups as arsenobetaine.
At the present state of knowledge, it might be concluded that there seems

to be a greater variation between freshwater biological species in their
capacity to methylate arsenic and to synthesize complex organic arsenic
compounds, as compared to marine species.
2. Ecotoxicology of Arsenic in the Aquatic Environment

Elevated concentrations of arsenic in surface waters, due to geological
anomalies or to pollution from industrial or mining activities, will
generate a variety of complex interactions with biotic and abiotic factors
which may affect the transport, bioavailability, metabolism and
ecotoxicity of arsenic. Consequently, the ecotoxicity and hence the
environmental risk of arsenic may be extremely variable depending on
the natural factors existing in the water body being exposed to the
elevated arsenic concentrations.
As mentioned in the previous sections, the speciation of arsenic and the

conversions between the different chemical forms are to a large extent
determined by the biotic components of the ecosystem. Thus, the arsenic
being released (e g from rocks and minerals) to the aquatic system will
change its chemical form - and thereby its toxic properties - along its
2
route through the ecosystem in close relationship with the activity and
the metabolic competence of the organisms through which it passes.
Furthermore, one of the major inorganic arsenic species in water,
arsenate, is chemically so similar to phosphate that organisms may be
protected by phosphate from the toxicity of arsenate. It is well-known
that phosphate usually exerts an overall control of the production of
freshwater ecosystems, where it usually is the limiting nutrient.
Consequently, in a natural, oligotrophic freshwater ecosystem with low
phosphate levels, the introduction of even low concentrations of arsenate
will produce severe detrimental effects, while a naturally eutrophic
system with moderate to high phosphate levels is much more tolerant to
arsenate exposure.
From the above it is clear that aquatic organism such as algae

(phytoplankton, periphyton and macro-algae) which rely upon dissolved
phosphate at low concentrations in the water as their main source of
phosphorus are particularly vulnerable to arsenate. Interference with
phosphate uptake at the cell surface and in phosphorylation reactions
within the cell is generally thought to be the main mode of action of
arsenate. Uncoupling of oxidative and photo-phosphorylation will occur,
since in the presence of arsenate unstable ADP-arsenate is formed, thus
regenerating ADP and preventing the formation of ATP. Once within the
algal cell, arsenate seems to be transformed to arsenite, MAA, DMAA,
arsenosugars and arsenolipids. Whether these compounds are the
outcome of a toxic interference with metabolism or products of a
detoxification mechanism has not yet been fully clarified. At least
arsenite and MAA are (or can be) reduced to sulfhydryl active agents
capable of enzyme inhibition at the biochemical level.
Based on a great amount of experimental exposures of selected aquatic

organisms and communities to arsenate in microcosms and mesocosms
with the aim of providing data necessary for an advance hazard
assessment of arsenic in the aquatic environment, a set of "Lowest
Observed Effect Levels" (LOEL) were determined (Table IV:2.1).
It is obvious that, at low phosphorus levels in the water (and in the cells),
arsenate is by far the most ecotoxic among the arsenic species. The often
held view that arsenite is the most ecotoxic arsenic species must
therefore be strongly questioned, at least when it comes to toxicity to
algae. Although the microalgae were the most sensitive organisms
(among all organisms investigated) to arsenate exposure, it should be
noted that the macroalga Fucus vesiculosus was severely affected at an
3
arsenate concentration of 8 pg As/1, and the freshwater macrophyte
Lobelia dortmanna was inhibited at 5 pg As/1, but only when the
phosphate concentration was very low.
Generally, both the invertebrate and the vertebrate aquatic fauna seems
to be quite insensitive towards direct effects of arsenic, at least in
comparison to green plants. Available toxicity data from short- and long
term experiments, where animals have been exposed to arsenic
compounds dissolved in the water, do indicate that concentrations have
to exceed at least 80 pg As/1 before any direct toxic responses can be
observed. The lowest reported effect concentrations were in the range
86-100 pg As/1, and the three species, arsenite, arsenate and MAA all
fell in this range. However, indirect effects on herbivores and higher
trophic levels have been repeatedly reported as a result of e.g.
restructuring of the primary producer community caused by low levels of
arsenate exposure.
System Environment Parameter LOEL, figAs/l

affected
Phytoplankton Marine, P-limited Cell growth 2,3
Phytoplankton Freshwater, P- Total cell volume 4.4
limited
Macrophyte,Lobelia Freshwater Loss of leaves 5,0
Periphyton Brackish water, Photosynthesis 6,0
P-limited
Macroalga,Fucus Brackish water, Production 8,0
P-limited
Periphyton Marine, P-limited PICT 8-15
Periphyton Marine, P- Photosynth, 23
limited biomass
Table IV: 2.1 Lowest Observed Effect Levels (LOEL) of arsenate in
experimental chronic exposures ofselected organisms or communities.
The systems are arranged in order of increasing tolerance to arsenate.
The above evaluation resulted in the following conclusions:
* Arsenate is the ecotoxicologically most significant of the occurring

arsenic species, due to its similarity with phosphate and its ability to
interfere with phosphorylation reactions in energy metabolism.
* Algae and other green plants are the primary targets of arsenate
exposure, both in marine and freshwater, phosphorus-limited
4
environments, where extremely low levels of arsenate exposure may
cause detrimental effects.
* In Scandinavian inland waters, the concentration of phosphorus in the

water is on average lower than in most inland waters in continental
Europe. Even in large lakes e.g. in Sweden and Norway, the mean
concentration of total phosphorus is <10 pg/1. and in small forest
lakes, it is usually <5 pg P/I, while the average level in European
lakes is reported to be 40-50 pg P/1.
* The major effect of long-term arsenate exposure at the algal

community level is a fundamental restructuring of the community
such that sensitive algal species disappear, while more tolerant
species remain. Consequently, the main effect can be expressed as a
reduction in biological (and genetic) diversity. This restructuring of
algal communities may have cascading effects at higher trophic
levels, such as impairment of the fecundity and the reproduction of
herbivore communities.
* Arsenic is not biomagnified in the food chain, but occurs in many

different chemical forms that are not fully characterized from an
ecotoxicological point of view. However, the predominant arsenic
species in marine and brackish-water animals, including fish (and
possibly also in freshwater fish) is arsenobetaine, which has been
shown to have a relatively low toxicity, both to aquatic organisms and
to higher predators.
* The sediments act as a sinks of arsenic, and benthic organisms can be

exposed to high arsenic loads in contaminated environments. Reduced
species of arsenic are likely to affect biota in such environments, but
high levels of iron, manganese and humic material in the sediments
tend to reduce the availability and toxicity of arsenic to sediment
dwelling organisms.
SAMMANFATTNING
1. Dominerande forekomstformer av arsenik i akvatisk

miljo
Arsenat ar den dominerande forekomstformen av arsenik i havsvatten,
beroende pa att det ar den termodynamiskt mest stabila formen i syrerika
vatten. Forutom arsenat patraffas vanligen ytterligare tre former av lost
arsenik i havs- och brackvatten: den reducerade, oorganiska foreningen
arsenit och tva metylerade foreningar, metylarsonsyra (MAA) och
dimetylarsinsyra (DMAA). Andra, mera sammansatta organiska
arsenikforeningar kan aven forekomma, men deras halter i vatten ar laga
och de detekteras vanligen inte vid anvandning av konventionella
analysmetoder.
I reducerande miljo, t ex i syrefattiga vatten och i sediment, ar arsenit

den mest stabila oorganiska arsenikformen, och denna form kan aven
patraffas i aeroba system. Dock sker oxidationen av arsenit till arsenat
vanligen snabbt i narvaro av syre.
Upptagshastigheten av arsenat i autotrofa organismer (vaxtplankton,

perifyton och makroalger) i den marina miljon ar relativt hog.
Upptagningen i vaxtcellema foljs av en snabb omvandling av arsenat till
lagmolekylara, metylerade arsenikformer (MAA och/eller DMAA), vilka
ater utsondras till vattenfasen. Den huvudsakliga omvandlingsreaktionen
resulterar dock i komplexa, organiska arsenikformer, arseniksocker
(dimetylarsinylribosider och trimetylarso-nioribosider), vilka upplagras i
vattenvaxtemas celler. Arseniksockerforeningama omvandlas sedan
vidare i ekosystemet till bl a arsenokolin och arsenobetain. Arsenobetain
ar den dominerande arsenikforeningen som pavisats i marina djur,
inklusive fiskar.
Arsenikens biogeokemi har grundligt studerats och beskrivits i den

marina miljon och merparten av den befintliga kunskapen om arsenikens
metaboliska omvandlingar i akvatiska ekosystem har forvarvats genom
studier i marin miljo. Dock har manga liknande studier bedrivits i
estuarie- eller brackvatten-ekosystem och det ar numera val belagt att det
huvudsakliga monstret i arsenikens naturliga omsattning ar likartat i
dessa vattenmiljoer i forhallande till rent marina miljoer. Emellertid
leder den vanligen hogre akvatiska produktionen i estuarier och kusthav
till att savSl algemas bildning som deras utsondring av arsenit och
DMAA ofta ar betydligt hogre i dessa miljoer an i det oppna havet.
6
Medan arsenikens forekomstformer och omvandlingar ar grundligt
studerade i marina eko-system, och aven relativt val undersokta i
brackvatten-ekosystem, sa ar tillgangen pa data rorande arsenikens
exakta forekomstformer och dess omvandlingar i sotvattensystem
betydligt mindre. I sjoar och vattendrag verkar pH-vardet och innehallet
av humusamnen, liksom fbrekomsten av hydratiserade jam-, mangan-
och aluminiumoxider, spela en relativt sett mera betydelsefull roll for
arsenikens forekomstform och biotillganglighet. Till exempel i sura sjoar
med hog humushalt bildar arsenik stabila komplex med humussyra,
vilket tenderar till att oka arsenikens mobilitet, dock utan att oka dess
biotillganglighet.
Biometylering av arsenik har experimentellt visats kunna utforas av

sotvattenorganismer, men den exakta arten och den kemiska strukturen
av de organiska arsenikforeningar som fore-kommer i cellema hos
sotvattenorganismer aterstar att klarlagga. Dock har atminstone spar av
den relativt otoxiska foreningen arsenobetain identifierats i fisk fran
sotvattenmiljo. Det har ocksa visats att de arsenikforeningar som
dominerar i flera sotvattenfiskar ar trimetylerade, d v s de har samma
antal metylgrupper som arsenobetain.
Pa nuvarande kunskapsniva kan slutsatsen dras att det verkar finnas en

storre variation mellan olika biologiska arter i sotvatten vad galler deras
kapacitet att metylera arsenik och att syntetisera komplexa organiska
arsenikforeningar, jamfort med vad som galler for marina arter.
2. Arsenikens ekotoxikologi i akvatisk miljo

Forhojda koncentrationer av arsenik i sjoar, vattendrag och kustvatten,
till fdljd av geologiska anomalier eller kontaminering fran industri- eller
gruvverksamhet, kan ge upphov till en mangfald komplexa samspel med
biotiska och abiotiska faktorer som kan paverka arsenikens transport,
biotillganglighet, metabolism och ekotoxicitet. Foljaktligen kan
arsenikens ekotoxicitet och darmed dess miljdrisk vara extremt variabel
beroende pa de naturliga faktorer som specifikt rader i den vattenmiljd
dar de forhojda arsenikkoncentrationema upptrader.
Som namnts tidigare, bestams arsenikens forekomstformer, liksom

omvandlingama mellan dessa, i hog grad av de biotiska komponentema i
ekosystemet. Saledes kommer den arsenik som introduceras (t ex fran
berggrunden) till det akvatiska systemet att andra sin kemiska form - och
darmed sina toxiska egenskaper - langs sin vag genom ekosystemet, i
7
hog grad beroende pa aktiviteten och den metaboliska formagan hos de
organismer genom vilka amnet passerar. Dessutom ar den viktigaste
oorganiska forekomstformen i vatten, arsenat, kemiskt sa lik fosfat att
organismema kan skyddas av fosfat fran arsenats toxicitet. Det ar valkant
att fosfat vanligen utovar en overgripande kontroll av produktionen i
sotvatten-ekosystem, dar det ofta utgor det begransande makronarings-
amnet. I ett naturligt, oligotroft sotvatten-ekosystem med laga fosfat-
nivaer kan foljaktligen tillforsel redan av laga arsenatkoncentrationer
resultera i kraftiga negativa effekter, medan naturligt eutrofa system med
moderata till hdga fosfatnivaer vanligen ar mycket mera okansliga for
arsenat-exponering.
Utiffan det ovanstaende ar det uppenbart att akvatiska organismer som

alger (fytoplankton, perifyton och makroalger), vilka ar beroende av lost
fosfat i laga koncentrationer i vattnet for sin huvudsakliga fosforfor-
sorjning, ar sarskilt kansliga mot arsenat. Stoming av fosfatupptagningen
vid cellvaggen och av fosforyleringsreaktionema inuti cellen anses
vanligen vara arsenatens viktigaste verkningsmekanism. Frikoppling av
den oxidativa fosforyleringen och/eller av foto-fosforyleringen kan aga
rum, eftersom instabil ADP-arsenat bildas i narvaro av arsenat, vari-
genom ADP regenereras och bildningen av ATP forhindras. Sedan
arsenat tagits upp av algcellen, reduceras foreningen till arsenit och
metyleras till MAA och/eller DMAA eller byggs in i mera komplexa
molekyler som arseniksocker och arseniklipider. Huruvida dessa
fbreningar ar resultatet av en toxisk paverkan pa cellmetabolismen eller
produkter av en avgiftningsmekanism har annu inte blivit fullstandigt
klarlagt. Atminstone arsenit och MAA kan reduceras till sulfhydryl-
aktiva amnen som har formagan att biokemiskt inhibera enzymer.
Baserat pa ett stort antal experimentella studier, dar utvalda akvatiska

organismer och samhallen har exponerats for arsenat i mikrokosmer och
mesokosmer med syftet att generera data som ar nddvandiga for en
avancerad riskanalys av arsenik i akvatisk miljo, har en lista over
"Lagsta Observerade Effekt-Nivaer" tagits ffam (Tabell 1).
Det ar uppenbart att arsenat ar den klart mest ekotoxiska arsenikformen

vid laga fosfornivaer i vattnet (och i cellema). Den ofta framforda
asikten att arsenit ar den mest toxiska fbrekomst-formen av arsenik
maste darfor starkt ifragasattas, atminstone nar det galler toxicitet mot
alger. Fastan mikroalger visade sig vara de kansligaste organismema
(bland alia testade organismer) mot arsenatexponering, bbr det noteras
att makroalgen Fucus vesiculosus (blastang) paverkades kraftigt vid en
8
arsenatkoncentration om 8 pg As/1, och sotvattenmakrofyten Lobelia
dortmanna (notblomster) inhiberades vid 5 pg As/1, men endast nar
fosfatkoncentrationen var mycket lag.
Generellt sett forefaller bade de akvatiska ryggradslosa och ryggrads-

djuren vara relativt okansliga mot arsenikexponering, atminstone i
jamfbrelse med grona vaxter. Tillgangliga toxicitetsdata fran saval
korttids- som langtidsexperiment, dar djuren bar exponerats for arsenik-
foreningar losta i vattnet, indikerar att koncentrationema maste over-
skrida atminstone 80 pg As/1 innan nagon direkt toxisk respons kan
observeras. De lagsta rapporterade effektkoncentra-tionema lag i inter-
vallet 86-100 pg As/1. Alla tre forekomstformema, arsenat, arsenit och
MAA, foil inom detta koncentrationsintervall. Emellertid har indirekta
effekter pa herbivorer och hogre trofiska nivaer flerfaldiga ganger
rapporterats som ett resultat av t ex omstrukturering av primarproducent-
samhallet, fbrorsakad av laga nivaer av arsenatexponering.
System Miljd Matparameter Effektniva,

pgAs/l
Fytoplankton Marin, P-begransad Celltillvaxt 2,3
Fytoplankton Sotvatten, P- Total cellvolym 4,4
begrdnsad
Makrofyt, Lobelia Sotvatten Bladforlust 5,0
Perifyton Brackvatten, P- Fotosyntes 6,0
begrdnsad
Makroalg, Fucus Brackvatten, P- Produktion 8,0
begransad
Perifyton Marin, P-begransad PICT 8-15
Perifyton Marin, P-begransad Fotosyntes, 23
biomassa
Tabell 1. Lagsta Observerade Effekt-Nivaer for arsenat vid
experimented, kronisk exponering av ndgra utvalda organismer och
samhaden. Malorganismerna dr listade i enlighet med okande tolerans
mot arsenat.
(PICT = Pollution-Induced Community Tolerance)
9
Utvarderingen leder till foljande slutsatser:
* Arsenat ar den ekotoxikologiskt mest betydelsefulla av arsenikens

forekomstformer i akvatisk miljd, pa grand av dess likhet med fosfat
och dess formaga att interferera med fosforyleringsreaktioner i
energimetabolismen.
* Alger och andra grona vaxter ar de primara malorganismema for

arsenatexponering, bade i marina och sdtvattenmiljoer som ar
fosforbegransade, dar mycket laga nivaer av arsenatexponering kan
framkalla skadliga effekter.
* I Skandinaviska inlandsvatten ar koncentrationen av fosfor i vattnet i

genomsnitt lagre an i de fiesta inlandsvatten i kontinentala Europa.
Aven i de stora sjoama i t ex Sverige och Norge ar medelkon-
centrationen av totalfosfor <10 pg/1, och i sma skogssjoar ar den
vanligen <5 pg P/1, medan medelnivan i sjoar i Europa ligger omkring
40-50 pg P/1.
* Den huvudsakliga effekten av langtidsexponering for arsenat pa

algsamhallesnivan ax en fundamental omstrakturering av samhallet,
sa att kansliga algarter forsvinner och endast toleranta arter kvarblir.
Saledes kan huvudeffekten uttryckas som en reduktion i biologisk
(och genetisk) diversitet. Omstruktureringen av algsamhallena kan ha
foljdeffekter pa hdgre trofinivaer, sasom nedsattning av fekunditeten
och fortplantningen hos vissa arter i vaxtatarsamhallet, pa grand av
"felaktig" naringstatus hos kvarvarande algarter.
* Arsenik biomagnifieras inte i naringskedjan, men forekommer i

manga olika kemiska former, vilka inte alia ar fullt karakteriserade
fran ekotoxisk synpunkt. Dock ar den dominerande organiska
arsenikformen i marina och brackvattendjur, och troligen ocksa i
sotvattenfisk, arsenobetain, som bar visats besitta en relativt lag
toxicitet, bade gentemot akvatiska organismer och konsumenter pa
hdgre trofisk niva.
* Sedimenten fungerar som en "sink" for arsenik, och bentiska

organismer kan exponeras for hoga arseniknivaer i kontaminerade
miljoer. Reducerade arsenikformer kan paverka biota i sedimenten,
men riklig forekomst av jam, mangan och humusamnen i dessa
miljoer tenderar att reducera tillgangligheten och toxiciteten av
arsenik gentemot sedimentlevande organismer.
10
I. INTRODUCTION
A very great number of review articles and books have been devoted to
arsenic in the environment and, particularly, to discussions about arsenic
speciation and transformation in the environment. Most of these reviews
were published in the 1970s and 1980s, and are listed by Maeda (1994).
As pointed out by this author, there seems to a significant difference in
the total concentration of arsenic, between terrestrial and freshwater
organisms on one hand and marine organisms on the other. Terrestrial
organisms in uncontaminated environments rarely contain more than 1
pg As/g dry weight (d.w.), whereas marine organisms contain from
several pg As/g to more than 100 pg As/g (Lunde, 1977, Francesconi
and Edmonds, 1993). Also in unpolluted rivers, ponds and lakes, the
arsenic concentrations in organisms are generally low, but are greatly
affected by local conditions.
The first reports of arsenic in marine organisms were published already

in the beginning of the century (e g Bertrand, 1902), and later work (e g
Jones, 1922; Cox, 1925; Chapman, 1926) established that marine
organisms naturally contain high levels of arsenic. These observations
prompted an upsurge of research on the biogeochemical cycling of
arsenic in the marine environment, in particular after the first
identification, in 1977, of the precise chemical form of one of the
organoarsenic compounds found in a marine animal. It was in this year,
Edmonds et al. (1977) identified arsenobetaine in the western rock
lobster (Panulirus cygnus).
Subsequent work has identified the presence of a large array of other

organic arsenic compounds in marine organisms, and the complex chain
of biotransformations of arsenic as well as its complete metabolic cycle
in marine ecosystems has been fairly well described. However, relatively
few studies have been directed to the full identification of chemical
species of arsenic in freshwater organisms and the arsenic transforma
tions along the freshwater food chain have only rarely been reported
(Maeda, 1994). The result is that, still today, arsenic compounds in the
marine environment are described in many books and reviews, but those
in the freshwater environment are usually reported without any details on
the exact identity of the chemical forms, and - even so - they are
discussed only in few publications. Also with regard to the brackish-
water or estaurine aquatic environment, the existing knowledge about
arsenic speciation and biotransformation in various organisms is less
11
developed than for the marine ecosystem, although more data are
available from estuarine waters than from inland waters.
This general lack of comprehensive information on arsenic speciation in

freshwater environ-ments makes the assessment of biological effects
more difficult than in the case of marine environments. It is evident that
a correct evaluation of the environmental risk associated with arsenic
exposure requires good knowledge about the precise chemical form of
arsenic to which different organisms are exposed during different stages
of their life cycles. Fortunately, a relatively large number of studies have
been devoted to the determination of the dissolved arsenic species,
occurring in the water column, both in brackish-water and in freshwater.
This allows at least an assessment of the biological effects caused by
direct exposure via the water to the different, soluble arsenic forms.
In preparing the present overview of arsenic species and effects in the

aquatic environment, it was considered most logical to start the
presentation of the natural cycling of arsenic in the field where the most
comprehensive data base exists. Therefore, a description of the
speciation and biotransformations of arsenic in the marine environment
.will be used as a background for the subsequent discussion of arsenic in
brackish-water and freshwater environments. It is obvious that human
impact, including discharges of arsenic, may be greatest in the last
mentioned environments. Here, the human activities are causing the
strongest increases in arsenic concentrations over the natural background
levels, and thereby the highest exposure of organisms to potentially toxic
arsenic species. Thus, estuaries, land-locked seas, lakes and rivers are the
aquatic environments where anthropogenic sources of arsenic may cause
more important ecological impacts than in the marine ecosystem.
12
II. SPECIATION OF ARSENIC IN
THE AQUATIC ENVIRONMENT
1. Marine Environment
1.1 Inorganic arsenic species

1.1.1 Marine waters
The concentration of total arsenic in the world's seas is fairly uniform,
about 2 pg/1 (Andreae, 1978). The concentration range in the Atlantic
Ocean has been given as 1.0 - 1.5 pg/1 (Sanders, 1980) and in the
English Channel as 2 - 4 pg/1 (Woolson, 1975), while the global mean
concentration in surface sea water has been suggested at 1.6 pg/1 (Burton
and Statham, 1982).
Arsenate, As(V), is the predominant form of arsenic in seawater, making

up about 80% of the total amount (Waslenchuk, 1978). However,
arsenite, As(III), occurs at concentrations greater than those expected
from purely thermodynamic considerations (Gohda, 1975). The
explanation for this apparent anomaly seems to be that arsenate is
reduced by marine bacteria (Johnson, 1972) and marine phytoplankton
(Johnson and Burke, 1978). The concentration of arsenite is usually
higher in the euphotic zone than below, which further supports that algae
are important in the production of this species.
1.1.2 Marine sediments / interstitial waters

While the mean arsenic content in the continental crust has been reported
at 1.5 - 2 pg/g (NAS, 1977) and 3 pg/g (Cullen and Reimer, 1989),
respectively, the average level of arsenic in deep sea sediments is much
higher. The average for world oceans is about 40 pg/g (Bostrdm and
Valdes, 1969). Arsenic levels in sediments from coastal regions and
estuaries are generally lower than those from the deep sea, and reported
values from uncontaminated coastal regions range from 3 to 15 pg/g
(Kennedy, 1976).
Total arsenic concentrations have been found to be lower in the

interstitial water than in the overlying water, suggesting removal of
arsenic onto the solid phases by adsorption or coprecipitation (Andreae,
1979). Both forms of inorganic arsenic were found in the inter-stitial
water, and the proportion of arsenite was always higher than that in
13
seawater, reflecting the different redox potentials of the two
environments (Francesconi and Edmonds, 1994).
1.1.3 Marine biota

Inorganic arsenic usually constitutes less than 10% of the total arsenic in
macroalgae, although a few exceptions to this rule have been reported:
Sargassum muticum contained 38% (Whyte and Englar, 1983) and
Hizikia fusiforme some 50-60% of inorganic arsenic (Shinagawa et al.,
1983). The concentration of total arsenic in the former species was
reported to be in the range 40-90 pg/g d.w..
No good data are available on the natural content of inorganic arsenic in

unicellular algae, but it may be assumed that the major part of arsenic in
these microalgae are organic arsenic compounds, in essence the same as
those formed by macroalgae (Francesconi and Edmonds, 1994), see
section 1.2.4.
The arsenic content of marine animals shows considerable variability.

Among the highest recorded values from uncontaminated areas were
>100 pg/g wet weight (w.w.) in plaice (Pleuronectes platessa) and the
gastropod Reishia bronni (Luten et al., 1982; Shiomi et al., 1984), and as
much as >2000 pg/g d.w. in the polychaete Tharyx marioni (Gibbs et al.,
1983). The dominant part of arsenic in soft tissues of marine animals has
been demonstrated to be in an organic form (see section 1.2.3). In fact,
various authors have shown that inorganic arsenic constitutes a very
small percentage, <2%, of the total arsenic in marine animals from
uncontaminated waters (see e g Maher, 1983).
In a recent re-evaluation of virtually all studies that have specifically

analysed the fraction of inorganic arsenic in marine animals (Edmonds
and Francesconi, 1993), it was concluded that the previous assumption
that inorganic arsenic constitutes 2-10% of the total arsenic in seafood
(GESAMP, 1986; Friberg, 1988) is not justified, see Figure 11:1.1. The
regression indicates that the proportion of inorganic arsenic in marine
animals falls from around 1% at very low total arsenic concentrations to
about 0.5% at total arsenic levels of around 20 pg/g.
However, in shells of marine animals, the inorganic forms seem to

predominate. For example, in the shells of four species of gastropods,
total arsenic levels of 1.8 - 16 pg/g were recorded, while the shells of
four bivalve species generally had lower levels. Both arsenate (66-92%
14
of total) and arsenite were present, and all samples contained low levels
of methyl- or dimethylated arsenic compounds (Cullen et al., 1989).
GESAMP
TOTAL ARSENIC (mg/kg)
Figure 11:1.1 Inorganic arsenic versus total arsenic in marine animals.

1 = crustaceans, 2 = bivalve molluscs, 3 = gastropod molluscs, 4=
cephalopod molluscs, 5=fish. The atypical dataofLunde (1973) are
shown boxed. "GESAMP" denotes the relationship assumed by GESAMP
(1986) and Friberg (1988). Linear regressions of inorganic on total
arsenic have been fitted, (a) excluding, and (b) including the data of
Lunde (1973). After Edmonds and Francesconi, (1993).
15
1.2 Organic arsenic species
1.2.1 Marine waters
Usually, small quantities of methylarsonic acid (MAA) and
dimethylarsinic acid (DMAA) are found in seawater, with somewhat
higher levels in the euphotic zone than below (Braman and Foreback,
1973; Andreae, 1979). Apart from the four simple forms of arsenic
(arsenate, arsenite, MAA and DMAA), no other dissolved arsenic species
have been identified in marine waters (Francesconi and Edmonds, 1994).
However, so-called "hidden arsenic" has been shown to make up an
average of 25% of the total arsenic in coastal waters (Howard and
Comber, 1989). The usual method for determining arsenic in seawater
does not allow detection of arsonium compounds (R4As+) or most other
organic arsenic compounds that occur in marine organisms. Therefore, it
cannot be excluded that organic arsenic compounds, except MAA and
DMAA, may be present at appreciable levels, but remain undetected by
standard analytical methods (Francesconi and Edmonds, 1994).
The possibility that arsenobetaine, the predominant arsenic species in

marine animals (see below), is also present in seawater has been
discussed by the latter authors: On the basis of uptake experiments with
mussels and lobsters, it was found that the mussles absorbed the
arsenobetaine from the spiked seawater much more efficiently than did
the lobsters, a result which is not in accordance with the situation found
in the natural populations. Therefore, the experimental outcome was
considered to indicate that direct uptake of arsenobetaine from seawater
is not a significant contributor to the arsenobetaine burden of mussels or
lobsters in their natural environment, and hence, arsenobetaine might not
be an important constituent of natural seawater (Francesconi and
Edmonds, 1994).
1.2.2 Marine sediments / interstitial waters

The methylated arsenic species MAA and DMAA have been found in
interstitial water of estuarine sediments (Ebdon et al., 1987) and the
same species together with a trimethylated arsenic species were detected
in interstitial water of deep sea sediments (Reimer and Thompson, 1988).
It is considered most probable that these methylated arsenicals are
formed by microbial methylation in situ, rather than from degradation of
biological debris in the sediment.
1.2.3 Marine animals

Already in 1926, Chapman described that the arsenic in lobster was a
nontoxic organic compound soluble in both alcohol and water, and
16
resistant to hot dilute hydrochloric acid. Lunde (1975) showed that the
same kind of organoarsenic compound was present in crustaceans,
molluscs and fish, and the compound was identified as arsenobetaine by
Edmonds et al. (1977). Subsequent work has revealed that arsenobetaine
is the major arsenic compound in a large range of marine animals, see
Table 11:1.1 (after Francesconi and Edmonds, 1993).
Among other organoarsenic compounds that have been identified in trace

amounts in marine animals, the following may be mentioned (after
Francesconi and Edmonds, 1994):
- tetramethylarsonium ion
- arsenocholine
- trimethylarsine oxide
- trimethylarsine
- dimethylarsinylribosides
- phosphatidylarsenocholine.
Animal group Arsenic concentration % ofarsenic present

(No. ofspecies) (pg/g wet weight) as arsenobetaine
Fish
Elasmobranchs (7) 3.1 -44.3 94 - >95
Teleosts (17) 0.1-166 48->95
Crustaceans
Lobsters (4) 4.7-26 77->95
Prawns /Shrimps (5) 5.5-21 55->95
Crabs (6) 3.5-8.6 79->95
Mollusks
Bivalves (4) 0.7- 2.8 44-88
Bivalves (7) 1.0- 2.3* 12-50
Gastropods (6) 3.1-117 58->95
Cephalopods (3) 49 72->95
Echinoderms (1) 12.4 60
Coelenterates (1) 7.5* 15
Sponges(2) 3.2-6.8* 13-15
* = Whole wet tissue.
Table 11:1.1 Arsenobetaine in marine animals (after Francesconi and

Edmonds, 1993). Unless specified, values refer to muscle tissue only.
The most important of these other organic forms of arsenic in marine

animals appears to be the tetramethylarsonium ion, which has been
17
detected in a variety of species (clams, gastropods, sea hare and sea
anemone). In a sea anemone, this compound was shown to be the major
water-soluble arsenic compound with more than 50% of the total water-
soluble arsenic (Shiomi et al., 1988), while in five species of clams, it
represented 20-48% of the total arsenic (Cullen and Dodd, 1989). Thus,
it may be concluded that the tetramethylarsonium ion is a common
constituent of mollusks, where it seems to occur predominantly in the
gills. The origin of the tetramethylarsonium ion in marine animals is still
unknown (Francesconi and Edmonds, 1994).
The remaining organoarsenicals identified in marine animals have, so

far, only been found in trace amounts. The arsenocholine was recently
demonstrated to occur, in amounts correspon-ding to 0.25% of total
arsenic, in plaice, the shrimp Pandalus borealis and the mussel Mytilus
edulis (E.H. Larsen, ref. in Francesconi and Edmonds, 1994).
Trimethylarsine oxide was identified as a natural component of some

species of fish, and it is supposed to result from metabolic
transformation of arsenobetaine within the animal (Norin et al., 1985a;
Hanaoka et al., 1992). It may also arise from methylation of arsenate by
the intestinal flora of the fish (Edmons and Francesconi, 1987).
Traces of the toxic compound trimethylarsine have been found in prawn

and lobster, and it is hypothesized that it is produced either by microbial
methylation of inorganic arsenic within the digestive gland of the
animals or from microbial breakdown of arsenobetaine via
trimethylarsine oxide (Whitfield et al., 1983; Hanaoka et al., 1992).
The dimethylarsinylribosides detected in some marine animals are

probably derived from ingested algal metabolites, since these compounds
are common constituents of marine algae (Edmonds et al., 1992).
The general picture emerging from the reviewed work is that

arsenobetaine is - by far - the most common and dominant arsenic
compound in marine animals. With few exceptions (examples mainly
from sponges and coelenterates), arsenobetaine makes up the bulk of the
total arsenic found in the marine animals, quite often more than 95%. All
the other organic arsenic compounds hitherto identified in marine
animals, except the tetramethylarsonium ion, seem to be produced only
in trace amounts and almost "by accident" through the action of micro
organisms associated with the animals.
18
1.2.4 Marine plants
Brown algae appear to be the marine plants containing the highest
concentrations of arsenic, up to 230 pg As/g d.w.. These levels are
considerably higher than those in red algae (<30 pg/g d.w.), in green
macroalgae (<23 pg/g d.w.), in unicellular plankton algae (about 9 pg/g
d.w.) and seagrasses (<0.6 pg/g w.w.) (Francesconi and Edmonds, 1994).
The precise chemical form of the arsenic in macroalgae was established

in 1981, when Edmonds and Francesconi isolated and identified the two
major organoarsenic compounds in the brown macroalga Ecklonia
radiata. Both turned out to be dimethylarsinylribosides, one acidic and
the other a basic compound (Figure II: 1.2). Later work in this area has
resulted in the identification of several other dimethylarsinylribosides in
various species of brown, red and green macroalgae (Francesconi and
Edmonds, 1994). It has been suggested that the distribution of
arsinylribosides among the different species of algae may have some
chemotaxonomic significance (Shibata et al., 1987), but this still has to
be demonstrated.
Figure 11:1.2. Structures of the first two identified dimethylarsinylri

bosides isolatedfrom algal sources. The compounds were purified by gel
permeation chromatography, thin-layer chromatography and HPLC, and
were then identified by means ofNMR and confirmed by X-ray
crystallograpnic analysis (from Francesconi and Edmonds, 1994).
Only one of the arsinylribosides isolated from macroalgae was lipid-

soluble. Although water-soluble organoarsenic compounds predominate
in macroalgae, unicellular algae often contain the bulk of their arsenic
19
(up to 95%) as lipid-soluble compounds (Cooney, 1981). It was shown
that the lipid-soluble arsenic compounds in unicellular algae were
susceptible to hydro-lysis by phospholipases, indicating the presence of
arsenic-containing phospholipids (Cooney et al., 1978). Subsequent work
by Edmonds and Francesconi revealed that unicellular algae, living as
symbionts in the mantle of the giant clam (Tridacna maxima), contained
five of the arsinylribosides previously found in macroalgae and, in
addition, four new arsinylribosides (Figure 11:1.3) and a novel taurine
derivative, (Francesconi and Edmonds, 1994).
Figure 11:1.3. Structures of dimethylarsinylribosides identified in

unicellular algae (after Francesconi and Edmonds, 1994).
An important observation is that, in addition to the predominant

dimethylarsinylribosides, also a trimethylarsonioriboside has been
detected (Figure 11:1.4), albeit in small amounts, both in macroalgae and
in unicellular algae (Shibata and Morita, 1988; Francesconi et al.,
1992a).
20
+
Me3As 0S03
HO OH
Figure 11:1.4. Structure of a trimethylarsonioriboside identified in

macroalgae and unicellular algae (after Francesconi and Edmonds,
1994).
Thus, the present state of knowledge clearly shows that unicellular and
macroalgae contain in essence the same kind of organoarsenic
compounds. As a consequence, it may be concluded that the biosynthesis
of arsenic-containing ribosides from arsenate, occurring in marine water,
seems to be a general property of marine algae, both macroalgae and
unicellular algae.
1.3 Biotransformation of arsenic - metabolic cycle
1.3.1 Uptake by algae

Marine algae are naturally exposed to arsenic, mainly in the form of
arsenate. In uncontami-nated surface waters, where nutrient depletion
may occur due to phytoplankton production, and consequently
concentrations of free phosphate usually are low, arsenate can be present
at levels comparable with or greater than those of phosphate (Johnson
and Pilson, 1972).
According to several workers, arsenate and phosphate compete for

uptake in marine algae, which was indicated by experimental exposure of
the unicellular marine alga Skeletonema costatum to arsenate at different
concentrations of phosphate (Sanders, 1979). Further support for this
hypothesis comes from the close chemical similarity between the two
elements, implying that algae might be unable to distinguish the arsenate
ion from its chemical analogue, the essential phosphate ion (Maugh,
1979). In other organisms it has been demonstrated that arsenate is taken
up by the phosphate transport system (Rothstein, 1963; Meharg and
Macnair, 1992), but the situation in marine algae is not quite clear. At
low phosphate concentrations, arsenate uptake by unicellular algae
21
increased with increasing phosphate concentrations (Andreae and
Klumpp, 1979), and there was no evidence for a common mechanism of
uptake for arsenate and phosphate in two species of brown macroalgae
(Klumpp, 1980). Therefore, it may be concluded that arsenate is taken up
by marine algae by more than one mechanism.
After having been transported into the algal cells, arsenate may begin to
exert a toxic action on the alga, causing inhibition of growth, inhibition
of carbon uptake, interference with phosphorus metabolism and changing
the algal cell morphology (Sanders, 1979; Bottino et al., 1978). It is
assumed that the production by the algae of organoarsenic compounds
might, at least in part, be a detoxification process.
1.3.2 Biosynthesis of arsenic-containing ribosides

At least three different pathways have been proposed for the formation of
arsenic-containing ribosides in marine algae. The scheme proposed by
Phillips and Depledge (1985) links the pathway for phospholipid
biosynthesis to those for the formation of arsenosugars. A second
proposal (Phillips, 1990) is based on the hypothesis that the enzymes of
the pentose phosphate pathway could utilize arsenate rather than
phosphate as a substrate. Although these proposals have some attractive
features, they are, at least partly, based on some speculative assumptions.
The most plausible pathway for the genesis of arsinylribosides in algae

was proposed in 1983 (Edmonds and Francesconi, 1983), and is based on
the early work by Challenger (1945) and Canton! (1953). The scheme
proposed by Challenger required sequential reduction of arsenic
followed by oxidative methylation. Subsequent to Cantoni's
identification of S-adenosyl-methionine as an active methyl donor in
enzymatic systems (Cantoni, 1953), this compound was considered to be
the likely source of methyl groups in the methylation of arsenic
(Challenger et al., 1954).
Recent work by Francesconi et al. (1992a) has given further support to

the idea that transformation of arsenic in algae proceeds according to a
similar pathway, with S-adenosyl-methionine donating its methyl group
and its adenosyl group to arsenic (Figure 11:1.5). However, it has also
been suggested that two different pathways for the algal biosynthesis of
methylated arsinylribosides may occur in nature (Phillips, 1994). It has,
moreover, been suggested that the dimethylarsinylribosides might be
able to participate in cellular redox reactions in the algal cells
(Francesconi and Edmonds, 1994).
22
0
0—As—0 Reduction
HO OH
Mtthylarsomc avid Dimvlhylarsinic acid (DiimMhylarsinyludeno.sine)

(MAA) (DM AA) (Compound 13)
X
0
OR
1
Reduction
then A
HO OH HO OH
S-Adenosylmethionine I HO OH B
(AdoMel) |
Figure 11:1.5. Proposed pathway for the biogenesis by algae of arsenic-

containing ribosides from arsenate. All proposed intermediates have
been identifiedfrom marine algal sources. AdoMet is the probable
source of the methyl and adenosyl groups (after Francesconi and
Edmonds, 1994).
1.3.3 Origin of arsenobetaine in marine animals

A great deal of research has been devoted to the problem of determining
the relative importance of the two possible sources of arsenobetaine,
water and food, to marine animals. For the time being, no evidence exists
to indicate that aquatic animals are capable of synthesizing arseno
betaine de novo from arsenate (Francesconi and Edmonds, 1994). Then,
the question remains whether or not the "hidden" arsenic species in water
may, at least partly, be composed of arsenobetaine and other methylated
forms of arsenic, that may be taken up from the water and - directly or
after transformation - contribute to the arsenobetaine burden of marine
animals. However, as mentioned in section 1.2.1, the results of
experiments undertaken are at variance with the situation observed in
23
natural populations. Thus, based on the data available, seawater does not
appear to be a significant source of arsenobetaine to marine animals. In
stead, the evidence suggests that marine animals accumulate
arsenobetaine primarily from their food (Francesconi and Edmonds,
1994).
The problem is that the food of primary consumers does not seem to
contain arsenobetaine. Although the levels of arsenic in algae are three to
four orders of magnitude higher than the levels in seawater, none of the
many studies of the composition of algal arsenic have demon-strated the
presence of arsenobetaine in marine algae. The presumed immediate
precursor of arsenobetaine, namely arsenocholine, was similarly not
detected in algae (Francesconi and Edmonds, 1994).
Since there is no experimental evidence indicating de novo synthesis of

arsenobetaine from ingested arsenate by fish (although indications exist
that small proportions of ingested arsenate can be converted to an
organic form, e g trimethylarsine oxide), the possibility remains that the
food of primary consumers contains a precursor that is converted to
arsenobetaine at a later stage in the food chain.
Food chain experiments were carried out by Cooney and Benson (1980)
with the unicellular alga Dunaliella tertiolecta and the lobster Homarus
americanus, and speciation of the arsenic compounds in the two trophic
levels was made after exposure of the alga to 74As as arsenate in the
seawater. In a similar experiment, Klumpp and Peterson (1981)
examined the arsenic transformation in the marine food chain: macroalga
(Fucus spiralis) —> herbivorous gastropod (Littorina littoralis) —>
carnivorous gastropod (Nucella lapillus), after exposure of the alga to
74As as arsenate. In none of these experiments it was possible to detect
any arsenobetaine in the consumers, which shows that neither the lobster
nor the gastropods were able to directly transform the ingested algal
arsenic compounds into arsenobetaine. However, in the latter study, most
of the 74As lable in the gastropods was associated with a single arsenic
compound with unknown identity. The chromatographic and
electrophoretic properties of the compound seem to fit those of the
tetramethylarsonium ion, which was later shown to be a common
constituent of mollusks (Cullen and Reimer, 1989). However, the main
conclusion from these experiments is that primary (and secondary)
consumers appear to be unable to biosynthesize detectable levels of
arsenobetaine (or arsenocholine) from directly ingested algal arsenic.
24
The next possibility to investigate was whether an intermediate (perhaps
microbially mediated) stage is necessary to render the algal arsenic into a
form that can be accumulated by animals. This view was supported when
it was found that under anaerobic conditions (in beach sediments) there
was an almost quantitative conversion of the naturally occurring algal
arsenic compounds into a single compound, subsequently identified as
dimethylarsinylethanol (Francesconi and Edmonds, 1994). No
arsenobetaine was detected. Since the new compound, dimethylarsinyle
thanol only requires further methylation and then oxidation of the
primary hydroxyl group for conversion to arsenobetaine via
arsenocholine or dimethylarsinylacetic acid, this pathway (Figure 11:1.6)
was hypothetically proposed for the natural formation of arsenobetaine.
?
MejAs cooh
Dimelhylaf.sinylocetlc acid
OXIDATION METHYLATION
O
» ANAEROBIC
DECOMPOSITION t Me3As\/C00"
(C3-C4 cleavage)
Dimethylarsinylethanol Arsenobetaine
Dimethylarsinyiribosides
METHYLATION OXIDATION
+ X
Arsenocholine
Figure ILL 6. Proposedpathwaysfor the formation ofarsenobetaine

from dimethylarsinyiribosides via the intermediate compound
dimethylarsinylethanol (after Francesconi and Edmonds, 1994).
The remaining problem was that attempts to carry out further

methylation of the dimethylated arsinyl intermediates by natural
processes outside the algae have been unsuccessful (Francesconi and
Edmonds, 1994). However, a new line of reasoning emerged from the
fact that, in addition to the dimethylated arsinylribosides that make up
the bulk of the algal arsenic, small amounts of the trimethylated
analogues were also detected in both macroalgae (Shibata and Morita,
1988) and unicellular algae, cf. section 1.2.4 (Francesconi et al., 1992a).
When one of the trimethylarsonioribosides was subjected to conditions
25
of anaerobic microbial activity, it underwent degradation to give a
virtually quantitative yield of arsenocholine (Francesconi et al., 1992b).
On the basis of these results, an alternative pathway for arsenobetaine
was proposed.
In order to confirm the possibility that any of the proposed pathways of

arsenobetaine formation does occur in nature, feeding experients were
carried out with yelloweye mullet (Aldrichetta forsteri). Separate groups
of fish received food containing known quantities of each of the
following organoarsenic compounds: (a) dimethylarsinylethanol, (b)
dimethyl-arsinylacetic acid, (c) arsenocholine, and (d) arsenobetaine.
After 3-4 weeks, the amount of arsenic in muscle tissue of the fish was
analysed and the amount of arsenic retained as a percentage of the total
arsenic ingested was calculated (Francesconi et al., 1989). It was found
that no arsenic was retained in the fish body after ingestion of
compounds (a) and (b), while 37-39% of the arsenic was retained after
ingestion of either of compounds (c) and (d). The chemical form of the
retained arsenic in the two latter groups was, in both cases,
arsenobetaine, but no arsenocholine was present (Francesconi et al.,
1990).
These results indicate that further methylation of the dimethylated

compounds did not occur within the fish, because the products of such a
process (arsenocholine and arsenobetaine) would have been retained by
the fish. Furthermore, the results support the assumption that
arsenocholine is the immediate precursor to arsenobetaine in marine
animals, and provide an explanation for the absence of significant
amounts of arsenocholine in marine animals: in fish, at least, arsenocho
line is so readily metabolized that none is detected (Francesconi and
Edmonds, 1994).
Whether dimethylarsinylribosides or trimethylarsonioribosides serve as

precursors to arseno-betaine in natural marine systems remains to be
established. However, the two proposed pathways are not mutually
exclusive, and it is assumed that the trimethylated compounds in algae at
least contribute to the arsenobetaine content in marine animals. The
degradation of arsenic-containing ribosides (both di- and trimethylated
compounds) into possible precursors of arsenobetaine has been shown to
occur only under anaerobic conditions, in microbially active environ
ments. Whether this actually takes place only in the sediments or can
occur also in anaerobic micro-environments in other marine compart
26
ments, e g in the water column or in the gut of the fish, is presently not
known (Francesconi and Edmonds, 1994).
1.3.4 Complete metabolic cycle of arsenic in the marine

environment
Philips (1990) has proposed a consolidated scheme for the inter
conversion of the various forms of arsenic found in marine environ
ments. This scheme, later modified by Philips (1994), see Figure 11:1.7,
was based on work by Philips and Depledge (1985) and by Edmonds and
Francesconi (1988), but also included a novel biosynthetic pathway for
the production of arsenosugars in macroalgae. In this hypothetical, new
pathway, it is assumed that the enzymes of the pentose phosphate
pathway utilize DMAA rather than phosphate as a substrate, resulting in
the synthesis of the dimethylarsinoyl derivative of 5-phospho-b-D-
ribosylamine, and this compound could act as a precursor of all the
documented arsenosugars found in marine macroalgae.
i
S'-Dimcthylarsinoyl- S'-Dimethylarsinoyl- S'-Dimethylarsinoyl-
glucosc ► ci-D-rtbulose —— --------► p-D-ribosylamine
Arscnolipids not
containing sugars
Arsenate
I’edenosyl
Arsenoeihanolamine
Trimethylarsine
/ oxide
Tetramcthylarsonium ion
Figure 11:1.7. Proposed pathways for the biosynthesis and catabolism of

the different arsenic species found in marine organisms (after Philips,
27
species
Arsenic, as many other elements, is taken down to the bottom of oceans
as sorptive aggregates with hydrous ferric and manganese oxides or with
organic matter. In sediments of the open ocean, the average level of
arsenic has been estimated at 40 pg/g (Bostrom and Valdes, 1969). The
enrichment of arsenic in iron-manganese nodules and crusts is well
known, resulting in concentration of 100 pg As/g to well in excess of
1000 pg As/g (Calvert and Price, 1977).
In coastal waters, it has been observed that intense biological activity in

the surface layers, and the subsequent uptake of arsenate into
phytoplankton, leads to depletion of dissolved arsenic from these layers,
compared to the concentrations measured below the thermocline, where
regeneration from particulates occurs (Andreae, 1979; Waslenchuk,
1978). When measuring the concentrations of dissolved arsenate and
arsenite in several basins off the California coast, Andreae (1979) found
that arsenate in sediment interstitial waters usually was somewhat lower
(1.3 pg/1) than in the bottom water (1.8 pg/1), and that the arsenate was
depleted near the sediment-water interface. It was suggested that
diffusion of arsenate from the water to the sediment may be occurring,
followed by adsorption to the solid phase.
On the other hand, Andreae (1979) also found that the arsenite
concentrations in sediment interstitial waters were higher (up to 0.25 pg/1
higher) than in the bottom water, indicating that this arsenic species may
diffuse out of the sediments. However, it was not clear whether or not the
arsenite can escape through the oxidized surface sediment layers into
bottom waters. Nonetheless, Sanders (1980) used the above data to
calculate the possible maximum flux of arsenite out of the sediments in
Georgia Bight, and he concluded that this was much lower than other
arsenic sources (river run-off, atmospheric deposition and deep-water
intrutions) in the studied marine area.
The mechanisms of arsenic sedimentation and the subsequent rates of

reduction and oxidation of arsenic compounds in the interstitial waters of
marine sediments are still largely unknown (Sanders, 1980). While
arsenic flux out of marine sediments has not been directly measured in
the field, this has been suggested to explain excess arsenic in bottom
waters in some coastal seas (Sanders et al., 1994). Many more studies
have been conducted to measure the arsenic flux from contaminated
estuarine sediments (see section 2.4).
28
In a recent experimental study (Ettajani et al., 1996), fine-particle marine
sediment was artificially contaminated with arsenate and then submitted
to in vitro desorption tests, in which enzymes and pH changes were used
to mimic the digestive processes in molluscs. Although different
enzymes combined with low pH (down to pH 4) induced the desorption
of 3-24% of sediment-bound arsenic, the accumulation of this element in
the soft tissues of oysters remained low after exposure to contaminated
particles (12.2 pg/g dry weight as compared to the control value of 8.9
pg/g, after 14 d exposure). However, minor cytological effects were
noted in the oysters exposed to sediment-bound arsenic, indicating that
this arsenic had a certain bioavailability and could be transported into the
soft tissues of the animals.
Weis and co-workers (see Weis and Weis, 1996a for references) have
conducted a series of studies of the leaching and the effects of metals
from chromated copper arsenate (CCA-) treated wood used as pilings
and bulkheads in the marine or estuarine environment. In the United
States, wood intended for marine use is treated with high amounts of
CCA, between 24 and 40 kg/m3. Weis et al. (1991) showed that all three
metals leach from the treated wood into sea water. Leaching for 2 weeks
in 28 %o sea water was 30 pg Cu/cm2, 0.8 pg Cr/cm2 and 8.0 pg
As/cm2, and the leaching rates generally decreased over time. It was
clearly shown that the released metals accumulated in epibiota on the
CCA-treated wood panels, but the arsenic cencentration decreased
steadily with each repeated submersion and removal of the wood (Weis
and Weis, 1996b). Also the sediments, particularly the fine fraction, and
the benthic animals near the CCA-treated wood were highly
contaminated with metals (Weis and Weis, 1994). The highest
concentrations in the fine sediments were found for copper, and the
lowest for arsenic, while copper and arsenic were both high in benthos.
Thus, the use of CCA-treated wood in the marine environment obviously
introduces bioavailable arsenic into the ecosystem, but after presoaking
of the wood for two months, the leaching and the subsequent
accumulation of arsenic in biota are reduced to low levels (Weis and
Weis, 1996b). Therefore, a proper presoaking of CCA-treated wood
before using it in the marine environment, might reduce the arsenic
leaching and the contamination of sediments and biota to insignificant
levels, maybe except in the close vicinity of the wooden structures.
29
1.5 Uptake in organisms and bioaccumulation
Arsenic uptake by phytoplankton and attached macroalgae forms the
most important pathway for arsenic entrance into marine food webs
(Sanders et al., 1994). Marine phytoplankton actively take up arsenate
occurring at natural concentrations, and seem to regulate arsenic levels in
the cells over a large concentration range independently of the phosphate
concentrations. Significant differences in regulating capacity exist
between different algal species (Andreae and Klumpp, 1979).
Arsenic levels in seaweeds (Fucus spiralis and Ascophyllum nodosum)

have been shown to reach a steady-state in 1 to 8 days, depending on the
species and external arsenic concentration. The uptake was increased in
direct proportion to increasing temperature. The accumulation of
arsenate was four times that of arsenite. Arsenic uptake requires energy,
which is derived from respiration rather than from photosynthesis
(Klumpp, 1980).
Only little uptake of dissolved arsenic from water occurs in marine

invertebrates or vertebrates (Edmonds and Francesconi, 1987; Sanders et
al., 1989; 1994). The relatively high uptake rate by algae, however,
allows a pathway for arsenic into higher trophic levels, as the organo-
arsenic compounds formed in algae are available to herbivores (Klumpp,
1980; Sanders et al., 1994). The food chain accumulation of arsenic from
Fucus spiralis in the snail Littorina littoralis was primarily in the soft
tissues, especially the digestive gland and gonads, while in the carnivore
Nucella lapillus, about 85% of the accumulated arsenic was associated
with the shell. Compared with the macroalgae, the marine snails exihibit
a much greater ability for eliminating arsenic from the tissues (Klumpp,
1980).
Further comments on uptake and bioaccumulation of arsenic in marine

animals are given in section 1.3.3 and corresponding phenomena in the
brackish water environment are presented in section 2.5.
1.6 Natural factors affecting speciation and bioavailability

As previously mentioned, arsenate is the predominant form of arsenic in
marine waters. In addition to arsenate, three other arsenic species are
commonly encountered in dissolved form: the reduced inorganic form,
arsenite, and two methylated forms, methylarsonate (MAA) and
dimethylarsinate (DMAA). Other, more complex organic forms of
arsenic may be present as well, but their concentrations are low, and they
30
are not generally detected using conventional analytical methods
(Sanders et al., 1994).
While arsenate is the thermodynamically more stable form in oxic

waters, arsenite is more stable in reducing environments such as anoxic
water or sediments, but it is also found in aerobic systems. Oxidation of
arsenite to arsenate, in the presence of oxygen, occurs rapidly, with a
residence time of 0.5 to 10 days in coastal waters (Sanders and Windom,
1980; Cutter, 1992). The rate of arsenite oxidation in seawater is
enhanced by increases in pH, salinity, temperature and arsenite
concentration (Johnson and Pilson, 1975). The relatively rapid oxidation
rate of arsenite implies that the occurrence of arsenite in marine oxic
waters is closely related to the biological processes responsible for its
formation through reduction, such as primary production in surface
waters and bacterial degradation in the layers below.
Phytoplankton species seem to differ in their ability to produce reduced

and methylated arsenic compounds, with some species capable of
producing arsenite, MAA and DMAA, and others producing only one or
none of these compounds (Andreae, 1983; Sanders and Riedel, 1993).
Arsenite formed in the sediments or at the sediment-water interface

through bacterial reducing activity may be rapidly oxidized back to
arsenate if the sediment surface is aerobic. It has been suggested that
Mn4+ and Fe3+ oxides present on the surface of sediment particles may
be responsible for catalyzing the oxidation of arsenite through an
electron transfer mechanism (Oscarson et al., 1980). The oxidation by
means of manganese seems to be more effective than that by iron. Over
long periods of time, however, also iron may play a significant role.
The simple, methylated arsenic species are produced biologically, either

by methylation of inorganic arsenic or by degradation of more complex
organoarsenic compounds such as arsenocholine and arsenobetaine
(Hanaoka et al., 1987; Anderson and Bruland, 1991). Methyl arsenic
species are more persistent than arsenite, with much longer degradation
times. Therefore, these species can persist in natural systems for
relatively long periods of time, and their presence does not depend so
much on the processes that led to their formation (Sanders et al., 1994).
The rate of uptake of arsenate in marine algae and invertebrates appears

to be higher than that of arsenite, possibly reflecting a higher
bioavailability of arsenate. Because of the chemical similarity between
31
arsenate and phosphate, arsenate is taken up by autotrophs along with
phosphate. Arsenate also interferes with the biochemical functions of
phosphate, particularly phosphorylation and ATP-production (Planas and
Healey, 1978; Blanck and Wangberg, 1988a). Therefore, when the ratio
of arsenate to phosphate is relatively high, arsenic toxicity to
phytoplankton becomes more likely (Wangberg and Blanck, 1990;
Sanders et al., 1994). Presumably, the arsenic transformation reactions
inside the algal cells have been evolved to minimize this toxicity by
altering and inactivating arsenate.
Arsenate adsorbed onto the surface of fine, suspended particles is not

entirely non-bioavailable. As was shown by Ettajani et al., (1996), a
certain fraction of the arsenic could be released from the particles under
pH and other conditions that mimic the environment inside the gut of
mollusks. It was also shown that such arsenate-laden particles could
induce slight toxic reactions in the mollusks (oysters).
In summary, in the relatively stable environment existing in marine

systems, arsenic is mainly present in a form, arsenate, which is readily
bioavailable. Since the concentration of phosphate in open marine waters
usually is low or very low, the rate of uptake of arsenate into autotrophs
is relatively high. The uptake is followed by a rapid transformation of
arsenate to complex organic arsenic species, which generally have a
lower toxicity than arsenate and arsenite.
2. Estuarine or Brackish Water Environment
2.1 Arsenic levels and speciation in water and sediments

2.1.1 Estuarine waters
Elements like arsenic, that are biologically and chemically reactive can
undergo considerable changes in chemical form and bioavailability,
particularly in estaurine areas (Sanders et al., 1994). The main difference
between truly marine and estaurine systems is that, while the former are
relatively stable, the latter are dynamic systems, subject to wide,
temporal and spatial, variations in physical, chemical and biological
parameters. Because of their high physical variability, estuaries and
brackish water sea ecosystems tend to be biologically simple,
characterized by high biomass and high productivity, low species
diversity and large, natural fluctuations in species abundance (Day et al.,
1989). The biological composition and dynamics of an aquatic
ecosystem determine, to a large extent, the various chemical forms of
arsenic and their relative concentration. Therefore, in temperate,
32
estuarine ecosystems, arsenic undergoes dynamic seasonal and spatial
changes in concentration and speciation.
The most typical feature of arsenic speciation in estuaries, as opposed to

the open sea, is the seasonal occurrence of relatively high concentrations
of reduced and methylated arsenic species, particularly during warm
summer months. For example, in English estuaries, the appearance of
reduced and methylated arsenic occurred after periods of high
phytoplankton productivity (Howard et al., 1982; 1984).
The temporal dynamics of arsenic speciation in a productive estuary has

been studied in Patuxent River, a subestuary of the Chesapeake Bay,
Maryland, U.S., and it was clearly shown that not only the total arsenic
concentration in the water greatly varied, but also the relative
distribution between different arsenic species (Riedel, 1993), Figure
11:2.1. A summer maximum of total arsenic was observed, which was
largely composed of arsenate (1 pg/1). The arsenate concentration fell
during winter to about 0.1 pg/1. Arsenite was irregularly present at low
concentrations. Peaks of DMAA occurred at various times throughout
the year, and appeared to be closely linked to dense dinoflagellate
blooms and resulting phosphate limitation. A peak of MAA occurred at
the same time as the summer peak of arsenate, following the spring
DMAA peak; thus, it is possibly a degradation product of DMAA
(Sanders et al., 1994). As an alternative, the MAA peak may be a result
of methylation by specific algal taxa (Sanders, 1985). These transforma
tions are further discussed in section 2.6.
33
1.2
B-Q MMA
■ ■ DMA
O O orsenite
*-# arsenate
A M J F M A M
DATE (1988-1989)
Figure 11:2.1. Arsenic concentration and speciation in the Patuxent

River from June 1988 to May 1989 (after Riedel, 1993 and Sanders et
a/., 7%%).
Within the Chesapeake Bay, a similar seasonal pattern was observed,

coupled with a spatial variability (Sanders, 1985). Almost all arsenic
entering the head-waters of the Bay is in the form of arsenate. Reduction
and methylation take place during the warmer months, resulting in
changes in the pattern of arsenic speciation down the main stem of the
Bay (Figure 11:2.2). Arsenite is produced in the upper regions with low
salinity (1-10 %o), while methylated species reach high concentrations in
the lower regions of the Bay (10-20 %o).
Quite similar patterns were observed in several other estuaries, for

example in Florida, England, Portugal and in the Baltic Sea. In almost all
cases, the appearance of enhanced concentrations of reduced and
methylated, dissolved species was well correlated with phytoplankton
production (Sanders, 1983; Froelich et al., 1985).
34
SALINITY (°/oo)
Figure 11:2.2. Arsenic speciation in the waters of Chesapeake Bay during

productive summer months. From bottom to top: arsenate, arsenite and
methylated arsenic species, (after Sanders et ah, 1994).
In the Baltic Sea, with its anoxic bottom water, a substantial reduction of
arsenate to arsenite was observed below the oxic-anoxic interface, at a
depth of about 170 m in the Gotland Deep (Andreae and Froelich, 1984).
The concentration of total arsenic increased from 0.6 pg/1 in the surface
water to almost the double below the redoxcline. In the uppermost water
layers, above the seasonal thermocline, almost half of the total arsenic
was in the form of arsenite, DMAA and MAA (Figure 11:2.3). Thus, the
arsenate was depleted in the euphotic zone. However, the methylated
species remained low in the whole water column from the depth of 40 m
down to the bottom. On the contrary, arsenite sharply increased in
concentration at the redoxcline and remained the dominating species in
the anoxic layers.
An interesting pattern was observed at the measuring stations in the Gulf

of Finland, where the dominating arsenic species, above the seasonal
thermocline, belonged to the methylated forms DMAA and MAA,
together making up 83% of total dissolved arsenic. The samples were
taken in June 1981, during the summer peak production period and the
35
high level of methylarsenicals in this area may depend on the relative
rate of methylation by algae.
The vertical distribution of different arsenic species in the Baltic Sea

water suggests that arsenate is taken up by phytoplankton, similarly to
phosphate, in the surface mixed layer. Arsenic is then, at least partially,
regenerated at depth, especially near the anoxic interface (Andreae and
Froelich, 1984). The arsenic-salinity relationships are plotted in Figure
11:2.4, from which it can be seen that the profile for each station begins
(at the surface) at low salinities and low arsenic concentrations. Then
there is an increase of arsenic with depth at constant salinity, indicating
rapid regeneration of arsenic in the seasonal thermocline. Below the
redoxcline (shown be an arrow) at stations BY11 and BY 15 in the
Gotland Deep, arsenic continues to increase at nearly constant salinity as
a consequence of regeneration of arsenic in the anoxic layers (Andreae
and Froelich, 1984).
AM "M
O O.S 1.0 2.5 3.0
Figure 11:2.3. Concentration profiles of different arsenic species in the

Baltic Sea water, at the Gotland Deep. Asj = total dissolved inorganic
As; Asj = total dissolved As (after Andreae and Froelich, 1984).
36
20
15-
1
10-
f
i i i i i . i i—.i i i i
10 15
SALINITY (%.)
Figure 11:2.4. Plots of total dissolved arsenic versus salinity atfive

stations in the Baltic Sea. BY5 is in the Bornholm Deep, BY11 and BY15
in the Gotland Deep, BY23 and BY26 in the Gulf ofFinland (after
Andreae and Froelich, 1984).
The average concentration level of total dissolved arsenic in the surface

waters of the Baltic Sea (0.6-0.7 jxg/1) is intermediate between the level
in rivers entering into northern Bothnian Bay (0.2 jj.g/1) and the level in
the North Sea (1.5 pg/1). In the Bothnian Bay, concentrations of total
arsenic were somewhat enhanced (0.65 pg/1), in 1987, due to local
contamination from a smelting complex (Hotter, 1993).
Arsenic flux from contaminated estuarine sediments has been examined

under controlled conditions in laboratory microcosms (Riedel et al.,
1987; 1989). The fluxes from undisturbed, oxic sediments were low or
undetectable. However, in the case of mechanical disturbance of the bed
by resuspension or by the activity of benthic infauna, substantial fluxes
of arsenate, arsenite, MAA and DMAA were observed (Sanders et al.,
1994). Sediments covered by anoxic waters showed even greater fluxes
of arsenic.
37
2.1.2 Estuarine sediments
Speciation studies of arsenic in estuarine sediments have not been found
in the literature, but it can be assumed that the relative amount of
arsenite is higher in the interstitial waters of sediments than in the
overlying water, particularly if the sediments are anoxic. However, in
one of the measuring profiles in the Baltic Sea, where the bottom water
was anoxic and the sulphide concentration relatively high (20 pM), the
arsenite concentration sharply decreased close to the sediment-water
interface and this was accompanied by an increase in the arsenate
concentration (Andreae and Froelich, 1984). Also the methylated species
MAA and DMAA may be higher at the sediment-water interface, due to
decomposition of the complex, methylated algal arsenic compounds.
The concentration of total arsenic in sediments of the Baltic Sea and the
Skagerrak is shown in Table 11:2.1.
Basin/ Sea Surface sediment (0-1 cm) Older sediment (>20 cm)
Bothnian Bay 109 7
Bothnian Sea 27 9
Baltic Proper 15 9
Skagerrak 2 9
Table 11:2.1. Mean concentrations of total arsenic in sediments from

different basins of the Baltic Sea and Skagerrak, in jug/g dry matter
(after Natter, 1993).
The data in Table 11:2.1 clearly indicate the influence of discharges from
the metal smelting complex on the western coast of the Bothnian Bay. At
a distance of 5-30 km from the smelter, arsenic levels in organic, surface
sediments ranged from 160 to 4,600 pg/g dry matter, in 1989 (Walterson
and Landner, 1996). However, the sediments of the Baltic Proper have a
lower arsenic content than ocean sediments (40 pg/g) and also lower
than the sediments in Skagerrak.
38
2.2 Arsenic levels and speciation in biota
Both the levels of total arsenic and the distribution between various
arsenic species in tissues of organisms living in brackish water are much
less known than in true marine organisms. However, a set of relevant
data, covering several trophic levels of the brackish-water ecosystem in
the Baltic Sea, was reported from a model ecosystem experiment (Notini
et al., ref. in Blanck et al., 1989). This experiment allowed studies of the
variation of the natural levels of arsenic over a complete annual cycle in
various benthic organisms from the littoral zone of the Baltic Sea. The
data were obtained from the control systems, consisting of large outdoor
pools fed with uncontaminated Baltic Sea water, containing 0.5-0.8 pg/1
of total, dissolved arsenic (Blanck et al., 1989). Samples of macroalgae
and invertebrates were analyzed for total arsenic as well as for the
inorganic arsenic fraction (Table 11:2.2).
Species Group Total arsenic % inorganic
Fucus vesicolosus Brown alga 20 5-7

d:o, young shoots 33 5-7
Ectocarpus siliculosus Brown alga 25 -
Cladophora sp. Green alga 3-9 -
Ceramium sp. Red alga 3-9 -
Mytilus edulis (soft tissue) Bivalve 12,5 <10
Cardium sp. -”- Bivalve 14,5 <10
Mya arenaria -”- Bivalve 5-15 55-65
Idothea balthica Crustacean 4,9 20-40
Nereis diversicolor Polychaete 10 60
Table 11:2.2 Arsenic concentration (jug/g dry weight) in the tissues of

various benthic organisms from the Baltic Sea, after exposure to
uncontaminated brackish water in large outdoor pools. Adapted after
Blanck et al., 1989.
As demonstrated in Table 11:2.2, the highest arsenic levels were found in

the benthic brown algae, which also contained the greatest amount of
organic arsenic compounds. Especially the detritus-feeding bivalve Mya
arenaria and and the predator polychaete worm, Nereis diversicolor,
contained a large fraction of inorganic arsenic (as recovered by HC1
distillation). This was in contrast with the (phytoplankton) filtering
bivalves Mytilus and Cardium, which exhibited low amounts of
inorganic arsenic.
39
A few field samples from the Baltic Sea have been investigated, mainly
in areas where exposure to anthropogenic arsenic occurs. A survey of
spring samples of zooplankton, in 1979, showed that the average content
of total arsenic in the animals was 15, 20 and 10 pg/g dry weight in the
Bothnian Bay, the Bothnian Sea and the Baltic Proper, respectively. The
reference value, in uncontaminated areas of the Baltic Sea is supposed to
be <10 pg/g d.w.
Gastropod snails (Lymnaea palustris) from the littoral zone of the

Bothnian Bay held a background level of 6 pg/g d.w. of total arsenic, and
in areas close to the arsenic-emitting smelter, the concentrations rose to
about 110 pg/g, in 1989, but only to about 12 pg/g d.w., in 1994, after a
sharp reduction of the arsenic emissions (Walterson and Landner, 1996).
Fish from uncontaminated parts of the Bothnian Bay were also analyzed,
and the muscle tissue of perch and pike contained 0.14-0.28 pg/g d.w.,
while the liver held 0.24-1.5 pg/g (Norin and Vahter, 1984). Baltic
herring from the same area had muscle tissue concentrations of total
arsenic of about 1.2 pg/g d.w., which was five to ten times less than the
arsenic concentrations in fish from the Swedish west coast (Ljunggren et
al., 1971). The mean relative amount of inorganic arsenic in fish from
this brackish-water area was between 5 and 10% of the total arsenic
content (Norin et al., 1985b), indicating that the distribution between
different arsenic species was similar to what has been found in marine
fish. It was furthermore indicated that some 5-10% of the organic
arsenic in the fish tissues was in the form of arsenocholine, while most of
the remainder consisted of arsenobetaine.
Based on the relatively scarce data on arsenic content and speciation in

organisms living in brackish water, it may be concluded that, generally,
the concentrations of total arsenic are lower than in marine organisms.
The difference appears to be particularly great when fish from the two
environments are compared. In the case of invertebrates, it appears that
bivalves and crustaceans from marine and brackish water areas show less
difference in the content of total arsenic, while gastropods have very
variable levels (cf. Table 11:2.2 and Table 11:1.1, where it should be noted
that concentrations are related to wet weight). Fish from both habitats
seem to contain very small fractions of inorganic arsenic, while the
picture becomes more complex when it comes to the different inverte
brate groups. Obviously, the feeding habits of invertebrates largely
determine the speciation of arsenic in their bodies, which means that no
general conclusions can be made regarding the relative amount of
40
inorganic arsenic occurring in a whole taxonomic group. However, the
available data do not indicate that there should exist any systematic
differences between invertebrates living in brackish water seas and those
living in marine areas.
Macroalgae, particularly brown algae, from marine ecosystems seem to

contain much higher
levels of total arsenic than the corresponding groups of algae in brackish
water ecosystems.
This difference may be due to the generally higher concentrations of
dissolved arsenic in marine waters, but possibly also to a more efficient
uptake of arsenate (which might be related to the usually lower
phosphate concentration) and a subsequent biosynthesis of arsenic-
containing ribosides in marine algae.
2.3 Biotransformation of arsenic

The rate of reduction and transformation of arsenate by phytoplankton
can undergo very dramatic variations in estuaries, due to the great
fluctuations in natural conditions in such habitats. For example,
correlations have been observed in the field between reduced and
methylated arsenic species and phytoplankton densities, chlorophyll-a
concentrations, and primary productivity (Sanders and Riedel, 1993).
Furthermore, phytoplankton species apparently differ in their ability to
produce arsenite, MAA and DMAA. This differential ability may
produce temporal and spatial trends in arsenic speciation within
estuaries, and these trends may be tied to changes in phytoplankton
species composition and the succession of dominant species (Sanders et
al., 1994). For example, Sanders (1985) noted a very strong correlation
between a dominant cryptophyte, Chroomonas sp., and the occurrence of
MAA in Chesapeake Bay (Figure 11:2.5). Another example is the
association of high concentrations of DMAA with a dramatic bloom of a
dinoflagellate (Riedel, 1993).
However, all algal blooms are not associated with elevated levels of
reduced and methylated arsenic. In the low-salinity regions of the Tamar
estuary in England, no increase of methylated arsenic was observed in
connection with the dominance of the freshwater centric diatom
Cyclotella atomus (Howard et al., 1988). A similar absence of arsenic
reduction during the spring diatom blooms was seen in other rivers in
England, but arsenic reduction was observed later in the spring (Howard
et al., 1984). The explanation might be either that diatom species do not
produce significant amounts of methylated arsenic or that the lack of
41
arsenic reduction is caused by the still high levels of phosphate in the
water early in spring, when the diatom blooms occur. At a later stage,
when the phosphate is depleted, the transformation of arsenic into
reduced and methylated forms can start (Sanders et al., 1994).
400-
300-
200-
100-
SAUNiTY (°/oo)
Figure 11:2.5. Relationship between the occurrence of methylarsonic

acid (A) and the densities of a dominant cryptophyte, Chroomonas sp., in
the waters of Chesapeake Bay (after Sanders et al, 1994).
42
The rates of arsenic reduction during phytoplankton blooms can be very
rapid. For example, in the Patuxent River, the maximum rates varies
from 130 ng/1, day in spring to >330 ng/1, day during midwinter dinofla-
gellate blooms (Sanders and Riedel, 1993). Viewed in relation to the bio
mass, the overall reduction rates varied from 2 to about 20 fg/cell, day at
arsenate concentrations between 0.5 and 2.0 pg/1 (Sanders et al., 1994).
However, cell densities are not the only deciding factor. Periods of
arsenate reduction are, in general, associated with periods of rapid
decline in phosphate concentrations (Sanders and Riedel, 1993). This
may reflect the existance of a causal relationship between phosphate
concentration in the surrounding medium and rate of uptake and
transformation of arsenic in phytoplankton cells. Thus, it may be
concluded that the most important controlling factors of the biotrans
formation of arsenic in estuaries and brackish water seas are the
phytoplankton species composition and arsenic-phosphorus dynamics.
One consequence of the prospensity of arsenic to change forms after its

introduction to the aquatic environment is a greater degree of uncertainty
about the effects of a release. Transformation of arsenate to arsenite or
DMAA, while an apparent benefit to the phytoplankton, may be more
detrimental to fauna components, which may be more sensitive to the
reduced and methylated forms (cf. Nissen and Benson, 1982), see further
discussion in section III.
2.4 Sinks, mobilization and bioavailability of arsenic species

The capacity of retaining arsenic being introduced into model
ecosystems of the type described in section 2.2 was investigated after
one year of continuous exposure to concentrations of arsenate in the
incoming water of 8 pg/1 and 75 pg/1, respectively (Notini et al., 1987).
The total amount of arsenate added to the systems was 22.5 g and 225 g,
and the percent retained was 5.3 and 1.4, respectively. The distribution of
arsenic between the different main components of the system is shown in
Table 11:2.3.
Added Sediment Fucus Filamentous Inverte Fish Total %of

amoun algae brates system added
A. 22,500 1,165 21 0 6 0 1,190 5,3
B. 225,000 3,140 0 27 22 1,4 3,190 1,4
Table 11:2.3. Distribution of added arsenic in model ecosystems after 1
year of exposure to 8 pg/l (A) and 75 pg/l (B) of arsenate. Values in mg
total arsenic (after Notini et al, 1987).
43
The reason why no arsenic was retained by the Fucus in the high
concentration pool was that the algae were killed at this level of arsenate
exposure. In both cases, about 98% of the retained amount was found in
the sediment, indicating that the sediment is the major sink for arsenic
being introduced into a littoral ecosystem.
In a similar type of experiment, using small, microcosm-type containers

with uncontaminated soft sediments from the deep areas of the Baltic
Sea and benthic organisms from the profundal community (Monoporeia
affinis and Macoma balthica), arsenic retention was studied over a period
of 222 days (Blanck et al., 1989). The microcosms received a continuous
flow of uncontaminated bottom water from the Baltic Sea and to the
incoming water, the following forms of arsenic were added: (a) arsenic-
contaminated phytoplankton (Skeletonema costatum), (b) dissolved
arsenate at concentrations of 20 and 100 pg/1, and (c) a mixture of
arsenate and ferric hydroxide (20 pg As + 40 pg Fe/1, and 100 pg As +
200 pg Fe/1). Of the total amount of arsenic added, about 20% was
retained in series (a), 1% in series (b), and 3% in series (c). Thus, iron
hydroxide is an efficient scavenger of aisenate in the water, increasing
the rate of arsenic deposition in the sediment. However, at least in
sediments containing benthic invertebrates, the most efficient retention
of arsenic was obtained when it was carried (probably in the form of
organic arsenic compounds) by algal cells.
It might not be possible to directly interpret these experimental results in

terms of sedimentation or fixation rates in natural systems. However, it
may be concluded that, in relative terms, arsenic bound to organic
material is more readily retained by the sediment compartment than is
arsenic in inorganic form, either dissolved or particulate. Furthermore, a
littoral system has a limited capacity to retain arsenic: with higher
amounts introduced, higher amounts are flushed through the system. As
far as the different species of dissolved arsenic are concerned, it has also
been demonstrated that arsenate and arsenite are readily sorbed to
sediment and suspended solids, while DMAA is less particle-reactive,
and is therefore more easily flushed through an estuary, where it is
formed as a result of phytoplankton production and methylation (Sanders
and Riedel, 1993). Arsenate introduced in relatively low concentrations
to a littoral system with dense communities of macroalgae is effectively
retained by the algae, and is transformed into arseno-sugars, which are
stored within the algal tissue.
44
During phytoplankton blooms in the Baltic Sea, arsenate is readily taken
up by the algae, methylated within the cells and partly excreted in the
form of MAA and (mainly) DMAA. This transformation is clearly seen
as a depletion of arsenate in the water of the euphotic zone and an
increase of DMAA (Figure 11:2.2). However, it can be assumed that most
of the arsenic taken up by the phytoplankton is transported towards the
bottom waters together with sedimenting dead algal cells. This is
reflected by the sharp increase in total dissolved arsenic, and particularly
of arsenite, in the bottom waters (Andreae and Froelich, 1984). This
sharp increase in total dissolved arsenic with depth has been observed
both in the Bornholm Basin (with low oxygen levels, but without any
hydrogen sulfide) and in the Gulf of Finland (without oxygen
depletion in the bottom water), see Figure 11:2.6. The lack of methylated
arsenic species in the bottom water also indicates that methylation of
arsenic by bacteria at the sediment-water interface is not probable. The
occurrence of MAA and DMAA is predominantly a result of the activity
of phytoplankton.
nM 0 I 2
0 2 4 6 8 10 12 (« <)
T4~r
8Y26
Figure 11:2.6. Concentration profiles of different arsenic species in the

Bornholm Basin (BY5) and in the Gulf ofFinland (BY26), in June 1981.
Asi = total dissolved inorganic As; As( = total dissolved arsenic (after
Andreae and Froelich, 1984).
It is not clear to what extent arsenite is remobilized at the sediment-

water interface under natural, undisturbed conditions. Andreae (1979)
has shown that arsenite in sedimentary pore waters may diffuse into the
overlying water column, but other investigators (e g Carpenter et al.,
45
1978) have failed to demonstrate the existence of any significant arsenic
flux from the sediments. The high arsenite concentrations near the
sediment in the Bornholm Basin (BY5) are probably a result of in situ
reduction of arsenate (Andreae and Froelich, 1984). Arsenite
concentrations in the anoxic bottom water in the Gotland Deep (Figure
11:2.2), rich in hydrogen sulfide, are very high, but also arsenate occurs
under these conditions, which is thermo-dynamically unexpected. The
explanation might be that arsenate may be present in the form of
thiocomplexes (thioarsenates), as suggested by Cotton and Wilkenson
(1972). Evidence for the formation of thioarsenates when sulfide is
added to seawater has been presented (Bertine and Lee, 1983).
In summary, the predominant arsenic species in surface waters of the

Baltic Sea, arsenate, is readily available for and taken up by
phytoplankton and macroalgae. Part of the arsenic taken up and
methylated by the algae is released in the form of arsenite, MAA and
DMAA. Part of the organic arsenic is brought by the dead algal cells to
the bottom water, where it is remobilized from the detritic material and
shows up mainly as arsenite. Arsenite is a relatively unstable species in
the oxic surface water layers, but is stable in the anoxic bottom water.
Thus, pelagic invertebrates and fish residing in the surface waters are
exposed to DMAA and MAA (in addition to arsenate), in particular
during and soon after algal blooms. The same might be true for benthic
animals in the macroalgal zone of the littoral. Benthic animals residing
on deep, oxic bottoms may be exposed to arsenite during the main part of
the year.

The previously described model ecosystem experiments, in which Baltic
Sea littoral ecosystems were continuously exposed to arsenate (and
transformation products) for about one year, have provided a great
amount of data on the bioaccumulation of arsenic (Notini et al., 1987).
When exposed to an arsenate concentration of 75 pg As/1, the dominant
phytal component of the ecosystem, Fucus vesiculosus, reached a steady-
state concentration in its tissues of 140 pg As/1, already after 2 days
exposure. However, this arsenate level was lethal to the brown alga,
causing complete elimination after 5-7 months. On exposure to 8 pg
As/1, the steady-state level in the algal tissue was 60-80 pg As/g d.w.
(Figure 11:2.7).
46
150 -
High dese
Low dose
Control
Day
Figure 11:2.7. Total arsenic concentrations in tissues ofFucus

vesiculosus, exposed to arsenate at 75 pgAs/l (X), 8 pgAs/l (O), and
0.5 pgAs/l (O) in brackish-water littoral mesocosms (after Notini et ah,
The green macroalga Cladophora reached arsenic concentrations of 260

pg/g d.w. in winter, but only about 50 pg/g d.w. in summer, when
exposed to 75 pg As/1, added as arsenate.
The fraction of organic arsenic in Fucus was >95% of total arsenic, under
natural conditions, but only about 60% of the total, when the alga was
exposed to 75 pg As/1, indicating that the ability of the alga to synthesize
organic arsenic compounds might reach a saturation level at increasing
exposure (Blanck et al., 1989).
The time required for arsenate-exposed blue mussels, Mytilus edulis, to

reach a steady-state concentration of arsenic (45 pg/g d.w.) in its soft
tissues was about 3 weeks (Notini et al., 1987). However, the body-
burden of arsenic in the mussles showed strong seasonal variations with
considerable increases during the spring phytoplankton bloom and the
47
maximum growth period of the macroalgae, Figure 11:2.8. The speciation
of arsenic in the water of the mesocosms was not determined, but it may
be assumed that the sharp increase in the body-burden of arsenic in the
mussels during spring reflects an increase in organic arsenic in food
particles (e g phytoplankton) as well as in the water. This is supported by
the observation that the other filter feeder or herbivorous species in the
model ecosystems (Cardium and the crustacean Idothea) also exhibited a
similar seasonal variation in arsenic content, with spring peaks.
Furthermore, the deposit-feeding bivalve Macoma balthica and the
carnivore polychaete Nereis diversicolor both showed maximum arsenic
concentrations in their body tissues at a somewhat later stage, in June-
July, after sedimentation of particles, probably containing organic
arsenic.
75 jug As/L
0.5 /jg As/L
Figure 11:2.9. Seasonal variation in total arsenic (pg/g d.w.) in the soft
tissues ofMytilus edulis exposed to arsenic (added as arsenate) in
brackish-water littoral mesocosms (after Notini et a!., 1987).
The importance of the food route for arsenic bioaccumulation was

further demonstrated in a 4-week experiment with the herbivore/
omnivore genera Lymnea and Gammarus. When arsenate was supplied
only via the water, no increase in arsenic body burden of the animals
took place, but when arsenic-laden algae were added, the animals
reached arsenic concentrations in the soft tissues comparable to the
levels of long-term exposed animals in complete model ecosystems
(Blanck et al., 1989).
48
The composition of total arsenic in the soft tissues of three mollusc
species after exposure to arsenate for one year in the model ecosystems
was determined by means of the HC1 distillation method. The inorganic,
HCl-distillable fraction was generally <20% of the total arsenic content
in Lymnea, Macoma and Cardium, but increased with higher arsenate
exposure in Cardium, see Figure 11:2.10.
Organic As
Inorganic As
OS 8 75.5 /ugAs/l
Cardium Macoma Lymnea
Figure 11:2.10. Concentrations of inorganic and organic arsenic (jxg/g

d.w.) in soft tissues of three mollusc species after one year arsenate
exposure (after Blanch et al. 1989)
When the benthic, soft bottom crustacean Monoporeia affinis was

exposed to arsenate in microcosms, it reached a steady-state in 220 days.
The arsenic concentrations in the animals at exposure to 100 pg As/1 was
about twice the control level of 4 mg As/g d.w. However, at
simultaneous exposure to arsenate and ferric iron, the bioaccumulation
was about double that when only arsenate was administered. In the same
experiment, it was found that the bivalve Macoma balthica accumulated
about five times more arsenic than M. affinis, with a tendency for higher
uptake in smaller animals (Sundelin, ref. in Blanck et al., 1989).
The observations made in the macrocosm and microcosm experiments

with Baltic Sea organisms were largely confirmed in studies of the
relative importance of different pathways of arsenic bioaccumulation
(via the water or the food-chain) in estuarine animals in the Chesapeake
Bay (Sanders et al., 1989). The uptake of arsenic from water and from
49
phyto-plankton was followed in the copepod Eurytemora affinis, the
barnacle Balanus improvisus and the oyster Crassostrea virginica. It was
found that dissolved arsenic was readily taken up by phytoplankton and
by shell material of the barnacle and the oyster. However, no dissolved
arsenic, at concentrations up to 56 pg/1, was incorporated into the soft
tissues of the animals during exposure periods of 3-4 weeks. When fed
phytoplankton containing elevated arsenic contents, all three animals
accumulated significant amounts of arsenic. Juvenile barnacles, mainly
feeding on phytoplankton, accumulated relatively more arsenic than
adults.
Compared to the 100-200% increase in arsenic content by phytoplankton

exposed to dissolved arsenic, the 25-50% increase in the investigated
invertebrate species via trophic transfer was relatively small (Sanders et
al., 1989). Thus, it may be concluded not only that dissolved inorganic
arsenic is relatively unavailable to estuarine invertebrates and
vertebrates, but also that there is no food-chain magnification of arsenic
in estuarine ecosystems. For many organisms, the arsenic uptake rates
will decline throughout the individual's development.
The possible biotic interactions and the pathways of arsenic uptake in a

simplified estaurine ecosystem are represented in Figure 11:2.11, based
on the results obtained by Sanders et al. (1989). The trophic pathway of
arsenic uptake is the major one affecting higher levels of the ecosystem.
As a result of the relatively low efficiency of arsenic bioaccumulation
from the food, the potential impacts from elevated arsenic levels in the
water are usually not important to trophic levels other than phyto
plankton. However, arsenic can also be incorporated into eggs and be
passed on to the next generation. Thus, under conditions of chronic
exposure, the second generation may start at higher arsenic concentration
and then, the youngest stages feeding on phytoplankton, may accumulate
arsenic more efficiently. For example, in experiments with copepods, it
was found that second-generation individuals showed a decreased ability
to develop to adults when cultured under conditions of chronic arsenic
exposure (Sanders et al., 1988). In conclusion, it is obvious that
bioaccumulation and the potential for impact of arsenic can be extremely
complex in an estuarine ecosystem.
50
DIRECT UPTAKE TROPHIC TRANSFER
NON-FEEDING
EGGS, LARVAE
SHELL DEPOSITION- ^ ADULT

r BARNACLES / BARNACLES
DISSOLVED
ARSENATE ZOOPLANKTON.
PHYTOPLANKTON
INCLUDING LARVAE
SHELL DEPOSITION-
JUVENILE OYSTERS
OYSTERS
ADULT OYSTERS
Figure 11:2.11. Pathways of arsenic uptake in a simple estuarine

ecosystem. Thickness of lines denotes the relative amount of arsenic
incorporated (after Sanders et al, 1989).

The data presented in the previous sections clearly show that the
thermodynamically most stable form of dissolved arsenic in brackish
water, i.e. arsenate, is readily available to aquatic plants, both
phytoplankton and attached micro- and macroalgae, because of its
chemical similarity to phosphate (Sanders and Windom, 1980). On the
other hand, dissolved arsenate has a low bioavailability to invertebrates
and vertebrates. However, arsenate can be readily transformed under the
influence of various natural factors. The most important factor in
productive estuaries or brackish water seas, such as the Baltic Sea, seems
to be the activity of the plant community, i.e. the primary production of
the attached macroalgae in coastal or shallow areas, and the phyto
plankton production in the open sea.
All examined phytoplankton communities have the capacity of

producing and releasing reduced arsenic, arsenite, as well as a variety of
methylated arsenicals into the water column, but the rate of reduction can
vary. The rate and extent of arsenate reduction and methylation apperas
to be dependent upon the concentration of arsenate, the dominant
phytoplankton species present, the season, and the degree of decline in
phosphate concentrations during bloom development (Sanders and
Riedel, 1993). For example, in the Chesapeak Bay, arsenite - a relatively
unstable chemical form - was present in significant quantities in the
surface waters only in late spring. Significant concentrations of MAA
51
and DMAA coincided with blooms of certain phytoplankton species. The
MAA detected in natural systems may be a degradation product of
DMAA. However, the latter compound is more stable than arsenite, and
may persist for some time in the water column. Arsenate and arsenite are
more readily sorbed to sediment and suspended particles than DMAA,
and may therefore be more rapidly transported to the bottom, together
with the organic arsenic compounds incorporated in dead algal cells.
In the anoxic bottom waters, arsenite usually is the predominant

dissolved arsenic species, and in waters containing hydrogen sulfide,
dissolved thioarsenates may also occur. Release of arsenic from
sediments to bottom water, in general, seems to be of minor importance
for the arsenic cycle.
In the pelagic communities, during periods without any major

phytoplankton blooms, arsenic is almost exclusively taken up by
invertebrates and vertebrates by food-chain transfer, most efficiently
from phytoplankton to herbivores. No food-chain biomagnification has
been demonstrated. The benthic communities may be exposed to
dissolved arsenic species such as arsenite and DMAA/ MAA, which
might be more bioavailable than arsenate. Benthic invertebrates may
therefore take up dissolved arsenic in addition to the complex organic
arsenic compounds contained in their food.
The main risk of arsenic exposure of pelagic, brackish-water animals

occurs during dense phytoplankton blooms involving specific algal
species, when concentrations of DMAA may be high in the euphotic
zone. Diatom blooms, induced at relatively high phosphate
concentrations in the water, apparently do not produce high
concentrations of methylated arsenicals. On the other hand, blooms of
the cryptophyte Chroomonas sp. and the dinoflagellate Katodinium
rotundatum have been shown to be associated with significant production
of dissolved methylated arsenicals (Sanders et al., 1994). The latter
phytoplankton species started its bloom in the winter, at low temperature
and low phosphate concentration (3 pg P/1), but high nitrogen
concentration (140-210 pg N/l) (Sanders and Riedel, 1993).
If we translate these data to the conditions in the Baltic Sea, it might be

assumed that the important spring blooms of diatoms (in March-May) do
not generate large quantities of reduced or methylated arsenic species,
while phytoplankton blooms later in the year, involving other algal
groups, may produce significant amounts of arsenite and DMAA.
52
Unfortunately, the phytoplankton species involved in the high production
of methylated arsenicals in the Gulf of Finland, in June 1981 (Andreae
and Froelich, 1984), were not reported. Nor is it known how efficient
cyanobacteria, e g Nodularia sp., which often bloom during the summer
and autumn in the Baltic Sea, are in reducing and methylating arsenate.
3. Freshwater Environment (Lakes and Rivers)
3.1 Arsenic speciation in water and sediments

3.1.1 Lake and river waters
While arsenic speciation has been thoroughly studied in marine
ecosystems, and also relatively well investigated in the brackish-water
environment, comparatively less data are available from inland waters.
However, as far as the dissolved arsenic species in the water column of
lakes are concerned, a series of studies have been carried out, mainly in
the U S. and Japan (see Maeda, 1994, for references).
The main difference between freshwaters and marine/ brackish-waters

that influences the speciation of arsenic is that in freshwaters, the pH and
the content of humic substances seem to play a relatively more important
role. The importance of pH for the speciation of inorganic arsenic is
clearly demonstrated in the classical Eh-pH diagram, presented by
Ferguson and Gavis (1972), Figure 11:3.1. As can be seen in the diagram,
the dominating inorganic species in aerobic waters at pH close to
neutrality is arsenate, which may be reduced to arsenite both abiotically
and biotically, at lower Eh values. Increased acidity enhances the
formation of arsenite, while high pH and high oxygen content favour the
oxidation to arsenate. Sulfides of arsenic - both solid and dissolved
species - predominate under reducing conditions in the presence of
reduced forms of sulfur (Ferguson and Gavis, 1972). In highly anaerobic
environments, volatile arsines may be formed (Woolson, 1977).
53
H,AsO,
HAsO*-
H.AsO,
i - HAsS-
-0.25
-0.50
-0.75
Figure 11:3.1 Eh-pH diagram for inorganic arsenic at 25 °C and 1 atm.

Solid species are enclosed in parentheses in cross-hatched areas (from
Ferguson and Gavis, 1972).
Arsenate forms strong complexes with dissolved humic material, the

stability of which increase with decreasing pH. Thus, in humic and acid
freshwaters, the mobility (but not the bioavaila-bility) of arsenic may be
higher than what would be expected from pureley thermodynamic
considerations (Reuther, 1989). On the other hand, arsenate can form
insoluble precipitates with calcium, iron and aluminium compounds in
natural water, although several of these reactions are slow in nucleation
and have slow growth rates (Lemmo et ah, 1983). It is generally assumed
that iron is a possible candidate for controlling dissolved arsenate in
natural freshwaters. However, since the formation of arsenic precipitates
with iron is so slow, any dissolved arsenic species are more likely to be
adsorbed on the surface of inorganic, suspended particles (Blanck et ah,
1989).
54
In uncontaminated freshwaters, the concentration of total dissolved
arsenic is generally lower than in estuarine and marine waters. This has
been clearly demonstrated in studies where the total dissolved arsenic
has been followed in estuaries of big rivers, from areas with a salinity of
0%o to areas influenced by seawater with a salinity of about 30%o. In
such estuaries in Canada, the arsenic concentrations gradually increased
from 0.08 to 0.5 pg As/1 in the freshwater area to about 1.4 fig As/1 in the
marine area (Tremblay and Gobeil, 1990). However, there are many
examples of high to very high levels of total dissolved arsenic in some
inland waters, where the geological conditions result in very high arsenic
leaching. Among the highest levels of dissolved arsenic in
uncontaminated river water, so far recorded, were found in River Mauri
in the Bolivian Altiplano (about 1,000 pg As/1) as well as in the lower
reaches of River Desaguadero, draining Lake Titicaca, where levels
between 360 and 580 pg As/1 were repeatedly recorded (PPO, 1996).
The natural background concentrations of total arsenic in the water of

Swedish lakes and streams are shown in Table 11:3.1.
Area Average (jug/l) Range (jug/l) Reference

Lakes SW Sweden 0.10-0.36 0,10-0,36 Borg, 1984
Lakes, Norrland 0,22 0,11-0,40 Borg, 1984
Lakes, Norrland 0,25 0,06-1,20 Bjorklund et al.,
1982
Streams, Norrland 0,2-0,4 Landstrom and
Wenner, 1965
Svartalven, W 0,27 Borg, 1984
county
Storan, Z county 0,08 Borg, 1984
Petikan, AC 1,7 Borg, 1984
county
Table 11:3.1 Background levels of total arsenic in naturalfreshwaters
in Sweden.
In small forest lakes in the area of influence of atmospheric fallout, in

the vicinity of the large copper and lead smelter, Ronnskarsverken, in
northern Sweden, the arsenic concentrations in the lake water were (in
1984) >5 pg As/1 wihtin 10 km from the source, and most of the lakes
within 40 km had >2 pg As/1, while lakes situated at more than 100 km
distance from the smelter usually had <0.5 pg As/1 (Rosen and Lithner,
55
1986). During a sampling campaign in August 1984, water samples from
10 lakes in the Ronnskar area were fractionated by means of filtration
(0.4 pm) and in situ dialysis (0.002 pm). Arsenic in the filtrate varied
between 61% and 100%, and the dialyzable arsenic ranged from 35% to
94% (mean 57%) of the amount found in unfiltered samples (Borg,
1986). The dialyzable fraction, which is supposed to be directly
bioavailable, varied as a function of the pH value and the content of
humic material. It was highest in lakes with low humus content and high
(>7) pH, and lowest in a lake with a pH-value of 5.9 and very high
humus content.
The distribution between inorganic and organic species of dissolved

arsenic in freshwater seems to be very much the same as in brackish-
water, and the same kind of natural factors appears to affect speciation.
The general picture emerging from several studies in lakes is that the
biological activity (phytoplankton production) in the surface euphotic
zone during summer is responsible for the formation of dissolved
methylated arsenicals, such as MAA and DMAA (Maeda, 1994). For
example, in lakes in California, the methylated species represented 1-
59% of the total arsenic in the lake water, with DMAA reaching high
concentrations only in the epilimnion, but MAA showing almost uniform
concentrations throughout the whole water column (Anderson and
Bruland, 1991). During the winter, when complete mixing of the lakes
occurred, the arsenate concentration was restored at the expense of the
methylated forms.
3.1.2 Freshwater sediments

Inorganic arsenic species predominate in freshwater sediments, but
traces of MAA and DMAA are generally present, usually with higher
levels of MAA than of DMAA, the latter being opposite to the situation
in the water column (Maeda, 1994). It is therefore assumed that DMAA
is demethylated to form MAA by sediment microorganisms. Both
DMAA and MAA have been shown to be demethylated by anaerobic
river sediments (Holm et al., 1979).
In the interstitial water of freshwater sediments, the arsenic

concentration was highest at pH values <4 and >9. It was suggested that
the mobilization of arsenic at low pH values is due to the dissolution of
hydrous oxides of manganese and iron, while the mobilization at high pH
values most probably depends on a competitive ligand exchange between
arsenate and phosphate (Clement and Faust, 1981). The competition
between arsenate and phosphate for sorption sites on suspended and
56
sediment particles was also observed in experiments carried out by
Reuther (1992), indicating that phosphorus-poor sediments would be a
more efficient sink for arsenate than phosphorus-enriched ones.
The sorptive behaviour of inorganic arsenic has been the subject of many
studies (see e g Gupta and Chen, 1978). Arsenate reaches adsorption
maxima for iron, manganese and aluminium hydroxides, and clay
minerals, at pH values between 4 and 7, while adsorption of arsenite
increases with pH, reaching a maximum at pH around 9. Thus, there are
several mechanisms contributing to the immobilization and incorporation
of arsenic into the bottom sediments of lakes and ponds, where it
remains at least as long as the overlying water remains aerobic (Maeda,
1994).
3.2 Arsenic levels and speciation in biota

Much less is known both about the total levels and the distribution of
arsenic species in freshwater biota than in biota from marine and
brackish-water ecosystems. However, available data seem to indicate
that arsenic levels in both plants and animals from uncontaminated fresh
water environments, in general, are lower than those found in waters
with higher salinity.
In oligotrophic lake water (conductivity = 3.4 mS/m; phosphate-P = 3-4

pg/1; arsenic = 0.1-1.0 pg/1; and pH = 6.2-6.S), the total arsenic content
in leaves and roots of the aquatic plant Lobelia dortmanna was 0.2-0.3
pg/g d.w., in the soft tissues of the mussel Anodonta cygnea, about 4
pg/g d.w., and in the hepatopancreas of crayfish (Astacus astacus), 3
pg/g d.w. (Reuther, 1992). The aquatic moss, Fontinalis spp., sampled
from uncontaminated lakes in northern Sweden, contained 1-3 pg As/g
d.w., but in mining areas, elevated levels of arsenic (11^40 pg/g d.w.)
were detected in the tissues of the moss (Bjorklund et al., 1982). The iron
content in the lake water was found to strongly influence the arsenic
level of the moss (Blanck et al., 1989).
Zooplankton sampled in various lakes in the Ronnskar area in northern

Sweden, where the water contained 0.4—3.7 pg As/1, also showed
relatively low concentrations of total arsenic, 2.3-4.8 pg/g d.w., but in a
lake with 32 pg As/1 in the water, the zooplankton exhibited an elevated
level of 12 pg As/g d.w. (Blanck et al., 1989).
Fish from the North American Great Lakes are reported to contain 0.03-
0.12 pg As/g d.w. (Traversy et al., 1975; Pillay et al., 1973), while in
57
small, uncontaminated forest lakes in northern Sweden, muscle tissue
from roach, perch and pike was reported to contain 0.06-0.09 pg As/g
d.w. (Norin and Vahter, 1984). This is less than half the concentration of
total arsenic in fish (perch and pike) from the Bothnian Bay (cf. section
2.2), and one to several magnitudes of order less than what is usually
found in marine fish (cf. section 1.2.3).
Perch from the arsenic contaminated lakes in the Ronnskar area were
found to contain between 0.1 and 1.4 pg As/g d.w. in the muscle tissue,
and these levels correlated well with the concentration of arsenic in the
water of lakes, where the pH was >5.8. Arsenic in the liver of the same
fish varied with the season, showing the highest levels in summer
The information is very scarce about the occurrence of organic arsenic

species in freshwater organisms, including fish. However, DMAA,
trimethylarsine oxide, arsenocholine and traces of arsenobetaine were
identified in fish from lakes in the Ronnskar area (Norin and Vahter,
1984; Norin et al., 1985b). Unfortunately, due to the low to veiy low
levels of total arsenic in these samples, it was not possible to quantify the
various organic arsenic species. However, the fraction of inorganic
arsenic in most of the fish species was determined to be 5-12% of the
total arsenic content, and this fraction tended to decrease with increasing
total arsenic concentrations (Norin et al., 1985b). Thus, in spite of the
lack of confirming data, there is little reason to believe that the
composition of the arsenic in freshwater fish should be radically different
from the composition found in marine and brackish-water fish.
3.3 Biotransformation of arsenic

While the biotransformation of arsenic compounds by organisms in
marine ecosystems has been thoroughly investigated (see section 11:1.3),
only few experimental or field studies have been made to elucidate the
biotransformation of arsenic in the freshwater environment. Most of
these few studies were conducted by Maeda and co-workers (Maeda et
al., 1990; 1992a; b; Maeda, 1994; Kuroiwa et al., 1994; 1995).
Unfortunately, no chemical identification of the methylated trans
formation products was carried out; the organic arsenicals were only
characterized as monomethylated, dimethylated and trimethylated
arsenic compounds, respectively. No other studies have been found in
the literature, where conclusive data on the identity of the organic
arsenicals formed by freshwater organisms are presented. Therefore, it is
still not possible to draw any definite conclusions about the possible
discrepancies between the metabolic cycle of arsenic in marine and
58
freshwater environments. However, available studies provide some clues
regarding the similarities, as will be shown in the following.
Already in the beginning of the 1970s, Lunde (1972) found that various
freshwater algae contained arsenic in the lipid phase, suggesting that this
arsenic was organically bound. Later, Nissen and Benson (1982) exposed
the blue-green alga Rhizoclonium sp. to 74As-arsenate for one week and
then extracted the cells with ethanol. It was found that almost all the
arsenic in the cells was present as lipid- or water-soluble "lipid-related"
compounds, which had chromatographic characteristics very similar to
those extracted from marine algae. Similar treatment of charophytes,
water ferns and higher plants revealed that the fraction of "lipid-related"
arsenicals was somewhat smaller, but always at least 60% of the total
(Cullen and Reimer, 1989). These results indicate that arsenate taken up
by various limnetic aquatic plants may be transformed into
arsinylribosides.
Maeda et al. (1992a) showed that the green alga Chlorella vulgaris,
when exposed to MAA, the cells contained both mono- and dimethylated
arsenic, while when exposed to either DMAA or arsenobetaine, the cells
contained only dimethylated or trimethylated arsenic, respectively. Thus,
this alga was capable of biomethylating MAA (but not DMAA), but was
incapable of demethylating any of the methylarsenicals.
In a food-chain experiment, where arsenic was accumulated via the food

from Chlorella to the herbivore Moina sp. and further to the carnivore
Poecilia sp. (guppy), almost all the arsenic in the algae was in inorganic
form, but in the herbivore some 15% was in dimethylated form, and in
the fish about 85% was in the trimethylated form (Maeda et al., 1992b).
In a similar food-chain experiment, including Chlorella, the freshwater

shrimp Neocaridina denticulata and the killifish (Oryzias latipes),
Kuroiwa et al. (1994) measured not only the amount and form of arsenic
in the different trophic levels, but also the amount of arsenic excreted
into the water by the shrimps when exposed to each of the following
compounds: arsenate, MAA, DMAA and arsenobetaine.
The algae in the food-chain experiment were cultured in the presence of

arsenate, but contained, after one week, 11% of methylated arsenicals.
The shrimps received arsenic for 7 days, only via the algae and contained
39% methylated arsenic, mainly dimethylated. Finally, the fish, after 7
days feeding with shrimp powder, contained 80% of trimethylated
59
arsenic. The concentration of total arsenic in the organisms decreased by
more than an order of magnitude for each trophic level, but steady-state
was probably not achieved.
The accumulation and excretion experiments indicated that both

methylation and demethylation occurred within the shrimps, and that the
excreta contained both inorganic arsenic and mono-, di- and trimethy-
lated compounds, regardless of the dosed compound.
To summarize the experiments dealing with freshwater

biotransformation of arsenic, it is clear that, in spite of the incomplete
and scattered data, the occurrence of biomethylation of arsenic has been
proven. The fact that great variations have been found in the capacity of
freshwater algae and higher plants to methylate arsenic indicates that the
difference between species in this respect might be greater in the fresh
water than in the marine environment. Whether or not the trimethylated
arsenic which predominates in freshwater fish is arsenobetaine, like in
marine fish, has not been proven, but at least traces of arsenobetaine
have been positively identified in some species of freshwater fish (Norin
et al., 1985b).

species
As mentioned in section 3.1.2, the fate of arsenic introduced into the
water column of a lake depends on the presence of precipitating and
sorbing agents, such as hydrated iron and aluminium oxides, and on the
affinity for complexation with inorganic and organic ligands, e.g. amino
acids, humic constituents and sulfide ions (cf. Reuther, 1986).
However, the most efficient mechanism for stripping arsenic from the
water column probably is related to the incorporation of arsenic into
phytoplankton and the subsequent removal by sedimentation from
surface waters of lakes. The efficiency of this mechanism for the
removal of arsenic from the water column was shown to depend on both
the concentration of arsenic and phosphate in the water (Reuther, 1992).
In large mesocosms continuously dosed with arsenate (final concentra
tions were 5 and 50 pg As/1) for 65 days, without and with simultaneous
addition of phosphate (final concentrations, 3 and 5 pg P/1), the amount
and the arsenic concentration of the settling material was measured. It
was found that the low arsenate dose without phosphate addition
generated about twice the amount of sediment as was formed with
phosphate addition, and in the latter case, the arsenic concentration was
60
twice as high (Table 11:3.2). This result may be explained by an
increased mortality of the phytoplankton in the absence of phosphate
addition, which generated a higher volume of settling material. In the
high arsenate dose, this effect was much stronger: a very high sedimenta
tion of dead algal cells at low, but almost no sedimentation at somewhat
higher phosphate concentration. The small amount of settling material in
the latter case with very high arsenic content can be assumed to consist
of dead cells of arsenic-tolerant algal species that were able to survive
long enough to accumulate high amounts of arsenic due to the higher
phosphate concentration (Reuther, 1992).
No. Treatments Settling material

Arsenate (pgAs/l) Phosphate (ug P/l) Dry weight (g) Tot. As (pg/g)
1. 0,1-1,0 3 1,8 1,5
2. 5,0 3 3,6 4,4
3. 5,0 5 2,0 10,6
4. 50 3 4,4 40,5
5. 50 5 0,5 76,0
Table 11:3.2 Amount ofsettling material and its arsenic content in five
flow-through mesocosms exposedfor 65 days to different concentrations
of arsenate and phosphate (after Reuther, 1992).
Leaching rates of arsenic from CCA-treated wood has been measured,

for 7 days, in water with different salinity (0, 6 and 12 %o, respectively).
It was found that the leaching rate in the freshwater was more than
double (70 pg/cm2) that recorded in the brackish-water test (about 30
pg/cm2) (Sanders et al., 1994).
The bioavailability of the various arsenic species to organisms at

different trophic levels has been studied in several uptake experiments in
the laboratory. Unfortunately, these experiments have, in general, been
conducted at high to very high exposure concentrations, and for rather
short exposure times, which make the results difficult to extrapolate to
the natural environment. However, some conclusions on the relative
bioavailability of arsenicals to different organisms may be justified,
based on these experiments.
Marin et al. (1992) investigated the relative bioavilability of different

arsenic species to rice (Oryza sativa), grown in nutrient solutions, inter
alia containing 10 mg P/1, enriched with arsenic compounds at
concentrations of 50,200 and 800 pg As/1. The bioavailability of arsenic
to rice followed the trend DMAA < arsenate < MAA < arsenite,
regardless of the concentration added, Figure 11:3.2. Upon absorption,
61
DMAA was readily translocated to the shoot, while the other three
arsenic species largely accumulated in the roots (Marin et al., 1992).
0.05 0.2 0.8

Arsenic concentration in nutrient solution
(mg / L)
Figure 11:3.2. Arsenic concentrations in shoots of rice, cultivatedfor 4

weeks in nutrient solutions containing different forms and concentrations
of arsenic (after Marin et al., 1992).
Maeda et al. (1992a) compared the availability and uptake of four arsenic
species to the green alga Chlorella vulgaris at nominal concentrations as
high as 10 mg As/1. After 7 days, the cell content of total arsenic was
about 5 times higher, when arsenate was added, than when either MAA,
DMAA or arsenobetaine was added. The three methylated species had
the same degree of bioavailability to the alga.
62
200 -
As(V) concentration in water (jig As/mL) DMAA concentration in water (jig As/mL)
2000
ee 1000
1 s 10
MAA concentration in water (jig As/mL) AB concentration in water (jig As/mL)
Figure 11:3.3. Total arsenic accumulated by the shrimp Neocaridina

denticulata from the water phase containing one offour different arsenic
species ( Kuroiwa et al., 1994)
In a similar experiment, the shrimp Neocaridina denticulata was

exposed for 7 days to the same four arsenic forms, dissolved in the water.
At an exposure concentration of 1 mg As/1, arsenate and MAA were
equally bioavailable, while DMAA was less available for uptake (Figure
11:3.3). Arsenobetaine was taken up most efficiently (Kuroiwa et al.,
1994), but this compound usually does not occur dissolved in water at
elevated concentrations in natural waters.
Experiments with another shrimp, Macrobrachium rosenbergii), which

were conducted at extremely high arsenic concentrations, confirmed the
above results. The availability of arsenate and MAA to the shrimps was
equally high, but DMAA was taken up at a rate about 20% of the rate
determined for MAA (Kuroiwa et al., 1995).
63
Finally, dissolved arsenate, occurring in high concentrations, is readily
bioavailable to killifish (Oryzias latipes), which accumulates arsenic
mainly in inorganic form, but 20-40% of the total arsenic in the fish was
recovered as methylated species, mainly monomethylated (Kuroiwa et
al., 1994).
Probably the main factor, in natural limnetic systems, determining the

bioavilability of the predominant arsenic species in lake water, arsenate,
to the most important organisms for the flux of arsenic into the food web,
is the actual concentration of phosphate. At low ambient concentrations
of both arsenate and phosphate, the complex interaction between the two
ions has important consequences both for the flux of arsenic into cells
and for the effects on populations and communities. These aspects will
be further discussed in section 111:3.

Although there are great differences between different algal species in
their capacity to accumulate arsenic from the water phase (Andreae and
Klumpp, 1979), it appears that there are no systematic differences in this
respect between freshwater and marine algae. Lunde (1973) cultivated
three species of freshwater and three species of marine unicellular algae
in freshwater and saltwater media, respectively, containing radioactive
arsenic ions. Arsenic enrichment in the freshwater algae was 240 to
2,800 times the concentration in the medium, while in the marine algae,
the enrichment was 710 to 2,900 times. Thus, freshwater algae seem to
have the same capacity to concentrate arsenic from the water phase as
the marine algae.
A culture of the green alga Chlorella vulgaris was isolated from a site
with high natural content of arsenic, and was found to tolerate arsenate
levels in the medium up to 10 g/1 (Maeda, 1994). When this culture was
grown in a medium containing 100 mg As/1, the arsenic level in the cells
reached 20 mg/g d.w., and when grown in the highest concentration
tolerated, 10 g As/1, a level of 50 mg/g d.w. was recorded. Maeda and
coworkers also investigated the role of pre-acclimation to arsenate of
Chlorella cultures on the degree of arsenic accumulation of the cells. It
was found that the higher the pre-acclimation concentration, the higher
was the degree of arsenic bioaccumulation in the cells at the stationary
growth phase.
64
No arsenate was bioaccumulated by Chlorella cells that had been
pretreated with the respiratory inhibitor dinitrophenol or with heat, while
only little effect of pretreatment with the photo-synthesis inhibitor
sodium azide on arsenic bioaccumulation was observed (Maeda, 1994).
Phosphate competitively inhibited arsenic accumulation by C. vulgaris,
and in some other algae, such as Chlamydomonas sp. and Phormidium
sp., arsenate reduced phosphate uptake. The cyanobacterium
Synechococcus leopoliensis was found to be almost insensitive to
arsenate, showed low arsenate uptake, and high discrimination for
phosphate (Planas and Healey, 1978; Budd and Craig, 1981; Maeda et
al., 1988).
In field studies in a series of lakes, contaminated with arsenic from

mining effluents, the bioconcentration in various vascular plants was
investigated (Dushenko et al., 1995). It was found that bioaccumulation
of arsenic usually was much higher in submerged plants, such as
Potamogeton pectinatus and Myriophyllum sp. than in emergent
species, such as Typha latifolia. Concentration factors (plant
tissue/sediment) were in the range of 1.3-3.4 in the first category of
plants, while the average concentration factor for Typha latifolia shoots
was only 0.04, and for roots, 0.59. It is well known that the two first
mentioned plant species primarily take up nutrients from the water
phase. No relationship could be demonstrated between tissue
concentrations of arsenic and environmental concentrations of
phosphorus. It was concluded that the lack of arsenate/ phosphate
interaction in the studied system might be due to the relatively high
levels of arsenic, caused by the mining effluent discharges (200-500 pg
As/1 in the water column), and that such interactions might only be
observed at low, natural arsenate concentrations.
Also in the controlled mesocosm experiments (designed as shown in

Table 11:3.2) run at relatively low arsenate concentrations (5 and 50
pgAs/1), no competitive inhibition of arsenic bioaccumulation in plants
caused by phosphate was observed (Reuther, 1992). On the contrary,
somewhat increased phosphate concentrations, in basins 3 and 5 (see
Figure 11:3.4), resulted in higher arsenic accumulation, accompanied
with enhanced biomass of both leaves and roots of Lobelia dortmanna..
The stimulation of arsenic bioaccumulation in the leaves of the plant by
the addition of small amounts of phosphate to the water was quite
conspicuous. On the other hand, phosphate addition did not seem to
stimulate the accumulation of arsenic in periphyton (Figure 11:3.4).
65
ppm dw
250
zee
150
As ppm dw
100
50
0
1
has in
Figure 11:3.4. Bioaccumulation of arsenic in leaves ofLobelia

dortmanna (upper part) and in periphyton (below) as afunction of
arsenate and phosphate concentrations. For explanation of treatments,
see Table 11:3.2 (after Reuther, 1992).
Based on the many freshwater food-chain experiments carried out by

Maeda and coworkers (e g Maeda et al., 1990; 1992b; Kuroiwa et al.,
1994; and review in Maeda, 1994), it can be concluded that the main
route for bioaccumulation of arsenic in higher trophic levels of
freshwater ecosystems is via the food, i e much the same as has been
66
observed in marine and brackish-water ecosystems. It is generally found
that organisms at lower trophic levels (unicellular algae as well as
aquatic plants) have a greater ability to accumulate arsenic than the
herbivorous or carnivorous organisms. Thus, arsenic is not biomagnified
in the freshwater food-chain, which is in striking contrast to the situation
for e g mercury.
Biomethylation of arsenic by freshwater organisms has been

experimentally proved, but the exact nature or the chemical structure of
the organic arsenic compounds present in the living cells of freshwater
organisms still have to be revealed.

As mentioned before, many observations support the existence of an
interaction between phosphate and arsenate in the water phase,
controlling the bioavilability and the uptake of arsenate into the cells of
aquatic plants. However, results presented by different researchers are
conflicting: in some cases, a competitive inhibition of arsenate uptake by
phosphate has been reported, while in other cases, phosphate seems to
have a stimulatory effect on the uptake and bioaccumulation of arsenic.
There are also some reports indicating that no relationship at all should
occur between phosphate and arsenate. These conflicting results will be
further discussed in Section III of this report, where effects of arsenic
exposure are described, because the assessment needs to take into
account the interaction of arsenate with the phosphorus metabolism of
cells, including effects on photosynthesis, respiration and other parts of
the energy metabolism.
In spite of the conflicting observations described in previous sections, it

appears that - in one way or another - the amount of phosphate available
to the aquatic plants determines the fate of arsenate introduced to a
freshwater aquatic system. Since the phosphate concentration can show
extremely great variations in freshwater ecosystems, both between lakes
or rivers and between seasons as well as between different water layers
and sediment strata, it is pertinent to devote a great interest to the
possible interactions between phosphate and arsenate in the assessment
of the environmental risks of arsenic.
In freshwater environments, other important natural factors determining

speciation and bioavailability of arsenic are the content of humic
material and the occurence of hydrous iron, manganese and aluminium
oxides in the sediment as well as in the water column. The adsorption of
67
arsenic to sediments, suspended solid particles and humic material is
related to the pH and the redox-potential. Once adsorbed, arsenicals are
not easily removed (Mok and Wai, 1994). Arsenate and arsenite differ in
adsorption characteristics: arsenate is charged and adsorbed over a wide
pH range, whereas arsenite is not, which is consistent with the greater
mobility of arsenite. The increase in mobility of arsenate under more
reducing conditions is generally attributed to the reduction of Fe(III) to
Fe(II), with subsequent release of arsenate, and to the reduction of
arsenate to arsenite. The arsenic-humic acid interactions may, at certain
pH values, especially at low pH, be as important as adsorption to
hydrous oxides. Increased acidity during sediment-water interactions
will result in decreased stability of the iron oxy-hydroxides, and this
changes the binding efficiency for arsenicals, thus mobilizing the arsenic
(Mok and Wai, 1994). However, in acid lakes with a high content of
humic material, the released arsenic is most probably complexed by
humic acid, resulting in an increased mobility of the arsenic, but without
any notable increase in its bioavailability.
It may be impossible to propose a general model for arsenic

biogeochemistry. Different ecosystems have specific blends of both
geochemical and biological controls over arsenic speciation, and contain
different types of biological communities. Once a given system has been
described, the patterns of arsenic speciation are explainable and potential
impacts can be identified, but they cannot necessarily be transferred to
another system. However, the continuing accumulation of information
concerning different types of systems does lead to a greater overall
understanding of arsenic biogeochemistry. It is clear that successful
predictions will require not only a background understanding of arsenic
biogeochemistry, but also a thorough understanding of the trophic
relationships of the particular system under examination (Sanders et al.,
1994).
4. Water Quality Characteristics in Inland European

Water Bodies of Relevance for Arsenic Speciation
Because of the chemical similarity between arsenate and phosphate, the
water quality characteristic that is most important for the uptake and
transformation of arsenic in living cells is phosphorus. Concentrations of
total phosphorus in lakes and rivers vary over a very broad range,
depending on the geological background and the type of soils existing in
the catchments, but even more important for determining the actual
phosphorus concentration are the type and the scope of human activities:
land use, amount of phosphate fertilizers and manure used in agriculture,
68
degree of phosphorus removal in sewage treatment, type of industrial
effluents and degree of treatment.
As a part of the large OECD Project on Eutrophication of Waters, the

concentration of phosphorus in more than 100 lakes and reservoirs in
Europe and North America was measured, mainly during the 1970s.
Based on these data, the mean annual concentration of total phosphorus
in 115 lakes and reservoirs has been reported as 47 pg P/1 (range: 3-750
pg P/1) and the mean annual concentration of phosphate in 99 lakes and
reservoirs as 16 pg P/1 (range: 0.2-890 pg P/1) (OECD, 1982). Although
some 35 North American lakes were included in the data base, the
average values are quite representative for European lakes and
reservoirs. The highest values of phosphorus are usually found in
shallow lakes in the plain districts of Central Europe. In these areas, the
average phosphorus concentrations in lake water are much higher than
the average concentrations in the Scandinavian lakes. However, the
results of the OECD programme on lakes and reservoirs in Europe and
North America have shown that, in most cases, phosphorus is the
limiting factor which determines the development of eutrophication
(OECD, 1982).
Generally speaking, in Europe, the situation is the following: in low-land

areas where a high percentage of land is used for agricultural purposes,
and the population density is high, the highest concentrations of
phosphorus are found in relatively shallow lakes, which therefore, tend
to be eutrophic. In mountainous, hilly and forested areas of Europe with
low degree of agricultural exploitation, the oligotrophic lakes are found
with low levels of dissolved phosphorus in the water. In some forested
areas, especially in Finland and Sweden, the lakes furthermore contain
high amounts of humic material dissolved in the water.
Below are given a few examples of the general levels of phosphorus in

some great lakes in Europe. Data are given as concentrations of total
phosphorus. This way of reporting phosphorus concentrations in lake
water is more justified than giving concentrations of reactive phosphorus
or phosphate, because the turnover of phosphorus in the lake water is
quite rapid, mainly due to the activity of bacterioplankton. Therefore, a
speciation of phosphorus at any given point in time is usually not
meaningful, at least not for the present purposes. The data given below
are compiled from Eurostat (1994).
69
Lake Ysselmeer (NL) 200 gg P/1
Lake Geneva (Leman) 52 gg P/1
Lake Peipus 40 gg P/1
Lake Ladoga 30 gg P/1
Lake Malar (Granfjarden) 30 gg P/1
Lake Vanem 10ggP/l
Lake Mjosa (N) 7 gg P/1
Lake Vattem 5 gg P/1
In small forest lakes in Scandinavia, the phosphorus concentrations are

generally in the range 5-10 gg P/1, in some cases <5 gg P/1.
Organisms, such as algae, that rely upon dissolved phosphate at low

concentrations in the water as their major source of phosphorus are
particularly susceptible to simultaneous exposure to the chemical
analogue arsenate. Interference with phosphate uptake at the cell surface
and in phosphorylation reactions wihtin the cell is generally supposed to
be the main mode of toxic action of arsenate. Furthermore, higher
concentrations of phosphorus in the water seem to counteract the toxicity
of arsenate to several aquatic plants. Another characteristic of lake water
that might interfere with the availability and toxicity of arsenate is its
content of humic material. Arsenate tends to adsorb or bind to humic
material, complexes which are quite stable at low pH values. Increasing
levels of humic material in the lake water tend to decrease the
availability and toxicity of arsenate to phytoplankton, but also the
impoverished light climate in brown-water lakes may reduce the uptake
of arsenate by algae, due to the lower rate of photosynthesis.
Therefore, the most critical conditions with respect to bioavailability,

uptake and toxicity of arsenate in the freshwater environment seem to
occur in small, dear-water lakes which are oligotrophic (low phosphorus
concentration), i e where there might be a strong competition between
arsenate and phosphate for uptake in algae.
70
EFFECTS OF VARIOUS ARSENIC SPECIES
IN THE AQUATIC ENVIRONMENT
1. Marine Environment
1.1 Effects on microorganisms

1.1.1 Sensitivity to arsenate
The sensitivity of different species of marine microalgae (phytoplankton
and periphyton) to arsenate varies over several orders of magnitude
(Blanck et ah, 1984). The toxicity of arsenate does not only vary with the
algal species or the algal phylum, but also with the concentration of
phosphate in the medium. The interactions between phosphate and
arsenate will be discussed in further detail in chapter 111:4. In this
section, only some general considerations about the mechanisms
determining the sensitivity of algae to arsenate will be mentioned.
It is generally assumed that phytoplankton communities in the open sea

are dominated by algal species with high affinity for nutrients, and are
adapted for the low and stable nutrient concentrations usually found in
open oceans (Sanders and Riedel, 1987). Phytoplankton species that have
a high affinity for phosphate appear to be better able to discriminate
between the necessary nutrient ion and the competing arsenate ion than
do species exhibiting lower nutrient affinity. Increased discrimination
should result in reduced arsenate uptake. However, even if marine algae,
in general, might be relatively efficient in keeping down the uptake of
arsenate, the differential sensitivity to arsenate exposure may have
important consequences for species succession within a natural phyto
plankton community (Sanders and Cibik, 1985).
There are two possible strategies by which algal species in a community

may be successful and dominate after exposure to arsenate stress:
(i) In order to be successful, a species may have a lower incorporation

rate of arsenate because of a higher degree of specificity for the
uptake of phosphate. Although slower growing, these algal forms
would not be susceptible to increased concentrations of arsenate and
would be able to dominate over more rapidly growing cells that were
incorporating larger amounts of arsenate.
71
(ii)Some algal species are very efficient at transforming arsenate into
less toxic, methylated forms, which are either incorporated into the
cell or released to the water, other species are not. By using the
strategy of transforming the arsenate, these species may be able to
dominate. Because the transformations require energy, cell growth
may be somewhat inhibited, but the species can continue to exist
within the community at lowered cell densities (Sanders and Riedel,
1987).
When cultures of the centric diatom Skeletonema costatum were

exposed to arsenate at low phosphate concentrations (1.6-2.5 pg P/1), the
arsenate concentration causing a 50% growth inhibition was found to be
5.0 pg As/1 (Sanders, 1979). When the phosphate concentration was
greater than 9.3 pg P/1, the growth rate was not affected by small
additions of arsenate. However, although enough phosphate was present
to reduce the arsenate toxicity, the algal population was still hampered
by an increased requirement for phosphate. This could reduce the
species' ability to compete with more resistant species.
Sanders and co-workers have tested a number of other marine micro

algae for sensitivity to arsenate (see Sanders and Riedel, 1987, for
references). It was found that the most sensitive species were the diatom
Rhizosolenia fragilissima and the chrysophyte Isochrysis galbana, which
suffered a 50% reduction in growth rate at arsenate additions of 2.3 pg
As/1 in low-phosphate seawater. Other diatoms, two dinoflagellates and
one chlorophyte species were found to respond to arsenate concen
trations in the range 6 to >98 pg As/1.
The relative sensitivity of different marine phytoplankton groups was

investigated in natural assemblages cultivated outdoors in large-volume
cultures for 15 days (Sanders and Vermersch, 1982). Three series with
the following arsenate concentrations were used: control: 1.1 pg As/1,
low dose: 7.7 pg As/1 and high dose: 20 pg As/1, in seawater with the
ambient phosphate level of 15.5 pg P/1. The total cell numbers were
reduced, compared to the control, by 57 and 67% in the low and the high
dose, respectively, and the chlorophyll a concentration was reduced by
30% in the treated cultures. The relative response of the different groups
of algae to the enhanced arsenate exposure is shown in Figure 111:1.1.
72
60 -
C E LL NUMBER
OF TOTAL
KEY
OTHER FLAGELLATES
DINOFLAGELLATES
:<fr,
PENNATES
CENTRICS
4 8 12
DAYS OF STRESS
Figure III: 1.1 Changes in relative abundance of the various taxonomic

groups of algae over time in large-volume cultures exposed to arsenate
stress. "Centrics" and "pennates" refer to diatoms. A = control; B = low
dose; C = high dose (after Sanders and Vermersch, 1982).
Blanck and Wangberg (1988a) studied the sensitivity of marine

periphyton communities to arsenate stress. It was found that, at low
levels of phosphate (<3 pg P/1), exposure to arsenate concentrations
between 8 and 20 pg As/1 initiated a restructuring of the community,
73
because some species were eliminated already at this low arsenate
exposure. Various responses were examined, and the results, given as
IC20 values, are presented in Table 111:1.1.
Test parameter IC20 (PgAs/l)

Species composition 15
Chlorophyll a accumulation 23
Total carbon accumulation 38
Total nitrogen accumulation 60
Photosynthesis per unit area 23
Table I1T.1.1. Sensitivity of marine periphyton communities to arsenate.
The communities were established during 3 weeks at a phosphate
concentration of <3 pg/l. All effects are expressed as IC20 values, i e the
arsenate concentration required to produce a 20% change in each
parameter, compared to the control (after Blanch and Wangberg,
jpagg).
When the periphyton communities were established under continuous

arsenate stress (750 pg As/1), they developed a tremendous increase in
tolerance to arsenate. The pre-exposed communities were >16,000 times
more tolerant to arsenate than control communities established at
background levels of arsenate. This increase in tolerance (PICT =
Pollution-Induced Community Tolerance) was obviously caused by
arsenate exerting a strong selection pressure on the algae, thus
restructuring the community and eliminating the arsenate-sensitive
components (Blanck and Wangberg, 1991). It is important to note that
this selection starts to eliminate the most sensitive components already at
low arsenate levels (about 8-15 pg As/1).
No data on the toxicity of arsenate to marine bacteria have been

encountered, but it might be assumed that bacteria do not belong to the
most sensitive taxa with regard to arsenate exposure.
1.1.2 Sensitivity to other dissolved arsenic species

The relative composition of the dissolved arsenic, i e the proportion of
reduced and methylated arsenic species, in the water phase is important
for the response of the ecosystem as a whole to arsenic exposure. For
many marine organisms, with the exception of algae, it is generally
assumed (based on laboratory tests) that arsenite and simple methylated
arsenic species (MAA and DMAA) are more toxic than arsenate.
Therefore, it is important to assess the overall effects of the release, by
growing algae, of arsenite, DMAA and MAA (by at least some species).
74
Since arsenite is unstable under oxidizing conditions and is rapidly
reconverted to arsenate, while both MAA and DMAA are stable in
marine systems, it is most important to evaluate the toxicity of the
methylated species to various marine organisms, including micro-algae.
Unfortunately, reports dealing with the toxicity of these species are
scarce.
Sanders (1979) carried out short-term toxicity tests with Skeletonema

costatum, which were exposed to either arsenite or DMAA at low
phosphate concentrations. He found that small addtions of arsenite (0.98
pg As/1) caused a slight inhibition of growth, although an addition of 20
pg As/1 resulted in almost the same inhibition. He concluded that
arsenate and arsenite caused inhibition at similar levels, and also noted
that it is difficult to know exactly whether the algal cells were exposed to
arsenite or arsenate, because of the rapid oxidation of arsenite. In
contrast to these results, DMAA caused no growth inhibition at a
concentration of 9.8 pg As/1, and even at 26 pg As/1; this arsenic form
had little or no effect on phytoplankton productivity. The reason for the
non-toxicity of DMAA was proposed to be its chemical dissimilarity
with phosphate and that it is not actively taken up by the algal cells
(Sanders, 1979).
Also Blanck et al. (1989) report that DMAA was non-toxic to all the
algal communities they tested, and that the EC50 value for inhibition of
photosynthesis was >75 mg As/1. However, MAA was foud to be
considerably more toxic, with a EC50 value close to that for arsenate, or
5 pg As/1. At low nutrient concentrations, arsenite was found to be at
least one order of magnitude less toxic than arsenate to all communities
tested, and the toxicity of arsenite did not show any obvious correlation
to the phosphorus concentration.
Thus, it appears that although arsenite is generally considered to be more

toxic than arsenate to higher marine life, arsenate has a more profound
effect on the growth and other cell functions of marine algae than does
arsenite. It has been speculated that marine algae erect a barrier against
the absorption of arsenite (Eisler, 1994), much the same way as they
exclude DMAA.
Only scattered data have been found on the sensitivity of marine bacteria
to arsenite and methylated arsenic species. However, when bacterial
cultures from the Sargasso Sea and from a site off the US east coast were
grown in arsenite-enriched media, the bacteria reduced all available
75
arsenate and utilized the arsenite during the exponential growth phase,
presumably as an essential trace nutrient (Johnson, 1972).
1.2 Effects on macroalgae and other plants

The red macroalga Champia parvula was exposed to various concen
trations of arsenate and arsenite in seawater and the toxic responses were
recorded (Thursby and Steele, 1984). On exposure to arsenate,
concentrations as high as 10 mg As/1 allowed normal growth, but the
sexual reproduction of the alga was impaired. The reproduction was
normal at arsenite concentrations in the range 65-95 pg As/1, but at 300
pg As/1, the alga did not survive.
The development of sporelings of another red macroalga, Plumaria

elegans, was arrested after short-term exposure to arsenite concentrations
of 580 pg As/1 (Eisler, 1994).
These marine macroalgae appear to be far more tolerant to arsenic

exposure than macroalgae in the brackish-water environment (see section
111:2.2), but available information is limited and no general conclusions
can be drawn on the relative sensitivity of marine macroalgae to arsenic
exposure.
1.3 Effects on invertebrates

Generally speaking, invertebrates appear to be quite resistant to
dissolved arsenic, which is in contrast with the often high sensitivity of
algae. Concentrations necessary to cause inhibition or death of
invertebrates, 100 - 1,000 pg As/1, are very much higher than those
found in natural marine systems (Sanders et al., 1994).
Results from conventional toxicity tests using endpoints such as survival

of adults, juveniles or larvae, condition index or fecundity, usually show
that direct effects of dissolved arsenate or arsenite occur only at
concentrations >100 pg As/1, as can be inferred from the summary of
toxicity data compiled by Eisler (1994), see Table 111:1.2.
No data have been found from toxicity tests examining the effects of
direct exposure of marine invertebrates to MMA or DMAA, dissolved in
the water. On the other hand, the main pathway of arsenic to inverte
brates is through the food, and therefore, they are predominantly exposed
to complex, organic arsenic compounds, such as dimethylated
arsinylribosides, arsenocholine and arsenobetaine.
76
I
Taxon Svecies As (us/l) Effect
O
Copepod Eurytemora affinis Reduced juvenile
o
survival
Copepod Acartia clausi As(III): 510 LC50 (96 hr)
Crab Cancer magister As(V): 230 Larvae, LC50 (96
hr)
Oyster Crassostrea gigas As(III): 330 Embryo, LC50
(96 hr)
Mysid Mysidopsis bahia As(III): 630-1,270 MATC, lifecycle
test
Mysid d:o As(V): 2,300 LC50 (96 hr)
Table 111:1.2. Toxicity data for arsenite and arsenate, selectedfrom tests
with the most sensitive marine invertebrates (after Eisler, 1994)
As indicated in Table 111:1.2, when studying the conventional endpoints,

marine invertebrates can be considered as remarkably resistant to
arsenic. However, when attention is directed towards biological
mechanisms at the cellular level, changes may be observed. This was
clearly indicated in oysters (Crassostrea gigas) exposed to arsenate at a
concentration of 10 pg As/1. Both the gill epithelium and the tissues of
the digestive tract showed cytological abnormalities, such as structural
alterations of mitochondria and nuclei, suggesting a disturbance of both
the cellural respiratory metabolism and nucleotide incorporation
(Ettajani et al., 1996). However, it was not possible to decide if these
modifications were pathological or adaptive.
1.4 Effects on marine fish

When testing the toxicity of arsenic to marine fish, most interest has
been devoted to arsenite. Available data indicate that various fish species
are quite resistant to short-term exposure to arsenite, the LC50 values
being in the range 3.8-27 mg As/1 (Eisler, 1994). Such levels of arsenite
do not occur in the natural marine environment. Thus, it may be
concluded that arsenic dissolved in the seawater does not constitute a
risk for fish.
As was the case with invertebrates, also fish are predominantly exposed
to arsenic via the food, i e most of the arsenic intake is in the form of
organic arsenic compounds. Marine teleosts seem to be unaffected at
arsenic levels in the muscle tissue of more than 100 pg As/g fresh
weight. Most of this arsenic is presumably in the form of non-toxic
arsenobetaine.
77
1.5 Effects at the ecosystem level
From a purely toxicity perspective, the most sensitive link in the marine
ecosystem is the phytoplankton. Some phytoplankton species can suffer
from growth reduction at arsenate concentrations as low as 3 pg As/1,
and concentrations of 5-10 pg As/1 have been shown to cause significant
reduction in growth as well as shifts in phytoplankton species
composition, because of the different sensitivity of various
phytoplankton species (Sanders and Vermersch, 1982; Sanders et al.,
1994; Blanck and Wangberg, 1988a).
The relative tolerance of higher trophic levels, described in the previous

sections, does not necessarily mean that these levels are free from
potential harmful effects. Arsenic may be used as an example of a
contaminant that has its primary effect at the base of the food chain. This
primary effect can have cascading, indirect impacts upon higher trophic
levels (Sanders et al., 1994). The potential effects on higher trophic
levels may not be limited to arsenic transfer through feeding. Also rapid
changes in phytoplankton species dominance and in community structure
can produce significant effects on the grazing community, if the
herbivores are feeding selectively with respect to phytoplankton species,
size or shape. Different types of food can have quite different nutritive
value. Therefore, the assessment of effects of arsenic cannot be limited
to one single trophic level; the ecosystem must be considered in its
entirety.
The existence of such integrated effects can be illustrated by the results

of several experiments, in which phytoplankton communities were
exposed to chronic, low-level arsenic doses (Sanders and Cibik, 1988;
Sanders et al., 1988; 1991; 1994). A common result in these experiments
was a replacement of larger, arsenic-sensitive centric diatoms with
smaller, more resistant species, both other diatoms and flagellated algae,
yielding a community dominated by smaller phytoplankton cells. For
example, at arsenate concentrations of 3 pg As/1 and higher, the growth
of the large, centric diatom Cerataulina pelagica was greatly inhibited,
and it was replaced by the smaller arsenate-tolerant Thalassiosira
pseudonana. In subsequent feeding experiments with the copepods
Acartia tonsa and Eurytemora affinis, it was found that when the diet
was based on smaller, arsenate-resistant algae, the fecundity of the
copepods was reduced, relative to the case when the diet consisted of
larger, arsenate-sensitive species (see Figure III: 1.2. Fecundity was
reduced even more when the copepods were fed on resistant species, that
had been exposed to high arsenate concentrations, and therefore had an
78
elevated arsenic content. Thus, although no direct effect of low arsenic
exposure could be detected on the copepods, an indirect effect was
observed, due to the arsenate-induced shift in phyto-plankton species
composition.
#--# Resistant + As
#-# Resistant
A A Sensitive
150-
100-
DURATION (days)
Figure 111:1.2. Fecundity ofAcartia tonsa, fed different mixtures of

phytoplankton species. The sensitive treatment means feeding on algae
sensitive to arsenate, the resistant treatment = feeding on arsenate-
resistant species, and resistant + As means feeding on resistant species
that had accumulated high levels of arsenic. All treatments received the
same amount offood, based on carbon content of cells (after Sanders et
al, 1994).
However, not all herbivores respond in the same way. For example,
rotifers and tintinnids exhibited higher growth rates when fed on the
arsenate-exposed phytoplankton community than when fed on the
unaltered community. Also larger herbivores, such as barnacles and
oysters, are essentially unaffected by arsenate dosing (Sanders et al.,
1988). It may therefore be concluded that herbivores which feed on-
79
larger species of phytoplankton may be hampered by the arsenate-
induced shift in the phytoplankton community structure, while micro
zooplankton which thrive on small phytoplankton cells react in an
opposite way and herbivores that can feed on a wide range of particle
sizes (barnacles and oysters) do not react to shifts in the size of dominant
phytoplankton (Sanders et al., 1994).
1.6 Arsenic criteria for protection of marine life

Only a few countries have established water quality criteria for arsenic in
the marine environment, although many countries have issued criteria for
freshwater. These criteria, usually expressed as the highest allowable
concentration of dissolved arsenic in the water phase, should not be
exceeded if harm to marine life is to be avoided. However, the data base
available to those who have developed such criteria apparently varies
from country to country and so do the political considerations that have
influenced the criteria-setting.
The most stringent criteria are those proposed by Norway (in Sweden no
arsenic criteria for marine waters exist). The main objective of the
Norwegian system of water quality criteria is to provide protection for
salmon, and is built upon a classification of water areas into four quality
classes. The different classes allow somewhat different types of
utilization or provide different level of protection. The criteria for total
arsenic are the following (Lindestrom, 1992):
Class 1: <2 pg As/1 No harm to any organisms and no limitations in

using fish as human food.
Class 2: 2-6 pg As/1 Sensitive organisms may be harmed, but no
problem for fish. Only small effects on
communities.
Class 3: 6-20 pg As/1 Harmful effects on salmon, reduced
communities with tolerant species dominating.
Class 4: >20 pg As/1 Unacceptable conditions for salmon. Large
damages on communities.
Marine water quality criteria in the U.K. include total arsenic, and refer
to the annual mean in samples that have been filtered through a 0.45 pm
filter. The criterion value is 25 pg As/1 (Lindestrom, 1992).
In the USA, the Environmental Protection Agency (EPA) has issued

limit values for many metals, including arsenic in seawater. However,
80
the criteria are explicitly given for arsenite, because it was considered
that data were insufficient for criteria formulation for arsenate or for any
organoarsenical (EPA, 1985a). Two different criteria have been
established for arsenite:
(i) The four-day average not to exceed more than once every 3 years =
36 pg As/1;
(ii) The one-hour mean not to exceed more than once every 3 years =
69 pg As/1.
It might be noted that it is highly improbable that such high concen

trations of arsenite would ever occur in marine waters, at least if the
water contains dissolved oxygen at levels that will allow marine fauna to
survive.
In conclusion, the only seawater quality criteria, among the three sets
presented above, that are of any practical use are those proposed by the
Norwegian authorities. They seem to be based on a realistic assessment
of the potential risks associated with long-term exposure to low levels of
total arsenic in the marine environment. They also seem to provide
sufficient protection - in the case of Class 1 criterion - to the most
sensitive among the marine organisms.
2. Estaurine or Brackish Water Environment

In the southern part of the Baltic Sea, the toxicity of arsenate to a
periphyton community was measured in terms of a 50% inhibition of the
photosynthesis. The effect concentration was determined at 6 pg As/1 at
phosphate concentrations varying between 1 and 5 pg P/1 (Blanck et al.,
1989).
No direct measuresments of arsenate toxicity to phytoplankton in natural

brackish-water from the Baltic Sea have been found in the literature.
However, in laboratory cultures of Scenedesmus obliquus, grown in a
diluted, synthetic seawater medium of l%o salinity, the toxicity of
arsenate and arsenite was determined at different phosphate
concentrations (Hofslagare et al., 1994). At concentrations of arsenate or
arsenite less than 7.5 pg As/1, no toxic effects were observed. Increasing
the arsenate concentration to 75 pg As/1 with no or medium (31 pg P/1)
phosphate addition resulted in a 22-34% reduction in carbon uptake of
81
the cells, but this inhibition was eliminated at phosphate levels of 310 pg
P/1 and higher. Arsenite at a concentration of 75 pg/1 did not reduce the
carbon uptake, but arsenite levels in the range 380-750 pg As/1 yielded
an 11% reduction of the carbon uptake. Thus, arsenite was clearly less
toxic to this green microalga than was arsenate (Hofslagare et al., 1994).
2.2 Effects on macroalgae and other plants

The mesocosm experiments described in sections 11:2.2 and 11:2.4, with
model ecosystems simulating the Baltic Sea littoral zone, also allowed
the toxicity of arsenate to the brown alga Fucus vesiculosus to be
determined. After one year of arsenate exposure in brackish-water, a
nominal arsenate concentration of 8 pg As/1 yielded a 50% reduction in
Fucus biomass, while exposure to 75 pg As/1 resulted in death and
complete elimination of this alga (Blanck et al., 1989). The tissue
concentrations of arsenic in algae exposed to 8 pg As/1 were in the range
of 70-80 pg As/g, and in algae grown at background levels of arsenate
(0.5 pg As/1), the tissue concentrations were about 20-30 pg As/g.
The apical growth of Fucus vesiculosus was measured in relation to the

tissue content of arsenic, and was found to decline with higher content of
arsenic in the tissues (Figure 111:2.1). This relationship was then used as
a basis for an assessment of the possible inhibiting effect of arsenic in
the field. In a coastal zone of the southern Baltic Sea, close to the outlet
from a municipal sewage plant, samples of Fucus were collected and the
growth over the last year was measured together with the content of
arsenic in the tissues (Blanck et al., 1989). It was found that the apical
growth was inhibited at tissue levels of arsenic from about 40-50 pg
As/g and upwards (Figure 111:2.1).
Also the rate of phosphate uptake in Fucus was affected by elevated

concentrations of arsenate in the water. In short-term experiments, the
phosphate uptake decreased to 40% of the control rate at arsenate
concentrations higher than 20 pg As/1, and at 100 pg As/1, the rate of P-
uptake went down to 15% of the control rate (Rosemarin, ref. in Blanck
et al., 1989).
In the mesocosms, the elimination of the Fucus community in the high

arsenate dose opened up this niche for oppurtunist species that can
survive the arsenic stress. An invasion of Spirogyra resulted in a dense
spring bloom in the high-dose mesocosm, which was replaced, in the
summer, by a variety of green and red macroalgae species as well as by a
82
periphyton community consisting of bluegreen and diatom microalgae
(Blanck et al., 1989). Thus, among the macroalgae, the brown algae, and
particularly the keystone species Fucus vesiculosus, appeared to be the
most arsenate-sensitive components, being inhibited already at low
levels of arsenate exposure, i e at concentrations below 8 pg As/1.
200 1
Zone affected by
sewage treatment
plant effluent
Fucus tissue arsenic ( /jg/g dw ) (winter max)
Figure 111:2.1. Apical growth (mm/year) ofFucus vesiculosus as a

function of the arsenic content in tissues (fig/g dry weight). Data from
the field (o) compared to data from mesocosm experiments (x) (from
Blanck et al, 1989).
In studies of the macroalgae communities that were able to grow on

CCA-treated wood in brackish-water, large differences in community
composition were found between the treated wood and control wood.
83
The most tolerant species were the red alga Ceramium sp., the green
algae Ulva lactuca and Enteromorpha intestinalis, while other species,
such as Ectocarpus sp., Polysiphonia sp. and Cladophora sp., usually did
not settle on the CCA-treated wood (Weis and Weis, 1992). However, it
is not possible to discriminate between the effect of the three metal salts
(copper, chromium and arsenic) and tell which one had the greatest
inhibiting effect on the algae.
Nonetheless, it has been clearly shown that low concentrations of

arsenate in brackish-water environments have a structuring influence on
the macroalgae communities, an effect which is exerted by the difference
in sensitivity between different species of algae. In particular, the brown
algae group seems to be very sensitive to arsenate exposure, among
which Fucus vesiculosus, which is - by far - the most important
structuring component of the littoral ecosystem in the Baltic Sea, is
severely affected at arsenate concentrations in the water as low as 8 pg
As/1 or maybe even lower (Notini et al., 1987).

It has generally been found that estaurine invertebrates are remarkably
resistant to dissolved arsenic. Usually, the arsenic concentrations must
exceed 100 to 1,000 pg As/1 before significant direct impact occurs
(Sanders et al., 1988). This resistance probably results from the relatively
low availability of dissolved inorganic arsenic to invertebrates.
Furthermore, the incorporation of complex organic arsenic species into
invertebrates also seems to be relatively low, e.g. arsenobetaine does not
seem to be available for assimilation and is eliminated unmetabolized
(Sanders et al., 1989). Thus, the potential for direct impact from arsenic
ingested via food is not likely to be significant in most estuarine or
coastal systems.
The relatively low degree of incorporation of arsenic compounds into

herbivores, and the apparent absence of food-chain magnification
suggests that for many organisms, the arsenic-uptake rates will decline
throughout an individual's development. For example, smaller
individuals principally feed on phytoplankton, which may result in high
arsenic uptake rates, but later, when these animals switch to feeding on
zooplankton, the arsenic uptake rates should decline (Sanders et al.,
1989). This declining exposure would also result in a reduced risk for
detrimental effects.
84
In the previously described mesocosm experiments, not even the high-
dose arsenic exposure (75 pg As/1) resulted in any reduction of the total
biomass of invertebrates, although the Fucus habitat disappeared from
the mesocosms (Notini and Rosemarin, ref. in Blanck et al., 1989).
However, different groups of invertebrates reacted in different ways.
Both gastropods and crustaceans declined in total biomass (Figure
111:2.2), while the biomass of Mytilus edulis almost doubled in the high
dose. The most conspicuous shift in the invertebrate community was a
decrease in herbivore biomass and a simultaneous increase in detritovore
and filter-feeder biomass. This probably was an indirect effect of the
drastic shift in habitat and ecosystem structure, rather than a direct toxic
effect of arsenic.
Sediment Wall
Stone Fucus
g
yug As/l
/ug As/L
Figure 111:2.2. Total biomass (g dry weight per pool) of the gastropods
Lymnea sp. and Theodoxus sp. (left) and of crustaceans (right) in
different habitats of brackish-water littoral mesocosms, exposed to
arsenatefor one year (after Notini and Rosemarin, ref. in Blanck et al,
798(0.
85
2.4 Effects on estuarine fish
The mesocosms referred to above also contained a few specimens of
fish: stickleback and flounder. The two levels of exposure to arsenate, 8
and 75 pg As/1 had no deleterious effects on these two fish species. The
total fish biomass in the high-dose pool was the same as in the controls,
after one year of exposure (Blanck et al., 1989). However, the growth
rate of the stickleback was lower, which was compensated by a greater
number of individuals. The reduced individual growth rate of the new
generation of fish in the high-dose pool might be explained by the
reduction in biomass of prey organisms (invertebrates). No similar effect
on the growth of flounders, mainly feeding on bivalves in the sediment,
was observed. The biomass of bivalves was not reduced.

Exposure of a brackish-water littoral ecosystem to arsenate (8 or 75 pg
As/1) for one year produced major changes in the structure of the
ecosystem, due to toxic effects on the keystone alga Fucus vesiculosus.
These changes had many features in common with the community shifts
caused by eutrophication and consisted in a major shift in the
composition of primary producers: from Fucus to short-lived,
opportunistic filamentous algae. The habitat-structuring Fucus, strongly
dominant on rock or stone substrates in shallow parts of the Baltic Sea,
normally functions as a nutrient store, providing a slow but steady flow
of carbon, nitrogen and phosphorus to higher trophic levels. Filamentous
algae, on the other hand, have a short life-span and a very much faster
nutrient turnover. When these algae become dominant, e g due to
inhibition or elimination of the arsenate-sensitive Fucus, the result is an
increased channeling of material through the detritus pathway. In the
experiments, this was observed as a greater content of organic matter in
the sediment and as a shift from herbivore to detritivore invertebrates,
but no change in the total invertebrate biomass over a period of one year.
In the long term, the disappearance of the Fucus habitat from a natural
bay of the Baltic Sea will probably result in a drastic impoverishment of
the invertebrate and the fish fauna. Under normal circumstances, many
species of invertebrates and fish migrate to the Fucus belt for feeding and
reproduction, and use this habitat as a nursery and sheltering area
Thus, also in the brackish-water environment, the sensitivity to arsenic

greatly differs between organisms and trophic levels. Even between
86
primary producers, the range of sensitivity to produce toxic responses on
exposure to arsenic is very large. However, it turns out that the keystone
species Fucus vesiculosus, which is the totally dominant biotic element
of littoral ecosystems in the Baltic Sea, is particularly sensitive to
arsenate exposure. Therefore, even at low concentrations of arsenate in
the water column, the whole system begins to restructure, causing a
whole array of cascading effects on higher trophic levels, effects that - in
many respects - resemble those occurring as a result of eutrophication of
coastal waters.
3. Freshwater Environment (Lakes and Rivers)

Laboratory tests of the toxicity of arsenate and arsenite to various
freshwater phytoplankton species have pointed out the great variability
in sensitivity between species. For example, in continuous-culture
experiments with Asterionella formosa, arsenate levels of up to 160 pg
As/1 neither caused reduced growth rate nor affected the uptake of
nutrients (Conway, 1978). In tests of five species of freshwater
phytoplankton in the presence of arsenate, 75 pg As/1 depressed the
growth rate of two of the species, while a third species required 750 pg
As/1 for the same degree of depression, and the two remaining species
were unaffected at concen-trations up to 7,500 pg As/1 (Planas and
Healey, 1978). Other workers have reported depression of the growth
rate of Chlamydomonas at an arsenate concentration of 75 pg As/1
(Christensen and Zielski, 1980) and of Scenedesmus obliquus at an
arsenate level of 48 pg As/1 (Eisler, 1994).
These highly variable results, even among species within the same
phylogenetic group, indicate that the effects of arsenate on freshwater
phytoplankton vary not only between species, but also within species,
depending on both the physiological status of the cells at the start of the
experiment, and the supply of nutrients in the culture medium
(Blomqvist and Heyman, 1990).
In similar laboratory tests with arsenite, the toxicity was usually found to
be lower: toxicity values of 1.7-2.3 mg As/1 have been reported for 4
different species (Eisler, 1994).
Relatively few experiments on the effects of arsenate on natural mixed

populations of fresh-water phytoplankton have been performed, and even
87
fewer on the response of natural periphyton communities to arsenate
exposure. In 1986, phytoplankton and periphyton communities from the
mesotrophic brownwater Lake Sormogen were tested with respect to the
inhibition of photosynthesis as a result of arsenate exposure (Wangberg
et al., 1991). The communities were sampled either directly from the
lake or from a (control) limnocorral in the lake without any treatment
(total arsenic concentration in the lake water was 1.0-1.6 pg As/1). The
results of the tests are summarized in Table 111:3.1.
Source Phytoplankton Periphyton

Lake, August 19 44 -
Lake, August 20 14 -
Lake, October 6,0 9,8
Limnocorral, August 44 -
Limnocorral, October 9,8 1,5
Table 111:3.1. EC50 values (pgAsfl) for inhibition ofphotosynthesis by
arsenate in phyto-plankton andperiphyton communities from Lake
Sormogen (after Wangberg et al., 1991).
The difference in toxicity recorded between the two consecutive days in

August was not statistically significant. The lowest effect concentration
found for phytoplankton was 6.0 pg As/1. The difference between the
effect concentrations obtained for periphyton in October has not been
explained by the authors.
The main purpose of the experiments in Lake Sormogen was to

investigate the effects on the development of the phytoplankton
community of low additions of arsenate to various limnocorrals during
the whole ice-free season (Blomqvist and Heyman, 1990). Two of the
limnocorrals received an arsenate concentration of 14 pg As/1 in the
beginning of June, whereupon the arsenate concentration declined to
levels between 3 and 6 pg As/1 in July and August. A third limnocorral
received an addition of arsenate which gave a peak concentration of 4 pg
As/1 in the beginning of June, and after that, the concentration was equal
to that in the control limnocorral (1.0-1.6 pg As/1). The phytoplankton
biomass declined in the two high-dose limnocorrals to levels between 16
and 28% of the control level in June, and remained at levels between 21
and 74% of the control level throughout the summer months. In the third
limnocorral, there was a decline in June to 56% of the control level, but
later, the biomass was restored to levels of 81-85% of the control level.
The originally very high species diversity was not affected by the
88
arsenate additions. Thus, the results did not show that arsenate had any
clear selective effect on the community, since negative effects were
found in virtually all common groups and species of algae (Blomqvist
and Heyman, 1990).
However, a more detailed investigation of the phytoplankton community

from the experiments in Lake Sormogen, carried out by Wangberg et al.
(1991), showed both that the arsenate treatments induced a decrease in
algal cell volume (the no-effect-concentration being 4.4 pg As/1) and that
a slight change in taxonomic composition of the community did occur.
The overall conclusion from these experiments in a brownwater

mesotrophic lake is that the lowest concentration of arsenate inducing
significant changes in the phytoplankton community, mainly depression
of total biomass, but without inducing any major changes in the
community structure, was about 4 pg As/1. The low effect concentration
(1.5 pg As/1) indicated for inhibition of photosynthesis in a periphyton
community must be regarded with precaution, since it could not be
replicated with periphyton from the lake itself.
Wangberg (1995) also investigated the phytoplankton communities in

eight different lakes being exposed to long-term arsenic contamination
through atmospheric fallout originating from the nearby metal smelter in
Ronnskar. A complicating factor is that these lakes were also contami
nated with several other metals, such as cadmium, copper, lead and zinc.
Both the number of species, the total cell volume and the possible
induction of increased tolerance to arsenic in the phytoplankton
communities (PICT) were investigated during three consecutive years.
Increased tolerance to arsenate, compared to the communities in four
reference lakes, was found only in the two most contaminated lakes,
Snesviken (28-48 pg As/1) and Burotjam (about 8 pg As/1). Snesviken
also exhibited the lowest number of phytoplankton species and both
lakes had higher total cell volumes than other lakes investigated.
Snesviken was one of the lakes with the lowest concentration of
phosphorus (5-7 pg P/1). Thus, the only lakes where a clear "pollution-
induced community tolerance" (PICT) was observed were the lakes
having arsenic concentrations in the water mass >8 pg As/1. At least the
most contaminated lake had a severe restructuring of the phytoplankton
community. However, it is difficult to conclude whether or not the
arsenic load on this lake was mainly responsible for these changes or to
what extent other metals contributed to the impact.
89
3.2 Effects on aquatic plants
The freshwater mesocosm experiments conducted by Reuther (1992)
allowed the determination of effects on the aquatic plant Lobelia
dortmanna caused by long-term exposure to arsenate with and without
phosphate addition (see section 11:3.4). After an exposure time of 65
days, the biomass of Lobelia, exposed to 50 pg As/1, was clearly
depressed, but a simultaneous addition of phosphate (to 5 pg P/1)
eliminated this inhibition. The average number of Lobelia leaves being
lost during the experiment was enhanced by exposure to arsenate levels
of both 5 and 50 pg As/1, and - again - the simultaneous addition of
phosphate completely eliminated this effect.
Studies of the effect of four different arsenic compounds, dissolved in

the water, on the growth and dry matter production of rice were
conducted by Marin et al. (1992). The results of these growth tests after a
four-week exposure period, are shown in Figure 111:3.1.
c
o
<3
D
T3
O
CO
E
*u
DMAA AS (V) As (III) MMAA

Arsenic chemical form in solution
Figure III: 3.1. Rice dry matter production as a function of arsenic

concentration and chemicalform (after Marin et al., 1992).
90
When arsenic was added as DMAA, at levels of 50 and 200 pg As/1,
there was a slight increase in total dry matter production, and no toxic
response was observed even at the highest concentration (800 pg As/1).
Arsenate did not affect the dry matter production of rice at any of the
tested concentrations. However, both arsenite and MAA were clearly
phytotoxic to rice. The most phytotoxic compund was MAA, giving a
significant effect already at a level of 50 pg As/1. Rice plants grown in
the highest concentration of MAA were stunted with necrosis in leaf tips
and margins. These symptoms indicated a limitation in the movement of
water into the plant resulting in death. The total dry weight of these
plants was only 34% as compared to the control (Marin et al., 1992).
In field surveys of arsenic-contaminated lakes, it was found that

phytotoxic symptoms (stunted shoot growth and necrosis) generally
occurred in Typha latifolia, when the arsenic concentrations in sediment
and in water exceeded 300 pg As/g and 400 pg As/1, respectively
(Dushenko et al., 1995).
Summing up, it appears that arsenate concentrations of 5 pg As/I, in

combination with very low phosphate levels, can produce slight
detrimental effects on some freshwater macrophytes. Other macrophytes
can tolerate arsenate concentrations up to at least 800 pg As/1. Among
the four most common dissolved arsenic compounds in freshwater, MAA
seems to be the most phytotoxic one, followed by arsenite, as shown in
growth tests with rice.

A great amount of toxicity data have been reported from laboratory tests
with various freshwater invertebrates being exposed to one or several of
the common, soluble arsenic compounds (see Eisler, 1994, for
overview). However, very few studies have been conducted in which
invertebrates have been exposed, via the food, to well specified,
complex, organic arsenic compounds. Such di- or tri-methylated
arsenicals are, however, generally considered to be of low toxicity.
In this section, only a small sample of toxicity data will be presented and
discussed, mainly data from tests with chronic exposure, or data from
series of tests in which the same test organism was exposed to different
arsenic compounds under comparable experimental conditions.
In Table 111:3.2, some toxicity data on freshwater invertebrates are

summarized (Eisler, 1994; Kuroiwa et al., 1994; 1995).
91
Species Compound As cone, jug As/l Type of effect
Daphnia magna As(III) 630-1,320 MATC, life-cycle
test
As(V) 520 Reprod. impairtment
of 16%
MAA >830 No deaths in 28 days
DMAA >1,100 No deaths in 28 days
Gammarus As(III) 88 LC20, 28 days
pseudolimnaeus As(V) 970 LC20, 28 days
MAA 86 LCiQ, 28 days
DMAA 850 LCo, 28 days
Neocaridina As(V) 1,500 LC50, 7 days
denticulata MAA 10,000 LC50, 7 days
DMAA 40,000 LC50, 7 days
As-betaine 150,000 LC50, 7 days
Macrobrachium As(V) 30,000 LC50, 5-7 days
rosenbergii MAA 100,000 LC50, 5-7 days
DMAA 300,000 LC50, 5-7 days
Table 111:3.2. Toxic effects of various arsenic compounds to freshwater
invertebrates.
The most sensitive among the tested organisms was the amphipod G.
pseudolimnaeus, which showed mortality at arsenic concentrations <100
pg As/1. Arsenite and MAA were, in this case, equally toxic, but in tests
with other organisms, it was generally found that the higher the number
of methyl groups in the molecule, the lower the toxicity. When
comparing the toxicity of arsenite and arsenate, it turned out that in one
case, arsenite was more toxic, while in another case, arsenate was the
most toxic form. Generally speaking, however, the most common
dissolved arsenic species, including arsenate, are much less toxic to
invertebrates than to some algae. Thus, invertebrates cannot be
considered as a critical group when assessing the direct toxicity of
arsenic to freshwater ecosystems.
3.4 Effects on freshwater fish

Also fish is quite tolerant to arsenic dissolved in the water. The
maximum acceptable toxicant concentration (MATC) when exposure
goes on for the whole life-cycle has been determined for a few fish
species. In the case of flagfish (Jordanella floridae), the MATC value for
arsenite was 2.1^1.1 mg As/1 (EPA, 1985b). Almost the same range was
obained for fathead minnow (Pimephales promelas), when exposed to
92
arsenite: MATC = 2.1-4.8 mg As/1, while arsenate was more toxic to the
latter species: MATC = 0.53-1.5 mg As/1 (EPA, 1985b).
The lowest effect levels found for freshwater fish in the literature were
100 pg As/1 as arsenate, which was reported to induce a 15% behavioral
impairment in gold fish, and 540 pg As/1 as arsenite, which after 28 days
exposure caused 50% mortality in rainbow trout embryos (Eisler, 1994).
Arsenic trioxide at a concentration of 300 pg As/1, caused slight
biochemical changes in plasma and gills and affected the migratory
behavior of coho salmon, but had no effect on growth or survival of the
smolts (Nichols et al., 1984).
When rainbow trout were exposed to arsenic compounds via the food,
the no-observed effect concentration for dietary arsenate was determined
at 13-33 pg As/g diet (Cockell et al., 1992). A dietary dose of arsenate in
the range 55-60 pg As/g diet caused gallbladder inflammation and a
mild to moderate responsive anemia in the fish. However, rainbow trout
fed a diet containing organic arsenic (DMAA or arsenobetaine) for 8
weeks, did not exhibit any toxic responses at doses of 120-1,600 pg As/g
diet (Cockell and Hilton, 1988).

Much the same as in the marine and the brackish-water environment,
also in freshwater ecosystems it is the primary producers, that are the
organisms most susceptible to toxic effects induced by the predominant
arsenic species, arsenate. However, the great variability in relative
susceptibility to arsenate, between different species and groups of
primary producers, found in the two first cases, does not seem to be as
conspicuous in the freshwater ecosystems so far examined. Therefore,
the typical shift in composition of the phytoplankton community under
arsenate stress might not be as common in lakes, and consequently, the
cascading, indirect effects on the higher trophic levels may also be less
obvious. However, so far, the number of freshwater ecosystems studied
in this respect is too small to allow any valid generalisations to be made.
3.6 Arsenic criteria for protection of freshwater aquatic life

Generally speaking, it must be concluded that when authorities in various
countries have established freshwater quality criteria for arsenic, their
way of reasoning has probably not been based on a thorough
understanding of the biochemistry and toxicology of arsenic in limnic
systems. The arsenic limit values in those countries where such exist, are
93
usually set at 50 (ig As/1 or higher (Lindestrom, 1992). No limit value for
arsenic in freshwater has been given by the Norwegian authorities.
In the Netherlands, there exists - in addition to the "standard" limit value

for arsenic, 50 pg/1 - a recently proposed, lower value, which represents
the "Maximal Acceptable Risk" (MAR) level. This value is based on the
95-percentile of NOEC recordings, and is set at 8.6 pg As/1 (Lindestrom,
1992). This value is not very different from the lowest arsenate levels
(4—8 pg As/1), which in Swedish field or mesocosm experiments caused
toxic responses to various green plants.
4. Mechanisms of Toxicity - Interaction with

Phosphorus
As pointed out several times before, arsenic is an element with an active
biochemistry. Because of the chemical similarity between arsenate (the
predominant inorganic arsenic form in aquatic systems) and phosphate,
arsenate is taken up by autotrophic organisms along with phosphate.
However, arsenate interferes with the important biochemical functions of
phosphate, in particular, uncoupling of oxidative and photo
phosphorylation may occur by a competitive interaction with phosphate
in the formation of ATP (Avron and Jagendorf, 1959). In the presence of
arsenate, unstable ADP-arsenate is formed, thus regenerating ADP, but
the arsenylated ADP is stable enough for arsenosugars to be formed
(Blanck et al., 1989). The rapid regeneration of ADP in the presence of
arsenate leads to a consumption of the electro-chemical gradient without
any ATP formation (Blanck and Wangberg, 1991).
In the water phase, when the ratio of arsenate to phosphate is relatively

high, arsenic toxicity to phytoplankton becomes more likely (Sanders et
al., 1994). Presumably, the transformation reactions, by which
methylated arsenic species are formed by algae, have evolved to
minimize this toxicity by altering arsenate and either eliminating it from
the cell in a less toxic form or storing it within the cell in the form of
non-toxic, complex molecules.
Arsenate can be transported by phosphate carriers in algal cells, although

it has been shown that the phosphate uptake mechanism of algae and
cyanobacteria, to some extent, can discriminate between phosphate and
arsenate (Blanck and Wangberg, 1991). In addition, arsenate can be
reduced to arsenite by algae and cyanobacteria, a compound that also
94
inhibits photosynthesis, but by a completely different mechanism
(Blanck and Wangberg, 1991).
Arsenite is also an intermediate in the detoxification pathway leading to

the excretion of methylated arsenic acids.
When comparing the relative toxicities of arsenic compounds, it is

necessary to consider the modifying effect of phosphate on the toxicity
of arsenate. At excess phosphorus concentration, the toxicity of arsenate
to algae is insignificant, while at low P/As quota in the cells, arsenate is
by far the most toxic among the arsenic species (Blanck et al., 1989).
The traditional view that arsenite is the most toxic arsenic species,
certainly does not hold for algae, and it may be questioned if it is
generally valid for other aquatic organisms. Rather, it seems that there is
a great variability in the relative sensitivity of different animal species
and taxa to the two inorganic dissolved arsenic forms.Of the two
methylated arsenic acids, MAA may have a relatively high toxicity to
aquatic organisms other than algae, while DMAA seems to have a low
toxicity to all organisms tested. The lack of toxicity of DMAA to algae is
consistent with the idea of the methylation pathway as a means of
detoxification of arsenate.
95
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Ill
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Portions of this document may be illegible

2. Estuarine or Brackish Water Environment 32

3. Freshwater Environment (Lakes and Rivers) 53

4. Water Quality Characteristics in inland European

2. Estaurine or Brackish Water Environment 81

3. Freshwater Environment (Lakes and Rivers) 87

4. Mechanisms of Toxicity - Interaction with

IV. LITERATURE REFERENCES 96

1. Predominant Arsenic Species in Aquatic

In reducing environments, such as anoxic water or sediments, arsenite is

The rate of uptake of arsenate into autotrophs (phytoplankton, periphyton

The biogeochemistry of arsenic has been thoroughly studied and

Biomethylation of arsenic by freshwater organisms has been

At the present state of knowledge, it might be concluded that there seems

2. Ecotoxicology of Arsenic in the Aquatic Environment

As mentioned in the previous sections, the speciation of arsenic and the

From the above it is clear that aquatic organism such as algae

Based on a great amount of experimental exposures of selected aquatic

System Environment Parameter LOEL, figAs/l

The above evaluation resulted in the following conclusions:

* Arsenate is the ecotoxicologically most significant of the occurring

* In Scandinavian inland waters, the concentration of phosphorus in the

* The major effect of long-term arsenate exposure at the algal

* Arsenic is not biomagnified in the food chain, but occurs in many

* The sediments act as a sinks of arsenic, and benthic organisms can be

1. Dominerande forekomstformer av arsenik i akvatisk

I reducerande miljo, t ex i syrefattiga vatten och i sediment, ar arsenit

Upptagshastigheten av arsenat i autotrofa organismer (vaxtplankton,

Arsenikens biogeokemi har grundligt studerats och beskrivits i den

Biometylering av arsenik har experimentellt visats kunna utforas av

Pa nuvarande kunskapsniva kan slutsatsen dras att det verkar finnas en

2. Arsenikens ekotoxikologi i akvatisk miljo

Som namnts tidigare, bestams arsenikens forekomstformer, liksom

Utiffan det ovanstaende ar det uppenbart att akvatiska organismer som

Baserat pa ett stort antal experimentella studier, dar utvalda akvatiska

Det ar uppenbart att arsenat ar den klart mest ekotoxiska arsenikformen

Generellt sett forefaller bade de akvatiska ryggradslosa och ryggrads-

System Miljd Matparameter Effektniva,

(PICT = Pollution-Induced Community Tolerance)

* Arsenat ar den ekotoxikologiskt mest betydelsefulla av arsenikens

* Alger och andra grona vaxter ar de primara malorganismema for

* I Skandinaviska inlandsvatten ar koncentrationen av fosfor i vattnet i

* Den huvudsakliga effekten av langtidsexponering for arsenat pa

* Arsenik biomagnifieras inte i naringskedjan, men forekommer i

* Sedimenten fungerar som en "sink" for arsenik, och bentiska

The first reports of arsenic in marine organisms were published already

Subsequent work has identified the presence of a large array of other

This general lack of comprehensive information on arsenic speciation in

In preparing the present overview of arsenic species and effects in the

THE AQUATIC ENVIRONMENT

1.1 Inorganic arsenic species

Arsenate, As(V), is the predominant form of arsenic in seawater, making

1.1.2 Marine sediments / interstitial waters

Total arsenic concentrations have been found to be lower in the

1.1.3 Marine biota

No good data are available on the natural content of inorganic arsenic in

The arsenic content of marine animals shows considerable variability.

In a recent re-evaluation of virtually all studies that have specifically

However, in shells of marine animals, the inorganic forms seem to

Figure 11:1.2. Structures of the first two identified dimethylarsinylri