Arsenic (As)

REPORT BY VIVIENE S. SANTIAGO MS 226

Outline
I. Introduction II. Arsenic Poisoning in Humans III. Arsenic in the Marine Environment
Sources Transport

Transformation
Bioaccumulation

Effects on Marine Biota

Introduction
ARSENIC AS AN ELEMENT | ARSENIC IN NATURE

Arsenic as an Element

Arsenic in Nature
3 major groups: Inorganic Arsenic Compounds, Organic Arsenic Compound and Arsine Gas

3+ inorganic As compounds
Arsenic trioxide (As2O3) Sodium arsenite (Na3AsO3)

5+ inorganic As compounds
Arsenic pentoxide (AsO5) Arsenic acid (H3AsO4)

Arsenic trichloride (AsCl3)

Arsenates [e.g. PbHAsO4 & Ca3(AsO4)2]

Arsenic in Nature
Organic Arsenic Compounds Arsanilic acid

Methylarsonic acid (MMA)

Dimetylarsinic acid (DMA)

Arsenobetaine

Arsenic Poisoning in Humans

ARSENIC-CONTAMINATED AREAS | SYMPTOMS | NOTABLE CASES

Arsenic Contaminated Areas

Source: http://upload.wikimedia.org/wikipedia/commons/5/57/Arsenic_contamination_areas.jpg

Symptoms
Headaches, confusion, severe diarrhea and drowsiness Convulsions and leukonychia striata Diarrhea, vomiting, blood in urine, cramping muscles, hair loss, stomach pain, more convulsions

Organs affected: lungs, skin, kidneys and liver

Coma and death

Source: http://upload.wikimedia.org/wikipedia/commons/f/fd/Mee%27s_lines.JPG

Notable Cases
Napoleon Bonaparte
Arsenic in wallpaper in house at St. Helena

Simon Bolivar
Drinking water contaminated (in Peru) + used As for therapeutic purposes

Emperor Guangxu
Poisoned by political enemies

Arsenic in the Marine Environment

SOURCES | TRANSPORT | TRANSFORMATION | BIOACCUMULATION | EFFECTS OF ARSENIC IN MARINE BIOTA

Arsenic in the Marine Environment

As in marine crustaceans and mollusks non-toxic (Chapman, 1926) Suggested that As may be an essential element for certain marine biota

As present in sea water predominantly arsenate. At normal seawater pH, arsenate exists as HAsO42- (Ferguson & Gavis, 1972) As chemically similar to phosphorus. Total dissolved As in seawater: 1.0-2.0 g/L

Fig 1. Arsenic species isolated from the marine environment

Source: Maher & Butler. Arsenic in the marine environment. Applied Organometallic Chemistry. 1988 2: 191-214.

Sources: Main Producers

Source: http://upload.wikimedia.org/wikipedia/en/b/be/World_Arsenic_Production_2006.svg

Sources
Pesticides Smelting/roasting sulfide minerals Volcanic eruptions Burning of vegetation/ wild fires Continental weathering

Combustion of fossil fuels Leaching of exposed waters from mining Accelerated erosion of land

Transport
As enters oceans from atmosphere (de Groot, 1973) As in freshwater associated with particulates (Crecelius et. al., 1975) As in oceans predominantly in dissolved form (Waslenchuk & Windom, 1978; Crecelius et. al.. 1975)

Transformation
Food contributes more As than seawater. Precursors of arsenobetaine most likely formed along food chain (Johnson & Braman, 1975)

Water-soluble and lipid-soluble forms of organic As have been detected in algae (Irgolic et. al., 1977; Cooney et. al., 1978)

Bioaccumulation
Marine algae contains As 2000-5000x greater than in seawater Algae, seaweed, mollusks and crustaceans can accumulate arsenate from seawater (Maher & Butler, 1988)

Arsenic uptake proportional to arsenate concentration until threshold achieved (Klumpp, 1980)
As uptake function of salinity, temperature, light and exposure. (Maher & Butler, 1988)

As not biomagnified in marine foodchains. (Ferguson & Gavis, 1972)

Effects of As in Marine Biota

Algae and microorganisms Mollusks Crustaceans

Echinoderms Fish Long-term effects

Algae and microorganisms

Growth of some marine phytoplankton inhibited especially when PO43- levels are low.

As (V) as toxic as As (III).

Arsenite toxic because of reactivity with sulfhydryl groups (GESAMP, 1988). Arsenate competes with phosphate in mechanisms requiring phosphate absorption and transport. (GESAMP, 1988)

Mollusks
Na3AsO3 on Eastern oysters have 48hr LC50 of 7.50 mg/L (Calabrese et. al., 1973)

Na3AsO3 on juvenile bay scallops have 48hr LC50 of 4.40 mg/L. (Nelson et. al., 1976)
As on mud snails: depresses O2 consumption (MacInnes & Thurberg, 1973)

Crustaceans
Organism Rainbow shrimp 96 hr LC50 40.6 mg/L (As2S3) Reference Curtis et. al., 1979

Dungeness crab

232 g/L (AsO33-)

Martin et. al., 1981

Echinoderms
As (III) and As (V) produces abnormalities in sea urchin gametes and embryos (Pagano et. al., 1982)

Competitive inhibition of phosphate and asenate is observed (Chambers & Whiteley, 1966)

Fish
Limited basis that As (III) is acutely toxic to fish (comparable to Hg, Cd, Cr, Zn, Cu) since only a few species of fish were tested. (Alderice & Brett, 1975; Holland et. al., 1960)

Select Marine Toxicity Data for Arsenic

Source: Canadian Council of Ministers of the Environment. Canadian Water Quality Guidelines for the Protection of Aquatic Life: Arsenic. (2001)

Long-term Effects
Inhibition of growth, photosynthesis, and reproduction Behavioral effects Limited species abundance (only tolerant species survive) [GomezCaminero et. al., 2001]

References
Chapman, AC. Analyst, 1926, 51: 548.

Ferguson, JF & Gavis, J. A review of the arsenic cycle in natural waters. Water Research, 1972. 6: 1259-1274.
De Groot, AJ. In: Goldberg, ED (ed) North Sea Science. 1973, MIT Press, Cambridge, Massachusetts, pp 308-326. Crecelius, EA. Arsenite and arsenate levels in wine. Bulletin of Environmental Contamination and Toxicology. 1977, 18: 227-230. Waslenchuk, DG & Windom, HL. Factors controlling the estuarine chemistry of arsenic. Estuarine Coastal Marine Science. 1978, 7: 455-464. Johnson DL & Braman, RS. The speciation of arsenic and the content of germanium and mercury in members of the pelagic Sargassum community. Deep-Sea Research. 1975. 22: 503.

Nelson DA, et. al. Biological effects of heavy metals on juvenile bay scallops, Argopecten irradians, in short-term exposures. Bulletin of Environmental Contamination and Toxicology. 1976. 16(3): 275-282. MacInnes, JR. & Thurberg, FP. Effects of metals on the behavior and oxygen consumption of the mud snail. Marine Pollution Bulletin. 1973, 4(12): 185-186. Curtis, MW et. al. Acute toxicity of 12 industrial chemicals to freshwater and saltwater organisms. Water Research. 1979. 13: 137-141. Martin, M. et. al. Toxicities of ten metals to Crassostrea gigas and Mytilus edulis embryos and Cancer magister larvae. Marine Pollution Bulletin. 1981. 12(9): 305-308. Pagano, G. et. al. Arsenic-induced developmental defects and mitotic abnormalities in sea-urchin development. Mutation Research. 1982, 104: 351-354.

Irgolic KJ et. al., Characterization of arsenic compounds fromed by Daphnia magna and Tetraselmis chuii from inorganic arsenate. Environmental Health Perspective. 1977. 19: 61-66. Cooney, RV, Mumma, RO & Benson, AA. Arsoniumphospholipid in algae. Proceedings of the National Academy of Sciences of the USA. 1980, 75(9): 4262-4264.
Klumpp, DW. Characteristics of arsenic accumulation by the seaweeds Fucus spiralis & Ascophyllum nodosum. Marine Biology. 1980. 58(4): 257-264. GESAMP. GESAMP Reposrts and Studies No. 28: Arsenic, mercury and selenium in the marine environment. 1988, United Nations Press, Geneva, pp 17-54. Calabrese, A et. al. The toxicity of heavy metals of embryos od the American Oyster Crassostrea virginica. Marine Biology. 1973. 18: 162-166.

Chambers, EL & Whiteley, HA. Phosphate transport in fertilized sea urchin eggs, I. Kinetic Aspects. Journal of Cell Physiology. 1966, 68: 289-308. Alderice DF. & Brett, JR. The toxicity of sodium arsenite to young chum salmon. Prog. Rep. Pacific Coast Stat. Fish. Res. Board Can. 1957, 108: 27-29.
Holland, AA. et. al. Toxic effects of organic and inorganic pollutants in young salmon and trout, State of Washington. Department of Fisheries Research Bulletin. 1960. 5: 264. Maher & Butler. Arsenic in the marine environment. Applied Organometallic Chemistry. 1988 2: 191-214. Gomez-Caminero, A. et. al, Environmental Health Criteria 224: Arseic and Arsenic Compounds. 2001. World Health Organization Publications, Geneva.