* : , , 18. Arsenic As , . Orpiment " " " " Orpiment .

Periodic Table of the Elements

As is a Group V element (like N and P) Replaces S in minerals and metabolic systems replaces P in minerals and ATP energy cycle

Sources of arsenic
Soil and Sediment Arsenic concentrations in soils depend in part on the parent materials from which the soils were derived, although they may be enriched by other sources, including anthropogenic sources. Typical natural concentration ranges are 0.1 to 40 mg/kg, with an average concentration of 5-6 mg/kg (NAS, 1977). The level of arsenic in soil derived from basalts tends to be higher than in soils of granitic origin, and concentrations of 20 to 30 mg/kg may be found in soils derived from sedimentary rocks (Yan-Chu, 1994). In areas of recent volcanism, soils average arsenic concentrations are approximately 20 mg/kg. Very high natural concentrations of arsenic (up to 8,000 mg/kg) may occur in soils that overlay deposits of sulfuric ores (NAS, 1977). Arsenic can be found in soil in the inorganic state bound to cations, and it can also be found bound to organic matter. Arsenic may be transferred to surface water and ground water through erosion and dissolution; plants may also uptake arsenic. Because arsenic can be fixed in inorganic and organic compounds in soil, soil may also be a sink for arsenic

Geothermal Waters
Geothermal water can be sources of arsenic in surface water and ground water. Welch et al., (1988) identified 14 areas in the Western United States where arsenic conditions in water exceed 50 g/L because of known or suspected geothermal sources. In these areas, dissolved arsenic concentrations ranged from 80 to 15,000 g/L. Welch et al.,found that mean dissolved arsenic concentrations in geothermal ground waters are higher than mean arsenic concentrations in nonthermal ground waters in any of the physiographic provinces in the United States.

Other Sources
Natural emissions of arsenic associated with volcanic activity and forest and grass fires are recognized to be significant. Indeed, volcanic activity appears to be the largest natural source of arsenic emissions to the atmosphere (ATSDR, 1998). Estimates of natural releases (of which volcanic arsenic emissions are the primary source).

natural sources, arsenic is released from a variety of anthropogenic sources (USEPA, 1998b), including: Manufacturing of metals and alloys Petroleum refining Pharmaceutical manufacturing Pesticide manufacturing and application Chemicals manufacturing Burning of fossil fuels Waste incineration These anthropogenic releases of arsenic can elevate environmental arsenic concentrations. Human exposure to arsenic can result in a variety of chronic and acute effects. In particular, there is evidence that associates chronic arsenic ingestion at low concentrations with increased risk of skin cancer, and that arsenic may cause cancers of the lung, liver, bladder, kidney, and colon (ATSDR, 1998). Because of the human health risks associated with

Mining and Smelting

Arsenic can be obtained from two of its ores, arsenopyrite and lollingite, by smelting in the presence of air around 650700 C (Kirk-Othmer, 1992), or arsenic trioxide (As2O3) in flue dust from the extraction of lead and copper can be captured (Ferguson, 1990). Subsequently, arsenic trioxide can be used to produce other arsenic compounds or purified to elemental arsenic. Arsenic trioxide was produced for commercial use in the United State at the ASARCO smelter in Tacoma, Washington, until 1985, at which time the smelter ceased operations (ATSDR, 1998). The USEPA Office of Air Quality Planning and Standards indicates that primary and secondary6 lead smelters, primary copper smelters

Exposure Arsenic is continually cycled through all environmental compartments. Arsenic can be elevated to high levels in water and soil because of the underlying geology or geothermal activity. In the aquatic environment arsenic concentrations can also become elevated in some estuaries and in waters near heavy industrial or mining and mineral-processing areas. The highest concentrations of arsenic in soil tend to be associated with mining waste. Mean total arsenic concentrations in air from remote and rural areas range from 0.02 to 4 ng/m3. Mean total arsenic concentrations in urban areas range from 3 to about 200 ng/m3; much higher concentrations (> 1000 ng/m3) have been measured in the vicinity of industrial sources. Reported concentrations of arsenic in surface waters are summarized in Fig. 6. Concentrations of arsenic in open ocean seawater are typically 12 g/litre. Arsenic is widely distributed in surface freshwaters, and background concentrations in rivers

Mean arsenic concentrations of 500 g/litre and a maximum of 25 mg/litre have been reported for geothermal waters. Enhanced arsenic levels of < 10 mg/litre have been reported near anthropogenic sources such as mining and agrochemical manufacture. Mean sediment arsenic concentrations range from 5 to 3000 mg/kg, with the higher levels occurring in areas of contamination. Reported concentrations of arsenic in soils are summarized in Fig. 7. Background concentrations in soil tend to range from 1 to 40 mg/kg, with a mean value of 5 mg/kg. Naturally elevated levels of arsenic in soils may be associated with geological substrata such as sulfide ores. Anthropogenically contaminated soils can have concentrations of arsenic up to several percent

Terrestrial plants
Arsenic species can enter into edible tissues of food crops through absorption (i.e. not just surface contamination) (Woolson, 1973; Helgesen & Larsen, 1998). Helgesen & Larsen (1998) demonstrated that bioavailability of arsenic pentoxide to carrots in soil from a wood preservative treatment plant (soil was contaminated with CCA) was 0.47 0.06% of total soil arsenic burden. This study showed that arsenite, arsenate, MMA and DMA were present in carrot tissue, where only arsenite and arsenate were present in soil. In soils dosed with arsenate (0 500 g/g) at the concentrations which inhibited growth of vegetable crops (green bean, lima bean, spinach, cabbage, tomato and radish), high levels of accumulation when found in the edible parts of radish (76 g/g) spinach (10 g/g) and green bean (4.2 g/g). Arsenic accumulation in Lima bean, cabbage and tomato ranged from 0.71.5 g/g. The studies of Woolson (1973) and Helgesen & Larsen (1998) highlight the potential of

Environmental levels Arsenic is a natural component of the earths crust, and found in all environmental media. Concentrations in air in remote locations range from < 1 to 3 ng/m3, but concentrations in cities may range up to 100 ng/m3. Concentrations in water are usually < 10 g/litre, although higher concentrations can occur near natural mineral deposits or anthropogenic sources. Natural levels in soils usually range from 1 to 40 mg/kg, but pesticide application or waste disposal can produce much higher values

1 -Air
Levels of arsenic in ambient air are summarized in Examples are given of mean total arsenic concentrations in remote and rural areas ranging from 0.02 to 4 ng/m3. Levels of arsenic in outdoor air near to urban and industrial sources are summarized in . Examples are given of mean total arsenic concentrations in urban areas ranging from 3 to 200 ng/m3; much higher concentrations (> 1000 ng/m3) have been measured in the vicinity of industrial sources. Arsenic in ambient air is usually a mixture of arsenite and arsenate, with organic species being of negligible importance except in areas of substantial methylated arsenic pesticide application or biotic activity. Schroeder et al. (1987) reviewed worldwide arsenic concentrations associated with particulate matter.

They identified arsenic levels ranging from 0.007 to 1.9 ng/m3 for remote areas, 1 to 28 ng/m3 for rural areas and 2 to 2320 ng/m3 in urban areas. The highest arsenic levels detected in the atmosphere were near non-ferrous-metal smelters. Typical background levels for arsenic are now 0.21.5 ng/m3 for rural areas, 0.53 ng/m3 for urban areas and < 50 ng/m3 for industrial sites (DG Environment, 2000).

Environmental effects of arsenic

The arsenic cycle has broadened as a consequence of human interference and due to this, large amounts of arsenic end up in the environment and in living organisms. Arsenic is mainly emitted by the copper producing industries, but also during lead and zinc production and in agriculture. It cannot be destroyed once it has entered the environment, so that the amounts that we add can spread and cause health effects to humans and animals on many locations on earth. Plants absorb arsenic fairly easily, so that high-ranking concentrations may be present in food. The concentrations of the dangerous inorganic arsenics that are currently present in surface waters enhance the chances of alteration of genetic materials of fish. This is mainly caused by accumulation of arsenic in the bodies of plant-eating freshwater organisms. Birds eat the fish that already contain eminent amounts of arsenic and will die as a

Risk evaluation Conventional, generic risk assessment would apply uncertainty factors to the lowest reported chronic effects concentration. For arsenic in freshwaters, this would be 5 g/litre for growth in algae. This concentration is similar to the upper limit of the natural range of arsenic concentrations in most surface freshwaters. It is almost four orders of magnitude lower than the highest natural concentrations of arsenic in geothermal regions. Since communities of organisms occur in surface waters across the whole natural range (0.05 25 000 g/litre), a single protective concentration target for arsenic is inappropriate. Although there is no direct evidence that populations of organisms living at the higher end of the range for most surface waters (around 2 g/litre) are less sensitive to arsenic than those at the bottom end of the range (0.05 g/litre), this might be inferred from laboratory and field evidence. There is clear laboratory and field evidence that populations living at much higher concentrations have adapted to high inorganic arsenic levels. may mitigate arsenic toxicity in the environment. Realistically, risk assessment for inorganic arsenic can only be done on a site-by-site basis taking into account background arsenic concentrations, local population tolerance and other local mitigating factors

For populations of organisms living in low inorganic arsenic environments with little possible mitigation (e.g. low phosphate levels), a concentration of around 5 g/litre would be protective of all but the most sensitive algae. Adapted populations at high natural inorganic arsenic concentrations will be specialized communities, possibly of lower biodiversity but probably of high conservation interest. Areas polluted by anthropogenic activity, therefore, present the risk manager with different options based on both practicability and desirability of remediation; if adapted communities have developed over time, these might be destroyed by remediation. Clearly the contamination of pristine areas with arsenic to levels which cause adaptation and decreased biodiversity is unacceptable.

What are the Potential Health Effects? The primary health concern with exposure to arsenic is cancer. Exposure to arsenic over many years can increase your chances of getting certain types of cancer, or other health effects, such as diarrhea, poor blood production, and abnormal heart beat. The health outcomes depend on the length of time that you are exposed to arsenic from any source, the amount of arsenic in your water, the amount of water that you drink, and your current level of health. The risk of developing health effects are the same for everyone, including children pregnant women and other

Effects on human health

Cancer Melanosis

Hyperkeratosis

Summary of Method The ICPMS methods have been described previously in Faires (1993) and Garbarino and Taylor (1994). The following sections only provide additional information specific to the elements that are being added to the method. Former methods and ICPMS method detection limits and calibration limits for new elements determined in filtered, acidified natural water [All concentrations are in micrograms per liter; MRL, minimum reporting level; MDL, method detection limit; CC, catalyzed colorimetry; DCPAES, direct current plasmaatomic emission spectrometry; FAAS, flame atomic absorption spectrophotometry; GFAAS, stabilized temperature graphite furnaceatomic absorption spectrophotometry; HGAAS, hydride generationatomic absorption spectrophotometry; ICPAES, inductively coupled

Accuracy of inductively coupled plasmamass spectrometric arsenic determinations in the presence of bromide using different correction equations. The error bars correspond to one standard deviation based on three instrumental measurements.

Sample Preparation Filtered, acidified natural-water samples analyzed by ICP MS for dissolve arsenic, boron, lithium, selenium, strontium, thallium, and zinc and other elements do not require additional processing. . Analytical Procedure Refer to Perkin-Elmer (1997a, 1997b) and NWQL Standard Operating Procedure IM0011.1 (T.M. Struzeski, U.S. Geological Survey, written commun., 1998) for details of the analytical procedure. In addition, the accuracy of

Statistical analysis of long-term ICPMS results for U.S. Geological Survey Standard Reference Water Sample T145 [ICPMS, inductively coupled plasmamass spectrometry; elemental results are in micrograms per liter; MPV, the most probable value; , the plus or minus symbol precedes the F-pseudosigma in the MPV column and the standard deviation in the experimental mean column; n, number of replicates used to calculate the experimental mean; p-value, level of significance; <, less than]

Short-term analytical variability as a function of elemental concentration for ICPMS [ICPMS, inductively coupled plasmamass spectrometry, the percent relative standard deviations are based on three sequential determinations in a 0.4-percent solution of concentrated nitric acid in deionized water; g/L, micrograms per liter; <MDL, less than the method detection limit; nd, not determined]

Average percent spike recoveries in reagentwater, surface-water and ground-water matrices by inductively coupled plasmamass spectrometry [mg/L, micrograms per liter; number following the plus or minus symbol () is the standard deviation on the basis of seven determinations accrued on separate days; high spike, 75 mg/L for all elements; na, not applicable because the difference between the spike concentration and ambient concentration was greater than a factor of 10; <MDL, concentration is less than the method detection limit; %, percent