Most environmental transformations of arsenic appear to occur in the soil, in sediments, in plants and animals, and in zones of biological activity in the oceans. Biomethylation and bioreduction are probably the most important environmental transformations of the element, since they can produce organometallic species that are sufficiently stable to be mobile in air and water. However, the biomethylated forms of arsenic are subject to oxidation and bacterial demethylation back to inorganic forms IPCS, , section 4. Three major modes of biotransformation of arsenic species have been found to occur in the environment: redox transformation between arsenite and arsenate, the reduction and methylation of arsenic, and the biosynthesis of organoarsenic compounds.
There is biogeochemical cycling of compounds formed by these processes Andreae, Arsenic is released into the atmosphere primarily as As 2 O 3 or, less frequently, in one of several volatile organic compounds, mainly arsines US EPA, Photolysis is not considered an important breakdown process for arsenic compounds Callahan et al. Arsenic can undergo a complex series of transformations, including redox reactions, ligand exchange and biotransformation Callahan et al.
Factors affecting fate processes in water include the Eh, pH, metal sulfide and sulfide ion concentrations, iron concentrations, temperature, salinity, and distribution and composition of the biota Callahan et al. Oscarson et al. The oxidation process was unaffected by flushing nitrogen or air through the system or by the addition of mercuric chloride.
The authors therefore concluded that the oxidation was an abiotic process, with microorganisms playing a very minor role in the system. They found that abiotic oxidation proceeded at a slow and constant rate with rapid oxidation occurring only in the presence of certain aquatic bacteria. Baker et al. They found that oxidation was primarily due to microbial activity. Oxidation obeyed first-order kinetics with a rate constant of 0. Under aerobic conditions the mixed microbial cultures of lake sediments were able to reduce arsenate to arsenite and also to oxidize arsenite to arsenate.
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However, under anaerobic conditions only reduction was observed Freeman et al. In seawater containing free dissolved oxygen, arsenate is the thermodynamically stable form of the element. Arsenite is present in amounts exceeding those of arsenate only in reduced, oxygen-free porewaters of sediments and in anoxic basins such as the Baltic sea. The presence of arsenite in seawater suggests that some reduction of arsenate occurs, and indeed Johnson demonstrated that bacterial arsenate reduction can take place under laboratory conditions.
Matsuto et al. Freeman isolated an Anabaena oscillaroides —bacteria assemblage from the arsenic-rich Waikato river New Zealand capable of reducing arsenate to arsenite. Wakao et al. Similarly, Macy et al. On the bassis of both aqueous and solid-phase observations, McGeehan found that arsenate was reduced to arsenite in flooded soil under batch conditions.
The biomethylation of arsenic was first recognized when arsines were produced from cultures of a fungus, Scopulariopsis brevicaulis Challenger, Further experiments have shown that growing cells of C. Cullen et al. They identified arsenite, methylarsonate, DMA and trimethylarsine oxide as intermediates in a biological synthesis of trimethylarsine. However, they tentatively conclude that methylarsonate does not occur as a free intermediate in the arsenate to trimethylarsine pathway. McBride et al. Methylated arsenic compounds were detected in aerobic sediments from various locations in Ontario Canada incubated with or without the addition of extraneous arsenic.
Two pure bacterial cultures, Aeromonas sp. Methylation occurred over the pH range 3. The amount of arsenic recovered in the methylated species ranged from 0 to 0. Maeda et al. Laboratory studies have shown that microorganisms present in both natural marine sediments and sediments contaminated with mine tailings are capable of methylating arsenic under aerobic and anaerobic conditions Reimer, In fact, most diatoms, dinoflagellates and macroalgae as well as freshwater higher plants, release protein-bound arsenic as a result of sequential methylation and adenosylation Benson et al.
Analysis revealed the presence of MMA, DMA and trimethylarsine oxide; however, volatile arsine and methylarsines were not detected. Small amounts of methylated arsenic compounds were detected and these were strongly bound with proteins or polysaccharides. Methylated arsenic compounds were found mainly in the lipid-soluble fractions and the major form was a dimethyl arsenic compound. No methylation occurred in algal cells Chlorella vulgaris exposed to arsenate under in vitro conditions; however, in vivo a small fraction of the arsenic accumulated was first transformed to methyl and dimethyl arsenic compounds during the early exponential phase and finally transformed to trimethylarsenic species Maeda et al.
The marine algae Ecklonia radiata and Polyphysa peniculus methylated arsenate to produce a dimethylarsenic derivative. S -adenosylmethionine is also likely to be the source of adenosyl and ribosyl groups in the arsenosugars. Edmonds et al. Arsenic-containing compounds are catabolized as they pass through the food web, yielding arsenobetaine as a stable end-product. Inorganic arsenic administered orally to brown trout Salmo trutta was detected in tissues as organoarsenical species, whereas arsenic administered by injection was taken up as inorganic arsenic and slowly converted to the organic form.
It was concluded that biosynthesis of arsenic was occurring in the gastrointestinal tract Penrose, Oladimeji et al. The major organic arsenical appeared to be an arsenobetaine-related compound. Similarly, Penrose et al. However, Wrench et al. The percentage of organic species was much higher than that found in phytoplankton and zooplankton in the same model ecosystem. Similarly, Maeda et al. The rates of photochemical decomposition of arsenite, DMA, MMA and arsenobetaine have been studied in both distilled water and seawater.
All species were found to degrade rapidly in aerated distilled water. In deaerated solutions the rate of oxidation of arsenite was almost two orders of magnitude slower. In seawater, the rates of photochemical decomposition were slower. This study suggests that UV irradiation is of limited use for the pretreatment of saline samples to convert organoarsenic species to As V before analysis. The implications for photochemical decomposition of arsenic species in natural waters is not clear, because sunlight is deficient in the lower-wavelength bands generated by the mercury lamp used in this study.
In addition, colloids and suspended particulates in the photic zone may play a significant role in arsenic decomposition in natural waters. Von Endt et al. In day tests in non-sterile soil 1. The predominant form of arsenic in water is usually arsenate Callahan et al. Most of the arsenic accumulated in marine organisms is in a water-soluble form of arsenic, namely arsenobetaine.
Hanaoka et al.
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Further experiments revealed the formation of trimethylarsine oxide during aerobic incubation of bottom sediments with arsenobetaine as the carbon source Kaise et al. Under aerobic conditions, arsenobetaine is converted to its metabolites to a much greater extent than other methylarsenicals. Under anaerobic conditions little or no degradation of arsenobetaine occurred, whereas trimethylarsine oxide and DMA were converted to less methylated compounds Hanaoka et al.
Degradation of arsenobetaine has also been demonstrated in the water column in the presence of suspended substances Hanaoka et al. Organoarsenical pesticides e. Arsine was produced in all three soils from all substrates but methylarsine and dimethylarsine were only produced from methylarsonate and DMA respectively. Both Pseudomonas sp. The authors concluded that reduction to arsine, not methylation to trimethylarsine, was the primary mechanism for gaseous loss of arsenicals from soil.
In day tests they found that 1. Degradation of MSMA has been shown to be associated with soil organic matter oxidation. Akkari et al. It was found that degradation followed first-order kinetics. The rate constant was temperature dependent only at soil water contents less than field capacity, and the temperature effect was less under flooded conditions. Half-lives for the clay and silty loam soils were and 88 days respectively. Under anaerobic flooded soil conditions MSMA degradation occurs by reductive methylation to form arsenite and alkylarsine gases.
The half-life values for the two soils indicate significantly faster degradation at 25 and 41 days respectively. The amount of sodium DMA mineralized was linearly related to the concentration of sodium DMA in the soil, indicating that the rate is first order.
Mineralization of sodium DMA increased with increasing soil moisture and temperature. Bioconcentration of arsenic under laboratory conditions occurs in aquatic organisms, primarily in algae and lower invertebrates. Biomagnification in aquatic food chains does not appear to be significant Callahan et al.
Terrestrial plants may accumulate arsenic by root uptake from the soil or by adsorption of airborne arsenic deposited on the leaves, some species accumulating substantial levels. Nostoc sp. Phytoplankton take up arsenate readily and incorporate a small proportion into the cell.
Most of the arsenate is reduced, methylated and released to the surrounding media. Phytoplankton batch cultures exposed to elevated levels of arsenate take up additional arsenic during the log phase of growth. Studies using 74 As indicate that the uptake rate varies from 0. Phytoplankton readily incorporated dissolved arsenic, with average arsenic residues increasing from 5. Accumulation in other biota was much lower than for phytoplankton Reuther, Mean BCFs for algae ranged from for sand microcosms to for lake mud microcosms. Algal arsenic concentrations were significantly greater in the litre microcosms and in the sand microcosms than in the 7-litre and sediment microcosms.
Maximum BCFs of — were observed during the log phase.
Approximately half of the arsenic taken up was estimated to be adherent to the extraneous coat of the cell with the remainder accumulated by the cell. Arsenate accumulation was affected by the growth phase; arsenic was most actively accumulated when the cell was exposed to arsenic during the early exponential phase Maeda et al.
Increased phosphate significantly decreased the uptake of arsenic in the culture Yamaoka et al. Yamaoka et al.
Klumpp studied the effect of a variety of factors on the uptake of labelled arsenic by the seaweed Fucus spiralis. Lee et al. Accumulation of arsenic reached steady state at 2—6 days in pool water at BCFs of — In deionized water maximum arsenic accumulation occurred after 8 days at a BCF of around Sanders et al.
In h tests, E. In day tests, B. In further experiments with oysters Crassostrea virginica no accumulation of arsenic from water was observed in day tests, but tissue concentrations increased significantly from 5. Generally, arsenic body burdens increased with increases in phytoplankton concentration and it appears that food contributes more to arsenic uptake than do seawater arsenic concentrations.
No relationship between arsenic uptake and seawater arsenic concentrations was found. Mean concentration factors after 20 days were low, at respectively 8. Arsenic loss was essentially biphasic, with biological half-times of approximately 3 and 32 days for the fast and slow compartments respectively. The active secretion of arsenic in the byssal threads contributed to the total elimination of the element from the mussels.
The elimination of 74 As by the crabs after ingestion of arsenic-contaminated mussels was dependent on the chemical form of the arsenic. After ingestion of mussel containing mostly lipid- and water-soluble arsenic species undetermined , biological half-times were 3. After ingestion of mussel containing mostly arsenite and residual arsenic, half-times were 1. Naqvi et al. Uptake of arsenic was dose-dependent but not time-dependent. Maximum whole-body residues were 1. Gibbs et al. A lower BCF of only Shrimps exposed to water concentrations ranging from 0.
Arsenic loss was biphasic with half-lives of 3 and 26 days for the fast and slow compartments respectively. Brine shimp Artemia sp. Barrows et al. The maximum BCF was found to be 4, with a half-life in tissues of 1 day. Nichols et al. Whole-body residues were below 0. For each of the arsenicals investigated, carcass arsenic concentration showed a dose—response relationship to dietary arsenic concentration and exposure rate. Inorganic arsenicals were accumulated from the diet to a greater degree than the organic forms. Arsenic accumulation was dose related, with residues ranging from 1. Arsenic species can enter into edible tissues of food crops through absorption i.
This study showed that arsenite, arsenate, MMA and DMA were present in carrot tissue, where only arsenite and arsenate were present in soil. Arsenic accumulation in Lima bean, cabbage and tomato ranged from 0. They found that tolerant plants transported a much greater proportion of arsenic to their shoots than non-tolerant plants. Phosphate 0. Arsenate tolerance involves reduced accumulation of arsenate through suppression of the high-affinity phosphate—arsenate uptake system Meharg et al. Arsenic was accumulated in a dose-dependent manner with arsenic residues of 0.
Otte et al. Concentrations of arsenic in shoots and roots of P. The arsenic concentration of rice plants correlated with the mean soil solution arsenate concentration in the clay soil and to the mean soil solution arsenite for the silt loam. The rate of arsenic uptake by plants increased as the rate of plant growth increased. Meharg et al. There was a steady-state increase in residues for depurated and undepurated worms and by 12 days earthworm residues were equivalent to those of the soil.
Arsenic residues were accumulated to three times soil levels by the end of the day exposure in depurated worms; however, undepurated worms did not appear to bioconcentrate arsenic beyond the level of the surrounding soil. Maximum concentrations in eggs were reached after 4—5 weeks at 0. Residual arsenic was negligible 2 weeks after the withdrawal of the drug from the feed.
Proudfoot et al. Mean arsenic residues of up to 1. Lower levels were accumulated in muscle tissue, with arsenic concentrations of up to 0. Eggs were collected on days 8—19 day of the experiment, and arsenic residues were consistent throughout this period. Mean concentrations were respectively 0. Hoffman et al. Arsenic accumulated in the liver at a concentration of 2. Birds maintained on a restricted protein and exposed to the same arsenic-contaminated diet accumulated 5.
Stanley et al. Arsenic was accumulated in a dose dependent manner; mean concentrations in adult livers were 0. Levels of arsenic in ambient air are summarized in Table 3. Examples are given of mean total arsenic concentrations in remote and rural areas ranging from 0.
Levels of arsenic in outdoor air near to urban and industrial sources are summarized in Table 4. 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. They identified arsenic levels ranging from 0. The highest arsenic levels detected in the atmosphere were near non-ferrous-metal smelters. Typical background levels for arsenic are now 0. Arsenic has been detected in rainwater at mean concentrations of 0. Peirson et al. Andreae collected rainwater samples from non-urban sites in California USA and state parks in Hawaii and found mean arsenic concentrations ranging from 0.
Samples from a rural site in Washington state USA contained a mean concentration of 1. Vermette et al. Reimann et al. Median arsenic concentrations 0. Arsenic concentrations ranged from 0. Levels of arsenic in seawater are summarized in Table 5. Levels of arsenic in estuarine water are summarized in Table 6. Penrose et al.
Total inorganic arsenic concentrations were 5.
Concentrations of monomethylarsenic ranged from 0. Levels of arsenic in surface freshwaters are summarized in Table 7. High levels of arsenic have been recorded in thermal waters. Levels of arsenic in groundwater are summarized in Table 8. The authors state that the arsenic appears to be of natural origin. Similarly, Matisoff et al. Del Razo et al. Chen et al. Arsenic levels in the well-waters of Hsinchu Taiwan were less than 0.
Arsenic contamination of groundwater from arsenic-rich sediment has been reported in both India and Bangladesh. Chatterjee et al. Mandal et al. During and Chatterjee et al. Arsenic concentrations in sediments are summarized in Table 9. Sediments in aquatic systems often have higher arsenic concentrations than those of the water Welch et al.
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Most sediment arsenic concentrations reported for rivers, lakes and streams in the USA range from 0. Similar findings were reported by de Bettencourt for the Tagus Estuary Portugal. Total arsenic concentrations upstream of industrial inputs were Concentrations ranged from 2. Levels of arsenic in soil are summarized in Table Most natural soils contain low levels of arsenic, but industrial wastes and pesticide applications may increase concentrations. Peat may contain considerable quantities of arsenic.
However, Shotyk analysed peat cores from the Jura mountains Switzerland and found mean total arsenic concentrations of 3. Higher levels of arsenic were found in the mineral sediments underlying the peat bogs, with mean concentrations of 6. Soil on agricultural land treated with arsenical pesticides may retain substantial amounts of arsenic.
Uptake and effects of arsenic on organisms are related to bioavailable arsenic rather than total arsenic. Kavanagh et al. The proportion of water-extractable arsenic in agricultural topsoils ranged from 0. Similarly, McLaren et al. Chemical speciation showed that arsenite ranged from 0. In a rat model, the absolute bioavailability of these contaminated soils relative to arsenite and arsenate ranged from 1.
The levels are higher in biota collected from mine waste sites, arsenic-treated areas, near smelters and mining areas, near areas with geothermal activity and near manufacturing sites of arsenical defoliants and pesticides Eisler, There is a substantial number of publications on the levels of arsenic in biota, and the following examples have been chosen to provide an overview. Reay reported a considerable accumulation of arsenic in freshwater plants in the Waikato river New Zealand.
Wagemann et al. Freshwater bivalves have been used to measure arsenic in several biomonitoring programmes. Mean concentrations of arsenic in bivalves ranged from 5. A highly significant relationship was observed between arsenic residues and the HNO 3 -extractable arsenic : iron ratio of suspended matter. Arsenic levels in mussels from the St Lawrence river Canada ranged from 2. Freshwater fish have not been shown to accumulate arsenic to the same degree as lower aquatic organisms.
Arsenic residues in freshwater fish have been monitored in the USA over a period of approximately 10 years. Mean total arsenic residues in freshwater fish near a copper smelter Sweden ranged from 0. Mean arsenic levels were 0. Arsenic residues have also been measured in fish from the San Joaquin valley area of California USA exposed to agricultural subsurface drainage water. Mean arsenic concentrations ranged from 0. Mean arsenic concentrations for striped bass Morone saxatilis from the same area ranged from 0.
Clark et al. Marine biota tend to accumulate much higher levels of arsenic than freshwater species see section 4. Very little information is available on arsenic levels in natural phytoplankton populations. Sanders a found that mean total arsenic concentrations in marine macroalgae ranged from 1. The absolute concentration of inorganic arsenic was not significantly different between groups, suggesting that the variation is due to metabolic differences between algal classes rather than to differences in the environmental concentration of arsenic.
Mean total arsenic concentrations in macroalgae collected in the South Atlantic ranged from 5. Lai et al. Mean arsenic residues were Similar levels mean values ranging from 1. Shellfish from the Arabian Gulf contained mean arsenic concentrations ranging from 3 to Concentrations of arsenic in estuarine organisms correlated more significantly with the arsenic : iron ratio in sediments than arsenic levels alone.
Arsenic residues in marine fish appear to show substantial variation. Hellou et al. The mean value was 60 times greater than that found for freshwater fish in the same study. However, higher concentrations have been reported, for example, Attar et al. Bohn reported mean arsenic concentrations for marine fish from West Greenland ranging from Maher , analysed a variety of marine biota and found mean total arsenic concentrations dry weight ranging from 2. Mean inorganic arsenic concentrations were low 0.
The arsenic content of plants grown on soils that had never been treated with arsenic-containing pesticides varied from 0. Plants grown on arsenic-contaminated soils may, however, contain considerably higher levels, especially in the roots. Benson et al.
Temple et al. Grass growing on plots which had been previously treated 7—11 years before with lead arsenate contained mean arsenic residues of 1. After a further 2 years mean arsenic concentrations were 0. Merry et al. Biomonitoring studies at six background sites in Norway found mean arsenic concentrations in moss Hylocomium splendens ranging from 0. A mean background concentration of 0. Lichen biomonitoring of arsenic in a geothermal area of central Italy revealed a mean concentration of 1. However, much higher concentrations 0.
Mean arsenic concentrations were 0. Arsenic concentrations ranged from trace levels to 0. Total arsenic concentrations ranging from 3. There was no correlation between the total arsenic concentrations in the earthworms and the soil. The major arsenic compounds detected in the earthworms were arsenous acid and arsenic acid; arsenobetaine, dimethylarsinic acid and two dimethylarsinoylribosides were also detected Geiszinger et al.
Of 18 osprey Pandion haliaetus livers analysed by Wiemayer et al. The bird with the highest concentration was in a weak condition with very low fat reserves. Erry et al. Mean arsenic residues of 0. However, in another two raptors sparrowhawk Accipiter nisus and barn owl Tyto alba arsenic levels were not elevated in south-west England.
The authors suggested that the difference could be attributed to differences in both diet and arsenic metabolism.
Goede found mean arsenic concentrations ranging from 0. Arsenic concentrations at a control site were 2. Mean arsenic levels in vegetation were 0. Mean whole-body arsenic residues in four species of small mammal ranged from 0. Significantly higher levels were found at the control site for three of the four species; the common shrew Sorex araneus , a carnivorous species, accumulated the highest levels of arsenic at both sites. Norstrom et al. Norheim et al. Arsenic is widely distributed and human exposure is inevitable. Exposure of the general population to the various species of arsenic inorganic and organic will vary according to local geochemistry and the level of anthropogenic activity and can occur through the intranasal, oral and dermal routes.
Arsenic in ambient air is associated with particulate matter and is predominantly a mixture of arsenite and arsenate. Organic species are of negligible significance except in areas where there has been substantial use of methylated arsenic pesticides or in areas with high biotic activity ATSDR, As discussed in section 5. The highest concentrations are found near non-ferrous-metal smelters. Arsenic has been found in all foodstuffs analysed. Although most monitoring data is given as the concentration of total arsenic, arsenic in foods is a mixture of inorganic species and organoarsenicals including arsenobetaine.
The actual total arsenic concentrations in foodstuffs from various countries will vary widely depending on the food type, growing conditions type of soil, water, geochemical activity, use of arsenical pesticides and processing techniques. Meats and cereals have higher concentrations than vegetables, fruit and dairy products.
Other age groups had lower estimated daily intakes of inorganic arsenic, varying from 1. Additional samples, and a wider range of foodstuffs, need to be analysed in various countries before a definite conclusion can be reached on the normal range of inorganic arsenic in foods. Mohri et al. Concentrations of arsenic in various food groups found in Canada are given in Table Very few data were found on the concentration of arsenic in human breast milk.
One study of 10 lactating women by Concha et al. Examples of mean total daily intakes of arsenic from food and beverages in different countries are given in Table The risk of arsenic exposure to populations living in or near arsenic-contaminated environments i. In particular, contamination of home-grown vegetables and reared livestock, or wild collected foods must be considered. Concentrations of arsenic in fresh surface water and groundwater, potential sources of drinking-water, are given in sections 5.
Arsenate is the predominant species, but some groundwaters have been found to contain a high proportion of arsenite section 5. Concentrations of methylated species in natural waters are usually less than 0. Unless stated otherwise in this section, monitoring data for drinking-water is reported as total arsenic. Additional data sources US EPA, provide support for this estimate, and have identified areas with higher concentrations of arsenic in drinking-water.
In areas with elevated geological concentrations of arsenic e. Of the samples of surface water, 3. Although ingestion of arsenic in soil and dust may not be a significant source of arsenic intake in adults, it may be significant for children, particularly in locations near industrial and hazardous waste sites. As described in section 5. In a rat model, soil from the cattle dip site had a bioavailability of 8. For CCA-contaminated soil the corresponding comparative bioavailabilities were Also using a rat model, Ng et al. The absolute bioavailability ranged from 1.
Freeman et al. When compared to the intravenous administration of sodium arsenate, the absolute bioavailability was reported as When compared to an oral dose gavage of sodium arsenate, the comparative bioavailabilities were Such data on availability of arsenic in soil needs to be considered in assessing human uptake of arsenic from soil for more details on bioavailability see Table Smokers are exposed to arsenic by the inhalation of mainstream cigarette smoke.
There is the potential for significant occupational exposure to arsenic in several industries, in particular non-ferrous smelting, electronics, wood preservation, wood joinery shops, arsenic production, glass manufacturing, and the production and application of arsenical pesticides.
Exposure is primarily through inhalation of arsenic-containing particulates, but ingestion and dermal exposure may be significant in particular situations. Refresh and try again. Open Preview See a Problem? Details if other :. Thanks for telling us about the problem. Return to Book Page. Today, with the advance of globalization, we see many foreign residents in Japan. We are now facing tasks - fostering medical interpreters, developing a system to accept foreign patients in medical institutions and etc.
We joined hands with Gunma University School of Medicine for medical interpretaion, and based on that know-how, we now Today, with the advance of globalization, we see many foreign residents in Japan. We joined hands with Gunma University School of Medicine for medical interpretaion, and based on that know-how, we now e-published "Multilingual Medical Questionnare"- a multilingual medical support system that can be used on smartphones and iPad.
This system is developed on the idea of helping patients who have language barriers for better communication. We will release selected categories of support system, such as "For Nurse" in the near future. We hope "Health Life Series" meets your expectations. Director Kiyomi Takizawa Roland Kiyola Piano in Oak Wood. Samsung The Serif 2. All Accessories. Breton Pride Shirt. NY Yankees Pride Hat. Walton Ford Parley for the Oceans Tote. Best Sellers.
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