Arsenic Medical and Biological Effects of Environmental Pollutants (1977) / Chapter Skim
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3 Distribution of Arsenic in the Environment
3 Distribution of Arsenic in the Environment
Pages 16-79
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From page 16... ...
In addition, many sulfides contain appreciable amounts of arsenic in solid solution; the most important of these is pyrite, which has a maximal arsenic content of about 5% (common range, 0.02-0.5%~. The arsenic-bearing sulfides and sulfosalts oxidize readily; under surface conditions, oxidation proceeds to arsenic trioxide and to the arsenate stage.
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From page 17... ...
Data on the concentration of arsenic in sedimentary rocks are summarized in Table 3-2. Shales, clays, phosphate rocks, and sedimen TABLE 3-2 Arsenic in Sedimentary Rocksa Arsenic Concentration, ppm No.
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From page 18... ...
The average is about 5-6 ppm, but it varies considerably among geographic regions. 159 Soils overlying sulfide ore desposits commonly contain arsenic at several hundred parts per million; the reported maximum is 8,000 ppm.
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From page 19... ...
The amount released for plant uptake is a function of the particular chemical and physical forms of individual arsenic compounds. The amount of available arsenic (extracted with 0.05 N hydrochloric acid and 0.025 N sulfuric acid)
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From page 20... ...
Extremely high arsenic concentrations have been reported in some groundwaters from areas of thermal activity,3~2448 from areas of rocks with high arsenic content,86 294~83 and in some waters of high dissolved-salt content.478 85~ Most of the other high values reported in rivers and lakes and in sediments (Tables 3-4 and 3-5) are probably due to industrial contamination.
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From page 21... ...
11,800-21,000 244 Washington 5.0-6.0 241 Oregon 0.00-1,700 294 United States, Puget Sound 1.5-1,200 186, 187 United States, rainwater: Rhode Island 0.82 659 Washington, Seattle 17 186 Argentina, Cordoba, drinking water 480-1,490 traces-300 315 42 Bosnia, Shebrenica, spring 4,607 385 Canada, well water 0.5-15 302 <2.3-7.500 883 Chile 800 86
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From page 22... ...
22 TABLE 3-4 (Continued) ARSENIC Arsenic Concentration, Water ,ug/liter (ppb)
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From page 23... ...
concentration in drinking water.8088~3 In view of recent reports of chronic arsenic poisoning attributed to the use of such waters in Chile86 and in Oregon,294 further study is imperative. The volcanic rocks from which the arsenic-rich waters come in Oregon are of a type that is common in the western United States.262
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From page 24... ...
Natural variations among plants, plant species, available soil arsenic, and growing conditions are all responsible in part for these discrepancies. There appears to be little chance that animals would be poisoned by consuming plants that contain arsenic residues from contaminated soils, because plant injury occurs before toxic concentrations could appear.
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From page 25... ...
These values are generally lower than those reported for marine fish, which range up to 32.4 ppm for cod. Shrimp contain arsenic at 3.8-128 ppm on a dry-weight basis.~72 A survey of canned seafood showed the following arsenic concentrations: clams, 15.9 ppm; oysters, 16.0 ppm; smoked oysters, 45.8 ppm; lobsters, 22.1 ppm; and shrimp, 19.9 ppm.203 Air Trace amounts of arsenic may be present in air.
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From page 26... ...
imports for consumption of white arsenic (arsenic trioxides, U.S. imports of arsenicals by class, and world production of white arsenic.812 In the United States, arsenic is produced entirely as a by-product of the smelting of nonferrous-metal ores.
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From page 27... ...
19e 514 Mexico 0.005 582 Russia: Rostov 0.8-6.0 74 3,000-5,000 m from copper smelter 58-160 687 300-4~000 m from power plant 3.8-24.8 - 687 Germany 1.0-297 706 aDust from copper smelter. Must remote from copper smelter.
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From page 29... ...
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From page 30... ...
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From page 31... ...
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From page 32... ...
U.S.S.R.(e) 7.8807,880 7,9407,990 United Statesww ww Total, excluding United States54,58854,987 46,33852,317 aDenved from Minerals Yearbook /973, ''white arsenic (arsenic trioxides)
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From page 33... ...
Arsenic trioxide is the raw material for arsenical pesticides, including lead
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From page 34... ...
Lead arsenate is a stomach poison, with very little contact activity when used on chewing insects. Calcium arsenate is more effective than lead arsenate in combating the cotton bollworm.45i Pesticides related to lead arsenate include lead arsenite, used to a limited extent as an insecticide and fungicide; lead m-arsenate; and monolead o-arsenate and trilead arsenate, used as insecticides.
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From page 35... ...
Cotton desiccant to of the 755tc concentrate facilitate mechanical harvesting Cacodylic acid 3-10 lb/acre (3.4-11.2 kg/ha) DSMA MSMA Calcium arsenate 48 (young rats)
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From page 36... ...
Herbicides The inorganic arsenicals, primarily sodium arsenite, have been widely used since about 1890 as weedkillers, particularly as nonselective soil sterilants.~78 Consequently, sodium arsenite found use around military and commercial installations along roadsides and on railroad rightsof-way. Its use for the control of crabgrass (Digitaria sanguinalis)
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From page 37... ...
of MSMA was consumed in the United states.829 Cacodylic acid is a contact herbicide that will defoliate or desiccate a wide variety of plant species. It has been used as a crop destruction agent (Agent Blue)
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From page 38... ...
Arsenic acid is applied once at a rate equivalent to 1.5 quarts (0.0014 me) of 75% o-arsenic acid per acre.
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From page 39... ...
Feed Additives Four organic arsenicals (arsanilic acid, 3-nitro-4-hydroxyphenylarsonic acid, 4-nitrophenylarsonic acid, and 4-ureidophenylarsonic acid, or carbarsone) , all substituted phenylarsonic acids, have qualified for feed-additive use under the Food Additive Law of 1958 (see Chapter 51.
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From page 40... ...
Drainage water after 20 years of such fertilization was reported to contain arsenic at 0.29 ppm. Drugs Inorganic arsenic compounds have been used in medicine since the dawn of history and have been claimed to be effective in many diseases or where a tonic was indicated.
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From page 41... ...
Arsenic compounds are still in use that are less toxic than lewisite but that are highly irritating to the skin, eyes, and respiratory tract, thereby causing dermal pain, lacrimation, sneezing, and vomiting. (The commonly used tear gas and mace apparently are not arsenicals, but alkylating agents related to chloroacetophenone.)
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From page 42... ...
is used in semiconductor technology. This material may be produced from the reduction of purified arsenic compounds, such as arsenic trioxide and arsenic bichloride, with hydrogen or the thermal dissociation of arsine.
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From page 43... ...
An excellent review of arsenic behavior in soil has recently been published.837 Arsenic in the environment can undergo oxidation, reduction, methylation, and demethylation in soil. Large residues have been found on orchard soils that received 30-60 lb of lead arsenate per acre (34-67 kg/ha)
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From page 44... ...
Because plants growing in high-arsenic soils have very little growth, human consumption of high arsenic residues through the plant food chain is unlikely. Plant growth is reduced as arsenic content increases.28 7~ For instance, a total arsenic content of about 300 pp ~ equivalent to extracted available arsenic at about 30 ppm in an average soil will reduce growth of many crops by about Who.
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From page 45... ...
, is generated in soil under both aerobic and anaerobic soil conditions from cacodylic acid.4~2 879 Trimethylarsine has also been isolated above grass.97 Residue accumulation in cotton soils should be slower than that in orchard soils, because less arsenic is applied with the organic arsenicals (1-2 ppm) than was applied with lead arsenate (3.3-6.6 ppm)
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From page 46... ...
The U.S. Geological Survey reported that 79~o of 727 samples examined from across the ARSENIC COMPOUNDS I N SOI L, LAND, WATER HAND THE SEA 1 VOLATILE ~ MlCROBlaL ARSINES DECOMPOSITION '^,~ 3 ALL ANIMAL LIFE (ORGANIC aRSENICALS)
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From page 47... ...
Questions have been raised over the arsenic added to the environment through phosphate detergents. Angino found that water treated with cold lime contained arsenic at 0.4 ppb.~8 Water at the intake contained 2.6-3.6 ppb before treatment.
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From page 48... ...
Results of Small and McCants appeared to refute this hypothesis.738 In an extensive survey of arsenic residues in soils and in cured leaves collected from major flue-cured tobacco-producing regions of North Carolina, soil arsenic concentrations ranged from 1 to 5 ppm (average, 2.8 ppm) , and leaf residues, from 0.5 to 3.5 ppm (average, 1.5 ppm)
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From page 49... ...
TABLE 3-14 Arsenic Content of Vegetables Grown in Soils Treated with Lead Arsenatea Arsenic, ppm, in Vegetables Grown in Soil Treated with Lead Arsenate at: Vegetable 250 lb/acre (280 kg/ha) 500 lb/acre (560 kg/ha)
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From page 50... ...
At these concentrations, edible dry plant contained arsenic at 0.7-76.0 ppm. There is evidence in the literature of beneficial effects on plant growth from relatively high arsenic concentrations in soils.
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From page 51... ...
Within the specified limits of growth stage, application rates, and application methods, arsenic residues in raw undelinted cottonseed vary from 0 to 0.2 ppm above controls. The analysis of a large number of cottonseed samples from control fields has shown background arsenic concentrations varying from the limit of detection of the method (about 0.05 ppm)
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From page 52... ...
As mentioned previously, arsenic acid is used as a desiccant in Texas and parts of Oklahoma. The FDA analyzed cottonseed products and various commodities from areas where arsenical defoliation was known to be practiced.96 The arsenic content of various commodities analyzed is shown in Table 3-15.
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From page 53... ...
The results were: chicken muscle, trace; rabbit muscle, 0.6 ppm; whole milk, trace; beef liver, 0.2 ppm; beef muscle, 0.05 ppm; beef kneebone, not detected; swine heart, trace; and sausage, trace. Arsenic concentrations may be increased in chickens and chicken products if they have received arsenic feed additives up to slaughter.
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From page 54... ...
Crustacea generally have the highest arsenic concentrations of the seafood species, and oil from fish contains more arsenic than the flesh. Bees have often been subject to injury wherever arsenic compounds are used, because only 4-S ,ug of arsenic is necessary to cause death.
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From page 55... ...
,ug Breakfast 766 0.06 0.23 46.0 Dinner 861 0.34 1.85 292.7 Supper 899 0.08 0.42 71.9 Total 2,526 410.6 Mean - 0.16 0.83 aDenved from Schroeder and Balassa.709 of Schroeder and Balassa709 appears to be high in relation to other estimates that are available on total arsenic consumption per day. The World Health Organization reported that average arsenic intakes for Canada, the United Kingdom, the United States, and France varied from 25 to 33 ,ug/day; specific values ranged from 7 to 60 ,ug/day.~ A survey of food made in Great Britain indicated that 100 ,ug of arsenic would be consumed daily from all sources.320 Analysis for arsenic resulted in the following values for foodstuffs: cereals, 0.18 ppm; fats, 0.05 ppm; fruits and preserves, 0.07 ppm; root vegetables, 0.08 ppm; milk, 0.05 ppm; meat, 0.10 ppm; and fish, 2.0 ppm.
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From page 56... ...
Arsenic trioxide is volatile, and nearly all of it is expelled from the ore as a sublimate during smelting. Crude flue dust is usually recycled to the furnace, with a consequent buildup of arsenic, sometimes to as much as Who.
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From page 57... ...
while the smelter was processing 9,070 tonnes of copper ore per day. Although no atmospheric concentrations were recorded, edible plants contained arsenic trioxide at up to 482 ,ug/g.
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From page 58... ...
Waste from Agricultural Uses of Pesticides and Herbicides · Cacodylic acid: Cacodylic acid is a contact herbicide used to defoliate or desiccate a wide variety of plant species and was used as a defoliant for crop destruction in South Vietnam. It is registered for use in lawn renovation or as a silvicide.
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From page 59... ...
· Arsenates (calcium, copper, lead, sodium, zinc, and manganeseJ: Only two of these compounds, calcium arsenate and lead arsenate, are used extensively as agricultural pesticides. The remaining arsenates are not prepared for agricultural or any other use in any significant quantity.
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From page 60... ...
There is no wholly satisfactory procedure for the recovery of contaminated soils, except removal and mixing with clean soil to dilute the arsenic. Because calcium arsenate and lead arsenate are almost always formulated as dusts, granules, or wettable powder and shipped in siftproof, multiwall paper bags, there is less residue in empty containers.
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From page 61... ...
If these animals are fed arsenic for therapeutic or growth-promoting purposes, all the arseniccontaining compounds fed may accumulate in waste lagoons. In a recent study, in arsenic concentrations were measured in lagoons under swine fed arsanilic acid at 0, 90, and 180 g/ton (0, 99.2, and 198.4 g/tonne)
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From page 62... ...
This dust and dust that remains in the stream and is collected on bag filters or electrostatic precipitators is mainly impure arsenic oxide, which is refined to commercial arsenic trioxide. ASARCO currently accepts crude arsenic-containing ores and intermediate smelter products on a broad scale.
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From page 63... ...
Current methods for storage are large siftproof and weatherproof silos at the site of ASARCO'S plant in Tacoma, Washington. It has been suggested that, with government subsidy, this system could become a national disposal site for all arsenic trioxide and related arsenic compounds.
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From page 64... ...
The commercial production process, according to Ottinger et al., has three steps: Arsenic trioxide reacts with sodium hydroxide to yield sodium arsenite, methanearsonic acid is produced by the addition of methylchloride, and the mixture is reduced with sulfur dioxide and methylated to produce cacodylic acid. There is no liquid waste from this process, because all liquid streams are cycled back into the system.
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From page 65... ...
· Copper acetoarsenite and sodium arsenite: As described by Ottinger et al., copper acetoarsenite is believed to be a mixture of cupric arsenite and the copper salt of acetic acid in a ratio of about 3: 1.6~° Paris green is manufactured by the reaction of sodium arsenite (made from the reaction of arsenic trioxide with sodium hydroxide) with copper carbonate and acetic acid by a batch process.
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From page 66... ...
The adequate management systems are: recycling and reuse; long-term storage; recovery of such metals as copper and lead and long-term storage of arsenic trioxide; and landfill in class 1 sites. In addition to the arsenic content of these pesticides, as is the case with the arsenates, the metal content should also be considered in the selection of an appropriate disposal system.
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From page 67... ...
Most manufacturers will accept unused packages of arsenicals, but the user is generally left to his own devices when disposing of TABLE 3-18 Method of Disposal of Principal Arsenic Compounds Manufactured in the United States Compound Arsenic Dioxide Cacodylic acid DSMA and MSMA Calcium arsenate Lead arsenate Copper acetoarsenite Sodium arsenite Current Disposal System 1. Entrapment of smelter flue dust and shipment to ASARCO for arsenic trioxide recovery 2.
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From page 68... ...
In many areas of the United States, a comprehensive program is needed whereby empty containers can be decontaminated or disposed of in a manner that will not create a hazard to the environment. THE ARSENIC CYCLE Frost proposed a closed organic arsenic cycle for the total environment in which some form of arsenic is present in all phases of the ecosystem (Figure 3-21.268 Very few of the organic arsenicals were identified, but a volatile arsine was suggested as present.
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From page 69... ...
Arsenicals do accumulate in soil, but redistribution mechanisms preclude hazardous accumulations at a given site.''701 This model does not include the application of arsenic trioxide to desiccate cotton before harvest. Inputs into the environment and a redistribution of arsenic in the terrestrial ecosystem are presented in Figure ~-4.
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From page 70... ...
.e c < \ 1 if..
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From page 71... ...
reported that input amounts to 200,000 kg of arsenic trioxide per year into the air via stack dust, 20,000-70,000 kg of arsenic per year into Puget Sound through dissolved arsenicals in its liquid effluent discharge, and 1,500,000 kg of arsenic per year in crystalline slag dumped into the Sound. The installation of more pollutioncontrol equipment at this smelter is planned, so the amount of arsenic released into the air and water will decrease significantly.
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From page 72... ...
Arsenic concentrations would be equivalent to 160 ppm in arsenical ore containing 0.8% copper and 12 ppm in nonarsenical ore containing 0.6% copper. The arsenic concentrations of rocks in the earth's crust are shown in Tables 3-1 and 3-2 as: granite, 1.5 ppm; other igneous, 2.0-3.0 ppm; limestone, 1.7 ppm; sandstone, 2.0 ppm; and shales and clays, 14.5 ppm We may assume rock distribution in nonferrous-metal deposits as: granite, 25%; other igneous, 25%; limestone, 25%; sandstone, 15%; and shale, logo.
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From page 73... ...
Information obtained in February 1974 showed that arsenic emission at smelters processing arsenical copper ores was much reduced from the 1968 emission and that the average arsenic emission from copper smelting was 2.1 lb/ton (1.05 kg/tonne) of metal.
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From page 74... ...
of · s: cn so of a' ~ No ~m ~ .
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From page 75... ...
In the blast furnace, the arsenic compounds are reduced to elemental arsenic, which combines with iron to form iron arsenide and dissolves in the metal; very little of the contained arsenic reaches the atmosphere. Table 3-20 shows an industrial balance for arsenic emission into the environment based on the estimated emission factors, the rate of consumption of mineral fuels, and the rate of production of nonferrous metals, including arsenic.
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From page 76... ...
It is the airborne arsenic trioxide residues that have been implicated in the arsenic-cancer question. This topic is discussed in Chapter 6.
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From page 77... ...
~75 499 Braman detected dimethylarsine and trimethylarsine or their oxidation products above grass that had been treated with sodium arsenite, methanearsonic acid, cacodylic acid, and phenylarsonic acid. 97 Volatile arsenicals were detected from soils treated with sodium arsenate, MSMA, and cacodylic acid.
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From page 79... ...
Man has modified the arsenic cycle only by causing localized high concentrations.
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