This action might not be possible to undo. Are you sure you want to continue?
Chemistry 371 Fall 2010 Erlend Sormo
As, 33, 72.9216 amu Oxidation states -3, 0, +3, +5 Metalloid
Historical uses of As ● As2O3: – – Popular poison Colourless. . 2006. The Elements of Murder: A History of Poison. J. odourless and easily incorporated into food and drink Symptoms similar to those of Cholera “Inheritance powder” Not possible to detect until the Marsh test in 1836 – – – 1) Emsley. "Arsenic". Oxford University Press.
http://www. International Program on Chemical Safety: Arsenic and Arsenic Compounds.Historical uses of As ● Agriculture: – Pesticides. herbicides.2 . insecticides ● i.inchem. Cacodylic acid.org/documents/ehc/ehc/ehc224.htm#3. (CH3)2AsOOH ● Industry: – Timber treatment with Chromated Copper Arsenate (CCA) ● Pharmaceuticals: – “Fowler's solution” (1% KH2AsO3) to treat malaria.e. cholera and syphilis (predating antibiotics) As2O3 has also been used to treat leukaemia – 1) Chemical Safety Information from Intergovernmental Organizations.
inchem. Realgar (AsS). Orpiment (As2S3) As is found in trace amounts in all living organisms – Fossil fuels ● – Marine sediments ● Marine organisms have higher As concentrations than terrestrial organisms ● Present in water in trace concentrations – – Seawater ~ 3 μg/L Fresh water – dependent surrounding geology 1)Chemical Safety Information from Intergovernmental Organizations. S. J. Arsenic in Groundwater in the Surrey-Langley Area. and the Ministry of Environment Lower Mainland Region Surrey.Natural occurrence of As ● Present in the earth's crust in an average of 2 ppm. B.2 2) Wilson. 2008.org/documents/ehc/ehc/ehc224. as a component in over 200 different minerals – Volcanic rocks ● Basalt and Volcanic Ash – Ores ● Arsenopyrite (FeAsS).C. Brown. . H.. International Program on Chemical Safety: Arsenic and Arsenic Compounds.htm#3.C. Schreier.. A technical report for Fraser Health Authority and Environmental Health Services B. http://www.
htm#3.2 . http://www.inchem.Sources of As in water ● Natural sources: ● Weathering and erosion of As containing minerals and soils – Geothermal dissolution ● High temperature geothermal waters increase solubility of As minerals – Geochemical reduction-oxidation processes ● Oxyhydroxide reduction – Organic matter as electron donors. mediated by certain bacteria Pyrite ores exposed to oxygen ● Pyrite oxidation – ● Volcanic eruptions – As containing aerosols can mix with water ● ● By dry deposition By getting washed out of the air by rainfall 1)Chemical Safety Information from Intergovernmental Organizations.org/documents/ehc/ehc/ehc224. International Program on Chemical Safety: Arsenic and Arsenic Compounds.
K. Arsenic: Environmental chemistry. health threats and waste treatment. R. Whiley: UK.Sources of As in water Figure 1: Solubility constants for various As-salts1 1) Henke. 2009 .
. S. . C.Mulligan. N. 366. of the Total Environ. Behaviour and Distribution. but leakage is frequent 1) Wang. 2006. herbicides or CCA ● Agriculture: – Runoff from decaying plants and soils sprayed with pesticides. herbicides or insecticides ● Combustion of As containing species: – Fossil fuels or wood treated with CCA ● Waste from mining operations or metal smelting plants: – – Smelting of metal ores (i. FeAsS) produces left over sludge Sludge is deposited. 701– 721.e. Sci.e.Sources of As in water ● Anthropogenic sources: ● Industrial emissions and waste: – From producing i. Occurrence of Arsenic Contamination in Canada: Sources.
Cambodia.who. Elements 2006. India and Nepal – Exposes between 40-50 million humans to unsafe levels of As on a daily basis ● Wells in the Surrey-Langley area have also shown unsafe levels of As. C. 2) http://www.int/en/ . Myanmar. Bangladesh. 103. Arsenic In Drinking Water: Impact On Human Health. 1) Hopenhayn. localized problem while aquifers affected by sediments is found worldwide and often over large areas Biggest problem as of today is shallow tube wells in areas with high concentrations of As in the soil ● ● WHO estimates that there are 10 million such tube wells in Thailand. 2 (2).Scope of the As problem ● As is found in both surface and groundwater ● Usually higher concentrations in aquifers – release from sediments Runoff and leaking usually responsible for contaminating surface waters ● ● Runoff is often a incidental.
harvard.physics.html .edu/~wilson/arsenic/countries/arsenic_project_countries.As-related problems Figure 2: Arsenic related problems worldwide1 1) http://www.
(2005). 807. Arsenic in shallow Cambodian groundwater Mineralogical mag. concentrated around the capital Phnom Pehn1 1) Polya et al.Wells in Cambodia Figure 3: Arsenic containing wells in Cambodia. . 69(5).
Fraser Health and the Ministry of Environment B. 2008.C. Canada1 1) Wilson et. . al. Arsenic in Groundwater in the Surrey-Langley Area.Wells in Surrey-Langley Figure 4: Arsenic containing wells in the Surrey-Langley area. BC.
Elements 2006.Scope of the problem ● Arsenic is one of the most serious environmental contaminants in the world: ● High toxicity – – Lethal dose for adults is 120 to 200 mg (As2O3) Chronic low level poisoning results in a wide spectre of diseases And new areas are being discovered In many countries drinking water is not routinely tested for As ● Vast amounts of people affected – – 1) Hopenhayn. Medscape's Continually Updated Clinical Reference. Arsenic In Drinking Water: Impact On Human Health. C. 103. http://emedicine.medscape. 2) Emedicine.com/article/1174215-overview . 2 (2).
C. 103. X. Arsenic Speciation. Elements 2006.. Li.. X. Lu. Analytical Chem. 2004. X. 26A-33A. C. 2 (2).Health effects ● Inorganic forms of As are the most toxic and the prevalent species in drinking water WHO has set the safe limit for As in drinking water to 10 mg/L ● ● Canada lowered the limit from 50 mg/L to 10 mg/L in 2006 ● The mechanisms of the toxicity of As species have not yet been fully understood Health effects have not been completely mapped out ● ● Evidence mainly comes from epidemiological work Animal studies have not provided good models ● ● Inorganic As is quickly absorbed in the gastrointestinal tract and goes through a series of metabolic steps before excretion ● About 80-70% of ingested inorganic As species are excreted as dimethylarsinic acid (DMA) which is used as a tracer ~70% is excreted through urine ● 1) Hopenhayn. Arsenic In Drinking Water: Impact On Human Health. 76 (1). . 2) Le. F.
C. bladder. Hypertension. 2 (2). infant mortality.Health effects ● Ingestion of As species through drinking water is known to cause: ● Cancer of skin. Elements 2006. Arsenic In Drinking Water: Impact On Human Health. Cerebrovascular disease (CVD). lungs and kidneys ● As ingestion has also been associated with elevated risks of: ● Vascular diseases – Vascular disease (PVD). low birth weight and prematurity 1) Hopenhayn. Coronary heart disease (CHD) ● Diabetes Neurological disorders Reproductive problems – ● ● Stillbirths. 103 .
2 (2). 103 . C.Health effects Figure 5: “Blackfoot disease”1 Figure 6: External signs of As poisoning . Elements 2006. Arsenic In Drinking Water: Impact On Human Health.skin cancer1 Figure 8: Patient from India with tumor due to As exposure1 1) Hopenhayn.skin keratoses and skin cancer1 Figure 7: External signs of As poisoning .
Hoinkis. .. T. S. M. A. Nanofiltration Membrane Process...As speciation in water ● Elemental As is not soluble in water A wide range of As salts are soluble in water depending on pH. Eng. Deowan. pE and ionic environment Main forms of As in water are As(III) and As(V) ● ● ● These ions react with water to produce: – Arsenous acid H3AsO3 [ As(III) ] ● Anoxic conditions Oxic conditions – Arsenic acid H3AsO4 [ As(V) ] ● 1) Uddin. Chem.. . Mozumder. S. I. M. J. 1248–1254. Islam. 30(). A. Technol. M.
com .appliedspeciation.As speciation in water Figure 9: Phase diagram of As species in water1 1) www.
.5 Works well for high conc. W.Removal techniques ● Precipitation by Calcium oxides: ● ● Precipitation by metal salts used since 1934 CaO or Ca(OH)2 added = various precipitates – – i. 32. R. Heijnen. 287-290. http://unu. iron and manganese ● ● ● Precipitates collected by filtration Operated at pH > 10..pdf . sulphate. Environment and Sustainable Development Program (ESD) 2008. Safe water technology for Arsenic removal. fluoride. Health 2010. H. Mechanisms Of Arsenic Removal From Water.e. Geochem. Ca(AsO4)2 – very low solubility Will also remove other ions like phosphates. 2) Johnston.edu/env/Arsenic/Han. As > 50 mg/L – Hard to get final yield below 1 mg/L ● Precipitates are not physically stable – Leaching frequent from deposits 1) Höll. Environ. H.
32.onto surface of highly basic quaternary amines R-[N(CH3)3]+Cl. 287-290. Geochem. Environ. . R-[N(CH3)3]+H2AsO4. Mechanisms Of Arsenic Removal From Water.+ Cl(R=matrix) ● ● Should be operated at pH close to neutral to avoid competition by OHShows good yields for removing As species Strong interference from sulphates and possibly nitrates – Efficient elimination for sulphate conc.+ H2AsO4. H. Health 2010. W. < 50 mg/L ● ● ● Regeneration by addition of NaCl Widely used technique for removal of many ionic contaminants – ● Functional groups can be changed to acidic to select for cations 1) Höll.Removal techniques ● Synthetic ion exchange resins: ● Resins are made of cross-linked polymer skeletons (polystyrene and divinylbenzene) with charged functional groups at the surface Arsenite and arsenate exchanged with Cl.
H. Geochem. Mechanisms Of Arsenic Removal From Water. titanium oxide and cerium oxide are commonly used – ● Granular Ferric Oxide (GFO) common in water treatment plants and household devices ● Metal oxides have slow sorption due to low surface area – Combination of nanomaterials and ferric oxides proved very efficient 1) Höll. Me-OH2-H2AsO4 ● The metal oxides is then filtered out and deposited Ferric oxides. Health 2010. 287-290.Removal techniques ● Sorption with hydrous metal oxides: ● Hydrolysed metal oxide surfaces contain hydroxyl groups At pH < pzc the hydroxyl groups are protonated Me-OH + H+ Me-OH2+ ● ● As anions can then be adsorbed onto the surface Me-OH2+ + H2AsO4. . W. 32. Environ.
KMnO4 Technique still at developmental stage. S. T. . I.Removal techniques ● Nanofiltration membrane process: ● Water is filtrated through a charged nanomaterial membrane under high pressure Size/charge exclusion – ● Nanoscale membrane pores filtrate As species by size ● Hydrous As ions are to small to be excluded by micro or ultra filtration – A highly negatively charged membrane excludes As species by charge ● Ions of same charge as membrane (co-ions) are inhibited most successfully ● Has shown excellent yields for As(V) Unacceptable yields for As(III) – ● At pH = 5-7 predominant specie is neutral H3AO3 ● Effect of charge exclusion lost – ● Can be solved by oxidizing As(III) to As(V) before filtration by i. Nanofiltration Membrane Process. M. 1248–1254. Technol.e. Mozumder.. but shows great promise 1) Uddin. . A. J. Deowan. 30(9). Chem. A... Eng. Hoinkis. Islam. M.. M. S.
R.edu/env/Arsenic/Han. Heijnen.pdf . H. http://unu.. Safe water technology for Arsenic removal. Environment and Sustainable Development Program (ESD) 2008.Removal techniques Figure 10: Arsenic removal plant1 1) Johnston.
Future outlook ● Surge of As related diseases will come – long term effects ● Mechanism of toxicity has to be figured out ● Problem bigger for underdeveloped countries ● ● Less frequent testing of drinking water Lack of technology for both testing and removal ● Cheap and efficient removal techniques has to be made available .