Arsenic in drinking water

Chemistry 371
Fall 2010
Erlend Sormo
 Arsenic
● As, 33, 72.9216 amu
● Oxidation states -3, 0,
+3, +5
● Metalloid
 Historical uses of As
● As2O3:
– Popular poison
– Colourless, 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, J. "Arsenic". The Elements of Murder: A History of Poison. Oxford University Press, 2006.
 Historical uses of As
● Agriculture:
– Pesticides, herbicides, insecticides
● i.e. Cacodylic acid, (CH3)2AsOOH
● Industry:
– Timber treatment with Chromated Copper Arsenate (CCA)
● Pharmaceuticals:
– “Fowler's solution” (1% KH2AsO3) to treat malaria, cholera and
syphilis (predating antibiotics)
– As2O3 has also been used to treat leukaemia

1) Chemical Safety Information from Intergovernmental Organizations. International Program on Chemical Safety: Arsenic and Arsenic Compounds.
http://www.inchem.org/documents/ehc/ehc/ehc224.htm#3.2
 Natural occurrence of As
● Present in the earth's crust in an average of 2 ppm, as a component in over
200 different minerals
– Volcanic rocks
● Basalt and Volcanic Ash
– Ores
● Arsenopyrite (FeAsS), Realgar (AsS), Orpiment (As2S3)
– Fossil fuels
● As is found in trace amounts in all living organisms
– 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. International Program on Chemical Safety: Arsenic and Arsenic Compounds.
http://www.inchem.org/documents/ehc/ehc/ehc224.htm#3.2

2) Wilson, J.; Schreier, H.; Brown, S. Arsenic in Groundwater in the Surrey-Langley Area; A technical report for Fraser Health Authority and Environmental
Health Services B.C. and the Ministry of Environment Lower Mainland Region Surrey, B.C. 2008.
 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 oxidation
– Pyrite ores exposed to oxygen
● 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. International Program on Chemical Safety: Arsenic and Arsenic Compounds.
http://www.inchem.org/documents/ehc/ehc/ehc224.htm#3.2
 Sources of As in water

Figure 1: Solubility constants for various As-salts1

1) Henke, K. R. Arsenic: Environmental chemistry, health threats and waste treatment; Whiley: UK, 2009
 Sources of As in water
● Anthropogenic sources:
● Industrial emissions and waste:
– From producing i.e. 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.e. FeAsS) produces left over sludge
– Sludge is deposited, but leakage is frequent

1) Wang, S.;Mulligan, C. N. Occurrence of Arsenic Contamination in Canada: Sources, Behaviour and Distribution. Sci. of the Total Environ. 2006, 366,
701– 721.
 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, 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, Cambodia,
Bangladesh, Myanmar, 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.

1) Hopenhayn, C. Arsenic In Drinking Water: Impact On Human Health. Elements 2006, 2 (2), 103.

2) http://www.who.int/en/
 As-related problems

Figure 2: Arsenic related problems worldwide1

1) http://www.physics.harvard.edu/~wilson/arsenic/countries/arsenic_project_countries.html
 Wells in Cambodia

Figure 3: Arsenic containing wells in Cambodia, concentrated around the capital Phnom Pehn1

1) Polya et al. Arsenic in shallow Cambodian groundwater Mineralogical mag. (2005), 69(5), 807.
 Wells in Surrey-Langley

Figure 4: Arsenic containing wells in the Surrey-Langley area, BC, Canada1

1) Wilson et. al. Arsenic in Groundwater in the Surrey-Langley Area. Fraser Health and the Ministry of Environment B.C. 2008.
 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
● Vast amounts of people affected
– And new areas are being discovered
– In many countries drinking water is not routinely tested for As

1) Hopenhayn, C. Arsenic In Drinking Water: Impact On Human Health. Elements 2006, 2 (2), 103.

2) Emedicine. Medscape's Continually Updated Clinical Reference. http://emedicine.medscape.com/article/1174215-overview

 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, C. Arsenic In Drinking Water: Impact On Human Health. Elements 2006, 2 (2), 103.

2) Le, X. C.; Lu, X.; Li, X. F. Arsenic Speciation, Analytical Chem. 2004, 76 (1), 26A-33A.
 Health effects
● Ingestion of As species through drinking water is known to cause:
● Cancer of skin, bladder, lungs and kidneys

● As ingestion has also been associated with elevated risks of:

● Vascular diseases
– Vascular disease (PVD), Hypertension, Cerebrovascular disease (CVD),
Coronary heart disease (CHD)
● Diabetes
● Neurological disorders
● Reproductive problems
– Stillbirths, infant mortality, low birth weight and prematurity

1) Hopenhayn, C. Arsenic In Drinking Water: Impact On Human Health. Elements 2006, 2 (2), 103
 Health effects

Figure 5: “Blackfoot disease”1 Figure 6: External signs of As poisoning - skin keratoses and
skin cancer1

Figure 7: External signs of As poisoning - skin cancer1

Figure 8: Patient from India with tumor due to As exposure1

1) Hopenhayn, C. Arsenic In Drinking Water: Impact On Human Health. Elements 2006, 2 (2), 103
 As speciation in water
● Elemental As is not soluble in water
● A wide range of As salts are soluble in water depending on pH,
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
– Arsenic acid H3AsO4 [ As(V) ]
● Oxic conditions

1) Uddin, M. T.; Mozumder, M. S. I.; Islam, M. A.; Deowan, S. A.; Hoinkis, J. Nanofiltration Membrane Process. Chem. Eng. Technol. , 30(), 1248–1254.
 As speciation in water

Figure 9: Phase diagram of As species in water1

1) www.appliedspeciation.com
 Removal techniques
● Precipitation by Calcium oxides:
● Precipitation by metal salts used since 1934
● CaO or Ca(OH)2 added = various precipitates
– i.e. Ca(AsO4)2 – very low solubility
– Will also remove other ions like phosphates, sulphate, fluoride, iron and
manganese
● Precipitates collected by filtration
● Operated at pH > 10.5
● Works well for high conc., As > 50 mg/L
– Hard to get final yield below 1 mg/L
● Precipitates are not physically stable
– Leaching frequent from deposits

1) Höll, W. H. Mechanisms Of Arsenic Removal From Water. Environ. Geochem. Health 2010, 32, 287-290.
2) Johnston, R.; Heijnen, H. Safe water technology for Arsenic removal. Environment and Sustainable Development Program (ESD) 2008.
http://unu.edu/env/Arsenic/Han.pdf
 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- onto surface of highly basic quaternary
amines
R-[N(CH3)3]+Cl- + H2AsO4-  R-[N(CH3)3]+H2AsO4- + Cl- (R=matrix)

● Should be operated at pH close to neutral to avoid competition by OH-

● Shows good yields for removing As species
● Strong interference from sulphates and possibly nitrates

– Efficient elimination for sulphate conc. < 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, W. H. Mechanisms Of Arsenic Removal From Water. Environ. Geochem. Health 2010, 32, 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-  Me-OH2-H2AsO4

● The metal oxides is then filtered out and deposited

● Ferric oxides, 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, W. H. Mechanisms Of Arsenic Removal From Water. Environ. Geochem. Health 2010, 32, 287-290.
 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.e. KMnO4

● Technique still at developmental stage, but shows great promise

1) Uddin, M. T.; Mozumder, M. S. I.; Islam, M. A.; Deowan, S. A.; Hoinkis, J. Nanofiltration Membrane Process. Chem. Eng. Technol. , 30(9),
1248–1254.
 Removal techniques

Figure 10: Arsenic removal plant1

1) Johnston, R.; Heijnen, H. Safe water technology for Arsenic removal. Environment and Sustainable Development Program (ESD) 2008.
http://unu.edu/env/Arsenic/Han.pdf
 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