1. The Silent Pandemic Caused by Drinking Metals in Deep Well Water Erika Mitchell, Ph.D. Bibudhendra Sarkar, Ph.D. Seth Frisbie, Ph.D. Donald Maynard, P.E.

2. A History of Drinking Water Since the beginning of human history until very recently, we have used only surface or dug well water for drinking.Since the beginning of human history until very recently, we have used only surface or dug well water for drinking. In 1862 the tubewell was invented by Col. Nelson W. Green and deep well water became easily accessible for drinking.In 1862 the tubewell was invented by Col. Nelson W. Green and deep well water became easily accessible for drinking. Today billions of people use deep well water for drinking.Today billions of people use deep well water for drinking. (Photograph by Peer Water Exchange, 2006) (Col. Nelson W. Green)

3. Surface and dug well water often has microorganisms that can make a person sick hours or days after drinking.Surface and dug well water often has microorganisms that can make a person sick hours or days after drinking. High dissolved oxygen (O 2 ) and the removal of ions by leaching gives surface and dug well water low concentrations of arsenic (As), manganese (Mn), and other metals.High dissolved oxygen (O 2 ) and the removal of ions by leaching gives surface and dug well water low concentrations of arsenic (As), manganese (Mn), and other metals. (Photograph of Vibrio cholera by Jozef Rosinský) A History of Drinking Water

4. In contrast, deep well water rarely has pathogenic microorganisms.In contrast, deep well water rarely has pathogenic microorganisms. Low dissolved O 2 and the accumulation of ions from leaching gives deep well water high concentrations of As, Mn, and other metals that can make a person sick after years or decades of regular drinking.Low dissolved O 2 and the accumulation of ions from leaching gives deep well water high concentrations of As, Mn, and other metals that can make a person sick after years or decades of regular drinking. (Images by Element Collection, Inc.) The diagnosis of chronic metal poisoning is made difficult by the 5 to 20 or more years of exposure needed to produce symptoms.The diagnosis of chronic metal poisoning is made difficult by the 5 to 20 or more years of exposure needed to produce symptoms. A History of Drinking Water

5. A History of Drinking Water in Argentina In the 1880s tubewells were first used in Northern Argentina.In the 1880s tubewells were first used in Northern Argentina. In 1916 Dr. Abel Ayerza found that both people and chickens had symptoms similar to pharmaceutical As poisoning.In 1916 Dr. Abel Ayerza found that both people and chickens had symptoms similar to pharmaceutical As poisoning. Later, Ayerza checked things in common and found As and vanadium (V) in the drinking water.Later, Ayerza checked things in common and found As and vanadium (V) in the drinking water. (Photographs by Ayerza, 1918)

6. Many premature deaths were caused by drinking surface water.Many premature deaths were caused by drinking surface water. The life expectancy during the mid-1960s was only 46 years.The life expectancy during the mid-1960s was only 46 years. A History of Drinking Water in Bangladesh Rivers, ponds, and dug wells were the only practical source of drinking water from at least 900 BC until the 1970s.Rivers, ponds, and dug wells were the only practical source of drinking water from at least 900 BC until the 1970s. A massive cholera outbreak began in 1963.A massive cholera outbreak began in 1963. (Photograph by Dhaka Hospital)

7. Approximately 10,000,000 tubewells have been installed since 1971 to supply safe drinking water.Approximately 10,000,000 tubewells have been installed since 1971 to supply safe drinking water. Within 1 generation the population changed from drinking surface water to drinking groundwater.Within 1 generation the population changed from drinking surface water to drinking groundwater. By 2000, approximately 97% of Bangladeshis drank tubewell water.By 2000, approximately 97% of Bangladeshis drank tubewell water. (Photograph by Steven Brace, 1995) A History of Drinking Water in Bangladesh

8. The symptoms of chronic As poisoning from drinking water usually take 5 to 20 years to manifest.The symptoms of chronic As poisoning from drinking water usually take 5 to 20 years to manifest. Chronic As poisoning from drinking tubewell water was first diagnosed in 1993.Chronic As poisoning from drinking tubewell water was first diagnosed in 1993. Melanosis of the chest Keratosis of the palms (Photograph by Dhaka Community Hospital and Richard Wilson, 2002) Keratosis of the feet Blackfoot disease A History of Drinking Water in Bangladesh

9. The first national-scale map of As concentration in Bangladeshs tubewell water was made in 1997.The first national-scale map of As concentration in Bangladeshs tubewell water was made in 1997. Approximately 75,000,000 Bangladeshis are at risk of death from skin, bladder, liver, and lung cancers caused by chronic As poisoning.Approximately 75,000,000 Bangladeshis are at risk of death from skin, bladder, liver, and lung cancers caused by chronic As poisoning. The source of As is geological.The source of As is geological. Map of As concentration (mg/L). A History of Drinking Water in Bangladesh

10. The Discovery of Other Toxic Elements in Bangladeshs Drinking Water AnalyteIndependent Standard Recovery (Analyte Added to Distilled Water) Sample Matrix Spike Recovery (Analyte Added to Drinking Water) Arsenic (As) 83% 89 11% Ferrous iron (Fe 2+ ) 93 10% 34 23% Total iron (Fe) 95% Not measured, at least 27% of samples developed the wrong color. At least 27% of the drinking water wells in Bangladesh apparently contain an analytical interference to the 1,10- phenanthroline methods for measuring ferrous iron and total iron.At least 27% of the drinking water wells in Bangladesh apparently contain an analytical interference to the 1,10- phenanthroline methods for measuring ferrous iron and total iron.

11. The Discovery of Other Toxic Elements in Bangladeshs Drinking Water In addition, the early onset of chronic As poisoning suggested that multimetal health effects are possible.In addition, the early onset of chronic As poisoning suggested that multimetal health effects are possible. The problems measuring iron and the early onset of chronic As poisoning were the first evidence that other toxic elements are widely distributed in Bangladeshs drinking water.The problems measuring iron and the early onset of chronic As poisoning were the first evidence that other toxic elements are widely distributed in Bangladeshs drinking water. (Photograph by NGO Forum, 2002)

12. 60% of Bangladeshs area contains groundwater with Mn concentrations greater than the WHO drinking water guideline.60% of Bangladeshs area contains groundwater with Mn concentrations greater than the WHO drinking water guideline. Manganese in drinking water is a potent neurotoxin, associated with violent behaviors and depression. It causes learning disabilities in children and Parkinson's-like symptoms in adults.Manganese in drinking water is a potent neurotoxin, associated with violent behaviors and depression. It causes learning disabilities in children and Parkinson's-like symptoms in adults. It causes liver and kidney damage, and is associated with hearing loss.It causes liver and kidney damage, and is associated with hearing loss. Map of Mn concentration (mg/L).

13. 3% of Bangladeshs area contains groundwater with Pb concentrations greater than the WHO drinking water guideline.3% of Bangladeshs area contains groundwater with Pb concentrations greater than the WHO drinking water guideline. Lead is a potent neurotoxin, associated with IQ deficits and learning disabilities in children and dementia in adults.Lead is a potent neurotoxin, associated with IQ deficits and learning disabilities in children and dementia in adults. It is also associated with kidney, liver, and heart disease, tooth loss, cataracts, hypertension, diabetes, and bladder cancer.It is also associated with kidney, liver, and heart disease, tooth loss, cataracts, hypertension, diabetes, and bladder cancer. Map of lead (Pb) concentration (mg/L).

14. < 1% of Bangladeshs area contains groundwater with Ni concentrations greater than the WHO drinking water guideline.< 1% of Bangladeshs area contains groundwater with Ni concentrations greater than the WHO drinking water guideline. Nickel is a potent carcinogen.Nickel is a potent carcinogen. It is also associated with lung, heart, and kidney disease and can induce spontaneous abortions.It is also associated with lung, heart, and kidney disease and can induce spontaneous abortions. Map of nickel (Ni) concentration (mg/L).

15. < 1% of Bangladeshs area contains groundwater with Cr concentrations greater than the WHO drinking water guideline.< 1% of Bangladeshs area contains groundwater with Cr concentrations greater than the WHO drinking water guideline. Cr(III) is the form most often found in drinking water. Chronic exposure inhibits DNA synthesis and the fidelity of DNA replication.Cr(III) is the form most often found in drinking water. Chronic exposure inhibits DNA synthesis and the fidelity of DNA replication. Cr(III) accumulates in the liver; persons with existing liver disease may be exceptionally susceptible to its toxic effects.Cr(III) accumulates in the liver; persons with existing liver disease may be exceptionally susceptible to its toxic effects. Map of total chromium (Cr) concentration (mg/L).

16. a Assuming Bangladesh has 158,570,535 people (July 2011 est.) and 97% of its population drinks well water. Estimated number of Bangladeshis drinking water with metal concentrations above WHO guidelines. Metal Carcinogenic Potential WHO Guideline (µg/L) Percent of Bangladeshs Area Exceeding WHO Guideline Number of Bangladeshis Drinking Unsafe Water a AsMnPbNiCr Known carcinogen Noncarcinogen Possible carcinogen Probable carcinogen Noncarcinogen1040010205049603 < 1 75,000,00092,000,0004,600,000 < 1,500,000 Tens of millions of Bangladeshis are drinking water that exceeds WHO health-based guidelines for As, Mn, Pb, Ni, and Cr.Tens of millions of Bangladeshis are drinking water that exceeds WHO health-based guidelines for As, Mn, Pb, Ni, and Cr. Chronic As poisoning is the most significant health risk.Chronic As poisoning is the most significant health risk. Multimetal health effects are possible.Multimetal health effects are possible.

17. Climate Change and Multimetal Exposure in Bangladesh Most of Bangladesh is less than 12 meters above sea level.Most of Bangladesh is less than 12 meters above sea level. In a normal monsoon season one-third of the cultivated land is flooded with a mixture of fresh and saltwater.In a normal monsoon season one-third of the cultivated land is flooded with a mixture of fresh and saltwater. (Photograph by Louise Gray, 2009) Flooding will likely increase the concentrations of As, Mn, and other metals by creating a reducing environment and by ion exchange.Flooding will likely increase the concentrations of As, Mn, and other metals by creating a reducing environment and by ion exchange.

18. Graph of As concentration (mg/L) versus oxidation-reduction potential (mV). Climate Change and Multimetal Exposure in Bangladesh This graph suggests that As is released from solids to Bangladeshs groundwater by reduction.This graph suggests that As is released from solids to Bangladeshs groundwater by reduction. If so, it is likely that flooding would also release a wide variety of other ions into groundwater by creating a reducing environment.If so, it is likely that flooding would also release a wide variety of other ions into groundwater by creating a reducing environment.

19. Map of As concentration (mg/L). Map of Cl - concentration (mg/L). These maps suggest this saltwater intrusion might release arsenite (H 3-x As(III)O 3 x- ) or arsenate (H 3-x As(V)O 4 x- ) from solids to Bangladeshs groundwater by anion exchange with chloride (Cl - ).These maps suggest this saltwater intrusion might release arsenite (H 3-x As(III)O 3 x- ) or arsenate (H 3-x As(V)O 4 x- ) from solids to Bangladeshs groundwater by anion exchange with chloride (Cl - ). If so, it is likely that saltwater intrusion would also release a wide variety of other ions into groundwater by both anion and cation exchange.If so, it is likely that saltwater intrusion would also release a wide variety of other ions into groundwater by both anion and cation exchange.

20. Satellite image of Bongaon, West Bengal, India. A Discovery of Multimetal Exposure in India

21. Map of As, Mn, and boron (B) concentrations (µg/L). As, Mn and B were found above WHO health-based drinking water guidelines in 50%, 19% and 6% of tubewells, respectively.As, Mn and B were found above WHO health-based drinking water guidelines in 50%, 19% and 6% of tubewells, respectively. The unsafe concentrations are shown in yellow.The unsafe concentrations are shown in yellow. A Discovery of Multimetal Exposure in India

22. Pb in nature is a mixture of 4 stable isotopes: 204 Pb (1.48%), 206 Pb (23.6%), 207 Pb (22.6%), and 208 Pb (52.3%).Pb in nature is a mixture of 4 stable isotopes: 204 Pb (1.48%), 206 Pb (23.6%), 207 Pb (22.6%), and 208 Pb (52.3%). Of these 4 isotopes, only 204 Pb is not a radiogenic nuclide.Of these 4 isotopes, only 204 Pb is not a radiogenic nuclide. The Uranium Series starts with 238 U and ends with 206 Pb.The Uranium Series starts with 238 U and ends with 206 Pb. The Actinium Series starts with 235 U and ends with 207 Pb.The Actinium Series starts with 235 U and ends with 207 Pb. The Thorium Series starts with 232 Th and ends with 208 Pb.The Thorium Series starts with 232 Th and ends with 208 Pb. Therefore, more than 98% of Pb is from the radioactive decay of 238 U, 235 U, and 232 Th.Therefore, more than 98% of Pb is from the radioactive decay of 238 U, 235 U, and 232 Th. Pb, U, and Th are in this villages drinking water.Pb, U, and Th are in this villages drinking water. There are WHO drinking water guidelines for Pb and U.There are WHO drinking water guidelines for Pb and U. There is no WHO drinking water guideline for Th.There is no WHO drinking water guideline for Th. A Discovery of Multimetal Exposure in India

23. Known regions of natural multimetal contamination in deep well water. Billions of people use deep well water for drinking.Billions of people use deep well water for drinking. However, very few systematic surveys of multiple metals in deep well water have been done at a national or regional- scale.However, very few systematic surveys of multiple metals in deep well water have been done at a national or regional- scale. More of these surveys are needed.More of these surveys are needed. A First Challenge for Drinking Water Chemists

24. No.Ele.ppmNo.Ele.ppmNo.Ele.ppmNo.Ele.ppm 12345678910111213141516171819OSiAlFeCaMgNaKTiHPMnFBaSrSCZrV455,000272,00083,00062,00046,60027,64022,70018,4006,3201,5201,1201,0605443903843401801621362021222324252627282930313233a33b35363738ClCrNiRbZnCuCeNdLaYCoScNbNGaLiPbPrB1261229978766866403531292520191918139.1939404142434445464748a48b505152535455a55b55cThSmGdErYbHfCsBrUSnEuBeAsTaGeHoMoWTb8.17.06.13.53.12.82.62.52.32.12.121.81.71.51.31.21.21.258596061626364a64b66676869707172a72b7475a75bTlTmIInSbCdAgHgSePdPtBiOsAuIrTeReRuRh0.70.50.460.240.20.160.080.080.050.0150.010.0080.0050.0040.0010.0010.00070.00010.0001 A Second Challenge for Drinking Water Chemists Abundance of elements in the earths crust. Elements with WHO drinking water guidelines are red. Only 16 of 76 (21%) elements in the earths crust have a WHO drinking water guideline. Many of the remaining elements are toxic and commonly found in groundwater. More guidelines are needed.Only 16 of 76 (21%) elements in the earths crust have a WHO drinking water guideline. Many of the remaining elements are toxic and commonly found in groundwater. More guidelines are needed.

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