Discovering the Largest Mass Poisoning in History Arsenic, Manganese, Uranium, and Other Toxic Metals in the Drinking Water of Argentina, Bangladesh, India, Myanmar, and Ultimately the World Erika Mitchell, Ph.D. Donald Maynard, P.E. Thomas Bacquart, Ph.D. George Springston, M.S. Laurie Grigg, Ph.D. Seth Frisbie, Ph.D. Bibudhendra Sarkar, Ph.D. Hannah Dustin, B.S. Kelly Bradshaw, B.S. Jeffrey Defelice, B.S.

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)

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

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

Graph of As concentration (mg/L) versus oxidation-reduction potential (mV). This graph suggests that As is released from solids to deep well water by low dissolved O 2.This graph suggests that As is released from solids to deep well water by low dissolved O 2. A History of Drinking Water

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)

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 (Photograph by Dhaka Hospital)

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

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 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

The first national-scale map of As concentration in Bangladesh’s tubewell water was made in 1997.The first national-scale map of As concentration in Bangladesh’s tubewell water was made in 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

The Discovery of Other Toxic Elements in Bangladesh’s 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.

Map of Fe concentration (mg/L). The Discovery of Other Toxic Elements in Bangladesh’s Drinking Water Locations of tubewells that contained interfering metals are labeled with the letter “E”.Locations of tubewells that contained interfering metals are labeled with the letter “E”. This suggests that other toxic metals besides As are widely distributed in Bangladesh’s drinking water.This suggests that other toxic metals besides As are widely distributed in Bangladesh’s drinking water.

The Discovery of Other Toxic Elements in Bangladesh’s 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 Bangladesh’s 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 Bangladesh’s drinking water. (Photograph by NGO Forum, 2002)

60% of Bangladesh’s area contains groundwater with Mn concentrations greater than the WHO drinking water guideline.60% of Bangladesh’s 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).

3% of Bangladesh’s area contains groundwater with Pb concentrations greater than the WHO drinking water guideline.3% of Bangladesh’s 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).

< 1% of Bangladesh’s area contains groundwater with Ni concentrations greater than the WHO drinking water guideline.< 1% of Bangladesh’s 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).

< 1% of Bangladesh’s area contains groundwater with Cr concentrations greater than the WHO drinking water guideline.< 1% of Bangladesh’s 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).

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 Bangladesh’s Area Exceeding WHO Guideline Number of Bangladeshis Drinking Unsafe Water a AsMnPbNiCr Known carcinogen Noncarcinogen Possible carcinogen Probable carcinogen Noncarcinogen < 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. Boron (B), barium (Ba), molybdenum (Mo), and uranium (U) have also been found above WHO health-based guidelines in Bangladesh.Boron (B), barium (Ba), molybdenum (Mo), and uranium (U) have also been found above WHO health-based guidelines in Bangladesh.

REMEDY #1: Testing Can Provide Safe Water to Millions Map of average arsenic concentration (mg/L). Map of minimum arsenic concentration (mg/L). 45% of Bangladesh’s neighborhoods contain groundwater with average arsenic concentrations greater than the 50-µg/L national standard.45% of Bangladesh’s neighborhoods contain groundwater with average arsenic concentrations greater than the 50-µg/L national standard. 15% of Bangladesh’s neighborhoods contain groundwater with minimum arsenic concentrations greater than this standard.15% of Bangladesh’s neighborhoods contain groundwater with minimum arsenic concentrations greater than this standard. Therefore, 85% of Bangladesh’s neighborhoods have at least 1 tubewell that does not require treatment for arsenic removal prior to drinking.Therefore, 85% of Bangladesh’s neighborhoods have at least 1 tubewell that does not require treatment for arsenic removal prior to drinking.

As a result of this discovery, groundwater testing has become a major component of an overall strategy for providing safe drinking water to the people of Bangladesh.As a result of this discovery, groundwater testing has become a major component of an overall strategy for providing safe drinking water to the people of Bangladesh. Tubewells are considered safe and marked with green paint if the arsenic concentration is less than or equal to the 50-µg/L national standard.Tubewells are considered safe and marked with green paint if the arsenic concentration is less than or equal to the 50-µg/L national standard. Conversely, tubewells are considered unsafe and marked with red paint if the arsenic concentration is greater than 50 µg/L.Conversely, tubewells are considered unsafe and marked with red paint if the arsenic concentration is greater than 50 µg/L. Testing Can Provide Safe Water to Millions (Photograph by The World Bank Group, 2005)

The vertical distribution of arsenic in groundwater (mg/L) based on adjacent pairs of “very deep” (67 to 335 m) and “shallow” (less than 28 m) tubewells. Drilling deeper tubewells can access water with markedly less arsenic.Drilling deeper tubewells can access water with markedly less arsenic. This approach should be used in the 15% of Bangladesh that cannot find drinking water with arsenic concentrations less than the national standard from existing tubewells within their village.This approach should be used in the 15% of Bangladesh that cannot find drinking water with arsenic concentrations less than the national standard from existing tubewells within their village. REMEDY #2: Drilling Deeper Tubewells May Access Safe Water

Drilling Deeper Tubewells May Access Safe Water

The quality of water entering and leaving a storage tank which supplies drinking water to 300 people. The arsenic concentration is lowered from 160 to < 2 µg/L.The arsenic concentration is lowered from 160 to < 2 µg/L. The oxygen in air converts arsenic and iron to a solid which settles to the bottom of the tank.The oxygen in air converts arsenic and iron to a solid which settles to the bottom of the tank. REMEDY #3: Treatment Can Provide Safe Water ParameterInfluentEffluent Arsenic (µg/L) Oxidation-reduction potential (millivolts) pH Conductivity (microsemans) Temperature ( o C) Total iron (µg/L) Sulfate (µg/L) Sulfide (µg/L) Chloride (µg/L) Phosphate (µg/L) NANANANANA < ,400 < 1,000 < 30 16,0001,300

Treatment Can Provide Safe Water

The Discovery of Multiple Toxic Elements in West Bengal’s Drinking Water The deep well water from neighboring West Bengal, India has unsafe concentrations of As, B, fluoride (F - ), Mn, and possibly thorium (Th).The deep well water from neighboring West Bengal, India has unsafe concentrations of As, B, fluoride (F - ), Mn, and possibly thorium (Th).

The Discovery of Multiple Toxic Elements in Myanmar’s Drinking Water The deep well water from neighboring Myanmar has unsafe concentrations of As, F -, Mn, and U.The deep well water from neighboring Myanmar has unsafe concentrations of As, F -, Mn, and U. This rapid switch to deep well water is exposing hundreds of millions of people in south Asia to unsafe concentrations of metals.This rapid switch to deep well water is exposing hundreds of millions of people in south Asia to unsafe concentrations of metals. This has been called the largest mass poisoning in history.This has been called the largest mass poisoning in history.

No.Ele.ppmNo.Ele.ppmNo.Ele.ppmNo.Ele.ppm OSiAlFeCaMgNaKTiHPMnFBaSrSCZrV455,000272,00083,00062,00046,60027,64022,70018,4006,3201,5201,1201, a33b ClCrNiRbZnCuCeNdLaYCoScNbNGaLiPbPrB a48b a55b55cThSmGdErYbHfCsBrUSnEuBeAsTaGeHoMoWTb a64b a72b7475a75bTlTmIInSbCdAgHgSePdPtBiOsAuIrTeReRuRh A Challenge for Drinking Water Scientists Abundance of elements in the earth’s crust. Elements with WHO drinking water guidelines are red. Only 14 of 76 (18%) elements in the earth’s crust have a WHO drinking water guideline. Many of the remaining elements are toxic and commonly found in groundwater. More guidelines are needed.Only 14 of 76 (18%) elements in the earth’s crust have a WHO drinking water guideline. Many of the remaining elements are toxic and commonly found in groundwater. More guidelines are needed.

Another Challenge for Drinking Water Scientists 50,000 ng/L 10,000 ng/L 7,000 ng/L 170 ng/L 10 ng/L The maximum allowable concentration of As in drinking water set by the governments of most developing counties The maximum allowable concentration of As in drinking water recommended by the WHO and set by the governments of most developed counties The detection limit for measuring As in drinking water by the arsenomolybdate method Causes an unacceptable risk of death from skin cancer, according to the WHO Causes an unacceptable risk of death from all cancers, according to the Harvard School of Public Health

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