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.

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.

WHO Guideline for Manganese in Drinking Water In 2011 the 400 µg/L drinking-water guideline for manganese (Mn) was discontinued with the assertion that since “this health-based value is well above concentrations of manganese normally found in drinking-water, it is not considered necessary to derive a formal guideline value”.In 2011 the 400 µg/L drinking-water guideline for manganese (Mn) was discontinued with the assertion that since “this health-based value is well above concentrations of manganese normally found in drinking-water, it is not considered necessary to derive a formal guideline value”. However, over 50 countries have drinking-water or potential drinking-water supplies with Mn concentrations above 400 µg/L.However, over 50 countries have drinking-water or potential drinking-water supplies with Mn concentrations above 400 µg/L. In Bangladesh alone, over 60,000,000 people are likely drinking water with Mn above 400 µg/L.In Bangladesh alone, over 60,000,000 people are likely drinking water with Mn above 400 µg/L.

The WHO 2011 decision to discontinue the drinking-water guideline for Mn was based on a literature review that did not include any references on human toxicity published after 2001; some recent studies suggest the former 400 µg/L guideline may have been too high to protect public health.The WHO 2011 decision to discontinue the drinking-water guideline for Mn was based on a literature review that did not include any references on human toxicity published after 2001; some recent studies suggest the former 400 µg/L guideline may have been too high to protect public health. Since 2001, chronic exposure to Mn in drinking water has been correlated with neurological disorders ranging from learning disabilities in children to Mn-induced parkinsonism in adults, as well as with all-cause cancer rates.Since 2001, chronic exposure to Mn in drinking water has been correlated with neurological disorders ranging from learning disabilities in children to Mn-induced parkinsonism in adults, as well as with all-cause cancer rates. And high maternal Mn has been associated with low birthweight and increased infant mortality.And high maternal Mn has been associated with low birthweight and increased infant mortality. WHO Guideline for Manganese in Drinking Water

These findings were published in the peer- reviewed journal Environmental Health Perspectives by the National Institutes of Health and sent to Dr. Margaret Chan, the Director- General of the WHO.These findings were published in the peer- reviewed journal Environmental Health Perspectives by the National Institutes of Health and sent to Dr. Margaret Chan, the Director- General of the WHO.

WHO Guideline for Manganese in Drinking Water

Robert Bos, Coordinator for Water, Sanitation, Hygiene and Health at the WHO replied, “Manganese is of aesthetic concern (taste, odour, staining of laundry and fixtures) at concentrations around 0.1 mg/l [100 µg/L]. This may lead to rejection of drinking- water at concentrations well below the WHO ‘health- based value’ of 0.4 mg/l [400 µg/L].”Robert Bos, Coordinator for Water, Sanitation, Hygiene and Health at the WHO replied, “Manganese is of aesthetic concern (taste, odour, staining of laundry and fixtures) at concentrations around 0.1 mg/l [100 µg/L]. This may lead to rejection of drinking- water at concentrations well below the WHO ‘health- based value’ of 0.4 mg/l [400 µg/L].”

WHO Guideline for Manganese in Drinking Water In other words, since manganese might affect the taste of drinking-water and stain laundry and plumbing fixtures at less than 400 µg/L, it is assumed that a person will not drink such water, so a 400 µg/L guideline is not needed.In other words, since manganese might affect the taste of drinking-water and stain laundry and plumbing fixtures at less than 400 µg/L, it is assumed that a person will not drink such water, so a 400 µg/L guideline is not needed.

WHO Guideline for Manganese in Drinking Water However, over 60,000,000 people in Bangladesh were found to have been drinking water with an average 940 µg/L of manganese for 6 years in 1998 (Frisbie et al. 2002).However, over 60,000,000 people in Bangladesh were found to have been drinking water with an average 940 µg/L of manganese for 6 years in 1998 (Frisbie et al. 2002). In another study, people in western Bangladesh were found to have been drinking water with 400 µg/L to 2,400 µg/L of manganese for an average of 9 years in 2002 (Frisbie et al. 2009).In another study, people in western Bangladesh were found to have been drinking water with 400 µg/L to 2,400 µg/L of manganese for an average of 9 years in 2002 (Frisbie et al. 2009).

In 2011 the WHO increased the drinking- water guideline for uranium from 15 µg/L to 30 µg/L.In 2011 the WHO increased the drinking- water guideline for uranium from 15 µg/L to 30 µg/L. The 30 µg/L health-based guideline was calculated using a “no-effect group” with “no evidence of renalThe 30 µg/L health-based guideline was calculated using a “no-effect group” with “no evidence of renal WHO Guideline for Uranium in Drinking Water damage” based on a study of human adults who drank water with a median uranium concentration of 25 µg/L for an average of 16 years.

The following was published in the peer-reviewed journal Environmental Science: Processes & Impacts by the Royal Society of Chemistry.The following was published in the peer-reviewed journal Environmental Science: Processes & Impacts by the Royal Society of Chemistry. WHO Guideline for Uranium in Drinking Water

However, this nominal “no-effect group” had statistically significant increases in diastolic blood pressure, systolic blood pressure, and glucose excretion in urine.However, this nominal “no-effect group” had statistically significant increases in diastolic blood pressure, systolic blood pressure, and glucose excretion in urine. Moreover, this “no-effect group” was a subpopulation from a larger study that had statistically significant increases in calcium fractional excretion, phosphate fractional excretion, diastolic blood pressure, systolic blood pressure, and diuresis.Moreover, this “no-effect group” was a subpopulation from a larger study that had statistically significant increases in calcium fractional excretion, phosphate fractional excretion, diastolic blood pressure, systolic blood pressure, and diuresis. These results suggest this group is not a true no- effect group.These results suggest this group is not a true no- effect group. WHO Guideline for Uranium in Drinking Water

Furthermore, the method used to calculate the no observed adverse effect level (NOAEL) for the current 30 µg/L health-based drinking-water guideline for uranium is illogical.Furthermore, the method used to calculate the no observed adverse effect level (NOAEL) for the current 30 µg/L health-based drinking-water guideline for uranium is illogical. The NOAEL was calculated by estimating the 95th percentile of exposure from the supposed no- effect group (1,094 μg/day), then an unspecified bootstrap method was used to construct a 95% confidence interval around this 95th percentile (637-1,646 μg/day).The NOAEL was calculated by estimating the 95th percentile of exposure from the supposed no- effect group (1,094 μg/day), then an unspecified bootstrap method was used to construct a 95% confidence interval around this 95th percentile (637-1,646 μg/day). The lower 95% confidence limit (637 μg/day) of the 95th percentile of exposure was selected as the NOAEL.The lower 95% confidence limit (637 μg/day) of the 95th percentile of exposure was selected as the NOAEL. WHO Guideline for Uranium in Drinking Water

This produces a NOAEL that is biased high and not representative of the exposures experienced by the study group.This produces a NOAEL that is biased high and not representative of the exposures experienced by the study group. The exposures experienced by this group would have been better represented by a mean or median, which was a method previously used by the WHO and readily accepted by the scientific community.The exposures experienced by this group would have been better represented by a mean or median, which was a method previously used by the WHO and readily accepted by the scientific community. Notably, the 637 μg/day NOAEL that was derived by the WHO is over 12.5 times greater than the 50 μg/day median exposure of the nominal no-effect group and yields a 30 µg/L drinking-water guideline that is most likely too high to protect public health.Notably, the 637 μg/day NOAEL that was derived by the WHO is over 12.5 times greater than the 50 μg/day median exposure of the nominal no-effect group and yields a 30 µg/L drinking-water guideline that is most likely too high to protect public health. WHO Guideline for Uranium in Drinking Water

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.

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