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Discovering the Largest Mass Poisoning in History

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1 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 Seth Frisbie, Ph.D. Bibudhendra Sarkar, Ph.D. Hannah Dustin, B.S. Kelly Bradshaw, B.S. Jeffrey Defelice, B.S. Erika Mitchell, Ph.D. Donald Maynard, P.E. Thomas Bacquart, Ph.D. George Springston, M.S. Laurie Grigg, Ph.D. Copyright © 2014 Seth H. Frisbie, Ph.D. All rights reserved.

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. 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. (Photograph by Peer Water Exchange, 2006) (Col. Nelson W. Green)

3 A History of Drinking Water (Photograph of Vibrio cholera
Surface and dug well water often has microorganisms that can make a person sick hours or days after drinking. High dissolved oxygen (O2) 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)

4 A History of Drinking Water (Images by Element Collection, Inc.)
In contrast, deep well water rarely has pathogenic microorganisms. Low dissolved O2 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. The diagnosis of chronic metal poisoning is made difficult by the 5 to 20 or more years of exposure needed to produce symptoms. (Images by Element Collection, Inc.)

5 A History of Drinking Water
This graph suggests that As is released from solids to deep well water by low dissolved O2. Graph of As concentration (mg/L) versus oxidation-reduction potential (mV).

6 A History of Drinking Water in Argentina (Photographs by Ayerza, 1918)
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. Later, Ayerza checked things in common and found As and vanadium (V) in the drinking water. (Photographs by Ayerza, 1918)

7 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. A massive cholera outbreak began in 1963. (Photograph by Dhaka Hospital) Many premature deaths were caused by drinking surface water. The life expectancy during the mid-1960s was only 46 years.

8 A History of Drinking Water in Bangladesh
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. By 2000, approximately 97% of Bangladeshis drank tubewell water. (Photograph by Steven Brace, 1995)

9 A History of Drinking Water in Bangladesh
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. Keratosis of the feet Blackfoot disease Keratosis of the palms (Photograph by Dhaka Community Hospital and Richard Wilson, 2002) Melanosis of the chest

10 A History of Drinking Water in Bangladesh
The first national-scale map of As concentration in Bangladesh’s 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. The source of As is geological. Map of As concentration (mg/L).

11 The Discovery of Other Toxic Elements in Bangladesh’s Drinking Water
Analyte Independent Standard Recovery (Analyte Added to Distilled Water) Sample Matrix Spike Recovery (Analyte Added to Drinking Water) Arsenic (As) 83% 89  11% Ferrous iron (Fe2+) 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.

12 The Discovery of Other Toxic Elements in Bangladesh’s Drinking Water
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. Map of Fe concentration (mg/L).

13 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. 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)

14 Map of Mn concentration (mg/L).
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. It causes liver and kidney damage, and is associated with hearing loss.

15 Map of lead (Pb) concentration (mg/L).
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. It is also associated with kidney, liver, and heart disease, tooth loss, cataracts, hypertension, diabetes, and bladder cancer.

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

17 Map of total chromium (Cr) concentration (mg/L).
< 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) accumulates in the liver; persons with existing liver disease may be exceptionally susceptible to its toxic effects.

18 Estimated number of Bangladeshis drinking water with metal concentrations above WHO guidelines.
Carcinogenic Potential WHO Guideline (µg/L) Percent of Bangladesh’s Area Exceeding WHO Guideline Number of Bangladeshis Drinking Unsafe Water a As Mn Pb Ni Cr Known carcinogen Noncarcinogen Possible carcinogen Probable carcinogen 10 400 20 50 49 60 3 < 1 75,000,000 92,000,000 4,600,000 < 1,500,000 a Assuming Bangladesh has 158,570,535 people (July 2011 est.) and 97% of its population drinks well water. 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.

19 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).

20 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. 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.

21 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”. 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.

22 WHO Guideline for Manganese in Drinking Water
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. And high maternal Mn has been associated with low birthweight and increased infant mortality.

23 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.

24 WHO Guideline for Manganese in Drinking Water

25 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].”

26 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.

27 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). 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).

28 WHO Guideline for Uranium in Drinking Water
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 renal 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.

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

30 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. 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.

31 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. 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.

32 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. 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.

33 A Challenge for Drinking Water Scientists
Abundance of elements in the earth’s crust. Elements with WHO drinking water guidelines are red. No. Ele. ppm 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 O Si Al Fe Ca Mg Na K Ti H P Mn F Ba Sr S C Zr V 455,000 272,000 83,000 62,000 46,600 27,640 22,700 18,400 6,320 1,520 1,120 1,060 544 390 384 340 180 162 136 20 21 22 23 24 25 26 27 28 29 30 31 32 33a 33b 35 36 37 38 Cl Cr Ni Rb Zn Cu Ce Nd La Y Co Sc Nb N Ga Li Pb Pr B 126 122 99 78 76 68 66 40 9.1 39 41 42 43 44 45 46 47 48a 48b 50 51 52 53 54 55a 55b 55c Th Sm Gd Er Yb Hf Cs Br U Sn Eu Be As Ta Ge Ho Mo W Tb 8.1 7.0 6.1 3.5 3.1 2.8 2.6 2.5 2.3 2.1 1.8 1.7 1.5 1.3 1.2 58 59 60 61 62 63 64a 64b 67 69 70 71 72a 72b 74 75a 75b Tl Tm I In Sb Cd Ag Hg Se Pd Pt Bi Os Au Ir Te Re Ru Rh 0.7 0.5 0.46 0.24 0.2 0.16 0.08 0.05 0.015 0.01 0.008 0.005 0.004 0.001 0.0007 0.0001 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.

34 Sources Primary: Frisbie, S.H., D.M. Maynard, and B.A. Hoque The nature and extent of arsenic-affected drinking water in Bangladesh. In Metals and Genetics. Ed. by B. Sarkar. Plenum Publishing Company. New York, NY. Pp Frisbie, S.H., R. Ortega, D.M. Maynard, and B. Sarkar The concentrations of arsenic and other toxic elements in Bangladesh’s drinking water. Environmental Health Perspectives. 110(11): Frisbie, S.H., E.J. Mitchell, D.M. Maynard, R. Ortega, and B. Sarkar Arsenic and multimetal environmental contamination in Bangladesh. Clinical Biochemistry. 37:1126. Frisbie, S.H., E.J. Mitchell, A.Z. Yusuf, M.Y. Siddiq, R.E. Sanchez, R. Ortega, D.M. Maynard, and B. Sarkar The development and use of an innovative laboratory method for measuring arsenic in drinking water from western Bangladesh. Environmental Health Perspectives. 113(9): Frisbie, S.H., E.J. Mitchell, L.J. Mastera, D.M. Maynard, A.Z. Yusuf, M.Y. Siddiq, R. Ortega, R.K. Dunn, D.S. Westerman, T. Bacquart, and B. Sarkar Public health strategies for western Bangladesh that address the arsenic, manganese, uranium and other toxic elements in their drinking water. Environmental Health Perspectives. 117(3): 410–416.

35 Sources Primary: Mitchell, E.J., S.H. Frisbie, and B. Sarkar Exposure to multiple metals from groundwater—a global crisis: Geology, climate change, health effects, testing, and mitigation. Metallomics. 3(9): Bacquart, T., K. Bradshaw, S.H. Frisbie, E.J. Mitchell, G. Springston, J. Defelice, H. Dustin, and B. Sarkar A survey of arsenic, manganese, boron, thorium, and other toxic metals in the groundwater of a West Bengal, India neighbourhood. Metallomics. 7(4): 653–659. Frisbie, S.H., E.J. Mitchell, H. Dustin, D.M. Maynard, and B. Sarkar World Health Organization discontinues its drinking-water guideline for manganese. Environmental Health Perspectives. 120(6): Frisbie, S.H., E.J. Mitchell, and B. Sarkar World Health Organization increases its drinking-water guideline for uranium. Environmental Science: Processes & Impacts. 15:1817–1823. Frisbie, S.H., E.J. Mitchell, and B. Sarkar. Urgent need to reevaluate latest World Health Organization guidelines for toxic metals in drinking water. (In review.) Bacquart, T., S.H. Frisbie, E.J. Mitchell, L. Grigg, C. Cole, and B. Sarkar. Multiple toxins contaminating the groundwater of Mingyan Township, Myanmar: Arsenic, manganese, fluoride and uranium. (In preparation).

36 Sources Secondary: 76th New York State Volunteers. Available: [cited 28 April 2011]. Ayerza, A Arsenicismo regional endémico. Bol Acad Nac Medicina. (1): Brace, S Bangladesh. Thomson Learning. New York, NY. P. 9. Central Intelligence Agency. Available: [cited 8 June 2011]. Dhaka Community Hospital, and R. Wilson. Pictures of Sufferers (Chronic Arsenic Poisoning). Available: [cited 7 September 2002]. Greenwood, N.N., and A. Earnshaw Chemistry of the Elements. Pergamon Press. New York, NY. Pp , , 1496. Hrozba cholery je stále reálna. Available: [cited 28 April 2011]. International Centre for Diarrhoeal Disease Research, Bangladesh. Available: [cited 21 June 2011].

37 Sources Secondary (Continued):
IRPMAIL.COM. Available: [cited 28 April 2011]. Knight, E.H Knights American Mechanical Dictionary. Houghton, Mifflin and Company. Boston, MA. Pp Peer Water Exchange. Available: [cited 28 April 2011]. The Photographic Periodic Table of the Elements. Available: [cited 28 April 2011].


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