The Silent Pandemic Caused by Drinking Metals in Deep Well Water Seth Frisbie, Ph.D. Donald Maynard, P.E. Erika Mitchell, Ph.D. Bibudhendra Sarkar, Ph.D. Copyright © 2011 Seth H. Frisbie, Ph.D. All rights reserved.

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)

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)

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.)

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)

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.

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)

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

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).

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.

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)

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.

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.

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.

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.

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. Chronic As poisoning is the most significant health risk. Multimetal health effects are possible.

Climate Change and Multimetal Exposure in Bangladesh 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. (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.

Climate Change and Multimetal Exposure in Bangladesh This graph suggests that As is released from solids to Bangladesh’s 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. Graph of As concentration (mg/L) versus oxidation-reduction potential (mV).

Map of As concentration (mg/L). Map of Cl- concentration (mg/L). These maps suggest this saltwater intrusion might release arsenite (H3-xAs(III)O3x-) or arsenate (H3-xAs(V)O4x-) from solids to Bangladesh’s 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.

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

A Discovery of Multimetal Exposure in India 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. Map of As, Mn, and boron (B) concentrations (µg/L).

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

A First Challenge for Drinking Water Chemists Known regions of natural multimetal contamination in deep well water. 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. More of these surveys are needed.

A Second Challenge for Drinking Water Chemists 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 16 of 76 (21%) 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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