Transcript The Nature, Extent, Health Risks, and Treatment of Metal

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.
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
• 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
• 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
(Images by Element Collection, Inc.)
produce symptoms.
A History of Drinking Water
0.500
Arsenic Concentration (mg/L)
• This graph suggests
that As is released
from solids to deep
well water by low
dissolved O2.
0.400
0.300
0.200
0.100
0.000
-200
-100
0
100
200
300
Oxidation-Reduction Potential (mV)
Graph of As concentration (mg/L) versus
oxidation-reduction potential (mV).
A History of Drinking Water in 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.
• 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
Arsenic (As)
Independent
Standard Recovery
(Analyte Added to
Distilled Water)
83%
Sample Matrix
Spike Recovery
(Analyte Added to
Drinking Water)
89  11%
Ferrous iron (Fe2+) 93  10%
34  23%
Total iron (Fe)
Not measured, at least 27% of
samples developed the wrong color.
95%
• At least 27% of the drinking water wells in Bangladesh
apparently contain an analytical interference to the 1,10phenanthroline methods for measuring ferrous iron and
total iron.
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).
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.
Metal
Carcinogenic
Potential
WHO
Guideline
(µg/L)
Percent of
Bangladesh’s Area
Exceeding WHO
Guideline
As
Mn
Pb
Ni
Cr
Known carcinogen
Noncarcinogen
Possible carcinogen
Probable carcinogen
Noncarcinogen
10
400
10
20
50
49
60
3
<1
<1
Number of
Bangladeshis
Drinking Unsafe
Water a
75,000,000
92,000,000
4,600,000
< 1,500,000
< 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.
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 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.
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.
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.
WHO Guideline for Manganese in Drinking Water
• These findings were published in the peerreviewed journal Environmental Health
Perspectives by the National Institutes of Health
and sent to Dr. Margaret Chan, the DirectorGeneral of the WHO.
WHO Guideline for Manganese in Drinking Water
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 drinkingwater at concentrations well
below the WHO ‘healthbased 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.
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).
WHO Guideline for Uranium in Drinking Water
• In 2011 the WHO
increased the drinkingwater 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.
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.
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 noeffect 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.
• The NOAEL was calculated by estimating the 95th
percentile of exposure from the supposed noeffect 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.
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.
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
No.
Ele.
ppm
No.
Ele.
ppm
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
35
31
29
25
20
19
19
18
13
9.1
9
39
40
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
2.1
2
1.8
1.7
1.5
1.3
1.2
1.2
1.2
58
59
60
61
62
63
64a
64b
66
67
68
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
0.08
0.05
0.015
0.01
0.008
0.005
0.004
0.001
0.001
0.0007
0.0001
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.
Sources
Primary:
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