Chronic
Arsenic Poisoning:
History, Study and
Remediation
Last updated May 5th 2008
Webmasters
Sammy Sambu and Richard Wilson
SUPPORT
THE
ARSENIC
FOUNDATION
Documented cases of
arsenic
problems in groundwater related to natural contamination (Smedley, Kinniburgh 2001).
Click on any of the annotated hotspots for details.
A map by Amini et al, Swiss
Federal Institute of Aquatic Science and Technology, showing the
modelled global probability of geogenic arsenic contamination can be
found here .
|
Keratoses of the foot
|
Arsenic
is found in groundwater
of many countries:
particularly South East Asia
& Bangladesh
(50 million with arsenic above
new EPA standard)
|
Multiple
skin cancers
|
A community meeting discussing
how to get pure water
|
|
Skin cancers |
Summary of the
acute and chronic effects of arsenic
.
Acute
effects
.
Arsenic has
been
used
since 3000 BC (Partington, 1935). In the United Kingdom, for example,
it
was used to extract iron from iron ore. It has long been known
that
arsenic is acutely toxic. Anyone who drinks arsenic in water at
60
parts per million (ppm) will soon die. There are several
toxicological
summary references for acute effects available on the web such as
SCORECARD,
ASTDR,
USEPA
and
LSUMC.
.
Beneficial
effects
.
Arsenic
has been
used
for many years for medicinal purposes. It used to be used
as
a cure for diseases such as syphilis and has been shown to assist in
curing
some leukemias. It was taken as a medicine in Fowler's Solution
for
well over a century. That arsenic at low levels is safe seemed to be
reinforced
by animal studies that seemed to show that arsenic is beneficial (to
animals)
at low doses. Indeed, the fact that laboratory animals could not be
persuaded to develop cancer misled
toxicologists throughout
the world and greatly contributed to the present catastrophe.
Others
have written about other possible
beneficial effects at very low levels. It is important to note that
the beneficial effects
are for different medical outcomes (end points) than either the acute
or
chronic adverse effects and that both beneficial and adverse effects
can
be observed simultaneously (as is well known for alcohol ingestion).
Another
detailed article about beneficial uses of arsenic can be found
here
. Mineral hot springs in the USA
still advertise
arsenic
pools and their users, including this webmaster, are convinced that the
effects are beneficial! (But arsenic penetrates the skin only slowly)
Chronic adverse effects
.
Chronic effects of prolonged low level exposure have
recently showed up. Among various
summaries we link to an information
site run by
ASTDR. Skin pigmentation,
keratoses and skin cancers were found
by Tseng in Taiwan in 1966 among
people who drank from arsenic contaminated wells
(but no effect was seen below about 150 parts per billion (ppb),
which might therefore be a
biological threshold) and a very high incidence of lung, bladder and
other cancers was
found in Taiwan by Dr Chien-Jen
Chen in
1986 and by
Dr
Allan
Smith and collaborators in Chile in 1993. These
convinced WHO to recommend
lowering the regulatory level from 50 ppb to 10 ppb for arsenic in
water.
It appears that there are no data on humans to contest the idea
that
prolonged exposure to low doses is dangerous. Although arsenic
was
used medicinally in "Fowler's Solution" (1% arsenite), prolonged
use
had led to these chronic skin effects. This was observed as early
as
1888 by Hutchinson. A follow up of a number of English patients treated
with
Fowler's Solution has been reported by Dr Susan Evans in published
literature,
in a report at the February 1998 conference in Dhaka and in a
presidential address by Susan Evans to the Liverpool Medical
Institute, which is available for
download in PDF format. This shows that the use of "Fowler's
solution"
(which is primarily medicinal arsenic) in the UK is probably
responsible
for 5 bladder cancer cases among the patients among whom only 1.6
were
expected from natural causes. The arsenic dose was equivalent to
an
average lifetime dose that would come from drinking water with about 25
ppb
of arsenic therein.
.
After
several years of low
level
arsenic exposure, various skin lesions appear. These are manifested by
hyperpigmentation
(dark spots), hypopigmentation (white spots) and keratoses of the hands
and
feet. After a dozen or so years skin cancers are expected. Twenty
or
thirty years after exposure to 500 ppb of arsenic, internal
cancers
(lung, kidney, liver and bladder) appear among 10% of all
exposed. Moreover, the dose-response relationship for these
internal cancers
is consistent with being linear with no threshold. Photographs of
a
number of victims of this poisoning are
available
both from
Bangladesh and from
Inner Mongolia.
Although the most dramatic effect was the
observation of internal cancers in Tawian, the most extensive
epidemiological studies have come from the work in Chile, in which Dr
Allan Smith of UC Berkeley has been heavily involved. They
find the extraordinarily surprizing result that ingested arsenic in Chile has
produced lung cancer at a rate greater than that of a heavy cigarette
smoker! Recently, the group identified an effect of arsenic
exposure to chldren - who have developing lungs -. Children
exposed to arsenic have ten times
the normal lung cancer incidence.
.
.
The
Effect of diet
An important
issue for coping with arsenic exposure is the effect of diet. A
general issue can be stated: there is frequently more than one
cause of a cancer or a lesion. For example lung cancer can be
caused by cigarette smoking or asbestos or both together, in a
synergistic way such that the risks multiply (rather than add) when
both are present. In the USA it has been found that people who
have a good diet of fresh fruit and vegetables (5 servings per day)
have half the risk of many cancers, including lung cancers caused by
cigarettes, as those without a good diet. By analogy, one might
expect that the lung cancer risk from arsenic will be less among those
with a good diet. Anecdotal indications from Bangladesh
suggests that a good diet reduces skin lesions, and the effect
is seen in West Bengal,
but the effect is small and the authors recommend that effort is better
spent on obtaining pure water. Nonetheless
epidemiological studies to confirm this are highly desirable.
Khaliquzzaman and Khan have calculated the "Arsenic Exposure of
Bangladesh Population through Food Chain" using known amounts in
food, in an unpublished World
Bank report. The amount is
less than from drinking water but
not much less.
There are several specific
chemicals
that have been suggested that would either (i) help to prevent arsenic
lesions
by rapid removal of arsenic from the body or (ii) help to cure arsenic
lesions.
Encouragement of methylation of the arsenic probably accelerates
methylation,
but the methylation has been suggested as a cause of internal cancers.
The specific chemical that has come to the mind of many health experts
is
selenium. It was noted in the 1930s that effects of excess
selenium
can be counteracted by adding arsenic to the diet because As and Se
combine.
Does the inverse take place? It is reported that areas with
high
incidence of arsenical lesions have low selenium in the water.
Some
victims have low selenium levels. Does adding selenium to
the
diet really help, either to prevent the lesions from forming (likely),
or
to treat them afterwards (less likely)? We have, with help from
others,
compiled a list of
references
and a
recent
paper on the subject.
Professor
Zuberi of Rajshashi University has suggested methionine to reduce
the arsenic lesions.
Dr. OGB
Nambiar
has suggested
that ferrous sulphate, after conversion to sulfide by bacteria
in the colon, absorbs arsenic and assists safe excretion. The
evidence
for these remains indirect, and there may be (as suggested above)
competing adverse effects. Only good epidemiology can tell
and this is under way in several places.
Regulatory
limits for continuous exposure.
The regulatory
limits on arsenic
exposure were set primarily to be sure
that these acute toxic effects
were avoided. The first regulatory limit of which the webmasters
are aware was set as a result of a
public inquiry (subsequent to arsenic being found in beer) of six
members chaired by the
physicist
William Thompson, first Lord Kelvin, in 1903. They recommended
that sake of liquids with more than 100 grains of arsenious oxide per
gallon (which works out at about 90 ppb of arsenic or 0.09 ug/l)
This was reduced two fold over the next century and
until
recently the limit set by Bangladesh, the United Kingdom,
and
the United States was 50 parts per billion (ppb). But the
discovery
that there are
adverse effects of continuous chronic exposure led WHO to lower
their recommendation to 10 parts per billion (10 ppb).
The European Union (EU) plans to enforce a standard of 10
ppb
by 2003. After a long travail , on October 31st 2001, the
administrator
of US EPA confirmed a new standard for drinking water of 10 ppb to be
enforced
by 2006. In
Australia
there does not seem to be a specific regulatory level but there are
work
rules for those working around mine tailings sites.
The US EPA has recently
come out with an extensive
review of mechanisms of action of
Dimethyl Arsenic (DMA) and its
possible mechanisms of action.
They cannot rule out a linear dose response at the lowest
doses. It is effectively impossible to
reduce
the content of arsenic in drinking water to a risk level of one in a
million
lifetime risk calculated with a linear dose-response relationship, a
risk
level and a calculational procedure frequently used by the U.S. EPA.
The
present 10 ppb standard is perhaps the first in which the U.S EPA
explicitly
compared costs and benefits and used a value of $6.1 million per
calculated
life saved. References to the extensive US national discussion
are
available on the
"countries" page and in
particular the section on
travail.
The
worldwide scope of the catastrophe
.
Arsenic contamination has become a
problem
in many parts of the world. At first as a result of
leaching
from mine tailings in Australia,
Canada,
Japan, Mexico, Thailand, United
Kingdom, and the
United States, but now also
from the arsenic in natural
acquifers now or recently used
for water supply in Argentina,
Bangladesh, Cambodia, Chile
, China, Ghana,
Hungary, Inner
Mongolia, Mexico, Nepal, New
Zealand, Philippines,
Taiwan, the
United States and Vietnam.
Arsenic was also widely used
as a pesticide.
20,000 tons a year was imported into the USA, and perhaps double that
amount
was used, to spray on crops in the USA alone. No attention was
paid
to the ultimate fate of the chemical,and in consequence
arsenic now appears in foodstuffs
. (
Papers describing data in some of these countries are listed by
country
in the list of useful references.
) It is
important
to
distinguish
the problems in Bangladesh, West Bengal and, to a lesser extent, Inner
Mongolia,
Chile, Nepal and Vietnam, from the problems that have been found
so
far in the rest of the world. These situations have in common
that
they are an alluvial plain where arsenic has been brought down from the
surrounding
hills for millenia. It seems that no one has looked carefully at
similar
geological situations such as the Mekong delta or the
Irrawaddy delta.
In most of the world exposures above 50 parts per billion (50
ppb)
are rare, and once observed, can easily be avoided. But the
sheer
scale of the problems in Bangladesh dwarfs the imagination. The
catastrophe
is much worse than the well known catastrophe of the Chernobyl nuclear
power
plant accident, the Bhopal isothiocyanate leak or the Kuwait oil
fires.
For 90% of the Bangladeshi communities, pure water is still
a
long time away.
The World Bank has recently completed a study for SE Asia which is
available on the web:
Arsenic Contamination of
Groundwater in South and East Asian Countries
Volume
I: Policy Report
Full Report (1,038kb
pdf)
Volume II: Technical Report
Full Report (2,879kb
pdf)
Paper 1: Arsenic Occurrence in Groundwater in South
and East Asia -- Scale, Causes, and Mitigation (715kb)
Paper 2: An Overview of Current Operational
Responses to the Arsenic Issue in South and East Asia (413kb)
Paper 3: Arsenic Mitigation Technologies in South
and East Asia (345kb)
Paper 4: The Economics of Arsenic Mitigation (335kb)
The situation
in Bangladesh
has received a lot of attention because it is the most important.
The
new Bangladeshi government has made the solution of the problem a
priority
as stated clearly by
Prime Minister Begum Khaleda Zia
as she opened the special WHO
workshop in Dhaka on January 14th -16th 2002.
You are invited to comment upon the
recommendations to the government of Bangladesh from the
participants of that workshop.
Professor
Chakriborti of Kolkata
(Calcutta), a
tireless
and enthusiastic worker in the field regularly issues his
reports
on the Bangladesh situation, has a year 2001 report
on Bangladesh which we have also
captured in a local file.
Another recent
draft
summary of the Bangladesh situation has been circulated for
comment
by
WATERAID
The best review of
the situation in Bangladesh is in
the
paper by
Feroze Ahmed, presented to the
International Workshop on Arsenic on
January 14-16
2002
in Dhaka. A recent (2002) review from the NGO forum is copied
here
from the NAISU website in pdf
or html
.
Why Does Arsenic Get into the Water?
This
is the subject of a whole issue of the journal Applied Geochemistry:
Bhattacharya, P., A. H. Welch, K. M.
Ahmed, G. Jacks and R. Naidu (Eds.)
Arsenic
in Groundwater of Sedimentary Aquifers.
Applied Geochemistry, 19(2), 163-260,
February 2004
The table of
contents, with links to
abstracts and full text,
Arsenic is
plentiful in the ground.. Yet it does not awlays appear in the
water supply. Scholars at the Cambridge
University Department of
Geography have identified the following mechanisms for arsenic entering
the water which vary between locations..
Alkali-desorption, Geothermal, Reductive dissolution and Sulphide
oxidation. lthough the worst
arsenic catastrophe is in Bangladesh, where 35
million people are exposed to levels above the US EPA standard, the
amount of arsenic in the soil is less than in many other areas,
including areas such as Massachussets, USA, where it does not,
nonetheless, appear in unsafe quantities in ground water. In most
of these areas, such as the delta of the
Ganges and Irrawaddy, and the bend of the Yellow river, arsenic has
come
down from the mountains over millenia, attached itself to iron, forming
iron pyrites, and
been deposited. Professor McArthur of UC London
argues: "It becomes increasingly clear that severe arsenic
pollution of ground water in most alluvial aquifers worldwide is
driven by the microbially-mediated metabolism of organic matter, with
FeOOH acting as the source of oxygen: the oxide is reduced during the
process and its sorbed arsenic is released to ground water. Despite the
widespread acceptance of this mechanism, much about it remains
obscure." One issue is whether the reduction takes place at
the surface before the water filters down to the aquifer in the monsoon
(as sugegsted by group (a) below) or whether it is reduced in the
aquifer itself.
Papers describing this mechanism
include:
(a) Two papers were
presented by Charles Harvey et al.: "On
the Spatial Variability of Arsenic Contamination in the
Groundwater of Bangladesh; A
Geochemical and Hydrological
Analysis of Arsenic Mobilization at a Field Site in Bangladesh" and a
brief report
in Science
(b) The group at Columbia
University
have also presented a
papers on the same topic of which
the most recent is: Redox
control of
arsenic mobilization in Bangladesh groundwater. Applied
Geochemistry, 19(2),
163-260, February 2004, 201-214. Y. Zheng, M. Stute, A. van
Geen, I. Gavrieli, R. Dhar, H. J. Simpson, P. Schlosser and K. M.
Ahmed.
(c) Professor
McArthur and colleagues at UCL in London have several reports available
of which the following may be downloaded -
Arsenic in groundwater: testing pollution mechanisms for sedimentary
aquifers in Bangladesh,
Their most recent paper is:
"Natural organic
matter in sedimentary basins and its relation to arsenic in anoxic
ground water: the example of West Bengal and its worldwide
implications," by J.M.
McArthur and others is available at http://www.es.ucl.ac.uk/research/lag/as/
This shows that the
arsenic pollution in West Bengal appears to be related spatially
to the distribution of organic matter in the aquifer. The authors also
argue that tectonics influence arsenic pollution, and that peaky
vertical profiles of arsenic pollution in ground water, seen widely
across the Bengal Basin, show that abstraction of water, for domestic
use and irrigation, is purging the shallow aquifer of arsenic
pollution." If so that is good news indeed.
In June of 2005, a
collaborative study between
the Department of Geological and Environmental Sciences, Parsons
Laboratory at M.I.T, the Consortium for Advanced Radiation Sources and
Department of Geophysical Sciences at the University of Chicago has
established that As may be released at the near-surface and is then
leached to greater depths. Among other things, they establish the
existence of a consistent input of Arsenic via sediment deposition.
Further details can be obtained at the SOS-Arsenic
website
.
An older idea was
that water was being drained from
the aquifer, allowing oxidation. A recent paper
describing arsenic contamination in
Perth, Australia - shows that there is one location, in Perth
where pyrite oxidation clearly WAS the source of the As (although there
is evidence that anerobic release from Fe oxyhydroxides is also taking
place deeper in the aquifer). But the
ideas that pyrite oxidation is the problem in Bangladesh whether
caused by recent
rapid
pumping that allowed for
oxidation and release of
arsenic, or by the man-made change in river
flow, such as the
barrage across
the Ganges are now considered to be untenable.
In the Americas, from Alaska in the north, through
Crater Lake in Oregon, Mono Lake and Searles lake in California,
volcanic lakes in Niceragua and Costa Rica, and on to the Andes, lie a
chain of volanic activity that brings arsenic to the
surface. This mecahnism of sulfate reduction in the
arsenic-rich soda lakes (Mono Lake and Searles lake) of is being
studied in detail by Dr Oremland and his group at the US Geological
Survey in Menlo Park. They attrbute the mechanism to bacteria,
but of course different bacteria from those responsible for the
reduction of iron pyrites in SE Asia and Bangladesh.
Presumably this is the same mechanism as is responsible for the arsenic
pollution in the mountains of Argentine and Chile where so
much epidemiological studies have been made.
Social Issues
Western experts from developed
countries often regard the arsenic pollution problem as a technical
problem to be solved by purely technical means. But that is
naive. There are tremendous social issues which control the
ability of anyone to help. One set of papers discussing these
has been
put on
the APSU website and is also
copied on this site.
Possible
solutions to the problems.
The first
and
most obvious necessity
is to
measure the arsenic levels in any ground water that is intended for
human use. The
next step is to
purify the water or, better still,
provide an alternate supply
of pure water. The way in which this is done varies from country
to
country. In SE ASIA, and Bangladesh in particular, two facets of
a solution seem to be agreed..
(1) There is no one solution for all places and
communities. It is vital to involve the local community in the
decision and even more important in the follow up and
maintenance.
(2) The solution in any community and location must based
upon the best possible scientific understanding. The webmaster
has attempted to summarize the possibilities in the remediation
page. Please add and correct. It is very
important to share data and experiences as
set
out in
declarations from four arsenic conferences in Dhaka held by
Dhaka Community Hospital.
Also please comment upon the
recommendations of the conference organized by WHO but sponsored by
the Bangladesh Government
in January 2002.
"It is an uncanny thought that
this lurking poison
(arsenic) is everywhere
about us, ready to gain unsuspected entrance to our bodies from
the
food we eat, the water we drink and the air we breathe"
Karl
Vogel, 1928.
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us
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about
to us at
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