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Arsenic is everywhere cause for

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Arsenic is Everywhere: Cause for Concern?


Published on 06 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782626633-FP001

     
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Arsenic is Everywhere: Cause


for Concern?
Published on 06 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782626633-FP001

William R. Cullen
University of British Columbia, Vancouver, Canada
Email: wrc@chem.ubc.ca

and

Kenneth J. Reimer
Royal Military College of Canada, Kingston, Canada
Email: reimer-k@rmc.ca
Published on 06 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782626633-FP001 View Online

Print ISBN: 978-1-78262-314-4


PDF eISBN: 978-1-78262-663-3
EPUB eISBN: 978-1-78262-984-9

A catalogue record for this book is available from the British Library

© William R. Cullen and Kenneth J. Reimer 2017

All rights reserved

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Preface

In 2008, in his book Is Arsenic an Aphrodisiac? The Sociochemistry of an


Element, Bill Cullen described the way in which arsenic and its compounds
have become embedded in our social fabric, for good and for ill, thereby cre-
ating a unique interface between society and chemistry. That book covered
a wide range of topics, including arsenic’s use as a poison and as a medicine
from the time of the ancient Romans to the present day; its role in war; and
its supposed (now disproven) associations with the death of Napoleon and
sudden infant death syndrome. It also described how arsenic is all around
us: in our soil, our water and the food we eat. It is at that point that we pick
up this story. This new book is not intended to be a second edition of the
first. Much has happened in the intervening years, and as arsenic is at least
as much on the public’s radar as it was before, we attempt to present this new
information (and misinformation) in a form that is easily deciphered and
understood by the reader.
We believe that the very word “arsenic” triggers fear and anxiety in human
society, such is the power of its historical associations with death. So it is
not surprising that the reaction of a parent to hearing from TV’s Dr Oz that
there is arsenic in apple juice was, “I didn’t know that I was giving poison to
my child!” The reality is that arsenic, a naturally occurring element, is every-
where around us so it would be surprising (to chemists) to not find at least
some arsenic in everything we eat and drink.
We explore the topic of arsenic’s ubiquitousness in our environment
in Chapter 2 and also illustrate the harm that it can cause when naturally
present in high concentrations in drinking water. In Bangladesh and West
Bengal, India, naturally occurring arsenic in the water has impacted the lives
of millions of people; the situation has been called the “largest mass poi-
soning of a population in history.” Unfortunately, despite some mitigation
efforts, 52 million people in these regions are still drinking water containing

Arsenic is Everywhere: Cause for Concern?


By William R. Cullen and Kenneth J. Reimer
© William R. Cullen and Kenneth J. Reimer, 2017
Published by the Royal Society of Chemistry, www.rsc.org

v
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vi Preface
arsenic above the commonly accepted limit of 10 ppb (with 20 million con-
suming concentrations of more than 50 ppb), and the impacts of this are
expected to be felt for generations to come. It may therefore come as a sur-
prise to many to learn in Chapter 3 that arsenic is involved in life processes
Published on 06 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782626633-FP005

and that at least one microbe requires arsenic for life. These processes have
been going on since the Earth’s beginnings, and through them, arsenic the
element is transformed into many different arsenic compounds, each with
its own distinct toxicity. One compound in particular, commonly found in
marine organisms, is not toxic at all.
In Chapter 4, we address the issue of the toxicity of arsenic, starting with
the most commonly held perception of arsenic as a poison, which, if given in
sufficient amount and a specific form, can cause death fairly quickly. More
complicated is determining the effects of day-to-day, “chronic” exposure to
arsenic in smaller amounts and in different chemical forms. While it is not
uncommon to hear it said that inorganic arsenic is the dangerous one and
that organic arsenic is safe, the reality is not that simple. A great deal of sci-
entific effort has gone into trying to answer the question of whether there is
a “safe dose” of arsenic or whether any amount may cause us harm. The jury
is still out on the answer, although it does appear that some individuals may
be more vulnerable to arsenic’s effects than others, especially in early life.
Yet, as we explore in Chapters 5 and 6, there has been a long history of use
of arsenic in medicine and in alternative medicine, and it provides the most
effective cure for a certain form of leukemia, APL.
Chapter 7 looks at our exposure to arsenic in our diet—yes, in our food.
(Arsenic is everywhere, after all!) As mentioned earlier, we should expect to
find arsenic in our food because plants and animals take up arsenic from
the natural environment. Research is being done around the globe to bet-
ter understand the implications of daily dietary exposure to arsenic and the
risks it might, or might not, pose. Those who are fortunate enough to not
have arsenic-contaminated drinking water and who can afford a varied diet
can manage their arsenic exposure. To assist with that, in Chapter 8 we invite
you to dinner and offer some information about the servings of arsenic you
might be putting on your plate. Overall, our hope is to demystify arsenic and
to provide you with tools to deal with the real, rather than perceived, risks.
In Is Arsenic an Aphrodisiac? Bill Cullen described how he got into the
arsenic field, and we repeat some of that information here. In 1953, in his
second year at the University of Otago, Dunedin, New Zealand, he listened
to a lecture by Dr Ted Corbett about the organic chemistry of arsenic and
was hooked. Bill knew from a very early age that he was going to be a chem-
ist but not what sort, so this was a very significant event. In 1956 he went
to Cambridge, England, to study for a PhD with Professor HJ Emeleus, who
suggested the study of a new class of arsenic compounds that contained flu-
orocarbon groups. In 1958 Bill accepted a position at the University of British
Columbia, Canada, and began independent research that built on his PhD
thesis. Throughout the ensuing years, arsenic was never very far from his
thoughts.
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Preface vii
Ken Reimer received his PhD from the University of Western Ontario,
Canada, in the field of organometallic chemistry, the interface between
inorganic and organic chemistry. He had always been interested in inter-
disciplinary science, and the role of metals in biological systems led him
Published on 06 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782626633-FP005

to postdoctoral work with Professor Brian James at the University of British


Columbia. It was there that he met Bill Cullen and learned about arsenic
(a metalloid) through the many fascinating discussions of the Bioinorganic
Chemistry Group. Ken began looking at arsenic when he started his first
full-time academic job at Royal Roads Military College in British Columbia,
Canada. The College had begun an oceanography program, and studying
arsenic in the sea and marine organisms was a natural choice for Ken. It also
began a life-long involvement with field work. Later, as Ken moved to the
Royal Military College of Canada in Kingston, Ontario, he became involved
in many applied projects, among them as the scientific authority for the
environmental remediation of the radar sites of the Distant Early Warning
Line—one of Canada’s largest environmental cleanup projects. The problem
there was not arsenic but rather PCB contamination that affected the food
sources of local Inuit. It became important to understand the concerns of
the Inuit and to share knowledge about the problem and possible solutions.
It was during this time that Ken became interested in risk communication,
and some of his most memorable professional experiences have come from
meetings in small community halls in the Arctic. Arsenic was, however,
always part of Ken’s basic research program, and sharing and communicat-
ing the realities of arsenic exposure to the public became a natural next step.
We have tried to write this book so that the non-chemist can follow the
fascinating but complicated story of arsenic in our lives. We hope that the
chemist will also find it instructive even though we have simplified the chem-
istry. We will not try to thank all of the many colleagues who have enriched
our lives along the way for fear of inadvertently leaving someone out, but we
are eternally grateful to all of them. There are some individuals, however,
who made this book possible. Thanks to Dr Iris Koch, our former student,
colleague and friend, who reviewed the entire manuscript and provided help-
ful assistance and encouragement. To Dr Michelle Nearing, Ken’s colleague
and last PhD student before retirement, we offer our gratitude for help with
the figures. John Lawless was always willing to assist with our technical
issues—and there were many—thanks John. Susie Rance, our tireless editor,
kept us focused on making the book grammatically correct, interesting and
accessible to the general audience (somehow “track changes” will never look
the same again). We thank Deborah Reimer for her constant support and
encouragement and for giving up so much golf time to incorporate all of the
references. Ken offers a special thanks to Sapphire and Mya, who reminded
him that one should take time from writing to pet the cats.
Bill Cullen
Ken Reimer
Published on 06 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782626633-FP009

To Sandra
Bill Cullen
Ken Reimer
To Deborah
Published on 06 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782626633-FP011

Abbreviations

ADI a cceptable daily intake BMDL05  ose at which the


d
ALARA as low as reasonably response is likely to be
achievable smaller than 5%
AMA Australian Medical bw body weight
Association CAM complementary and
APL acute promyelocytic alternative medicine
leukemia CFS Center for Food Safety
As3MT arsenic methyltransferase CSF cancer slope factor
As(iii) arsenite (H3AsO3) DMA(v) dimethylarsinic acid
As(v) arsenate (H3AsO4) DOC dissolved organic
As2O3 arsenolite, white oxide (white carbon
arsenic) DPHE Department of Public
As2S3 yellow sulfide, orpiment Health Engineering
As4S4 realgar (red arsenic) (Government of
AsB arsenobetaine Bangladesh)
AsH3 arsine DSHEA Dietary Supplement Health
AsLp arsenolipid and Education Act
AsS arsenosugar dw dry weight
ATSDR US Agency for Toxic EDI estimated daily intake
Substances and Disease EFSA European Food Safety
Registry Authority
AYUSH (Indian) Department of ESPHGAN European Society for
Ayurveda, Yoga and Natu- Paediatric Gastroenter-
ropathy, Unani, Siddha and ology Hepatology and
Homeopathy Nutrition
BMD benchmark dose EU European Union
BMDL lowest dose that might FAO Food and Agriculture
give the particular Organization of the United
response Nations

Arsenic is Everywhere: Cause for Concern?


By William R. Cullen and Kenneth J. Reimer
© William R. Cullen and Kenneth J. Reimer, 2017
Published by the Royal Society of Chemistry, www.rsc.org

xi
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xii Abbreviations
FDA  S Food and Drug
U MMA(v)  onomethylarsonic
m
Administration acid
FSA Food Standards Agency MOA mode of action
(UK) NASA National Aeronautics and
FSANZ Food Standards Space Administration
Published on 06 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782626633-FP011

Australia New Zealand NCCIH US National Center for


HPLC-ICP MS high-performance Complementary and
liquid chromatography Integrative Health
coupled to an induc- NCCN National Comprehensive
tively coupled mass Cancer Network
spectrometer ng nanogram
HQ hazard quotient NGO non-governmental
HRW Human Rights organization
Watch NHP natural health product
IARC International Agency NOAA (US) National Oceanic
for Research on and Atmospheric
Cancer Administration
iAs inorganic arsenic NOAEL no observed adverse effects
IATP Institute for level
Agriculture and NRC (US) National Research
Trade Policy Council
ICDDR,B International Centre NTNC non-transient,
for Diarrhoeal non-community
Disease Research, OBRS organic brown rice syrup
Bangladesh ORV off-road vehicle
IRIS Integrated Risk Infor- PM particulate matter
mation System ppm parts per million
JECFA Joint FAO/WHO Expert PWTI provisional tolerable weekly
Committee on Food intake
Additives RfD reference dose
LD50 lethal dose, 50% ROS reactive oxygen species
(amount of a chemical, SAM S-adenosylmethionine
given all at once, that SNFA Swedish National Food
causes the death of Agency
50% of a group of test T&CM traditional and
animals in a relatively complementary medicine
short time tAs total arsenic
LOAEL lowest observed TCLP toxicity characteristic
adverse effect level leaching procedure
M metre TCM traditional Chinese
MCL maximum medicine
contaminant level TDI tolerable daily intake
MCLGs maximum contaminant TETRA tetramethylarsonium ion
level goals TMA trimethylarsine
mg kg−1 d−1 milligrams per TMAO trimethylarsine oxide,
kilogram of body (CH3)3AsO
weight per day UK United Kingdom
View Online

Abbreviations xiii
UNICEF  nited Nations Children’s
U WHO  orld Health Organization
W
Fund XANES X-ray absorption near edge
US United States structure
US EPA United States Environmental XAS X-ray absorption spectroscopy
Protection Agency µg microgram
Published on 06 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782626633-FP011
Published on 06 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782626633-FP015

Contents

Chapter 1 An Introduction to Arsenic  1

1.1 Some Background  1


References  6

Chapter 2 Arsenic Is Everywhere  8

2.1 I ntroduction  9
2.2 Arsenic in the Earth’s Crust  10
2.3 Arsenic in the Hydrosphere  13
2.3.1 Abundance of Arsenic in Water  13
2.3.2 Factors Influencing the Concentration
of Arsenic in Water  14
2.3.3 Geographical Distribution of High Arsenic
Concentrations in Water and Arsenic-related
Health Effects  17
2.3.4 Water Treatment Technologies for the
Removal of Arsenic  21
2.3.5 Arsenic-Contaminated Water in Bangladesh  23
2.4 Arsenic in the Atmosphere  32
2.4.1 Global Arsenic Circulation  32
2.4.2 Arsenic in Dust  34
2.4.3 Arsenic in House Dust  36
2.4.4 Biovolatilization of Arsenic  36
2.4.5 Hot Springs and Fumaroles as Sources of
Atmospheric Arsenic  38
2.4.6 Biomonitoring for Arsenic in Air  39

Arsenic is Everywhere: Cause for Concern?


By William R. Cullen and Kenneth J. Reimer
© William R. Cullen and Kenneth J. Reimer, 2017
Published by the Royal Society of Chemistry, www.rsc.org

xv
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xvi Contents
2.5 A
 nthropogenic Acts and Disasters as Arsenic
Spreaders  40
2.5.1 Coal Ash Spills  40
2.5.2 Mine Tailings Spills  41
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2.5.3 Unintended Consequences  42


2.5.4 Gold Mining and Arsenic Contamination—
Giant Mine, Canada  42
References  45

Chapter 3 Some Non-Human Arsenic Eaters  49

3.1 I s Arsenic Essential for Life on Earth?  50


3.2 Extraterrestrial Life with Arsenic  51
3.3 Arsenic Is Involved in Life Processes  54
3.3.1 Energy-Generating Oxidation and
Reduction Processes  54
3.3.2 Arsenic Oxidation  57
3.3.3 Detoxification  59
3.4 More Biotransformations of Arsenic  60
3.5 Biotransformation of Arsenic by Bacteria and Fungi  63
3.5.1 Arsenic in Mushrooms  66
3.6 Plants as Arsenic Eaters  67
3.7 Earthworms as Arsenic Eaters  70
3.8 Arsenic Methylation by Mammals (and Others)  72
3.9 Aquatic Organisms as Arsenic Eaters  73
3.9.1 Marine Environment  73
3.9.2 Freshwater Environment  74
3.9.3 The Mystery of Arsenobetaine: Where
Does this Non-Toxic Arsenic Compound
Come From?  74
3.10 A Summary of Arsenic Compounds Found in the
Environment  75
3.11 More on Arsenic Speciation  76
3.11.1 How Do We Detect and Measure Arsenic
Compounds?  76
3.11.2 How Are Different Arsenic Compounds
Made?  78
References  80

Chapter 4 The Toxicity of Arsenic  85

4.1 S ome Background  86


4.2 Acute Arsenic Poisoning  86
4.3 Chronic Arsenic Poisoning  89
4.3.1 Health Effects  89
4.3.2 Early Life Exposure and Long-Term Latency  92
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Contents xvii
4.4 H ow Much Arsenic is Safe?  94
4.4.1 Risk  95
4.4.2 Some Basic Toxicology  95
4.4.3 Risk Assessment  99
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4.4.4 Application of Risk Assessment Information:


US Drinking Water Standard  103
4.4.5 US EPA Reassessment of Arsenic Toxicity  105
4.4.6 Low-Dose Arsenic: In Search of a Risk
Threshold  105
4.5 How Does Arsenic Cause Disease?  108
4.6 Do We Differ in Our Susceptibility to
Arsenic-Induced Disease?  110
4.7 Other Ways of Assessing the Potential Risks
from Arsenic Exposure: An International Perspective  112
4.8 Organic Arsenic Species  114
4.9 Arsenic-Based Pesticides and Herbicides  116
4.9.1 Arsenic Trioxide  116
4.9.2 Lead and Calcium Arsenates  117
4.9.3 Organic Arsenical Pesticides and Herbicides  118
4.9.4 Herbicidal Warfare in Vietnam  119
References  121

Chapter 5 Medicinal Arsenic  129

5.1 E arly Medicinal Uses of Arsenic  130


5.1.1 The Arsenic Eaters of Styria  131
5.1.2 Fowler’s Solution and Other Arsenical
Remedies  136
5.2 Some Help from Traditional Chinese Medicine  139
5.2.1 Acute Promyelocytic Leukemia  139
5.2.2 Realgar and Orpiment  142
5.3 Arsenic Versus Solid Tumours  143
5.4 Organoarsenicals in Medicine  143
5.4.1 Robert Bunsen  144
5.4.2 Aryl Arsenicals  146
5.5 Veterinary Medicine  151
5.5.1 Heartworm  151
5.5.2 Roxarsone and Chickens  151
5.5.3 Phar Lap and Other Horses  155
References  157

Chapter 6 Arsenic and Alternative Medicines  161

6.1 S ome Background on Alternative Medicines  162


6.2 Ayurvedic Medicine (Traditional Indian Medicine)  166
6.3 Traditional Chinese Medicine  172
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xviii Contents
6.4 A Word on Aphrodisiacs  177
6.5 Homeopathy  179
6.6 “Cures” for Chronic Arsenic Poisoning  184
References  185
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Chapter 7 Arsenic in Food  190

7.1 S ome Early History  191


7.2 The Arsenic Content of Food  193
7.3 The Significance of Arsenic Speciation to
Exposure to Arsenic in Food  197
7.3.1 Arsenic Speciation  197
7.3.2 How Do We Find Out What Arsenic Species
Are In Our Food?  201
7.4 How Much Arsenic Do We Eat?  202
7.4.1 Dietary Surveys of Total Arsenic and
Inorganic Arsenic  202
7.4.2 Global Dietary Exposures to Inorganic
Arsenic  207
7.5 Does the Arsenic We Eat Pose a Risk or Not?  211
7.5.1 Some Background  211
7.5.2 The Views of International Regulatory
Agencies  211
7.5.3 Global Incidence of Cancer  213
7.5.4 What Is an Acceptable Risk Due to Arsenic
in Our Food?  214
7.5.5 Are There Regulations Governing How Much
Arsenic There Can Be in Food?  215
7.5.6 Summary  216
References  217

Chapter 8 Arsenic and the Evening Meal  221

8.1 A n Invitation to Dinner  221


8.2 The Pre-Dinner Cocktail Hour  222
8.2.1 A Pre-Dinner Drink?  222
8.2.2 Bottled Water  226
8.2.3 A Cigarette with that Cocktail?  227
8.3 The Salad: A Heaping Serving of Vegetables and
Mushrooms  228
8.4 The Fish Course  230
8.4.1 Health Benefits Versus Risks of Eating Fish  230
8.4.2 Unknowns: What About Other Organic
Arsenic Compounds in Fish?  233
8.4.3 A Myth Regarding “Toxic” Shrimp
and Vitamin C  234
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Contents xix
8.4.4 A lgal Products and Other Seafoods with
High Inorganic Arsenic Content  235
8.5 The Meat Course: Beef, Pork or Chicken?  237
8.6 Some Starch on Your Plate? Wheat, Maize (Corn)
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and Potatoes  241


8.7 The Rice Story  241
8.7.1 Some Background  241
8.7.2 Arsenic in Rice  242
8.7.3 Concerns Regarding Arsenic Exposure
from Rice: Europe  244
8.7.4 Arsenic in Rice: The US Experience  246
8.8 Dessert and a Nightcap  253
8.9 A Post-Dinner Chat  255
Appendix 8.1 European Guidance on Rice
Consumption  255
References  257

Subject Index  266


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Chapter 1

An Introduction to Arsenic

This chapter provides an introduction to the element arsenic and to its posi-
tion in the consciousness of the general public as number one in the poison
index. Its association with poison has even led to the satirical suggestion
that it should be removed from the chemistry periodic table—this despite
the fact that it is one of the natural elements that make up the Earth. Many
people are uncomfortable with chemicals, and within this general che-
mophobia, arsenophobia has a particularly powerful position. The associ-
ation has been used to great effect in plays such as Arsenic and Old Lace, but
has also been used to add emotional wallop to sell everything from lingerie
to paint to music. This chapter reinforces how arsenic is uniquely embedded
in our social fabric, probably to a greater degree than any other element.

1.1 Some Background


This book is an updated and more focused follow-up to Is Arsenic an Aphrodi-
siac? The Sociochemistry of an Element, by co-author W. R. Cullen, published
by the Royal Society of Chemistry in 2008.1 The 2008 book covered a wide
range of topics, some of which will not be revisited here because we feel that
enough has been said about, for example, arsenic’s role in crime (a substan-
tial role), chemical warfare (also substantial), sudden infant death syndrome

Arsenic is Everywhere: Cause for Concern?


By William R. Cullen and Kenneth J. Reimer
© William R. Cullen and Kenneth J. Reimer, 2017
Published by the Royal Society of Chemistry, www.rsc.org

1
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2 Chapter 1
(not involved), and the death of Napoleon (a myth). Some mention will be
made of other topics previously covered when necessary, to place them in con-
text and add new information, but otherwise the material and the approach
in this volume are different with more of a focus on sociochemistry, which we
define as what takes place at the interface between society and chemistry. We
Published on 06 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782626633-00001

are convinced that arsenic has the broadest, deepest and most fascinating
sociochemistry of all of the elements. As the interface between society and
arsenic is demonstrated largely by the effects of arsenic on life, human and
other, this work explores primarily how we are all exposed to arsenic in one
form or another and examines whether this exposure is a cause for concern.
To begin, the word “arsenic” appeared in the English language in 1389.2
Arsenic is one of the 98 natural elements (Box 1.1) that make up our universe
and ranks somewhere between 46th and 54th in the composition of the earth’s
crust, between 24th and 28th in seawater, and about 31st in the human body.3
However, it is firmly fixed at number one in the mental poison index of most
of the world’s inhabitants, even though quite a few other elements and their
compounds are much more toxic (think, for example, of non-toxic carbon as dia-
mond and carbon dioxide and toxic carbon as strychnine and sodium cyanide).
“Toxic arsenic” has become embedded in our social fabric, for good and
for ill, as is exemplified in a very old (and corny) joke:
  
A woman walks into a drugstore and asks the pharmacist for some arsenic.
“Ma’am, what do you want to do with arsenic?” asks the pharmacist.
“Kill my husband,” answers the woman.
“I can’t sell you arsenic to kill a person.”
The lady lays down a photograph of a man and a woman in a very compro-
mising position. The man in the picture is her husband and the woman
is the pharmacist’s wife. He takes the photograph in his hand and nods.
“I didn't realize you had a prescription.”
  
Arsenic has become so synonymous with poison that Pulitzer Prize-
winning author Deborah Blum is sure of the answer when she asks in a blog
post, Is arsenic the worst chemical in the world?4 In a satirical piece, some par-
ents of school children in Colorado, United States, suggested that arsenic
should be removed from the ubiquitous charts known to chemistry students
as the periodic table of the elements. Such negative reactions are part of a
widespread aversion to, and even fear of, chemistry and chemicals, regardless
of the actual danger that they pose. This fear even has a name: chemophobia.
Chemophobia is well acknowledged by society as a whole. According to
science writer Valerie Brown,5 “individuals mentally assess risk in a similar
way, but risk perception is shaped by several largely unconscious emotional
processes shared by scientists and non-scientists alike. The human brain
is hard-wired to react quickly and defensively to perceived threats of any
kind. This includes physical threats, sights, sounds, smells, and even words
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An Introduction to Arsenic 3

Box 1.1 Alchemical symbols.

Many symbolic designations for arsenic have been used through his-
tory beginning with alchemy. Alchemy came to the western world from
China and India in the Middle Ages. Alchemists were primarily interested
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in transforming base metals, such as lead, into precious metals, such as


silver and gold. They developed a secret writing system to prevent oth-
ers from stealing their work and in the process devised symbols to repre-
sent the elements (some even hid their secrets in musical notation). One
alchemical symbol for arsenic is shown at the head of this chapter, and
others are used in subsequent chapter headings (all of these can be viewed
on the website of the Royal Society of Chemistry). T-shirts decorated with
these symbols are available on the Web. The modern chemical symbol for
arsenic, “As,” is also prominently featured on clothing, much of which is
designed by Arsenic Addiction. One of the authors of this book occasion-
ally wears an “Arsenic Tester” T-shirt, a gift from a conference attendee.
Modern chemical symbols provide a shorthand abbreviation for the ele-
ments. Some of these are easier to understand than others—for example,
C for carbon—but others, such as Pb for lead, are less obvious because
they have their origins from another language (the original Latin name
for lead was plumbum).
The elements of most relevance to this book include the following:
As for arsenic P for phosphorus N for nitrogen
S for sulfur O for oxygen Si for silicon

or memories associated with fear or danger. For example, the word ‘chemi-
cals’ has been shown to trigger an unconscious fear reaction in members of
the general public, leading to chemophobia.” Arsenophobia is this emotion
focused on this particular element.
This general association of arsenic with poison began to emerge at the
time of the industrial revolution of the 1700s, when arsenic trioxide for use
as a rat poison became easily accessible, as described in Chapter 2 of Cullen’s
2008 book.1 All details of the numerous criminal poisoning trials involving
the use of arsenic were reported in the popular broadsheets, whose authors
pandered to the basest interests of the general public.
When the World Health Organization (WHO) moved ultraviolet light tan-
ning beds to its highest cancer risk category in 2010, the message was publi-
cised by comparing the danger with that of arsenic: “Tanning beds as deadly
as arsenic.” That same year, political pundit John Feehery wrote that US Pres-
ident Obama had said about the stimulus package that it was “the best thing
since sliced bread [but that the] Republicans say it was the worst thing since
the invention of arsenic.” And, still in the United States, Republican Karl Rove
accused the Democrats of adding “arsenic to the nation’s political wells.”6
Then there is the term “the arsenic hour,” which first appeared in 1975 and
which refers to the time of day when both children and parents have come
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4 Chapter 1
home tired and hungry (though what the use of arsenic might be in the par-
ents’ minds during this hour is open to conjecture):

Between the nap and the twilight


Published on 06 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782626633-00001

When blood sugar is starting to lower,


Comes a pause in the day’s occupations,
That is known as the Arsenic Hour.7

But arsenophobia is not restricted to the general public—even scientists


have the disease. The arsenic entry in the Periodic (Table of) Videos, pro-
duced by a well-known team based at the University of Nottingham, UK,8
provides an extreme example. The phrase “toxic” is used numerous times,
incorrectly, in the video in relation to a vial of elemental arsenic.
Elemental arsenic is in fact not toxic to humans, but a few arsenic com-
pounds are very toxic and have been used for criminal purposes from the
time of the ancient Romans to the present day. This negative view of the ele-
ment has been reinforced in the crime fiction of authors such as Dorothy
Sayers and Agatha Christie. Arsenic also plays a major role in more serious
fiction, such as in the classic American short story “A Rose for Emily” by Nobel
Prize–winning author William Faulkner (1949) and in Gustave Flaubert’s
Madame Bovary. But the biggest contributor to the image continues to be
the play Arsenic and Old Lace by Joseph Kesselring, a perennial favourite first
performed on Broadway in New York in 1941 and followed by a very popular
movie version released in 1944. The play was inspired by the case of multiple
poisoner Amy Archer Gilligan, who in life was not at all like the sweet and
kind Brewster sisters (for details, see Chapter 5 in Cullen’s 2008 book).
The phrase “arsenic and old lace” has become a cliché and has spawned
numerous books and articles, with titles such as “Arsenic and Old Lead”
(environmental cleanup), “Arsenic and Old Mustard” (chemical weapons)
and “Arsenic and Old Myths” (the history of chemistry). On the less seri-
ous literary side, we find Arsenic Lullaby, a blacker-than-black comic book
series by Douglas Paszkiewicz, and Arsenic Soup for Lovers: When Chicken Soup
Doesn’t Work, by Georgia Z Post, which “contains very short stories for very
busy people with emphasis on the darker side of human nature.” And these
are available to read in bed at the Arsenic and Old Lace Bed and Breakfast in
Eureka Springs, Arkansas.
In academic circles, Arsenic Lobster is the name of a website used by
Columbia College Chicago poetry students, and the Ladies Underground Tea
& Arsenic Society at the University of Southern Maine is a group dedicated to
the discussion of current politics, literature, body image issues (and more!).
Amethyst Arsenic is an online publisher of poetry, art and music, and Arsenic
Mag “lives at the intersection of sexy and artistic.”
Speaking of “sexy” associations: The Belgium-based lingerie label Arsenic
et Vieilles Dentelles (Arsenic and Old Lace) appeared in 2013, “bringing you
to taste, in total freedom, the beauty of a forbidden poison.”9
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An Introduction to Arsenic 5
The Lady Arsenic & Tickety Bob Boutique is the merchandise arm of the
band Arsenic Addiction (more on them below), but if you don’t find what you
like there, you could try Arsenic Lace, A is for Arsenic or Arsenic Fashions
for your alternative apparel and accessories, or West 49, a Canadian retailer
that has the banner Amnesia/Arsenic. The Arsenic & Old Lace Occult Shop is
Published on 06 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782626633-00001

dedicated to providing quality products and advice to the pagan and Wiccan
communities, while Arsenic Number 17 by TOYKOMILK is the rather sur-
prising name of an “unusual aromatic fragrance of rich and exciting dark
components.”
The “A word” has such an emotional wallop that it can be used to sell
almost anything. It can be used to create brand recognition through an asso-
ciation with fear or anxiety about the product, and clever marketers have
capitalized on this reflex. For example, Apple goes to great lengths to sell its
products as “green” and environmentally friendly and tells customers that its
glass is arsenic-free (while neglecting to mention that it uses arsenic in the
electronic components).
The musical world, especially its darker side, seems to be fascinated by
the idea of arsenic. Arsenic of Jabir is a band whose words are “laced with
metaphors, ambiguity, cryptic historical references and sometimes dry, even
black humour.” The name makes reference to the Arabian alchemist Jabir ibn
Hayyan, who was known as Geber, the first to prepare arsenic trioxide. The
band Arsenic Addiction, described on its website as “dedicated to the dead as
opposed to the living,” has an album titled “An Undertaker’s Lament,” which
contains tracks titled “Lady Death Narcissus,” “Black Lullaby” and “Scream
of the Banshee.” Arsenic Addiction also throws a live show that is described
as an interactive funeral mass featuring an after-service teatime and Victo-
rian pornography.
Chad Urmstone of the band State Radio wrote the song “Arsenic and
Clover,” which is based on his experience of catching a parasite in Zimbabwe
and taking what might have been arsenic in the form of a local remedy to kill
the bug.
Arsenic is also the name for a pricey paint colour available from a high-
end English paint company, Farrow and Ball. We quote company director
Sarah Cole: “The name of our vibrant green paint, Arsenic, makes reference
to Napoleon in a playful way. The green verdigris colour was first used as
the ground for our Napoleonic Bee Wallpaper; however, Napoleon was also
thought (mistakenly) to have been poisoned by the arsenic used to make the
pigment for the green wallpaper in his bathroom in St. Helena.”10
Elizabeth Miller, a marketing professor at the University of Massachusetts–
Amherst, co-wrote a 2006 study about strange colour and flavour names.
They found that consumers preferred these ambiguous names in the world
of hedonic products. “When they’re thinking about what does this mean,
or trying to solve the puzzle of why was this particular name used, you get
a boost in interest in both cases.”11 Thus the educated target market for the
paint colour called Arsenic can give themselves a pat on the back for making
the (even if incorrect) connection between Napoleon, arsenic and the colour
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6 Chapter 1
green (while dipping deep into their pockets). But why would KHE Bikes &
BMX Parts name bike parts the Arsenic Fork and the Arsenic Handlebar?
Possibly an attractive association with danger?
Finally, to revert to childhood innocence, some of us grew up listening
to side-splitting jokes that depended on punch lines containing the phrase
Published on 06 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782626633-00001

“arse a nic.” So we will have some sympathy for a well-known chemist who in
the 1920s invested a lot of time trying to synthesize the arsenic equivalent of
an organic molecule named indole, only to have his efforts frustrated by the
nomenclature committee, which decided that the compound he had finally
prepared should be named “arsindole” rather than “arsole.” Some years later,
the committee could not escape awarding the name “arsole” to an even more
deserving compound, featured prominently in the advertising campaign of a
major chemical supplier, Synthonix.
We hope that this brief introduction has whet your appetite to learn more
about arsenic. It will surprise many that arsenic is all around us, as it is part
of our natural environment and is not just present as a result of human activ-
ity (Chapter 2). In Chapter 3 we will see how the US National Aeronautics
and Space Administration (NASA) thought (erroneously) that arsenic could
act as a substitute for phosphorus, thereby paving the way for some unusual
extraterrestrial life. We will learn, however, that arsenic can be used in life
processes and that many organisms, from bacteria to plants to people, can
transform arsenic compounds into different ones. There is no question that
arsenic can be poisonous, but the health risks depend on the amount we
are exposed to (the dose) and the arsenic compound; one arsenic-containing
compound that we frequently consume in food is completely non-toxic (Chap-
ter 4). The use of arsenic in medicines and alternative remedies is explored in
Chapters 5 and 6, respectively. Since arsenic is present everywhere, it is logi-
cal to expect to find it in our food and drink (Chapter 7), despite the “shock”
that the media expresses when there are reports of arsenic in our apple juice,
wine, chicken and rice. In Chapter 8, we issue a dinner invitation and pro-
vide a look at the arsenic we might be putting on our plates. It is important
to realize that we are all exposed to arsenic and to understand under which
circumstances exposure to arsenic may or may not pose a real health con-
cern, rather than the perception of one.

References
1. W. R. Cullen, Is Arsenic an Aphrodisiac? The Sociochemistry of an Element,
Royal Society of Chemistry, 2008.
2. S. M. Gerber and R. Saferstein, More chemistry and crime: From marsh
arsenic test to DNA profile, American Chemical Society, 1997.
3. J. Tyson, ISRN Anal. Chem., 2013, 2013, 24.
4. D. Blum, 2012, http://www.wired.com/2012/06/is-arsenic-the-worst-
chemical-in-the-world/.
5. Reproduced from Environmental Health Perscpectives: V. J. Brown, Envi-
ron. Health Perspect., 2014, 122, A276, Reproduced from Environmental
Health Perspectives http://ehp.niehs.nih.gov/122-a276/.
View Online

An Introduction to Arsenic 7
6. K. Rove, Wall St. J. Eur., 2010, http://www.wsj.com/articles/SB1000142405
2748703735804575535701710358606.
7. M. Kelly and E. Parsons, The Mother's Almanac I, Main Street Books, 1975.
8. Chemists at the University of Nottingham, Periodic Table of Videos,
http://www.periodicvideos.com/.
Published on 06 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782626633-00001

9. Arsenic et Vieilles Dentelles, http://arsenicetvieillesdentelles.com/.


10. P. Green, N. Y. Times, 2011, http://www.nytimes.com/2011/10/20/garden/
eve-ashcraft-the-paint-doctor-is-in.html?_r=0.
11. E. G. Miller and B. E. Kahn, J. Consum. Res., 2005, 32, 86.
Published on 06 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782626633-00008

Chapter 2

Arsenic Is Everywhere

When most people hear the word arsenic, they think of poison and assume
that its presence is human-caused, so it may come as a surprise to learn that
arsenic is found naturally in our rocks, soil, water and air. This chapter pro-
vides information about the sources of arsenic, natural and anthropogenic,
in our world and the amount we might expect to find in different environ-
ments. It is true that exposure to a certain amount of arsenic can kill fairly
quickly, but because it is colourless, odourless and tasteless, people can reg-
ularly consume sub-lethal amounts in drinking water without knowing it is
present. This “chronic exposure” can lead to a range of health effects, from
skin lesions to cancer. Much of what we know about the effects of chronic
exposure has been learned since the 1980s, through studies of regions such
as Bangladesh, where even today 20 million people are impacted by naturally
occurring arsenic in drinking water. The chapter describes how some micro-
organisms convert arsenic in soil into a gaseous form that is released to the
atmosphere, a process that plays an important role in global arsenic circula-
tion, and concludes with examples of arsenic releases into the environment
caused by human decisions and mistakes.

Arsenic is Everywhere: Cause for Concern?


By William R. Cullen and Kenneth J. Reimer
© William R. Cullen and Kenneth J. Reimer, 2017
Published by the Royal Society of Chemistry, www.rsc.org

8
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Arsenic Is Everywhere 9

2.1 Introduction
Contrary to public perception, arsenic is not found in the environment only
as a result of human activity—it is everywhere in our environment and is
naturally present in rocks, soil, water and air. In this chapter, we look at the
Published on 06 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782626633-00008

distribution of arsenic in the world around us as a consequence of natural


processes and as a result of human actions. For the non-chemists, some
basic chemistry principles can be found in Box 2.1.

Box 2.1 Some basic chemistry.

It is not necessary to be a chemist to follow the main ideas in this book,


but there are some fundamental principles of chemistry that will help you
gain a better understanding of the information and an appreciation of
what we are talking about.
The Earth is made up of elements, of which there are 98 that are natu-
rally occurring. Another 20 elements are officially recognized but are only
produced by scientists, usually by colliding atoms together in a particle
accelerator, and they last for only a few moments (this may sound unusual,
but the successful team gets bragging rights and is able to name the new
element). About 25 of the naturally occurring elements are required for
life, and 96% of the human body is composed of just four of these: carbon
(C), hydrogen (H), nitrogen (N) and oxygen (O).
An element is the simplest type of matter with unique physical and
chemical properties. It is composed of atoms, which contain protons
(which are positively charged), electrons (negatively charged) and usu-
ally neutrons (not charged). An element is identified by the number of
protons it has; this number is called its atomic number. A compound
consists of two or more elements that are bonded chemically. This means
that the elements are not just mixed together; their atoms have joined
together in a specific proportion through a chemical reaction. Each
unit of a compound consists of a fixed number of atoms of each ele-
ment; the number of atoms is represented by the subscripts in a chemi-
cal formula, and this number is always the same for this compound. For
example, As2O3 is composed of two atoms of arsenic and three atoms
of oxygen.
One of the most important features of a compound is that its properties are
different from those of its constituent elements. This allows just under 100
elements to produce such a wide variety of different compounds, each
with its own physical, chemical and toxicological properties. This is the
reason that arsenic compounds (which we collectively call arsenicals) vary
in their toxicity, from highly toxic to harmless.
We often confuse the concept of compounds with mixtures. Mixtures
can have a variable composition, and their properties are dependent on
how much of each component is added. For example, the “chocolatiness”
(continued)
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10 Chapter 2

Box 2.1 (continued)

of a cake will depend on how much cocoa was added. A slurry of mud and
water will vary in its “muddiness” depending on the relative amounts of
water and soil present.
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To summarize, a chemical compound has a fixed composition and its


own unique properties, in contrast to a mixture, which can have a variable
composition and which retains some properties of its constituents.

2.2 Arsenic in the Earth’s Crust


The natural concentration of arsenic in the Earth’s crust is about 2 ppm
(2 mg of arsenic per kilogram of crust). However, concentrations in some
sedimentary rocks, such as sandstone, can be as high as 900 parts per
million (ppm).1 (See Box 2.2 for a discussion of units such as ppm.) Elemen-
tal arsenic, although not common, is occasionally found in veins in some
rocks. Arsenic is more commonly found in combination with other elements
like iron, oxygen, and sulfur, forming minerals numbering more than 200.2,3
The most common of these is arsenopyrite (FeAsS), also known as mispickel
(a name borrowed from German). Two sulfides (compounds comprising
arsenic combined with sulfur)—realgar (As4S4), which is red, and orpiment
(As4S6), which is yellow—are also common arsenic-containing minerals. The
white arsenic oxide (As2O3) occurs in two mineral forms, arsenolite and clau-
detite. Although it is not an arsenic mineral, iron pyrite (FeS2), also known as
“fool’s gold,” can contain up to 4% of the element. Arsenian (“arsenic-rich”)
pyrite (Fe(S,As)2) is probably the largest source of arsenic in ore deposits. Nat-
urally high arsenic concentrations can also be found in many oxide minerals
in which the arsenic is part of the mineral structure or is adsorbed to it; this
is particularly true of iron and manganese oxides. (We can think of adsorp-
tion as the “sticking” of something to the surface of something else.) Arsenic
also adsorbs to clays, especially those with high iron content.
Arsenic is also found in coal, sometimes in quite large quantities. Concen-
trations in coal of between 2.5 and 17 ppm are common, but up to 35 000
ppm has been reported. Crude oil contains less arsenic—from 0.002 to 1.6
ppm. Combustion of fossil fuels redistributes arsenic in the environment.
Another anthropogenic (human-caused) redistribution occurs in the pro-
cess of mining of gold, which is often found in association with arsenic min-
erals, especially arsenopyrite: the gold recovery process results in several
arsenic-contaminated by-products, usually with very high arsenic concentra-
tions.2,4 These two anthropogenic contributions of arsenic to the environ-
ment are discussed in more detail in Section 2.5.
Apart from volcanic activity, weathering of minerals through wind and
water erosion is the main way in which arsenic is distributed (mobilized) into
soil, water and air. Once there, the arsenic can become transformed through
a variety of chemical or biological (biogeochemical) processes, a subject that
will be discussed in Chapter 3.
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Arsenic Is Everywhere 11

Box 2.2 Some units of concentration.

Throughout this book, we discuss the amount of arsenic that is present in


various media, such as water, soil and food. Scientists use a variety of ways
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to express amount; we use an approach that is common in environmental


science, referring to the concentration of arsenic in the substance con-
taining it: parts (of arsenic) per million (parts of substance it is in) (ppm)
or parts per billion (ppb).
You will be very familiar with percentages, which are parts per hun-
dred; 1% is one part in 100 parts, or 1 in 100. We convert numbers to
percentages by multiplying the ratio of two numbers by 100. For exam-
ple, 10 marks out of a total of 20 marks on a test = 10/20 × 100 = 50 parts
per 100, or 50%.
One part of something in a million parts = 1 part per million = 1 ppm.
The concentration of one milligram (mg), which is 1/1000 of a gram (g),
of arsenic in one kilogram (kg), which is 1000 g, of a mineral would be cal-
culated as follows: 1 mg/1 kg = 0.001 g/1000 g = 1 g/1 000 000 g, or 1 ppm.
One part of something in a billion parts = 1 part per billion = 1 ppb. If
we had one microgram (µg) (one millionth of a gram) in one kilogram of
mineral, the concentration would be 1 µg per 1 kg = 0.000001 g per 1000 g
= 1 g per 1 billion = 1 ppb.
Thus far, our examples are on a solid mass-to-solid mass basis, but we
can use the same approach for examining concentrations of arsenic in
water. One litre of water has a mass of 1 kg, so 1 µg arsenic in a litre of
water = 1 µg per 1 kg, which, using the calculation described above, would
mean an arsenic concentration of 1 ppb.
One drop of water in a car’s gas tank would mean a water concentration
in the gas of about 1 ppm, but if there were one drop of water in a large
tanker truck full of gas, the water concentration would be more like 1 ppb,
one one-thousandth of the concentration in the car. As you can proba-
bly visualize, these concentrations are quite low. But note that 10 ppb is
commonly used as the maximum acceptable concentration for arsenic in
drinking water.
To summarize:
1 milligram in a kilogram = 1 mg per kg = 1 ppm; 1 microgram in a kilo-
gram = 1 µg per kg = 1 ppb.
1 milligram in a litre = 1 mg per L = 1 ppm; 1 microgram in a litre = 1 µg
per L = 1 ppb.
Some additional conversions that may be useful:
1 kg = 1000 g = 2.2 pounds.
1 mg = one thousandth of a gram.
1 µg = one millionth of a gram.
1 L = 1000 millilitres (mL) = 0.26 US gallons = 0.22 imperial gallons.
1 mL = one thousandth of a litre.
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12 Chapter 2
Soils are complex mixtures of eroded minerals, organic matter, water and
other substances. The arsenic content of soil typically reflects the erosion
of arsenic-containing minerals as well as any anthropogenic inputs. Normal
concentrations of arsenic in surface soil worldwide are between 5 and 10
ppm, with an average of around 7 ppm, but there can be tremendous vari-
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ability, depending on the local geology.1 This is evident in an example for the
continental United States.
The US Geological Survey created one of the most detailed maps of arsenic in
soil anywhere in the world.5 The data were obtained by sampling soil in nearly
5000 US locations, from various depths (including the 5 cm of surface soil) each
sampling location representing an area of 1600 km2. The average arsenic con-
centration found was 6.4 ppm, but the range for uncontaminated sites (that is,
where arsenic is naturally occurring) is very large, from less than 0.6 ppm to 830
ppm (see Figure 2.1). There are some very lightly shaded areas on the map where
arsenic concentrations are less than 0.6 ppm (for example, in Florida), but there
are also several dark locations (for example, in the northeastern United States)
where the arsenic concentration of soil is in the highest category (15–717 ppm).
As no soil samples were collected from within 5 km of major industrial facilities,
this variability can be attributed mainly to natural processes.
It is important to realize that almost all soil contains some arsenic. This
may come as a surprise to many people, as we have become accustomed to the
idea that the presence of arsenic is due only to human intervention, but this

Figure 2.1 
Arsenic concentrations in surface soils (0–5 cm) in the continental United
States. (Produced using data available from the United States Geological
Survey.5).
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Arsenic Is Everywhere 13
is not the case. There is no question, however, that anthropogenic practices,
such as the historical use of arsenic-based pesticides, the release of gold min-
ing wastes and the combustion of fossil fuels, can add the amount of arsenic
in the surrounding environment. Arsenic concentrations in the hundreds to
multiple thousands of ppm have been found in industrially contaminated soil
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(soil affected by mines, chemical factories, etc.). Later in this chapter we give
the example of the legacy left by a large gold mine (Section 2.5.4).
In Chapter 4, we examine how potential hazards caused by exposure to arse-
nic in soil are assessed and how soil quality criteria (maximum acceptable con-
taminant levels) are derived. For the moment, it is important to know that very
little arsenic is absorbed through the skin (dermal absorption). Accidental soil
ingestion can certainly occur, especially when children are playing outside and
put dirty hands in their mouths, but most of the arsenic that we find naturally
occurring in soil is not very bioavailable—that is, most of the arsenic passes
through us without being absorbed into the blood stream. This is not always
the case, however, for soil impacted by industrial activity.

2.3 Arsenic in the Hydrosphere


2.3.1 Abundance of Arsenic in Water
The arsenic concentration in seawater is very constant, at 1–2 ppb, except in estu-
arine areas (where seawater and river water meet), where it can be influenced by
shoreline discharges or by rivers impacted by mining or other industrial effluent.
In freshwater, the concentration range spans four orders of magnitude, ranging
from less than 0.5 ppb to more than 5000 ppb. On occasion, even the top of this
range can be exceeded in groundwater (water below the surface of the Earth,
such as that accessed by wells).2 To give these numbers some perspective, the
standard for maximum arsenic concentration in drinking water adopted by the
World Health Organization (WHO) and many other countries is 10 ppb.
Rivers typically have low arsenic concentrations (less than 1 ppb), espe-
cially in areas with only small amounts of arsenic in the bedrock. Higher
values—for example, between 10 and 70 ppb—occur where there are inputs
of arsenic from geothermal sources such as hot springs and geysers (for
example, in the western US and New Zealand). In an arid part of Chile, arse-
nic levels in a river have been seen to reach 21 800 ppb as a result of geo-
thermal input of arsenic combined with evaporation of the water during dry
periods, which further concentrates the arsenic. The amount of arsenic in
rivers can be influenced by industrial effluent; concentrations of many hun-
dreds of ppb have been found in river water downstream from gold mines.
The concentration of arsenic in lakes is generally either similar to or lower
than that found in river water. Exceptions are closed lakes that are subject to
high evaporation and/or geothermal inputs; an example of the combination
of these effects is the large, shallow, salty Mono Lake in California, where
arsenic levels reach 10 000–20 000 ppb.
Typical concentrations of arsenic in groundwater around the world are less
than 10 ppb, but there are instances where the concentration is extremely
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Andrews
ANDRÉE
Andrée
aneurysms
anew
ang
angareb
Angel
Angeles
Angelo
anger
angered
Angiolillo
angle
angles
Anglican
Anglicans
Anglo
Angmagsalik
Angola
Angoni
Angoniland
Angora
angry
anguish
Anhui
animal
animals
animate
animated
animosities
animosity
animus
Anio
Ankaratoa
Ankauf
Anna
Annals
Annam
Annapolis
Anne
annex
annexation
annexationists
annexations
Annexed
annexing
annihilate
annihilated
annihilation
Anniversary
anno
announce
announced
Announcement
announcements
announces
announcing
annoyance
annoyed
annoying
Annschütz
annual
annually
annuities
annul
annull
annulled
annulling
annulment
annuls
annum
anointed
anomalous
Anopheles
another
answer
answerable
answered
Answering
answers
antagonism
antagonist
antagonistic
antagonists
antagonize
antagonized
antagonizing
Antananarivo
ANTARCTIC
ante
antecedents
Antemnae
ANTEMNÆ
Antemnæ
Anthem
Anthoine
Anthony
Anthoüard
Anthracite
anthrax
Anthropological
Anthropology
Anti
anticipate
anticipated
anticipates
Anticipating
anticipation
anticipations
ANTIGUA
Antilles
antipathy
antipodes
antiquarian
antiquaries
antiquary
antiquated
antique
Antiquities
Antiquity
Antisemitic
antisepsis
Antiseptic
antithesis
antitoxin
Antitoxine
Anton
Antonio
ants
Antwerp
Anvers
Anvil
anxieties
anxiety
anxious
anxiously
any
anybody
Anyone
anything
anywhere
anywise
Anzeiger
Anæsthetics
ao
Aoki
aorta
apace
Apache
Aparicio
apart
apartments
apathy
apex
aphasia
aphasic
Aphthonios
Apia
apiece
Apokorona
apologetic
apologia
apologies
apologising
apology
Apostle
Apostles
Apostolic
apostolical
Apostolici
Apostolicæ
appalling
apparatus
Apparent
apparently
appeal
appealed
appealing
Appeals
appear
appearance
appearances
appeared
appearing
appears
appease
appeased
appeasing
appellant
appellants
appellate
appellation
appellations
appendage
appended
appendicitis
Appendix
appertain
appertaining
appetite
applaud
applauded
Applauding
applause
apples
Appleton
appliances
applicable
applicant
applicants
application
applications
applied
applies
apply
Applying
appoint
appointed
appointee
appointees
Appointing
appointive
appointment
Appointments
appoints
Apponyi
apportion
apportioned
apportioning
Apportionment
apportionments
appraised
appraisement
Appraisers
appreciable
appreciate
appreciated
appreciates
appreciating
appreciation
apprehend
apprehended
apprehending
apprehension
apprehensions
apprehensive
Apprentices
apprenticeship
apprise
apprised
approach
approached
approaches
approaching
approbation
appropriate
appropriated
appropriately
appropriateness
appropriates
appropriating
Appropriation
appropriations
Approval
approve
approved
approves
approving
approximate
approximated
approximately
approximates
approximating
approximation
appurtenance
appurtenances
appurtenant
Apra
April
apt
Apthorp
aptitude
aptly
aqueduct
AQUILA
aquiline
Arab
Arabe
Arabia
Arabian
Arabic
arable
Arabs
Araneto
Arayat
Arbiter
Arbitral
arbitrament
arbitrarily
arbitrariness
arbitrary
arbitrate
arbitrated
arbitrating
ARBITRATION
Arbitrator
arbitrators
arbitrium
ARC
arcading
arch
archaeological
archaeology
Archangel
Archbishop
Archbishops
archduchies
Archduke
archeological
archeology
Archibald
ARCHIPELAGO
archipelagoes
Architect
architects
architectural
architecture
architraves
archive
archives
Archivist
ARCHÆOLOGICAL
archæological
archæologist
Archæology
Archœology
Arctic
Arcy
Ardagh
ardent
ardently
ardor
arduous
are
area
areas
Arecibo
Arellano
arena
Areopagus
Argentina
Argentine
Argentines
argon
argue
argued
arguing
Argument
argumentatively
arguments
Argun
Argyle
Argyll
Arian
Arica
arid
Arikis
Ariokh
arise
arisen
arises
arising
aristocracy
aristocratic
arithmetic
arithmetical
Arithmetically
Arizona
Ark
ARKANSAS
Arku
arm
armament
armaments
Armand
armchairs
armed
Armenia
Armenian
Armenians
armes
Armies
arming
armistice
Armistices
Armitage
Armitt
Armored
armories
armory
Armour
Armoury
arms
Armstrong
ARMY
armée
Arnawai
Arnold
arose
Around
arouse
aroused
arousing
Arpad
arraign
arraigned
arraigning
arraignments
arrange
arranged
Arrangement
arrangements
arranges
arranging
array
arrayed
arrears
Arrest
arrested
arresting
arrests
Arretez
arrival
arrivals
arrive
Arrived
arrives
arriving
arrivé
arrogance
arrogant
arrogate
arrogated
arrows
Arrêté
arsenal
arsenals
Arsenio
arson
Arsène
ART
Artacho
arterial
arteries
artery
ARTHUR
Article
articles
artifice
artificer
Artificial
artificiality
artificially
ARTILLERY
artillerymen
artisans
artist
artistic
artistically
artists
artizans
arts
As
ASA
ascend
ascendancy
ascendant
ascended
ascendency
ascending
ascends
Ascension
ascent
ascertain
ascertained
ascertaining
ascertainment
Asch
ascribe
ascribed
ascribes
ascribing
Asehkenazim
aseptic
Aserraderos
Ash
ashamed
Ashanti
Ashantis
Ashbel
ashes
Ashmolean
ashore
ASIA
Asian
Asiatic
Asiatics
aside
Asingan
ask
Askalon
Asked
asking
asks
Asmar
Asnyk
Asoka
aspect
aspects
aspersed
asphalt
asphyxiating
aspirant
aspirants
aspiration
aspirations
aspire
aspired
aspiring
assail
assailant
assailants
assailed
assailing
Assam
assassin
assassinate
assassinated
assassination
ASSASSINATIONS
assassins
Assault
assaulted
assaults
assemblage
assemble
assembled
assembles
assemblies
assembling
assembly
assemblymen
assent
assented
assents
Asser
assert
asserted
asserting
assertion
assertions
asserts
assess
assessed
assessing
assessment
assessments
asset
assets
assign
assigned
assigning
assignment
assigns
assimilate
assimilated
assimilation
Assiout
Assisi
assist
assistance
Assistant
assistants
assisted
assisting
assists
Assiut
Assizes
Associate
Associated
associates
associating
Association
ASSOCIATIONS
Assouan
Assuan
assume
assumed
assumes
assuming
Assumption
Assumptionist
assumptions
assurance
Assurances
assure
Assured
assuredly
assures
assuring
Assyria
Assyrian
Assyriologist
Assyriologists
Assyriology
astonished
astonishes
astonishing
astonishment
Astor
astounded
astounding
astronomer
astronomers
Astronomical
Astronomy
Asturias
astute
asunder
Asylum
Asylums
At
Atacama
Atago
ATBARA
ate
Ateneo
Athabasca
atheism
atheistic
Athenian

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