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Textbook Arsenic Is Everywhere Cause For Concern William R Cullen Ebook All Chapter PDF
Textbook Arsenic Is Everywhere Cause For Concern William R Cullen Ebook All Chapter PDF
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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
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A catalogue record for this book is available from the British Library
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Preface
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 Sandra
Bill Cullen
Ken Reimer
To Deborah
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Abbreviations
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
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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
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Contents
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
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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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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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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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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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
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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
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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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):
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
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“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/.
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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/.
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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.
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
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10 Chapter 2
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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Arsenic Is Everywhere 11
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.