CH1115

Chemistry and the

Environment

Dr S.S.Phull
MB124
s.phull@aston.ac.uk
Case Study
Mercury
 MERCURY

MERCURY IS A PERSISTENT and naturally

occurring metal that has provoked substantial
concern because methylmercury (an organic
form) accumulates in fish and can cause subtle
neurological deficiencies in children who have
been exposed to it in the womb. Many countries
now advise anglers to limit wild fish consumption
because of contamination by methylmercury.

by Randall Lutter and Elisabeth Irwin

 What is mercury?
• Mercury is found naturally in the environment in several
forms.
• In its elemental form, it is a shiny, silver-white, liquid
metal used in thermometers, electrical switches,
fluorescent lightbulbs, thermostats and many other
products.
• It can be combined with other elements to form inorganic
compounds.
• Mercury can evaporate to form colourless, odourless
mercury vapours.
• Mercury can combine with organic material to form
organic compounds such as methylmercury, which is
produced primarily by bacteria and is the form which
poses the greatest concern for environmental exposure.
 Mercury in the environment?
• Mercury is present in the environment due
to human activity as well as natural
sources such as volcanoes and forest
fires.
• The scope of mercury releases relevant to
determining the causes of contamination
in waterways may be regional or even
global rather than local because mercury
travels long distances in the air.
 Types of Mercury?
• Organic mercury. The most potentially harmful form of
mercury is the highly toxic methylmercury, the most
common organic form in the environment.
• It is found mainly in inland waters and the marine
environment, where mercury entering the water is
converted to methylmercury by bacterial action.
• Living organisms such as ocean plankton can easily
absorb methylmercury, removing it from the aquatic
system, but unfortunately this introduces it into the food
web, where it can find its way into food consumed by
humans and animals.
 Types of Mercury?
• Elemental mercury. This is mercury in its pure form,
which is commonly used in human activities.
• If it is not contained, mercury slowly evaporates into the
air, forming a vapour. It can remain in the atmosphere for
around one and a half years and it can travel long
distances.
• Elemental mercury can eventually react in the
atmosphere to form inorganic mercury, which is then
typically deposited on land or in water.
 Types of Mercury?
• Inorganic mercury.
• Inorganic mercury compounds are formed when
mercury combines with inorganic elements,
examples being mercury sulphide (HgS) and
mercury oxide (HgO).
• Most of these are coloured powders or crystals.
• They tend to stay in the atmosphere for a shorter
time than elemental mercury because they are
more soluble in rainwater and more reactive.
Model of Mercury Speciation and Transformations in Air, Water and Sediments
(Figure from Stein et al., 1996). Reproduced with permission from Critical
Review Environmental Science and Technology.
 Mercury in the environment?
• Mercury is persistent, mobile and bioaccumulative in the
environment, meaning it is retained in organisms.

• Most of the mercury found in the environment is

inorganic.

• Today, inorganic mercury primarily enters the

environment through emissions to the air from several
sources.

• Examples of sources include emissions of coal-fired

power plants, burning municipal and medical waste, and
natural processes such as erosion of ores and volcanic
activity.
 Mercury in the environment?
In aquatic systems, inorganic
mercury can be converted to
methylmercury.

Methylmercury is quickly taken

up into higher organisms through
the food chain and is retained in
their bodies.

It reaches the highest levels in large

predatory fish and in birds and
mammals which consume fish.

Levels of methylmercury in fish are typically 100,000 times

those in the water in which they swim.
 Mercury in the environment?
• While the risks associated with localised, personal
mercury exposure have been known or suspected for a
very long time, it is only in the last 60 years that the global
significance and scale of mercury pollution caused by
humans has been understood.
• This has come about as scientists have learned more
about how mercury behaves in our environment,
unearthing the damaging legacy created by centuries of
man-made emissions.
• It is estimated that, over the past 500 years, human
activity has resulted in the release of between 1 and 3
million tonnes of mercury into the environment (Streets et
al., 2017).
 Mercury in the environment?
• Between 1932 and 1968, a Japanese factory released
industrial waste containing high levels of methylmercury
into local waterways, resulting in widespread pollution of
Minamata Bay and the contamination of fish and shellfish
species in the region.
• In the 1950s, local residents became alarmed by the
strange behaviors of animals and an increase in the
incidence of developmental disorders in newborns.
• In 1959, epidemiological studies revealed that
communities living near Minamata Bay, who traditionally
depended on fish and shellfish for their diet, had been
unknowingly exposed to high levels of methylmercury.
• The devastating health effects subsequently became
known as Minamata disease.
 Mercury in the environment?
• Between 1971 and 1972 in Iraq, widespread consumption
of grain coated with an organic mercurial fungicide
caused the largest mercury poisoning epidemic ever
recorded.
• A total of 6,530 individuals were diagnosed with mercury
intoxication and hospitalized, of which 459 died.
• However, it is believed that this figure is severely
underestimated.
• Infants exposed in utero by mothers who consumed the
contaminated grain demonstrated developmental
disorders similar to Minamata disease.
• Children exposed at lower doses experienced delays in
neuro-cognitive development and ataxia.
 Global Mercury Reservoir
• Global Mercury Reservoir is the amount of mercury
circulating worldwide at any one time; the other 60
percent came from anthropogenic sources in the
UnitedStates.

• Both natural and anthropogenic emissions contribute to

the global mercury reservoir, and although significant
uncertainty exists as to the length of time that some forms
of mercury persist in the atmosphere, an authoritative
estimate of annual global input to the reservoir is about
4,900 t.
Global Mercury Reservoir
 Mercury in the environment?
• There is substantial uncertainty about the share
of worldwide emissions that originates from
human activity.

• One study concluded that natural sources,

industrial sources, and the “recycling” of
anthropogenic mercury each account for about
one-third of the mercury burden in the global
atmosphere at a given moment.

• Recycling occurs when mercury in water

volatilizes and contributes to the build up of
atmospheric mercury concentrations.
 Mercury in the environment?
• Mercury releases from ongoing human activity can be
divided into four broad categories.

• Mining
• Alkali Production
• Fossil fuel combustion for power and heating
• Waste Incineration
Mercury in the environment?

Global atmospheric emissions of industrial

mercury (from UNEP, 2008).
 TOXIC EFFECTS
• The toxic effects of mercury depend on its
chemical form and the route of exposure.
• Methylmercury [CH3Hg] is the most toxic form.
• It affects the immune system, alters genetic and
enzyme systems, and damages the nervous
system, including coordination and the senses of
touch, taste, and sight.
• Methylmercury is particularly damaging to
developing embryos, which are five to ten times
more sensitive than adults.
• Exposure to methylmercury is usually by
ingestion, and it is absorbed more readily and
excreted more slowly than other forms of
mercury.
 TOXIC EFFECTS
• Elemental mercury, Hg(0), the form released from broken
thermometers, causes tremors, gingivitis, and excitability
when vapors are inhaled over a long period of time.

• Although it is less toxic than methylmercury, elemental

mercury may be found in higher concentrations in
environments such as gold mine sites, where it has been
used to extract gold.

• If elemental mercury is ingested, it is absorbed relatively

slowly and may pass through the digestive system without
causing damage.

• Ingestion of other common forms of mercury, such as the

salt HgCl2, which damages the gastrointestinal tract and
causes kidney failure, is unlikely from environmental
sources.
TOXIC EFFECTS
 Methylation
• Bacteria in water bodies transform water-
borne elemental, divalent, or inorganic
mercury into methylmercury (CH3Hg+), the
organic form that accumulates as it moves
into higher levels of the food chain.
• Methylation occurs both in sediment and in
the water column after mercury has entered
the aquatic environment through methods
such as atmospheric deposition, runoff, and
groundwater flow from the upper levels of
soil.
What factors affect the
methylation?
 What factors affect the
methylation?
• Methylation is a product of complex processes that move
and transform mercury.
• Atmospheric deposition contains the three principal forms
of mercury, although inorganic divalent mercury (HgII) is
the dominant form.

• Once in surface water, mercury enters a complex cycle in

which one form can be converted to another.

• Mercury attached to particles can settle onto the sediments

where it can diffuse into the water column, be resuspended,
be buried by other sediments, or be methylated.

• Methylmercury can enter the food chain, or it can be

released back to the atmosphere by volatilisation.
 What factors affect the
methylation?
• The concentration of dissolved organic carbon (DOC) and
pH have a strong effect on the ultimate fate of mercury in
an ecosystem.

• Studies have shown that for the same species of fish

taken from the same region, increasing the acidity of the
water (decreasing pH) and/or the DOC content generally
results in higher mercury levels in fish, an indicator of
greater net methylation.

• Higher acidity and DOC levels enhance the mobility of

mercury in the environment, thus making it more likely to
enter the food chain.
 What factors affect the
methylation?
• Mercury and methylmercury exposure to
sunlight (specifically ultra-violet light) has
an overall detoxifying effect.

• Sunlight can break down methylmercury to

Hg(II) or Hg(0), which can leave the
aquatic environment and re-enter the
atmosphere as a gas.
 What factors affect the
methylation?
• Mercury and methylmercury exposure to
sunlight (specifically ultra-violet light) has
an overall detoxifying effect.

• Sunlight can break down methylmercury to

Hg(II) or Hg(0), which can leave the
aquatic environment and re-enter the
atmosphere as a gas.
 Dose Response Calculation
Question
• In the human body, the half-life of methyl mercury
is 70 days and for mercury (Hg2+) it is 6 days.
• Explain why there is such a marked difference in
the half-lives and why methyl mercury is so much
more toxic than inorganic mercury?
• Calculate the maximum body accumulation of
each type of mercury at a constant ingestion rate
of 2mg Hg /day.
 Dose Response Calculation
• The extent to which a substance
accumulates in a human depends upon the
rate, R, at which it is ingested and the
mechanism of elimination.
• Rate of intake = R

• The rate of elimination is directly

proportional to the concentration, C – First
order process.
 Dose Response Calculation
• If the rate constant for the process is
defined as k, the rate of elimination is
therefore kC
• Rate of elimination is kC.
• If none of the substance is initially present,
in an organism, C=0, then the rate of
elimination is zero.
• As concentration builds up due to
ingestion, (ingestion concentration Ci),
then rate of elimination increases also.
 Dose Response Calculation
• The rate of elimination will increase until it
matches the rate of intake, if R is constant.
• After this “equilibrium” point is reached, the
concentration does not vary i.e. it reaches
a maximum value, Cmax, it is at a steady
state.
• At steady state;
• Rate of elimination = Rate of intake
 Dose Response Calculation
• Remember for first order processes ,
• (i) k = ln2 / t½ i.e. k = 0.693 / t½
• And
• (ii) d[c]/dt = kCi
• Differentiating equation and rearranging
you get:
• Cmax / Ci = e-k [1/(1-e-k)].
• Cmax = max accumulated concentration.
• Ci = ingestion rate and k = rate constant.
 Dose Response Calculation

Question
• In the human body, the half-life of methyl
mercury is 70 days and for mercury (Hg2+)
it is 6 days.
• Calculate the maximum body accumulation
of each type of mercury at a constant
ingestion rate of 2mg Hg /day.
 Dose Response Calculation
• Cmax / Ci = e-k [1/(1-e-k)].
• For CH3Hg
• k= 0.693 / t½
• k =0.693 / 70 days
• = 0.0099 days-1
• Cmax = 2 (mg/day) x e-0.0099 x 1 / (1 - e-0.0099 )
• Cmax = 198mg
•
• For Hg
• k= 0693 / t½
• k= 0.115
• Cmax / Co = e- k [1/(1-e-k)]
• Cmax = 16.33 mg