Trace Elements and Contaminants PDF

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Navrátil T, Minařík L (2002) Trace elements and contaminants, in Earth’s System: history and
natural variability. In: Cílek V, Smith RH (eds) EOLSS-UNESCO. Eolss Publishersx Oxford
TRACE ELEMENTS AND CONTAMINANTS
T. Navrátil, Institute of Geology, Academy of Sciences, Prague, CR

L. Minařík, Institute of Geology, Academy of Sciences, Prague, CR
Keywords:
toxicity, contaminants, bioaccumulation, biomagnification, trace elements, organic substances, environment,
impact, As, Cd, Pb, Hg, DDT, dioxin, pollution, industry, agriculture, deposition, emissions, teratogen, mutagen,
TCE, pesticides, PCBs, PAHs, BTEX, freons, metals, water, air, soil, groundwater, mobility, speciation,
dispersion, contamination sources, geochemistry, health impact, sediments, traffic, carcinogen, half-life,
background, human activity.
Contents:
Summary
1. Trace elements
1.1. Primary dispersion
1.2. Secondary dispersion
1.3. Tertiary dispersion
1.4. The main sources of trace element contamination
1.5. Environmental impacts of selected trace elements: Arsenic, Cadmium, Mercury and Lead
2. Organic contaminants
2.1. Pesticides (DDT and other compounds)
2.2. Plochlorinated biphenyls (PCBs)
2.3. Poly-aromatic hydrocarbons (PAHs): Naphtalene, Anthracene, Phenantrene and Benzopyrene
2.4. Benzene, toluene, xylene (BTEX)
2.5. Dioxins
2.6. Trichlorethene (TCE)
2.7. Freons
3. Recommendations
Bibliography
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Glossary:
Background concentration: concentration that is natural for a given substance and is not usually
dangerous.
Bioaccumulation: retention of a substance in the body persists past excretion. Substance is stored in the body
for a long time.
Biomagnification: process whereby concentration of a substance in the body increases with constant input. For
example, plants with a low contamination level may be eaten by animals in such quantities that the animals are
more contaminated than the plants.
Carcinogen: substance or agent that is proven to cause or initiate cancer.
Contaminant: substance foreign to natural systems or substance present in unnatural concentrations; unwanted
substance that has entered food, soil, water or air. May be a chemical, a radioactive product or a living organism
(e.g. bacteria).
Half-life: the period of time necessary for half of a substance in a closed systém to degrade or decay by
biological, chemical or physical means.
Mobility: parameter of a substance which determines its movement from dne environmental medium to another.
Mutagen: substance or agent that has the potential to change genetic material (DNA or RNA), causing disease
that may be inherited.
Speciation: form or state of an element which reflects the current conditions in the surrounding environment.
Teratogen: substance or agent that can cause structural or functional birth defects in the offspring of exposed
adults.
Toxic substance: substance that causes damage to humans, animals or other organisms even in very low
concentrations.
Summary
Contamination of the environment refers to the tertiary dispersion of chemical substances from localized sources
into worldwide distribution in the environment, caused by human activities. The exponential trend in growth of
production or consumption of many trace elements in the early 20th century has slowed, over the last two
decades, to moderate growth or a stagnant trend. However, the natural cycles of some elements have been
significantly disturbed by the anthropogenic impacts of recent years. Other new substances have entered the
environment and their cycles have just begun.
Some of the chemicals entering the environment are not considered dangerous for natural ecosystems. Other
substances have direct and/or indirect influences on life forms and can cause serious damage. Toxic metals such
as mercury, cadmium, arsenic and lead, as well as many other organic substances, tend to accumulate in certain
reservoirs (soil, sediments, etc.) from which they may be released by various processes of remobilization. They
may also change form or speciation and become available to the biological food chain, thereby affecting life,
including human life, by causing chronic and acute disorders. Trace metals are not usually eliminated from the
ecosystems by natural processes, in contrast to most organic pollutants.
Although the most dangerous organic substances are those that have the potential to bioaccumulate and
biomagnify, toxicity and other related parameters of the substances such as mutagenity, teratogenity, etc. also
determine the potential threat.
1. Trace Elements
Only 10 elements (oxygen, silicon, iron, aluminum, calcium, potassium, sodium, magnesium, titanium, and
hydrogen) of the naturally occurring 89 account for over 99 per cent of the Earth’s crust by weight. The other 79
elements (including the inert gases), which together form less than 0.5 per cent by weight, are known as the trace
elements. They do not play a fundamental role in the make-up of the Earth´s crust but their significance in
economy, ecology, agriculture, medicine, toxicology and many other areas is completely disproportional to their
low crustal abundances. The term ”trace element” has no precise definition in the earth sciences, because the
concentration of an element in a given phase can be so low that it is considered a trace element, whereas the
same element can constitute a main part of another phase. For example, Al is a main element in most common
rocks and soils, but is a trace element in vegetation and water. In contrast, Fe is a trace element in quartz, and is a
main element in mafic minerals.
In geochemistry, the most frequently used definition is: trace elements (also known as microelements) are
chemical elements whose concentration in the Earth’s crust is less than 0.1 per cent by weight. See trace
elements, contaminants.
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1.1. Primary Dispersion

In order to understand the role played by trace elements in the environment, we must investigate the main
mechanisms of dispersion to find out how trace elements achieved their present distribution within the Earth. In
the course of primary dispersion, trace elements become concentrated along with major elements in certain types
of geological formations. During the crystallization of rocks from the cooling and solidifying melt, the major
constituents form a sequence of minerals dependent on the prevailing temperature and pressure. The
microelements usually occupy spaces in the lattices of these minerals according to the rules of diadochic
substitution.
These processes are largely controlled by the elements’ valence, ionic radius and electronegativity. In the case of
the first row transition elements, crystal-field stabilization energies are also important. On this basis it is possible
to explain why individual trace elements may or may not be incorporated into particular coordination sites in the
common rock-forming minerals, thereby effectively substituting the major elements that normally occupy these
sites.
Unlike the major elements, where concentrations rarely vary by more than a factor of two over a wide range of
geological formations, the concentration of trace elements varies very considerably from material to material.
1.2 Secondary Dispersion

Secondary dispersion of elements from the bedrock into the surface environment occurs as a result of physical
and chemical weathering, which transforms fresh rock, which is frequently non-porous, into soft and porous soil
. Physical weathering breaks the rock into smaller particles, thereby increasing the surface area of the material
which is exposed to air and water. Atmospheric oxygen and water are the main agents of chemical weathering.
During chemical weathering, primary minerals, which have been formed at high temperatures and pressures
mostly in the absence of air and water, are changed into phases that are stable under surface conditions. Surface
conditions are characterized by low temperatures and pressures and also by the presence of air and water. The
order of rock-forming minerals’ relative stability is in general the reverse of that in Bowen’s reaction series
during the crystallization of igneous rocks.
The redistribution of chemical elements involves interactions between bedrock and water from atmospheric
precipitations containing dissolved gases.
The newly formed phases are particulate and colloidal material, whose physical properties are intermediate
between bedrock, water and fragments of minerals which are resistant to weathering. The fate of a trace element
in solution then depends on the behavior of its aqueous species. This behavior can be related to such parameters
as ionic potential and effective hydrated ionic diameter. The trace element may be either leached from weathered
material into surface and subsurface water or precipitated from solution as hydroxide, oxyhydroxide, carbonate,
sulfate, phosphate etc.. It can also be incorporated into a newly formed phase. Less frequently, it may be
adsorbed onto the charged surfaces of clay particles or organic matter.
The secondary dispersion of trace elements is strongly affected by Eh, pCO2 and pH and the stability of host
minerals which are subject to decomposition in particular weathering environments.
Both primary and secondary dispersions také place spontaneously, independently of human activities. However,
some exceptions do exist. For example, acidic atmospheric precipitation accelerates rock weathering by the
addition of H+ (hydrogen) ions. Hydrogen ions then release some cations from the structure of primary phases. In
addition, nutrients are leached away out of the soils formed on the bedrock, while toxic metals become more
mobile and more readily available. See weathering.
1.3 Tertiary Dispersion

Recent industrial development has caused substantial enrichment in basic environmental media such as soil,
vegetation, water and air, resulting in geochemical neoanomalies that may contain up to 1000 times the normal
crustal trace element content. The normal crustal trace element concentration is usually described as the
”background concentration”. The trace elements concentrated in neoanomalies are often metals, especially heavy
metals (density > 6 g.cm-3). Some of them are essential for life processes in trace quantities but in higher
concentrations are all toxic to organisms. Metals and non-metals enter the environment whenever they or their
compounds are pulverized, heated and dissolved during industrial usage. The extent of their emission will
depend on the nature and efficiency of the particular industrial process. Considerable neoanomalies of many
trace elements are found around mines, smelters, and industrial complexes, along roads and in most urban areas.
Mankind is creating new pathways for the dispersion of many chemical elements in a manner which could be
termed tertiary dispersion or pollution. At present, the natural geochemical cycles of some trace elements are
considerably disrupted by human activities.
1.4 The Main Sources of Trace Element Contamination

The main sources and some pathways of trace element movement in the environment are shown in Figure 1 and
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in the text as follows:
Figure 1. Sources, reservoirs and pathways of the trace elements and other chemical substances.
Manmade Sources
1. Industrial emissions
2. Vehicular emissions
3. Domestic emissions
Natural Sources
4. Volcanic eruptions
5. Forest fires
Pathways
6. Ground deposition
7. Surface runoff
8. Dry deposition
9. Air/Water gas exchange
10. Air/Water gas exchange
11. Wet deposition
12. Groundwater, surface water runoff
Reservoirs
13. Soil, bedrock
14. Water
15. Atmosphere (gases, particles etc.)
Mining, Smelting and Industrial Processing of Ores and Metals: While the world population has doubled in
the second half of the 20th century, the production of five heavy trace metals (copper, lead, nickel, tin, and zinc)
has increased more than eightfold. Mining and smelting have been the cause of major pollution problems for as
long as they have been practised. In the year 2000, for example, a large quantity of cyanide escaped into the
waters of the Tisa and Danube rivers during gold mining and processing in the ore district of Baia Mare
(Romania). This event has initiated a giant ecological catastrophe in south-east Europe, whose impact can be
compared to that of the Chernobyl accident in 1986.
Presently, particular interest from an environmental point of view is directed towards sulfidic mining waste. The
sulfidic ore bodies have remained practically unchanged in the bedrock for very long periods. However, when
brought into contact with atmospheric oxygen and water, traces of metal sulfides in waste material are oxidized
to produce an acidic leachate containing heavy metals. The highest-priority problems are associated with the
enormous masses of mine tailings. Their global quantity of approximately 18 billion m3 per year is in the same
order of magnitude as the actual sediment discharge to the oceans. A simplified estimation suggests that due to
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the extraction of lower grade ores in future, the production of mine wastes will double within a period of 20 – 30
years. In addition, current rates of mining exceed the natural rates of cycling for a number of trace elements. For
heavy metals such as Cu, Pb, Zn, and Cr the rates of mobilization from mining are estimated to exceed by a
factor of ten the rates of mobilization from natural cycling. See contamination.
On the other hand, the downward trend in use of raw materials in industrialized countries should be borne in
mind. Mature economies became increasingly tied to high technology that requires less intensive use of raw
materials, thanks to miniaturization and substitution. Future development will depend crucially on the extent and
quality of recycling.
Coal Combustion: Coal combustion is the second serious source of trace element contamination of the
environment. In particular, the combustion of pulverized coal in modern furnaces for power production results in
a variety of products. The organic matter is converted mainly to sulfur oxides, nitrogen oxides, carbon dioxide,
carbon monoxide and water, which are the main constituents of the flue gases. The mineral matter is
decomposed to give several mineral phases and aluminosilicate glassy material. Trace elements are distributed
between the bottom slag and the fly ash (the incombustible residue, mostly of micron and submicron size, which
is carried along with the combustion gases). Most trace elements in coal are usually associated with the fly ash
removed from the gases, some are associated with slag, and a small amount reaches the atmosphere in fine fly
ash particles. There are two environmental effects: first, the disposal of the slag and retained fly ash, and second,
the dispersion of some trace elements in the stack gases. There is some evidence that very fine particles of fly
ash escaping with the stack gases to the atmosphere may have a higher trace element content (especially of
volatile elements such as As, Sb, Su, Pb, etc.) than the large particles. In addition, different metals may also
show distinct density distributions. It has been noted that metals such as Be, Cd, and Hg tend to be concentrated
in light density fractions of fly ash, whereas Co, Cr, Mn, Ni, V, and Zn tend to concentrate in higher density
fractions. See coal combustion.
Traffic: Another potential source of metal pollution of urban areas and soils adjacent to highways is traffic.
Innumerable studies indicate that lead concentrations in soils near highways are high and decline exponentially
as a function of distance from the highways. Meteorological situation, vegetation, topography and traffic
intensity are the major factors that influence Pb concentrations in roadside soils. Fortunately, emission of lead
compounds into the environment has been considerably reduced by the use of unleaded fuel in vehicles since the
1980s. Other modes of transportation such as trains and aircraft also contribute to the contamination of the
environment by heavy metals (Cd, Ni, Pb, V, Pt and Zn). However, the extent of contamination from these
sources has not been clearly assessed.
Chemical Industry: A further source of trace element contamination is the chemical industry. Economic
growth in the chemical industry has been induced by increases in production. Thus, for example, the global
production of sulfuric acid has increased more than sevenfold from 20 million tons recorded before World War
II to 140 million tons in the late 1990s. A sharp increase in the production of fertilizers and pesticides has also
been observed. It is estimated that 80,000 different chemicals are produced worldwide. Plastics are by far the
most important products of the chemical industry, but production of fine and special chemicals is also rising.
This area includes e.g. detergents, cleansers, softeners and catalysators.
The problem with this product group is that it frequently uses of a mixture of chemicals whose ecological and/or
toxicological safety cannot be guaranteed. These sources are summarized in Table 1. As can be seen from this
table, the same trace elements are contained in many different contamination sites. In addition to the sources of
contamination mentioned above, there are municipal wastes, agricultural wastes, sewage sludge etc., containing
various quantities and species of trace elements.
paints and coatings As Cd Cr Pb Cu Hg Sb Zn
crude oil processing As Cr Pb Zn
iron and steel production As Cd Cr Pb Cu Hg Sb Zn
nonferrous metal refinery As Cd Cr Pb Cu Hg Sb Zn
plastic industry Cd Cr Pb Zn
batteries, accumulators As Cd Cr Pb Cu Hg Sb Zn
plant protection As Cr Pb Hg Zn
Table 1. Sources of selected chemical compounds.
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1.5 Environmental Impacts of Selected Trace Elements: Arsenic, Cadmium, Mercury

and Lead
Microgramal (µg) concentrations of trace elements comprise part of the natural environment of living organisms
(humans, animals, and plants) in the air, in the water, and in the soil. The human body even requires at least ten
metals in various concentrations. Trace metals such as Mn, Zn, Co, Mo, Cu, etc. are essential components of
metabolic catalysis. The term ”essential component” means that there is a specific concentration range for each
individual function which is necessary for the proper progress of that function. However, in many cases we do
not know this ”optimal range” of concentrations. The occurrence of unsuitable concentration ranges is more
frequent (e.g. for growth or biomass production) than the presence of an optimal concentration level.
Metals and metalloids are present in a variety of compounds such as free ions, inorganic complexes, organic
complexes, metal species bound to high molecular organic material (lipids, humic acids, polysaccharides), or
sorbed on clays and colloids in the environment. Their ”speciation” plays an important role in estimating
mobility, biological activity and toxicity.
Arsenic Cadmium Mercury Lead

Atomic number 33 48 80 82
Atomic weight 74.72 112.40 200.60 207.20
Density at 20 oC (g cm-3) 5.7 8.7 13.6 11.3
Melting point (oC) --- 321 -39 327
Boiling point (oC) 615 (subl.) 765 357 1750
Valency 3+ 5+ 2+ 1+ 2+ 2+ 4+
Ionic radius (A) 0.46 0.58 1.03 - 1.10 1.26 0.86
Electronegativity 1.9 2.1 1.7 1.8 1.9 1.6 1.8
Natural associations accessory sulfides with Zn in ores, rock with Ag, Sb, Se, Pb and sulfide ore deposits,
coherency with Au forming minerals Bi in sulfide deposits potassium feldspar
Aqueous species H2AsO4- Cd2+ Hg22+, Hg(OH)2 Pb2+, PbCO3,
2- +
HAsO4 CdHCO3 HgCl2, Pb(OH)+
o
HAsO2 Cd(OH)2 soluble org. matter soluble org. matter
Soil species adsorbed on ferric adsorbed on Fe,Mn HgCl2, organic matter Pyromorphite
oxyhydroxides and oxyhydroxides and Pb5(PO4)3Cl, clays
organic matter organic matter and organic matter
Atmospheric species AsH(CH3)2,As(CH3) industrial aerosol mercury vapor from PbBrCl,
3As2O3 aerosol from (together with Zn) degassing of surface PbBr2,Pb(OH)Br
coal combustion materials aerosol from
industrial
combustion engines
Anthropogenic emissions 18 000 5 500 3 600 400 000
Natural emissions (t yr-1) 10 000 290 2 500 4 000

Industrial sources arsenopyrite, (ZnS), byproduct of cinnabar (HgS) galena (PbS)
byproduct of Cu Zn smelting
smelting
Limits for drinking water 10 5 1 10
(EU directive) (µg L-1)
Daily intake (µg kg-1 body 0.7 (max.) 0.28 (avg.) 0.14 (avg.) 1.2 (avg.)
weight, Netherlands
directive)
Table 2. Basic physical, chemical and environmental characteristics of selected trace metals.
Methyl mercury, for example, is more toxic to animals than elemental Hg because it can easily pass the blood-
brain barrier, causing injury to the cerebellum and cortex. Similarly, the hexavalent chromium Cr6+ is much more
toxic than trivalent chromium Cr3+. Some elements are nutrients for plant and/or animal life at low
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concentrations and toxic at high concentrations. However, general limits cannot be declared. It should be
emphasized that the metals of the 6th row (period) are potentially the most toxic elements of the periodic chart
(Os, Ir, Pt, Au, Hg, Tl, Pb). However, the relatively poor water solubility of their salts masks their high toxicity.
This article is concerned with those toxic trace elements, namely arsenic, cadmium, mercury and lead, which
may have a considerable impact on the global environment. The basic characteristics of these elements are
summarized in Table 2.
Arsenic (As)
Geochemistry: Arsenic is a metalloid which occurs in the elemental state to a small extent. There are sulfides
and sulfosalts (complex sulfides) of arsenic, which include the element in both trivalent and pentavalent states.
Arsenopyrite (FeAsS) is the most abundant ore mineral. In rock-forming minerals, arsenic can probably
substitute Si, Al, Fe3+, and Ti4+. Magnetite, ilmenite, pyrite, pyrrhotine, and hematite show relatively high
concentrations of arsenic. Natural arsenites are rare but pentavalent arsenic in the orthoarsenates is very
common. Arsenic in its primary minerals tends to be transferred by oxidation processes to AsO43- ions.
In slightly reducing environmental conditions arsenites predominate, while arsenates are most common in well
oxygenated and high Eh environments . As3+ and As5+ ions are subject to a series of biological transformations in
aquatic systems. Such processes yield a large number of compounds such as polymethylarsins, arsenobetaines,
arsenocholines, etc. Arsenic is predominantly bound to sediments in most water courses. The main species in the
sediments are aluminum arsenate, iron arsenate, and As bound to organic matter. It is known that As5+ is
relatively immobile when combined with iron compounds, particularly with ferric oxyhydroxides. Desorption of
arsenic from sediments is controlled by Eh, pH, arsenic concentration in the interstitial water of sediments, and
changes in the total and extractable iron. Under reduction conditions, oxyhydroxides of iron are dissolved and
release As3+ into the groundwater. Under acid conditions, the As3+ ion is fairly mobile and most arsenates, like
the phosphates, would tend to dissolve into solution.
It may be noted that the amount of arsenic in sedimentary material is much greater than the amount of arsenic
from weathered igneous rocks. In fact a large proportion of the arsenic is precipitated by colloids such as ferric
hydroxide and therefore collects in hydrolysate sediments, and the As content of the ocean remains well below
the limit of toxicity for inhabited organisms.
The predominant natural inputs of arsenic to the atmosphere are volcanic exhalations and biological activities.
However, the contribution from these sources is small in comparison with emissions of anthropogenic origin
(Table 2).
Anthropogenic sources: The largest proportion of commercially-output arsenic compounds comes from the
recovery of arsenious oxide as a byproduct in smelting of ores (copper, lead, tin, etc.). The level of production
from this process is in fact in excess of normal demand. World production of arsenic (as As2O3) is approximately
60,000 tons annually. The major uses of As are insecticides, rodenticides, pharmaceuticals and detergents.
Because of its volatility (it sublimes at 650 °C) arsenic readily enters the atmosphere, presumably as As2O3 from
fossil fuel combustion. Arsenic emissions inevitably yield relatively high residues in rainfall, which then
contaminates surface water and soil. It has been observed that the total As in rainfall is positively correlated with
rainfall acidity.
The major sources of pollution from this element are agricultural chemicals such as fungicides, rat poisons, and
insecticides.
Although the anthropogenic sources of arsenic continue to increase in many developing countries, there has been
some decline in emission patterns in Western industrialized countries.
Health Effects: In its toxicology, arsenic is a cumulative poison which inhibits thio (SH) groups in enzymes.
Chronic poisoning leads to loss of weight and loss of appetite, with accompanied gastrointestinal disorders
similar to gastroenteritis. Acute poisoning in humans is characterized by central nervous systém effects, leading
to coma and eventual death.
Inorganic As3+ is methylated in the liver of most mammals, and As5+ is reduced in the blood prior to methylation
in the liver.
It appears that the arsenic species present in human urine reflect both metabolism to reduce toxicity, and the
nature of the contaminating source. The International Agency for Research in Cancer classifies As in group 1:
inadequate evidence for carcinogenity in animals and sufficient carcinogenity evidence (skin and lung) in
humans. Daily intake into the human body is 0.7 micrograms of As per kg of body weight. Many nations, plus
the World Health Organization, have adopted a recommended standard of 50 µg.L-1 for arsenic in drinking
water. The European directive is 10 µg As.L-1. See arsenic, arsenicosis.
Cadmium (Cd)
Geochemistry: Cadmium is known to be a chalcophile element. Thus it tends to be found in sulfide deposits.
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Independent Cd-minerals are little more than mineralogical curiosities. The tetrahedral covalent radius of
cadmium is similar to that of zinc and it can therefore enter sphalerite (ZnS) structures. The crustal abundance of
Cd is 0.13 µg.g-1. Relatively higher values are typical for shales and clays (0.30 µg Cd.g-1). Uncontaminated
soils may also contain enriched Cd because of its accumulation in humic material. It is estimated that about 10
per cent of the cadmium in soils is associated with organic matter. Natural cadmium levels in air are determined
to be 0.2 µg.m-3 in rural areas.
Cadmium is relatively mobile in aquatic systems. Its most frequent species are Cd2+, Cd(OH)3-, Cd(OH)42-,
CdCO3, and various organic and inorganic complexes. The affinity of ligands to complex with Cd in many
freshwaters follows the order: humid acids, CO32-, OH-, Cl-, SO42-. The solubility of cadmium hydroxide
complexes decreases as pH increases, owing to the formation of solid Cd(OH)2. In freshwaters the dominant fate
is a process of sorption to suspended solids such as clay. Coprecipitation with dissolved iron and manganese is
also important for the environmental fate of cadmium.
Cadmium in uncontaminated freshwater sediments is usually detected at 0.1-1.0 µg g-1 dry weight. In most
surface waters, both dissolved and particulate cadmium are routinely detected. On a worldwide basis the
particulate Cd/dissolved Cd distribution coefficients range from 104 to 105 in most large world rivers.
It should be emphasized that the global annual anthropogenic flux exceeds the emission from natural sources
such as volcanoes, windborne soil particles, sea salts and biogenic particles by dne order of magnitude. There is
no definite indication that Cd has any biological significance.
Anthropogenic sources: The major specific sources on a worldwide basis are atmospheric deposition, smelting
and refining of nonferrous metals, manufacturing processes related to chemicals and metals, and domestic waste
water. Only about 15 per cent of the atmospheric deposition comes from natural sources. It has been calculated
that about 1,000 tons of Cd are released each year into the atmosphere from smelters and from factories
processing cadmium. This figure represents about 45 per cent of the total pollution by this heavy metal. A further
52 per cent comes from the incineration or disposal of Cd-containing products. The tendency of cadmium to
enter the atmosphere is partly due to its relatively high volatility. The boiling point of pure Cd metal is
765oC,compared to the boiling points of lead (Pb) (1750oC) and zinc (Zn) (907oC).
Discharges of cadmium into natural waters derive partly from the galvanizing industry. Another source of water
pollution is the nickel-cadmium battery industry. Fertilizers and fungicides containing Cd together with Zn are
also potential sources of pollution.
World production of refined cadmium has increased and in the 1990s accounted for approximately 20,000 metric
tons per year (Fig 2). There were some deviations from this regular trend after World War II and in the period
between 1970 and 1980.
Figure 2. World production and emissions of Cd in the 20th century
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The primary use of Cd is in electroplating other metals or in alloys for protection against corrosion, and in the
manufacture of storage batteries, glass, ceramics, pigments and some biocides.
Health effects: The uptake of cadmium by living organisms occurs through water, air and food. Cadmium is
highly toxic to humans. Acute Cd poisoning can result from inhalation of cadmium fumes or dust or from
ingestion of heavily contaminated food or water. Acute inhalatory cadmium poisoning is more widespread than
poisoning by cadmium ingestion. After gaining entrance into the body cadmium is accumulated mainly in the
soft tissues. More than half the body’s burden of cadmium is found in the kidneys and liver.
A disease especially associated with cadmium poisoning has been recognized in Japan. This disease, known as
”itai-itai”, results in multiple fractures arising from osteo malacia.
There is nonsignificant evidence that cadmium is carcinogenic via the oral route. The International Agency for
Research on Cancer has classified Cd and its compounds in group 2B: limited evidence of carcinogenity in
animals. The daily intake into human body is 0.28 µg kg-1. The drinking water standard is 5 µg l-1 of cadmium.
See cadmium.
Mercury (Hg)
Geochemistry: Mercury is an element with extremely low abundance in the Earth’s crust (0.08 µg g-1).
However, it is readily obtained by mining operations because of its tendency to accumulate in sulfide deposits.
The dominating mercury mineral is cinnabar (HgS) and at least another 30 common ores and minerals
alsocontain Hg in relatively high concentrations.
Mercury occurs in three states: Hgo, Hg+, and Hg2+. It readily binds to a large number of inorganic and organic
ligands. The Hg2+ forms the strongest covalent bonds with the chloride anion. The mercuric ion hydrolyzes with
Hg(OH)2 to form the dominant species at pH > 4. Mercury also forms stable complexes with a variety of organic
ligands, particularly those containing S, amino acids and hydroxycarboxylic acids. Inorganic Hg can be
methylated in the environment to form highly soluble species that are more toxic than elemental Hg. These
compounds are readily absorbed and concentrated by plants and animals (bioaccumulated) and enter the higher
members of the foodchain such as humans in a process of biomagnification. The rate of methylation is typically
highest in the surficial sediments, and decreases with increasing sediment depth. The rate of methylation is
influenced by numerous factors, of which the most important are temperature, the sulfide content of the
sediments and the dissolved oxygen level. It is assumed that the association of Hg with sediments ranges from
relatively weak Van der Waals forces to strong covalent bonding, coprecipitation with iron-manganese oxides
and incorporation within crystal lattices. Basic information about the properties, association and distribution of
Hg in the environment is presented in Table 2.
Sources of mercury: The estimate of strictly natural mercury sources and their relative importance compared to
anthropogenic contributions is a fundamental concern of studies on the global balance and mercury cycling in
the environment. It is very difficult to differentiate between natural and anthropogenic mercury emissions, since
all Hg is subject to the same transport and transformation processes and many of them are more or less
influenced by human activities. Due to the high volatility of mercury the separation of natural and anthropogenic
sources cannot be distinguished with precision. Sources classified as purely geological can be considered to be
natural and undisturbed by anthropogenic influence: these are wind erosion, degassing of Hg-mineralized soil
and rock formation, volcanic eruptions and other geothermal activity, and the escape of Hg from the Earth’s
subsurface crust. Globally, emissions of mercury from natural sources are comparable to anthropogenic
emissions (table 2).
Combustion of fossil fuels is the major anthropogenic source of mercury emissions on a global scale. Other
important anthropogenic sources include waste incineration, mining and smelting.
It has been estimated that the annual increase in anthropogenic Hg emissions into the atmosphere is in the order
of 3 to 5 per cent for developing countries. This figure is comparable to anthropogenic emissions in the Western
industrialized countries before 1989. However, emissions in those countries have remained at a stable level since
then. Global production of Hg was 3,800 metric tons in 1930, increasing to 8,300 in 1960 but decreasing to
7,100 tons in 1980. Production in recent years has remained relatively low (approximately 6,000 metric tons per
year) as a reflection of the environmental and health problems associated with mercury use.
Health effects: Once absorbed, mercury is generally distributed in the body, binding to sulphydryl groups in
many proteins. Methylated Hg is found mainly in the erythrocytes and brain. Humans exposed to excessive
levels of methyl Hg may develop central nervous systém symptoms. Acute mercury poisoning is usually
characterized by nausea, vomiting, and diarrhea with bleeding, followed by death from gastro-intestinal and/or
kidney lesions. In 1953, many people living in fishing villages along Minamata Bay (Japan) died from a
mysterious disease, later identified as a result of mercury poisoning. Further investigations revealed that the
victims had eaten shellfish contaminated with mercury effluent from a nearby plastic factory. The disease
became known as ”Minamata disease”. Another case occurred in 1972: 450 villagers in Iraki (Japan) died after
eating grain that had been dusted with a mercury-containing pesticide. There is inadequate evidence for
carcinogenity of Hg for animals or humans.
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The daily intake into the human body is 0.14 µg per kg of body weight. The World Health Organisation
recommends a maximal value of 1 µg l-1 Hg in drinking water. See Minamata disease, mercury,
bioaccumulation.
Lead (Pb)
Geochemistry: It can safely be said that no trace element pollutant has been studied more extensively than lead.
An enormous amount of literature has been published concerning lead pollution and the effects of Pb on the
environment.
Lead belongs to the IV.A elemental group but unlike C and Si shows a marked decrease in covalence. Lead
occurs in stable Pb2+ and Pb4+ oxidation states. With an average crustal concentration of 16 µg g-1, lead is a
relatively common element in the Earth’s crust. It is characterized by the large variety of its natural compounds.
The majority of lead minerals have been formed from low-temperature hydrothermal solutions. Out of the many
minerals, only three are mined as lead ores: galena PbS, cerrusite PbCO3 and anglesite PbSO4. In the rock-
forming minerals, lead is enriched in feldspars. The Pb content in soils is the same as its crustal abundance
because of lead’s stability in the geochemical cycle. In soils, lead ions can be adsorbed on clays or associated
with humic and fulvic acids, forming moderately strong chelates.
Vegetation contains on average 0.5 µg g-1 of Pb (expressed on a dry weight basis). In aqueous solution, lead
forms a number of complexes with many of the major anions, including hydroxides, carbonates, sulfides and
sulfates.
Freshwaters usually contain more lead than the oceans. Approximately 99 per cent of the lead entering the
oceans with the suspended load of rivers is deposited in the sediments of estuaries and continental shelves. The
greater proportion of dissolved Pb reaches the open sea,where its residence time is approximately 100 – 200
years.
Lead undergoes methylation in the environment to form organic derivates such as (CH3)Pb+. This process is
mediated by bacteria in sediments.
Anthropogenic sources: The primary sources of Pb contamination of soils, water and air are leaded fuel
combustion, pyrometallurgical nonferrous metal production, steel and iron manufacturing, coal combustion,
cement production, and dumping of sewage sludge. It has been estimated that 96 per cent of all lead emissions
originate in anthropogenic sources. Consumption of leaded gasoline has decreased in countries which have
restricted Pb gasoline addition, but some countries continue to use leaded gasoline.
Global production of lead was 1,700,000 tons in 1930, increasing to 3,100,000 tons in 1980. In the year 2000,
production remains at around 3,100,000 tons. Lead continues to be used in large quantities in storage batteries,
metal products, pigments, and chemicals. However, lead use in fuel has decreased dramatically.
Health Effects: Lead is moderately toxic to plants and animals. Its toxicity is higher than that of chromium,
manganese, zinc and barium, but lower than that of cadmium, mercury and copper. It is generally assumed that
tetraethyl lead is more toxic than either the methylated derivates or inorganic compounds.
Lead poisoning produces loss of appetite, weakness, anemia and colic. Other effects include hypertension, renal
dysfunction, and damage to the peripheral nervous systém. Acute poisoning by lead is relatively rare. The
International Agency for Research on Cancer classifies lead in group 3: inadequate evidence for carcinogenity in
humans and sufficient evidence for carcinogenity for some salts in animals. The daily intake into the human
body is 1.2 µg Pb kg-1. The recommended maximal concentration in drinking water is 10 µg l-1.
See lead, gasoline, traffic.
4.2 Organic Contaminants

Organic substances are substances based on carbon and hydrogen atoms. These substances may also be called
hydrocarbons. Hydrocarbons have an ability to incorporate other elements. When elements other than hydrogen
or carbon are added the substance may be called derivate.
When compared to trace element contamination of the environment there is no or very little background
concentration of the organic contaminants. A number of organic contaminants exist in the environment but the
most closely monitored are carcinogens, mutagens and teratogens. The majority of organic contaminants are
introduced into the environment by human activities, although some enter via natural processes e.g. volcanic
eruptions, forest fires etc.
Some organic contaminants can be broken down easily in the environment, but others are very resistant.
Resistant substances are known as Persistent Organic Pollutants (POPs). Persistent organic pollutants are
compounds that can remain in the environment for many months or years. Generally POPs have very low water
solubility and high lipid (fat) solubility. This causes them to accumulate in the fatty tissues of living organisms.
Some of them may participate in phenomena such as bioaccumulation or biomagnification. Bioaccumulating
substances include pesticides, polychlorinated biphenyls, dioxins, and furans. These contaminants are dangerous
because of their effects on living creatures and the environment. They enter living organisms in numerous ways
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e.g. through ingestion of contaminated food, breathing of contaminated air or presence in a contaminated
environment. The tendency of these substances to persist in the environment and to build up in plant and animal
tissues poses the greatest risk to human health and the environment. See organic contaminants.
2.1 Pesticides (DDT and other compounds)

The word pesticides refers to a broad range of chemicals used for crop protection. A number of pesticides exist,
of which the four most important groups are:
• insecticides, used to control insects;
• rodenticides, used to control rodents;
• herbicides, used to control weeds; and
• fungicides, used to control mold, mildew and fungi.
Farmers have to contend with some 80,000 plant diseases, 30,000 species of weeds, 1,000 species of nematodes
and more than 10,000 species of insects. That is why they use pesticides.
By their nature most pesticides are toxic substances, some of which have been identified as carcinogens in
extremely high dosages. Some basic pesticides are listed in table 3.
Aldrin Arsenic Bromomethane
Chlordane DDT Endrin
Hexachlorobenzene Metoxychlor Mirex
Naphthalene Phenol Toxaphene
Table 3. Examples of pesticides.
DDT
Dichlorodiphenyltrichloroethane (DDT) was widely used to control insects on agricultural crops and insects that
carry diseases like malaria and typhus. DDT is now prohibited for use as a common pesticide. Dne of the reasons
DDT was banned was the book Silent Spring (1962) by Rachel Carson, which revealed the effects of DDT on
living creatures and alarmed governments and authorities into action. However, it is still used in several
countries of the world.
Swiss scientist Paul Müller was awarded the 1948 Nobel Prize in Physiology and Medicine for his discovery of
DDT’s insecticidal properties in 1939. Technical grade DDT is a mixture of three forms. All of these are white,
crystalline, tasteless, and almost odorless solids. Its chemical structure is shown in figure 3. DDT began to enter
the environment after its mass usage as an insecticide. Large amounts of DDT were directly applied to soil,
water and air because it was sprayed on the crops. DDT in soil usually breaks down to form DDE or DDD but
lasts for a very long time.
Figure 3. Chemical structure of DDT.
DDT entered surface water either directly when the water was sprayed during insecticide application, or
indirectly when rain-washed soil containing DDT entered surface waters.
Its half-life is estimated to be in the range of 2 – 15 years. DDT in air lasts for only a short time. It sorbs tightly
to soil and does not move down through the soil quickly to groundwater supplies. DDT may attach to small
particles and be carried by the wind. It can be stored in water sediments by the settling of particles with attached
DDT molecules.
DDT in soil can be absorbed by some growing plants and by the animals or people who eat these crops. In water,
DDT can be absorbed by small aquatic organisms and then concentrate in the fish which eat these organisms.
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The levels of DDT in animals or fish can be higher than in the environment because fat cells store DDT.
Once inside the body, DDT can break down to form DDE or DDD. DDE and DDD can be broken down into
other metabolites that pass out of the body in urine. These compounds are stored most readily in fatty tissue.
However, the amounts of DDT in the body decrease if exposure is reduced. DDT metabolites leave the body
very slowly in urine, but may also leave in breast milk.
As an insecticide, DDT kills insects by acting as a nerve gas, although the effects on the nervous systém are not
understood. Another issue that scientists have long speculated about is the fact that DDT, along with other
organic contaminants, can move through the atmosphere from relatively warm regions and condense at colder,
higher latitudes. This process, known as the global distillation effect, could be the reason why high
concentrations of some pollutants are found in the Earth’s Arctic regions where the pollutants have never been
used. Unknown volumes of DDT are stored in the ice of the Arctic regions.
Although DDT saved approximately 25 million people it is now causing phenomena such as sperm decline, birth
defects, etc. It also came close to eliminating some species of animal altogether. DDT is known to cause eggshell
thinning in birds: the most damaged are carnivorous birds such as the bald eagle. The International Agency for
Research on Cancer (IARC) has determined that DDT, DDE, and DDD are possibly carcinogenic in humans. See
DDT, pesticides.
2.2 Polychlorinated Biphenyls (PCBs)

Polychlorinated biphenyls (PCBs) are a group of compounds produced commercially by directly chlorinating
biphenyl. Polychlorinated biphenyl (PCB) is any molecule which has multiple chlorine atoms attached to the
carbon atoms of a biphenyl nucleus (figure 4).
Figure 4. Example of polychlorinated biphenyl molecule structure.
There are no known natural sources of PCBs in the environment. PCBs enter the environment as mixtures
containing a variety of individual components. They have no known smell or taste. PCBs are either oily liquids
or solids and range in color from colorless to light yellow. In general, PCBs are non-flammable and water-
insoluble. They have high boiling points and low electrical conductivity. Chemically and thermally they are
stable.
These physical properties made PCBs extremely desirable for a wide variety of industrial applications, including
dielectric heat transfer fluids, hydraulic fluids, solvent extenders, flame retardants, organic diluents, dielectric
fluids, inks, dyes, paints and adhesives. Small quantities of these chlorinated pollutants are also generated as an
inadvertent byproduct in the production of a host of unrelated materials, including certain paints, plastics, and
paper coatings.
PCBs were first used around 1929. Use of them other than in electric capacitors was banned between 1977 and
1980. Before 1977, PCBs entered the air, water, and soil during their manufacture and use. New sources of
contamination are waste sites containing PCB wastes. Other sources of contamination are recent leaks and fires
in transformers or capacitors.
PCBs in air can be present in both solid and liquid aerosols. PCBs may remain in the air for an average of more
than 10 days depending on the type of PCB. Once in the air, PCBs can be carried long distances by the wind.
In water, most of the PCBs tend to stick to particles and sediments. Extremely small amounts of PCBs can
remain in water for years. PCBs bind strongly to soil and sediments and may remain bound for several years.
PCBs have been also found in groundwater. PCBs can partially evaporate from soil surfaces to air. In general,
the breakdown of PCBs in the water and soil occurs over several years, or even decades. Sediments containing
PCBs at the bottom of a large body of water such as a lake, river, or ocean generally seem to act as reservoirs
from which PCBs may be released in small amounts to the water.
PCBs in water concentrate (bioaccumulate) in fish and can reach levels hundreds or thousands of times higher
than the levels in water.
A common way for PCBs to enter the human body is through eating meat or fish products or other foods that
contain PCBs. PCBs can also enter the human body through breathing indoor air in buildings that have electrical
parts containing PCBs.
PCBs in the human body may change into other related chemicals called metabolites. Some metabolites of PCBs
may be as harmful as the unchanged PCBs, but there is no conclusive experimental evidence to support this
assumption. Some metabolites may pass out of the body in feces in a few days, but others may stay in fat and
the liver for months or years. PCBs build up in milk fat and can enter the bodies of breastfeeding infants .
A widespread human poisoning episode in Western Japan (called ”Yusho,” or ”oil disease”) was at first
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attributed to the consumption of rice bran oil contaminated with PCBs, although subsequent analysis has shown
the presence of some thermal PCB degradation products. Another similar case occurred in Taiwan (”Yu-Cheng”)
and increased concern over the safety of PCBs.
In the Japan and Taiwan episodes mentioned above, consumption of PCB-contaminated rice bran oil resulted in
a severe form of acne called chloracne, fatigue, nausea, and liver disorders. An increase in liver cancer mortality
was also detected in the Yusho incident.
Workers exposed to PCBs were known to have a higher concentration of PCBs in the blood but mortality in this
case is believed to have been due to the presence in the rice bran oil of substances generated from the thermal
breakdown of PCBs. These substances, furans (similar to dioxins) and quaterphenyls, are far more toxic than
PCBs. The International Agency for Research on Cancer has determined that PCBs are probably carcinogenic to
humans. See PCB.
2.3 Poly Aromatic Hydrocarbons (PAHs): Naphtalene, Anthracene, Phenantrene and

Benzopyrene
Poly Aromatic Hydrocarbons (PAHs) are a class of very stable organic molecules whose structure is based on
fused benzene units. These molecules are flat, with each carbon having three neighboring atoms.
There are natural sources of PAHs such as thermal geological reactions (e.g. volcanic eruptions) and natural
fires.
Because of their low vapor pressures, some PAHs are present at ambient temperatures in air, both as gases and
associated with particles. The lighter PAHs, such as phenanthrene, are found almost exclusively in the gas phase;
the heavier PAHs, such as benzopyrene, are almost always adsorbed onto particles. PAHs are relatively
insoluble in water but dissolve in fats and oils.
These molecules are highly carcinogenic and they are also very common. PAHs are a standard product of
burning common fuels, such as coal, oil, wood and gas. Tobacco smoke is a very important source in indoor air .
Removal of PAHs from the atmosphere is facilitated by photo-oxidation. PAHs react rapidly with NOx, HNO3,
SO2, SO3, and H2SO4. These reactions tend to yield carcinogens of increased potency. The best-known PAHs
are:
light: naphthalene, anthracene and phenantrene (Figure 5)
heavy: benzopyrene (Figure 6)
Figure 5. Chemical structures of naphthalene, anthracene, and phenanthrene.
Figure 6. Chemical structure of benzopyrene.
Naphthalene has molecules composed of two benzene rings. It occurs as a white crystalline solid. It is also the
most abundant distillate of coal tar. Naphthalene is an important hydrocarbon raw material used in the
manufacture of phthalic anhydride (used in dye making), of celluloid and hydronaphthalenes (used in lubricants),
and of motor fuels. A very common use of it is as a household fumigant against moths. At dne time, it was used
as an insecticide. Naphthalene enters the atmosphere through emissions and exhaust produced by its presence in
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fuel oil and gasoline. Another major contributor of naphthalene in the atmosphere is the aluminium smelting
industry, whichaccounted for about 21per cent of the total atmospheric emissions measured in Canada in 1991.
Entry into the soil and water compartments mainly arises due to discharges and spills during the storage,
transportation and disposal of fuel oil and coal tar. Short-term low exposure to naphthalene may cause eye and
skin irritation. At slightly higher levels (above 10 µg g-1), headaches, fatigue and nausea occur. If naphthalene is
ingested it has the potential to cause hemolytic anemia, a condition that involves the breakdown of red blood
cells. Naphthalene is a suspected human carcinogen, and has been proven to cause damage to the kidneys and to
the liver. Chronic exposure can lead to reproductive defects including fetal damage and decreasing fertility.
Higher incidences of lung and skin tumors have been reported for people who have been occupationally exposed
to naphthalene and other PAHs.
Anthracene is common in the natural environment. It has a crystalline structure, is pale yellow in color, and
exhibits a weak aromatic odor. Anthracene, like many PAHs, is used in the production of fast dyes as well as
fibers and plastics. Anthracene can also be used in insecticides and as a wood preservative. This compound is
widely abundant. It is found in any type of coal or tar. Anthracene is released into the environment from a
variety of sources. It can be released via non-point sources as well as industrial effluents from dye and pesticide
manufacture. Its natural sources are coal and tar, and it can be released by the incomplete combustion of organic
compounds. It is therefore a constituent of the exhaust from automobiles, lawn mowers, and charcoal grills. It
can also seep into the ground and surface water from coal piles. Anthracene exposure can cause skin and eye
irritation, which may be aggravated by sunlight. Repeated exposure may cause alteration of skin pigments as
well as cancerous growth, although there is no carcinogenic data for anthracene. Inhaled anthracene can cause
bronchitis-like symptoms. There is limited information on human reproductive implications. Anthracene may
cause genetic mutations in cells. It is not currently considered a toxic substance.
Anthracene released to the ground would sorb to the soil and would represent a minimal problem for
groundwater contamination. Anthracene would be subject to biodegradation in the ground. It would not
hydrolyze due to the lack of functional groups. The half-life for biodegradation of terrestrial released anthracene
is about 100 to 150 days. Its strong adsorption to particulate matter reduces its bioavailability.
Most of the anthracene released into the atmosphere would volatilize or sorb to particulate matter. It would be
subject to photolysis immediately. A very short half-life is associated with its atmospheric fate, in the order of
hours to days depending on the degree of adsorption. The non-adsorbed compound will have a shorter half-life
than the adsorbed compound:it is broken down via ozonation and hydroxide radical photolysis.
Phenanthrene is an isomer of anthracene. Instead of three rings in a line, as in anthracene, phenanthrene has dne
of its rings removed from the line. Their structure is very similar and so are their properties.
Phenanthrene is used in the production of dyes. It is also used in the manufacture of explosives, and is an
important raw material for phenanthrene-based drugs. This leads directly to its use in biochemical research for
the pharmaceutical industry.
There is no drinking water standard for phenanthrene, and it can be disposed of on land. However, much of the
recoverable phenanthrene is either used for on-site energy production (incineration) or recycled by simple
separation and purification techniques. Release of phenanthrene into the water would also be governed by
sorption. Most of the released compound should be removed from the water by sorption to particulate matter and
dissolved organic matter. The degree of sorption depends upon the sorption mechanism, which depends in turn
on the type of sorbent.
Benzopyrene (3,4-benzopyrene) is the largest of the four compounds, with five rings (figure 5). It also has a
faint aromatic odor. Pure benzopyrene is pale yellow, and is found as monoclinic or orthorhombic crystals.
Benzopyrene is the only dne of the four compounds that is a known human carcinogen.
Benzopyrene is formed when gasoline, garbage or any plant or animal materials are burned, so it is usually
present in soot and smoke. It is also found in the coal tar pitch industry, and is used to join electrical parts
together. It is also present in creosote, a chemical used for wood preservation.
The largest sources of benzopyrene in the air are open burning and home heating with wood and coal. Factories
that produce coal tar also release small amounts of benzopyrene into the air. It is estimated that more than 100
metric tons per year of the total benzopyrene emissions into the atmosphere are a result of coal-fired residential
furnaces, coke production, forest fires, and burning coal refuse banks. More than 10 metric tons of benzopyrene
are released from coal-fired industrial boilers, residential fireplaces, iron and steel sintering, commercial
incinerators, open burning of automobile components and leaves, trucks and automobiles, and tire wear.
The general population may be exposed to benzopyrene in dust, soil, and other particles.
Food grown in contaminated soil or air may contain benzopyrene. Benzopyrene has been found in various types
of cereals, vegetables, fruits, and meats. It is also a component of tobacco products, and is dne of the cancer-
causing agents in cigarette smoke.
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Benzopyrene is a known precursor to cancer-causing metabolites in laboratory animals. Various studies have
determined that benzopyrene is toxic. It is converted by cytochrome P450 to a variety of oxides that react with
DNA, making them highly mutagenic.
Benzopyrene released into the atmosphere would likely be associated with particulate matter and could be
subject to moderately long-distance transport. The degree of transport depends on the particle size distribution
and climatic conditions, which determine the rate of wet and dry deposition. Benzopyrene released into soil
would adsorb very strongly to the soil and would not leach to the groundwater. It would not hydrolyze.
Evaporation from soils and surfaces would not be significant due to the benzopyrene’s higher molecular weight.
Benzopyrene released into water would also adsorb very strongly to sediments and particulate matter. It would
be expected to bioconcentrate in aquatic organisms without metabolism. Benzopyrene would undergo significant
photo-degradation near the surface of waters. Adsorption to sediments and particulates could significantly retard
biodegradation, photo-degradation, and evaporation.
Biodegradation tests of benzopyrene in soils have resulted in a range of reported half-lives between 2 and 1.9
years. Based on these values and the apparent lack of a significant competing fate process, biodegradation may
be an important process in soils. See PAHs.
2.4 Benzene, Toluene and Xylene (BTEX)

Benzene is a colorless liquid with a sweet odor. Benzene evaporates into air very quickly and dissolves slightly
in water. It is highly flammable. The chemical structures of benzene, toluene and xylene are shown in figure 7.
Figure 7. Chemical structures of benzene, toluene and xylene.
Benzene found in the environment derives from both human activities and natural processes. Benzene was first
discovered and isolated from coal tar in the 19th century. Industrially, benzene is made mostly from petroleum
sources. Various industries use it to make other chemicals, such as styrene, cumene (for various resins), and
cyclohexane (for nylon and synthetic fibers). Benzene is also used in the manufacture of some types of rubbers,
lubricants, dyes, detergents, drugs, and pesticides. Natural sources of benzene, which include volcanoes and
forest fires, also contribute to its presence in the environment.
Benzene is commonly found in the environment. The main sources of benzene in the environment are industrial.
Since tobacco contains high levels of benzene, tobacco smoke is another source of benzene in air. Industrial
discharge, disposal of products containing benzene, and gasoline leaks from underground storage tanks can
release benzene into water and soil.
Benzene can pass into air from water and soil surfaces. Once in the air, benzene reacts with other chemicals and
breaks down within a few days. Benzene in the air can attach to rain or snow and be carried back down to the
ground.
Benzene in water and soil breaks down slowly. It is slightly soluble in water and can pass through the soil into
groundwater. Benzene in the environment does not build up in plants or animals.
Benzene is converted to products known as metabolites in the liver and bone marrow. Some of the harmful
effects of benzene exposure are believed to be caused by these metabolites.
Toluene is a clear, colorless liquid with a distinctive smell. It is added to gasoline along with benzene and
xylene. Toluene occurs naturally in crude oil and in the tolu tree. It is produced in the process of making gasoline
and other fuels from crude oil, in making coke from coal, and as a byproduct in the manufacture of styrene.
Toluene is used in making paints, paint thinners, fingernail polish, lacquers, adhesives, and rubber and in some
printing and leather tanning processes.
Toluene enters surface water and groundwater (wells) from spills of solvents and petroleum products as well as
from leaking underground storage tanks at gasoline stations and other facilities. Leaking underground storage
tanks also contaminate the soil with toluene and other petroleum-product components.
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Toluene does not usually remain in the environment. It is readily broken down into other chemicals by
microorganisms in soil and evaporates from surface water and surface soils. Toluene dissolved in well water
does not break down quickly while the water is undergroundbecause there are few microorganisms in
groundwater. Once the water is brought to the surface, the toluene will evaporate into the air. The toluene in the
air will combine with oxygen and form benzaldehyde and cresol, which can be harmful.
Toluene can be taken up into fish and shellfish, plants, and animals living in water that contains toluene, but it
does not concentrate or build up to high levels because most animal species can transform the toluene into other
compounds that are excreted.
In animals, the main effect of toluene is on the nervous system. Animals exposed to moderate or high levels of
toluene may also show slightly adverse effects in their liver, kidneys, and lungs.
The International Agency for Research on Cancer (IARC) has not classified toluene for carcinogenic effects.
There are three forms of xylene in which the methyl groups vary on the benzene ring: meta-xylene, ortho-xylene,
and para-xylene (m-, o-, and p-xylene). These different forms are referred to as isomers. The term total xylenes
refers to all three isomers of xylene. Mixed xylene is a mixture of the three isomers. Xylene is primarily a
synthetic chemical. Xylene also occurs naturally in petroleum and coal tar and is formed during forest fires. It is
a colorless, flammable liquid with a sweet odor.
It is used as a solvent (a liquid that can dissolve other substances) in the printing, rubber, and leather industries.
Along with other solvents, xylene is also used as a cleaning agent, a paint thinner , and in varnishes. It is found
in small amounts in airplane fuel and gasoline. Xylene is used as a material in the chemical, plastics, and
synthetic fiber industries and as an ingredient in the coating of fabrics and papers. Isomers of xylene are used in
the manufacture of certain polymers, such as plastics. Xylene evaporates and burns quickly.
Xylene is a liquid, and it can leak into soil, surface water (creeks, streams, rivers), or groundwater, where it may
remain for months or more before it breaks down into other chemicals. However, because it evaporates easily,
most xylene (if not trapped deep underground) goes into the air, where it remains for several days. In the air,
xylene is broken down by sunlight into other less harmful chemicals.
Xylene very quickly evaporates into the air from surface soil and water, remaining there for several days until it
is broken down by sunlight. .
Most xylene in surface water evaporates into the air in less than a day. The rest of it is slowly broken down into
other chemicals by small living organisms in the water. Only very small amounts are taken up by plants, fish,
and birds.
Xylene evaporates from soil surfaces. If it is below the soil surface, it will remain there for several days and may
travel down through the soil and enter groundwater. Small living organisms in soil and groundwater may
transform it into other less harmful compounds, although this happens slowly. It is not clear how long xylene
remains trapped deep underground in soil or groundwater, but it may be months or years. Xylene remains longer
in wet soil than in dry soil. If a large amount of xylene enters soil from an accidental spill, a hazardous waste
site, or a landfill, it may travel through the soil and contaminate drinking water wells. Only a small amount of
xylene is absorbed by animals that live in water contaminated with xylene.
One of the breakdown products of xylene, methylbenzaldehyde, is harmful to the lungs of some animals. See
benzene, toluene, xylene.
2.5 Dioxins
The chlorinated dibenzo-p-dioxins are a class of compounds that are loosely referred to as dioxins. There are 75
possible dioxins. The most frequent contaminant of the environment is 2,3,7,8- tetrachlorodibenzo-p-dioxin
(2,3,7,8-TCDD, further just TCDD). It is a colorless solid with no known odor and its structure is shown in
figure 8.
Figure 8. Chemical structure of TCDD.
Although TCDD occurs naturally (volcanic eruptions, forest fires), it is not intentionally manufactured by any
industry, except as a reference standard. It can be inadvertently produced in very small amounts as an impurity
during manufacturing processes. Among the main sources of dioxins are chlorine bleaching used in pulp and
paper mills, production of some herbicides, and incineration of municipal and industrial waste. TCDD is also
included in some wood preservatives and as an impurity in PCBs.
Dioxins are highly persistent compounds. They can be transported in the atmosphere over long distances, and
traces can thus be found throughout the environment. Dioxins are fat soluble and bioaccumulate in most animals;
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this causes their presence in the natural and human food chains. Bioaccumulation occurs mostly in the fat and
fatty organs. Small amounts may also be found in skin, muscle and other organs.
In general, absorption is greater when dioxins and furans are ingested or inhaled than through dermal exposure.
Persons eating highly contaminated fish in quantities well in excess of the general population may approach or
exceed the guideline for intake. Elevated levels in some fish and shellfish near pulp and paper mills that use
chlorine bleaching have necessitated closure of the affected fisheries in order to protect human health.
According to one estimate of ambient exposure, breathing air constitutes 2 percent, drinking water less than 0.01
percent, and consuming foods 98 percent of the total human exposure to TCDD. Contaminated foods are
predominantly fish and dairy products.
Dioxins have toxic effects in parts per trillion because they are powerful hormone-disrupting agents. The most
consistent effect of exposure (through inhalation, ingestion, or dermal contact) is chloracne. Other effects that
have been observed include fluctuations in serum levels of liver enzymes; pulmonary deficiency; sensory
changes such as numbness, nausea, headaches, loss of hearing etc.
A conclusive link between cancer in humans and dioxins and furans has not been established. The International
Agency for Research on Cancer (IARC) considers dioxins and furans to be possibly carcinogenic to humans.
Dioxins were the primary toxic component of Agent Orange (the herbicide used in the Vietnam war), were found
at Love Canal in Niagara Falls, NY and were the basis for evacuations at Seveso (Italy) and in other industrial
accidents. See Seveso, dioxins.
2.6 Trichlorethene (TCE)

Trichloroethene is a nonflammable, colorless liquid at room temperature with a somewhat sweet odor and a
sweet, burning taste. This manmade chemical does not occur naturally in the environment. Trichloroethene is
now mainly used as a solvent to remove grease from metal parts. It is also used as a solvent in other ways and is
used to make other chemicals.
By far the biggest source of trichloroethene in the environment is evaporation from factories that use it to
remove grease from metals. It can also enter the air and water when it is disposed of at chemical waste sites. It
evaporates easily but can remain in the soil and in groundwater. TCE can be degraded by processes such as
photo-oxidation and biodegradation. TCE does not partition to aquatic sediments except to those with a high
organic substance content. Once it is in the air, about half will be broken down within a week. When
trichloroethene is broken down in the air, phosgene, a lung irritant, can be formed. Chemical products of the
degradation have been shown to be toxic to animals and are probably toxic to humans. It will take days to weeks
to break down in surface water; in groundwater the breakdown is much slower because of the much slower
evaporation rate. In subsurface soils the sorption and desorption of trichloroethene is slow. Thus, subsurface
liquid TCE may continue to contaminate groundwater aquifers and soils long after its sources have been
eliminated. It is found in some foods; the trichloroethene found in foods is believed to come from contamination
of the water used in food processing, or from food processing equipment cleaned with trichloroethene. TCE is
unlikely to bioaccumulate significantly.
Trichloroethene enters the human body through breathing air or drinking water containing it. It can also enter
body through skin contact. If inhaled, about half the amount will enter the bloodstream and organs; the rest will
be exhaled. If TCE is drunk in water, most of it will be absorbed into the bloodstream. Once in the blood, the
liver changes much of the trichloroethene into other chemicals. The majority of these breakdown products pass
out of the body in urine within a day. Some of the trichloroethene or its breakdown products can be stored in
body fat for a brief period, and thus may build up in the body if exposure continues.
Trichloroethene was once used as an anesthetic for surgery. People who are exposed to large amounts of
trichloroethene can become dizzy or sleepy and may become unconscious when exposed to very high levels.
Inhalation of large amounts may cause death. Animals that were exposed to moderate levels of trichloroethene
had enlarged livers, and high-level exposure caused liver and kidney damage. We do not have any clear evidence
that trichloroethene alone can cause leukemia or any other type of cancer in humans. See TCE.
2.7 Freons
"Freon" is not a chemical term but rather a trade name that describes a whole class of chemicals. Freons are
hydrocarbon derivatives that contain fluorine, and often chlorine and bromine, attached to hydrocarbon
molecules. They are generally colorless, odorless, nontoxic, non-corrosive, and nonflammable.
The origin of freons is industrial although methyl chloride (CH3Cl) and methyl bromide (CH3Br) are also
produced by marine organisms. Freons are used as foam-blowing agents, solvents, propellants, and fire
extinguishers. The most commonly used freons are CFC-12 (CCl2F2), CFC-11 (CCl3F), CFC-22 (CHClF2). Fully
halogenated methanes CCl2F2 and CCl3F have very stable molecules and their lifetime is in the range of 60 to
130 years. The freons are also categorized as hard (causing heavy damage) and soft (causing lighter damage).
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During the use of freons for various purposes, they are released into the atmosphere. The decay of freons in the
atmosphere is dependent on the season (temperature) among other factors. Ultraviolet light usually causes freons
to decay in the top layers of the stratosphere. This reaction is catalyzed by low temperatures and sufficient
periods of sunlight. This is why the ozone layer is most depleted at the Earth's poles. After the decay of the freon
molecule, the chlorine forms reactive radicals such as Cl- and ClO-, which then react with ozone O3, resulting in
a reduction in thickness of the ozone layer. This is causing increasing transmission of ultraviolet solar radiation.
In comparison with chlorine, released fluorine is relatively inert. Free F- forms hydrogen fluoride (HF) which is
stable in the stratosphere. Chlorine forms HCl which is rapidly decomposed by OH- radicals. Released Br- which
analogously forms hydrogen bromide (HBr) is less abundant and its importance may possibly increase in the
future.
Species Relative abundance (parts per Source Comment

billion by volume)
CH3Cl 6.0x10-1 Biological Short-lived
CCl2F2 6.0x10-1 Industrial Increasing
CCl3F 6.0x10-1 Industrial Increasing
CCl4 6.0x10-1 Industrial Increasing
CH3CCl3 6.0x10-2 Industrial Increasing
CF4 6.0x10-2 Industrial Increasing
CH3Br 6.0x10-2 Industrial, biological Possibly increasing
Table 4.Selection of manufactured and used freons.
Increased transmission of ultraviolet rays towards the Earth's surface is dangerous for all life forms. For animals,
including humans, it may result in various types of skin cancer and eye damage. But the more important concern
is damage to the ecological conditions of various microorganisms (vegetation, bacteria and viruses) which are
very important for the maintenance of global equilibrium. See freons, ozone depletion, ozone hole.
3. Recommendations
Industry and government should focus on the development of novel, cost-effective remediation and disposal
techniques. Issues connected with deposition of the trace elements and environmental contaminants will clearly
be resolved by reducing emissions.
The old environmental impact remediation methods are undergoing further development and it is necessary to
continue to seek effective, economically affordable and environmentally sensitive techniques. It should be said
that some effective processes of contamination remediation have been developed: an example is the
biodegradation of some organic materials by bacteria.
Consumption of natural resources will decrease when humans acknowledge and work towards goals such as
product minimalisation and recycling.
Research on pathways, modes of exposure, and process mechanisms must continue in order to detect and
develop important new techniques in environmental science.
Bibliography
Azcue J.M. (Editor) (1998): Environmental Impact of mining activities:Emphasis on Mitigation and Remedial
Measures, 220 pp, New York: Springer Verlag. [Review of new remediation techniques and a number of case
studies throughout the world]
Ebinghaus R., Turner R.R., de Lacerda L.D., Vasiliev O., Salomons W. (Eds.) (1999). Mercury Contamined
Sites, 538 pp, Berlin: Springer - Verlag. [Natural and anthropogenic Hg sources and their impact on the
environment, international case studies]
Förstner, U. (1998). Integrated Pollution Control, 505 pp, Berlin: Springer - Verlag. [Information about organic
and inorganic contaminants of soil, water, air with descriptions of remediation techniques]
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Förstner, U., Wittmann G.T.W. (1981). Metal Pollution in the Aquatic Environment, 486 pp, Berlin: Springer
Verlag. [Comprehensive study of trace elements in aquatic systems, sediments and organisms]
Nriagu J.O. (Ed.) (1980). Cadmium in the Environment, Part 1 Ecological Cycling, pp 682, John Wiley. [Global
cycle of Cd, its distribution in waters, atmosphere, soils, and its interactions with organic matter]
Siegel F.R. (Ed.) (1979). Review of Research on Modern Problems in Geochemistry, 290 pp, Unesco
Publication, Earth Science, Vol. 16. [The distribution of chemical elements in individual geospheres, weathering
processes and soil formation, air pollution, the role of some elements in the nutrition of plants, animals and
humans]
Thornton J. (1983). Applied Environmental Geochemistry, 501 pp, London: Academic Press. [The forms of trace
elements in soils, waters, and plants, analytical methods, case studies from Great Britain and Scandinavia]
Wania, F. & Mackay, D., 1996: Tracking the distribution of Persistent Organic Pollutants. Control strategies for
these contaminants will require a better understanding of how they move around the globe. Environmental
Science and Technology. Feature Article. Vol.30, No.9, 390-396. [Requirements and issues for future control
over persistent organic pollutants]
Wedepohl K.H. (Ed.) (1969-78). Handbook of Geochemistry II.1 - II.5., Berlin: Springer - Verlag. [Basic data on
the distribution of all chemical elements in the lithosphere, hydrosphere, and atmosphere]
19

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TRACE ELEMENTS AND CONTAMINANTS

T. Navrátil, Institute of Geology, Academy of Sciences, Prague, CR

1.1. Primary Dispersion

1.2 Secondary Dispersion

1.3 Tertiary Dispersion

1.4 The Main Sources of Trace Element Contamination

in the text as follows:

paints and coatings As Cd Cr Pb Cu Hg Sb Zn

crude oil processing As Cr Pb Zn

iron and steel production As Cd Cr Pb Cu Hg Sb Zn

nonferrous metal refinery As Cd Cr Pb Cu Hg Sb Zn

Table 1. Sources of selected chemical compounds.

1.5 Environmental Impacts of Selected Trace Elements: Arsenic, Cadmium, Mercury

Arsenic Cadmium Mercury Lead

Natural emissions (t yr-1) 10 000 290 2 500 4 000

Figure 2. World production and emissions of Cd in the 20th century

4.2 Organic Contaminants

2.1 Pesticides (DDT and other compounds)

Aldrin Arsenic Bromomethane

Chlordane DDT Endrin

Hexachlorobenzene Metoxychlor Mirex

Naphthalene Phenol Toxaphene

Table 3. Examples of pesticides.

Figure 3. Chemical structure of DDT.

2.2 Polychlorinated Biphenyls (PCBs)

Figure 4. Example of polychlorinated biphenyl molecule structure.

2.3 Poly Aromatic Hydrocarbons (PAHs): Naphtalene, Anthracene, Phenantrene and

Figure 5. Chemical structures of naphthalene, anthracene, and phenanthrene.

Figure 6. Chemical structure of benzopyrene.

2.4 Benzene, Toluene and Xylene (BTEX)

Figure 7. Chemical structures of benzene, toluene and xylene.

Figure 8. Chemical structure of TCDD.

2.6 Trichlorethene (TCE)

Species Relative abundance (parts per Source Comment

Table 4.Selection of manufactured and used freons.

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