VŠB – Technical university of Ostrava
METALS AND THE
ENVIRONMENT
Learning text
Malcharcziková Jitka
Ostrava 2016
Name: Metals and the Environment
Author: Malcharcziková Jitka
Edition: first, 2016
Number of pages: 70
Learning text for degree course Progressive Technical Materials, Faculty of Metallurgy
and Materials Engineering
Proofreading: not performed.
Last edit: 06/2016
© Malcharcziková Jitka
© VŠB – Technical University of Ostrava
Study regulations
1
STUDY REGULATIONS
Metals and the Environment
For the subject “Non-ferrous Metal Recycling / Metals and the Environment” in the 3rd
/4th
semester of the follow-up studies of the branch “Progressive Technical Materials” you
have obtained an educational lecture notes for the combined study comprising also study
regulations.
1. Prerequisites
The subject has no prerequisites.
2. The objectives of the subject and outputs from the education
The aim of the subject is to introduce students to issues of metals affecting particular
segments of the living environment and possibly also humans.
After studying the subject, a student should be able to:
Knowledge:
- Describe and characterize potential sources of heavy metal pollution of air, water and
soil,
- Describe and characterize the toxic and ecotoxic effects of selected metals, specific
pollution sources and routes,
Skills:
- Evaluate ecological and economic aspects of the use of materials containing metals,
- Apply the theoretical knowledge for the environmental management system.
For whom the subject is intended
The subject falls within the follow-up study of the branch “Progressive Technical
Materials” of the study program “Materials Engineering”, but it can also be studied by
applicants from any other branch.
Recommended procedure for studying each chapter:
The lecture notes are divided to parts – chapters, which correspond to the logical dividing
of the studied subject matter, but they are not of the same volume. The assumed time for
the study of the chapter may differ significantly, therefore large chapters are further
divided to numbered subchapters and these correspond to the structure of the lecture notes
described below.
Study regulations
2
First, go through each chapter carefully. Then check-up whether you’ve learned the basic
terms of the chapter. If not, we recommend to go back to look for the given term in the
text. Answer the questions to the topic. After having comprehended the chapter, you can
go on. The individual chapters mostly do not continue in the content of the previous ones,
so chapters may be studied in an order by your own choice. The given time for studying
the text serves only as a general guide.
A way to communicate with lecturers:
Within this subject, these lecture notes will be provided and a topic for a seminar project
will be given. Topics and requirements for elaboration of the seminar project will be given
over to students within tuition, or may be sent by e-mail upon asking a teacher. The
elaborated seminar project can be sent 1x via e-mail to the teacher to be checked. After
incorporating the comments, the corrected version will be given to the teacher via e-mail as
well as in the printed form. All questions will be replied by e-mail, through contacting the
teacher by sending an e-mail. For the e-mail communication we recommend to use the
University e-mail address and to state the message subject properly. In extraordinary cases,
the teacher may be also contacted by phone. Detailed instructions for studying and contacts
to the teacher will be given to students at the beginning of the course in which they will be
present.
Content
3
Content
1. Heavy metal based pollutants in air, water and soil 4
1.1. Basic terms 4
1.2. Pollutants in air 9
1.3. Pollutants in water 10
1.4. Pollutants in soil 10
2. Pollution sources and routes 12
2.1. Basic principles of transport of pollutants in the environment 12
2.2. Bioaccumulation, biotransformation 13
3. Integrated prevention, information sources in toxicology 16
3.1. IPPC, BREF, BAT 16
3.2. REACH and Material Safety Data Sheets 18
3.3. The environmental pollution registers 20
3.4. Tools and guidelines to reduce the negative impacts of production on the environment 21
4. Influence of lead on the environment 26
4.1. Lead 26
4.2. Potential sources of pollution 27
4.3. Toxicity and ecotoxicity of lead 28
5. Influence of cadmium on the environment 30
5.1. Cadmium 30
5.2. Potential sources of pollution 30
5.3. Toxicity and ecotoxicity of cadmium 32
6. Influence of arsenic on the environment 34
6.1. Arsenic 34
6.2. Potential sources of pollution 34
6.3. Toxicity and ecotoxicity of arsenic 36
7. Influence of mercury on the environment 39
7.1. Mercury 39
7.2. Potential sources of pollution 40
7.3. Toxicity and ecotoxicity of mercury 42
8. Influence of copper and aluminum on the environment 46
8.1. Copper, influence on the environment, toxicity and ecotoxicity, potential
sources of pollution 46
8.2. Aluminum, influence on the environment, toxicity and ecotoxicity, potential
sources of pollution 47
9. Influence of chromium and nickel on the environment 51
9.1. Chromium, influence on the environment, toxicity and ecotoxicity, potential
sources of pollution 51
9.2. Nickel, influence on the environment, toxicity and ecotoxicity, potential
sources of pollution 53
10. Influence of tin, zinc, selenium and other heavy metals on the environment 57
10.1. Influence of tin on the environment, its toxicity and ecotoxicity, potential
sources of pollution 57
10.2. Influence of zinc on the environment, its toxicity and ecotoxicity, potential
sources of pollution 60
10.3. Influence of selenium on the environment, its toxicity and ecotoxicity, potential
sources of pollution 61
10.4. Influence of other metals on the environment, their toxicity and ecotoxicity 62
11. The environment and legislation 65
11.1. Waste Act, the basic terminology 65
11.2. Waste manegement 66
Annexes 70
Heavy metal based pollutants in air, water and soil
4
1. Heavy metal based pollutants in air, water and soil
Study time: 2 hours
Objective After reading this paragraph, you will be able to
define the basic terms of toxicology and ecotoxicology
describe and characterize the toxic and ecotoxicological effects of selected
metals, specify the sources and routes of contamination
Lecture
About 80 elements in the periodic table of the elements belong to metals, 30 of them are called
toxic metals. However, plenty of metals are essential for the organism in trace concentrations -
such as Cr, Cu, Zn or Fe, which are a part of some enzymes. Their deficiency may develop in a
serious disease.
1.1 Basic terms
Trace metals - metals occurring in organisms or in the living environment in very low
concentrations corresponding to only few ppm.
Heavy metals - metals the density of which is higher than 5 gcm-3
(e.g. Cd, Hg, Pb).
Toxic metals - metals, which in specific concentrations have harmful effects on humans and other
biotic ecosystem components.
Within “toxicology” the term “heavy metals” also covers other metals and metalloids (half-
metals), such as arsenic, which have toxic effects. Along with development of new knowledge on
negative effects of particular metals and with regard to the actual occurrence of metals in new types
of wastes, characteristics complementing a term ‘heavy metals’ have been defined step by step.
Toxicologically significant ellements are on the Fig. 1.1.
Heavy metals
Heavy metals: • Heavy or toxic metals are typically meant selected metals, the negative effect of which on
animal and plant organisms has been proven.
• Heavy metals also include some elements from the transition area and some non-metals (As,
B, Se).
• Radioactive metals are not categorized as heavy metals; their evaluation is performed with
regard to another type of toxic effect preferentially determined by the emitted radiation effect.
Using available groundwork on toxicity of particular metals, the following classification is
proposed according to a rate of their unwholesomeness:
I. HIGHLY HAZARDOUS METALS - Cd, Hg, Pb
II. MEDIUM HAZARDOUS METALS - Ag, Al, As, Be, Cu, Co, Cr, Ni, V, Zn
III. LOW HAZARDOUS METALS - Ba, Fe, Ga, Ge, Mo, Mn, Sb, Sn, Ti, W
Heavy metal based pollutants in air, water and soil
5
Fig. 1.1 Toxicologically significant ellements (PTE by DRÁPALA, J., VŠB-TUO, 2007)
Some sources give this descending order of toxicity of metals:
for vegetable production: Hg, Cu, Ni, Pb, Cd, Co and other metals
for livestock production: Cd, Hg, Pb, As and other metals.
Plenty of heavy metals are considerably toxic for humans, animals and plants, their dangerousness
is increased by a summation effect – they are stored and accumulated in the organism through the
food chain. Some of them are carcinogenic, others mutagenic or teratogenic.
It is generally stated that the mutagenic activity of metals ascends in the order:
(Cr > Be > As > Ni > Hg > Cd > Pb),
and the carcinogenic capability ascends in the order:
(As > Cr > Ni > Be > Pb = Cd = Hg).
Hg, Pb, Cd, Cu, Zn exhibit a high accumulation coefficient.
Toxicity of heavy metals relate to their passability through cell membranes, their capability to bind
to proteins and thus their ability to accumulate in some tissues.
Many metals block the activity of enzymes with -SH groups, thus influencing vital functions.
Hazardousness and toxicity depends not only on the total concentration of the metal in the
environment, but also on the form of occurrence of the metal.
Occurrence forms:
1. according to solubility
solved forms
non-solved forms
2. according to the physical-chemical principle
inorganic forms
organic forms.
Toxicologically significant ellements
PERIODIC TABLE OF ELEMENTS
Heavy metal based pollutants in air, water and soil
6
If intoxication by more metals at the same time occurs, their simultaneous effect may be
influenced:
amplification of effects = synergetic acting (e.g. Cd + Zn, Ni + Zn, Hg + Cu),
attenuation of effects = antagonistic acting (e.g. Zn in a form of salts reduces the
carcinogenic effect of cadmium, metals reduce the carcinogenic effect of benzo(a)pyrene).
Toxicity of substances
Toxicology is a science of adverse effects of substances on a living organism.
Toxicity reflects the degree of toxicity of the substance to the target organism or tissue.
Toxicity of substances depends on:
a chemical structure
a route of entry into the organism
receptivity (sensitivity) of a target organism
a time period of acting (exposure)
a daytime of acting
a physical condition, sex, age, weight of an individual etc.
Poison, or a toxic substance, in the widest sense of the word is a substance capable of producing
an adverse effect. However, each substance may produce an adverse effect under specific
conditions – the dose determines the degree of effect. More or less, only those substances are
considered poisons, which are capable of producing an adverse effect – poisoning – even with
small doses.
Dose - quantity of a substance that enters the organism and is absorbed.
Xenobiotic – a foreign chemical substance in an organism that is not normally present within that
organism, is not either a natural product of that organism or an intermediate product of the physical
metabolism.
In toxicology, substances are categorized conventionally to several categories according to a lethal
dose capable to kill an adult human of average size (about 70 kg, Tab. 1.1) – only refers to an
acute, immediate effect (does not include a long-term exposure).
Tab. 1.1 Categorizing of subtances conventionally to several categories according to a dose capable
to kill an adult human of average size
Categories Approximate lethal dose after
ingestion
Example
[mg/kg] The total quantity
for human
1. Practically non-toxic >15 000 More then liter BaSO4
2. Slightly toxic 5 – 10 000 0,5 – 1 liter ethanol – lethal dose for
children is about 3,5 g/kg
3. Moderately toxic 500 – 5 000 0,05 - 0,5 liter NaCl, FeSO4
4. Highly toxic 50 - 500 1 spoon – 0,05 liter Cd2+
, Pb2+
, methanol
5. Extremely toxic 5 – 50 7 drops – 1 spoon BaCO3, KClO3
6. Supertoxic < 5 Trace amount, less then
7 drops
nicotin, As3+
, botulotoxin
Poisoning = intoxication – a damage of vital functions of an organism in consequence of a toxic
substance acting.
Exposure time is a period of time for which an organism is exposed to effects of some toxic
substance.
Heavy metal based pollutants in air, water and soil
7
There are two types of toxicity:
• acute – one-time exposure,
• chronic – repeated exposure to relatively small doses.
For chronic toxicity is exposure time a highly important parameter.
Toxicity of a specific compound is determined by its structure, solubility in water and in acidic
environment (stomach), which means absorbability in the organism. This depends on a way of
exposure (entry gate) – “which way and how a substance gets to the organism” (ingestion,
inhalation, skin absorption …).
Branches of toxicology
Toxicology has many branches overlapping both one another and the fields of other scientific
disciplines.
Branches of toxicology:
chemical toxicology – synthesis, preparation, separation, kvalitative and kvantitative
analysis,
farmacological toxicology – effect on organism, side effect, synergism, antagonism ….
biochemical toxicology – metabolism of action at the molecular level, toxins metabolism
clinical toxicology – diagnostic and healing of poisoning
industrial toxicology – toxic substances occurring in the industry, their detection and
analysis, determine the max. allowable concentrations and doses, exposure tests ...
food toxicology – natural toxic substances, additives, preservatives ….
veterinary toxicology – toxicic substances in animal feed, their content in product of
animal origin
agriculture toxicology – toxic substances in the agricultural products
military toxicology – chemical warfare agents
ecotoxicology – toxicology of environmental.
Ecotoxicology
This is a boundary field between toxicology and ecology, dealing with effects of foreign substances
on freely living organisms in their environment (environmental toxicology). In a broad sense, this
involves a transfer of pollutants from the environment to a human directly from environment
components (water, air, soil) or indirectly through natural or human-directed food chains (food
production).
Ecotoxicological tests
Ecotoxicological tests monitor reactions of a specified organism (e.g. a rat, mouse, fish, algae …)
when exposed to a known substance with a known concentration; risks following from the
exposure of the observed chemical substance to the organism can be deduced from the reaction of
the organism, the results of tests can be possibly approximated to humans.
Interaction of toxic substances with living organism
Foreidn substances (xenobiotics) bind to a certain place in an organism, the so-called receptor,
thus influencing some important vital function (Fig. 1.2). In the literature now receptors have
particular names, usually by a target molecule.
Heavy metal based pollutants in air, water and soil
8
Xenobiotic
Complex
Functional change
Fig. 1.2 Scheme of effects of xenobiotic
Varied effects may show after acting of a foreign substance:
mild nausea
digestive problems
disorders of the nervous system
death.
A foreign substance may either act on the place of entry (locally – skin, mucosa of the respiratory
or gastrointestinal tract) or in another target place in the system after the distribution in the
organism, then this is a system effect.
According to a process (mechanism) of acting, effects are divided as follows:
Direct toxic effect – a substance acts by its mere presence in the critical point of the
organism, it is not bound to a receptor (to a target molecule)
Biochemical effect – a substance interacts with a target molecule (receptor), influences
some biochemical action and through this some of vital functions (most frequently this is
the inhibition of enzymes)
Immunotoxic effect - changes in the immune system manifesting themselves as a decrease
in immunity (immunosuppression) or an inadequate reaction (allergic reaction)
Mutagenity – a change in genetic information leading to a change in properties of
following generations
Carcinogenity - change in a genetic information leading to growth of malignant tumors
Teratogenity – malformations of a fetus leading to birth of a defective individual.
Metals monitoring in the environment
Why are metals a hazardous group for health of organisms and need to be monitored in the
environment?
1) Toxicity – often in very low concentrations (e.g. LD50 As2O3 for humans 200 - 300 mg)
2) Bioaccumulation in the organism
3) Carcinogenity (Cd, As, Cr VI
, Ni, Be)
4) Nondegradability (indecomposableness), Persistence (stability)
5) Increase in concentrations in the environment (mainly in last 100 years).
Anthropogenic ways of entry of metals to the environment
The most frequent anthropogenic ways of entry of metals to the environment (through human
activity):
• mining
• metallurgy
• waste waters (+ runoff)
• textile industry
Heavy metal based pollutants in air, water and soil
9
• production of dyes and plastics
• vehicles and automotive industry
• agricultural industry (Cd, fertilizers, pesticides …)
• fossil fuel burning (As, Cd, …)
• waste incineration, etc.
1.2 Pollutants in air
Pollution of air – occurrence of gaseous, liquid and solid state substances foreign to nature.
The most significant anthropogenic pollution sources (through human activity):
• combustion processes (fossil fuel burning in combustion engines, in energy producing
devices, in small household furnaces)
• metallurgy
• chemical industry
• agricultural industry
• waste incineration…
Why is dust dangerous? • The source of fine dust particles is transport, power plants, industry, household furnaces or
building works.
• They may initiate respiratory diseases, reduce lung functions and increase death rate.
• Other pollutants including carcinogenic substances may bind to particles.
• High concentrations of microscopic particulate matter, less than 10 micrometers (PM10), or
2.5 micrometers (PM2.5), belong to the most serious air problems.
• Particulate matter also includes metals (Fig. 1.3), for example lead occurs in a fraction of
PM1.0 size (particles less than 1 μm).
https://dspace.vutbr.cz/bitstream/handle/11012/39680/Kratky_diplomka.pdf?sequence=1
Fig. 1.3 Metal particles in comparison with dust particles and pollen
Emissions and immission
Emissions and air pollution express the concentration of smog and other pollutants in the air.
Emissions are measured at source (eg. chimney), while air pollution in its nearby area.
Emissions (from the Latin emitter, polluters) are air pollutants. Maximum concentrations are at
their source (chimney, exhaust, ...) and their concentration gradually decreases due to mixing with
air and others. They may be natural or anthropogenic (human) sources.
Heavy metal based pollutants in air, water and soil
10
Immission (air pollutant, pollutant) is emmission, which came into contact with the environment.
They can accumulate in soil, water or in organisms. In practice, the air pollutions are heavy metals
or other pollutants that are stored in the environment. Immissions are a consequence of emissions.
The most common toxic metals occurring in air are above all lead, cadmium, arsen, nickel and
mercury. Most of these metals are present in the form of particles of very small size, fraction size
PM1,0 (particles less than 1 μm).
1.3 Pollutants in water
The main source of water pollution are waste waters from:
• ore mining and processing
• from metallurgical works, rolling mills, surface finishing of metals
• photography industry, leather manufacture, textile and chemical industry
• agriculture (e.g. Cd from phosphate fertilizers)…
Metals are in a form of:
• simple cations or anions
• complex inorganic and organic compounds.
The most common toxic metals occurring in waters are above all lead, cadmium and mercury.
These metals have a high ability to cumulate in sediments; gradual deposition of water organisms
occurs then. Therefore a content of metals needs to be monitored not only in a liquid phase, but
also in sediments and water organisms.
Classification of dangerousness (toxicity) of metals in waters – Attachment No. 1 to Act No.
254/2001 Coll. (Water Act):
especially dangerous substances
• organotin compounds,
• Hg and its compounds,
• Cd and its compounds
dangerous substances
• metalloids, metals and their compounds – zinc, copper, nickel, chromium, lead, selenium,
arsenic, antimony, molybdenum, titanium, tin, barium, beryllium, boron, uranium,
vanadium, cobalt, thallium, tellurium, silver.
1.4 Pollutants in soil
The main soil pollution sources are:
• immissions from industrial and power engineering plants (coal combustion)
• metallurgical plants
• waste from mining
• agricultural industry (fertilizers based on chemicals, sewage sludge, …) …
Metals are in a form of:
• elementary (metal) form
• simple cations or anions
• complex inorganic and organic compounds.
The most common toxic metals occurring in soils are above all lead, cadmium, mercury and
arsenic.
Soil pollution has a very long-term, or even permanent, character (in contrast to water and air,
which can be diluted and cleaned from pollutants). The fact that pollutants transfer into feed and
food (enter the food chain) has highly negative effects.
Heavy metal based pollutants in air, water and soil
11
Sumary of terms
At the end of the chapter are repeated the main terms that you should acquire:
Toxicology, toxicity of substances
Ecotoxicology
Heavy metals
Question to the topic
1. What is toxicology and ecotoxicology?
2. What is toxicity?
3. What is the difference between acute and chronic toxicity?
4. How can toxic substances interact with living organisms?
5. Explain the term of heavy metals withim toxicology.
References
[1] RAMACHANDRA RAO, S. Resource Recovery and Recycling from Metallurgical Wastes. Elsevier,
London, 2006. ISBN 978-0-08-045131-2.
[2] ASHBY, M. F. Materials and the Environment: Eco-Informed Material Choice. Elsevier Butterworth-
Heinemann, Waltham, 2013, p. 616. ISBN 978-0-12-385971-6.
[3] MANAHAN, S. E. Toxicological chemistry and biochemistry. 3rd
ed. Boca Raton: CRC Press, 2003, p.
783. ISBN 1-56670-618-1.
[4] MANAHAN, S. E. Environmental chemistry. 8th
ed. Boca Raton: CRC Press, 2005. ISBN 1-56670-633-
5.
[5] LANDIS, W. G., YU, M. H. Introduction to environmental toxicology: impacts of chemicals upon
ecological systems. 3rd
ed. Boca Raton: CRC/Lewis Publishers, 2004. ISBN 1-56670-660-2.
[6] YU, M. H., TSUNODA, H., TSUNODA, M. Environmental toxicology: biological and health effects of
pollutants. 3rd
ed. Boca Raton: CRC Press, 2011, p. 375. ISBN 978-1-4398-4038-2.
[7] GRUIZ, K., MEGGYES, T., FENYVESI, E. Environmental toxicology. Boca Raton: CRC Press, Taylor
& Francis Group, 2015. ISBN 978-1-138-00155-8.
Pollution sources and routes
12
2. Pollution sources and routes
Study time: 2 hours
Objective After reading this paragraph, you will be able to
define the basic principles of the movement of pollutants in the environment
describe the basic principles of bioaccumulation and biotransformation of
heavy metals in organisms
Lecture
2.1 Basic principles of transport of pollutants in the environment
Pollutants get to the environment from various sources and are transported on the basis of their
physical-chemical properties and participate in biogeochemical cycles in particular components of
the living environment – air, water, soil (Fig. 2.1).
Through food, inhalation and other routes they enter organisms, where their transformation to
harmless metabolites occurs (detoxification), which can be excreted easily, or they form harmful
reactive products.
Fig. 2.1 Scheme of the sources of heavy metal pollution
http://pubs.usgs.gov/circ/circ1133/images/fig21.jpeg
Pollution sources and routes
13
Foreign substances (xenobiotics) can have lethal (deadly) or sublethal effects, some of them may
undergo biotransformation, bioaccumulation, transfer to other organisms through the food chain.
Follow-up, it results in a response in the affected population, society and ecosystem.
Heavy metals can be introduced into the environment by different processes from many sources.
The sources of heavy metals from anthropogenic activities may be a coal power plants, waste
incinerators, combustion processes, transportation, metallurgical and chemical industry, mining,
agriculture, textile and leather industry, glass factories, sewage treatment plants etc. Metals in the
environment released from natural sources, such as soil erosion, volcanic activity or extensive
forest fires (Fig. 2.1).
2.2 Bioaccumulation, biotransformation
Along with technological development the production and consumption of non-ferrous metals,
which were produced in incomparably less amounts - such as beryllium, titanium, germanium,
gallium, vanadium, selenium, molybdenum, tungsten - has increased dramatically. The production
and application of classic non-ferrous metals and their alloys - such as aluminum, lead, copper,
nickel, chromium, antimony, mercury … - has increased noticeably. An increase in concentration
of these metals in the living environment increases, which is a serious problem!
Metals do not undergo chemical degradation and accumulate in underground soil layers.
Soil microorganisms and aqueous microflora cause that a part of toxic metals enter the bond with
organic substances, by which in many cases their toxicity multiplies or significantly changes. (e. g.
alkylated mercury and arsen). Elements undergoing biomethylation (alkylation) in the natural
environment are Nickel (Ni), Tin (Sn), Antimony (Sb), Mercury (Hg), Lead (Pb), Arsen (As),
Selenium (Se), Germanium (Ge). Toxic metals transfer to the human food chain!
Bioaccumulation, biotransformation
Bioaccumulation is the storage of some substances in organs or tissues of living organisms. In
human most often accumulate in the liver, kidneys, bones, fat tissues. As bioaccumulation indicates
growth as the concentration of chemical in the organism. It occurs usually in the context of the so-
called „Food pyramid“ (Fig. 2.2).
Fig. 2.2 Food pyramid and bioaccumulation of heavy metals
Biotransformation is the chemical modification made by an organism on a chemical compound.
The reaction is catalyzed by enzymes.
Schematic depiction of alkylation and biotransformation of mercury as a result of the metabolic
activity of bacteria (B) and schematic depiction of alkylation and biotransformation of arsenic as a
result of the metabolic activity of bacteria (B) and fungi (P) are shown in figure 2.3 [BENCKO, V.,
CIKRT, M., LENER, J. Toxické kovy v životním a pracovním prostředí člověka. Praha, Grada,
1995.].
http://provegan.cz/bioakumulace-pojem-pro-titulni-stranky-novin-a-casopisu-1175/
Pollution sources and routes
14
Fig. 2.3 Scheme of alkylation and biotransformation of mercury and arsenic (BENCKO, V.,
CIKRT, M., LENER, J. Toxické kovy v životním a pracovním prostředí člověka)
Phytoremediation
Some plants are able to accumulate heavy metals - cadmium, chromium, lead, cobalt, silver,
selenium and mercury. Bioaccumulation potential can also be used positivly, eg. for soil
decontamination.
Phytoremediation is the use of plants and soilmicroflora to soil decontamination.
Phytoremediation is a cost-effective plant-based approach of remediation that takes advantage of
the ability of plants to concentrate elements and compounds from the environment and to
metabolize various molecules in their tissues.
Phytoremediation is an alternative or complimentary technology that can be used along with or, in
some cases in place of mechanical conventional clean-up technologies that often require high
capital inputs and are labour and energy intensive. Phytoremediation is an in situ remediation
technology that utilises the inherent abilities of living plants. It is also an ecologically friendly,
solar-energy driven clean-up technology, based on the concept of using nature to cleanse nature
Sumary of terms
At the end of the chapter are repeated the main terms that you should acquire:
Bioaccumulation
Biotransformation
Phytoremediation
Question to the topic
1. What are the basic principles of the movement of pollutants in the environment?
2. What is bioacumulation?
3. What is biotransformation?
4. Which metals can be subject to biotransformation?
CH3Hg
+
Pollution sources and routes
15
References
[1] RAMACHANDRA RAO, S. Resource Recovery and Recycling from Metallurgical Wastes.
Elsevier, London, 2006. ISBN 978-0-08-045131-2.
[2] ASHBY, M. F. Materials and the Environment: Eco-Informed Material Choice. Elsevier
Butterworth-Heinemann, Waltham, 2013, p. 616. ISBN 978-0-12-385971-6.
[3] MANAHAN, S. E. Toxicological chemistry and biochemistry. 3rd
ed. Boca Raton: CRC Press, 2003,
p. 783. ISBN 1-56670-618-1.
[4] MANAHAN, S. E. Environmental chemistry. 8th
ed. Boca Raton: CRC Press, 2005. ISBN 1-56670-
633-5.
[5] LANDIS, W. G., YU, M. H. Introduction to environmental toxicology: impacts of chemicals upon
ecological systems. 3rd
ed. Boca Raton: CRC/Lewis Publishers, 2004. ISBN 1-56670-660-2.
[6] YU, M. H., TSUNODA, H., TSUNODA, M. Environmental toxicology: biological and health
effects of pollutants. 3rd
ed. Boca Raton: CRC Press, 2011, p. 375. ISBN 978-1-4398-4038-2.
[7] GRUIZ, K., MEGGYES, T., FENYVESI, E. Environmental toxicology. Boca Raton: CRC Press,
Taylor & Francis Group, 2015. ISBN 978-1-138-00155-8.
Integrated prevention, information sources in toxicology
16
3. Integrated prevention, information sources in toxicology
Time to the study: 2 hours
Objective After reading this paragraph, you will be able to
define the basic terms of integrated prevention – IPPC, BAT, BREF
describe and characterize the REACH system and safety data sheets
apply their theoretical knowledge for Environmental Management System
Lecture
3.1 IPPC, BREF, BAT
The integrated prevention is a set of measures oriented on pollution prevention, reduction of
emissions into air, water and soil, a decrease in waste production and evaluation of waste disposal
in order to achieve a high overall level of the environment protection.
Technical level of equipment, above all as to the achieved level of emissions and amount of wastes,
material and energy demandingness and environmental management methods and tools, is
compared to BAT (Best Available Techniques).
These are incorporated in European reference documents on the best available techniques (BREF),
which are for particular fields elaborated and published by technical institutions of the European
Commission with representation of all member countries.
Integrated Pollution Prevention and Control – IPPC
The process of the integrated pollution prevention and control is a process, the aim of which is
to improve the living environment quality and to achieve a higher level of the environment
protection in general.
A principle of the integrated prevention is minimization of negative impacts of industrial and
agricultural activities on the environment, the control of origination and transfer of pollution and a
support of environmental approaches in industrial and agricultural plants.
This covers information on the Best Available Techniques (BAT), BREF reference documents and
the Integrated Pollution Register of the environment.
The Integrated Pollution Prevention and Control – IPPC – process was implemented in the legal
order of the Czech Republic on January 1, 2003, when the Act no. 76/2002 Coll. on integrated
pollution prevention and control, on the integrated pollution register and on amendment to some
laws (the Act on integrated prevention) came into force. On March 19, 2013, Act no. 69/2013
Coll. was published in the Collection of Laws; this act amended the Act no. 76/2002 Coll. on
integrated pollution prevention and control, on the integrated pollution register and on amendment
to some laws (the Act on integrated prevention), subsequently amended, and some other laws. The
act came into force on the day of promulgation.
Objectives and principles: • To prevent an increase in pollution of the living environment through preventive and
corrective actions,
Integrated prevention, information sources in toxicology
17
• To prevent the pollution transfer from one environment component to another,
• To utilize raw materials, other materials and energies effectively,
• To prevent waste production and to ensure recovery,
• To adopt precautions needed to avoid accidents and eliminate their potential
consequences,
• To reduce administrative demandingness for companies by issuing a single integrated
permit,
• To negotiate individual conditions of a permit for individual entrepreneurs,
• To ensure transparency of administrative procedures for issuing the integrated permits
towards the public, a possibility for the public to be engaged in the decision process
Best Available Techniques – BAT
The technical level of equipment, above all as to the achieved level of emissions and amount of
wastes, material and energy demandingness and environmental management methods and tools, is
compared to the Best Available Techniques - BAT.
BAT are the most effective and most advanced stages of development of activities and their
operational methods, determining applicability of a certain technique as a base for determination of
emission limits to prevent or at least reduce emissions and negative impacts on the complex living
environment, while maintaining technical and economic availability. Thus, this is a comparison of
parameters of techniques and procedures using predetermined indicators (e.g. a specific emission to
the living environment or the energy consumption per production unit).
Through application of BAT as the pollution prevention a higher environmental protection level
can be achieved.
With regard to the continuous development of techniques, the BAT standards, determined as a
result of negotiations between the public and private sector, have been continuously moved.
The system of information exchange on the best available techniques serves as a base for these
negotiations, data processing and information intermediation.
The “Information Exchange Agreement” was concluded between resorts and subjects responsible
for exchange of information on BAT. The Ministry of Industry and Trade, the Ministry of the
Environment, the Ministry of Agriculture, CENIA (the Czech Environmental Information Agency)
and the Czech Environmental Inspection are participants in this agreement.
A new information web www.ippc.cz was put into service for this purpose.
The method and scope of organization of the system for the exchange of information on best
available techniques is set in the Decree of the Government no. 63/2003 Coll. BREF reference
documents are the result of the process of the exchange of information on best available
techniques.
Reference documents – BREF
The results of the negotiations and the exchange of information on best available techniques are
summarized in the so-called reference documents on the best available techniques (BREF
documents) for particular categories of facilities.
The BREF reference documents review information on the European best available techniques.
BREF are elaborated for particular industrial branches and cover data on industrial processes, used
technologies, emission limits applied in EU member countries, priority material flows and
monitoring.
BREF provides information on the technological level achieved within the given branch. The
presented information is neither legally binding nor enforceable, however, this is a standard for
decisions, whether a respective technology and operating method meet the requirements of IPPC
act and whether a permit to operate the industrial facility will be issued.
A base of each BREF document is a description of BAT and information on the future BATs.
For the BREF documents overview see „http://www.ippc.cz/obsah/referencni-dokumenty/“.
The very BREF documents are divided to BREF sectoral documents and BREF cross-sectoral
documents.
Integrated prevention, information sources in toxicology
18
3.2 REACH and Material Safety Data Sheets
Sources of toxicological information
A basic information source concerning a description of health, fire-fighting, chemical and
manipulation risks related to handling a chemical substance, a mixture of substances or an
industrial product, or possibly a waste containing chemical compounds:
• Material Safety Data Sheets
• Electronic databases.
Regulation REACH
REACH is an abbreviation for a Regulation EC no. 1907/2006 on Registration, Evaluation,
Authorisation and Restriction of Chemicals, which came into force in 1. 6. 2007.
Registration of chemicals under that REACH is introduced gradually, depending by the danger of
chemical substances and mixtures, and also by their volume (Fig. 3.1).
Fig. 3.1 Phases of REACH implementation
The purpose of this regulation is above all to ensure an effective functioning of a common market
for chemical substances within the European Community, protection of human health and living
environment against undesirable impacts of chemical substances. REACH in its form of regulation
is superior to other legal regulations within its field and in its complexity covers rules for trade,
production and use of chemical substances within EU. A new system of chemical substances
control has to ensure that by 2020 at the latest only chemical substances (separate or contained in
preparations or in objects) with known properties are used, in a way harmless to human health and
the environment. REACH does not apply to wastes, transport of dangerous substances, non-isolated
intermediate products, substances in transit (subjected to customs supervision) and radioactive
substances. REACH regulation applies to chemical substances on their own, in mixtures and
Integrated prevention, information sources in toxicology
19
products (if they are intentionally released) and determines new rules for trade of chemicals. A
distributor of chemicals is obliged to meet requirements pursuant to REACH regulation.
Materials Safety Data Sheets MSDS
Materials Safety Data Sheets (MSDS) are an important source of information.
Material safety data sheet is fitted with a date and includes these items:
1. Identification of the substance/mixture and of the company/undertaking;
2. Hazards identification;
3. Composition/information on ingredients;
4. First aid measures;
5. Firefighting measures;
6. Accidental release measure;
7. Handling and storage;
8. Exposure controls/personal protection;
9. Physical and chemical properties;
10. Stability and reactivity;
11. Toxicological information;
12. Ecological information;
13. Disposal considerations;
14. Transport information;
15. Regulatory information;
16. Other information.
Substances and mixtures classified as hazardous
Substances and mixtures classified as hazardous shall be labelled with a label including data
given in a regulation EU-GHS/CLP (Globally Harmonized System of Classification and Labelling
of Chemical:
- information on a supplier, identification of the product (the so-called identifiers of the product),
the nominal quantity of the substance/mixture in the packages (for the broad public), hazard
pictograms if needed, signal words if needed (Danger/Warning), standard hazard statements if
needed (the so-called H-statements), appropriate precautionary statements if needed (the so-called
P-statements), supplemental information if needed.
Labeling – the graphic symbol, signal words, H-statements and P-statements.
Hazard pictogram • a square set at a point (diamond shape), a black symbol on a white background with a red
border,
• earlier symbol in a square on the orange field,
• the same symbol can be used for more classes of danger.
Example:
The “Health hazard” symbol (the human silhouette) shall be assigned to the substances/mixtures
classified as:
• respiratory tract irritation
• mutagens
• carcinogens
• substances/mixtures toxic for reproduction
• having specific target organ toxicity– after single exposure (more serious category)
• having specific target organ toxicity– after repeated exposure
Integrated prevention, information sources in toxicology
20
Fig. 3.2 Hazarg pictogram - The “Systemic health hazards” symbol
There are two signal words: “Danger” – for more hazardous categories and “Warning” – for less
hazardous categories. In certain, less frequent cases, signal words need not to be stated.
3.3 The environmental pollution registers
The environmental pollution registers have been created for many reasons. The purpose of registers
is to contribute to enhancement of the integrated approach to the environmental protection and to
support a more eco-friendly behavior. Countries, as well as industrial enterprises, need data on the
living environment pollution to define their environmental strategy and as an environmental
management tool. Registers have a cardinal importance in providing information to the public,
which can obtain difficult-to-access data this way and has an opportunity to contribute to
development of the national register. The public control urges more responsible ecological
behavior of individual companies.
Registers are based on the mandatory and regular reporting, including information on pollution of
particular components of the environment. Thus, substances having significant effects on the
environment and human health are monitored (e.g. green-house gases, substances that can cause
acid rain, heavy metals, carcinogenic substances etc.).
The environmental pollution registers:
European Pollutant Releases and Transfer Register (E-PRTR)
European Pollutant Emission Register (EPER)
Integrated Pollution Register of the environment (IPR)
European Pollutant Releases and Transfer Register (E-PRTR)
E-PRTR is a publicly accessible electronic database of pollutants, their releases and transfers. E-
PRTR has been set-up with the aim to improve the public access to information concerning the
living environment pollution by means of a coherent and integrated European pollution register,
which subsequently contributes to pollution reducing, providing data to subjects taking part in
decisive processes and provides the public with the opportunity to be involved in the environment
related decisions.
In accordance with E-PRTR, member states must report data on releases and transfers of pollutants
every year, when the specified threshold values were exceeded.
Based on the UN-ECE Protocol on Pollutant Release and Transfer Registers, the Regulation (EC)
No. 166/2006 of the European Parliament and of the Council was issued on January 18, 2006,
concerning the establishment of a European Pollutant Release and Transfer Register. EU member
states must set up national registers of emissions from industrial sources so that they are able to
meet requirements of the European legislation and they must then report the information on
emissions from these sources to the European Commission. By this reason, member states must
adjust their national registers and reporting processes to meet demands according to E-PRTR
regulation. Data is collected compulsorily since 2007.
DANGER
Integrated prevention, information sources in toxicology
21
The European PRTR contains information about:
• Releases of pollutants to air, water and land (the register covers 91 pollutants listed in
Annex II in total, including threshold values),
• Waste transfers (distinguishing hazardous waste and other waste),
• Off-site transfers of pollutants present in waste-water treated outside the facility,
• Releases of pollutants from diffuse sources (if available).
Integrated Pollution Register of the environment (IPR)
This is a publicly accessible information system of the public administration of the Czech Republic
under the competent authority of the Ministry of the Environment and operated by CENIA, the
Czech Environmental Information Agency.
IPR provides information on emissions to air, water and soil and on transfers of 93 reported
substances, which are reported to the register directly by the environment polluters based on
meeting the defined criteria.
IPR is one part of the Shared Environmental Information System (SEIS).
The list and information on substances reported to the IRP are available at
http://www.irz.cz/node/20.
Among substances reported to the IRP include some heavy metals:
Arsen and compounds (as As)
Chromium and compounds (as Cr)
Cadmium and compounds (as Cd)
Copper and compounds (as Cu)
Nickel and compounds (as Ni)
Lead and compounds (as Pb)
Mercury and compounds (as Hg)
Organotin compounds (as total Sn)
Tributyltin and compounds
Trifphenyltin and compounds
Zinc and compounds (as Zn).
3.4 Tools and guidelines to reduce the negative impacts of production
on the environment
At present, the endeavor of enterprises to reduce negative impacts of their activities on the living
environment has been increasing. This trend is motivated both by ever increasing legislative
pressure and also by willingness of companies to reduce their negative impacts outside the scope of
legislative regulations. These tools cover The Environmental Management System EMS, integrated
pollution prevention and control IPPC, product innovation, waste management and others.
The Environmental Management System (EMS)
The Environmental Management System (EMS) is a management system oriented on
monitoring and improvement of all activities in the organization that affect, or may affect, quality
of the living environment or employees’ health and safety. The environmental management system
is a voluntary tool.
For example, EMS is focused on waste prevention, more effective utilization of raw materials and
fuels, water consumption and waste water treatment, emissions into air, releases of hazardous
substances, water and soil contamination and others.
Implementation of EMS comprises several specific steps designed to help a company to achieve a
defined goal – to reduce its environmental impacts and increase efficiency of the environment
management.
Integrated prevention, information sources in toxicology
22
When setting and implementing the Environmental Management System, two “standards” shall be
followed:
• The Regulation (EC) No. 761/2001 of the European Parliament and of the Council (see
EMAS (Eco-Management and Audit Scheme))
• The international technical standard ISO 14001 (ČSN EN ISO 14001:2005).
Product innovation and the environment
One of the methods to enhance a company’s competitiveness is implementation of new products,
services or technologies that are also more eco-friendly. The aim of the product innovation is
reducing the energy and material demandingness of a product, of a distribution method, an increase
in a proportion of re-usable components, material recycling and others.
The product innovation refers to: A design of a product with regard to the environment –
ECODESIGN, Promotion of eco-friendly products – ECOLABELING, Life cycle analysis (LCA).
ECODESIGN
Ecodesign is an approach to a product development and innovation involving, apart from technical,
economic and other requirements, also impacts of the product on the living environment. In the
phase of the product development, engineers and designers have an opportunity to influence 70 –
80 % of all environmental impacts of the product. However, an important presupposition is
knowledge of relationships of chosen materials, technological procedures and a concept of the
product with impacts on the environment. For objective assessment of the overall impacts of the
product on the environment, it is important to assess all life cycle phases of the product from the
selection of used raw materials, over the stages of its use by users, to its removal or utilization at
the end of the product service life
The product life cycle, Life cycle analysis
The product life cycle begins at obtaining natural raw materials and energies needed for its
production. Raw materials are processed to semi-finished products and during the manufacturing
process the product gains its final form. Then the product gets to a consumer and fulfils the
function it has been intended for. In this
phase, in accordance with its character, it
may consume energies related to its
functionality, service fluids (oils) and
requires maintenance. At the end of its
service life, the product becomes waste, or
in some case its functionality can be
renewed through modernization, renovation
or utilization of unworn components.
Materials of the product can be further used
through suitable recycling or through
energy recovery in incineration plants and
thus energy can be obtained from the
product materials. Unusable materials are
taken to dumping sites. Each life cycle
phase is associated with origination of
wastes and with other impacts on the living
environment. The Figure 3.3 shows
significant areas worth noticing by teams
involved in development of products.
Fig. 3.3 The life cycle analysis
https://conceptdraw.com/a2014c3/preview
Integrated prevention, information sources in toxicology
23
ECOLABELLING
Ecolabelling, or a system of marking of ecological products or services, belongs among voluntary
preventive tools of the environment protection. These tools are not legally enforceable. Their aim is
to improve the environmental profile of a company, to gain competition advantages on the market
or, for example, addressing a new group of customers. The term eco-labeling represents marking of
products or services more eco-friendly compared to other comparable products. An impact of
individual products on the living environment is assessed during its whole life cycle, which means
from the manufacturing phase to the end of its service life. Up-to-date eco-labeling is based above
all on a system of certifications and granting permissions to use eco-labels. Along with the
certificate the manufacturer also gains an opportunity to use the eco-label for a certain time-limited
period (Fig. 3.4).
http://vitejtenazemi.cz/cenia/index.php?p=ekoznaceni_ecolabelling&site=spotreba
Fig. 3.4 Example of eco-labels
WASTE MANAGEMENT
Waste management is a set of all activities oriented on waste prevention, waste treatment and
disposal and the following care for a site where wastes are permanently dumped, together with
monitoring and regulation of all these actions. The rules for waste management are regulated in Act
no. 185/2001 Coll., on Waste and Amendement of Some Other Acts.
In accordance with the law of the European Community, this Act regulates
• the rules on the prevention of waste production and on waste management while respecting
the areas of environmental protection, the protection of human health and sustainable
development
• the rights and obligations of persons in the waste management sector
• the competence of the public administration authorities.
Waste management means the gathering, concentration, collection, purchase, sorting, transport,
storage, treatment, recovery and disposal of waste.
Czech Republic European Union Scandinavia
Germany Austria Canada Slovakia
Integrated prevention, information sources in toxicology
24
Ecomapping
Ecomapping is another tool that can help companies to implement the environmental management
system. Ecomapping is based on making the so-called ecomaps, i.e. schemes which visualize not
only relations inside the company, but also relationships of the company and the surroundings, with
regard to the particular environmental sectors and issues of their protection. Thus the company gets
the general overview on its current environmental performance.
Ecomaps help to quickly identify the most significant environmental hazards in the company, to
define and determine importance of the problems and to propose actions for environmental
protection improvements.
Very important is to determine material flows within the company and particular manufacturing
processes.
Cleaner production
Cleaner production is the continuous application of an integrated preventive environmental
strategy applied to processes, products and services to increase overall efficiency and reduce risks
to humans and the living environment.
Cleaner production in the Czech Republic is confirmed in the Resolution no. 165 from 9/2/2000, by
which the National Programme of Cleaner Production was adopted (NPCP). Cleaner production is
also bound by Act no. 69/2013 Coll. on integrated pollution prevention and control. Legislative
tools of the cleaner production strategy help companies to improve the environmental protection
level and also help public administrative when issuing operation permits. The cleaner production
strategy can be well used when implementing the environmental management systems according to
ISO 14001 and according to the Regulation of the European Parliament and of the Council (EC)
no. 761/2001 (EMAS II regulation).
Cleaner production is a form of preventive strategy of the environmental protection applied within
the entire production sphere. The main idea of this strategy is to identify and minimize sources
causing the environmental pollution. The cleaner production strategy is a world-wide initiative
applied not only in the industrial and agricultural production, but also in transportation, the sector
of commerce and services, offices etc…. Along with reducing negative impacts on the living
environment, a decrease in consumption of raw materials and energies is achieved and through this
a significant cost reduction in companies.
Sumary of terms
At the end of the chapter are repeated the main terms that you should acquire:
Integrated Pollution Prevention and Control IPPC
Best Available Techniques BAT
BREF documents
The environmental pollution registers
Environmental Management System (EMS)
Ecodesign
The product life cycle
Waste management
Cleaner production
Integrated prevention, information sources in toxicology
25
Question to the topic
1. What the goals and principles of the IPPC?
2. What is BAT?
3. What contain documents BREF?
4. What is the basic meaning of environmental pollution registers?
References
[1] Reference documents under the IPPC Directive and the IED [on-line]. Joint research centre.
[cit. 16-07-01]. Available from
http://eippcb.jrc.ec.europa.eu/reference/BREF/NFM_Final_Draft_10_2014.pdf>.
[2] Best Available Techniques (BAT) Reference Document for the Non-Ferrous Metals Industries [on-line]. Joint research centre, European Commission, 2014, 1191 p. Available from <
http://eippcb.jrc.ec.europa.eu/reference/BREF/NFM_Final_Draft_10_2014.pdf>.
Influence of lead on the environment
26
4. Influence of lead on the environment
Study time: 2 hours
Objective After reading this paragraph, you will be able to
• describe the basic properties of this metal
• define the inputs and routes of environmental contamination
• define the toxicity and ecotoxicity of this metal
Lecture
4.1 Lead
Lead has a low thermal and electrical conductivity. It is resistant to concentrated acids and other
chemical agents. It is a malleable and ductile metal. Lead has good castability. These properties
give it great functional value, both in its pure form or in alloys and compounds. The vapours and
compounds of lead are poisonous! According to the technical classification of metals include lead
to the group of general (heavy) non-ferrous metals with low melting point.
Fig. 4.1 Global production (primary, secundary) and usage of lead
http://www.ila-lead.org/lead-facts/statistics
Influence of lead on the environment
27
Application Lead is a toxic metal, therefore its use in many applications is restricted. Nowadays, substitution in
some applications is usual (unleaded petrol, zinc wheel weights for counterbalance, drinking water
plastic distributions …), however, lead is still used in other applications (car battery manufacturing,
protection against radiation, ammunition, reservoirs for concentrated sulfuric acid, cable sheaths
…).
4.2 Potential sources of pollution
Heavy metals like lead, once getting into the atmosphere, are able to travel over long distances.
They may contaminate soil even thousands of kilometers away from the pollution source. Thanks
to the drastic restriction of lead content in car petrol in Europe, a range of critically burdened areas
has been reduced significantly.
Regarding its hazardousness, its use is limited in some electronic and electrical apparatuses by the
so-called RoHS guidance along with mercury, cadmium and other substances.
Sources of pollution Natural sources of lead entering the environment:
• naturally in a form of dust from erosions
• volcanos
• sea water aerosols
• forest fires (dust, smoke).
Anthropogenic sources of lead entering the environment:
• combustion processes – mainly combustion of coal and heating oils
• mining and treatment of ferrous and nonferrous ores
• manufacturing of accumulators
• waste incineration
• glass-making industry (glazing components)
• production of dyes
• corrosion of water pipelines, of soldered joints of copper pipelines
• water may be also contaminated by releases from badly managed waste sites
• mine waters
• application of sewage sludge and industrial composts
• other sources.
Note: Formerly, combustion engines were a significant contamination source – tetraethyl lead
[Pb(C2H5)4] was added into gasoline as an anti-knock additive. Today it is replaced by organic
compounds.
Legislation – limits Lead (Lead and its compounds (asPb)) is monitored in the Integrated Pollution Register (IPR) in
releases into air, water, soil and in transfers of substances in wastes and waste waters.
Reporting threshold for emissions and transfers:
into air 200 kg/year,
into water 20 kg/year
into soil 20 kg/year.
The risk component of the environment are: air, water, soil.
For transfers in wastes the threshold value is determined to 50 kg/year and in waste waters to 20
kg/year.
When exceeding some of these values, reporting duty arises for operators.
BREF and BAT documents valid for lead and compounds (as Pb):
Non-ferrous Metals Industries
Iron and Steel Production
Influence of lead on the environment
28
Ferrous Metals Processing Industry
Refining of Mineral Oil and Gas
Production of Pulp, Paper and Board
Manufacture of Glass.
4.3 Toxicity and ecotoxicity of lead
Lead may enter the human organism from air via pulmonary inhalation. Another route is by means
of food. Lead exposure leads to malfunction of plenty organs: kidneys and livers, nervous system,
erythrocytes (Fig. 4.2), arteries and muscles. Large exposures result in going blind, brain damage,
spasms and even death. Lead negatively influences an embryo growth and possibly affects its
viability as well.
Fig. 4.2 Damage to red blood cells, gingiva colored lead
Lead has not an essential significance for humans. 90 % of accepted lead tends to accumulate in
bones, negatively influencing haematogenesis, because it blocks production of hemoglobin. Lead
ions are carcinogenic and lead is classified as a probable carcinogen for human lungs and kidneys.
Typical symptoms of lead poisoning are paleness of face and lips, constipation and loss of appetite,
colic, anemia, headaches, abdominal cramps, chronical kidney nephritis, brain damage and
malfunctions of the central brain system.
Treatment consists in a procedure known as chelation therapy – binding to accumulated lead,
which is then excreted in urine. Even traces of lead in surroundings and food may result in
permanent supply into the organism and subsequent serious diseases, because lead accumulates in
the body and can be excreted only with difficulties.
Lead is hard to get rid of for the body. As soon as lead enters the organism, it is deposited in bones
and teeth (Fig. 4.2). Lead may end up there for many years and gradually releases to blood, from
where slowly excretes through kidneys to urine and through livers to bile.
Sumary of terms
At the end of the chapter are repeated the main terms that you should acquire:
Basic characteristics of lead.
Potential sources of lead contamination.
Toxicity and ecotoxicity of lead.
Question to the topic
1. What are basic characteristics of lead?
2. What are potential sources of lead contamination?
https://www.studyblue.com/notes/note/n/ped-2014-study-guide-2013-14-sam-/deck/8790614 http://www.atsdr.cdc.gov/csem/csem.asp?csem=7&po=12
Influence of lead on the environment
29
3. What are the symptoms of lead poisoning?
References
[1] Reference documents under the IPPC Directive and the IED [on-line]. Joint research centre.
[cit. 16-07-01]. Available from
<http://eippcb.jrc.ec.europa.eu/reference/BREF/NFM_Final_Draft_10_2014.pdf>.
[2] Best Available Techniques (BAT) Reference Document for the Non-Ferrous Metals
Industries [on-line]. Joint research centre, European Commission, 2014, 1191 p. Available from
< http://eippcb.jrc.ec.europa.eu/reference/BREF/NFM_Final_Draft_10_2014.pdf>..
[3] RAMACHANDRA RAO, S. Resource Recovery and Recycling from Metallurgical Wastes.
Elsevier, London, 2006. ISBN 978-0-08-045131-2.
[4] ASHBY, M. F. Materials and the Environment: Eco-Informed Material Choice. Elsevier
Butterworth-Heinemann, Waltham, 2013, p. 616. ISBN 978-0-12-385971-6.
[5] MANAHAN, S. E. Toxicological chemistry and biochemistry. 3rd
ed. Boca Raton: CRC Press, 2003,
p. 783. ISBN 1-56670-618-1.
[6] MANAHAN, S. E. Environmental chemistry. 8th
ed. Boca Raton: CRC Press, 2005. ISBN 1-56670-
633-5.
[7] LANDIS, W. G., YU, M. H. Introduction to environmental toxicology: impacts of chemicals upon
ecological systems. 3rd
ed. Boca Raton: CRC/Lewis Publishers, 2004. ISBN 1-56670-660-2.
[8] YU, M. H., TSUNODA, H., TSUNODA, M. Environmental toxicology: biological and health
effects of pollutants. 3rd
ed. Boca Raton: CRC Press, 2011, p. 375. ISBN 978-1-4398-4038-2.
[9] GRUIZ, K., MEGGYES, T., FENYVESI, E. Environmental toxicology. Boca Raton: CRC Press,
Taylor & Francis Group, 2015. ISBN 978-1-138-00155-8.
[10] WALKER, C. H. Principles of ecotoxicology. 3rd
ed. Boca Raton: CRC/Taylor & Francis, 2006.
ISBN 0-8493-3635-X.
[11] NORDBERG, G., et al. Handbook on the toxicology of metals. 3rd
ed. Burlington:
Elsevier/Academic Press, 2007, p. 975. ISBN 978-0-12-369413-3.
[12] Toxicological profiles. Toxic substances portal [on-line]. Available from < http://www.atsdr.cdc.gov/toxprofiles/index.asp>.
Influence of cadmium on the environment
30
5. Influence of cadmium on the environment
Study time: 2 hours
Objective After reading this paragraph, you will be able to
describe the basic properties of this metal
define the inputs and routes of environmental contamination
define the toxicity and ecotoxicity of this metal
Lecture
5.1 Cadmium
Cadmium is an especially dangerous harmful substance that belongs to the group of heavy metals
and has a high toxic potential for aqueous environment.
Application
The largest amount of cadmium (about ¾) is used for the manufacture of batteries, mainly Ni-Cd
and solar types. Further, it is used for production of pigment, as a stabilizer for plastic materials, for
alloying of copper and for fabrication of protective coatings and for metal-coating. Other processes
where cadmium is used cover the manufacture of low-melting-point alloys, soldering metals,
semiconductors and household appliances. To a lesser extent, metallic cadmium is used in nuclear
technology to absorb neutrons. Some cadmium compounds are used as fungicides.
5.2 Potential sources of pollution
Environmental impacts Cadmium tends to stick to fly ash, dust and soil particles and clay soils. The bond is strongest with
fly ash and clay particles. Therefore cadmium released into the atmosphere binds to emitted fly ash
particles. These particles may remain in the atmosphere for more than one week before they
transfer into water or soil through the atmospheric deposition. This way cadmium may be able to
travel over long distances. On the ground, cadmium binds to clay or dust particles. In this form it
may be washed-out by rainwater into the aqueous environment or may be accumulated by
organisms. The accumulation in organisms is very high, therefore cadmium accumulation in food
chains occurs. The above described property can be called bioaccumulation. High concentrations of
cadmium in the soil solution adversely influence the ability of soil microorganisms to decompose
the organic matter as well as pollutants. This inhibition is a result of reduction of a range of
bacteria in soil.
Mobility of compounds in the aqueous environment depends on their solubility. While cadmium
oxides and sulfides are relatively insoluble, chlorides and sulfates are soluble. Concentration of
cadmium in bottom sediments is typically more than ten times higher than in water. Adsorption of
cadmium on soils and silicon and aluminum oxides strongly depends on pH value and increases
along with the increasing alkalinity of the environment. Cadmium is highly toxic for water
organisms, salmonids react most sensitively. It also enhances toxicity of other metals (zinc, copper
etc.) and negatively influences self-cleaning ability of water.
Influence of cadmium on the environment
31
Fig. 5.1 Sources of Cadmium pollution
Sources of pollution Natural sources of cadmium entering the environment:
Volcanic eruptions including eruptions of subsea volcanoes belong to the most significant natural
sources of cadmium.
Anthropogenic sources of cadmium entering the environment:
Cadmium emissions into the atmosphere caused by humans (anthropogenic) are approximately 8x
higher than natural emissions. Cadmium is released into air during its mining, production and
processing. Combustion of fossil fuels and municipal and hospital waste is also an important
source. A source of cadmium emissions into waters are waste waters from electro-galvanizing and
from manufacturing of Ni-Cd batteries. The atmospheric deposition and soil rain-wash are other
sources. A source of cadmium release into soil is mainly the atmospheric deposition of municipal
industrial aerosols, fertilization by phosphate fertilizers contaminated by cadmium and putting
sewage sludge to agricultural fields (Fig. 5.1).
The main anthropogenic emissions of cadmium cover:
• mining and processing of cadmium;
• fossil fuels and waste burning;
• fertilization by phosphate fertilizers containing cadmium;
• utilization of sewage sludge (combustion, application on agricultural land);
• electro-galvanizing and Ni-Cd accumulators manufacturing.
Cadmium is a highly toxic element being able to accumulate in food chains. It may occur in all
sectors of the living environment and accumulate in soils and sediments with a risk of a potential
forced release e.g. through a change in pH. Its toxic effects on humans are really extraordinarily
serious. Therefore careful monitoring of emissions and effort for their minimization is highly
legitimate.
Legislation – limits Cadmium (Cadmium and its compounds (as Cd)) is monitored in the Integrated Pollution
Register (IPR) in releases into air, water, soil and in transfers of substances in wastes and waste
waters.
Reporting threshold for emissions and transfers:
into air 10 kg/year,
into water 5 kg/year
http://www.jnuenvis.nic.in/cadmium.html
Influence of cadmium on the environment
32
into soil 5 kg/year.
The risk component of the environment are: air, water, soil.
For transfers in wastes the threshold value is determined to 5 kg/year and in waste waters to 5
kg/year.
When exceeding some of these values, reporting duty arises for operators.
BREF and BAT documents valid for cadmium and compounds (as Cd):
Non-ferrous Metals Industries
Iron and Steel Production
Ferrous Metals Processing Industry
Refining of Mineral Oil and Gas
Intensive Rearing of Poultry and Pigs
Production of Pulp, Paper and Board
Manufacture of Glass.
5.3 Toxicity and ecotoxicity of cadmium
Cadmium is not an essential element, however, it may replace zinc in biochemical structures of the
organism, thus disturbing functionality of some enzymes. Cadmium is a highly toxic element,
dramatically damaging kidneys (Fig. 5.2). It has a very high accumulation coefficient, therefore
detoxification is slow and there is a danger of chronic poisoning.
According to the EPA classification, Cd is classified as a probable human carcinogen, may cause
lung and prostate cancer. It is teratogenic (fetus damaging). Other significant effects include
malfunction of livers, bones, lungs and gastrointestinal tract. Chronic exposures may also damage
heart and immune system. Cd enhances toxic effects of other metals, for example zinc and copper.
It is one of potential causes of high blood pressure, damages reproductive organs, initiates
destruction of erythrocytes, cadmic ions also cause wastage and embrittlement of bones.
The most famous case of cadmium poisoning was called Itai-Itai disease. Itai-itai disease was
found in the cadmium (Cd) polluted Jinzu River basin in Toyama Prefecture starting around 1912.
Due to the cadmium poisoning, the fish in the river started to die, and the rice irrigated with river
water did not grow well. The cadmium and other heavy metals accumulated at the bottom of the
river and in the water of the river. This water was then used to irrigate the rice fields. The rice
absorbed heavy metals, especially the cadmium. The cadmium accumulated in the people eating
contaminated rice. One of the main effects of cadmium poisoning is weak and brittle bones. Spinal
and leg pain is common, and a waddling gait often develops due to bone deformities caused by the
cadmium. The pain eventually becomes debilitating, with fractures becoming more common as the
bone weakens. Other complications include coughing, anemia, and kidney failure, leading to death
Fig. 5.2 Kidney and bones demage
http://www.elephonic.com/2014/japa
ns-environmental-past-itai-itai/
http://gogreenphilippines.blogspot.cz/
Influence of cadmium on the environment
33
Sumary of terms
At the end of the chapter are repeated the main terms that you should acquire:
Basic characteristics of cadmium.
Potential sources of cadmim contamination.
Toxicity and ecotoxicity of cadmium.
Question to the topic
1. What are basic characteristics of cadmium?
2. What are potential sources of cadmium contamination?
3. What are the symptoms of cadmium poisoning?
References
[1] Reference documents under the IPPC Directive and the IED [on-line]. Joint research centre.
[cit. 16-07-01]. Available from
<http://eippcb.jrc.ec.europa.eu/reference/BREF/NFM_Final_Draft_10_2014.pdf>.
[2] Best Available Techniques (BAT) Reference Document for the Non-Ferrous Metals
Industries [on-line]. Joint research centre, European Commission, 2014, 1191 p. Available from
< http://eippcb.jrc.ec.europa.eu/reference/BREF/NFM_Final_Draft_10_2014.pdf>..
[3] RAMACHANDRA RAO, S. Resource Recovery and Recycling from Metallurgical Wastes.
Elsevier, London, 2006. ISBN 978-0-08-045131-2.
[4] ASHBY, M. F. Materials and the Environment: Eco-Informed Material Choice. Elsevier
Butterworth-Heinemann, Waltham, 2013, p. 616. ISBN 978-0-12-385971-6.
[5] MANAHAN, S. E. Toxicological chemistry and biochemistry. 3rd
ed. Boca Raton: CRC Press, 2003,
p. 783. ISBN 1-56670-618-1.
[6] MANAHAN, S. E. Environmental chemistry. 8th
ed. Boca Raton: CRC Press, 2005. ISBN 1-56670-
633-5.
[7] LANDIS, W. G., YU, M. H. Introduction to environmental toxicology: impacts of chemicals upon
ecological systems. 3rd
ed. Boca Raton: CRC/Lewis Publishers, 2004. ISBN 1-56670-660-2.
[8] YU, M. H., TSUNODA, H., TSUNODA, M. Environmental toxicology: biological and health
effects of pollutants. 3rd
ed. Boca Raton: CRC Press, 2011, p. 375. ISBN 978-1-4398-4038-2.
[9] GRUIZ, K., MEGGYES, T., FENYVESI, E. Environmental toxicology. Boca Raton: CRC Press,
Taylor & Francis Group, 2015. ISBN 978-1-138-00155-8.
[10] WALKER, C. H. Principles of ecotoxicology. 3rd
ed. Boca Raton: CRC/Taylor & Francis, 2006.
ISBN 0-8493-3635-X.
[11] NORDBERG, G., et al. Handbook on the toxicology of metals. 3rd
ed. Burlington:
Elsevier/Academic Press, 2007. ISBN 978-0-12-369413-3.
[12] Toxicological profiles. Toxic substances portal [on-line]. Available from <
http://www.atsdr.cdc.gov/toxprofiles/index.asp>.
Influence of arsenic on the environment
34
6. Influence of arsenic on the environment
Study time: 2 hours
Objective After reading this paragraph, you will be able to
describe the basic properties of this metal
define the inputs and routes of environmental contamination
define the toxicity and ecotoxicity of this metal
Lecture
6.1. Arsenic
This is a half-metal, but with regard to its negative impacts is classified as heavy metal.
Application A considerable part of As is consumed for the manufacture of preparations for wood preserving
and in agriculture for the manufacture of pesticides. Free arsenic has only a limited practical
function; it is most frequently used as a part of special alloys – with Pb, less with Cu. Important are
semiconductors GaAs and InAs.
Arsenic compounds are quite widely used in glass-making for glass refinement, although in
relatively low concentrations. In spite of their toxicity, in tenths of percent they are a part of many
glass-making charges, because technologically they are difficult to substitute. The insoluble arsenic
sulphide As2S3 is known as the King’s Yellow pigment and is used in leather tanning as a dehairing
agent. Cupric hydrogen arsenite CuHAsO3 is known as the Scheele’s Green pigment.
6.2 Potential sources of pollution
Arsenic strongly accumulates in sediments and may also accumulate in the food chain. Its toxic
effect is serious. Therefore As can be classified as a highly dangerous substance above all for
human health, but also for many organisms.
Environmental impacts
Arsenic is released into the air mainly by human activities. From the air it gets into the soil or water
by fallout or by washing rain. There may persist for a very long time, because it has considerable
ability to accumulate in sediments. Arsenic is a major component of some minerals enhanced
across the world. Water from large areas of occurrence of these minerals may contain an above-
average concentration of As. The problem with drinking water from wells is in Bangladesh and
Cambodia. Water from deep wells is contaminated with arsenic from minerals in the subsoil.
Arsenic is also found in coal. The average concentration is 0.5-100 mg.kg-1
.
Arsenic is occurs in oxidation state 3+ and 5+ or organically bound in the waters.
Sources of pollution Natural sources of arsenic entering the environment:
• weathering of rocks,
• in copper, silver and lead ores.
Anthropogenic sources of arsenic entering the environment:
• fossil fuel burning,
Influence of arsenic on the environment
35
• processing of ores,
• metallurgical industry,
• agricultural industry (insecticides),
• wood protective agents,
• glass additives,
• smoking,
• pharmaceuticals for veterinary medicine,
• mine waters,
• power plant fly ash (combustion processes),
• water from badly managed dumping sites.
Marine organisms collected inorganic arsenic from seawater and transformed to organic
compounds by methylation. Between methylated compounds with As includes Arsenobetain (AsB)
arsenocholin (AsC), arsenosugars (AsS) and arsenolipids (AsL) (Fig. 6.1).
Fig. 6.1 Arsenic cycle
Legislation – limits Cadmium (Arsenic and its compounds (as As)) is monitored in the Integrated Pollution Register
(IPR) in releases into air, water, soil and in transfers of substances in wastes and waste waters.
Reporting threshold for emissions and transfers:
into air 20 kg/year,
into water 5 kg/year
into soil 5 kg/year.
The risk component of the environment are: air, water, soil.
For transfers in wastes the threshold value is determined to 5 kg/year and in waste waters to 50
kg/year.
When exceeding some of these values, reporting duty arises for operators.
http://onlinelibrary.wiley.com/doi/10.1111/j.1574-6976.2002.tb00617.x/pdf
Influence of arsenic on the environment
36
BREF and BAT documents valid for arsenic and compounds (as As):
Manufacture of Glass
Non-ferrous Metals Industries
Refining of Mineral Oil and Gas.
6.3 Toxicity and ecotoxicity of arsenic
Toxicity and a way of absorption of arsenic compounds by the organism depend on solubility of a
compound. Poorly soluble arsenic trisulphide is nontoxic. Metallic arsenic is non-poisonous,
however, it is metabolized to toxic substances in the organism. All other arsenic-containing
substances are toxic. Arsenic bound in organic substances is usually less toxic than arsenic from
inorganic compounds. As3+
compounds are about five times to twenty times more toxic than
As5+
(Fig. 6.2). Humans intake arsenic from food - 70 %, from drinking water - 29 % and from air
– 1 %. However, majority of arsenic present in food is in a form of organic complexes, which are
less toxic.
Fig. 6.2 Extent of As toxicity depending upon the number of methyl groups bound
Compounds – highly toxic, an ability to accumulate in organisms – in livers and kidneys, in hair,
nails and skin. Symptoms of arsenic poisoning are excessive keratinization of skin and its grey-
greenish colour, white strips in nails and garlic odour present in breath (Fig. 6.3). Arsenic
compounds can even cross the placenta and damage a fetus. In high concentrations arsenic is toxic
even for plants.
Fig. 6.3 Aldrich-Mees lines
Aldrich-Mees
lines
http://www.intechopen.com/books/on-biomimetics/biomimetic-and-bio-inspired-catalytic-
system-for-arsenic-detoxification-bio-inspired-catalysts-with-
http://www.mywallpaper.top/mees-lines-on-nails.html http://www.baike.com/gwiki/%E7%B1%B3%E6%B0%8F%E7%BA%BF
Influence of arsenic on the environment
37
Arsenic is a carcinogen, causes lung and skin cancer, increases a probability of tumors in livers,
kidneys and urinary bladder. High acute As exposures damage cells of the nervous system, livers,
kidneys, stomach, intestines and skin. The inhalation exposure results in sore throat and irritation of
lungs.
Arsenicosic disease - the result of long term arsenic exposure
With long-term exposure to arsenic is first spots appear on the skin, then into the hyperkeratosis
and skin cancer (Fig. 6.4).
Fig. 6.4 Symptoms of Arsenicosic disease
Sumary of terms
At the end of the chapter are repeated the main terms that you should acquire:
Basic characteristics of arsenic.
Potential sources of arsenic contamination.
Toxicity and ecotoxicity of arsenic.
Question to the topic
1. What are basic characteristics of arsenic?
2. What are potential sources of arsenic contamination?
3. What are the symptoms of arsenic poisoning?
References
[1] Reference documents under the IPPC Directive and the IED [on-line]. Joint research centre.
[cit. 16-07-01]. Available from
<http://eippcb.jrc.ec.europa.eu/reference/BREF/NFM_Final_Draft_10_2014.pdf>.
[2] Best Available Techniques (BAT) Reference Document for the Non-Ferrous Metals
Industries [on-line]. Joint research centre, European Commission, 2014, 1191 p. Available from
< http://eippcb.jrc.ec.europa.eu/reference/BREF/NFM_Final_Draft_10_2014.pdf>..
[3] RAMACHANDRA RAO, S. Resource Recovery and Recycling from Metallurgical Wastes.
Elsevier, London, 2006. ISBN 978-0-08-045131-2.
[4] ASHBY, M. F. Materials and the Environment: Eco-Informed Material Choice. Elsevier
Butterworth-Heinemann, Waltham, 2013, p. 616. ISBN 978-0-12-385971-6.
http://www.iflscience.com/health-and-medicine/five-most-poisonous-substances-polonium-mercury/
http://ihrrblog.org/2010/06/17/groundwater-arsenic-poisoning-in-bangladesh-an-interview-with-dr-manzurul-hassan/ http://soesju.org/arsenic/arsenicContents.htm?f=health_effect.html
Influence of arsenic on the environment
38
[5] MANAHAN, S. E. Toxicological chemistry and biochemistry. 3rd
ed. Boca Raton: CRC Press, 2003,
p. 783. ISBN 1-56670-618-1.
[6] MANAHAN, S. E. Environmental chemistry. 8th
ed. Boca Raton: CRC Press, 2005. ISBN 1-56670-
633-5.
[7] LANDIS, W. G., YU, M. H. Introduction to environmental toxicology: impacts of chemicals upon
ecological systems. 3rd
ed. Boca Raton: CRC/Lewis Publishers, 2004. ISBN 1-56670-660-2.
[8] YU, M. H., TSUNODA, H., TSUNODA, M. Environmental toxicology: biological and health
effects of pollutants. 3rd
ed. Boca Raton: CRC Press, 2011, p. 375. ISBN 978-1-4398-4038-2.
[9] GRUIZ, K., MEGGYES, T., FENYVESI, E. Environmental toxicology. Boca Raton: CRC Press,
Taylor & Francis Group, 2015. ISBN 978-1-138-00155-8.
[10] WALKER, C. H. Principles of ecotoxicology. 3rd
ed. Boca Raton: CRC/Taylor & Francis, 2006.
ISBN 0-8493-3635-X.
[11] NORDBERG, G., et al. Handbook on the toxicology of metals. 3rd
ed. Burlington:
Elsevier/Academic Press, 2007. ISBN 978-0-12-369413-3.
[12] Toxicological profiles. Toxic substances portal [on-line]. Available from <
http://www.atsdr.cdc.gov/toxprofiles/index.asp>.
Influence of mercury on the environment
39
7. Influence of mercury on the environment
Study time: 3 hours
Objective After reading this paragraph, you will be able to
describe the basic properties of this metal
define the inputs and routes of environmental contamination
define the toxicity and ecotoxicity of this metal
Lecture
7.1 Mercury
According to the technical classification of metals include mercury to the group of general (heavy)
non-ferrous metals. This metal is in the liquid state at normal temperature. It is remarkably weight
and it has good electrical conductivity. The most important practical application has mercury in the
form of their alloys with other metals - amalgams. Mercury reacts with Ag, Au, Cu, Zn, Cd, Na,
while with iron metals such as Fe, Ni and Co does not react.
Mercury belongs among elements, the effect of which on the human organism health is
unambiguously negative. MERCURY IS HIGHLY TOXIC. Higher mercury concentrations may
contaminate soil and water, in which mercury may transform into especially dangerous organic
forms moving upwards in the food chain, being bioaccumulative and dangerous above all for the
nervous system. A limit for water pollution by mercury is 0.05 micrograms of Hg/l for inland
aboveground waters. Under certain conditions, 1 mg of mercury may contaminate up to 20 000
liters of water. It is highly important to monitor products and following mercury-containing wastes
and dispose of them properly! To substitute mercury in various applications is highly desirable!
Application In spite of its considerable toxicity, mercury is used in many applications. Mercury is primarily
used for the manufacture of industrial chemicals (in production of chlorine, bicarbonate and NaOH)
and in electronics (switching devices, measuring instruments) and electrotechnics (mercury
discharge lamps). Lighting units with a mercury content (fluorescent tubes, mercury lamps) have
higher luminous efficiency than classic bulbs with a tungsten filament. Elemental mercury must not
be used anymore as a filling in temperature meters and pressure meters for measuring the
atmospheric pressure.
Mercury also finds its use for fabrication of amalgams, for instance the dental amalgam. Formation
of amalgam with gold is used in gold mining from ores with a high metal content.
Mercury is also used as a catalyst in the manufacture of urethane foam and antrachinon.
Some medicaments (diuretics, antiseptics, dermatologics) contain mercury or its compounds. It is
often contained in paintings as antibacterial additives and fungicides.
Mercury finds its applications in the analytical chemistry (polarography).
Mercury fulminate (mercury azide) is known as an explosive mercury. This compound is used for
the manufacture of pyrotechnical exploders.
Influence of mercury on the environment
40
7.2 Potential sources of pollution
Environmental impacts
Majority of mercury in the environment occurs in a form of metallic mercury and inorganic
compounds. Metallic mercury is liquid under the normal conditions, however, partial evaporation
occurs. In air, transformation to other forms may occur and mercury may be transported over long
distances.
Some microorganisms (bacteria, phytoplankton, fungi) may transform inorganic mercury to organic
compounds (Fig. 7.1). Mercury remains in the environment for a long time period, especially if
bound to small soil particles. These particles typically remain on surfaces of sediments and soils
and do not move into underground waters. In the aqueous environment they settle on the bottom.
Organic mercury may accumulate in food chains (bioaccumulation), while inorganic mercury does
not enter food chains. The highest contents of organic mercury can be found in sea fish bodies (Fig.
7.2), mushrooms may also contain high mercury concentrations. On the contrary, accumulation in
plants is not very high.
Fig. 7.1 Process of mercury biotransformation
Sources of pollution Natural sources of mercury entering the environment - weathering of natural deposits and volcanic
eruptions.
Anthropogenic sources of mercury entering the environment:
• combustion of fossil fuels and wastes;
• emissions come from mining and processing of mercury-containing ores;
• application of mercury-containing fertilizers and fungicides;
• batteries;
• electrochemical manufacture of chlorine and lye (amalgam method);
• agriculture (herbicides and fungicides);
• medical practice (temperature meters and dental amalgam);
• catalytic processes;
• other sources.
http://femsre.oxfordjournals.org/content/27/2-3/355
Influence of mercury on the environment
41
Fig. 7.2 Process of mercury bioacumulation
The most of mercury emissions are of the anthropogenic source. Approximately 80 % of mercury
released from human activities are emitted into air in a form of metallic mercury. About 15 % of
total mercury emissions get to soil from fertilizers, fungicides, municipal waste and through the
atmospheric deposition. The remaining 5 % are released into water by means of industrial waste
waters.
Mercury, once entering the environment, remains there for good. In the course of time, only
transformations of its form occur. Organically bound mercury slowly transforms into the
inorganically bound form. To a lesser extent, the process proceeds reversely, with some bacteria in
water and soil co-acting. This route is typical for formation of methylmercury.
Insoluble inorganic mercury binds to sediment particles either as aerobic sediment (Hg0) or
anaerobic sediment (HgS). Both the forms are capable of chemical oxidation according to the
equations:
Hg0 Hg
2+ + 2 e
-
HgS + 4 H2O Hg2+
+ SO42-
+ 8 H+ + 8 e
-
Mercuric cations – through anaerobic bacteria in sediments, they may bind in a form of
monomethylmercury CH3Hg+and dimethylmercury (CH3)2Hg – overally designated as
methylmercury; they are slightly soluble in water(1-2 ppb) and therefore they transfer into the
aqueous.
Dimethylmercury – a volatile substance escapes also into the atmosphere. Dimethylmercury in
the atmosphere transforms through photolysis to elemental mercury, methane and ethane.
Methylmercury in the aqueous environment transfers into water organisms. Mercury in fish occurs
in a form of methylmercury.
Legislation – limits Mercury (Mercury and its compounds (as Hg)) is monitored in the Integrated Pollution Register
(IPR) in releases into air, water, soil and in transfers of substances in wastes and waste waters.
http://www.constantinealexander.net/2013/09/06/
Influence of mercury on the environment
42
Reporting threshold for emissions and transfers:
into air 10 kg/year,
into water 1 kg/year
into soil 1 kg/year.
The risk component of the environment are: air, water, soil.
For transfers in wastes the threshold value is determined to 1 kg/year and in waste waters to 5
kg/year.
When exceeding some of these values, reporting duty arises for operators.
Mercury is one of the most toxic elements. It is present in all components of the living
environment.
BREF and BAT documents valid for mercury and compounds (as Hg):
Production of Chlor - alkali
Refining of Mineral Oil and Gas
Industrial Cooling Systems
Non-ferrous Metals Industries
Iron and Steel Production.
7.3 Toxicity and ecotoxicity of mercury
Toxicity is influenced by the form of mercury and exposure duration – elemental mercury is often
excreted without any effect to the organism. Mercury vapours after inhalation are quickly absorbed
by the blood circulation and transported to the target organ – brain, where mercury is deposited.
Inorganic compounds are toxic, whereas mercurous compounds are less toxic than mercuric ones.
Methylmercury is the most dangerous mercury compound. This can originate from inorganic
compounds through methanogenic bacteria in the anaerobic environment especially in sediments of
fresh as well as salt waters. Liquid methylmercury or dimethylmercury originates through this
process. Methylmercury belongs among embryotoxic and mutagenic substances.
Mercury belongs among elements, the effect of which on the human organism health is
unambiguously negative. It is a cumulative poison, excreting from the organism only very slowly.
Hg concentrates particularly in kidneys and to a lesser extent also in livers and spleen. It may
remain in kidneys as long as tens of years. Kidneys are just the most endangered organ in a case of
chronic mercury poisoning. Chronic poisoning symptoms are often non-specific – from cold
extremities, hair loss, gastrointestinal disorders, various neurological and psychical disorders, to
serious effects such as anemia, rheumatic diseases or a kidney disease.
At a single high dose of mercury, abdominal pain, diarrhea and vomiting may occur. Mercury may
also affect fertility.
Organic mercury compounds cause damage in brain and nervous system. Suckling and unborn
babies belong among the most endangered group Symptoms of poisoning: impairment of speech,
hearing, walking and peripheral vision, loss of coordination and muscle weakness.
The acute exposure to mercury vapours may cause pneumonia, damage of kidneys and an increase
in blood pressure.
Toxicity of particular mercury compounds depends above all on their solubility in water. From this
point of view, the most hazardous are compounds with divalent mercury Hg2+
.
On the contrary, toxicity of elemental mercury itself is practically zero; it enters organic tissues
only with difficulties. Mercury vapours are much more harmful, however, they get into air very
slowly.
Particularly dangerous are organometallic compounds of mercury – methylmercury,
dimethylmercury! Dimethylmercury is a liquid substances, the lethal dose for an adult is only 0.1
ml.
Mercury in medicine
Some vaccines may contain mercury. Mercury is in the form of mercury salts, ie. Thiomersal which
is used as a preservative in some vaccines.
Influence of mercury on the environment
43
Another subject of research is the use of dental amalgams. Amalgam dental fillings containing up
to 50% of mercury.
Poisoning from the chemical industry
In the fifties of the 20th century (1953) hit Japan's Minamata Bay of mysterious epidemic: Many
people become blind, became deaf, lost her teeth, loss motor skills. Other people failed kidneys. In
one fishing village at once sickened 116 people and 43 of them died. After three years it was found
that the cause mercury poisoning. Along with wastewater from a nearby chemical plant for the
production of acetaldehyde (Fig. 7.3), mercury fell into the sea and poisoned fish. People were
eating poisoned fish and other marine animals. The consequences are evident in today. Organic
mercury poisoning is therefore known as Minamata disease.
Minamata disease is a neurological syndrome caused by mercury poisoning.
Fig. 7.3 Principle of leakage of methylmercury in the production of acetaldehyde
Chisso-Minamata syndrom - signs, symptoms (Fig. 7.4):
• ataxia – impaired locomotor coordination
• numbness in the hands and feet
• muscle weakness
• damage to hearing, vision and speech
• abnormal eye movements
• shaking hands
• sometimes paralysis and coma
• death follows within a few weeks after the onset of symptoms
• there is also an inborn form, where the presence of mercury in the mother's body adversely
affects the fetus.
Poisoning of fungicides
Fungicides - compounds containing mercury (Phenylmercury, eg. Agronal) was used to protect the
corn seeds for sowing. Thus, there has been a poisoning of several dozen people - Iraq in 1961,
Pakistan in 1963, Guatemala in 1966. The rest of the seeds has been consumed.
Also poisoning can occur when feeding livestock and fish seed residues.
Poisoning from mining
Mining and processing of gold is used elemental mercury that is released into the river. Here is to
convert it into methylmercury (methylation). Mercury accumulates mainly in fish (catchment area
of Tapajos river in the Amazon, Brazil).
http://www.minamata195651.jp/pdf/kyoukun_en/
kyoukun_eng_all.pdf
Influence of mercury on the environment
44
Fig. 7.4 Symptoms of mercury poisoning
Sumary of terms
At the end of the chapter are repeated the main terms that you should acquire:
Basic characteristics of mercury.
Potential sources of mercury contamination.
Toxicity and ecotoxicity of mercury.
Question to the topic
1. What are basic characteristics of mercury?
2. What are potential sources of mercury contamination?
3. What are the symptoms of mercury poisoning?
References
[1] Reference documents under the IPPC Directive and the IED [on-line]. Joint research centre.
[cit. 16-07-01]. Available from
<http://eippcb.jrc.ec.europa.eu/reference/BREF/NFM_Final_Draft_10_2014.pdf>.
[2] Best Available Techniques (BAT) Reference Document for the Non-Ferrous Metals
Industries [on-line]. Joint research centre, European Commission, 2014, 1191 p. Available from
< http://eippcb.jrc.ec.europa.eu/reference/BREF/NFM_Final_Draft_10_2014.pdf>..
[3] RAMACHANDRA RAO, S. Resource Recovery and Recycling from Metallurgical Wastes.
Elsevier, London, 2006. ISBN 978-0-08-045131-2.
[4] ASHBY, M. F. Materials and the Environment: Eco-Informed Material Choice. Elsevier
Butterworth-Heinemann, Waltham, 2013, p. 616. ISBN 978-0-12-385971-6.
[5] MANAHAN, S. E. Toxicological chemistry and biochemistry. 3rd
ed. Boca Raton: CRC Press, 2003,
p. 783. ISBN 1-56670-618-1.
[6] MANAHAN, S. E. Environmental chemistry. 8th
ed. Boca Raton: CRC Press, 2005. ISBN 1-56670-
633-5.
[7] LANDIS, W. G., YU, M. H. Introduction to environmental toxicology: impacts of chemicals upon
ecological systems. 3rd
ed. Boca Raton: CRC/Lewis Publishers, 2004. ISBN 1-56670-660-2.
https://en.wikipedia.org/wiki/Minamata_disease https://cz.pinterest.com/pin/312789136593454047/
Influence of mercury on the environment
45
[8] YU, M. H., TSUNODA, H., TSUNODA, M. Environmental toxicology: biological and health
effects of pollutants. 3rd
ed. Boca Raton: CRC Press, 2011, p. 375. ISBN 978-1-4398-4038-2.
[9] GRUIZ, K., MEGGYES, T., FENYVESI, E. Environmental toxicology. Boca Raton: CRC Press,
Taylor & Francis Group, 2015. ISBN 978-1-138-00155-8.
[10] WALKER, C. H. Principles of ecotoxicology. 3rd
ed. Boca Raton: CRC/Taylor & Francis, 2006.
ISBN 0-8493-3635-X.
[11] NORDBERG, G., et al. Handbook on the toxicology of metals. 3rd
ed. Burlington:
Elsevier/Academic Press, 2007. ISBN 978-0-12-369413-3.
[12] Toxicological profiles. Toxic substances portal [on-line]. Available from <
http://www.atsdr.cdc.gov/toxprofiles/index.asp>.
Influence of copper and aluminum on the environment
46
8. Influence of copper and aluminum on the environment
Study time: 2 hours
Objective After reading this paragraph, you will be able to
describe the basic properties of these metal
define the inputs and routes of environmental contamination
define the toxicity and ecotoxicity of these metal
Lecture
8.1 Copper, influence on the environment, toxicity and ecotoxicity,
potential sources of pollution
Copper
Copper is reddish metal, which excellently conducts electricity and heat - very high thermal and
electrical conductivity. It is a malleable and ductile metal, corrosion-resistant, because the formed
oxide layer protects it from further corrosion. According to the technical classification of metals
include copper to the group of general (heavy) non-ferrous metals with medium melting point.
Application Copper is used mainly for the manufacture of electrical conductors, as an alloying element in many
alloys, for the manufacture of alloys, brasses, bronzes and other special alloys, in glass-making for
glass dyeing. Copper is also used for the manufacture of tubes and pipes, electromagnets, electrical
relays, integrated circuits, circuit breakers and corrosion resistant plates, roofing materials. It is
used for surface finishing (copper coating) and in chemical industry (dyes, glazes, catalysts).
Copper is also used in textile industry, where is bound in textile dyes. It is also a component in
algaecides (destroys chlorophyll, e.g. preparations for algae and anabaena killing in swimming-
pools).
Potential sources of pollution
Sources of pollution Natural sources of copper entering the environment:
• weathering,
• volcanic eruptions,
• forest fires,
• biomass decomposition.
Anthropogenic sources of copper entering the environment:
• mining and copper ores processing;
• combustion of fossil fuels and wastes;
• waste waters from surface finishing of metals;
• application of algaecides
• other sources.
Influence of copper and aluminum on the environment
47
Environmental impacts
Copper transfers from air into water and soil through the atmospheric deposition. Copper in soils is
strongly bound to organic substances and clay particles. Therefore majority of copper remains in
surface parts of soil and is not transported deeper. Copper solubility is limited by solubility of
cupric hydroxide, by co-precipitation with less soluble metal hydroxides and adsorption. In summer
seasons, hydrogen sulfide may form and copper may precipitate in a form of cupric sulfide at the
bottom of deeper water tanks.
Legislation – limits Copper (Copper and its compounds (as Cu)) is monitored in the Integrated Pollution Register
(IPR) in releases into air, water, soil and in transfers of substances in wastes and waste waters.
Reporting threshold for emissions and transfers:
into air 100 kg/year,
into water 50 kg/year
into soil 50 kg/year.
The risk component of the environment are: air, water, soil.
For transfers in wastes the threshold value is determined to 500 kg/year and in waste waters to
50 kg/year.
When exceeding some of these values, reporting duty arises for operators.
BREF and BAT documents valid for copper and compounds (as Cu):
Textiles Industry
Non-ferrous Metals Industries
Iron and Steel Production
Intensive Rearing of Poultry and Pigs
Refining of Mineral Oil and Gas
Large Volume Organic Chemical Industry
Production of Chlor - alkali
Production of Pulp, Paper and Board.
Toxicity and ecotoxicity
Copper belongs among essential elements for the human organism. It is necessary for growth and
development of bones, connective tissues, brain, heart and other organs. Cu is important for
creation of hemoglobin and some enzymes and for iron absorption and metabolism. It is also
important for effective utilization of vitamin C. Deficiency of copper in children results in the
physical and mental retardation. High doses of copper cause stomach ache and intestinal pain,
insult of livers and kidneys and anemia. Some copper compounds irritate skin, may cause
inflammations after repeated exposures. They may also initiate conjunctivitis.
Copper is an essential element for animals and higher plants, however, in higher amounts is
considerably toxic for water organisms (algaecides).
8.2 Aluminum, influence on the environment, toxicity and ecotoxicity,
potential sources of pollution
Aluminum
Aluminium is metal with very high thermal and electrical conductivity. It is a malleable and ductile
metal, corrosion-resistant, because the formed oxide layer protects it from further corrosion.
According to the technical classification of metals include aluminium to the group of light non-
ferrous metals with medium melting point. With other metals it creates many alloys which are
widely used in the industry - alloys have low density and sufficient strength.
Influence of copper and aluminum on the environment
48
Application Application of aluminum is considerably broad and covers many industrial branches, among them
mechanical engineering, foundry industry, chemical and electrotechnical industry, then the
manufacture of glass, dyes and pigments and water utilities plants. To a lesser extent, printing
industry belongs here, too.
Potential sources of pollution
Environmental impacts
Sources of pollution Natural sources of aluminum entering the environment:
• decomposition of clay minerals (anorthite CaAl2Si2O8, albite NaAlSi3O8), alum slates.
Anthropogenic sources of aluminum entering the environment:
• waste waters from surface finishing of aluminum etc.,
• acid atmospheric deposition – a decrease in pH of rainfall in relation with anthropogenic
activities is a cause of mobilization of aluminum in soils and thus Al concentration in
waters increases,
• other sources.
Environmental impact Al is toxic for water organisms, therefore releases into waters are monitored. Aluminum transfers
into water through treatment by coagulation by aluminum sulfate. As a result of acid rains the
aluminum migration in soil increases, which is also one of causes of the increase in aluminum
concentration in underground and aboveground waters. Aluminum occurs in waters either in
dissolved, or suspended form and in colloid dispersion.
The main problem of the living environment in the primary production of aluminum is formation of
polyfluorinated hydrocarbons and fluorides during electrolysis, production of solid waste from
baths (electrolytes) and production of solid wastes during the manufacture of aluminum oxide.
Similarly, in production of secondary aluminum, there is a possibility of emissions of dust and
dioxins from badly operated furnaces and wrong combustion and production of solid wastes (salted
slags, contaminated furnace linings, scumming and dust from filters).
Legislation – limits Aluminium and its compounds are included in the Register of duty (water).
Aluminum is a dangerous harmful substance, belongs into a group of metals and is toxic for
aqueous environment.
The risk component of the environment are: water.
BREF and BAT documents valid for aluminum and compounds (as Al):
Non-ferrous Metals Industries.
Toxicity and ecotoxicity
Aluminum is toxic for fish, which may show itself in acidified waters as a result of acid rainfall.
Toxicity depends considerably on forms of aluminum occurrence.
Aluminum is given into context with the Parkinson’s and Alzheimer’s disease (not proven, the
Alzheimer’s disease destroys brain cells and the brain tissue shrinks, which results in a complex of
functional problems and disorders). Aluminum is deposited in specific parts of the brain in patients
(Fig. 8.1).
Inhalation of fine dusts of compounds, particularly aluminum oxide, may cause pulmonary
aluminosis (lung damage).
Influence of copper and aluminum on the environment
49
Aluminum is toxic for fish, phytotoxicity of Al has been proven.
Simple dissolved monomer forms of occurrence have a toxic effect, complex forms are usually less
toxic than simple ions.
Fig. 8.1 Damage to the brain in Alzheimer's disease
Sumary of terms
At the end of the chapter are repeated the main terms that you should acquire:
Basic characteristics of copper and aluminum.
Potential sources of copper and aluminum contamination.
Toxicity and ecotoxicity of copper and aluminum.
Question to the topic
1. What are basic characteristics of copper and aluminum?
2. What are potential sources of copper and aluminum contamination?
3. What are the symptoms of copper and aluminum poisoning?
References
[1] Reference documents under the IPPC Directive and the IED [on-line]. Joint research centre.
[cit. 16-07-01]. Available from
<http://eippcb.jrc.ec.europa.eu/reference/BREF/NFM_Final_Draft_10_2014.pdf>.
https://www.alz.org/braintour/healthy_vs_alzheimers.asp http://periodontics-dentalimplants.com/alzheimers-and-gum-disease/
http://www.voanews.com/content/vitimin-d-may-help-avert-alzheimers-disease-dementia/1973271.html
Influence of copper and aluminum on the environment
50
[2] Best Available Techniques (BAT) Reference Document for the Non-Ferrous Metals
Industries [on-line]. Joint research centre, European Commission, 2014, 1191 p. Available from
< http://eippcb.jrc.ec.europa.eu/reference/BREF/NFM_Final_Draft_10_2014.pdf>..
[3] RAMACHANDRA RAO, S. Resource Recovery and Recycling from Metallurgical Wastes.
Elsevier, London, 2006. ISBN 978-0-08-045131-2.
[4] ASHBY, M. F. Materials and the Environment: Eco-Informed Material Choice. Elsevier
Butterworth-Heinemann, Waltham, 2013, p. 616. ISBN 978-0-12-385971-6.
[5] MANAHAN, S. E. Toxicological chemistry and biochemistry. 3rd
ed. Boca Raton: CRC Press, 2003,
p. 783. ISBN 1-56670-618-1.
[6] MANAHAN, S. E. Environmental chemistry. 8th
ed. Boca Raton: CRC Press, 2005. ISBN 1-56670-
633-5.
[7] LANDIS, W. G., YU, M. H. Introduction to environmental toxicology: impacts of chemicals upon
ecological systems. 3rd
ed. Boca Raton: CRC/Lewis Publishers, 2004. ISBN 1-56670-660-2.
[8] YU, M. H., TSUNODA, H., TSUNODA, M. Environmental toxicology: biological and health
effects of pollutants. 3rd
ed. Boca Raton: CRC Press, 2011, p. 375. ISBN 978-1-4398-4038-2.
[9] GRUIZ, K., MEGGYES, T., FENYVESI, E. Environmental toxicology. Boca Raton: CRC Press,
Taylor & Francis Group, 2015. ISBN 978-1-138-00155-8.
[10] WALKER, C. H. Principles of ecotoxicology. 3rd
ed. Boca Raton: CRC/Taylor & Francis, 2006.
ISBN 0-8493-3635-X.
[11] NORDBERG, G., et al. Handbook on the toxicology of metals. 3rd
ed. Burlington:
Elsevier/Academic Press, 2007. ISBN 978-0-12-369413-3.
[12] Toxicological profiles. Toxic substances portal [on-line]. Available from <
http://www.atsdr.cdc.gov/toxprofiles/index.asp>.
Influence of chromium and nickel on the environment
51
9. Influence of chromium and nickel on the environment
Study time: 2 hours
Objective After reading this paragraph, you will be able to
describe the basic properties of these metal
define the inputs and routes of environmental contamination
define the toxicity and ecotoxicity of these metal
Lecture
9.1 Chromium, influence on the environment, toxicity and ecotoxicity,
potential sources of pollution
Chromium
Cr is also hard and brittle metal with a melting point of 1863 °C. It is characterized by high
chemical resistance and very low reactivity. It is one of the hardest elemental metals.
Application Majority of chromium is used in metallurgy in alloy making, then in metal-coating, for the
manufacture of mirrors, in chemical industry and leather tanning. A significant sector is also the
manufacture of chromium pigments used in dye making and printing industry, photography
industry, for wood impregnation and many other branches.
Potential sources of pollution
Z hlediska znečišťování prostředí i v souvislosti s profesionální expozicí nelze pominout využití
chrómu při galvanické povrchové úpravě kovů. Odhaduje se, že chrómu, v důsledku jeho
všestranného použití v různých odvětvích průmyslu, je v různém rozsahu exponováno kolem 10
procent všech pracujících.
Sources of pollution Natural sources of chrome entering the environment:
• weathering,
• volcanic eruptions,
• forest fires.
Anthropogenic sources of chrome entering the environment:
• pigments for dyes,
• wood protecting preparations,
• metal coating,
• ore processing plants,
• metallurgical works,
• leather processing,
• the manufacture of cement,
• fossil fuel burning,
Influence of chromium and nickel on the environment
52
• other sources.
Environmental impacts Chrom je v nízké koncentraci přítomen ve všech typech půd a dále v sopečném prachu a plynech.
Všechen chrom přírodního původu je ve stavu Cr3+. Cr3+ se silně váže na záporně nabité půdní
částice, proto jen malá část proniká z půdy do podzemních vod. Ve vodě se většina Cr3+ váže na
částice nečistot a spolu s nimi klesá ke dnu, velká část nenasorbovaného Cr3+ tvoří nerozpustné
koloidní hydroxidy. Proto je obvykle ve vodě přítomno pouze malé množství rozpuštěného Cr3+.
Cr6+ je velmi toxický pro vodní organismy. Na rozdíl od Cr3+ se vyskytuje ve formě záporně
nabitých komplexů, proto se nesorbuje na půdní částice a je mnohem mobilnější. Cr6+ je však
velmi silné oxidační činidlo, v přítomnosti jakékoliv organické hmoty se poměrně rychle redukuje
na Cr3+. Proto nebezpečí vysokých koncentrací Cr6+ hrozí jen v blízkosti jeho zdroje. Pokud
nejsou organické látky přítomné, je Cr6+ za aerobních podmínek stabilní po dlouhou dobu.
V anaerobním prostředí se Cr6+ redukuje velmi rychle. Chrom se nehromadí v potravních
řetězcích.
V ovzduší je chrom navázán na prachové částice. Průměrná doba setrvání v atmosféře je 10 dní,
poté suchou nebo mokrou depozicí přechází do vody nebo půdy.
Legislation – limits Chrome (Chrome and its compounds (as Cr)) is monitored in the Integrated Pollution Register
(IPR) in releases into air, water, soil and in transfers of substances in wastes and waste waters.
Reporting threshold for emissions and transfers:
into air 100 kg/year,
into water 50 kg/year
into soil 50 kg/year.
The risk component of the environment are: air, water, soil.
For transfers in wastes the threshold value is determined to 200 kg/year and in waste waters to
50 kg/year.
When exceeding some of these values, reporting duty arises for operators.
BREF and BAT documents valid for chrome and compounds (as Cr):
Manufacture of Glass
Tanning of Hides and Skins
Textiles Industry
Production of Pulp, Paper and Board
Production of Chlor - alkali
Large Volume Organic Chemical Industry
Refining of Mineral Oil and Gas
Industrial Cooling Systems
Intensive Rearing of Poultry and Pigs
Non-ferrous Metals Industries
Iron and Steel Production
Ferrous Metals Processing Industry.
Toxicity and ecotoxicity
Chromium in small amount is constantly present in the human body and has a considerable
biological importance. Cr influences metabolism of saccharides and fats. Metallic chromium is
considered nontoxic (protection of kitchen utensils and cutlery), however, may cause people to
develop an allergy. There are considerable differences in toxicity of various chromium compounds,
obviously related to valence states of chromium. Impacts of CrII and Cr
III compounds are
negligible, impacts of CrVI
compounds are very severe. Cr belongs among essential elements in a
form of CrIII+
cation. CrIII+
has high ability of complexing.
For fish, CrIII
is more toxic!
Influence of chromium and nickel on the environment
53
Chromium may induce long-term adverse effects in the aqueous environment. Cr6+
is toxic for
aqueous flora, fauna and living beings.
Salts of hexavalent chromium are toxicologically highly important:
• CrVI
is a dominating form in water under common physical-chemical conditions,
• hexavalent chromium salts (chromans) are strong allergens,
• CrVI
is highly toxic (in contrast to low toxic CrIII
), • carcinogenic (lung cancer), some hexavalent compounds are also mutagenic, damaging
livers and kidneys (nephrotoxic and hepatotoxic effects) and causing internal hemorrhage,
• their possible teratogenity has been also investigated.
• Soluble compounds CrVI
affect skin (ulcers, skin inflammations, blisters). Allergic skin
disorders may occur as well (Fig. 9.1).
Fig. 9.1 Skin damage when exposed to chromium
9.2 Nickel, influence on the environment, toxicity and ecotoxicity,
potential sources of pollution
Nickel
Nickel belongs among few elements, the effect of which on the human organism health is
unambiguously negative.
Nickel is metal with electrical conductivity (value coresponds to 25% copper conductivity). It is
magnetic to 346 ° C. It is a malleable metal, corrosion-resistant (resistent to alkalis). Nickel is
resistant to atmospheric influences and water and therefore it is used as a thin nickel layer (nickel
plating) on the surface less resistant metals. According to the technical classification of metals
include nickel to the group of general (heavy) non-ferrous metals with medium melting point.
Application A large proportion of nickel is used for the manufacture of stainless and heat-resistant steels and for
the manufacture of nickel alloys (superalloys, Monel, Alnico, resistivity materials …). It is also
used in batteries, as a catalyst and other chemicals, in glass making industry and metal coating.
Nickel is a component in the so-called white gold, an alloy of gold, nickel, copper and zinc.
Potential sources of pollution
Nickel may enter water naturally through dissolution of minerals of the bottom or may be present
in rain water. Anthropogenic sources are above all waste waters from surface finishing of metals
and also waste waters from metallurgy of non-ferrous metals. Another source can be nickel-coated
http://www.toxicology.cz/modules.php?name=News&file=article&sid=29
Influence of chromium and nickel on the environment
54
parts of equipment being in a contact with water. An increase in nickel concentration in soil may be
caused by application of sewage sludge. Combustion processes and refining of oil and gas take a
significant part, too.
Sources of pollution Natural sources of nickel entering the environment:
• weathering,
• volcanic eruptions,
• forest fires,
• aerosols from sea level,
• soil dusts and volcanic ash,
• a part of atmospheric nickel comes from meteoric dust.
Anthropogenic sources of nickel entering the environment:
• fossil fuel and waste burning,
• refining of oil and gas,
• mining and processing of nickel; manufacturing and refining,
• application of sewage sludge onto soil,
• ore processing and mining,
• metallurgical works,
• batteries,
• metal coating,
• smoking,
• alloys,
• other sources.
Environmental impacts Nickel present in air may get to soil or water through the atmospheric deposition.
Nickel binds to iron- and manganese-containing particles, which often occur in soil and sediments.
Therefore majority of nickel present in the environment occurs here.
Toxicity for some aqueous organisms is relatively high, therefore its permissible concentration in
water supply rivers is limited more strictly than in drinking water.
Plants take up nickel from soil mainly through roots, they are able to accumulate it. By pH
decreasing the nickel mobility increases and thus also intercepting by plants.
Legislation – limits Nickel (Nickel and its compounds (as Ni)) is monitored in the Integrated Pollution Register (IPR)
in releases into air, water, soil and in transfers of substances in wastes and waste waters.
Reporting threshold for emissions and transfers:
into air 50 kg/year,
into water 20 kg/year
into soil 20 kg/year.
The risk component of the environment are: air, water, soil.
For transfers in wastes the threshold value is determined to 500 kg/year and in waste waters to
20 kg/year.
When exceeding some of these values, reporting duty arises for operators.
Nickel is dangerous mainly for aqueous organisms. Therefore it is more strictly limited in
aboveground waters than in drinking waters.
BREF and BAT documents valid for nickel and compounds (as Ni):
Textiles Industry
Production of Pulp, Paper and Board
Production of Chlor - alkali
Refining of Mineral Oil and Gas
Influence of chromium and nickel on the environment
55
Intensive Rearing of Poultry and Pigs
Non-ferrous Metals Industries
Iron and Steel Production
Ferrous Metals Processing Industry.
Toxicity and ecotoxicity
Nickel is present in trace amounts in the organism, e.g. in some enzymes. However, its biological
function is not known yet. Some nickel compounds (chloride, nitrate, sulfate or phosphate) exhibit
toxic effects on the human organism. The most poisonous nickel compounds include nickel oxide,
nickel sulfide and nickel tetracarbonyl Ni(CO)4. Carcinogenic is above all dust originating in
processing of nickel and nickel-coated components; it initiates cancer of lungs, nasal and cervical
mucous membrane; mutagenity in the human organism has not been proven yet. Symptoms of the
acute nickel poisoning are above all damaged digestive tract and disorders of the central nervous
system. Chronic poisoning may lead to damage of heart muscle, kidneys and the central nervous
system. A contact with nickel may cause skin dermatitis called nickel contact dermatitis (scabies).
It appears like flare and later skin eczema may occur at permanent contact with nickel objects (Fig.
9.2).
Fig. 9.2 Skin damage when exposed to nickel
A long-term exposure to high nickel doses causes weight reduction, malfunction of heart and livers
and inflammation of the skin. Nickel occurs in the cigarette smoke in a form of highly toxic nickel
tetracarbonyl
Sumary of terms
At the end of the chapter are repeated the main terms that you should acquire:
Basic characteristics of chromium and nickel.
Potential sources of chromium and nickel contamination.
Toxicity and ecotoxicity of chromium and nickel.
Question to the topic
1. What are basic characteristics of chromium and nickel?
2. What are potential sources of chromium and nickel contamination?
3. What are the symptoms of chromium and nickel poisoning?
http://www.medicinenet.com/image-
collection/nickel_contact_dermatitis_picture/picture.htm http://xplorechemistry.blogspot.cz/2012/06/nickel-allergy.html
Influence of chromium and nickel on the environment
56
References
[1] Reference documents under the IPPC Directive and the IED [on-line]. Joint research centre.
[cit. 16-07-01]. Available from
<http://eippcb.jrc.ec.europa.eu/reference/BREF/NFM_Final_Draft_10_2014.pdf>.
[2] Best Available Techniques (BAT) Reference Document for the Non-Ferrous Metals
Industries [on-line]. Joint research centre, European Commission, 2014, 1191 p. Available from
< http://eippcb.jrc.ec.europa.eu/reference/BREF/NFM_Final_Draft_10_2014.pdf>..
[3] RAMACHANDRA RAO, S. Resource Recovery and Recycling from Metallurgical Wastes.
Elsevier, London, 2006. ISBN 978-0-08-045131-2.
[4] ASHBY, M. F. Materials and the Environment: Eco-Informed Material Choice. Elsevier
Butterworth-Heinemann, Waltham, 2013, p. 616. ISBN 978-0-12-385971-6.
[5] MANAHAN, S. E. Toxicological chemistry and biochemistry. 3rd
ed. Boca Raton: CRC Press, 2003,
p. 783. ISBN 1-56670-618-1.
[6] MANAHAN, S. E. Environmental chemistry. 8th
ed. Boca Raton: CRC Press, 2005. ISBN 1-56670-
633-5.
[7] LANDIS, W. G., YU, M. H. Introduction to environmental toxicology: impacts of chemicals upon
ecological systems. 3rd
ed. Boca Raton: CRC/Lewis Publishers, 2004. ISBN 1-56670-660-2.
[8] YU, M. H., TSUNODA, H., TSUNODA, M. Environmental toxicology: biological and health
effects of pollutants. 3rd
ed. Boca Raton: CRC Press, 2011, p. 375. ISBN 978-1-4398-4038-2.
[9] GRUIZ, K., MEGGYES, T., FENYVESI, E. Environmental toxicology. Boca Raton: CRC Press,
Taylor & Francis Group, 2015. ISBN 978-1-138-00155-8.
[10] WALKER, C. H. Principles of ecotoxicology. 3rd
ed. Boca Raton: CRC/Taylor & Francis, 2006.
ISBN 0-8493-3635-X.
[11] NORDBERG, G., et al. Handbook on the toxicology of metals. 3rd
ed. Burlington:
Elsevier/Academic Press, 2007. ISBN 978-0-12-369413-3.
[12] Toxicological profiles. Toxic substances portal [on-line]. Available from <
http://www.atsdr.cdc.gov/toxprofiles/index.asp>.
Influence of tin, zinc, selenium and other HM on the environment
57
10. Influence of tin, zinc, selenium and other heavy metals on the
environment
Study time: 2 hours
Objective After reading this paragraph, you will be able to
describe the basic properties of these metal
define the inputs and routes of environmental contamination
define the toxicity and ecotoxicity of these metal
Lecture
10.1 Influence of tin on the environment, its toxicity and ecotoxicity,
potential sources of pollution
Tin
Tin is well ductile and corrosion resistant metal. Metallic tin is resistant to acids, which are used in
iron protecting against corrosion, e.g. in the production of food cans. According to the technical
classification of metals include tin to the group of general (heavy) non-ferrous metals with low
melting point.
Tin is a dangerous harmful substance, belongs into a group of heavy metals and is toxic for
aqueous environment (in particular organostannic compounds are highly toxic)
Application Metallic tin is acid resistant and this property is used for protection of iron against corrosion, e.g. in
the manufacture of cans.
Organic compounds of tin are used as catalysts in chemical industry (manufacture of polyurethane),
as stabilizers in the manufacture of plastic materials (stabilization of PVC) and also as agricultural
biocides (selective effect: against dry rots, fungi, insects, but they are only slightly toxic for higher
living beings). Fungicides and wood protective coatings use toxic effects of organostannic
compounds (anti-fouling ship paintings). Organostannic compounds for wood protection are
prohibited in the Czech Republic and Slovak Republic!
Potential sources of pollution
As a result of anthropogenic activities, tin compounds get into the living environment. This entry is
determined both by application of these compounds in manufacturing and by direct use of these
compounds.
Products with a content of organic tin compounds are also used in households and the waste then
becomes other source of tin in the environment. These wastes are dumped to dumping sites, which
become pollution sources for aqueous ecosystems and air due to water leakage through waste
layers and transfer of more volatile components into the gaseous phase. Dumping sites also
represent an environment with suitable conditions for the increased chemical and biological
transformation of tin.
Influence of tin, zinc, selenium and other HM on the environment
58
Incineration is another method of disposal of this household waste and if the tin waste is
incinerated, the atmospheric emission factors range between 1.0 to 10 g of tin per one ton of burnt
municipal solid waste.
A major proportion of contaminating substances, which contain tin, is associated with soil particles.
Adsorption onto this fraction is an important control mechanism of distribution and fate of
organostannic compounds in the environment. This adsorption behavior is influenced by types of
exchanging cations, pH value, salinity and mineralogical and chemical composition of the
environment and the molecular structure of organic tin compounds.
Inorganic compounds of tin bind to soil and sediment and their evaporation from water is not
probable.
Since water and sediment are contaminated by organic tin compounds (Fig. 10.1) and these
substance have ability to accumulate in fats, an increased content of these substances is present in
water animals. These compounds may transfer from there into humans through contaminated food.
Fig. 10.1 Environmental contamination by tin
Ion types of organic tin compounds in the marine environment change through biotransformation to
volatile compound types. Thus these volatile types of compounds get into air, which becomes a
source of organic tin compounds for land ecosystems.
Elemental tin and inorganic tin compounds are not volatile under the environmental conditions.
However, tin compounds may be carried by air particles over long distances, during this transport
their physical and chemical changes may occur (inorganic tin compounds in the environment may
undergo oxidation-reduction reactions, ligand exchange and precipitation reactions, at degradation
of organostannic compounds a removal of organic groups bound to tin cation occurs, and that
through processes of photolysis, biological and chemical cleavage.
Bioaccumulation Tin compounds may enter the organism through the body surface from water or sediment, the so-
called bioaccumulation; another route is through the food chain. The result of these processes is
accumulation, which is often directly proportional to the concentration of the compound in the
environment. The lipophilic character of organostannic compounds is a cause of their ability to
remain in the environment.
Since tributyltin is extremely toxic for more organisms, the most of studies are focused just on this
compound. Generally, the biological availability by trapping through the water phase appears more
significant than the biological availability of organic tin compounds by means of the food chain.
1 Sea, rivers, lakes 2 Wastewater 3 Incinerator 4 Landfills 5 Air pollution 6 Soil 7 Groundwater
antifouling paints
fertilizers, agrochemicals
PVC catalysators
biocids
https://dspace.vutbr.cz/bitstream/handle/11012/6399/Diplomov%C3%A1%20pr%C3%A1ce.pdf?sequence=1
Influence of tin, zinc, selenium and other HM on the environment
59
Sources of pollution Natural sources of tin entering the environment:
• weathering and volcanic eruptions.
Anthropogenic sources of tin entering the environment:
• antifouling coats
• releases to water from PVC pipes;
• aplication of biocids and desinfectans;
• application of wood preservatives;
• contamination from waste dump;
• other sources.
Environmental impacts Waste waters distributed through plastic tubes, where organostannic compounds are used for
stabilization against photochemical and thermal changes (e.g. PVC water distribution tubes).
These are particularly mono- and dibutylstannic compounds.From the point of view of toxicity,
organostannic compounds are the most unsound. These are mainly trialkylstannic, dialkylstannic
and monoalkylstannic compounds and then triarylstannic compounds.
Tin occurs in waters, both inorganically and organically bound.
Legislation – limits Tributyltin and its compounds is monitored in the Integrated Pollution Register (IPR) in releases
into air, water, soil and in transfers of substances in wastes and waste waters.
Reporting threshold for emissions and transfers:
into air - kg/year,
into water 1 kg/year
into soil 1 kg/year.
The risk component of the environment are: water.
For transfers in wastes the threshold value is determined to - kg/year and in waste waters to 1
kg/year.
When exceeding some of these values, reporting duty arises for operators.
BREF and BAT documents valid for tributyltin and compounds:
Iron and Steel Production.
Toxicity and ecotoxicity
Tin is a trace element, for which no specific biochemical function has been clearly identified to
date. Some studies state that tin is an essential trace element, nevertheless, it has been proven that
organic compounds of tin are toxic. Increased doses of Sn have toxic effects.
At ingestion, tin toxicity level is mild, partly due to its poor absorption and low retention in tissues.
Metallic Sn is only slightly toxic, in contrast to highly toxic organic compounds (mainly
organostannic compounds). Chronic exposure to tin may cause retardation of growth and anemia.
The increased Sn intake influences the activity of many enzymes and it is assumed that metabolism
of Zn, Cu and Ca may be affected as well. Higher toxicity can be found at intake of organic tin
compounds, which attack the central nervous system. Changes in the myelin and spongiform
degeneration of brain occur, which shows itself as ataxia and a complete paralysis may occur and
even death.
Organic tin compounds - toxic compounds: butyltin C4H9SnX3, dibutyltin (C4H9)2SnX2 and
tributyltin (C4H9)3SnX.
Tributyltin compounds may enter the body via inhalation, oral route or through a contact with skin.
Poisoning in humans is mostly a result of the professional exposure. The main symptoms are
upper respiratory tract irritation, bleeding of nasal septum, skin and eye irritation, even skin
Influence of tin, zinc, selenium and other HM on the environment
60
inflammation may occur. Regarding a lack of information as to tributyltin effects on human
health, it is necessary to rely on animal testing. Symptoms of acute exposure include a change in a
level of blood fats, a decrease in the number of erythrocytes, effects on the endocrine system
(mainly the thyroid gland and pituitary), livers, spleen, thymus, biliary duct and brain. Tin
may also damage the nervous and immune system. A long-term exposure to low doses slows down
the growth.
10.2 Influence of zinc on the environment, its toxicity and ecotoxicity,
potential sources of pollution
Zinc
Pure zinc is used for zinc coating of semifinished products (tubes, wires, sheets) as a protective
layer against corrosion. Zinc compounds are very important as well, for example ZnO is widely
applied in the manufacture of coatings and in rubber industry. Zinc alloys are used for foundry
purposes, because they have excellent castability and better strength properties than pure zinc.
Zinc is resistant to petrol, alcohol, slightly alkaline solutions. Is resistant to corrosion in air, it is
covered with a layer of basic carbonate, in water of normal hardness is resistant, in distilled water
is subject to corrosion, water vapor significantly damaging it. Zinc is well thermoformable and can
be easily. According to the technical classification of metals include zinc to the group of general
(heavy) non-ferrous metals with low melting point.
Application Zinc finds an important application as the anticorrosive protective material particularly for iron and
its alloys. Zinc has very good properties for the manufacture of castings – molten zinc perfectly
fills a casting mould due to its exquisite fluidity. This way metal components highly resistant
against atmospheric effects (noncorrosive) are manufactured, however, they may not withstand
heavy mechanical loading because zinc has not a high mechanical resistance.
In a large extent, zinc is used for the manufacture of zinc alloys. Zamak belongs among the most
significant alloys. Zinc is also used as an alloying element in alloy making (brass, red bronze).
Zinc took a quite important part in the manufacture of galvanic cells.
Zinc finds also its application in the manufacture of wheel weights for counterbalance as a
substitute for toxic lead.
Other fields of the use of zinc: for the manufacture of other metals (desilvering of lead in the
Parkes process), paintings (the most known lithopone – a mixture of zinc sulfide and barium
sulfate) and zinc white ZnO, anticorrosive painting for iron – finely pulverized zinc blende (zinc
sulfide ZnS, e.g. paintings for bridges and machine parts).
Potential sources of pollution
Sources of pollution Natural sources of zinc entering the environment:
• weathering and volcanic eruptions.
Anthropogenic sources of zinc entering the environment:
• metal coating,
• pigments for dyes and ceramic glazes,
• alloys (brass, bronze),
• agriculture,
• municipal waste,
• smoking.
Environmental impacts
Legislation – limits Zinc (Zinc and its compounds (as Zn)) is monitored in the Integrated Pollution Register (IPR) in
releases into air, water, soil and in transfers of substances in wastes and waste waters.
Influence of tin, zinc, selenium and other HM on the environment
61
Reporting threshold for emissions and transfers:
into air 200 kg/year,
into water 100 kg/year
into soil 100 kg/year.
The risk component of the environment are: air, water, soil.
For transfers in wastes the threshold value is determined to 1000 kg/year and in waste waters to
100 kg/year.
When exceeding some of these values, reporting duty arises for operators.
BREF and BAT documents valid for zinc and compounds (as Zn):
Production of Pulp, Paper and Board
Production of Chlor - alkali
Large Volume Organic Chemical Industry
Refining of Mineral Oil and Gas
Industrial Cooling Systems
Intensive Rearing of Poultry and Pigs
Non-ferrous Metals Industries
Iron and Steel Production
Ferrous Metals Processing Industry.
Toxicity and ecotoxicity
Zinc belongs to essential elements, a certain specified concentration is essential for humans. A
deficiency of zinc may cause neuropsychological abnormalities, dermatitis and malfunction of the
immune system. However, a high concentration of zinc may result in health problems. Inhalation of
zinc oxide fumes is associated with the so-called metal fume fever (fatigue, headaches, cough, high
temperature, proteins in urine). Soluble zinc salts are toxicologically more significant – zinc sulfate
heptahydrate (white vitriol) and zinc chloride.
Toxicity of zinc compounds:
Zinc sulfate heptahydrate (white vitriol)
• just in small doses has an emetic effect, in higher concentrations etches skin
• a lethal dose for a human is 3-5 g
Zinc chloride
• more toxic than the white vitriol
• the acute poisoning may lead to nephritis and the heart muscle malfunction
Zinc dimethyldithiocarbamate
• a component of preparations for plant protection
• causes sensitivity to alcohol (antabus effect)
• digestive tract irritation, hepatotoxic and nephrotoxic effects
• suspected of carcinogenity.
10.3 Influence of selenium on the environment, its toxicity and
ecotoxicity, potential sources of pollution
Selenium
Selenium belongs among half-metals - in term of its effects is usually mentioned together with
heavy metals. Selenium is a dangerous harmful substance, belongs into a group of metals and is
highly toxic for aqueous environment.
Application Nowadays the technological importance of selenium consists in the manufacture of photocells. In
this term, copper indium gallium selenides are highly perspective compounds and today selenium
Influence of tin, zinc, selenium and other HM on the environment
62
based photoelectric cells serve as electric power sources above all in cosmic research for power
supply of instruments on the orbit through solar panels.
Selenium containing photocells are also used as exposure meters for measurements of the
incidental light intensity, for example in cameras and video-cameras.
Other areas of use: metal alloying, photocells, semiconductors, catalyst of plastic materials, dyeing
of glass, ceramics and synthetic resins; fighting against pests in agriculture (e.g. sodium selenate);
in medicine selenium sulfides and polysulfides against seborrhea (hair shampoo), in veterinary
medicine.
Potential sources of pollution
Selenium has a considerable ability to accumulate in plant and animal tissues.
Originally selenium considered highly toxic substance, but this idea was later corrected.
Tin is one of the essential trace elements necessary for the organism.
Sources of pollution Natural sources of selenium entering the environment:
• weathering and volcanic eruptions.
Anthropogenic sources of selenium entering the environment:
• ore processing
• municipal waste
• fossil fuel burning
• semiconductors.
Legislation – limits Selenium is listed in a list of relevant dangerous substances for the hydrosphere from 2009.
BREF and BAT documents valid for selenium and compounds (as Se):
Non-ferrous Metals Industries.
Toxicity and ecotoxicity
Selenium belongs among essential elements, is a part of metalloenzymes. It is biomethylized, but
only in oxidation conditions. A dividing line between a deficiency and toxic effect is very narrow
with this element. Its presence reduces toxicity of cadmium, mercury, methylmercury and other
substances (antagonism). Higher doses of selenium have toxic effects, but acute poisoning in
humans is not common.
Elemental selenium is nontoxic or practically nontoxic. Inhalation of fine dust particles or
elemental selenium fumes strongly irritates the respiratory tract mucosa and may eventually cause
pulmonary edema. Selenium may cause local sensitivity or allergic reactions of skin. Poisoning
may result in dermatitis, damage of nails and teeth and affects the central nervous system.
Majority of selenium compounds is highly toxic – higher toxicity than in arsenic compounds.
Colourless gas selane H2Se (hydrogen selenide) is highly toxic (horseradish odour) – has irritable
effects, hepatotoxic and nephrotoxic effects. Selane is the most poisonous selenium compound -
LC50 is 0.05 ppm at exposure for 8 hours. Selenium dioxide has similar effects as arsenic trioxide.
10.4 Influence of other metals on the environment, their toxicity and
ecotoxicity
More and more metals and even in larger amounts enter the living environment due to
anthropogenic activities. Some metals, such as selenium, tungsten, …, have been used lately only
in minimum amounts and their transfer into the living environment have been very limited.
Contents of some metals in the environment have been increasing due to their use in modern
Influence of tin, zinc, selenium and other HM on the environment
63
applications (special alloys, semiconductors, electrotechnics, plastic materials, chemicals, …).
Therefore their potential effect on human organism and other living organisms has not been
investigated thoroughly yet. So, a brief overview of found or currently observed negative properties
of selected metals is given in this chapter.
Other toxicological significance metals
• Antimony
• Beryllium
• Manganese
• Molybdenum
• Vanadium
• Tungsten
• Cobalt
• Silver
• Thallium
• Bromine.
Toxicity of tungsten and its compounds
Metallic tungsten is not toxic. Tungsten is not a biogenic element, nevertheless, it can substitute
molybdenum in some biogenic processes (creation of enzymes) thanks to their similarity. Workers
in production of tungsten carbide may be exposed, affecting of respiratory tract may occur
(coughing, reduced efficiency of the respiratory system, pulmonary inflammation diseases), then a
weight loss and eventually death. A synergetic effect of cobalt is investigated, because tungsten
carbides may increase solubility of highly toxic cobalt in body fluids. Tungsten trioxide WO3 is
harmful to health at ingestion, irritates skin and may cause serious eye irritation. It is used as a
pigment for dyeing of ceramics (green colour), plasma spraying (W coating).
Sumary of terms
At the end of the chapter are repeated the main terms that you should acquire:
Basic characteristics of tin, zinc and selenium.
Potential sources of tin, zinc and selenium contamination.
Toxicity and ecotoxicity of tin, zinc and selenium.
Question to the topic
1. What are basic characteristics of tin, zinc and selenium?
2. What are potential sources of tin, zinc and selenium contamination?
3. What are the symptoms of tin, zinc and selenium poisoning?
References
[1] Reference documents under the IPPC Directive and the IED [on-line]. Joint research centre.
[cit. 16-07-01]. Available from
<http://eippcb.jrc.ec.europa.eu/reference/BREF/NFM_Final_Draft_10_2014.pdf>.
[2] Best Available Techniques (BAT) Reference Document for the Non-Ferrous Metals
Industries [on-line]. Joint research centre, European Commission, 2014, 1191 p. Available from
< http://eippcb.jrc.ec.europa.eu/reference/BREF/NFM_Final_Draft_10_2014.pdf>..
[3] RAMACHANDRA RAO, S. R. Resource Recovery and Recycling from Metallurgical Wastes.
Elsevier, London, 2006. ISBN 978-0-08-045131-2.
Influence of tin, zinc, selenium and other HM on the environment
64
[4] ASHBY, M. F. Materials and the Environment: Eco-Informed Material Choice. Elsevier
Butterworth-Heinemann, Waltham, 2013, p. 616. ISBN 978-0-12-385971-6.
[5] MANAHAN, S. E. Toxicological chemistry and biochemistry. 3rd
ed. Boca Raton: CRC Press, 2003,
p. 783. ISBN 1-56670-618-1.
[6] MANAHAN, S. E. Environmental chemistry. 8th
ed. Boca Raton: CRC Press, 2005. ISBN 1-56670-
633-5.
[7] LANDIS, W. G., YU, M. H. Introduction to environmental toxicology: impacts of chemicals upon
ecological systems. 3rd
ed. Boca Raton: CRC/Lewis Publishers, 2004. ISBN 1-56670-660-2.
[8] YU, M. H., TSUNODA, H., TSUNODA, M. Environmental toxicology: biological and health
effects of pollutants. 3rd
ed. Boca Raton: CRC Press, 2011, p. 375. ISBN 978-1-4398-4038-2.
[9] GRUIZ, K., MEGGYES, T., FENYVESI, E. Environmental toxicology. Boca Raton: CRC Press,
Taylor & Francis Group, 2015. ISBN 978-1-138-00155-8.
[10] WALKER, C. H. Principles of ecotoxicology. 3rd
ed. Boca Raton: CRC/Taylor & Francis, 2006.
ISBN 0-8493-3635-X.
[11] NORDBERG, G., et al. Handbook on the toxicology of metals. 3rd
ed. Burlington:
Elsevier/Academic Press, 2007. ISBN 978-0-12-369413-3.
[12] Toxicological profiles. Toxic substances portal [on-line]. Available from <
http://www.atsdr.cdc.gov/toxprofiles/index.asp>.
[13] Tin and tin compounds. Background and environmental exposures to tin and tin
compounds in the united state [on-line]. Available from
<http://www.atsdr.cdc.gov/toxprofiles/tp55-c2.pdf>.
The environment and legislation
65
11. The environment and legislation
Study time: 2 hours
Objective After reading this paragraph, you will be able to
define the basic terms of waste management
describe the basic distribution of waste and waste management
activities
Lecture
11.1 Waste Act, the basic terminology
All manufacturing and non-manufacturing activities are accompanied by the generation of waste.
Waste
The term WASTE according to Act no. 185/2001 of the Coll. - Waste is any movable item the
owner disposes of or intends to or is obliged to dispose of.
The division of wastes (basic, for normal use) depends on the terms of assessment, and the criteria
can include, e.g. the origins, the properties of waste, its impact on the environment and on humans,
etc.
Wastes can be divided:
a) according to their basic physical characteristics:
• solid
• liquid
• gaseous
• mixed
b) according to their origin:
• industrial
• construction
• agricultural
• municipal
• overburden from surface mining
• sludge from wastewater treatment plants
• and others
c) according to their environmental impact:
• other
• special - special waste, which is a harmful substance or which has significantly
hazardous properties to humans or the environment (Fig. 11.1), it can also be
hazardous waste.
The environment and legislation
66
http://www.reach-compliance.ch/ghsclp/ghspictograms/
Fig. 11.1 Pictogram GHS 09 – Environment
Sources and occurrence of wastes
According to the source and the occurrence of wastes, they are divided into:
• circulation waste (production – own production, different production)
• new production waste (processing)
• amortization waste (consumer).
11.2 Waste management
Waste management is a set of actions aimed at preventing the generation of wastes, at waste
treatment and the follow-up care of the sites where the wastes are permanently deposited, and the
control of these activities.
The issue of waste management is primarily governed by Act no. 185/2001 of the Coll. - "Waste
Act".
In compliance with the European Community law, this Act stipulates:
• rules for waste prevention and for waste management in compliance with the protection of
the environment, the protection of human health and sustainable development,
• the rights and obligations of persons involved in waste management,
• and the competence of public administration authorities.
Waste management, according to the law, means in particular gathering, concentration, collection,
purchase, sorting, shipping and transport, storage, treatment, use and disposal of waste.
The basic activities in waste management are:
1. Prevention of the occurrence of waste;
2. Reduction of the occurrence of waste;
3. Waste management:
• Waste collection;
• Shipments of waste;
• Storage of waste;
• Waste treatment;
• Use of wastes;
• Disposal of wastes.
The individual activities may overlap, complement and influence each other (Fig. 11.2).
The environment and legislation
67
Fig. 11.2 Scheme of waste management
The waste management is based on the prevention and reduction of the production of wastes. If the
wastes already exist, they must be treated in such a way to maximize their use as secondary raw
materials and to minimize their negative impact on the environment. Waste prevention is
represented by waste-free or low waste technologies. These processes are, however, very energy
intensive and the generation of waste is transferred into power supply.
Waste management legislation
Waste Act - "Act no. 185/2001, on wastes and on the amendments of certain other acts", in short
"Waste Act". This Act establishes an obligation to the originators and entitled persons to classify
waste according to the Catalogue of Wastes for the purpose of waste management.
Act stipulates, in compliance with the European Community law:
• rules on waste prevention and waste management while respecting the protection of the
environment, the protection of human health and sustainable development, while reducing
the negative impacts of the use of natural resources and the improvement of the efficiency
of such use,
• the rights and duties of the persons involved in waste management,
• and the responsibilities of public administration authorities in waste management.
The Catalogue of Wastes Decree no. 93/2016 of the Ministry of Environment, lays down the Catalogue of Wastes, the List
of Hazardous Wastes and the lists of wastes and countries for the purpose of export, import and
transit and the procedure for granting consent to export, import and transit wastes (the Catalogue of
Wastes).
The actual Catalogue of Wastes is presented in Annex of this Decree.
Wastes are classified under six-catalogue numbers of waste types, divided into three pairs of
numbers. The first two digits refer to the group of wastes, the second two digits indicate the
subgroup and the third two digits the type of waste.
WASTE MANAGEMENT
2.1 Prevention of
the occurrence of
waste
2.3 Waste
management
2.2 Reduction of
the occurrence of
waste
2.3.1 Collection
2.3.2 Shipment
2.3.3 Storage
2.3.4 Treatment
2.3.5 Use
2.3.6 Disposal
The environment and legislation
68
Hazardous wastes in the list are marked with an asterisk (*) behind the catalogue number. Wastes
without stars are classified as "other", i.e., they are not hazardous.
The waste catalogue contains 20 group of wastes.
Eg. 15 01 Containers 15 01 10* Containers with residues of hazardous substances or contaminated by these
substances
List of hazardous waste properties is given in Annex no. 1.
Recycling
Recycling = recirculation - returning back into the production process.
Waste recycling means the reuse of production, processing and consumption waste materials,
substances and energies as a source of secondary raw materials in its original or modified form.
It can be considered as a strategy focused on reusing waste in order to preserve the natural
resources and energies, while simultaneously reducing the impact of pollutants on the environment.
Recycling enables you to secure part of the raw material inventories, to reduce the production costs
of raw materials and to reduce the environmental burden caused by production of waste.
Recycling technology
Recycling is performed by means of a recycling technology. Recycling technology is a set of
interconnected manufacturing processes, procedures and operations aimed at the conversion of
waste into a secondary raw material.
Recycling technologies try to reduce the generation of waste by using low-waste technological
processes, where the same manufacturing process or directly related processes use almost all the
generated waste materials.
Low-waste technology is sometimes referred to as "waste-free technology".
It's such a method of production in which the most rational and most comprehensively utilize raw
materials and energy in the cycle:
raw material sources - production - consumption - secondary raw materials.
Low-waste technologies are usually economically and energetically more demanding.
Conventional recycling technology – is recycling in terms of the treatment and reuse of already
generated waste. The recycling technology in this case is a set of successive processes, procedures,
technological operations, etc., aimed at the conversion of waste into a secondary raw material
A typical feature of recycling technology is its relative independence in the technological scheme:
production - waste - production.
While in case of low-waste technologies, the appropriate procedures for waste processing must be
part of the production technology, the conventional recycling technologies are generally conducted
separately - often in the form of additional investments designed to improve the economic and
environmental efficiency of existing production processes.
Material flows
It is very important to know the material flows. There are many illustrations of material flows -
from the simplest ones, showing only the movement of materials - up to the balanced ones,
showing the movement of material in the company.
Recovery of waste
Everyone is, during his/her activities or within the scope of his/her duties within the limits of the
"Waste Act", obliged to ensure the priority use of wastes before their disposal. The material use of
wastes takes precedence over other uses of waste.
The environment and legislation
69
The possible ways of utilization of waste:
• recycling of waste (organic waste composting, recycling plastic, glass, paper, metals, etc.);
• energy utilization of waste (incineration);
• recycling with energy use (biogas production from organic waste).
The methods of waste utilization are listed in Annex No. 3 to Act. no. 185/2001 of the Coll.
Methods of waste disposal
The methods of waste disposal are presented in Annex no. 4 to Act. no. 185/2001 of the Coll..
Other basic terms
Other basic terms are set by Act 185/2001 of the Coll.
Sumary of terms
At the end of the chapter are repeated the main terms that you should acquire:
Waste
Waste management
Recycling
Recycling technologies
Material flows
Question to the topic
1. What is the definition of waste?
2. What are the types of waste?
3. What is the subject of the Waste Act?
4. What Catalog of waste contains and what it is used?
5. Explain the term of recycling, and what are recycling technology?
References
[1] ASHBY, M. F. Materials and the Environment: Eco-Informed Material Choice. Elsevier Butterworth-
Heinemann, Waltham, 2013, 616 s. ISBN 978-0-12-385971-6.
[2] Act no. 185/2001 of the Coll, on wastes and on the amendments of certain other acts, Czech
Republic.
[3] Decree no. 93/2016 of the Ministry of Environment, Catalogue of Wastes, Czech Republic.
[4] Directive no. 2008/98 / EC, EU.
Annexes
70
Annexes
Annex no. 1 Annex III of Directive 2008/98 / EC - List of hazardous waste properties
Code Hazardous waste property
HP1 Explosive
HP2 Oxidising
HP3 Flammable
HP4 Irritant
HP5 Single Target Organ Toxicity (STOT)/ Aspiration
HP6 Acute toxicity
HP7 Carcinogenic
HP8 Corrosive (Wastes which on application can cause skin corrosion.)
HP9 Infectious
HP10 Toxic for reproduction
HP11 Mutaganic
HP12 Release of an acute toxic gas cat 1, 2 or 3 (Wastes which release acute toxic gases cat. 1, 2
or in contact with water or an acid.)
HP13 Sensitising
HP14 Ecotoxic
HP15 Yielding another substance (Waste capable of exhibiting a hazardous property listed
above not directly displayed by the original waste).