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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


5.3. Toxicity and ecotoxicity of cadmium 32

6. Influence of arsenic on the environment 34

6.1. Arsenic 34


6.3. Toxicity and ecotoxicity of arsenic 36

7. Influence of mercury on the environment 39

7.1. Mercury 39


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


9. Influence of chromium and nickel on the environment 51

9.1. Chromium, influence on the environment, toxicity and ecotoxicity, potential


9.2. Nickel, influence on the environment, toxicity and ecotoxicity, potential


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


10.2. Influence of zinc on the environment, its toxicity and ecotoxicity, potential


10.3. Influence of selenium on the environment, its toxicity and ecotoxicity, potential


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

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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


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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


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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.


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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.


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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


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• 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.


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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.


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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


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


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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/


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


Bioaccumulation

Biotransformation

Phytoremediation


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

+


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.


ed. Boca Raton: CRC Press, 2003,

p. 783. ISBN 1-56670-618-1.


ed. Boca Raton: CRC Press, 2005. ISBN 1-56670-

633-5.




[6] YU, M. H., TSUNODA, H., TSUNODA, M. Environmental toxicology: biological and health

effects of pollutants. 3rd


[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


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,


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• 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.

http://www.ippc.cz/obsah/referencni-dokumenty/






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


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


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

http://eko-net.cir.cz/-registry-znecistovani-zivotniho-prostredi-jsou-budovany-z-mnoha-duvodu-smyslem-registru-je-prispet-k-posileni-integrovaneho-pristupu-v-ochrane-zivotniho-prostredi-a-k-podpore-setrnejsiho-chovani-staty-ale-i-prumyslove-podniky-potrebuji-data-o-znecisteni-zivotniho-prostredi-k-formulaci-environmentalnich-politik-a-jako-nastroj-ekologickeho-rizeni-zasadni-vyznam-maji-registry-pri-informovani-verejnosti-ktera-ma-moznost-ziskat-obtizne-dostupne-udaje-a-zaroven-ma-verejnost-moznost-podilet-se-na-vyvoji-narodniho-registru-verejna-kontrola-pusobi-na-odpovednejsi-ekologicke-chovani-jednotlivych-podniku-

http://eko-net.cir.cz/evropsky-registr-emisi-znecistujicich-latek-eper-

http://eko-net.cir.cz/-registry-znecistovani-zivotniho-prostredi-jsou-budovany-z-mnoha-duvodu-smyslem-registru-je-prispet-k-posileni-integrovaneho-pristupu-v-ochrane-zivotniho-prostredi-a-k-podpore-setrnejsiho-chovani-staty-ale-i-prumyslove-podniky-potrebuji-data-o-znecisteni-zivotniho-prostredi-k-formulaci-environmentalnich-politik-a-jako-nastroj-ekologickeho-rizeni-zasadni-vyznam-maji-registry-pri-informovani-verejnosti-ktera-ma-moznost-ziskat-obtizne-dostupne-udaje-a-zaroven-ma-verejnost-moznost-podilet-se-na-vyvoji-narodniho-registru-verejna-kontrola-pusobi-na-odpovednejsi-ekologicke-chovani-jednotlivych-podniku-


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.

http://www.irz.cz/node/20


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


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


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


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


25


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


• 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


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


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


Basic characteristics of lead.

Potential sources of lead contamination.

Toxicity and ecotoxicity of lead.


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


29

3. What are the symptoms of lead poisoning?

References



<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>..







p. 783. ISBN 1-56670-618-1.



633-5.









[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


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.


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.


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.




http://www.jnuenvis.nic.in/cadmium.html


32




kg/year.


BREF and BAT documents valid for cadmium and compounds (as Cd):



Ferrous Metals Processing Industry


Intensive Rearing of Poultry and Pigs


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/


33

Sumary of terms


Basic characteristics of cadmium.

Potential sources of cadmim contamination.

Toxicity and ecotoxicity of cadmium.


1. What are basic characteristics of cadmium?

2. What are potential sources of cadmium contamination?

3. What are the symptoms of cadmium poisoning?

References













p. 783. ISBN 1-56670-618-1.



633-5.











ISBN 0-8493-3635-X.


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





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.


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,


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.







kg/year.


http://onlinelibrary.wiley.com/doi/10.1111/j.1574-6976.2002.tb00617.x/pdf


36

BREF and BAT documents valid for arsenic and compounds (as As):

Manufacture of Glass


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


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


Basic characteristics of arsenic.

Potential sources of arsenic contamination.

Toxicity and ecotoxicity of arsenic.


1. What are basic characteristics of arsenic?

2. What are potential sources of arsenic contamination?

3. What are the symptoms of arsenic poisoning?

References











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


38



p. 783. ISBN 1-56670-618-1.



633-5.











ISBN 0-8493-3635-X.


ed. Burlington:




Influence of mercury on the environment

39

7. Influence of mercury on the environment

Study time: 3 hours





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.


40



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


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


http://www.constantinealexander.net/2013/09/06/


42







kg/year.


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


Industrial Cooling Systems


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.


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


44

Fig. 7.4 Symptoms of mercury poisoning

Sumary of terms


Basic characteristics of mercury.

Potential sources of mercury contamination.

Toxicity and ecotoxicity of mercury.


1. What are basic characteristics of mercury?

2. What are potential sources of mercury contamination?

3. What are the symptoms of mercury poisoning?

References













p. 783. ISBN 1-56670-618-1.



633-5.




https://en.wikipedia.org/wiki/Minamata_disease https://cz.pinterest.com/pin/312789136593454047/


45








ISBN 0-8493-3635-X.


ed. Burlington:




Influence of copper and aluminum on the environment

46

8. Influence of copper and aluminum on the environment

Study time: 2 hours


describe the basic properties of these metal


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.


47


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







For transfers in wastes the threshold value is determined to 500 kg/year and in waste waters to

50 kg/year.


BREF and BAT documents valid for copper and compounds (as Cu):

Textiles Industry





Large Volume Organic Chemical Industry


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,


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.


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.



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.


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).


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


Basic characteristics of copper and aluminum.

Potential sources of copper and aluminum contamination.

Toxicity and ecotoxicity of copper and aluminum.


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




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


50










p. 783. ISBN 1-56670-618-1.



633-5.











ISBN 0-8493-3635-X.


ed. Burlington:




Influence of chromium and nickel on the environment

51

9. Influence of chromium and nickel on the environment

Study time: 2 hours





Lecture

9.1 Chromium, influence on the environment, toxicity and ecotoxicity,


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.


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,


• 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,


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








50 kg/year.


BREF and BAT documents valid for chrome and compounds (as Cr):

Manufacture of Glass

Tanning of Hides and Skins

Textiles Industry









Ferrous Metals Processing Industry.


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!


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,


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.


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


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,


• 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.







20 kg/year.


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





55






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


Basic characteristics of chromium and nickel.

Potential sources of chromium and nickel contamination.

Toxicity and ecotoxicity of chromium and nickel.


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


56

References













p. 783. ISBN 1-56670-618-1.



633-5.











ISBN 0-8493-3635-X.


ed. Burlington:




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





Lecture

10.1 Influence of tin on the environment, its toxicity and ecotoxicity,


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!


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.


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


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.


into air - 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.


BREF and BAT documents valid for tributyltin and compounds:

Iron and Steel Production.


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


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,


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).


Sources of pollution Natural sources of zinc entering the environment:


Anthropogenic sources of zinc entering the environment:

• metal coating,

• pigments for dyes and ceramic glazes,

• alloys (brass, bronze),

• agriculture,

• municipal waste,

• smoking.


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.


61







100 kg/year.


BREF and BAT documents valid for zinc and compounds (as Zn):











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


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.


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:


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.


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


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


Basic characteristics of tin, zinc and selenium.

Potential sources of tin, zinc and selenium contamination.

Toxicity and ecotoxicity of tin, zinc and selenium.


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







[3] RAMACHANDRA RAO, S. R. Resource Recovery and Recycling from Metallurgical Wastes.



64





p. 783. ISBN 1-56670-618-1.



633-5.











ISBN 0-8493-3635-X.


ed. Burlington:




[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


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.


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).


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


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.


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


Waste

Waste management

Recycling

Recycling technologies

Material flows


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).

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