Chlorinated hydrocarbons in the environment – monitoring and effect monitoring
Thousands of chemicals are traded on the market, but only in a few cases is full information available on their distribution and their effects on man and the environment. In addition to real time monitoring of chemicals, it is, thus, necessary to establish an environmental specimen bank (ESB) for th...
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| Дата: | 2005 |
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| Формат: | Стаття |
| Мова: | English |
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Фізико-хімічний інститут ім. О.В. Богатського НАН України
2005
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| Назва видання: | Актуальні проблеми транспортної медицини |
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| Цитувати: | Chlorinated hydrocarbons in the environment – monitoring and effect monitoring / A.A.F. Kettrup // Актуальні проблеми транспортної медицини. — 2005. — № 1. — С. 29-40. — Бібліогр.: 45 назв. — англ. |
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irk-123456789-209582013-02-13T02:05:43Z Chlorinated hydrocarbons in the environment – monitoring and effect monitoring Kettrup, A.A.F. Проблемные статьи Thousands of chemicals are traded on the market, but only in a few cases is full information available on their distribution and their effects on man and the environment. In addition to real time monitoring of chemicals, it is, thus, necessary to establish an environmental specimen bank (ESB) for the retrospective monitoring of chem¬icals in the future. The base of ESB are representative bioindicators of systematically collected biological and environmental samples. As a result of extremely low storage temperature (T = < - 150°C) it is guaranteed that the samples are not subject to chemical changes during the long-term storage. Furthermore we need in addition an effect monitoring, using in vitro testing like for example P 450 1A1 enzyme expression. В настоящее время на рынке присутствует огромное количество химических веществ, но только в некоторых случаях доступна полная информация об их распространенности и воздействиях, оказываемых ими на человека. В дополнение к мониторингу химических веществ, проводимому в реальном времени, необходимо создать банк образцов химических веществ, присутствующих в окружающей среде для проведения в будущем ретроспективного мониторинга. Основой такого банка данных могут стать репрезентативные биоиндикаторы систематически собираемых биологических образцов и образцов, присутствующих в окружающей среде. Поскольку температура хранения образцов в банке крайне низкая ( Т< - 150°C) существует гарантия того, что образцы не будут подвергаться химическим изменениям во время длительного хранения. Но помимо прочего, нам необходим эффективный мониторинг, где бы использовались in vitro тест - системы, например, для определения экспрессии энзима 450 1А1. 2005 Article Chlorinated hydrocarbons in the environment – monitoring and effect monitoring / A.A.F. Kettrup // Актуальні проблеми транспортної медицини. — 2005. — № 1. — С. 29-40. — Бібліогр.: 45 назв. — англ. 1818-9385 http://dspace.nbuv.gov.ua/handle/123456789/20958 547.264.131:502 en Актуальні проблеми транспортної медицини Фізико-хімічний інститут ім. О.В. Богатського НАН України |
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Digital Library of Periodicals of National Academy of Sciences of Ukraine |
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English |
| topic |
Проблемные статьи Проблемные статьи |
| spellingShingle |
Проблемные статьи Проблемные статьи Kettrup, A.A.F. Chlorinated hydrocarbons in the environment – monitoring and effect monitoring Актуальні проблеми транспортної медицини |
| description |
Thousands of chemicals are traded on the market, but only in a few cases is full information available on their distribution and their effects on man and the environment. In addition to real time monitoring of chemicals, it is, thus, necessary to establish an environmental specimen bank (ESB) for the retrospective monitoring of chem¬icals in the future. The base of ESB are representative bioindicators of systematically collected biological and environmental samples. As a result of extremely low storage temperature (T = < - 150°C) it is guaranteed that the samples are not subject to chemical changes during the long-term storage.
Furthermore we need in addition an effect monitoring, using in vitro testing like for example P 450 1A1 enzyme expression. |
| format |
Article |
| author |
Kettrup, A.A.F. |
| author_facet |
Kettrup, A.A.F. |
| author_sort |
Kettrup, A.A.F. |
| title |
Chlorinated hydrocarbons in the environment – monitoring and effect monitoring |
| title_short |
Chlorinated hydrocarbons in the environment – monitoring and effect monitoring |
| title_full |
Chlorinated hydrocarbons in the environment – monitoring and effect monitoring |
| title_fullStr |
Chlorinated hydrocarbons in the environment – monitoring and effect monitoring |
| title_full_unstemmed |
Chlorinated hydrocarbons in the environment – monitoring and effect monitoring |
| title_sort |
chlorinated hydrocarbons in the environment – monitoring and effect monitoring |
| publisher |
Фізико-хімічний інститут ім. О.В. Богатського НАН України |
| publishDate |
2005 |
| topic_facet |
Проблемные статьи |
| url |
http://dspace.nbuv.gov.ua/handle/123456789/20958 |
| citation_txt |
Chlorinated hydrocarbons in the environment – monitoring and effect monitoring / A.A.F. Kettrup // Актуальні проблеми транспортної медицини. — 2005. — № 1. — С. 29-40. — Бібліогр.: 45 назв. — англ. |
| series |
Актуальні проблеми транспортної медицини |
| work_keys_str_mv |
AT kettrupaaf chlorinatedhydrocarbonsintheenvironmentmonitoringandeffectmonitoring |
| first_indexed |
2025-07-02T21:30:08Z |
| last_indexed |
2025-07-02T21:30:08Z |
| _version_ |
1836572274502664192 |
| fulltext |
2929292929
ACTUAL PROBLEMS OF TRANSPORT MEDICINE � # 1, 2005
ÀÊÒÓÀËÜÍÛÅ ÏÐÎÁËÅÌÛ ÒÐÀÍÑÏÎÐÒÍÎÉ ÌÅÄÈÖÈÍÛ � ¹ 1, 2005 ã.
IntroductionIntroductionIntroductionIntroductionIntroduction
According to the “European Inventory of
Existing Commercial Substances” EINECS (af-
ter GDCh/BUA) [1], more than 100.000 differ-
ent chemical substances are produced world-
wide. 1000 to 2000 new chemicals are entering
the market every year in addition to those already
in circulation. For most of them we lack sufficient
information about their effects on man, animals
and plants and about their further reaction and
fate in the environment (2). New technologies
always produce unintended and unpredicted
waste and impact. According to the single inte-
grated EU waste list (CD 2000/532/EC, COM
2000) 347 final, COM (2001)216 final), the ma-
jority of waste from organic chemical processes
(code 07) and significant part of waste from in-
organic chemical processes (code 06) is con-
sidered as a hazardous waste. A large number
of European Community legislation in force and
in preparation is focused on various chemical
waste and waste chemicals. It can be found in
the EUR-Lex register 15.10.30.30. “Waste Man-
agement and clean technology”, internet site:
http://www.europa.eu.int/eur-lex/en/lif/reg/en
register 15103030.html.
Usually the introduction of chemicals into
the environment represents an irreversible step.
A considerable number of chemicals reaching
the environment do not degrade or only very
slowly. They accumulate in the environment and,
having distributed, become ubiquitous of certain
pollutants e.g. PCBs, herbicides, chlorinated in-
secticides. Persistent biologically active chemi-
cals, even at concentrations below our ability to
analyze or detect, can pose serious pervasive
and possible irreversible threats to human health
and the integrity of the biosphere (3).
Numerous industrial countries have
passed laws to assess the hazards of chemicals
for man and the environment. EU legislation on
chemicals is collected in the register EUR-Lex
15.10.20.50 “Chemicals, industrial risk and bio-
technology” in the internet site
h:http://www.europa.eu.int/eur-lex/en/
lif/reg/en register 15102050.html.
ÓÄÊ 547.264.131:502
CHLORINATED HYDROCARBONS IN THE ENVIRONMENT –CHLORINATED HYDROCARBONS IN THE ENVIRONMENT –CHLORINATED HYDROCARBONS IN THE ENVIRONMENT –CHLORINATED HYDROCARBONS IN THE ENVIRONMENT –CHLORINATED HYDROCARBONS IN THE ENVIRONMENT –
MONITORING AND EFFECT MONITORINGMONITORING AND EFFECT MONITORINGMONITORING AND EFFECT MONITORINGMONITORING AND EFFECT MONITORINGMONITORING AND EFFECT MONITORING
Kettrup A.A.F.
Technical University of Munich
Department of Ecological Chemistry and Environmental Analysis
Weihenstephaner Steig 23
85350 Freising-Weihenstephan
Among others, it comprise the Council Di-
rective 76/769/EEC (1976) relating to the re-
strictions on the marketing and use of certain
dangerous substances and preparations, with
numerous amendments, the last one of 1999 (OJ
L 207.06.08.1999 p.18), as well as three lists of
priority substances established by commission
Regulations (EC) No 1179/94 (1994), No. 2268/
95 (1995) and No 143/97 (1997) as foreseen un-
der Council Regulation (EEC) No 793/93 (1993).
The principles for assessment of risks to man and
environment of different chemicals were laid
down in Commission Directive 93/67/EEC
(1993), Regulations (EC) No 1488/94 (1994), as
well as in Commission recommendations 1999/
721/EC (1999) and C (2001) 439 of March 2001.
Living organisms and their associations,
are enormously heterogeneous, complex and
open systems characterized by poorly defined
boundaries. Under the best circumstances, we
can evaluate most quantitative features of bio-
logical systems only for certain properties and
only by using certain samples or subsets of the
class. Results are always statistical in nature and
extrapolation from the sample to the class is nec-
essary. Many environmental factors that can-
not be reproduced or represented in the labo-
ratory or by models can modify the environmen-
tal behaviour and effects of chemicals. The er-
ror in forecasts based upon trend extrapolations,
without knowing the relationships of environ-
mental variables may become enormously en-
larged with time. Recognizing the actual form of
a trend among reasonable alternatives is diffi-
cult and often subjective. Thus, the level of un-
certainty of most forecasts and assessment of
chemical impacts upon man and the environ-
mental is often quite high. Even today, we re-
peatedly confront serious and unexpected con-
sequences of our technologies, products and
wastes. Politicians can only develop effective
damage protection and risk contaminant strate-
gies, if they have reliable scientific information
available.
So, these problems are resulting in a lack
of knowledge regarding damages in environ-
ÀÊÒÓÀËÜÍÛÅ ÏÐÎÁËÅÌÛ ÒÐÀÍÑÏÎÐÒÍÎÉ ÌÅÄÈÖÈÍÛ � ¹ 1, 2005 ã.
3030303030
ACTUAL PROBLEMS OF TRANSPORT MEDICINE � # 1, 2005
ment, human health risks, incorrect assess-
ments and predictions. Persistent organic pol-
lutants (POP’S) are still under discussion, espe-
cially halogenated organic pollutants (4).
Effective damage protection and risk con-
taminant strategies can only be developed by
policy makers if they have reliable basic infor-
mations on chemical disposal.
So, after ca. 30 years discussion on POP’s
in the environment in 1998 valid definition was
made as follows (UN ECE):
POP’s are
· chemicals with potential for long range
atmospheric transport
· chemicals with relatively high environ-
mental persistency (eigher half-live
· in water>2 month or half-live in soils or
sediments>6month)
· chemicals which can be bioaccumulated
(log Kow>5 or fish/water
bioconcentration factor >5000)
Three years ago UNEP started a global survey
on POP’s in the environment following the so-
called “Stockholm convention” on the protec-
tion of human health and the environment from
POP’s
· by getting rid of existing POP’s
· by avoiding further production and use
of POP’s
· by minimising emissions of POP’s which
can’t be eliminated
The idea that organisms can provide an indica-
tion of the quality of their environment is wide-
spread and at least as old as agriculture (5). It
is not possible to establish any clear definition
for the term “bioindicatior” considering the
large number of literature published in the last
decades. The following definitions are sug-
gested congruenting to many European au-
thors (6):
· Bioindication is the use of an organism (
a part of an organism or a society of or-
ganisms) to obtain information on the
quality (of a part) of its environment. Or-
ganisms which are able to give informa-
tion on the quality (of a part) of its envi-
ronment are bioindicators.
· Biomonitoring is the continuous obser-
vation of an area with the help of
bioindicators, which in the case may also
be called biomonitors. With the aid of or-
ganisms trends in time and space con-
cerning the distribution and ecological
effects of environmental chemicals can
be observed by a semi-quantitative eval-
uation of the results.
Biological samples from the environment
are mainly used and analysed as representatives
for larger entities or similar or related environ-
mental compartments. This requires the selec-
tion of standardized (bio)indicatior systems,
which react with known specifity and sensitivity
to environmental chemicals and have the capa-
bility of spatial and/or temporal integration. Such
indicator systems can be efficiently and
reproducibly analysed and evaluated vicarious-
ly for the total entity of sensitive targets in the
environment to be observed, which are often
extremely variable with respect to the space,
time and physiology. Bioindicator systems in
such cases, where potential integral effects of
complex or unknown immission types have to be
detected and quantified. Such effects may oc-
cur on different levels from specific organs of
single organism up to whole ecosystems.
Bioindicators are also preferred in such cases,
where they offer advantages due to their high
sensitivity towards a broad spectrum of sub-
stances or because of their ability to accumu-
late a substance over an extended period of time
or to integrate its influence in an area of known
and relevant size. This is namely the case, if the
sensitiveness of available analytical methods for
dangerous substances it too low to find them in
other environmental compartments like air, wa-
ter and soils.
The most important property for using
organisms as bioindicators is the bioavailibility
of a chemical.
In case of an earthworm (e.g. Lumbricus
terrestris) the bioavailibility is dependent from:
— properties of the chemical
- Kow
- dissociation constant
- affinity to charged surfaces
— properties of the soil
- organic matter content
- pH
- clay content
— properties of the organism
- uptake kinetics
- physiological condition
In case of an earthworm it is relatively easy
to determine the age and the physiological con-
3131313131
ACTUAL PROBLEMS OF TRANSPORT MEDICINE # 1, 2005
АКТУАЛЬНЫЕ ПРОБЛЕМЫ ТРАНСПОРТНОЙ МЕДИЦИНЫ № 1, 2005 г.
0
1
2
3
4
5
6
7
8
9
10
11
12
13
HCB
-HCH
Diel
o,p-DDT
p,p-DDT
p,p-DDE
p,p-DDD
B 52
B 101
B 138
B 153
B 180
c [ng/g f .w.]
Fig. 1: Sum of chlorinated hydrocarbons in Lumbricus
terrestris sampled in the area of Leipzig
2-
C
hl
or
ph
e
no
l
4-
C
hl
or
ph
en
ol
4-
C
hl
or
-3
-m
et
hy
lp
he
no
l
2,
4
+
2
,5
-D
ic
hl
or
ph
en
ol
2,
6-
D
ic
hl
or
ph
en
ol
2,
3,
4-
T
ric
hl
or
ph
en
ol
2
,3
,5
-T
ric
hl
or
ph
en
ol
2,
3,
6-
T
ric
hl
o
rp
h
en
ol
2,
4,
5-
T
ric
hl
or
p
he
no
l
2,
4,
6-
T
ric
h
lo
rp
he
no
l
2,
3,
4,
5-
T
et
ra
ch
lo
rp
he
n
ol
2,
3,
4,
6-
T
et
ra
ch
lo
rp
h
en
ol
2,
3,
5,
6-
T
e
tr
ac
hl
or
p
he
no
l
T
et
ra
ch
lo
r-
2-
m
et
ho
xy
p
he
no
l
P
en
ta
ch
lo
rp
he
n
ol
1
9
94 1
99
5
19
9
6
19
9
7
19
9
8 1
9
9
4
1
9
95 19
96 1
9
97 1
99
8
0
50
100
150
200
250
300
Leipzig
Saartal
µg/kg f.w.
Fig. 2: Amount of different chlorinated phenols in
Lumbricus terrestris
Using earthworms as bioindicator it is possible to show
that the soil contamination with chlorinated phenols is
quite the same in the area of Leipzig (former GDR) and
Saarbrьcken near the French border.
dition. Furthermore it is easy to sample an suffi�
cient amount of the specimen. Earthworms like
Lumbricus terrestris or Aporrectodea longa are
good bioindicators for chlorinated hydrocarbons
as can be shown in fig. 1.
It is obvious that 2,4,6�chlo�
rophenol show the highest con�
centration in earthworms in both
areas. Chlorphenols are used as
an intermediate in the chemical in�
dustry but also as disinfectants,
biocides, preservatives and pesti�
cides.
In addition to the concentra�
tions of toxic substances and their
metabolites biological specimen
can also be analysed for essential
components and a broad spec�
trum of possible biochemical,
physiological, morphological and/
or genetical effects. Organisms
and biological communities nor�
mally do not react to single com�
ponents or substances in their en�
vironment. They show the effects
of the totality of all the acting sub�
stances and environmental fac�
tors. Decisive for the use of bio�
logical specimen is their
ecotoxicological relevance, that
means the relevance or indicative
function of the found effects for
other living organisms and com�
munities including men.
Idea of Environmental Speci�
men Banking
With respect to effects of
pollutants, their quantities and dis�
tribution under natural conditions
the acquisition of reliable informa�
tion requires a systematic program
of environmental monitoring in
which concentrations of hazard�
ous chemical substances are
measured in suitable environmen�
tal specimen of various trophic
stages and food chains. But actu�
al monitoring of the environment
can only be as good as our present
knowledge and as analytical pos�
sibilities allow. From among the
multitude of substances found in
the environment only those can be
monitored, which have already
been recognized to be hazardous substances�
and thus, the quality of regulatory decisions�suf�
fers from the act that no results are available on
pollutant burdens of former times or that the data
which are available are ambiguous (7).
ÀÊÒÓÀËÜÍÛÅ ÏÐÎÁËÅÌÛ ÒÐÀÍÑÏÎÐÒÍÎÉ ÌÅÄÈÖÈÍÛ � ¹ 1, 2005 ã.
3232323232
ACTUAL PROBLEMS OF TRANSPORT MEDICINE � # 1, 2005
Before this background at the beginning
of the 70s the idea of using biological samples
as reference material to furnish proof of environ-
mental pollution was put forward by Frederick
Coulston of the Albany Medical College (Albany/
NY), and Friedhelm Korte of Institute of Ecolog-
ical Chemistry, GSF-Forschungszentrum, Mu-
nich-Neuherberg.
In an environmental specimen bank (ESB)
carefully selected, relevant environmental sam-
ples are stored systematically at temperatures
below - 150°C immediately after collection. In
this way no, or as small as possible, chemical
changes occur over a long period of time. Base-
line levels of contaminants in the environment
can be established by taking samples at the
present time for future demand in ecological-
chemical research. Long-term storage of sam-
ples with indicator functions represents an nec-
essary complement to the actual monitoring of
the environment and a safety net in the assess-
ment of chemical risk.
A systemically established archive of frequently
collected representative environmental speci-
men samples fullfill the following important func-
tions [3,7-9]:
· They may be used for the determination
of the environmental concentrations of
those substances, which, at the time of
storage, were not recognized to be haz-
ardous or which at present cannot be
analysed with adequate accuracy (retro-
spective monitoring)
· They may serve as reference samples for
the documentation of the improvement
of analytical efficiency and for the verifi-
cation of previously obtained monitoring
results.
· Early detection of environmental increas-
es in hazardous chemicals thought to be
under control is possible. Also, the effec-
tiveness of restrictions, regulations, or
management practices that have been
applied to the community, the environ-
mental or to the manufacture, distribu-
tion, disposal, or use of toxic chemicals
can be assessed.
· Depending upon the analysis and evalu-
ation of stored materials ESB can save
considerable time and money when un-
expected impacts are observed.
· Sources of chemical may be identified.
Often, by the time a chemical is recog-
nized as a health or environmental prob-
lem it is sufficiently wide-spread to defy
identification of the principal sources of
pathways.
· ESB can offset the lack of reliable data
on pollutant burdens of earlier times be-
cause inconsistencies or ambiguities
among available data usually limit as-
sessments and regulatory decisions.
In Germany the Federal Minister for Re-
search and Technology supported a compre-
hensive pre- and pilot phase of ESB between
1976 and 1984. During this period the techni-
cal feasibility regarding the sampling of differ-
ent species, handling and shipping of samples,
deep freezing, homogenisation, ultra trace
analysis, packing materials, logistics, storage
temperature and documentation was con-
firmed [10]. The results were so encouraging
that in 1985 the German government decided
to set up a permanent ESB under the responsi-
bility of the Federal Ministry for the Environ-
ment, Nature Conservation and Reactor Safety
(BMU), coordinated by the Federal Environ-
mental Agency (Umweltbundesamt). Two
specimen banks are subsumed under the gen-
eral heading of the German ESB:
· The Specimen Bank for Environmental
Specimens at the Institute of Applied
Physical Chemistry of the Research
Center Jülich (KFA) and since 2000 at the
Fraunhofer Institute of Environmental
Chemistry and Ecotoxicology/
Schmallenberg
· The Specimen Bank for Human Organ
Specimens at the Institute of Pharmacol-
ogy and Toxicology of the University of
Münster.
The work was distributed among these and
some other institutions depending on their
special scientific capabilities:
· Institute of Biogeography/University of
the Saarland
· Institute of Ecological Chemistry of the
Natl. Research Center of Environment
and Health/Munich-Neuherberg
· Biochemical Institute for Environmental
Carcinogens/Großhansdorf
· ERGO/Hamburg
In Germany environmental specimen
banking has been successfully established as a
permanent environmental surveillance tool.
The banking activities are focused on the
preparation, characterisation and storage of
representative samples from different ecosys-
3333333333
ACTUAL PROBLEMS OF TRANSPORT MEDICINE � # 1, 2005
ÀÊÒÓÀËÜÍÛÅ ÏÐÎÁËÅÌÛ ÒÐÀÍÑÏÎÐÒÍÎÉ ÌÅÄÈÖÈÍÛ � ¹ 1, 2005 ã.
tems in Germany. Based on reliable and well-
documented analytical procedures the ob-
tained monitoring results offers the opportunity
for long-term control of environmental pollu-
tion by spatial differences and time-dependent
trends.
In the meantime an international cooper-
ation of ESB’s in the Federal Republic of Ger-
many, USA, Canada, Japan, Finland, Sweden,
Norway and Denmark has been established
[11,12].
Sampling areas and specimen types Sampling areas and specimen types Sampling areas and specimen types Sampling areas and specimen types Sampling areas and specimen types
Sampling areas have been chosen as to
· practicability e.g. accessibility, public
ownership (National Park), no conflict
· with the protection of biotopes and spe-
cies, high level of information, nearby
· suitable institutions for research
The list of a present fourteen areas (see Fig. 3)
comprises the major ecosystems and habitat
types that occur within the Federal Republic of
Germany including
· limnic and marine ecosystems,
· urban industrial ecosystems,
· forest and agricultural ecosystems and
· semi-natural ecosystems.
Continuous sampling is now performed in the
River Elbe
River Elbe
River Elbe
River Elbe
River Elbe
Greifswald
River Rhine
River Rhine
River Rhine
River Rhine
Bonn
Berlin
Ulm
Urban Industrial Area
of Saarland
Tertiary Hill Area
of Bavaria
Berchtesgaden NP
Bavarian
Forest NP
Pfalz Forest
Solling
Mьnster
Urban Industrial
Area of Halle/Leipzig
NP Hochharz
Bornhцved
Lake Area
National Park of the
Vorpommern Bodden
Area
German Wadden Sea
National Parks
Type of Ecosystem
Near Nature
Ecosystems
Managed Forest
Ecosystems
Agricultural
Ecosystems
Urban Industrial
Ecosystems
Freshwater
Ecosystems
Marine and
Coastal
Ecosystems
Human samples
- Spruce
- Beech
- Earthworms
- Roe deer
- Soils
- Spruce
- Beech
- Earthworms
- Roe deer
- Soils
- Spruce
- Beech
- Earthworm
- Roe deer
- Feral pigeon
- Soil
- Zebra mussel
- Bream
- Sediments
- Spruce/Pine
- Beech/Poplarl
- Earthworm
- Roe deer
- Feral pigeon
- Soil
- Zebra mussel
- Bream
- Sediments
- Zebra mussel
- Bream
- Sediments
- Bladder wrack
- Lugworm
- Common mussel
- Viviperous blenny
- Herring gull
Specimens
0 200 km
Fig. 3 . Sam pling areas and specim ens types (after K lein et. al) [13]
form a national network of Ecological Assess-
ment Parks coordinating Environmental Speci-
men Banking with long-term ecological research
and environmental monitoring [13-15]. An over-
all concept has been developed by a committee
of experts under the auspices of the BMU, tak-
ing into consideration different types of ecosys-
tems with corresponding representative sam-
pling areas according to the following criteria:
· stability of utilization,
· assured long-term-use,
· sufficient minimal size,
· availability of suitable samples
following areas:
— The national parks of mud flats in
Schleswig-Holstein and Lower Saxony
(North Sea) and the Baltic Sea as ma-
rine ecosystems.
— River Elbe and River Rhine as limnic ec-
osystems.
— Saarland and the Halle/Leipzig/
Bitterfeld area as urban-industrialized
regions.
The selection and assignment of repre-
sentative specimen of the terrestrial, limnic
and marine ecosystems for the ESB was un-
dertaken by a committee of experts in consid-
eration of the above mentioned indicator func-
ÀÊÒÓÀËÜÍÛÅ ÏÐÎÁËÅÌÛ ÒÐÀÍÑÏÎÐÒÍÎÉ ÌÅÄÈÖÈÍÛ � ¹ 1, 2005 ã.
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ACTUAL PROBLEMS OF TRANSPORT MEDICINE � # 1, 2005
Fig. 4: Location of the sampling stations of
breams (Abramis brama) from the River
Elbe and sites of chemical plants
tions so that a broad spectrum of different
types of matrices (all trophic level) and media
(air, sediment, soil) with environmentally rele-
vant concentrations of xenobiotics is available
(see Fig 3) [13,15].
Furthermore, the following requirements
must be fulfilled for using a matrix as
bioindicator:
· The chemicals must be accumulated
comparable to levels occurring in the
environment.
· Contamination trends in the environment
must correspond to those in the matrix.
· The matrix should have a widespread dis-
tribution and must be available in time
and place to a sufficient extent
· The organism should be sedentary and
easy to identify.
· The species should accumulate the pol-
lutants without being killed or rendered
incapable of reproduction.
Standardized sampling guidelines in the
sense of standard operating procedures (SOP)
are the basis for the comparability, reliability,
and repeatability of the banked samples.
They contain detailed instructions for the
· selection of sampling sites and speci-
mens;
· sampling;
· providing cover for repeatability of sam-
pling;
· area and sample characterization;
· sample treatment and long-term stor-
age;
· documentation of sampling and storage
conditions;
· chemical analysis;
· data processing and evaluation and
· quality assurance.
Nevertheless, sampling of biological and
other environmental specimens is always influ-
enced by factors which may modify the expo-
sure as well as the accumulation behaviour of
the specimen types in relation to xenobiotics,
e.g. by climatic factors, weather conditions
and changes in the population sampled or in
the structure of the whole ecosystem [16].
Ecological and biometrical sample char-
acterization provides basic information about
changes in the quality of the sampled material
and its comparability with previous and follow-
ing samples from the same area or the same
specimen type sampled in other areas. On the
other hand biological sample characterisation
can also given information about ecological
and ecotoxicological effects to the population
sampled.
In environmental specimen banking sam-
ples of different specimen types and ecosystems
are frequently sampled, characterized, proc-
essed and stored with considerable effort in or-
der to maintain the precautions necessary for
deferred analysis on initially unknown substanc-
es or parameters. Quality assurance is therefore
an absolute demand and an innovative challenge
in ESB. Errors made during the sampling in the
field, transportation and sample pre-treatment
can seldom be recognized and never corrected
afterwards during the following analytical meas-
urements. Thus, the quality assurance system for
ESB includes the whole process from planning,
sampling, ecological and biometrical character-
isation, packing, transportation, storage, ho-
mogenisation and sub sampling up to the ana-
lytical procedures and the evaluation of the re-
sults [17,18,20].
An average 2,5 kg of material per speci-
men per sampling site was collected producing
nearly 250 standardized sub samples of approx-
imately 10 g.
Chlorinated hydrocarbons as pollutants inChlorinated hydrocarbons as pollutants inChlorinated hydrocarbons as pollutants inChlorinated hydrocarbons as pollutants inChlorinated hydrocarbons as pollutants in
ESB samplesESB samplesESB samplesESB samplesESB samples
3535353535
ACTUAL PROBLEMS OF TRANSPORT MEDICINE � # 1, 2005
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For the determination of
chlorinated hydrocarbons GC/
ECD or HRGC/HRMS were used.
More details about the applied
method are given in (26-29).
Numerous chlorinated in-
secticides and industrial chlorinat-
ed hydrocarbons (e.g.
polychlorinated biphenyls (PCBs)
or polychlorinated dibenzo-p-
dioxins and dibenzofurans (PCDD/
F) are extremely resistant to deg-
radation in the environment.
Residues of these xenobiotics
have been identified throughout
the world although most of them
have been banned since the 70s.
Because of their toxicological
properties and accumulation ef-
fects, long-term studies on their
residues levels are essential to un-
derstand the environmental con-
tamination in the past and to pre-
dict future trends.
The former German Demo-
cratic (GDR) was one of the major producers of
elemental chlorine in East Europe. Due to eco-
nomical reasons the production and application
of low volatile CHC played a more important role
in the chemical pest control in agriculture and
forestry of East Germany than in the Western
countries [35]. Under the pressure of worldwide
application restrictions the production has
ceased since the early 70s (DDT) or late 80s (lin-
dane, toxaphene) respectively. Thus, the differ-
ent economic and technical development of the
two German states led to partly different patterns
of environmental pollution. Reliable data of the
pollution situation, especially of the industrialized
areas, in the former GDR were not available on
account of the strict political restriction regime.
In order to detect the efficiency of legislative reg-
ulations for the environmental redevelopment,
which were initiated directly after the
reunification, and for the assessment of the en-
vironmental pollution a special sampling cam-
paign was performed in representative areas of
the former GDR in 1990/91 [36]. These samples
can be regarded as a basis for monitoring the
development of spatial and temporal trends in
Eastern Germany (27,28).
Breams (Abramis brama) are freshwater
fish with a small migration radius. They are an
ideal organism for monitoring freshwater and
sediment contamination because their feeding
habits are characterized by permanent direct
contact with the sediments
On aime of the sampling campaign was the
Abbreviations of the sampling sites
River Elbe Lake area of Mecklenburg
EP Prossen MW Wanzkaer See
EL Löschwitz MZ Zwirn-See
EV Vockerode MS Schweingarten-See
EA Aken ML Lutowsee
EB Barby MZI Zierker See
EH Heinrichsberg MH Haussee
EC Cumosen MR Rödliner See
MT Großer See von Teterow
MST Stechlin-See
Fig. 5: Comparison of the DDE and DDD mean concentrations in bream muscle
homogenates (Abramis brama) from the River Elbe and the lakes of Mecklenburg in
1990/91 (WW: wet weight)
Fig. 6: Comparison of the HCH mean concentrations in bream muscle homogenates
(Abramis brama) from the River Elbe and the lakes of Mecklenburg in 1990/91 (WW:
wet weight) (Abbr.: cf. Fig. 7)
Fig. 7: Comparison of the mean concentrations of selected CHC in bream muscle
homogenates (Abramis brama) from the River Elbe and the lakes of Mecklenburg in
1990/91 (WW: wet weight) (Abbr.: cf. Fig. 7)
ÀÊÒÓÀËÜÍÛÅ ÏÐÎÁËÅÌÛ ÒÐÀÍÑÏÎÐÒÍÎÉ ÌÅÄÈÖÈÍÛ � ¹ 1, 2005 ã.
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ACTUAL PROBLEMS OF TRANSPORT MEDICINE � # 1, 2005
characterization of the CHC burden along the
German part of the River Elbe and to monitor the
expected recovery of the river. Rot the past 20
years the River Elbe has been one of the most
polluted rivers in Europe (37). Due to political
changes in the Eastern part of Europe and es-
pecially in East Germany, various industries, who
discharged their waste water into the river Elbe,
were either closed or reduced their production
activities. In order to characterize local variations
of the CHC burden seven stations were selected
with regard to various types and magnitudes of
industrial pollution as shown in Fig. 4 (30).
In addition, bream samples were collect-
ed in 9 lakes of Mecklenburg which were mainly
influenced by agriculture, livestock fattening and
forest industry. Figures 8-10 present a compar-
ison of the main contaminants in bream muscle
homogenates from the River Elbe and the lake
area of Mecklenburg.
As shown in Figures 5- 7 fish caught at the
upper Elbe (Prossen and Loschwitz) exhibited
Fig. 8: Comparison of the mean concentrations of selected CHC in bream liver ho-
mogenates (Abramis brama) from different German rivers in 1995
the highest concentrations of DDE, OCS and
PCB. This observation is probably a result of the
considerable pollution of the River Elbe from in-
dustrialized areas (e.g. Pardubice, Neratovice,
Usti) of the former CSFR [30].
A significant decrease of these contami-
nants was found between stations Löschwitz and
Vockerode. Between Vockerode and
Heinrichsberg the levels remained nearly con-
stant. The analytical data obtained for HCB con-
centrations in breams indicate a declining trend
downstream of Barby. The high HCB contami-
nation is considered to be an effect of the dis-
charges from chemical plants in the former CSFR
as well as of the influxes from the River Mulde
(upstream from Aken) and River Saale (upstream
from Barby). The increase of the HCH content in
fish from these stations is also linked to the in-
fluence of both tributaries of the River Elbe (Fig-
ure 7).
The major polluters of the River Mulde
were the chemical plants in the Bitterfeld/Wolfen
area, although the production of chlorinated
pesticides has stopped several years ago [35].
The CHC burden in the River Saale originated
from Buna, Leuna and the pulp mill industry. Lin-
dane and DDT containing wood preserving
agents (e.g.Hylotox IP/Hylotox 59) were pro-
duced in Leuna. The high contamination levels
of HCH in bream at the station Heinrichsberg
might be explained by the influence of discharg-
es from the pesticides plant Fahlberg-List, locat-
ed in Magdeburg. The results are consistent with
waste water analysis of the plant and river sedi-
ment in 1990, which showed that both matrices
were extremely contaminated by HCH [37]. Al-
though the production of lindane has ceased
since 1981, the pesticides were highly accumu-
lated in the river sediments.
Another interesting aspect can be seen
3737373737
ACTUAL PROBLEMS OF TRANSPORT MEDICINE # 1, 2005
АКТУАЛЬНЫЕ ПРОБЛЕМЫ ТРАНСПОРТНОЙ МЕДИЦИНЫ № 1, 2005 г.
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
Saale
Mulde
Weil
Iffezheim
Koblenz
Bimmen
Gьdingen
Rehlingen
Elbe Saale/
Mulde
Rhine Saar
Prossen
Zehren
Barby
Cumlosen
Blankenese
mg/kg fat
-HCH
-HCH
-HCH
Fig. 9: Comparison of the mean HCH concentrations in bream liver homogenates
(Abramis brama) from different German rivers in 1995
els were comparable to those found in fish from
the River Elbe on account of the intensive agri�
culture in this region. Slightly higher PCB con�
centrations were found in breams from the Lake
Stechlin�See and the Lake Zierker See. The Lake
Stechlin�See is situated in a nature reserve which
is influenced by the local recreation traffic from
Berlin as well as by a former nuclear power sta�
tion “Rheinsberg”. The elevated PCB levels in the
Lake Zieker See could be attributed to the long�
term influx of untreated waste water from the city
Neustrelitz.
Figures 8 and 9 illustrate results on the
major CHC contaminates in bream livers from 5
different German rivers, obtained within the ESB
routine program in 1995 [42]. Since 1994 bream
samples have been periodically taken in the Riv�
er Saar and since 1995 also in the
River Mulde, River Saale and River
Rhine (Fig. 8).
Samples were also obtained
from stations along the River Elbe
(Prossen, Zehren, Barby,
Cumlosen, Blankenese), four sta�
tion along the River Rhine (Weil am
Rhein, Iffezheim, Koblenz and
Bimmen), one station situated up�
stream of the River Saar
(Gьdingen) and Rehlingen located
downstream under the industrial�
ized area of Saarbrьcken. The sam�
ples from the River Mulde were col�
lected near Dessau and fish of the
River Saale between Halle and
Wettin.
It is apparent that the sta�
tions on the upper Elbe still exhib�
ited the highest concentrations of
HCB, DDE and PCB. High values
for HCB and DDE were also found
in samples from the River Mulde.
This observation is mainly a result
of the former industrial emissions
of the chlorine industry and a
leaching dumpsite at Bitterfeld.
Wilken reported, that there had
been further pesticide emitters in
the area upstream of the River
Mulde in Saxony, especially with
respect to DDT. In West Germany
the HCB and DDE concentrations
were much lower in comparison
with the levels in East Germany.
Breams caught near the Rhine
station Iffezheim contained HCB
at higher levels because of a
former chemical plant located
the dominant DDT metabolite in fish from the Riv�
er Elbe [38]. It is a degradation product of 4,4'�
DDT by anaerobic conversion as well as a
byproduct of the DDT synthesis. In sediment of
the River Elbe and the River Mulde DDD levels
were generally higher than those of DDE [39].
Interestingly, the recorded DDE values from the
upstream stations (Prossen and Lцschwitz) were
twice as high as those of DDD. From Vockerode
to Cumlosen DDD/DDE, ratios ranged between
1.3 � 1.7. This results seems to imply that the
DDD burden of sediments is well reflected by
breams.
With the exception of the DDT metabolites
the CHC burden in breams from Mecklenburg
was considerably lower in comparison with fish
from the River Elbe as could be expected due to
the absence of chemical industries. The DDE lev�
Limnic ecosytem:
Elbe (Lцschwitz, 1991)
33,3 % PCB
(333,2 ng/g WW)20,7 % HCB
(208 ng/g WW)
13 % OCS
(130 ng/g WW)
2,1 % HCH
(21,5 ng/g WW)
1,9 % Rest
(19,0 ng/g WW)
28,9 % DDT
(290,0 ng/g WW)
Urban industrialized ecosystem:
Saarland (Rehlingen, 1995)
80,2 % PCB
(723,6 ng/g FG)
18,5 % DDT
(167 ng/g WW)
0,9 % HCH
(8,4 ng/g WW)
0,4 % Rest
(3,5 ng/g WW)
Agricultural ecosystem: Lake area
of Mecklenburg (Zierker See, 1991)
17,0 % PCB
(29,8 ng/g WW)
1,1 % HCH
(1,9 ng/g WW)
2,1 % Rest
(3,8 ng/g WW)
79,7 % DDT
(139,6 ng/g WW)
Fig. 10: Comparison of the proportion of different CHC pollutant classes in bream liv-
ers (Abramis brama) from East and West Germany
ÀÊÒÓÀËÜÍÛÅ ÏÐÎÁËÅÌÛ ÒÐÀÍÑÏÎÐÒÍÎÉ ÌÅÄÈÖÈÍÛ � ¹ 1, 2005 ã.
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ACTUAL PROBLEMS OF TRANSPORT MEDICINE � # 1, 2005
because of a former chemical plant located
upstream, which produced pentachlorophenol
[42]. The highest DDT amount in fish from
West Germany were found in the River Saar at
Rehlingen, in contrast to its small HCB levels.
Elevated levels of PCB were detected in
breams from the lower Rhine at Bimmen and
from the lower Saar at Rehlingen. The increas-
ing concentrations along the River Rhine are
partly a result of the influx of the River Mosel (up-
stream of Koblenz), containing high amounts of
PCB [43]. The river Saar is strongly influenced
by emissions from the mining industry situated
in the Saar region.
The data shown in Figure 9 clearly indicate
the HCH pollution of the River Mulde. Wilken et.
al. [36] reported that sediments and soils from
River system Mulde are still highly contaminat-
ed by pesticides and PCDD/F although the in-
dustrial emission has stopped. These sediment-
bound pollutants can be remobilised and may
lead to a secondary contamination of the River
Elbe by pollutant transport. Therefore, it remains
to be seen how long the recovery of the River
Elbe will take.
Generally HCH patterns of breams from
East Germany differ from those found in fish from
West-Germany. The g-isomer predominates in
the Western samples, whereas higher levels of
the a and b-isomers are detected in the fish from
the Eastern part of Germany.
The comparison of the CHC patterns in
bream livers exhibits significant distinctions be-
tween the different ecosystems (Fig. 10). DDT
metabolites and PCB contributed to one third
each to the total CHC burden of bream livers from
the limnic ecosystem of the River Elbe. PCB were
the major organochlorine contaminants (70%) in
breams of a typical industrialized area (Saarland)
in West Gemany in contrast to agricultural areas
of East Germany, where DDT metabolites were
the dominant pollutants (80%).
This surprising result that DDT metabolites
show high amounts in environmental samples of
Eastern Germany can also be demonstrated in
pigeon eggs.
The collected specimens have been suc-
cessfully utilized for the characterization of the
environmental pollution by CHC n the former
GDR.
The dominant position of the DDT group
in nearly all Eastern samples clearly reflects the
central role of DDT in the pest control of the
former GDR. For this pollutants class significant
spatial differences between East and West Ger-
many were detected in terrestrial, atmospheric
and limnic environments. The HCH concentra-
tions in animal samples were considerably low-
er. With the expedition of local hot spots of pol-
lution the lindane contamination of both German
parts was in the same range, whereas the con-
centration of a- and b-HCH isomers, byproducts
of the lindane production, appeared to be high-
er in samples from East Germany, especially in
the vicinity of former pesticide plants. Relatively
low PCB levels were observed in specimens from
the East compared to West Germany due to low
usage of PCB in the former GDR.
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ÀÊÒÓÀËÜÍÛÅ ÏÐÎÁËÅÌÛ ÒÐÀÍÑÏÎÐÒÍÎÉ ÌÅÄÈÖÈÍÛ � ¹ 1, 2005 ã.
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ACTUAL PROBLEMS OF TRANSPORT MEDICINE � # 1, 2005
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SummarySummarySummarySummarySummary
Thousands of chemicals are traded on the
market, but only in a few cases is full information
available on their distribution and their effects on
man and the environment. In addition to real time
monitoring of chemicals, it is, thus, necessary
to establish an environmental specimen bank
(ESB) for the retrospective monitoring of chem-
icals in the future. The base of ESB are repre-
sentative bioindicators of systematically collect-
ed biological and environmental samples. As a
result of extremely low storage temperature (T =
< - 150°C) it is guaranteed that the samples are
not subject to chemical changes during the long-
term storage.
Furthermore we need in addition an effect
monitoring, using in vitro testing like for exam-
ple P 450 1A1 enzyme expression.
ÕËÎÐÑÎÄÅÐÆÀÙÈÅ ÓÃËÅÂÎÄÎÐÎÄÛ Â
ÎÊÐÓÆÀÞÙÅÉ ÑÐÅÄÅ – ÌÎÍÈÒÎÐÈÍÃ È
ÅÃÎ ÝÔÔÅÊÒÈÂÍÎÑÒÜ
À.À.Ô. ÊåòòðóïÀ.À.Ô. ÊåòòðóïÀ.À.Ô. ÊåòòðóïÀ.À.Ô. ÊåòòðóïÀ.À.Ô. Êåòòðóï
 íàñòîÿùåå âðåìÿ íà ðûíêå
ïðèñóòñòâóåò îãðîìíîå êîëè÷åñòâî
õèìè÷åñêèõ âåùåñòâ, íî òîëüêî â íåêîòîðûõ
ñëó÷àÿõ äîñòóïíà ïîëíàÿ èíôîðìàöèÿ îá èõ
ðàñïðîñòðàíåííîñòè è âîçäåéñòâèÿõ,
îêàçûâàåìûõ èìè íà ÷åëîâåêà.  äîïîëíåíèå
ê ìîíèòîðèíãó õèìè÷åñêèõ âåùåñòâ,
ïðîâîäèìîìó â ðåàëüíîì âðåìåíè,
íåîáõîäèìî ñîçäàòü áàíê îáðàçöîâ
õèìè÷åñêèõ âåùåñòâ, ïðèñóòñòâóþùèõ â
îêðóæàþùåé ñðåäå äëÿ ïðîâåäåíèÿ â
áóäóùåì ðåòðîñïåêòèâíîãî ìîíèòîðèíãà.
Îñíîâîé òàêîãî áàíêà äàííûõ ìîãóò ñòàòü
ðåïðåçåíòàòèâíûå áèîèíäèêàòîðû
ñèñòåìàòè÷åñêè ñîáèðàåìûõ áèîëîãè÷åñêèõ
îáðàçöîâ è îáðàçöîâ, ïðèñóòñòâóþùèõ â
îêðóæàþùåé ñðåäå. Ïîñêîëüêó òåìïåðàòóðà
õðàíåíèÿ îáðàçöîâ â áàíêå êðàéíå íèçêàÿ (
Ò< - 150°C) ñóùåñòâóåò ãàðàíòèÿ òîãî, ÷òî
îáðàçöû íå áóäóò ïîäâåðãàòüñÿ õèìè÷åñêèì
èçìåíåíèÿì âî âðåìÿ äëèòåëüíîãî õðàíåíèÿ.
Íî ïîìèìî ïðî÷åãî, íàì íåîáõîäèì
ýôôåêòèâíûé ìîíèòîðèíã, ãäå áû
èñïîëüçîâàëèñü in vitro òåñò – ñèñòåìû,
íàïðèìåð, äëÿ îïðåäåëåíèÿ ýêñïðåññèè
ýíçèìà 450 1À1.
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