Aquatic Pollutants. Transformation and Biological Effects

505 Pages·1978·11.82 MB·English

by  O. Hutzinger

AQUATIC POLLUTANTS:
Transformation and Biological Effects
Proceedings of the Second International Symposium on
Aquatic Pollutants
Noordwijkerhout (Amsterdam), The Netherlands
September 26-28, 1977
Edited by
O. HUTZINGER
University of Amsterdam
and
I.H. VAN LELYVELD and B.C.J. ZOETEMAN
National Institute for Water Supply, Leidschendam
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First edition 1978
British Library Cataloguing in Publication Data
International Symposium on Aquatic
Pollutants, 2nd, Amsterdam, 1977
Aquatic pollutants.
1. Water - Pollution - Congresses
I. Title II. Hutzinger, Otto III. Lelyveld,
IH IV.Zoeteman, BCJ
628.Γ68 TD420 77-30670
ISBN 0-08-022059-2
In order to make this volume available as economically and as rapidly as possible the
authors' typescripts have been reproduced in their original forms. This method
unfortunately has its typographical limitations but it is hoped that they in no way
distract the reader.
Printed in Great Britain by William Clowes & Sons Limited
London, Beccles and Colchester
Preface
Water, like air, is a precious resource which is taken for granted by most people
except in areas where this commodity is scarce, as for instance in arid and semi-
arid regions.
With increasing population densities in many areas of the world less and less ground-
water is becoming available for water supplies and more and more surface water has
to be processed for this purpose. This means that municipal water works often have
to deal with heavily contaminated raw water since, as with the River Rhine for
instance, someone's waste is somebody elsefs resource downstream.
Water contaminated with sewage can, in principle, be treated even when the BOD val-
ues are very high. Certain components in municipal and in industrial waste in parti-
culer are difficult to remove by most conventional treatment methods. These chemicals,
often referred to as micropollutants, are usually anthropogenic (man-made) compounds
which are resistant to biodegradation, often bioaccumulate and sometimes possess
toxic or other undesirable properties.
The emphasis of the 2nd International Symposium on Aquatic Pollutants was entirely
on the compounds described above. The three days of the symposium were roughly
divided into
(1) Sources of pollutants, analytical methods, data banks and the natural back-
ground of organic compounds;
(2) transport, biodegradation, photodegradation and related transformations; and
(3) biological and toxicological effects.
The organizers of this symposium have attempted to attract internationally known
specialists for the respective areas to be discussed. We express our gratitude to
the scientists who have given their time and who have contributed to the success of
this Symposium as speakers and authors.
We hope that this volume will be useful as a review of the present knowledge but
also to stimulate further thought and research.
The organizers of the Symposium thank the following organizations for financial
assistance: The European Economic Community, the Dutch National Institute for
Water Supply and the U.S. National Cancer Institute.
ix
Welcome Speech
P. SANTEMA
Director National Institute for Water Supply, Voorburg,
The Netherlands
Ladies and Gentlemen,
It is a great pleasure to me to welcome all of you, and particularly those coming
from abroad, at the 2nd International Symposium on Aquatic Pollutants which is
organized by the National Institute for Water Supply and the University of Amster-
dam.
This 2nd Symposium is a follow-up of a symposium held in April 1974 in Athens,
Georgia, U.S.A. on the same topic. North-America en Western Europe, although
geographically divided by immense quantities of water, are becoming more and more
close neighbours, which is proven once again by this occasion. It is the purpose
of this symposium to further strengthen the international collaboration of all
those people in science, industry or governmental agencies devoting their activities
to control the pollution of the aquatic environment by hazardous chemical compounds.
The Organizing Committee has tried to compose a program covering all environ-
mental aspects of chemicals introduced into water. The program includes papers on
the origin of chemical pollution, transport and transformation of aquatic pollutants
and last but not least their effects on aquatic organisms and man. The program has
been focussed on the recent developments in the countries of the European Communi-
ties as well as other countries in Western Europe. Furthermore main contributions
come from other parts of the world, including the U.S.A., Canada, Israel and Japan.
There are 3 plenary lectures, scheduled at the start of each of the symposium
days. These plenary lectures are meant to present a general framework for the
detailed scientific papers which will be discussed the coming days.
The first plenary lecture covers the problems in setting sanitation strategies
based on toxicological and environmental concepts. After this lecture by Dr. van
Esch, the lecture on the second day deals with industry's point of view on pollu-
tion abatement, presented by Dr. van Lookeren Campagne, followed on the last day
by a survey of european legislation on aquatic contamination by Mr. de Geer.
Finally the most controversial items, resulting from the 3 symposium days, can be
evaluated in a panel discussion chaired by Mr. van der Veen on Wednesday afternoon.
I am certain that the presence of so many eminent speakers as well as the
large interest of about 200 participants will make this symposium a successful one.
I am very happy that you all came to Noordwijkerhout even though many of you had to
travel over large distances for this purpose. I trust that your participation in
this symposium will be sufficiently pleasant and instructive to let you forget for
a moment your desire to visit Amsterdam, the windmills and other attractive spots
of this country.
Ladies and gentlemen,
as it is time to really open this symposium I am very pleased to introduce to you
Mr. Reij, Director General for Environmental Protection of the Ministry of Public
Health and Environmental Protection of The Netherlands, who will now present his
opening address.
XI
Opening Address
W. C. REIJ
Director General for Environmental Protection, Ministry of Health and
Environmental Protection, Leidschendam, The Netherlands
Like air, water is transported over large distances. It easily passes
national borders and political barriers and in this way also chemical contaminants
are carried with the water from one country to another and from man to the organisms
living in the fresh and salt water environment. This free circulation of water and
its contaminants makes it essential to consider water pollution problems in an
international perspective. I am therefore happy that this 2nd International Sympo-
sium on Aquatic Pollutants could be organized and particularly that it is held in
this country, which, although small, is confronted with severe problems of
pollution of the aquatic environment.
As you may know The Netherlands is a country with a good deal of surface
water. About 7% of the national surface area consists of water. The North Sea forms
the national border to the North and to the West. At the Eastern border the Rhine
river enters the country and the smaller rivers Meuse and Scheldt cross the Southern
border. In the centre of the country the IJssellake is situated.
However this apparent abundance of water in The Netherlands is misleading. An
example in this respect is that Lake Geneva in Switzerland alone contains 18 times
as much water as all the Dutch lakes and water courses together. Furthermore water
of good quality has become scarce. During the past century the main fresh water
source, the River Rhine, has changed from a river yearly supplying the population
with many thousands of tons of salmon into a river, now often characterized as the
open sewer of Western Europe. Around 1960 the last salmon was reported in this
river. Already in 1940 fish from the river was unfit for consumption due to the
bad taste.
Nowadays the River Rhine carries the waste water from a population of about
40 million inhabitants of Western Europe as well as the waste water of several of
world's largest centres of chemical industry in Basel, Frankfurt, the Ruhr area
and Rotterdam.
Therefore it is not surprising that at present the water can only be used as a
source for drinking water supply at the expense of high treatment costs, that it
is unfit for recreational purposes such as swimming and that it poses a potential
threat to the aquatic ecosystems in lakes, estuaries and the North Sea.
Besides surface water one might suppose that the rather high frequency of
rainy days in this country would result in the availability of large quantities
of groundwater. However due to the high population density, the average volume of
rain water per head of the population is so low that in this respect The Netherlands
is one of the driest areas of the world, after Hong Kong and Singapore. The
Netherlands is supplied on the average with only 5 m3 of rain per head per day,
in comparison to countries like Israel at 7.5, the United Kingdom at 12, Japan at
Xlll
xiv W. C. Reij
18 and the U.S.A. at nearly 100 m per head per day. This means that the available
groundwater in this country is a very precious water source of which the quality
has to be carefully protected. For this purpose a special law relating to the pro-
tection of the soil against pollution is presently being prepared by the Ministry
of Health and Environmental Protection. In the framework of this law a number of
preventive regulations have to be specified aiming at, amongst others, protection
of groundwater catchment areas for potable water supply. This can be realized by
specifying protection zones in which certain potential contaminating activities
are not allowed or are bound to strict limitations. Besides preventive actions it
has been recently shown that particular attention has to be paid to detection of
already existing cases of groundwater pollution by certain hazardous chlorinated
chemicals such as trichloroethene. The existence of a relatively widespread con-
tamination of our groundwater resources with persistent chemicals once more illus-
trates the need to prevent such a pollution, as remedial actions are almost impos-
sible or only effective after long periods, contrary to pollution abatement in the
case of river water. A further potential source of ground water pollution is the
contribution of contaminated rainwater, an area which is now given closer consi-
deration than in the past.
Due to the relative scarcity of groundwater, the rivers Rhine and Meuse
are of great significance to the aquatic environment and the public water supply
of The Netherlands. The high degree of pollution of these industrialized river
basins is however in conflict with the different usages of these surface waters,
resulting in an urgent need to realize on short term effective remedial activities.
As such activities should necessarily have an international basis it is of great
significance that recently international agreement has been reached on this problem.
After an agreement in principle on a directive of the Council of the European
Communities in 1975, relating to the prevention of the discharge of chemical sub-
stances into the aquatic environment, a convention against the chemical pollution
of the Rhine was signed in December 1976 by the Ministers of the countries concerned.
These agreements provide an essential framework for the realization of the sanitation
priorities relating to chemicals of the so called black and grey lists.
In order to arrive at a detailed sanitation strategy much additional infor-
mation is needed. This information has to be generated by scientists and should
include detailed data on origin, transport, transformation and biological effects
of chemical pollutants. Here lies the direct connection between the themes of this
symposium and the information needed for operational decisions. There exists a
close relationship between the availability of scientific data and the realization
of sanitation measures. Lack of sufficient information would inevitably result in
diminishing progress in improving the quality of the aquatic environment. An
example in this respect is the drastic reduction of discharges into the river
Rhine of endosulphan and mercury.
I am convinced that new data on the behaviour and biological effects of chemicals
will significantly contribute to the establishment of a cleaner aquatic environ-
ment in the coming years. This symposium offers unique opportunities to evaluate
the impact of contaminating chemicals on aquatic organisms and on the health of
man, exposed to those chemicals during swimming or by means of consumption of
drinking water derived from the contaminated sources. In my opinion quantification
of the persistency of chemicals in the aquatic environment and their biological
effects on aquatic organisms and man should be the main purposes of research efforts
in this area.
Mr. Chairman, ladies and gentlemen,
I would like to open this meeting with the hope that the international gathering
here will contribute to the advancement of effective procedures needed for the
protection and sanitation of the aquatic environment of Western Europe and other
parts of the world. I wish you a successful meeting.
Aquatic Pollutants and their Potential
Biological Effects
G.J. VAN ESCH
National Institute for Public Health, Bilthoven, The Netherlands
When looking at the map, as a first impression, it seems that the quantity
of water on earth is inexhaustible, but only λ% is available as sweet water. From
this 1%, 99% is in the bottom and about \% as surface water. The consumption of
water by man is increasing and we are faced with an ever-increasing demand for
potable water. It will be clear, as was stated at the United Nations Conference
on Water Resources held in 1976, that "clean" water is a major need for the pros-
perity of the world population now and still more in the near future.
Improvement of our public health, combating of diseases and the high mortali-
ty, cannot be realized without the availability of sufficient drinking water and
a well-balanced diet and clean air. Clean water is up till now for millions of
people living in certain areas of the world self-evident but more than 1500 mil-
lions of people do not have the disposal over sufficient potable water. But even
in the former areas there will perhaps come a time that there will be a water
shortage, quantitively and/or qualitatively.
This is the reason that all over the world research is going on to find ways
to purify surface waters and reclaim potable water from municipal waste waters
and from effluents.
A big problem in the purification and reclamation of potable water from pol-
luted water is the presence of thousands and thousands mainly man-made chemicals
that are directly or indirectly released into the environment. Although the con-
centrations of these pollutants are still rather low, many of these compounds are
toxic to human and/or animal life, some of them are mutagenic and/or carcinogenic
or have serious ecological implications. It is therefore necessary to evaluate the
potential risks to man and the environment of these chemicals.
IMPACT OF AQUATIC POLLUTION ON THE HEALTH OF MM
In discussing the influence of aquatic pollutants on the health of man, there
are three main ways of exposure: dermal contact during recreation (swimming); oral
intake of drinking water and the consumption of fish and other waterorganisms.
During bathing and swimming the main contact of man with surface water will
be dermal contact. This aspect did up till now not get much attention. In general
the concentrations of the pollutants will be low so that it is not likely that
these levels will induce irritation of the skin and/or mucous membranes. There are
1
2 G. J. van Esch
a few compounds, such as the well-known dioxins and possibly benzofurans and a few
other compounds, that may perhaps induce reactions in certain persons. This aspect
should not be ignored completely and attention should be given to the occurrence
of these cases.
In principle it can be stated that drinking water has to be as pure as possi-
ble. To achieve this a wide range of national and international drinking water
quality standards are or will be established. Up till now these standards concern
mainly inorganic chemicals and a number of chemical and physical criteria. Quality
standards for organic chemicals are mostly still absent.
For the establishment of standards for drinking water, fish and waterorganisms
it is necessary to have the disposal of data on the occurrence of these contami-
nants in food, drinking water and air. Besides this information, data on shortterm
and longterm toxicity, reproduction, teratogenicity, mutagenicity and carcinogeni-
city, data on biotransformation (pharmacokinetic studies) and bioaccumulation are
necessary. Furthermore it is of great importance to have data on the total body
burden and about the presence of the contaminants in human organs and tissues.
For a small number of compounds these data are available but for most of the
pollutants occurring in surface water, drinking water and food this is not the
case. Because we are dealing with a great number of compounds, to begin with, it
is necessary to select those compounds that have the greatest impact on the health
of man and his environment. The compounds can be selected on the basis of toxicity,
carcinogenicity and/or mutagenicity and/or on the basis of persistence and bioac-
cumulation. It is clear that carcinogens (and possibly mutagens) and bioaccumula-
ting compounds should have the highest priority. How do we know which compounds
bioaccumulate and enter in a foodchain? In our Institute bioaccumulating compounds
got attention in the last years. The following study was carried out:
Clean cultivated crustaceae (Daphnia magna) were placed in Rhine River water (pho-
tograph 1). After a few hours the organisms are collected and a chlorogram is made
in comparison with a comparable control group with a mass-spectrometer. At the
same time riverwater, fish (eel) and a bird (grebe) was collected and analyzed at
the same way. So an impression of bioaccumulation was got in Ma simple foodchain"
= riverwater - daphnia - fish - bird. In comparison also a chlorogram was made
from human fat (Figs. 1, 2, 3, h and 5).
The grebe and man are both standing near the end of a foodchain, and surprisingly
the chlorograms look alike. Besides the well-known chlorinated pesticides as DDT
and others, also unknown compounds are present, that have to be identified to find
the ultimate source and consequently to take measures of these compounds by legal
actions.
Besides the bioaccumulating compounds a great number of compounds is present
in surface water, groundwater, reclaimed water and even in drinking water. The
levels of these compounds are mostly in the range of a few μg/l and it is still
an unanswered question whether drinking water containing a number of these com-
pounds have a serious impact on the health of man. To answer this question one
could study each individual compound separately on toxicity and calculate an ac-
ceptable daily intake as is done for foodadditives and pesticides. But because
mixtures of compounds are present the approach is also followed to test extracts
of these waters on mutagenicity and in longterm studies to see whether these ex-
tracts are toxic, mutagenic and/or carcinogenic.
Another approach is to carry out epidemiological studies with different po-
pulation groups that consume different type of waters and estimate whether there
is a relationship between mortality, incidence of tumours, heart- and vessel di-
seases or other diseases.
All these studies will give information but at the end it is necessary to
know which compounds have negativ effects on the health of man, so that steps
can be taken to prevent exposure in future.
As already was stated the low levels of these pollutants in drinking water
seem to be not of great importance because even for the most toxic pesticides the
Aquatic Pollutants 3
quantities that can be consumed by man, and that are considered to give no harm,
are in the order of 100-500 ug/day with his diet. When we consider chloroform,found
regularly in drinking water in levels of B few ug up to 300 μg/l, the latter con-
centration is still at least a factor of 15 lower than the acceptable daily intake
by man per day, calculated on the basis of longterm toxicity studies applying a
safety factor of 100. So the intake via water is at least 1500 times lower than
the doses that did not give an toxic effect in animals. However, in the case of
chloroform the total body burden has to be taken into account, for instance the
intake via toothpaste, in which up to h% chloroform is used, is important in con-
sidering the impact of chloroform on the health of man. When discussing chloroform
we are apart from the toxicity directly involved in the problem of carcinogenicity.
A question as: "do there exist no-effect levels for carcinogens", is well-known.
But we must realize that this question will not be answered soon. That means that
we have to deal with the presence of carcinogens in food and drinking water, with-
out having the answer. To protect man and the environment, it can be stated in
principle that carcinogens should not be present and that every effort should be
made to eliminate these pollutants.
Another important question is "what is a carcinogen"? Also this question is
difficult to answer, but there seems to be some evidence that not all compounds
that induce tumours are real carcinogens. Real carcinogens induce tumours in dif-
ferent animal species in general with low dose-levels. The tumours that are in-
duced are mostly of a specific type. Aflatoxins, give livercarcinomas, vinylchlo-
rid, angio sarcomas and the different type of nitrosamines induce different type
of tumours in specific target organs. The induction of tumours by the other com-
pounds can be possibly explained by
a. non-specific irritation for example U-ethyl-sulphonylnaphthalene-1-sulfonamide
administrated orally to mice, gives bladderstones, that induce hyperplastic re-
actions of the bladderepithelium and consequently bladdertumours occur.
b. hormonal dysfunction, for example high dose levels of an anti-thyroid agent.
c. cocarcinogenic or promoting agents.
d. microsomal enzyme induction, by certain chlorinated hydrocarbons may have an
negative or positive effect on tumour induction by a carcinogen.
e. suppression or overstimulation of the immune system, for example immunosuppres-
sion gives an increase in sensitivity for the induction of tumours.
Furthermore the dose level necessary to induce tumours is of importance, it shows
the difference in potency of the different carcinogens. Certain carcinogens such
as aflatoxin induce already tumours in animals at a daily dose level of a few μgfs,
while others have to be given in levels of 50, 100 or even 1000 mg/kg bodyweight/
day (table 1). This aspect has also to be'taken into account, because, as Drückrey
has proved, that the daily dose level of a carcinogen and the time of ad-
ministration are related to the induction time of the tumours. When low daily dose
levels are given, the induction time of the tumours will be long. It even happened
that no tumours are induced, the induction time is longer than the lifespan of the
animal. With high dose levels the induction time is short. It will be clear that
the intake of low levels of a chemical by man, that induce tumours in animals
with high to very high daily dose levels, will have a very long latency period to
induce tumours and the risk for man will be therefore much lower than for real
carcinogens such as aflatoxins and nitrosamines. At last there seems to be evi-
dence that the statistical chances that a hit of a carcinogen on a proper region
of DNA will be considerably higher with high dose levels than with low dose levels
of a carcinogen since the relative modes of detoxification are higher at low dose
levels. Furthermore in recent years also so-called DNA-repair enzymes have been
discovered, enzymes that detect and remove carcinogen-altered DNA.
All these reasons make it acceptable to believe that the impact from real
carcinogens is much more serious than from the other "tumour inducing compounds"
and that even for the last group of compounds perhaps no-effect levels exist.
It will be clear that much more research has to be done in the field of car-
cinogenesis before we are sure that this suggested difference really exists. How-
4 G. J. van Esch
TABLE 1 DOSE-LEVELS OF HALOGENATED COMPOUNDS IN COMPARISON WITH REAL CARCINOGENS
NECESSARY TO INDUCE A (APPROX.) MINIMAL NUMBER OF TUMOURS OR NO TUMOURS
Animal Daily dose-level in mg/kg b.w.
species
tumours no tumours
Γ77)
vinylchloride rat 9
chloroform mice/rat 60 15 (?)
DDT mice 0.5
rat - 10
dieldrin mice 0.05 (?) -
rat 2.5
trichloroethylene mice TOO
(clear effect)
rat - 500-1000
carbontetrachloride mice 1250
(clear effect)
rat - 50-200 (?)
aflatoxin B trout 0.0001
1
rat 0.005
DENA rat 0.075 0.0125
DMN mice o.k
rat - 0.1 (?)
AAF mice 2.5 1.25
Butteryellow rat 2.5 (?) 0.75 (?)
DMAS rat 0.05
(clear effect)
ß-naphthalamine hamster ±50 (?)
rat 5 (?)
Benzo(a)pyrene mice +20
rat 2.25
Saccharine rat 1250 500