Table Of ContentPERSISTENT ORGANIC
POLLUTANTS
Environmental Behaviour and Pathways
ofHuman Exposure
PERSISTENT ORGANIC
POLLUTANTS
Environmental Behaviour and Pathways
of Human Exposure
edited by
Stuart Harrad
University of Birmingham, United Kingdom
SPRINGER SCIENCE+BUSINESS MEDIA, LLC
Library of Congress Cataloging-in-Publication Data
Persistent organic pollutants : environmental behaviour and pathways of human exposure /
edited by Stuart Harrad.
p.cm.
Includes index.
ISBN 978-1-4613-5620-2 ISBN 978-1-4615-1571-5 (eBook)
DOI 10.1007/978-1-4615-1571-5
1. Persistent pollutants-Environmental aspects. 2. Organic compounds-Environmental
aspects. 3. Persistent pollutants-Bioaccumulation. 4. Organic
compounds-Bioaccumulation. 1. Harrad, Stuart, 1962-
ŢDI96.073 P47 2000
628.5'2-dc21
00-046211
Copyright © 2001 Springer Science+Business Media New York
Originally published by Kluwer Academic Publishers in 2001
Softcover reprint ofthe hardcover Ist edition 2001
AII rights reserved. No part of this publication may be reproduced, stored in a
retrieval system or transmitted in any form or by any means, mechanical, photo
copying, recording, or otherwise, without the prior written permission ofthe publisher,
Springer Science+Business Media, LLC .
Printed on acid-free paper.
For Gill and Caitlin
CONTENTS
List ofContributors viii
Preface ix
1 Budgetand Source Inventories:Issues and Challenges
Gev HEduljee
2 AtmosphericFate and Behaviour 29
Matt FSimcik
3 Transferof POPs into Vegetation: Implications and Mechanisms 53
Gian Marco Currado andStuartHarrad
4 Transportand Fate inFood Animals 79
GeorgeFFries
5 Human Exposure and Fate 105
A KDLiem, CEJCuijpers andMJZeilmaker
6 Assessing BioaccumulationFactorsofPersistentOrganic 145
Pollutants inAquatic Food-Chains
FrankA PCGobas
7 TemporalTrends inEnvironmental Contamination 167
Gordon Sanders
8 Long-RangeTransport:Implications for PolarRegions 211
Crispin J Halsall
9 An EasternEuropeanPerspective 233
Ivan Holoubek
Index 267
List of Contributors
Gev H Eduljee - Environmental Resources Management (ERM), Eaton
House, Wallbrook Court,North Hinksey Lane, Oxford, OX2OQS, UK.
MattFSimcik-Environmentaland OccupationalHealth, School ofPublic
Health, University ofMinnesota,MinneapolisMN55455, USA.
Gian Marco Corrado - Laboratory of the Government Chemist,
Teddington, Middlesex, TWII OLY, UK.
Stuart Harrad - Division ofEnvironmentalHealth and Risk Management,
University ofBirmingham,Birmingham,BI52IT, UK.
George F Fries - 2205 Bucknell Terrace, Silver Spring, Maryland 20902,
USA.
A K D Liem - National Institute ofPublic Health and the Environment
(RIVM), 3720 BABilthoven, TheNetherlands.
C E JCuipjers -National Institute ofPublic Health and the Environment
(RIVM), 3720BABilthoven, TheNetherlands.
M JZeilmaker - National Institute ofPublic Health and the Environment
(RIVM),3720 BABilthoven, TheNetherlands.
Frank A P C Gobas - School ofResource Management, Simon Fraser
University,Burnaby, British Columbia, Canada, V5A IS6.
GordonSanders -Battelle-Institute, Geneva Research Centres, 7Route de
Drize, 1227 Carouge/Geneva,Switzerland
Crispin J Halsall - Environmental Science Department, University of
Lancaster, Lancaster, LAI 4YQ, UK.
Ivan Holubek - RECETOX - TOCOEN & Associates, Veslarska 230B,
63700 Brno, CzechRepublic.
Preface
Persistent Organic Pollutants (POPs) continue to be the subject ofconcern amongst
the public, as well as the scientific and policy-making communities. Whilst the
ultimate origin ofthis concern istheir adverse effects (bothproven andsuspected) in
both humans and wildlife, there are other factors involved. In particular, a key
feature of these chemicals is that whilst ambient concentrations in air and water
present little direct hazard via inhalation and ingestion respectively,their propensity
for transfer through the food chain means that species at the top ofthe ecological
pyramid - including humans -can be exposed to concentrations ofconcern via their
diet. Furthermore, their ability to undergo long-range atmospheric transport means
that they represent a truly cross-boundary problem for mankind - a fact recognised
by the international efforts being conducted under the auspices of the United
Nations' EnvironmentProgramme andEconomic Commission forEurope.
While the fundamental importance of research into the human health and
ecotoxicological impacts ofPOPs is fully recognised, this aspect ofPOPs research
(which could easily fill a book by itself) is left to other volumes. Instead,this book
focuses on the sources, environmental cycling, food chain transfer, and human
exposure and fate aspects ofthis important class ofchemicals. Other topical issues
are also addressed, viz: temporal trends in contamination; the implications oftheir
transport to polar regions;andthesignificance ofthe former Warsaw Pact nations of
central andeastern Europe asbothaglobal reservoir andsource ofPOPs.
The aim throughout has been to include sufficient introductory material to be of
relevance to final year undergraduates, Masters and PhD students in Environmental
Science/Chemistry; whilst also providing the up-to-date, detailed, and authoritative
coverage required byacademics, environmental consultants,andpolicy-makers.
As co-author ofonechapter, Iam onlytoo aware ofthetime andeffort expended
bycontributors tothisbook.Ibelievethatthat whatfollowsdoesjusticetotheir hard
work, andwould liketotakethisopportunity to express mythanks tothem all.
StuartHarrad
Birmingham,July 2000
1
BUDGET AND SOURCE
INVENTORIES:
Issues and Challenges
G H Eduljee
1.1 INTRODUCTION
Persistent Organic Pollutants (POPs) are chemicals that are resistant to degradation
viamechanisms suchasphotolysis,chemical attackorbiological action. Introduction
ofthese chemicals into the environment can result in their accumulation in soils,
sediments, and in human and ecological foodchains, where they can induce toxic
effects in humans and the environment. POPs are almost entirely man-made, and
according to the United NationsEnvironment Program (UNEP) over 300 chemicals
withproperties thatwouldclassifythemasPOPsaresubjectto bansorother controls
in one or more countries worldwide. They include pesticides such as DDT, mirex,
aldrin and lindane, and industrial chemicals or byproducts such as polyaromatic
hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo
p-dioxins(PCDDs)andpolychlorinated dibenzofurans (PCDFs).
POPs can be transported over long distances, particularly through air, depositing
andaccumulating inregions farremoved fromthesource ofthe release (Rappe etai,
1989; Knap and Binkley, 1991; Mackay and Wania, 1995; van Pul et ai, 1998;
Kallenborn et ai, 1998). Concern over the presence of POPs in the global
environment and in the foodchain led to the initiation in 1992 of an assessment
programme under the auspices of the United Nations Economic Commission for
Europe (UN/ECE) to determine which chemicals should be targeted for concerted
international action. Under the framework of the UN/ECE Convention on Long
Range Transboundary Air Pollution (LRTAP) a methodology was developed by the
UK Department of the Environment and subsequently refined by Environment
Canada,to screen and identify chemicals ofpotential concern. In June 1998a POPs
Protocol to the LRTAP Convention was signed by 32 countries and the European
Community at the fourth Environment for Europe Ministerial Conference inAarhus,
Denmark. Sixteen substances identified through the screening procedure were
targeted foraction. Theseare listedinTable 1.
S. Harrad (ed.), Persistent Organic Pollutants
© Kluwer Academic Publishers 2001
2 PERSISTENTORGANICPOLLUTANTS
Table 1:POPs Listedunderthe UN/ECE(LRTAP) and UNEPInitiatives(seetextfor
relevanceofphysicochemical properties)
POP Vapour HalfLife Aquatic Log
Pressure(pa) in BCF Kow
Air
(Hours)
POPs onboth thellNlECE
and llNEP Lists
Aldrin 0.0086 0.5 20,000 3.01
Chlordane 0.0013 6.2 37,800 5.54
DDT (DDD andDDE) 0.00002 177 29,400 6.53
Dieldrin 0.00042 40 14,500 5.61
PCDDs 0.0000000814 233 49,000 7.70
PCDFs 0.0000000814 233 49,000 7.70
Endrin 0.00009 1.4 12,600 5.34
Heptachlor 0.04 6.0 20,000 5.50
Hexachlorobenzene 0.0015 17,520 23,000 6.20
Mirex 0.00004 No data 18,100 6.89
PCBs 0.0048 2,400 100,000 6.80
Toxaphene 26 120 33,000 3.30
AdditionalPOPs onthe
llNlECEList
Chlordecone(Kepone) 0.00004 No data 3,900 4.50
Hexabromobiphenyl 0.01 No data 18,100 No
data
PAHs 0.0000008 I.1 2,6390 6.50
(B[a]P) 29 425 3.37
10.4
(Naphthalene)
Lindane 0.0056 360 1,400 3.89
("(-
Hexachlorocyclohexane)
In a parallel development, a global initiative to take action on 12 POPs was
agreed by 92 countries in July 1998 under the auspices ofUNEP. These POPs are
also listed in Table 1. Under Executive Body Decision 1998/2, a procedure was
adopted for adding POPs to the UNEP list in Table 1. The proposed substance
should demonstrate:
(1) Potential for long range transboundary atmospheric transport: evidence
that thesubstance hasavapourpressure below 1,000Pa and an atmospheric
half-life greaterthan two days. Alternatively, monitoring data showing that
the substance isfound inremote regions:and
(2) Toxicity: potential to adversely affect human health and/orthe environment;
and
BUDGETANDSOURCEINVENTORIES 3
(3) Persistence:evidence that the substance's halflife in water is greater than
twomonths,orthat itshalflifeinsoils isgreater than sixmonths, orthat its
halflifeinsedimentsisgreaterthan sixmonths.Alternatively,evidence that
the substance isotherwisesufficientlypersistentto be ofconcernwithinthe
scopeoftheprotocol; and
(4) Bioaccumulation: (a) evidence that the bioconcentration factor (BCF) or
bioaccumulation factor (BAF) is greater than 5,000 or the log Kow is
greater than 5; or (b) alternatively, if the bioaccumulative potential is
significantly lowerthan (a) above, other factors such asthe hightoxicity of
the substance,thatmakeitconcernwithinthescopeoftheprotocol.
Other factors such as production, uses, socio-economic factors, alternatives, cost
andbenefitsarealsotobeconsidered.
The second session of the UNEP Intergovernmental Negotiating Committee was
held inNairobi inJanuary 1999,atwhichitwasagreed that "conducting inventories
would be an essential step in implementing an international instrument on POPs."
The third session ofthe Committeeisscheduledto convene inGeneva in September
1999, at which the draft text of an internationally binding instrument for
implementinginternationalactiononthe listedPOPswillbediscussed..
A wide range of measures are stipulated in the UN/ECE Protocol and in the
UNEP initiative, including production and use bans, phase-outs, restricted uses,
emission controls, and conditions for disposal. In selecting these measures, it is
necessaryto establishaknowledgebasecoveringissuessuchasthefollowing:
• What are the key sources ofthese chemicals? What quantities have been
released toair,waterandland,andoverwhattimescale?
• What are the transport and fate mechanisms acting upon these chemicals
followingtheirrelease? Whataretheresultingconcentrations inthe various
environmental compartments and how might these change over time after
controls ontheuseofPOPshavebeenputinplace?
• What are the human health and ecotoxicological consequences ofexposure
toPOPsthroughair,water,soilandthefoodchain?
A source inventory and environmental budget is an important first step in
developing indicators for monitoring ecosystem health (Cole et ai, 1998) and
appropriate risk control strategies for POPs. A source inventory identifies the
principal sources or activities responsible for the release of a POP into a given
environmental medium (air, water, land) together with the quantities released from
each source or activity. Using the inventory, it is then possible to rank sources in
order of importance, to target the major sources or those which pose the greatest
exposure risk, and finally to prioritise risk control measures, an important policy
objective. An environmental budget is an estimation of the burden ofthe POP in
each receiving environmental compartment that acts as a sink or reservoir for the
chemicalfollowing itsrelease. Source inventoriesand environmental budgets can be
linked through an accounting procedure, balancing inputs of a POP to the
environment withthe total environmental burden. In spatial and temporal terms, the
massbalance istypically conducted ona regional, national or global scale, and over
