chemicals in the environment: implications for global sustainability

The impact of chemicals on the environment and humanhealth is a cause of increasing concern Although manystudies continue to be carried out on this subject mostaddress only individual chemicals or particular groups ofchemicals such as metals or radioactive substances Inthis paper we consider the availability of data andknowledge about potentially harmful chemicals from thenational to international scale and suggest a strategy tohelp prevent chemical pollution or deficiencies damagingglobal sustainability into the 21st century The maingroups of chemicals considered are(i) Potentially harmful inorganic elements such as As Cd

Hg and Pb known to have adverse physiological effectsat low levels and elements and species such as Se I andNOx that can be essential or harmful depending ontheir concentration speciation and bioavailabilityChemical elements such as Ga In and the PGEs thatare increasingly used in the development of newmaterials including nanotechnology applications arealso discussed briefly

(ii) Radioactive substances including naturally occurringradioisotopes such as 238U and its decay products226Ra and 222Rn and processed materials such asdepleted uranium (DU) which affect the environmentand human health because of their radiological andchemical toxicity Data on isotopes from the nuclearindustry such as the relatively short-lived isotopes137Cs and 90Sr are also discussed including fromaccidental releases such as Chernobyl in 1986Isotopes with longer half-lives such as 243Am and 240Puwhich are important in the development of nuclearwaste management strategies are also considered

(iii) Persistent organic pollutants (POPs) including manysynthetic chemicals such as dichlorodiphenyltrichloro-ethane (DDT) polychlorinated biphenyls (PCBs)and polybrominated diphenyl ethers (PBDEs) flameretardants and their metabolites which are char-acterised by their persistence bioaccumulation(lipophilicity) and toxicity (PBT) properties Othersynthetic chemicals such as perfluorooctanesulphonate (PFOS) which have different bio-accumulation properties are considered briefly

(iv) Human and veterinary pharmaceuticals of whichthere is increasing evidence of their presence in theenvironment These substances are of particularconcern because many are designed to targetspecific biological receptors and hence can havepotentially deleterious effects at exceptionally lowconcentrations

All these groups of chemicals include endocrine disruptingchemicals (EDCs) capable of disrupting animal andhuman hormone systems (including sex and thyroid)

Geochemical databases such as those prepared by theForum of European Geological Surveys (FOREGS) andthe British Geological Survey (BGS) provide systematicinformation on levels of inorganic chemicals in theenvironment Similarly airborne radiometric databasesprovide systematic information on the distribution ofradioactive substances Examples of such data are used todemonstrate how the distribution of chemicals in theenvironment can be mapped and how modelling andmonitoring systems derived from them are of strategicimportance in understanding the impact of chemicals onecosystems and human health from the national to globalscale There is concern however about the lack of suchsystematic data for organic chemicals It is argued that suchsystematic data for all chemicals is crucial for sustaining theEarthrsquos life-support systems into the 21st century

J A Plant (also Professor of Geochemistry at ImperialCollege London UK for correspondence ndash E-mailjplantimperialacuk) S Reeder (E-mail srebgsacuk)and B Smith (E-mail bsmibgsacuk) are at the BritishGeological Survey Keyworth Nottingham NG12 5GG UKA Korre (E-mail akorreimperialacuk) and N Voulvoulis(E-mail nvoulvoulisimperialacuk) are at ImperialCollege Department of Environmental Science amp TechnologyPrince Consort Road London SW7 2BP UK

copy 2005 Institute of Materials Minerals and Mining andAustralasian Institute of Mining and Metallurgy Publishedby Maney on behalf of the Institutes Manuscript received 21July 2004 accepted in final form 6 July 2005

Keywords Harmful inorganic chemicals Radioactive sub-stances Persistent organic and pharmaceutical pollutantsGeochemical mapping monitoring and modelling essentiality

Applied Earth Science (Trans Inst Min Metall B) June 2005 Vol 114 B65DOI 101179037174505X62857

Chemicals in the environment implications for globalsustainability

Jane A Plant Anna Korre Shaun Reeder Barry Smith and Nikolaos Voulvoulis

INTRODUCTIONThere is growing awareness world-wide of relation-ships between ecosystem and human health and thedistribution of chemicals in the environment (RCEP2003) There is also an increasing realisation that

although geohazards such as volcanoes and earth-quakes are dramatic and cause sudden and significantloss of life the threat from chemicals which isfrequently insidious can cause even greater loss of lifeand debility over the longer term (Skinner and Berger

2003) The problem of chronic exposure to potentiallytoxic chemicals in the environment is also articulatedby the European Environment Agency and the UnitedNations Environment Programme (EEAUNEP1999) The increase in concern about chemicals in theenvironment is reflected by the growing number ofEuropean Union (EU) Directives and national andinternational conventions relating to chemicals

In addition to damage to human health caused bytoxicity conditions damage can also be caused bydeficiency conditions The World Health Organization(WHO) for example has calculated that 800 millionpeople world-wide are at risk of serious diseases suchas goitre and cretinism the latter because of iodinedeficiency in mothers during pregnancy (UNICEF-WHO Joint Committee on Health Policy 1994)

In this paper we first review data on problemsassociated with inorganic substances for which in thecase of many of the 92 naturally occurring chemicalelements there is now much systematic data on theirdistribution in soils sediments and water at thenational and increasingly international scale Thesedata can be used for understanding the distributionbehaviour and potential impact of such chemicals incomplex and highly varied surface environmentsworld-wide ranging from glaciated to tropicalterrains Some of the latter contain deeply leachedancient landscapes suggested in some cases to datefrom the Proterozoic (Butt 1989 Daniels 1975) Wealso discuss similar systematic information forradioactive substances

In contrast to inorganic and radioactive substancesthe situation for synthetic organic substances includingpersistent organic pollutants POPs such as pesticideresidues phthalates and other plasticisers surfactantsand detergents and waste products from incinerationsuch as dioxins is characterised by a paucity ofsystematic data information and knowledge There isincreasing awareness as a result of recent monitoringand modelling studies (Sweetman and Jones 2000Halsall et al 2001 Prevedouros et al 2004) of damageto ecosystems and man caused by the long-rangetransport of these chemicals and their accumulation athigh latitudes (EEAUNEP 1999) Moreover it hasbeen estimated that there are about 30 000 syntheticindustrial chemicals on the market of which relativelylittle is known even about their hazardous (PBT)properties (EEAUNEP 1999) Their distribution andbehaviour in the environment is also poorly understoodmaking meaningful exposure and risk assessmentalmost impossible

In the case of pharmaceuticals or their residues thereis currently no regulatory requirement on their use ordisposal even within the US or EU despite theirpotentially high ecotoxicitytoxicity Studies of sewageeffluent and surface water in the UK and world-widehave shown many pharmaceuticals including the femalecontraceptive pill 17α-ethinyl oestrodial (EE2) forexample to occur at concentrations with the potentialto cause harm (Sumpter 2002 Pickering and Sumpter2003 Plant and Davis 2003)

All of the groups of chemicals discussed both

inorganic (eg Pb and Cd) and organic (eg PCBs DDT)include substances that can disrupt the endocrine systemof many species including humans (UKEA 2000) Morethan 70 EDCs are now listed on the UK Institute ofEnvironment and Healthrsquos relational database ofinformation on potential endocrine disrupters (IEHREDIPED website)

Among OECD countries Japan appears to be theonly nation that uses environmental monitoring data toevaluate the risks of such chemicals in the environment(RCEP 2003) Here we show how systematicgeochemical and radiometric data strongly support suchan approach and can be used to inform government andthe public of potential threats to the health of ecosystemsand humans posed by deficiencies or excesses ofchemicals in the environment

CHEMICALS OF CONCERN IN THEENVIRONMENT

Potentially harmful and essential inorganic chemicalelements and speciesTwo main groups of inorganic chemical elements andspecies are of particular importance for healthpotentially harmful chemical elements and speciesand those that can be essential or harmful dependingon their concentration speciation and bioavailabilityThe level of many of these chemicals can varynaturally as a result of geology or climatic historyalthough their natural background has frequentlybeen altered by the activity of humans includinghistorical mineral working industrialisation andurbanisation New materials including those used innanotechnology are increasingly introducing newapplications for many chemical elements that have notpreviously been of environmental concern eg Ga Inand the PGEs (Table 1)

Potentially harmful elementsPotentially harmful elements (PHEs) known to haveadverse physiological significance at relatively lowlevels for which there is little or no evidence ofessentiality include As Ag Be Cd Pb Hg (Skinnerand Berger 2003) and possibly some of the rare earthelements (REEs Smith et al 1998a) Arsenic Pb andHg are used here as examples

Acute toxicity from As can cause severe gastro-intestinal symptoms fluid loss and circulatorycollapse psychotic symptoms neurological changesincluding demyelination of the peripheral nervoussystem andor severe heart disease Chronic exposureis linked to increased risk of cancer including of theskin liver lung and bladder (Tchounwou 2000 Wonget al 1992) Significant adverse effects of As-contaminated groundwater including from naturallyarsenical aquifers have been reported from ArgentinaBangladesh Chile China Ghana Hungary IndiaMexico Taiwan the UK and the US (Naidu andNadebaum 2003) In Mongolia and parts of Chinawhere arsenical groundwater is used for irrigation itmay also be ingested via crops or animals or through

B66 Applied Earth Science (Trans Inst Min Metall B) June 2005 Vol 114

Plant et al Chemicals in the environment implications for global sustainability

dermal absorption during wetland farming ChronicAs poisoning as a result of burning arsenical coalwhich affects at least 3000 people in GuizhouProvince China has been described by Zheng et al(1996) and Finkelman et al (2002 2003) Arsenic hasalso been used traditionally in biocides in agricultureand industry and more recently in the electronicsindustry The transfer of As from the geosphere to thesurface where it adversely affects ecosystems andhuman health is poorly understood There is ageneral lack of knowledge about the distribution ofAs in the Earthrsquos surficial materials because thiselement was rarely determined in geochemical surveysprior to about 1990 (Plant et al 2004)

Lead is a cumulative neurotoxin that poses the highestrisk to children partly because of the development stage oftheir neurological system and partly because there is agreater likelihood of hand to mouth transmission It hasbeen associated with decreased learning ability anddelinquent behaviour in later life (Needleman et al 1996)Apart from natural emissions of Pb and problemsassociated with historical mineral working and refining itsdistribution from ore deposits into the environment hasbeen mainly from sources such as plumbing commercialagrochemicals Pb-based paints sewage sludge wastewater and petroleum additives Calculations by Mielkeand Reagan (1998) suggest 5middot9 Mt of Pb from thepetroleum additives tetraethyl and tetramethyl lead(TELTML) have left 4ndash5 Mt of Pb in the environmentmainly in urban areas in the US alone

Mercury is another powerful neurotoxin that canhave health impacts (Table 2) It is a highly toxic tracemetal that becomes especially concentrated in aquaticfood webs although one well-known example of Hgaffecting human health was caused by the accidentalconsumption of Hg-treated grain in Iraq in 1971(Bakir et al 1973) Adverse human health impacts

caused by the highly neurotoxic organomercuryspecies monomethyl mercury (MMHg) are mostfrequently related to consumption of contaminatedfish (Fitzgerald and Clarkson 1994 US NationalResearch Council 2000 Fitzgerald and Lamborg2004) Natural degassing of the Earthrsquos crustcombined with emissions from burning fossil fuels isestimated to contribute up to 150 000 t of Hg a yearHigh natural Hg concentrations occur in particularzones of the Earthrsquos crust such as the tectonicallyactive area around the Pacific Ocean (Turekian andWedepohl 1961 Fitzgerald and Lamborg 2004

Applied Earth Science (Trans Inst Min Metall B) June 2005 Vol 114 B67


Table 1 Some new main uses of chemicals

Commodity New main uses 2002 production Reserves Comment

Arsenic trioxide Electronics 35 000 t 875 000 t Reserves are calculated as 25x annual production

Gallium Electronics (solid state transistors) 61 t 150 000 t Not all recoverable because of strong binding in bauxite and zinc ores

Germanium Electronics (semi-conductors) 68 t NA By-product of Pb and Zn processinggamma-ray detectors

Indium Alloyed with tin in full LCD 335 t 2500 t Reserve base is 6000 t By-product of Zn and plasma TV screens refining

PGEs ndash Pt Autocatalysts jewellery fuel cells 171 000 kg 71 Mkg 80 Mkg reserve base Reserves for total PGE

PGEs ndash Pd Autocatalysts jewellery 193 000 kg

Rare earths Glass polishing ceramics petroleum 85 500 t 88 Mtrefining autocatalysts and electronics

Rhenium Petroleum refining catalysts super 23 100 kg 2middot4 Mkgalloys in aerospace industry coatings for electronic contacts

Tantalum Electronics as Ta-capacitors 1530 t 39 000 t 110 000 t reserve basemobile phones

British Geological SurveyUnited States Geological Survey

Table 2 Symptoms of mercury (vapour) toxicity (after Lindhet al 2003)

Acute (1 mg mndash3) Chest painsShortness of breathCoughCoughing bloodImpairment of pulmonary functionPneumonitis`

Chronic Violent muscular spasmsPricking or burning sensationsTrembling handwritingIrritabilityExcitabilityInsomniaHallucinationsShynessNerve painDrowsinessDeliriumFine tremorLoss of tasteLoss of hearingLoss of memoryLoss of smellDeath

Lindh et al 2003) Most modern metal mining whichin the past caused release of natural Hg from oredeposits is now carried out to extremely highenvironmental standards minimising Hg pollutionbut historical problems remain For example Hg wascontained in the mine tailings in the Aznacollarincidence in Spain that caused serious environmentaldamage (Grimalt and MacPherson 1999) The mainproblem of Hg contamination from mining now isrelated to artisanal gold mining (Porcella et al 1997)Dental amalgams also contribute to environmentalmercury levels through release of mercury vapour orincineration of dental waste and also humancremation (Selinus et al 2005)

Essential chemical elements and speciesThe chemical elements and species identified asessential to animal and plant life include K Na Ca PClndash SOx and NOx as well as the first row transitionelements Fe Mn Ni Cu V Zn Co and Cr and MoSn Se and I (Mertz 1986 WHO 1996)

Some of the disorders associated with deficiency orexcess of these elements are given in WHO (1996)Recent reviews of the importance of geochemistry as acontrolling factor in Se deficiencies and excesses tohuman health include those of Fordyce et al (2000a)Plant et al (2004) and for I Johnson et al (2003) and

Fordyce et al (2003) Table 3 illustrates the consequencesof I and Se deficiencies and excesses

Boron has not yet been shown to be necessary foranimals although it is essential for higher plants and hasbeen suggested by some authors to be toxic to humans(WHO 1996) All trace elements are toxic if ingested orinhaled at sufficiently high levels for long enough periodsof time Se F and Mo are examples of elements that havea relatively narrow concentration range (of the order of afew micrograms per gram) between deficiency and excess(toxic) levels In the case of F for example more than 10million people in Guizhou Province China suffer fromvarious forms of fluorosis as a result of the high F indomestic coal combined in some cases with high F inwater The condition has also been reported from 13other regions of China (Ando et al 1998 2001) Typicalsymptoms of fluorosis include mottling of teeth andskeletal deformation including knock knees bow legsand spinal curvature In children especially whencombined with nutritional deficiencies it can causesevere bone deformation

The difficulties of diagnosing disease in animals andman particularly sub-clinical conditions related to traceelement deficiencies or excesses are discussed by Mills(1996) Except in some specific cases such as As(Smedley et al 2001 Plant et al 2003a) Hg toxicity(Fitzgerald and Lamborg 2004) or I deficiency disorders(IDD Johnson et al 2003 Fordyce et al 2003)symptoms may be non-specific and diagnosis based ontissue or blood sampling is costly The concentration ofessential trace elements such as Se in crops (rice cornsoybean) was shown by Levander (1986) to correlateclosely with their concentration in the soil in which theyare grown although the relationship has been shown tobe more complex (Appleton et al 1998 Johnson et al1999) Presently much effort is focused on groundwateras the principal pathway for many PHEs to humans Thesituation is however more complicated with soil cropsand animals aerosols dust and surface waters also beingsignificant pathways for most elements (Plant et al2003a) Work by Williams et al (1999) usingphysiologically based extraction tests (PBETs) and riskassessment has shown that in non-industrialisedcountries soil is likely to be an equally significantexposure pathway for As as groundwater This is likely tobe the case for most PHEs in developing countries wheresignificant soil contamination can occur duringharvesting and food preparation processes (Smith et al1998a) especially where geophagy is practised(Abrahams 2002 2004)

In higher animals including humans assimilationof essential and potentially harmful inorganicchemicals occurs by ingestion of nutrients andcontaminants from food crops animal tissues anddrinking water or the inadvertent ingestion of soil bydermal absorption andor by respiration (WHO1996) Ideally geochemical data on soil and duststream sediment and ground and surface water shouldbe available to identify assess and model sources andpathways of such chemicals likely to lead to toxicity ordeficiency conditions with the potential to harmecosystems and humans



Table 3 Some human health impacts of iodine and seleniumdeficiencies and excesses

IODINEDeficiency

Iodine is an essential component of thyroid hormones Inadequate supply of iodine leads to insufficient production of these hormones resulting in disease statescollectively known as iodine deficiency disorders (IDD) The consequences are

(i) Mental retardationreduced IQ(cretinism in infants)

(ii) Defects in the development of the nervous system

(iii) Goitre (enlarged thyroid)(iv) Physical sluggishness(v) Growth retardation(vi) Reproductive failure(vii) Increased child mortality

(Venkatesh-Mannar and Dunn 1995)Excess

An excess of iodine has a negative impact on thyroid function

(i) Hashimotorsquos thyroiditis(ii) Iodine hyperthyroidism (jodbasedow)(iii) Iodide goitre(iv) Thyroid carcinoma

(Koutras et al 1980)SELENIUM

DeficiencyKeshan disease ndash an endemic degenerative heart diseaseKaschin-Beck disease ndash an endemic osteoarthropathy which causes deformity of effected joints(Fordyce et al 2000b)

ExcessSelenosis ndash resulting in hair and nail loss and nervous system disorders(Fordyce et al 2000b)

Chemical speciationThe speciation of chemical elements affects theirdistribution mobility and toxicity This has been knownfor a long time in the case of the common anions(HCO3

ndash NO3ndash SO4

2ndash) and more recently for a widerange of chemical elements in the surface environment(Stumm and Morgan 1981 Buffle 1988)

The importance of chemical speciation in relatinggeochemical data to health was first established byagricultural scientists (Underwood 1979 Levander1986) Considerable developments have been made inthe prediction of chemical speciation by modellingthermodynamic and kinetic equilibria (Bassett andMelchior 1990 Stumm 1991) and by experimentaldeterminations (Buffle 1988 Marabini et al 1992)Biochemical processes induced by microbial plantand animal activity are also important controls onboth speciation and mobility but these were relativelypoorly understood until recently (Ehrlich 1990Deighton and Goodman 1995)

Some of the most important controls on traceelement speciation and mobility include hydrogen ionactivity (pH) redox potential (Eh) temperaturesurface properties of solids the abundance andspeciation of potential ligands major cations andanions the presence or absence of dissolved andorparticulate organic matter and biological activity Thetwo most important factors directly controllingmobility and solubility are Eh and pH The solutionchemistry of an element is affected profoundly bychanges in oxidation state while dissolution reactionsincluding hydrolysis inorganic complexationcomplexation with smaller organic anions (such asoxalate) and sorptiondesorption are all controlled bypH Under conditions of high pH anions andoxyanions (such as those of Te Se Mo U As P andB) are more mobile and most cations (such as those ofCu Pb Hg and Cd) are less mobile while at low pHthe reverse is generally true Where humic substancesor biological by-products are present however stableorgano-metallic complexes (which can behave asanions) can form increasing trace-element mobilityThe kinetics of inter-species interactions also act as

important controls on speciation particularly wherenatural systems are disturbed by the influence ofhumans

Geochemical interaction between the geospherehydrosphere and biosphere depends partly onsorption processes and partly on chemical speciationSome elements for example Al Ti and Cr arerelatively poorly assimilated by plants althoughothers such as Cd Se Mo and Co can readily crossthe soilndashplant barrier and enter the food cycle (Loehr1987) In soils sorption of elements by clay mineralsand organic material is the predominant fixingmechanism with soil pH controlling sorptionprocesses and metal solubilitybioavailability Manymetal cations such as Cu Pb Cd and Hg are moresoluble in the low pH conditions induced by naturalorganic acids and root exudates

Speciation studies are of particular importance inareas affected by land degradation deforestation orpollution caused by (mainly historical) miningindustrial activity energy generation or urbanisationand they can be used to optimise ameliorationstrategies and improve management practices Aknowledge of the factors controlling speciation indifferent environments can be used to predict thepotential for absorption of PHEs

Speciation and lability both in the naturalenvironment and in the gastro-intestinal tract exert amajor influence on the uptake and assimilation oftrace nutrients and PHEs (WHO 1984 WHO 1994Powell and Thompson 1993) For example Al whichis the commonest metal at the Earthrsquos surface occursin both inert and bioavailable forms and its potentialtoxicity depends on its chemical form or speciation Itcan occur in a large number of dissolved aqueousspecies especially in conditions of low or high pH Incertain species of animals particularly fish andplants Al can have adverse physiological effects intrace amounts (Sposito 1989) or be bound oncolloidal organic carbon or silica which limit itsbioavailability and therefore its toxicity

The toxicity of other elements also depends ontheir chemical form Arsenic for example is most



Table 4 Chemical forms of arsenic and selenium

Element and formal oxidation state Major chemical forms

As(ndashIII) Arsine [H3As]As(ndashI) Arsenopyrite [FeAsS] loellingite [FeAs2]As(0) Elemental arsenic [As]As(III) Arsenite [H2AsO3

ndash H3AsO3]As(V) Arsenate [AsO4

3ndash HAsO42ndash H2AsO4

ndash H3AsO4]Organic As (V and III) Dimethylarsinate [DMA (CH3)2AsO(OH)] monomethylarsonate [MMA(V) CH3AsO(OH)2

or MMA(III) CH3As(OH)2] arsenobetaine [AsB (CH3)3As+CH2COOndash] arsenocholine [AsC (CH3)3As+ CH2CH2OH]

Se(ndashII) Selenide [Se2ndash HSendash H2Se]Se(0) Elemental selenium [Se]Se(IV) Selenite [SeO3

2ndash HSeO3ndash H2SeO3]

Se(VI) Selenate [SeO42ndash HSeO4

ndash H2SeO4]Organic Se Dimethylselenide [DMSe CH3SeCH3] dimethyldiselinide [DMDSe CH3SeSeCH3]

selenomethionine [H3N+CHCOOndash CH2CH2SeMe] selenocysteine [H2N

+CHOOndashCHSeH]

After Plant et al 2004

toxic in the As3+ gaseous state with decreasing toxicityin the sequence As3+ gt As5+ gt methyl-As (Abernathy1993 Chen et al 1994) Unlike Hg which is mosttoxic when it is methylated the toxicity of As is muchlower in organic species such as arsenobetaine andarsenocholine in which it can occur at highconcentrations in fish (Plant et al 2004) Arsenic andselenium interact with each other in various metabolicfunctions in animal models (Davis et al 2000)Human selenosis at the population level is rare and isgenerally related to excesses from food rather thandrinking water The principal species of As and Se areshown in Table 4

Monomethylmercury (MMHg) is the most harmfulform of Hg to organisms demonstrating biocon-centration and biomagnification and it has a longresidence time in organisms Most of the Hg in fishand their eggs is present as MMHg and this is themain source of mercury to humans (de Larcerda andSalomons 1998 Campbell et al 2003) Fish embryoexposure to methylmercury may occur viaenvironmental interaction or by maternal transferWell-known examples of MMHg affecting humanhealth include the occurrence of Minamata disease inJapan in 1953 which was caused by eating fishcontaminated with waste-water discharge from afactory (Irukayama 1977)

Geochemical techniques can be used to identify notonly the total amount of each element in soil dust orwater for example but also the amount which isbioavailable This is more important than the totalamount but is less easy to establish Several workershave developed and applied physiologically basedextraction tests (PBETs) that attempt to predict thebioavailability (the total fraction of an element that isavailable for absorption during transit through thedigestive tract) of a given trace element (Davis et al1992) Such tests have significant advantages overconventional sequential leach tests because theyattempt to reproduce physiological factors such asstomach emptying time and the ratio of solid todigestive fluids as well as the pH and Eh of uppergastro-intestinal tract solutions in particular target

groups such as young children In the case of As thevalues for bioavailability in the upper intestine(neutral pH) are consistently significantly greater thanthose estimated from simple acid stomach solutions(Ruby et al 1996) Although such tests need furthercalibration and validation they represent animportant step forward in understanding exposurepathways for both potentially toxic trace and essentialtrace elements (Renner 1998)

Radioactive substancesThese comprise both naturally occurring and man-made radioactive substances the toxicity andcarcinogenicity of which depend on their chemicalproperties and the nature of their ionising radiationTheir adverse health impacts also depend on theirbiological and radioactive half-lives

The principal chemical elements contributing tonatural terrestrial radioactivity are those in the U andTh decay chains and K In nature U has two primaryisotopes 238U and 235U which occur today in the ratioof 99middot3 238U to 0middot7 235U These together with 232Thhave long and complex decay series (eg Kaye andLaby 1986 Burns and Finch 1999) The principalhazards posed by U are its chemical toxicity and theradiological properties of some of its decay productsespecially those that are alpha emitters such as 226Raand 222Rn which are of concern if they are inhaled oringested because of their association with cancerparticularly lung cancer in the case of 222Rn

Radioactivity may also be introduced into theenvironment as a result of contamination from a widerange of anthropogenically produced radionuclidesincluding the manufacture testing and use of nuclearweapons nuclear accidents and to a lesser extent nuclearpower generation some radionuclides are also now usedfor domestic medical and industrial applications

Since the development of nuclear power radioactiveisotopes including those of Am C Cs H I Kr Np PuSr Te and Xe have been released into the naturalenvironment as water soil and airborne contaminants(Shutov et al 2002) While much of this has beenassociated with known and licensed releases some



1 Sources of radiation exposure contributing to average effective dose in the UK (NRPB data from Appleton 2004)

significant releases have been associated with nuclearweaponsrsquo testing for example at the Hanford site in theUS (Siegel and Bryan 2004) and with nuclear accidentssuch as those at Chelyabinsk near Kyshtym Russia in1957 (Medvedev 1979) at Windscale in 1958(Chamberlain and Dunster 1958) and at ChernobylUkraine in 1986 (Abagyan et al 1986) The Goianiaincident in Brazil in 1987 which involved themishandling of a medical 127Cs source previously used forradiotherapy involved acute contamination at a muchmore local scale with serious human health impacts(IAEA 1998)

Nevertheless the average dose from these sourcesover most of the Earthrsquos surface is generally smallcompared to natural radioactivity For example theaverage dose experienced by a UK citizen and itssources are shown in Figure 1 This indicates the verysmall doses from the nuclear industry compared tonatural radioactivity or to medical diagnostics or food

Naturally occurring radionuclides226Radium and 222Rn are decay products of the muchmore abundant U isotope 238U and are of particularimportance due to their impact on human health andtheir role in the discovery of radioactivity in the early20th century While of little environmental significance214Bi is an important decay product of 238U because it isthe isotope by which lsquoequivalent Ursquo (eU) is determinedquantitatively using gamma ray spectrometry and it is adecay product of 226Ra and 222Rn

The radio-elements within the U and Th decaychains have different chemical behaviour and canbecome separated in the surface environment fromtheir parents (U and Th) leading to fractionation andsecular disequilibrium This is most common wherethere are recent surficial deposits of U decay productsthat result in eU analyses that do not reflect the totalU concentration Nevertheless eU may closely reflectareas of high radon potential for example over theDerbyshire Peak District of central England (see Plate4 Jones et al 2002a)

Uranium and the other two important natural radio-elements Th and K are strongly partitioned into thecontinental crust and are especially concentrated incertain types of granites and organic rich black shalesand phosphatic sediments (Plant et al 1999) Someaverage radio-element contents are given in Table 5

The natural radio-elements 232Th and 40K areassociated with many U deposits Thorium can be ofenvironmental significance because it reaches highlevels in certain types of mineral deposits such asheavy mineral sands (Gilbert and Park 1986) andisotopes within its decay chain emit high energy (2middot7MeV) gamma rays The average Th to U ratio in mostunmineralised rocks is 3middot5 to 1 High levels ofpotentially toxic elements such as As are also oftenclosely associated with high levels of U for examplewith the Variscan Cornubian Batholith in thehistorical mining district of south-west England(Appleton 1995a 1995b) Such associations increasethe potential environmental and health problems of Uconcentrations and mineralisation and have been citedas co-factors with 222Rn in links between mine dustsand lung cancer (The Royal Society 2001 WHO2001) Other naturally occurring radionuclides thatoccur in small amounts include 237Np 239Pu and 99Tc(Siegel and Bryan 2004)

The concentration factor of U from average crustalabundance (2middot8 mg kgndash1) to ore grade ranges fromapproximately 100 in the case of low-grade depositssuch as the Roumlssing deposit Namibia (0middot03 U) toabout 65 000 in the case of high-grade deposits such asthe McArthur River deposit in Canada (18middot5 U)The surface expression of the deposits however iscontrolled by a variety of natural factors specific toeach mining district Frequently deep-seated high-grade deposits such as McArthur River have little orno surface radiometric or geochemical expression in



Table 5 Average radio-element content in rocks and waters

U K Th

Crustal abundance (mg kgndash1) 2middot7 17 500 10Ultramafics (mg kgndash1) 0middot001 hellip 0middot003Basalt (mg kgndash1) 0middot6 hellip 2middot2Granodiorite (mg kgndash1) 3 hellip 10Andesite (mg kgndash1) 2 hellip hellipGranite (mg kgndash1) 4middot8 hellip 17Shale (mg kgndash1) 4 hellip 12Sandstone (mg kgndash1) 2middot2 hellipLimestone (mg kgndash1) 2 hellip 2Soil (mg kgndash1) 1 hellip 13River water (microg kgndash1) 0middot0004 hellip 0middot0001Sea water (microg kgndash1) 0middot003 hellip hellip

Data for U and Th from Taylor (1964 1966) except river water data(Th from Turekian (1969) U from Reeder et al (1972)) data foraverage crustal abundance for K from Weaver and Tarney (1984)

Table 6 The five most economically important types of U deposits

Type of deposit Examples

Unconformity-related deposits Athabasca Basin including Cigar Lake McArthur River Key Lake Cluff Lake (Canada)Nabarlek Jabiluka Ranger (Australia)

Sandstone deposits Colorado Plateau (USA) Koenigstein (Germany)

Quartz-pebble conglomerate deposits Witwatersrand Basin (RSA) Elliot Lake (Canada)

Vein deposits Saint Sylvestre Limousin (France) the polymetallic Jachymov orefield Western Erzegebirge (Germany) Pribram District (Czech Republic)

Breccia complex deposits Olympic Dam (Australia)

IAEA 1996 OECD 1998

contrast to low grade near-surface deposits such asthat of Roumlssing The five most economically importanttypes of U ore deposits are shown in Table 6

Anthropogenic sources of radioactivityPrior to the advent of nuclear fission technology in1942 U was used mainly for colouring glass ceramicglazes (Plant et al 1999) and to a much less extent asa remedy for diabetes (WHO 2001) Following thepioneering work of Marie Curie and others in theearly 1900s U ores were also used as a source of thedecay product 226Ra in the treatment of cancer as wellas for producing luminescent displays and paints untilthe mid-1960s Contamination from the latter hasrequired significant remediation of contaminatedairfields and military sites where it was used until themid-1960s

In 1942 demonstration of the controlled nuclearfission of 235U led to the development of its use in nuclearweaponry and energy and the production of lsquoenrichedrsquouranium at an industrial scale Since that time the mostimportant environmental impacts have been fromnuclear weaponsrsquo testing (fission and fusion) and to alesser extent nuclear power generation including fromnuclear fuel fabrication nuclear reactors and repro-cessing plants (Siegel and Bryan 2004) The increase inthe numbers of miners and workers exposed to U as aresult of these applications appears to have had arelatively insignificant effect on their health overall (TheRoyal Society 2001) Radioactive and associated heavymetal and As contamination can reach high levels in Utailings in areas of former U mining In the US forexample 230 Mt of tailings are now stored at 24remediated sites (Siegel and Bryan 2004) In the formerSoviet Union (FSU) contamination from U mining isgenerally more serious partly because of fewer environ-mental and health and safety controls in the past andpartly because of the use there of strong mineral acids insolution mining operations (Siegel and Bryan 2004)

Nuclear fuel is produced by the enrichment ofnatural 235U from about 0middot7 to about 3middot5 Themain residue lsquodepletedrsquo U (DU) which contains

about 0middot2 235U and only small amounts of decayproducts has been used for several applicationsbecause of its similar physicochemical properties to Uand its significantly lower radioactivity Applicationsinclude pigments chemical catalysts counter weightsand shielding Depleted U has also been used in fast-breeder nuclear reactors to produce fuel and weapons-grade Pu (predominantly 239Pu typically with less than7 240U) by neutron activation Since the 1970s whenalloys with a high DU content were developed forarmour-piercing artillery and anti-tank shells becauseof their high density self-sharpening and pyrophoricproperties they have caused contamination followingsome military conflicts (Fig 2)

The use of these weapons in the First Gulf War in1991 and subsequent wars in the Balkans and Iraq hasbeen linked by some scientists to an increasedincidence of cancers birth defects and syndromes inthose exposed (Fahey 1998) Such concerns havedemonstrated the need for better information onbackground levels and chemical speciation ofnaturally occurring radionuclides such as U to helpassess the impact of exposure to humans (WHO 2001The Royal Society 2001 2002) Recent studies havealso highlighted the need for improved understandingof the chemical toxicity of U particularly in drinkingwater supplies where animal and human models showa dose dependent toxicological response at extremelylow levels (Kurttio et al 2002)

Whilst of little economic importance in the past Thhas been used in the manufacture of ceramics carbon arclamps and welding electrodes although Zr Y and somelanthanides are now commonly substituted for Th in Mgalloys used in aerospace applications to reduce levels ofradioactivity (USGS 2004)

Anthropogenic radionuclidesThe principal sources of anthropogenic radionuclidesare associated with the nuclear fuel cycle especiallynuclear weaponsrsquo production testing and nuclearaccidents and to a lesser extent nuclear powergeneration which produces small quantities of wasteThe principal difference between the chemistry andimpacts of anthropogenic and naturally occurringradioactive isotopes reflects their generation by thefission of the heavy nuclei of 233U or 239Pu

Over 300 different intermediate weight fissionproduct isotopes are formed as a result of splitting theheavy U or Pu nuclei (Fig 3) with half-lives varyingfrom fractions of a second to months or years Fromcurrent knowledge of the impacts of radiation onhuman health the most important are generallyconsidered to be 90Sr and 137Cs

The residual radiation hazard from a nuclearexplosion in the form of radioactive fallout and neutron-induced activity also includes unfissioned materialespecially U and Pu that are dispersed but are generallyof relatively minor importance Nuclear-induced activitywhereby elements such as Na Mn Al and Si in rocksoil air or water near the nuclear explosion captureneutrons also occurs although this process normallyaffects only a limited area (NATO 1996)



2 Back scattered electron microprobe image showingdepleted uranium-rich particle from Kosovo(Milodowski 2001)

Following their release all such radionuclides becomepart of a large number of geochemical cycles with thepotential for exposure to ecosystems and humansIndeed anthropogenic radionuclides are now used astracers in such cycles and processes at various scales Forexample releases of 137Cs from Chernobyl in 1986 havebeen used to improve understanding of the migrationand attenuation processes of radionuclei in soils andmodels of atmospheric dispersion (NEA 2002)

Nuclear weaponsrsquo manufacture testing and accidentsAtmospheric and subsequently underground nuclearweaponsrsquo testing were carried out by the FSU Francethe UK and the US throughout the cold war until theearly 1990s The health impact of nuclear weaponstesting has been estimated to have resulted in 80 000additional cases of cancer (25 fatality rate) amongstpeople who lived or were born in North Americabetween 1951 and 2000 alone (CDC 2001 IEER2002) Large-scale radioactive contamination is alsoassociated with nuclear weaponsrsquo production (Siegeland Bryan 2004) One of the most extensive areas ofradioactive contamination known is associated withthe Chelyabinsk-65 complex for nuclear weaponsproduction near Kyshtym Russia Between 1948 and1992 over 5middot5 x 1019 Bq of radioactive waste wasproduced from the Mayak facility there More than4middot6 x 1018 Bq of long-lived radioactive isotopes weredischarged into lakes and other surface storage siteswhile between 1950 and 1951 other wastes weredischarged directly into the Techa river By 1993 gt 4 Mm3

of ground water had been contaminated by long-livedfission products from the lake Several nucleardisasters have also been associated with the plant In

1957 for example the explosion of a storage flask forhigh level waste released 7middot4 x 1017 Bq of radioactivityinto the atmosphere (Medvedev 1979)

The best-known nuclear accident was at Chernobylin the Ukraine in 1986 when 137Cs (8middot5 x 1016 Bq) 131I(1middot76 x 1018 Bq) and 133Xe (6middot5 x 1018 Bq) were releasedinto the environment the total amount of Pu(isotopes 238 239 240 and 241) released was around 6x 1015 Bq (NEA 2002) Emissions of 137Cs from theaccident account for almost 10 of the totalradioactivity emitted to the environment as a result ofnuclear weaponsrsquo testing The nuclides were emitted asgases aerosols and fuel element particles The mobilecomponents adhered rapidly to atmospheric particleswith a bimodal size distribution of around 1middot5 and 10-micron activity median aerodynamic diameter (AMAD)(NEA 2002)

These releases were significantly greater than thoseassociated with earlier nuclear accidents They werefor example about 1000-times greater than thoseemitted during the 1958 Windscale fires and about amillion times the levels released during the Three MileIsland incident in the US in 1979 They arenevertheless significantly less than 1 of the totalamount of radioactivity released during the period ofuse and atmospheric testing of nuclear weaponsbetween 1945 to the present day (NEA 2002UNSCEAR 2000) After almost 20 years the impactsof the Chernobyl incident and nuclear weaponstesting are still measurable in the UK (see Plate 6)although levels of airborne 137Cs and in rainwater arenow below analytical detection limits (Defra 2001)

The trans-boundary nature of contamination byanthropogenic radionuclides has led to significantimprovements in standardising methods for their measure-ment in environmental samples and the establishment ofinternational monitoring frameworks For example theEuropean Union Radiological Data Exchange Platform(EURDEP) Radioactivity Environmental Monitoring(REM) project and the Urgent Radiological InformationExchange (ECURIE) have been established in Europe toensure rapid early warning of nuclear accidents

Following the events of 11 September 2001 there isincreasing concern about the potential use of lsquodirtybombsrsquo whereby radioactive material is releaseddeliberately into a centre of population by terroristsMonitoring the impact of such events will requirehigh-resolution methods The Goiania incident inBrazil (IAEA 1998) provides an example of asituation where the decontamination of people andtheir properties required the establishment of detailedmonitoring networks

Increasingly a wide variety of industrial researchand home products including medical diagnosticequipment (60Co 137Cs and 99mTc) industrial thick-ness gauges (60Co) smoke alarms (241Am) andtelephones (3H) use man-made radioactive isotopesMonitoring the environmental fate of these and otheranthropogenic radionuclides in the environmentrequires detailed remotely sensed data and airborneradiometric monitoring coupled with integratedinformation management systems



3 Yield of radioisotopes produced by nuclear fission(Crouch 1958)

Nuclear wasteInventories of nuclear reactor high-level waste (HLW)generally include spent fuel and the products of thereprocessing of such materials Initially the hazardfrom such material is mainly from short-livedradionuclides such as 137Cs and 90Sr whereas between103 and 105 years most of the hazard is due to thedecay of 241Am 243Am 239Pu 240Pu and 237Np After 105

years the isotopes 99Tc 210Pb and 226Ra dominate thesmall amount of remaining radioactivity The toxicity(hazard) of such spent fuel is about the same as orecontaining 0middot2 U equivalent to naturally occurringrelatively low-grade U-ore deposits (Siegel and Bryan2004) It has been argued (Oxburgh 2002) that therisk of an adverse health impact from ionisingradiation from a properly constructed nuclear wasterepository would be less than the increase involved inmoving from Dorset where the natural backgroundradioactivity is low to live in Cornwall where it isexceptionally high as a result of mineralised granitesand their historical working

Persistent organic pollutants (POPs)Persistent organic pollutants (POPs) include tens ofthousands of chemicals such as polychlorinated biphenyls(PCBs) that have primarily industrial applications otherssuch as organochlorines and organophosphates used asbiocides in agriculture (Ragnarsdottir 2000) and dioxinsand furans which are the unintentional by-products ofindustrial operations or energy generation Huge amountsof such synthetic chemicals have been introduced into theenvironment over the last hundred years Many have notbeen tested for even the most basic indications of hazardto the environment or human health (Fig 4) and currentmonitoring of their distribution and impact on theenvironment is quite inadequate (RCEP 2003) Indeedthe present status of our knowledge of these chemicals wassummed up by the Royal Commission as ignorancelsquooutweighing knowledge at every stage of assessing andevaluating synthetic chemicalsrsquo(RCEP 2003)

Several organisations have developed criteria toidentify the POPs of greatest concern The UKrsquosChemicals Stakeholder Forum criteria for persistencebioaccumulation and toxicity are shown in Table 7 Theapproximately 100 chemicals of concern identified byscreening the IUCLID database using these criteria arenow available on the Chemical Stakeholder Forum

website lthttpwwwdefragovukenvironmentchemicalscsfconcernindexhtmgt hosted by Defra

Some chemicals bio-accumulate by mechanisms notcovered by these criteria For example PFOS binds toblood proteins rather than accumulating in body fat Thissubstance which can be used to protect textiles and leatheragainst water damage in fire-fighting foams and to treatpaper containers for fast foods has been detected inhuman blood and breast milk (Kubwabo et al 2004Olsen et al 2003 Olsen et al 2004) It is associated withcancer especially of the bladder The current regulatoryapproach to the management of synthetic organicchemicals is based almost entirely on a risk assessmentapproach as described in Table 8

In practice risk assessment for both the aquatic andterrestrial environment usually involves calculation ofthe predicted exposure concentration (PEC) and thepredicted no-effect concentration (PNEC) and theirratio PECsoilPNECsoil on the basis of toxicity data foraquatic or soil organisms or alternative equally simplecalculations for higher animals including humans Fewdata are available on the hazards or distribution in theenvironment of most of the 30 000 synthetic industrialchemicals which include many persistent organicpollutants estimated to be on the market in Europe (Fig4) Moreover regulatory monitoring is presently basedmainly on water sampling which is likely to under-



4 Relationship between industrial POPs on the marketand their risk assessment in risk management (EEAUNEP 2002)

Table 7 The Stakeholder Forum first tier criteria for chemicals of greatest or high concern

Criterion First tier thresholds

Persistence (P) t12 water gt 2 months OR soilsediment gt 6 monthsBioaccumulation (B) log Kow gt 5 unless BCF lt 5000 (greatest concern)

log Kow gt 4 unless BCF lt 500 (high concern)Toxicity (T) L(E)C50 lt 1 mg lndash1 OR NOEC lt 0middot1 lndash1

vP and vB (No T) Substance of concern but less so than PBTsSafety net Expert judgement from the ACHS on a case-by-case basis for substances of equivalent concern

t12 is the half-life of the chemical in water soil or sedimentlog Kow is the partition coefficient between octanol and water that relates to the solubility in fatsThe bioconcentration factor (BCF) is the accumulation of a chemical in the tissue of an organismL(E)C50 is the concentration that is lethal for 50 of the population exposedNOEC no observable effect concentration is the highest concentration of the chemical at which no effects are identifiedACHS 2003

estimate seriously levels of these substances in theenvironment Some POPs are likely to partition to thesolid phase while others are dispersed via the air Becauseof the cycling of these compounds between environ-mental compartments it can be difficult to distinguishbetween their sources and sinks (Vallack et al 1998)

Current regulatory approaches based on riskassessment have failed to anticipate some of thedeleterious effects of chemicals For example theimpact of organochlorine pesticides on birds (Carson1962 Hickey and Anderson 1968 Edwards 1973Ratcliffe 1980 Newton and Haas 1984) and mammalpopulations (Chanin and Jeffries 1978) humansickness and deaths from the use of organophosphatepesticides (Stine and Brown 1996 Ragnarsdottir2000) the adverse effects of PCBs on the health ofhumans and ecosystems (Stringer and Johnston 2001Harrington and Macdonald 2002) the uptake andbio-accumulation of polybrominated diphenyl ethers(PBDEs) used as flame retardants and the endocrinedisrupting effects of the biocide tributyltin (TBT) andmany other POPs were not predicted

Serious chemical accidents involving POPs have alsooccurred For example in 1986 a fire in a chemicalwarehouse caused 11 pesticides to enter the Rhine in largequantities near Basel at the border of SwitzerlandGermany and France (UNEP 2002) The organo-phosphate (OP) ester pesticides included disulfotonthiometon propetamphos ethylparathion etrimfos andfenitrothion Measurements of dissolved OPs allowed theplume to be followed over 700 km to the North Sea Theaccident demonstrated that large quantities of OPs can betransported by a major river with limited degradation byphotolysis hydrolysis or biodegradation This hampersaccurate modelling of the fate of the other OPs whichenter the Rhine (Ragnarsdottir 2000) Other seriouschemical accidents have included a leak of poisonousmethylisocyanate gas from a pesticide plant in BhopalIndia in 1984 and explosions at chemical plants at SevesoItaly in 1976 and Flixborough UK in 1974

Endocrine-disrupting POPsMany POPs have endocrine-disrupting properties andare known to have carcinogenic reprotoxic orneurotoxic effects on living organisms They includesuch compounds as alkylphenols (APs) alkylphenolpolyethoxylates (APEOs) polyaromatic hydrocarbons(PAHs) polychlorinated biphenyls (PCBs) phthalates

bisphenol-A (BPA) polybrominated flame retardants(PBDEs) dioxins furans many pesticides and steroidhormones such as synthetic oestrogens used in thefemale contraceptive pill and hormone replacementtherapy (Arcand-Hoy et al 1998) Natural oestrogensand Pb and Cd have also been found to have endocrine-disrupting properties (Birkett and Lester 2002EEAUNEP 1999 Plant and Davis 2003) As ourknowledge of endocrine disruption increases so does thelist of chemicals shown to have such properties

Many EDCs have been found to be ubiquitous inthe environment (Birkett and Lester 2002) Sourcesinclude discharges from sewage treatment works farmeffluents landfill leachates drainage from agriculturalland urban sources and rainfall Some of the mostimportant pathways of EDCs to humans are via foodand drink including from chemicals used in plasticpackaging and can linings Some of the mostimportant groups of such chemicals of concern areconsidered briefly below

Natural and synthetic steroidsA report by the Food and Agricultural OrganizationndashWorld Health Organization Joint Expert Committee onFood Additives (JECFA 1988) found that levels ofoestradiol oestrone progesterone and testosterone inanimal tissue were all significantly increased (at least 2-fold) in steroid-treated cattle compared with untreatedherds In Europe the use of such steroids in meatproduction has been banned since 1989 Intensivefarming practises also produce appreciable con-centrations of oestrogens and significant concentrationsof steroid hormones (eg oestradiol oestroneprogesterone testosterone) have also been found inuntreated fish poultry eggs pork cheese milk and milkproducts (Hartmann et al 1998) These authors foundthat milk products supply 60ndash80 of ingested female sexsteroids the remaining 20 being derived from otheranimal products such as meat fish and eggs Theconcentration of oestradiol in run-off and in the soilfrom land fertilised with chicken litter has beenmeasured and demonstrates sizeable lsquoedge of fieldrsquo losses(Finlay-Moore et al 2000) A study of effluent con-centrations (Shore et al 1993) detected high concent-rations of oestrogens from agricultural settlementsThese are low compared to levels assumed to beproduced by the body For example human steroid pro-duction has been suggested to far exceed the uptake from



Table 8 The four elements of current risk assessment

Hazard identification The identification of the inherent capacity of a chemical to cause adverse effects without regard to the likelihood or severity of such effects

Hazard characterisation Following exposure to a chemical the quantitative evaluation of the nature of adverse effectsincluding assessment of toxic potency (the relative toxicity of a chemical) and where possible a dose-response assessment

Exposure assessment The quantitative evaluation of the likely exposure of the environment and via the environment humans to a chemical

Risk characterisation The quantitative estimation of the probability that an adverse effect will occur and of its severity and duration in a given population under defined exposure conditions based on the three previous elements

The first two elements comprise the hazard assessmentRCEP 2003

food with levels of progesterone 20 times higher thanintake in some children with oestradiol and testosteroneproduction levels 1000 times higher (Hartmann et al1998) The extent to which this reflects bio-accumulationfrom steroids in food has not been determined however

Natural and synthetic steroid oestrogens arepresent in sewage effluent and receiving waters at farlower concentrations than industrial chemicals(Garcia-Reyero et al 2001) However their potency isgenerally three orders of magnitude higher than mostother EDCs (Christiansen and Korsgaard 1998Miyamoto and Klein 1998) For example effluentfrom a Swedish sewage treatment works of predomin-ately domestic sources identified 17α-ethinyl-oestradiol (EE2) from the female contraceptive pilland hormone replacement therapy (HRT) at levels 45times higher than that shown to be oestrogenic to fish(Larsson et al 1999) EE2 has been shown to inducevitellogin production in male rainbow trout at levelsas low as 0middot1 ng lndash1 (Purdom et al 1994) The growthand development of testes in maturing male trout hasbeen shown to be retarded by 50 due to a single doseof EE2 at 2 ng lndash1 (Jobling et al 1996) resulting in sexreversal in fish more generally (Martin-Robichaud etal 1994)

Bisphenol-A (BPA)Industrial chemicals with endocrine-disruptingproperties include bisphenol-A (BPA) which ismanufactured in large quantities for the plasticsindustry and for flame retardants (Fromme et al2002) It is used widely in households and industryand is present in raw sewage waste-water effluentsand in sewage sludge (Furhacker et al 2000) Underthe US Toxic Substances Control Act (TSCA) theenvironmental concentrations in treated effluent mustnot exceed 0middot1 mg lndash1 (Dorn et al 1987) Reproductiveeffects including inhibition of spermatogenesis havebeen observed on fathead minnow (Pimephalespromelas) (Sohoni et al 2001) Although levels ofBPA in surface water are usually one to several ordersof magnitude lower than those causing effects in testorganisms (Staples et al 1998) and the potential forbio-accumulation in aquatic organisms is low (Guumlldenet al 1998) the risk associated with sediment soiland food is likely to be much greater

PhthalatesPhthalates have been used for more than 40 years inthe manufacture of PVC and other resins asplasticisers and in insect repellents (Fromme et al2002) Di-(2-ethylhexyl)-phthalate (DEHP) which isof greatest concern has been detected in surfacewaters sewage effluents sewage sludge and sediments(Watanabe et al 1987) The toxicity to aquaticorganisms increases with increasing alkyl chain lengthbecause of a corresponding increase in log Kow anddecreasing solubility (Call et al 2001) CalculatedPNECs for some of these substances suggest they areof concern for aquatic organisms and benthic species(Staples et al 2000) New evidence indicates thatlevels of phthalate metabolites in human maternal

blood correlate with indices of feminisation in theirhuman male babies (Swan et al in press)

DioxinsDioxins polychlorinated dibenzodioxins (PCDDs)and polychlorinated dibenzofurans (PCDFs) are nolonger produced commercially but are by-products ofvarious industrial and combustion processesincluding the incineration of wastes and fossil andbiomass hydrocarbon fuels (Vallack et al 1998)Dioxin exposure to humans is mainly from foodespecially animal fats from dairy products beefpoultry pork and fish (especially farmed fish)although average daily intakes for Europeans andAmericans appear to be within the WHO recommendedvalues of 1ndash4 pg of International Toxicity Equivalents(I-TEQ) kgndash1 of body weight (Huwe 2002)

Tributyltin (TBT)Tributyltin (TBT) enters the environment mainly from itsuse as an anti-fouling biocide Evidence of the damagingeffect of tri-organotins on the reproduction and growthof various marine organisms has led many countries toregulate or ban their use leading to a considerabledecrease in concentrations in coastal and fresh water(Voulvoulis et al 1999) Several studies indicatehowever that contamination of sediments by organotincompounds is still wide-spread with ecotoxicologicalconsequences (Chau et al 1997) Tributyltin is one ofthe best examples of severe effects on wildlife at thepopulation level (Van der Kraak 1998) Both lethal andsub-lethal effects have been observed in biota includingseverely retarded larval development masculinisation offemale (imposex) behavioural changes and shelldeformation in oysters (Oehlmann et al 1995) In someareas TBT exposure has resulted in sterility leading tospecies extinction (Minchin et al 1996) Imposex hasbeen determined at levels of 3 ng lndash1 TBT and a no-effectconcentration (NOEC) has yet to be identified (Burtonand Scott 1992)

SurfactantsSurfactants are predominantly used in detergentsThose of most concern are the alkylphenols (AP) andtheir ethoxylates (APEO) particularly nonylphenol(NP)-containing compounds Direct sources ofhuman exposure include residues of NP and NPEOsin food as a result of the use of pesticides vegetableand fruit waxes detergents and disinfectants in foodmanufacturing and packaging (Environment Canada2000) A recent study has detected 4-nonylphenol in arange of foodstuffs including human breast milk(Guenther et al 2002) Cosmetic products can also bedirect sources of exposure for humans Alsononoxynolndash9 (NP9EO) is used as a spermicide incontraceptive products (Environment Canada 2000)Surfactants are more toxic to aquatic organisms thanmammals (Fent 1995) A recent survey of wild roachin UK rivers found a high percentage of males witheggs in their testes and female egg yolk in their bloodattributed to exposure to such surfactants (Jobling etal 1998)



Polycyclic aromatic hydrocarbons (PAHs)Polycyclic aromatic hydrocarbons (PAHs) are formedfrom both natural and anthropogenic sources largely bythe incomplete combustion of organic matter Naturalsources of PAHs include forest fires volcanic activity andthe release of petroleum hydrocarbons by marine seepsThe principal sources of anthropogenic PAHs are thecombustion of fossil and biomass fuels stubble burningaluminium smelting refuse burning coke ovenspetroleum processing and vehicle emissions (Baek et al1991) Other sources include sewage sewage sludgecigarette smoke gas leakage and fuel spills and leakage(Bedding et al 1995) PAHs in sediment are available toboth benthic and demersal aquatic organisms (Landrumet al 1991 Munkittrick et al 1995) with the direct intakeof particulates contributing a significant proportion ofuptake (Woodhead et al 1999)

Polychlorinated biphenyls (PCBs)In the past polychlorinated biphenyls (PCBs) havebeen used in a wide variety of industrial applicationsbecause of their high stability and electrical resistance(Stangroom et al 1998) Although PCB productionhas been banned in most countries since the 1980s itis estimated that over 1 Mt of PCBs have beenmanufactured (Stangroom et al 1998) with aboutone-third of this quantity already in the environment(Jones et al 1991 Vallack et al 1998) PCBs haveaccumulated in food chains including in aquatic andmarine species because of their high biostability andlipophilicity (Brouwer et al 1998) Thus sources ofhuman exposure to PCBs are generally from foodparticularly animal fats especially meat and dairyproducts fish and fish products In water highlychlorinated PCBs are dominant (Tyler and Millward1996) PCBs exhibit a high affinity for total organiccarbon (TOC) which also influences their bio-availability (Ferraro et al 1990) Biomagnificationhas been demonstrated in the marine food chain withincreasing total PCB concentrations correlating withincreasing trophic level (Borga et al 2001)

Polybrominated diphenyl ethers (PBDEs)Flame retardants especially brominated compounds(PBDEs) have been used in plastics textiles electroniccircuitry and other materials (de Wit 2000) Thesesubstances are persistent lipophilic have been shownto bio-accumulate (de Wit 2002) and are used world-wide in vast quantities (Darnerud et al 2001) Sewagesludge concentrations of PBDEs reflect householdindustrial traffic and other non-point sources(Sellstrom 1999) All the brominated flame retardants(including PBDE HBCD TBBPA) have beenreported in sewage sludge samples (Sellstrom 1999)Directive 200311EC of the European Parliamentincreases the restrictions on the marketing and use ofseveral potentially hazardous substances includingPBDEs and octabromodiphenylether (OBDE)

PesticidesSeveral very persistent pesticides including organo-chlorines synthetic pyrethroids organophosphates

carbonates chlorophenoxy herbicides and triazines arealso known to exhibit endocrine disrupting properties(Bulger et al 1978 Ireland et al 1980 Bedding et al1982 Bulger and Kupfer 1983) An estimated 2middot4 Mt ofpesticides per annum are used world-wide (US EPA2004) and are absorbed by plants (Vallack et al 1998)before bio-accumulating in meat and dairy productsPesticide residues especially in animal fat are animportant source of exposure to humans andorganochlorine pesticide residues have been found inhuman fat and breast-milk (Harris et al 2001) Thereis much evidence linking organochlorine insecticideexposure to endocrine disrupting effects on wild-lifeincluding thinning of eggshells damage to the malereproductive system and behavioural changes such assame sex nesting (Colburn 1995 LeBlanc 1995)Resistant lipophilic pesticides that do not bind to thesoil enter watercourses and can accumulate in theaquatic food chain

PharmaceuticalsPharmaceuticals including human veterinary andrecreational drugs are a highly variable group of organiccompounds with the potential to cause harm toecosystems and humans They receive considerablepharmacological and clinical testing during develop-ment but knowledge of their ecotoxicity is generallypoor Thousands of tons of pharmacologically activesubstances are used annually but surprisingly little isknown about their fate in the environment A largeproportion of an administered dose (up to 90) may beexcreted unchanged while metabolites can be convertedback to the active compound by bacterial action (Joneset al 2001) In addition many unused medicines aredisposed of into the sewage system so that much urbansewage is contaminated with pharmaceuticals Recentstudies have demonstrated that there is incompleteelimination of many pharmaceuticals during sewagetreatment and concentrations in the high nanogram tolow microgram per litre range have been found insurface water groundwater and marine systems(Ayscough et al 2000) Drugs can accumulate in land-fills posing a threat to surface and groundwater (Ahel etal 1998) Moreover the continual introduction ofdrugs through sewage effluents may have significantimpacts on exposed aquatic organisms (Daughton andTernes 1999) One of the problems is that conventionalsewage treatment technologies vary greatly in theirability to remove drug residues (Heberer et al 2002Reinhard et al 2003 Snyder et al 2003) and in someinstances have even been shown to increase thebioactivity of the pharmaceutical residues (Jones et al2003) Activated carbon filtration which is used bysome states in the US continues to be one of the mosteffective known methods of removing drug and othercontaminant residues from drinking water (Ternes et al2002 Boyd et al 2003 Petrovic et al 2003)

Drugs are used to affect biochemical processes inhumans or veterinary animals and exposure of otherspecies to them may have adverse or even fatal effects(Rand 1995) Moreover the use of pharmaceuticals isexpected to increase following the completion of the



human genome project and because of the increasingage of the population One major concern is thatantibiotics found in sewage effluent may cause increasedresistance amongst natural bacterial populations andthe increase in the number of bacterial strains resistantto multiple antibiotics has been attributed by severalauthors to the increase in discharges of antibiotics towaste-water (Willis 2000) Guidelines for testingenvironmental impacts of new pharmaceuticals havebeen introduced in the US and a draft environmentalrisk assessment for new pharmaceuticals has beenprepared for the EU The issue is complicated by the factthat mixtures of only a few compounds have beenshown to affect ecosystems in laboratory-scale studiesThe tolerance of organisms will depend however on theduration of exposure to chemical (and non-chemical)stresses which could behave synergistically Hence riskassessments should take account of the possiblecumulative effects of pharmaceuticals or they are likelyto lead to a significant underestimation of risks (Jones etal 2002b)

GEOCHEMICAL AND RADIOMETRICSURVEYS TO SUSTAIN THE EARTHrsquoSLIFE-SUPPORT SYSTEMS

Geochemical surveysAs concern about the environment has increasedemphasis has been placed by national governmentsinternational agencies and development banks onstudies concerned with such issues as the quality ofwater resources waste and pollution related tohistorical mining industrialisation or urbanisationand soil degradation Such studies make an importantcontribution to applied environmental research byimproving understanding of the chemical processesoperating at the Earthrsquos surface The limitation ofthese types of studies is that they tend to investigateonly one specific medium groundwater studies inparticular tend to be carried out in isolation fromthose of surface water stream sediment or soil Thereis also a tendency to study one or two chemicalelements in detail rather than an extensive range of

elements species or compounds Moreover there arefew systematic studies of the approximately 30 000synthetic industrial organic chemicals estimated to beon the market or of pharmaceuticals Hence suchstudies fail to provide a complete picture of thepotential cocktail of chemicals to which ecosystemsand humans are exposed or information oninteractions between chemical species in differentenvironmental compartments Methods of samplinganalysis and data interpretation also vary greatly(Plant et al 1996 1997) Moreover such studies aregenerally published in the journals of learned societiesand are communicated mainly to other experts in thesame field with relatively little impact on society as awhole A quite different approach is needed if anysubstantial impact is to be made on global environ-ment problems related to chemicals these need to beat the strategic level rather than in the usual presentpost hoc lsquofire-fightingrsquo mode

In most industrialised Western countries geologicalsurvey organisations now provide strategic informationon the chemistry of the Earthrsquos land surface Initiallygeochemical surveys based on rapid low-cost analysisof easily collected surface samples (Hawkes and Webb1962 Rose et al 1979) were carried out to explore formetalliferrous mineral deposits (Plant and Hale1995) Relatively little emphasis was placed onstandardising methods which were often based onorientation studies to optimise exploration forparticular types of target ore in different terrains(Darnley et al 1995 Plant and Hale 1995 Plant etal 1996 1997) More recently geochemical surveymethods have been greatly extended and refinedespecially for environmental applications (Plant et al2000) An increased range of sample media is beingstudied including stream sediments soil and surfaceand shallow groundwater samples Sampling isincreasingly carried out to rigorous internationallyagreed standards (Darnley et al 1995 Salminen etal 1998) with analysis based on state of the artsensitive high-precision methods (Sandstroumlm et al2003) Sophisticated methods of data processing andinterpretation are used including thermodynamicmodels and speciation codes and strict quality controland quality assurance procedures are maintainedthroughout all survey operations In this paper theBritish Geological Surveyrsquos Geochemical BaselineSurvey of the Environment Programme (G-Base) andthe extension of such work over Europe as part of theFOREGS Geochemical Baseline Programme are usedas examples of this new approach to studying chemicalsin the environment The principal features of the G-Baseprogramme in Britain are given in Table 9 Examples ofthe maps of Cu in stream sediments over the area ofBritain covered to date by the programme (and thelocation of the Humber Trent region) are shown inPlate 1 Maps for the Humber-Trent region showingthe distribution of Se and Sb in surface soils areshown in Plates 2 and 3

Such data provide excellent information on pHconductivity and the total concentrations of morethan 60 determinands and can be used to provide



Table 9 Geochemical Baseline Survey of the Environment (G-BASE) in Britain

Geochemical mapping for economic and environmental applications

High resolution 1 sample site per 1ndash2 km2

Multi-media Stream sediments and concentratesSurface stream waterssoils (2 or more horizons)

Multi-element 35 elements by XRFs(sediments and soils)14 elements by ICP-AES (now 24 elements by ICP-MS)Water + pH HCO3 conductivity DOC and a range of anions

Fully quality controlled

British Geological Survey

fundamental process information For example thedata on major ions can be shown as a percentage oftotal negative or positive charge ionic dominance asdescribed in Hem (1985) They can also berepresented as three colour component images basedon the diagrams developed by Piper (1944) to showvariations in the relative proportions of cations (Na+K+ Mg2+ and Ca2+) and anions (HCO3

ndash SO42ndash NO3

ndash

and Clndash) respectively In the UK such maps clearlyassociate high NO3

ndash concentrations with areas ofintensive agriculture areas of high acid precipitationwith low buffering capacity (low Ca2+ and low Mg2+

with high SO42ndash) and areas of acid mine drainage with

high SO42ndash and Clndash in areas of former coal working

(BGS 1999) Critical load maps can be prepared usingmodels and displayed in a similar way as can mapsshowing the degree of calcite or gypsum solubilitybased on their solubility diagrams Moreover sincethe surface waters studied have low ionic strength(interquartile range of ionic strength from 0middot001 to0middot1007 M with a maximum of 0middot146 M) geochemicalspeciation codes such as PHREEQ and WATEQ can beapplied for example in modelling the bioavailability ofPHEs such as Pb (Smith et al 1998b)

The variety of media sampled the wide range ofelements and species analysed and the high sampledensity used provide a better means of assessing overallenvironmental quality than data normally collected byregulatory agencies for monitoring purposes Work byAppleton (1995b) and Breward (2003) for example hasshown the value of soil and sediment data in identifyingareas of Cu Pb Zn As Cd and Sn contamination whichwould otherwise have gone unidentified especially bythe use of methods based on records of historical landuse Such data can also be used to calculate the relativecontribution to the surface environment of natural andman-made sources of these chemical elements

Recently statistical methods have been used tooptimise soil field sampling patterns and to estimateuncertainty due to sampling and chemical analysis andto assist in assessing the risk of soil contamination(Fergusson and Stewart 1992 Ramsey and Argyraki1997 Goovaerts 1997)

Distinguishing contamination from the naturalbackground of chemicals has become increasinglyimportant Previously this has been done for exampleby collecting different horizons in soil profiles andstatistical analysis (Selinus and Esbensen 1995) Thesemethods are based on relating a proportion of apollutant measured in soil with that of the samecontaminant in the parent material and attributing thedifference to anthropogenic sources This approach failshowever to identify specific sources of pollutants andallows only a qualitative interpretation of the resultsmoreover the results cannot be applied where nobaseline data are available Recently methodologiescombining traditional statistics and geostatistics withmodern spatial data analysis techniques and geographicinformation systems (GIS) have been used to distinguishbetween anthropogenic emissions and natural levels ofchemical elements for sites with complex geologicalbackgrounds and poorly recorded mining histories

(Korre 1999ab) and to quantify and map different soilcontamination sources and to distinguish them fromnatural sources (Korre and Durucan 1999)

Radiometric surveysHigh-resolution airborne radiometric surveys such asthe Hi-Res survey recently carried out by the BGSover northern England (Lahti and Jones 2003 Peartet al 2003) provide detailed comprehensive data onthe distribution of the naturally occurring radio-elements eU Th and K and other radioactive sub-stances The data on eU is particularly valuable foridentifying radon-affected areas requiring specialbuilding regulations or the modification of existingbuildings (Plate 4)

The distribution of 137Cs from the Chernobyl accidentin 1986 can also be mapped (Plate 6) as well as otherareas of radioactive contamination from differentsources As in the case of geochemical data radiometricdata can be plotted in various ways to identify particularenvironment problems (Plate 5) The airborne platformcan also be used to collect other data such as electricalconductivity which provides an excellent non-invasivemethod of obtaining information on the distribution ofpollution plumes from land-fill sites (Beamish 2003)some of the sites identified have been proved by drilling(Klinck et al 2004)

High-quality modern regional geochemical andairborne radiometric data especially when used incombination provide a highly effective method ofmapping and modelling a wide range of environmentalproblems in real time Where such data for inorganicand radioactive chemicals are available they can be usedto predict avoid and mitigate a whole range of problemscaused by such chemicals in the environment Moreoveroutputs can be represented analysed modelled andvisualised in clear attractive graphical displays usingGIS to assist policy makers regulators and the generalpublic to understand problems in context and to agreeappropriate action

Persistent organic pollutants (POPs)Although issues of environmental pollution by POPshave been attracting increasing attention world-widethere are few systematic data available on theirdistribution for modelling or monitoring Problems ofthe long-range transport and accumulation in theenvironment and the impact of these chemicals onhuman health are being studied within the frameworkof many international programs such as those ofOSPAR (Oslo and Paris Convention) WHO andUNEP These fail however to address the need tomap and monitor levels of these pollutantssystematically Once introduced into the environmentperhaps intentionally as an agrochemical or unin-tentionally as a by-product of combustion many suchchemicals or their metabolites remain in the environ-ment for years sometimes decades Because of theirslow degradation and their low solubility in water thisleads to their high bioaccumulation in soils sedimentsand subsequently the fatty tissues of land animals andfish



Dioxins and related compounds have recently beenthe subject of a consultation paper from theDepartment for the Environment and Rural Affairs(Defra) in the UK They have also been the focus ofan EU study aimed at compiling relevant data frommember states (DETR 1999) which highlighted theproblems arising from the lack of standardised dataover Europe Other European studies also focusmainly on dioxins and PCBs (Federal Ministry for theEnvironment 2000 European Commission 2004)The disparity between the availability of data on evenpersistent synthetic organic chemicals such as PAHsand inorganic chemicals is highlighted using the UKas an example in Figures 5 and 6

The (UNEP) Stockholm Convention on POPs willinitially monitor and reduce levels of 12 chemicals DDTaldrin dieldrin endrin chlordane heptachlor hexa-chlorobenzene mirex toxaphene PCBs dioxins andfurans that are persistent widespread and toxic (Ritter etal 1995) although DDT properly used is of value incontrolling malaria The convention ratified by 50countries also has a mandate to reduce the levels of othersuch compounds in the environment as research becomesavailable This information will be generated by the GlobalMonitoring Programme (GMP) and the Regional BasedAssessment of Persistent Toxic Substances (RBAPTS)These surveys aim to co-ordinate the various regional andnational monitoring studies in order to produce more



5 Surveys of PAH concentrations in UK soils (Smith et al 2002) National surveys are available only for Waleswith limited local studies of urban areas

6 Surveys of inorganic substances in UK sediments (Smith et al 2002) Extensive national coverage is available forinorganic substances for England and Wales and Northern Ireland in the Wolfson Atlas regionally for much ofBritain and Northern Ireland as a result of the BGS G-BASE programme and locally as a result of the BGSMineral Reconnaissance Programme

accurate and representative data but to date no attempthas been made to use available sample archives The treatyalso encourages member nations to reduce or prohibit theproduction of these compounds in addition to carefullycontrolling their use and the disposal of any stockpiles

PharmaceuticalsThe occurrence of pharmaceuticals in the environmentand the extent to which they pose a risk to the environ-ment and humankind has been investigated only since theearly 1990s and there are still few systematic data available

An initial risk assessment for the UK of more than 60compounds thought to account for more than half of theknown tonnage of pharmaceutical consumption(Ayscough et al 2000) suggested that the substances ofmost concern were paracetamolacetaminophen aspirinand dextropropoxyphene (pain killers) fluoxetine(antidepressant) oxytetracycline (antibiotic) propranolol(for heart disease and migraine) aminotriptyline (forneuralgia) and thioridazine (for adult schizophrenia)

Recently the United States Geological Survey carriedout the first nation-wide reconnaissance of the occurrenceof pharmaceuticals hormones and other organiccontaminants in water (Kolpin et al 2002) The mostfrequently detected compounds were coprostanol (faecalsteroid) cholesterol (plant and animal steroid) NN-diethyltoluamide (insect repellent) caffeine (stimulant)triclosan (disinfectant) tri(2-chloroethyl) phosphate (fireretardant) and 4-nonylphenol (detergent breakdownproduct) Samples commonly contained more than onecontaminant and there were as many as 38 substances insome samples Little is known about the potentialinteractive effects that occur from such complex mixtures

and their breakdown products and their overall effect onhuman health and the environment (Halling-Sorensen etal 1998 Webb 2001)

Other monitoring programmes in Europe such as theEuropean Union Poseidon Project and others of a smallerscale (Boxall et al 2002 Hilton et al 2003) and similarstudies in the Americas (Brownawell and Iden andRoberts and Bouwer both in progress) have detected pain-killers cholesterol regulators antiseptics chemotherapyagents antibiotics and hormones in water

GLOBAL GEOCHEMICAL BASELINESExtending modern systematic geochemical surveyssuch as those conducted by the BGS and other nationalgeological surveys over the Earthrsquos land surface wouldclearly provide one of the most effective methods ofaddressing environmental concerns caused by chemicalsworld-wide Standardised sampling and analyticalprocedures are required for such an exercise Theconcept of internationally standardised geochemicalmapping procedures originated in the 1970s under theauspices of the International Atomic Energy Agencyspecifically for U (IAEA 1973 1976) In 1988 formalsupport was obtained from the IUGSUNESCOInternational Geological Correlation Programme(IGCP) to determine the status of geochemical mappingthroughout the world and to develop recommendationsfor providing data showing the geochemical diversity ofthe Earthrsquos land surface This effort has evolved into thepresent Task Group on Global Geochemical Baselinesunder the auspices of the IUGS and the IAGC (Darnleyet al 1995 Plant et al 2000) Table 10 shows the three



Table 10 Main phases of the Global Geochemical Baselines Task Group

Phase I (1988ndash1992) IGCP 259 International Geochemical MappingAssessment of requirements and methods for global geochemical mapping involving international working group of expertsRecommendations published in A global geochemical database for environmental and resource management (Darnley et al 1995)

Phase II (1992ndash1997) IGCP 360 Global Geochemical BaselinesEstablishment of world-wide network of professional geochemistsDevelopment of a set of methods for GRN samplingPublication of detailed Field Sampling Manual (Salminen et al 1998)

Phase III IUGSIAGC Working Group on Global Geochemical BaselinesCompletion of collection of the GRN samplesIncreased standardisation of all geochemical survey methods world-wide

Plant et al 2000

Table 11 Present organisational structure of the Task Group on Global Geochemical Baselines

Steering committeeHonorary President A G Darnley CanadaCo-leaders J A Plant British Geological Survey (BGS)

D Smith United States Geological SurveyScientific Secretary Shaun Reeder BGSTreasurer A Demetriades IGME Greece

Leaders of Project CommitteesAnalytical G Hall Geological Survey of CanadaSampling and Regional Co-ordination R Salminen GTK FinlandPublic Relations and Finance A Demetriades IGME Greece

Website lthttpwwwbgsacukbgsw3arggiugsiugshomehtmgtPlant et al 2000



Plate 1 Geochemical image of Cu in stream sediments prepared by the BGS G-BASE programme The distributionof copper in stream sediments over Scotland Wales Northern Ireland and Central England the highest levelsshown in red reflect particular types of bedrock such as basalt mineralisation or contamination Low levels occurmainly over crystalline metamorphic rocks of northern Scotland

Table 12 Summary of requirements for a global geochemical database

bull Commonly available representative sample media collected in a standardised manner

bull Continuity of data across different types of landscape

bull Adequate quantities of the designed sample media for future reference and research requirements

bull Analytical data for all elements of environmental or economic significance

bull Lowest possible detection limits for all elements

bull Determination of the total amount of each element present

bull Tight quality control at every stage of the process

Plant et al 2000

phases in the evolution of the Task Group and Table 11outlines the current organisational structure

The goal of the Task Group is to implement therecommendations from the IGCP 259 project asdetailed in Darnley et al 1995 The primary recom-mendation from this project was to establish a networkof geochemical reference samples for the land surface ofthe Earth based on a Global Reference Network (GRN)of approximately 5000 sample cells (available atlthttpwwwbgsacukiugsgt) The media sampled atsites within each cell would include stream or lakesediment soil floodplain sediment humus (if present)and surface water (if present) The resulting databasemust meet the requirements as summarised in Table 12and will serve multiple purposes

(i) Document the composition of a variety of surficialmaterials at sites evenly spaced over the landsurface of the Earth

(ii) Provide locally relevant standard referencematerials for use in the region collected

(iii) Provide reference points for levelling or normal-ising national geochemical data sets

(iv) Allow the preparation of a global geochemical atlasincluding in digital form available over the internet

(v) Provide an archive of samples on which additionalwork may be done

(vi) Provide sites for recurrent monitoring in thefuture to facilitate the recognition and quanti-fication of changes from either natural orhuman-induced processes



Plate 2 Geochemical image of Se in surface soils prepared by the BGS G-BASE programme The highest Se levelsoccur over the base metal mineralisation of the Derbyshire Peak the industrial areas of the Yorkshire coalfieldand around the edges of the Fens Geological boundaries from the BGS 1250 000 scale map series are shown inblack

Plate 3 Geochemical image of Sb in surface soils prepared by the BGS G-BASE programme The highest Sblevels are over the Carboniferous shales of East Staffordshire and West Derbyshire and contamination to thenorth of the Humber Estuary Geological boundaries from the BGS 1250 000 scale map series are shown in black

Over 120 countries have participated in the programmeto date The recommended sampling analytical anddata processing methods are described in a detailedsampling manual prepared by Salminen et al (1998)and an analytical manual by Sandstroumlm et al (2003)

A considerable amount of work on developinggeochemical baselines using the GRN methodology isbeing carried out in Southern Africa Colombia BrazilIndia Korea and other CCOP countries GRN-basedsampling has been completed for China parts of Russiaand in 26 European countries (Plant et al 1997Salminen et al 1998) Unfortunately to date nofunding has been obtained to determine even a limitedrange of synthetic organic chemicals or pharmaceuticalsin this programme

The FOREGS Geochemical Baseline MappingProgrammeThe FOREGS Geochemical Baseline MappingProgramme is described briefly as an example of stage2 of the IUGSIAGC Global Geochemical BaselineProgramme (Table 10) The FOREGS programme ledby Professor Reijo Salminen of the Geological Surveyof Finland was initiated following the preparation ofan inventory of systematic geochemical datasetsacross Europe which showed considerable variationin sampling and analytical methods used nationally(Plant et al 1996 1997) The new programme hasconducted multi-media sampling at approximately 850sites selected on the basis of the GRN in 26 Europeancountries An integrated GIS-based system of all



Plate 4 Equivalent uranium data from the BGS Hi-Res programme The distribution of high equivalent uraniumlevels (pink) indicates the high radon potential of the Derbyshire Peak District which is underlain byCarboniferous limestone The area covered by the survey is shown in the small inset map



Plate 5 The distribution of natural radioactivity over the East Midlands from the BGS Hi-Res programme Highlevels of equivalent uranium (blue) indicating high radon potential occur over the Carboniferous limestones of theDerbyshire Peak District the tributaries of the Trent that drain from it as well as over the Jurassic phosphaticlimestones of Northamptonshire High levels of potassium (red) occur over the Permian Sherwood Sandstone

Plate 6 Contamination from 137Cs from the BGS Hi-Res programme High levels of 137Cs reflect depositionfollowing the Chernobyl accident in 1986 and pollution from the Sellafield nuclear reprocessing plant

environmental samples collected during the programmeas a tool for decision makers is now available atlthttpwwwgsffipublforegsatlasmap_comparehtmlgt The resulting database also provides a baselineagainst which all national datasets can be levelled(Salminen et al 1998) All of the samples have beenarchived in the Geological Survey of the SlovakRepublic and are available for further study as the needarises They could also be used to determine some of the

more persistent organic chemicals if a source of fundingcould be found

The study area includes 26 European countriesincluding the Canary Islands and covers a total landarea of approximately 4middot45 Mkm2 Sampling wascarried out by the FOREGS Geological Surveys andassociated organisations between 1998 and November2001 Analyses were carried out between 1999 and2003 in nine Geological Survey laboratories with one



Plate 7 Geochemical image showing the distribution of As in water prepared by the FOREGS GeochemistryProgramme (Salminem et al 1998) Note the high levels of As over the volcanic regions of Italy the IberianPyrite Belt and Variscan Crystalline Massifs such as the Spanish Meseta and the Massif Central in France Highlevels over South East England and North West Europe may reflect pollution Low levels occur over thecrystalline rocks of the Fennoscandian Shield and Caledonian belt and over Alpine rocks including those ofGreece



Plate 8 Geochemical image showing the distribution of Se in water prepared by the FOREGS GeochemistryProgramme (Salminem et al 1998) The highest levels of selenium occur mainly over sedimentary basins ofIreland South East England Southern Spain and Portugal North West France Holland Germany Denmarkand Poland Levels are also high over the volcanic regions of Italy and over Southern Greece The lowest levelsoccur over the crystalline rocks of the Fennoscandian Shield and the Caledonides of Scotland Alpine rocks ofCentral Europe and Variscan Crystalline massifs including the Massif Central of France

Table 13 FOREGS samples analysis

Waters Humus Top and sub-soils Floodplain and stream sediments

Survey Method Survey Method Survey Method Survey Method

BGR ICP-MSICP-AES GSSR Sample preparation GSSR Sample preparation GSSR Sample preparationBGS IC NITG ICP-MS NITG GranulometryTOC GSSR TOCBGS DOC MAFI Hg BGR XRF BGS XRFNGU Hg GTK ICP-MS BRGM ICP-MS

PGI ARICP-AES GTKPGI ARICP-AESMAFI Hg MAFI Hg



Plate 9 Geochemical image showing the distribution of Ni in topsoil prepared by the FOREGS GeochemistryProgramme (Salminem et al 1998) One of the main regional changes in the levels of nickel occursapproximately along the Trans European Suture Zone (TESZ) that trends WNWndashESE across North WestEurope from Holland to Southern Poland The TESZ separates the rocks of the Fennoscandian Shield and EastEuropean Craton and their sedimentary cover from younger Variscan rocks to the South and West The highestNi values occur over Greece reflecting the presence of large ophiolite slabs in the Alpine rock sequence there andto a lesser extent over volcanic areas of Italy and the Canary Islands

laboratory performing particular determinations forall samples of a specific type (Table 13)

The distribution of chemical elements in all mediais presented on the world wide web as geochemicalmaps showing both interpolated baseline values usinga colour scale and the element concentrations ofindividual sampling points as superimposed circles ordots The exponential dot size function increases fromthe minimum value (or the detection limit) to the 98thpercentile of observed values Values higher than the98th percentile are represented by large shaded dots

The maps of the baseline concentration levels oftrace elements are first interpolated and smoothedonto a regular 64 x 64 km2 grid with values calculatedusing a moving weighted median based on a circularwindow with a radius of 300 km using a methoddescribed by Gustavsson et al (1997) The estimatedconcentration of each cell is the weighted median ofsample values and is shown by a graded colour scaleselected to represent the background distribution ofchemical elements based on percentiles

Examples of maps for the distribution of Se and Sbin water are shown in Plates 7 and 8 and of Ni intopsoil in Plate 9

Maps showing the distribution of U together witha preliminary interpretation are described in Plant etal (2003b) These data used together with plots fornormalised petrogenetic elements (spider diagrams)and chondrite normalised REEs clearly show that allthe areas of highest U concentration in soil andsediment across Europe are related to granitesemplaced during crustal extension No areas of highconcentration related to contamination from thenuclear industry have been identified to date

It is clear from the preliminary interpretation of theFOREGS geochemical data that the data and theirrepresentation in map form although of relatively lowresolution provide invaluable insight on thedistribution of chemicals at the European scale Alsomuch information can be determined by using variouscombinations or ratios of chemical elements and bystudying their concentrations in different media Theinfluence of bedrock geology glaciation andsuperficial deposits is the major control on thedistribution of many elements for example the REEsU K and Th in soils and stream sediments On theother hand the distribution of other substances suchas levels of NO3

ndash in water appear to reflectanthropogenic contamination and high NO3

ndash levelsclosely follow the distribution of areas of intensiveagriculture

Much more detailed analysis and modelling of thedata are required ideally using higher-resolutionnational data sets levelled using the new FOREGSbaseline data for chemicals in all of the differentmedia Kriging and multivariate statistical analysismethods including principal component and factoranalysis tools are being used in combination with GISanalysis Anthropogenic contamination will bedistinguished from geogenic variation using othermethods of statistical analysis including canonicalcorrelation (Korre and Durucan 1999) Further

interpretation and thermodynamic modelling of thedata for all chemical elements using data for otherdeterminands such as pH electrical conductivity andtotal organic content is also required and shouldprove to be of considerable economic environmentaland fundamental scientific significance for the area ofEurope covered by the FOREGS geochemicalbaseline survey This type of analysis is already beingcarried out for a selected number of base metals forrisk analysis purposes

CONCLUSIONS AND RECOMMENDATIONSPersistent organic pollutants such as certainorganochlorine pesticides and polychlorinatedbiphenyls and potentially harmful inorganic elementssuch as As Cd and Hg enter and accumulate indifferent compartments in the environment (eg watersoil sediment) Each of these compartments mayprovide a pathway whereby the substances could pose arisk to human animal and ecosystem health

Systematic information on levels of inorganicchemicals in the environment has been generated for afew countries by national geological surveys Thevalue of merging these national-scale geochemicaldata sets to develop international-scale data and mapsis frequently limited by a narrow focus on one samplemedium a tendency to study only one or two elementsrather than an extensive range of elements and bydifferent sampling and analytical protocolsSystematic data on the abundance and distribution ofsynthetic organic compounds in the environment atinternational scales are almost non-existent

Standardised geochemical baseline data for allinorganic radioactive and organic chemicals of concernshould be prepared to cover the land surface of theEarth Much more work is required on persistentorganic pollutants many of which have been emittedinto the environment only over the last 60 years Themethods used and the proposed data should be madeavailable to all countries via the world wide web Such adatabase would be of strategic importance in identifyingareas of high potential risk to human animal andecosystem health and would provide a basis formitigating any problems related to chemicals in theenvironment prior to the development of serious effectsfor example by optimising land use planning Such adatabase would empower all nations to participate inactively reducing the use and impact of chemicals whichpresently threaten the Earthrsquos life support system and itssustainability into the 21st century

ACKNOWLEDGEMENTSThanks are due to the following geochemists who haveled their national contribution to the FOREGS baselinegeochemistry programme M J Batista GeologicalSurvey of Portugal M Bidovec Geological Survey ofSlovenia A Demetriades Institute of Geology andMineral Exploration Greece W De Vos GeologicalSurvey of Belgium M Duris Czech Geological SurveyP Frizzo University of Padova Italy A Gilucis State



Geological Survey of Latvia V GregorauskieneGeological Survey of Lithuania J Halamic Institute ofGeology Croatia P Heitzmann Swiss NationalHydrological and Geological Survey G JordanGeological Survey of Hungary J Kivisilla GeologicalSurvey of Estonia G Klaver TNO-NITG TheNetherlands P Klein Geological Survey of Austria ALima University of Napoli II Federico Italy J LisPolish Geological Institute J Locutura GeologicalSurvey of Spain K Marsina Geological Survey ofSlovak Republic P J OrsquoConnor Geological Survey ofIreland S Aring Olsson Geological Survey of Sweden R-T Ottesen Geological Survey of Norway G SabatiniUniversity of Siena Italy R Salminen GeologicalSurvey of Finland I Salpeteur Geological Survey ofFrance H Sandstroumlm Geological Survey of FinlandU Siewers Federal Institute for Geosciences andNatural Resources A Steenfelt Geological Survey ofDenmark and Greenland T Tarvainen GeologicalSurvey of Finland and B de Vivo University of NapoliII Federico Italy

We also thank our colleagues Kevin Bonel forpreparing Table 1 Mick Lee for providing Plates 4 5 and6 Chris Johnson and Neil Breward for preparing Plates 12 and 3 John Garrod for helping with Table 7 and JaanaPakkanen and Charlotte Rich for preparing andcompiling the manuscript

The paper is published with the permission of theDirector of the British Geological Survey and the ProjectLeader of the FOREGS programme Professor ReijoSalminen of the Geological Survey of Finland

The authors thank Eion Cameron John GroomOlle Selinus and Dave Smith for their helpful andconstructive comments on the manuscript

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1986 Information on the Chernobyl accident and itsconsequences prepared for IAEA Atomic Energy 3(5)

ABERNATHY C O 1993 Draft drinking water criteriadocument on arsenic US-EPA Science Advisory Boardreport contract 68-C8-0033

ABRAHAMS P W 2002 Soils their implications to humanhealth Sci Total Environ 291 1ndash32

ABRAHAMS P W 2003 Human geophagy a review of itsdistribution causes and implications 31-35 In SkinnerH C W and Berger A R (Eds) Geology and healthclosing the gap New York NY Oxford University PressISBN 0-19-516204-8

ACHS (ADVISORY COMMITTEE ON HAZARDOUSSUBSTANCES) 2003 Sixth annual report Departmentfor Environment Food and Rural Affairs

AHEL M MIKAC N COSOVIC B PROHIC E andSOUKUP V 1998 The impact of contamination from amunicipal solid waste landfill (Zagreb Croatia) onunderlying soil Water Sci Technol 37 203ndash210

ANDO M TADANO M ASANUMA S et al 1998 Healtheffects of indoor fluoride pollution from coal burning inchina Environ Health Perspect 106 239ndash244

ANDO M TADANO M YAMAMOTO S et al 2001 Healtheffects of fluoride pollution caused by coal burning SciTotal Environ 271 107ndash116

APPLETON J D 1995a Radon and background radioactivityfrom natural sources characteristics extent and relevanceto planning and development in Great Britain BritishGeological Survey Technical Report WP952

APPLETON J D 1995b Potentially harmful elements fromnatural sources and mining areas characteristics extentand relevance to planning and development in GreatBritain British Geological Survey Technical ReportWP953

APPLETON J D JIAXI L ZHANG Q JOHNSON C C GEX FORDYCE F M and ZHANG G 1998 Selenium incereals compared with other geochemical predictors ofhuman selenium status in China In Programme andAbstracts of the First Asia Pacific Symposium onEnvironmental Geochemistry Hong Kong 2ndash4December 1998

APPLETON J D 2004 Radon in air and water lsquoMedicalGeologyrsquo In Selinus O (Ed) Medical GeologyReference Earth Sciences Information in Support ofPublic Health Academic Press London

ARCAND-HOY L D NIMROD A C and BENSON W H1998 Endocrine-modulating substances in theenvironment estrogenic effects of pharmaceuticalproducts Int J Toxicol 17 139ndash158

AYSCOUGH N J FAWELL J FRANKLIN G and YOUNGW 2000 Review of Human Pharmaceuticals in theEnvironment Environment Agency Report 106Environment Agency Bristol UK

BAEK S O FIELD R A GOLDSTONE M E KIRK P WLESTER J N and PERRY R 1991 A review ofatmospheric polycyclic aromatic hydrocarbons sourcesfate and behaviour Water Air Soil Pollut 60 279ndash300

BAKIR F DAMLUJI S F AMIN-ZAKI L et al 1973Methylmercury poisoning in Iraq Science 181 230ndash241

BASSETT R L and MELCHIOR D C 1990 Chemicalmodelling of aqueous systems an overview ACSSymposium Series 416 1ndash14

BEAMISH D 2003 Characterising landfills from the air FirstBreak 21 67ndash72

BEDDING N D MCINTYRE A E PERRY R and LESTER JN 1982 Organic contaminants in the aquatic environment1 Sources and occurrence Sci Total Environ 25 143ndash167

BEDDING N D TAYLOR P N and LESTER J N 1995Physicochemical behaviour of polynuclear aromatichydrocarbons in primary sedimentation I Batch studiesEnviron Technol 16 801ndash812

BGS 1999 Regional geochemistry of Wales and part of west-central England stream water British Geological SurveyKeyworth Nottingham

BIRKETT J W and LESTER J N (Eds) 2002 Endocrinedisruptors in wastewater and sludge treatment processesCRC Press Boca Raton Florida USA

BORGA K GABRIELSEN G W and SKAARE J U 2001Biomagnification of organochlorines along a Barents Seafood chain Environ Pollut 113 187ndash198

BOXALL A B A FOGG L BLACKWELL P A KAY P andPEMBERTON E J 2002 Review of Veterinary Medicinesin the Environment ndash RampD Technical Report P6-0128TR Environment Agency Bristol UK

BOYD G R REEMSTMA H GRIMM D A and MITRA S2003 Pharmaceuticals and personal care products(PPCPs) in surface and treated waters of Louisiana USAand Ontario Canada Sci Total Environ 311 135ndash149

BREWARD N 2003 Heavy-metal contaminated soilsassociated with drained fenland in Lancashire UKrevealed by BGS Soil Geochemical survey Appl Geochem18 1663ndash1670



BROUWER A AHLBORG U G ROLAF VAN LEEUWEN FX and FEELEY M M 1998 Report of the WHO workinggroup on the assessment of health risks for human infantsfrom exposure to PCDDs PCDFs and PCBsChemosphere 37 1627ndash1643

BROWNAWELL B J and IDEN C R Occurrence and Fate ofPharmaceuticals and Personal Care Products inGroundwater Environments Project in progress StateUniversity of New York at Stony Brook EPA GrantNumber R829007 lthttpesepagovncer_abstractsgrantsbrownawellhtmlgt

BUFFLE J 1988 Complexation reaction in aquatic systemsan analytical approach Ellis Horwood Chichester

BULGER W H and KUPFER D 1983 Estrogenic action ofDDT analogs Am J Ind Med 4 163ndash173

BULGER W H MUCCITELLI R M and KUPFER D 1978Studies on the in vivo and in vitro estrogenic activities ofmethoxychlor and its metabolites Role of hepatic mono-oxygenase in methoxychlor activation BiochemPharmacol 27 2417

BURNS P C and FINCH R J 1999 Wyartite crystallographic evidence for the first pentavalent-uraniummineral Am Mineral 84 1456ndash1460

BURTON G A and SCOTT K J 1992 Sediment toxicityevaluation Their niche in ecological assessments EnvironSci Technol 26 2068ndash2075

BUTT C R M 1989 Genesis of supergene deposits in thelateritic regolith of the Yilgarn Block Western AustraliaEconomic Geology Monograph 6 460-470 In Keays RR Ramsay W R H and Groves D I (Eds) TheGeology of Gold Deposits The Perspective in 1988Economic Geology New Haven

CALL D J COX D A GEIGER D L et al 2001 Anassessment of the toxicity of phthalate esters to freshwaterbenthos 2 Aqueous exposures Environ Toxicol Chem 201798ndash1804

CAMPBELL L M DIXON D G and HECKY R E 2003 Areview of mercury in Lake Victoria East Africaimplications for human and ecosystem health J ToxicolEnviron Health Part B 6 325ndash356

CARSON R 1962 Silent Spring The New Yorker June 1962Presently published by Houghton Mifflin Company 2002

CDC 2001 A Feasibility Study of the Health Consequences tothe American Population From Nuclear Weapons TestsConducted by the United States and Other NationsDepartment of Health and Human Services Centers forDisease Control and Prevention Report to CongressAugust 2001

CHAMBERLAIN A C and DUNSTER H J 1958 Depositionof radioactivity in north-west England from the accidentat Windscale Nature 182 629ndash630

CHANIN P and JEFFRIES D 1978 The decline of the otterLutra lutra L in Britain an analysis of hunting recordsand discussion of causes Biol J Linneaus Soc 10 305ndash328

CHAU Y K MAGUIRE R J BROWN M YANG F andBATCHELOR S P 1997 Occurrence of organotincompounds in the Canadian aquatic environment fiveyears after the regulation of antifouling uses of tributyltinWater Qual Res J Can 32 453ndash521

CHEN S L DZENG S R and YANG M H 1994 Arsenicspecies in the Blackfoot disease area Taiwan Environ SciTechnol 28 877ndash881

CHRISTIANSEN T and KORSGAARD B 1998 Effects ofnonylphenol and 17β-oestradiol on vitellogenin synthesistesticular structure and cytology in male eelpout Zoarcesviviparus J Exp Biol 201 179ndash192

COLBURN T 1995 Pesticides ndash How research has succeeded

and failed to translate science into policy endocrinologicaleffects on wildlife Environ Health Perspect 103 81ndash86

CROUCH E A C 1958 Fission product and transuranicelements In O R Frisch (Ed) The Nuclear HandbookGeorge Newnes London

DANIELS J L 1975 Palaeogeographic development ofWestern Australian Precambrian Geological Survey ofWestern Australia Memoir 49 437ndash450

DARNERUD P O ERIKSEN G S JOHANNESSON TLARSEN P B and VILUKSELA M 2001 Polybrominateddiphenyl ethers Occurrence dietary exposure andtoxicology Environ Health Perspect 109 49ndash68

DARNLEY A G BJOumlRKLUND A GUSTAVSSON N et al1995 A Global Geochemical Database for Environmentaland Resource Management Recommendations forInternational Geochemical Mapping Earth ScienceReport 19 UNESCO Publishing Paris

DAUGHTON C G and TERNES T A 1999 Pharmaceuticalsand personal care products in the environment agents ofsubtle change Environ Health Perspect 107 907ndash938

DAVIS A RUBY M V and BERGSTROM P D 1992Bioavailability of arsenic and lead in soils from the ButteMontana Mining District Environ Sci Technol 26461ndash468

DAVIS C UTHUS E and FINLE J 2000 Dietary seleniumand arsenic affect DNA methylation in vitro in Caco-2cells and in vivo in rat liver and colon J Nutr 1302903ndash2909

DEFRA 2001 Monitoring of Radioactivity in Air and Rainwaterin the UK Annual Results Report 1999 DETRRAS00008Published 8 May 2001 Defra London

DEIGHTON N and GOODMAN B A 1995 The speciation ofmetals in biological systems 307ndash334 In Ure A M andDavidson C M (Eds) Chemical Speciation in theEnvironment Blackie Glasgow

DE LACERDA L D and SALOMONS W 1998 Mercury fromgold and silver mining a chemical time bomb SpringerBerlin 85ndash95

DETR 1999 Compilation of EU Dioxin Exposure and HealthData UK Department of the Environment Transportand the Regions

DE WIT C A 2000 Brominated Flame RetardantsStockholm Swedish EPA (Report 5065) 94

DE WIT C A 2002 An overview of brominated flameretardants in the environment Chemosphere 46 583ndash624

DORN P B CHOU C and GENTEMPO J J 1987Degradation of Bisphenol A in natural watersChemosphere 16 1501ndash1507

EAAUNEP (EUROPEAN ENVIRONMENT AGENCY ANDUNITED NATIONS ENVIRONMENT PROGRAMME)1999 Chemicals in the European Environment LowDoses High Stakes The EEA and UNEP AnnualMessage 2 on the State of Europersquos Environment

EDWARDS C A 1973 Environmental Pollution by PesticidesLondon and New York Plenum

EHRLICH H L 1990 Geo-microbiology Marcel DekkerNew York

ENVIRONMENT CANADA 2000 Priority Substances ListAssessment Report Nonylphenol and its ethoxylates 134

EUROPEAN COMMISSION 2004 Integrated Monitoring ofdioxins and PCBs in the Baltic Region TechnicalWorking Group on Integrated Monitoring ndash TheEuropean Commission

FAHEY D 1998 Case Narrative Depleted UraniumExposures Swords to Plowshares National Gulf WarResource Center the Military Toxics Project 3rd ednSeptember 20 1998



FEDERAL MINISTRY FOR THE ENVIRONMENT 2000Data on Environmental Pollution by DioxinsUmweltbundesamt

FENT K 1995 Endocrinically active substances in theenvironment State of the art Endocrinically ActiveChemicals in the Environment Berlin Umwelt BundesAmt

FERGUSSON J E and STEWART C 1992 The transport ofairborne trace-elements copper lead cadmium zinc andmanganese from a city into rural areas Scie Total Environ121 247ndash269

FERRARO S P LEE II H OZRETICH R J and SPECHT DT 1990 Predicting bioaccumulation potential a test of afugacity-based model Arch Environ Contam Toxicol 19386ndash394

FINKELMAN R B OREN W CASTRANOVA V et al 2002Health impacts of coal and coal use possible solutions IntJ Coal Geol 50 425ndash443

FINKELMAN R B BELKIN H E CENTENO J A andBAOSHAN Z 2003 Geological epidemiology coalcombustion in China 45ndash50 In Skinner H C W andBerger A R (Eds) Geology and health closing the gapNew York NY Oxford University Press ISBN 0-19-516204-8

FINLAY-MOORE O HARTEL P G and CABRERA M L2000 17β-estradiol and testosterone in soil and runofffrom grasslands amended with broiler litter J EnvironQual 29 1604ndash1611

FITZGERALD W F and CLARKSON T W 1994 Mercuryand monomethylmercury present and future concernsEnviron Health Perspect 96 159ndash166

FITZGERALD W F and LAMBORG C H 2004Geochemistry of mercury in the environment 107ndash148In Lollar B S (Ed) Environmental Geochemistry Vol 9In Holland H D and Turekian K K (Eds) Treatise onGeochemistry Elsevier-Pergamon Oxford

FORDYCE F M JOHNSON C C NAVARATNA U R BAPPLETON J D and DISSANAYAKE C B 2000aSelenium and iodine in soil rice and drinking water inrelation to endemic goitre in Sri Lanka Sci Total Environ263 127ndash141

FORDYCE F M ZHANG G GREEN K and LIU X 2000bSoil grain and water chemistry in relation to humanselenium-responsive diseases in Enshi District ChinaAppl Geochem 15 117ndash132

FORDYCE F M 2003 Database of the iodine content of foodand diet populated with data from published literatureCR03084N British Geological Survey KeyworthNottingham

FORDYCE F M JOHNSON C C DISSANAYAKA C B andNAVARATNE U R B 2003 Environmental iodine iniodine deficiency disorders with a Sri Lankan example61ndash64 In Skinner H C W and Berger A R (Eds)Geology and health closing the gap New York NYOxford University Press

FROMME H KUumlCHLER T OTTO T PILZ K MUumlLLER Jand WENZEL A 2002 Occurrence of phthalates andbisphenol A and F in the environment Water Resh 361429ndash1438

FURHACKER M SCHARF S and WEBER H 2000Bisphenol A emissions from point sources Chemosphere41 751ndash756

GARCIA-REYERO N GRAU E CASTILLO M LOPEZ DEALDA M J BARCELO D and PINA B 2001 Monitoringof endocrine disrupters in surface waters by the yeastrecombinant assay Environ Toxicol Chem 20 1152ndash1158

GILBERT J M and PARK JR C F 1986 The Geology of Ore

Deposits Freeman and Co New YorkGOOVAERTS P 1997 Geostatistics for natural resources

evaluation Applied Geostatistics Series OxfordUniversity Press New York USA

GRIMALT J O and MACPHERSON E 1999 Special issue Theenvironmental impact of the mine tailing accident inAznacollar (south-west Spain) Sci Total Environ 242 1ndash2

GUENTHER K HEINKE V THIELE B KLEIST E PRASTH and RAumlCKER T 2002 Endocrine disruptingnonylphenols are ubiquitous in food Environ Sci Technol36 1676ndash1680

GUumlLDEN M TURAN A and SEIBERT H 1998Endocrinically active chemicals and their occurrence insurface waters Report No UBA FB 97-068 BerlinFederal Environmental Agency (Umweltbundesamt) 246

GUSTAVSSON N PAMPIO E and TARVAINEN T 1997Visualisation of geochemical data on maps at theGeological Survey of Finland J Geochem Explor 59197ndash207

HALLING-SOslashRENSEN B NORS NIELSEN S LANZKY P Fet al 1998 Occurrence fate and effects of pharmaceuticalsubstances in the environment ndash A review Chemosphere36 357ndash393

HALSALL C J SWEETMAN A J BARRIE L A and JONESK C 2001 Modelling the behaviour of PAHs duringatmospheric transport from the UK to the Arctic AtmosEnviron 35 255ndash267

HARRINGTON L A and MACDONALD D W 2002 A Reviewof the Effects of Pesticides on Wild Terrestrial Mammals inBritain Wildlife Conservation Research Unit

HARRIS C A WOOLRIDGE M W and HAY W M 2001Factors affecting the transfer of organochlorine pesticideresidues to breastmilk Chemosphere 43 243ndash256

HARTMANN S LACORN M and STEINHART H 1998Natural occurrence of steroid hormones in food FoodChem 62 7ndash20

HAWKES H E and WEBB J S 1962 Geochemistry inMineral Exploration Harper and Row New York

HEBERER T REDDERSEN K and MECHLINSKI A 2002From municipal sewage to drinking water fate andremoval of pharmaceutical residues in the aquaticenvironment in urban areas Water Sci Technol 46 81ndash88

HEM J D 1985 Study and interpretations of the chemicalcharacteristics of natural waters USGS Water-SupplyPaper 2254

HICKEY J J and ANDERSON D W 1968 Chlorinatedhydrocarbons and eggshell changes in raptorial and fisheating birds Science 162 271ndash273

HILTON M J THOMAS K V and ASHTON D 2003Targeted Monitoring Programme for Pharmaceuticals inthe Aquatic Environment ndash RampD Technical Report P6-01206TR Environment Agency Bristol UK

HUWE J K 2002 Dioxins in food a modern agriculturalperspective J Agric Food Chem 50 1739ndash1750

IAEA 1973 Uranium exploration methods Proceedings of apanel April 10ndash14 1972 IAEA Vienna 1ndash320

IAEA 1976 Radiometric reporting methods and calibrationin uranium exploration Technical Report Series 174IAEA Vienna 1ndash57

IAEA 1996 Guidebook to accompany IAEA map of worlddistribution of uranium deposits International AtomicEnergy Agency Vienna

IAEA 1998 Dosimetric and medical aspects of theradiological accident in Goiania in 1987 IAEA-TECDOC-1009 International Atomic Energy AgencyVienna

IEER 2002 Fact Sheet on Fallout Report and Related



Matters Institute for Energy and Environmental Research(IEER) 28 February 2002 Maryland USA

IEH Relational Database of Information on PotentialEndocrine Disrupters (REDIPED) lthttpwwwleacukiehdatabasesredipedhtmlgt

IRELAND J S MUKKU V R ROBISON A K andSTANCEL G M 1980 Stimulation of uterine deoxy-ribonucleic acid synthesis by 111-trichloro-2-(p-chloro-phenyl)-2-(o-chlorophenyl)ethane opprime-DDT BiochemPharmacol 24 1469

IRUKAYAMA K 1977 Case history of Minamata 2ndash56 InTsubaki T and Irukayama K (Eds) Minamata DiseaseMethylmercury poisoning in Minamata and NiigataJapan Kodansha Ltd and Elsevier Amsterdam

JECFA 1988 The joint FAOWHO Expert Committee onFood Additives Residues of some veterinary drugs inanimals and foods Food and Agriculture Organisation ofthe United Nations FAO Food and Nutrition paper 41

JOBLING S NOLAN M TYLER C R BRIGHTY G andSUMPTER J P 1998 Widespread sexual disruption inwild fish Environ Sci Technol 32 2498ndash2506

JOBLING S SHEAHAN D OSBORNE J A MATTHIESSENP and SUMPTER J P 1996 Inhibition of testiculargrowth in rainbow trout (Oncorhynchus mykiss) exposedto estrogenic alkylphenolic chemicals Environ ToxicolChem 15 194ndash202

JOHNSON C C GE X GREEN K A and KIU X 1999Selenium distribution in the local environment of selectedvillages of the Keshan Disease belt Zhangjakou DistrictHebei Province Peoplersquos Republic of China ApplGeochem 15 385ndash401

JOHNSON C C FORDYCE F M and STEWART A G 2003Environmental Controls in Iodine Deficiency DisordersProject Summary Report British Geological SurveyCommissioned Report CR03058N lthttpwwwbgsacukdfid-kar-geoscienceiddCR_03_058Npdfgt

JONES D G EMERY C DAVIS G R STRUTT M H andRAINEY M P 2002a Application of airborne gamma-rayspectrometry to natural and technologically enhancednatural radioactivity examples from central BritainSeventh International Symposium Natural RadiationEnvironment (NRE-VIII)

JONES K C BURNETT V DUARTDAVIDSON R andWATERHOUSE K S 1991 PCBs in the environmentChem Britain 27 435ndash438

JONES O A H VOULVOULIS N and LESTER J N 2001Human pharmaceuticals in the aquatic environment areview Environ Technol 22 1383ndash1394

JONES O A H VOULVOULIS N and LESTER J N 2002bAquatic environmental assessment of the top 25 Englishprescription pharmaceuticals Water Res 36 5013ndash5022

JONES O A H VOULVOULIS N and LESTER J N 2003Potential impact of pharmaceuticals on environmentalhealth Bull World Health Organ 81 768ndash769

KAYE G W C and LABY T H 1986 Tables of physical andchemical constants and some mathematical functions15th edn London Longman

KLINCK B A BEAMISH D and TRICK J 2004Hydrochemical characterisation of the SherwoodSandstone Group in the vicinity of Thoresby CollieryNottinghamshire British Geological Survey InternalReport IR0425

KOLPIN D W FURLONG E T MEYER M T THURMANE M ZAUGG S D BARBER L B et al 2002Pharmaceuticals hormones and other organic wastewatercontaminants in US streams 1999ndash2000 a nationalreconnaissance Environ Sci Technol 36 1202ndash1211

KORRE A 1999a Statistical and spatial assessment of soilheavy metal contamination in areas of poorly recordedcomplex sources of pollution I Factor analysis forcontamination assessment Stochastic EnvironmentalResearch and Risk Assessment (SERRA) 13 260ndash287

KORRE A 1999b Statistical and spatial assessment of soilheavy metal contamination in areas of poorly recordedcomplex sources of pollution II Canonical correlationanalysis and GIS for the assessment of contaminationsources Stochastic Environmental Research and RiskAssessment (SERRA) 13 288ndash316

KORRE A and DURUCAN S 1999 A methodology for thestatistical and spatial assessment of soil contaminationaround mining districts Min Ind (Trans Inst Min MetallA) 108 181ndash191

KOUTRAS D A MATOVINOVIC J and VOUGHT R 1980The ecology of iodine In Stanbury J B and Hetzel B S(Eds) Endemic Goitre and Endemic Cretinism IodineNutrition in Health and Disease Wiley New York 185ndash195

KUBWABO C VAIS N and BENOIT F M 2004 A pilot studyon the determination of perfluorooctanesulfonate andother perfluorinated compounds in blood of Canadians JEnviron Monit 6 540ndash545

KURTTIO P AUVINEN A SALONEN L et al 2002 Renaleffects of uranium in drinking water Environ HealthPerspect 110 337ndash342

LAHTI M and JONES D G 2003 Environmentalapplications of airborne radiometric surveys First Break21 35ndash42

LANDRUM P F EADIE B J and FAUST W R 1991Toxicokinetics and toxicity of a mixture of sediment-associated polycyclic aromatic hydrocarbons to theamphipod Diporeia sp Environ Toxicol Chem 10 35ndash46

LARSSON D G J ADOLFSON-ERICI M PARKKONEN JPETTERSSON M BERG A H OLSSON P E et al 1999Ethinyloestradiol ndash an undesired fish contraceptiveAquatic Toxicol 45 91ndash97

LEBLANC G A 1995 Are environmental sentinels signallingEnviron Health Perspect 103 888ndash890

LEVANDER O A 1986 Selenium 209ndash279 In Mertz W(Ed) Trace elements in human and animal nutritionAcademic Orlando 5th edn

LINDH U GROumlNQUIST S-O CARLMARK B andLINDWALL A 2003 Mercury a toxic metal 31ndash35 InSkinner H C W and Berger A R (Eds) Geology andhealth closing the gap New York NY Oxford UniversityPress ISBN 0-19-516204-8

LOEHR R C 1987 Advancing knowledge on protection of thelandsoil resource assimilative capacity for pollutants77ndash101 In Draggan S et al (Eds) Geochemical andhydrologic processes and their protection Praeger NewYork

MARABINI M A PASARIELLO B and BARBARO M 1992Inductivity coupled plasma mass spectrometrycapabilities and application Microchem J 46 302ndash312

MARTIN-ROBICHAUD D J PETERSON R H BENFEY T Jand CRIM L W 1994 Direct feminization of lumpfish(Cyclopterus lumpus) using 17β-estradiol-enrichedArtemia as food Aquaculture 123 137ndash151

MEDVEDEV Z A 1979 Nuclear Disaster in the UralsNorton New York

MERTZ W 1986 Trace elements in human and animalnutrition US Dept of Agriculture Academic Orlando

MIELKE H W and REAGAN P L 1998 Soil is an importantpathway of human lead exposure Environ HealthPerspect 106 217ndash229

MILLS C F 1996 Geochemical aspects of the aetiology of



trace element related diseases 1ndash5 In Appleton J DFuge R and McCall G J H (Eds) EnvironmentalGeochemistry and Health Geological Society LondonSpecial Publication

MILODOWSKI A E 2001 Scanning electron microscopy ofuranium particulate in two soil samples at a DepletedUranium munitions strike site from the Kosovo ConflictBritish Geological Survey Commercial ReportCR01261

MINCHIN D STROBEN E OEHLMANN J BAUER BDUGGAN C B and KEATINGE M 1996 Biologicalindicators used to map organotin contamination in CorkHarbour Ireland Marine Pollut Bull 32 188ndash195

MIYAMOTO J and KLEIN W 1998 Environmentalexposure species differences and risk assessment PureAppl Chem 70 1829ndash1845

MUNKITTRICK K R BLUNT B R LEGGETT MHUESTIS S and MCCARTHY L H 1995 Developmentof a sediment bioassay to determine bioavailability ofPAHs to fish Aquatic Ecosystem Health Manage 4169ndash181

NAIDU R and NADEBAUM P R 2003 Geogenic arsenic andassociated toxicity problems in the groundwater-soil-plant-animal-human continuum In Skinner H C Wand Berger A R Geology and health closing the gapNew York NY Oxford University Press ISBN 0-19-516204-8

NATO 1996 NATO Handbook on the Medical Aspects ofNBC Defensive Operations Part I ndash Nuclear A MedPndash6(B) Washington DC

NEA 2002 Chernobyl Assessment of Radiological andHealth Impact 2002 Update of Chernobyl Ten Years OnOECD Paris France

NEEDLEMAN H L RIESS J A TOBIN M J BIESCKER GE and GREENHOUSE J B 1996 Bone lead levels anddelinquent behaviour JAMA 275 1727ndash1728

NEWTON I and HAAS M B 1984 The return of thesparrowhawk British Birds 77 47ndash70

OECD NUCLEAR ENERGY AGENCY 1998 UraniumResources production and demand OECD Paris

OEHLMANN J SCHULTE-OEHLMANN U STROBEN EBAUER B BETTIN C FIORNI P et al 1995Androgenic effects of organotin compounds in molluscsEndocrinically Active Chemicals in the EnvironmentBerlin Umwelt Bundes Amt

OLSEN G W CHURCH T R MILLER J et al 2003Perfluorooctanesulfonate and other fluorochemicals inthe serum of American Red Cross adult blood donorsEnviron Health Perspect 111 1892ndash1901

OLSEN G W CHURCH T R LARSON E B et al 2004Serum concentrations of perfluorooctanesulfonate andother fluorochemicals in an elderly population fromSeattle Washington Chemosphere 54 1599ndash-1611

OXBURGH R 2002 Making a meal of our nuclear wasteGeoscientist 12 4ndash-13

PEART R J CUSS R J BEAMISH D and JONES D G 2003Eye in the sky high resolution airborne geophysics canhelp locate and map potential environmental hazards inthe UK Geoscientist 13 4ndash7

PETROVIC M S GONZALEZ S and BARCELO D 2003Analysis and removal of emerging contaminants inwastewater and drinking water Trends Anal Chem 22685ndash696

PICKERING A D and SUMPTER J P 2003 Comprehendingendocrine disrupters in aquatic environments Environ SciTechnol 37 331Andash336A

PIPER A M 1944 A graphic procedure in the geochemical

interpretation of water analysis Amn Geophys UnionTrans 25 914ndash923

PLANT J A and DAVIS D L 2003 Breast and prostatecancer sources and pathways of endocrine-disruptingchemicals 95ndash99 In Skinner H C W and Berger A R(Eds) Geology and health closing the gap New YorkOxford University Press ISBN 0-19-516204-8

PLANT J A and HALE M 1995 Drainage GeochemistryHandbook of Exploration Geochemistry vol 6 ElsevierAmsterdam

PLANT J A SIMPSON P R SMITH B and WINDLEY B F1999 Uranium ore deposits ndash products of the radioactiveearth 255ndash319 In Burn P C and Finch R (Eds)Uranium Mineralogy Geochemistry and theEnvironment Mineralogical Society of America

PLANT J A KLAVER G LOCUTURA J SALMINEN RBRANA K and FORDYCE F M 1996 Forum ofEuropean Geological Surveys (FOREGS) GeochemistryTask Group 1994-1996 British Geological Survey (BGS)Technical Report WP14

PLANT J A KLAVER G LOCUTURA J SALMINEN RBRANA K and FORDYCE F M 1997 The Forum ofEuropean Geological Surveys Geochemistry Task Groupinventory 1994ndash1996 J Geochem Explor 59 123ndash146

PLANT J A SMITH D SMITH B and REEDER S 2000Environmental geochemistry at the global scale J GeolSoc 157 837ndash849

PLANT J A SMITH D and REEDER S 2003aEnvironmental geochemistry on a global scale 129ndash134In Skinner H C W and Berger A R (Eds) Geologyand health closing the gap New York Oxford UniversityPress ISBN 0-19-516204-8

PLANT J A REEDER S SALMINEN R SMITH D BTARVAINEN T DE VIVO B et al 2003b The distributionof uranium over Europe geological and environmentalsignificance Appl Earth Sci (Trans Inst Min Metall B)112 B221ndashB238

PLANT J A KINNIBURGH D G SMEDLEY P LFORDYCE F M and KLINCK B A 2004 Arsenic andselenium 17ndash66 In Lollar B S (Ed) EnvironmentalGeochemistry vol 9 In Holland H D and Turekian KK (Eds) Treatise on Geochemistry Elsevier-PergamonOxford

PORCELLA D B RAMEL C and JERNELOV A 1997Global mercury pollution and the role of gold mining anoverview Water Air Soil Pollut 97 205ndash207

POWELL J J and THOMPSON R P H 1993 The chemistryof aluminium in the gastrointestinal lumen and its uptakeand absorption Proc Nutr Soc 52 241ndash253

PREVEDOUROS K MACLEOD M JONES K C andSWEETMAN A J 2004 Modelling the fate of persistentorganic pollutants in Europe Parameterisation of agridded distribution model Environ Poll (specialissue)128 251-261

PURDOM C E HARDIMAN P A BYE V J ENO N CTYLER C R and SUMPTER J P 1994 Estrogenic effectsof effluents from sewage treatment works J Chem Ecol 8275ndash285

RAGNARSDOTTIR K V 2000 Environmental fate andtoxicology of organophosphate pesticides J Geol Soc157 859ndash876

RAMSEY M H and ARGYRAKI A 1997 Estimation ofmeasurement uncertainty from field samplingimplications for the classification of contaminated landSci Total Environ 198 243ndash257

RAND G M 1995 Fundamentals of aquatic toxicologyLondon Taylor amp Francis



RATCLIFFE D 1980 The peregrine falcon Calton PoyserREEDER S W HITCHON B and LEVINSON A A 1972

Hydrogeochemistry of the McKenzie River DrainageBasin I Factors affecting inorganic compositionGeochim Cosmochim Acta 36 825ndash865

REINHARD M MONTGOMERY-BROWN J LOUIE J S andGROSS B 2003 From effluent to new water performanceevaluation and quality assurance Chimia 57 561ndash566

RENNER R 1998 Growing acceptance of soil contaminantbioavailability kicks off national meetings Environ SciTechnol News 32 528Andash529A

RITTER L SOLOMON K R FORGET J STEMEROFF Mand OrsquoLEARY C 1995 Persistent organic pollutants ndash anassessment report on DDT Aldrin Dieldrin EndrinChlordane Heptachlor Hexachlorobenzene MirexToxaphene Polychlorinated Biphenyls Dioxins andFurans The International Programme on ChemicalSafety (IPCS)

ROBERTS A L and BOUWER E J Pharmaceuticals andAntiseptics Occurrence and Fate in Drinking WaterSewage Treatment Facilities and Coastal Waters Projectin Progress Johns Hopkins University EPA GrantNumber R829004lthttpcfpub2epagovncer_abstractsindexcfmfuseactiondisplayabstractDetailabstract1061report01gt

ROSE A W HAWKES H E and WEBB J S 1979Geochemistry in mineral exploration 2nd edn New YorkAcademic Press

RCEP 2003 24th report Chemicals in products safeguardingthe environment and human health ISBN 0 10 158272 2

ROYAL SOCIETY 2001 The health hazards of depleteduranium munitions Part 1 Policy document 601London The Royal Society

ROYAL SOCIETY 2002 The health hazards of depleteduranium munitions Part 2 London The Royal Society

RUBY M V DAVIS A SCHOOF R EBERLE S andSELLSTONE C C 1996 Estimation of lead and arsenicbioavailability using a physiologically based extractiontest Environ Sci Technol 30 422ndash430

SALMINEN R TARVAINEN T DEMETRIADES A et al1998 FOREGS Geochemical Mapping Field ManualGeological Survey of Finland Guide vol 47

SANDSTROumlM H et al 2003 FOREGS analytical manuallthttpwwwgsffiforegsgeochemanalyticalmanpdfgt

SELINUS OS ALLOWAY B CENTENO J FINKELMAN RB FUGE R et al 2005 Essentials of medical geologyAmsterdam Elsevier

SELINUS O S and ESBENSEN K 1995 Separatinganthropogenic from natural anomalies in environmentalgeochemistry J Geochem Explor 55 55ndash66

SELLSTROM U 1999 Determination of somepolybrominated flame retardants in biota sediment andsewage sludge Unpublished PhD dissertation StockholmUniversity

SHORE L S GUREVITZ M and SHEMESH M 1993Estrogen as an environmental pollutant Bull EnvironContam Toxicol 51 361ndash366

SHUTOV V N TRAVNIKOVA I G BRIK G Y GOLIKOV VY and BALANOV M I 2002 Current contamination by137Cs and 90Sr or the Tecta River basins in the Urals JEnviron Radioact 61 91ndash109

SIEGEL M D and BRYAN C R 2004 Environmentalgeochemistry of radioactive contamination 205ndash262 InLollar B S (Ed) Environmental Geochemistry vol 9 InHolland H D and Turekian K K (Eds) Treatise onGeochemistry Elsevier-Pergamon Oxford

SKINNER H C W and BERGER A R 2003 Geology and

health closing the gap Oxford University Press ISBN 0-19-516204-8

SMEDLEY P L KINNIBURGH D G HUQ I LUO Z D andNICOLLI H B 2001 International perspective on arsenicproblems in groundwater 105ndash149 In Chappell W RAbernathy C O and Calderon R L (Eds) ArsenicExposure and Health Effects IV Elsevier Oxford

SMITH B CHENERY S R N COOK J M et al 1998aGeochemical and environmental factors controllingexposure to cerium and magnesium in Uganda JGeochem Explor 65 1ndash15

SMITH B HUTCHINS M G RAWLINS B G LISTER T Rand SHAND P 1998b Methods for the integrationmodelling and presentation of high-resolution regionalhydrochemical baseline survey data J Geochem Explor64 67ndash82

SMITH B RAWLINS B G FERGUSON A J FORDYCE FHUTCHINS M G FINNAMORE J R et al 2002Information on Land Quality in the UK BackgroundLevels of Organic and Inorganic Contaminants inEngland Environment Agency RampD Technical SummaryPS275

SNYDER S A WESTERHOFF P YOON Y and SEDLAK DL 2003 Pharmaceuticals personal care products andendocrine disruptors in water implications for the waterindustry Environ Eng Sci 20 449ndash469

SOHONI P TYLER C R HURD K et al 2001 Reproductiveeffects of long-term exposure to bisphenol A in thefathead minnow (Pimephales promelas) Environ SciTechnol 35 2917ndash2925

SPOSITO G 1989 The environmental chemistry ofaluminium CRC Boca Raton FL

STANGROOM S J COLLINS C D and LESTER J N 1998Sources of organic micropollutants to lowland riversEnviron Technol 19 643ndash666

STAPLES C A DORN P B KLECKA G M BRANSON DR OrsquoBLOCK S T and HARRIS L R 1998 A review ofthe environmental fate effects and exposures of bisphenolA Chemosphere 36 2149ndash2173

STAPLES C A PARKERTON T F and PETERSON D R2000 A risk assessment of selected phthalate esters inNorth American and Western European surface watersChemosphere 40 885ndash891

STINE K E and BROWN T M 1996 Principles of toxicologyLewis New York

STRINGER R and JOHNSTON P 2001 Chlorine and theenvironment ndash an overview of the chlorine industryDordrecht The Netherlands Kluwer

STUMM W 1991 Aquatic chemical kinetics WileyInterscience New York

STUMM W and MORGAN W 1981 Aquatic chemistryWiley New York

SUMPTER J P 2002 Endocrine disruption and feminizationin fish Toxicology 178 39ndash40

SWAN S et al 2005 Environmental health perspectives in pressSWEETMAN A J and JONES K C 2001 Modeling historical

emissions and environmental fate of PCBs in the UK InLipnick R L Jansson B Mackay D and Petreas M(Eds) Persistent Bioaccumulative and Toxic Chemicals IIAssessment and New Chemicals ACS Symposium Series773 American Chemical Society Washington

TAYLOR S R 1964 Abundance of chemical elements in thecontinental crust a new table Geochim Cosmochim Acta28 1273ndash1284

TAYLOR S R 1966 Application of trace element data toproblems in petrology Phys Chem Earth 6 135ndash213

TCHOUNWOU P B 2000 Health risk assessment and



management of arsenic and other toxic and hazardousmetals in drinking water 21-23 In Centeno J A et al(Eds) Metal ions in biology and medicine vol 6 J LibbyLondon Eurotext

TERNES T A MEISENHEIMER M MCDOWELL D et al2002 Removal of pharmaceuticals during drinking watertreatment Environ Sci Technol 36 3855ndash3863

TUREKIAN K K 1969 Oceans streams and atmosphere297ndash323 In Wedepohl KH (Ed) Handbook ofGeochemistry Springer Berlin

TUREKIAN K K and WEDEPOHL K H 1961 Distributionof the elements in some major units of the Earthrsquos crustGeol Soc Am Bull 72 175ndash192

TYLER A O and MILLWARD G E 1996 Distribution andpartitioning of polychlorinated dibenzo-p-dioxinspolychlorinated dibenzofurans and polychlorinatedbiphenyls in the Humber Estuary Marine Pollut Bull 32397ndash403

UKEA 2000 Endocrine-disrupting substances in theenvironment The Environment Agencyrsquos Strategy TheEnvironment Agency Bristol UK March 2000

UNDERWOOD E J 1979 Trace elements and human healthan overview Philos Trans R Soc London B B228 5ndash14

UNEP 2002 Technological disasters lthttpwwwunepieorgpcapelldisastersliststechnologicalhtmlgt

UNICEF-WHO JOINT COMMITTEE ON HEALTH POLICY1994 World Summit for Children ndash Mid-decade goalIodine Deficiency Disorders Geneva January 1994

UNSCEAR 2000 Sources and Effects of Ionising RadiationUnited Nations Scientific Committee on the Effects ofAtomic Radiation Report to the General Assembly withscientific annexes vol I Sources

US EPA 2004 2000ndash2001 Pesticide Market Estimates Usagelthttpwwwepagovoppbead1pestsales01pestsalesusage2001htmltable3_1gt

USGS 2004 Minerals Commodity Summaries 2004 UnitedStates Geological Survey Washington

US NATIONAL RESEARCH COUNCIL 2000 Toxicologicaleffects of methylmercury National Academy PressWashington DC

VALLACK H W BAKKER D J BRANDT I et al 1998Controlling persistent organic pollutants - what nextEnviron Toxicol Pharmacol 6 143ndash175

VAN DER KRAAK G 1998 Observations of endocrine effectsin wildlife with evidence of their causation Pure ApplChem 70 1785ndash1794

VENKATESH-MANNAR M G and DUNN J T 1995 Saltiodization for the elimination of iodine deficiencyInternational Council for the Control of Iodine DeficiencyDisorders

VOULVOULIS N SCRIMSHAW M D and LESTER J N1999 Alternative antifouling biocides Appl OrganometallChem 13 135ndash143

WATANABE I KASHIMOTO T and TATSUKAWA R 1987Polybrominated biphenyl ethers in marine fish shellfishand river and marine-sediments in Japan Chemosphere16 2389ndash2396

WEAVER B L and TARNEY J 1984 Empirical approach toestimating the composition of the continental crustNature 310 575ndash577

WEBB S F 2001 A Data-based Perspective on theEnvironmental Risk Assessment of Human Pharma-ceuticals I ndash Collation of Available Ecotoxicity DataPharmaceuticals in the Environment K KummererBerlin Springer 175ndash201

WHO 1984 Guidelines for drinking water quality Volume 2Health criteria and other supporting information World

Health Organization GenevaWHO 1994 Environmental health criteria World Health

Organization GenevaWHO 1996 Trace Elements in Human Nutrition and Health

World Health Organization GenevaWHO 2001 Depleted Uranium Sources Exposures and

Health Effects World Health Organization GenevaWILLIAMS T M RAWLINS B G SMITH B and BREWARD

N 1999 In-vitro determination of arsenic bioavailability incontaminated soil and mineral beneficiation waste from RonPhibun southern Thailand a basis for improved human riskassessment Environ Geochem Health 20 169ndash177

WILLIS C 2000 Antibiotics in the food chain their impact onthe consumer Rev Med Microbiol 11 153ndash160

WOODHEAD R J LAW R J and MATTHIESSEN P 1999Polycyclic aromatic hydrocarbons in surface sedimentsaround England and Wales and their possible biologicalsignificance Marine Pollut Bull 38) 773ndash790

WONG O WHORTON M D FOLIART D E andLOWENGART R 1992 An ecologic study of skin-cancerand environmental arsenic exposure Int Arch OccupEnviron Health 64 235ndash241

ZHENG B YU X ZHAND J and ZHOU D 1996 Environ-mental geochemistry of coal and endemic arsenism insouthwest Guizhou PR China 30th InternationalGeologic Congress Abstracts 3 410

Authors

Jane Plant CBE DSc FRSE FRSA FRSM FIMM CEngFGS CGeol is Professor of Geochemistry in the DEST CEPat Imperial College London Her research interests centreon economic and environmental geochemistry She hasparticular expertise in baseline geochemical mappingmonitoring and modelling She is an expert on uraniumgeochemistry and natural radioactivity and thegeochemistry of arsenic and selenium She is chairman ofthe UK Governments Advisory Committee on HazardousSubstances and a member of the Chemical StakeholdersForum She is also a member of the Royal Commission onEnvironmental Pollution She has served as a member of theCBI Minerals Committee and MIRO Council and ispresently on the council of the Parliamentary Science andTechnology Committee In 1997 she was awarded the CBEfor Services to Earth Sciences and has an HonoraryDoctorate from the Open University Exeter UniversityKingston University Keele University Abo TunkuUniversity and Leicester University (for academic andscholarly distinction) and has been appointed a SeniorAcademic Visitor to the Macauley Institute Aberdeen andSenior Research Fellow at the Natural History Museum In1999 she was elected a Freeman of the City of London anda member of the Society of Water Conservators She wasalso awarded the Lord Lloyd of Kilgerran Award from theFoundation of Science and Technology in recognition ofher contribution to the application of fundamentalgeochemical modelling

Nick Voulvoulis BSc (Hons) MSc DIC PhD DMS CBiolMBiol FRGS joined Imperial College London as a lecturer(August 2000) and has worked on a number of researchcontracts in the area of environmental assessment and wasteand wastewater management Reflecting a major researchtrend within the College his research is focused onenvironmental pollution by hazardous substances likebiocides pesticides and pharmaceuticals and environmental



management issues His research activities also involve thedevelopment and application of environmental analysismethods multicriteria analysis and risk assessment forenvironmental decision making In addition his work alsocovers areas associated with the potential application ofdecision making tools such as multicriteria analysis and riskassessment in environmental management This researchaims to develop methodologies to establish the influence ofdifferent parameters of environmental quality andperformance and indicators of effects that relate directly toenvironmental decision making problems and impacts toenvironmental quality and human health

Barry Smith PhD CChem CSci MRSC is head of theSustainable Soils Programme of the British GeologicalSurvey in Nottinghamshire His research interests centre onenvironmental geochemistry and the Earths near surfaceenvironment He has particular expertise in geochemistryand health contaminant transport and integratedenvironmental mapping He is an expert on the behaviour ofuranium in the natural environment and has compiledreviews on the environmental fate and health impact ofdepleted uranium for WHO and the Royal Society He

currently chairs the Ministry of Defences IndependentReview Board set up to monitor their research programmeof depleted uranium and represents the BGS on the CabinetOffices Soil Guideline Value Taskforce

Shaun Reeder BSc (Hons) is an experienced analyticalgeochemist with over 18 years experience in field samplingand site investigation inorganic analysis and laboratorymethod development pore-water extraction andcharacterisation and geochemical data interpretation He iscurrently the British Geological Surveys LaboratoryOperations Manager Shaun has held the positions of BGSQuality Manager (1996ndash2000) and BGS Quality Systems andPolicy Advisor (2000 to present) He has also held thepositions of UKAS Quality Manager for the AnalyticalGeochemistry Laboratories (1994ndash1996) and Deputy UKASManager (1996ndash2005) with responsibility for development andmanagement of an accredited laboratory-based QualitySystem He is currently BGS Project Leader and ScientificSecretary to the IUGSIAGC Working Group on GlobalGeochemical Baselines the FOREGS Geochemistry WorkingGroup the FOREGS Data Management Group and theFOREGS Analytical Working Group



2003) The problem of chronic exposure to potentiallytoxic chemicals in the environment is also articulatedby the European Environment Agency and the UnitedNations Environment Programme (EEAUNEP1999) The increase in concern about chemicals in theenvironment is reflected by the growing number ofEuropean Union (EU) Directives and national andinternational conventions relating to chemicals

In addition to damage to human health caused bytoxicity conditions damage can also be caused bydeficiency conditions The World Health Organization(WHO) for example has calculated that 800 millionpeople world-wide are at risk of serious diseases suchas goitre and cretinism the latter because of iodinedeficiency in mothers during pregnancy (UNICEF-WHO Joint Committee on Health Policy 1994)

In this paper we first review data on problemsassociated with inorganic substances for which in thecase of many of the 92 naturally occurring chemicalelements there is now much systematic data on theirdistribution in soils sediments and water at thenational and increasingly international scale Thesedata can be used for understanding the distributionbehaviour and potential impact of such chemicals incomplex and highly varied surface environmentsworld-wide ranging from glaciated to tropicalterrains Some of the latter contain deeply leachedancient landscapes suggested in some cases to datefrom the Proterozoic (Butt 1989 Daniels 1975) Wealso discuss similar systematic information forradioactive substances

In contrast to inorganic and radioactive substancesthe situation for synthetic organic substances includingpersistent organic pollutants POPs such as pesticideresidues phthalates and other plasticisers surfactantsand detergents and waste products from incinerationsuch as dioxins is characterised by a paucity ofsystematic data information and knowledge There isincreasing awareness as a result of recent monitoringand modelling studies (Sweetman and Jones 2000Halsall et al 2001 Prevedouros et al 2004) of damageto ecosystems and man caused by the long-rangetransport of these chemicals and their accumulation athigh latitudes (EEAUNEP 1999) Moreover it hasbeen estimated that there are about 30 000 syntheticindustrial chemicals on the market of which relativelylittle is known even about their hazardous (PBT)properties (EEAUNEP 1999) Their distribution andbehaviour in the environment is also poorly understoodmaking meaningful exposure and risk assessmentalmost impossible

In the case of pharmaceuticals or their residues thereis currently no regulatory requirement on their use ordisposal even within the US or EU despite theirpotentially high ecotoxicitytoxicity Studies of sewageeffluent and surface water in the UK and world-widehave shown many pharmaceuticals including the femalecontraceptive pill 17α-ethinyl oestrodial (EE2) forexample to occur at concentrations with the potentialto cause harm (Sumpter 2002 Pickering and Sumpter2003 Plant and Davis 2003)

All of the groups of chemicals discussed both

inorganic (eg Pb and Cd) and organic (eg PCBs DDT)include substances that can disrupt the endocrine systemof many species including humans (UKEA 2000) Morethan 70 EDCs are now listed on the UK Institute ofEnvironment and Healthrsquos relational database ofinformation on potential endocrine disrupters (IEHREDIPED website)

Among OECD countries Japan appears to be theonly nation that uses environmental monitoring data toevaluate the risks of such chemicals in the environment(RCEP 2003) Here we show how systematicgeochemical and radiometric data strongly support suchan approach and can be used to inform government andthe public of potential threats to the health of ecosystemsand humans posed by deficiencies or excesses ofchemicals in the environment

CHEMICALS OF CONCERN IN THEENVIRONMENT

Potentially harmful and essential inorganic chemicalelements and speciesTwo main groups of inorganic chemical elements andspecies are of particular importance for healthpotentially harmful chemical elements and speciesand those that can be essential or harmful dependingon their concentration speciation and bioavailabilityThe level of many of these chemicals can varynaturally as a result of geology or climatic historyalthough their natural background has frequentlybeen altered by the activity of humans includinghistorical mineral working industrialisation andurbanisation New materials including those used innanotechnology are increasingly introducing newapplications for many chemical elements that have notpreviously been of environmental concern eg Ga Inand the PGEs (Table 1)

Potentially harmful elementsPotentially harmful elements (PHEs) known to haveadverse physiological significance at relatively lowlevels for which there is little or no evidence ofessentiality include As Ag Be Cd Pb Hg (Skinnerand Berger 2003) and possibly some of the rare earthelements (REEs Smith et al 1998a) Arsenic Pb andHg are used here as examples

Acute toxicity from As can cause severe gastro-intestinal symptoms fluid loss and circulatorycollapse psychotic symptoms neurological changesincluding demyelination of the peripheral nervoussystem andor severe heart disease Chronic exposureis linked to increased risk of cancer including of theskin liver lung and bladder (Tchounwou 2000 Wonget al 1992) Significant adverse effects of As-contaminated groundwater including from naturallyarsenical aquifers have been reported from ArgentinaBangladesh Chile China Ghana Hungary IndiaMexico Taiwan the UK and the US (Naidu andNadebaum 2003) In Mongolia and parts of Chinawhere arsenical groundwater is used for irrigation itmay also be ingested via crops or animals or through


































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chemicals in the environment: implications for global sustainability

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