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Bulletin THE ROYAL SOCIETY OF CHEMISTRY ENVIRONMENTAL CHEMISTRY GROUP 1 July 2003 News of the ECG .................................................... 2 DGL 2003 ..................................................................... 3 EU Water Framework Directive ................. 4 Monitoring the environment .......................... 7 Arsenic hyperaccumulation ............................ 8 Arsenic in UK soils ........................................... 11 Arsenic’s carcinogenicity .............................. 13 Loe Pool Management Forum ................... 14 News of the ESEF ............................................... 16 News of the EHSC ............................................. 16 Book review ............................................................. 17 Forthcoming symposium: Chemical risk assessment ............................. 17 Young Environmental Chemists Meeting 2003 .......................................................... 18 Forthcoming symposium: Ecotoxicology ........................................................ 20 Meeting report: Coastal Futures .............. 21 Recent books at the RSC library ............. 22 The contents page of this ECG Bulletin may be seen on the Internet at http://www .rsc.or g/lap/rsccom/dab/ scaf003.htm BULLETIN EDITOR Dr Rupert Purchase, 38 Sergison Close, Haywards Heath, West Sussex RH16 1HU. Tel: 01444 455673 e-mail [email protected] Chairman Dr Andrea Jackson, School of the Environment, University of Leeds, Leeds LS2 9JT. Tel: 0113 233 6728 Fax: 0113 233 6716 andrea@env .leeds.ac.uk Vice-Chairman & Hon. Treasurer Dr Brendan Keely, Department of Chemistry, University of York, Heslington, York YO10 5DD. Tel: 01904 432540 [email protected] Hon. Secretary Dr Leo Salter, Centre for Science, Cornwall College, Trevenson Road, Pool, Redruth, Cornwall TR15 3RD. Tel: 01209 616192 Fax: 01209 616193 [email protected] CONTENTS ECG Bulletin – July 2003 RSC ENVIRONMENTAL CHEMISTRY GROUP OFFICERS (from March 2003) Loe Pool, Cornwall Conserving the vision of Arthur Symons: The Loe Pool Management Forum, p.14

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BulletinTHE ROYAL SOCIETY OF CHEMISTRY

ENVIRONMENTAL CHEMISTRY GROUP

1

July 2003

News of the ECG .................................................... 2

DGL 2003 ..................................................................... 3

EU Water Framework Directive ................. 4

Monitoring the environment .......................... 7

Arsenic hyperaccumulation ............................ 8

Arsenic in UK soils ........................................... 11

Arsenic’s carcinogenicity .............................. 13

Loe Pool Management Forum ................... 14

News of the ESEF ............................................... 16

News of the EHSC ............................................. 16

Book review ............................................................. 17

Forthcoming symposium:Chemical risk assessment ............................. 17

Young Environmental ChemistsMeeting 2003 .......................................................... 18

Forthcoming symposium:Ecotoxicology ........................................................ 20

Meeting report: Coastal Futures .............. 21

Recent books at the RSC library ............. 22

The contents page of this ECG Bulletinmay be seen on the Internet athttp://www.rsc.org/lap/rsccom/dab/scaf003.htm

BULLETIN EDITORDr Rupert Purchase,38 Sergison Close,Haywards Heath,West SussexRH16 1HU.Tel: 01444 455673e-mail [email protected]

ChairmanDr Andrea Jackson,School of the Environment,University of Leeds,LeedsLS2 9JT.Tel: 0113 233 6728Fax: 0113 233 [email protected]

Vice-Chairman &Hon. TreasurerDr Brendan Keely,Department of Chemistry,University of York,Heslington,York YO10 5DD.Tel: 01904 [email protected]

Hon. SecretaryDr Leo Salter,Centre for Science,Cornwall College,Trevenson Road,Pool,Redruth,Cornwall TR15 3RD.Tel: 01209 616192Fax: 01209 [email protected]

CONTENTS

ECG Bulletin – July 2003

RSC ENVIRONMENTAL CHEMISTRY GROUP OFFICERS(from March 2003)

Loe Pool, Cornwall

Conserving the vision of Arthur Symons:The Loe Pool Management Forum, p.14

Environmental Chemistry Group Bulletin July 2003

2

News of the Environmental Chemistry Group CommitteeThe Environmental ChemistryGroup Committee hasundergone some changesrecently and each committeemember now has a particularresponsibility. This will allow

Nottingham, and Ecotoxicology –monitoring and caring for theenvironment, a joint meeting withAnalytical Division, East Anglia Region.This will be held at the RSC’s ThomasGraham House in Cambridge on 14th

October 2003. See the RSC’sConferences Web pages for furtherdetails of these meetings. Please do nothesitate to get in touch if you have anidea for a meeting or conference.Finally, a reminder that the RSC is keenfor members to submit their e-mailaddresses. Please e-mail the RSC [email protected]

Dr ANDREA JACKSON,ECG Chairman,June 2003

Group members access to thecommittee either for specificinformation concerning theECG or to suggest futureactivities for the Group – forexample ideas for future

meetings. Please feel free tocontact the appropriateCommittee member if you haveany suggestions to make.

In terms of our activities, we arecontinuing to work closely with othergroups within the Royal Society ofChemistry. For example, we haverepresentation on the EnvironmentalHealth and Safety Committee (http://www.rsc.org/lap/rsccom/ehsc/ehsc.htm),and we are actively involved with thesub-group of EHSC that oversees RSC’smembership of the UK ChemicalStakeholder Forum – a DEFRA bodythat advises Ministers (http://www.defra .gov.uk/environment /chemicals/csf/index.htm).We are also strongly represented on theRSC’s newly formed Environment,Sustainability and Energy Forum(ESEF), which aims to co-ordinate allRSC activities with respect to theenvironment. All members of the ECGare automatically members of ESEF at

no extra charge. The opportunity for anymember to ‘opt out’ of the Forum willbe given on the registration form.As you may already be aware, our mainevent is the Distinguished GuestLecture, which is held on an afternoonin March every year at the LinneanSociety and is free to all members of theEnvironmental Chemistry Group. TheGroup’s Annual General Meeting is alsoheld during the afternoon. The meetingin March this year was very wellattended, and we hope that the topic forthe 2004 meeting, EnvironmentalChemistry from Space, will prove aspopular. This meeting will be held on3rd March 2004.Other meetings to look out for are theYoung Environmental ChemistsMeeting, to be held on 10th September2003 at the British Geological Survey in

ECG Committee Member E-mail contact Role on ECG CommitteeDr Andrea Jackson (School of the [email protected] ChairmanEnvironment University of Leeds, Leeds LS2 9JT)

Dr Brendan Keely (Department of Chemistry, [email protected] Vice-Chairman & Honorary TreasurerUniversity of York, Heslington,York YO10 5DD)

Dr Leo Salter (Cornwall College, CPR Campus, [email protected] Honorary SecretaryTrevenson Road, PoolRedruth, Cornwall TR15 3RD)

Dr Kim Cooke (Sira Ltd, South Hill, [email protected] Young Environmental ChemistChislehurst, Kent BA7 5EH) Meeting organiser

Dr Chris Harrington (De Montfort University, [email protected] Group publicityDepartment of Chemistry, The Gateway, Leicester LE1 9BH)

Bob Hazell (Royal Society of Chemistry, [email protected] RSC Environmental Health andBurlington House, Piccadilly, London W1J 0BA) Safety Committee Representative

Professor Steve Hill (School of Environmental [email protected] Group publicitySciences, University of Plymouth, Plymouth PL4 8AA)

Dr John Hoskins (27 Furzefield Crescent, [email protected] RSC Occupational and EnvironmentalReigate RH2 7HQ) Toxicology Group representative

Dr Mike Leggett (British Standards Institution, [email protected] Distinguished Guest Lecture organiser389 Chiswick High Road, London W4 4AL)

Dr Rupert Purchase (38 Sergison Close, [email protected] Newsletter EditorHaywards Heath, West Sussex RH16 1HU)

Environmental Chemistry Group Bulletin July 2003

3

Does biology or chemistry determine the availability of toxic metalsin soils and sediments?Professor Bill Davison fromLancaster University, thisyear’s ECG DistinguishedGuest Lecturer, summarises thepresentation he gave to theECG at The Linnean Society ofLondon in March 2003.

Environmental chemists and biologistshave long known that they cannot studytheir subjects in isolation. The linkagesbetween chemical and biological processesare key to a fundamental understanding ofmany environmental systems. This isparticularly true in soils and sedimentswhere chemical transformations are usuallydependent on microbial activity and solutesupply is easily limited.

Transport of solutes in soils andsediments is dominated by diffusion.When considering supply to plant rootsor to microorganisms, the criticaldiffusional distance where gradients aresteep is about 1 mm (Barber, 1995).Therefore to appreciate fully how thechemical supply operates measurementsmust be made on the same or smallerscale. The work of the groups at Aarhusand Bremen, led by Revsbech andJorgensen, on the development andapplication of microelectrodes has led theway with respect to high-resolutionmeasurements of oxygen and nutrients.During the 1990s we developed atLancaster the technique of DGT(diffusive gradients in thin films) that canprovide sub-mm scale information ontrace metals (Davison and Zhang, 1994).

In DGT metals are trapped on a bindingagent (Chelex resin) after they havediffused through a layer of gel of well-defined thickness. The simple, plasticdevices are deployed for a known time(hours to days) and the accumulatedmetal is measured on retrieval. Whenthey are deployed in sediments, or soilswith high moisture content, the removalof metal by the Chelex causes a depletionof metal in the soil solution adjacent tothe device. If the metal in soil solution isin dynamic equilibrium with the metalon the soil particles, it will be released

into solution, counteracting the depletion.The balance between removal by DGTand resupply from the solid phasedetermines the extent of depletion insolution and the concentration, C, at theinterface between the soil and the device.The well-defined geometry andproperties of the diffusion layer allowscalculation of the mean concentration ofmetal at the surface of the device duringits deployment, CDGT, from the measuredaccumulated mass.

A dynamic, numerical model of the DGT-soil system, DIFS (DGT Induced Fluxesin Soils), has shown how theconcentrations of metals in solution, andin associated solid phases, change withtime (Harper et al., 1998). This dependson the kinetics of release from solid phaseto solution and the size of the solid phasepool. For most situations, depletion ofmetal, and therefore the effect on the soil,does not extend beyond 1 mm, even fordeployments in excess of a day. DGThas been used for different times, toprovide the first measurements of thesolid phase pool size and the kinetics ofrelease in relatively undisturbed soil.

The major way that a plant perturbs themetal chemistry of the soil system is byremoving metal. DGT does exactly thesame thing. Therefore, it can be used as asurrogate for this plant process. CDGT isdetermined by both the concentration insoil solution and its resupply from the solidphase. The effective solution con-centration, that DGT or a plant experiences,is enhanced by this solid phase supply. Thiseffective concentration, CE, can becalculated directly from CDGT asmeasured by DGT. A series of studiesfrom around the world have shown thatCE correlates extremely well withconcentrations of metals in plants for awide range of metals and soil types(Davison et al., 2000; Zhang et al., 2001).As DGT responds only to the chemicaland physical processes in the soil, itfollows that these are the major processescontrolling plant uptake. Therefore, inthis case, the chemistry of the 1 mm layerof soil adjacent to the uptake surface (theroots of the plant) controls the acquisitionof metals by plants.

DGT can be configured into thin, plasticprobes that may be inserted intosediments. On retrieval the binding layercan be sliced into thin strips prior toanalysis, or it can be dried and analysedby laser ablation ICP-MS at any spatialresolution down to 30 microns. Theresulting vertical profiles of metals insediments show classic changes inconcentration associated with redoxzones, but additionally there is often finestructure on a scale of about mm (Zhanget al., 1995). Highly localisedremobilisation of Zn and Mn has beenobserved at the surface of a microbial mat(Davison et al, 1997). Measurements intwo dimensions in sediments have shownthat the spiky signals are due to releaseof metals from highly localised,approximately spherical microniches(Davison et al., 1997; Fones et al., 2003).A combined probe that measuressulphide and metals simultaneouslyshowed that metals could be releasedconcomitantly with sulphide from theorganic matter that fuels sulphatereduction or from iron oxides that aresimultaneously reduced (Motelica-Heinoet al., 2003). This suggests that withinthe microniche there is a consortialmicrobial community that facilitates thedifferent chemical transformations.Outside the microniche chemical controltakes over as metals and sulphide areremoved according to the solubility offresh sulphide phases.

Whether or not microniches involvesulphate reduction, organic matter mustfuel them. Translocation of parcels ofreactive organic matter to depth withinthe sediment can only be brought aboutby macrobenthos. Decomposition of theparcel of organic matter is thenmicrobially mediated. Clearly then, inthis case, the biology is controlling thechemistry.

The precise nature of chemical andbiological interactions can only beappreciated if measurements are made onthe correct scale. DGT is a goodsurrogate for plant uptake because bothplants and DGT perturb the soil systemon the same scale (ca. 1 mm) andconsequently consider similar rates of

Environmental Chemistry Group Bulletin July 2003

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supply. Information gleaned from DGTis then directly relevant to plant uptake.Metals released from microniches ofpresumably microbial colonies are onlyobserved if measurements are able todetect their short range (ca. 1 mmdiameter), near spherical distribution. Totruly appreciate the details of chemical-biological interactions, it is necessary tostudy these highly localisedenvironments. This new understandingcan then be used to inform larger scalemodels and practical problems. Forexample the power of DGT as anassessment tool for potentiallybioavailable metal is greatly enhanced bythe firm base of underpinning scientificunderstanding.

References

Barber, S. A. Soil NutrientBioavailability; a Mechanistic Approach,Wiley, New York, 1995.

The EU’s Water Framework DirectiveIn the first of two talks at thehalf-day symposium, whichaccompanied this year’s ECGDGL, Professor Brian Mossfrom the School of BiologicalSciences at University ofLiverpool, spoke on theopportunities offered forimproving the coastal andfreshwater environments by theEuropean Water FrameworkDirective.

Introduction

We are on the threshold of using someof the most revolutionary newlegislation, the European WaterFramework Directive, ever to improveour coastal and freshwater environments.Yet it may be undermined by governmentconservatism, commercial vestedinterests, civil service lack of flair, andthe historic baggage of watermanagement in the UK. It will involvemuch greater absolute involvement byboth chemists and biologists, though therelative role of chemists will decrease a

little. Natural waters are enormouslycomplicated because of the pre-eminenceof living organisms in modifying thechemical template provided by theunderlying geology. They are by nomeans simple chemical systems. TheWater Framework Directive recognisesthis: it requires major changes in the waywe monitor and manage natural waters.At present in the UK we do not even dohalf a job, and the maps produced byDepartments of the Environment over thepast twenty years showing apparentlysteady improvements in water quality aregrossly misleading at best when it comesto a comprehensive view of the state ofour habitats.

The Water FrameworkDirective

The Water Framework Directive is longand apparently complicated but inprinciple it is simple. We must start tomanage whole catchments (River Basinsin the phraseology of the Directive), notjust the water-filled rivers and lakes (forwhatever happens in the catchmentsdetermines to a large extent what happensin the lakes and rivers); we must reducethe concentrations of a specified list of

highly toxic substances to below thedetection levels of the most sensitivemethods available; and we mustdetermine the ecological quality of all ouraquatic habitats according to a scale from‘high’ (virtually no human impact)through ‘good’ (slight deviation from‘high’), ‘moderate’, ‘poor’ and ‘bad’.Then we must restore all our habitats(subject to some derogations) to goodecological status by 2015. In contrast,at present we have little legislation forregulating land use in catchments, weallow specified levels of toxic substancesto persist on the basis of toxicologicaltests which, although repeatable in thelaboratory, may have little relevance towhat happens in complex ecosystems,and we monitor water quality, largelychemically, rather than ecologicalquality. Furthermore we monitor itessentially in respect of gross organicpollution, a problem of nineteenthcentury origin, now largely solved, andignore several much larger modernproblems.

The key to the Water FrameworkDirective is restoration of ecologicalquality. All other provisions ultimatelylead to this. We have therefore toestablish schemes which measure quality,

Davison, W.; Zhang, H. (1994) In situspeciation measurements of tracecomponents in natural waters using thin-film gels. Nature, 367, 546-548.

Davison, W.; Fones, G. R.; Grime, G. W.(1997) Dissolved metals in surfacesediment and a microbial mat at 100micron resolution. Nature, 387, 885-888.

Davison, W.; Hooda, P. S.; Zhang, H.;Edwards, A. C. (2000) DGT measuredfluxes as surrogates for uptake of metalsby plants. Adv. Environ. Res., 3, 550-555.

Fones, G. R.; Davison, W.; Hamilton-Taylor, J. (2003) Fine scaleremobilisation of metals in the surfacesediments of the North East Atlantic.Geochim. Cosmochim. Acta, submitted

Harper, M.; Davison, W.; Zhang, H.;Tych, W. (1998) Solid phase to solutionkinetics in sediments and soils

interpreted from DGT measured fluxes.Geochim. Cosmochim. Acta, 62, 2757-2770.

Motelica-Heino, M.; Naylor, C.;Davison, W. (2003) Simultaneous releaseof metals and sulphide in lacustrinesediment. Environ. Sci. Technol.,submitted.

Zhang, H.; Zhao, F.; Sun, B.; Davison,W.; McGrath, S. P. (2001) A new methodto measure effective soil solutionconcentration predicts copper availabilityto plants. Environ. Sci. Technol. 35, 2602-2607.

Zhang, H.; Davison, W.; Miller, S.; Tych,W. (1995) In situ high resolutionmeasurements of fluxes of Ni, Cu, Fe andMn and concentrations of Zn and Cd inporewaters by DGT. Geochim.Cosmochim. Acta, 59, 4181-4193.

Environmental Chemistry Group Bulletin July 2003

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within the detailed provisions stated inAnnexes to the Directive, even thoughthese lag somewhat behind currentecological understanding. The Directivesays we must first establish a typology, ageographical pigeonholing of differentsorts of habitats, and then for each of thecategories we must define the conditionsfor high quality sites. These parametersmust include, for example in rivers,invertebrates, aquatic plants and fish, thephysical structure of the habitat, and waterchemistry and we must then prescribewhat is meant by lesser degrees of statususing the same system. This will meanusing perhaps twenty or thirty variables,mostly biological, compared with thecurrent five or so, largely chemical. Amajor problem is that tangible high qualitysites are extremely scarce and probablyabsent in the more populated parts ofEurope, including the UK. However, weare allowed to use a variety of approaches,including expert judgement and historicalrecords, to establish what we mean byhigh quality conditions.

What is a river of highecological status like?

For rivers, for example, we can do thisfrom studies of north-temperate systemsthat have not been so severely damagedby engineering operations in the interestsof hydroelectric generation, floodcontrol, agriculture and waste disposalas those in the UK. I will take such ageneralised river to make the points. Thispristine river will have a catchmentcovered with natural vegetation, mostlyforest, which will retain and recycle soilnutrients so that even in soft rock areas,the phosphorus and nitrogenconcentrations in the water will be verylow (a few micrograms for phosphorus,a couple of hundred micrograms ofnitrogen at most). The upper reaches ofthe river will be overhung with forest andeven as the river widens, there will be agreat deal of tree debris in the channel.The debris and the rocks will accumulateleaves and small branches in many small,and some large, temporary debris dams.

This material is the main source of energyfor the ecosystem of the upstream river.It is poor in nutritional quality, however,because the forest, before shedding them,will have translocated valuable nutrientsfrom the leaves into trunks and roots for

re-use the following spring. However, theleaf debris in particular is colonised by aspecialist group of fungi, thehyphomycetes, capable of absorbingnitrogen and phosphorus from lowconcentrations and converting thecellulose and lignin of the debris tofungal protein. The colonised leaves arethen fed upon by invertebrates in a groupcalled the shredders, which includefreshwater shrimps and the larvae ofcrane flies (‘daddy long-legs’). Thesetear the leaves apart as they seek out thefungal protein. They are messy feedersand create a stream of fine particles,many of them faecal material, whichpasses downstream.

Downstream, as the river widens andmore light penetrates the forest canopy,diatoms and other algae will grow on thebed rocks, again drawing on the scarcedissolved nutrients in the water. Suchalgal films are fed upon by another groupof invertebrates, the scrapers, such asfreshwater limpets and mayfly nymphs,which also dislodge particles to enter theflow. The fine particles from shreddersand scrapers as well as material washedin from the catchment become colonisedby micro-organisms, which again convertrefractory into much more palatablematerial. They are subsequently eitherfiltered from the current by invertebratecollectors with nets or filtering limbs –blackfly larvae or caddis nymphs, forexample, or collect in the quieter nooksof the channel, where burrowinginvertebrates like midge larvae andoligochaete worms feed on them. In turnthese invertebrates are eaten by small fishor larger invertebrate predators so thatthere is a major link between thecatchment forest and the production ofthe river community.

Salmon, bears and nutrients

However, there is a much more excitingtwist to this otherwise mundane story offood webs. North-temperate rivers intheir pristine state support populations ofbig salmonid fish. These fish aremigratory. They are born in the rivers butmigrate to the sea after a year or so,spending several years as predators onother fish in the Atlantic or PacificOceans, accumulating nutrients in theirbodies. Later they move back to the riversystem where they themselves were born,

recognising it from the subtly differentwater chemistry of every river, despitemuch dilution in the estuaries and coastalwaters. They are unconsciously betterchemists than we are. Once they enterthe river systems, the salmon do not feedbut use up a lot of stored energy onmigration. Some die before reaching thespawning grounds and all from time totime congregate below waterfalls waitingfor suitable conditions for the jump theymust eventually make.

The carcasses and the vulnerable waitingfish are readily collected by brown bears,a major part of whose diet is made up offresh (or slightly ‘off’) salmon. In turn,the bears, when they move through theforest in search of other components oftheir diet, such as berries or meat, excreteand defaecate and cycle nutrientsultimately derived from the sea to theforest. This we know from studies of thestable isotope signatures of nitrogen inthe ocean, the fish, the bears’ faeces –and the trees. Close to the river, as muchas 25% of tree nitrogen is ultimatelybrought from the sea by the salmon andthe bears - a link now among the sea, theriver and the forest. But there is more.

Salmon that reach the headwaterspawning grounds have accomplished along journey and they now will expendabout half of their energy and materialsin producing eggs or milt. They excavatedepressions called redds in the gravelbeds of the rivers and bury the fertilisedeggs in coarse gravel, away frompredators but where oxygen-rich watercan flow freely around them through theinterstices between the stones. Almost allthe adults then die, their carcasseslittering the bottom. In the debris-cluttered pristine channel, these nutrient-rich bodies are held by the tree debris todecompose in situ, providing thenutrients the fungi and algae will needto provide the protein-rich food for theinvertebrates. In turn, these will be thefood for the young salmon when theyhatch and have used all of their yolk sac.In Pacific rivers where forestryoperations have prevented accumulationof tree debris, salmon recruitment hasfailed for lack of such nutrients for thecarcasses have been rapidly washed backto the sea. The pristine river thus showsa quite wonderfully efficient use andrecycling of the resources of catchment,forest, river and ocean.

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Floodplain rivers

The river system changes as it reacheslower ground and has become big withthe extension of its catchment. Its channelmust widen to accommodate the waterthat comes down in winter and it makes awide bed called the floodplain. Its summerchannel also meanders to accommodateeven the summer water flow. It is a gravemistake to think of such a river asunfortunately flooding what should be dryland from time to time. The floodplain isa natural part of the river, necessary toaccommodate the flows and providingsome of the most diverse habitats on earth.The floodplain has a complicated structurebecause material is deposited in floods toform banks and islands and to cut offmeanders as ox bow lakes. The siltdeposited supports swamps and wetgrasslands of great richness andproductivity. The outer reaches of thepristine floodplain, as they dry down insummer, provide lush grass which attractsgrazing animals and their predators. Fishspecies migrate up and down river andsideways into the floodplain to spawn inspring. Birds and invertebrates abound.Every great National Park has floodplainrivers at its heart.

These are the pristine systems, the modelsfor ‘high ecological status’ under the WaterFramework Directive. Under modesthuman impact they provide valuablegoods and services – recreational fisheries,high quality water supply in the upperreaches, flood storage, which mitigatesdamage downstream, water treatment(through denitrification, for example) andeven self-contained livelihoods for manytraditional peoples, in the lower reaches.Natural habitats of all kinds provide goodsand services annually which still amountto three times the combined gross productsof all the World’s economies put together.But they are easily damaged if theirmanagement does not recognise thecontinuous interlinking, or connectivity, ofall of them, as illustrated by the riversdescribed above. Past management hasbeen exceptionally myopic.

The damage

Upland rivers

Look at a typical upland river, forexample in the Pennines, the LakeDistrict or the Southern Uplands of

Scotland. It may look fine to a lay eye,but usually it will be much damaged. Itswater will be acidified from atmosphericpollution from industry or, increasingly,from vehicle exhausts. Its banks willhave no woodland, indeed will have beenseriously overgrazed so that the channelhas widened and shallowed and the waterwill heat up in summer to temperaturestoo high to support even brown trout, letalone the more demanding salmon – thatis if the salmon could get there. Mostrivers are occluded by dams or weirs thatare impassable. And even if the fish couldget over or round those, spawning sitesare scarce. Land erosion oraccumulations of refractory needles fromplanted exotic conifers clog the spawninggravels.

Lowland rivers

In the lowlands, there are no rivers whosefloodplains are intact. The presumptionhas been that the floodplains are land, tobe protected from water in the interestsof development or agriculture. Thesummer channels have been deepenedand straightened to move water as fastas possible to the sea. There is little floodstorage so heavy storms bring majordamage downstream. Flood protectionhas to be increased downstream toprotect property and is very expensive,ugly and, even if of use to man locally,is of no use at all to beast. Intensiveagriculture pollutes the water with largesupplies of nitrogen and phosphorus,destroying systems evolved to cope withsmall supplies of nutrients and replacingthem with clogging filamentous algalgrowth and sometimes toxic blooms. Wehave almost no knowledge of the subtleeffects of a huge number of chemicalsliberally discharged into the water froma myriad of agricultural and urbanactivities.

‘How to lie with maps’

Yet we pretend otherwise. We producemaps of water quality that actuallymeasure only the degree of pollution bygross organic matter and allege that theyrepresent river quality. Blue lines onthem, indicating excellent status, merelymean that the oxygen concentrations andbiological oxygen demand meet pre-determined arbitrary categories andsupport an invertebrate community thatrequires high oxygen concentrations. The

yellow and orange lines of poor and badquality decrease in length at every re-drawing and the improvement of the riversystem is lauded. But it is not improvingoverall at all! The maps are fiction if theyare purported to represent river quality.Most of our upland rivers (whose streamsare not included on the maps) areacidified or structurally impaired. All ofour rivers are altered by increasednutrient loading, and almost all ourlowland rivers are severely engineered.

In truth, the maps accurately representthe solution of the nineteenth centuryproblem of discharge of raw sewage,tannery and food waste, and the like intoour rivers. It was a major problem, but itis no longer the key problem for rivermanagement in the twenty-first century.Our present systems of monitoring andmanaging rivers are historical baggage.The Water Framework Directive isdesigned to face the twenty-first centuryproblems. But the problem may be thatthe thinking which has pervaded watermanagement so far will hamper thesuccessful operation of the Directive.

Implementing the Directive:technical problems and ‘FifthColumns’

The Directive requires management ofcatchments. This means dealing withdiffuse pollutants which are much moredifficult to control than the point sourcesof industrial and waste water effluentpipes. Planning control of land use hasbeen resisted by the land-owningcommunity for decades. Control of listedtoxic substances may appear less difficultbut total removal of them from wastewater poses major problems especiallyfor chemical engineers. Removal fromdiffuse sources may mean banning oftheir use. Many are pesticides. But themajor problems come in defining the‘good’ ecological status required forrestoration of rivers, lakes, estuaries andcoastal waters by 2015.

‘Good’ is defined in the Directive as onlyslightly deviant from ‘high’ and couldconceivably mean the reintroduction ofthe brown bear as a key component of afully functioning upland river system.This is unlikely but a far morecomprehensive approach to riverrestoration will be required. Floodplains

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that have been drained will, in manyareas have to be reconnected to thesummer channel. Even beforecontemplation of that will beconsiderable argument about how todefine status categories. The Directiveimplies, and the current thinking of mostwater managers is, that there is a singleset of conditions and a single collectionof organisms that can be used to defineecological status in a given place. Thisis a reflection of previous chemicallyconditioned thinking. The reality is thatecosystems exist in multiple stable statesand it is not possible to give a single setof conditions even for high status at agiven site. Many species substitutions arelikely and normal as a result of accidentsof biogeography and natural randomlocal extinction and re-colonisation. Thestatistical approaches that currentlygovern river classification on chemicalbases will simply no longer work;ecological systems are much morecomplex than solution chemistry, thoughthis nonetheless remains as a keycomponent of the assessment.

These technical problems can be solvedwith the will to solve them. There is, alas,increasing evidence of a fifth column inWhitehall. The consultation documentsissued by the Environment Agency and

the Scottish Environmental ProtectionAgency have already suggested the re-writing of the Directive to change themeaning of ‘high’ status so that standardsfor ‘good’‘ status can be reduced. Thisis undoubtedly illegal. There is strongresistance to the idea that floodplains areparts of rivers, ridiculous though this willseem to professional hydrologists andecologists, and the most recentconsultation paper from DEFRA reprintsthe water quality maps with theimplication that these are a good basisfor defining ecological status. This toois nonsense. There is opinion within theEnvironment Agency, reflected in theconsultation documents, that what cannotbe defined as precisely as a chemicalconcentration will simply be ignored.The upshot could therefore be merelyderisory low standards, tightened pointsource pollution control, use of thederogation provisions to exclude manysites as too expensive to improve,concentration only on the sitesdesignated under the European HabitatsDirective as special areas of conservationand continued neglect of the widercountryside. In time there would then beprosecutions in the European Court ofJustice, as there have been over the UK’sfailure to implement other Directives,that on Nitrates, for example, properly.

But all that takes time.

Better, if the spirit of the legislation isrespected, we could have a far moreinteresting, stimulating and valuablecountryside than the present desperatelydamaged one. It would be a tragedy ifmajor changes do not come about as aresult. The Water Framework Directivehas much wider implications thanperhaps even Government presentlyrealises. To manage river basins wiselyto create ecological status in thewaterways that will hold muster tostandards elsewhere in Europe means anintegration of policies on farming,housing, air pollution, industrialdevelopment, waste disposal,conservation and economics. The presentadministrative structure which separatesthese among different ministries andagencies is undoubtedly inadequate tocope. The future may lie in catchment-based organisations with a responsibilitytowards the whole catchment not somesectional use of it. These are potentiallyexciting times for chemists and biologistsalike. It will be tragic if the dead hand ofpast attitudes gets in the way.

Web link: The Water FrameworkDirective http://www.defra.gov.uk/environment/water/wfd/

Biological monitoring versus chemical analysis in environmentalmonitoringIn the second talk at this year’sDGL half-day symposium,Professor Mike Depledgefrom the UK’s EnvironmentAgency reviewed sometechniques for monitoring thehealth of the environment.

For the Environment Agency (EA), thepurposes of monitoring are to detectpotential threats to humans andecosystems and ensure that they areinvestigated. The monitoring shouldcover baseline and abnormalconcentrations of materials in differentmedia and should also observe the healthof organisms and the health links tochemical species, speciation, toxicologyand bioavailability.

Pollutants affect the health of organismsvia molecular, biochemical, physio-logical, individual and ultimatelypopulation responses, and the quality oforganism health can therefore beinvestigated by examining immuno-toxicity, genotoxicity, neurotoxicity,endocrine disruption and metabolictoxicity. This can be achieved withbiomarkers - responses which use tissuesamples, body fluid samples or wholeorganisms to measure signals of exposureto, and/or the adverse effects of,chemicals or radiation. The bestbiomarker is one that offers a precisemeasure of Darwinian fitness.

One such example of a biomarker is themeasurement of heart rate which can beperformed using an infrared photo-transducer on species such as crabs. Forthe rock crab in Otago Harbour, NewZealand, the observed increase in median

heart rate correlated with the (increasing)pollution gradient from the harbourmouth to the harbour interior. Otherbiomarkers include behavioural studies(the speed and frequency of directionalchanges of crabs increases with pollutionexposure), success in habitat occupancyby marine crustaceans, the immuno-competence of Mytilus edulis (commonmussel), and the Comet assay and/ormicronucleus assay for work at the singlecell level.

Some of these techniques are cheap,quick and robust and they are useful inhelping the creation of monitoringsystems in developing countries. TheRapid Assessment of Marine Pollution(RAMP) scheme is a UN supportedtechnology transfer programme, which isassisting this process. But the EA alsoneeds to develop effective techniques forcontinuous remote monitoring. Currently

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the EA pays £20 million for water samplecollection each year but only £11 m forthe analysis of the 3.8 milliondeteminants associated with the 268 00samples collected. Although the EA hasa £750 m budget, only 1.3% of this iscurrently allocated to R&D. Hence theresearch necessary for the introduction

of changes in monitoring practice(particularly those related to the WaterFramework Directive) will require somechanges in funding priorities.

Web links for RAMP:

http://ioc.unesco.org/goos/RAMP_article.htm

http://coexploration.org/ramp/index.htm

Summary by Dr LEO SALTER,Cornwall College,Pool, Redruth, Cornwall

Arsenic hyperaccumulation in ferns: a reviewThe first report of a fern, whichcould accumulate arsenic, waspublished by Lena Ma et al. inNature in 2001 (see Environ-mental Chemistry GroupNewsletter No. 15, February2002). This publicationgenerated great interest, notonly as the first report of a fernthat showed hyperaccumulationcharacteristics, but also becausethe fern, Pteris vittata, was ahighly efficient accumulator ofarsenic. Publications reportingsimilar hyperaccumulationcharacteristics in othermembers of the Pteris familyquickly followed. The Pterisfamily is not native to theBritish Isles, but it has nowbeen shown that Pteris cretica,found naturalised in Cornwall,exhibits arsenic hyper-accumulation characteristics. Inthis review, Carolyn Wilkinsand Leo Salter from CornwallCollege describe some of thecharacteristics of ferns thatdistinguish them from the morefamiliar flowering plants andreview the research that hasrecently been published onferns as arsenic hyper-accumulators.

Fern biology

Ferns are ubiquitous in rain forests.However, ferns can be found in a widerange of terrestrial environments in every

continent, and adaptation to these variedhabitats means that ferns also have a largerange of differing growth characteristics.For example, frond length can range froma few millimetres to several metres, frondscan manifest many different shapes andferns can be epiphytic or can bewaterborne as well as soil or rock based.

Ferns are not flowering plants.Reproduction is a two-part cycle withalternation of generations in which thesporophyte generation is prominent.Spores are produced, usually on theunderside of the fertile fronds, in groupsof sporangia (the sori) that show distinctpatterns. The sori are often protectedby a membrane, the indusa, in the earlystages of spore development. As sporesmature, the sporangium tends to darkenin colour. The sporangium bursts, thespores are ejected into the environmentand then germinate on damp surfaces toform a freestanding gametophyte in theform of a prothallus. Both male andfemale reproductive organs are containedin the prothallus and in wet conditionsthe male cells migrate to fertilise thefemale reproductive structure. Theprothallus can be self-fertilising or crossfertilisation can take place. As a resultof fertilisation, sporelings are formed thatcan develop into mature ferns.

A brief introduction and description ofthe life cycle of ferns can be found atwww.amerfernsoc.org

Fern palaeobotany

Ferns and fern allies are very ancient.The fossil evidence shows that fiveclasses of ferns and fern allies werepresent in the Devonian period and theydominated the vascular plants until theMesozoic era when angiospermsproliferated. The true ferns or Pteropsidahave been present since early in theCarboniferous period. The order

Pteridales was first recorded from theMiocene period. In Cornwall the ancientferns Osmunda and Ophioglossum sp. arerepresented, as are several of the ancientfern allies (e.g. Equisetum, Selaginella,Botrychium and club mosses).

Fern classification

In the past, fern classification has beenbased on fern morphology.Distinguishing characteristics such asspore shape and distribution were usedto identify various ferns. Recently,extensive research on fern classificationhas been reported by Hassler and Swale(http://www.caverock.net.nz/~bj/fern)and Pryer et al. (1995) in whichmorphological characteristics and rbclsequencing have been used to produce aphylogenetic classification. Linkingthese classifications to arsenicaccumulation by ferns might lead to theidentification of the evolutionarycharacteristics that produce arsenicaccumulation (Meharg, 2002a,b) andthis, in turn, would add to the repositoryof knowledge designed to help theoptimisation of these properties. So far,two genera of fern have been found toaccumulate arsenic (Pteris andPityrogramma). These are bothmembers of the Order Pteridales.However, as 10% of all ferns belong tothis order it is, therefore, quite possiblethat other ferns that accumulate arsenicwill be discovered in the future.

Metal hyperaccumulation

It has long been recognised (Baker,(1981); Baker, (1987); Baker andWhiting, (2002)) that some angiospermsgrowing on metalliferous substrates canaccumulate large amounts (percentages)of heavy metals in the above groundbiomass. The potential of these plantsfor phytoremediation (the removal ofcontaminants by plants) has generated

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much academic and some commercialinterest (Raskin et al., 1994).

Plants growing on metalliferous soils caneither take up large amounts of the metalinto the above ground biomass(accumulators), or can block thetransport of metals between root andshoot (excluders). Accumulator plantshave the facility to concentrate metalsfrom soils that contain low as well as highconcentrations of metals. Plants thatshow exceptional uptake of metals areknown as hyperaccumulators, the termfirst being used to describe plants thatwere found to contain over 0.1% nickelin the dried tissue (Brooks et al., 1977).The threshold of 0.1% does not apply toall metal hyperaccumulation, ‘hyper-accumulator’ is an arbitrary term used todescribe plants with the ability toaccumulate at least an order of magnitudemore of a particular metal than ‘normal’plants. In the case of zinc, 1% of zinc inthe dry plant tissue would suggesthyperaccumulation whereas for gold, 1mg/kg of gold would indicate hyper-accumulation (Baker and Brooks, 1989).

Hyperaccumulator plants are oftenindigenous to particular metalliferoussubstrates and this feature is used as thebasis for geobotanical exploration.Within the last quarter century, there havebeen many hyperaccumulator genotypesrecorded, especially zinc and cadmiumhyperaccumulators from the calaminesoils of Europe, nickel and chromiumhyperaccumulators from serpentine soilsworldwide (and especially NewCaledonia) and copper hyper-accumulators from the Copper Belt ofCentral Africa. However, although fernshave been noted to be growing onmetalliferous substrate, no ferns havebeen reported in the literature as metalhyperaccumulator plants.

Hyperaccumulation ofarsenic

Metalloid hyperaccumulator plants(plants that take up metalloids such asmercury, arsenic, uranium and selenium)are not as well documented as metalhyperaccumulators with the exception ofselenium hyperaccumulators that wererelated to the occurrence of ‘loco’ diseasein horses in the USA (Rosenfeld andBeath, 1964). Arsenic accumulation hasbeen reported in grasses (Porter andPeterson, (1975); Meharg and Hartley-

Whitaker, (2002)). However, the firstreport of arsenic hyperaccumulation bya fern (Pteris vittata) (Ma et al., 2001)created much interest among scientistsresearching metal hyperaccumulation.Pteridophytes (or ferns and horsetails)are little known phyla of the plantkingdom. As mentioned above, they areancient plants with a long fossil recordand they are very diverse both in habitatand morphology. Pteris, one of the twogenera that have been found, so far, toaccumulate arsenic have been detectedin rocks from the Miocene period (C.Page, private communication).However, it is not possible to say whetheror not that the arsenic accumulationcharacteristic appeared in this period. Itmay be that it is a trait that has emergedand died out several times in theevolutionary history of the ferns.Recently, in addition to their arsenichyperaccumulating properties there hasbeen a resurgent interest in fern-basedmedicinal compounds.

Research into arsenicaccumulation by plants

Arsenic tolerant flora has been found inthe South West of England on highlyacidic mine waste containing 10,000 –30,000 mg/kg arsenic in the surfacehorizons (Porter and Peterson, 1975).Plant cover was sparse but grasses withup to 0.7% arsenic were present.Agrostis tenuis samples from soils with10 000 mg/kg arsenic showed extremevariability of uptake of arsenic rangingfrom 3 to 3000 mg/kg arsenic (Porter andPeterson, 1975). Arsenate, the dominantform of arsenic in well-drained soils,competes for uptake with phosphate inplants and alteration of the phosphatetransport system is necessary if plants areto suppress arsenic uptake (Meharg andMacnair, 1992). Mycorrhizal associationsare common on metal(loid) contaminatedsoils and these are known to increasephosphate transport to the host plants.However, the same mycorrhizalassociations also appear to enhancearsenic resistance. A comprehensivereview by Meharg and Hartley-Whitaker(2002) of arsenic uptake by plantssuggests very complex interrelationshipsbetween mycorrhizal associations andbetween phosphate and arsenatetransport within the plants. Themechanisms have yet to be fullyunderstood.

Arsenic accumulation by ferns wasinvestigated by Lombi et al. (2002). Itwas reported that 96% of the arsenicappeared to be held in the pinnae of thefern and less than 2% of this arsenic waspresent in the spores. Furthermore, thearsenic content of the pinnae increasedwith maturity with basal pinnae havingup to 3 times as much arsenic as thenewly formed pinnae. The majority ofthe arsenic was found as arsenite(As(III)) (75%) with the remainder asarsenate (As(V)). However, maturefronds appeared to have more As(V) thanyoung fronds, suggesting that there is re-oxidation of As as fronds mature. TheAs(III)/As(V) partitioning found byLombi et al., (2002) was similar to thatreported by Ma et al. (2001) andFrancesconi et al. (2002). It is suggested(Lombi et al., (2002)) that the arsenic isstored in cell vacuoles which would beanalogous to the process of heavy metalstorage in metal hyperaccumulatorplants.

Ferns that hyperaccumulatearsenic

At present, Pityrogramma calemelanos(Francesconi et al., (2002)) and severalspecies of the Pteris family (Ma et al.,(2001); Meharg and Hartley-Whitaker,(2002); Zhao et al., (2002)) have beenreported to be arsenic hyper-accumulators. However, not all thePteris family are hyperaccumulators andresearch is now starting on trying toidentify the characteristics of the speciesthat accumulate arsenic (McGrath,private communication). Pityrogrammais a close relative of the Pteris family.

So far, no British native ferns have beenshown to accumulate arsenic but Pteriscretica, a fern that has naturalised inCornwall, does hyperaccumulate arsenic.However, although two native ferns,Athyrium filix-femina (Lady Fern) andPhyllitis scolopendrium (Harts TongueFern), appear to be primary colonisers ofarsenic rich mine waste in Cornwall, they donot accumulate arsenic (present study).

Possible uses of arsenichyperaccumulating plants

Anthropogenic and naturalconcentrations of arsenic result incontaminated land and contaminatedwater supplies. Arsenic is present in

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some metallogenic provinces (e. g.Cornwall) and gives rise to elevated soilconcentrations. In mining areas, spoilheaps can have arsenic concentrations ofmore than 1% while areas that have beenpolluted by arsenic calcining operationscan have an order of magnitude greaterarsenic concentration. The acceptedstandard for garden and parkland soilsin the UK is 40 mg/kg; in West Cornwall,it is not unusual to have over 250 mg/kgarsenic in garden soil. Wood treatmentplants and various agricultural operationsalso give rise to elevated arsenic in soil.

Arsenic is related to several seriousmedical conditions. It is, therefore,necessary to clean up areas in which thepopulation is vulnerable to arsenictoxicity. Phytoremediation is a costeffective, low technology treatment thatuses plants to decrease the concentrationsof toxic materials in soils and waters.The ferns that hyperaccumulate arsenicare candidates for phytoremediation asthey are fast growing, can be harvestedseveral times a year and are capable ofremoving substantial amounts of arsenicfrom the surrounding soil. Francesconiet al. (2002) approximately calculatedthe reduction in arsenic concentrationfrom a soil containing 500 mg/kg As thatPityrogramma calomelanos couldachieve in one year in a field trial inThailand as a 2% reduction.

The problem of disposal of arsenic richvegetation has not yet been resolved.Francesconi et al. (2002) suggesteddisposal to a marine environment whereany anionic arsenic would rapidly bealtered to non-toxic organic arseniccompounds such as arsenobetaineMe3As(+)CH2CO2

(-). Members ofRothamsted Research and RTZ arecurrently researching other mineralprocessing techniques that may beapplied to recycling arsenic richvegetation. Conventional incinerationof Municipal Solid Waste may also besuitable for the disposal of arsenic richvegetation.

References

Baker, A. J. M. (1981) Accumulators andexcluders – strategies in the response ofplants to heavy metals. Journal of PlantNutrition, 3, 643-654.

Baker, A. J. M. (1987) Metal tolerance.New Phytologist, 106, 93-111.

Baker, A. J. M.; Brooks, R. R. (1989)Terrestrial higher plants whichhyperaccumulate metallic elements – areview of their distribution, ecology andphytochemistry. Biorecovery, 1, 81-126.

Baker, A. J. M.; Whiting, S. N. (2002) Insearch of the Holy Grail – a further stepin understanding metal hyper-accumulation? New Phytologist, 155, 1-4.

Brooks, R. R.; Lee, J.; Reeves, R. D.;Jaffre, T. (1977) Detection of nickel-iferous rocks by analysis of herbariumspecimens of indicator plants. Journalof Geochemical Exploration, 7, 49-77.

Francesconi, K.; Visoottiviseth, P.;Sridokchan, W.; Goessler, W. (2002)Arsenic species in an arsenichyperaccumulating fern, Pityrogrammacalomelanos: a potential phyto-remediator of arsenic-contaminatedsoils. JournaI of the Science of the TotalEnvironment, 284, 27-35.

Hassler, M.; Swaler, B. ‘World of Ferns’Website http://www.caverock.net.nz/~bj/fern

Lombi, E.; Zhao, F. J.; Fuhrmann, M.;Ma, L. Q.; McGrath, S. P. (2002) Arsenicdistribution and speciation in the frondsof the hyperaccumulator plant Pterisvittata. New Phytologist, 156, 195-203.

Ma, L. Q.; Komar, K. M.; Tu, C.; Zhang,W. H.; Cai, Y.; Kennelley, E. D. (2001)A fern that hyperaccumulates arsenic: ahardy, versatile, fast-growing plant helpsto remove arsenic from contaminatedsoils. Nature, 409, 579.

Meharg, A. A. (2002a) Arsenic and oldplants. New Phytologist, 156, 1-8.

Meharg, A. A. (2002b) Variation inarsenic accumulation – hyper-accumulation in ferns and their allies.New Phytologist, 157, 25-31.

Meharg, A. A.; Hartley-Whitaker, J.(2002) Arsenic uptake and metabolism inarsenic resistant and non-resistant plantspecies. New Phytologist, 154, 29-43.

Meharg, A. A.; MacNair, M. R. (1992)Suppression of the high-affinityphosphate-uptake system – a mechanism ofarsenate tolerance in Holcus lanatus L.Journal of Experimental Botany, 43, 519-524.

McGrath, S. P.; Zhao, F. J.; Lombi, E.(2002) Phytoremediation of metals,

metalloids, and radionuclides. Advancesin Agronomy, 75, 1-56.

Porter, E. K.; Peterson, P. J. (1975)Arsenic accumulation by plants on minewaste (United Kingdom). Journal of theScience of the Total Environment, 4, 365-371.

Pryer, K. M.; Smith, A. R.; Skeg, J.(1995) Phylogenetic relationships ofextant ferns based on evidence frommorphology and rbcl sequences.American Fern Journal, 85, 205-282

Raskin, I.; Kumar, P. B. A.; Dushenkov,S.; Salt, D. E. (1994) Bioconcentrationof heavy metals by plants. CurrentOpinion in Biotechnology, 5, 285-290.

Rosenfeld, I.; Beath, O. A. (1964)Selenium – Geobotany, Biochemistry,Toxicity and Nutrition. Academic Press,NY and London.

Tu, C.; Ma, L. Q. (2002) Effects ofarsenic concentrations and forms onarsenic uptake by the hyperaccumulatorladder brake. Journal of EnvironmentalQuality, 31, 641-647.

Visoottiviseth, P.; Francesconi, K.;Sridokchan, W. (2002) The potential ofThai indigenous plant species for thephytoremediation of arseniccontaminated land. Journal ofEnvironmental Pollution, 118, 453-461

Wang, J.; Zhao, F. J.; Meharg, A. A.;Raab, A.; Feldmann, J.; McGrath, S. P.(2002) Mechanism of arsenichyperaccumulation in Pteris vittata.Uptake kinetics, interactions withphosphate and arsenic speciation. PlantPhysiology, 130, 1552-1561.

Wilkins, C.; Salter, L. (2002) An arsenicaccumulating fern in Cornwall. Geo;Newsletter of the Royal GeologicalSociety of Cornwall, no 19, 4-5.

Zhao, F.J.; Dunham, S. J.; McGrath, S.P. (2002) Arsenic hyperaccumulation bydifferent fern species. New Phytologist,156, 27-31

Web links: www.amerfernsoc.orgwww.caverock.net.nz/~bj/fern

CAROLYN WILKINS and LEOSALTER,Cornwall College,Pool, Redruth, Cornwall.June 2003

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Arsenic in UK soils and the new intervention valuesGuidance has recently beenpublished by the UKgovernment on the assessmentof risks to human health fromland contamination, includingSGV’s (soil guideline values)for a range of inorganiccontaminants. The interventionvalue (SGV) for residentialareas and allotments for arsenic(As) is 20 mg kg-1. The tieredrisk analysis approachadvocated in UK guidancesuggests that further site-specific studies should beundertaken when a statisticallyderived upper mean value at asite exceeds the guideline valuefor specific land use types.Recent chemical analysis ofsoils in one region of the UK(including the City of Sheffield)undertaken by the BritishGeological Survey (BGS)shows that natural soil arsenicconcentrations above the SGVare widespread. Barry Rawlins,Bob Lister and Mark Cavefrom the BGS describe thissurvey and comment on theimplications of the results.

Introduction

Trace metals and metalloid elementssuch as arsenic occur naturally in allsoils, typically at low concentrations.Where soils have developed overmineralised rocks, or where humanactivities have caused contamination,their concentrations may be much higher,and may represent a hazard (Table 1). InApril 2000, the Contaminated LandRegulations in England [1] came intoforce, and placed duties on localauthorities to inspect their areas toidentify sites which fall into its definitionof ‘contaminated land’, and required itsremediation in line with the ‘suitable foruse’ approach. A risk-based approach istaken in the UK to defining contaminated

land, which is in turn based on the linkagebetween a source (the contaminant), apathway (such as the consumption offood) and a receptor (for example, ahuman being). In the case of humanbeings, the harm, which may be causedby a contaminant, is a human healtheffect, such as the development of cancerfrom a carcinogenic compound.

The guidance on the definition ofcontaminated land refers to the use of‘relevant information’, which isscientifically based, authoritative andrelevant to the assessment of risks arisingfrom the presence of contaminants in soil[2]. Guidance has recently beenpublished on the assessment of risks tohuman health from land contamination[3], which includes Soil Guideline Values(SGV’s) for inorganic contaminants suchas arsenic [4]. Where the concentrationis above the SGV, there is a ‘need toconsider whether the presence of thecontaminant justifies taking remedialaction.’ Local authorities and otherstakeholders use a tiered approach toassessing the risks from contaminatedland [3]. Scientifically derived genericSGV’s are used in the first tier of the risk-based approach to screen those siteswhich may pose a risk to human healthand warrant further attention.

In the case of arsenic, the published SGVfor residential areas and allotments is 20mg kg-1 [4]. The risk associated with soilarsenic is principally via consumption offood and the ingestion of soil and dusts(or soil particles attached to food). Inthis paper we define soil as the natural,unconsolidated mineral and organicmaterial occurring above bedrock andQuaternary deposits at the surface of theEarth. Soil ingestion by adults in the UKis generally inadvertent, although thefrequent hand-to-mouth activity ofchildren can lead to the ingestion of moresignificant quantities of soil. There issurprisingly little published data on theconcentration of arsenic in UK soils atthe regional scale. For example, the soilgeochemical atlas of England and Wales[5], which summarises data from theNational Soil Inventory, did not includearsenic in its list of elements. However,data recently released by the BritishGeological Survey [6] show that thenatural arsenic content of soils in a region

of north-east England (including the Cityof Sheffield) often exceed the SGV forresidential areas and allotments.

Soil geochemical surveys

As part of its G-BASE (GeochemicalBaseline Survey of the Environment)project in the UK, BGS (the BritishGeological Survey) collects and analysessoils regionally and in urbanenvironments. A recent regional surveycomprised 6,400 topsoil samples in ruralareas in north-east England at an averagedensity of 1 sample per 2 squarekilometres. Soil sampling sites wereselected on a systematic basis from everysecond kilometre square of the BritishNational Grid. Site selection in eachsquare was random, subject to theavoidance where possible of roads,tracks, railways, human habitation andother disturbed ground. The region has avariety of soil parent material typesincluding lithologies ranging from theCarboniferous Limestone and CoalMeasures rocks in the west to CretaceousChalk in the east, and several types ofunconsolidated, Quaternary deposit.

An urban survey was also undertaken inthe City of Sheffield at a higher densityof 4 samples per square kilometre. Inthe urban survey, soil sampling isundertaken on the least disturbed,undeveloped area of ground closest to thecentre of each 500 m square cell. Typicalland use types are domestic gardens,allotments, parks or recreational ground.

At each survey site, five holes wereaugered at the corners and centre of asquare with a side length of 20 metresusing a hand auger. The soil sampleswere taken at depths of between 0 and15 cm, after removal of any surfaceorganic matter. The soil samples fromeach five holes were combined to forman aggregated sample. All soils weredisaggregated following drying andsieved to 2 mm and this fraction wasanalysed by X-Ray Fluorescence todetermine the total concentration of 24major and trace elements (includingarsenic). The analytical detection limitfor arsenic was 1 mg kg-1. An analysisof variance performed on data for arsenicin soil sub-samples showed thatanalytical error accounted for only 1.6%of the total variance in the dataset.

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The regional survey

The sample locations were transferred toa geographical information system andthe soil samples were classified by parentmaterial type using combined versionsof solid geology and Quaternary mapsin digital form. The influence of parentmaterial could be clearly seen in thespatial distribution of arsenicconcentrations. Soils developed overJurassic and Cretaceous ironstonedeposits have the highest natural arsenicconcentrations (maximum value 227 mgkg-1), whilst those over the CarboniferousCoal Measures, Jurassic Limestone, andrecent alluvial and peat deposits alsohave naturally elevated values. Despitesoils over these deposits having thehighest levels, they also have a broadrange of concentrations, with the smallestvalues being typical of other parentmaterial types. Arsenic in soilsdeveloped over the Carboniferous CoalMeasures is likely to be derived from anassociation with the mineral pyrite,commonly found in coal-bearing rocks[7]. Consistently low arsenic valuesoccur where soils have developed overthe Permo-Triassic Sherwood Sandstone.Further north, where Quaternary depositsoverlay the Sandstone, the arsenic valuesare more varied. Likewise along the coastof Lincolnshire, arsenic concentrationsreflect the distributions of marinealluvium and glacial drift. By classifyingeach sample point by its underlyingparent material, we have calculated thatthis accounts for 33% of the variation intotal arsenic concentration.

Natural arsenic concentrations above theSGV of 20 mg kg-1 are commonthroughout the region, occurring ataround 20% of sites. Appreciation of the

typical concentrations of a range ofpotentially harmful compounds in soilsthat develop over different parentmaterial types as shown here are usefulas they put into context the results of site-specific investigations.

Urban survey of Sheffield

Although understanding the regionaldistribution of soil arsenic is useful inproviding an overview, contaminatedland investigations (for which SGV’s areused) are far more common in the urbanenvironment. Soils in Sheffield arelargely derived from Coal Measures,although those in part of the west of theCity overly Millstone Grit.Approximately two-thirds (63%) of the569 samples had total arsenicconcentrations above the 20 mg kg-1 SGVfor residential areas and allotments.These data are presented as individualpoints because the uncertainty ofinterpolating values between samplelocations in urban areas is much greaterthan the rural environment. Two furtherfactors need to be considered incomparing the urban survey data withthis SGV. First, contaminated landinvestigations typically involve theanalysis of numerous soil samples acrossa site, whilst the urban survey datapresented here are from a composite soilsample of five auger holes at anindividual site. Second, the guidance [3]states that a mean value test should beapplied to soil chemical data frompotentially contaminated sites (based onthe upper 95% confidence limit of themeasured mean) to determine whetherthe SGV has been exceeded. Despitethese qualifications, it is clear that resultsof site investigations across much of the

City are likely exceed the threshold andrequire further, detailed risk assessments.

Improving human riskassessment using abioaccessibility test

Where arsenic occurs naturally at highconcentrations, site-specific riskassessments could include the use of alaboratory test to determine thebioaccessibility of soil arsenic. TheSGV’s are based on the assumption that100% of the ingested arsenic is taken upby the systemic circulation. However, ifarsenic is bound to the soil in a non-reactive form, which is not available forabsorption in the human gut, the actualbioaccessibility, and therefore exposure,may be greatly reduced. To assess thefraction of arsenic in the soil that is likelyto be ‘bioaccessible’, and hence improvehuman health risk assessment, extractiontests can be applied to soil samples thatmimic the conditions in the humangastro-intestinal tract [8]. This in vitromethod mimics the pH and oxidising/reducing conditions in the humanstomach and small intestine, and theresidence times of ingested material. Thestomach phase of the test is acidic (pH2.5), whilst the intestinal phase is neutral(pH 7). The concentration of arsenic inthe test solution as a proportion of itsconcentration in the soil is used toestimate bioaccessibility (asoperationally defined by the method).Such data, which include the total,bioaccessible fraction and form ofarsenic, should then be used inconjunction with epidemiological andtoxicological information to form thebasis of a model that will provide asensible prediction of the risk to humanhealth from arsenic in soils.

Table 1 - Arsenic facts

General• occurs naturally in rocks, soil, water,

air, plants, and animals• the 20th most common element in the

earth’s crust and the 12th mostcommon element in the humanbody.

• typical arsenic minerals:arsenopyrite (FeSAs), realgar (AsS),arsenolite (As2O3)

• industrial uses: wood preservatives,paints, dyes, metals, drugs, soaps,semi-conductors, and pesticides.

Environmental SourcesCoal combustion, ore roasting andsmelting, pig and poultry sewage,phosphate fertilisers

Health RisksLong-term, chronic effects of exposureto low concentrations of arsenic includeskin, bladder, lung, and prostate cancer.Non-cancer effects of ingesting lowlevels of arsenic include cardiovasculardisease, diabetes, anaemia, reproductiveproblems, immunological disorders, and

neurological ailments. Gastrointestinalirritations, convulsions, and death canoccur at very high doses.

Soil Guideline values* for land-usetypes (published March 2002):Residential and allotments – 20 mg kg-1

Commercial / Industrial – 500 mg kg-1

* based on total inorganic arsenic in soiland derived assuming a sandy soil type[9]

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References

[1] DETR. The Contaminated Land(England) Regulations 2000.Department of the Environment,Transport and the Regions,London, 2000.

[2] DETR. The Contaminated Land(England) Regulations 2000:Annex 3, Chapter A - StatutoryGuidance on the Definition ofContaminated Land. Departmentof the Environment, Transportand the Regions, London, 2000.

[3] DEFRA and EnvironmentAgency (2002a) Assessment ofRisks to Human Health from LandContamination: An Overview ofthe Development of GuidelineValues and Related Research,Report CLR7. Available from TheR&D Dissemination Centre,WRC plc, Swindon, Wilts.

[4] DEFRA and EnvironmentAgency (2002b) Soil GuidelineValues for Arsenic Contamination(SGV1). http://www.defra.gov.uk/environment / landl iabi l i ty /pubs.htm#new. Accessed 08August 2002.

[5] McGrath, S. P.; Loveland, P. J.The Soil Geochemical Atlas ofEngland and Wales. 1992,Glasgow: Blackie Academic andProfessional.

[6] Soil geochemical data availablefrom the British GeologicalSurvey can be found on thewebsite at http://www.bgs.ac.uk/geoindex. Accessed 08 August2002.

[7] Spears, D.A.; Manzanares-Papayanopoulos, L. I.; Booth, C.A. The distribution and origin oftrace elements in a UK coal; theimportance of pyrite. Fuel, 1999,78, 1671-1677.

[8] Ruby, M.V.; Davis, A.; Schoof,R.; Eberle, S.; Sellstone, C. M.Estimation of lead and arsenicbioavailability using aphysiologically based extractiontest. Environmental Science &Technology, 1996, 30, 422-430

[9] DEFRA and Environment Agency(2002c). The ContaminatedLand Exposure Assessment(CLEA) Model: Technical Basisand Algorithms. Report CLR10.Available from The R&DDissemination Centre, WRC plc,Swindon, Wilts.

Acknowledgement

The ECG Committee thanks ProfessorBarry Smith of the BGS for permissionto reproduce this modified version of apaper, which was originally published,with Figures, in Civil Engineering,November 2002, 187-190 (Paper 12731).

Another mechanism for arsenic’s carcinogenicityArsenic is a human carcinogen.However, the mechanisms of arsenic’sinduction of carcinogenic effects havenot been identified clearly (cf. ECGNewsletter Issue No. 15, p. 19). It haspreviously been shown thatmonomethylarsonous acid (MMA(III))and dimethylarsinous acid (DMA(III))are genotoxic and can damagesupercoiled phiX174 DNA and the DNAin peripheral human lymphocytes inculture. These trivalent arsenicals arebiomethylated forms of inorganic arsenicand have been detected in the urine ofsubjects exposed to arsenite and arsenate.

New work now indicates that reactiveoxygen species (ROS) are intermediatesin the DNA-damaging activities ofMMA(III) and DMA(III). Using thephiX174 DNA nicking assay it was foundthat the ROS inhibitors Tiron, melatonin,and the vitamin E analogue Troloxinhibited the DNA-nicking activities ofboth MMA(III) and DMA(III) atlow micromolar concentrations. The spintrap agent 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) also was effective atpreventing the DNA nicking induced byMMA(III) and DMA(III.) Electron spin

resonance studies using DMPOidentified a radical as a ROS intermediatein the DNA incubations with DMA(III).This radical adduct was assigned to theDMPO-hydroxyl free radical adduct onthe basis of comparison of the observedhyperfine splitting constants and linewidths with those reported in theliterature. The formation of the DMPO-hydroxyl free radical adduct wasdependent on time and the presence ofDMA(III), and was completely inhibitedby Tiron and Trolox and partiallyinhibited by DMSO. Using electrospraymass spectrometry, micromolarconcentrations of DMA(V) weredetected in the DNA incubation mixtureswith DMA(III). These data are consistentwith the conclusions that the DNA-damaging activity of DMA(III) is anindirect genotoxic effect mediated byROS-formed concomitantly with theoxidation of DMA(III) to DMA(V).

DNA damage induced by methylatedtrivalent arsenicals is mediated byreactive oxygen species. Nesnow, S. etal., Chemical Research in Toxicology,2002, 15, 1627-1634.

Environmental Chemistry Group Bulletin July 2003

14

The Loe Pool Management ForumBy Loe Pool

THE pool glitters, the fishes leap in the sunWith joyous fins, and dive in the pool again;I see the corn in sheaves, and the harvestmen,And the cows coming down to the water one by one.Dragonflies mailed in lapis and malachiteFlash through the bending reeds and blaze on the pool;Seaward, where trees cluster, the shadow is cool;I hear a singing, where the sea is, out of sight;It is noontide, and the fishes leap in the pool.

Arthur Symons(1865-1945)

(Carvalho & Moss, 1995).

In June 1996 the Loe Pool ManagementForum (LPMF) was established and fourmain objectives were identified (Wilson& Dinsdale, 1998):

1. To bring about a change from analgae-dominated turbid water stateto a macrophyte-dominated clearwater state characteristic ofmesotrophy.

2. To establish more natural seasonalfluctuations in water levels andcreate conditions for a more diverseshoreline and submerged flora.

3. To maximise the nature conservationvalue of Loe Pool and its catchment.

4. To interest and involve thecommunity in the management ofLoe Pool and its catchment.

The management approaches used toachieve these objectives are discussed inthis article.

Management

The Environment Agency via its systemof LEAPs (Local Environment AgencyPlans) is responsible for certain aspects(fisheries, flood defence, water quality,water abstraction) of Loe Pool and itscatchment. Their funding (1997-1998)provided the catalyst to develop aManagement Plan and they continue tocontribute resources for its

implementation. The Management Plan(Wilson & Dinsdale, 1998) classed themanagement issues into a number oflinked but conceptually distinguishabletopics; some of these (agriculture,sewage, water-level, fish) are discussedbelow.

Agriculture

Agricultural effects on the Pool (diffuseN and P inputs, contributions to riversiltation and conservation decrements towetland sites in the catchment) are beingminimised by the designation of thecatchment under the CountrysideStewardship Scheme (CSS). Theintroduction of 10 m buffer zones (andextension to 50 m) on arable fieldmargins proximate to the Pool, the useof wetlands as nutrient traps and attemptsby the NT to develop holisticmanagement plans with their tenantfarmers around the Pool are linked toCSS implementation. A recent reportcommissioned by the National Trustdeals with some of these issues andidentifies processes by which they canbe resolved, (Haycock, 1999).

Sewage

Direct phosphorus inputs will(eventually) be reduced by theintroduction (2004) of tertiary treatment(phosphate stripping) at the South-WestWater (SWW) Helston STW via theimplementation of the UWWT (UrbanWaste Water Treatment) directive(Geatches, 1997). During the summermonths close to 100% of theorthophosphate loading derives from theHelston STW (Wilson & Dinsdale,1998) and modelling used to support itsUWWT designation suggested that 90-100% removal of orthophosphate wouldmeet the appropriate criteria.Implementation of phosphate strippingat the Helston STW is the most vitalprerequisite for any attempts atremediation of the Pool. Questions existconcerning the amount of phosphate inthe Pool sediment and the rate at whichthis will be released under a regime ofreduced phosphorus input into the Pooland, inter alia, the rate at which the Poolchemistry and ecology will begin toreflect the reduced phosphorus input.

Introduction

Loe Pool (a site managed by the NationalTrust (NT)) is a shallow coastal lake inCornwall, UK of maximum depth 10 m(mean 4 m) and surface area 0.56 km2

(National Grid Reference SW 647250).The main inflow (River Cober) has adrainage area of 54 km2. Loe Pool is thelargest freshwater lake in Cornwall andhas important amenity value (approx. 30000 visitors p.a. (NT, 1998)) andconservation value (Site of SpecialScientific Interest, (Nature ConservancyCouncil, 1986)). The lake is separatedfrom the sea by a shingle bar which isthe only British site of the Sandhill RusticMoth (Spalding, 1988) and also holdsrare plants and invertebrates, (Murphy,1986; NT, 1996). The bar is a dynamicsystem and its ecology is influenced bylandward movement and frequentbreaking, (Coard, 1987). Fluctuations inPool water levels and salinity are alsolinked to the breaching of the bar (lastbreached in 1984). Chief amongst theinsults to the Pool is the phosphorusinputs from the Helston SewageTreatment Works (STW) and the STWat the Royal Naval Air Station (RNAS)at Culdrose and nitrogen inputs fromdiffuse sources (chiefly agricultural).Since 1968 (and possibly earlier)elevated nutrient levels in the Pool haveled to algal blooms – in particular thepotentially toxic blue green algaeMicrocystis aeruginosa and Water Net(Hydrodictyon reticulatum). Consequenton this has been the elimination ofsubmerged macrophytes, the existence ofpopulations of coarse fish (perch, rudd)and a reduction of conservation interest,

Environmental Chemistry Group Bulletin July 2003

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Pending the installation by SWW ofphosphate stripping at the Helston STWthe LPMF is now giving attention to thesmaller RNAS Culdrose STW and toother, diffuse sources of phosphorus.

Water-level

Although Loe Pool was originally amesotrophic lake with abundantunderwater vegetation it is now an algae-dominated system with very limited plantgrowth. This has occurred principallybecause of nutrient enrichment but alsobecause until recently, in order toimprove dilution and inhibit algalgrowth, the water level in Loe Pool wasmanipulated in accordance with a waterregime of high summer and low winterlevels. Because this unnatural regimewas singularly unsuccessful in inhibitingalgal growth and was also detrimental toshoreline flora, it has been agreed toadjust the height of the adit weir underthe bar to 3.5 m AOD in order to establisha mean water level in the Pool of 3.7-3.8m AOD during autumn. Any threat offlooding to Helston would be dealt withby rapid lowering of the weir, (Haycock,1999). A winter–high/summer–lowregime is planned which would benefitthe inundation/benthic plantcommunities partly because they areadapted to summer exposure and partlybecause they would not be submergedduring periods of algal-induced stress inthe Pool, (Stewart, 2000). A winter–high/summer–low regime would also benefitshoreline flora – though carefulmonitoring is planned to record the effectof this regime on communities on theseasonally exposed shore, (Wilson &Dinsdale, 1998).

Canalisation of the lower River Cober in1988 (& 1946) compromised the ecologyof Loe Pool and the surrounding area.First, it is thought to have initiated thedrying out of one of Cornwall’s largestremaining Willow (Salix spp.) carr areas(established during the early 20th centuryon the silts and clays from upriver miningactivities). Secondly, continued dredgingof the channel (1992, 1998) introducedJapanese Knotweed (Fallopia japonica)and Himalayan Balsam (Impatiensglandulifera) into the Willow and swamparea. Thirdly, dredging activity increasedaccess to the Willow carr and this hasdamaged its conservation value. Andfourthly, canalisation reduced the

effectiveness of the carr as a pre-Poolnutrient trap.

Intra-agency discussions within the EAare taking place so that minimal dredgingwill occur in the future and the river isallowed to re-form its own meanderingcourse through the carr. Discussions arealso being held concerning the creationof settling ponds for silt from agricultureand from urban sources (run-off).

Fish

Loe Pool’s role as a fishery not only hashistorical importance but also hasrelevance to its future amenity value.Native brown trout (Salmo trutta L.) area feature of the Pool and although theyare locally referred to as ‘land-locked seatrout’ they are most likely not unique sub-species. However, there does appear tobe a migratory fraction and the use ofthe River Cober for spawning and as arefuge from the consequences of algalblooms in the Pool emphasises the needfor a whole catchment management plan.Environmental insults to the Pool and thecatchment have caused the troutpopulation to decline (e.g. in 1976 thepresence of algal blooms caused thesuffocation of 2000 fish (mostly trout)(Turk, 1985)). Rudd (Scardinuserythrophthalmus L.) (introduced in the1940s) and perch (Perca fluviatilis L.)(from an upstream commercial coarsefishery) are also present. Loe Pool is nowdominated by perch and sincecolonisation the population has grownrapidly and is likely to continue to do so.The presence of large numbers ofjuvenile perch feeding on zooplanktonaids the occurrence of algal blooms andthis further exacerbates the effects ofeutrophication. However, Loe Pool stillcontains the only trout population nativeto a Cornwall lake and appropriatemanagement of this resource couldprovide high quality commercial anglingopportunities, (Rule, 2000).

References

Carvalho, L.; Moss, B. (1995) TheCurrent Status of a Sample of EnglishSites of Special Scientific Interest Subjectto Eutrophication, Aquatic Conservation:Marine and Freshwater Ecosystems, 5,191-204.

Coard , M.A. (1989) PalaeolimnologicalStudy of the History of Loe Pool, Helston,and its Catchment, Unpublished PhDThesis, Plymouth Polytechnic.

Geatches, T. (1997) Loe Pool UrbanWaste Water Directive Sensitive Area(Eutrophic) Designation, Final draft,Environment Agency, Bodmin.

Haycock, N.E. (1999) The NationalTrust: Farm Buffer Zone Options. Reportbased on a survey of National Trustholdings in the Loe Pool Catchment,National Trust, Penrose.

Murphy, R.J. (1986) A Study of Loe Bar,Cornish Studies, 14, 23-33.

Nature Conservancy Council (1986)Citation, Loe Pool Site of SpecialScientific Interest, Nature ConservancyCouncil, Peterborough.

National Trust (1996) BiologicalEvaluation – Loe Bar, Report to NationalTrust, National Trust, Penrose.

National Trust, (1998), Penrose andMounts Bay Estates Management Plan,Report to National Trust, National Trust,Penrose.

Rule, M. (2000) Loe Pool CatchmentManagement Project, First AnnualReview, February 2000, EnvironmentAgency, Bodmin.

Spalding, A. (1988) Luperina nickerliileechi – Sandhill Rustic Moth at Loe Bar,Cornwall 1986-1988, Report to EnglishNature.

Stewart, N.F. (2000) Survey of the Botanyand Vegetation of Loe Pool, Helston,1999, National Trust, Penrose.

Turk, S.M. (1985) Pollution History ina Pool, West Briton, 22 August.

Wilson, H.; Dinsdale, J. (1998) Loe PoolCatchment Management Project, FinalReport, Environment Agency, Bodmin.

Dr LEO SALTER,Cornwall College,Pool, Redruth, Cornwall

Environmental Chemistry Group Bulletin July 2003

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News of the Environment, Sustainability and Energy ForumSince the last issue of the ECGBulletin, planning for theRSC’s new Environmental,Sustainability and EnergyForum (ESEF) has continued.A meeting to discuss futuredevelopments was held inFebruary at Burlington Houseunder the Chairmanship of PaulWhitehead. Representativesfrom the key subject groups,including Dr Andrea Jackson(ECG) attended the meeting.Paul Whitehead, currently chairof the Environmental, Healthand Safety Committee hasagreed to chair ESEF as aninterim measure.

• The RSC is committed to providingstaff support for the ESEF, and it isexpected that a new member of staff,who will also be responsible for theproduction of a regular Forumnewsletter, will be recruited by theautumn.

• Membership of the ESEF will befree and members of theEnvironmental Chemistry Group,the OETG, the Water ScienceForum, and other RSC SubjectGroups will be invited to join.

• The RSC is currently searching fora permanent chair for the ESEF whowill guide the Forum through itsinauguration.

• The first tasks that the ESEF willtackle are its terms of reference,rules and publicity. ESEF web pages

will be available by the autumn, anda publicity leaflet will be distributed.

• At least two conferences are plannedfor 2004 plus one or two workshops.

• The ESEF will have links to externalorganisations including the NERCand DEFRA.

Dr SEAN McWHINNIE,Manager, Science Policy,Royal Society of Chemistry,Burlington House,Piccadilly, London W1J 0BA.June 2003

News of the RSC’s Environment, Health and Safety CommitteeThe Environment, Health and SafetyCommittee (EHSC) is producing theRSC’s response to the currentconsultation on the EU Chemicals WhitePaper. Details are available at http://eu ropa .eu . in t / comm/en te rp r i se /chemica l s /chempol /whi tepaper /consultation.htm. Other RSC groups,including the ECG have been invited tomake an input to this submission. Thecurrent EHSC Note on the White Paperis being revised and updated.

The EHSC continues to oversee theRSC’s involvement with the UKChemical Stakeholder Forum (CSF) – seehttp://www.defra.gov.uk/environment/chemicals/csf. It met the Chairman of theCSF (Lord Selborne) to discuss concernsabout the operation of CSF and therelated Advisory Committee onHazardous Substances. EHSC madecomments to the DEFRA enquiry into theoperation of CSF. EHSC is also indiscussions with the CSF about the EUChemicals White Paper.

EHSC has approved work plans forMessage Notes and Guidance Notes. Theformer are intended to help improve

public understanding of public risk. Theywill be aimed at opinion makers such asMPs and teachers rather than directly atthe public. Two papers are in preparationwith the provisional titles What is apoison? and Are we right to worry aboutchemicals? Message Notes will only bethe start of a process of education andpersuasion rather than an end inthemselves. Guidance Notes will aim toprovide essential professional guidancefor RSC members. They will offer ‘bestpractice’ advice rather than simple factualinformation.

EHSC is producing a paper on‘substitution’. This will complement theexisting position statement (see http://w w w. r s c . o rg / l a p / r s c c o m / e h s c /substitution.htm). It will aim to providesolutions via risk-based substitutionrather than re-state the problems withhazard-based substitution.

EHSC is continuing work on an updateto the RSC booklet COSHH inLaboratories and to make it morecompatible with HSE publicationCOSHH Essentials.

BOB HAZELLRoyal Society of Chemistry,Burlington House,Piccadilly,London W1J 0BAJune 2003

Environmental Chemistry Group Bulletin July 2003

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Book reviewproduction, employment and economicdevelopment in Japan became dominant,

“Concerns for human and environmentalhealth did not enter the national policy-making process which had longsacrificed rural society and ecosystemsfor urban prosperity.”

Masato’s narrative focuses on hispersonal loss – his father, family, thefishing community on the Shiranui Sea– and how the events at Minamataunpicked the traditions and value systemsof that community.

“ . . . Chisso easily dominated regionalpolitics . . . . The company played therole of beneficent overlord, neverallowing residents to forget thatMinamata exists at the grace of Chisso.”

The life of the Ogata clan in the fishingvillage of Oki was shattered in 1959when Masato was six years old and hisfather announced that his hands werenumb. But it was not until the early1970s that Masato “ . . . understoodclearly that I was one of the manyMinamata disease sufferers.”

The book has a strangeness (perhapsbecause of its setting in Japan), it isunsettling (because of the issues it leavespendant) but it is certainly thought-producing and, for students, it offers avaluable introduction to Minamata.

Masato says,

“ . . . in order to avoid the pain, we turnthe situation into a business negotiation.”

“Just take this money and put up withyour lot,” we say, dismissing the sufferersfrom our thoughts. Responsibility isexchanged for money, and somethingcrucial is lost in the process.

And, consequently, he rejectedcompensation, withdrawing hisapplication for it because,

“ . . . it gradually became clear to methat Chisso, the prefecture, and thenational government could respond onlyfrom within the system, that it wasimpossible for any of them to acceptfundamental responsibility.”

But he reflects,

“If I had worked for Chisso or within thegovernment administration, is it possiblethat I would have behaved exactly as theydid? I cannot deny the possibility.”

The book deserves a wide readership.For me it brought into clear focus the factthat when politicians and industrialiststalk honestly about the benefits that theirproducts have brought to the world theytend to neglect or, at best, neglect toemphasise, the attached environmentaland human costs. And that when it comesto the sacrifice of the one for the many,it is best for all sorts of reasons (not theleast financial) to offer choice and not tocreate collateral victims at the behest ofany government, management,shareholders or accountants.

Dr LEO SALTER,Cornwall College,Pool, Redruth, Cornwall

Rowing the Eternal Sea –the Story of a MinamataFisherman

Oiwa Keibo – narrated by OgataMasato, translated by Karen Colligan-Taylor.Rowman & Littlefield (www.rowmanlittlefield.com), Lanham, 2001.ISBN 0-7425-0021-7 (pbk), 192 pp,£18,95.

In this book, Ogata Masato tells howmethyl mercury affected his life, family,culture and identity and in a verypersonal way he then challengesassumptions that quality of life andmaterial wealth are intrinsically linked.This is not new; but the voice is clear,universal and poignant and the situationin Minamata that created this voiceepitomises the foolishness that bedevilsthe interactions between the chemicalindustry, human beings and theenvironment.

From 1932-1968 the Chisso Corporationwas at,

“ . . . the vanguard of Japan’s chemicalindustry . . . . Releasing methyl mercuryin its untreated effluent.”

and,

“Even before the discharge of mercury,however, pollution incidents had affectedthe local fishery. The earliestcompensation payments by Chisso tofishing co-operatives for a fishery declinedate from 1926.”

Post-war, the drivers for industrial

Forthcoming symposiumHow useful will genomics,proteomics and metabonomicsbe to assess chemical risk inhumans?

A discussion meeting organised by:

The Royal Society of Chemistry’sOccupational and EnvironmentalToxicology Group

at

Society of Chemical Industry14/15 Belgrave Square,London SW1X 8PSTel: +44 (0) 20 7598 1500Fax: +44 (0) 20 7598 1545

on

5th September 2003

Registration approximately £80

Speakers include Professor TimZacharewski (Michigan)

For details, contact Dr Andy Smith, MRCToxicology Unit,Hodgkin Building, Leicester UniversityLancaster Road, Leicester LE1 9HNe-mail [email protected]: 0116 252 5617, Fax: 0116 252 5616

Environmental Chemistry Group Bulletin July 2003

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Environmental Chemistry Group Bulletin July 2003

19

Young Environmental Chemists Meeting 2003

Wednesday 10th September 2003At the British Geological Survey, Keyworth, Nottingham, UK

(http://www.bgs.ac.uk/contacts/sites/keyworth/kwhome.html)

The meeting is intended as a forum for young environmental chemists to present their research anddiscuss recent developments in the field. It will start at 9:30 am with coffee and registration andthere will be talks, poster presentations and plenty of opportunities to mingle.

Professor Barry Smith of the British Geological Survey will be chairing the meeting and the day will include:

Environmental Chemistry GroupEnvironmental Chemistry Group

• A guest speaker from theEnvironment Agency giving apresentation on the future ofenvironmental chemistry in the UK.

• Representatives from the RSC andother companies.

• A year’s free subscription to theJournal of EnvironmentalMonitoring for the winner bestposter competition (kindly donatedby the RSC).

Prospective authors should submit an abstract of 200-400 words by 18th July and include the names of the authors and theiraffiliations, indicating the presenting author. This should be accompanied by the attached registration form and a cheque madepayable to the “Environmental Chemistry Group” for £10 for RSC members or £15 for non-RSC members.

Young Environmental Chemists Meeting 2003Wednesday 10th September 2003 @ British Geological Survey, Keyworth, Nottingham, UK

Registration Form

Name: _______________________________________________________________________________________________________________________________________

Affiliation: ________________________________________________________________________________________________________________________________

Address: __________________________________________________________________________________________________________________________________

E-mail: ______________________________________________________________________________________________________________________________________

Tel: ____________________________________________________________________________________________________________________________________________

Fax: __________________________________________________________________________________________________________________________________________

Submitting Abstract: YES / NO

Abstract Title: __________________________________________________________________________________________________________________________

Special Dietary Requirements: ______________________________________________________________________________________________

Will you be requiring transport from Nottingham Station: YES / NO(A mini bus should be available for £5 return depending on interest)

Please send registration forms and abstracts to Dr Kim Cooke, Sira Ltd, South Hill, Chislehurst, KentBR7 5EH. Tel: 020 8468 1720; Fax: 020 8467 7097; email: [email protected]

Environmental Chemistry Group Bulletin July 2003

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Forthcoming symposium

Ecotoxicology: Monitoringand Caring For OurEnvironment

A one day meeting on Tuesday14 October 2003 at The RoyalSociety of ChemistryHeadquarters, Thomas GrahamHouse, Cambridge SciencePark, Milton Road, Cambridge,UK

Organised by the RSC’s EastAnglia Region AnalyticalDivision and theEnvironmental ChemistryGroup

Every year, thousands of tons ofchemicals are discharged into ourenvironment as waste products of eitherindustrial or household use. Not so longago, few people cared about what effectsthese chemicals were having on the

environment, but that situation haschanged as people have come to realisehow fragile our ecosystems are and howthis could affect all of us. Regulatoryagencies, research institutions andresponsible industrial companies are allworking to develop and applymethodology to monitor, understand andprevent the decline of our environment.This meeting brings together theseexperts and covers many of the areas/classes of compounds of currentconcern.

Programme

09.45 onwards Registration and coffee.10.25 – 10.30 Chairman’s Welcome and Introduction.10.30 – 11.15 What is Ecotoxicology, and how are environmental standards set for things like endocrine

disruptors? Dr G. Brighty, The Environment Agency, Wallingford.11.15 – 12.00 The Fate and Effects of Veterinary Medicines in the Environment. Dr A. Boxall, Centre for

Ecochemistry, University of Cranfield.12.00 – 12.45 Pesticides in the Environment – Linking Fate & Effects, Methods and Data Interpretation.

Dr K. Barrett, Consultant.12.45 – 14.00 Lunch14.00 – 14.45 The Biocidal Products Directive. Environmental Risk Assessment Strategies - where are we

now and where are we going in the future? Dr J. Chadwick, Health & Safety Executive, Bootle.14.45 – 15.30 Aquatic Ecotoxicology and the Marine Environment. Dr J. Thain, Centre for Environment,

Fisheries & Aquaculture Science, Burnham on Crouch.15.30 – 16.15 “Science in the box” – A Procter & Gamble Science Website to share Human & Environmental

Risk Assessments & LCA to a wide range of the public. Dr E. Saouter, Procter & GamblePublic Relations Dept, Geneva, Switzerland.

16.15 – 16.30 Final Questions and Answers – All Speakers.16.30 – 16.35 Chairman’s Closing Remarks.

For further details contact Brian Woodget, Tel/Fax + 44 (0) 1438 811903, Email [email protected].

Registration Fees:- RSC Members £60, Non-Members £80, Students & Unwaged Members £30. To register, please completethe form below and send with a cheque made out to “East Anglia Region AD Trust” to Mr B. Woodget, 5, Meadow Close,Datchworth, Herts, SG3 6TD, UK.

Delegate Name: ____________________________________________________________________________________________________________________________________________

Affiliation: __________________________________________________________________________________________________________________________________________________

Address: _____________________________________________________________________________________________________________________________________________________

_________________________________________________________________________________________________________________________________________________________________

Telephone: ________________________________________________________________ Fax: ________________________________________________________________________

Email: ________________________________________________________________________________________________________________________________________________________

Registration Fee enclosed: £ ________________

Special dietary requirements: __________________________________________________________________________________________________________________________

Environmental Chemistry Group Bulletin July 2003

21

Meeting report: Coastal Futures 2003Coastal Management forSustainability organised its 10th

Coastal Futures meeting onJanuary 22nd and 23rd 2003(‘Coastal Futures 2003: Reviewand Future Trends’) at theBrunei Gallery LectureTheatre, School of Oriental andAfrican Studies, University ofLondon. Leo Salter reports onthe meeting and its acronyms.

Attendance was by around 200 delegatescomprised of a wide range ofprofessionals working across manyagencies and companies includingstatutory and non-statutory environmentorganisations, civil servants, industry(water, energy, resources) and localauthorities with direct interests withcoastal and marine issues.

The first day surveyed the developingpolicy context, the findings of the MarinePollution Monitoring ManagementGroup (MPMMG), the significance ofthe Strategic Environmental Assessment(SEA) Directive (2001/42/EC) (and theassociated role of the Office of theDeputy Prime Minister) and the Port ofLondon Authority’s view of itsenvironmental responsibilities (inrelation to the Habitats Directive, theWater Framework Directive, the CROW(Countryside and Rights of Way) Act andthe Thames Estuary Partnership). Onepaper, referring to the MinisterialDeclaration of the Fifth InternationalConference on the Protection of theNorth Sea and the development of an‘ecosystem approach’ described theoutcomes as ‘Great for consultants butc—p for the environment’. The theme

of Offshore Wind Energy was alsointroduced and estimates are that themarket for this will be worth £8b by2007. Predictions are that 4-6 GW willbe installed in the UK by 2010.Currently, although there are 18developers at 18 sites, the planning andlegislative process is hugely complex(e.g. 8 different consent procedures forthe Solway Firth). The proposedstrategic regions for development are theWash Area, the Thames Estuary andLiverpool Bay. Other papers revieweddevelopment in Marine and CoastalWaters (Department for Transport),spatial planning (the Crown Estate andindustry representatives) and a paper “40years of Conservation (?) of StrangfordLough, N. Ireland” was given by theCEO of the Ulster Wildlife Trust (“If,with the use of every UK conservationdesignation we cannot ensure theconservation of obvious marine speciesdoes not this position question other UKconservation activity in the marineenvironment?”).

The second day commenced with a paper“Archaeology in the coastal and marineenvironment” by the Head of MaritimeArchaeology at English Heritage. Thisseemed to suggest that a similar processof designation was likely for MarineHeritage sites as for terrestrial sites. Thiswas followed by presentations on thespatial designation of MEHRAs (MarineEnvironmental High Risk Areas) and theconcept of regional fisheriesmanagement as an outcome of the reformof the CFP (Common Fisheries Policy)(Countryside Council for Wales andSouth Western Fish Producers Ltd.). Akeynote presentation was given by ElliotMorley (Minister for Fisheries andNature Conservation). The finalafternoon looked at “The Irish Sea Pilot”as a regional scale framework for marine

nature conservation and the alsoconsidered the implications of CFPreform on Irish fisheries. Ecosystemmanagement approaches to the marineenvironment and the use of no-take zonesto protect biodiversity and fisheries werealso discussed.

In general these last papers focused onfisheries and the unresolved conflictsbetween short-term commercial interestsand those of the fish and sustainablefishing. The minister had a good graspof the detail of the issues but thenegotiated outcomes in terms of ECfisheries policy were neitherscientifically justified nor likely toachieve anything (in spite of the messagefrom Canadian fishermen that they inretrospect wished they had listened to thescientific advice). Subsequent paperscastigated the Minister’s stance butunfortunately he had left. Edward Fahy(Assistant Inspector-Inshore Fisheries,Marine Institute Fisheries ResearchCentre, Dublin) presented dataconcerning the development of Ireland’sinshore fisheries which were adevastating indictment of muddledthinking by the EC and the inability ofnational governments to enforce, monitoror direct fishing effort whilstsimultaneously completely ignoring theimpacts of industrial scale fishing on themarine environment. The final paper(No-take zones, NTZs) by CallumRoberts (University of York) presentedthe case for NTZs as a mode of fisheriesmanagement. This was so clearly arguedand evidenced that it clearly exposed thecrass inanity of political inaction.

Dr LEO SALTER,Cornwall College,Pool, Redruth, Cornwall

Environmental Chemistry Group Bulletin July 2003

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Recent books on the environment and on toxicology at the RSClibraryThe following books and monographs onenvironmental topics, toxicology, andhealth and safety have been acquired bythe Royal Society of Chemistry library,Burlington House, during the periodJanuary to June 2003.

Acrolein

World Health Organization, Geneva,2002, ISBN/ISSN: 924153043X, 46 pp.,Accession No: 20030098, West Gallery628.5

Advancing Sustainability throughGreen Chemistry and Engineering

Lankey, R.L. (ed.), American ChemicalSociety, Washington DC, 2002, ISBN/ISSN: 0841237786, 264 pp., AccessionNo: 20030219, West Gallery 628.5:54

Analysis of Environmental EndocrineDisruptors

Keith, L.H. (ed.), American ChemicalSociety, Washington, DC, 2000, ISBN/ISSN: 084123650X, 173 pp., AccessionNo: 20030130, West Gallery 628.5:615.9

Bromoethane

World Health Organization, Geneva,2002, ISBN/ISSN: 9241530421, 26 pp.,Accession No: 20030097, West Gallery628.5

Chemicals in the Environment: Fate,Impacts, and Remediation

Lipnick, R.L. (ed.), American ChemicalSociety, Washington, DC, 2001, ISBN/ISSN: 084123776X, 508 pp., AccessionNo: 20030082, West Gallery 628.5:54

Control of Asbestos at WorkRegulations 2002

Stationery Office, London, 2002, ISBN/ISSN: 0110429184, 25 pp., AccessionNo: 20030091, Reference Shelves REF614.8 R

Control of Lead at Work Regulations2002

Stationery Office, London, 2002, ISBN/ISSN: 0110429176, 20 pp., AccessionNo: 20030092, Reference Shelves REF614.8 R

Control of Substances Hazardous toHealth Regulations 2002

Stationery Office, London, 2002, ISBN/ISSN: 0110429192 44 pp., AccessionNo: 20030093, Reference Shelves REF614.8 R

Derivation of Assessment Factors forHuman Health Risk Assessment

ECETOC, Luxembourg, 2003, 86 pp.,Accession No: 20030303, West Gallery615.9

Environment Business Directory, 20039th edition

GEE, London, 2002, ISBN/ISSN:1860899633, 219 pp., Accession No:20030070, Reference Shelves REF058.7:628.5 R

Health, Safety and EnvironmentLegislation: A Pocket Guide

Day, R., Royal Society of Chemistry,Cambridge, 2003, ISBN/ISSN:0854044973, 332 pp., Accession No:20030141,West Gallery 614.8:328.34

Nuclear Site Remediation: FirstAccomplishments of the Environ-mental Management Science Program

Eller, P.G. (ed.), American ChemicalSociety, Washington, DC, 2001, ISBN/ISSN: 0841237182, 464 pp., AccessionNo: 20030119, West Gallery 628.5

Persistent, Bioaccumulative, and ToxicChemicals I: Fate and Exposure

Lipnick, R.L. (ed.), American ChemicalSociety, Washington DC, 2000, ISBN/ISSN: 0841236747, 308 pp., AccessionNo: 20030229, West Gallery 615.9

Persistent, Bioaccumulative, and Toxic

Chemicals II: Assessment and NewChemicals

Lipnick, R.L. (ed.), American ChemicalSociety, Washington DC, 2000, ISBN/ISSN: 0841236755, 276 pp., AccessionNo: 20030216, West Gallery 615.9

Recognition of, and Differentiationbetween, Adverse and Non-adverseEffects in Toxicology Studies

ECETOC, Luxembourg, 2002, 56 pp.,Accession No: 20030302, West Gallery615.9

Toxicological Chemistry andBiochemistry3rd edition

Manahan, S.E., Lewis Publishers, BocaRaton, 2003, ISBN/ISSN:1566706181,425 pp., Accession No.: 20030067,West Gallery 615.9:54

Environmental Chemistry Group Bulletin July 2003

23

Organic PollutantsAn Ecotoxicological Perspective

Colin Walker, University of Reading, retired, UK

Taylor & Francis

246x174: 304pp:illus. 60 b+w line drawings

Hb: 0-7484-0961-0: £65.00Pb: 0-7484-0962-9: £27.99

• Written by an internationally respected lecturer and researcher of many years experience

• Can be used as part of undergraduate teaching, postgraduate research, or dipped into as a reference by professionals in the relevant fields

• No other single source gives such clear and concise information on these increasingly important compounds

This much needed book is a companion to the highly praised Principles of Ecotoxicology. It covers organic pollutants ingreater depth and detail than has been covered in a textbook before. The first part covers such issues as:• Chemical warfare• Metabolism of pollutants in animals and plants• Environmental fate, and effects within ecosystems

This is followed by discussion of particular pollutants such as:

• Organochloride insecticides• PCBs• Dioxins• Organometallic Compounds• Polycyclic aromatic hydrocarbons• Anticoagulent rodenticides

amongst others. The book concludes with coverage of ecotoxicity testing, biomarkers and bioassays and future prospectsfor improved assessment of the dangers these compounds pose.

It breaks new ground in offering a concise source of information on these compounds at a level suitable for senior undergraduates and postgraduates. Professionals working within the fields of environmental science will also find it a valuable reference.

‘This publication is a valuable resource to all those studying environmental science’.- Chemistry and Industry

Contents: 1. Chemical Warfare 2. Factors Determining the Toxicity of Organic Pollutants to Animals and Plants 3. Influence of the Properties of Chemicals on Their Environmental Fate 4. Distribution and Effect of Chemicals inCommunities and Ecosystems 5. The Organochlorine Insecticides 6. Polychlorinated Biphenyls (PCBs) and PolybrominatedBiphenyls (PBBs) 7. Polychlorinated Dibenzodioxins (PCDDs) and Polychlorinated Dibenzofurans (PCDFs) 8. Organometallic Compounds 9. Polycyclic Aromatic Hydrocarbons (PAHs) 10. Organophosphorous and CarbamateInsecticides 11. The Anticoagulant Rodenticides 12. Pyrethroid Insecticides 13. The Ecotoxicological Effects of Herbicides14. Dealing with Complexity - the Toxicity of Mixtures 15. The Environmental Impact of Organic Pollutants

Environmental Toxicology from Taylor & Francis

To find out more on this, or any other toxicology book from Taylor & Francis, visit our online resource centre at: www.toxicologyarena.com

or alternatively contact: [email protected] tel: +44 (0) 20 7842 2021to request a free copy of our new 2003/4 Toxicology catalogue

This issue of the ECG Bulletin was printed by Griffin House Printers, Haywards Heath, West Sussex RH16 3NG Tel: 01444 456673