July 2017 ECG Bulletin - The Royal Society of Chemistry Bulletin July 2017_tcm18-249545.pdf · ECG...

July 2017

ECG Bulletin

Diesel emissions and air quality. This edition features a meeting report and articles from our 2017 DGL sympo-sium and lecture on the chemistry, health effects, and policy of diesel emissions. On pp. 12-14, Distinguished Guest Lecturer Professor Frank Kelly writes about his group’s research on the health effects of diesel emissions. Environmental Briefs. We publish our first Early Careers Environmental Briefs, written by students in the envi-ronmental sciences. Harrison Frost writes about sources and legislative control of particulate emissions (pp.

20-21), and Georgina Smith reports on policies controlling hydrofluorocarbon emissions (pp. 22-23). We welcome further suggestions for this series. Also in this issue. ECG member Brian Graham tells us about his work at the National House Building Council (p. 3); Julia Fahrenkamp-Uppenbrink reviews “The long shadows — a global environ-mental history of the second world war” (p. 4); and Roger Reeve and Gra-ham Mills report from the third in a se-ries of biennial one-day meetings on the analysis of complex environmental matrices (pp. 5-8).

Royal Society of Chemistry—Environmental Chemistry Group—Bulletin—July 2017 2

ECG Bulletin ISSN1758‐6224 Print 2040‐1469 Online . PublishedbytheRoyalSocietyofChemistry’s RSC EnvironmentalChemistry Group ECG , Burlington House, Piccadilly,LondonW1J0BA,UK.Seewww.envchemgroup.comforarticlespublishedintheECGBulletinsince2007.ExecutiveEditorJuliaFahrenkamp‐Uppenbrinkecgbulletin@hotmail.co.ukProductionEditorsRowenaFletcher‐Wood,ScienceOxfordrowena. letcher‐[email protected],[email protected],UniversityofBirmingham;ZoëFleming,UniversityofLeicester;IanForber,Scienti icAnalysisLaboratories;BrianGraham,NationalHouseBuildingCouncil;MartinKing,RoyalHolloway,UniversityofLondon;SteveLeharne,GreenwichUniversity;LauraNewsome,UniversityofManchester;RupertPurchase,HaywardsHeath;RogerReeve,UniversityofSunderland;GlynnSkerratt,UniversityofStaffordshire

Environmental Chemistry Group Twitter:@RSC_ECG,Facebook:RSCEnvironmentalChemistryGroupMembershipdetails:www.rsc.org/ecgChair:ZoëFleming,[email protected] Vice‐Chair:MartinKing,RoyalHolloway,UniversityofLondon [email protected] HonorarySecretary:TomSizmur,[email protected] HonoraryTreasurer:IanForber,Scienti icAnalysisLaboratories [email protected] ThisandpreviousissuesoftheECGBulletinareavailablewithoutchargeatwww.rsc.org/ecg.Bulletin©RSC–ECG2017RegisteredCharityNumber207890

Contents

ECGInterview:BrianGraham 3

BookReview:Thelongshadowsofwar,byJuliaFahrenkamp‐Uppenbrink 4

Meetingreport:What’snewintheanalysisofcomplexenvironmentalmatrices,byRogerReeveandGrahamMills 5

Meetingreport:Insidetheengine—fromchemistrytohumanhealth,byLauraNewsome 9

DGLarticle:AirPollutionandhealth:knowledgegainedfromjourneystoUmea,LondonandBeijing,

byFrankKelly 12

Article:Dodieselvehiclescausepoorairquality?byClaireHolman 15

Article:Airpollutionandtraffic:searchingforthemissingemissions,byJacquelineF.Hamilton 18

ECGEarlyCareersEnvironmentalBrief:SourcesandlegislativecontrolofPM2.5pollution,byHarrisonFrost 20

ECGEarlyCareersEnvironmentalBrief:Policiescontrollinghydrofluorocarbonemissions,byGeorginaSmith 22

TheECGBulletinisprintedonpapermadefromwoodpulpsourcedfromsustainableforests,andissuitableforarchivalstorage.ThisissueoftheECGBulletinwasprintedbyPrizmaticPrintSolutions,www.prizmatic.co.uk;01444239000.Allarticlesrepresenttheinformedviewoftheauthor s atthetimeofwriting,notthatoftheECGortheRSC.Theywerenotpeerreviewedandnoguaranteeregardingtheaccuracyorotherwisecanbegivenbytheauthor s ,theECGortheRSC.

Coverimage:Rushhourtraf iconacityroad.Credit:RepinaValeriya/Shutterstock

http://www.prizmatic.co.uk

mailto:[email protected]







ECG committee member Brian Graham is an analytical chemist working in the contaminated land industry. His job is to ensure that soil contamination is remediated before building commences. What inspired you to become a chemist? I always had an interest in how thingswork or why things happen. Becoming a scientisttherefore was a natural choice for me. Chemistryprovides lotsofopportunitiesbecause it canbeused tohelp people and solve problems. From paints topharmaceuticals, chemistry is challenging andinteresting, and it was that variety of options thatattractedme.

Why did you specialise in environmental chemistry? I enjoy workingoutdoors and have an interest in conservation. I alsofoundanalyticalchemistryinterestinganddidanMScinEnvironmentalAnalysis,thuscombiningtwoareasthatIenjoyed. Without proper environmental protection,peoplewillnotbesafe.IhopeinmyownsmallwayIamhelpingtheplanetandpeople.

Could you describe your current job? As Senior Geo‐environmental Engineer at the NationalHouseBuildingCouncil NHBC ,myroleistoensurethatlandonwhichourcustomerswanttobuildissuitableforthese building projects. When contamination is foundprior to building, I assess the reports of the builder’sconsultanttoensurethatthesiteinvestigationhasbeencarriedouttothecorrectstandard. Ifremediationworkis needed, I check to ensure that theworkwas carriedoutcorrectlyandthatthelandissuitableforoccupation.

What is your advice for anyone considering a career in this area? Environmental protection is and will continue to beimportantaspressuresgrowon limited foodandwaterresources,andaswasteinallitsformsbecomesabiggerissue. In the contaminated land industry,we have gone

fromland illingalmostallwastesinthe1990stousingawhole variety of treatment approaches, such asbioremediation, solidi ication and groundwatertreatments; many more treatments are likely to bedeveloped. Most of them require use of scienti ictechniques,oftenbasedonchemistry.Thesechangeswillcreate opportunities and careers for chemists andmake chemistry a promising career choice, especially ifourimportantworkbecomesbetterrewardedinfuture.Iwould advise trying out as many different areas ofchemistry as possible and before committing to onespeci ic area — you never know what you might likeuntilyoutry.

What are some of the challenges of communicating science? One of the bigchallengesispersuadingpeoplethatwhatwedoisusefuland protects them, their families and the environment,and that environmental regulations are not just someother burden on their lives. There are success storiessuch as removing lead frompaint andproviding a non‐toxicversionthatworksjustaswell,andmakingobjectsout of materials that can be recycled, when previouslythey would have been sent to land ill. Many morechallenges remain for chemists to improve theenvironment.

What is the most rewarding aspect of your career so far? I have found it mostrewardingwhen Ihavebeenable tohelppeoplewithadif icult issue and enabled them to overcome thatchallenge.Ihavealsoenjoyedworkingonmanydifferenttypesofprojectovertheyears,fromindividualhousestosomeofthebiggestinfrastructureprojectsintheUK.

If you weren’t a scientist what would you do? If I was not a scientist I would probablyworkinIToroutdoorsinconservation.

The ECG Interview:

Brian Graham


The human horror of the Second World War has been the subject of a multitude of books, films, and personal narratives. The book The Long Shadows, edited by Simo Laakkonen, Richard Tucker, and Timo Vuorisalo, shows that the war’s environmental impacts were also pervasive, not only in countries involved in the war but also in others that supplied resources for the war effort. Some of these long shadows of the war still persist today. Perhaps the irst image that comes to mind whenthinking of the environmental effects of the SecondWorldWaristhedevastationcausedbyaerialbombing,particularly at Hiroshima and Nagasaki. In a series ofinsightful and well written essays, The Long Shadowshighlightssomelessobviousenvironmentaleffects,fromforest clearing and ethnic con lict in Burma to theindustrialsupplychainsthatlinkedforestdestructioninBritish Guiana to chemical pollution and hydropowerconstruction in Canada. The common thread is thepervasivenatureofmodernindustrialwar,whichleavesnopartofsocietyortheenvironmentuntouched.Forexample,Paul Josephsonexplains thatas theSovietarmyretreated fromtheGermanadvance in1941, theytookmostresourceswiththemanddestroyedwhattheyhadtoleavebehind.Overthenextfouryears,anareaofabout ivemillionsquarekilometresoftheformerSovietUnion became a constant battle ield, with most majorcities levelled, woods burned, infrastructure destroyed,and the debris of modern industrial war, fromunexplodedordnance tospilledchemicals,polluting thecountryside. Industrial production and settlementshiftedpermanentlytopreviouslysparselyregionsinthenorthandwestofthecountry.Afterthewar,concernforthe environmentwas brushed aside. Particularly in theproductionofplutonium,theSovietspaid“littleattentiontothegrotesqueenvironmentalcosts,”withimpactsthatwerestillfeltwhentheSovietUnionbrokeupin1991.IntheforestsofNorthernIndiaandBurma,thewaralsoleft environmental scars with persistent impacts. As

RichardTuckerreports,from1937,roadbuildingacrossregionsof theHimalayaspreviously largely inaccessibletomodern transport, opened up vast tracts of forest toexploitation. In India, displaced people cleared hillforests forsurvival.Throughouttheregion, thepostwarperiod was marked by increased ethnic con lict; inBurma, con lict between newly armed local tribes andnationalistsledtoadecades‐longcivilwar.Theresultingdisruption of resource management systems causedsubstantialandongoingenvironmentaldegradation.Butthetentaclesofmodernindustrialwarreachedevenfurther.AsMatthewEvendendescribes,ever increasingamountsofaluminiumwereneededastheSecondWorldWar progressed, principally for aircraft production.Large tracts of forestwere cleared in British Guiana tomine bauxite; according to Evenden, the resultinglandscapeswere “best describedas lunar.”Themineralwas then transported by fossil‐fuelled ship to Canada,where a vast system of hydropower damswas built togeneratethepowerneededtosmeltbauxiteandproducealuminium metal. Effects on isheries were seen asunavoidablecollateraldamage;chemicalpollutantsfromaluminium production continue to linger in the jordbeds.Afterthewar,newusesforaluminiumindomesticproductswerequicklyfound,showingthelinksbetweenwartimeandpeacetimeproduction.PerhapsthemostunexpectedangleisthattakenbyOutiAmpuja, who discusses what he terms the acousticecologyofwar,basedinpartoninterviewswithFinnishveterans.Ampuja inds thatwhenaskedaboutwartimesounds, veterans quickly talk about their feelings,particularly their fears, rather than recounting events.Many soldiers and civilians have lasting memories ofwartime sounds. One veteran talks of how a breakingbranch can mentally take him back to the front;thunderstorms can cause panic, and wartime soundsin iltrate the veterans’ dreams. I was reminded of mymother’s panicwhen sheheard the soundof low‐ lyingaircraft, even decades after her wartime childhood. AsAmpuja writes, the wartime experiences of sound canliveoninthemindsofthefollowinggenerations.Inthisas in many other ways, we are still living with theenvironmentaleffectsoftheSecondWorldWar.The Long Shadows, edited by Simo Laakkonen, RichardTucker, and Timo Vuorisalo, OSU Press, 2017. ISBN9780870718793

Book review

The long shadows of war Julia Fahrenkamp-Uppenbrink ([email protected])

mailto@[email protected]


Over 70 delegates and speakers attended this one-day meeting on 3rd March 2017 at the Royal Society of Chemistry, Burlington House, London. The meeting was organised by the RSC’s Environmental Chemistry Group (Dr Roger Reeve), Separation Science Group (Professor Graham Mills) and Water Science Forum. Speakers discussed the monitoring and screening of a wide range of regulatory and emerging pollutants (such as pharmaceuticals and personal care products) and the detection of potentially hazardous compounds in dusts and consumer products. There were also exhibitions by instrument manufacturers and suppliers of laboratory consumables.Seven presentations weregiven by UK academicinstitutions, governmentagencies, and industry, withkeynotelecturesbyDrJaroslavSlobodnik EnvironmentalInstitute, Slovak Republic onthe harmonisation oftechniques used to analyseemerging environmentalpollutants in European riverbasins and Professor Jacob deBoer Vrije Universiteit,Amsterdam, Netherlands onthe use of direct probe massspectroscopy to analyseexposure of humans tobrominated and non‐brominated lame retardantsfromhouseholddust.

ProfessorGrahamMills University of Portsmouth,UK opened the meeting, welcomed the delegates andchaired the morning session. The irst presentation,‘Screening of complex forensic and environmentalsamplesusinghigh resolutionanalysis and in silicodatamining tools’, was given by Dr Leon Barron King’sCollege London, UK . Analysis of contaminants in riverwater and wastewater can be divided into targetedanalysis of known compounds and untargeted analysis.Untargeted analysis indicates, in the irst instance, allresolvable components. Between these approaches,suspect screening is employed. In silico methods canhelp identify chemicals during suspect screening.Applicationofthistechniqueidenti iedpharmaceuticals,personal care products, illicit drugs, and explosives.Possibleinputsofpharmaceuticalsintotheenvironmentare shown in Figure 1. The methodology for analysingthe medical drugs 100 mL water sample, solid‐phaseextraction, with liquid chromatography‐high resolutionmass spectrometry produced 166 components forscreening, of which 40 were selected for quantitativeanalysis. Arti icial neural network analysis of thecomponents can predict chromatographic retentiontimesandwasusedforthepreliminaryidenti icationofnewcompounds in thesamples.LogD the logarithmof

Meeting report

What’s new in the analysis of complex environmental matrices 2017 Roger Reeve (University of Sunderland, [email protected]) and Graham Mills (University of Portsmouth, UK , [email protected])

Figure1.Possibleinputsofpharmaceuticalsintoenvironmentalwaters.




thedistributioncoef icientD ,logP thelogarithmofthepartition coef icient P , number of C/O groups andbenzene rings contributed most to the itting. Thisanalysis complemented identi icationbydatamining ofthe high resolution mass spectroscopy data. Althoughthesemethods are an aid to identi ication, they arenotintendedtoreplacethetraditionaluseofstandards,butinstead intended to be used to optimise the analyticaleffortneededtoquantifyalargenumberofcomponents.

Dr Andrew Sweetman Lancaster University, UK discussed ‘Use of passive samplers as a potentialcompliance tool within the EU Water FrameworkDirective’.Passivesamplerscanbeusedovermanydays,givingtimeweightedaverageresultsasanalternativetoaveraging several sequential grab water samples. Thespeci ictypeofsamplerinvestigatedwasDGT diffusivegradients in thin ilms , originally developed todetermine metal lability, but now being developed forantibiotics, personal care products, pharmaceuticals,pesticides and lame retardants. A diffusion layer issandwiched between two resin gels HLB resin is usedmost commonly , as shown in Figure 2. The sampler isdeployed in the environment and left to sequesterpollutants over 1‐2 weeks, after which time theaccumulated components are extracted from the resinand the masses determined. Using knowledge of the

diffusion rates masses can be related back to thedissolved concentration in the environment. Thedissolvedconcentrationre lectsthebiologicallyavailablefraction, but does not directly provide ‘totalconcentrations’ required by the EU Water FrameworkDirective. An estimate of this value can bemade usingpartition theory. In ield tests, the method has beencomparedwithauto‐samplingandgrabwatersampling.Successful ield trials of this technique have beenconducted in the Liuxi river, China Figure 3 and at awastewater treatment plant. Furtherwork isneeded tode inesamplingratesandoperatingrangeandtoassessthe potential of DGT samplers for predicting ‘totalconcentrations’forawiderangeofchemicals.ProfessorColinCreaser LoughboroughUniversity,UK ,inhispresentation‘Combiningionmobilityspectroscopywith mass spectroscopy for the analysis of complexsamples: the potential for environmental analysis’,introduced this technique, which at present hasrelatively fewapplications,butshowsgreatpromise forenvironmentalanalysis.Twoformatswerediscussed.Indrift‐tubeion‐mobilityspectroscopy DTIMS separationis achieved by the differential mobilities of ions in thepresence of an electric gradient and a buffer gas. Fieldasymmetric ionmobility spectroscopy FAIMES hasanoscillating ieldwhich selects individual ions, similar toquadrupole mass ilters in conventional massspectrometers, but it is able to be used at atmosphericpressure. As a stand alone instrument, the technique istransportableandhas ieldbasedapplications.Itiseasyto use, has rapid response and high sensitivity, but anarrow dynamic range 1‐2 orders of magnitude andlow resolution, limiting applications to simplemixturessuch as BTEX benzene, toluene and xylenes . Toovercome the limited resolution within the laboratory,the technique can be coupled to conventionalquadrupole or time of light mass spectrometers.Applications included electrospray ionisation‐DTIMS‐quadrupolemassspectrometryforthetargetedanalysisof sulfonylureaherbicides in riverwaterandhaloaceticacids in water. For non‐targeted analysis, collisionalcross‐sections,whicharederivedfromthedrifttime,canbe correlated with library or other standards foridenti icationofanalytes.Thisaspectwas illustratedbyidenti ication of cyclophosphamides inwastewater. Useof the techniques gives improved performance overstandard methods for targeted high throughputquantitativeanalysisandincreasedpeakcapacityfornon‐targetedapplications.ProfessorStuartHarrad UniversityofBirmingham,UK discussedtheproblemof‘Brominated lameretardantsinwaste consumer articles’. There is widespread use ofthese compounds in consumer products such as carpet

Figure2.Diffusivegradientsinthin ilms DGT Pas‐siveSampler.


underlaysandfurniture,inbuildinginsulationfoamandalso inelectronicwaste.Their concentrations inhumanmilkappeartobeincreasingovertimewhilstotherhighmolecular mass neutral pollutants such aspolychlorinated biphenyls PCBs are decreasing. Newlegislationnowrequireselectronicwastetobeseparatedfrom otherwaste streams and thematerial recovery is

tightlycontrolled.Inlessdevelopedcountries,electronicwaste disposal may be more rudimentary and thecompoundsmayenterthewiderenvironmentandhencethefoodchain.Exposuretobrominated lameretardantsvia eating food produced around the rudimentaryrecyclingplantsinTaizhouCity,EasternChinahasbeenshown to be signi icantly higher than in remotelocations. Laboratory work investigated a change inleachingrateswithvariationofdisposalconditionssuchas contact time, temperature and the waste matrix.

Leaching from furniture and waste fabrics appearedfacile, leading to the conclusion that more sustainablewaste management for these products as well as forelectronic waste is needed. The immensity of theproblem was con irmed by a detailed analysis ofbrominated lame retardant concentrations in a widerangeofconsumerproducts.Theuseofhandheldx‐rayluorescence XRF spectrometers was suggested fordisposedproduct analysis monitoringbromine ratherthan conventional gas chromatography‐massspectroscopy or liquid chromatography‐massspectroscopy; preliminary testing suggested a lowincidenceoffalse‐positiveresults. Themorning inishedwiththe irstkeynotelecturebyDrJaroslavSlobodnik EnvironmentalInstitute,Kos,SlovakRepublic on ‘Non‐target screening of environmentalpollutants in the contextof risk assessmentofEuropeanriver basins: the NORMAN network perspective’. TheNORMAN network within the EU http://www.normandata.eu has been set up to enhance theexchange of information on emerging environmentalsubstances, their validation and harmonisation ofanalytical techniques. There is currently no satisfactoryexplanation of the ecological status of most Europeanriver basins; current priority substancesdonot explainalltheeffects.Thislackofanexplanationmaybeduetoemerging pollutants pharmaceuticals, personal careproducts, biocides, transformation products . Attentionisusuallyfocussedonwell‐knowncontaminantsandlessonmetabolites and transformation products. Individualpollutants are also assessed assuming they occur inisolation and not inmixtures. Of themany compoundspresent, only a few determine the risk, hence the needfor prioritisation. The NORMAN network and ECOTOXdatabase provides a methodology and resources forprioritisation. Suspect and non‐target screeningapproaches should be integrated into the screeningprocess. Prioritisation should be determined on abroader basis than in current schemes and may beachievable by establishing open‐access databases andmultivariate analysis of environmentally detectedchemicalpatternsandtoxicitypro iles.Lunchtime provided an opportunity for delegates tonetwork and inspect the sponsors’ exhibitions. Afterlunch, Professor Mills introduced the second keynotespeaker, Professor de Boer, after which the afternoonwas chaired by Dr Roger Reeve University ofSunderland,UK .Professor de Boer Vrije Universiteit, Amsterdam,Netherlands discussed ‘Human exposure toenvironmental contaminants: direct probe time‐of lightmass spectroscopy reveals a multitude of chemicals

Figure4.FieldtestingofDGTpassivesamplerscap‐turesawiderangeofantibiotics


indoors ’. The talk centred around lame retardants,starting with brominated compounds and then non‐brominated alternatives, including chloroparaf ins andphosphorus‐based compounds. There are neurotoxicityconcerns for the latter group. Samples of indoor dustcontaincomplexmixturesof lameretardantsaswellasotherchemicals.Directprobemassspectroscopy,whichintroduces the solid sample directly into the ionisationchamber of themass spectrometer, has been used as afastscreeningtechnique typically5minpersample forcompliance with legislation. As many retardants arehighly non‐polar, atmospheric pressure chemicalionisation APCI and APPI atmospheric pressurechemical ionisation and photoionisation are suitableionisationtechniques.Themethodavoidslossesfoundintechniquesusingextraction/separation.

Monitoring taste and odour substances in drinkingwater is a regulatory requirement linked to acceptable‘wholesomeness’ of potable water. Mr Gavin MillsSevernTrentWaterPLC,UK described‘Advancesintheidenti ication of tastes and odours in drinking water’including the current state of the art methodology.Sample preparation for injection into the gaschromatograph is automated using Instrument TopSample Preparation ITSP cartridges. These providesolidphaseextractioncleanupof thesampleaspartofthe automation system. Gas chromatography triplequadrupolemassspectrometryisusefulforroutineworkwhereas gas chromatographyquadrupole timeof light,with greater sensitivity and selectivity, allowssimultaneous determination of targeted and non‐targeted compounds. A supplementary ‘detector’, anodourportallows individuallyelutingcompounds tobematched to the odours. Examples were given ofidenti ication and determination of low‐level ‘tasty’compounds found in water samples, one of which wasnotevenpresentoninternationaldatabases.Ms Erika Castringano and Mr Luigi Lopardo fromProfessor Barabara Kasprzyk‐Hordern’s group at theUniversityofBath,UKgaveapresentationthataskedthequestion ‘Can urban water pro iling inform ourunderstanding of the state of environmental and public

health?’ The main example, provided for context,concerned the misuse of pharmaceutical drugs, whichappear in wastewater. The drugs as with mostpharmaceuticals are chiral and single enantiomers areused for legitimatemedicinal application.Drugsboughtonthestreetare lesspureandcancontainamixtureofthe enantiomers. Analysis of the water samples byextraction‐LC‐MS using chiral LC columns allows theconcentrations of the enantiomers to be determinedleadingtoanestimationoftherelativeproportionsofthelegaland illicituseof thedrugs. Investigationsofwaterpro iling have been extended to endocrine disruptorsand determination of metabolic biomarkers. In vitrostudiescombinedwithurbanwateranalysiscanbeusedtodeterminepublicexposure.

DrMarkPerkins AnatuneLtd., UK in hispresentation ‘VOCmeasurements in ambientairusingSelectedIonFlowTubeMass Spectrometry –automationandcalibrationconsiderations’ describeddevelopments in thetechnique to produce anautonomous airmonitoring system. The

workwas in collaborationwith DrMarvin Shaw at theUniversityofYork,UK.Theselected‐ion low‐tubemassspectrometer SIFT‐MS technique Figure 4 involvesthe chemical ionisation of the analyte by selectedpositive precursor ions. These ions are produced fromhumidi iedairbyamicrowaveplasmawhichmeansnoexternal gas supplies are needed allowing autonomousield use. Although the technique allows concentrationsto be determined directly without standards usinglibraryreactionratedata,highaccuracycalibrationusestraceable gas standards. Prior to deployment,optimisation included sensitivity and limit of detection.Current ield trials in Beijing, China are evaluating therobustnessandreproducibilityoftheSIFT‐MSinroutineield deployment, and determining the accuracy andprecision of the SIFT‐MS formeasuring real time tracelevelVOCmixingratios.TheabovesynopseswerepreparedbyRogerReeveandGraham Mills based on the presentations and slidessuppliedbythespeakers.Theindustrymeetingsponsorswere Agilent Technologies, Anatune Ltd., Hichrom Ltd.,Imspex Diagnostics Ltd., Kinesis, Markes Internationaland Thames Restek Ltd. Financial support is alsoacknowledged from the Environment Sustainably andEnergy Division of the RSC, which facilitated theattendanceofthetwointernationalspeakers.

Figure4.SelectedIonFlowTubeMassSpectrometry


The 2017 ECG Distinguished Guest Lecture and symposium was held on 1st March 2017, exploring the chemistry of diesel engine emissions, emissions policy, and how this is affecting human health. The ECG Distinguished Guest Lecture was given by Professor Frank Kelly, King’s College London. In the introductory talk, Dr Claire Holman UniversityCollegeLondon/BrookCottageConsultants exploredthelinksbetweendieselvehiclesandpoorairquality.Today,media interestinthistopic ishigherthanithasbeenatany time since the late 1980s/early 1990s. The key airpollutants in most of our citiesare nitrogen dioxide NO2 andine particulate matter PM inurban areas, both of which arepredominantlyemittedbydieselengines. Indeed, most of the airqualitymanagementareasintheUK are due to highconcentrations of NO2. Thebiggest contributor to NOxoxides of nitrogen, includingNO2 isroadtraf ic 80% .Vehiclemanufacturerstendtoprefertoimprovevehicleemissionsbyimprovingtheengineratherthanaddinganadditional component to treat the exhaust. However,there is a trade‐off between generating CO2, NOx andparticulates;ofteniftheengineisimprovedtotreatonetypeofemissionthenissuescanarisewithanothertype.For example, reducing CO2 and hydrocarbon emissionscanleadtoanincreaseNOxemissions.CO2istheprimarycauseofclimatechange,whichisaglobalissuerequiringglobal agreement whereas air pollution is a moreregional or national issue, where local and nationalactioncanhavedirectbene itsforlocalinhabitants.Thisdisconnect results in an interesting tension betweeneffortstotackleclimatechangeandairpollution.

Vehicleemissionsaremeasured ina laboratoryusingachassisdynamometertocon irmcompliancewiththeEUType Approval test. Emission test results show thatemissions fromdiesel carshave improved substantiallyinthelastdecade,butarestillconsiderablyhigherthanthose forpetrolcars.Yet, currentlyaround30%ofcarsand 50% of new cars are diesel, largely because ofincentivesforbuyingthemastheywereperceivedtobebetter for the climate lower CO2 emissions perkilometre travelled . Critically, the reduction inemissionsobservedinthelaboratorytestshavenotbeenre lectedindatafromrealdrivingconditions,whicharetypicallyuptosixtimesgreater.All new cars have some sort of abatement technologyitted, but to aid performance these are not always

activated under all drivingconditions. In fact, many carmanufacturers installed ‘defeatdevices’, which switch offpollution control technologyafter a certain period of time orbelow a threshold temperatureto avoid engine damage. Forexample, the vehicles producedbyonemanufacturerswitchesofftheir pollution control after 22minutes and it has been notedthat the typical laboratory

emission test lasts 20 minutes , and others may bepredominantly switched off in temperatures typical ofnorthernEuropeanclimates.AlthoughVolkswagenreceivedmuchofthebadpress,DrHolman concluded that their most recent modelsactually had one of the lowest on‐road emissions,compared to other manufacturers, although their on‐road real world emissions were still nearly double thetestcycle limit forNOx.Asaresultof these issues, from2019 all new vehicleswill be subject to a ‘real driving’emissionstestwiththepermittedlimitinitiallybeing2.1timesthatforthelaboratorytestsin2019,andthiswilldecreaseto1.5timesby2020/21.Dr Jacqueline Hamilton University of York began hertalk by noting that diesel use is increasing worldwide,

Meeting report

Inside the engine — from chemistry to human health Laura Newsome (Univ. of Manchester, [email protected])

Many car manufacturers in-stalled ‘defeat devices’,

which switch off pollution control technology after a

certain period of time or be-low a threshold temperature

to avoid engine damage.



not just in Europe, and by 2040 diesel will be thepredominant fuel globally. After exiting the engine inmodern vehicles, diesel emissions in modern vehiclesincluding NOx, CO, CO2, PM, volatile organic carboncompounds VOCs and unburnt fuel pass through anoxidisingcatalyst, thenadieselparticulate ilter,beforebeing emitted as exhaust. VOCs are important as theycan be oxidised to form ozone, are implicated in theoxidationofNOtoNO2andcanformsecondaryorganicaerosols SOAs throughcondensationontopre‐existingaerosols.BothozoneandSOAsareknowntobetoxic.The concentrations of pollutants measured in theatmosphere by lying a plane over Londonwere muchlarger than calculations based upon the NationalEmissions Inventory would suggest. There has beencontroversy over the rolethat diesel plays ingenerating SOA. Althoughlevels of smallerhydrocarbons in the air arefalling, the speaker arguedthat the largely neglected intermediate size C10 volatile organic compoundsfromdiesel exhaustmaybekey to understanding theconcentrations of SOAs inthe atmosphere. This isbecoming more importantas diesel cars are nowknown to be the largestcontributor to urban SOAformation when they makeup more than 10% of carsontheroad.Measuring VOC emissions is dif icult and has thereforeoften been overlooked. They are present at parts perbillion to parts per trillion concentrations in a complexmatrix air , and have a vast range of polarities andisomeric complexity. A new technique called twodimensional mass spectrometry GC‐GC‐MS canseparate out over 600VOCs from an urban air sample.This is a powerful tool to identify the sources ofhydrocarbons in the atmosphere and, potentially, theircontribution to SOA formation. Two dimensional gaschromatography has been used to measure VOCs inLondon air and in diesel exhaust in laboratory testconditions, and the most recent deployment is in aprojectlookingatairqualityinBeijing.While the National Emissions Inventory shows goodagreement with atmospheric measurements formoleculeswithfewcarbonatoms,thosegreaterthanC10insizecanbeunderestimatedbyafactorof70.However,

thisdiscrepancycanbeaccountedforoncetheemissionof intermediateVOCs fromdieselengines is included inthemodels.DrHamiltonconcludedthatdieselemissionscontributeupto30%ofSOAintheUK.Theshifttodieselin the UK has changed the balance of hydrocarbons intheatmosphere,butthisshifthasbeenunnoticedduetoa lack of measurement infrastructure. However, newresearch is now highlighting the importance ofpollutantsotherthanCO2andNO2fromdieselemissions.SimonBirkett CleanAirLondon explainedthatmodernair quality legislationwas irst introducedby theCleanAir Act of 1956 following the Great London Smog in1952. However, London currently has some of thehighest NO2 concentrations in the world. Mr Birketttherefore asserted that similar pioneering action needs

tobetaken.In the 1980s, concernsrose about lead inpetrol, leading to thedevelopment of thethree way catalyticconverter. TheThatcher governmentplayed a key role indeveloping UKenvironmental policy,which was irstpublished in the ‘ThisCommon Inheritance’report in 1990 anddiscussed unleadedpetrol, carbon dioxideand ozone. Even in

1990/1991,therewasknowledgeandawarenessofthehealtheffectsofdieselemittedparticles the1992issuementioned that small particles from diesel fuel maycontributetocancer .Butitwasnotuntil2012thattheInternational Agency for Research on Cancer classi ieddiesel fuel as carcinogenic. During the early 1990s, afocus on fuel ef iciency and hence lower CO2 emissionsmeant that diesel was nevertheless prioritised. Sincethen, all successive governments have promoted dieseltoactonclimatechangeconcerns.Mr Birkett compared effect of diesel emissions on airquality today to passive smoking in the 1970s; healthimpactswereacknowledgedby theWHO,butefforts totackle the problem still took decades. Moreover, hecalleditironicthatincreasingdieselusehasnotloweredcarbon dioxide emissions, as originally intended. Thespeakercalledfora“OneAtmosphere”strategythatdoesnot focus just on air quality or on carbon dioxide, butrathertacklesbothatthesametime.HisambitionwouldbetoridLondonofallfossilfuelsby2033—thiswould

London has some of the highest NO2 concentra ons in the

world. Credit: Brian Minkoff/Shu erstock


require acting now as, for example, new diesel taxisregisteredthisyearwillbearoundfor15years.ThesymposiumclosedwiththeECGDistinguishedGuestLecturer,ProfessorFrankKelly King’sCollegeLondon ,who spoke on “Traf ic Pollution and Health in London,Umea andBeijing”.Hebegan his talk bydescribing theWHO air pollution pyramid; at the bottom all peopleexposed to air pollution have unnoticed butconsequential physiological changes. Moving up, aproportion of people will have symptoms such asrunningeyesandasthma,andatthetopofthepyramidthere are 29,000 annual deaths in the UK linked toparticlesintheatmosphere PM2.5 .Umea in Sweden has pristine air and world classresearchfacilitiesandisthusaperfectplacetostudytheeffectsofairpollutionusinganozoneexposurechamberorbyperforminginvestigativebronchoscopyonmedicalstudent volunteers aftercontrolled exposure to airpollution. A two‐hour exposureto ozone caused anin lammatory response, withneutrophils shown to enter thelungs. This effect was alsoobserved after exposure todieselexhaustatconcentrationscommonly found in theenvironment, as well as theexpression of genes associatedwith an immune systemresponse,andactivationofbronchialmucosalcells.The immune response to particulates in our lungsdamages the tissues and causes long term impacts.Macrophagesengulfblack carbonparticles fromdieselexhaust in the lungs, and try to destroy them as theywouldabacterialinvaderbyproducingfreeradicals.Asthere is no bacterium to absorb the free radicals, theyendupkillingthemacrophagesandcausingsmalllevelsof cellular damage. Moreover, particles contain metalsandorganiccompounds,soalsocausecomplexchemicalreactionsatthelungsurface.Damageaccumulatesover timeand can lead todiseasesuchaschronicexposuredisease,buttheresponsetoairpollutionvarieswidelybetweensubjects.Thisvariationis typical ofhumanexposure studies, andan importantaspect of this research is to understand which factorsaffectthisvariationandwhy.Professor Kelly described experiments that he and hiscoworkershadconductedusingOxfordStreetandHydeParkinLondonasanaturallaboratorytostudyexposureto ‘high’and ‘low’pollution levels.The irstexperiment

involved asking asthmatics to take a two hour walkbeforemeasuring their lung function using spirometry.Not only was lung function reduced after exposure toOxford Street pollution and compared to those whowalkedinHydePark ,itwasalsostillreduced22hourslater. Researchers in Germany found that you have ahigher risk of coronary artery calci ication which canleadtoheartattacks thecloseryoulivetoamainroad,soProfessorKellyusedtheOxfordStreetandHydeParknaturallaboratorytoseewhateffectairpollutionhadonpeople with lung disease. Results showed increasedairway resistance in ischaemic heart disease patientsand increased airway dysfunction and arterial stiffnessinpatientssufferingfromchronicobstructivepulmonarydisease.A six year study called EXHALE of children at schoolsclose to main roads, conducted in East London,investigated how exposure toNOx,NO2, PM10andPM2.5

might impact on their lungdevelopment. The resultsshowed that everydayexposure to air pollution hadan adverse effect on lunggrowth in children. Thoseexposed to 35 μg/m3 NO2 hadlost 105 ml of lung capacity5.5% ; those with higherexposuresof55μg/m3hadlost165ml 8.7% .Ifthisde icit isnot remedied before thechildren stop growing, they

will have reduced lung capacity throughout their lives.The researchers also found evidence for black carbonfromdieselinthechildren’slungs.Around65%oftheirexposure was from their journey to school or in theplayground.In the inal part of his lecture, Professor Kelly shiftedattentiontohisrecentworkinChina.TheproblemsseeninLondonpale into insigni icancecomparedtothoseinmany parts of East Asia today,where heavy traf ic andindustrial emissions cause severe smog in cities, whileindoor air pollution from cooking stoves dominates inrural areas. Ambient air pollution is the fourth biggestkillerinChinaandindoorairpollutionisthe ifth.Mostvehicles in China run on petrol. In ongoing work inBeijing, the researchers have recruited two groups of120 subjects at two sites, one in the city and one in anearby rural location. They are using sophisticatedpersonalmonitorstogainadetailedpictureofindividualexposuretoarangeofpollutants,comparetheeffectsofoutdoor and indoor air pollution, and identify theresulting health impacts, with physiological and geneexpressionstudies.

A six year study called EX-HALE of children at schools

close to main roads, conduct-ed in East London, … showed that everyday exposure to air

pollution had an adverse effect on lung growth in children.


Article

Air Pollution and health: knowledge gained from journeys to Umea, Lon-don and Beijing Frank Kelly (King’s College London, [email protected])

In cities across the globe, road transport is an important source of air pollutants that are linked to acute and chronic health effects. In the last 20 years, my research group has investigated these associations in human challenge chamber studies in Umea, Sweden, real world exposure scenarios in London, and recently in the megacity Beijing, China. In this article, I review our findings and those from other groups to show that humankind must advance beyond a fossil fuel-based road transport system.

The main particulate matter PM componentsoriginatingfromroadtraf icareengineemissions,largelycomprising elemental carbon and organic carbon, andnon‐exhaust sources that are often characterised byelevated concentrations of transitionmetals frombrakewear copper, antimony , tire abrasion zinc , and roadsurface wear and dust resuspension iron . The largestsingle source is derived from diesel exhaust. Indeed,owing to the increased market penetration of dieselengines in many European countries and the fact thatthey generate up to 100 times as many particles ascomparable gasoline engines with three‐way catalyticconvertors, diesel exhaust particles contributesigni icantlytotheairshedinmanyoftheworld’slargestcities.Owing to the toxic and ubiquitous nature of vehiclederived particles, our early work at the University of

Rushhourtraf iconacityroad.Credit:RepinaValeriya/Shutterstock



Umea see the photo focused on controlled dieselexhaustexposurestudiestounderstandthemechanismsthrough which diesel exhaust exacerbates respiratorydisease, as identi ied in epidemiological research. Toinvestigate effects on theairways,humanvolunteershealthy and/or mildasthmatic were exposedfor one to two hours towhole diesel exhaustparticulates and theassociated gas phaseemissions from an idlingengine at concentrationsranging fromenvironmentally relevantto those commonlyexperienced inbusydiesel‐dominated traf icenvironments.By performing blood,bronchoalveloar lavage, and bronchial mucosal biopsysampling after exposure, these studies have beeninstrumental in uncovering a systemic and pulmonaryin lammatory response, attributed in part to theoxidativepropertiesofexhaustPM 1‒7 .Thisexposurealso upregulates redox‐sensitive transcription factorsand their associated upstreamstress‐related mitogen‐activatedprotein kinases in the bronchialepithelium of humanairways 6 . Signalling cascadessuch as these likely act as thetrigger by which diesel PMinduce expression ofproin lammatory cytokines inairwaytissue.These events, in turn, provide acellularbasisfortherapidin luxofneutrophils,lymphocytes,andmast cells from the circulation to the source of thein lammatory focus, namely the airways, as well as thesystemic response in the form of neutrophilia andselective lymphopenia in the peripheral blood. Theseindings supported the well‐established and highlyregulated fashion in which neutrophils and otherin lammatorycellsfromthebloodtransitintotissue.Thisoccurs in association with an upregulation of adhesionmolecules on the endothelial cells and their respectiveligands on the leukocytes, alongwith release of chemo‐attractantsfromtheepithelialandin lammatorycells.Although diesel exhaust consists of several pollutants,includinggases oxidesofnitrogen,carbon,andsulphur

and PM components, it is unlikely that the NO2concentrations 0.7 or 1.6 ppm in the diesel exhaustused in these studies played any major role in theobservedin lammatoryevents.Inastudyusingasimilar

protocol,exposuretoNO2alone,atsimilarorhigherconcentrations for alonger duration up to 2ppm NO2 for 4 hours failed to elicit adhesionmolecule upregulation orsigni icant changes inin lammatory cells in thebronchial mucosasampledatthesametimepoint; this observationsuggests that the PMcontent of diesel exhaustis the responsiblepollutant 8 .Away from orthodox,

controlledexposurechamberstudies,wenextundertookworkinLondon.Usingthecityasthelaboratory,weusedreal world exposure scenarios to investigate therespiratoryeffectsofshort‐termexposuretodieseltraf ic9 .Inadultswithmildtomoderateasthma,walkingfortwohoursalongabusycitystreetwheretraf icisentirely

diesel powered as opposedto in a nearby park resultedin a signi icant butasymptomatic reduction inlungfunction.Inlinewithourstudiesofhumansinexposurechambers and our currentunderstandingof the chainofmolecular events, roadsidetraf icexposuresalsoinducedin lammatorychanges 9 .This evidence from researchinUmeaandLondonsupports

an interactive chain of events linking pollution‐inducedpulmonary and systemic oxidative stress, in lammatoryevents,andtranslocationofparticleconstituentswithanassociated risk of vascular dysfunction, atherosclerosis,and ischemic cardiovascular andobstructivepulmonarydiseases. It is now clearly recognised that exposure tocombustion‐related PM, at concentrations experiencedby populations throughout the world, contributes topulmonary and cardiac disease through multiplemechanistic pathways that are complex andinterdependent.IncontrasttotheUK’slongindustrialheritage,Chinahasundergone rapid industrialisation over the past few

Exposure to combustion-related PM, at concentrations experienced by populations

throughout the world, contrib-utes to pulmonary and cardiac

disease through multiple mech-anistic pathways that are com-

plex and interdependent.

ThepristineairinUmea,Swedenmakesitpossibletodocontrolledexposureexperimentstodeterminethehealtheffectsofairpollution.Credit:AndreasGradin/Shutterstock


decades, adding thousands of kilometres of urban roadandhundredsofmillionsofvehicles.PMemissionsfromtraf ic have contributed to increasingly poor air qualityinBeijing seethephoto 10 ,threateningpublichealth11 . The severity of air pollution in Beijing was irstacknowledgedwhenChinawasbidding for theOlympicGamesinthe1990s.Toaddresstheproblem,in1998theBeijingmunicipalgovernment introducedthe irstof16stagesofairpollutioncontrolmeasures.Initialmeasuresmainly focusedonshuttingdownsmallindustrial and domestic coal burning stoves andcontrollingdustfromroadandconstructionsites,aswellas phasing out old vehicles that did notmeet emissionstandards.DuringtheBeijingOlympicsin2008 12 andtheAsia‐Paci icEconomicCooperationmeetinginBeijingin 2014, aggressivemeasureswere taken to reduce thenumber of vehicles on the road by allowing cars to beusedononlycertaindaysoftheweek,determinedbythelast digit of the car license number. This measureresulted in substantial temporary reductions incongestion and pollution concentrations in Beijing andwasconsideredsosuccessfulthatitwasmadearoutinerule immediatelyaftertheOlympics.Today,everycar isallowed to drive four days per ive weekdays. Theseefforts to control air pollution in Beijing have shownsome success. Concentrations of PM2.5 that is, PMwithdiametersof2.5μmorless havestartedtofallinrecentyears.However, these bene its have been compromisedto someextentby the rapid growth in vehiclenumbersfrom1.5millionin2000to5.6millionin2015.In2016withfundingfromtheUK’sNaturalEnvironmentResearch Council NERC and the Medical ResearchCouncil MRC undertheNewtonProgramme,westarted

work on a new project in Beijing,termed AIRLESS Effects of airpollution on cardiopulmonarydisease in urban and peri‐urbanresidents in Beijing . We areexaminingtheimpactofairpollutiononthehealthofresidentswholiveinthecentreofBeijing,comparedwithresidents who live outside theBeijingurbansprawl inaruralarea.The120individualsintheruralareaare exposed to pollution from coal/biomass type burning, whereas incentralBeijing thepollution ismoretraf ic‐based. We provide thevolunteers with personal air qualitymonitors and measure theirexposure for 24 hours a day forseven days. These data provide uswithauniqueviewoftheirpersonalexposuretoairpollution.Wearealso

takingbiologicalsamplesincludingbloodandurinefromthese individuals, andwe are looking for signals to thespeci ic pollutants that they are being exposed to.Withthis approach, we will learn if the pollution in Chinaresultsinthesametypeofbiologicalresponseswehaveseem previously in Umea and London; if not, we willhaveabetterunderstandingofwhydifferenttypesofairpollutionleadtoparticularbiologicalresponses.

References 1. S. S. Salvi et al., American Journal ofRespiratory and

CriticalCareMedicine159,702 1999 .2. S. S. Salvi et al., American Journal ofRespiratory and

CriticalCareMedicine161,550 2000 .3. I. S. Mudway et al., Archives of Biochemistry and

Biophysics42,200 2004 .4.J.Pourazaretal.,RespiratoryMedicine98,821 2004 .5.N.Stenforsetal.,EuropeanRespiratoryJournal23,82

2004 .6.J.Pourazaretal.,AmericanJournalofPhysiology‐Lung

CellularandMolecularPhysiology289,L724 2005 .7.A.F.Behndigetal.,EuropeanRespiratory Journal27,

359 2006 .8. A. Blomberg et al., American Journal of Respiratory

andCriticalCareMedicine156,418 1997 .9. J.McCreanor et al.,NewEngland Journal ofMedicine

357, 2007 .10. Y. Chen et al., Environmental Pollution 212, 269

2016 .11.G.Yangetal.,Lancet381,1987 2013 .12.M.Wangetal.,AtmosphericChemistryandPhysics9,

8247 2009 .

SmogcoveredcitycenterofBeijingon11thOctober2014.Credit:TonyV3112/Shuttterstock


Poor air quality in the UK is mainly caused by diesel vehicle emissions. Although improvements have been made in the latest generation of diesel vehicles, testing under real driving conditions showed that their emissions of nitrogen oxides are still six times greater than the EU limit value. Diesel engines also emit airborne particulate matter which is thought to contribute to more than 5% of all UK deaths. A new emissions testing regime will begin in 2019, but there is long way to go before health-based air quality objectives will be met. AirpollutionisamajorissueintheUK.Exposuretosmallairborneparticles knownasPM2.5 contributestoabout6%ofalldeathsinEngland,withadditionaldeathsandillhealthcausedbyexposuretonitrogendioxide.Approximately two thirds of local authorities havedeclared air qualitymanagement areas,mainly for highNO2 concentrationsdue to emissionsofnitrogenoxidesNOx from road traf ic. Furthermore, the EU annualmeanNO2limitvalueisexceededin38outofthe43airqualitymonitoring zones in the UK. In December 2015the Government published its national air quality plan“Tacklingnitrogendioxideinouttownsandcities”.Thisstatesthat“onaveragetransportisresponsiblefor80%ofNOxemissionsattheroadsideinareaswhereweneedto act to reduce levels”. Diesel vehicles are the largestsourceofNOx.Whilstheavydutyvehiclessuchaslorriesand buses tend to be diesel fuelled, and have been formany years, the number of diesel light duty vehiclescarsandvans hasbeenincreasing.ThesevehicleshavemuchhigherNOxemissionsthantheirpetrolequivalents,but despite this they were promoted by successivegovernments through more favourable taxation due totheirlowercarbondioxideemissions.

NOx and particulate matter PM are commonlyproducedduringcombustionprocesses.NOxisgenerallyconsideredtobeacombinationofnitricoxide NO andnitrogendioxide NO2 .Mostof theNOxemissions fromdieselvehiclesareasNO,whichisrapidlyoxidisedinairto NO2. PM is a heterogeneous mixture of pollutantsemittedfrommanysources,includingcombustion.PMisalso formed in theatmosphere fromairpollutants suchasNOx,sulphuroxidesandorganiccompounds.Generally there is a trade‐off in emissionsbetween fuelef iciency andhenceCO2emissions ,PMandNOx.Foragiven fuel ef iciency or CO2 emission an engine can becalibrated tohave either lowNOxor lowPMemissions,not both. For low CO2 emissions there are likely to behighNOxemissions.Consequently,theemissionlimitsforNOx are more lenient for diesel than for petrol cars.However,therearePMemissionlimitsfordieselvehiclesbutnotformostpetrolvehicles,asgenerallypetrolcarshavevirtuallynoPMemissions.New vehiclesmust pass a series of type approval tests.Caremissionsaretestedinalaboratoryonarollingroadasthecarisdrivenoverastandardtestcycle.Petrolcarsachieve the emission limits in the laboratory by awidemargin;dieselcarslessso.However,remotesensingandportable emission measurement systems have shownthat emissions from diesel cars are much higher whendriven on the road than under laboratory conditions.Thisisnotthecaseforpetrolcars,whichachievesimilarresultsinthelaboratoryandontheroadandoutperformdiesel in both environments. There has been littleimprovement in NOx emissions from diesel vehiclesboth heavy and light duty until very recently. Forexample, the latest generation of diesel vehicles havebeen shown to have lower on‐roadNOx emissions thanearliergenerations;withEuro6cars,forexample,havingabouthalftheemissionsofEuro5cars.This is not a newly identi ied problem. As far back as1993theQualityofUrbanAirReviewGroup ofwhichIwas a member concluded that “…unless someimprovements in theemissions fromdieselvehiclescanbe achieved, there must be considerable concern overany increase in theproportionofdiesel vehiclesonour

Article

Do diesel vehicles cause poor air quality? Claire Holman (Brook Cottage Consultants Ltd/University College London, [email protected])



urban streets as their impact on urban air quality isundoubtedly quite serious” page69 in 1 . Thedieselshareofthenewcarmarkethasincreasedfrom20%toalmost 50% since that report was published. In someotherEuropeancountries,theshareiscurrentlyaround70%. Greece used to have the lowest share in the EUuntil 2011, when a ban on diesel cars in the country’stwo largest cities, Athens and Thessaloniki, wasremoved. In just four years diesel car sales increasedfrom4%toover60%.For many years France had one of the highestproportionsofdieselcars,reachingapeakofover75%in2008.TheFrenchcarmanufacturers,particularly thePSA PeugeotandCitroen group,wereamongtheearlypromotersofdiesel cars. In theearly1980s,diesel carswerereliable,durable,andfuelef icient,butunre inedtodrive. Two technical advances led to diesel carsbecomingasattractivetomotoristsaspetrolcars;turbo‐charginganddirectinjectiondiesel,andfrom2001theirfueleconomybene itsledtheUKGovernmenttoprovidetaxincentivesthroughaCO2basedvehicleexciseduty.New post 2015 Euro 6 petrol cars havemuch highercarbon monoxide and hydrocarbon emissions than anequivalent generation of diesel car, and slightly higherCO2 emissions. On the other hand, the NOx and PMemissionfromdieselcarsaremuchhigher.Thepoliticalpressure to reduce CO2 emissions led to some petrolenginesbecomingmoresimilartodieselengines,andasa result their NOx and, particularly, PM emissions arehigher. This new type of engines are known as directinjectiongasolineorGDIenginesandaresubjecttoaPMlimitforthe irsttime.

The NOx emission limit is more lenient than for petrolbecauseofthedif icultyinreducingNOxemissionsfromdieselcars;dieselcarsarepermittedtoemit33%moreNOxthanpetrolcars.Thisis,however,onlyoneelementofthedieselNOxproblem.Whileon‐roadNOxemissionsfrompetrol carsmeet the limitvalue, those fromdieselcars are many times higher. The vehicle emissionstesting programme 2 found that on average, Euro 6diesel cars emittedmore than six times the limit valuewhendrivenontheroad.The other problem with diesel cars is that they havemuchhigherprimary direct NO2emissionsthanpetrolcars. Primary NO2 emissions have a large in luence onNO2 concentrations close to busy roads. Researchers atKing’sCollege Londonhaveanalysed trends in ambientNO2 concentrations 3 at roadside locations inLondonover the periods 2005‐2009 and 2010‐2014. Between2005 and 2009 there was an increase in NO2concentrations. However, over the second period therewasanaveragereductionofNO2ofnearly10%aswellas a large reduction in PM2.5 28% and black carbon11% 4 .Thetrendswerenotfullyexplainedbylowerlevels of traf ic and therefore it is likely that thereduction was due to a decrease in primary NO2emissions. Despite the general downward trend inroadsideNO2concentrations,thiswasnotobservedatallroadsidemonitoringsites.In relation to high NOx emissions from diesel cars, ananalysis 5 of the results of the real‐world emissiontesting programmes was undertaken by severalEuropean governments in response to the Volkswagenemissions scandal, and showed that there is a huge

AcaremissionstestingcentreinTurin,Italy,in2014.Newdieselcarswillsoonhavetopassmorestringentemis‐sionstests.Credit:MikeDotta/Shutterstock


variationinNOxemissionswhenmeasuredasthevehicleis driven on the road, with ironically Volkswagen carsperforming the best, but the emissionswere still abouttwice the laboratory‐based limit value. The worstperforming vehicles, from Renault, Nissan, Fiat andSuzuki, had NOx emissionsmore than 14 times the limitvalue. These high real worldemissions are caused by arange of strategies that carmanufacturers have adoptedfor managing the pollutioncontrol system. These includeboth the engine managementsystem recognising thelaboratory test cycle, andswitching off the emissioncontrols after 22 minutes thetest cycle lasts about 20minutes . Other manufacturers switch off the systemwhentheambienttemperatureistoocoldortoohot,orwhen the engine isunder load i.e.whenemissions arehigh .TheaveragetemperatureinsouthernEnglandisinthe range of 12 to 15 °C, yet two car manufacturersswitch their pollution control systems off when theambienttemperatureislessthan17°C.A new real driving emission RDE test is to beintroducedfornewcartypesfromSeptember2017,andforallnewcarsfromSeptember2019.Thiswilllimitrealdriving emissions to 2.1 times greater than thelaboratory based limit value. A second stage is to beintroduced from January2020/2021 to reduce theRDEemissionsto1.5timesthelaboratorylimit.Tomeetthesenewrequirements,manufacturersmayneedtocombineemission abatement technologies, such as selectivecatalytic reduction and lean NOx traps, to ensure theywork effectively over the whole operating range of adiesel engine. This may be a challenge for small dieselcars,especiallyifmuchlargeron‐boardstoragetanksforAdBlue 6 areneeded,asthereislittlesparespace.Finally, are the bene its of diesel cars regarding lowerCO2 emissions real? Similar to the NOx emissions, CO2emissions measured in laboratory tests are also muchlowerthantherealdrivingemissions.Comparisonoftheof icial CO2 emissions with large databases of real fuelconsumption data 7 suggests that the differencebetweenthelaboratoryandrealworldCO2emissionshasgrown since 2001,when theUK irst gave an incentivefor low CO2 emitting cars. In 2001, real world CO2emissions were 8% higher than laboratorymeasurements, but this had risen to 40% in 2015. Thegreatest differences between realworld and laboratoryemissionswere forhybridvehicles but thesamplesize

was much smaller , followed by diesel and then petrolcars. The of icial CO2 emissions data show similaremissions from petrol and diesel cars; given that realworld CO2 emissions from diesel cars are greater thanthosemeasuredinthelaboratory,theremayinrealitybe

little difference between thetwo car types. However, dieselcars tend to be larger thanpetrol cars, and comparingaverage emissions could beconsideredunfair.In summary, emissions of airpollutants frompetrol cars arewellcontrolled.ControllingNOxemissions from diesel vehicleshas evolvedmore recently andfor many years has not beeneffective. There is some

evidencethatthemostrecentdieselvehicleshaveloweremissions than earlier generations and this shouldaccelerate with the introduction of RDE tests for cars.Therewill,however,remainsomeuncertaintyuntilthesevehicles are in use and independently tested. In manytownsandcitiesthereremainsalongwaytogotoensurethathealthbasedairqualitystandardsareachieved.

References and notes 1. Dieselvehicleemissionsandurbanairquality,Secondreport of the Quality of Urban Air Group, 1993,available at https://uk‐air.defra.gov.uk/assets/documents/reports/empire/quarg/quarg_94.pdf.

2. Vehicleemissionstestingprogramme,DepartmentforTransport, 2016, available at https://www.gov.uk/government/uploads/system/uploads/attachment_data/ ile/548148/vehicle‐emissions‐testing‐programme‐web.pdf

2. A.FontandG.Fuller,AtmosphericEnvironment218,413 2016 .

3. Blackcarbonisformedbytheincompletecombustionofcarboncontainingfuels.

4.Routes to Clean Air, Institute of Air QualityManagement,Bristol,11‐12October2016,seehttp://iaqm.co.uk/event/routes‐to‐clean‐air‐2016/

5.AdBlueistheureaadditiveusedtoformammoniaon‐board,whichisusedtocreateareducingenvironmenttoenablethecatalysttoremovetheNOxinthevehicleexhaust.

6.International Council for CleanTransportation, Fromlaboratorytoroad:a2016updateofof icialand‘real‐world’fuelconsumptionandCO2valuesforpassengercars in Europe, 2016, available at http://www.theicct.org/sites/default/ iles/publications/ICCT_LaboratoryToRoad_2016.pdf.

Remote sensing and portable emission measurement sys-tems have shown that emis-

sions from diesel cars are sig-nificantly higher when driven on the road than under the la-

boratory conditions. This is not the case for petrol cars.

https://uk%E2%80%90air.defra.gov.uk/assets/documents/reports/empire/quarg/quarg_94.pdf

https://www.gov.uk/government/uploads/system/uploads/attachment_data/file/548148/vehicle-emissions-testing-programme-web.pdf

http://iaqm.co.uk/event/routes-to-clean-air-2016

www.theicct.org/sites/default/%F4%80%8F%90iles/publications/ICCT_LaboratoryToRoad_2016.pdf


Since the U.S. Environment Protection Agency issued a Violation Notice of the Clean Air Act to the car manufacturer Volkswagen in 2015, nitrogen dioxide (NO2) emissions from diesel engines have received considerable public attention (1). Diesel cars also emit other pollutants, including volatile organic compounds (VOCs). Recent studies suggest that models underestimate the contribution to VOCs from diesel cars.Over the last 10 years, diesel fuel usage has increaseddramaticallyworldwide.ExxonMobilpredictsthatdieselfuel will be the number one transport fuel globally by2040 2 . In the UK, the fraction of newly registeredvehiclesusingdieselfuelhasrisenfromlessthan10%in1991toalmost50%in2015.RecentmeasurementsfromLondonsuggestthatemissioninventoriesunderestimatetheemission luxofNO2by30to40%,mainlyasaresultofunder‐representationofroadtraf icemissions 3 .Althoughmanydieselcarspassemission testingduringstringent but predictable laboratory tests, emissions ofNO2 can be many times higher under normal drivingconditions 4 . Diesel vehicles use a range of differentemission control technologies to oxidise or removeharmfulpollutantssuchascarbonmonoxide,particulatematter, nitrogen oxides NOx and volatile organiccompounds VOCs . The latter two are controlledtogetherasNOx VOC,andnewvehiclesmustmeettheEURO VI emission standard of 170 mg/km. Mountingevidence suggests that diesel vehicle emissions of NOxare toohighundernormaldrivingconditions,butwhatabouttheotherpollutants?Andshouldwecare?VOCs play a key role in urban atmospheric chemistry.Their oxidation can lead to the formation of additionaltoxicpollutants, includingozoneandparticulatematter.The UK’s national atmospheric emission inventoryincludesdieselVOCemissions,buttheyarepredictedtobe small compared to those from gasoline and naturalgas burning.Measurements of VOCs in the atmosphere

canbedif icult,becausetheconcentrationsareverylowparts per trillion and awide range of volatilities andpolaritiesarepresent.Thediesel fractionisparticularlychallengingtomeasureasaresultofincreasingisomericcomplexityascarbonnumberincreases.Gasoline vapours are usually analysed with gaschromatography,butthehighercarbonnumberindieselleads to poor resolution and an unresolved complexmixture. Comprehensive two‐dimensional gaschromatography GC GC isahigh‐resolutiontechniquethat couples two GC columns of different selectivity. Amodulatorconcentratesdiscretebundlesofeluentfromthe irst column and injects them onto the secondcolumn,where a very fast separation takes place 10seconds .Thisapproachgiveshigherpeakcapacityandsensitivityandprovidesstructuredchromatograms.The University of York has developed a ield portableGC GC instrument to study the role of diesel VOCemissions. The instrument was deployed during theClean Air For London Clear lo project in NorthKensington in 2012 5 . This collaborative projectinvolved multiple institutions from across the UK andwas funded by the Natural Environment ResearchCouncil.HourlyVOCmeasurementsweremadeusingtheGC GC to studyVOCswith6 to13carbons, andadualchannelGCsystemwasused tostudyVOCswith1 to7carbons 6 . In the example GC GC chromatogramshown in Figure 1, each spot represents an individualcompound.Asthecarbonnumberincreasesalongthex‐axis,thecomplexityofthesamplealsoincreases;bytheendoftheanalysis,therearetoomanyisomerstoalloweach individual spot to be isolated. The structurednature of the GC GC contour space allows us to groupsimilar compounds such as all aliphatic compoundswith12carbons andquantify theircontribution to theatmosphere. The results showed that although diesel‐related VOCs only represented 20 to 30% of the totalhydrocarbon mixing ratio, they comprised more than50% of the atmospheric hydrocarbon mass and are adominant local source of secondary organic aerosols.Thus, emissions fromdiesel vehicles candominate gas‐phasereactivecarbon incitieswithhighproportionsofdiesel vehicles and, in London, were predicted tocontributeupto50%oftheozone‐productionpotential.

Article

Air pollution and traffic: searching for the missing emissions Jacqueline F. Hamilton (University of York, [email protected])



Comparing these urban air measurements with the UKemission inventoryshowsasubstantialunderreportingofdiesel‐relatedhydrocarbons—anunderestimationofafactor4forC9species,risingtoafactorofover70forC12during winter. Laboratory and ambient measurementsgivedifferentresultsfortheimportanceofdieselversusgasolineemissionsintheformationofsecondaryorganicaerosols, a typeofparticulatematter 7 .Todeterminethe impact of the diesel VOCs observed in London, thisadditional source needs to be added to emissioninventories used in air qualitymodeling.Ots et al. usedtheEMEP4‐UKmodeltostudytheimpactofdieselVOCson secondaryorganic aerosol production in theUK 8 .They added the diesel emissions as pentadecane andused the same emission pro ile as in London for everyEuropeancountry.AdditionofdieselVOCsimprovedthemodel‐measurement agreement for SOA, with dieselemissionsaccounting,onaverage,for30%oftheannualSOAproducedinthemodel.Further work is needed to understand the factors thatcontrol VOC emissions from diesel vehicles. The COM‐PART Combustion Particles in the Atmosphere,Properties, Transformation, Fate and Impact projectaims to improve understanding of diesel exhaustemissionsandwhathappensaftertheyarereleased.ThisNERC funded project, involving the UniversitiesManchester, York and Birmingham, will study theemissions of a diesel engine under different real worlddriving conditions. The exhaust from a 1.9 L VWdieselengine is injected into an atmospheric simulationchamber Manchester Aerosol Chamber . The chamberhasaseriesoflights,whichcanbeturnedontosimulatedifferentsunlightconditions.Initialresultsshowthatthe

temperature of both the engine and the emissionscontrols are key factors in determining not only theamountofVOCbutalsothecompositionofemissions.These studies highlight that emissions of VOCs fromdiesel engines can signi icantly impact other toxicpollutants in London and other cities across Europewhere diesel use is high. As diesel use has risen, theimpactonVOCemissionshasbeenlargelyunnoticeddueto the lack of meaningful measurement infrastructure.The control of NO2 frommodern diesel vehicles entailssigni icant policy challenges for many developed cities.Theremayalsobeasimilar,butcurrentlyunrecognized,policychallengetocontrollingreactivecarbonemissionsandtheircontributionstosecondarypollutants.

References 1. https://www.epa.gov/vw/documents‐related‐

volkswagen‐violations‐model‐years‐2009‐2016.2. ExxonMobil,OutlookforEnergy:Aviewto2040

2016 .3. A.R.Vaughanetal.,FaradayDiscussions189,455

2015 .4. D.C.Carslaw,G.Rhys‐Tyler,Atmospheric

Environment81,339 2013 .5. S.I.Bohnenstengeletal.,BulletinoftheAmerican

MeteorologicalSociety96,779 2015 .6. R.E.Dunmoreetal.,AtmosphericChemistryand

Physics15,9983 2015 .7. D.R.Gentneretal.,EnvironmentalScienceand

Technology51,1074 2017 .8. R.Otsetal.,AtmosphericChemistryandPhysics16,

6453 2016 .

Figure1.ExampleGC GC‐FIDchromatogramfromLondonduringwinter.Thex‐andy‐axesshowretentionsonthe irstandsecondcolumns,respectively,withtheintensityofthecompoundshownbythecolouredcontours.Thenumberofcarbonatomsinmoleculesincreasesalongthex‐axis.Theareaslabelled1to8representaliphaticgroupsfromC6toC13.Theotherlabelsare 9 benzene, 10 toluene, 11 C2substitutedmonoaromatics, 12 C3substitutedmonoaromatics, 13 C4substitutedmonoaromatics, 14 naphthalene,and 15 C10monoterpenes.


Fine particulate matter (PM2.5) is a complex mixture of solid and liquid particles suspended in the air. It is produced directly through industrial processes, and indirectly through reactions in the atmosphere. Due to the impacts of PM2.5 on human health and the climate, EU legislation currently focuses on reducing the general background concentration of PM2.5. The future for legislative control in the UK after Brexit is uncertain. PM2.5 isablankettermusedtodescribe ineparticulatematter with an aerodynamic diameter of 2.5 μm orsmaller. The aerodynamic diameter of airborneparticulatematterisde inedasthediameterofaspherewith a density of 1000 kg/m3 and the same settlingvelocityas theparticulateof interest 1 .Thispropertytakes into account the often highly irregular shapes oftheparticulates,whichaffecttheirsettlingvelocities.Theaerodynamic diameter determines the depth ofpenetrationintothelungsuponinhalation,andthereforethetypeandseverityofanyhumanhealthimpacts.PM2.5 consists of an amalgamation of suspended solidand liquid particles, which have a range of differentsources and hence highly variable morphologies andchemical compositions. PM2.5 composition is dominatedby sulphates and nitrates, formed from gaseouscombustion products. PM2.5 also contains polyaromatichydrocarbons PAHs , volatile organic compoundsVOCs , elemental carbon, trace metals such ascadmium, lead, and copper , and water, which isadsorbedontotheparticulates 2 .PM2.5isamuchmorepersistentpollutantthanthelargerPM10 ine particulates with aerodynamic diameters of10μmorsmaller .Dueto its inerparticlesize,smalleraerodynamic diameter, and lower settling velocity, itremains suspended in the atmosphere formuch longerandcanbedepositedthousandsofkilometresawayfromthe original emission source 2 . It has an atmospheric

half‐life of several days or even weeks and can bedeposited on buildings, causing damage by catalysingcorrosion reactions 2 . PM2.5 also penetrates morereadily into indoor environments, where it is morebioavailabletohumans 3 .

Anthropogenic SourcesDirect PM2.5 emissions come largely from combustionprocesses Figure1 .Coal,gasoline,anddieselallreleasePM2.5 during combustion; they are widely used aroundtheworldintransportation,energyproduction,andhightemperature industrial processes such as smelting andsteel production. Wood burning ires are also animportant source. In the UK, non‐exhaust vehicleemissions including brake and tyre wear and roadabrasion areoneofthelargestgrowingsourcesofPM2.5.Thesesourcesareexpectedtoincreasewiththenumberofvehiclesontheroads 1 .The conversion of primary gaseous pollutants, such assulphurdioxide,nitrousoxides,andorganiccompounds,resultsintheformationofsecondaryPM2.5.Thesegasesreactintheatmosphereandundergonucleation,formingvery ine particles, which then coagulate together andincrease insize 2 .Particulates formed in thiswayarecalledtransformationproductsandcanaccountforupto50%ofthetotalPM2.5insomeareas 4 .

ECG Early Careers Environmental Briefs (ECGECEB No 1)

Sources and legislative control of PM2.5 pollution Harrison Frost (University of Reading, [email protected])

Figure1–AconceptualmodelforPM2.5showsthemainprimaryandsecondaryanthropogenicsourcesinred,thepathwaysingreen,andthereceptorsinblue.



Major ImpactsHuman Health. Various epidemiological studies haveidenti iedPM2.5pollutionasanimportantenvironmentalriskfactorforcardiopulmonarydiseasesandlungcancer5 .When inhaled, the ineparticle size allowsPM2.5 tobedepositedinthegasexchangeregionofthelungs.Thisregion contains the alveoli, which have a morevulnerable and sensitive epithelium than the thicker,mucus‐protected bronchioles. Exhalation of PM2.5 isslowerthanforlargerparticles,allowingthemtopersistin the lungs and increasing the probability of transferacrossthealveolarepitheliumintothebloodstreamandlymphaticsystem 2 .ClimateChange.The interactionsofPM2.5withradiativeforcing and atmospheric processes generally result intemperaturereduction.Thesecondaryaerosols inPM2.5exert a negative radiative forcing effect by directlyre lecting insolationandbyincreasingcloudcover.Thisisbecause ineparticulatesactascondensationnucleiforwater molecules, resulting in cloud formation. Cloudsformed from PM2.5 condensation nuclei have moredroplets, but each droplet is smaller. This reduces thelikelihood of precipitation; the clouds persist in theatmosphereforlongerandre lectmoreinsolation 1 .PM2.5 with a high elemental carbon content exerts apositiveradiativeforcingeffectbecausetheblackcarbonabsorbs reradiated insolation. However, the magnitudeof this effect has not been accurately quanti ied 1 .What isclear isthatthescaleofPM2.5pollutionandtheassociatedproblems,stresstheimportanceofconsistentlegislationandcooperationbetweendifferentcountries.

Legislative Control No threshold has been identi ied below which PM2.5exposureposesnorisktohumanhealth 4 .Asaresult,EU legislation emphasises general reduction of PM2.5emissionsoverlargeareas.TheDirectiveonAmbientAirQuality and Cleaner Air for Europe 2008/50/EC introduced average exposure indicator target values toreduceexposuretoPM2.5atapopulationlevel 1 .Thesenational exposure reduction targets are relative to the2010 baseline AEI of the member state Table 1 . AEIvalues are calculated by averaging the three yearrunning mean concentrations, measured at urbanbackgroundlocationsacrossthememberstate.

ConclusionsDue to the variable composition of PM2.5 pollution andthe limited research compared to other pollutants, it isunclearwhichspeci icconstituentscausetheimpactstohumanhealthdiscussedabove.It isclear,however,thatincreasedPM2.5 exposure increases both thenumber ofhospitaladmissionsandtheriskofmanydiseases.

EU legislation rightfully attempts to reduce generalpublicexposure.TheUK,althoughsoonnolongerapartoftheEU,mustactivelycontinuetoadoptEUdirectivesrelated toPM2.5 intonational law.Cooperationbetweenthe UK and other European countries is required tocontrolthispersistentandtransmissiblepollutant,asairpollutiondoesnotrespectinternationalboundaries.

References 1. DepartmentforEnvironmentFoodandRuralAffairs

DEFRA , Air quality expert group: Fine ParticulateMatter PM2.5 in the United Kingdom, 2012,available at https://uk‐air.defra.gov.uk/assets/documents/reports/cat11/1212141150_AQEG_Fine_Particulate_Matter_in_the_UK.pdf.

2. W. E.Wilson, H. H. Suh, Journal of the Air &WasteManagementAssociation47,1238 1997 .

3. C.A.Pope,D.W.Dockery,JournaloftheAir&WasteManagementAssociation56,709 2006 .

4. World Health Organisation, WHO Air QualityGuidelines: Global Update 2005, see http://www.euro.who.int/__data/assets/pdf_ ile/0005/78638/E90038.pdf.

5. C. A. Pope, R. T. Burnett, M. J. Thun, E. E. Calle, D.Krewski, K. Ito, G. D. Thurston, Journal of theAmericanMedicalAssociation287,194704 2002 .

HarrisonFrostwrotethisEnvironmentalBriefinpartialful ilmentofamoduleinEnvironmentalPollution,whichcontributed to his degree in Environmental Science attheUniversityofReading.Heconductedhisdissertationprojectonthemodi icationofbiocharwithmanganesetoenhance arsenic, phosphorous and cadmium sorption,whichinvolvedaresearchvisittoUniversidadAutonomadeMadridinSpain.Upongraduation,Harrisonwillstayat the University of Reading to participate in an MScprogrammeinEnvironmentalPollution.

Initial PM2.5Concen‐tration μg/m3

Reduction target % to bemetby2020

8.5 0

8.5– 13 10

13– 18 15

18– 22 20

22 Allappropriatemeasures toachieve18μg/m3

Table1.NationalexposurereductiontargetssetbytheEU 2008/50/EC .FromDEFRA,2012.

https://uk-air.defra.gov.uk/assets/documents/reports/cat11/1212141150_AQEG_Fine_Particulate_Matter_in_the_UK.pdf

http://www.euro.who.int/__data/assets/pdf_file/0005/78638/E90038.pdf


Hydrofluorocarbons (HFCs) are synthetic halocarbons that are used in refrigeration and cooling, aerosols, fire-extinguishing equipment, and solvents. Emissions of these chemicals have risen since the mid-1990s as they increasingly replaced chlorofluorocarbons (CFCs) (Figure 1). HFCs reflect the long-wave radiation emitted from the Earth back to the Earth surface, causing a warming effect. They have a global warming potential (GWP) of up to 40,000 and an atmospheric lifetime of up to 260 years. Efforts are underway in the European Union and beyond to reduce HFC use and emissions as part of climate change mitigation policies. The identi ication of the ozone hole in 1974 led tointernational efforts to restrict the use of ozone‐destroying chemicals. These efforts culminated in thesigning of the Montreal Protocol on Substances thatDepletetheOzoneLayer,whichwasagreedin1987andenteredintoforcein1989.TheProtocolaimedtophase

out chloro luorocarbons CFCs , halons, and otherchlorinated gases with high ozone‐depleting potentialsODPs by2000.TheMontrealProtocol isthoughtofasone of the most successful pieces of environmentallegislation, having been signed by 197 countries. As adirect result of the Protocol, 97% of ozone depletingsubstanceshadbeenphasedoutby2010.Prior to HFCs, CFCs were used in refrigeration and airconditioning.CFCshaveanoverallclimatecoolingeffect,becausetheirhighODPof0.8to1.0 relativetotheODPofCFC11 ,offsetstheirhighGWPofaround15,000.HFCsreplaced CFCs because they have an ODP of less than0.001;however,thismeansthattheimpactoftheirGWPis signi icant, resulting in an overall warming effect.Industries favored the replacement of CFCswith HFCs,because they are chemically similar to each other andHFCscouldthusbeusedinexistingrefrigerantsystems.However, concern about the contribution of HFCs toglobalwarminghasledtoeffortstorestricttheiruse.

Policy controls on HFCsTheMACDirective–EU 2006 1 .Thisdirectiveaimstoban the use of luorinated greenhouse gases includingHFCs in mobile air conditioning MAC units in newvehiclesby2017 Directive2006/40/EC .However, thedirective only includes luorinated gases F‐gases thathave a GWP higher than 150. It thus allows warming

ECG Early Careers Environmental Briefs (ECGECEB No 2)

Policies controlling hydrofluorocarbon

emissions Georgina Smith (University of Reading, [email protected])

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Figure1.Decline inCFCemissionsafter theMontrealProtocol signing in1987,phase‐out target, and rise inHFCemissions.Datafrom 5 .



agents up to 150 times more powerful than CO2 tocontinue tobeused. It also fails to account for existingMACunitsthatuseF‐gaseswithaGWPabove150.RegulationsonF‐gases–EU 2006,amended2014 2 .Policies were set out to reduce production andconsumptionofF‐gasesthroughouttheEU.Thepoliciesaim to reduce emissions from leakages and faultyequipment.The2014amendmentsaim to reduceF‐gasemissions to 33% of 2014 emission levels by 2030RegulationNo.517/2014 .Kigali Amendment on HFC uses 2016 3 . The KigaliAmendment of the Montreal Protocol is a globalagreement to limit and reduce HFC emissions. It isestimated that this agreementwill prevent emission of

~70billiontonnesofCO2‐equivalentstotheatmosphereby 2050. Under the agreement, developed countriesmust start to reduceHFCemissionsby2019,withHFClevels of just 10% of current levels by 2036. However,developingcountriesdonothavetostartreducingHFCsuntil2028,or2031forsomecountries Figure2 .

Do international policies work?The success of the Montreal Protocol shows thatinternational policies can work. However, China andIndiaareresistingtherapidimplementationoftheKigaliamendment. Both countries produce large amounts ofHFCs, and their resistance is thus likely to impede thesuccessofphasingoutHFCs.The impacts of HFCs on the climate were identi ied inthe mid‐2000s. The delay in politicising these issuesinternationally, combined with the delayed targetreduction schedule, mean that more HFCs will beemitted. This could have serious impacts on keepingglobalwarmingbelowa2°Ctemperaturerise,thelimitdecidedoninthe2015ParisAgreement.Furthermore,thereisaneedforsuitablealternativestoHFCs. These replacements need to be thoroughlyanalysed for long‐term impacts on the environment to

prevent any unintended consequences. Potentialalternatives to HFCs for refrigeration includehydro luoroole ins HFO , which are unsaturated HFCswithalowerGWPandashortatmosphericlifetime 4 ;hydrocarbons,whichhavelowGWPsoflessthan5.5,butraisesafetyconcernsover lammability;andCO2,withaGWP of 1. However, production of CO2 refrigerantsultimatelycomesfromfossilfuels.

References1. Directive 2006/40/EC, Relating to emissions from

air‐conditioning systems in motor vehicles andamending Council Directive 70/156/EEC, Of icialJournaloftheEuropeanUnion,OJL161,12‐18

2. Regulation No. 517/2014, On FluorinatedGreenhouseGasesandRepealingRegulation EC No.842/2006,Of icialJournaloftheEuropeanUnion,OJL150/195

3. IISD, 2016. Summary of theTwenty‐EighthMeetingof the Parties to the Montreal Protocol: 10‐14October2016.EarthNegotiationsBulletin,131 19

4. S. Seidel, J. Ye, S. O. Andersen, A. Hillbrand, Not‐In‐Kind Alternatives to High Global Warming HFCs,Centre for Climate and Energy Solutions, October2016Brief.

5. NAEI, 2016. National Atmospheric EmissionsInventory. Pollutant Information:Hydro luorocarbons. Available at: http://naei.defra.gov.uk/overview/pollutants?pollutant_id HFCs.Accessedon07/11/2016.

GeorginaSmithwrotethisEnvironmentalBriefinpartialful ilmentofamoduleinEnvironmentalPollution,whichcontributed to her degree in Environmental Science atthe University of Reading. She conducted her BScdissertation project on terrestrial microplasticdistribution and toxicity to Daphnia magna and wasawarded the Franklin Sibly Prize for her performanceduringherBSc.Upongraduation,Georgina is startingarole as an Environmental Consultant with GolderAssociates.

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Figure2.HFCemissionreductiontargets,comparedto2014levels,intheKigaliAmendment,2016.Datafrom 3 .


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