AcidRain

Aciddepositionconsistsofdeliveryofacid
substancesorprecursors,principallysulfur
andnitrogenoxides,acids,andsalts,from
theatmospheretotheearthsurface
(Schwartz1989)
Wetdepositionrain
Drydepositionadsorption,adhesion
Cloudandfogdroplets
 pHofrain

pKg=1.41
pK1=6.35
pK2=10.33
pHofpurewater?
 Background
Acidprecipitationrecognizedover100yearsago
Smith18401870(SO42higherinurbanareas)
Sweden1950sand60s
regionalproblem
decreaseinrainpH
sourceofairinfluencedrainpH
LikensstartedworkintheUSintheearly1970s
huge$$$$inthe1980s
CurrentresearchSchwartz(1989)AcidDeposition:
UnravelingaRegionalPhenomenon,Science243:753.
 CurrentResearch
EmissionsWhatarethesources?
rates
distribution
cost
AtmosphericProcesses
concentrations
reactionmechanisms
transportandreactionrates
removalrates
EffectsWhydowecare?
 Major sources of Nitrogen and Sulfur
N/1012 g/y S/10 12 g/y
NH3 Solids
Biogenic 122 sea salt 44
NOx dust 20
stratosphere 1 Reduced
lightning 5 biogenic 98
biogenic 8 Partially oxid.
biomass comb. 12 fossil fuel 104
F
fossil fuel 20 Volcanoes 5
SpatialDistributionofEmissions
SpatialDistributionofEmissions

NitrogenOxides
 AffectedSourcesintheEPAsAcidRainProgram
Affected sources are
determined by NOx and
SO2 emission rates and
fuel consumption.

Phase I began in 1995,

affecting 445 of the larger
emitting units.

Phase II began in 2000

and includes smaller
plants as well, affecting
over 2000 units.

http://www.epa.gov/airmarkets/progsregs/
HistoricalTrends
 TheCurrentLimits
USStandard(AtmosphericConcentration)

SO2 1.2mol/m3
NO2 2.1mol/m3
Depositionlimits(suggested)
SO2 2040mol/m2yr(wetanddrydeposition)
NO2 4080mol/m2yr(wetanddrydeposition)

http://www.epa.gov/ord/htm/CAAA2002report2colrev4.pdf

http://www.epa.gov/airmarkets/arp/index.html
 Emissions
NewtonslawofairpollutionWhatgoesupmustcomedown!
Fromemissionrateswecandefineadepositionrate,butnota
distribution!
OHIOrivervalley
SO2 360mmol/m2yr.
NO2 210mmol/m2yr.
Northeast
SO2 130mmol/m2yr.
NO2 120mmol/m2yr.
Theselevelsare210timeslowerthanemissionlevels!
Wheredotheacidicemissionsgo?
 DepositionofNOxandSO2
Wetdeposition
Rain,snow,fog
SO2andNOxformHNO3andH2SO4
Solublegassesthatdissolveinraindrops
TheHcationgoesintosolution,causingacidrain
Drydeposition
Particulatesandaerosolsabsorbedbyplantsordeposited
onsurfaces
Ammoniaandsulfuricacidformammoniumsulfate,a
particlethatwatercondensesaroundtoformcloudsand
thusaerosols.Landdirectlyonsurfaces.
IfNitricAciddoesntgointosolution,itcandirectly
depositontheground
 OverviewSO2Chemistry
SO2rapiddrydeposition(notwater
soluble)
SO42,H2SO4almostentirelyasaerosols
(verysoluble)
 SO2Chemistry
CombustionprocessesproduceSO2.
SO2canbedrydepositedtotheearthorcan
beoxidizedintheatmosphere
Gasphasereactions:(15%hr)
SO2 OH M HOSO2
HOSO2 O2 SO3 HO2
SO3 H2 O M H 2 SO4
__ __ __ __ __ __ __ __ __ __ __ __ __ __ _
net OH SO2 O2 H 2O H2 SO4 HO2
 SO2Chemistry
Aqueousphase(cloudbasedreactions):
10%/minute

SO2 H2 O HSO3 H SO3 2 H
2
HSO3 H 2O2 M SO4 H H2 O
or
HSO3 O3 SO42 O2 H
 SimpleChemicalModel
O3,OH,H2O2 H2O
Oxidation Dissolution
SO2 H2SO4 2H++SO42

SO2
DryDeposition
WetDeposition

afterParks(1985)
 OverviewNO2Chemistry
NONotsurfaceactive(notwatersoluble)
NO2drydeposition
HNO3veryvolatile,soluble,surfaceactive
 NO2Chemistry
CombustionprocessesproduceNOx.
NOxcanbedrydepositedtotheearthorcan
beoxidizedintheatmosphere
Gasphasereactions:(hours)
NOx O3 NO2 O2
NO HO2 NO2 OH
NO2 OH M HNO3
 NO2Chemistry
Gas/Liquid(cloudbasedreactions):
 SimpleChemicalModel
O3,OH,H2O2 H2O
Oxidation Dissolution
NO2 HNO3 H++NO3

NO
DryDeposition
WetDeposition

afterParks(1985)
 AcidRainDistribution
Water
Ofallacidiclakes(largerthan10acres),75%areacidicbecauseofacidrain.Thisistruefor50%of
acidicstreamsaswell.
Mosteffectedlakeareasareinmountainousregions.
Effectedstreamsarethosewhichrunoverthinsoil.
Land
Areasofthinsoil(NortheastUnitedStates)displaymoreeffectsfromacidrainasthereislittleorno
bufferingoftheacid.
Nutrientsaredestroyedandtoxicmetalsarereleasedinacidicsoil.
Vegetation
Theleavesoftreesandplantsarestrippedofnutrientsbyacidrain.
Mosteffectedaretreesathighelevationwhichareconstantlysurroundedbyacidicclouds.
Others
Metals,paintsandstoneexposedtoacidrainarecorroded.
$61millionisspenteachyearoncoatingnewcarsandtruckssoldintheUStopreventpossible
damagebyacidrain.
Sulfateparticlesaccountfor50to70percentofthevisibilityreductionintheeasternpartofthe
UnitedStates

www.epa.gov LindseyBoyle
 GeochemicalEffectsofAcidRain
Theabilityofsoilstoneutralizesomeoralloftheacidityofacidrainwateriscalledbufferingcapacity.Highbuffering
capacitiesleadtosoilsthatdonotbecomeacidified.Differencesinsoilsareanimportantreasonwhysomeareasthat
receiveacidrainshowmoredamagethanotherareasthatreceivethesameamount.Theabilityofforestsoilstoresist
aciditydependsonthethicknessandcompositionofthesoil,aswellasthetypeofbedrockbeneaththeforestfloor.
MidwesternstateslikeNebraskaandIndianahavesoilsthatarewellbuffered.PlaceslikeNewYork'sAdirondackand
CatskillMountains,havethinsoilswithlowbufferingcapacity.AlkalineSoilsneutralizetheaciddirectlyandhavethe
highestbufferingcapacity.
H++CaCO3Ca2++HCO3
Granitesoilsandvolcanicrocksarenotgoodatneutralizingacid.
Thickersoilsarebetterthanthinonesbecausetheyhavealargerionexchange.Soilswithnegativeandpositivelycharged
particleswillhavehydrogenreplacethepositivelychargedparticles.ThisisbadbecausetheNa,NH 4,Caetc.are
importantasnutrientsandwhentheyareleachedawayitbufferstheacidbutleavestheplantswithlittlenutrients.Thin
soilshavesmallerbufferingcapacitiesbecauseallnutrientsareleachedeasily.
Theecologicaleffectsofacidraincanalsobeseeninthewaterenvironments.Acidrainflowstowatersourcesafter
fallingonland,buildings,androads.MostlakesandstreamshaveapHbetween6and8,althoughsomelakesare
naturallyacidicevenwithouttheeffectsofacidrain.Acidrainprimarilyaffectssensitivebodiesofwater,whichare
locatedinwatershedswhosesoilshavealimitedabilitytoneutralizeacidiccompounds.Lakesandstreamsbecomeacidic
whenthewateritselfanditssurroundingsoilcannotbuffertheacidrainenoughtoneutralizeit.Inareaswherebuffering
capacityislow,acidrainalsoreleasesaluminumfromsoilsintolakesandstreams;aluminumishighlytoxictomany
speciesofaquaticorganisms.

NatalieMaida
Source:EPA,
geocities
DamageTo
Trees
 AcidDepositionBiology

Freshwater Lakes

Since only about 10% of the water in lakes and streams comes from rainfall, the acidity of water of freshwater lakes and streams is mostly determined by the soil
and rock types of an area. An area that is most vulnerable to acidification is one that has granite or peat-based soil. Acidification of a lake occurs over a period of
time, but initially acidification of freshwater, causes it to be clear blue. This is due to the settling of decaying organic matter.

Wildlife

Even though the total amount of living organisms remains constant, the diversity of an acidified body of freshwater drops significantly. Soft bodied animals like
leeches, snails, and crayfish die with a very little change in acidity, which is often an indicator of acidification. Acidification of freshwater greatly affects fish
populations. A decrease in pH is often paired with an increase in toxic metals like aluminum and mercury. A decrease in pH and elevated aluminum concentration
will increase fish mortality, decrease fish growth, decrease egg production and embryo survival, and result in physiological impairment of adult fish. Aluminum in
the water can precipitate onto fish gills, which would inhibit diffusion and result in respiratory stress. Acid rain is extremely detrimental to amphibian
populations. Most amphibians lay their eggs in small, shallow ponds which receive most of their water from rainfall. A very small amount of acidic rainfall would
kill any embryos in these small ponds.

Trees

Acid rain does not directly kill trees. Acidic water dissolves the nutrients and minerals in the soil and washes them away before trees and plants can absorb them
out of the ground for use. Acid rain also releases toxic substances such as aluminum into the soil which in very small amounts are very harmful to trees. Trees
high up in the mountains are more at risk to receive acid, from acidic clouds and fog. The trees are often bathed in these clouds, which eats away at the waxy
protective coating on the leaves. After this occurs, the leaves cannot perform photosynthesis and the trees are left unhealthy, weak, and usually die from disease
or from insect attacks.

Matt Aschaffenburg,
http://www.doc.mmu.ac.uk/aric/eae/Acid_Rain/acid_rain.html
pHoflakewaterasafunctionof
time
 Metalsandacidrain
Thesolubilityofmanymetalsareafunction
ofpH
ExampleAl
Al2O3.nH2O+3H+>Al3++H2O
SpeciationofAl:Al3+,AlOH2+,Al(OH)2+,
Al(OH)4
SpeciationDiagram
AlSpeciation
 AlConcentrationasafunctionofpH

AlinfishgillsinhibitsNaandCatransporteffects
gastransport
AlalsoprecipitatesinthegillsasAl(OH)3(s)
 Costs
Totalstructural,ecological,andenvironmentalcostsareestimatedat
5billiondollarsperyear
Forests $1.75B
Agriculture $1.00B
CorrosionofBuildings$2.00B
Tourismandfishing $0.25B

ReduceSO2Emissionsby40% $12B
ReduceSO2Emissionsby50% $24B
ReduceSO2Emissionsby70% $56B
1990CleanAirAct0ver50%reductioninemissionsbytheyear
2000
 CleanAirAct
PhasesandReductions
TitleIVoftheCleanAirActsetagoalofreducingannualSO2emissionsby10million
tonsbelow1980levels.Toachievethesereductions,thelawrequiredatwophase
tighteningoftherestrictionsplacedonfossilfuelfiredpowerplants.

PhaseIbeganin1995andaffected263unitsat110mostlycoalburningelectricutility
plantslocatedin21easternandmidwesternstates.Anadditional182unitsjoinedPhaseI
oftheprogramassubstitutionorcompensatingunits,bringingthetotalofPhaseI
affectedunitsto445.Emissionsdataindicatethat1995SO2emissionsattheseunits
nationwidewerereducedbyalmost40%belowtheirrequiredlevel.

PhaseII,whichbeganintheyear2000,tightenedtheannualemissionslimitsimposedon
theselarge,higheremittingplantsandalsosetrestrictionsonsmaller,cleanerplantsfired
bycoal,oil,andgas,encompassingover2,000unitsinall.Theprogramaffectsexisting
utilityunitsservinggeneratorswithanoutputcapacityofgreaterthan25megawattsand
allnewutilityunits.

TheActalsocalledfora2milliontonreductioninNOxemissionsbytheyear2000.A
significantportionofthisreductionhasbeenachievedbycoalfiredutilityboilersthat
willberequiredtoinstalllowNOxburnertechnologiesandtomeetnewemissions
standards.
http://www.epa.gov/airmarkets/arp/ov
erview.html
HistoricalTrends
 Solutions?
SourceReceptorRelations(SRR)
Relationshipslinkingsourcesanddeposition
WidenumberofapproachesareusedtoestablishSRR
Nocurrentmodelisacceptable
General:localsourcesaremoreimportantthanwethought
Drydepositionisimportant
Weknowwhatacidrainisdoingtotheenvironment
Schwartzasks:
Doweknowenoughtoregulate?
Doweknowenoughtoemit?