Microsoft Word - Assessment of Filamentous Algae in the Greenbrier River

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AssessmentofFilamentousAlgaeintheGreenbrierRiver

andOtherWestVirginiaStreams

JamesSummers,WVDEP‐DWWM

December17,2008

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 Duringthesummerof2007,WVDEPreceivednumerouscomplaintsregardingtheamountof

algaeintheGreenbrierRiver.MostofthecomplaintscenteredontheCaldwelltoAldersonsectionof

theriver;andatleastonecomplaintwasreceivedaboutthelevelofalgaefurtherupstream

inthe

Denmararea.SeveralemployeesofWVDEPwerefamiliarwiththeproblemandindicatedthatthealgae

bloomhadbeenoccurringatvariousintensitiesfordecades;someassertedthatthealgaehadbeen

gettingworse,andperhapsstartingearlier,thanithadhistorically.

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 InSeptember2007,ameetingwithin

theWVDEPDivisionofWaterandWasteManagement

washeldtodiscusstheproblem.Results ofwaterqualitysamplesfromtheWatershedAssessment

Branchsampledatabase(WAB‐Base)weresummarizedatthemeeting.TheWAB‐Baseresultsshowed

elevatedlevelsofphosphorusinHowardCreek.HowardCreekflows intotheGreenbrier

Riverat

Caldwellwherethealgaeproblemwasreportedtobegin.WAB‐Baseresultsalsoshowedthat

phosphoruslevelsinHowardCreekweresignificantlyhigherbelowtheWhiteSulphurSprings sewage

treatmentplant(WSSSTP)thanabovetheplant.

TheWSSSTPhadahistoryofsolids“washout”whichresulted

insludgebedsinHowardCreek.

SevengolfcoursesandafishhatcheryarelocatedonHowardCreek,upstreamoftheWSSSTP.

Additionally,significantcattlepasturingoccursintheGreenbrierbasinupstreamofHowardCreek,and

thegradientoftheriverlessenssomewhatnearCaldwell.Itwassuggestedthat

thesoilparticlesfrom

theupstreampasturesthatarehighinphosphorusweresettlingoutinthislowergradientsectionon

theriver,allowingsomeofthephosphorusboundtothesoiltobereleasedintothewatercolumn. 

Perhapsallthesefactorswerecombiningtofuela“perfectstorm”of

algae.Therewasnoconsensusin

theSeptembermeetingonwhattheprimarysourceofthealgaeproblemwas.

 ATMDLeffortfortheGreenbrierriverbasinwasalreadyunderway.Allthefieldworkforthis

TMDLhadbeencompleted,makingavailablealargeamountofrecentwaterquality,biological,

and

pollutantsourcetrackingdata.Duringthe12monthsofmonitoringat130stations,theonlyviolationof

waterqualitystandardswasforfecalcoliformbacteria.Nutrientsamplesweretakenatseveral

locations;therewerenoviolationsliste dfornitrate,andcurrentlythereisnowaterqualitystandardfor

phosphorus

inWVstreams.Therefore,TMDLswerenotrequiredfornutrients.Pollutantsource

trackingeffortsfocusedonlyonthefecalcoliformimpairments,notonnutrientsources.Oneoutcome

oftheSeptembermeetingwastoperf ormadditionalsourcetrackingonHowardCreekandthe

GreenbrierRivertobetterquantifythenutrientsourcesthat

couldbecontributingtothealgaeproblem.

NutrientSourceTracking

 Observationsofthelocationandintensityofthealgae,bothontheGreenbrierRiverand

HowardCreek,weremade;theaccumulationandimpactofsedimentwasevaluatedinthe“lower

gradient”sectionoftheGreenbrierRivernearCaldwell;historicalriver

flowandrainfalldatawas

assessed;areviewofWAB‐Basenutrientdatawasmade;additionalsamplingincludedastormevent

samplingonHowardCreek,alowflow“snapshot”ofnutrientlevelsinHowardCreek,andawinter

samplingeventcoordinatedwithDEPEnvironmentalEnforcementinspectionstaffwhichincluded

concurrentstreamsamplingandComplianceSamplingInspectionsoftheWSSSTPandfishhatchery.

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Photo1.GreenbrierRiveratHillsboro

STPdischargewherealgaebegins

(9‐12‐08).

Photo3.GreenbrierRiveratmouthof

HowardCreek(9‐25‐07).

Photo2.GreenbrierRiver200‐300feet

belowtheHillsboroSTP discharge

(10‐17‐07).

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Photo4.GreenbrierRiveratabove

FortSpring‐betweenRonceverteand

Alderson(8‐29‐08).

Photo5A.Differentspeciesofalgae

growingincoldwaterofDavisSpring

(8‐25‐08).

Photo5B.Vigorousperiphyton

growthonarocktakenfrom

TuscaroraCreeknearMartinsburg

(11‐11‐08).

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Photo6.SouthForkofSouthBranch

PotomacRiveratMoorefieldbridge

(8‐17‐08).

Photo7.TygartValleyRivernear

Elkins,abovequarry(9‐25‐08).

Photo8.CacaponRivernearYellow

Spring‐belowWardensville(9‐25‐08).

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Photo9.HydrillabedsonNewRiver

withsomefilamentousalgae

development.NearGladeCreek

campground(9‐17‐08).

Photo10.Filamentousalgaealong

edgeofNewRiverjustaboveGauley

Bridge(9‐17‐08).

Photo11.Hydrillabedsinthe

CaldwellpooloftheGreenbrierRiver

aboveHowardCreek(9‐25‐07).

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RiverFlowandRainfall

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 ArchivesfromtheUSGSgagingstationatAldersonandtheNationalWeatherServicewere

reviewed.Whilethesummerprecipi tationandriverflowhavebeenbelowaverageforthreeofthelast

fouryears,theriverflowwasnotexceptionallylow‐fromanhistoricalperspective

(seeAttachment4).

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SedimentImpactandRootedAquaticVegetati on

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 SedimentaccumulatesintheGreenbrierRiverinthelong poolatCaldwell.Thisisoneofthe

fewplacesontheriverwherethetypicalrockysubstrateofGreenbrieriscompletelycoatedwith

sediment.Movingfromthetopofthepool

down,itwasnotedthatasthesedimentincreasedthe

amountofrootedaquaticvegetation(notalgae)increaseddramaticallyandeventuallycover edthe

entireriverbottom(Photo11).Thistypeofrootedvegetation,genusHydrilla,growsinlargebedsin

severalotherriverswheresedimentaccumulated,mostnotablytheNew

River.SeePhoto9.

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 Asarule,whereversedimentaccumulatedintheGreenbrierRiver,therootedvegetation

thrived.ThisnutrientrichsedimentmostlikelyresultsfromagriculturalactivitiesintheGreenbrier

watershed.NobiologicalimpairmentsoccurredintheGreenbrierbasinduringthepre‐TMDL

monitoring,indicatingthegradientishigh

enoughtomovethesedimentdownstreamwithonlyminimal

accumulationintheGreenbrier.

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AlgaeDistribution

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 IntheupstreamsectionoftheGreenbrierRiverintheDenmararea,thereisaveryclearstarting

pointforthealgae–immediatelybelowthesewagetreatmentplantdischargeforthetownof

Hillsboro

(Photo1and2).Hillsboro’sdischargeisabout20timessmallerthanthatfromWSSSTPorRonceverte

STP,sothealgaebloomisrelativelyshortlived.Itbeginswaningjustbeforethesewagedischargefrom

theDenmarCorrectionalCenterenterstheriver;therethealgaebloomincreasesand

continuesdown

theriver,againforonlyarelativelyshortdistance,untilitisgone.

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 FilamentousalgaedoesnotshowupsignificantlyintheCaldwellpooluntilHo wardCreek,which

drainstheWhiteSulphurSpringsarea,enterstheGreenbrierRiver.Atthispointfilamentousalgaeclogs

theHydrillabedsand

fillsthewatercolumn(Photo3).Thealgaegraduallydispersesacrosstheriver

overthenexthalfmileofriffles.OncetheriverreachesRoncevertethealgaeiswelldispersed.When

thedischargefromtheRoncevertesewagetreatmentplantenterstheriver,thealgaeagainfillsthe

watercolumnalongthe

sideoftheriverintowhichtheplanteffluentisdischarged.

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 BelowRoncevertethelevelofalgaldevelopmentcontinuestobesignificantthroughFortSpring

andAlderson(Photo4).AslighttemporaryincreaseisfoundbelowtheAldersonsewagetreatment

plantdischarge,butthealgaelevelisalreadyhigh

enoughthatthesmallerdischargefromAlderson

doesn’thavethedramaticincreasethatisseenbelowHowardCreek(WhiteSulphurSprings)and

Ronceverte.SignificantlevelsofalgaecontinuethroughPenceSpringsandbegintapering offbyTalcott.

Afewsporadicsmallalgaebloomswerenotedondowntherivertoits

mouth(Attachment1).

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 ThereisnoalgaebloombelowtheDurbinsewagetreatmentplantdischargetotheGreenbrier

River.AnalgaebloomwasnotedbelowMarlintoninmid‐summer2008,butdisappearedbySeptember.

Thisisprobablyduetoavaryingcalciumlevelintheriveratthispoint.(The

criticalroleofcalciumwill

beexplainedlaterinthisreport.)

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 AwayfromtheGreenbriermainstem,theamountoffilamentousalgaefoundonHowardCreek

itselfwassurprisinglylowcomparedtotheGreenbrierRiver.Rootedaquaticvegetationdominatesthe

creekwheresedimentaccumulatesandperiphytonthrivesontherockysubstrateinotherplaces.Even

thoughtherewaslessfilamentous

algaethanoriginallyexpected(found latertobeduetothe

calcium/hardnesslevel)therewereareaswherefilamentousalgaeaccumulatedinHowardCreek,and

particularlyofnoteweretheareasupstreamoftheWSSSTPdischarge.Sevengolfcourses,atrout

hatchery,andsomeminimalpasturingarelocatedonHowardCreek

upstreamoftheWSSSTP.

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SourceCharacterization

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 Fertilizerinformationwasgatheredfromsixofthesevengolfcourses.Nutrientcontent,

applicationratesanddates, soilandwatersampleresults,managementpractices,andother

informationwascompiledandevaluatedbyWVDEP.(Theseventhcourseisthefarthestupstreamand

located

onasectionofHowardCreekwherenofilamentousalgaewasnoted;fertilizerapplicationrates

fromtheothercourseswereusedtoestimatetheloadingfromthiscourse.)Researchconductedjointly

byOhioStateUniversityandtheUSDAstudiednutrientlossratesfromgolfcourses;thephosphorusloss

ratewas6.2%

ofthetotalapplied,or0.51kg/ha/year(Kingetal,2004).TheseUSDAvalueswereused

tocalculatethecombinedannualp hosphorusloadingcontributionfromthegolfcourses onHoward

Creek.Thecombinedphosphoruslossfromthegolfcoursestotaled200‐300lbs/year,orabout3%of

thetotalphosphorus

loadinginHowardCreekatitsmouth.



 Duringthepre‐TMDLmoni toring,WVDEPhadtakenmonthlysamplesforoneyearonHoward

Creeknearitsmouth,justbelowtheWSSSTP,justabovetheWSSSTP,andupstreamofsixofthegolf

courses.Thisintensivesamplinghelpedtosegregate

theWSSSTPloadingfromothercategoriesof

sources(Figure1).Grabsamplesofthestreamtakenduringthelowflowconditionsofearlyfallof2007

andaseriesofstreamsamplestakenduringastormeventbothshowedsimilarresults(Attachment3).



Figure1.

PhosphorusLoadingatVariousLocationsAlongHowardCreek.Streamloadings(lbs/day)arebasedon

pre‐TMDLsampleresultstakenMaythroughOctober2004.TheloadingfromtheWhiteSulphurSpringsSTPwas

calculatedfromeffluentsampleresults.



8



Figure2.PhosphorusLoading(lbs/day)DuringComplianceSamplingInspections.





ComplianceSamplingInspectionswereconductedconcurrentlyattheWSSSTPandthenational

fishhatchery;HowardCreekwassampledduringthesametimeasthecompositeeffluentsampleswere

takenfromthehatcheryandWSSSTTP.Again,theWSSSTPaccountedformostofthephosphorus

loadinginHoward

Creek(Figure2).Ge nerally,theWSSSTPaccountedfor80‐90%ofthetotal

phosphorusloadinginHowardCreekthroughouttheyear.



 TheconclusiondrawnfromthenutrientsourcetrackingwasthatthealgaeintheGreenbrier

Riverresultsprimarilyfromthedissolvedphosphorusinmunicipalsewagetreatmentplanteffluent



combiningwithnitrogenfromahostofsources(agriculture,municipaldischarges,andfailingseptic

systems).



KeystoAlgaeDevelopment



 Aftertheinitialpollutantsourcetrackingwasperformed,onequestionwasobviousandhadto

beanswered:Ifthealgaebloomisdriv enbysewagetreatmentdischarges,whyisthe

algaebloomso

severeonsomeportionsoftheGreenbrierRiverandnotpresentonmanyotherriversinthestate.A

queryofWAB‐Base,whichcontainsover30,000samplesfromacrossthestate,turnedupaclear

differenceintwoimportantparameters–alkalinityandhardness.Thesetwoparameters,

alongwith

pH,serveascontrollingvariablesandstronglyinfluencethebehaviorofotherconstituentspresentin

water(Weiner,pp53).



9



 Bothalkalinityandhardnessareindirectmeasuresofmultipleconstituents,andareusually

expressedasanequivalentconcentrationofCaCO

.Hardnessisapropertyofcations(Ca

andMg

)

whilealkalinityisapropertyofanions(HCO

‐1

,CO

‐2

,PO

‐3

,andOH

‐1

).



ThresholdAlkalinity



 Significantly,noalgaebloomswerenotedonstreamswherethealkalinitywaslessthan30mg/l.

Lowalkalinity(lessthan25mg/l)keepsphosphorusfrombeingavailableasanutrient(Wurts,1992)and

couldevenlimitalgaegrowthduetolowmineralizedcarbonlevels.Analkalinityof

greaterthan50mg/l

isrecommendedforproductiveaquacultureponds(Brunson,1999).InWestVirginia,lowalkalinity

riverswithmunicipalsewagetreatmentplantdischargesincludetheElkRiver,CherryRiver,Little

KanawhaRiver,andtheupperGreenbrierRiver(Durbinarea).Algaebloomshavenotbeendocumented

ontheserivers.



Hardness

Ceiling



 Further,nosignificantalgaebloomswerepresentonseveralotherriverseventhoughample

phosphorus,nitrogen,andalkalinitywerepresent.WhenreviewingtheWAB‐Basedata,itwasnoted

thatthehardnesslevelonthesestreamstendedhigherthanontheGreenbrierRiver(seeTable4,p14).

Hardness

ontheGreenbrierdidnotexceed100mg/l.ThehardnessontheWestForkRiverbelowthe

WestonSTPdischargewas250‐400mg/l.SincehardnessisameasureofCa

andMg

+2

cations

(sometimesironandaluminumcanmildlyinfluence totalhardness),aliteraturesearchwasconducted

todetermineiftherewasanyresearchontheroleofcalciumandmagnesiuminthedevelopmentof

algaeinnutrientrichwaters.Thereisa bodyofresearchonthetopic,anditconcludesthat

calciumand

magnesiumarekeyfactorsinalgaedevelopment.Detailsaregiveninthe“LiteratureReview.”



Nutrients



 AstoichiometricformulaforalgaehasbeenestimatedasC

106

181

P(Craggs,2005).One

poundofphosphorouscanthenproducearound78poundsofalgae.(Somesourceshave reportedthis

as350pounds,butthisisincorrectly basedonthemolarratiosinalgae,notthemassratios).Nitrogen

andphosphorusareincorporatedintothealgaecellstructureatapproximatelya

16:1nitrogento

phosphorusmolarratio(Redfield,1958). But becausenitratesleachfromthesoilmorereadilythan

phosphorus,nitrogenisgenerallymuchmoreavailablethanphosphoroustoaquaticvegetati on. 

Consequently,algaegrowthinmostsurfacewaterswillbelimitedbyphosphorous(Weinerpp98).

Removingphosphorusis,chemically,themost

efficientwaytolimitalgaegrowth (Kennedy,2004).



 Underidealsummergrowingconditions,algaebloomscanoccurwithinorganicphosphorus

concentrationsaslowas0.005‐0.01mg/l(Weiner,pp101;Kawaga,1989).Weineralsonotesthat

whenphosphorouslevelsincreaseandcausealgaegrowthtobelimitedbyeither

carbonornitrogen,

longtermmechanisms(CO

diffusionfromatmosphereandchangesinbiological growthmechanisms)

acttocompensateforthesedeficienciesandalgalgrowth oncemorebecomesproportionaltothe

phosphorousconcentration(Weiner,pp100).



 IntheGreenbrierRiver,algaebloomswereoccurringwithPconcentrationsaslowas0.01‐.014

mg/l.Theamountofalgae

formationincreasedwithanincreaseinPconcentrationsfoundbelowthe

dischargesofthesewagetreatmentplants.(Seegrap hin Attachment1.)



10



 Thisisnottosaythatphosphorusismoreimportantthannitrogeninthegrowthofalgae,only

thatgrowthtendstobelimitedbyphosphorus inmostcases.Nitratesareverysolubleandcomefroma

numberofsourcesincludingpasturing,cropandlawnfertilizers,failingseptic

systems,andtreated

sewagedischarges.Consequently,nitratesareratherubiquitousinriversystems.IntheGreenbrier

River,summernitrate‐nitriteconcentrationsrunabouthalftheirwinterlevel,despitethemuchhigher

wintertimeriverflowwhichdilutesthephosphorusconcentration.ThesummerN:Pmassratiointhe

GreenbrierRiveraboveHoward

Creekisabout23:1.Thereisessentiallyenoughnitrateloadinginthe

GreenbrieratRonceverte,220lbs/day,tofuelthealgaegrowthforthecombinedphosphorus loading

frombothWSSSTPandRonceverteSTP,eveniftheentirenitrateloadfromthesesewagetreatment

plantdischargeswasremoved.Phosphorusseems

tobethekeytonotonlyunderstandingthealgae

problem,buttoalleviatingitaswell.



OtherFactors(Turbidity&Temperature)



 Severalotherstreamshadachemistry(alkalinity, hardness,phosphorus,andnitrogen

concentrations)thatseemedfavorableforalgaedevelopment,butnoalgae bloomhadbeenreported.

Whentheserivers

werevisited,manyhadsignificantalgaedevelopment.Thesestreamsinclude

portionsoftheCacaponRiver,BluestoneRiver,NewRiver,andTy gartValleyRiver.TheNorthForkof

theHughesRiverhadsomelowtomoderatealgaedevelopment,butwassomewhatsuppressedgiven

itschemistry;however,waterturbiditywasclearlya

factorinlimitingthealgaedevelopmentonthe

NorthForkofHughes.Otherstreamswithfavorablechemistrywhichdidnothavesignificantlevelsof

filamentousalgaehadobviouslimitingfactorsforalgalgrowth,mostoftenturbidity(KanawhaRiverand

BrushForkofBluestone)ortemperature(PineyCreek).



 Giventheseobservations,

itseemslikelythatalkalinityandhardness,alongwiththeknown

factorsofnitrogen,phosphorus,andturbidity,playakeyroleinfilamentousalgaedevelopmentinWest

Virginia’sstreams.Itisreasonedthataminimumalkalinityisnee dedtomakethephosphorous

availableforplantuptake,andthatathigher

hardnesslevelsCa/Mgprecipitationwithphosphorous

occurs,makingthephosphorusmuchlessavailableforalgaedevelopment.



LiteratureReview



 Understandingtherelationshipbetweenalgaeandphosphorusiscomplicatedbythefactthat

analgaecell’sabilitytousespecificformsofphosphorusisstronglyinfluencedbyseveralfactors,

includingpH,hardness,theamountofdissolvedoxygen,andtemperature(Florida,2000).Other

environmentalfactorssuchasshading,grazing,turbidity,

andsubstrateconditioncanmaintainlowalgal

biomassdespiteabundantnutrients(DoddsandWelch,2000).Further,algaeinstreamsandrivers

occurinmultipleforms,suchassestoniccellswhicharesuspendinthewatercolumn,periphytonwhich

growsonthesubstrate,andfilamentousmats;thesevariousformsmaydiffer

intheirresponseto

nutrientenrichmentandthedegreetowhichtheyareaffectedbyotherenvironmentalfactors(Royer,

2008).



 Theenvironmentalbehaviorofphosphorousislargelygovernedbythege nerallylowsolubility

ofmostofitsinorganiccompounds,anditsstrongadsorptiontosoilparticles(Weiner,pp97).Einsele

andMortimerdemonstratedinthelate1930sandearly1940sthatsedimentsretainphosphorousby

fixationtoiron.Theseresults createdawidespreadopinionthatphosphoroussedimentologywas

completelylinkedtoironchemistry,althoughitwasknownthatcalcareoussedimentsbehaved

differently(Bostrometal,1988).Ithasbecomeevi dent

inmorerecentresearchthatphosphorus



11



exchangebetweensedimentandwaterisahighlycomplexphenomenonandincludesmanyinterrelated

chemical,biological,andphysicalprocesses(Bostrometal,1988).



 Orthophosphate,themineralizedformofphosphoruswhichisusedbythealgae,associates

withparticlesbyseveraltypesofbonding,fromphysicaladsorption,to

co‐precipitation,tochemical

bondsofdifferentstrengths(complex,covalent,andionicbonds)(Bostrometal,1988).

Supersaturationand/orundersaturationofphosphatesaltsmayalsooccur,furthercomplicatingthe

studyofthechemicalprocesseswhichgovernphosphorusavailability(Diaz,1994).



 Theroleofcalciuminphos phoruswaterchemistryhas

receivedfarlessattentionthaniron‐

phosphorusinteractions(Bostrometal,1988).However,severalresearchershaveinvestigatedthe

connectionofcalciumtophosphorusuptakeinalgae.Magnesiumions, withthesameplustwocharge

ascalcium,behavesimilarlytocalciumandaresometimesconsideredtogetherwithcalciumintheir

combinedimpact

onalgaegrowth.



 BedoreetalfoundthatintheupperIllinoisRiver,pHcombinedwithCaandMgactivityarethe

dominantchemicalcontrolsonphosphoruschemistry(2008).Vasatareportedthattheoptimal

concentrationsofCaandMgfortheproductivityofalgaedecreasedwithincreasingPconcentration,

and

KawagaetalfoundaregulatingeffectofdissolvedCaandMgontheP‐nutritionofalgae,i.e.their

Ca‐Mgindexcouldpredictboththeamountofsuspendedphytoplanktonandtheamountofphosphorus

containedinthesestonicalgae(1989).MasayoshifoundaCa/Mgratiolessthan4

hadanegativeeffect

onalgalgrowth,andaCa/Mgratiogreaterthan5enhancedgrowth(2000).



 Theeffectofcalciumandmagnesiumonphosphorusprecipitationisvariabledepending

onthechemicalandphysicalconditionsofthewatersystem.Bedorefoundhighlyvariableassociations

ofphosphorusinsedimentinstreams

impactedbymunicipalsewagetreatmentplanteffluents.Infive

differentsamplelocations,20‐70%ofPwasFe‐associated,20‐50%ofPwasboundinorganic

compounds,and5‐35%ofPwasassociatedwithcalciumminerals(2008).Bedorealsonotedthat

naturallyhardwaterstreamsandriversregularly

experiencehighionicstrength,greatlycomplicatingin‐

streamchemistry.Plantetal(2002)establishedthatphosphorusco‐precipitateswithcalciteinhighly

alkalineaquaticenvironments,althoughthismaybeinhibitedasdissolvedpho sphoruslevelsapproach

0.6mg/lduetothecessationofcalcitegrowth.Otherreportshavealsosuggestedthatphosphorus

co‐

precipitatesoncalciteinhardwaterrivers(Avimelech1980;Salinger1993).HartleysuggestedthatCa‐P

precipitationisanaturalmechanism tocontroleutrophicationinhardwaterlakes(1997).LongtermP‐

accumulationintheEvergladeswaslinearlycorrelatedwithCa

accumulation(Reddyetal1993).



 Thatcalciumandmagnesiumconcentrationsarestronglylinkedwithalgaegrowthiswell

establishedbyresearchandobservation.Generally,theCa‐Mgionsacttocont rol theavailabilityof

phosphorusforalgaeuptakebythefor mationofrelativelyinsolublephosphateprecipitates.The

specificsofthe

phosphateprecipitationarecomplexandcanvarywiththeindividualchemistryofeach

riversystem.AlthoughthecomplexitiesofthemechanismsofCa‐Pprecipitationisnotfullyunderstood,

theconsensusisthatthechemistryoftheaqueousphasefromwhichprecipitationtakesplaceisof

paramountimportance(Koutsoukos,2000).



PhosphatePrecipitation



 Phosphorusbasedanionsoccurinseveralformsandaremostoftenassociatedwithcalcium,

magnesium,sodium,iron,andaluminumcations.Allofthecompoundshavedifferentsolubilities,most



12



ofwhichvarysignificantlywithpH,and formationofsomePcompoundswillalwaysbefavoredover

othersdependingonthegeneralchemicalenvironment(alkalinity,hardness,conductivity,pH,redox

potential,ironavailability,etc.)inwhichformationoccurs.Table1showsthenegativelogofthe

solubilityproductconstants(K



)forseveralsimplephosphatecompounds;whileall(exceptsodium)

arefairlyinsoluble,calciumphosphateisthemostinsolubleand iscloselyfollowedbymagnesium

phosphate.



Table1.SolubilityofSelectedPhosphateSalts





Table2.SolubilityofCalcium‐PhosphateMinerals:FromOctacalciumPhosphate(Chow,2001)

Compound Abbreviation Formula‐log

(Ksp)@25

C

Monocalciumphosphatemonohydrate MCPM Ca(H

PO4)

0

Highlysoluble

Monocalciumphosphateanhydrous MCPA Ca(H

PO4)



Highlysoluble

Dicalciumphosphateanhydrous DCPA CaHPO4

6.9

Dicalciumphosphatedihydrate DCPD CaHPO4

2H

0

6.6

Calcitewithco‐precipitatedP CCP CaCO



8.47

alpha‐Tricalciumphosphate

α‐TCP

(PO4)



25.5

beta‐Tricalciumphosphate

βTCP

(PO4)



28.9

TetraCalciumphosphate TTCP Ca

(PO4)

O

38

OctacalciumPhosphate OCP Ca

H

(PO4)

5H

0

46.9

Hydroxyapatite HAP Ca

OH(PO4)



58.3

Fluorapatite FAP Ca

F(PO4)



60.5



 TheCa‐Pfamilyofcompoundsmaytakeonseveraldifferentchemicalforms(Table2).

Solubilityproductconstantsareexperimentallydetermined,andthereissomedisagreementinscientific

researchandpublicationoverthereportedKspvaluesforsomeoftheCa‐Pcompounds.Perhapsthe

mostimportantcausefor

inconsistentreportingisthemetastabilityofsomeCa‐Psaltsinrelationto

othermorestableforms(Morenoetal,1966).(Metastablesaltsformanapparentequilibriumin

solution,butchangequicklytoamorestableformwithonlyaslightchangeofconditions.Thisfurther

complicatestheunderstandingof

thespecificchemicalmechanismsofCa‐Pprecipitation.)Thereis,

however,agenerallyacceptedorderofrelativesolubility.

MCP >> DCP > TTCP > α-TCP > β-TCP >> OCP>HAP

RoleofMagnesium

 Hydroxyapatite(HAP)canaccountforupto80%ofphosphateprecipitation,buttheformation

ofHAPcanbeinhibitedbythepresenceofmagnesiumions(Cragg,2005).InhibitionofHAPformation

resultsintheformationofotherCa‐Pprecipitates,mainlyOCPandTCP(Diaz,1994).Mg‐

Pprecipitates

canalsobeproduced.Magnesiumformssimilarchemicalcompositionsascalciumwiththephosphate

CompoundFormula ‐log(Ksp)@25

C

AluminiumphosphateAlPO

 20

CalciumphosphateCa

(PO

)

 27

Iron(III)phosphatedihydrate

FePO

O

15

MagnesiumphosphateMg

(PO

)

 24

SodiumPhosphateNa



Highlysoluble



13



ion:magnesiumphosphatemonobasic(Mg(H

)

),dibasic(MgHPO

),andtribasic(Mg

(PO

)

).The

solubilityofmagnesiumsaltsisgenerallyonlyslightly higherthanthatofcalciumsalts.Allthese

compoundshavelowsolubilityproducts.

 DiazfoundtheCa‐Pequilibriumofstreamwaterwithvarioushardnesslevelscouldbe

controlledbyOCP,β‐TCP,HAP,orpossiblyaCa‐Mg‐Fe‐

Pcomplex.WhichCa‐Pmineralcontro lledthe

equilibriumdependedonpHandCa‐Mgconcentrations.Itwassuggestedhighermagnesium

concentrationsinharderwatermayberesponsiblefortheformationoftheselesssolubleCa‐Pforms

wheneverdolomite(notcalcite)isthethermodynamicallydominantphaseofcarbonate.Ithas

been

reportedthataMg

/Ca

ratiogreaterthan0.6indicatesthatdolomiteisthethermodynamicallystable

phase,andcalcitethedominantphaseofwaterswhereratiosarelessthan0.6(Hsu,1963).

LiteratureSummary



1. Phosphorusiscommonlythelimitingfactorforalgaegrowth.

2. CaandMgplayakeyroleincontrollinginstream

phosphoruschemistrybyformingnumerous

phosphateprecipitates.

3. Whenphosphorousisinsolidform,itisunavailableforalgaetouse.

4. Dolomiticstreamsarehigherinmagnesiumcontent,andinsolubleMg‐Pprecipitatescanformin

thesewaters.

5. Ca‐Mg‐Pchemistryisverycomplex,andprecipitateformation

isdependentonstream‐specific

chemistry.



ApplicationinWestVirginia



 MoststreamsinWestVirginiacaneasilybeclassifiedasbeingdominatedbyeitherthecalciteor

dolomitebydeterminingtheMg

/Ca

ratioduringlowflowsummerconditions.Dolomitic streams

includetheTugFork,Coal,Guyandotte,andMudrivers.SteamsnearequilibriumincludethelowerElk,

Birch,upperKanawha,lowerGauley,Shenandoah,andNewrivers.Stronglycalcitestreamsincludethe

Greenbrier,upperGauley,upperElk,LittleKanawha,Hughes,WestFork,Tygart,Cheat,

Monongahela,

SouthBranchPotomac,andCacaponrivers.Theselistsshowthatstreamsfromthesouthern coalfields

regionofthestatearedolomiticstreams.Magnesiumisexpectedtoplayadominantroleinthe

phosphoruschemistryinthesestreams.



 TheCa‐MgIndexproposed byKawagawasbasedondatafor

sestonicalgaeinlakes,butitalso

yieldsinterestingresultswhenappliedtoWestVirginiarivers.Theirindexisproposedasthe



log[Ca

/Mg

]‐0.5log[Ca

+2

+Mg

],



whereCaandMgareexpressedinmolarconcentrations,notmg/l.



Table3rankstheCa‐MgIndexforseveralWVrivers;thoseriverswithalkalinitybelowthe

thresholdvalueforalgaedevelopment(average30mg/l)arenotshowninthetable.Thetableshows

anexcellentcorrelation

betweentheCa‐MgIndexandthelevelofalgaedevelopment.Itmustbenoted

thattheonlyfactorremovedfromconsiderationhereislowalkalinity;otherfactors,suchasnutrient

contentandturbidity,alsoimpactalgaedevelopmentandlargelyexplainvariationsinthelevelofalgae

developmentinTable3

.



14



Table3.Ca‐MgIndexforWestVirginiaRivers

River Ca‐Mg

Index

Algae

Development

GreenbrierRiver 2.15 Severe

TygartValleyRiver 2.10 High

SouthBranchPotomacRiver 2.08 Low‐Moderate

NorthForkHughesRiver 2.05 Low

SouthFork/SouthBranchPotomacRiver 2.01 Moderate

CacaponRiver 1.92 High

BluestoneRiver 1.81 Moderate‐High

WestForkRiver 1.80 None

MonongahelaRiver 1.77 None

NewRiver 1.74 Moderate

NorthBranchPotomacRiver 1.71 None

KanawhaRiver 1.68 None

GuyandotteRiver 1.65 None

ShenandoahRiver 1.54 None

TugFork 1.50 None

BirchRiver 1.50 None

CoalRiver 1.25 None



Table4.ModifiedCa‐MgIndexforWestVirginiaRivers

River Modified

Ca‐MgIndex

Avg.Hardness

(mg/l)

Algae

Development

GreenbrierRiver 3.26 65 Severe

NorthForkHughesRiver 3.24 63 Low



TygartValleyRiver 3.18 70 High

NewRiver 3.1 79 Moderate



KanawhaRiver 3.08 85 None

T



CacaponRiver 3.10 96 High

SouthFork/SouthBranchPotomacRiver 2.95 112 Moderate

BluestoneRiver 2.94 121 Moderate‐High

SouthBranchPotomacRiver 2.88 130 Low‐Moderate

GuyandotteRiver 2.86 145 None

WestForkRiver 2.85 190 None

MonongahelaRiver 2.84 149 None

TugFork 2.79 178 None

NorthBranchPotomacRiver 2.78 214 None

ShenandoahRiver 2.76 174 None

BirchRiver 2.74 221 None

CoalRiver 2.51 284 None

MudRiver 2.49 373 None

T=Algaelevelreducedbyturbidity.D=Algaelevelprobablyreducedbydepthofpools inriver.



15



ForthesampleresultsfromWAB‐BaseusedtocalculatetheCa‐MgIndex,thefirsthalfofthe

equation(log[Ca

/Mg

])accountedforanaverageof10.2%ofthetotalIndexscore.Thelargest

percentageimpactwasonstreamswiththelowestoverallCa‐Mgconcentrations,i.e.theGreenbrier

andTygartwhereitaccountedfor15‐20%oftheIndexscore.AModifiedIndex,‐log[Ca

+2

+Mg

],was

calculatedandshowninTable4.Theresultsshowasimilarrankingoftherivers,andagood(perhaps

evenbetter)correlationbetweenthemodifiedindexandtheamountoffilamentousalgae

development.



ThisModifiedIndexisasimplefunctionoftheCa

andMg

molarconcentrations;sois

hardness.ItseemshardnesscouldindeedbeusedasabasicindicatorofaWestVirginiastream’s

propensitytogrowfilamentousalgae.Ahardnessleveloflessthan100mg/lappearsidealforalgae

development.Suppressionofalgalgrowthseemstooccuraround120‐150mg/l.

Andverylittle

filamentousalgalgrowthisseenwhenthehardnesslevelisabove150mg/l(exceptinAMDimpacted

streamswherethelowpHdrivesP‐availabilitymorethanCaandMgdo).Inter estingly,thisisasimilar

rangetothehardnessscaleusedforpredictingsoapperformance,mineral

deposits,andmetalstoxicity.



Table5.HardnessScale(Weiner,pp77)







Hardnesswasoriginallyusedasameasureoftheabilityofwatertoprecipitatesoapand

interferewithlathering.Theinterferenceoccursasaresultofcalciumionreplacingsodiumionsinthe

soapmolecules;the

sodiumcarboxylates(likesodiumphosphates)areverysoluble,butthecalcium

carboxylates(likecalciumandmagnesiumphosphates)arerelativelyinsolublewhentheyform.This

interfereswiththesurfacetensioncreatedbythesoap,reducingthelather.Itisnoteworthythatthe

negativelogofKspvaluesforthecalciumcarboxylates used

insoaprangefrom7‐19(Bulatovic2007);

thisisasimilar,butslightlylower,rangetotheKspvaluesoftheexpectedandobservedCa/Mg‐P

precipitateswhichoccurinhardwater–indicatingthattheCa/Mg‐Pprecipitateswouldbegintoform

atsomewhatlowerconcentrations.Thisis

exactlywhatobservationsofalgaedevelopmentindicate.



Thisconceptalsolinesupwell withDiazetal,whofoundthatphosphorussolubilityatcalcium

concentrationslessthan50mg/l(equatingto125mg/lhardness)wasnotaffectedbypHintherangeof

pH6‐9.Butwheretherewas

highcalciumlevels(>100mg/l)appreciableamountsofphosphate

precipitatedasthepHwas raisedfrom6to9.Diaz pointsoutthatotherresearchershavefoundthatP

precipitationisminimal atCaconcentrations<50mg/landwaterpH<8.0(Fergusonetal1970,1973;

Jenkinsetal,1971;Otsuki

andWetzel,1972;andFeenstraanddeBryun,1979).Fergusonetalreported

DegreesofHardness mgCaCO3/L Effects



Soft   <75  Noscaledesposits

Efficientuseofsoap

Increasedissolutionofmetals.toxicity



ModeratelyHard 75‐120 Above100mg/l,significantscaledepositsmayform

Requiresmoresoapforcleaning

Notobjectionableformostpurposes



Hard   120‐200 Scalebuildupandstaining

occurs

Needssoftenedat~180mg/l



VeryHard  >200  Requiressofteningforhouseholdand 

 commercialuse



16



thataCaconcentrationof80mg/landawaterpH>8,wereneededtoprecipitate80%ofthePin

municipalwastewater(19 70,1973).AndStrangandWareham(2006)reportedsignificantP‐removal

throughHAPprecipitationinasewagestabilizationpondwithahardnessof190mg/land

Caof60mg/l.



Basedontheobservations,evidence,andresearchitseemsthatasoundexplanationforthe

lackofalgaeinthemanyWestVirginiastreamswithnaturallyhardwateristheprecipitationofcalcium

and/ormagnesiumphosphates,whichmakesthephosphateunavailableinthewatercolumnfor

uptake

byfilamentousalgae.Thisisespeciallytrueofthedolomiticstreamsinthesoutherncoalfields.



OtherFactors



Turbidity/Substrate



 Lowergradientstreamswithsedimentladensubstrateconsistentlyhavehigherlevelsof

turbidity,evenduringperiodsoflowflow,duetorecurringsuspensionoffinesediments(Royer,2008).

Suchstreams

donotsupportalgaegrowthsincelightpenetrationisdrastically reducedbytheturbidity.

Cladophora,whichisthedominanttypeoffilamentousalgaeintheproblematicareasinWestVirginia,

generallybeginsitsgrowth attachedtoarockysubstrateorotherhardsurface(Harris,2005).Partsof

theNorthFork

ofHughesRiver,LittleKanawhaRiver,KanawhaRiver,BrushCreek,DunkardCreek,and

otherswouldfallintothiscategoryofstreamswithaturbidwatercolumnandsiltysubstrate.



 SecchitubereadingsfromtheHughesRivershowvariationofthewaterclarityatdifferent

pointsalongthestream.Clarityvaried

withbottomconditionsintheriver,andshowednolongitudinal

pattern.Onethingwasclear,though–filamentousalgaegrewintheleastturbidareasoftheriver.



Table6.RoleofTurbidityinAlgaeDevelopmentWestVirginiaRivers

River Location SecchiTubeDepth AlgaeDevelopment

NorthForkofHughes NorthBend 114 High

NorthForkofHughes Cairo 84 Low

NorthForkofHughes BelowCairo 76 None

NorthForkofHughes NearMouth 104 Low

SouthForkHughes Smithville 103 None

LittleKanawha GilmerStation 114 None

LittleKanawha BelowGlenville 96 None

Kanawha Charleston 108(verygoodday) None

Elk Gassaway&MinkShoals >120 None

SouthBranchPotomac OldFields >120 Low‐moderate

TygartValleyRiver AboveNorton >120 High

Greenbrier Ronceverte >>120 High



Temperature



 ThetemperaturerangeforCladophoragrowthisbetween15‐25

C(Harris,2005).Nosignificant

amountsoffilamentousalgaewerefoundgrowinginanycoldwaterstreams(maximumtemperatureof

C)inWestVirginia,althoughanotherspeciesoffilamentousalgaewasgrowingintheDavisSpring(at

FortSpring)andTroutRun(nearFranklin).Itwasnotedthatastheaveragetemperatureofthe

GreenbrierRiveratAldersonslippedbelow20

Cthisfall,algaebegandying,andthediurnalpHandDO

swingslessened–evenastheflowintherivercontinuedtodecrease.SeegraphsinAttachment2.



17



Table7.AverageSummerTemperatureforSelectedStreams



Temperatureand/orshadearesuspectedtobethekeysuppressionfactorsinPineyCreek,anda

secondaryfactorinupperIndianCreekofNewRiverandSecondCreekofGreenbrierRiver.(Hardness

wasstilltheprimaryfactorinIndianand

Secondscreeks.)



Non‐filamentousAlgae



 Otherformsofalgaemaythriveinthenutrientrichwatersofstreamswhichhavesuppressed

filamentousalgaedevelopment.TuscaroraCreek,forexample,isatributaryofOpequonCreekand

receivesflowfromtheMartinsburgSTP.TheaveragehardnessofTuscaroraCreekisover300

mg/l.

Withnofilamentousalgaedevelopment inthisstream,itisexpectedthatthephosphateisprecipi tating

outofthewaterontothebottom.Excessiveperiphytondevelopmentnotedontherockysubstrateof

TuscaroraCreek(seePhoto5B)seemstosupportofthisconclusion.Similarcolonieswerenotedinthe

mainstemofOpequonCreekandlessvigorousdevelopmentwasobservedintheCoalRiver.The

interfaceoftherock,phosphatesalts,andwaterwouldprovidethemostlikelysiteforphosphorus

release/exchangeduringequilibriumshifts.Theperiphytondevelopmenthasnotresultedinpublic

outcry,andwasnotpartofthescope

ofthisinvestigationoffilamentousalgaedevelopment.No

judgmentisbeingmadeinthisreportastowhethertheperiphytoncoloniesconstituteorcontributeto

anywaterqualityproblem.

MeasuringFilamentousAlgae



 Schaller(2004)andMorgan(2006)employedsimilarmethodsformeasuringfilamentousalgae

instreamsduringtheirresearch.

Atagivenstreamtransect,atapeisstretchedacrossthestream;

wettedwidthandportionsofthestreamcoveredbyalgaearerecorded.Atonelocationalongthe

transectwherethebottomiscompletelycovered,allalgaeandplantmaterialiscollectedina314cm



area.Thematerialcollectedisrinsed,dried,and weighedinalaboratory,andthenexpressedasmass

perunitarea.Theseresearchersusedthatvaluetoestimatemeanbiomassforthestreamreach.



 ThismethodwasusedasabasisforalgaemeasurementinWestVirginiainthefall2008.



MeasurementsweremadeonseverallocationsontheGreenbrierRiver,theNorthForkofHughesRiver,

andatonelocationontheSouthBranchofPotomacRiver.Themeasurementsweredoneasatrialto

determinethefeasibility ofthemethod;nolabworkwasdonedetermineadryweight.

Anadditional

measurementwasmadeofthealgaedepthacrossthetransect,sothatamountofwatercolumnimpact,

notjuststreambottom,couldbecalculated.ResultsaresummarizedinTa ble8andshowngraphically

inAttachment1.



Stream AverageTemperature(

C)

(May–October)

MaximumTemperature(

C)

PineyCreek(mp0) 18.6 21.2

IndianCreek(mp26.2) 18.6 20.1

SecondCreek(mp0) 18.5 23.3

KnappsCreek(mp0) 18.3 21.6

OpequonCreek(mp0) 18.0 21.9

DavisSpring 13.4 14.3

GreenbrierRiver 21.4 26.7



18



Table8.AlgaeaccumulationatSelectedSites.

RiverandLocation BottomCover(%) WaterColumnFill(%)

SouthBranch@OldFields 53 3.7 

NorthForkHughesatNorthBend 54 60

NorthForkHughesatCairo 23 4

Greenbrier‐Hillsboro1 40 18

Greenbrier‐Hillsboro2 53 28

Greenbrier‐Caldwell 53 32

Greenbrier–CoffmanHillRd. 80 27

Greenbrier‐nearRt62bridge1 41 16

Greenbrier‐nearRt62bridge2 85 7

Greenbrier‐Ronceverte 74 50

Greenbrier‐USAlderson 64 23

Greenbrier‐1milebelowAlderson 39 10

Greenbrier‐Lowell 46 9



WVDEPwillcontinueworkinthesummerof2009todevelopameasurementindexwhichmight

beusefultodefineanacceptablelevelofalgaldevelopmentthatstillmaintainsunhindered recreational

usesofthestream,includingfishing,swimming,andaestheticenjoyment.



SummaryofConclusions



1. Dissolvedphosphorusdischargedfrom

sewagetreatmentfacilitiesalongtheGreenbrierRiveris

abletocombinewithnitratesintheriverfromavarietyofsourcesandcauseobjectionable

algaeblooms.

2. Similar,butlesssevere,bloomsarealsooccurringontheBluestone,New,Cacapon,Tygart

Valley,SouthForkoftheSouthBranchofthePotomac,

andNorthForkofHughesRiver.

3. Lackofalkalinitykeepsthealgaebloomsfromoccurringonseveralrivers:Elk,Cherry,Little

Kanawha,andupperGreenbrier.Aminimumalkalinityof30‐40mg/lisneededforfilamentous

algaebloomstooccur.

4. Hardness,intheformofcalciumandmagnesium,

preventsalgaebloomsfromoccurringon

severalotherrivers:WestFork,Tug,Shenandoah,Guyandotte,Mud,andCoalRivers.The

mechanismforsuppressingthealgaeistheprecipitationofCa‐PandMg‐Psaltswhichmakes

thephosphorusunavailableforuptakebythefilamentousalgae.

5. Hardnesslevelsexceeding150mg/l

appeartoinhibitalgaegrowth.Somesuppressionof

growthmaybeginoccurringwhenhardnessexceeds100mg/l.TheSouthBranchofPotomac

Riverappearstohavesuppressedfilamentousalgaedevelopment.

6. Hardwaterriverswithelevatedphosphorustendtohaveenhanced periphytondevelopmenton

thesubstrate,probablyduetoits

abilitytoutilizeprecipitatedphosphorusatthesubstrate

interface.

7. Algaebloomsonsomerivers,includingtheKanawhaRiver,areinhibitedbyturbidity.

8. EnhancedphosphorusremovalatsewagetreatmentfacilitiesalongtheGreenbrierRivershould

substantiallyreducethealgaebloomoccurringinthatriver.



19



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

21



Attachment1





Milepoint



60 58 56 54 52 50 48 46 44 42 40 38 36 34 32 30 28 26 24 22 20 17 15 13 12 10 8 6 4 2 0

PercentImpacted

AlgaeImpactonGreenbrierRiver

BottomCover

WaterColumnFill

Phosphorusug/l

CaldwellRonceverteAldersonTalcott



22



Attachment2



2008Data



2008Data



23



2008Data



2008Data



24



Attachment3



DryConditionsSnapshot

TotalPhosphorusLoading(lbs/day)



tormEvent

PhosphorusConcentrations(mg/l)

duringa2”rainfallevent



25



Attachment4



GreenbrierRiveratAlderson

Deviationfromtheaveragesummerflow,JunethroughOctober,1896‐2007

(Theaveragesummerflowwas807cfs)



26



SDG

‐800

‐400

400

800

1200

1600

1896 1906 1916 1926 1936 1946 1956 1966 1976 1986 1996 2006

Deviationfromaverge(cfs)