Effect of temperature and illumination on pyrite oxidation between pH 2 and 6.docVIP

Effectoftemperatureandilluminationonpyriteoxidationbetween pH2and6 MartinSchoonen,aAliciaElsetinow,bMichaelBordaaandDanielStronginb aDepartmentofGeosciences,SUNY-StonyBrook,StonyBrookNY11794-2100,USA. E-mail:mschoonen@ Article bDepartmentofChemistry,TempleUniversity,PhiladelphiaPA19122,USA Received19thMay2000,Accepted13thJune2000 PublishedontheWeb4thJuly2000 Theeffectofheatandilluminationwithvisiblelightontheoxidationofpyritewithdissolvedmolecularoxygen insolutionsbetweenpH2and6hasbeeninvestigatedusingacombinationofsurfacescienceexperimentsand batchoxidationexperiments.Therateoftheoxidationofpyriteisstronglydependentontemperature.Itis, however,notpossibletocastthetemperaturedependenceinasimpleArrheniusequationbecausethe magnitudeoftheactivationenergydependsontheprogressvariablechosen.Activationenergiesbasedon protonreleaserate,sulfatereleaserate,andtotalironreleaseratevarybyasmuchas40kJmol±1 ,suggesting thattheoxidationmechanismofthesulfurandironcomponentofpyritearelargelyindependentofeachother. Thisdifferenceinmechanismcanalsoexplainwhythereactionratesonthebasisofthesethreedifferent progressvariablesdonotshowthesamepHdependence.Exposedtovisiblelight,therateofpyriteoxidation isundermostconditionsacceleratedbylessthanafactoroftwo.Someofthisaccelerationmaybeaccounted forbyalight-inducedheatingofthepyritesurface.Surfacescienceexperimentsemployingphotoelectron spectroscopyshownoevidenceforsigni?cantchangesinthechemicalcompositionofthesurfaceasafunction ofexposuretovisiblelight.Thebatchsorptionexperimentsshow,however,thatthereactionstoichiometry changessomewhat,whichindicatesthattheremightbeachangeinreactionmechanismasaresultofexposure tovisiblelight. Introduction pyrite surface and induce the formation of etch pits, which increase the reactive surface area.5 Because the microbial catalysis of the process is thought to be largely due to the catalysis of reaction -3) and not through a direct enzymatic reaction, it is important to understand the abiotic oxidation process