地下水中環丁砜和胺的混合行為：對污染物遷移的影響.pdf

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1、Sulfolane and Amine Mixing Behaviour in Groundwater:Implications for Pollutant TransportProfessor Erica PensiniWhat is sulfolane?Sulfolane is used to sweeten sour gas and as a phase splitter in carbon capture and storage Sulfolane hampers fertility studies are ongoing to assess toxicity Sulfolane pl

2、umes exist across the globe Sulfolane biodegrades only under aerobic conditions,and it is reported to be highly mobile due to its solubility in water,butis this always the case?Sulfolane Miscibility in Water The miscibility of sulfolane in water is due to hydrogen(H)bonding between the oxygen of the

3、-S=O groups and the hydrogens of waterHHHOSulfolane Miscibility in Water The miscibility of sulfolane in water is affected by groundwater chemistry:IONS:naturally present or due to industrial activities,e.g.,sulfate ions released from leaching of S piles Bacterial activity:amino acid and proteins,mo

4、re abundant if contaminant-degrading bacteria proliferate Co-contaminants,such as amines and hydrocarbonsSulfolane Miscibility in Water:Effect of Ions Sulfate ions in groundwater directly compete with sulfolane for H bonding with water,decreasing its miscibility Chloride salts have a less marked eff

5、ect NaOH also decreases sulfolane miscibility in waterHHHONa+Na+vv2-Bartokova,B.,Marangoni,A.G.,Laredo,T.and Pensini,E.,2023.Phase behavior of sulfolane:Potential implications for transport in groundwater.Colloids and Surfaces A,677,p.132451.Sulfolane Miscibility in WaterMOLE PERCENTWEIGHT PERCENT*B

6、ased on bulk separation and optical microscopySulfolane Miscibility in Water Depending on the concentration of sulfolane and sulfate salts,we observe bulk separation,emulsificationinto micron-sized droplets or molecular clustersSULFOLANEWATERNa2SO4+WATERSULFOLANE FLOATS ON THE WATER RICH PHASE,ALTHO

7、UGH IT IS HEAVIER THAN PURE WATERThe Water Rich Phase is Viscous and DenseSulfolane Miscibility in WaterPensini,E.,Marangoni,A.G.,Bartokova,B.,Fameau,A.L.,Corradini,M.G.,Stobbs,J.A.,Arthur,Z.and Prvost,S.,2024.Sulfolane clustering in aqueous saline solutions.Physics of Fluids,36(3).Separated Sulfola

8、ne Droplets are Negatively ChargedZeta potential()of sulfolane droplets in water,emulsified with 0.06 M Na2SO4Effect of Miscibility on Sulfolane Sorption and Migration Sulfate salts delay sulfolane migration in model clay fractures and decrease overall mass recovery at the outlet by promoting sorpti

9、onBartokova,B.,Marangoni,A.G.and Pensini,E.,2024.Effect of sulfolane demixing and sorption on its migration through model fractured and porous media.Water,Air,&Soil Pollution,235(2),p.97.Clay sorbed onto sulfolane emulsified by Na2O4 Sulfates(e.g.,Na2SO4)also promote sulfolane sorption onto limeston

10、e Sulfolane sorption onto minerals is limited in pure water25 m100 m100 mLimestone sorbed onto sulfolane emulsified by Na2O4Effect of Miscibility on Sulfolane Sorption and MigrationEffect of Ions on Sulfolane Partitioning between Oil and Water Implications on Migration Sulfate and chloride salts pro

11、mote sulfolane partitioning into immiscible co-contaminants(e.g.hydrocarbons)Sulfolane can be found above the water table Sulfolane vertical migration in sandy aquifers is delayedHydrocarbonWATERBartokova,B.,Marangoni,A.G.,Laredo,T.and Pensini,E.,2023.Phase behavior of sulfolane:Potential implicatio

12、ns for transport in groundwater.Colloids and Surfaces A,677,p.132451.Without Salts Sulfolane Emulsifies Toluene in Water,Likely Promoting MigrationBartokova,B.,Marangoni,A.G.and Pensini,E.,2024.Effect of sulfolane demixing and sorption on its migration through model fractured and porous media.Water,

13、Air,&Soil Pollution,235(2),p.97.Sulfolane Sorption onto Minerals Effect of Amino Acids(Due to Hydrocarbon-Degrading Bacteria)Amino acids(present due to bacterial activity)foster sulfolane sorption onto iron oxidesIMPLICATIONS ON TOXICITY?Based on IR data,we propose HNSO interactions*Erica Pensini,Ca

14、itlyn Hsiung,and Nour Kashlan.Arginine Linker Enhances Sulfolane Sorption onto Iron Oxide.Colloids Surfaces C(2024),submitted.Sulfolane Partitioning Effect of Bacterial ActivityDo amino acids,proteins and bacterial biosurfactants generated during bacterial activity affect sulfolane miscibility in wa

15、ter?Source:Marshall,T.,Paschos,A.,Marangoni,A.G.,Yang,F.and Pensini,E.,2021.Injectable cationic traps and sticky bacterial emulsifiers:A safe alliance during diesel bioremediation.Colloids and Surfaces A,613,p.126051.We are testing sulfolane solubility in water in the presence of active diesel-degra

16、ding cultures,which produce biosurfactants,amino acids etc.Rhamnolipids(bacterial biosurfactants)demix tetrahydrofuran from waterSource:Patel,V.,Marangoni,A.G.,Ghazani,S.M.,Laredo,T.,Stobbs,J.and Pensini,E.,2023.Effect of bacterial surfactants on the phase behavior of miscible pollutants in water.Co

17、lloids and Surfaces C,1,p.100013.Diesel emulsified by bacterial biosurfactantsORHow do Surfactants Induce Separation?How do Surfactants Induce Separation?WATER IS EJECTEDSOLVENT IS EJECTEDDROPLET COALESCENCE IS RELATED TO SURFACTANT SELF ASSEMBLYDynamic process:when one solvent goes in the other,the

18、 process resumesSURFACTANT HEAD PRIMARILY INTERACTS WITH WATERHow do Surfactants Induce Separation?How do Surfactants Induce Separation?HEADS INTERACT STRONGLY WITH SOLVENTWATER SEPARATIONH2OBartokova,B.,Marangoni,A.G.and Pensini,E.,2024.Role of heads and tails on tetrahydrofuran-and dimethyl sulfox

19、ide-water separation by glycerol and sucrose esters.Physics of Fluids,36(7).How do Surfactants Induce Separation?How do Surfactants Induce Separation?Can We Harness Surfactants for Sulfolane Can We Harness Surfactants for Sulfolane Remediation?Remediation?AIR SPARGING+SURFACTANTSURFACTANT-SULFOLANE

20、COMPLEXSELECTIVE WATER EVAPORATIONENHANCED WATER EVAPORATION FROM AIR-LIQUID INTERFACESULFOLANE ACCUMULATION ON AIR BUBBLES*Ongoing research Caitlyn HsiungRemoval of Sulfolane by CyclodextrinRemoval of Sulfolane by Cyclodextrin Inside of the basket is hydrophobic,outside is hydrophilic We can pick t

21、he right basket size to fit in sulfolaneRemoval of Sulfolane by CyclodextrinRemoval of Sulfolane by Cyclodextrin80 mg sulfolane removed/g cyclodextrinalfa cyclodextrin in wateralfa cyclodextrin in sulfolane-waterCan We Harness Surfactants for Sulfolane Can We Harness Surfactants for Sulfolane Remedi

22、ation?Remediation?Amines are Found Alongside Sulfolane Alkanolamines and diisopropylamine(DIPA)are used alongside sulfolane for carbon capture and storage,and to sweeten sour gas They are also found in cosmetic formulations and household products(without sulfolane)In the absence of adequate wastewat

23、er treatment,we can expect them to migrate in groundwaterDIPA Sorbs onto Minerals Even Without Salts,but Only Without SulfolaneDIPA(g DIPA/g sorbent)Sulfolane(g sulfolane/g sorbent)Clay0.230.040.050.01Limestone0.220.03NegligibleIron oxide0.180.02NegligibleGypsum0.210.02Negligible(Study with other am

24、ines will follow)SALTS LIKELY CHANGE THIS SCENARIOSulfolane Solubilizes DIPA in Water,Without Salts*Erica Pensini,Alejandro G.Marangoni,Sylvain Prevost.Sulfolane facilitates diisopropylamine dissolution in water,potentially enhancing pollutant transport.Journal of Molecular Liquids(2024),under revie

25、w.Study with sulfolane and other amines is ongoingSALTS LIKELY CHANGE THIS SCENARIOProperties of Amine Mixtures with Water Alkanolamines are soluble in pure water,DIPA yields dispersions(nano-sized droplets)Salts further decreases DIPA miscibility in waterDIPA wt%Saltwt%salt102030405060708090NaCl11L

26、1L1L1L2L2L2L2L2L+SNaCl21L1L2L2L2L2L2L2L2L+SNa2SO411L1L2L2L2L2L1L+S1L+S1L+SNa2SO421L2L2L2L2L2L+S1L+S1L+S1L+SSalts Decrease the Solubility of DIPA in Water Sulfate and chloride salts decrease the miscibility of DIPA in water 1wt%DIPA in waterTaurine Decreases the Solubility of Amines in Water The effe

27、ct is most marked with DIPA,but it is also seen with alkanolaminesIMPLICATIONS ON TOXICITY?Erica Pensini,Caitlyn Hsiung,and Nour Kashlan.Potential Toxic Effects Linked to Taurine Interactions with Alkanolaminesand Diisopropylamine.DiscoverWater(2024),accepted.Interactions between Carboxylic Acids an

28、d Amines:Gelation by Fatty AcidsPensini,E.,Gregori,S.,Marangoni,A.G.,Ghazani,S.M.,Su,Z.,Chen,A.,&Kashlan,N.(2024).Ethanolamine piezoelectric hydrogels structured by oleic acid lamellae.Journal of Molecular Liquids,397,124185.Erica Pensini,Peter Meszaros,Nour Kashlan,Alejandro G.Marangoni,Stefano Gre

29、gori,Saeed Mirzaee Ghazani,Joshua van der Zalm,Aicheng Chen.Ferroelectric soft materials formed with alkanolamines and unsaturated fatty acids.Journal of Molecular Liquids(2024),revision requested.Properties of Amine Mixtures with Water-Potential for Electrokinetic Treatment Solutions and mixtures o

30、f DIPA and alkanolamines are electrically conductive,rendering electrokinetic separation a viable approachInteractions between Carboxylic Acids and AminesCitric acid ejects DIPA from water*Ongoing research Nour KashlanIn a Nutshell:Water Chemistry and Co-Contaminants are Key to Miscibility,Sorption

31、and Migration!Salts demixsulfolane from water,promote its sorption onto minerals and hamper its migration Amino acids promote sulfolane sorption onto iron oxides Salts oppose hydrocarbon solubilization by sulfolane Salts demixDIPA from water,while sulfolane enhances its solubility in pure water Solu

32、bility with salts and alkanolamines has yet to be studied The amino acid taurine decreases DIPA miscibility Carboxylic acids affect the miscibility of DIPA in water and fatty acids gel alkanolamines in waterTHANK YOU!34BibianaBartokovaKey Collaborator:Alejandro MarangoniGrad Students wanted!Adam Leo

33、ntowich,Jarvis Stobbs,Amanda Quirk,Scott Rosenthal,Zach ArthurSylvain PrevostPENSINI LABUniversity of GuelphNour Kashlan and Caitlyn HsiungPeter MeszarosSaeed GhazaniGEOSYNTEC CONSULTANTS|1Development and Demonstration of Site-Specific Sulfolane Management and Remediation StrategiesSarah Walker,PhD.

34、PG.Srinivasa Varadhan,PhD.PE.PEngGEOSYNTEC CONSULTANTS|2AgendaSulfolane OverviewDemonstrated Case StudiesKey Takeaways2GEOSYNTEC CONSULTANTS|3SULFOLANE OVERVIEWGEOSYNTEC CONSULTANTS|4Sulfolane OverviewGeosyntec-North CarolinaGeosyntec-OntarioMinimalPrimarily aerobic biodegradationPrimarily into shoo

35、ts/leavesSURFACE WATER(CH2)4SO2GEOSYNTEC CONSULTANTS|5State of Science Sulfolane RemediationTechnologyMechanismFull-scalePilotLaboratoryGAC SorptionPhysicalCalifornia(gw)-Ex-situ Aerobic BioremediationBiologicalCalifornia(gw)Alberta(gw/soil)Alaska(gw),Taiwan(gw)In-situ Aerobic BioremediationBiologic

36、alCalifornia(gw)-Anaerobic BioremediationBiological-Australia(gw),Canada(gw)Soil Washing/Advanced Oxidation Processes(AOP)Physicochemical-Canada?(soil/gw)In-situ Chemical OxidationPhysicochemical-Taiwan(gw)Alberta(gw),Taiwan(gw)PhytoremediationBiological-Source unknown(gw)Case Study 1&4 Case Study 3

37、 Case Study 4 GEOSYNTEC CONSULTANTS|6DEMONSTRATED CASE STUDIESGEOSYNTEC CONSULTANTS|7Fixed Bed BioreactorUses granular activated carbon(GAC)as a medium for fixed biofilm growthEffective for large sulfolane loading May require management of biomass through backwashing and for GAC hydraulicsGAC serves

38、 dual purpose by sorbing some sulfolane and potentially increasing treatment capacityGEOSYNTEC CONSULTANTS|8Moving Bed Bioreactor(MBBR)Conventional wastewater MBBR technology for groundwater Mixed constituent setting:Fumigants,ammonia,high TDSSulfolane removal 1,000(parts per billion)ppb to less tha

39、n the detection limit(3.3 ppb)Geosyntec-CaliforniaGEOSYNTEC CONSULTANTS|9Moving Bed BioreactorLaboratory and field pilotingParameter optimization Microbial inoculum Nutrient requirements Water quality modification Sensitivity testing Effect of mixed constituentPre/Post-Treatment needsO&M optimizatio

40、n1101001,00010,00002004006008001000120014001600Sulfolane(g/L)Time(hrs)InfluentLead Reactor EffluentLag Reactor Effluent10%media20%mediaGEOSYNTEC CONSULTANTS|10BiospargingPulsed oxygen sparging 240 bgs Reduce sulfolane flux to supply wellTreatability test showed indigenous sulfolane degrading populat

41、ionProximity to supply wells needs careful assessment of remediation needs/water quality effectsGeosyntec-CaliforniaBiosparge zoneOxygen sparging setupPumping wellGEOSYNTEC CONSULTANTS|11GAC&On-Site RegenerationGAC does not have sorption capacity for sulfolane=excessive GAC consumptionCountercurrent

42、 aeration to promote sulfolane degradation in the bed to restore GAC capacitySuccessfully restored 90%GAC capacity 4 timesCan be applied in a batch setup to reduce waste disposal costs GEOSYNTEC CONSULTANTS|12Other TechnologiesIn situ aerobic bioremediation Cold temperaturesNutrient limitation at hi

43、gh sulfolane concentrationsDegradation 12 ug/L/day 2.9 mg/L/day;retarded in hydrocarbon co-contaminated systemAnaerobic Batch Tests Very slow kinetics(site/water chemistry specific)Thiolane generated as intermediate and inhibitorySoil Washing+Advanced Oxidation Procedure(AOP)or ISCOHigher recovery/l

44、ower flush requirement for permeable soilsUV/peroxide,ozone,alk ozone effective but oxidant demand driven by co-contaminants,scavengersPhytoremediationPrimarily tested in wetlands(cattails);Accumulates in foliage and some metabolism suspectedLeaf/biomass decay may result in partial releasePreferenti

45、al over other similar co-contaminants(DIPA)GEOSYNTEC CONSULTANTS|13KEY TAKEAWAYSGEOSYNTEC CONSULTANTS|14Key TakeawaysSulfolane moves fast but can also disappear fast!Key factors:-Proper understanding of CSM-GW flow=sulfolane migration(no retardation)-Degradation kinetics and technology limitationsGe

46、osyntec-CaliforniaGeosyntec-CaliforniaRecent technology development/path forward:-Biomarkers;new microbial communities for colder temperatures-Innovative adaptation of conventional technologies-Passive/semi-passive technologiesGEOSYNTEC CONSULTANTS|15GEOSYNTEC CONSULTANTS|15Questions?Srinivasa Varadhan,PhD.PE.PETHANKS FOR LISTENING!