European Regulatory Developments, Standardization And .

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European regulatory developments,standardization and geochemical speciationas basis for long-term release evaluationH.A. van der Sloot*, D.S. Kosson**, A.C. Garrabrants** ,O. Hjelmar***, R.N.J. Comans#, A. van Zomeren&*Hans van der Sloot Consultancy, Langedijk, The Netherlands** Vanderbilt University, Nashville, Tennessee, USA*** DHI, Horsholm, Denmark# WUR, Wageningen, The Netherlands& ECN, Petten, The NetherlandsWEACAU-III: Workshop on Environmental Aspects of Coal Ash UsesNCAB May 13, 2013, Volcani Center ARO, Bet Dagan, Israel

Presentation - overview European standardisation Validation of test methods US EPA, CEN/TC292, CEN/TC351 Regulatory developments in EU Chemical Speciation Example of modelling material mixtures Conclusions

Development of Standards and Materials CoveredTestSoil, sediments,compost andsludgepH dependence testISO/TS21268-4Percolation testEPA 1313 *ISO/TS21268-3EPA 1314 *MatrixMonolith testEPA 1315 *Compacted granular testEPA 1315Redox capacityAcid rock drainageReactive surfacesWasteMining wasteConstruction productsPrEN14429PrEN14497EPA 1313PrEN14405EPA 1314PrEN15863EPA 1315NEN7347EPA 1315NEN 7348&PrEN14429PrEN14497EPA 1313PrEN14405EPA 1314PrEN14429#EPA 1315EPA 1315EPA 1313CEN/TC351/TS-3EPA 1314CEN/TC351/TS-2EPA 1315CEN/TC351/TS-2EPA 1315NEN 7348EN15875ISO/CD12782parts 1-5* EPA methods included in SW846&ViennaAgreementWI of CEN/TC292#Not yet adopted in CEN/TC 351 (very relevant for CPR)Same basic testing approach in different fields

Regulatory context EUConstruction Products Directive (EU CPD)Construction Products Regulation (EU CPR - 2013).European Landfill Directive (EU LFD)End of Waste regulation (EU EoW)Waste Catalogue (EU WC)Hazardous Waste Directive (EU HW)REACH RegulationSoil Quality Regulation – Fertilizer useGroundwater DirectiveWith multiple regulations: preferably not multiple testing and multipleimpact judgement approaches for the same material or product

Considerations for End of Waste (EoW) criteria The limit values for End of Waste criteria would have to bequite strict, if all requirements on (waste) materials under thewaste regulation would be eliminated based on EoW testing. Additional requirements will be necessary to make the EoWsystem work for ‘alternative’ materials. Options are: Requirement on retrieval of material after intended useSpecification of accepted uses of the materialMinimum distance to groundwaterMinimum distance to surface waterRestrictions of the height of the applicationRestrictions on the allowed rate of infiltration

Issues with the Hazardous Waste Directive-Classification of waste as hazardous or non-hazardous has far reachingconsequences for any handling or treatment of complex waste materials.-For materials resulting from thermal processes and other mixed materialsresulting from industrial processes, the identification of specific mineralassociations as required by current hazard assessment approaches iscomplicated.-Total content is clearly a very poor tool to assess hazard because it is oftenassumed that all of the substance is present in its most hazardous form.-Ecotox testing, which is assumed to provide a better assessment, has seriousproblems in the interpretation of waste test data. Other ways to assess thehazardous nature of such materials are needed to ensure that possible beneficialuses of “alternative” materials is not prevented by a miss-classification.-Currently, an approach based on LEAF type test methods is proposed to avoidunjustified classification of materials as hazardous based on misinterpretation ofnon-leachable content.

Processes in a Road Base Application - definitionsImpact assessment (regulator)Release scenario or sourceterm descriptionPrecipitationConditions(producer)during intendedO2CO2 useRoad stabilisation material (e.g.alternative construction material) Intended useRoad shoulder, soilTransportmechanisms:Surface run-offChemicalmechanisms:Intended usePercolationSolubility controlAdsorptionDEPhysical factors:Groundwater flowDispersionChemical factors:pHSoluble saltsPermeabilityParticle sizeBuffer capacityPorosityChemical form (speciation) RedoxOrganic matterNL

Steps in chemical speciation modelling1. pH dependence leaching test on granular material or size reduced monolithicmaterial for chemical speciation purposes2. Measurement of release from granular materials using a percolation test orrelease from monolithic specimen using a tank (mass transfer rate) test3. Speciation modelling to identify relevant mineral phases (SI-indices)4. Refined description of multi-element leaching behaviour in a pH dependencetest based on the selected minerals and other relevant processes (adsorption,Fe, Al, DOC, etc.) providing a chemical speciation fingerprint (CSF)5. The resulting chemical speciation fingerprint (CSF) is used as input for thechemical reaction/transport modelling to describe the release from apercolation test or from a monolithic specimen (tank test simulation)6. Model the field scenario using the CSFs for the different layers of materialinvolved using external factors (carbonation, oxidation, biologically mediatedreactions) and realistic estimates of infiltration (e.g., preferential flow)Note: for various materials CSFs are available to facilitate modeling of similar materials

Modeling releaseThe input to the multi-element chemical speciation model consists of: metal availabilities (from pH dependence test max value) selected potentially solubility controlling minerals active Fe-and Al-oxide sites Clay content particulate organic matter and a description of the DOCconcentration as a function of pH (from pH dependence test) Selection of relevant redox condition (pe) Evaluation of pH, major, minor and trace elements, along withionic strength, DOC and TIC

INPUT FOR SPECIATION MODELING (CSF)Prediction caseSpeciation sessionMaterialCoal fly ash NCAB OR R13 ZnSiO3Coal fly ash NCABCoal fly ash Orot Rabin (P,1,1)DOC/DHA [DOC] ed fraction DOC0.2Sum of pH and pe13.00L/S10.0000 l/kgClay1.000E-03 kg/kgHFO1.000E-04 kg/kgSHA2.000E-05 kg/kgPercolation material Coal fly ash NL (C,1,1)Avg L/S first perc. fractions0.3000 l/kgReactant concentrationsReactantmg/kgReactantmg/kgReactantAl 34679.00CrO4-221.17Mn 2H3AsO44.81Cu 25.95MoO4-2H3BO3116.31H2CO32072.00Na Ba 221.42Fe 3155.40Ni 2Ca 220832.18K 200.61Pb 2Cd 20.16Li 10.52PO4-3Cl220.78Mg 24032.33Sb[OH]6Selected MineralsAA 2CaO Fe2O3 8H2O[s]AA CalciteAA TricarboaluminateCa2Cd[PO4]2AA 3CaO Al2O3[Ca[OH]2]0 5 [CaCO3]0 5 11 5H2O[s]AA CaO Al2O3 10H2O[s]AkerminiteCa3[AsO4]2:6H2OAA 3CaO Al2O3 6H2O[s]AA Fe[OH]3[am]alpha-TCPCa4Cd[PO4]3OHAA 3CaO Al2O3 CaCO3 11H2O[s]AA Fe[OH]3[microcr]AnalbiteCaZincateAA 3CaO Fe2O3 CaCO3 11H2O[s]AA GypsumAnorthiteCd[OH]2[C]AA Al[OH]3[am]AA PortlanditeBaSrSO4[50%Ba]Cr[OH]3[C]AA BruciteAA Tobermorite-Ibeta-TCPFerrihydriteDHA ntiteManganiteNi[OH]2[s]Ni2SiO4OCPOtavite[DHA] (kg/l)Polynomial coeficients1.371E-07C0-6.960E 07C31.275E-034.000E-08C40.000E 001.000E-08C50.000E -2H4SiO4SO4-2Sr 2VO2 Zn rontianiteTenoriteWairakiteWillemiteZinciteZnSiO3

Multi element leachability prediction Israeli coal fly ash[Ba 2] as function of pHConcentration (mol/l)1.0E-031.0E-04[Ca 2] as function of pH1.0E-011.0E 61.0E-031.0E-071.0E-05pH dependence test1.0E-041.0E-082345678910 11 12 13 14112[H3AsO4] as function of 14[MoO4-2] as function of pH[CrO4-2] as function of pH1.0E-031.0E-021.0E-04Concentration (mol/l)1.0E-061.0E-0511.0E-03Column -051.0E-081.0E-101.0E-071.0E-0712345678910 11 12 13 1412[Ni 2] as function of E-101.0E-082345678pH910 11 12 13 1434567891011[Zn 2] as function of pH1.0E-0512[Pb 2] as function of pH1.0E-031.0E-09Fixed set ofminerals andsorptionparameters issuitable to predictrelease behaviourfor different flyashes.1.0E-061.0E-061.0E-09Concentration (mol/l)[SO4-2] as function of pH1.0E 011.0E-03Model predictionL/S 10 andL/S 1412345678pH91011121314Alkaline ashesbehave verysimilarly. As yetno column testdata for Israelicoal ashavailable.

Pb leachability modelling and partitioning[Pb 2] as function of pHPartitioning liquid-solid, [Pb 2]1.0E-06Column tration (mol/l)Concentration (mol/l)Model predictionL/S 10 and1.0E-05L/S 0.323456789290%80%70%60%50%40%30%20%10%0%Israeli coal fly ash56788pHFreeDOC-bound91011456788910 11 12 13 3[VO4]2PbMoO4[c]ClayPb 2 fractionation in the solid phase121314Fraction of total concentration (%)Fraction of total concentration (%)Pb 2 fractionation in solution100%43pHpH dependence test31.0E-0910 11 12 13 deClayPb2V2O7Pb3[VO4]2PbMoO4[c]Pb[OH]2[C]14

Modelling percolation test data- The starting point for modelling percolation test data is the Chemical SpeciationFingerprint (CSF) obtained from the pH dependence test- Additional parameters are:o Column dimensionso Flow rateo Fraction of mobile vs. stagnant zone (dual porosity model)o Initial pHo Measure for diffusion from stagnant zoneNote: Percolation with radial diffusion model implemented in new LeachXS (in testing phase)

Modelling percolation test data – Alkaline coal fly ash (NL)Cumulative release of Na [Na ] as function of L/S1,0E-01Concentration (mol/l)Cum. release linecoal ive release of Mg 213Cum. release (mg/kg)1,0E 0012,51211,5pH10L/SpH as function of 0E-050,11L/S (l/kg)Percolation testdata can bedisplayed indifferent unitsto coverdifferentaspects ofrelease.100,010,11L/S10L/S isindependent oftime andreflects releasebehaviour atdifferent timescales

Cr release modelling under oxidised and reducing conditionsCr as function of L/S at pH pE 15Cr as function of L/S at pH pE 12.8101010.10.010.010.111010Model1Alkalinecoal flyash0.10.010.011000.11L/S10.00depth E-061.0E-071.0E-080.00depth (m)FeOxideFreeDOC-bound100Profile Cr after 20 days pH pE 121.0E-031.0E-070.0010L/SConcentration (mol/l)Concentration (mol/l)Concentration Profile for Cr after 3 days pH pE 12.81.0E-06Free101L/SDepth profile for Cr after 20 days1.0E-080.00Concentration (mg/l)Concentration (mol/l)Concentration (mol/l)100Cr as function of L/S at pH pE 12POM-boundFeOxide3.336.6710.0013.33depth A]Cr release very sensitive to redox status. pH pe of 12.8 is the condition in the test, but atpH pe 12 a significant reduction in Cr release is noted (relevant for the field).

Modelling a Mixture of Soil, Sewage Sludge and Coal Fly AshCa as function of pHGeochemicalmodelling basedon individualmaterials CSFs.Partitioning liquid-solid, CaConcentration (mol/l)Concentration .0E-041.0E-051.0E-061.0E-05123456789210 11 12 13 14pHFreeAA CalciteCa3[AsO4]2:6H2OOCPCalciteCu as function of um910 11 12 13 Partitioning liquid-solid, Cu1.0E-04Concentration (mol/l)1.0E-04Concentration (mol/l)3DOC-boundAA .0E-091.0E-101.0E-111.0E-1212345678910 11 12 13 1423456788910 11 12 13 14pHCoal fly ash ISSoilSQD NL unrestrictedModel Soi:Slu:CFA mix 70:20:10Sewage ndTenoritepHPartitioning isgiven for themixture (Soil 70,Sludge 20 andFly ash 10%).Soil qualitydegree shouldbe seen asexampleevaluation interms of pHdomain and limitvalue

Modelling a Mixture of Soil, Sewage Sludge and Coal Fly AshPO4-3 as function of pHPartitioning liquid-solid, PO4-31.0E-02Concentration (mol/l)Concentration .0E-071.0E-041.0E-051.0E-08123456789210 11 12 13 1434FreeFeOxidebeta-TCPBobieriteCa4Cu[PO4]3OHpHZn as function of atite[2]10 11 12 13 O[c]Partitioning liquid-solid, al fly ash Orot RabinSoilSQD NL Unrestricted567pH8910 11 12 13 14Model Soi:Slu:CFA mix 70:20:10Sewage 910 11 12 13 14POM-boundWillemiteLDH ZnPartitioning isgiven for themixture.DOC fromsewage sludgedominant forrelease ofmetals1.0E-04Concentration (mol/l)Concentration (mol/l)1.0E-03Geochemicalmodellingbased onindividualmaterials CSFs.FeOxide pHZincite

Modelling a Mixture of Soil, Sewage Sludge and Coal Fly AshB as function of pHB releaseincreased by coalfly ash. Noregulatory limitsin SQD.Partitioning liquid-solid, BConcentration (mol/l)Concentration ndPOM-boundFeOxideClayPartitioning liquid-solid, CdCd as function of pH1.0E-06Concentration (mol/l)1.0E-06Concentration 1.0E-101.0E-111.0E-121.0E-1321.0E-101234Coal fly ash Orot RabinSoilSQD NL Unrestricted56789 10 11 12 13 14pHModel Soi:Slu:CFA mix 70:20:10Sewage Cd on the borderand no effect ofCd from coal flyash on release.DOC complexesfrom sludgedominate metaland organiccontaminantrelease from soil(as well asecotoxicresponse)

Modelling a Mixture of Soil, Sewage Sludge and Coal Fly AshCr as function of pHPartitioning liquid-solid, 61.0E-071.0E-081.0E-091.0E-101.0E-10123456789210 11 12 13 14pHModel Soi:Slu:CFA mix 70:20:10Sewage sludgeCoal fly ash Orot RabinSoilSQD NL Unrestricted345678 8pH910 11 12 13 ]3[A]PbCrO4Pb as function of pHPartitioning liquid-solid, Pb1.0E-04Concentration (mol/l)1.0E-04Concentration (mol/l)Pb according to thisevaluation notcritical1.0E-04Concentration (mol/l)Concentration .0E-061.0E-07DOC – Cr IIIcomplex drivesremaining 6789Coal fly ash ISSewage sludgeSQD NL Unrestricted2FreeDOC-bound8 8 9 10 11 12 13 Ca2Pb[PO4]2PbCrO410 11 12 13 14pHSoilModel Soi:Slu:CFA mix 70:20:10Cr (more leachablefrom coal ash) isreduced by sludge toCr III and thus lessleachable in contactwith soil and sludgethan in ash alone.34567Pb3[VO4]2

Conclusions The three main leaching tests as presented and now harmonised betweenUS and EU provide an adequate basis for coal ash testing. There is noneed for additional testing tools to assess release from coal ash and coalash containing products. The impact assessment approaches need to be consistent across materialtypes, intended use applications and release of substances of concern. Regulatory criteria development should avoid diverging criteria leading tounnecessary burden for industry with redundant testing and limitations touse for obscure reasons. Relevant leaching information should be used in assessing theconsequences of draft limit values on re-use and recycling targets inconjunction with maintaining environmental standards. Observations onfield behaviour in addition to laboratory testing data is important in thisrespect.

ConclusionsThe combination of standardised and validated laboratory tests like pH dependence andpercolation test with geochemical modelling provides a solid basis for assessing releasebehaviour under field conditions in terms of carbonation level, redox state, organic matterinteraction and liquid-to-solid ratio.The comparison of leaching test results with field data allows conclusions on the degree towhich changes have occurred due to carbonation, oxidation/reduction or interaction withreactive surfaces and/or wash-out. This understanding provides the basis for assessinguncertainties, which are of relevance in drafting regulatory criteria.The modelling of material mixtures in conjuction with testing is more efficient becausetesting requirements are significantly reduced. This relates, for instance, to optimizingmixing ratios in stabilisation recipes and to determine maximum ash usage rates as a soilamendment.The example of a soil- sludge- fly ash mixtures illustrates the limitations of regulationsbased on total content and also shows that the testing and modelling combinationpresented here allow much further reaching conclusions on release behaviour thancurrently practiced

Comparison of effect of carbonate increase on Ca release incomparison with measurements on field samplespH dependent Emission of CaRelease (mg/kg)100000100000Modelled Ca release matcheswell with field observations1000010000100010001 % carbonate1001003.4 % carbonate4.5 % carbonate1010112345667811 12 13 149 10 11pHCoal fly ash Israel C35Coal fly ash Israel C41Coal fly ash Israel D911Coal fly ash Israel FM2Coal fly ash Israel JASRIS CFA SOUTH AFRICANL CFA pH dependenceCoal fly ash OR

Disposal, treatment and beneficial use regulationsWastePretreatment?YYYPotential ?NCPD/CPRcriteria**?Stable - nonreactive?YNYYNon-Haz WasteLandfillYMeet HazWastecriteria?Beneficial useHaz WasteLandfillNTreatmentEoW End of WasteEoL End of LifeCPD Construction Products DirectiveCPR Construction Products RegulationYRecycling?NEoL

DIFFERENT IMPACT SCENARIOS .LandfillDrinkingwater wellContaminatedsoil16 Dec. 2003DG ENVDrinking waterpipesMiningRoad baseCoastal offConstructionsewerAgriculture

. SIMILAR PROBLEMRoadbase[conc]SOURCE TERMDifferent for each scenario material, changes over time(carbonation, redox), etc.L/STRANSPORTIMPACTPoint of complianceTransport in unsaturatedzone and saturated zone topoint of compliance Similar for each scenarioIn first instance a generic sensitive soilsystem is assumed, which can later beadapted to the actual situation

Compacted granular test NEN7347 CEN/TC351/TS-2 EPA 1315 EPA 1315 EPA 1315 EPA 1315 Redox capacity NEN 7348& NEN 7348 Acid rock drainage EN15875 Reactive surfaces ISO/CD12782 parts 1-5 Vienna Agreement * EPA methods included in SW846 & WI of CEN/TC292 # Not yet

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