Leaching TestsSupported byTestAmerica

Leaching tests are tools to estimate thepotential release of constituents of potentialconcern (COPC) from waste material after itsdisposal, or to assess the waste treatment, or to evaluate the material for beneficial use.

Overview of LeachingIn environmental testing, leaching is the process totransfer constituents from a solid (waste, soil, sludge,sediment, combustion residues, coal combustion residue(CCR), stabilized materials, construction materials, ormining wastes) to an aqueous phase or contact liquid.The extent to which constituents in the solid phase willtransfer is dependent on site conditions and materialspecific physical, chemical, and biologic conditions andthe length of time involved.

There are a variety of leaching tests and no oneleachate test can be used to evaluate the leachingbehavior of a wide variety of materials over a broadrange of field scenarios. The following describes twocurrent SW-846 leaching methods, ANSI/ANS 16.1and four new SW-846 methods.

Current Methods SW-846 1311 & 1312;Low-level Radioactive Wastes ANSI/ANS-16.1;LEAF Methods SW-846 1313, 1314, 1315 & 1316

Method 1311Toxicity Characterization Leaching Procedure (TCLP)

TCLP is designed to simulate the leaching a waste willundergo if disposed of in a sanitary landfill.

TCLP has a specific list of regulated compounds withregulatory levels based on health based concentrationlimits and dilution attenuation factors developed using asubsurface fate and transport model. Federal regulationfor the use of TCLP can be found in 40 CFR 261.24. If theTCLP extract contains any one of the TC constituents inan amount equal to or exceeding the concentrationsspecified in 40 CFR 261.24, the waste possesses thecharacteristic of toxicity and is a hazardous waste.

TCLP is appropriate for its intended use as a screeningtest for wastes which may be disposed of in a solid wastelandfill or similar conditions. TCLP does not simulate therelease of contaminants to non-groundwater pathways.

Method 1312Synthetic Precipitation Leaching Procedure (SPLP)

SPLP was designed to estimate the mobility/leachabilityof both organic and inorganic analytes in liquids, soilsand wastes in a mono-disposal situation. The extractionfluid is based on the region of the country where thesample is located. The SPLP extraction fluid is intendedto simulate precipitation. East of the Mississippi River theextraction fluid is at a pH of 4.2 and west of the river thepH is 5.0.The method indicates that the user compareconstituents of concern concentrations in the 1312extract with levels identified in the appropriateregulations. There are no federal regulations requiring theuse of SPLP.

Since the 1990s, there has been concern that TCLP orSPLP would be used outside of their intended use orusers may not be familiar with the resultinglimitations of the data. TCLP and SPLP are single pointbatch leachate tests based on pH. Different factorscan affect the leaching potential of constituents ofconcern. They include: pH, redox conditions,liquid-to-solid ratio (L/S), and solubility. Other factorswhich can affect the leaching potential of organicconstituents of concern include: partitioning orsolubility, presence of organic carbon, andnon-aqueous phase extraction.

Method 1311Toxicity Characteristic Leachate Procedure(TCLP)

Method 1312Synthetic Precipitation Leachate Procedure(SPLP)

This is a single point leachate test. Predicts the mobility of both organics and inorganicsanalytes in landfills. It is used to classify material as hazardous or non-hazardous forpurposes of disposal in a landfill.

This is a single point leachate test. Predicts the mobility of both organics and inorganicsanalytes into ground and surface waters. SPLP fluid simulates precipitation.

CURRENT METHODS

ANSI/ANS-16.1Measurement of the Leachability of SolidifiedLow-Level Radioactive Wastes by a Short-TermTest Procedure

This standard was designed for low-level radioactive wastes to determine the leachingcharacteristics of the solidified material. This standard can be used to measure the leachresistance of any waste solidified into a well-defined geometric shape.

LEAF or SW-846 EPA Method 1313Liquid-Solid Partitioning as a Function ofExtract pH for Constituents in Solid Materialsusing a Parallel Batch Extraction Procedure

LEAF or SW-846 EPA Method 1314Liquid-Solid Partitioning as a Function ofLiquid-to-Solid Ratio for Constituents in SolidMaterials using an Up-Flow Percolation ColumnProcedure

LEAF or SW-846 EPA Method 1315Mass Transfer Rates of Constituents inMonolithic or Compacted Granular Materialsusing a Semi-dynamic Tank LeachingProcedure

LEAF or SW-846 EPA Method 1316Liquid-Solid Partitioning as a Function ofLiquid-to-Solid Ratio for Constituents in SolidMaterials using a Parallel Batch ExtractionProcedure

This method is designed to provide aqueous extracts representing the liquid-solidpartitioning (LSP) curve as a function of pH for inorganics and non-volatile organics in solidmaterials.

This method is designed to provide the liquid-solid partitioning (LSP) of inorganicconstituents and non-volatile organics in granular solid material as a function ofliquid-to-solid (L/S) ratio under percolation conditions.

This method is designed to provide the mass transfer (release rates) of inorganic analytescontained in a monolith or compacted granular material. Under diffusion controlled releaseconditions, as a function of leaching time.

This method is designed to provide the liquid-solid partitioning (LSP) of inorganic andnon-volatile organics at the natural pH of the solid material as a function of liquid-to-solidratio (L/S) under conditions that approach liquid-solid chemical equilibrium.

Executive Methods Summary

LOW-LEVEL RADIOACTIVE WASTES

NEW LEAF METHODS

CURRENT METHODS

*See Back Cover for the Expanded Methods Summary.

ANSI/ANS-16.1-2003 [R2008]American National Standards Institute/America Nuclear SocietyMeasurement of the Leachability of Solidified Low-Level NuclearWastes by a Short-Term Test Procedure.

This method is the American Nuclear Society’sstandardization of the International Atomic EnergyAgency’s 1971 standard leachate test. The goal is tohave a standard leachate test for low level radioactive

material to allow for data comparisons. The test providesa leachability index, which quantifies the leachingcharacteristics of a solidified material and the release ofradioisotopes that come in contact with the material. It isa short-term exposure under controlled conditions with awell-defined leachant. This method can also be used tomeasure the leach resistance of any solidified waste in awell-defined geometric shape.

LOW-LEVEL RADIOACTIVE WASTES

Leaching Environmental Assessment Framework(LEAF)U.S. EPA initiated the review and a validation processof four leachate tests for consideration for inclusion inSW-846. The sources of these methods are frompublished leaching methods and internationalstandards with additional collaboration betweenVanderbilt University and the Energy Research Centreof the Netherlands and DHI in Denmark.

The LEAF Methods are a suite of leaching tests whichinclude batch, column, and tank tests which can beinterpreted individually or integrated. They provideinformation on the leaching behavior of a solidmaterial over a wide range of potential scenarios.

The central mechanism for the leachate tests are eitherequilibrium or mass transfer control. Equilibriumcontrol release occurs for slow percolation through aporous or granular material. Mass transfer rate controlrelease occurs when flow is at the external boundary

of a monolith or percolation is very rapid relative tomass transfer of constituent release to the percolatingwaters.

These methods are applicable to a wide range of solidmaterials including combustion residues, coalcombustion residues (CCR), soils, sediments, industrialprocess residues, and construction materials with thefocus on disposal, beneficial use, waste delisting, andthe evaluation of treatment effectiveness.

LEAF is a tiered testing approach which increases indetail and complexity depending on the purpose of thetesting. Tier 1 testing is for screening purposes and canbe a single batch extraction or modified versions ofleaching tests. Tier 2 is equilibrium based testing tocharacterize the liquid solid portioning over a broadrange of scenarios as a function of pH andliquid-to-solid ratio (L/S). The equilibrium testing forTier 2 includes Methods 1313, 1314 and 1316. Tier 3 isthe mass transfer testing using Method 1315.

NEW LEAF METHODS

LEAF Method 1313Liquid-Solid Partitioning as a Function of Extract pH forConstituents in Solid Materials using a Parallel Batch Extraction

LEAF Method 1313 is a leaching method which requiresparticle-size reduced solids material. Using dilute acidsand bases at pH values ranging from 2 to 13 and naturalconditions, ten eluates are generated from the solidmaterial in parallel extractions. The eluates are thenanalyzed for the constituents of concern as a function ofpH. The constituents of concern can be inorganics andnon-volatile organics. This data can be used to estimatethe liquid-solid partitioning of the constituents ofconcern.

LEAF Method 1314Liquid-Solid Partitioning as a Function of Liquid-to-Solid Ratio forConstituents in Solid Materials using an Up-flow PercolationColumn Procedure

LEAF Method 1314 is a column leaching method whichrequires particle-size reduction to accommodate thecolumn diameter. It is an equilibrium based up-flowpercolation column test. The constituents of concern canbe inorganics and non-volatile organics. This leaching testis used to characterize the liquid/solid partitioningbetween solid phase and the eluate as a function of theliquid to solid ratio. This method provides five options forthe generation of the eluate and the subsequentpreparation of the analytical samples based on the levelof detailed data which is required.

LEAF Method 1315Mass Transfer Rates of Constituents in Monolithic or CompactedGranular Materials using a Semi-dynamic Tank LeachingProcedure

LEAF Method 1315 is a flux based leachate method forthe analysis of a monolith or compacted granularmaterial. The material is continuously immersed inreagent water at a specified liquid to solid surface area.The constituents of concern are inorganics. This leachingtest provides the mass transfer rates of the constituentsof concern under diffusion controlled release conditionsas a function of leaching time through the material.

LEAF Method 1316Liquid-Solid Partitioning as a Function of Liquid-to-Solid Ratiofor Constituents in Solid Materials using a Parallel BatchExtraction Procedure

LEAF Method 1316 is a leaching method which requiresparticle-size reduced solids material. Using natural pH ofthe solid material, five eluates are generated from thesolid material in parallel extractions over a range ofliquid to solid ratios. The eluates are then analyzed forthe constituents of concern. The constituents of concerncan be inorganics and non-volatile organics. This datacan be used to estimate the liquid/solid partitioning ofthese constituents of concern.

This method is intended to be usedas part of an environmentalleaching assessment for theevaluation of disposal, beneficialuse, treatment effectiveness andsite remediation options.

Scope: U.S. EPA Method 1313 is designed to provide aqueousextracts representing the liquid-solid partitioning (LSP)curve as a function of pH for inorganic constituents,semi-volatile organic constituents and non-volatileorganic constituents in solid materials. The LSP curve isevaluated as a function of final extract pH at aliquid-to-solid ratio of 10 mL extractant/g dry sample andconditions that approach liquid-solid equilibrium. Thismethod also yields the acid/base titration and bufferingcapacity of the tested material.

The method is a leaching characterization method that isused to provide values for intrinsic material parametersthat control leaching of inorganic and some organicspecies under equilibrium conditions. The test is intendedas a means for obtaining a series of extracts of a solidmaterial, which may be used to estimate the LSP ofconstituents as a function of pH.

Summary of Method:The method consists of nine parallel extractions of aparticle-size reduced solid material in dilute acid or baseand reagent water. The table below details the leaching

time required based on the particle size of the sample. Inaddition, the table indicates the minimum dry samplemass required for leaching.

A schedule of acid and base additions is formulated froma pre-test titration curve or prior knowledge indicatingthe required equivalents/g acid or base to be added tothe series of extraction vessels so as to yield a series ofeluates having specified pH values in the range of 2-13 (2,4, 5.5, 7, 8, 9, 12, 13, and natural). The pre-test titrationcurve is utilized to determine the actual amount of acidor base added to the samples to hit the method specifiedpH values or client driven pH values.

If the natural pH falls within the method subscribed pHvalues then a pH value of 10.5 will be performed. Inaddition to the nine test extractions, three method blankswithout solid material are carried through the procedurein order to verify that analyte interferences are notintroduced as a consequence of reagent impurities orequipment contamination.

The twelve bottles are tumbled in an end-over-endfashion for a specified contact time, which depends onthe particle size of the sample. At the end of the specifiedcontact interval, the liquid and solid phases are separated

pH

13131313

Liquid-Solid Partitioning as a Function of Extract pH using a Parallel BatchExtraction Procedure

Application Note

Extraction Parameters as Function of Max. Particle Size

Particle Size US Sieve Max Dry Contact Suggested(85% wt less Size (mass g-dry) Time (hrs) Vessel Sizethan) (mm) (mL)0.3 50 20 ± -0.02 24 ± 2 2502 10 40 ± -0.02 48 ± 2 5005 4 80 ± -0.02 72 ± 2 1,000

10

1

0.1

0.01

0.0012 7 12

pH

Conc

entr

atio

n (m

g/l)

pH dependent concentration of Ni

via centrifugation. Extract pH,conductivity, and ORPmeasurements are then made on analiquot of the liquid phase and theremaining eluate is filtered thru a0.45 micron filter. Analytical samplesof the filtered eluate are collectedand preserved as appropriate for thedesired chemical analyses. The eluateconcentrations contaminants ofpotential concern (COPC) aredetermined and reported.Note: The end user can requestspecific pH ranges.

Data Results:An LSP curve can be generated foreach COPC following chemicalanalyses of all extracts by plottingthe target analyte concentration inthe liquid phase as a function of themeasured extract pH for eachextract.

The shape of the LSP curve isindicative of the speciation of theCOPC in the solid phase withcharacteristic LSP curve shapes.

Cationic Species: The LSP curvetypically has a maximumconcentration in the acidic pH rangethat decreases to lower values atalkaline pH.

Amphoteric Species: The LSP curvestend to be similar in shape to cationicLSP curves with greaterconcentrations in the acidic pHrange. However, the concentrationspass through a minimum in the nearneutral to slightly acidic pH rangeonly to increase again for alkaline pHvalues.

Oxyanionic Species: The LSP curveoften show maximum in the neutralto slightly alkaline range

Highly Soluble Species: The LSPcurve is only a weak function of pH.

In Summary:The method provides solutionsconsidered indicative of eluate underfield conditions, only where the fieldleaching pH is the same as the finallaboratory extract pH and the LSP is

controlled by aqueous phasesaturation of the constituent ofinterest.

The maximum mass of constituentreleased over the range of methodpH conditions (2<pH<13) may beconsidered an estimate of themaximum mass of the constituentleachable under field leachingconditions for intermediate timeframes and the domain of thelaboratory tests.

References:U.S. EPA. SW846 Method 1313October 2012http://www.epa.gov/osw/hazard/testmethods/sw846/new_meth.htm

U.S. EPA. Background Information forthe Leaching EnvironmentalAssessment Framework (LEAF) TestMethods EPA 600/R-10/170.November 2010

Additional Information:Recommend bottle type for samples:32-ounce jarSample Size: Minimum 800 grams. Samplesize will vary based on analysis requestedPreservation: NoneHolding Time: Holding time for leachategeneration is within 1 month of receipt. Theanalytical holding times do apply to theenvironmental samples generated and whichare subsequently analyzed for COPCsConstituents of Potential Concern:Inorganics and non-volatile organicsApproximate Turnaround for Leaching andSubsequent Analysis: 24 to 72 hours forleaching, depending on particles size of thematerial; 21 days for analysis, for a total of28-day turnaround.

SW-846 Method 1313pH

1313

14

12

10

8

6

-6.1 -4.1 -2.1 -0.1 1.9 3.9 5.9 7.9 9.9 11.9Acid Addition [meq/g-dry]

Elua

te p

H

Series 1Natural pH Indicator

1

0.1

0.012 7 12

pH

Conc

entr

atio

n (m

g/l)

pH dependent concentration of Mo

10000

1000

100

10

12 7 12

pH

Conc

entr

atio

n (m

g/l)

pH dependent concentration of Na

Pre-test Titration Curve

LSP Curve of Cationic Species

LSP Curve of Oxyanionic Species

LSP Curve of Highly Soluable Species

The method is intended to be usedas part of an environmentalleaching assessment for theevaluation of disposal, beneficialuse, treatment effectiveness, andsite remediation options.

Scope:U.S. EPA Method 1314 is designed to provide theliquid-solid partitioning (LSP) of inorganic constituentsand non-volatile organic constituents in a granular solidmaterial as a function of liquid-to-solid ratio (L/S) underpercolation conditions. The first eluates of the columntest may provide insight into the composition of the poresolution either in a granular bed or in the pore space oflow-permeability material.

The method is intended as a means for obtaining a seriesof extracts of a granular solid material which may be usedto show eluate concentrations and/or cumulative releaseas a function of L/S which can be related to a time scalewhen data on mean infiltration rate, density, and heightof application are available.

Summary of Method:In preparation of solid materials for use in this method,particle-size reduction or exclusion of samples with largegrain size is used to enhance approach towardliquid-solid equilibrium over the residence time of eluantin the column. A 30 cm, straight cylindrical column withan inner diameter of 5 cm is currently being used. The

particle size of the material must be <1/20 of the columndiameter. Based off of this information, the currentparticle size is 2.5 mm.Eluant is introduced into a column of moderately-packedgranular material in an up-flow pumping mode. Theeluate collection performed as a function of thecumulative L/S. Up-flow pumping is used to minimize airentrainment and flow channeling. The default eluant formost material is reagent water. The flow rate ismaintained between 0.5-1.0 L/S per day to increase thelikelihood of local equilibrium between the solid andliquid phases, due to residence times longer than 1 day.

Eluate volumes are chemically analyzed for acombination of inorganic and non-volatile organicanalytes depending on the constituents of potentialconcern (COPC). The entire eluant volume up to 10mL/gdry sample is collected in nine specific aliquots of varying

131413141314

Liquid-Solid Partitioning as a Function of Liquid-to-SolidRatio for Constituents in SolidMaterialsusing an Up-flow Percolation Column Procedure

Application Note

Multiple Columns for Method 1314

volume. A limited subset of eluantsvolumes within the same L/S rangemay be collected and analyzed forregulatory and compliance purposes.The table below reflects collectiontimes of a sample.

Data Results:The method provides options for thepreparation of analytical samplesthat provide flexibility based on thelevel of detail required:

Option A – CompleteCharacterization: Eluateconcentrations may be used inconjunction with informationregarding environmentalmanagement scenarios to estimateanticipated leaching concentrations,release rates, and extent of release forindividual material constituents inthe management scenariosevaluated. The nine eluate collectionsare analyzed and reported.

Option B – Limited Analysis: Undera limited analysis approach, nineeluate collections and analysis of sixanalytical samples are required. Ifevaluation is based on eluateconcentrations, six eluate fractionsare chemically analyzed. If evaluationis based on cumulative release, someeluate fractions are composited byvolume-weighted averaging tocreate a set of six analytical samples.The concentrations of compositedanalytical samples cannot beinterpreted along with eluatefractions on the basis ofconcentration.

Option C – Index Testing: For thedetermination of consistencybetween the subject material andpreviously characterized materials,nine eluate collections and analysisof three analytical samples arerequired. If consistency is to bedetermined by eluate concentrations,three discrete eluate fractions arechemically analyzed. If consistency isto be determined by cumulativerelease, some eluate fractions arecomposited by volume-weightedaveraging to create a set of threeanalytical samples. Theconcentrations of compositedanalytical samples cannot beinterpreted along with eluatefractions on the basis ofconcentration.

Eluate concentrations ofcontaminants of concern are thenplotted versus the cumulativeliquid-to-solid ratio.

SW-846 Method 13141314

In Summary:The method provides eluatesolutions considered indicative ofleachate under field conditions onlywhere the field leaching pH iscontrolled by the alkalinity or acidityof the solid material and the fieldleachate is not subject to dilution orother attenuation mechanisms. Thecumulative mass of constituentreleased over an L/S range may beconsidered an estimate of themaximum mass of that constituentto be leached under field leachingover intermediate time frames andthe domain of the laboratory test pH.

References:U.S. EPA. SW846 Method 1314January 2013http://www.epa.gov/osw/hazard/testmethods/sw846/new_meth.htm.

U.S. EPA. Background Information forthe Leaching EnvironmentalAssessment Framework (LEAF) TestMethods EPA 600/R-10/170.November 2010

Additional Information:Recommend bottle type for samples:32-ounce jarSample Size: Minimum 1,200 grams. Samplesize will vary based on analysis requestedPreservation: NoneHolding Time: Holding time for leachategeneration is within 1 month of receipt. Theanalytical holding times do apply to theenvironmental samples generated and whichare subsequently analyzed for COPCsConstituents of Potential Concern:Inorganics and non-volatile organicsApproximate Turnaround for Leaching andSubsequent Analysis: 14 days for leaching;42 total days for leaching and analysis.

1

0.10.1 1 10

L/S (L/Kg)

Conc

entr

atio

n (m

g/l)

As concentration as function of L/S

Collection Times of a Sample

Eluate Concentrations versusCumulative L/S

Fraction Label Sum L/S Ratio Fraction Volume Scheduled Collection(mL/g-dry) (mL) (date/time)

– 0 10 11/28/12 8:20 AMT01 0.20 164 11/28/12 2:02 PMT02 0.50 260 11/28/12 11:05 PMT03 1.00 434 11/29/12 2:11 PMT04 1.50 434 11/30/12 5:16 AMT05 2.00 434 11/30/12 8:22 PMT06 4.50 2,170 12/3/12 11:50 PMT07 5.00 434 12/4/12 2:56 PMT08 9.50 3,906 12/10/12 6:47 AMT09 10.00 434 12/10/12 9:53 PM

The leaching characterization methodprovides intrinsic materialparameters for release of inorganicspecies under mass transfer-controlled leaching conditions. Themethod is intended as a means for

obtaining a series of eluants which may beused to estimate the diffusivity of constituentsand physical retention parameter of the solidmaterial under specified laboratory conditions.

Scope:U.S. EPA Method 1315 is designed to provide the masstransfer rates of inorganic analytes contained in a monolithicor compacted granular material, under diffusion-controlledrelease conditions, as a function of leaching time.

The geometry of the monolithic samples may berectangular, cubes, wafers, or cylinders. Samples may alsohave a variety of faces exposed to the eluant forminganything from 1-dimensional through 3-dimensional masstransfer cases. In all cases, a minimum sample size of 5 cm inthe direction of mass transfer must be employed and theliquid-surface-area ratio (L/A) must be maintained at 9 +/- 1mL/cm2. Note: The surface area of the sample must bedetermined by the laboratory or an outside contractor.

Monolith samples should be suspended or held in theleaching fluid such that at least 98% of the entire samplesurface area is exposed to eluant and the bulk of the eluantis in contact with the exposed sample surface.

Mass Transfer Rates of Constituents in Monolithic or Compacted Granular Materialusing a Semi-dynamic Tank Leaching Procedure

Application Note

Summary of Method:The method comprises leaching of continuouslywater-saturated monolithic or compacted granularmaterial in an eluant-filled tank with periodic renewal ofthe leaching solution. Samples are contacted with reagentwater at the specified L/A. The leaching solution isexchanged with fresh reagent water at nine pre-determined intervals listed below:

The sample is freely drained and the mass is recorded tomonitor the amount of eluant absorbed into the solidmatrix at the end of each leaching interval. The eluate pH,specific conductance, and ORP are measured for each timeinterval. Analytical samples are collected and preservedaccordingly based on the determinative methods to beperformed on the eluate. Note: Though the methodreferences analyzing for inorganic parameters, TestAmerica isevaluating options of analyzing for volatiles andsemi-volatiles.

Pre-determined Intervals of Leaching Solution Exchange

Fraction Interval Interval CumulativeLabel Duration (hrs) Duration (hrs) Leaching Time (d)T01 2.0 ± -0.25 – 0.08

T02 23.0 ± -0.5 – 1.0T03 23.0 ± -0.5 – 2.0T04 – 5.0 ± -0.1 7.0T05 – 7.0 ± -0.11 14.0T06 – 14.0 ± -0.1 28.0T07 – 14.0 ± -0.1 42.0T08 – 7.0 ± -0.1 49.0T09 – 14.0 ± -0.1 63.0

13151315

SW-846 Method 13151315

Data Results:Eluate concentrations are plotted as afunction of time, as a mean intervalflux, and as cumulative release as afunction of time.

In Summary:The method is a characterizationmethod and does not provide a solutionconsidered to be representative ofeluate under field conditions. Thismethod is similar in structure and use topredecessor methods such as MT001.1,NEN 7345, ANSI 16.1, and ASTM C1308.However, this method differs fromprevious methods in that: (a) leachingintervals are modified to improvequality control, (b) sample preparationaccounts for mass transfer fromcompacted granular samples, and (c)mass transfer may be interpreted bymore complex release models thataccount for physical retention of theporous medium and chemical retentionat the pore wall through geochemicalspeciation modeling.

References:U.S. EPA. SW846 Method 1315 January 2013http://www.epa.gov/osw/hazard/testmethods/sw846/new_meth.htm.

U.S. EPA. Background Information forthe Leaching EnvironmentalAssessment Framework (LEAF) TestMethods EPA 600/R-10/170. November2010

Additional Information:Recommend bottle type for samples:32-ounce jarSample Size: 20 cm squared (monolith orcompacted granular material). Preservation: NoneHolding Time: There is no holding timedefined to generate the leachate from themonolith. The analytical holding times doapply to the environmental samplesgenerated and which are subsequentlyanalyzed for COPCsConstituents of Potential Concern:Inorganics and non-volatile organicsApproximate Turnaround for Leachingand Subsequent Analysis: 63 days forleaching; 84 days for analysis and leachingturnaround.

1000

100

10

1

0.1

0.010 20 40 60 80

Leaching Time [days]

Ars

enic

[µg/

L]

1000

100

10

1

0.1

0.010 20 40 60 80

Leaching Time [days]

Cadm

ium

[µg/

L]

FSSL-AFSSL-B

1000

100

10

1

0.1

0.010 20 40 60 80

Leaching Time [days]

Sele

nium

[µg/

L]

FSSL-AFSSL-B

1000

100

10

1

0.1

0.010 20 40 60 80

Leaching Time [days]

Vana

dium

[µg/

L]

FSSL-AFSSL-B

FSSL-AFSSL-B

1.E-03

1.E-04

1.E-05

1.E-06

1.E-07

1.E-08

1.E-090.01 0.1 1 10 100

Mean Interval [days]

Ars

enic

Flu

x [m

g/m

2 S]

FSSL-AFSSL-B

slope = -1/2

1.E-05

1.E-06

1.E-07

1.E-08

1.E-090.01 0.1 1 10 100

Mean Interval [days]

Cadm

ium

Flu

x [m

g/m

2 S]

FSSL-AFSSL-B

slope = -1/2

1.E-04

1.E-05

1.E-06

1.E-07

1.E-08

1.E-090.01 0.1 1 10 100

Mean Interval [days]

Sele

nium

Flu

x [m

g/m

2 S]

FSSL-AFSSL-B

slope = -1/2

FSSL-AFSSL-B

1.E-03

1.E-04

1.E-05

1.E-06

1.E-07

1.E-08

1.E-090.01 0.1 1 10 100

Mean Interval [days]

Vana

dium

Flu

x [m

g/m

2 S]

slope = -1/2

Interval Concentration Graphs

Interval Flux Graphs

The method is intended to be usedas part of an environmentalleaching assessment for theevaluation of disposal, beneficialuse, treatment effectiveness, andsite remediation options.

Scope:U.S. EPA Method 1316 is designed to provide theliquid-solid partitioning (LSP) of inorganic constituentsand non-volatile organic constituents at the natural pH ofthe solid material as a function of liquid-to-solid ratio(L/S) under the conditions that approach liquid-solidchemical equilibrium.

The eluate concentrations at a low L/S provide insightinto pore solution composition either in a granular bed(e.g., soil column) or in the pore space oflow-permeability materials (e.g., solidified monolithic orcompacted granular fill).

Summary of Method:This method consists of five parallel extractions of aparticle-size reduced solid material in reagent water overa range of L/S values from 0.5 to 10 mL eluant/g drymaterial. In addition to the five test extractions, a methodblank without solid sample is carried through theprocedure in order to verify that analyte interferences arenot introduced as a consequence of reagent impurities orequipment contamination.

In total, six bottles (i.e., five test positions and onemethod blank) are tumbled in an end-over-end fashionfor a specified contact time based on the maximumparticle size of the solid. At the end of the contactinterval, the liquid and solid phases are roughlyseparated via settling or centrifugation. Extract pH, ORP,and specific conductance measurements are then takenon an aliquot of the liquid phase. The bulk of the eluateis clarified by pressure or vacuum filtration in preparationfor constituent analysis. Analytical aliquots of theextracts are collected and preserved accordingly basedon the determinative methods to be performed. Theeluate constituent concentrations are plotted as afunction of L/S and compared to QC and assessmentlimits.

Data Results:A constituent LSP curve can be generated for each COPCafter chemical analysis of all extracts by plotting theconstituent concentration in the liquid phase as afunction of L/S used for each extraction. The curveindicates the equilibrium concentration of the COPC as afunction of L/S at the natural pH.

In Summary:This method is a leaching characterization method used toprovide intrinsic material parameters that control leachingof inorganic species under equilibrium conditions. Thistest method is intended as a means for obtaining anextract (i.e., the eluate) of a solid material which may beused to estimate the solubility and release of inorganicconstituents under the laboratory conditions described in

13161316

Liquid-Solid Partitioning as a Function of Liquid-to-SolidRatio in Solid Materialsusing a Parallel Batch Procedure

Application Note

SW-846 Method 13161316

this method. Extract concentrationsmay be used in conjunction withinformation regarding environmentalmanagement scenarios to estimateanticipated leaching concentrations,release rate and extent for individualmaterial constituents in themanagement scenarios evaluated.Extract concentrations may also beused along with geochemicalspeciation modeling to infer themineral phases that control the LSP inthe pore structure of the solidmaterial.

References:U.S. EPA. SW846 Method 1316October 2012http://www.epa.gov/osw/hazard/testmethods/sw846/new_meth.htm

U.S. EPA. Background Information forthe Leaching EnvironmentalAssessment Framework (LEAF) TestMethods EPA 600/R-10/170.November 2010

Additional Information:Recommend bottle type for samples:32-ounce jarSample Size: Minimum 1,000 grams. Samplesize will vary based on analysis requestedPreservation: NoneHolding Time: Holding time not applicableto the generation of the eluate. The analyticalholding times do apply to the environmentalsamples generated and which aresubsequently analyzed for COPCsConstituents of Potential Concern:Inorganics and non-volatile organicsApproximate Turnaround for Leaching andSubsequent Analysis: 24 to 72 hours forleaching, depending on particle size of thematerial; 21 days for analysis, for a total of28-day turnaround.

12

11

10

9

8

70 2 4 6 8 10

LS Ratio [mL/g-dry]

Elua

te p

H

FDG Filter CakeFly Ash

100

10

1

0.1

0.01

0.001

0.0001

0.000010 2 4 6 8 10

LS Ratio [mL/g-dry]

Ars

enic

[mg/

L]

1000

100

10

1

0.1

0.01

0.001

0.00010 2 4 6 8 10

LS Ratio [mL/g-dry]

Calc

ium

[mg/

L]

10000

1000

100

10

1

0.1

0.01

0.001

0.00010 2 4 6 8 10

LS Ratio [mL/g-dry]

Pota

ssiu

m [m

g/L]

1000

100

10

1

0.1

0.010 2 4 6 8 10

LS Ratio [mL/g-dry]

Thal

lium

[µg/

L]

100000

10000

1000

100

10

1

0.1

0.010 2 4 6 8 10

LS Ratio [mL/g-dry]

Sulfa

te [m

g/L]

FDG Filter CakeFly Ash

FDG Filter CakeFly Ash

FDG Filter CakeFly Ash

FDG Filter CakeFly Ash

FDG Filter CakeFly Ash

ML

MDL

ML

MDL

MLMDL

MLMDL

ML

MDL

Extraction Parameters as Function of Maximum Particle Size

Example Schedule for Extraction Setup

Equilibrium Concentration as a Function of L/S at the Natural pH

Test Target L/S Minimum Moisture Moisture Volume RecommendedPosition Dry Mass “As Tested” “As Tested” Reagent Bottle Size

(g-dry) Sample (g) Sample (g) Water (mL) (mL)T01 10.0 20 22.2 2.2 198 250T02 5.0 40 44.4 4.4 196 250T03 2.0 100 111.1 11.1 189 500T04 1.0 200 222.2 22.2 178 500T05 0.5 400 444.4 44.4 156 100B03 QC 200 250Total 844.4 1120

Particle Size US Sieve Max Dry Contact Suggested Vessel(85% wt less than) (mm) Size (mass g-dry) Time (hrs) Size (mL)0.3 50 20 ± -0.02 24 ± 2 2502 10 40 ± -0.02 48 ± 2 5005 4 80 ± -0.02 72 ± 2 1,000

LEAF Method 1313Liquid-SolidPartitioning as aFunction of ExtractpH for Constituentsin Solid Materialsusing a ParallelBatch ExtractionProcedure

LEAF Method 1314Liquid-SolidPartitioning as aFunction ofLiquid-to-Solid Ratiofor Constituents inSolid Materials usingan Up-FlowPercolation ColumnProcedure

LEAF Method 1315Mass Transfer Ratesof Constituents inMonolithic orCompacted GranularMaterials using aSemi-dynamic TankLeaching Procedure

LEAF Method 1316Liquid-SolidPartitioning as aFunction ofLiquid-to-Solid Ratiofor Constituents inSolid Materials usinga Parallel BatchExtraction Procedure

NEW LEAF METHODS

ANSI/ANS-16.1-2003 [R2008]Measurement of theLeachability ofSolidified Low-LevelRadioactive Wastesby a Short-Term TestProcedure

LOW-LEVEL RADIOACTIVE WASTES

Method 1311ToxicityCharacteristicLeachate Procedure(TCLP)

Method 1312SyntheticPrecipitationLeachate Procedure(SPLP)

CURRENT METHODS

Larry Matko – Technical Director412.963.7058 Larry.Matko@TestAmericaInc.com

Carrie Gamber – Senior Project Manager412.963.7058 Carrie.Gamber@TestAmericaInc.com

Debbie Lowe – Laboratory Director412.963.7058 Debbie.Lowe@TestAmericaInc.com

Patricia McIsaac – Product Manager703.623.3872 Patricia.McIsaac@TestAmericaInc.com

TestAmerica Lab Network

TestAmerica LocationsSupporting LEAF

Pittsburgh412.963.7058

TestAmerica Locations Supporting LEAF:

This is a single point leachate test. Predicts the mobility of bothorganics and inorganics analytes in landfills. It is used to classifymaterial as hazardous or non-hazardous for purposes of disposal in alandfill. Summary Description: Samples are preliminarily evaluatedfor solids and particle size. The liquid to solid ratio is 20:1. Thesample is then leached with appropriate fluid. A pH 2.9 acetic acid isused for moderately to high alkaline material and pH 4.9 acetatebuffer is used for all other materials. The total time for the leachategeneration is 18 hours.

This is a single point leachate test. Predicts the mobility of bothorganics and inorganics analytes into ground and surface waters.SPLP fluid simulates precipitation. Summary Description: Samplesare preliminarily evaluated for solids and particle size. The liquid tosolid ratio is 20:1 and the samples are then leached with appropriatefluid. The extraction fluid is based on the region of the countrywhere the sample is located. For samples east of the Mississippi Riverthe extraction fluid pH is 4.2 and for materials west the pH is 5.0. Thetotal time for the leachate generation is 18 hours.

This standard was designed for low-level radioactive wastes todetermine the leaching characteristics of the solidified material.This standard can be used to measure the leach resistance of anywaste solidified into a well-defined geometric shape. SummaryDescription: Leaching of continuously water saturated monolithicor compacted granular material in an eluate-filled tank withperiodic renewal of the leaching solution. L/S ratio of 10 mL eluateper cm2 of surface area. Eluate is collected at predetermined timesand analyzed for COPCs. Eluate is centrifuged and filtered forCOPCs. Total time of test can be as long as 43 days.

This method is designed to provide aqueous extracts representingthe liquid-solid partitioning (LSP) curve as a function of pH forinorganics and non-volatile organics in solid materials. SummaryDescription: This is a pH dependent batch leaching procedure. Tenparallel extractions of a particle sized reduced solid material in diluteacid or base and reagent water. Series of eluates having pH valuesranging from 2-13 as well as natural condition. Liquid solid ratio is10:1. Eluate is centrifuged and filtered and then analyzed forconstituents of concern. Total time to generate the eluate is 5 daysfor material with 85% or greater solids or 8 days for material withless than 85% solids.

This method is designed to provide the liquid-solid partitioning[LSP] of inorganic constituents and non-volatile organics in granularsolid material as a function of liquid to solid (L/S) ratio underpercolation conditions. Summary Description: This is a dynamicleaching procedure. Eluate is introduced into a column with packedparticle sized reduced solid material in an up-flow pumping mode.Flow rate is maintained between 0.5-1.0 L/Day. Eluate is collected atpredetermined times, filtered and analyzed for constituents ofconcern. Total time to generate the eluate is approximately 14 days.

This method is designed to provide the mass transfer (release rates)of inorganic analytes contained in a monolith or compactedgranular material. Under diffusion controlled release conditions, as afunction of leaching time. Summary Description: This is a hybridbatch and dynamic leaching procedure. Leaching of continuouslywater saturated monolithic or compacted granular material in aneluate-filled tank with periodic renewal of the leaching solution. L/Sratio of 9 mL eluate per cm2 of surface area is used. Eluate iscollected at predetermined times and analyzed for constituents ofconcern. Eluate is centrifuged and filtered for constituents ofconcern. Total time to generate the eluate is approximately 63 days.

This method is designed to provide the liquid-solid partitioning(LSP) of inorganic and non-volatile organics at the natural pH of thesolid material as a function of liquid-to-solid ratio (L/S) underconditions that approach liquid-solid chemical equilibrium.Summary Description: Five parallel extractions of a particle-sizereduced solid material in reagent water over a range of L/S valuesfrom 0.5 to 10 mL eluate/g dry material. Depending on particle size,sample is tumbled between 24 and 72 hours. Eluate is centrifugedand filtered for constituents of concern. Total time to generate theeluate of test is 2 days.