An Overview of Leaching Assessment for Waste Disposal and Materials Use Session 1 Assessment Framework and Leaching Fundamentals

Hans A. van der Sloot, Ph.D. Hans Meeussen, Ph.D. David S. Kosson, Ph.D. Florence Sanchez, Ph.D.

Department of Civil and Environmental Engineering

WASCON 2003

Current Application of Leaching Tests

Waste classification
Hazardous versus Non hazardous

Site assessment and remediation endpoints

Contaminated soils Brownfields sites

Treatment process effectiveness

Best Demonstrated Available Technology (BDAT) Determination of Equivalent Treatment (DET)

Source term evaluations

Release flux Risk assessment DOE performance assessments

Waste management options

Alternative disposal and utilization scenarios

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Primary Raw Materials Alternative raw materials Granular compliance test

Stage 1 Raw material supplies Recycling of construction debris Supply of information on technical and environmental quality Stage 3: Construction Process Stage 2: Manufacture of construction materials and elements

Characterisation of monolith leaching behaviour

Energy

End of Life Dust, noise emissions Characterisation of granular leaching Energy

Stage 5: Demolition

Monolith compliance leaching test Environmental impact (dusting)

Stage 4: Service Life

Release into the environment

CHARACTERIZATION AND COMPLIANCE LEACHING TESTS IN DIFFERENT STAGES OF THE BUILDING CYCLE

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Questions To Be Answered
Which management options are acceptable?
e.g., treatment processes, residual contamination levels, reuse or disposal options

Which wastes are suitable for disposal in a specific disposal facility? Is this secondary material acceptable for use in commerce?
e.g., as construction material, life cycle assessment

Different questions need to be answered for different perspectives and roles in management !
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Description Of The Scenario Relevant For The Specified Question

ROADBASE APPLICATION
ENV 12920

RUN-OFF
INFILTRATION

GROUNDWATER

Material supply and processing Geotechnical specifications of the application and materials used Hydrology of the application

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Leaching Assessment Approaches

Design laboratory tests to mimic key aspects of field scenarios
Requires unique test for each scenario Uncertain comparability between scenarios Extrapolation (scale-up, extended time frames) is uncertain

Carry out small-scale field assessments

Very specific to specific waste and scenario Good for validation, but expensive and require long testing times

Design laboratory tests to measure fundamental, intrinsic leaching characteristics and use mass transfer models to extend results to release estimates for specific scenarios
Requires knowledge of controlling factors and use of appropriate models Most versatile approach and allows comparability amongst materials and scenarios

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Objectives of a Framework for Evaluation of Contaminant Release

Provide conservative but realistic estimates
Broad range of waste types, constituents of concern, environmental conditions and management options

Utilize testing strategies that can be carried out using standard laboratory practices in reasonable time frames Provide for release estimates that consider site-specific conditions Facilitate better waste management decisions, while reducing overall management costs and improving environmental protection Provide tiered approach to balance information needs with evaluation costs

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Recommended Approach to Leaching Evaluation

Define potential release scenarios and leaching parameters needed Calculate release based on management scenario(s) and field conditions
default scenarios site-specific conditions compare with prior knowledge (i.e., database)

Select test methods to measure needed leaching parameters

Evaluate acceptance based on projected impact Test waste or material to determine leaching parameters
default criteria site-specific impact estimate comparability with prior analogous experience

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A Tiered Approach to Regulatory Use

MATERIAL
WASTE, SOIL OR PRODUCT

MANAGEMENT SCENARIO
Specific disposal or utilization scenario Default cases

Default Scenario

Specific or Default Scenario

TIER 1

Tier 1 SCREENING

TIER 2

Tier 2A EQUILIBRIUM Compliance

Tier 2B EQUILIBRIUM Characterization

Tier 2C EQUILIBRIUM Quality Control (Material specific)

Random compliance testing

TIER 3

Tier 3A MASS TRANSFER RATE Compliance

Tier 3B MASS TRANSFER RATE Characterization

Tier 3C MASS TRANSFER RATE Quality Control (Material specific)

LEVEL A

LEVEL B

LEVEL C

User determines extent of testing needed based on waste quantity, potential management options, and prior knowledge

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Hierarchical Approach
Conservative Estimates (over-estimation of release) with less data
Total > Potential > Equilibrium Mass Transfer limited

Characterization Testing
Detailed baseline evaluation of leaching behaviour for a class of materials

Compliance Testing
Is the material tested the same as previously characterized class of materials? Prior characterization data available from similar material Small quantity of material to be managed with limited options

Quality Control Testing

Is the material changing significantly over time or from batch to batch? Prior characterization data available, history with compliance testing For management of large quantities of material with on-going production

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Release Scenarios General Approach

Material
Treatment Option Yes Percolation
Fundamental leaching properties
Equilibrium data

Mgmt Scenario

Flow-around
Fundamental leaching properties
Availability data, Equilibrium data, Mass Transfer data

Site information* Assessment model

Site information* Assessment model

Release Estimate
* Site-specific information or Default scenarios

No

Acceptable Impact?

Yes

Exit

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Characterization of Material Properties

Concept Leaching vs. Total Composition
Cumulative release [mg/kg]

LS [L/kg] TIME [year]

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Intrinsic Material Leaching Characteristics

Aqueous-solid equilibrium as a function of pH
Solubility Adsorption Release Potential Acid/base neutralization capacity

Aqueous-solid equilibrium as a function of LS

Pore-water composition Ionic-strength effects Species wash-out or depletion

Mass transfer rates

Release mechanism (diffusion, surface dissolution, coupled dissolution-diffusion, multiple processes) Release rate (when not equilibrium controlled)

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Material Physical Characteristics

Needed for detailed evaluation Moisture content Physical form (granular, monolithic) Porosity Permeability Density

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Main Types of Leaching Tests

Equilibrium-based leaching tests
Carried out on size reduced material Aims to measure contaminant release related to specific chemical conditions
pH Liquid-to-solid ratio

Mass transfer-based leaching tests

Carried out either on monolithic material or compacted granular material Aims to determine contaminant release rates by accounting for both chemical and physical properties of the material

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Relationships in Equilibrium Test Results

10000

LS =10 LS =5 LS =2

1000

LS =10 LS =5 LS =2

R e l e a s e ( mg/ k g)

100

C o nc . ( mg/ l )

1000

100

10

10

Si
1 3 5 7 9 11 13

Si

0.1

pH

11

pH

13

10000

10000

Cl
R e l e a s e ( mg/ k g) C o nc . ( mg/ l )

Cl

LS =10 LS =5 LS =2

1000

1000

LS =10 LS =5 LS =2
100 3 5 7 9 11

100

pH

13

11

pH

13

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Comparison of Different Leaching Tests

Contaminated Soil
100 1000

100

10

Leached (mg/kg)

10

Leached (mg/kg)

0.1

0.1

Contaminated soil CSO2

1 3 5 7 9

Cr
0.01 11 1 3

EDTA Hac CaCl2 NaNO3 EN-12457-3 SCE PrEN 14429 SCE PrEN 14429 Total AR 5 7 9

Cd
11 13

0.01

pH

pH

pH dependence test as basis of reference

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Consistent Leaching Behavior

Most relevant pH range for cement-bound materials

Leached [mg/kg]

ANC [mol/kg]

ECRICEM
pH pH

Chemical speciation important for recycling, reuse and end-of-life judgment (carbonation)

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Consistent Leaching Behavior

Compliance and Characterization (MSWI Bottom Ash)
Leached [mg/kg]- Cumulative

Cu - Washout of soluble species

Leached [mg/kg]

pH

LS [L/kg]

CEN TC 292 Validation study EN 12457 1 - 4

pH

Leached [mg/kg]- Cumulative

Leached [mg/kg]

Sb - Solubility control release

LS [L/kg]

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Liquid-to-Solid Ratio Effects

10000

1000

Cumulative release (mg/kg)

Release processes derived from percolation test Cl - wash-out SO4 - solubility Zn - changes in pH

100

10

Cl S Zn

0.1 0.1 1 10

L/S (l/kg)

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Batch LS Testing - Cement-based Material

13.5

Liquid-to-Solid Ratio Effects

3000 2500 Na [mg/L] 2000 1500 1000 500 0

0 2 4 6 8 LS Ratio [mL/g] 10

13.3 pH 13.1 12.9 12.7

10

LS Ratio [mL/g dry]

1000 800 Ca [mg/L] 600 400 200 0 0 2 4 6 8 10 LS Ratio [mL/g]

0.4 0.3 0.2 0.1 0.0 0 2 4 6 8 10 LS Ratio [mL/g]

As [mg/L]

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Comparison of Laboratory and Field Results

10 1

Cum . re le a se , [Ni] (m g/kg)

100

100 10 1 0.1 0.01 0.001 0.0001

[Ni] (m g/kg)

0.1 0.01 0.001 0.0001 0.00001

Lab

Field

0.00001 0.000001 3 5 7

Ly s im eter
0.01 0.1 1 10 100

0.000001

pH

11

13

0.0001 0.001

L/S (l/kg)

Consistent behaviour in different scales of testing

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Leaching Behavior of Construction Materials - Concrete

Leached [mg/m2] pH

Leached [mg/kg]

Time [days]

Aluminum release from cement in concrete drinking water pipes

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Aging Effects on Leaching

Chemical factors
Carbonation reaction of alkaline material with atmospheric CO2 to form carbonates, resulting in (i) shift in pH to between 7-9, (ii) respeciation, (iii) change in adsorptive surfaces Acidification reaction with mineral or organic acids to reduce natural pH of the material Oxidation or reduction may cause (i) valence state changes (e.g., Cr6+ to Cr3+), (ii) re-speciation (e.g., sulfide precipitation), (iii) change in adsorptive surfaces (e.g., Fe3+ to Fe2+) Reduction in ionic strength or key species (e.g., Ba) by washout

Physical factors
Formation of surface layers (may cause sealing effects) Formation of cracks, increasing surface area

Heterogeneity results from aging (e.g., surface layers, internal gradients, near field external gradients)
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Carbonation and Matrix Solubility

Portland Cement Matrix

Calcium [mg/L]

Ca

pH

As

Arsenic [mg/L]

pH

Cadmium [mg/L]

Cd

pH

Pb

Lead [mg/L]

pH

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Lead Release
Cumulative release Flux

Cumulative Pb release [g/m2]

Cumulative leaching time [days]

Pb flux [g/m2 s]

Total time [days]

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Arsenic Release
Cumulative release Flux

Cumulative As release [g/m2]

Cumulative leaching time [days]

As flux [g/m2 s]

Total time [days]

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Effects of Dissolved Organic Carbon (DOC)

1000 BA100% BA90% BA99% BA70% BA97% Compost

Cu
100

10

0.1

Binding to particulate organic matter

3 5 7

DOC mobilization

0.01

pH

11

13

Influence of DOC from compost added in different mixing ratios on Cu mobilization in MSWI bottom ash heated at 500 C to remove all residual carbon

Leached mg/kg

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Effects of Reducing Conditions

5 1

Ba

Leached (mg/l)

0.1

0.01

0.001 -200

-100

100

200

300

400

500

600

EH

Ba leaching from steel slag as a function of Eh

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Comparison With Regulations

Leached [mg/kg]

Leached [mg/kg]

RELEVANT pH DOMAIN FOR CONCRETE

pH

pH

Compliance of Portland cement concrete during recycling or end-of-life conditions with the building material decree (BMD)
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Characterization and Compliance Tests

Leached [mg/kg] Leached at LS 10 [mg/kg] Leachability controls Release with time

Hierarchy in Testing

Characterization

pH

LS [L/kg] Own pH LS=10

Compliance

pH

Leached [mg/kg]

Leached at LS 10 [mg/kg]

LS [L/kg]

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Department of Civil and Environmental Engineering

Summary
Measurement of intrinsic leaching parameters allows flexibility in assessment and comparison of materials and scenarios. Equilibrium release as a function of pH, LS and mass transfer rate measurement provide important information. Hierarchal approach allows flexibility in amount of testing needed and effectively uses prior knowledge. Life cycle analysis, including consideration of aging effects, needed when uncontrolled use is considered.

Department of Civil and Environmental Engineering