EPA 600/R-12/704 October 2012 | www.epa.gov/ord
United States
Environmental Protection
Agency
I
sed as a
Supplemental Cementitious Material on the Leaching
Constituents from Cements and Concretes
Office of Research and Development
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EPA-600/R-12/704
October 2012
The Impact of Coal Combustion Fly Ash Used as a Supplemental
Cementitious Material on the Leaching of Constituents from
Cements and Concretes
Hans A. van der Sloot1, David S. Kosson2, Andrew C. Garrabrants2, and Joshua Arnold2
1 Hans van der Sloot Consultancy
1721 BV Langedijk, the Netherlands
2 Vanderbilt University
Civil and Environmental Engineering
Nashville, TN 37235
Category III / Applied Research
EPA Contract No. EP-C-09-027
Work Assignment No. 3-07
Prepared for
Susan A. Thorneloe
U.S. Environmental Protection Agency
Office of Research and Development
National Risk Management Research Laboratory
Air Pollution Prevention and Control Division
Research Triangle Park, NC 27711
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
Acknowledgements
This study was conducted under the United States Environmental Protection Agency (USEPA) Contract
Number EP-C-09-27 coordinated by ARCADIS-US, Inc. (ARCADIS). Partial financial support was provided
by the U.S. Department of Energy, Office of Environmental Management, under Cooperative Agreement
Number DE-FC01-06W07053 entitled "The Consortium for Risk Evaluation with Stakeholder Participation
IN" awarded to Vanderbilt University.
The authors also thank Tim Taylor (USEPA Office of Resource Conservation and Recovery), Susan
Thorneloe and Nick Hutson (USEPA Office of Air Quality, Planning, and Standards)) as well as Peter
Kariher (ARCADIS) for their guidance and contributions during the development of this report.
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
Abstract
Using available data from Europe and the United States (US), this report compares the leaching of
Portland cement-based materials that have been prepared with and without coal combustion fly ash.
The objective of this report is to illustrate whether there is evidence based on existing data that the use
of fly ash in cement and concrete products may result in increased leaching of constituents of potential
concern (COPCs) compared to cement and concrete products that do not contain fly ash. Results of pH
dependent leaching and cumulative release from monolith leaching, as described in the Leaching
Environmental Assessment Framework (LEAF) are used for the evaluation. LEAF data is also compared
with relevant single point leaching test data.
The available data suggest that the use of coal combustion fly ash in cement materials, for different
combinations of fly ash source and usage rates, will not increase leaching of some constituents to levels
greater than typical ranges for cement materials not containing fly ash. However, there are data
limitations that preclude making broad-based claims for some usage rates and fly ashes including those
resulting from changes in air pollution control at coal-fired power plants. Based on available data (31
cement mortar and concrete samples containing coal fly ash in comparison to 21 cement and mortar
samples that did not contain coal fly ash), results indicate that some (and probably a large portion) of
coal fly ashes currently being produced can be used in cement and concrete formulations without
causing greater leaching of COPCs than observed from analogous cement materials not containing fly
ash and without causing adverse environmental impacts. The range of fly ash sources and usage rates
for cement materials with pH dependent and monolith leaching test data available is more limited than
the full range of typical fly ash usage rates and typical fly ash leaching behavior. For example, fly ash
substitution rates for cement of up to ca. 45 wt% is typical in US large commercial concrete applications,
while the predominance of materials reported here have ca. 20-35 wt% fly ash substitution. In addition,
the data evaluated in this report does not consider changes in leaching from cement-based materials
that may occur if the characteristics of coal fly ash used in cement-based materials change in response
to changes in air pollution control requirements at coal fired power plants.
The LEAF methodology, specifically including pH dependent and monolith leaching test data as a basis
for evaluation, provides a more robust approach than single point leaching tests for evaluating the
potential environmental impacts from use of coal fly ash in cement and concrete materials because LEAF
considers the likely range of leaching pH over the lifecycle and the physical form of the materials (i.e.,
monolithic). Leaching of individual constituents from cement materials exhibits characteristic
concentration as a function of pH responses. Future work is recommended using the LEAF methodology
to evaluate coal combustion residues (CCRs) that are specifically marketed for use in producing
cementitious materials and reflect changes occurring in air pollution control at coal-fired power plants.
The focus of future work would be to confirm the findings from this report and to identify any materials,
usage rates, or other conditions that might lead to release of COPCs that could be of concern to human
health and the environment. This approach would support continued use of fly ash in cement and
concrete products while ensuring protection of human health and the environment.
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
Executive Summary
The objective of this report is to compare the leaching of portland cement-based materials that have
been prepared with and without coal combustion fly ash to illustrate whether there is evidence that the
use of fly ash in cement and concrete products may result in increased leaching of constituents of
potential concern (COPCs) compared to cement and concrete products that do not contain fly ash. This
report evaluates in a new context the leaching results obtained from studies carried out for other
purposes, and as such, the observations and conclusions of this report should be considered indicative
of performance but not inclusive of the full range of range of possible coal fly ashes used in cement and
concrete, usage rates (fly ash can typically be up to 50 wt% of the dry mixture of cementitious
materials), or leaching performance of the resulting materials.
In summary, the cement mortar and concrete data sets evaluated include the following:
pH dependence leaching test results for 13 cement mortar and concrete samples without fly ash
in the European Union (ED) data set, including one sample from Thailand, compared with 11
cement mortar and concrete samples prepared with fly ash, including one sample from Brazil
and Chile. The specific sources and leaching characteristics (e.g., liquid-solid partitioning as
functions of pH or liquid-to-solid ratio, rates of mass transport) of the fly ash used are unknown.
Mass transfer leaching test results (monolith tests) for 21 cement mortar and concrete samples
without fly ash in the ED data set, including one sample from Thailand, compared with 27
cement mortar and concrete samples prepared with fly ash. The specific sources and leaching
characteristics of the fly ash used are unknown.
pH dependence leaching test (Method 1313) and mass transfer leaching test results (Method
1315) for four cement mortar and concrete samples containing fly ash. The sources and
leaching characteristics of the fly ashes (two types) used are known.
Single extraction leaching test results (either synthetic acid precipitation or deionized water
batch extraction) for one fly ash used at three rates (0- control, 30 and 50 wt% substitution for
Portland cement) and two additional fly ash samples at three usage rates (0 - control, 30 and 60
wt%). The sources of the fly ash are known but the fly ash leaching characteristics under
relevant conditions are not known.
The following types of comparisons are made:
The range of leaching performance for cement mortars and concrete predominantly from the
ED formulated without fly ash is compared to ED cement mortars and concretes formulated
with fly ash (10-30 wt% replacement of cement by fly ash) as a primary constituent. In this
comparison, the leaching characteristics and specific origin (e.g., coal source, facility
configuration, and handling processes) of the fly ash materials are not known although the fly
ash was required to meet specifications according to ED standard EN 197-1. The 90 percent
confidence intervals for observed leaching of constituents are provided for ED cement mortars
IV
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
formulated with fly ash and the analogous mortars and concreted prepared without fly ash.
Release levels are compared with Dutch regulatory criteria for construction products in service
life. The 90 percent confidence intervals for ED cement mortars and concretes formulated with
fly ash were used as the reference basis for comparison with the other (United States and
Canada) data sets because this case represented the greatest number of independent samples.
The range of leaching performance for a series of cement mortar samples prepared using typical
slag cement mixtures using portland cement, slag and fly ash with different amounts of fly ash
(23.5 - 55.8 wt% fly ash in the dry mixture) is compared to leaching from the fly ash used in the
formulations alone. The 90 percent confidence intervals with respect to leaching from the ED
cement mortars formulated with fly ash are included to place these comparisons in context to
the ED dataset. The leaching of the fly ash used in samples from the Cement Barriers
Partnership (CBP), a project supported by the United States Department of Energy (USDOE), is
also compared to leaching of a broader set of fly ash samples.
Leaching performance of a blended cementitious paste representative of
solidification/stabilization (S/S) formulation and the fly ash used in that paste. The 90 percent
confidence intervals from ED cement mortars and concrete formulated with fly ash are included
to place these materials in context to the ED dataset.
Results from testing several mortars using synthetic precipitation leaching procedure (SPLP) or
deionized water are also compared with the 90 percent confidence intervals with respect to
leaching from the ED cement mortars formulated with fly ash. US Environmental Protection
Agency (USEPA) health based numbers (HBNs) are also included in this comparison to put the
data sets in context with environmental risk thresholds.
Testing results from the Leaching Environmental Assessment Framework (LEAF) methods and analogous
ED methods, specifically results from pH dependent and monolith leaching tests, were used as the basis
for evaluation in this report. Leaching test results (pH dependence test and monolith test results) from
31 cement mortar and concrete samples containing coal fly ash are compared to leaching test results
from 21 cement mortar and concrete samples that did not contain coal fly ash. In addition, results from
testing of cement mortars and concrete samples using the Synthetic Precipitation Leaching Procedure
(SPLP) and deionized water are compared with the broader set of results and HBNs.
Based on the evaluation of available data for the leaching of cement mortars and concrete with and
without partial replacement of cement with coal combustion fly ash, the following observations can be
made:
The leaching behavior of individual constituents from cement mortars and concrete made with
coal fly ash exhibits characteristic leaching behavior (e.g., the shape and general order of
magnitude of the LSP curve is "systematic" for each COPC regardless of the details of the
material) as a function of pH responses that are controlled by the cement chemistry.
When leaching is compared between cement mortars and concrete with and without coal fly
ash, cement mortars and concrete containing fly ash had somewhat higher upper bounds for the
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
ranges of leached concentrations for barium, cobalt, copper, molybdenum, phosphorus,
antimony, silicon (at pH>6) and vanadium (at 4
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
large portion) of coal fly ashes can be used in cement and concrete formulations without causing a
greater range in leaching of COPCs than observed from analogous cement materials not containing fly
ash and without causing adverse environmental impacts. The range of fly ash sources and usage rates
for cement materials with pH dependent and monolith leaching test data available is more limited than
the full range of typical fly ash usage rates and typical fly ash leaching behavior (i.e., leaching of the fly
ash is unknown for most cases evaluated here and fly ash leaching of constituents of potential concern
has been demonstrated to vary over up to four orders of magnitude in concentration). In addition,
while the data are indicative of expected leaching behavior for fly ashes currently being produced, the
data evaluated in this report does not consider changes in leaching from cement-based materials that
may occur if the characteristics of coal fly ash used in cement-based materials change in response to
recent changes in air pollution control requirements for coal fired power plants. To the extent that such
changes affect the fly ash characteristics, the available data sets do not allow evaluation of the impacts
of the following potential changes to air pollution controls at coal fired power plants: (i) addition of
activated carbon or halogenated activated carbon, (ii) a shift in the coal types burned or blends thereof
to achieve new air pollution control limits, (iii) presence or increase in ammonia in the ash because of
excess ammonia injected as part of SCR NOx controls, and (iv) the inclusion of sorbent from use of dry
sorbent injection systems (i.e., trona (sodium sesquicarbonate), sodium carbonate or hydrated lime).
This study should be viewed as the beginning of a collection of robust leaching characterizations for fly
ash and fly ash amended cementitious materials, high fly ash replacement materials such as
solidification/stabilization formulations, and other utilization applications. It is prudent to develop a
characterization and quality control program to determine which combinations of fly ash and cement
formulations have leaching characteristics within the typical range for cement materials without fly ash.
Furthermore, without comparison to risk-informed criteria, potential increases in leaching of some
COPCs, demonstrated through direct comparisons between materials with and without fly ash, does not
indicate that the use of fly ash as a supplemental cementitious material will result in adverse impacts to
human health or the environment. Thus, the approach taken in this report should be used to develop
an evaluation basis (e.g., thresholds, regulatory guidance structure, and quality control program) for the
acceptability of leaching characteristics greater than the typical range for cement-based materials
without fly ash. The systematic behavior of COPC leaching from cement materials produced using fly
ash will allow determination of the general coal sources and coal combustion facility configurations that
result in ash that is acceptable for use at intermediate or high usage rates (i.e., 10-30 wt% or up to 50%
of the cement dry mixture), and reduce the extent of needed quality control testing.
VII
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
Table of Contents
Acknowledgements ii
Abstract iii
Executive Summary iv
Table of Contents viii
List of Figures x
List of Tables x
Acronyms and Abbreviations xi
Introduction 1
Approach 2
pH-Dependent Leaching Tests 3
Single Extraction Leaching Tests 4
Data Sources and Materials Evaluated 5
European Mortar and Concrete Samples 5
US Fly Ash, Mortar and Concrete Samples (CBP) 6
Cement Admixture Paste Samples 6
Concrete Pavement Study (Cheng et al., 2008) 7
Concrete Prepared with Canadian Fly Ash (Zhang et al., 2001) 7
Limitations of the Data Sources and Materials Evaluated 8
Quality Assurance and Quality Control 8
Data Management Using LeachXS 9
Results and Discussion 10
Comparison of CEM I and CEM II/B-V Cement Mortars (EU data) 10
Comparison of CBP Cement Grout, Mortar and Concrete with Fly Ash (US data) 15
Comparison of Cement Admixture Paste Containing Fly Ash 15
Comparison of Studied Fly Ash Samples with Other Fly Ash Characterization 16
Comparison of Single Extraction Leaching Test Results (US and Canadian data) with pH Dependence
Leaching Test Results and Health Based Numbers 16
Conclusions 22
References 24
Appendices
VIM
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
Appendix A. pH Dependent Leaching of ED Cement Mortars: CEM I (without fly ash) and CEM
II/B-V (with fly ash) 28
Appendix B. Comparisons of Leaching Results and Statistics (i.e., Median and Maximum
Values) for pH-Dependent Leaching from Cements and Concretes with and
without Fly Ash 36
Appendix C. Cumulative Release from Monolith Leaching of ED Cement Mortars and
Concretes: CEM I (without fly ash) and CEM II/B-V (with fly ash) 41
Appendix D. Approach for Criteria Development for Monolithic Materials in the Dutch Soil
Quality Decree (2007) 52
Appendix E. Effect of Carbonation on Monolith Leaching of ED Cement Mortars: CEM I
(without fly ash) and CEM II/B-V (with fly ash) 55
Appendix F. pH Dependent Leaching of CBP Cement Mortars and Concrete Containing Fly Ash 59
Appendix G. Cumulative Release from Monolith Leaching of CBP Cement Mortars Containing
Fly Ash 63
Appendix H. pH Dependent Leaching of a Fly Ash (CFA2) and a Fly Ash-Containing Cement
Mortar (MBD2) 67
Appendix I. Cumulative Release fom Monolith Leaching of a Fly Ash-Containing Cement
Mortar (MBD2) 70
Appendix J. pH Dependent Leaching of Fly Ash Samples (FAF and CFA2) Compared to the
Range of USEPA Fly Ash Leaching Data 74
Appendix K. pH Dependent Leaching of ED CEM II/V-B and Single Extraction Leaching Results
(Cheng et al., 2008 and Zhang et al., 2001) Compared to the USEPA Health-based
Numbers 57
IX
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
List of Figures
Figure 1. pH-dependent leaching test results for arsenic, boron, chromium and molybdenum from ED
mortar samples of CEM I (Portland-without fly ash; left side graphs) and CEM II/B-V (P+CFA -
with fly ash; right side graphs). Dashed lines indicate mean and 90% confidence intervals. A
sample legend is provided in Appendix A 11
Figure 2. Mass transfer testing results for cumulative release of arsenic, boron, chromium and
molybdenum from ED mortar samples of CEM I (Portland-without fly ash; left side graphs) and
CEM II/B-V (P+CFA - with fly ash; right side graphs). Grey data represent concretes (vs.
mortars) with fly ash replacement. Dashed lines indicate mean and 90% confidence intervals.
Horizontal solid line represents the Dutch regulatory criterion for unrestricted use of
construction products. A sample legend is provided in Appendix C 12
Figure 3. Annotated graph showing leaching data relative to health based numbers (HBNs) over a
relevant pH range for cementitious materials 17
Figure 4. Statistical representation (mean with 90% confidence limits) of concentrations of the ED CEM
II/V-B cement mortars and concretes containing fly ash and literature single extraction test
results (Cheng et al., 2008; Zhang et al., 2001) compared to health based numbers (HBNs) over
a relevant pH range of 7 to 13 19
Figure 5. Statistical representation (mean with 90% confidence limits) of concentrations of the ED CEM
II/V-B cement mortars and concretes containing fly ash and literature single extraction test
results (Cheng et al., 2008; Zhang et al., 2001) compared to health based numbers (HBNs) over
a relevant pH range of 7 to 13 20
List of Tables
Table 1. Component Compositions for CBP Mortars and Concrete samples 6
Table 2. Component Compositions for Concrete Pavements (Cheng et al., 2008) 7
Table 3. Component Compositions for Concrete Samples (Zhang et al., 2001) 8
Table 4. Comparison of Release from CEM I and CEM MB Mortars and Concretes with Dutch Regulatory
Criteria 14
Table 5. Comparisons of the ratio of the maximum value of the 90 percent confidence interval to the
HBN (Max/HBN) and the maximum value of the mean values to the HBN (Mean/HBN) 21
Table C-l Maximum permissible addition value for soil (MPAS) and groundwater (MPAg) used in the
derivation of emission limits for granular construction products in the Dutch Soil Quality
Decree 52
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
Acronyms and Abbreviations
BGM backfill grout mortar
BMD Building Materials Decree (Dutch regulation)
CBP Cementitious Barriers Partnership
CCR(s) coal combustion residue(s)
CEN Comite Europeen de Normalisation (European Standardization
Committee; http://www.cen.eu)
COPC(s) constituent of potential concern
ED European Union
HBN health based numbers (USEPA)
L/A liquid-to-surface area ratio
LEAF Leaching Environmental Assessment Framework
L/S liquid-to-solid ratio
LSP liquid-solid partitioning
MBD2 material blank in deionized water (second of two materials)
MPA maximum permissible addition (Dutch SQD criteria)
MPC maximum permissible concentration (Dutch SQD criteria)
NEN Nederlands Normalisatie Instituut (Dutch Standardization Institute)
RvA Raad voor Accreditatie (Dutch Accreditation Council; http://www.rva.nl)
SCM(s) supplemental Cementitious material(s)
SPLP Synthetic Precipitation Leaching Procedure (USEPA, SW-846 Method 1312)
SQD Soil Quality Decree (revision to Dutch BMD)
S/S solidification/stabilization
SVC structural vault concrete analogous mortar
TCLP Toxicity Characteristic Leaching Procedure (USEPA, SW-846 Method 1311)
VCT vault concrete
USDOE United States Department of Energy
USEPA United States Environmental Protection Agency
XI
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
Introduction
The potential environmental impacts of disposal and beneficial use of coal combustion residues (CCRs)
have recently come under increased scrutiny. The United States Environmental Protection Agency
(USEPA) has proposed alternatives for regulating management of coal fly ash (75 Federal Register
35127). In 2010, 26 of the 68 million tons of coal combustion fly ash produced in the US were used in
commercial applications (ACAA, 2012). Approximately 11 million short tons were used as supplemental
cementitious materials (SCMs), replacing a portion of portland cement powder used in concrete,
concrete products and grout. Other large volume uses of coal fly ash in the US include use as raw feed
for cement production (2.0 million tons), placement in structural fill and embankments (4.7 million
tons), various mining applications (2.4 million tons), and as a matrix component in waste
solidification/stabilization (3.3 million tons). These uses are considered beneficial because addition of
fly ash to cement-based materials (i) improves the physical and durability characteristics, (ii) conserves
landfill space by utilizing otherwise disposed materials, and (iii) reduces the need for and environmental
impacts associated with processing new raw materials. However, default use of CCRs as SCMs without
the consideration of resulting environmental impact potentially may lead to adverse impacts to soil or
groundwater and surface waters. Thus, in the case of CCRs used within the cement industry, there is a
need for evaluation of both the potential environmental impacts from use of coal fly ash in cement and
cement products, as well as potential impacts from disruption to the availability of coal fly ash for
commercial use in these materials. Leaching is considered a primary pathway for environmental impact
of cement products containing coal fly ash through the release of constituents of potential concern
(COPCs) to soils and runoff that can impact surface water or groundwater.
The objective of this report is to compare the leaching of portland cement-based materials that have
been prepared with and without coal combustion fly ash to illustrate whether there is evidence that the
use of fly ash in cement and concrete products may result in increased leaching of COPCs compared to
cement and concrete products that do not contain fly ash. A subsidiary objective is to determine if there
is evidence that incorporation into cement materials increases the leaching of COPCs from fly ash,
thereby potentially increasing COPC release from fly ash through the use in cement and concrete. The
following types of comparisons are made in the report:
The range of leaching performance for cement mortars from the European Union (EU)
formulated without fly ash is compared to EU cement mortars and concretes formulated with fly
ash as a primary constituent. In this comparison, the leaching characteristics and specific origin
(e.g., coal source, facility configuration, and handling processes) of the fly ash materials are not
known although the fly ash was required to meet specifications according to EU standard EN
197-1.1 Test data are compared with Dutch regulatory criteria for construction products in
service life.
1 EN 197-1 specifies physical properties of suitable fly ash and major chemical constituents (i.e., calcium, silica, iron) but does
not contain specifications regarding constituents of potential concern from an environmental perspective.
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
The range of leaching performance for a series of US cement mortar samples with different
amounts of fly ash, taken from the Cementitious Barriers Partnership (CBP),2 is compared to
leaching from samples of the component fly ash material used in the mortar formulations. In
addition, the 90 percent confidence intervals with respect to leaching from the ED cement
mortars containing fly ash are included in this comparison to place the results into context with
the EU dataset.
Leaching performance of a blended Cementitious paste representative of solidification/
stabilization (S/S) formulation and the fly ash used in that paste. The 90 percent confidence
intervals from EU cement mortars with fly ash substitution are included to place these materials
in context to the EU dataset.
Leaching evaluation using single extraction leaching tests in comparison to results from multi-
extraction pH dependence granular batch testing and monolith testing. Single extraction and pH
dependence leaching test results are also compared to USEPA health based numbers (HBNs).
This report evaluates the results obtained from studies carried out for other purposes in a new context,
and as such the observations and conclusions of this report should be considered indicative of
performance but not inclusive or necessarily representative of the full range of possible coal fly ashes
used in cement and concrete or leaching performance of the resulting materials.
Approach
Traditionally, the results of one or more leaching tests have been used to estimate the leaching
potential of waste or other materials in situations where the material is placed in a landfill or used on
the land. The goal of leach testing has been to assess potential contaminant release and the likelihood
of soil, surface water or groundwater contamination resulting from specific management scenarios for
wastes and other materials. The current regulatory leaching tests in the US are single-batch extraction
procedures designed to simulate leaching under conditions considered to represent a plausible
"mismanagement" scenario for a hazardous waste disposed in a municipal waste landfill. These tests
were not specifically designed to address potential beneficial use applications such as fly ash use in
cements and concretes.
The Leaching Environmental Assessment Framework (LEAF) is an environmental assessment
methodology consisting of a set of leaching test methods, scenario-based leaching assessment models,
and information management tools designed to provide more robust estimates of constituent leaching
under a wider range of potential field conditions than current approaches based on single-extraction
tests. The methodology for leaching assessment using LEAF is based on a tiered testing approach
(Kosson et al., 2002). As opposed to the scenario simulation tests currently in wide use, the LEAF
leaching methods are intended to generate characteristic leaching behavior data for a material over a
2 The Cementitious Barrier Partnership is a research program supported by the Office of Environmental Management at the US
Department of Energy. The project is aimed at improving the prediction of performance of Cementitious materials used in
nuclear processing and waste management applications (see www.CementBarriers.org for more information and reports
prepared under this program).
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
broad range of test conditions designed to encompass the range of plausible conditions for actual
management. The resulting data can be applied to assess leaching potential under anticipated field
conditions for one or more management scenarios. For evaluation of cements and concretes containing
fly ash, batch pH dependence and monolith mass transfer leaching tests are the most appropriate
because they account for range of potential leaching pH during the material's lifecycle and the physical
form of the material. The LEAF approach has been developed in close coordination with ED efforts to
adopt a similar set of test methods in Europe through the European Standardization Committee (Comite
Europeen de Normalisation; CEN).
Several research studies have used the LEAF test methods or the European counterparts to characterize
leaching from portland cement-based materials and from the components used in the material
formulation. Within these studies, the primary fundamental leaching characteristics for cement-based
materials have been (i) leaching as a function of pH as the result of Method 1313, CEN/TS 14429 or
CEN/TS 14497 and (ii) monolithic mass-transfer rate leaching using Method 1315, NEN 7345, CEN/TC
351 TS-2 or CEN/TS 15863, often referred to as "diffusion testing" or "tank leaching tests." In all cases,
eluates produced from the leaching tests were analyzed by inductively coupled plasma optical emission
spectroscopy or inductively coupled plasma mass spectroscopy to measure concentrations of leached
constituents. These leached concentrations, or derived measurements such as cumulative release, are
then used in the data analysis presented in this report. In addition, test results from two studies using
single point leaching tests (i.e., the Synthetic Precipitation Leaching Procedure (SPLP, USEPA Method
1312) and deionized water leaching (ASTM D3987-85) are compared to results from the multipoint pH
dependence leaching tests.
pH-Dependent Leaching Tests
Method 1313 is an equilibrium-based leaching test designed to provide aqueous extracts representing
the liquid-solid partitioning (LSP) curve of constituents as a function of eluate pH value. This procedure
consists of nine parallel batch extractions at targeted pH values and one extraction at the natural pH3 of
the material. The solid material may require particle size reduction by crushing in order to facilitate the
approach to solid-liquid equilibrium within a reasonable extraction timeframe. Dilute acid or base in
deionized water is added to each extraction according to a pre-test titration in order to achieve final
extract pH values at specified target values ranging between 2 and 13 at a liquid-to-solid ratio (L/S) of 10
mL/g-dry after 24 hours4. The pH and conductivity of the final extract solution are recorded and
vacuum- or pressure-assisted filtration is used to separate the liquid and solid phases prior to chemical
analysis of the eluate. Eluate concentrations for constituents of interest are plotted as a function of
eluate pH allowing for comparison to quality control and assessment limits.
The European pH-dependence methods, CEN/TS 14429 (2005) and CEN/TS 14497 (2005), are similar to
Method 1313 in both test structure and intent with directly comparable results (Garrabrants et al.,
3 The natural pH (also referred to as "own pH") is the final eluate pH response of a deionized water extraction of a solid material
|i.e., no acid or base added) conducted at an L/S 10 mL/g-dry.
1 24 hours is the specified extract
are specified for larger particles.
4 24 hours is the specified extract time for materials size reduced to a particle size of less than 300 |am. Longer extraction times
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
2012a). In the CEN methods, separate sample portions are extracted in parallel in dilute acid or base
solutions in order to reach stationary pH values at the end of the extraction period at a fixed L/S of 10
mL/g. At least eight final pH values are required, covering at a minimum the range from pH 4 to pH 12
(including the lowest value pH < 4 and the highest value pH > 12). The maximum pH differential
between final pH points shall not exceed 1.5 pH units. The primary difference between these two
methods is how the extraction solution is introduced to the test portion. For CEN/TS 14429, sample
portions are contacted with extraction solutions in a closed vessel with acid/base introduction through
initial addition of extraction fluid. At the start of the test, the extraction solutions are prepared and
divided evenly into three fractions. A fraction of extraction solution is added to the extraction bottle at
the start of the test, after 30 minutes, and after 2 hours. For CEN/TS 14497, sample portions are placed
into a partially open vessel with reagent water and acid or base is introduced via automated pH control.
Monolithic Mass Transfer Rate Leaching Tests
Method 1315 involves leaching of a continuously water-saturated monolithic or compacted granular
material in a water-filled tank with periodic renewal of the leaching solution. The vessel and sample
dimensions are chosen so that the sample is fully immersed in the leaching solution. Samples are
contacted with reagent water at a liquid-to-surface area ratio (L/A) of 9 ฑ 1 mL/cm2 sample surface area.
The leaching solution is exchanged with fresh reagent water at nine pre-determined intervals over a
cumulative period of 63 days. For the CBP samples, leaching with periodic leachant renewals was
extended to a cumulative period of 231 days. The eluate pH and specific conductance is measured for
each time interval and analytical samples are collected and preserved based on the determinative
methods to be performed. These data are used to estimate release rate and mass transfer parameters
(i.e., observed diffusivity) for each constituent of interest. For the comparative purposes of this report,
cumulative release as a function of time is plotted for each constituent of interest.
Determination of constituent release and mass transfer rates from monolithic materials was performed
according to NEN 7345 (1994), CEN/TC 351 TS-2 (2009) or CEN/TS 15863 (2009) for EU mortar and
concrete samples. These methods are very similar in approach and operation to Method 1315. The
differences between the test methods include minor differences in details, such as the specified L/A
ratio, the number of leaching cycles and the times of leachant renewal, which are not considered critical
for determining rates of cumulative release (Garrabrants et al., 2012b).
Single Extraction Leaching Tests
SPLP (USEPA SW-846 Method 1312; USEPA 1992b) is a single batch extraction carried out with synthetic
acidic precipitation at a liquid/solid ratio of 20 mL/g and a contacting extraction period of 18ฑ2 hours.
Testing carried out by Cheng et al (2008) used SPLP Extraction Fluid 1 which is specified as a 60/40
weight percent mixture of sulfuric and nitric acids added to reagent water to attain a pH of 4.20 ฑ 0.05.
The pH of the resulting eluate is measured at the time of eluate filtering and influenced by the
composition of the material extracted. For cementitious materials, the eluate pH is expected to be
alkaline. ASTM International D3897-85 (ASTM 1990), also used by Cheng et al (2008), is similar to SPLP
but is carried out using deionized water as the extraction fluid.
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
Zang et al (2001) carried out single batch extractions of 10.2 cm diameter by 2.0 cm thick disks cut from
Portland cement cylinders (see following section). Each disk was submerged in a synthetic acid
precipitation prepared similarly to the SPLP Extraction Fluid 1 but adjusted to a pH of 4.5. Each sample
was submerged in the extraction fluid at a liquid to solid ratio of 5 mL/g for up twenty-four weeks. The
extraction fluid was sub-sampled and analyzed at 6 time periods, with results reported for extractions
after 20 weeks of contact for cadmium, chromium, copper, iron, nickel, lead, selenium and zinc. Results
from extraction after 24 weeks of contact were reported for arsenic.
Results from the above studies that used the Toxicity Characteristic Leaching Procedure (TCLP; USEPA
SW-846 Method 1311; USEPA, 2012a) or other extractions with acetic acid under different conditions
were not included in this evaluation because (i) acetic acid is used to mimic co-disposal with municipal
solid waste, which is not the management scenario being considered here, and (ii) acetic acid can result
in complexation and therefore increased concentrations of some COPCs (i.e., lead) in resulting extracts
which is not considered relevant.
Data Sources and Materials Evaluated
European Mortar and Concrete Samples
A series of standard mortar samples, prepared using Type I (CEM I) portland cements according to the
European cement standard EN 197-1 manufactured predominately at several European facilities, were
characterized using pH-dependent leaching tests (CEN/TS 14429 or CEN/TS 14497) and mass transfer
leaching tests (CEN/TC 351TS-2 or CEN/TS 15863). Standard mortar samples were prepared using 22
wt% cement, 68 wt% sand and 11 wt% water (water-to-binder ratio of 0.50) in accordance with the
European standard EN 196-1 (2005). Mortar samples for leaching evaluation were removed from molds
after curing for 24 hours and cured at 20 ^C and 95% relative humidity for an additional 27 days in
plastic bags. The comparison set of mortars which include fly ash were prepared in a similar manner
using CEM II/B-V cements, which are blended cements containing 21-35% fly ash substituted for cement
powder (van der Sloot, 2000; van der Sloot et al., 2001a; van der Sloot et al., 2008a).
In order to illustrate the range of cumulative release for constituents in concretes as well as the above
cement mortars, leaching test data for concrete 15-cm cubic samples from Dutch national studies also
have been included in the evaluation of the ED CEM II/B-V mortar samples.5 Test results were taken
from studies evaluating fly ash replacement in mortar and concrete using worldwide sub-bituminous
coal sources in the range of 10-30% replacement (van der Sloot et al., 1985; van der Sloot and Weijers,
1987). In addition, test results on uncarbonated and carbonated mortars (with and without fly ash)
were taken from a study evaluating the effect of carbonation of concrete samples with 20% cement
replacement by coal fly ash on leaching conducted for a Dutch cement producer (ECN, 2000). The
effects of carbonation are considered relevant because carbonation through reaction of alkali in cement
with atmospheric carbon dioxide is a primary aging mechanism for cementitious materials that can
5 Often, mortars are used instead of concrete to assess leaching during laboratory testing. This approach assumes that the
coarse aggregate present in the concrete but not used in the mortar is chemically inert. However, no studies have been
identified that provide a direct comparison of the leaching performance for mortars and concretes that have the same
formulation except for the presence of the coarse aggregate.
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
change both the chemical (i.e., decreasing pH and changing chemical speciation) and physical properties
(i.e., change in porosity and pore structure) of the material.
US Fly Ash, Mortar and Concrete Samples (CBP)
Leaching behaviors of three cementitious reference mortars containing a well-characterized fly ash
(sample FAF) have been studied as part of the Cementitious Barriers Partnership (Arnold et al., 2011).
The mortar formulations include a flowable stable (zero-bleed) infill/backfill grout (material code BGM),
a structural vault concrete-analogous mortar (material code SVC), and a vault concrete (material code
VCT). The binders used in these materials include ternary blends (Type l/ll cement, blast furnace slag
and Class F fly ash) for BGM and SVC and a quaternary blend (Type V sulfate-resistant cement, blast
furnace slag, Class F fly ash binder, silica fume) for VCT. Formulations for each of the sample types are
provided in Table 1.
In addition to characterization of the blended materials, leaching tests were performed on the
component source materials including ground granulated blast furnace slag, coal combustion fly ash
(material code FAF), quartz concrete sand, and Type l/ll portland cement powder.
Table 1. Component Compositions for CBP Mortars and Concrete samples.
Component
Type l/ll Cement (ASTM C 150)
Type V Cement
Grade 100 Blast Furnace Slag (ASTM C 989)
Type F Fly Ash (ASTM C 618)
Silica Fume
Water (maximum)
Quartz Sand (ASTM C 33)
No. 67 Granite Aggregate (ASTM C 33)
Fly ash in cementitious dry mixture
BGM
(wt%)
5.9
-
13.5
6.6
-
11.8
62.3
-
25.3
SVC
(wt%)
5.4
-
8.0
16.9
-
14.6
55.0
-
55.8
VCT
(wt%)
-
5.5
7.3
4.3
1.2
6.9
24.7
50.1
23.5
Notes:
BGM = backfill grout mortar
SVC = structure vault concrete analogous mortar
VCT = vault concrete
Cement Admixture Paste Samples
A study of solidification/stabilization (S/S) of a reference waste stream from nuclear waste treatment
was carried out which included leaching characterization of a fly ash (sample CFA2) and a matrix blank
(sample MBD2) consisting of a Portland cement paste containing the same fly ash (Garrabrants et al.,
2008). The MBD2 consists of a tertiary binder of fly ash, steel slag and Portland cement with a final
water-to-binder ratio of 0.4, resulting in a final composition of 28 wt% fly ash, 28 wt% slag, 5 wt%
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
cement and 40 wt% water (45.9 wt% fly ash in the cementitious dry mixture). The MBD2 samples were
cured at least 30 days in sealed containers prior to leach testing. Characterization included pH-
dependent leaching and monolith leaching according to methods SR02.1 and MT01, respectively, which
are predecessors to Method 1313 and Method 1315 (Kosson et al., 2002). In this study, a cement mix
not containing fly ash was not characterized separately, so the only comparison that can be made is
between fly ash leaching and the leaching of the cementitious material containing the same fly ash.
Concrete Pavement Study (Cheng et al, 2008)
Cheng et al. (2008) carried out a study examining the leaching of simulated concrete pavements
prepared with and without coal fly ash. A Class F fly ash obtained from a power plant located in Ohio
(US) was used in the concrete preparation at 0, 30 and 50 wt% of the dry cement material mixture
(Table 2). Samples of each concrete mix were cured for four weeks prior to leaching evaluation using
SPLP and ASTM D3897 (deionized water extraction). However, separate leaching analysis of the fly ash
using either test was not reported. Runoff samples were also collected from the simulated pavement
after intervals of cyclic loading intended to simulate traffic on the pavement.
Table 2. Component Compositions for Concrete Pavements (Cheng et al., 2008).
^^H^^^^^l
Type l/ll Cement
Type F Fly Ash (ASTM C 618)
Water (maximum)
Sand
No. 57 Aggregate
Fly ash in cementitious dry mixture
PC
(wt%)
16.2
-
6.0
31.2
46.6
-
PC30
(wt%)
11.4
4.8
6.0
31.2
46.6
30
PC50
(wt%)
8.1
8.1
6.0
31.2
46.6
50
Concrete Prepared with Canadian Fly Ash (Zhang et al., 2001)
Zhang et al (2001) carried out a study examining the leaching of concrete samples prepared using ASTM
Class F coal fly ash obtained from two Canadian sources: Lingan, Nova Scotia (burning bituminous coal)
and Forestburg, Alberta (burning sub-bituminous coal). Concrete samples were prepared using Lingan
fly ash as 30 and 60 wt% of the dry cement material mixture and with Forestburg fly ash as 30 wt% of
the dry cement material mixture (Table 3). Multiple water-to-cement (w/c) ratios were used in the
concrete mixes. A control concrete that did not contain fly ash also was evaluated. Concrete mixes
were cured for 28 days prior to leaching evaluation using concrete disks submerged in synthetic acid
precipitation for up to 24 weeks as described earlier.
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
Table 3. Component Compositions for Concrete Samples (Zhang et al., 2001).
Sample
Component
Type 1 Cement
Fly Ash
Water
Sand
Coarse Aggregate
Fly ash in cementitious dry mixture
Fly ash source
Water/(cement+fly ash) ratio
TO
(wt%)
13.6
0.0
6.8
31.7
47.9
0
-
0.5
T2
(wt%)
9.7
4.2
6.9
31.5
47.7
30
Lingan
0.5
T5
(wt%)
9.9
4.2
7.1
31.4
47.5
30
Forestburg
0.5
T14
(wt%)
5.6
8.3
7.0
31.7
47.5
60
Lingan
0.5
T15
(wt%)
12.1
5.2
6.9
30.3
45.5
30
Lingan
0.4
T17
(wt%)
6.9
3.0
6.9
33.2
49.9
30
Lingan
0.7
Limitations of the Data Sources and Materials Evaluated
The following are key limitations of the data sources and materials evaluated in this report:
The EU mortar and concrete samples were prepared using pre-packaged blended cement
formulations, and therefore the source and leaching characteristics of the fly ash used in these
materials are unknown. Thus, it is unknown whether the fly ash materials used had high,
medium or low leaching with respect to COPCs. However, fly ash used in CEM II/B-V cements
must conform to EU standard EN 197-1, which specifies physical properties, loss on ignition,
chloride content and reactive calcium content but does not consider constituents typically of
environmental concern.
The US mortar and concrete samples (CBP samples and MBD2) were prepared with additional
admixtures, including reducing materials (e.g., blast furnace slag or steel slag) which can impact
the leaching chemistry for several constituents.
The studies by Cheng et al. (2008) and Zhang et al. (2001) did not include relevant separate
leaching characterization of the fly ash and only limited (e.g., single point) leaching of the
resulting cement and concrete materials.
None of the studies examined included a representative comparison of (i) the range of fly ash
types with COPC leaching that typifies the ranges of leaching observed for US fly ash sources, (ii)
the effect of fly ash loading up to typical high loading rates in US commercial concretes (e.g., ca.
45 wt% fly ash substitution for cement), including comparison using the same components
without fly ash, (iii) the effect of material aging, including extended cure times and carbonation,
on COPC leaching, (iv) the impact of using mortar samples as surrogates for testing concrete.
Quality Assurance and Quality Control
Two laboratories, Vanderbilt University (VU) and The Energy Research Centre of The Netherlands (ECN)
were responsible for the leaching characterization of fly ash, cement mortars and concrete discussed in
this report. VU carried out the leaching characterization of CBP fly ash, mortar and concrete samples, as
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
well as the cement admixture paste sample (MBD2) as part of research on behalf of the Department of
Energy, Office of Environmental Management. At VU, leaching procedures and chemical analyses were
carried out under the same quality assurance and quality control procedures specified in the Quality
Assurance Project Plan for characterization of coal combustion residues for research carried out on
behalf of USEPA (USEPA, 2011).
ECN carried out all leaching characterization of European cement and concrete samples included in this
report. ECN has for more than two decades been a national and international leader in developing and
carrying out leaching characterization methods. Since 1983, ECN has been actively involved in the
development of leaching tests in support of national (The Netherlands) and European legislation (European
Landfill Directive, 2002; Requirement 3 on Health and Environment in the Construction Products Directive,
1989; End of Waste Directive; in development) through chairmanship of working groups in the national
standardisation body (Nederlands Normalisatie Instituut, NEN) and the European standardisation
organisation CEN. ECN is a qualified laboratory for chemical analysis and for leaching tests under the quality
assurance program RvA (Raad voor de Accreditatie) with annual external independent audits on the basis
of NEN-EN-ISO 17025. ECN operates under ISO 9000 practice. ECN has participated in many
interlaboratory comparison (round-robin) studies for leaching characterization methods which has
demonstrated its proficiency (van der Sloot et al., 1994, 1995, 2001b; Hohberg et al., 2000; de Groot et
al., 1996). ECN also participated in a recently completed interlaboratory comparison study for Method
1313: Liquid-Solid Partitioning as a Function of Eluate pH using a Parallel Batch Extraction Procedure that
demonstrated ECN's proficiency in leaching characterization as well as the comparability of results
between USEPA Method 1313 and the European pH-dependence methods, CEN/TS 14429 and CEN/TS
14497 (Garrabrants et al., 2011).
Specific quality assurance and quality control programs were not reported for Cheng et al (2008) or
Zhang etal. (2001).
Data Management Using LeachXS
Comparisons of leaching test results and statistical representations of leaching behavior were managed
using LeachXS6, a program designed specifically to facilitate data management, visualization, and
modeling for the large volume of data resulting from robust leaching characterization (van der Sloot et
al., 2008b). From the previous studies, the leaching data had been stored in materials databases within
LeachXS. Materials were combined into a single materials database, allowing for statistical calculations
and comparisons of leaching data. LeachXS contains graphic and report facilitation tools allowing for all
comparisons to be output as graphs into Microsoftฎ Excel spreadsheets.
6 LeachXS is the full-feature version of LeachXS Lite used in recent EPA fly ash characterization research (Kosson et al., 2009) for
data management and visualization developed by ECN, Vanderbilt University and DHI (Denmark). The Lite version is freely
available for download (free license registration required) at http://vanderbilt.edu/leaching/downloads/leachxs-lite.
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
Results and Discussion
In summary, the cement mortar and concrete data sets evaluated include the following:
pH dependence leaching test (CEN/TS 14429 or CEN/TS 14997) results for 13 cement mortar and
concrete samples without fly ash in the ED data set, including one sample from Thailand,
compared with 11 cement mortar and concrete samples prepared with fly ash, including one
sample from Brazil and Chile. The specific sources and leaching characteristics of the fly ash
used are unknown.
Monolith mass transfer leaching test results (CEN/TC 351 TS-2 or CEN/TS 15863) for 21 cement
mortar and concrete samples without fly ash in the ED data set, including one sample from
Thailand, compared with 27 cement mortar and concrete samples prepared with fly ash. The
specific sources and leaching characteristics of the fly ash used are unknown.
pH dependence leaching test (Method 1313) and mass transfer leaching test results (Method
1315) for four cement mortar and concrete samples containing fly ash. The sources and
leaching characteristics of the fly ashes (two types) used are known.
Single extraction leaching test results (either synthetic acid precipitation or deionized water
batch extraction) for one fly ash used at three rates (0 -control, 30 and 50 wt% substitution for
Portland cement) and two additional fly ash samples at three usage rates (0 - control, 30 and 60
wt%). The sources of the fly ash are known but the fly ash leaching characteristics under
relevant conditions are not known.
Comparison of GEM I and GEM II/B-V Cement Mortars [EU data]
Figures 1 and 2 provide comparisons of leaching from CEM I and CEM II/B-V standard mortars for
arsenic, boron, chromium and molybdenum based on pH dependent leaching and monolith leaching,
respectively. Complete results of the analyzed constituents from leaching tests are provided for (i) pH-
dependent leaching in Appendix A with further comparative analysis on a percentile bases in Appendix B
and (ii) monolith leaching in Appendix C. For the pH-dependent data, each of the constituents has a
characteristic response of leaching concentration as a function of pH, which is similar for both the
cement materials without and with fly ash. From previous studies (Kosson et al., 2009), it is known that
fly ash from different sources exhibit several different characteristic leaching concentration as a function
of pH responses for each constituent. Thus, cement chemistry appears to control the overall leaching of
COPCs from the concrete and mortar materials.
10
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
Concentration of As as function of pH (Portland)
1
Concentration of As as function of pH (P + CFA)
1
Concentration of B as function of pH
Concentration of B as function of pH
Concentration of Cr as function of pH
100
I
1
M
2
o
u
0.001
0.01
Concentration of Cr as function of pH
100
1
c
o
u
0.001
0.01
10 12 14
Concentration of Mo as function of pH
10 i-
Dl
C
o
u
Concentration of Mo as function of pH
10 -.
Figure 1. pH-dependent leaching test results for arsenic, boron, chromium and molybdenum from EU
mortar samples of CEM I (portland-without fly ash; left side graphs) and GEM II/B-V (P+CFA - with fly ash;
right side graphs). Dashed lines indicate mean and 90% confidence intervals. A sample legend is provided in
Appendix A.
11
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
Cumulative release of As (Portland)
Cumulative release of As (P+CFA)
ฃ
.1
0.1
Time (days)
Cumulative release of B
0.1
Time (days)
Cumulative release of B
0.1
Time (days)
Cumulative release of Cr
0.1 1
Time (days)
Cumulative release of Cr
0.1
Time (days)
Cumulative release of Mo
0.1
Time (days)
Cumulative release of Mo
Time (days)
Time (days)
Figure 2. Mass transfer testing results for cumulative release of arsenic, boron, chromium and molybdenum
from EU mortar samples of GEM I [portland-without fly ash; left side graphs] and GEM II/B-V [P+CFA - with
fly ash; right side graphs]. Grey data represent concretes [vs. mortars] with fly ash replacement. Dashed
lines indicate mean and 90% confidence intervals. Horizontal solid line represents the Dutch regulatory
criterion for unrestricted use of construction products. A sample legend is provided in Appendix C.
12
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
Based on pH dependent leaching test results, there does not appear to be a significant difference in
leaching between the cements with or without fly ash replacement for several constituents including:
aluminum, arsenic, boron, cadmium, potassium, magnesium, manganese, molybdenum, nickel, lead,
sulfur, selenium and zinc. Differences between the cases were considered significant if the upper or
lower bounds of the ranges differed by more than approximately one half an order of magnitude.
Somewhat higher upper bounds for the ranges of leached concentrations from CEM II/B-V mortars
(cement with fly ash replacement) are indicated for barium, cobalt, copper, phosphorus, antimony, silica
(at pH > 6) and vanadium (at 4 < pH < 8)7. For all cases, however, there is an insufficient data set to
conclude that elevated leaching is statistically significant. Rather, these observations suggest that some
ash sources (i.e., fly ashes with high concentrations of leachable constituents of potential environmental
concern) when used in concrete and other cementitious materials may result in increased leaching of
some constituents from the product material. Calcium leaching has a wider range for CEM II/B-V
cement mortars, perhaps resulting from the varied calcium reactivity and concentration in fly ash from
different sources.
Analysis of monolith leaching test eluates indicated greater range and greater cumulative release from
fly ash amended cement mortars (CEM II/B-V mortars) in some cases for boron, cadmium and
molybdenum. Maximum chromium release was slightly lower for cases with fly ash replacement than
for cases without fly ash. Cumulative release for the remaining constituents appeared similar for both
cement mortar types, without and with fly ash. Concrete samples produced using fly ash containing
cement (gray symbols) showed increased cumulative release of arsenic, antimony, boron and
molybdenum relative to the corresponding CEM II/B-V cement mortars. While it is unlikely that the
presence of the coarse aggregate in the concrete samples resulted in a chemical change relative to the
mortar samples, the presence of the coarse aggregate may result in an important change in the physical
structure (i.e., pore structure) of the cement paste, as well as the ratio of cement paste to aggregate
surface area within the concrete. This observation indicates the need for further research comparing
the leachability of concrete in comparison to corresponding mortars.
A comparison is made between the cumulative release up to 64 days as obtained in NEN 7345 (i.e., a
monolith leaching test very similar to CEN/TS 15863 and Method 1315) and the regulatory criteria for
construction products as defined in the Dutch Soil Quality Decree (SQD, 2007), which follows after the
Building Materials Decree (1995)8. In Table 4, the maximum release (expressed in mg/m2 at 64 days) for
both portland cement mortar and mortar containing coal fly ash is given in comparison with the
regulatory limit values (at 64 days) of the SQD for unrestricted use. The Dutch standards were
developed considering maintaining soil quality, surface and groundwater quality and protection of
human health (see Appendix D for a summary). Relevant or equivalent standards tied to cumulative
release from diffusion testing do not exist in the US.
Apparent differences in the leaching of iron between the cements with and without fly ash are most likely the impact of
different detection limits used in the individual studies. This observation is made considering the constant values of iron
concentration at alkaline pH values, which is typical of a non-detected value graphed at the detection limit and is also
consistent with known iron chemistry.
8 This was the first national environmental regulation for construction materials based on leaching assessment.
13
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
Table 4. Comparison of Release from CEM I and CEM IIB Mortars and Concretes with Dutch Regulatory
Criteria.
Analyte
Arsenic
Barium
Cadmium
Chromium
Copper
Molybdenum
Nickel
Lead
Antimony
Selenium
Vanadium
Zinc
Symbol
As
Ba
Cd
Cr
Cu
Mo
Ni
Pb
Sb
Se
V
Zn
Limit value
Dutch SQD
(mg/m2)
260
1500
3.8
120
98
144
81
400
8.7
4.8
320
800
Max value
CEMI
(mg/m2)
0.76
77
0.08
6.2
3.7
0.35
2
20
1.1
1.6
45
3.8
Max value
CEM II/B V
(mg/m2)
3.8
168
0.48
4.4
3.5
7.9
3.8
11.3
4.9
6.2
5.5
8.6
The Max value is the maximum in cumulative release up to 64 days observed from leaching tests carried out on
samples as described in this report.
The comparison between cumulative release and the SQD limit values indicate that in most cases the
increase in release due to inclusion of fly ash in cement mortar may not be important as the release
remains well-below Dutch regulatory criteria derived from an impact assessment to soil and
groundwater. However, in the case of cadmium and antimony, maximum leaching values from cements
with fly ash approach within an order of magnitude of the SQD limit. Furthermore, in the case of
selenium, maximum release from fly ash amended materials exceeded the limit value for unrestricted
use by about 20%; however, the selenium maximum release value is based on a limited number of data
and should be confirmed over a broader range of data. Furthermore, comparison with regulatory
criteria for The Netherlands should not be taken to imply regulatory criteria for the United States.
The impact of carbonation on the monolith test results for a single set of samples also is presented
separately as Appendix E. Notably, carbonated samples of CEM I cement mortars had increased
leaching of arsenic relative to the uncarbonated sample and the carbonated CEM II/B-V cement mortar
had the greatest observed release of arsenic within this data comparison set. This is consistent with
other studies on cement stabilized materials that indicated that carbonation resulted in a shift in arsenic
release as a function of pH and much higher arsenic leaching concentrations (Garrabrants et al., 2004).
Carbonated CEM I cement mortar had greater leaching of copper, antimony and vanadium compared to
the corresponding uncarbonated mortars. CEM I carbonated samples had reduced leaching for barium,
cadmium and nickel, while no significant change for chromium, molybdenum and zinc. Carbonation of
CEM II/B-V cement mortars seem to result in somewhat increased leaching of vanadium and zinc and
somewhat decreased leaching of barium and chromium of arsenic, antimony, copper and vanadium
14
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
relative to the corresponding noncarbonated samples. These observations suggest that the possibility of
increased leaching of arsenic and vanadium during aging and recycling or disposal of cement should be
carefully considered.
Comparison of GBP Cement Grout. Mortar and Concrete with Fly Ash [US data]
Results of the leaching comparisons for the CBP mortar, grout and concrete are provided in Appendix F
and Appendix G for pH-dependent leaching and monolith leaching, respectively. Based on pH-
dependence, the fly ash (FAF) source material resulted in significantly higher leaching concentrations of
arsenic, boron, cadmium, molybdenum, antimony, selenium and vanadium than the grout (BGM),
mortar (SVC) and concrete (VCT). The higher leaching observed from fly ash than from fly ash amended
cement materials appears to be the result of significant chemical interaction (e.g., adsorption and
mineral precipitation) of arsenic, cadmium, selenium and antimony with the cementitious matrix,
whereas the observed higher leaching in fly ash of boron, molybdenum and vanadium appear to be
primarily the result of fly ash dilution in the cement matrix. Chromium concentrations are lower in the
cement materials, most likely because of the reducing characteristics of formulations containing blast
furnace slag. Leaching of beryllium, cobalt, copper, nickel, lead, thallium and zinc is essentially the same
for both the fly ash and cement materials, except for thallium in SVC which was below detection limits.9
Barium and uranium leaching was less from the fly ash than from the cement as a result of the higher
content of these constituents in portland cement. For all of the evaluated constituents except arsenic at
pH less than 6, leaching as a function of pH from the CBP cement materials was either consistent with or
less than the observed leaching from the ED mortars and concrete samples containing fly ash as shown
by the 90 percent confidence intervals for CEM II/V-B samples superimposed on the CBP material
figures.
Monolith leaching results indicated that cumulative release from the CBP cement materials was within
or less than the range observed for the ED samples containing fly ash (90 percent confidence intervals
for CEM II/V-B samples). The increase in cumulative lead release for BGM after approximately two days
is unknown.
Comparison of Cement Admixture Paste Containing Fly Ash
Results of the leaching comparisons for the cement admixture paste containing fly ash (MBD2) are
provided in Appendix H and Appendix I for pH dependent leaching and monolith leaching, respectively.
For pH dependent leaching, greater leaching of antimony, cobalt, copper, nickel and selenium was
observed from admixture pastes than from the fly ash, which may be the result of contributions of these
constituents from the steel slag whereas greater leaching of barium is likely from portland cement.10
Chromium leaching was decreased in the cement admixture paste compared to the fly ash which is likely
9 The likely reason for non-detected values for thallium for sample SVC is unknown.
10 Although the steel slag used in this study was not characterized separately, elevated leaching of antimony, cobalt nickel and
selenium has been indicated from characterization of other steel slag samples. Barium is a common constituent in Portland
cement.
15
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
the result of the reducing properties of the cement admixture due to the addition of steel slag.11 The
reduction in leaching of molybdenum and vanadium in the cement admixture paste is likely the result of
dilution of the fly ash in the cement material. Comparison to the superimposed mean and 90%
confidence intervals for CEM II/V-B samples showed that the leaching from the cement admixture paste
was greater than that for the ED mortars and concrete samples containing fly ash for arsenic, boron,
cadmium, nickel (slightly), selenium and vanadium (at pH < 6). However, these observations may be a
consequence of the addition of the steel slag rather than the fly ash. The leaching of the other
constituents was either consistent with or less than the ED mortars and concretes.
Monolith leaching results indicated that cumulative release from the cement admixture paste was
within or less than the range observed for the ED samples containing fly ash (90 percent confidence
intervals for CEM II/V-B samples) for all constituents except iron for which ED data were available. Iron
leaching likely was increased because of the strongly reducing nature of the matrix as a result of steel
slag usage in the formulation.12
Comparison of Studied Fly Ash Samples with Other Fly Ash Characterization
Appendix J presents results of pH-dependent leaching of the fly ashes (FAF and CFA2) used in the
cement materials described above in comparison with the 5th and 95th percentiles of leaching
concentrations from the set of fly ash samples (35 samples) evaluated by USEPA as part of a study on
characterization of coal combustion residues (Kosson et al., 2009)13. This comparison indicates that
sample FAF had greater leaching for arsenic (37, is
indicated using vertical red dashed lines14. Results less than the applicable analytical method detection
limit (MDL) are indicated in red using open symbols when variable MDLs were used in a study, or as a
11 In this matrix, steel slag was added because of its reducing properties with the intention of increasing retention of
technetium in nuclear waste management applications. The steel slag used was not available for separate leaching
characterization.
12 Iron(ll) is considerably more soluble than iron(lll) at neutral to alkaline pH.
13 This report provides leaching characterization of 35 fly ash samples obtained from 22 US facilities with a range of coal types
being burned and air pollution control systems that may impact fly ash characteristics.
14 Lower initial pore water pH values (e.g., pH ca. 11) are associated with some portland cement mixtures with significant
amounts of admixture materials (e.g., some type of fly ash). Narrower pH ranges may be applicable for specific cement and
concrete materials under well-defined environmental exposure conditions.
16
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
bar over the observed pH range for a single MDL Leaching test results are also compared to health
based numbers (HBNs, red dashed linejused as a reference threshold for the constituent of interest15.
However, COPC leaching in this representation are estimates of liquid-solid partitioning (or equilibrium)
concentrations that may potentially leach from cement materials containing fly ash without accounting
for the physical form or the material (i.e., a monolithic material with low permeability with a tortuous
pore structure through which CO PCs must transport to the surface of the material prior to release).
upper and lower 90%
confidence limits
^Concentration of As as function of gh
1 v^.
1 \E^
01
^^
o
4=
o
u
0.01
0.001
0.0001 -
0.00001
mean response of fly
ash/cement blend
range of relevant pH
values(pH 7-13)
single extraction leaching
data (Cheng eta I, 2008
and/or Zhang et al, 2001)
EPA health based
numbers (HBNs)
leaching data at
method detection limit
(MDL; open symbols)
Figure 3. Annotated graph showing leaching data relative to health based numbers (HBNs) over a
relevant pH range for cementitious materials.
Any assessment of the environmental impact of these releases also needs to consider the dilution and
attenuation of these constituents in run off, transport through the vadose zone and in ground water,
and the plausibility of drinking water well contamination resulting from the release. Dilution and
attenuation factors (DAFs) for metals have been estimated to be potentially as low as 2 to 10 on a
national basis or as high as 8,000 at a particular site with hydrogeology that indicated low transport
potential16. Therefore, comparison with thresholds greater than the HBN and developed for specific
scenarios may be appropriate. Selected results from single extraction leaching tests (Cheng et al., 2008
and Zhang et al., 2001) are compared with the median and 90 percent confidence intervals from the ED
CEM II/V-B cement mortars and concretes containing fly ash in Figure 4 and Figure 5 using the
nomenclature illustrated in Figure 3; a full set of comparisons is provided in Appendix K. Results of the
single extraction leaching tests are consistent with the corresponding results obtained from pH
The HBN for each COPC is derived as the lower value of the allowable concentration based on the scenario either of (i)
drinking water ingestion or (ii) fish ingestion. The relevant threshold value for each scenario is based on the median exposure
for children age 1 through adult, with either a lifetime excess cancer risk of IxlO"5 or a hazard quotient of 1.
16 See 60 FR 66372, December 21,1995, for a discussion of model parameters leading to low DAFs, particularly the assumption
of a continuous source landfill. Implied DAFs for the metals of interest here can be found at 60 FR 66432-66438 in Table C-2.
Site specific high-end DAFs are discussed in 65 FR 55703, September 14, 2000.
17
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
dependent leaching tests with the exceptions of barium, calcium, strontium and potassium, where lower
leaching concentrations from the single extraction tests are likely the consequence of partial
carbonation of the samples during preparation and testing (Garrabrants et al., 2004). Many of the test
results were less than the analytical MDLs reported for the corresponding study. Reported MDLs are
indicated on the respective constituent graphs as unfilled symbols.
A clear limitation of the single extraction batch tests is that the results provide insight into the leaching
behavior only at a single pH and therefore do not allow for evaluation of leaching over the potential
range of leaching pH conditions anticipated during the lifecycle of material use. In contrast, the pH
dependence leaching test results provide insights into where leaching is anticipated to decrease,
increase or remain the same as the material changes in response to aging and environmental conditions.
This information is most effectively used in conjunction with results from mass transfer leaching tests
(i.e., monolith diffusion leaching test such as Method 1315 or NEN 7345, CEN/TC 351 TS-2 or CEN/TS
15863)
HBNs are also compared with the leaching test results in Figure 4 and Appendix K. This comparison
indicates that HBNs are exceeded at the mean concentration for pH dependent leaching over the pH
domain of 7 to 13 by arsenic, chromium and cobalt. HBNs are exceeded by the 90 percent confidence
interval additionally by molybdenum, lead, antimony, selenium, strontium and vanadium. The ratio of
the maximum value over the pH domain (7-13) of the 90 percent confidence interval to the
corresponding HBN is provided in Table 5. Values less than one indicate the expected leaching
concentration from pH dependent leaching tests is always expected to be less than the HBN. As
indicated earlier, the comparison of pH dependent leaching test results to HBNs does not consider
reductions in leaching concentrations resulting from the physical form of the material, nor dilution and
attenuation from the point of release at the material interface to the point of compliance (e.g., a down-
gradient aquifer or drinking water well). Thus, when the physical form of the material and the range of
dilution and attenuation factors are considered, a very large fraction of the cases are likely to not have
adverse impacts to human health based on current HBNs. The ratio of the mean or maximum value to
the HBN provided in Table 5 provides an indication of the dilution and attenuation factor as a result of
the physical form of the material or natural conditions from the location of material use to the point of
compliance that would be needed to avoid adverse impact for the indicated fraction of the cases. These
results also indicate that the constituents in fly ash most likely to limit usage rates of fly ash in concrete
and other cement products are antimony, arsenic, chromium, cobalt and molybdenum because the ratio
of the maximum value over the pH domain divided by the respective HBN is greater than 10.
18
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
Concentration of As as function of pH
Concentration of B as function of pH
Concentration (mg/L) Concentration (mg/L)
3 P 1-0 g P 0
T T ฐ ฐ eelSo
Concentration (mg/L)
> I b P o i
8 8 b P ,-5
1
1
1
1
1
C
^ ~
1 X
X
/" i
- H
r^^^
^* ซ
.
HBN |
^ >
M
N
x.
fc
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i
i
2 4 6 8 10 12 1
PH
oncentration of Ba as function of pH
1 | HBN |
; -t:il I
* 4..
i
' i
c
-
!I:
- *
<
^^
4 6 8 10 12 1
PH
oncentration of Co as function of pH
\
^
^^
;
^j^
~~ix
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\
\
\
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[
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pH
lean -90 % Conf. Lim. -
0 % Conf. Lim. + Zhang monolith
hengASTM Cheng SPLP
cr
^
"c" 1
o
ง
ง 0.01 -
U
4 ;
0.1
? 0.01
e
o
-& -ti
Concentration (mg/L) Concentrat
0 0
8 g P 0 8 g ซ
O O O P (-. OOC
ooooP i-^ o o c
iซ. ^
- 1
| HBN|
^
^"^ .
*
^ V^
^
t*
4 6 8 10 12 1
PH
Concentration of Cd as function of pH
^^
*ป.
*-
1
L
1
'\I_
X 1
-k
1
HBN
^
"*" ~
24681
PH
oncentration of Mo as function o
- i
^x'1
^ ^
1
-" T"
r
!
"""^
X
"" N| MDL I
\\
0 12 1
f pH
/I .
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MDL **
N '
|
1
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PH
MDL
Figure 4. Statistical representation (mean with 90% confidence limits) of concentrations of the EU
CEM ll/V-B cement mortars and concretes containing fly ash and literature single extraction test
results (Cheng et al., 2008; Zhang et al., 2001) compared to health based numbers (HBNs) over a
relevant pH range of 7 to 13.
19
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
Concentration of Pb as function of pH (P + CFA)
Concentration of Sb as function of pH
01
^>
1
0 01 -
nnm -
\
V
x
^^
^ ^
i
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L.
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1
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14
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g 0.01
g
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) I
s
^^
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^-
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0 1
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N
2 1
PH
Concentration of Se as function of pH
PH
Concentration of Sr as function of pH
3
a o-1-
c 0.01
O
g
u
1
) I
*r ,
__ _
\ (.
1
^-
=-(
1
1
1
1
1
> ฃ
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i
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1
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^
^
^
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i *
^ ^
ซ^
1
i
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i
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5
Dt
ปง 10
!
= i
g
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> i
- .
\ (.
U--
> :
p
! 1
H
-^
^
1 <
o
0 1
3N |
o
o d
2 1
Concentration of V as function of pH
1 -
n nnm -
^^
^^
1 1 1 1 1 1
i
r~ ~
^f
^'
! i 1 1 1 i 1
.^
^
HB
X
-\ V
\
M
10
12
14
PH
-Mean
-90 % Conf. Lim. +
A Cheng ASTM
-*-MDL
-90 % Conf. Lim. -
Zhang monolith
Cheng SPLP
Figure 5. Statistical representation (mean with 90% confidence limits) of concentrations of the EU
CEM ll/V-B cement mortars and concretes containing fly ash and literature single extraction test
results (Cheng et al., 2008; Zhang et al., 2001) compared to health based numbers (HBNs) over a
relevant pH range of 7 to 13.
20
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
Table 5. Comparisons of the ratio of the maximum value of the 90 percent confidence interval to the
HBN (Max/HBN) and the maximum value of the mean values to the HBN (Mean/HBN).
Constituent
Aluminum
Antimony
Arsenic
Barium
Boron
Cadmium
Chromium
Cobalt
Copper
HBN
(mg/L)
51
0.0204
0.00294
10.2
10.2
0.0255
0.00881
0.0153
0.51
Ratio
Max/HBN
0.23*
10
61
0.73
0.19
0.50
730
370
1.8
Ratio
Mean/HBN
0.01
0.89
8.0
0.22
0.08
0.034
54
32
0.025
Constituent
Iron
Lead
Manganese
Molybdenum
Nickel
Selenium
Strontium
Vanadium
Zinc
HBN
(mg/L)
35.7
0.015
2.40
0.255
1.02
0.0299
20.4
0.459
6.48
Ratio
Max/HBN
0.10
4.0
6.3
25
1.1
1.6
1.9
3.4
0.016
Ratio
Mean/HBN
0.0086
0.59
0.34
0.20
0.17
0.31
0.63
0.28
0.004
Notes:
This comparison does not consider the dilution and attenuation of these constituents in run off, transport
through the vadose zone and in ground water, and the plausibility of drinking water well contamination
resulting from the release.
*For aluminum only, the single extraction leaching test results were greater than the 90% confidence interval
and therefore the maximum single extraction leaching test result was used in the ratio.
21
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
Conclusions
The available data suggest that the use of coal combustion fly ash in cement materials, for different
combinations of fly ash source and usage rates, will not increase leaching of some constituents to levels
greater than typical ranges for cement materials not containing fly ash. However, there are data
limitations that preclude making broad based claims for some usage rates and fly ashes including those
resulting from changes in air pollution control at coal-fired power plants. Based on available data (31
cement mortar and concrete samples containing coal fly ash in comparison to 21 cement and mortar
samples that did not contain coal fly ash), results indicate that some (and likely a large portion) of coal
fly ashes can be used in cement and concrete formulations without causing a greater range in leaching
of COPCs than observed from analogous cement materials not containing fly ash and without causing
adverse environmental and health impacts. The range of fly ash sources and usage rates for cement
materials with pH dependent and monolith leaching test data available is more limited than the full
range of typical fly ash usage rates and typical fly ash leaching behavior. In addition, the data evaluated
in this report does not consider changes in leaching from cement-based materials that may occur if the
characteristics of coal fly ash used in cement-based materials change in response to recent changes in
air pollution control requirements at coal fired power plants. To the extent that such changes affect the
fly ash characteristics, the available data sets do not allow evaluation of the impacts of the following
potential changes to air pollution controls at coal fired power plants: (i) addition of activated carbon or
halogenated activated carbon, (ii) a shift in the coal types burned or blends thereof to achieve new air
pollution control limits, (iii) presence or increase in ammonia in the ash because of excess ammonia
injected as part of SCR NOx controls, and (iv) the inclusion of sorbent from use of dry sorbent injection
systems (i.e., trona (sodium sesquicarbonate), sodium carbonate or hydrated lime).
Based on the evaluation of available data for the leaching of cement mortars and concrete with and
without partial replacement of cement with coal combustion fly ash, the following observations can be
made:
The leaching behavior of individual constituents from cement mortars and concrete made with
coal fly ash exhibits characteristic leaching concentration as a function of pH behavior that is
controlled by the cement chemistry.
When leaching is compared between cement mortars and concrete with and without coal fly
ash, cement mortars and concrete containing fly ash had somewhat higher upper bounds for the
ranges of leached concentrations for barium, cobalt, copper, molybdenum, phosphorus,
antimony, silicon (at pH > 6) and vanadium (at 4 < pH < 8) based on pH dependent leaching tests
(with the expected field pH to range from 7 to 13). Based on monolith leaching tests, higher
upper ranges of leaching were observed in some cases containing fly ash only for boron,
cadmium and molybdenum.
In comparison to Dutch national criteria for leaching from construction materials, only selenium
approached or exceeded the limit value for unrestricted beneficial use in one case out of
seventeen. In addition to selenium, only maximum values for antimony and cadmium were
within an order of magnitude of the Dutch regulatory limits.
22
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
USEPA HBNs were exceeded at the median concentration for pH dependent leaching over the
pH domain of 7 to 13 by arsenic, chromium and cobalt. HBNs are exceeded by the 90 percent
confidence interval additionally by molybdenum, lead, antimony, selenium, strontium and
vanadium. However, the comparison of pH dependent leaching test results to HBNs does not
consider reductions in leaching concentrations resulting from the physical form of the material,
nor dilution and attenuation from the point of release at the material interface to the point of
compliance (e.g., a down-gradient aquifer or drinking water well).
Leaching of COPCs from fly ash was not significantly increased by incorporation of the fly ash in
cement materials, based on comparison between leaching test results of fly ash alone and fly
ash in cement materials. This suggests that use of fly ash in concrete will not increase the
overall leaching of COPCs from fly ash into the environment.
Arsenic leaching from fly ash was decreased for several cases by incorporation into cement
materials. Also, chromium leaching is decreased when reducing materials (such as ground
granulated blast-furnace slag) are used as part of the cement material formulation.
Using the pH dependent and monolith leaching test data, as described in the LEAF methodology,
provides a more robust approach than single point leaching tests for evaluating the potential
environmental and health impacts from use of coal fly ash in cement and concrete materials
because LEAF considers the likely range of leaching pH over the material's lifecycle and the
physical form of the materials (i.e., monolithic). Single extraction leaching tests cannot
adequately describe the leaching characteristics of COPCs accounting for the likely
environmental pH domain and physical form.
This study should be viewed as the beginning of a collection of robust leaching characterizations for fly
ash and fly ash amended cementitious materials, high fly ash replacement materials such as
solidification/stabilization formulations, and other utilization applications. It is prudent to develop a
characterization and quality control program to determine which combinations of fly ash and cement
formulations have leaching characteristics within the typical range for cement materials without fly ash.
Furthermore, without comparison to risk-informed criteria, potential increases in leaching of some
COPCs, demonstrated through direct comparisons between materials with and without fly ash, does not
indicate that the use of fly ash as a supplemental cementitious material will result in adverse impacts to
human health or the environment. Thus, the approach taken in this report should be used to develop
an evaluation basis (e.g., thresholds, regulatory guidance structure, and quality control program) for the
acceptability of leaching characteristics greater than the typical range for cement-based materials
without fly ash. The systematic behavior of COPC leaching from cement materials produced using fly
ash will allow determination of the general coal sources and coal combustion facility configurations that
result in ash that is acceptable for use at intermediate or high usage rates (i.e., 10-30 wt% or up to 50%
of the cement dry mixture), and reduce the extent of needed quality control testing.
23
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
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Agency, http://www.epa.gov/osw/hazard/testmethods/sw846/pdfs/1312.pdf.
25
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
USEPA (2011). QAPP for the EPA Intel-laboratory Validation Study of Proposed SW846 Leaching
Methods. Quality Assurance Project Plan, Category Ill/Technology Development, Project No:
RN990272.0007.
van der Sloot, H.A., E.G. Weijers, D. Hoede and J. Wijkstra (1985). Physical and Chemical Characterization
of Pulverized Coal Ash with Respect to Cement-based Applications, ECN-178, Netherlands Energy
Research Foundation, Petten, the Netherlands.
van der Sloot, H.A. and E.G. Weijers (1987). Physikalische und chemische Kenndaten von 50
Kohlenstaubaschen mit Blick auf die Verwendung als Betonzusatzstoff, VGB Kraftwerkstechnik 67(5),
527-534.
van der Sloot, H.A, G.J.L van der Wegen, D. Hoede and G.J de Groot (1994). Intercomparison of leaching
tests for stabilized waste. In: Environmental aspects of Construction with waste materials. Eds. J.J.J.M.
Goumans, H.A. van der Sloot, and Th.G. Aalbers, Elsevier Science Publishers, Amsterdam, 63-76.
van der Sloot, H.A., G.J.L. van der Wegen, D. Hoede, G.J de Groot and Ph. Quevauviller (1995).
Intercomparison of leaching tests for stabilized waste. Commission of the European Communities, EUR
16133 EN, 1995.
van der Sloot, H.A., and D. Hoede (1997) Long-term leaching behaviour of cement mortars, ECN-C-97-
042, ECN, the Netherlands.
van der Sloot, H.A., Hoede, D., Rietra, R.P.J.J. (1998) Leaching behaviour of artificial aggregates - ED
project BRST-CT98-5234, ECN-C-01-014, ECN, the Netherlands.
van der Sloot, H.A. (2000). Comparison of the characteristic leaching behaviour of cements using
standard (EN 196-1) cement-mortar and an assessment of their long-term environmental behaviour in
construction products during service life and recycling, Cement and Concrete Research 30, 1079-1096.
van der Sloot, H.A., D. Hoede, R.P.J.J. Rietra, R. Stenger, Th. Lang, M. Schneider, G. Spanka, E.
Stoltenberg-Hansson, and A. Lerat (2001a). Environmental Criteria for Cement-based Products, ECRICEM
I, ECN C-01-069, Netherlands Energy Research Foundation, Petten, the Netherlands.
van der Sloot, H.A., O. Hjelmar, J. Bjerre Hansen, P. Woitke, P. Lepom, R. Leschber, B. Bartet, N. Debrucker
(2001b). Validation of CEN/TC 292 Leaching Tests and Eluate Analysis Methods PrEN 12457 part 1- 4, ENV
13370 and ENV 12506 in co-operation with CEN/TC 308. ECN-C-01-117.
van der Sloot, H.A. (2001c) ECN on Study for ENCI, personal communication.
van der Sloot, H.A., A. van Zomeren, R. Stenger, M. Schneider, G. Spanka, E. Stoltenberg-Hansson, and
P., Dath (2008a). Environmental CRIteria for CEMent-based products (ECRICEM) Phase I: Ordinary
Portland Cements and Phase II: Blended Cements, Executive Summary, ECN-E-08-011, Netherlands
Energy Research Foundation, Petten, the Netherlands.
26
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Material on The Leaching of
Constituents from Cements and Concretes
van der Sloot, H.A., P.F.A.B. Seignettte, J.C.L. Meeussen, O. Hjelmar, and D.S. Kosson (2008b). A
database speciation modelling and decision support tool for soil, sludge, sediments, wastes and
construction products: LeachXS-Orchestra, in the Second International Symposium on Energy from
Biomass and Waste, Venice, 17-20 November 2008.
van der Sloot, H.A. (2009) ECN on Quality Control of Cement, personal communication.
van der Sloot, H.A., van Zomeren, A., Meeussen, J.C.L, Hoede, D., Rietra, R.P.J.J., Stenger, R., Lang, Th.,
Schneider, M., Spanka, G., Stoltenberg-Hansson, E., Lerat, A., Dath, P. (2011) Environmental criteria for
cement based products ECRICEM. Phase I: Ordinary Portland Cement & Phase II: Blended Cements and
methodology for impact assessment. ECN-E-11-020, ECN, the Netherlands
Verschoor, A.J., J.J.P. Lijzen, H.H. van den Broek, R.F.M.J eleven, R.N.J. Comans, and J.J. Dijkstra (2008)
Revision of the Dutch Building Materials Decree: Alternative Emission Limit Values for Inorganic
Components in Granular Building Materials in Proceedings of 9th International Symposium on
Environmental Geo-technology and Global Sustainable Development, Hong Kong.
Zhang, M.H., M.C. Blanchette, and V.M. Malhotra (2001) Leachability of trace metal elements from fly
ash concrete: Results of column-leaching and batch leaching tests. ACI Materials Journal, 98:126-136.
27
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Appendix A. pH Dependent Leaching of EU Cement Mortars: CEM I (without fly ash)
and CEM II/B-V (with fly ash)
Notes:
Gray dashed lines indicate 90 percent confidence intervals; black dashed lines indicate mean
values.
Circled values indicate "own pH" (end point pH when extracted with deionized water at 10
mL/g)
Use of the same color for data sets indicates samples from the same facility taken at different
times.
Legend:
Sample
name
Country
Description
Reference
Portland cements
Cement
Cement
Cement
Cement
Cement
Cement
Cement
Cement
Cement
Cement
Cement
Cement
Cement
mortar CEM
mortar CEM
mortar CEM
mortar CEM
mortar CEM
mortar CEM
mortar CEM
mortar CEM
mortar CEM
mortar CEM
mortar CEM
mortar CEM
mortar CEM
IBS
IB7
ID1
IB1
IN2
IN6
IB6
IB9
ID2
INI
INS
INS
ITH1
Belgium
Belgium
Germany
Belgium
Norway
Norway
Belgium
Belgium
Germany
Norway
Norway
Norway
Thailand
Cement
to EN 19
Cement
to EN 19
Cement
to EN 19
Cement
to EN 19
Cement
to EN 19
Cement
to EN 19
Cement
to EN 19
Cement
to EN 19
Cement
to EN 19
Cement
to EN 19
Cement
Cement
mortar
6-1 (W/
mortar
6-1 (W/
mortar
6-1 (W/
mortar
6-1 (W/
mortar
6-1 (W/
mortar
6-1 (W/
mortar
6-1 (W/
mortar
6-1 (W/
mortar
6-1 (W/
mortar
6-1 (W/
mortar
mortar
according
C=0.5) 1
according
C=0.5) 1
according
C=0.5) 1
according
C=0.5) 1
according
C=0.5) 1
according
C=0.5) 1
according
C=0.5) 1
according
C=0.5) 1
according
C=0.5) 1
according
C=0.5) 1
according
according
QC of cement by testing
van
and
van
and
van
and
van
and
van
and
van
and
van
and
van
and
van
and
van
and
van
van
ECN
derSloot and
van derSloot,
derSloot and
van derSloot,
derSloot and
van derSloot,
derSloot and
van derSloot,
derSloot and
van derSloot,
derSloot and
van derSloot,
derSloot and
van derSloot,
derSloot and
van derSloot,
derSloot and
van derSloot,
derSloot and
van derSloot,
derSloot et al
derSloot et al
,2009
Hoede,
2000
Hoede,
2000
Hoede,
2000
Hoede,
2000
Hoede,
2000
Hoede,
2000
Hoede,
2000
Hoede,
2000
Hoede,
2000
Hoede,
2000
., 2011
., 2011
1997
1997
1997
1997
1997
1997
1997
1997
1997
1997
cement mortar
28
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Sample name
Country
Description
Reference
Blended cements with coal fly ash
Concrete CEM MB NL2
Cement mortar CEM MB Bll
Cement mortar CEM MB BR1
Cement mortar CEM MB Cll
Cement mortar CEM MB Fl
Cement mortar CEM MB D5
Cement mortar CEM MB D6
Concrete CEM MB NL1
Netherlands
Belgium
Brazil
Chile
France
Germany
Germany
Netherlands
Cement mortar CEM MB B17 Belgium
Cement mortar CEM MB N4 Norway
Cement mortar CEM MB D5 Germany
Concrete cube, 20 %
cement replacement by
coal fly ash, carbonated by
CO2 bubbling during
leaching
Cement mortar according
ECN,2001
Cement mortar according
toENlSS-HWAXIS)1
Cement mortar according
toENlSS-HWAXIS)1
Cement mortar according
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot and Hoede, 1997
and van der Sloot, 2000
Van der Sloot etal., 2002
Van der Sloot etal., 2002
ECN,2001
van der Sloot etal., 2011
Cement mortar according van der Sloot et al., 2011
toEN196-l(W/C=0.5)112
Cement mortar according van der Sloot et al., 2011
Cement mortar with 20 %
cement replacement
Cement mortar with 20 %
cement replacement
Concrete cube with 20 %
cement replacement by
coal fly ash
Cement mortar according
Note:
1 After de-molding at the age of 24 hours, the mortar samples for the leaching tests were cured at
20 9C and 95 % relative humidity for another 27 days in plastic bags to prevent pre-leaching.
2 The cement used in this mortar was type CEM II A-V rather than CEM II B-V. This minor distinction does not
influence the observations or conclusions in this report.
-ป- Concrete cube IIBNL2
B Cement mortar IIB BR1
-5K- Cement mortar IIB Fl
A Cement mortar IIB D6
Cement mortar IIB B17
X Cement mortar IIB D4
-90% Conf. Lim -
Cement mortar IIB Bll
9 Cement mortar IIB Cll
ACement mortar IIB D5
ปConcrete cube IIB N LI
Cement mortar IIB N4
^ -Mean
-90% Conf. Lim +
- Cement mortar C EM I B3
- Cement mortar C EM I B7
- Cement mortar C EM I D1
-Cement mortarCEM I Bl
-Cement mortar CEM I N2
- Cement mortar C EM I N 6
Cement mortar CEM ITH1
90%Conf. Lim. -
--Cement mortar CEM I B6
Cement mortar CEM I B9
A Cement mortar CEM I D2
-- Cement mortar C EM I N1
-- Cement mortar C EM I N 5
--Cement mortar CEM I N3
-Mean
-90 % Conf. Lim. +
29
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Concentration of Al as function of pH (Portland)
o
u
0.0001
Concentration of As as function ofpH
Concentration of Al as function of pH (P + CFA)
1000
Ol
o
u
0.0001
Concentration of As as function of pH
10 12 14
Concentration of B as function of pH
Concentration of B as function of pH
Concentration of Ba as function of pH
Concentration of Ba as function of pH
10 T
0.1
30
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Concentration of Ca as function of pH (Portland)
100000
01
.2
4J
ฃ
o
u
10000
1000 -
10 12 14
Concentration of Ca as function of pH (P + CFA)
100000
10000
o
's
o
u
1000 -
Concentration of Cd as function of pH
0.1 i
Concentration of Cd as function of pH
Concentration of Co as function of pH
Concentration of Co as function of pH
O
U
0.0001
10 12 14
O
u
0.0001
Concentration of Cr as function of pH
Concentration of Cr as function of pH
01
o
u
0.01
0.001
o
u
0.001
31
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Concentration of Cu as function of pH (Portland)
10
Concentration of Cu as function of pH (P + CFA)
Ol
.2
4J
2
o
's
0.0001 - f
0.00001
Concentration of Fe as function of pH
1000
100
10 -
1
0.1
0.01
0.001
0.0001
Concentration of Fe as function of pH
1000
Concentration of K as function of pH
Concentration of K as function of pH
1000 t
1000 T
Concentration of Mg as function of pH
PH
Concentration of Mg as function of pH
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
ง
u
Concentration of Mn as function of pH (Portland)
100
10
Concentration of Mn as function of pH (P + CFA)
Concentration of Mo as function of pH
1
Concentration of Mo as function of pH
1
Concentration of Ni as function of pH
Concentration of Ni as function of pH
01
o
u
0.0001
10 12 14
Concentration of P as function of pH
Concentration of P as function of pH
33
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Concentration of Pb as function of pH (Portland)
1 -E
Concentration of Pb as function of pH (P + CFA)
1 -E
0.0001
1000
Concentration of S as function of pH
PH
Concentration of S as function of pH
1000 -E
0.1
Concentration of Sb as function of pH
1 -E
Concentration of Sb as function of pH
0.00001
Concentration of Se as function of pH
1 -E
Concentration of Se as function of pH
1 T
34
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Concentration of Si as function of pH (Portland)
10000
Concentration of Si as function of pH (P + CFA)
10000
Ol
e
.2
4J
2
o
u
1000 -
Concentration of Sr as function ofpH
Concentration of Sr as function of pH
100 -p
Concentration of V as function of pH
o
's
o
u
Ol
^>
e
.2
4J
n
10
1
Concentration of V as function of pH
L
o
u
0.001
0.0001
0.0001
10
12
PH
Concentration of Zn as function of pH
Concentration of Zn as function of pH
14
35
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Appendix B. Comparisons of Leaching Results and Statistics (i.e., Median and Maximum
Values) for pH-Dependent Leaching from Cements and Concretes with and
without Fly Ash
Legend:
Cements without Fly Ash
Cement mortar CEM I H3 B(P,1,1)
Cement mortar CEM I H7 B(P,1,1)
A Cement mortar CEM I Dl D(P,1,1)
Cement mortar CEM I HI B(P,1,D
Cement mortar CEM I Nl N(P,1,1)
NOR-1(P,1,D
NOR-3(P,1,D
^ Median - Cement w/o FA
.-90th Percentile - Cement w/o FA
Cement mortar CEM I H6 B(P,1,1)
Cement mortar CEM I H9 B(P,1,1)
A Cement mortar CEM I D2 D(P,2,1)
* Holcim_Thailand_SCCC(P,l,D
Cement mortar CEM I N2 N(P,1,1)
NOR-2(P,1,D
^ Maximum - Cement w/o FA
-75th Percentile- Cement w/o FA
Cements with Fly Ash
ป Cement mortar IIB-V NL(P,1,1)
O Cement mortar OPC MB Braz(P,l,l)
X Cement mortar OPC VAF(P,1,1)
A Cement mortar PCAD EU(P,1,31)
ซ--HOL7(P,l,l)
Maximum - Cement w FA
Median - Cement w FA
Minimum - Cement w FA
Cement mortar OPC MB B(P,1,1)
O Cement mortar OPC MB Chile(P,l,l)
A Cement mortar PCAD EU(P,1,3)
ป Cement NL(P,1,1)
B--NOR-4(P,1,1)
-90th Percentile - Cement w FA
___. 10th Percentile - Cement w FA
Median and Maximum
Maximum - Cement w/o FA Maximum - Cement w FA
Median - Cement w/o FA Median - Cement w FA
36
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of Constituents from Cements and Concretes
Cements without Fly Ash
Cements with Fly Ash
Median and Maximum
pH dependent concentration of Sb
pH dependent concentration of Sb
pH dependent concentration of Sb
j1
1 o.i -
c
B 0.01 -
2
2 o.oc
5
o.ooc
1 ฐ
c
o
Concentrat
s ง p c
0 0 ?
ion (mg/L)
ฃ
Concentrat
3
* h
k
&
^
^-~
JB
ft-
.
L
#
O ' '
1 o.i -
c
o
43 0.01 -
Z
c
ง
U
1
Z^Ttr^Scr-
c ฐ^.!!r.:-<
^
^~ ^^
._~x
^^ ^^
ซ-
1
2 4 6 8 10 12 14 2 4 6 8 10 12 1
pH pH
pH dependent concentration of As pH dependent concentration of As
i -
>
,
1
i ^
*
u
c
Q
s
*
.
pp
^.^
-,:ฃ
i
:
*^
? i
1
^
t
(
>o *
i ;
1 B
(9
J1 ;
01
<^*
1 ! ..
r^^Tj
^:>'k.^
ฃ 1 : 'ป*.-ซซ'
2 :
3
i 10 12 14 2468
^^1
_"* ~
^^^*4
~~ฃ~-
^
A
ซn
$
-fc. *
Concentration (mg/L) Concentration (mg/L)
5 1 1 p o i i ง o
01
c
o
1
2
3
10 12 14 :
i .
i
i -
!
S''~.
T^Ft
2 4 6 8 10 12 1'
PH
pH dependent concentration of As
i
s
^H
x
-N
^"^-^-
^
=-^
2 4 6 8 10 12 1
PH
pH dependent concentration of Ba
"-^^
^^^^^^
^ .ซ
4 6 t
"^^
i 10 12 1<
PH
PH
PH
37
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of Constituents from Cements and Concretes
Cements without Fly Ash
pH dependent concentration of B
n
Cements with Fly Ash
pH dependent concentration of B
Median and Maximum
pH dependent concentration of B
^ 0.1
c
o
ion (mg/L) Concentration (mg/L) Concentrat
1 b P 0 1 b P e
* i-^ o o o o P 0 oooF
oooo. oooc
2
c
Sn m .
3
ncnAEifc: *. ^
j ^ -^
*ฅ
*S?;
<^
I-
ฎ
2 4 6 8 10 12 1
PH
F>H dependent concentration of Cd
> _
^^1^^^ ^^
246
f
pH dependent concent
in
>* W
m
A
1
8 1
H
ration
-ซ J
^^
^
0
1
0 12 1
of Cr
t
"S
0
ฎ
n
5 i
ฃ 0.1
c
o
* *
ion (mg/L) Concentration (mg/L) Concentrat
1 b P 0 1 b P e
* i-^ o o o o P o o o o .
oooo. oooc
z
+1
c
Sn m .
3
^~
S^
^
^
"^ .^
~~ซซ
^~
m
(*)
2 4 6 8 10 12 1
PH
\>H dependent concentration of Cd
[
r
1
'
^^
LJ
2
pH dep
i \-
^
B- HP -1
0 <
> v^
^
4 6 8 10 12 1
PH
endent concentration of Cr
^
k. ^
2 4 6 8 10 12 14 24
PH
^
Nj
* *-<
31
/
\
^
^
1
* *
Concentration (mg/L) Concentration (mg/L)
o o
8 b P 0 8 b P 0
o o o o . ,-, o o o . ,-,
ooooP ooooP i-
E ^ "
2 01
s
c
Sn m -
3
Pr
!
[
>
1 dep
[
^Mi
_ ^
=^;
\x
4 6 8 10 12 1
PH
undent concentration of Cd
[
^^
V^-
* ^^
^^"^^
-
^^t
2 4 6 8 10 12 1
PH
pH dependent concentration of Cr
^
^-
1
X
\
6 8 10 12 14 2 4 6 8 10 12 1
pH pH
38
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of Constituents from Cements and Concretes
Cements without Fly Ash
Cements with Fly Ash
Median and Maximum
pH dependent concentration of Co
pH dependent concentration of Co
pH dependent concentration of Co
5 10 -
! "
ฃ o.i -
2
(U
U
ง 0.001 -
U
2
P
1 o.i -
c
o
Concentrat
I b f
I O C
2
P
1
"5; o.i
ฃ
1 ฐ'01
i o.ooi
c 0.0001
o
u
0.00001
=*
*H
c
468
P
H dependent concent
}
O
^>
4lfl
1
H
ration <
t=ซ+
^D
1
tit*
^^ 1^
2 ni
2
^ 0 01 -
s
5 o.ooi
u
\
-ฑ*
S
1
I
^
"^
_*ij<
^
^atr_'
m-S^
-v"'
X.
*
*
Concentration (mg/L)
3
3 b P o H
3 O O . 1-^ C
* I-1 I-1 I-1 I-1 O C
J J J J J J
^ป^^
s^~
^
'x
^J
* ^ ., -
Xx"
D 12 14 2 4 6 8 10 12 14 2 4 6 8 10 12 V
pH pH
if Pb pH dependent concentration of Pb pH dependent concentration of Pb
^ <<
r
5
4 6 8 10 12 1
PH
hi dependent concentration of Mo
>
-r
bcfl
A
\^"
gf
\
i
K
,-?+
&
^-
2 4 6 8 10 12 1
PH
1 o.i -
c
o
2
c
o
u
4 2
P
1
"5 o.i
ฃ
1 ฐ'01
i o.ooi
c 0.0001
3
0.00001
4
\ j
1
C
\
Lv
\
s
fe*r.
tx"m-w
m=~m-
,o. ,
:--*-,
'^
"^
t '
4 6 8 10 12 1
PH
hi dependent concentration of Mo
-f \
^
!$
iป-*^
^ฃ
ฃi
^
i
2 4 6 8 10 12 1
pH
H i-H i-H T
ฐ ง ]
(~|/6lU) UOj)BJ)U3
C
o
u
4 ;
pt
i
"5 o.i
ฃ
1 ฐ'01
i o.ooi
c 0.0001
3
0.00001
4
V
. \ ^*
i*-**
"S - -
^ "
4 6 8 10 12 1
pH
H dependent concentration of Mo
r
''
.ซ- *"-
. -
*-*.
_^_ซ
-
>
-<
2 4 6 8 10 12 14
pH
39
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of Constituents from Cements and Concretes
Cements without Fly Ash
Cements with Fly Ash
Median and Maximum
pH dependent concentration of Se
I
0.1
0.01
0.001
0.0001
0.00001
0.000001
10
12
PH
14
pH dependent concentration of Se
^
c
S
2
c
pH dependent concentration of Se
0.01
0.001
0.0001
5 o.ooooi
u
0.000001
PH
10
12
14
pH dependent concentration of V
"? n 1 -
,ง,
c
o
2
c
o
u
n nnm .
ป*
"
'
O
^
m
ซ
' \
N
^^^
8
PH
10
12
14
pH dependent concentration of V
1 -E-
0.1 -
B o.oi
2
8 o.ooi -
c
o
u
o.oooi
v
c
8
PH
10
12
14
pH dependent concentration of V
40
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Appendix C. Cumulative Release from Monolith Leaching of EU Mortars and
Concretes: CEM I (without fly ash) and CEM II/B-V (with fly ash)
Notes:
Black horizontal solid lines represent cumulative release leaching criteria from the Dutch Soil
Quality Decree.
Aqua colored symbols indicate carbonated samples to simulate accelerated aging.
Gray symbols indicate concrete samples.
Gray dashed lines indicate 90 percent confidence intervals; black dashed lines indicate mean
values of the data sets shown.
Legend:
Sample name
Country
Description
Reference
Portland
Cement mortar CEM I B3 Belgium
Cement mortar CEM I B7 Belgium
Cement mortar CEM I D2 Germany
Cement mortar CEM I Nl Norway
Cement mortar CEM I Dl Germany
Cement mortar CEM I Bl Belgium
Cement mortar CEM I B6 Belgium
Cement mortar CEM I B9 Belgium
Cement mortar CEM I N2 Norway
Cement mortar CEM I N5s Norway
Cement mortar CEM I N5 Carb Norway
Cement mortar CEM I B6s Belgium
Cement mortar CEM I Dls Germany
Cement mortar according to
ENige-lfW/C^.S)1
Cement mortar according to
ENISS-HWAXIS)1
Cement mortar according to
ENISS-HWAXIS)1
Cement mortar according to
ENISS-HWAXIS)1
Cement mortar according to
ENISS-HWAXIS)1
Cement mortar according to
ENige-lfW/C^.S)1
Cement mortar according to
ENISS-HWAXIS)1
Cement mortar according to
ENISS-HWAXIS)1
Cement mortar according to
ENISS-HWAXIS)1
Cement mortar according to
Cement mortar according to
EN196-1
(W/C=0.5) Carbonated high
CO2 prior to leaching
Cement mortar according to
Cement mortar according to
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot etal., 2011
van der Sloot etal., 2011
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot and Hoede, 1997
and van der Sloot, 2000
41
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Sample name
Country
Description
Reference
Portland
Cement mortar CEM I Bis Belgium
Cement mortar CEM I N2s Norway
Cement mortar CEM I D2s Germany
Cement mortar CEM I B3s Belgium
Cement mortar CEM I B7s Belgium
Cement mortar CEM I Nls Norway
Cement mortar CEM I N5 Norway
Cement mortar CEM ITH1 Thailand
Cement mortar according to
ENISS-HWAXIS)1
Cement mortar according to
ENISS-HWAXIS)1
Cement mortar according to
ENige-lfW/C^.S)1
Cement mortar according to
ENISS-HWAXIS)1
Cement mortar according to
ENISS-HWAXIS)1
Cement mortar according to
ENISS-HWAXIS)1
Cement mortar according to
QC of cement by testing
cement mortar
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot and Hoede, 1997
and van der Sloot, 2000
van der Sloot etal., 2011
ECN,2009
Blended cements and concretes with coal fly ash
Cement mortar CEM MB D4 Germany
Cement mortar CEM MB B7 Belgium
Cement mortar CEM MB N4 Norway
Cement mortar CEM MB NL 1 Netherlands
Cement mortar CEM MB NL 2 Netherlands
Cement mortar CEM MB NL 3 Netherlands
Cement mortar CEM MB NL 4 Netherlands
Cement mortar CEM MB NL 5 Netherlands
Cement mortar CEM MB NL 6 Netherlands
Cement mortar CEM MB NL 7 Netherlands
Cement mortar CEM MB NL 8 Netherlands
Cement mortar CEM MB NL 9 Netherlands
Cement mortar CEM MB NL 10 Netherlands
Concrete CEM MB NL 10 Netherlands
Cement mortar according to van der Sloot et al., 2011
Cement mortar according to van der Sloot et al., 2011
Cement mortar according to van der Sloot et al., 2011
Cement mortar with 20%
cement replacement2
Cement mortar with 20%
cement replacement2
Cement mortar with 20%
cement replacement2
Cement mortar with 20%
cement replacement2
Cement mortar with 20%
cement replacement2
Cement mortar with 20%
cement replacement2
Cement mortar with 20%
cement replacement2
Cement mortar with 20%
cement replacement2
Cement mortar with 20%
cement replacement2
Cement mortar with 20%
cement replacement2
Concrete cube with 20 %
cement replacement by coal
fly ash
Van der Sloot and
and van der Sloot
Van der Sloot and
and van der Sloot
Van der Sloot and
and van der Sloot
Van der Sloot and
and van der Sloot
Van der Sloot and
and van der Sloot
Van der Sloot and
and van der Sloot
Van der Sloot and
and van der Sloot
Van der Sloot and
and van der Sloot
Van der Sloot and
and van der Sloot
Van der Sloot and
and van der Sloot
ECN,2001
Weyers, 1987
et al., 1985
Weyers, 1987
etal., 1985
Weyers, 1987
et al., 1985
Weyers, 1987
et al., 1985
Weyers, 1987
et al., 1985
Weyers, 1987
et al., 1985
Weyers, 1987
etal., 1985
Weyers, 1987
et al., 1985
Weyers, 1987
et al., 1985
Weyers, 1987
et al., 1985
42
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Sample name
Country
Description
Reference
Blended cements and concretes with coal fly ash
Concrete CEM MB NL 10 Carb2 Netherlands
Concrete CEM MB NL 10 CarbS Netherlands
Concrete CEM MB NL1
Concrete CEM MB NL 2
Concrete CEM MB NL 3
Concrete CEM MB NL 4
Concrete CEM MB NL 5
Concrete CEM MB NL 6
Concrete CEM MB NL 7
Concrete CEM MB NL 8
Concrete CEM MB NL 9
Concrete CEM MB NL 11
Concrete CEM MB NL 12
Netherlands
Netherlands
Netherlands
Netherlands
Netherlands
Netherlands
Netherlands
Netherlands
Netherlands
Netherlands
Netherlands
Concrete cube with 20 %
cement replacement by coal
fly ash. Carbonated prior to
testing
Concrete cube with 20 %
cement replacement by coal
fly ash. Carbonated prior to
testing
Concrete cube with 20 %
cement replacement by coal
fly ash.2
Concrete cube with 20 %
cement replacement by coal
fly ash.2
Concrete cube with 20 %
cement replacement by coal
fly ash.2
Concrete cube with 20 %
cement replacement by coal
fly ash.2
Concrete cube with 20 %
cement replacement by coal
fly ash.2
Concrete cube with 20 %
cement replacement by coal
fly ash.2
Concrete cube with 20 %
cement replacement by coal
fly ash.2
Concrete cube with 20 %
cement replacement by coal
fly ash.2
Concrete cube with 20 %
cement replacement by coal
fly ash.2
Concrete cube with 20 %
cement replacement by coal
fly ash.2
Concrete cube with 20 %
cement replacement by coal
fly ash.2
ECN,2001
ECN,2001
Van der Sloot and Weyers, 1987
and van der Sloot et al., 1985
Van der Sloot and Weyers, 1987
and van der Sloot et al., 1985
Van der Sloot and Weyers, 1987
and van der Sloot et al., 1985
Van der Sloot and Weyers, 1987
and van der Sloot et al., 1985
Van der Sloot and Weyers, 1987
and van der Sloot et al., 1985
Van der Sloot and Weyers, 1987
and van der Sloot et al., 1985
Van der Sloot and Weyers, 1987
and van der Sloot et al., 1985
Van der Sloot and Weyers, 1987
and van der Sloot et al., 1985
Van der Sloot and Weyers, 1987
and van der Sloot et al., 1985
van der Sloot etal., 1998
Van der Sloot and Weyers, 1987
and van der Sloot et al., 1985
Notes:
1 After de-molding at the age of 24 hours, the mortar samples for the leaching tests were cured at
20 9C and 95 % relative humidity for another 27 days in plastic bags to prevent pre-leaching
2 Number denotes different fly ash resulting from processing coal from worldwide sources in Dutch coal fired power
plants.
43
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Cumulative release of Al (Portland)
Cumulative release of Al (P+CFA)
E 1000 r
Time (days)
Cumulative release of As
0.1
1
Time (days)
Cumulative release of As
0.1
Time (days)
Cumulative release of B
Time (days)
Cumulative release of B
Time (days)
Cumulative release of Ba
Time (days)
Cumulative release of Ba
0.1 1
Time (days)
44
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
I
ฅ
J
Cumulative release of Ca (Portland)
Cumulative release of Ca (P+CFA)
100000
0.1
Time (days)
Cumulative release of Cd
Time (days)
10 -r
Cumulative release of Cd
0.1
0.01
Time (days)
Cumulative release of Cl
Time (days)
Cumulative release of Cl
10
-"H
100
1 10
Time (days)
Cumulative release of Co
Time (days)
Cumulative release of Co
1
Time (days)
0.01
Time (days)
45
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Cumulative re lease of Cr (Portland)
Cumulative release of Cr (P+CFA)
E 100 -
E 100 -
I
u
1
Time (days)
Cumulative release of Cu
0.1 1
Time (days)
Cumulative release of Cu
|
u
Cumulative release of Fe
Cumulative release of Fe
Cumulative release of K
Cumulative release of K
o.i i
Time (days)
46
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Cumulative release of Mg (Portland)
Cumulative release of Mg (P+CFA)
I
ฅ
I
s
1 10
Time (days)
Cumulative release of Mn
Time (days)
Cumulative release of Mn
0.1
0.1
1
Time (days)
Cumulative release of Mo
Time (days)
Cumulative release of Mo
I
ฅ
I
s
I
u
Time (days)
Cumulative release of Na
0.1 1
Time (days)
Cumulative release of Na
1
Time (days)
0.1 1
Time (days)
47
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Cumulative release of Ni (Portland)
Cumulative release of Ni (P+CFA)
I
ฅ
s
I
ฅ
I
ฃ
o.i i
Time (days)
Cumulative release of P
o.i i
Time (days)
Cumulative release of P
I
0.1 1
Time (days)
Cumulative release of Pb
0.1 1
Time (days)
Cumulative release of Pb
Time (days)
Cumulative release of Sb
0.1
1
Time (days)
Cumulative release of Sb
Time (days)
0.1 1
Time (days)
48
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Cumulative release of Se (Portland)
Cumulative release of Se (P+CFA)
o.i
Time (days)
Cumulative release of Si
Time (days)
Cumulative release of Si
Time (days)
Cumulative release of SO4
Time (days)
Cumulative release of SO4
I
ฅ
3
2; 1000 -
Time (days)
Cumulative release of Sr
Time (days)
Cumulative release of Sr
o.i i
Time (days)
0.1 1
Time (days)
49
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Cumulative release of V (Portland)
Cumulative release of V (P+CFA)
E 100 -
Time (days)
Cumulative release of Zn
1 10
Time (days)
-Cement mortar CEM I B3 Cement mortar CEM I B6
-Cement mortar &tfnUJ!>tiปe release ofฃn Cement mortar CEM I Dl
^- Cement mortar CEM I Bl
ICement mortar CEM I N2
Cement mortar CEM I D2
> Cement mortar CEM I B3
^- Cement mortar CEM I B7
ICement mortar CEM I Nl
I Cement mortar CEM I N6s
h- Cement mortar CEM I N5
Cement mortar CEM ITH1
-Mean cum. release
Conf. Limit +
A-^Sement mortar CEM I D2
B-JtemenLraortar CEM I Nl
A JCement mortar CEM I Dl
:ement mortar CEM I Bl
:ement mortar CEM I B6
--Jfement nWtar CEM I B9
-Cement mortar CEM I N2
3
gement mortar CEM I N5s
3
D Mortar CEM I N5 Carbonated
0.01
slope=0.5aol al
^ -90 % Conf. Limit -
^^^Soil Quality Decree-unrestr. use
100
Time (days)
Cumulative release of Zn
E 100 -
1 10 1C
Time (days)
Concrete CEM IIB NL Carb.3 ป Concrete CEM IIB NL10 Carb.2
-Concrete CEM IIB NCWlttUlative releaSe O^ZftH mortar CEM IIB B7
ปCement mortar CEM IIB NL10
ปCement mortar CEM IIB NL3
ปCement mortar CEM IIB NL5
-งment mortar CEM IIB NL6 Cement mortar CEM IIB NL7
~ - ปCement mortar CEM IIB NL9
ป Concrete CEM IIB NL8
ป Concrete CEM IIB NL6
Concrete CEM IIB NL4
ป Concrete CEM IIB NL2
D Concrete CEM IIB NL12
Cement mortar CEM IIB N4
slope=0.5
-gsment mortar CEM IIB NL1
-lEment mortar CEM IIB NL2
-l^menllMbrtar CEM IIB NL4
Tient mortar CEM IIB NL6
Tient mortar CEM IIB NL8
2L
- (generate CEM IIB NL10
ijfcncrete CEM IIB NL7
igincrete CEM IIB NL5
(fpncrete CEM IIB NL3
gincrete CEM IIB NL1
-Cement mortar CEM IIB B7
-Cementmortar CEM IIB D4
MeanC
90 % Conf. Limit +
0.1
r 90% Conf. Lirjjj- 100
Decree-unrestr-use
50
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Concentration of Hg as a function of time
Cumulative release of Hg
J m
Ol
E 0.01
SMI*
g 0.001
E o.oooi
% 0.00001
o 0.000001
!
[
!
[
: *
!
[
0.01 0
'
W
=/z
11 10 10
Time (days)
E 0.0001
u
0.01
Concentration of Tl as a function of time
0.1 1 10
Time (days)
Cumulative release of Tl
1 10
Time (days)
100
1 10
Time (days)
100
-Cement mortar NORD1 D(M,1,1)
ซ--Cement mortar NORD2 D(M,1,1)
^--Cement mortar NORH1 NL(M,1,1)
-(--Cement mortar NORH3 NL(M,1,1)
G--Cement mortar NORMS NL(M,1,1)
Cement mortar NORH7 NL(M,1,1)
-Cement mortar NORH9 NL(M,1,1)
^--Cement mortar NORN1 NL(M,1,1)
ir-Cement mortar NORN2 NL(M,1,1)
NOR2(M,2,1)
NOR4(M,2,1)
-Cement NL(M,2,1)
-Concrete_reference_gravel(M,l,l)
-NOR2(M,2,1)
-NOR4(M,2,1)
51
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Appendix D. Approach for Criteria Development for Monolithic Materials in the
Dutch Soil Quality Decree (2007)
From 1995-2008, the Dutch Building Materials Decree (BMD) has regulated the potential impact of
construction materials on the environment. The decree specifies the environmental quality criteria for
the application of stony materials (including excavated soil) in construction, and does not distinguish
between primary, secondary and waste materials. After 10 years of experience with the BMD, a revision
of the Decree was found necessary, for reasons of costs and transparency following the publication of
several amendments with exemptions.
The aim of the revision, currently the Soil Quality Decree that came into force in July 2008, was to
develop a simplified and more transparent regulation containing a consistent set of emission limit
values, which warrant the protection of soil and groundwater quality with minimal restrictions for the
re-use of (secondary) materials.
In the derivation of emission limits for inorganic substances, maximum permissible concentrations
(MPCs) have been used as the environmental quality criteria (compliance values). At the MPC level,
ecosystems are not significantly affected by chemical exposure. For inorganic substances occurring at
natural background concentrations, the MPC is transformed to a corresponding maximum permissible
addition (MPA), using MPC = MPA + background (see Verschoor et al., 2008, and references therein).
The MPA values for the regulated inorganic substances are listed in Table C-l. No MPA values are
available for Cl, Br, F and SO4 in soil and, as a consequence, emission limit values for these substances
are solely based on their effect on groundwater.
Table D-l Maximum permissible addition value for soil (MPAS) and groundwater (MPAg) used in the
derivation of emission limits for granular construction products in the Dutch Soil Quality Decree.
Component
Antimony
Arsenic
Barium
Cadmium
Chromium
Cobalt
Copper
Mercury
Lead
Molybdenum
Symbol
Sb
As
Ba
Cd
Cr
Co
Cu
Hg
Pb
Mo
MPAS
(mg/kg)
0.53
0.9
180
0.79
0.38
2.4
3.4
1.9
55
39
MPAg Component
(Hg/L)
6.2
24
29
0.34
8.7
2.6
1.1
0.23
11
29
Nickel
Selenium
Tin
Vanadium
Zinc
Bromide
Chloride
Fluoride
Sulphate
Symbol
Ni
Se
Sn
V
Zn
Br
Cl
F
SO4
MPAS
(mg/kg)
0.26
0.11
34
1.1
16
n.a
n.a.
n.a.
n.a.
MPAg
(Hg/D
1.9
5.3
20
3.5
7.3
8,000
200,000
1,500
100,000
n.a. = not available
52
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
An important premise in the criteria development for monolithic products in the Soil Quality Decree is
that the release from 1 m2 of construction products or stabilized monolithic waste impacts on 1 m2 of
soil surface. Through this assumption the real surface area of a construction product impacting on soil is
not taken into consideration. This simplification is used to ensure a straightforward approach without
diversification in multiple sizes and shapes found in reality.
The release from construction products is derived from the test results in the laboratory test (Tank leach
test) in the following manner:
soil ~ ave,64d ' extrap ' temp
where /so// is the release to soil from a monolithic product expressed in mg/m2 over J years,
Eave, 64d is the release from monolith leach test in mg/m2,
j'extrap is the factor of extrapolating release from 64 days to J years taking into account
thickness (m), wet/dry periods, and effective diffusion coefficient (De), and
/temp is the correction factor for temperature difference between laboratory (20 ฐC) and
field conditions. Taking an average temperature of 10 ฐC in the Netherlands results in a
factor of about 0.7 (Aalbers et al., 1993).
The extrapolation factor for release in 64 days to J years had been established in the Building Materials
Decree (1995) by Aalbers et al (1993). The factor considers the thickness of the product and
wetting/drying cycles of exposed products by considering the times that a product is wet due to
exposure to rain (% of time wet). The extrapolation factor also considers the effective diffusion
coefficient (substance dependent). Thus, thick products that have a high effective diffusion coefficient
(worst case condition) require a larger factor than thinner products with a low effective diffusion
coefficient. In the Building Materials Decree, default values for various building products have been
derived.
For wetting/drying cycles, a distinction is made between permanently wetted products (in ground or
surface water), where the correction factor for wetting/drying is 1 (Application type A), and products
exposed to rain above ground in which case the correction is factor of 0.1 (assumed for the case of 10%
wet time) (Application type B).
For Application type A, the overall value of fextrap varies from 1 to 15 depending on the product
thickness and the effective diffusion coefficient. In the calculations for the Soil Quality Decree
the same parameter settings were used for this application type as for the Building Materials
Decree, namely a factor of 15 corresponding with a product thickness of 0.3 m and a De of 10"10
m2/s.
For Application type B, the overall fextrap value varies from 1 to 5. In the calculations for the Soil
Quality Decree the same parameter settings were used for this application type as for the
Building Materials Decree, namely a factor of 5 corresponding with a product thickness of 0.2 m
and a De of 10"10 m2/s.
53
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
The time dependent release expressed in mg/m2 as a function of time is converted to concentrations by
taking the average annual infiltration into account (expressed in L/m2) and proportionally divided over a
year as needed. The resulting concentration time function is used as input for the chemical reaction
transport model, which couples the source term with the concentrations in groundwater at the point of
compliance.
54
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Appendix E. Effect of Carbonation on Monolithic Leaching of EU Cement Mortars:
CEM I (without fly ash) and CEM II/B-V (with fly ash)
Legend:
--Cement mortar CEM I N5
n Mortar CEM I N5 Carbonated
NL-BBK-Open Application
slope=0.5
-^ConcreteCEM IIBVNL
c Concrete CEM IIB V NL Carbonated 2
o Concrete CEM IIBV NL Carbonated 1
NL-BBK-Open Application
slope=0.5
55
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Cumulative release of As (Portland)
Cumulative release of As (P+CFA)
10000 - ,
' 1000 -
1 -r
0.1 -r
0.01
0.1
E
3
u
Time (days)
Cumulative release of Ba
Time (days)
Cumulative release of Ba
I ' '
1 :
Time (days)
Cumulative release of Cd
Time (days)
Cumulative release of Cd
E
01
I
ซ
ฃ
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
E
I
.2
ฃ
E
u
E 100
"",
Dl
I 10i
ฃ
| 0.1 i
(J
Cumulative release of Cu (Portland)
Cumulative release of Cu (P+CFA)
1 10
Time (days)
Cumulative release of Mo
1 10
Time (days)
Cumulative release of Mo
1 10
Time (days)
Cumulative release of Ni
1 10
Time (days)
Cumulative release of Ni
1 10
Time (days)
Cumulative release of Pb
Cumulative release of Pb
57
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Cumulative release of Sb (Portland)
Cumulative release of Sb (P+CFA)
1 10
Time (days)
Cumulative release of Se
1 10
Time (days)
Cumulative release of Se
Time (days)
Cumulative release of V
Time (days)
Cumulative release of V
Cumulative release of Zn
Cumulative release of Zn
Time (days)
58
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Appendix F. pH Dependent Leaching of CBP Cement Mortars and Concrete
Containing Fly Ash
Notes:
Results are compared to mean and 90 percent confidence intervals of cumulative release from
European cement mortars and concrete containing fly ash (CEM II/B-V) as presented in
Appendix A.
Legend:
-e-BGM(P,l,l) O ownpH A BGM(P,1,2) O own pH
-6-FAF(P,l,l) O ownpH A FAF(P,1,2) O own pH
-e-SVC(P,l,l) O ownpH A SVC(P,1,2) O own pH
-9-VCT(P,l,l) O ownpH A VCT(P,1,2) O own pH
59
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
pH dependent concentration of As
pH dependent concentration of B
10 12 14
pH dependent concentration of Be
pH dependent concentration of Ba
12 14
pH dependent concentration of Cd
pH dependent concentration of Co
pH dependent concentration of Cr
pH dependent concentration of Cu
60
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
pH dependent concentration of Mo
pH dependent concentration of Ni
ฃ 0.01 -r
0.001 - r
0.0001
10 12 14
pH dependent concentration of Pb
pH dependent concentration of Sb
12 14
10 12 14
O
u
pH dependent concentration of Se
pH dependent concentration of Tl
10
0.001
10 12 14
pH dependent concentration of U
pH dependent concentration of V
10 12 14
61
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
pH dependent concentration of Zn
0.0001
62
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Appendix G. Cumulative Release from Monolith Leaching of CBP Cement Mortars
and Concrete Containing Fly Ash
Notes:
Results are compared to the mean and 90 percent confidence intervals of cumulative release
from ED cement mortars and concrete containing fly ash (CEM II/B-V) as presented in Appendix
C.
Legend:
-BGM(M,1,1)
-SVC(M,1,1)
-VCT(M,1,1)
slope=0.5
90 ฐ/o Conf. Limit - EU
-BGM(M,1,2)
-SVC(M,1,2)
-VCT(M,1,2)
Mean of EU mortars PCA
90 ฐ/o Conf. Limit + EU
63
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Cumulative release of As
Cumulative release of B
0.001
o o.oi
1 10
Time (days)
Cumulative release of Ba
100
1 10
Time (days)
Cumulative release of Cd
100
01
V
1_
V
>
'&
JO
1 0.0001
3 0.01
1 10
Time (days)
Cumulative release of Cr
0.1
1 10
Time (days)
100
1000
1000
100 1000
1000
1000
01
^>
V
13
V
ฃ
I
s
JO
3
u
0.01
0.01 0.1 1 10 100 1000
Time (days)
Cumulative release of Be
10
v
ฃ
v
a
JO
3
U
01
^>
Si
10
V
jo
3
01
^>
V
in
ซ
ฃ
s
JO
3
1
':
or belc
X^
e concentr<
w detectior
^
_^
tions at
limits.
X
0.01 0.1 1 10 100 10
Time (days)
Cumulative release of Co
Cumulative release of Cu
,
or belc
x^
e concentr
w detectior
^
\ limits.
0.01 0.1 1 10 100 10
Time (days)
All eluate concentra
or below detectior
^
limits.
0.01 0.1 1 10 100 10
Time (days)
64
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Cumulative release of Mo
Cumulative release of Ni
01
^>
v
in
jo
3
|
U
100
All eluate concentrations for VCT
at or below detection limits.
0.001
0.01
1 10
Time (days)
100
1000
100
Si
I
ฃ
v
B
JO
3
U
0.01
All eluate concentrations for VCT
at or below detection limits.
0.01 0.1 1 10 100 1000
Time (days)
Cumulative release of Pb
Cumulative release of Sb
01
^>
V
in
V
a
a
ฃ 0.001
0.01
1 10 100
Time (days)
1000
01
^>
v
in
I
ฃ
v
0.001
0.0001
0.01 0.1 1 10 100 1000
Time (days)
Cumulative release of Se
Cumulative release of Tl
1 10
Time (days)
100
1000
All eluate concentrations for VCT
at or below detection limits.
Ol
8!
I
V
_>
B
a
0.1 -:
Z 0.01 -r
ฃ 0.001 I I
0.01 0.1 1 10 100 1000
Time (days)
Cumulative release of U
Cumulative release of V
se (mg/m2)
D
-* 1-
lulative reles
I f
* h
1
All eluate concentra
or below detection
X
X
~s
tions at
limits.
/
3 0.01 0.1 1 10 100 10
Ol
^>
V
in
V
a
O
0.01
0.001 I I
U
Time (days)
0.01 0.1 1 10 100 1000
Time (days)
65
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
SMI*
V
13
V
ซ
a
O
ฃ 0.01
Cumulative release of Zn
u
0.01
1 10
Time (days)
100
1000
66
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Appendix H. pH Dependent Leaching of a Fly Ash (CFA2) and a Fly Ash-Containing
Cement Mortar (MBD2)
Notes:
Results are compared to mean and 90 percent confidence intervals of cumulative release from
ED cement mortars and concrete containing fly ash (CEM II/B-V) as presented in Appendix A.
Legend:
- CFA2(P,1,1)
D CFA2(P,1,2)
-MBD2(P,1,1)
Mean CEM IIB EU
90 % Conf. Lim.+ CEM IIB EU
O own pH
O own pH
O own pH
90 % Conf. Lim.- CEM IIB EU
67
-------
77?e Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
pH dependent concentration of As
pH dependent concentration of B
Concentration (mg/L)
1 1 1 ง P
centration (im
l-> C
c "--1
o
u
Concentration (mg/L) Concentration (mg/L)
o o c
b P o b P o c
OOP H-. OOP0 H
I-1 I-1 I-1 !-> O O O O y r-,
-
r
ra
ฐ&
!
~~"
1 '
-**a
x
x
-^
.
.TQ
V
'r^a
cfC>
L-
]
0 2 4 6 8 10 12 1
PH
pH dependent concentration of Ba
ซ
^j
i;
)
Pi
1
1
1
1
1
1
P
--
- .
j^-j
^@-
-=^.
.e-0^
s^^ *
^
t
2 4 6 8 10 12 1
PH
H dependent concentration of Cd
^
Bq
as,
^>
^>
^
\J
--^
v
V
^'
%
^" \ *
^tjqj o ILJ E^fc^]
V
0 2 4 6 8 10 12 1
PH
1 dependent concentration of Cr
\
^
-~ ^~
"\
^
ป-/
. _/
_ ซ . .
Q*
~-eP
-^
\
\
%
si
f
^
0 2 4 6 8 10 12 1
G"
I
c
o
E
| 0.1-
o
u
4 C
10
J1
Ol
43
n
43 0.01
ง
g 0.001
u
0.0001
4
1000
3 100
f 10
| o.i
g 0.01
c
3 0.001
0.0001
4
1
01
ฃ 0
c
O
w 0.0
E
g o.oo
0 0.000
0.0000
4
V
3 c
C
^ฉ^.
"""* ' i
.
"5
-6k
^\
X
0
) 2 4 6 8 10 12 1
PH
pH dependent concentration of Be
-
-
5
\
\
a.
\.
t
)
0 2 4 6 8 10 12 1
PH
pH dependent concentration of Co
"
"
- r
--
0
pt
0
1
1
1
1
1
1
^e
%i
i
\
^
e^^
+~
\
^
'^,
1 ~N
~B-H1-
^
\ N
"V,
k ^S
V
n n
X
V
3g
P
--A/
2 4 6 8 10 12 1
PH
1 dependent concentration of Cu
^J^
^^\
^-
" [
" [
Sk
s
" ^^
X
1
d
^
2
,
]
0 2 4 6 8 10 12 1
pH
PH
68
-------
77?e Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
pH dependent concentration of Mo
pH dependent concentration of Ni
J1
1
I
43
n
43 0.01 -
ง
g 0.001 -
u
-
J
&SP
eF
.^
^_
.
/
.--
^
J
e
5 10 -
Ol
E .
c
o
E
g 0.01 -
0 0.001 -
'
5
c
y
, \
^
C^
'^..
\
L
^^
^
V
^\-
^-^
CD
)
3
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 1
pH pH
pH dependent concentration of Pb pH dependent concentration of Sb
j1
.ง
c
o
Concentral
i l i
-1 I-1 h
\
^
\
\V
I
\
^
-
^
-"'
X
r
C
O
E
1
o
u
V
k
^* ^
3 ฉ-
t.
^^^ ^^
er^*
^
ง
f
3
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 1
pH pH
pH dependent concentration of Se pH dependent concentration of Tl
centration (m
1 P
* I-1 h
1 1 !
o
u
%>
\
1
5
X
^
*
^^
H3-.g_
C?
^
:~J
-*?
'n ^
^
^
"
3
f
G"
C
O
E
1
ซ 0.001 -
o
u
\
rHn
^
H-ซ-
in n
nrY7
*)
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 1
pH pH
pH dependent concentration of U pH dependent concentration ofV
c
o
Concentral
1 ง f
> 0 C
1 h-1 h
^
B-e-
D D
DCfl
to . .
Concentration (mg/L)
) P o
> o P 1-1 c
' (-* (-* (-* O C
1 1 1 1 |
0 2 4 6 8 10 12 14 0
$\t
w
r -
\
^*
. .ซซ*
-&ซ.
^^
*
^*
-^v
^
\m ]
^^
\
3
ฃ
)
2 4 6 8 10 12 1
PH
PH
69
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Appendix I. Cumulative Release from Monolith Leaching of a Fly Ash-Containing
Cement Mortar (MBD2)
Notes:
Results are compared to mean and 90 percent confidence intervals of cumulative release from
ED cement mortars and concrete containing fly ash (CEM II/B-V) as presented in Appendix C. A
gray solid diagonal line is included as a reference line indicating ideal simple Fickian diffusion
controlled release behavior.
Legend:
-MBD2(M,1,1)
-MBD2(M,1,2)
-MBD2(M,1,3)
slope=0.5
Mean Cum. Release CEM IIB EU
90 % Conf. Limit - CEM IIB
90% Conf. Limit + CEM IIB
70
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Cumulative release of As
Cumulative release of B
1000 -E
100 -
I
u
0.01
0.1
Time (days)
Cumulative release of Ba
100
0.01
Cumulative release of Be
1000
n
a>
0.001
All eluate concentrations at
orbelowthe detection limit.
0.01
0.1
Time (days)
Cumulative release of Cd
100
0.01 0.1 1 10
Time (days)
Cumulative release of Co
Cumulative release of Cr
Cumulative release of Cu
M
release (mgj
p
i-i
Cumulative
1 P
D 0
-1 I-1
All eluate concentrations at
orbelowdetection limits.
J
0.01 0.1 1
Time (days)
10
100
0.01 0.1 1 10
Time (days)
100
100
^ 1U
fM
O 1
^>
Sn 1 -
U.I
8
ฃn m -
0)
"5
! >
>
*
/
^
^
*^^~^ '
-+s~^~
0 -a-
1^*^
^> -1
M
f
^ n 1 -
g
n
u
1 2
2 n m
'^
ra
3
3
All eluate concentrations at
orbelowthe detection limit.
0.01 0.1 1 10 100 0.01
Time (days)
^
^
^^
^
0.1 1 10 10
Time (days)
100
71
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Cumulative release of Mo
Cumulative release of Ni
mg
I
u
o.ooi
0.01 0.1 1 10
Time (days)
100
,ง
a
n
3
3
m -
:
All eluate concentrations at
orbelowdetection limits.
^
^^
0.01 0.1 1 10
Time (days)
100
Cumulative release of Pb
Cumulative release of Sb
100 -E
0.01
0.1 1
Time (days)
100
0.01 0.1 1 10
Time (days)
100
Cumulative release of Se
Cumulative release of Tl
100
I o.oi -t
I
u
0.001
0.01
0.1 1 10
Time (days)
100
^ 1 -r
Ol
a
3 ฐ'1 "t
1
4J
JO
3
3
U 0.01
All eluate concentrations at
orbelowdetection limits.
0.01 0.1 1 10
Time (days)
100
Cumulative release of U
Cumulative release of V
0.01
0.1 1
Time (days)
100
100
0.01 0.1 1 10
Time (days)
100
72
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Cumulative release of Zn
0.01
0.1
100
Time (days)
-ซ-MBD2(M,l,l)
*MBD2(M,1,2)
*-MBD2(M,l,3)
slope=0.5
-Mean Cum. Release CEM IIB EU
-90 % C onf. Limit - CEM IIB
-90 % Conf. Limit + CEM IIB
73
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Appendix J. pH Dependent Leaching of Fly Ash Samples (FAF and CFA2) Compared
to the Range of USEPA Fly Ash Leaching Data
Notes:
Results for FAF and CFA2 are compared to the mean, 5th and 95th percentiles for all fly ash
samples in Kosson et al. (2009) plus EaFA from Garrabrants et al. (2012).
Legend:
- CFA2(P,1,D
A CFA2(P,1,2)
- FAF(P,1,D
A FAF(P,1,2)
Merged-AIIFIyAsh-LPerc5(P,l,l)
Merged-AIIFIyAsh-Median(P,l,D
Merged-AIIFIyAsh-UPerc95(P,l,D
74
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
pH dependent concentration of As
pH dependent concentration of B
E
ฃ
3
8
10 -
n 1 -
! """-^
:
: ฃ
^^
!
^ 4
~*~ -ปป
^ *
m
8
PH
10
12
14
pH dependent concentration of Ba
01
^>
,0
'&
E
o
u
100 -E
0.1 -
0.01
B
to
k.
=
0
u
0.0001 -
0.00001
8
PH
10 12
14
Ol
^>
,0
'&
E
o
u
pH dependent concentration of Co
100 -i
ฃ
3
pH dependent concentration of Cr
100 -E
0.001
o
u
pH dependent concentration of Cu
0.0001 -
0.00001
8
PH
10
12
14
Concentra
pH dependent concentration of Mo
10 -E
I
I-*
0.0001
X
8
PH
*^
10
12
14
75
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
pH dependent concentration of Ni
_o
'ฃ
ID
I
O
u
10 12
14
PH
pH dependent concentration of Se
10
O
u
0.1 -:
0.01
X
^
10 12 14
PH
O
u
pH dependent concentration of V
100
PH
10 12
14
76
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Appendix K. pH Dependent Leaching of EU CEM II/V-B and Single Extraction Leaching
Results (Cheng et al., 2008 and Zhang et al., 2001) Compared to the USEPA
Health-based Numbers
Legend:
-Mean
-90 % Conf. Lim. +
A Cheng ASTM
-*MDL
90 % Conf. Lim.
Zhang monolith
Cheng SPLP
Concrete cube IIB NL2
B Cement mortar IIB BR1
* Cement mortar IIB Fl
ACement mortar IIB D6
Cement mortar IIB B17
X Cement mortar IIB D4
-90 % Conf. Lim -
-Cement mortar IIB Bll
-Cement mortar IIB CI1
-Cement mortar IIB D5
-Concrete cube IIB NL1
-Cement mortar IIB N4
Mean
90 % Conf. Lim +
77
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Concentration of Al as function of pH (P + CFA)
01
i
1000
100
10
0.1
g 0.01
0.001
0.0001
e
O
u
\\
\\
V
lit
10 12
PH
14
e
o
B
Concentration of Al as function of pH (P + CFA)
1000
100 -[
Q o.ooi
0.0001
0.01
10 12 14
Concentration of As as function of pH
Concentration of As as function of pH
0 0001 -
.-
y
X
X
!^_ _
Jt-
^
^^* ^
r=^=x
HBN 1
" X
MD
^
N
^ [
1
^^
Q
P
i
ซ
10 12 14
PH
10 12 14
Concentration of B as function of pH
01
e
o
U
1 .
1
1
-1
+ . .
[h
**>
^^ ^^^ I
BN |
^^
V1*..
1
f*
10 12
14
Concentration of B as function of pH
01
e
o
U
PH
0.01
0.001
Concentration of Ba as function of pH
100
01
*~>
1
S
u
3
10 -
1 -r
0.1 -r
0.01
10
12
14
Concentration of Ba as function of pH
01
*~>
1
s
u
3
PH
0.01
78
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Concentration of Ca as function of pH (P + CFA)
s-^
_l
^_>
c
o
i
v
3
m .
___
:
j .
i
^^^ i
Mป
^^ ^^
*
^
10 12 14
PH
Concentration of Cd as function of pH
01
o
u
u.i -
0 001
nnnm -
i
ซ^
^-.
*- ^
i^
\L
I*'
^**
i
i
HE
^_
~ -
~~
N
_/
--
/
^MC
k
\
L
10
12
PH
Concentration of Co as function of pH
14
5 10 -
Ol
E
Concentration (
I 1 g P
-1 I-1 I-1 I-1 1-
\
^
^^
1
^|^
""{^
-N_
i
Nos
data
V
\
\
^ ^^
\
*-
ngle point
available
vg
V. ** '
[
1
1
!
3
i
10
12
14
pH
Concentration of Cr as function of pH
01
*~>
2
0.001
Concentration of Ca as function of pH (P + CFA)
100000
10000
e
O
B
= 1000
10 12 14
Ol
O
u
Concentration of Cd as function of pH
0.1 -F
0.01 -
0.001
0.0001
0.00001
Concentration of Co as function of pH
4
^\
O
u
0.0001
Concentration of Cr as function of pH
01
*~>
2
0.001
79
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Concentration of Cu as function of pH (P + CFA)
10
Concentration of Cu as function of pH (P + CFA)
10
Concentration of Fe as function of pH
01
.2
2
2
8
ง
u
1000
100
10
0.1
0.01
0.001
0.0001
s
v
^
^
\
L .
\ ^
\
1 No single point
i data available
1
' T- -
""""i
[
-J_.
| HBN 1
. ,^
. ___
1
^^^ ^^_
246
10 12 14
Concentration of Fe as function of pH
1000
PH
o
.ง
I
ง
Concentration of Mg as function of pH
1000
100
10
"
0.01
0.001
f
__ __
^^.'
j .
x,
*^N
^_ %
n
s
*-s
^\
\ N.
\
J\DL | *f
4
0
10
12
14
Concentration of Mg as function of pH
PH
Concentration of K as function of pH
1000 -E
Concentration of K as function of pH
1000 -E
100 -r
Ol
^>
1
100 -r
ง
u
3
10
10
12
PH
14
10
12
PH
14
80
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Concentration of Mn as function of pH (P + CFA)
100
Concentration of Mn as function of pH (P + CFA)
10
1
0.1
0.01
0.001
0.0001
0.00001
f
r
r
r
^^
V.
No single point
data available
. . .
....
_ _ 1
i rx
|^.
. ^
|
|
1
N- -
^ V
\ '
\
V
~^
- -
MDL
\.^r
1
10
12
14
PH
Concentration of Mo as function of pH
01
^>
o
e
o
u
0.01
n nm -
n nnm -
n nnnm -
[
[
[
!
^
^
^
I
T
i
i
i
i
i
'
VIOL W
^^
in!
r-*"
i
i
O |
i
10
12
PH
Concentration of Ni as function of pH
14
3 10 -
o
E ,
1 01
ฃ
Sn m -
U.Ul
u
!
\
^-
1
1
^^v
^r--
!
HBN
N
\
a^^
1
1
1
1
MDL
we- ซ
; !
2 4 6 8 10 12 1
PH
Concentration of P as function of pH
ration (mg/L)
3 P h.
* I-1 I-1 C
ง
U
X
X^
^^
j*
-f-
1
1
1
x.
-^.
>
^"
*ป
^
2 4 6 8 10
v
\
12 1
Concentration of Mo as function of pH
10 -I
Concentration of Ni as function of pH
100 -i
01
*~>
1
s
u
3
0.001
0.0001
10 12 14
Concentration of P as function of pH
PH
81
-------
The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Concentration of Pb as function of pH (P + CFA)
Concentration of Pb as function of pH (P + CFA)
s-^
_l
^_>
c
o
i
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82
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The Impact of Coal Combustion Fly Ash Used as a Supplemental Cementitious Materials on The Leaching of
Constituents from Cements and Concretes
Concentration of Si as function of pH (P + CFA)
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83
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