Characterization of Coal Combustion Residues from Electric Utilities Using Wet Scrubbers for Multi-Pollutant Control July 2008


&EPA
United States
Environmental Protection
Agency
EPA-600/R-08/077
   July 2008
       Characterization of
       Coal Combustion
       Residues from Electric
       Utilities Using Wet
       Scrubbers for Multi-Pollutant
       Control

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                                                        EPA/600/R-08/077
                                                        July 2008
Characterization of Coal Combustion Residues from
       Electric Utilities Using Wet Scrubbers for
                   Multi-Pollutant Control
                        F. Sanchez1, D. Kosson1,
               R. Keeney2, R. Delapp1, L. Turner3, and P. Kariher2

                         Vanderbilt University
               Department of Civil and Environmental Engineering
                           Nashville, TN 37235

                             2ARCADIS
                       4915 Prospectus Drive, Suite F
                           Durham, NC 27713

                          3Turner Technology
                           Nashville, TN 37235

                      Category III /Applied Research
                        Contract No. EP-C-04-023
                        Work Assignment No. 4-26
                       Project No. RN990234.0026
                  U.S. Environmental Protection Agency
                   Office of Research and Development
              National Risk Management Research Laboratory
                Air Pollution Prevention and Control Division
                           Cincinnati, Ohio

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                                            Notice

The U.S. Environmental Protection Agency (EPA) through its Office of Research and Development
funded the research described here under Work Assignment No. 4-26 of Contract Number EP-C-04-023
to Vanderbilt University. It has been subjected to the Agency's peer and administrative review and has been
cleared for publicationas an EPA document.  Reference herein to any specific commercial product, process,
or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its
endorsement or recommendation. The views and opinions of authors expressed herein do not necessarily state
or reflect those of EPA or any agency thereof.

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                                           Foreword

The U.S. Environmental Protection Agency (EPA) is charged by Congress with protecting the Nation's
land, air, and water resources. Under a mandate of national environmental laws, the Agency strives to
formulate and implement actions leading to a compatible balance between human activities and the ability
of natural systems to support and nurture life. To meet this mandate, EPA's research program is
providing data and technical support for solving environmental problems today and building a science
knowledge base necessary to manage our ecological resources wisely, understand how pollutants affect
our health, and prevent or reduce environmental risks in the future.

The National Risk Management Research Laboratory (NRMRL) is the Agency's center for investigation
of technological and management approaches for preventing and reducing risks from pollution that
threaten human health and the environment.  The focus of the Laboratory's research program is on
methods and their cost-effectiveness for prevention and control of pollution to air, land, water,  and
subsurface resources; protection of water quality in public water systems; remediation of contaminated
sites, sediments and ground water; prevention and control of indoor air pollution; and restoration of
ecosystems.  NRMRL collaborates with both public and private sector partners to foster technologies that
reduce the cost of compliance and to anticipate emerging problems. NRMRL's research provides
solutions to environmental problems by: developing and promoting technologies that protect and improve
the environment; advancing scientific and engineering information to support regulatory and policy
decisions; and providing the technical support and information transfer to ensure implementation of
environmental regulations and strategies at the  national, state, and community levels.

This publication has been produced as part of the Laboratory's strategic long-term research plan.  It is
published and made available by EPA's Office  of Research and Development to assist the user
community and to link researchers with their clients.
                                            Sally Gutierrez, Director
                                            National Risk Management Research Laboratory
                                               in

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Characterization of Coal Combustion Residues II
ACKNOWLEDGMENTS

Extensive input on the research program design was provided by G. Helms, U.S. EPA, Office of
Solid Waste (Washington, D.C.).
Laboratory testing described herein was carried out by ARCADIS with technical support from
Vanderbilt  University.  R.  Delapp was responsible for the chemical analyses  carried out at
Vanderbilt University. Technical assistance also was provided by A. Garrabrants.
K. Ladwig and the Electric Power Research Institute (EPRI) are gratefully acknowledged for
assistance in  obtaining coal  combustion residue samples  and providing information from the
EPRI database on coal combustion residues.
S. Thorneloe is the U.S. EPA project officer for this research.
Note: R. Keeney substantially participated in the work reported here and the preparation of this
report but left employment of ARCADIS prior to the completion of this study and report.
                                           IV

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Characterization of Coal Combustion Residues II

TABLE OF CONTENTS
Acknowledgments	iv
Abstract	v
Glossary of terms	vi
Executive Summary	ix
Table of Contents	xii
List of Tables	xv
List of Figures	xvi
1. Introduction	1
  1.1. Regulatory Context	6
     1.1.1. Waste Management	6
     1.1.2. Air Pollution Control	6
  1.2. Configurations of U.S. Coal Fired Power Plants and Multi-pollutant Control
  Technologies	7
     1.2.1. Current Air Pollution Control Technologies	8
     1.2.2. Wet Scrubbers, NOx Controls and Multi-pollutant Controls	11
  1.3. Coal Combustion Residues	12
  1.4. Residue Management Practices	13
     1.4.1. Beneficial Use	13
     1.4.2. Land Disposal	14
  1.5. Leaching Protocol	16
2. Materials and Methods	20
  2.1. CCR Materials for Evaluation	20
     2.1.1. Facilities Using Inhibited or Natural Oxidation of Scrubber Residues (Producing
     Scrubber Sludge or Fixated Scrubber Sludge)	24
      2.1.1.1. Facility A (Natural Oxidation and SNCR)	24
      2.1.1.2. Facility B (Natural Oxidation and SCR)	24
      2.1.1.3. Facility K (Natural Oxidation and SCR)	25
      2.1.1.4. Facility M (Inhibited Oxidation and SCR)	25
     2.1.2. Facilities Using Forced Oxidation of Scrubber Residues (Producing FGD Gypsum) 26
      2.1.2.1. Facility N (Forced Oxidation)	26
      2.1.2.2. Facility O (Forced Oxidation and SCR)	26
      2.1.2.3. Facility P (Forced Oxidation and SCR and SNCR)	26
      2.1.2.4. Facility Q (Forced Oxidation and SCR)	27

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Characterization of Coal Cumbustion Residues II

2.2. Leaching Assessment Protocols 27
2.2.1. Alkalinity, Solubility and Release as a Function of pH (SR002.1) 27
2.2.2. Solubility and Release as a Function of LS Ratio (SR003.1) 28
2.3. Analytical Methods 28
2.3.1. Surface Area and Pore Size Distribution 28
2.3.2. pH and Conductivity 28
2.3.3. Moisture Content 28
2.3.4. Carbon Content Organic Carbon/Elemental Carbon Analyzer 28
2.3.5. Dissolved Inorganic Carbon (DIG) and Dissolved Organic Carbon (DOC) 29
2.3.6. Mercury (CVAA, Method 3052, and Method 7473) 29
2.3.7. Other Metals (ICP-MS, Method 3052, and Method 6020) 30
2.3.7.1. ICP-MS Analysis 30
2.3.8. X-Ray Fluorescence (XRF) 32
2.3.9. MDL and ML for Analytical Results 32
2.4. Quality Assurance ASSESSMENT 33
2.4.1. Homogenization of Individual CCR Samples and Aliquots for Analyses 33
2.4.2. Leaching Test Methods and Analytical QA/QC 33
2.4.3. Improving QA/QC efficiency 34
2.5. Interpretation and Presentation of Laboratory Leaching Data 35
2.5.1. Interpretation of Mechanisms Controlling Constituent Leaching 36
2.6. Field pH probability distribution 38
2.7. Estimated leachate concentration as a function of pH 41
3. Results and Discussion 43
3.1. Total elemental content by digestion 43
3.2. total elemental content by xrf 51
3.3. Laboratory Leaching Test Results 57
3.3.1. Typical Characteristic Leaching Behavior as a Function of pH andLS 58
3.3.2. Comparisons of the Ranges of Constituent Concentrations from Laboratory Testing
with Measurements of Field Samples and the EPA Risk Report Database 77
4. Summary of Results, Conclusions and Recommendations 87
5. References 94
Appendices 97
A. Quality Assurance Project Plan A-l
B. Total Elemental Content by Digestion B-l
vi

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Characterization of Coal Combustion Residues II


   C. Elemental Total Content (by XRF), Carbon, Loss on Ignition and
      Specific Surface Area	C-l
   D. pH Titration and Constituent Leaching as a Function of pH (SR002 test results)	D-l
   E. pH and Constituent Leaching as a Function of LS (SR003 test results)	E-l
   F. Curve Fits	F-l
   G. Additional Facility Information 	G-l
                                         vn

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                                       Characterization of Coal Cumbustion Residues II

LIST OF TABLES
Table 1. Summary of facility configurations and sample identification contained in this report.
   Facilities are identified by code letter only (e.g., "Facility A") to preserve the confidentiality
   of the CCR source. All fly ash samples are ASTM Class F	5
Table 2. General Characteristics of Coals Burned in U. S. Power Plants (EPA, 2005)	7
Table 3. Projected Coal-Fired Capacity by APC Configuration as per data collection in 1999
   (EPA, 2005).  CCR samples evaluated in this report are from configurations indicated by
   shaded (light gray) rows. Current capacity reflects date of data collection for EPA report
   (EPA, 2005)	10
Table 4. Beneficial uses of CCRs (ACAA, 2007).  Total production of CCRs during 2006 was
   124,795,124 short tons	15
Table 5. MDL and ML of analysis of DIC and DOC	29
Table 6. Method detection limits (MDLs) and minimum level of quantification (ML) for ICP-
   MS analysis on liquid samples	31
Table 7. Comparison of summary statistics for field pH data and pH probability distributions
   used in Report 1 and this report	41
Table 8. Fly Ash. Summary of results	90
Table 9. FGD Gypsum. Summary of results	91
Table 10. Scrubber Sludge.  Summary of results	92
Table 11. Fixated Scrubber Sludge.  Summary of results	93
                                         Vlll

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Characterization of Coal Combustion Residues II

LIST OF FIGURES
Figure 1. Flow diagram describing processing and nomenclature of FGD scrubber residues and
   samples included in this study	2
Figure 2. Multi-pollutant control systems in coal fired power plants	12
Figure 3. Life-cycle evaluation of coal combustion residues (EPA, 2002)	13
Figure 4. Uses of CCRs based on 2006 Industry Statistics (ACAA, 2007)	16
Figure 5. Fly ash (FA) comparisons (CFA, AFA, DFA, etc refer to sample identification codes;
   see Table 1). Shorthand is used for when SCR is in use ("on") or not in use ("off')	20
Figure 6. Gypsum (Gyp-U, Gyp-W) comparisons (NAU, NAW, OAU, etc. are sample
   identification codes;  see Table  1)	21
Figure 7. Scrubber sludge (ScS) comparisons (CGD, AGD, DGD, etc. are  sample identification
   codes; see Table  1).  Shorthand is used for when SCR is in use ("on") or not in ("off)	22
Figure 8. Fixated scrubber sludge  (FSS) and fixated scrubber sludge with lime (FSSL)
   comparisons (DCC, BCC, KCC, etc. are sample identification codes; see Table 1)	23
Figure 9. Coefficient of variation (C.V.) from XRF elemental analysis of 10 subsamples of
   FSSL sample MAD after mixing by coning and quartering	33
Figure 10. An example of extract concentrations as a function of pH from  SR002.1	38
Figure 11. Probability distributions for field pH used in Report 1 (LogLogistic) and this report
   (BetaGeneral). Summary statistics for the field data and the probability distribution used in
   this report (BetaGeneral) are provided to the right of the graph	40
Figure 12. Example  of regression fit and corresponding coefficients for a 5th order polynomial
   equation used to represent solubility and release as a function of pH (antimony for fly ash
   from Facility B with SCR bypassed (DFA))	42
Figure 13 and Figure 14.  Mercury and Aluminum. Comparison of total elemental content by
   digestion	45
Figure 15 and Figure 16.  Antimony and Arsenic.  Comparison of total elemental content by
   digestion	46
Figure 17 and Figure 18.  Barium and  Cadmium. Comparison of total elemental content by
   digestion	47
Figure 19 and Figure 20.  Chromium and Cobalt. Comparison of total elemental content by
   digestion	48
Figure 21 and Figure 22.  Lead and Molybdenum. Comparison of total  elemental  content by
   digestion	49
Figure 23 and Figure 24.  Selenium and Thallium. Comparison of total elemental  content by
   digestion	50
Figure 25. Fly Ash - Total content by  XRF	52
Figure 26. Gypsum - Total content by XRF	53
Figure 27. Scrubber Sludge - Total content by XRF	54
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                                      Characterization of Coal Cumbustion Residues II

Figure 28. Fixated Scrubber Sludge- Total content by XRF	55
Figure 29. Fixated Scrubber Sludge with Lime - Total content by XRF	56
Figure 30. Mercury - Examples of characteristic leaching behavior as a function of pH (SR002.1
   results)	61
Figure 31. Aluminum.  Examples of characteristic leaching behavior as a function of pH	62
Figure 32. Antimony. Examples of characteristic leaching behavior as a function of pH	63
Figure 33. Arsenic. Examples of characteristic leaching behavior as a function of pH	64
Figure 34. Barium. Examples of characteristic leaching behavior as a function of pH	65
Figure 3 5. Boron. Examples of characteristic leaching behavior as a function of pH	66
Figure 36. Cadmium. Examples of characteristic leaching behavior as a function of pH	67
Figure 37. Chromium.  Examples of characteristic leaching behavior as a function of pH	68
Figure 38. Chromium.  Examples of characteristic leaching behavior as a function of pH	69
Figure 39. Cobalt. Examples  of characteristic leaching behavior as a function of pH	70
Figure 40. Lead. Examples of characteristic leaching behavior as a function of pH	71
Figure 41. Molybdenum. Examples of characteristic leaching behavior as a function of pH.... 72
Figure 42. Molybdenum. Examples of characteristic leaching behavior as a function of pH.... 73
Figure 43. Selenium. Examples of characteristic leaching behavior as a function of pH	74
Figure 44. Selenium. Examples of characteristic leaching behavior as a function of pH	75
Figure 45. Thallium. Examples of characteristic leaching behavior as a function of pH	76
Figure 46. Natural pH (pH in  distilled water atLS=10) observed in SR02 extracts	79
Figure 47 and Figure 48. Mercury and Aluminum. Comparison of maximum, minimum and
   natural pH concentrations observed in SR02 and SR03 extracts over the pH domain 5.4<
   pH<12.4	80
Figure 49 and Figure 50. Antimony and Arsenic.  Comparison of maximum, minimum and
   natural pH concentrations observed in SR02 and SR03 extracts over the pH domain 5.4<
   pH<12.4	81
Figure 51 and Figure 52. Barium and Boron.  Comparison of maximum, minimum and natural
   pH concentrations observed in SR02 and SR03 extracts over the pH domain 5.4< pH< 12.4.
   	82
Figure 53 and Figure 54. Cadmium and Chromium. Comparison of maximum, minimum and
   natural pH concentrations observed in SR02 and SR03 extracts over the pH domain 5.4<
   pH<12.4	83
Figure 55 and Figure 56. Cobalt and Lead. Comparison of maximum, minimum and natural pH
   concentrations observed in SR02 and SR03 extracts over the pH domain 5.4< pH< 12.4. .  84
Figure 57 and Figure 58. Molybdenum and Selenium.  Comparison of maximum, minimum and
   natural pH concentrations observed in SR02 and SR03 extracts over the pH domain 5.4<
   pH<12.4	85

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Characterization of Coal Combustion Residues II


Figure 59.  Thallium.  Comparison of maximum, minimum and natural pH concentrations
   observed in SR02 and SR03 extracts over the pH domain 5.4< pH< 12.4	86
                                      XI

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Characterization of Coal Cumbustion Residues II

ABSTRACT

This report evaluates leaching characteristics of air pollution control residues from coal-fired
power plants that use acid gas scrubbers, which may also reduce air emissions of mercury and
other pollutants. Leaching of mercury and other constituents of potential concern (COPCs)
during land disposal of coal combustion residues (CCRs)1 is evaluated in this report. The data
presented in this report will be used in a future report to evaluate the fate of mercury and other
COPCs from the management of CCRs resulting from the use of multi-pollutant control
technologies. This research is part of an on-going effort by U.S. Environmental Protection
Agency (EPA) to use a holistic approach to account for the fate of mercury and other metals in
coal throughout the life-cycle stages of CCR management including disposal and beneficial use.
The specific objectives of the research reported here are to:
1. Evaluate the potential for leaching to groundwater of mercury and other COPCs (i.e.,
aluminum, antimony, arsenic, barium, boron, cadmium, chromium, cobalt, lead,
molybdenum, selenium, and thallium) removed from the flue gas of coal-fired power plants
by facilities that use wet scrubbers as part of a multi-pollutant control strategy to reduce air
emissions.
2. Provide the foundation for assessing the impact of enhanced mercury and multi-pollutant
control technology on leaching of mercury and other COPCs from CCR management
including storage, beneficial use, and disposal; and,
3. Perform these assessments using the most appropriate evaluation methods currently
available. The laboratory leach testing followed the approach developed by Kosson, et al.
(2002), which considers the effects of varying environmental conditions on waste constituent
leaching.
Air pollution control residues (fly ash, gypsum, and scrubber sludge samples) were obtained
from coal combustion electric utility facilities using wet scrubbers. A range of facility
configurations was selected representing differences in air pollution control technology
configurations and coal rank. Each of the residues sampled has been analyzed for selected
physical properties, and for total content and leaching characteristics of selected COPCs. Results
of laboratory leaching tests were used to develop estimates of constituent release under field
management scenarios. Laboratory leaching test results also were compared to field observations
of leaching.
This report includes results for 23 CCRs (5 fly ashes, 6 gypsum samples, 5 scrubber sludges, 7
fixated scrubber sludges) sampled from eight facilities. Each CCR sampled was evaluated in the
laboratory for leaching as a function of pH and liquid-to-solid ratio. Results are presented for
mercury, aluminum, antimony, arsenic, barium, boron, cadmium, chromium, cobalt, lead,
molybdenum, selenium and thallium.
1 Coal combustion residues (CCRs) refer collectively to fly ash, scrubber residues and other air pollution
control solid residues generated during the combustion of coal collected through the associated air
pollution control system. Resultant CCRs may be managed as separate or combined residue streams,
depending on individual facility configuration.

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Characterization of Coal Combustion Residues II
GLOSSARY OF TERMS
ACT
Al
APC
APPCD
As
ASTM
B
Ba
BET
BML
CAIR
CAMR
Cd
CCRs
CCV
Co
COPCs
Cr
C.V.
CVAA
DIG
DOC
DOE
DI
DRC
dw
DWEL
EPA
EPRI
ESP
ESP-CS
ESP-HS
Activated Carbon Injection
Aluminum
Air Pollution Control
Air Pollution Prevention and Control Division
Arsenic
American Society for Testing and Materials
Boron
Barium
Brunauer, Emmett and Teller (method for quantification of surface area)
Below Method Limit
Clean Air Interstate Rule
Clean Air Mercury Rule
Cadmium
Coal Combustion Residues
Continuing Calibration Verification
Cobalt
Constituents of Potential Concern
Chromium
Coefficient of Variation
Cold Vapor Atomic Adsorption
Dissolved Inorganic Carbon
Dissolved Organic Carbon
United  States Department of Energy
Deionized (i.e., deionized water)
Dynamic Reaction Chamber
dry weight basis
Drinking Water Equivalent Level
United  States Environmental Protection Agency
Electric Power Research Institute
Electrostatic Precipitator
Cold-side Electrostatic Precipitator
Hot-side Electrostatic Precipitator
                                         xni

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                                      Characterization of Coal Cumbustion Residues
FF
FGD
FID
FO
FSS
FSSL
Gyp-U
Gyp-W
Hg
HHV
Ho
ICP-MS
ICV
In
IO
I.Ox.

LOI
LS
M
Max
MCL
MDL
Mg Lime
Min
ML
Mo
NETL
NIOSH
NO
NOx
NSPS
OC/EC
ORD
Fabric Filter (bag house)
Flue Gas Desulfurization
Flame lonization Detector
Forced Oxidation
Fixated Scrubber Sludge
Fixated Scrubber Sludge with Lime
Unwashed Gypsum
Washed Gypsum
Mercury
Higher Heating Value
Holmium
Inductively Coupled Plasma-Mass Spectrometry
Initial Calibration Verification
Indium
Inhibited Oxidation
Inhibited Oxidation (this abbreviation used in some figures to improve
clarity)
Loss On Ignition
Liquid-to-Solid Ratio (LS ratio)
Molar
Maximum
Maximum Contaminant Level (for drinking water)
Method Detection Limit
Magnesium Enriched Lime (often also referred to as "mag-lime")
Minimum
Minimum Level of Quantification
Molybdenum
National Energy Technology Laboratory (DOE)
National Institute of Occupational Safety and Health
Natural Oxidation
Nitrogen Oxides
New Source Performance Standards
Organic Carbon/Elemental Carbon
Office of Research and Development (EPA)
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Characterization of Coal Combustion Residues II
OSWER
PAC
Pb
PM
PRB
PS
QA/QC
RCRA
RFA
SAB
SCA
Sb
ScS
SCR
SNCR
SDA
Se
S02
SPLP
SRM
s/s
SWDA
TC
TCLP
Tl
XRF
Office of Solid Waste and Emergency Response
Powdered Activated Carbon
Lead
Particulate Matter
Sub-bituminous coal mined in Wyoming's Powder River Basin
Particulate Scrubber
Quality Assurance/Quality Control
Resource Conservation and Recovery Act
Reference Fly Ash
U.S. EPA Science Advisory Board
Specific Collection Area
Antimony
Scrubber Sludge
Selective Catalytic Reduction
Selective Non-Catalytic Reduction
Spray Dryer Absorber
Selenium
Sulfur Dioxide
Synthetic Precipitation Leaching Procedure
Standard Reference Material
Stabilization/Solidification
Solid Waste Disposal Act
Toxicity Characteristic
Toxicity Characteristic Leaching Procedure
Thallium
X-Ray Fluorescence
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Characterization of Coal Cumbustion Residues II

EXECUTIVE SUMMARY

This report evaluates changes that may occur to coal combustion residues (CCRs)2 in response to
changes in air pollution control technology at coal-fired power plants, which will reduce
emissions from the flue gas stack by transferring pollutants to fly ash and other air pollution
control residues. Congress has directed EPA to document that the Clean Air Act regulations do
not have the net effect of trading one environmental burden for another. The Air Pollution
Prevention and Control Division (APPCD) of EPA's Office of Research and Development
(ORD) is conducting research to evaluate potential leaching and cross media transfers of
mercury and other constituents of potential concern (COPCs) resulting from land disposal or
beneficial use of CCRs. The focus of this report is to present data that will be used to evaluate
the fate of mercury and other metals from the use of wet scrubbers at coal-fired power plants.
Leaching tests are being conducted on the residues to determine the potential transfer of
pollutants from the residues to water resources or other environmental systems (e.g., soils,
sediments).
The specific objectives of the research reported here are to:
1. Evaluate the potential for leaching to groundwater of mercury and other COPCs (i.e.,
aluminum, antimony, arsenic, barium, boron, cadmium, chromium, cobalt, lead,
molybdenum, selenium, and thallium) removed from the flue gas of coal-fired power
plants by facilities that use wet scrubbers as part of a multi-pollutant control strategy to
reduce air emissions.
2. Provide the foundation for assessing the impact of enhanced mercury and multi-pollutant
control technology on leaching of mercury and other COPCs from CCR management
including storage, beneficial use, and disposal; and,
3. Perform these assessments using the most appropriate evaluation methods currently
available. The laboratory leach testing followed the approach developed by Kosson, et al.
(2002), which considers the effects of varying environmental conditions on waste
constituent leaching.
Air pollution control residues were obtained from coal combustion electric utility facilities using
wet scrubbers. A range of facility configurations was selected representing differences in air
pollution control technology configurations and coal rank. Each of the residues sampled has been
analyzed for selected physical properties, and for total content and leaching characteristics.
Results of laboratory leaching tests were used to develop estimates of constituent release under
field management scenarios. Laboratory leaching test results also were compared to field
observations of leaching.
2 Coal combustion residues (CCRs) refer collectively to fly ash and other air pollution control solid
residues generated during the combustion of coal collected through the associated air pollution control
system. Resultant CCRs may be managed as separate or combined residue streams, depending on
individual facility configuration.
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Characterization of Coal Combustion Residues II

This report includes results for 23 CCRs (5 fly ashes, 6 gypsum samples, 5 scrubber sludges, 7
fixated scrubber sludges) sampled from eight facilities. The samples are considered to be
representative of likely facility configurations indicative of 84 and 74 percent, respectively, of
the current and future facility configuration types with acid gas scrubbers based on generating
capacity; however, only a limited number of facilities representing each configuration type have
been sampled. A range of coal ranks typically combusted is also represented. Each CCR sampled
was evaluated in the laboratory for leaching as a function of pH and liquid-to-solid ratio. Results
are presented for mercury, aluminum, antimony, arsenic, barium, boron, cadmium, chromium,
cobalt, lead, molybdenum, selenium and thallium.
The selected testing approach was chosen for use because it evaluates leaching over a range of
values for two key variables [pH and liquid-to-solid ratio (LS)] that both vary in the environment
and affect the rate of constituent release from waste. The range of values used in the laboratory
testing encompasses the range of values expected to be found in the environment for these
parameters. Because the effect of these variables on leaching is evaluated in the laboratory,
prediction of leaching from the waste in the field is expected to be done with much greater
reliability.
In addition, results from laboratory leaching evaluation were compared to field leachate
concentrations from CCR management facilities available from a U.S. EPA database and an
Electric Power Research Institute (EPRI) database to determine if laboratory testing results
reasonably represented field observations.
Summary of Conclusions
The data presented in this report will be used in a future report that provides a probabilistic
assessment of plausible management practices to evaluate the fate of mercury and other COPCs.
Leach results contained in this report are compared to health-based values to identify where there
may be potential concerns. The intended use of these results is to suggest that for values less than
MCLs or DWELs there is unlikely a potential for environmental concern. The thresholds used
here for preliminary screening do not account for additional dilution and attenuation processes
that may occur under field management scenarios4. Therefore the results are considered
environmentally conservative and actual release rates would be less. For values greater than
MCLs or DWELs, additional research is needed to determine potential release rates.
Based on the results of testing and evaluations in this study, the following conclusions are drawn:
1. For each CCR type, the following constituents exceeded either the maximum
contaminant level (MCL) or drinking water equivalent level (DWEL) in at least one
laboratory leaching test condition over the range of pH and LS ratios considered, and
therefore potentially may present unacceptable environmental risks under some
management scenarios. These cases warrant more detailed evaluation, including
consideration of site-specific conditions.
3 Fly ash is collected by the participate collection device, such as an electrostatic precipitator; gypsum is
dewatered material collected from forced oxidation flue gas desulfurization; scrubber sludge is collected
from natural or inhibited oxidation flue gas desulfurization; and fixated scrubber sludge is a mixture of
scrubber sludge, fly ash and often with additional lime added.
4 Dilution and attenuation factors are specific to individual sites and management scenarios and may
range from less than 10 to greater than 100.

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(i) Fly ash - antimony, arsenic, boron, cadmium, chromium, molybdenum,
selenium and thallium.
(ii) FGD gypsum - boron, cadmium, molybdenum, selenium and thallium.
(iii) Scrubber sludge - mercury, antimony, arsenic, boron, chromium, lead,
molybdenum, selenium and thallium.
(iv) Fixated scrubber sludge - mercury, antimony, arsenic barium, boron, cadmium,
chromium, lead, molybdenum, selenium and thallium.
However, (i) typically, evaluation results from only a subset of samples of a given
material type exceeded the indicated criteria, and (ii) never did the full range reported
exceed the indicated threshold.
2. Leaching of individual constituents may vary over several orders of magnitude,
depending on the conditions of the management scenario. Thus, these results can be used
to suggest design conditions that would reduce or minimize constituent release (e.g., pH,
and other conditions).
3. Leaching concentrations do not correlate with total content except for specific
constituents in selected materials where the constituent (i) is weakly retained, and (ii)
leaching concentrations have a low variability relative to pH. Thus, total content is not a
good indicator of leaching.
4. Results of this study suggest that it appears that Cr teachability is associated with the use
of post-combustion NOx controls. This is based on a limited set of paired samples from
the same facility operating with and with SCR or SNCR in use. This finding will be
further evaluated as additional data are collected.
5. The systematic leaching behavior of COPCs observed in the range of samples evaluated
suggests that the geochemical mechanisms controlling leaching can be discerned and
quantified using geochemical speciation modeling, which in turn, can serve as the basis
for evaluating and improving design of CCR management scenarios. Development of
generalized geochemical speciation models for the CCR materials evaluated in this study
is recommended.
The new information reported here provides an expanded basis for future assessments and may
impact risk evaluations. Ranges of concentrations of some constituents in laboratory leaching
test extracts and field data included in this study suggest different applicable concentration
ranges for risk evaluation other than used in the recent risk assessment on coal combustion waste
found in docket # EPA-HQ-RCRA-2006-0796
(http://www.regulations.gov/fdmspublic/component/main).
This is the second of a series of reports that will evaluate the potential for leaching of COPCs
from CCRs from coal-fired power plants that use wet scrubbers. The first report focused on the
use of sorbents for enhancing mercury capture at coal-fired power plants. (Sanchez et al., 2006)
The third report will evaluate CCRs from facilities with different air pollution control
configurations and coal ranks that were not previously covered in the first two reports. The
fourth and final report will provide a probabilistic assessment of the leaching potential of
mercury and other COPCs based on plausible management strategies. The data will be used to
correlate leaching characteristics to coal rank, air pollution control configurations, and
combustion facility characteristics.

xviii

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                                        Characterization of Coal Cumbustion Residues II


1. INTRODUCTION

Changes are occurring to air pollution control technology at coal-fired power plants  which will
reduce emissions from the flue gas  stack by transferring pollutants to fly ash and other air
pollution control residues.  Congress has directed EPA to  document that the  Clean Air Act
regulations do not have the net effect of trading one environmental burden for another. The Air
Pollution  Prevention  and  Control  Division (APPCD) of EPA's  Office of Research  and
Development (ORD) is conducting research to  evaluate potential leaching and cross media
transfers of Constituents of Potential Concern (COPCs) resulting from land disposal or beneficial
use of coal combustion residues (CCRs). This report is part of a series of reports being prepared
to document the fate of mercury and other metals found in coal that are being controlled at the
power plant stack through implementation of multi-pollutant control technology.
The focus of this report is to present an evaluation  of air pollution control residues that  may
result from the use of SO2 scrubbers  as mercury  control technology at coal-fired power plants,
and the potential for transfer of pollutants from the resulting residues to water resources or other
environmental systems  (e.g.,  soils,  sediments).  The residues  studied for this report  were
unwashed and washed flue gas desulfurization (FGD) gypsum, scrubber sludge, fixated scrubber
sludge, and fly ashes generated from power plants that have SO2 scrubbers. This report compares
the impact of NOx  control technology [selective catalytic reduction (SCR) and selective non-
catalytic reduction (SNCR)] on characteristics of CCRs obtained from the same facilities during
periods when the NOx control was and was not in use.
The potential for leaching of mercury and other COPCs during land disposal or beneficial use of
the CCRs is the more narrow focus of this assessment. This research is part of an on-going effort
by EPA to use an integrated, comprehensive approach  to account for the fate of mercury and
other  metals  in  coal throughout the life-cycle stages of CCR  management (Thorneloe et al.,
2008; Sanchez  et al., 2006). Related  research  and  assessment  on  environmental  fate of
constituents during  CCR management  includes  conducting  thermal  stability  studies, leach
testing, and probabilistic assessment modeling to determine fate of mercury and other  metals that
are in coal combustion  residues  resulting  from implementation of multi-pollutant  control
technology (Kilgroe et al., 2001; EPA, 2002).
CCRs include bottom ash, boiler slag, fly ash, scrubber  residues and other miscellaneous solids
generated during the combustion of coal. Air pollution control can concentrate or  partition metals
to fly ash and scrubber residues. The boiler slag and bottom  ash are not of interest in this study
because enhanced mercury emission controls  are not expected to change their composition. Use
of multi-pollutant controls minimizes air emissions of mercury and other metals by the transfer
of the metals  to the fly ash and  other CCRs.  This  research will help determine  the fate of
mercury and other COPCs from the management of CCRs through either disposal or reuse.  Fly
ash may include unburned carbonaceous  materials and  inorganic materials in coal that do not
burn,  such as oxides of silicon, aluminum,  iron, and calcium. Fly ash is light enough to be
entrained in the flue  gas stream and captured in the air pollution control equipment.
The type and characteristics of FGD scrubber residue produced is primarily a function of (i) the
scrubber sorbent used (i.e., limestone, lime, magnesium enriched lime referred to as Mg lime, or
alkaline fly ash), (ii) the extent of oxidation during  scrubbing (i.e., forced oxidation, natural
oxidation, or  inhibited oxidation),  (iii) post-scrubber processing, including possibly  dewatering
or thickening, drying,  water rinsing, or blending with  other materials,  and  (iv)  coal rank

                                           1

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Characterization of Coal Combustion Residues II
combusted. The presence and leaching characteristics of the constituents of potential concern in
scrubber residues is a consequence of the coal combusted, process sequence employed, process
conditions, process additives and use or disposal scenario.  Figure 1 illustrates the processes used
in the production of materials that were sampled for this study, sample nomenclature, and the
typical management pathways for each material. FGD gypsum is defined here as the by-product
of the SC>2 wet scrubbing process when the scrubber residue is subjected to forced oxidation. In
forced oxidation systems, nearly all of the by-product is calcium sulfate dihydrate (CaSCVH^O).
The resulting wet gypsum is partially dewatered  and then either disposed in a landfill (unwashed
gypsum;  Gyp-U) or water rinsed  (in some cases) and dried to produce washed gypsum (washed
gypsum;  Gyp-W) that then potentially can be used in wallboard manufacturing or agricultural
applications. Scrubber sludge (ScS) is the by-product of the SC>2 wet scrubbing process resulting
from  neutralization of acid gases at  facilities  that  use  either  inhibited  oxidation or  natural
oxidation of  scrubber residue. In inhibited oxidation systems, nearly  all  of the by-product is
calcium sulfite hemihydrates  (CaSO3»/^H2O). In natural oxidation systems, the by-product is a
mixture of CaSOs'/ffl^O and CaSCVH^O.  Scrubber sludge typically will be either partially
dewatered in a thickener and then disposed in a surface impoundment, or after thickening, further
dewatered  and mixed  with fly  ash to  form fixated scrubber  sludge (FSS).  In  most  cases,
additional lime is also blended with the scrubber sludge  and fly ash to form fixated scrubber
sludge with lime (FSSL). The blend of fly ash and scrubber sludge is typically between 0.5 to 1.5
parts fly ash  to 1 part  scrubber sludge on a dry weight basis, with 0  or 2-4% additional lime
added (FSS or FSSL,  respectively). Fixated  scrubber sludge typically is either disposed in a
landfill or supplied to a beneficial use (e.g., fill in mining applications).  This report evaluates the
characteristics  of fly ash,  FGD  gypsum, scrubber  sludge, and  fixated  scrubber sludge (as
produced with or without lime) from several coal combustion facilities.
      Absorber
  (Forced Oxidation)
Facilities N, O, P, Q
     Absorber
(Inhibited Oxidation
or Natural Oxidation)
Facilities A, B, K, M
            Wet Gypsum

     Dewatering
              -Landfill (Agriculture?)
               (Unwashed Gypsum; Gyp-U)
       Rinsing
       & Drying
             (Washed Gypsum; Gyp-W)
     Wallboard
                          Thickener  	+ Impoundment
                                  (Scrubber Sludge; ScS)
                            Drying
                               I
                       Mixing of Scrubber Sludge
                           Fly Ash and Lime
                                  (Fixated Scrubber Sludge)
                                  (FA+ScS; FSS)
                                  (FA+ScS+lime; FSSL)

                           Landfill or
                         Beneficial Use
Figure 1.  Flow diagram describing processing and nomenclature of FGD scrubber residues and
samples included in this study.

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Characterization of Coal Cumbustion Residues II

When coal is burned in an electric utility boiler, the resulting high combustion temperatures
vaporize the Hg in the coal to form gaseous elemental mercury (Hg°). Subsequent cooling of the
combustion gases and interaction of the gaseous Hg° with other combustion products result in a
portion of the Hg being converted to gaseous oxidized forms of mercury (Hg2+) and particle-
bound mercury. The specific chemical form — known as the speciation — has a strong impact
on the capture of mercury and other metals by boiler air pollution control (APC) equipment.
(EPA, 2001)
Mercury and other elements partition between the combustion gas, fly ash and scrubber residues.
Depending upon the gas conditioning, presence or absence of NOx control and other air
pollution control technology in use, there may be changes occurring to the fly ash that may affect
the stability and mobility of mercury and other metals in the CCRs. Similarly, NOx control and
SC>2 scrubber technology may affect the content, stability and mobility of mercury and other
metals in scrubber residues.
In response to wider use of multi-pollutant control, changes are occurring in air pollution control
at coal-fired power plants to reduce emissions of nitrogen oxides, sulfur oxides, and mercury.
How these changes in air pollution control is the focus of this research. The fate of mercury and
other COPCs in fly ash and scrubber residues is of interest as part of the overall lifecycle
evaluation of impact of air pollution control technology and the management of CCRs either
through disposal or beneficial use. This research is evaluating changes to air pollution control
residues as a result of more widespread implementation of these multi-pollutant technologies,
and the impacts of land disposal or commercial use of the residues.
The specific objectives of the research reported here are to:
1. Evaluate the potential for leaching of mercury and other COPCs removed from coal-
fired power plant air emissions by different types of air pollution control technology
that includes acid gas scrubbers, particulate, and sorbents;
2. Provide information to be used in separate reports to assess the fate of mercury and
other COPCs from enhanced or expanded use multi-pollutant control technologies.
This will include consideration of potential leaching of mercury and other COPCs
during the life-cycle management of CCRs during storage, beneficial use and
disposal; and
3. Perform these assessments using the most appropriate evaluation methods currently
available. The laboratory leach testing followed the approach developed by Kosson,
et al. (2002), which considers the effects of varying environmental conditions on
waste constituent leaching.
This is the second of a series of reports that will address the potential for cross-media transfer of
COPCs from CCRs. The first report focused on the use of sorbent injection (activated carbon
and brominated activated carbon) for enhanced mercury control (Sanchez et al., 2006).
Subsequent reports will address:
• CCRs from coal-fired power plants that use air pollution control technologies other than
evaluated in earlier reports necessary to span the range of coal-types and air pollution control
technology configurations (report 3);
• Assessment of leaching for COPCs under additional management scenarios, including
impoundments and beneficial use on the land (report 4); and,

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Characterization of Coal Combustion Residues II

• Broader correlation of CCR leaching characteristics to coal rank, combustion facility
characteristics and geochemical speciation within CCRs supported by information and
analysis on additional trace elements and primary constituents (report 4).
Table 1 provides a summary of facility configurations, including samples and sample
identification for testing, described in this report. For simplicity in presentation, the use of NOx
controls is indicated as either "off or "on" (i.e., SNCR Off, SNCR On, SCR Off, SCR On),
recognizing that SCR not in use (SCR Off) reflects that either the system was bypassed or
ammonia was not added, and SNCR not in use (SNCR Off) indicates that urea was not added.
Sampled CCRs were subjected to multiple leaching conditions according to the designated
leaching assessment approach. Leaching conditions included batch equilibrium5 extractions at
acidic, neutral and alkaline conditions at an LS of 10 mL/g, and LS from 0.5 to 10 mL/g using
distilled water as the leachant. The leach testing results are used to evaluate the likely range of
leaching characteristics during land disposal (i.e., landfill or surface impoundment). Results of
the laboratory leaching tests carried out in this study were compared to the range of observed
constituent concentrations in field leachates reported in a U.S. EPA database (EPA, 2007) and an
Electric Power Research Institute (EPRI) database (EPRI, 2006). The testing results presented
here will be used for evaluating disposal and beneficial use scenarios in subsequent reports.
As part of this research program, a QA/QC plan consistent with EPA requirements was
developed for the leaching assessment approach and reported earlier (Sanchez et al., 2006). The
QA/QC methodology included initial verification of acceptable mercury retention during
laboratory testing through evaluation of a mass balance around testing procedures (Sanchez et
al., 2006). Modifications to the QA/QC program to reduce the experimental and analytical
burden while maintaining confidence in the resulting data, based on program results to date, are
presented in this report.
Laboratory testing for leaching assessment was carried out at the EPA National Risk
Management Research Laboratory (Research Triangle Park, North Carolina) with technical
assistance from Vanderbilt University and ARCADIS.
5 In the context of leaching tests, the term "equilibrium" is used to indicate that the test method result is a
reasonable approximation of chemical equilibrium conditions even though thermodynamic equilibrium
may not be approached for all constituents.

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                                                                         Characterization of Coal Cumbustion Residues II


Table 1.  Summary of facility configurations and sample identification contained in this report. Facilities are identified by code letter
only (e.g., "Facility A") to preserve the confidentiality of the CCR source. All fly ash samples are ASTM Class F.

Facility
Code
A
A
B
B
K
M
M
N
O
P
Q
Coal
Rank1
Bit
Bit
Bit
Bit
Sub-Bit
Bit
Bit
Bit
Bit
Bit
Sub-Bit
Post-
Combustion
NOx Control2
SNCR-BP (off)
SNCR (on)
SCR-BP (off)
SCR (on)
SCR (on)
SCR-BP (off)
SCR (on)
None
SCR (on)
SCR & SNCR
none
Particulate
Control3
Fabric Filter
Fabric Filter
ESP-CS
ESP-CS
ESP-CS
ESP-CS
ESP-CS
ESP-CS
ESP-CS
ESP-CS
ESP-HS
FGD Scrubber Type
Lime or
Mg Lime
Limestone
Limestone
Mg Lime
Mg Lime
Mg Lime
Limestone
Limestone
Limestone
Limestone
Limestone
Limestone
Oxidation
Natural
Natural
Natural
Natural
Natural
Inhibited
Inhibited
Forced
Forced
Forced
Forced
Sample Types and Identification4
FA
CFA
AFA
DFA
BFA
KFA






Gyp-U







NAU
OAU
PAD
QAU
Gyp-W







NAW
OAW


ScS
CGD
AGO
DGD
BGD
KGD






FSS
ccc
ACC









FSSL


DCC
BCC
KCC
MAD
MAS




 Bit - bituminous; Sub-Bit - sub-bituminous
2SNCR - selective non-catalytic reduction;  SNCR-BP - SNCR by-passed during winter months; SCR & SNCR - residues combined
 from facility with both SCR and SNCR
3ESP-CS - cold-side electrostatic precipitator; ESP-HS - hot-side electrostatic precipitator.
4FA - fly ash; Gyp-U - unwashed gypsum; Gyp-W - washed gypsum; ScS - scrubber sludge; FSS - fixated scrubber sludge (a
 mixture of fly ash and scrubber sludge); FSSL - fixated scrubber sludge with lime (a mixture of fly ash and scrubber sludge with
 additional lime added). The three-letter identification codes are shown for each facility and sample type (e.g., CFA, CGD).

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Characterization of Coal Combustion Residues II
1.1. REGULATORY CONTEXT

1.1.1. Waste Management
The management of coal combustion residues is subject to the Resource Conservation and
Recovery Act (RCRA), which is the federal law regulating both solid and hazardous wastes, as
well as state regulatory requirements. Subtitle C of RCRA pertains to hazardous waste; other
solid, non-hazardous wastes fall under RCRA Subtitle D. Subtitle C wastes are federally
regulated while Subtitle D wastes are regulated primarily at the state level. The original version
of RCRA did not specify whether CCRs were Subtitle C or D wastes. In 1980, the Solid Waste
Disposal Act (SWDA) amendments to RCRA conditionally excluded CCRs from Subtitle C
regulation pending completion of a study of CCR hazards. Since that time, CCRs have been
regulated at the state level under Subtitle D.
The SWDA amendments to RCRA required EPA to prepare a report to Congress identifying
CCR hazards and recommending a regulatory approach for CCRs. In this report (EPA, 1988) and
the subsequent regulatory determination, EPA recommended that CCRs generated by electric
utilities continue to be regulated under RCRA Subtitle D (See 58 FR 42466, August 9, 1993).
Other residues generated at coal-fired electric utilities were not included in this 1993 decision.
EPA conducted a follow-up study specifically aimed at low-volume, co-managed wastes6 and
issued another Report to Congress (EPA, 1999) with a similar recommendation. In April 2000,
EPA issued a regulatory determination exempting these wastes from hazardous waste regulations
(see 65 FR 32214, May 22, 2000). However, concern was expressed over the use of CCRs as
backfill for mine reclamation operations, and it was determined that this practice should be
regulated under a federal Subtitle D rule. It was also decided by EPA that federal regulations
under Subtitle D are needed for CCR when they are disposed in surface impoundments and
landfills. Currently, the agency is in the process of developing these regulations
(http://www.epa.gov/epaoswer/other/fossil/noda07.htm). The results presented in this report, and
subsequent reports, will help provide the information needed to identify the release potential of
mercury and other metals that have been removed from stack gases into air pollution control
residues, over a range of plausible management options. These data will help identify those
conditions that will either reduce or enhance releases to the land so that the effects of different
management conditions can be factored into any controls developed under the regulations.

1.1.2. Air Pollution Control
On March 10, 2005, EPA announced the CAIR (FR 25612, May 2005) which is expected to
increase the use of wet scrubbers and selective catalytic reduction (SCR) units to help reduce
sulfur dioxide and nitrogen oxides emissions from coal-fired power plants. On March 15, 2005,
EPA announced the CAMR (FR 28606, May 2005) for reducing mercury emissions through the
use of a cap and trade program. Power plants are the largest remaining source of anthropogenic
mercury emissions in the county. The CAMR established "standards of performance" that limit
mercury emissions from new [through new source performance standards (NSPSs)] and existing
(through emission guidelines) coal-fired power plants through the creation of a market-based
cap-and-trade program that will reduce mercury emissions in two phases. The first phase caps
Co-managed wastes are low-volume wastes that are co-managed with the high-volume CCRs.

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Characterization of Coal Cumbustion Residues
national annual mercury emissions at 38 tons through co-benefit reductions achieved through
controlling sulfur dioxide (802) and nitrogen oxides (NOx) emissions under CAIR. In the second
phase, due in 2018, coal-fired power plants will be subject to a second cap, which will reduce
mercury emissions to 15 tons per year upon full implementation. On February 8, 2008, the D.C.
Circuit vacated EPA's rule removing power plants from the Clean Air Act list of sources of
hazardous air pollutants. At the same time, the court vacated the CAMR. EPA is reviewing the
court's decisions and evaluating its impacts, (http://www.epa.gov/mercuryrule/) On July 11,
2008, the D.C. Circuit vacated EPA's Clean Air Interstate Rule. EPA is reviewing the court's
decisions and evaluating its impacts.
Congress has directed EPA to document that the Clean Air Act regulations are not trading one
environmental burden for another. The Air Pollution Prevention and Control Division (APPCD)
of EPA's Office of Research and Development (ORD) is conducting the current research to help
identify any potential pollutant transfers resulting from land disposal or beneficial use of
mercury-enriched CCRs. The research results presented in this report are part of that effort.
In response to the evolving implementation of advanced air pollution control technology for
coal-fired power plants, this research is directed towards understanding changes in CCR
characteristics that may increase environmental burdens from land disposal of CCRs or impact
CCR usage in commercial applications.

1.2. CONFIGURATIONS OF U.S. COAL FIRED POWER PLANTS AND
MULTI-POLLUTANT CONTROL TECHNOLOGIES
In the U.S., there are approximately 1,100 units at approximately 500 coal-fired electricity
generating facilities. These facilities represent a range of coal ranks, boiler types, and air
pollution control technologies. The current combined capacity of U.S. coal-fired power plants is
307 GW (DOE-EIA, 2007). The coal rank burned and facility design characteristics affect the
effectiveness of multi-pollutant control technologies that are or could be used at these plants. The
U.S. coal-fired power plants typically burn one of three types of fuel: (1) bituminous coal (also
referred to as "high rank" coal), (2) sub-bituminous coal, and (3) and lignite (sub-bituminous
coal and lignite are referred to as "low rank" coals). Some of the characteristics of interest
related to the possible environmental impacts of burning these different coal ranks are given in
Table 2 (EPA, 2005).
Table 2. General Characteristics of Coals Burned in U. S. Power Plants (EPA, 2005).

Coal
Bitu-
minous
Sub-
bitu-
minous
Lignite
Mercury
ppm (dry)
Range
0.036-
0.279
0.025 -
0.136
0.080-
0.127
Avg
0.113
0.071
0.107
Chlorine
ppm (dry)
Range
48 -
2730
51
1143
133 -
233
Avg
1033
158
188
Sulfur
% (dry)
Range
0.55 -
4.10
0.22 -
1.16
0.8 -
1.42
Avg
1.69
0.50
1.30
Ash
% (dry)
Range
5.4 -
27.3
4.7 -
26.7
12.2 -
24.6
Avg
11.1
8.0
19.4
HHVa
BTU/lb (dry)
Range
8646 -
14014
8606 -
13168
9487 -
10702
Avg
13203
12005
10028
a Higher Heating Value.

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Characterization of Coal Combustion Residues II


1.2.1. Current Air Pollution Control Technologies
The key air pollutants of concern released by coal fired power plants include particulates, 862,
NOx, mercury and  other metals7. A range of pollution control technologies is used to reduce
particulate, SC>2, and NOx and these technologies also impact the emission of mercury and other
metals. The pollution control technology type and configurations vary across facilities.
7 Concerns regarding carbon dioxide emissions from coal fired power plants are beyond the scope of this
report.

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Characterization of Coal Cumbustion Residues II

Table 3 shows the current and projected coal-fired capacity by air pollution control technology
configuration. This report emphasizes wet scrubbers since their use is expected to double or
triple in response to implementation of CAIR. Post-combustion particulate matter controls used
at coal-fired utility boilers in the United States can include electrostatic precipitators (ESPs),
fabric filters (FFs), particulate scrubbers (PSs), or mechanical collectors (MCs). Post-combustion
SC>2 controls can consist of a wet scrubber (WS), spray dryer adsorber (SDA), or duct injection.
Post-combustion NOx controls can involve selective catalytic reduction (SCR) or selective
noncatalytic reduction (SNCR).
In response to current and proposed NOx and 862 control requirements, additional NOx control
and flue gas desulfurization (FGD) systems for SO2 control are expected to be installed and more
widely used in the future. Some estimates project a doubling or tripling of the number of wet
scrubbers as a result of CAIR implementation. Over half of the U.S. coal-fired capacity is
projected to be equipped with SCR and, or, FGD technology by 2020.
The mercury capture efficiency of existing ESPs and FFs appears to be heavily dependent on the
partitioning of mercury between the particulate and vapor phases and the distribution of mercury
species (e.g., elemental or oxidized) in the vapor phase. In general, ESPs and FFs which are
designed for particulate control are quite efficient at removing mercury in the particulate phase;
however, the overall mercury removal efficiency in these devices may be low if most of the
mercury entering the device is in the vapor phase (MTI, 2001). Many factors contribute to the
observed differences in mercury removal efficiency, such as the mercury oxidation state.
Differences in mercury contents of U.S. coals also result in a range of mercury concentrations in
the flue gas from the boiler. In general, it is easier to achieve higher mercury percent removal
with higher mercury inlet concentrations (MTI, 2001). Further, the chlorine content of the coal
may have an impact on mercury removal because the oxidation state of mercury is strongly
affected by the presence of halides in the flue gas. In general, the higher the chlorine content of
the coal, the more likely the mercury will be present in its oxidized state, enhancing the
likelihood of its removal from the gas stream. The addition of NOX controls may improve the
mercury capture efficiency of particulate collection devices for some cases. (EPA, 2001)

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Characterization of Coal Combustion Residues II
Table 3.  Projected Coal-Fired Capacity by APC Configuration as per data collection in 1999
(EPA, 2005). CCR samples evaluated in this report are from configurations indicated by shaded
(light gray) rows.  Current capacity reflects date of data collection for EPA report (EPA, 2005).
Air Pollution Control Configuration
Cold-side ESP
Cold-side ESP + Wet Scrubber
Cold-side ESP + Wet Scrubber + ACI
Cold-side ESP + Dry Scrubber
Cold-side ESP + SCR
Cold-side ESP + SCR + Wet Scrubber
Cold-side ESP + SCR + Dry Scrubber
Cold-side ESP + SNCR
Cold-side ESP + SNCR + Wet Scrubber
Fabric Filter
Fabric Filter + Dry Scrubber
Fabric Filter + Wet Scrubber
Fabric Filter + Dry Scrubber + ACI
Fabric Filter + SCR
Fabric Filter + SCR + Dry Scrubber
Fabric Filter + SCR + Wet Scrubber
Fabric Filter + SNCR
Fabric Filter + SNCR + Dry Scrubber
Fabric Filter + SNCR + Wet Scrubber
Hot-side ESP
Hot-side ESP + Wet Scrubber
Hot-side ESP + Dry Scrubber
Hot-side ESP + SCR
Hot-side ESP + SCR + Wet Scrubber
Hot-side ESP + SNCR
Hot-side ESP + SNCR + Wet Scrubber
Existing or Planned Retrofit Units

New Builds of Coal Steam Units
Fabric Filter + SCR + Wet Scrubber

Total All Units
Current
Capacity, MW
111,616
41,745
-
2,515
45,984
27,775
-
7,019
317
11,969
8,832
4,960
-
2,210
2,002
805
267
559
932
18,929
8,724
-
5,952
688
684
474
304,955

Current
Capacity, MW
-

304,955
2010 Capacity,
MW
75,732
34,570
379
3,161
35,312
62,663
11,979
4,576
2,830
10,885
8,037
4,960
195
2,950
2,601
805
267
557
932
11,763
10,509
538
3,233
6,864
1,490
474
298,263

2010 Capacity,
MW
221

298,484
2020 Capacity,
MW
48,915
33,117
379
5,403
22,528
98,138
13,153
2,534
6,088
7,646
9,163
4,960
195
1,330
4,422
2,363
345
557
1,108
10,160
10,398
538
1,847
9,912
1,334
627
297,161

2020 Capacity,
MW
17,292

314,453
Note: IGCC units are not included as part of this list.
Note: Current capacity includes some SCR and FGD projected to be built in 2005 and 2006.
Note: 2010 and 2020 is capacity projected for final CAIR rule.
Note: IPM projects some coal retirements and new coal in 2010 and 2020.
                                          10

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                                         Characterization of Coal Cumbustion Residues II


1.2.2. Wet Scrubbers, NOx Controls and Multi-pollutant Controls
Wet FGD scrubbers are the most widely used technology for SCh control. Scrubbers are typically
installed downstream of particulate control (i.e., ESP or FF). Removal of PM from the flue gas
before it enters the wet scrubber reduces solids in the scrubbing solution and minimizes impacts
to the fly ash that might affect its beneficial use.
FGD technology uses sorbents and chemical reactants such as limestone (calcium carbonate) or
lime (hydrated to  form calcium hydroxide) to remove sulfur dioxide from the flue gas created
from coal combustion. Limestone is ground into a fine powder and then combined with water to
spray the slurry into combustion gases as they pass through a scrubber vessel. The residues are
collected  primarily as calcium sulfite  (a  chemically  reduced  material  produced  in  natural
oxidation or inhibited oxidation scrubbers), or can be oxidized to form calcium sulfate or FGD
gypsum (using forced oxidation). The most widely used FGD systems use either forced oxidation
scrubbers with limestone addition, or  natural/inhibited oxidation scrubbers with lime or Mg-lime
addition8. Wet scrubbers  that use forced oxidation produce calcium sulfate (gypsum) and are
expected to be the most prevalent  technology because of the potential beneficial use  of gypsum
and easier management and handling of the residues.  There are also dry FGD systems that
include spray dryer absorbers, usually in combination with a FF (EPA, 2001;  Srivastava et al.,
2001).
NOx  emissions are controlled through the use  of low NOx producing  burners  and use of a
selective catalytic reduction (SCR) system in the flue gas that is  capable of a 90% reduction of
flue  gas  NOx  emissions. SCR is typically installed  upstream  of  the  PM  control  device.
Sometimes  selective non-catalytic reduction (SNCR) is  used for NOx control,  although use of
SNCR is less frequent.
Figure 2 illustrates options for multi-pollutant control  at power plants.
8 As of 1999: Total FGD units - 151; limestone forced oxidation (FO) - 38 units (25%); limestone natural/inhibited
oxidation - 65 (43%); lime FO (all forms other than Mg-Lime) -1 (<1%); lime natural/inhibited oxidation (all forms
other than Mg-lime) - 23 (15%); Mg-lime FO - 0 (0%); Mg-lime natural/inhibited oxidation - 25 (17%)
It is estimated that the numbers of natural/inhibited systems has remained nearly the same since 1999, and the
limestone FO units have increased significantly. In the future, limestone FO units will increase significantly, and all
types of natural/inhibited units will likely decrease (Ladwig, 2007).
                                            11

-------
Characterization of Coal Combustion Residues II
Oxidizing Wet Scrubber Stack
Catalysts
Coal & Air
SCR PM Control
Figure 2. Multi-pollutant control systems in coal fired power plants.
Improvements in wet scrubber performance to enhance mercury capture depend on oxidizing
elemental mercury (Hg°) to Hg2+ by using additives to the flue gas or scrubber. A DOE-funded
study found that wet scrubbers remove about 90% of the oxidized gaseous mercury (Hg2+) in the
flue gas but none of the elemental mercury (Pavlish et al., 2003). The percentage of total Hg
removed by multi-pollutant controls (paniculate and scrubber devices) is influenced by coal
chlorine content, which determines the Hg oxidation status exiting the particulate control and
entering the scrubber. Mercury removal efficiency by wet scrubbers ranges from 30 to 60% for
cold-side ESPs as coal chlorine content is increased from 50 to 1000 mg kg"1. Mercury removal
efficiency for hot-side ESPs is less effective ranging from 20 to 50% as coal chlorine content is
increased from 200 to 1000 mg kg"1 (Pavlish et al., 2003). Other factors that influence mercury
capture are the amount of carbon and chlorine in the fly ash. Fuel blending, addition of oxidizing
chemicals, controlling unburned carbon content in the fly ash, and addition of a mercury-specific
oxidizing catalyst downstream of the particulate matter control can help improve mercury
capture (Thorneloe, 2006; EPA, 2005).

1.3. COAL COMBUSTION RESIDUES
The range of air pollution control technologies and configurations determines the characteristics
of the coal combustion residues. In 2006, 125 million tons of coal combustion residues were
produced with -53 million tons being used in commercial, engineering, and agricultural
applications. (ACAA, 2007). CCRs result from unburned carbon and inorganic materials in
coals that do not burn, such as oxides of silicon, aluminum, iron, and calcium. Fly ash is the
unburned material from coal combustion that is light enough to be entrained in the flue gas
stream, carried out of the process, and collected as a dry material in the APC equipment. APC
can concentrate or partition metals in fly ash and scrubber sludge. Bottom ash and boiler slag are
not affected by APC technology and, therefore, these materials are not being evaluated as part of
this study. Bottom ash is the unburned material that is too heavy to be entrained in the flue gas
12

-------
                                       Characterization of Coal Cumbustion Residues
stream and drops out in the furnace. Boiler slag, unburned carbon or inorganic material in coal
that does not burn, falls to the bottom of the furnace and melts.
Changes  in  multi-pollutant  control  in  response   to  CAIR  implementation,  voluntary
improvements by  facilities,  and changes in state requirements,  will reduce air emissions of
mercury and other pollutants that will be transferred from the flue gas to the APC residues. The
purpose of this research is to evaluate the impact of these changes on CCRs, with a focus on
changes in metals concentrations in CCRs, and  the potential for subsequent release  of these
metals to the environment under different plausible management  (disposal or reuse) conditions
(Figure 3). The  properties of fly ash and scrubber residues are likely to change as a result of
changes in air pollution control to reduce emissions of concern from coal-fired power plants.
Changes in CCRs that may occur include increased content of mercury and other metals (e.g.,
arsenic, selenium, chromium)    The chemical and physical properties  may  also change as a
results of sorbents and other additives being used to improve air pollution control.
  Implement CAIR
      or CAAAR
                             Combustion
•••+*****
                                                          Lower
                                                          Concentration of
                                                          Hgjn Flue Gas
                                     • » * ******** ••*»•»»
               CCR Disposal
                                                        Increased
                                                        Concentration of
                                                            ant) other
                                              CCR Use in
                                              Commercial
                                              Application's
                                                                     Fly Ash
                                                                 Scrubber Sludge,/
                                           Greater Potential
                                           for Hg
             Greater
             for Mg Releases?

  CAIR: Clean Air Interstate Rule
  CAWLR; Cl«aT Air Mercury Sule

Figure 3. Life-cycle evaluation of coal combustion residues (EPA, 2002).
1.4. RESIDUE MANAGEMENT PRACTICES
CCRs can be disposed in landfills or surface impoundments or used in commercial applications
to produce concrete  and  gypsum wallboard, among other products. The major pathway of
concern for release from land disposal and some beneficial use applications is leaching to
groundwater. Research on the impact of CCR disposal on the environment has been conducted
by many researchers and has been summarized by the EPA (1988, 1999). However, most of the
existing CCR data are for CCRs prior to implementation of mercury or multi-pollutant controls.

1.4.1. Beneficial Use
In the United States, approximately 40% percent (49.6 million tons) of all CCRs produced are
reused in  commercial applications or other uses that  are considered beneficial  and avoid
                                          13

-------
Characterization of Coal Combustion Residues II

landfilling. Forty-eight percent (23.8 million tons) of CCRs is fly ash which is used in
commercial applications such as making concrete/grout, cement, structural fill, and highway
construction (ACAA, 2005; Thorneloe, 2003). Eight million tons of the FGD gypsum that was
produced (or 68%) was used in making wall board (ACAA, 2005). Table 4 and Figure 4 present
the primary commercial uses of CCRs, and a breakdown of U.S. production and usage by CCR
type.
Some of the beneficial uses may have the potential to release mercury from the CCRs by several
pathways. Of particular concern are high-temperature processes. In cement manufacturing, for
example, CCRs are inputs to the cement kiln. Virtually all mercury will be volatilized from
CCRs when CCRs are used as feedstock to cement kilns. Even where mercury can be captured
by the controls on cement kilns, approximately two-thirds of cement kiln dust captured by the
control devices is reintroduced into the kiln. Therefore, a significant fraction of the mercury in
CCRs introduced into cement kilns may be emitted to the air at the cement plant. Some mercury
may also be revolatilized when CCRs are used as filler for asphalt, or when FGD material is used
in wallboard manufacturing. A separate report is being prepared to document the finding on the
thermal stability of Hg and other metals when used in high-temperature processes.
The fate of mercury and other metals is also a potential concern when CCRs are used on the land
(mine reclamation, building highways, soil amendments, agriculture and in making concrete,
cement) or to make products that are subsequently disposed (e.g., disposal of wallboard in
unlined landfill).
For several commercial uses, it appears less likely that mercury in CCRs will be reintroduced
into the environment, at least during the lifetime of the product. However, the impact of
advanced mercury emissions control technology (e.g., activated carbon injection) on beneficial
use applications is uncertain. There is concern that the presence of increased concentrations of
mercury, certain other metals, or high carbon content may reduce the suitability of CCRs for use
in some applications (e.g., carbon content can limit use in Portland cement concrete).

1.4.2. Land Disposal
There are approximately 600 land-based CCR waste disposal units (landfills or surface
impoundments) being used by the approximately 500 coal-fired power plants in the United States
(EPA, 1999). About 60% of the 122 million tons of CCRs generated annually are land disposed.
Landfills may be located either on-site or off-site while surface impoundments are almost always
located on-site with the combustion operations. Although the distribution of units is about equal
between landfills and surface impoundments, there is a trend toward increased use of landfills as
the primary disposal method.
14

-------
Vkitderbilt IS
   I'nivorsiiv
Characterization of Coal
  Cumbustion Residues
                    Report
    Table 4. Beneficial uses of CCRs (ACAA, 2007).  Total production of CCRs during 2006 was 124,795,124 short tons.
CCR Categories (Short Tons)
CCR Production Category Totals2
CCR Used Category Totals3
CCR Use By Application4
1. Concrete/Concrete Products/Grout
2. Cement/Raw Feed for Clinker
3. FlowableFill
4. Structural Fills/Embankments
5. Road Base/Sub-base/Pavement
6. Soil Modification/Stabilization
7. Mineral Filler in Asphalt
8. Snow and Ice Control
9. Blasting Grit/Roofing Granules
10. Mining Applications
11. Wallboard
12. Waste Stabilization/Solidification
13. Agriculture
14. Aggregate
15. Miscellaneous/Other
CCR Category Use Tools
Application Use to Production Rate
Fly
Ash
72,400,000
32,423,569
Fly
Ash
15,041,335
4,150,228
109,357
7,175,784
379,020
648,551
26,720
0
0
942,048
0
2,582,125
81,212
271,098
1,016,091
32,423,569
44.8%
Bottom
Ash
18,600,000
8,378,494
Bottom
Ash
597,387
925,888
0
3,908,561
815,520
189,587
19,250
331,107
81,242
79,636
0
105,052
1,527
647,274
676,463
8,378,494
45.0%
FGD
Gypsum
12,100,000
9,561,489
FGD
Gypsum
1,541,930
264,568
0
0
0
0
0
0
0
0
7,579,187
0
168,190
0
7,614
9,561,489
79.0%
FGD Wet
Scrubbers
16,300,000
904,348
FGD Wet
Scrubbers
0
0
0
131,821
0
0
0
0
232,765
201,011
0
0
0
0
338,751
904,348
5.5%
Boiler
Slag1
2,026,066
1,690,999
Boiler
Slag1
0
17,773
0
126,280
60
0
45,000
41,549
1,445,933
0
0
0
0
416
13,988
1,690,999
83.5%
FGD Dry
Scrubbers1
1,488,951
136,639
FGD Dry
Scrubbers1
9,660
0
9,843
0
249
299
0
0
0
115,696
0
0
846
0
46
136,639
9.2%
FGD
Other
299,195
29,341
FGD
Other
0
0
0
0
0
1,503
0
0
0
0
0
27,838
846
0
46
29,341
9.8%
1 As submitted based on 54 percent coal burn.
2 CCR Production totals for Fly Ash, Bottom Ash, FGD Gypsum, and Wet FGD are extrapolated estimates rounded off to nearest 50,000 tons.
3 CCR Used totals for Fly Ash, Bottom Ash, FGD Gypsum, and Wet FGD are per extrapolation calculations (not rounded off).
4 CCR Uses by application for Fly Ash, Bottom Ash, FGD Gypsum, and Wet FGD are calculated per proportioning the CCR Used Category
Totals by the same percentage as each of the individual application types' raw data contributions to the as-submitted raw data submittal total
(not rounded off).
                                                                15

-------
Characterization of Coal Combustion Residues II
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-------
                                         Characterization of Coal Cumbustion Residues II


disposed, CCRs are typically  monofilled  or  disposed  with other CCRs.  However, CCR
composition can change over time, due to reactions with the atmosphere (e.g., carbonation and
oxidation), changes in the source of coal or coal rank burned, or due to installation of additional
pollution control equipment.
Many leaching  tests  have been developed by regulatory  agencies, researchers, or third-party
technical standards organizations, and are described in the published literature. States and others
have expressed concern with the variety of leaching protocols  in use, the lack of correlation of
test results with field  conditions and actual leaching, and lack of comparability of available data
because  of incomplete reporting of test conditions. There is also limited  or no quality assurance
(QA) information for many of these tests. Leaching tests such as the Toxicity Characterization
Leaching Procedure (TCLP)9 (which reflects municipal solid waste co-disposal conditions) or
the synthetic precipitation leaching procedure (SPLP), or any number of deionized water based
tests may be inappropriate, or are  at least not optimal for evaluating the leaching potential of
CCRs as they are actually managed (i.e., monofilled or codisposed with other CCRs). These tests
either presume  a set of prevailing landfill conditions (which may or  may not exist at CCR
disposal  sites; e.g., TCLP), try to account for an environmental factor considered to be important
in leaching (e.g., SPLP), or presume that the waste as tested in the laboratory will define the
disposal  conditions  (such as deionized  (DI) water  tests). Most existing  leaching  tests are
empirical, in that results are presented simply as the contaminant concentrations leached when
using the test, and without  measuring or reporting values for  factors  that may affect waste
leaching, or that provide insight into the chemistry that is  occurring in leaching. Most tests are
performed as a single batch test, and so do not consider the effect of variations in conditions on
waste constituent leaching10.
In searching for a reliable procedure to characterize the leaching potential of metals from the
management of CCRs, EPA sought an approach that  (i) considers key  aspects of the range of
known  CCR  chemistry  and management  conditions (including  re-use);  and  (ii) permits
development of data  that are comparable across U.S. coal and CCR types.  Because the data
resulting from this research will be used to support regulations, scrutiny  of the data is expected.
 The Toxicity Characterization Leaching Procedure (TCLP) was not included as part of this study for
two reasons. First, EPA previously made a waste status determination under RCRA that coal combustion
residues are non-hazardous (65 FR 32214, May 22, 2000). Therefore, use of TCLP was not required as
indicated under the RCRA toxicity characteristic regulation for determination of whether or not CCRs
were hazardous. Second, TCLP was developed to simulate co-disposal of industrial waste with municipal
solid waste as a mismanagement scenario, and to reflect conditions specific to this scenario. However, the
vast majority of CCRs are not being managed through co-disposal with municipal solid waste, and the test
conditions for TCLP are different from the actual management practices for most CCRs. In seeking a
tailored, "best-estimate" of CCR leaching, the leaching framework provides the flexibility to consider the
effects of actual management conditions on these wastes, and so will be more accurate in this case.


10 Many factors are known or may reasonably be expected to affect waste constituent leaching. The
solubility of many metal salts is well known to vary with pH; adsorption of metals to the waste matrix
varies with pH; redox conditions may determine which metal salts are present in wastes; temperature may
affect reaction rates; water infiltration can affect the leaching rate, and also affect leaching chemistry and
equilibrium.


                                            17
-------
Characterization of Coal Combustion Residues II


Therefore, the use of a published, peer-reviewed protocol is also considered to be an essential
element of this work.
EPA ORD has worked  closely with EPA's Office of Solid Waste and Emergency Response
(OSWER) to identify an appropriate leaching protocol for evaluating CCRs. The protocol that
has been adopted is the "Integrated Framework for Evaluating Leaching in Waste Management
and Utilization of  Secondary Materials"  (Kosson  et al.,  2002) and  referred to here as the
"leaching framework."  The  leaching framework  consists  of a tiered  approach to leaching
assessment. The general approach under the leaching framework is to use laboratory testing to
measure intrinsic leaching characteristics of a material (i.e., liquid-solid equilibrium partitioning
as a function of pH and  LS  ratio,  mass  transfer rates)  and then use  this information in
conjunction with mass transfer models to estimate constituent release by leaching under specific
management  scenarios (e.g., landfilling).  Unlike  other laboratory  leaching  tests, under this
approach, laboratory testing  is not intended to directly simulate  or  mimic field  conditions.
Development work to-date on the leaching  framework has focused on assessing metals leaching,
and this  work includes  equilibrium batch testing  (over a range of pH and LS  ratio values),
diffusion-controlled mass transfer, and percolation-controlled (column) laboratory test methods
in conjunction with mass transfer models, to estimate release for specific management scenarios
based on testing results from a common set of leaching conditions. EPA OSWER and ORD
believe that this approach successfully addresses the concerns identified above, in that it seeks to
consider the effect  of key  disposal  conditions on  constituent leaching, and to understand the
leaching chemistry of wastes tested.
The following attributes of the leaching framework were considered as part of the selection
process:
•  The leaching framework will permit development of data that are comparable across U.S.
   coal and CCR types;
•  The leaching framework will permit comparison with existing laboratory and field leaching
   data on CCRs;
•  The leaching framework was published in the peer-reviewed scientific literature (Kosson et
   al., 2002);
•  On consultation with EPA's OSWER, it was recommended as the appropriate protocol based
   on review of the range of available test methods  and assessment approaches; and
•  On consultation with the Environmental Engineering Committee of the Science Advisory
   Board (June 2003), the  committee considered the leaching framework responsive to earlier
   SAB  criticisms of EPA's approach to leaching  evaluation, and also was considered broadly
   applicable and appropriate for this study
For this study, the primary leaching tests used from the leaching framework were Solubility and
Release as a Function of pH (SR002.1) and Solubility and Release as a Function of the Liquid-
Solid Ratio (LS) (SR003.1)11. These tests represent equilibrium-based leaching characterization
11 LS refers to liquid to solid ratio (mL water/g CCR or L water/kg CCR) occurring during laboratory
leaching tests or under field conditions. SR002.1 is carried out at LS=10 with several parallel batch
extractions over a range of pH, while SR003.1 is carried out using several parallel batch extractions with

                                           18
-------
                                         Characterization of Coal Cumbustion Residues II


(Kosson et al., 2002). The range of pH and LS ratio used in the leaching tests includes the range
of conditions (pH and LS ratio)  observed for current CCR management practices.  Results of
these tests provide  insights into the physical-chemical  mechanisms controlling  constituent
leaching. When used in conjunction with mass transfer and geochemical speciation modeling, the
results can provide conservative12 but realistic estimates of constituent leaching under a variety
of environmental conditions (pH, redox, salinity, carbonation) and management scenarios.
Laboratory testing for leaching assessment was carried out at the U.S. EPA National  Risk
Management Research Laboratory (Research Triangle Park, NC) with technical assistance from
Vanderbilt University.
deionized water at LS= 0.5, 1, 2, 5 and 10. Under field conditions, LS refers to the cumulative amount of
water passing through the total mass of CCR subject to leaching.
12 In this report, "conservative" implies that the constituent release estimates are equal to or greater than
actual expected release under field conditions.


                                            19
-------
Characterization of Coal Combustion Residues II


2. MATERIALS AND METHODS

2.1. CCR MATERIALS FOR EVALUATION
The 23 CCR materials tested in this study include five fly ash, four unwashed gypsum, two
washed gypsum, five scrubber sludges, two fixated scrubber sludges  and five fixated scrubber
sludges with lime obtained from eight coal fired power plants (Table 1). The facilities and CCRs
that were sampled were selected to allow comparisons
   (i)  between different CCR types from a given facility (Facilities A, B and K),
   (ii)  between CCRs of the same type from the  same  facility  without and with  post-
       combustion NOx control, either by SNCR (Facility A) or SCR  (Facility B),
   (iii) the impact of different FGD scrubber types on scrubber sludge  and "as managed" FSS or
       FSSL (Facilities A, B, K and M),
   (iv) the influence of coal rank (bituminous vs. sub-bituminous) being combusted in facilities
       with similar APC technology configurations (Facility B and K with SCR on),
   (v)  unwashed and washed gypsum from the same facility (Facilities N  and O), and
   (vi) unwashed gypsum from four facilities (Facilities N, O, P and Q). This set of 23 CCRs
       reflects 84 and 74 percent, respectively, of the current and expected future facility
       configuration types with acid gas scrubbers based on generating capacity, but only a
       limited number of facilities within each configuration type. Figure 5, Figure 6,
   (vii) Figure 7, and Figure 8 diagram the layout of comparisons that will be used in
       presentation of data for fly ash, gypsum, scrubber sludge, fixated scrubber sludge and
       fixated scrubber sludge with lime, respectively.
      Facility A
      Coal: low sulfur bituminous
      APC: NO+SNCR+FF
      Facility B
      Coal: low sulfur bituminous
      APC: NO+SCR+ESP(CS) [Mg lime]

      Facility K
      Coal: sub-bituminous
      APC: NO+SCR+ESP(CS) [Mg lime]
CFA
(SNCR Off)

AFA
(SNCR On)
DFA
(SCR Off)

BFA
(SCR On)
  KFA
(SCR On)
Figure 5. Fly ash (FA) comparisons (CFA, AFA, DFA, etc refer to sample identification codes;
see Table 1). Shorthand is used for when SCR is in use ("on") or not in use ("off).
                                      20
-------
                                Characterization of Coal Cumbustion Residues
  Facility N
  Coal:  bituminous
  Facility O
  Coal:  bituminous
  Facility P
  Coal:  bituminous

ous
P(CS)

ous
:R+ESP(CS)


ous
:R & SNCR +ESP(CS)

Gyp-U
NAU
(unwashed)

OAU
(unwashed)


PAD (U)
(unwashed)









Gyp-W
NAW
(washed)

OAW
(washed)


QAU
(unwashed)
/\
  Facility Q
  Coal:  sub-bituminous
  APC:  FO+SCR+ESP(CS)

Figure 6.   Gypsum (Gyp-U, Gyp-W) comparisons  (NAU,  NAW,  OAU, etc.  are sample
identification codes; see Table 1).
Errata: Subsequent tables and figures indicate the Facility N has SCR in use. That is not correct.
This will be corrected in Report 4 and does not change the leach testing results.
                                   21
-------
Characterization of Coal Combustion Residues II
 Facility A
 Coal: low sulfur bituminous
 ARC: NO+SNCR+FF
 Facility B
 Coal: low sulfur bituminous
 ARC: NO+SCR+ESP(CS) [Mg lime]


 Facility K
 Coal: sub- bituminous
 ARC: NO+SCR+ESP(CS) [Mg lime]
  CGD
(SNCROff)
  AGO
(SNCROn)
  DGD
 (SCR Off)
  BGD
 (SCR On)
             KGD
           (SCR On)
Figure 7. Scrubber sludge (ScS) comparisons (CGD, AGD, DGD, etc. are sample identification
codes; see Table 1). Shorthand is used for when SCR is in use ("on") or not in ("off).
                             22
-------
                            Characterization of Coal Cumbustion Residues
FSS: Fly Ash + Scrubber Sludge (FA+ScS)
 Facility A (FSS1
 Coal: low sulfur bituminous
 ARC: NO+SNCR+FF
ccc
(SNCROff)

ACC
(SNCROn)
FSSL: Fly Ash + Scrubber Sludge + Lime (FA+ScS+lime)
 Facility B (FSSL)
 Coal: low sulfur bituminous
 ARC: NO+SCR+ESP(CS)  [Mg lime]

 Facility K (FSSL)
 Coal: sub-bituminous
 ARC: NO+SCR+ESP(CS)  [Mg lime]


 Facility M (FSSIJ
 Coal: bituminous
 ARC: IO+SCR+ESP(CS)
DCC
(SCR Off)

BCC
(SCR On)
  KCC
(SCR On)
MAD
(SCR Off)

MAS
(SCR On)
Figure 8.  Fixated scrubber sludge (FSS) and fixated scrubber sludge with lime (FSSL)
comparisons (DCC, BCC, KCC, etc. are sample identification codes; see Table 1).
                              23
-------
Characterization of Coal Combustion Residues II
2.1.1. Facilities Using Inhibited or Natural  Oxidation of Scrubber Residues (Producing
       Scrubber Sludge or Fixated Scrubber  Sludge)
2.1.1.1. Facility A (Natural Oxidation and SNCR)
Facility A is a 440-MW coal-fired power plant  with a reverse-air fabric filter followed by a wet
FGD  system. The unit burns ~1  percent sulfur eastern bituminous coal. The unit operated at
nominally full load for the duration of the test program. The unit is equipped with a pulverized-
coal boiler and in-furnace selective SNCR; urea was injected into the boiler during the course of
operations within the duration of the  initial part of this  test program. However, urea was not
injected into the boiler for the final comparison test ("SNCR off). Gas exiting the  furnace is
split between two flues equipped with comparable control equipment. Paniculate is removed
with a reverse-air fabric filter. Flue gas is then scrubbed through a multiple tower wet  FGD unit;
FGD is a limestone natural-oxidation design. The two flues are joined prior to exhausting to a
common stack. The annular stack rises 308 feet above the top of the incoming flue. The stack is
operated in a saturated condition with  no reheat. The fly  ash and FGD waste are combined and
then dewatered before landfill disposal.
Facility A was sampled in September  2003. Three samples were collected in September 2003
when the SCR was operating: one fresh fly ash sample collected from the ash hopper (sample
AFA), one scrubber sludge filter cake sample  collected  after the centrifuge but before mixing
with other materials in the pug mill (sample AGD), and one fixated scrubber sludge sample
collected after mixing the  scrubber sludge with fly ash and magnesium-enhanced lime  in the pug
mill (sample ACC). Three additional samples were collected from the same locations in February
2004 when the SCR was not in use (samples CFA,  CGD and CCC, respectively). Each sample
consisted of two 5-gallon pails of the material, and all were collected by plant personnel.
2.1.1.2. Facility B (Natural Oxidation and SCR)
Facility B is a 640 MW  coal-fired power  plant with cold side ESP followed by a wet FGD
system with Mg-lime. The unit burns medium to high sulfur eastern bituminous coals. The unit is
equipped with a pulverized coal boiler and  selective catalytic reduction composed of vanadium
pentoxide  (¥265) and tungsten trioxide  (WOs), on  titanium dioxide (TiCh) supporting matrix.
One set of samples was collected during the season of elevated ozone, when ammonia  is injected
into the  ductwork in front  of the  SCR  catalyst,  resulting  in a flue gas mixture with  a
concentration of 320 ppm ammonia as it enters the catalyst. Samples were also collected during
the winter when ammonia was not being injected ("SCR off). Particulate is removed with a
cold-side ESP. Flue gas is then scrubbed through a wet FGD unit; FGD is an inhibited mag-lime
design. The FGD sludge is thickened and then mixed with fly ash and magnesium-enhanced lime
before landfill disposal in a clay-lined  site.  Refer to appendix G for a process  flow-diagram for
facility A.
Three samples were collected in September, 2003 when the  SCR was operating: one give gallon
bucket of the  fly ash (BFA)  from  the  hoppers, partially  dewatered scrubber sludge by
centrifuging (BGD), and centrate cake (BCC)  or scrubber sludge fixated with fly ash and Mg
lime (MgO).  Three additional samples were collected from the same locations in February, 2004
when the  SCR  was not in use (samples DFA,  DGD,  and DCC, respectively). Each sample
consisted  of one 5-gallon bucket of the material, and all  were collected a Natural Resource
Technology contractor to EPRI.
                                          24
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                                       Characterization of Coal Cumbustion Residues
Coal analysis information for facility B was provided by EPRI. Results of the analysis on the
medium to high sulfur bituminous coal for sulfur was 3.24% by weight, ash was 12.4%, moisture
was 6.1%, heat of combustion was 12,000 BTU/lb, chloride was 615 ug/g, and mercury was 0.08
ug/g.
2.1.1.3. Facility K (Natural Oxidation and SCR)
Facility K is two tangentially fired 400 MW coal-fired boilers with cold  side ESP followed by a
wet flue gas desulfurization system with wet Mg-lime natural oxidation.  These units  burn
medium sulfur eastern bituminous coals from Ohio, Pennsylvania and West Virginia. Flue gas is
scrubbed through a  common wet FGD unit; FGD is  a wet Mg-lime natural oxidation design.
FGD sludge is mixed with fly ash and quicklime for stabilization prior to  disposal.
Two samples were  collected on November 29, 2004: one scrubber  sludge  filter cake before
mixing in the pug mill (sample KGD), and one fixated  scrubber sludge collected after mixing the
scrubber sludge with fly ash and 2-3% lime in the pugmill (sample KCC). On January  12, 2005,
one fly ash sample  was collected directly from the ESP before the ash storage  silo (sample
KFA).  Each sample consisted of four 5-gallon  pails of the material, and all  were collected by
plant personnel.
2.1.1.4. Facility M (Inhibited Oxidation and SCR)
Facility M is a  1,000+ MW power plant. The plant burns bituminous coal in  a dry-bottom
pulverizer boiler. Cold-side ESPs are used on  all units for  particulate control,  and wet FGD
systems are used to reduce SO2 emissions on two units. The wet FGD systems utilize limestone
slurry and  an inhibited oxidation process. The FGD sludge,  consisting primarily of calcium
sulfite, is pumped  from the absorber to a thickener. Liquid overflow from the thickener is
recycled  back into the  FGD system,  and the thickened  sludge is pumped to a series of drum
vacuum filters for further dewatering. Water removed by the drum vacuum  filters is recycled
back into the FGD system, and the filter cake is  taken by conveyor belt to a pug mill, where it is
mixed with dry fly ash and dry quicklime for stabilization. The resulting scrubber FGD solids are
taken by conveyor to a temporary outdoor stockpile,  and then transported by truck either to a
utilization site or to an on-site landfill.  The currently  active portion of the landfill is lined and
includes leachate collection. An older inactive portion of the landfill is  clay-lined but does not
have leachate collection.
Three samples were  obtained from the Pug Mill  Area by the EPRI contractor during the week of
March  6, 2006 when the SCR was not operating: fly ash, vacuum drum filter cake, and fixated
scrubber sludge with lime (only FSSL was evaluated as part of this study, sample MAD).  In
each case, the samples were collected daily during the four day sample collection (four daily
samples of each), for compositing in the laboratory. All of the samples were collected into clean
5 gallon plastic pails. Excess sample was containerized and discharged back into the appropriate
system. The drum filter cake was sampled daily from the conveyor belt leading into the pug mill.
Two of the three drum filters were running simultaneously; both were feeding  the conveyor belt.
The  same  drums were running each  day  of sampling. Each 5  gallon bucket was sealed
immediately after collection and the  lid secured with duct tape. The dry  fly ash sample was
obtained directly from  the day  tank via a hose connected to a sampling port. Each 5 gallon
bucket was sealed immediately after collection and the lid  secured with duct tape.  FSS was
                                          25
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Characterization of Coal Combustion Residues II


sampled from the conveyor belt on the outlet side of the pug mill on the first, third and fourth
days. A clean, short handled spade was used to collect sample from the conveyor belt into a 2
gallon bucket.  The  sample in the bucket was placed on a clean piece of 3 mm plastic sheeting;
then more sample was collected from the conveyor belt into the bucket and added to the sheet
until at least 6 gallons  of sample was collected.  Each sample was  homogenized on the sheet
using the spade and placed into a 5 gallon bucket, sealed immediately, and the lid secured with
duct tape. A similar process was used to collect  three more samples the week of May 9 when the
SCR was in use (FSSL sample MAS).

2.1.2. Facilities Using Forced Oxidation of Scrubber Residues (Producing FGD Gypsum)
2.1.2.1. Facility N (Forced Oxidation)
Facility N is a wall fired 715 MW coal-fired power plant with cold side ESP followed by a wet
FGD system with wet limestone forced oxidation.  The unit burns medium to high sulfur eastern
bituminous coals approximately 3% sulfur.  The gypsum is washed,  dried and then sold to the
wallboard industry.
Facility N was sampled on June  1, 2006.  Five  gallon buckets  of  the washed  and unwashed
gypsum were  collected by RMB Consulting &  Research Inc. (Raleigh, NC)  personnel and
provided for analysis.
2.1.2.2. Facility O (Forced Oxidation and SCR)
Facility O is a tangentially fired 500 MW coal-fired plant with cold side ESP followed by a wet
FGD system with wet limestone forced oxidation. The unit is equipped with a pulverized coal
boiler and ammonia based SCR. This unit  burns high sulfur eastern bituminous coals.  Slurry
from the  absorber goes to  a primary  hydrocyclone  for initial  dewatering.  The gypsum
(hydrocyclone underflow) is dried on a vacuum  belt and washed to remove chlorides, before use
in wallboard.
Two samples were collected from the FGD gypsum drying facility by compositing samples
collected on June 10, 11,  and 12, 2006 when the  SCR was  operating. On each day, two gallon
pails of unwashed gypsum and washed/dried gypsum were collected. The unwashed gypsum was
collected from the vacuum belt  prior to the chloride spray wash. The washed/dried gypsum was
collected from the  end  of the vacuum belt. The three  daily samples were sent  to Arcadis for
compositing to form sample OAU (unwashed gypsum) and sample OAW (washed gypsum). All
samples were collected by plant personnel.
2.1.2.3. Facility P (Forced Oxidation and SCR and SNCR)
Facility P is two wall fired 200 MW coal-fired boilers with cold side ESP  followed by  a wet
FGD system with wet limestone forced oxidation. Unit 1 is equipped with SNCR and Unit 2 is
equipped with SCR. These units burn medium sulfur  eastern bituminous coals. Particulate  is
removed with a cold-side ESP. Flue gas is then scrubbed through a common wet FGD unit; FGD
is a wet limestone forced oxidation design. The gypsum provided was not washed.
Facility P was sampled in October 2006 when both SCR  and SNCR were operating and the
residues from Unit  1 and Unit 2 were commingled during collection.  A five gallon bucket of the
washed gypsum was collected by plant personnel.
                                         26
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                                        Characterization of Coal Cumbustion Residues
2.1.2.4. Facility O (Forced Oxidation and SCR)
Facility Q is a 1800 MW  coal fired  plant with  hot  side ESP followed by a wet flue gas
desulfurization  system with wet limestone forced oxidation. This unit burns sub-bituminous
coals. Particulate is removed with a hot-side ESP. Flue gas is then scrubbed through a wet FGD
unit; FGD is a wet limestone forced oxidation design that includes the addition of dibasic acid to
the absorber13. The gypsum provided was not washed and was sampled on Oct. 30, 2006 by an
EPRI contractor (Natural Resource Technology).  A five gall bucket of the unwashed gypsum
was shipped to ARCADIS for analysis on May 4, 2007.

2.2. LEACHING ASSESSMENT PROTOCOLS
Laboratory testing for this study focused on leaching as a function of pH and LS ratio as defined
by the leaching framework. This test set is considered Tier  2  testing (equilibrium-based)  for
detailed characterization, which was selected  to  develop a  comprehensive data set of CCR
characteristics. Mass transfer rate testing (Tier 3, detailed characterization) may be carried out in
the future for specific cases where results from equilibrium-based  characterization indicate a
need for detailed assessment.

2.2.1. Alkalinity, Solubility and Release as a Function of pH (SR002.1)
Alkalinity, solubility  and release as a  function of pH were  determined according  to method
SR002.1  (Kosson et  al., 2002). This protocol consists of 11 parallel  extractions  of particle size
reduced material, at a LS ratio of  10 mL extractant/g dry sample. In this method, particle-size
reduction  is used to  prepare large-grained samples for extraction so that the approach toward
liquid-solid equilibrium is enhanced and mass  transport through large particles is minimized.
For the samples evaluated in this study, minimal  size reduction was required. Each extraction
condition  was carried out in triplicate  using 40 g of material for each material evaluated. In
addition,  three  method blanks were  included, consisting of the DI water, nitric acid and
potassium hydroxide used for extractions. Typical  particle size of the tested materials was less
than 300  |im using standard sieves  according to  ASTM E-l 1-70(1995). An acid or base addition
schedule is formulated based on initial screening for eleven extracts with final solution pH values
between 3 and 12, through addition of aliquots of nitric acid or potassium hydroxide as needed.
The exact schedule is adjusted based on the nature of the material;  however, the range of  pH
values includes the natural pH of the  matrix that may  extend  the pH  domain  (e.g., for very
alkaline or acidic materials). The final LS ratio is 10 mL extractant/g dry sample which includes
DI water, the  added acid or base, and the amount of moisture that is inherent to the waste matrix
as determined by moisture content analysis. The  eleven extractions were tumbled in an end-over-
end fashion at 28  ± 2 rpm for 24 hours  followed by filtration separation of the solid phase from
the extract using a 0.45 |im polypropylene filter. Each extract then was analyzed for constituents
of interest. The  acid and base neutralization behavior of the materials is evaluated by plotting  the
pH of each extract as a function of equivalents of acid or base added  per gram of dry solid.
Concentration of constituents of interest for each extract is plotted as a function  of extract final
pH to provide liquid-solid partitioning equilibrium as a function of pH. Initially, the SR002.1 test
was carried out in triplicate; however, replication was reduced to  two replicates  of the test
13 Dibasic acid (DBA) is a commercial mixture of glutaric, succinic, and adipic acids:
HOOC(CH2)2.4COOH.
                                           27
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Characterization of Coal Combustion Residues II


method for later samples based on good replication and consistency amongst the early results
(Sanchez et al., 2006).

2.2.2. Solubility and Release as a Function of LS Ratio (SR003.1)
Solubility and release as a function of LS  ratio was determined according to method SR003.1
(Kosson et al., 2002). This protocol consists of five parallel batch extractions over a range of LS
ratios (i.e., 10, 5, 2, 1, and 0.5 mL/g dry material), using DI water as the extractant with aliquots
of material that has been particle size reduced. Typical particle size of the material tested was
less than 300 jim. Between 40 and 200 g of material were used for each extraction, based on the
desired LS ratio. All extractions are conducted at room temperature (20 ± 2 °C) in leak-proof
vessels that are tumbled in an end-over-end fashion at 28 ± 2 rpm for 24 hours. Following gross
separation of the solid and liquid phases by centrifuge or settling, leachate pH and conductivity
measurements are taken  and the phases  are separated by  pressure filtration using 0.45-|im
polypropylene filter membrane. The five leachates are collected, and preserved as appropriate for
chemical analysis. Initially,  the  SR003.1 test was carried out in triplicate; however, replication
was reduced to two replicates of the test method for later samples based on good replication and
consistency amongst the early results.

2.3. ANALYTICAL METHODS

2.3.1. Surface Area and Pore Size Distribution
A Quantachrome Autosorb-1 C-MS chemisorption  mass spectrometer was used to perform 5-
point Brunauer,  Emmett, and Teller (BET) method surface area, pore volume,  and pore size
distribution analysis on each as-received and size-reduced CCR. A 200 mg sample was degassed
under vacuum at 200  °C for  at least one hour in the sample preparation manifold prior to analysis
with N2 as the analysis gas.  Standard materials with known surface area were routinely run as a
QC check.

2.3.2. pH and Conductivity
pH and conductivity were  measured for all aqueous  extracts using an Accumet 925 pH/ion
meter. The pH of the leachates was measured using a combined pH electrode accurate to 0.1 pH
units. A 3-point calibration  was performed  daily using pH buffer solutions at pH 4.0, 7.0 and
10.0.  Conductivity of the leachates was measured using a standard conductivity probe. The
conductivity  probe was calibrated using  appropriate  standard conductivity solutions for the
conductivity range of concern. Conductivity meters typically are accurate to + 1% and have a
precision of + 1%.

2.3.3. Moisture Content
Moisture content of the "as received" CCRs was determined using American Society for Testing
and Materials (ASTM) D  2216-92. This  procedure  supersedes the method indicated in the
version of the leaching procedure published by Kosson et al. (2002).

2.3.4. Carbon Content Organic Carbon/Elemental Carbon Analyzer
Organic carbon (OC) and elemental carbon (EC) content of each CCR tested was measured using
a Sunset Lab  thermal-optical EC/OC analyzer using the thermal/optical method (NIOSH Method
5040). The sample collected on quartz fiber filters is heated under a completely oxygen-free

                                          28
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                                       Characterization of Coal Cumbustion Residues II


helium atmosphere in a quartz oven in four increasing temperature steps (375 °C, 540 °C, 670 °C
and 870 °C) at 60 second ramp times for the first three temperatures  and a ramp time of 90
seconds for the final temperature. The heating process removes all organic carbon on the filter.
As the organic compounds are vaporized, they are immediately oxidized to carbon dioxide in an
oxidizer oven  which follows the sample  oven. The  flow  of helium containing the produced
carbon dioxide then flows to a  quartz methanator oven where the carbon dioxide is  reduced to
methane. The methane is then detected by a flame ionization detector (FID). After the sample
oven is cooled to 525 °C, the pure helium eluent is switched to an oxygen/helium mixture in the
sample oven. At that time, the  sample oven temperature is stepped up to 850 °C. During  this
phase, both the original elemental carbon and the residual carbon produced by the pyrolysis of
organic compounds during the first phase are oxidized to carbon dioxide due to the presence of
oxygen in the eluent. The carbon dioxide is then converted to methane and detected by the FID.
After all carbon has been oxidized  from  the  sample, a known volume and concentration of
methane is injected into the sample oven. Thus, each sample is calibrated to a known quantity of
carbon as a means of checking the operation of the instrument.
The calibration range for these  analyses was from 10 to 200 jig/cm2 of carbon using a sucrose
solution as the standard. The detection limit of this instrument is approximately 100 ng/cm2 with
a linear dynamic range from 100 ng/cm2 to  1 g/cm2.

2.3.5. Dissolved Inorganic Carbon (DIC) and Dissolved Organic Carbon (DOC)
Analyses of total  organic carbon and inorganic carbon were performed on a Shimadzu model
TOC-V CPH/CPN. Five-point calibration curves, for both dissolved inorganic carbon (DIC)  and
non-purgeable dissolved organic carbon (DOC) analyses, were generated for an analytical range
between 5 ppm and 100 ppm  and are  accepted with a correlation coefficient of at least 0.995. An
analytical blank and check standard at approximately 10 ppm were run every 10 samples. The
standard was required to be within 15% of the specified value. A volume of approximately 16
mL of undiluted sample is loaded for analysis. DIC analysis is performed first for the analytical
blank and standard and then the samples. DOC analysis is carried out separately after completion
of DIC analysis. DOC analysis begins with addition  of 2 M (mole/L)  of hydrochloric acid to
achieve a pH of 2 along with a sparge gas flow rate of 50 mL/min to purge inorganic carbon
prior to analysis. Method detection limit (MDL) and minimum level of quantification (ML) are
shown in Table 5.
Table 5. MDL and ML of analysis of DIC and DOC.

DIC
DOC
MDL (ug/L)
70
90
ML (ug/L)
200
200
2.3.6. Mercury (CVAA, Method 3052, and Method 7473)
Liquid samples were preserved for mercury analysis by additions of nitric acid and potassium
permanganate and then prepared prior to analysis according to the following method. For each
87 mL of sample,  3 mL of concentrated nitric acid and 5 mL of 5  wt% aqueous potassium
permanganate  solution were added prior to  storage.  Immediately before cold  vapor atomic
absorption (CVAA) analysis, 5 mL of hydroxylamine were added to clear the sample and then
the sample was digested according to ASTM Method D6784-02 (Ontario Hydro) as described for

                                          29
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Characterization of Coal Combustion Residues II


the permanganate fraction (ASTM,  2002).  On completion of the digestion,  the  sample was
analyzed for mercury by CVAA. Samples with known additions of mercury for matrix analytical
spikes also were digested as described above prior to CVAA analysis.
Sample preparation of the  solids and filters was carried out by HF/HNOs microwave digestion
according to Method 3052 (EPA, 1996) followed by CVAA analysis as indicated above. No
additional preservation or digestion was carried out prior to CVAA analysis.
Mercury analysis of each digest, extract and leachate was carried out by CVAA according to
EPA SW846 Method 7470A "Mercury in Liquid Waste (Manual Cold Vapor Technique)" (EPA,
1998a). A Perkin Elmer FEVIS 100 Flow Injection Mercury System was  used for this analysis.
The instrument was calibrated with known standards ranging from 0.025 to 1 |J,g/L mercury.
Solids also were analyzed by Method 7473 "Mercury in Solids  and Solutions  by Thermal
Decomposition, Amalgamation, and  Atomic Absorption Spectrophotometry" (EPA, 1998b). A
Nippon MD-1  mercury system was used for this analysis. The instrument was calibrated with
known standards ranging from 1 to 20 ng of mercury.  The method detection limit for mercury in
solids is 0.145 |ig/kg.

2.3.7. Other Metals (ICP-MS, Method 3052, and Method 6020)
Liquid samples for ICP-MS analysis were preserved through addition of 3 mL  of concentrated
nitric acid (trace  metal grade) per 97  mL of sample. Known quantities of each analyte were also
added to sample  aliquots  for analytical  matrix spikes. Solid samples were digested by EPA
Method 3052 (EPA, 1996) prior to ICP-MS analysis.
2.3.7.1. ICP-MS Analysis
ICP-MS analyses of aqueous samples  from laboratory  leaching tests were carried  out at
Vanderbilt University (Department of Civil  and  Environmental Engineering)  using a  Perkin
Elmer model ELAN DRC II in both standard and dynamic reaction  chamber (DRC)  modes.
Standard analysis mode was used for all analytes except for As and Se, which were run in DRC
mode with 0.5 mL/min of oxygen as the reaction gas. Seven-point standard curves were used for
an analytical range between approximately 0.5 jig/L and 500  jig/L and completed before each
analysis. Analytical blanks and analytical check standards at approximately 50 jig/L were run
every 10 samples and required to be within 15% of the specified value. Samples  for analysis
were diluted gravimetrically to within the targeted  analytical range using 1% v/v Optima grade
nitric acid (Fisher Scientific). Initially, analyses for 10:1 dilutions were performed  to minimize
total dissolved loading to the instrument. Additional dilutions at 100:1 and 1000:1 were analyzed
if the calibration range was exceeded with the 10:1 dilution.  50  jiL of a 10 mg/L internal
standard consisting of indium  (In) (for mass range below 150) and  holmium  (Ho) (for mass
range over 150) was added to 10 mL of sample aliquot prior to analysis. Analytical matrix spikes
were  completed  for one of each of the  replicate  extracts from SR002.1. For each analytical
matrix spike, a volume between 10 jiL and 100 jiL  of a 10 mg/L standard solution was added to
10 mL of sample aliquot. Table 6 provides the element analyzed, method  detection limit (MDL)
and minimum level of quantification (ML). Analyte concentrations  measured that are less than
the ML and greater than the MDL are reported as estimated value using the instrument response.
The values reflect the initial 10:1 dilution used for samples from laboratory leaching tests.
                                          30
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                                       Characterization of Coal Cumbustion Residues
Table 6.  Method detection limits (MDLs) and minimum level of quantification (ML) for ICP-
MS analysis on liquid samples.*
Symbol
Al
Sb
As
Ba
Be
B
Cd
Ca
Cs
Cr
Co
Cu
Fe
Pb
Li
Mg
Mn
Mo
Ni
K
Re
Rb
Se
Si
Ag
Na
Sr
Tl
Sn
Ti
U
V
Zn
Zr
Units
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
M9/L
MDL
1.25
0.60
1.09
0.75
0.85
0.63
0.40
1.86
0.60
0.47
0.51
0.87
1.55
0.28
0.80
1.17
0.47
0.75
0.90
1.86
0.30
0.70
0.78
1.85
2.10
1.12
0.47
0.63
0.87
0.61
0.36
0.79
1.15
0.60
ML
2.00
2.00
2.00
2.00
2.00
2.00
1.00
5.00
2.00
1.00
2.00
2.00
5.00
1.00
2.00
2.00
1.00
2.00
2.00
5.00
1.00
2.00
2.00
5.00
5.00
2.00
1.00
2.00
2.00
2.00
1.00
2.00
2.00
2.00
* All elements indicated in Table 6 have been analyzed, however, only elements indicated in
bold are reported as part of the leaching studies.  The elements that were included in the leaching
studies were selected based on input from EPA program offices due to potential concern for
human health and the environment.
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Characterization of Coal Combustion Residues II
2.3.8. X-Ray Fluorescence (XRF)
XRF analysis was performed on each CCR to provide additional information on each CCR total
elemental composition. For each CCR two pellets were prepared as follows. 3000 mg of material
was weighed and mixed with 1.5 mL  (100 mg dry solids) of liquid binder to give a 32 mm
diameter pellet weighing 3150 mg with  a material-to-diluent ratio  of 0.05. For high carbon
content samples 3.0 ml (100 mg dry solids) of liquid binder was used to give a 32 mm diameter
pellet weighing 3300 mg with a material to diluent ratio of 0.1. XRF intensities were collected on
each side of each pellet using Philips SuperQ data collection  software and evaluated  using
Omega Data System's UniQuant 4 XRF "standardless" data analysis  software. The UQ/Fly  ash
calibration was used to analyze the samples. The pellets were evaluated as oxides. Known fly  ash
Standard Reference Materials (SRMs) were also run to assess the accuracy of the analysis. This
information is useful  in supplementing CVAA and TCP results.

2.3.9.  MDL and  ML for Analytical Results
The MDL is defined by 40 CFR Part  136, Appendix B,  July 1, 1995, Revision 1.11 as "the
minimum concentration of a substance  that can  be measured and reported with 99% confidence
that the analyte concentration is greater than zero and is determined from analysis of a sample in
a given matrix containing the analyte."
The MDL was determined statistically from  data generated by the analysis of seven or more
aliquots of a spiked reagent matrix14 and verified by the analysis of calibration standards near the
calculated MDL according to EPA (2003). The MDL then was determined by multiplying  the
standard deviation of the replicate measurements by the appropriate Students t value for a 99%
confidence level  (two tailed)  and n-1  (six) degrees of freedom and also  multiplying by  the
minimum dilution factor required for matrix preservation and analysis.
The ML is defined by 40 CFR Part 136, 1994 as "the lowest level at which the entire analytical
system must give a recognizable signal and  acceptable  calibration  point for the  analyte."
According to EPA (2003), the ML is intended to be the nearest integer value (i.e., 1,  2 or 5x10",
where  n is an integer) to 10 times the standard deviation observed for determination of the MDL.
This value is also multiplied by the  minimum dilution factor  required for preservation and
analysis of the sample matrix to obtain the ML reported here.
Mercury, as measured by CVAA, required modification  of the calculation of the MDL and ML
because very consistent replication resulted in calculation  of a MDL  lower than the instrument
detection limit. For this case, the standard deviation of  seven replicate analyses of 0.025 |ig/L
was 0.00069. Therefore, the MDL was  set equal to the instrument detection limit of 0.001 |ig/L
times the minimum dilution factor from sample preparation (3.59) to result in an MDL of 0.0036
Hg/L. The ML was  set to  10 times the instrument detection limit and rounded to  the nearest
integer value as above. The resulting ML was 0.01 |ig/L.
14 Establishing spikes in an actual leaching extract matrix is not possible because the sample being
extracted dictates the matrix composition by virtue of the constituents that partition into the resulting
aqueous extract, which varies by test position and material being tested. However, the extract aliquots are
diluted at least 10:1 with 1% nitric acid (prepared from Optima grade nitric acid, Fisher Scientific), and
the COPCs are dilute in the resulting analytical sample.  Therefore, the 1% nitric acid solution was used
as the matrix for MDL and ML determinations.
                                           32
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                                        Characterization of Coal Cumbustion Residues
2.4. QUALITY ASSURANCE ASSESSMENT

2.4.1. Homogenization of Individual CCR Samples and Aliquots for Analyses
To  ensure sample homogeneity the fly ashes were mixed using a Morse  single can tumbler
model 1-305 as described in Sanchez et al. (2006). Scrubber sludges that were flowable slurries
were mixed using a  paddle mixer. Gypsum and fixated scrubber sludge samples were mixed by
repetitively coning 15  and quartering while passing through a mesh screen. After mixing, ten
Subsamples  were taken  from FSSL  sample MAD  and analyzed by XRF  to evaluate the
homogeneity of the resultant material; Figure 9 presents the coefficient of variation for the XRF
results.  These  results indicate  that total  content  variability for  primary and  most  trace
constituents is less than 20% for this set of samples.
4U'
db


2U

ID
























M.







.1















I ..








    • Fac. M, SCR off, FSSL (MAD)

Figure 9.  Coefficient of variation (C.V.) from XRF elemental analysis of 10 subsamples of
FSSL sample MAD after mixing by coning and quartering.

2.4.2. Leaching Test Methods and Analytical QA/QC
One of the requirements of this project was to establish a QA/QC framework for the leaching
assessment approach developed by Kosson et al. (2002).  The developed QA/QC framework
incorporates  the use of blanks,  spiked  samples, and  replicates. Appendix  A provides the
complete Quality Assurance Project  Plan, as updated for this phase  of the  study. For each
designated leaching test condition (i.e., acid or base addition to establish end-point pH values
and LS value), triplicate leaching test  extractions were completed (i.e., three separate aliquots of
CCR were  each  extracted  at the designated test condition) for early samples, while duplicate
extractions were  used after evaluation of initial results. The three types of method blanks were
the deionized water case, the most concentrated  nitric  acid  addition case, and the  most
15 "Coning and quartering" is a term used to describe how the material is mixed. The approach is to pass
the material through a screen so that a "cone" forms in the collection container.  Then the cone is bisected
twice into quarters (quarter sections of the cone) and each section then is passed sequentially through the
screen again to form a new cone. This sequence is repeated several times to achieve desired mixing.
                                          33
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Characterization of Coal Combustion Residues II


concentrated potassium hydroxide addition case. Each method blank was carried through the
entire protocol, including tumbling and filtration, except an aliquot of CCR was not added.
During  analysis for  mercury  and elemental species by  ICP-MS,  analytical  spikes  for the
constituents of interest were carried out for one replicate of each test case to assess analytical
recoveries over the complete range of pH and liquid matrix conditions. Multipoint  calibration
curves using at least seven standards and an initial calibration verification (ICV) using a standard
obtained from  a different source than the calibration  standards were completed daily  or  after
every 50 samples,  whichever was more frequent. In addition, instrument blanks  and  continuing
calibration verification (CCV)  standards were analyzed  after every 10 analytical samples and
required to be within 10 percent of the expected value. Samples are rerun if they are not within
10 percent of the expected value.  CCV standards and instrument blanks also were run at the end
of each batch of samples.
For both ICP-MS  and CVAA analyses, each sample was analyzed along with  a matrix spike,
which is an aliquot of the sample plus a known spike concentration of the element  of interest.
The  "spike  recovery" was  required to be  within 80 -  120% of the expected value for an
acceptable analytical result.

2.4.3. Improving QA/QC efficiency
Throughout the study, the approach to  QA/QC was regularly reviewed to seek out opportunities
for increased evaluation efficiency without unacceptable degradation of precision or accuracy in
results. Based on evaluation of results  from the first several facilities  (Sanchez et al, 2006), the
number of replicates for Method SR002.1 (solubility as a function of  pH) and Method SR003.1
(solubility as a function of liquid/solid ratio) was reduced from three to two. Results from this
study (Sanchez et al., 2006 and this report) show that the precision between duplicate  analyses is
acceptable and that the triplicate set does not significantly increase the quality  of the data set.
This finding follows from recognition that (i) the data sets  generated by Method SR002.1 and
SR003.1 must provide both  consistency between replicate extractions  and analyses, and internal
consistency  between results at different pH and LS ratio, and (ii) precision is controlled primarily
by the degree of homogeneity of the  CCR under evaluation  and representative sub-sampling,
rather than by the intrinsic variability of the leaching test methods. There were a total of 11,743
observations for the 14 parameters evaluated in  detail  in this report (pH and  13  constituents of
interest). Review of the resulting data sets indicated 15 outlier pH values of 846 measurements16
and an  additional  19 outliers out of 10,897 measurements of specific constituents.  Thus, the
overall error rate was less than 2%. Implementation of a reduction in the number of replicates
has greatly improved laboratory efficiency without compromising data  quality.
Data were screened for outliers based on comparison of individual  data points (i)  relative to
replicate extractions (i.e., parallel  extractions of aliquots of the same material under the  same
extraction conditions), and  (ii) relative to the other  data points in the extraction series  (i.e.,
parallel  extractions of aliquots of the same  material at different pH (SR02) and LS  conditions
16 When a pH measurement is determined to be an outlier, then all constituent measurements associated
with the particular extract sample are also considered outliers because they would be incorrectly evaluated
as release as a function of pH. This resulted in excluding (15)x(13)=195 individual constituent
measurements.
                                            34
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                                        Characterization of Coal Cumbustion Residues II


(SR03)) because of the expected systematic  response behavior.  The pH was considered  an
outlier when the final  pH of the extract deviated from the other replicates by more than 0.5 pH
units and  corresponding constituent analyses  did not follow systematic  behavior indicated  by
other extracts across multiple constituents. Individual constituents were considered outliers when
results of  constituent analyses deviated from the systematic behavior indicated by results in the
extraction series (as a  function of pH or as a function of LS) by more than one-half to one order
of magnitude. Results  were screened through inspection of the appropriately plotted results.
Data  quality  indicators (DQIs)  were  measured for all  parameters  continuously  during the
leaching experiments and during analytical tasks. Chemical (ICP, CVAA,  XRF, 1C, EC/OC) and
physical (surface area, pore size distribution and density) characterization  data were reduced and
reports were generated automatically by the instrument software. The primary analyst reviewed
100% of the report data for  completeness to ensure that quality control checks met established
criteria. Sample analysis  was repeated for  any  results  not meeting acceptance  criteria.  A
secondary review was performed by the Inorganic Laboratory Manager to validate the analytical
report. A data quality  report  for the CCR leach testing results will be provided in the fourth and
final report of this  research. The data quality report will cover the leach test results documented
in Report  1 (Sanchez et al., 2006), Report 2 (this report), and a third report (in preparation). The
fourth  report summarizes the data from  the first three reports  and  provides probabilistic
assessment of the potential release rates  of mercury and  other  metals based on plausible
management practices.

2.5. INTERPRETATION   AND   PRESENTATION   OF   LABORATORY
LEACHING DATA
Complete  laboratory  leaching results  for each CCR type  and test method are presented  in
Appendices D and  E. Appendix D presents results for Solubility and Release as a Function of pH
(SR002.1). Appendix  E presents results for Solubility and  Release as a Function of LS  ratio
(SR003.1). Results are organized  by CCR type  (fly ash,  gypsum,  scrubber sludge, fixated
scrubber sludge), with pH results followed by mercury and then other constituents of interest
(aluminum, antimony, arsenic, barium, boron, cadmium, chromium, cobalt, lead, molybdenum,
selenium and thallium). For SR002.1, pH results  are a titration curve of pH  as a function  of
milliequivalents of acid or base, with acid additions considered positive (+) and base additions
considered negative (-). For SR003.1, pH results are a curve of pH as a function of LS ratio.
For Solubility and Release as a Function of pH (SR002.1), results for each  CCR type are grouped
as described in  Figure 5 through Figure 8. Results are presented as extract concentrations as a
function of pH.  The "natural" pH17 of the system is indicated as a vertical  line to the average pH
and a horizontal line to the y-axis indicating the corresponding extract concentration. Included
with each  figure are horizontal lines at the drinking water maximum concentration level (MCL)
or drinking water equivalent level (DWEL)18,  and analytical limits (ML and MDL) to provide a
frame of reference  for the results. Also included with each figure are the 5 and  95 percentile for
pH  (vertical lines)  from field observations  of leachate from landfills and  surface impoundments
17 "Natural pH" or "own pH" of a material refers to the equilibrium pH when the material is placed in
deionized water at a ratio of 10 g CCR per 100 mL of water.
18 MCL and DWEL values used are as reported in (EPA, 2006).
                                           35
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Characterization of Coal Combustion Residues II


for combustion residues (see Section 2.5.1). An annotated example of the results is provided as
Figure 10.
For Solubility and Release as a Function of LS ratio (SR003.1), results are presented as extract
concentrations as a function of LS ratio. Also indicated are the relevant MCL, ML and MDL or
DWEL.

2.5.1. Interpretation of Mechanisms Controlling Constituent Leaching
Constituent (e.g., mercury, arsenic, and selenium)  concentrations observed in laboratory  leach
test extracts and in field leachate samples may  be the result of several mechanisms and factors.
The  discussion  presented here focuses on constituent leaching  and source term modeling
approaches. Source term is defined here as the flux or amount of constituent released from the
waste or secondary material (e.g., CCRs). Factors controlling constituent release and transport in
and within the  near field of the  CCRs are  often distinctly different from the  factors and
mechanisms which are important for subsequent vadose zone or groundwater transport outside of
the near field area.
In general, constituents are present in the waste or secondary material either as adsorbed species,
co-precipitated as amorphous or crystalline solid phases, or incorporated as trace components in
solid phases. If chemical equilibrium  conditions are approached (as is the approximate case for
the laboratory and field sample conditions discussed in this report), then the functional behavior
of the aqueous solution concentration reflects the nature of the constituent species in the waste or
secondary  material,  the  presence  of any co-constituents  in the aqueous  phase influencing
aqueous  solution  speciation (e.g., effects  of high ionic  strength,  chelating or  complexing
constituents), and the presence of species in the solution that may compete for adsorption sites if
adsorption is the controlling solid phase mechanism. If the constituent is present in the waste or
secondary  material as  an  adsorbed species,  many different  adsorption/desorption characteristic
patterns are possible  (Ruthven, 1984; Duong, 1998).
The simplest case is when the constituent of interest is present at very low concentration in the
waste or secondary material, relatively weakly adsorbed, and the presence of complexing and, or,
competing species in solution is at a  constant concentration. For this case, leaching test results
will indicate a constant  concentration as a function of pH at  a fixed LS ratio, and linearly
increasing  concentration  as LS ratio  decreases  at  constant pH.  This  case  is  represented
mathematically as a linear equilibrium partitioning  function, where the critical  constant  of
proportionality is the partitioning coefficient, commonly known as Kd. Linear partitioning and
use of Kd values is a common approach for mathematically modeling contaminant transport at
low contaminant concentrations in soils. Assumption of linear partitioning is a valid and useful
approach when the necessary conditions (discussed above) are fulfilled19.
For mercury adsorbed on activated carbon or char particles in fly ash,  a complex combination of
adsorption mechanisms is indicated. During laboratory leaching tests,  mercury concentrations in
the leaching test extracts are relatively constant over the pH range and LS ratio of interest, and
19 Often specific Kd values are a function of pH because of competition for adsorption sites by hydrogen
ions. However, often a single Kd or range of Kd values are used in contaminant fate and transport models,
without specific relationship between pH and Kd which can result in misrepresentation of actual
contaminant behavior.
                                            36
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                                         Characterization of Coal Cumbustion Residues II


independent of total mercury content in the CCR. In addition, the total mercury content in the
CCR is very low. These results are indicative of adsorption phenomena where, in the adsorbed
state, interactions between adsorbed mercury species are stronger (thermodynamically) than the
interactions between the adsorbed mercury species and carbon surface20. This observation has
been supported by  the observation of mercury dimer formation during sorption (Munro et al,
2001)  and  the occurrence  of  chemisorption  as the  dominant adsorption mechanism  at
temperatures above 75  °C  (consistent with conditions in air pollution control devices; Vidic,
2002).  In other studies, this phenomenon has been observed as the  formation  of molecular
clusters on the adsorbent surface (Ruthven, 1984; Duong, 1998; Rudzinski et al., 1997). For this
case, use of a Kd approach would underestimate release because desorption is best represented as
a constant aqueous concentration until depletion occurs.
A third case is encountered when the constituent of interest is present in the waste or secondary
material (e.g., CCR) as a primary or trace constituent in either an amorphous or crystalline  solid
phase and there may be complexing or chelating  co-constituents in the aqueous phase. Observed
aqueous concentrations are a non-linear  function of  pH and LS ratio, and  reflect aqueous
saturation with respect to the species of interest under the given conditions (pH, co-constituents).
For these  cases, an  approximation of field conditions  can be  made  empirically based  on
laboratory testing and observed saturation over the relevant domain (as  applied in this report) or
geochemical speciation modeling coupled with  mass transfer modeling can be used  to assess
release under specific field scenarios (the subject of a future report). Use of a Kd approach would
not be appropriate for  these cases because constituent  concentrations will remain relatively
constant at a given pH until the controlling solid phase is depleted and control is shifted to a new
solid phase or mechanism.
                        5th %tile for field pH
95th %tile for field pH
               Concentration
               at own pH
        SR2-DFA-A

  SR2HSR002.1    Replicate A
           }5iflCTin1« namfr
Figure 10.  An example of extract concentrations as a function of pH from SR002.1.
20 For this case, the first mercury molecule is adsorbed more weakly than subsequent mercury molecules
because the adsorbed mercury-mercury interaction is stronger than the adsorbed mercury-carbon surface
interaction [see Sanchez et al. (2006) for further discussion].
                                           37
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Characterization of Coal Combustion Residues II
2.6. FIELD pH PROBABILITY DISTRIBUTION
A probability distribution of field leachate pH values from coal combustion waste landfills was
derived, as described below, from  the set of field pH observations included in the EPA Risk
Report (EPA, 2007). The pH probability distribution used in this report considers additional data
beyond the pH probability distribution used in Report 1 (Sanchez et al, 2006), which was based
solely on relevant data from the EPA Office of Solid Waste database (EPA, 2000) and included
158  observations from six CCR disposal facilities. The  data set developed for the EPA Risk
Report  included (i)  observations  from the  comprehensive  database  of landfill  leachate
characteristics developed  by  the  EPA's Office  of Solid Waste (EPA,  2000),  (ii)  field
observations from literature, primarily from EPRI reports, (iii) additional data reported to EPA,
and  (vi) pH  observations  from laboratory leaching tests. Only pH measurements from field
samples (i.e., leachate, pore water) were selected for use in development of the resulting pH
probability distribution.  The resulting data set included 580  observations from 42 CCR landfill
disposal facilities and was  highly unbalanced, with some  sites having only  a few (e.g., less than
five) observations and some sites having many observations (e.g., greater  than 20). To prevent
the unbalanced data from skewing the resulting probability distribution, the minimum, 25th,  50th,
75th percentile, and maximum values of observations for each individual facility were compiled
into  a single  data set. For  facilities with fewer than five  observations, all  observations for that
facility were  included. This data set then served as the basis for fitting a statistical distribution
function. For each data set, different distribution functions were used to fit the data and the one
providing  the best data fit based on the chi-square test was selected. The  resulting field pH
probability distribution was truncated and normalized to the pH range of the field data.
The resulting pH probability distribution developed in this report is compared in Figure 11 and
Table 7 to the pH probability distribution used in Report  1. The new pH probability distribution
reflects a similar range of pH, but has a more alkaline median value, and in general, has greater
weighting in the pH range between 8 and 12.  The probability distribution used in this report is
considered more representative than what was used in Report 1 because of a larger dataset using
results from recent studies by EPA and EPRI.  (EPA, 2006; EPRI, 2006)
Field pH observations were also evaluated for surface impoundments receiving CCRs from coal
combustion facilities with FGD scrubbers in use. Pore water pH values measured in samples
obtained from within the  settled CCRs were selected from the EPRI  database. Resulting pH
observations  were across  the same range  as the landfill  field  pH  observations,  but  were
insufficient to develop  an independent  pH  probability  distribution. Therefore, the same pH
probability distribution was used for landfill and surface impoundment facilities in this report.
                                           38
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                                        Characterization of Coal Cumbustion Residues
PH
Min
5th percentile
50th percentile
90th percentile
95th percentile
Max
Field data
2.75
5.40
10.53
12.20
12.40
12.80
Fitted
distribution
-7.42
5.84
10.38
12.18
12.43
12.81
Simulated
2.76
5.85
10.24
11.94
12.43
12.43
         2  3
10 11  12 13
           EPA leach 2000
           • Fitted distribution (LogLogistic, (1))
           EPA Risk database & EPA leach 2000
           • Fitted distribution (BetaGeneral, (2))
            Distributions
            LogLogistic(4.7386, 2.9538, 3.4815)
            BetaGeneral(9.0369, 1.5076,-7.4214, 12.814)
Figure 11.  Probability distributions for field pH used in Report 1 (LogLogistic) and this report
(BetaGeneral).  Summary statistics for the field data and the probability distribution used in this
report (BetaGeneral) are provided to the right of the graph..


Table 7.  Comparison of summary  statistics for field pH data and pH probability distributions
used in Report 1 and this report.


Minimum
5th percentile
50th percentile
90th percentile
95th percentile
Maximum
Field Data
Report 1
5.40
5.80
7.70
NR
12.09
12.80
This Report
2.75
5.40
10.53
12.20
12.40
12.80
Distribution Used in Release
Estimates
Report 1
4.92
5.97
7.63
NR
10.63
12.50
This Report
2.76
5.85
10.24
11.94
12.43
12.43
NR=not reported.

2.7. ESTIMATED  LEACHATE CONCENTRATION AS  A  FUNCTION OF
     pH
For each CCR tested, results from SR002.1 (Alkalinity, Solubility and Release as a Function of
pH) were used to develop an empirical functional relationship between solution pH and expected
concentration for each constituent of interest. For each  constituent  within each CCR case, a
polynomial  function was  regressed  to the  results from SR002.1 (Alkalinity,  Solubility and
                                           39
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Characterization of Coal Combustion Residues II
Release as a Function of pH) to provide the expected leachate concentration as a function of
solution pH. Up  to a fifth order polynomial was used for the regression.  An  example of a
regression  fit and corresponding equation for  solubility and  release as a function of pH is
presented in Figure 12. The coefficients provided in the table reflect the order of the polynomial
used.  For all cases, the lowest order polynomial possible  based on the R-square (no further
increase for higher order) was used.  Also included with each figure of regression fit is the 5th
and 95th percentile for pH (vertical line) from field observations of leachate  from landfills and
surface impoundments for combustion residues.  Regression  fit results are provided in Appendix
F for each case examined (i.e., for each constituent in each CCR tested).
  100000
   10000
    1000-|
                                     1295%14
            D  SR2-DFA - A
            A  SR2-DFA-C
 SR2-DFA - B
•Fit curve
                                                   Antimony
                     log (ug/L)
Number
of points
pH range of
validity
                       0.0000 PH5
                       0.0008 pH4
                       -0.0399 pH3
                       0.5519 pH2
                       -2.7978 pH
                     6.031866 pH°
                         0.97 R2
   33
        2.2-12.4
                                                                      -th
Figure 12.  Example of regression fit and corresponding coefficients for a 5  order polynomial
equation used to represent solubility and release as a function of pH (antimony for fly ash from
Facility B with SCR bypassed (DFA)).
                                           40
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                                       Characterization of Coal Cumbustion Residues II


3. RESULTS AND DISCUSSION

The EPA Risk Report (EPA, 2007) identified the following COPCs based on the potential for
either human health or ecological impacts using a screening risk assessment:  aluminum (Al),
arsenic (As), antimony (Sb), barium (Ba), boron (B), cadmium (Cd), cobalt (Co), chromium (Cr),
lead  (Pb), mercury  (Hg), molybdenum (Mo), selenium (Se), and thallium  (Tl).21  Thus, the
evaluation provided  here focuses on the same thirteen constituents and can be used in future risk
and environmental assessments.

3.1.  TOTAL ELEMENTAL CONTENT BY DIGESTION
Total elemental compositions using digestion22, on a dry weight basis, for COPCs for the CCRs
evaluated are compared by constituent in Figures 13 through 24; tabular results are provided in
Appendix B. Boron  was not analyzed because it is used in the digestion process and therefore
analysis would not yield meaningful results.
Mercury.  Mercury  content exhibited a similar range (0.01 to 1.0 ug/g) for all  CCR types. Use of
SNCR (Facility A) resulted in increased mercury content in the fly  ash and decreased mercury
content in the scrubber sludge, compared to when the SNCR was not in use.  In contrast,  use of
SCR (Facility B) resulted in decreased mercury content in  the fly  ash and  increased mercury
content in  the scrubber sludge, compared  to  when  the SCR was  bypassed.  For all  three
comparative cases (Facilities A,  B and M) use of the NOx control increased the total mercury
content in the fixated scrubber sludge. Mercury content in gypsum was significantly lower in the
washed gypsum than in the unwashed gypsum for comparative cases (Facilities N and  O).
Aluminum. Aluminum content was  approximately an order of magnitude greater in  the fly ash
samples than in the  scrubber sludge  samples from facilities without SCR and than  in gypsum
samples with and without SCR. Facilities with SCR operating (samples BGD, KGD) had greater
aluminum content in scrubber  sludge  than the other  scrubber sludges, likely because  of the
addition of aluminum with the SCR catalyst. Fixated scrubber sludge samples had intermediate
Al content,  reflective of the blending of fly  ash with scrubber sludge.
Antimony. Antimony content ranged over similar levels for fly ash,  scrubber sludge and fixated
scrubber sludge;  gypsum had lower  antimony content except for the  sample from Facility  Q.
Samples from both  Facilities K and Q had greater antimony content than  comparative FGD
residues from  other facilities (scrubber sludges and fixated scrubber sludges for Facility  K,
gypsum for Facility  Q) perhaps as a consequence of greater antimony content in sub-bituminous
coal  burned by these facilities than bituminous  coal burned by the  other facilities. The  SNCR
samples had higher antimony contents in the fly ash, scrubber sludge  and fixated scrubber  sludge
for Facility A than the samples collected with SNCR off. The  SCR samples had higher antimony
contents in  the fly ash from Facility B and  the fixated scrubber sludges from Facilities A, B and
21 The database used in the EPA Risk Report (EPA, 2007) for the assessment was based on both
measurements of field samples (e.g., leachate, pore water) and single point laboratory leaching tests (e.g.,
TCLP, SPLP).  The database was sparse with respect to measurements of field samples for many
constituents.
22 Digestion Method 3052 and ICP-MS analysis by Method 6020; see Section 2.3.7.


                                          41
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Characterization of Coal Combustion Residues II


M, although the reason for the high level of antimony in sample BCC cannot be explained by the
relative antimony content in samples BFA and BGD.
Arsenic. Gypsum had very low arsenic content (<5  |ig/g) compared to the other residue types.
Arsenic content in  scrubber sludge was significantly less than in fly ash for residue from the
same facility. Use of NOx controls resulted in decreased arsenic content in the fly ash, increased
content in the scrubber sludge (Facilities A and B) and decreased content in the fixated scrubber
sludge (Facilities A, B and M; reflecting the relative contributions of fly ash and scrubber sludge
in fixated scrubber sludge) for comparative samples.
Barium. Barium content  was similar in scrubber sludge and gypsum for all facilities except for
sample BGD (unexplained), and lower than barium content in fly ash by approximately an order
of magnitude. The  relatively low barium content in  unwashed gypsum from Facility O is also
unexplained.
Cadmium. Cadmium content was low in the gypsum (<0.69 ng/g) and scrubber sludges (<1.72
ug/g) and generally total content of the gypsum was half that in fly ash (<1.51 ng/g). The greater
cadmium content in sample BGD relative to  sample  DGD may be a consequence of the use of
post-combustion NOx control using SCR.
Chromium. Chromium content in gypsum (< 19.3 ng/g) and scrubber sludges (< 139 ng/g) was
low and approximately an order  of magnitude less  than in fly ash samples (<194). Scrubber
sludge samples without SCR in operation also had chromium content similar to that of gypsum.
Scrubber sludge samples  without SCR in use also  had chromium content similar to that of
gypsum.  Elevated  chromium content  in scrubber sludge samples BGD and KGD may be
associated with the use of post-combustion NOx control using SCR.
Cobalt. Cobalt content in gypsum was low and approximately an order of magnitude less than
in fly ash samples.  Scrubber sludge samples  without SCR in operation also had cobalt content
similar to that of gypsum. Elevated cobalt content in scrubber sludge  samples BGD and KGD
may be associated  with SCR catalyst addition.  The relatively low cobalt content in fixated
scrubber sludge samples BCC and KCC relative to corresponding fly  ash and scrubber sludge
samples is unexplained.
Lead.  Lead content in gypsum was low and less than one third of the lead content in fly ash
samples. Scrubber sludge samples without SCR in operation also had lead content similar to that
of gypsum. The relatively  low lead content in fixated scrubber sludge samples BCC and KCC in
relationship to corresponding fly ash and scrubber sludge samples is unexplained.
Molybdenum.  A similar range in molybdenum  content was found in fly ash, scrubber sludge
and fixated scrubber sludge samples, with lower content by approximately one third in gypsum
samples, with the exception of gypsum sample QAU.
Selenium. All samples were less than 5 jig/g, except for samples for fly ash and fixated scrubber
sludge from Facility A and unwashed  gypsum from Facilities P  and Q.  The upper bound for
these samples was less than 30 |ig/g.
Thallium.  All gypsum samples had thallium content less than 3 |ig/g. Fly ash, scrubber sludge,
and fixated scrubber sludge samples all had a similar range of thallium  content between 2 and 5
|ig/g, except scrubber sludge and fixated scrubber sludge from Facility B with  SCR and fly ash
and fixated scrubber sludge  from Facility K.  Both  of these observations of greater thallium
content (between 5 and 13 |ig/g) may result from the SCR catalyst addition.

                                          42
-------
                                      Characterization of Coal Cumbustion Residues
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Characterization of Coal Combustion Residues II

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Nat.




< 2- <
LL "i L
<. 2. o
< CD £
LL LL L

Ox




Arsenic (As)





Nat. Ox. Forced Ox.


1
, • n 1




Nat. Ox. .Ox
-


n_


1






i ^ y.<9,Do^ < 5 < 5 < < ii <, £• P2. ;£, ^ S
a ^ < ~r tn CD 2" 2. $ ° ^ — ^ < < °D GO ^ ;r ~r
^" . ^ * 	 ' LJ Q_ * ' ' . ' . -> ^
J- LJ-i_i_LJ-LLLL U . (j . fg (j LL LL LL fC fC
fOurouLLro LJ-LL
u- re u_ re LL
LL LL
Fly Ash
ScrubberSludge
Gypsum
Fixated ScrubberSludge

Figure 15  and Figure 16. Antimony and Arsenic.  Comparison of total elemental content by
digestion (key: - = NOx control off; + = NOx control on; U = unwashed gypsum; W = washed
gypsum; Nat.  Ox.  = natural  oxidation;  Forced Ox. = forced oxidation;  I.Ox. =  inhibited
oxidation).
                                         44
-------
                                      Characterization of Coal Cumbustion Residues
10,000
1,000 |
O)
O) 1UU
3.
1 n





Nat.



	 	 ^ H
<3




h
c,
c




<
a:
IT





Ox.




<
- £
c




+•
f <
0 i
— "• •»,
a i

Fly Ash



f

^
£








Nat

Barium (Ba)
O>



.
E
is
c
<


1

^£



,
c.
(L
C
a.



(.
_


+ +
tn (r)
OD ^



Forced Ox.

ni I
II

=> > ^ >
< > < 5
(TJ U (TJ u
LL, ro LL, ro
LL, LL,
ScrubberSludge






Nat. Ox.










\

.Ox.




=>=> ^ + ^++^ +
<< y. < s. s. ^. I I
Q^O. <^mm^r- —
Q"O' ^cj^u1-'..
LL
ro LL, LL,
J_
Gypsum
Fixated ScrubberSludg

3



O)
O) 1.0 ;-|



Nat.



Ox.



-------
Characterization of Coal Combustion Residues II
Chromium (Cr)

O)
3.
1 nn

Nat. Ox.

I"



Nat.O>


i n




Forced Ox.


ml L_n_i . "
Nat. Ox.

n 1
Inn
.Ox.


m

sf <" I? <" 5=)=) ^ + ^++^ +
~i.~2.ST5' j^jjj^^
LJ- ro LJ- ro "" LJ-
LJ- LJ-
Fly Ash ScrubberSludge Gypsum Fixated ScrubberSludge

1
Figure 19 and Figure 20.  Chromium and Cobalt.  Comparison of total  elemental content by
digestion (key: - = NOx control off; + = NOx control on; U = unwashed gypsum; W = washed
gypsum;  Nat.  Ox.  = natural  oxidation;  Forced  Ox. = forced oxidation; I.Ox.  = inhibited
oxidation).
                                         46
-------
                                      Characterization of Coal Cumbustion Residues

IzU ~
1UU
oU
0)
O) 60
2.

zU


Lead (Pb)
Nat. Ox.

-i





•


•






Nat. Ox.





_. n
1 + ' + + ' +
< ~Z)>-Q=)
m" S" S.
ra ra
LL LL




Nat.
Ox.

In
n








Forced Ox.


n II n II n
Nat. Ox.



L^ CO ^^ (1 ^^ f~\ ^^ ^^ ^^ ^* ^^ ^? ^^ ^"^ ^J rf" L^ r
^(J^ U ' L) t i (J ~2. ' — ' O * — ' Cf m U U
^rcrti tTSm^rcrc • Z . O u • LL^/L
LL1-1- LLLL.U-LLLL U.u.rDU LLU-L
LL re LL rc LL
LL LL
Fly Ash | ScrubberSludge
Gypsum



.Ox

I





t- + +
IT G~ Q i/T
J U < <
3 ^ ^ ^
^"^^
T3 (T3 U u
L. LL rD 00
Fixated ScrubberSludg<
3
Figure 21 and Figure 22.  Lead and Molybdenum.  Comparison of total elemental content by
digestion (key: - = NOx control off; + = NOx control on; U = unwashed gypsum; W = washed
gypsum; Nat.  Ox.  = natural  oxidation;  Forced  Ox. = forced oxidation; I.Ox.  = inhibited
oxidation).
                                         47
-------
Characterization of Coal Combustion Residues II
20
O)
0) 15
3.
10
5
0

Selenium (Se)
Nat. Ox.
PI



nil
Nat. Ox.




n 1 n I 1

< < < < < £ a £ a a
U^-Q^^- Q (D ^ O (D
<<"oDm^ < 5" oT ST iT

Forced Ox.




n • n •
^* -z. — o jr* —
2 ' " O ' — " . Cf
fO U fO (1 LL fD
LL O3 LL re LL
LL i i
Nat. Ox. .Ox.




n I 1 n 1

LL LL
Fly Ash | ScrubberSludge Gypsum Fixated ScrubberSludge

Thallium (Tl)

*?

0_

Nat. Ox.

nil
-L. + -L. + +
-------
                                       Characterization of Coal Cumbustion Residues
3.2. TOTAL ELEMENTAL CONTENT BY XRF
Total elemental compositions, on a dry weight basis, for major and some trace constituents in
each of the CCRs evaluated are compared in grouping  by  CCR type (i.e., fly ash, gypsum,
scrubber sludge, fixated scrubber sludge) in Figure 25 through Figure 29; tabular results are
provided in Appendix C. Major elemental constituents present in CCRs but not detected by XRF
analysis include oxygen and carbon. Elements that may be analyzed by XRF but were below the
detection limit are  indicated in the figures  on the x-axis but  without  any  reported value
represented. Separate analyses were carried out for carbon  and are also included in Appendix C.
Fly Ash.  Elemental constituents typically present in fly ash at concentrations greater than  1
percent (10,000 mg/kg) are aluminum, calcium,  iron, potassium, and  silicon.  Elemental
constituents typically present at concentrations between 0.1 and 1  percent are barium, chloride,
magnesium, sodium, phosphorus,  strontium, sulfur, and titanium.
Gypsum. Elemental constituents typically present in gypsum  at concentrations  greater than  1
percent (10,000  mg/kg) are calcium and  sulfur. Elemental constituents typically  present at
concentrations between 0.1 and 1 percent are chloride (unwashed gypsum), fluoride (unwashed
gypsum), iron, magnesium, sodium (unwashed gypsum) and silicon.
Scrubber  Residue.    Elemental  constituents  typically  present  in  scrubber  residue  at
concentrations greater than 1 percent (10,000 mg/kg) are aluminum (SCR on), calcium,  iron
(SCR on), magnesium, silicon (SCR on) and sulfur. Elemental constituents typically present at
concentrations between 0.1 and 1 percent are aluminum (except with SCR on), chloride, fluoride,
iron (except with SCR on), potassium, sodium (SCR on), silicon (except with  SCR on), and
titanium (SCR on).
Fixated Scrubber Sludge. Elemental constituents typically present in fixated scrubber sludge at
concentrations greater than  1 percent (10,000 mg/kg) are aluminum, calcium, iron, potassium,
silicon and sulfur. Elemental constituents typically present at concentrations between 0.1 and  1
percent are barium, chloride, sodium, phosphorus and strontium.
Fixated  Scrubber  Sludge with Lime.  Elemental constituents typically present  in fixated
scrubber sludge with lime at concentrations greater than 1  percent (10,000 mg/kg) are aluminum,
calcium,  iron, magnesium  (Mg  lime  scrubbers), silicon, and  sulfur.  Elemental  constituents
typically present at concentrations  between  0.1  and  1  percent  are  chloride,  potassium,
magnesium (non-Mg lime scrubbers), sodium, and titanium.
                                          49
-------
Characterization of Coal Combustion Residues II

100,000
10,000 i
O)
"5) 1,000
3.
100
10


—




















a) Fac.A. (NO+SNCR+FF)
I
1





\










n
1


r.
r| r
-Fly Ash D CFA (SNCR Off) BAFA(SNCROn)


1 nn nnn
1 n nnn *
O)
B) 1,000 4
100
10
1




















1
1

1
1



li
I





r














n

-j
~Z l/l fO I— fO -Q QJ - — • Q l— ^ || QJ fQ QJ ^^ fQ GO C O fQ 0 '-^ ^L O O U QJ J^ ^— t/1 j — ^> ^> ^— C i^j
^« ^t CO CQ (J (j (i ^^ (j CJ (j ^^ 1 1 (n (n __l ^r ^— ^— ~^p -^ ^— r\ w t/1 t/l ^1 ^^ ^> l^sl '^
b) Fac. B. (NO+SCR+ESP, Mg lime -Fly Ash DDFA(SCROff) BBFA(SCROn)

1 nnn nnn
1 nn nnn
1 n nnn
O)
O) l.UUU l
2.
1UU
1 .






















H







||














ill

c) Fac. K. (NO+SCR+ESP, Mg lime -Fly Ash •KFA(SCROn)
Figure 25. Fly Ash - Total content by XRF.
                                       50
-------
                                    Characterization of Coal Cumbustion Residues
1 nnn nnn
1 nn nnn
1 n nnn
0)
100
10
















1
1







r


















< "" ro CO IT!~D ^ U ° U ^ LL. OJ ro OJ^ ro QDC O rD_Qga__a_Q U OJ^ 1-l/l'p>&>- C'-j
a) Fac. N. (FO+SCR+ESP) -Gypsum DNAU (Unwashed) • NAW (Washed)


1 nn nnn
1 n nnn
0)
100
10
-I _
















1
1
ft








1
1
r^


















b) Fac. O. (FO+SCR+ESP) -Gypsum DOAU (Unwashed) •OAW(Washed)


1 nn nnn
1 n nnn
"5) 1,000 i
3.
100
10
1







n









1










1













|




Fac. P. (FO+SCR&SNCR+ESP) - Gypsum
c^ r ^ /r^ rr-n rm\ ^ D PAD (U) (Unwashed) • QAU (Unwashed)
^) Fac. Q. FO+SCR+ESP -Gypsum v /v ' v '
Figure 26. Gypsum - Total content by XRF.
                                       51
-------
Characterization of Coal Combustion Residues II

1 nn nnn
1 n nnn *
0)
"5) 1,000 ]
100
10
1 _




































a) Fac.A.(NO+SNCR+FF)-ScrubberSludge D CGD (SNCR Off)
















• AGO (SNCR On)


1 nn nnn

0)
O) l.UUU
3.
100
10 1



































r

















I I

b) Fac. B. (NO+SCR+ESP, Mglime -ScrubberSludge DDGD(SCROff) •BGD(SCROn)


1 nn nnn
1 n nnn
O)
*?TI 1 nnn •.
1 nn
1 n



















h




















c) Fac. K. (NO+SCR+ESP, Mglime -ScrubberSludge i











Mill

• KGD(SCROn)
Figure 27.  Scrubber Sludge - Total content by XRF.
                                        52
-------
                                     Characterization of Coal Cumbustion Residues

100,000
10,000 :
O)
"5) 1,000 ;
3.
100
10















It
1


_


|-






1

- —


r

1

_
I




Fac. A. (NO+SNCR+FF)- Fixated ScrubberSludge D CCC (SNCR Off) •
IAC


C(SNCR On)
Figure 28.  Fixated Scrubber Sludge - Total content by XRF.
                                        53
-------
Characterization of Coal Combustion Residues II
  1,000,000



    100,000  !



     10,000  ]

  O)

  "Si  1,000
       100



         10













1

























n n n
                                       i OJ ^ rc 00 C O TO _Q • — Q_ _Q _Q u Qj'iT;
                                       I U   —' ^ ^ ^ Z Z ^   Q.CC1/'^^1
a)  Fac. B. (NO+SCR+ESP, Mg lime) - FSSL
                                                  D DCC (SCR Off)
                                                                  BCC (SCR On)
1,000,000



 100,000 ]



  10,000



    1,000



     100



      10
  O)
             —;i/;rDi-rD-Daj7~iO1-3ii  ajrDaj^rDQOcorD-Q'-5Q--Q^2uaj',7i1r'/iC>>>-
             <  I
 , Fac. K. (NO+SCR+ESP, Mg lime) - FSSL
                                                                  KCC(SCROn)
  1,000,000



    100,000
  O)
  10,000 ]



   1,000



     100 ]



      10 i


       1
                                       t

             < < £ m 3 S u D 5 u u
                                           ra ooc o
 c)    Fac. M. (IO+SCR+ESP)- FSSL
                                               D MAD (SCR Off)
                                                                  j,Kri/ip>>>
                                                                  l/1      >



                                                                  MAS (SCR On)
Figure 29. Fixated Scrubber Sludge with Lime - Total content by XRF.
                                              54
-------
                                        Characterization of Coal Cumbustion Residues
3.3. LABORATORY LEACHING TEST RESULTS
Appendix D  and Appendix E provide graphical  presentation of the results of Solubility and
Release as a Function of pH (SR002.1)  and Solubility and Release as a Function  of LS
(SR003.1), respectively, for the 13 constituents of interest in this report. Within each appendix,
results are grouped by  CCR type (fly ash, gypsum, scrubber sludge, FSS, FSSL) and with each
CCR type grouping, comparisons are made by constituent of interest. First discussed below are
typical characteristic results for pH and each of the 13 constituents of interest (Section 3.3.1)
followed by   a  discussion  (Section  3.3.2)  comparing  the ranges of observed  constituent
concentrations (from both test methods) with measurements reported elsewhere on field leachate
and pore water samples for CCR disposal sites and the database used in the EPA Risk Report
(EPA,  2007). Complete data also have been developed for  other constituents to facilitate
evaluation  of geochemical speciation of constituents of concern and  provide  more thorough
evaluation of leaching under alternative management scenarios in the future if warranted.
For each CCR evaluated, results of the leaching tests provide the following information:
•  Leachate  concentrations for the constituents of interest as a function of pH over the range of
   reported field management conditions (from test method SR002.1);
•  pH titration curves  (from test method SR002.1). This information is useful in characterizing
   the CCR and assessing how it will respond to environmental stresses  and material  aging (e.g.,
   carbon dioxide uptake, acid precipitation, co-disposal, mixing with other materials); and,
•  Leachate  concentrations for the constituents of interest, pH and electrical conductivity as a
   function of LS ratio when contacted with distilled water (from test method  SR003.1). This
   information provides insight into  the initial  leachate concentrations expected during land
   disposal and effects of pH and ionic strength at low LS ratio. Often these concentrations can
   be  either  greater than or less than concentrations observed at higher LS ratio (i.e., LS=10
   mL/g as used in SR002.1) because of ionic strength and co-constituent concentration effects.
The  MCL  is  used as a reference threshold for the  constituent of interest. However, releases
identified  here  are  estimates of concentrations  potentially  leaching from  landfills. Any
assessment of the environmental  impact of these releases  needs to consider the dilution and
attenuation of these constituents in ground water, and the plausibility of drinking  water well
contamination resulting from the release. Dilution  and attenuation factors for  metals (DAFs)
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 potential23. Therefore, comparison
with thresholds greater  than the MCL and developed for specific scenarios may be appropriate.
23 See 60 FR 66372, Dec. 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.


                                           55
-------
Characterization of Coal Combustion Residues II


3.3.1. Typical Characteristic Leaching Behavior as a Function of pH and LS
Figure 30 through Figure 45 provide comparisons of typical leaching behavior as a function of
pH for each constituent, as examples reproduced from Appendix D. These comparisons illustrate
on an empirical basis some of the differences in leaching behavior for different CCRs that result
from  the combination of the  coal  rank combusted, combustion conditions and  specific
combustion facility design and operation. Also noted but not shown is the observed behavior for
each constituent as  a function of LS at the material's natural pH (see Appendix E). Elements
with predominantly oxyanionic species (e.g., boron,  molybdenum, selenium,  etc.) typically
exhibited non-linearly increasing extract concentrations as LS was decreased from  10 mL/g to
0.5 mL/g, in many cases increasing by a factor of 5 or 10 or greater.
These  figures illustrate that for a particular  constituent, the chemistry controlling release or
aqueous-solid equilibrium may be similar within a material type (i.e., mercury behavior for fly
ash or  scrubber sludge) or across material types (i.e., the same behavior for aluminum in fly ash
and fixated scrubber sludge) but that there are not necessarily generalized behaviors present for
each constituent across all samples within a material type or between material types. The most
robust  groupings of  leaching behavior  will result from the development of geochemical
speciation models of the  materials that account for the underlying  solid phase speciation  (e.g.,
solid phases,  adsorption behavior) and modifying solution characteristics (e.g., dissolved organic
matter, pH, ionic strength, co-dissolved constituents). Development of the needed geochemical
speciation models,  and associated leaching  behavior  groupings  as  a  function of coal  rank,
combustion facility design, and CCR type, will be the basis of a subsequent report. The resulting
models and groupings, in turn, are  expected to allow for  more  detailed constituent  release
predictions based on limited testing for a broader set of facilities.
Mercury.  Figure 30 (a, b) compares  the impact  of SNCR usage (Facility A) on the  release
behavior of mercury from fly ash. The increased mercury release, reaching a maximum at pH~8,
when SNCR  is in use, is  likely a consequence of additional ammonium  present and consequent
formation of an ammonium mercury complex in solution (Wang, 2007). For all fly ash samples
except AFA  (Facility A, SNCR[+]), the  mercury  release  indicated apparently random scatter
with solution concentrations ranging from 0.01  to 0.1  |ig/L. This behavior is  similar  to that
reported earlier in this  study (Sanchez et al.,  2006) and is indicative of adsorption of elemental
mercury as the primary release mechanism. For gypsum samples, mercury release was either (i)
similar to that observed for fly  ash (Figure 30d, Facility P), (ii) at very low concentration  near or
below the MDL (Facility  O, unwashed and washed; Facility N washed) potentially indicative of
adsorption  onto carbon char,  or (iii) had increased release  at pH<6 potentially indicative of
adsorbed ionic mercury being  displaced by hydrogen ions at acidic pH (Facility A, unwashed;
Facility Q). For scrubber sludge, mercury release was either  (i) similar to that observed for fly
ash, (ii) had increasing release concurrent with decreasing pH at pH<8 (Facility B, Figure  30c),
or (iii) had increased release at pH~8 (local  peak,  indicative of ammonium complexation) and
then increasing release with decreasing pH at pH<6 (Facility K). For FSS, behavior was either (i)
analogous to that observed for fly ash (Facility A), or (ii) analogous to that observed for scrubber
sludge illustrated in Figure 30c (Facilities B, K, M). Mercury extract concentrations were not
significantly affected by LS.
Aluminum.  Figure 31 (a, b)  compares the impact of SNCR usage (Facility A) on the  release
behavior of aluminum from fly ash and illustrates one of the three types of aluminum behavior
observed across the CCR types. One  type  of observed aluminum behavior was  amphoteric


                                           56
-------
                                        Characterization of Coal Cumbustion Residues II


behavior (minimum release at pH~6-8, with increasing release as pH decreases and increases
outside  of this  range) with a local maximum of approximately 10,000 |ig/L at pH~12 and a
maximum of ca.  100,000 to  1,000,000 |ig/L at pH~3. The  concentration of the minimum at
68 (fly ash from facility B; scrubber
sludge from facilities B, K). Several samples exhibited increasing release with  decreasing pH for
pH<6 and a local maximum at pH~10 (Figure 31c, scrubber  sludge from Facility A; FSS from
Facility B). In addition,  several samples exhibited relatively  constant release  (ca. 100 |ig/L) at
pH>8 with increasing release with decreasing pH at  pH<8  (Figure  3Id,  scrubber sludge for
facility B with SCR[-]; FSS from facilities A, B, K). Aluminum extract concentrations typically
were  either relatively constant or decreasing (salting out) with decreasing  LS. The notable
exception was the scrubber sludge from facility B with  SCR off (DGD) and FSS from facility M
with SCR on (MAS), where aluminum concentration increased with decreasing LS.
Antimony.  Figure 32a illustrates antimony behavior with local maxima at  pH~8  and pH<3,
which was observed for fly ash from facilities A and  B, and FSS from facility A. Figure 32b
illustrates behavior that  was observed for gypsum from Facility Q and scrubber sludge from
Facility A. For gypsum samples other than from Facility Q, antimony release appeared random at
concentrations of 4 with a general  slight increase in concentration at
pH<4. Figure 32c and d illustrates behavior that was observed for the remaining CCR samples.
For some samples,  antimony  concentrations in extracts increased  by up to a factor of 5  with
decreasing LS, while it remained constant or decreased for other samples.
Arsenic. Figure 33 illustrates the four typical release behaviors observed for arsenic release as a
function of pH. Each of these four behaviors was observed for a least one of the samples from
each material type (fly ash, gypsum, scrubber sludge, FSS). Leaching from  gypsum generally
was less than  10 |ig/L for pH>6 and reached a maximum of approximately 30-100 |ig/L at pH<5.
Arsenic concentrations in extracts were either constant or increased by up to  a factor of 2  with
decreasing LS.
Barium. Figure 34 illustrates the four typical release behaviors observed for barium. For fly ash,
barium was either relatively constant at approximately 100 |ig/L as a function of pH or exhibited
increases at pH<  4 (Figure 34a) and pH>9 to approximately 1000 |ig/L  (i.e., facility K). For
gypsum, Figure 35d illustrates the typical behavior. Behaviors illustrated by Figure 34b  and c are
typical of that observed for scrubber sludge and FSS, with  both behaviors observed for  both
material types.  Barium extract concentrations remained constant with decreasing LS, with the
exception of fly ash from facility A, where barium concentrations increased by  up to a factor of 5
with decreasing LS.
Boron.  Figure 35 (a, b, c) illustrates the three typical release behaviors for boron: (i) decreasing
concentration with increasing pH  for pH>8 (Figure 35a, fly  ash from facilities A, B; scrubber
sludge from facility K; FSS from facilities A, M),  (ii) relatively constant concentration with a
slight decrease at 810  (Figure 35d). Comparison of Figure
35c and d illustrates the reduction in teachable boron achieved through the washing step (facility
N, unwashed  and washed). Boron concentrations in extracts were either constant or increased by
up to a factor  of 10 with decreasing LS.

                                           57
-------
Characterization of Coal Combustion Residues II


Cadmium.  Figure 36 illustrates typical release behavior for cadmium, which is similar for all
cases. The maximum concentration at pH<4 reflects the total content in the sample, and the slope
and pH shift in the increasing cadmium concentration with decreasing pH typically reflects the
presence or absence of complexants in solution (e.g., chloride or DOC). Cadmium concentrations
in extracts were either constant or increasing with decreasing LS.
Chromium.   Figure 37 and Figure  38 illustrate  typical release  behavior for chromium.
Comparison of the pairs Figure 37a and b, Figure 37c and d, and Figure 38a and b illustrate the
effect of NOx control on chromium release from fly ash, scrubber sludge, and FSS respectively
for Facility B. Use of SCR at this facility appears to result in a larger fraction of the chromium in
the residue being oxidized (Cr+6), forming chromate, which is more soluble at neutral pH. The
SCR catalyst  used for Facility  B  may  have contributed to increased overall total chromium
present in the CCRs from that facility when SCR was in use. Increased teachability of chromium
as a consequence of NOx control was also observed  for Facility A (comparing results for
SNCR[-] with SNCR[+]), even  though total chromium content was similar for cases with and
without NOx control. Figure 38c and d illustrates the typical amphoteric behavior for reduced
chromium (Cr+3), which was observed for gypsum samples. Chromium concentrations in extracts
were either constant (for cases with low teachable chromium), or increasing by up to a factor of
10 (cases with Cr+6 as the apparently dominant chromium form) with decreasing LS.
Cobalt. Figure  39 illustrates typical  release behavior for cobalt,  which is similar for all CCRs
tested.  Cobalt release increases with  decreasing pH at pH<8, with the maximum concentration
reflecting the total teachable content and the slope and relative pH shift in the slope typically
reflecting the presence or absence of complexants in solution. Cobalt concentrations in extracts
(where greater than the MDL) were typically increasing by up to a factor of 5 with decreasing
LS.
Lead.  Figure 40 illustrates typical release behavior for lead, which generally is expected to be
amphoteric (Figure 40a,  c). However,  many samples did not have sufficient lead content or
complexants present in solution to produce amphoteric behavior at pH<12 (Figure 40b, d). Lead
concentrations in extracts were not significantly changed at decreasing LS.
Molybdenum.  Figure 41 and Figure 42 illustrate typical release behaviors for molybdenum.
Figure 41a illustrates  increased  concentration peaking at pH~8 most likely  from  complexation
with ammonium present from use of  SNCR (Facility A). Note the similar release behavior
observed for fly ash,  FSS and gypsum illustrated  by Figure  41b and Figure 42b, c, albeit at
different orders of magnitude in concentration. Figure 41c,  d and Figure 42b, d  illustrate three
additional observed behaviors, present across multiple CCR types. Molybdenum  concentrations
typically increased with decreasing LS, in some cases by a factor much greater than  10 (e.g., FSS
from Facility A).
Selenium.  Figure  43 and Figure 44 illustrate typical selenium release behaviors observed for fly
ash, scrubber sludge and FSS. For gypsum, selenium release was either constant as a function of
pH (facilities O,  P) or amphoteric (facilities N, Q).   Selenium concentrations in extracts typically
increased by up to a factor of 6 with decreasing LS.
Thallium.  Figure 45 illustrates typical release behavior for thallium. Most cases were either
analogous to Figure 45a or Figure 45c (increasing concentration with decreasing pH at pH<9) or
Figure 45d (relatively constant as a function of pH). For gypsum, washing resulted  in at least an
                                           58
-------
                                        Characterization of Coal Cumbustion Residues
order of magnitude reduction in the observed leaching concentrations (facilities N, O). Thallium
concentrations typically increased by up to a factor of 5 with decreasing LS.

MCL

" n 1 -
~~ 0.1
§? 0.044
0)
U.U1
2
ML
— MDL
a) Fly;

10 -
MCL
D)
J± 0.1
o) 0.040
.01
Onrn -



-»-
_ . _



-F-V




IS




*?
. 	 ,



o
— . ,



AA A
a O|-7^
-1- - -



:





• —


•(0.3
4 6 8 10 12 14
PH
DSR2-CFA-A OSR2-CFA-B
ASR2-CFA-C
\sh - Fac. A. (NO+SNCR[-]+FF)


&


	
_ . _

D
o


—


75


••


A
n

n
	 <
• —




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-!•




D&'
_ . _




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• —



2 4 6 8 10 12 14
ML PH
— MDL
c)
ScrubberSlu
DSR2-DGD-A OSR2-DGD-B
ASR2-DGD-C

dge - Fac. B. (NO+SCR[-]+ESP, Mg Lime)
MCL
„ 0.116
-1 n 1 -
~~ U. 1
0)
U. U1




* "
- A A
2
ML
— MDL
b) F|YAs

10
MCL
A _
I
" n 1 -
~~ U. I
" 0.029
D)
1 0.01 -



[




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a(
-4V-
AD
• —


&
ot

— •


D
A1
_.._



^
L




1
• —

10.5
4 6 8 10 12 14
PH
• SR2-AFA - A » SR2-AFA - B
A SR2-AFA - C
h - Fac. A. (NO+SNCR[H
h +FF)




r
4
^™
o
2
ML
— MDL
d)
Gypsum
D
1 1



	
U



3
A




•
_ I




c
]
— . ,



. •
i i i









1 1 1

6.7
4 6 8 10 12 14
PH
• SR2-PAD - A * SR2-PAD - B

- Fac. P. (FO+SCR[+]&SNCR[+]+ESP)
Figure 30. Mercury - Examples of characteristic leaching behavior as a function of pH (SR002.1
results).
                                           59
-------
Characterization of Coal Combustion Residues II

1UUUUUU
100000
10000 -
1804
innn -I
|_l' IUUU
0) -inn -
,=^ 100
< ln .
10
1 -
®

»HH






T*
.-£
A






L.
-e.





& —
D ^
R





	 1
d
ftD





L*










	


°'1 10.3
2 4 6 8 10 12 14
- ML PH
— Mm
a) Fly
DSR2-CFA-A OSR2-CFA-B
ASR2-CFA-C
Ash - Fac. A. (NO+SNCR[-
+FF)

1000000
100000
10000 "
•-p 1000
=! 496
0) .nn .
=L 100
< m -
1U
1 -
.1
ML
— MDL
c)
Scrubbe

ESa







6b







V

—




EL
y
±
_qjp





o^j







r






i





7.3
4 6 8 10 12 14
PH
D SR2-CGD - A O SR2-CGD - B
ASR2-CGD -C

r Sludge- Fac. A. (NO+SNCR[-]+FF)

1UUUUUU
100000
13427
10000 -
innn
|_l' IUUU
0) -inn -
,=^ 100
< -in -

i
.1 -
^-
ML
— MDL
b) Fly
^









[







r







/OA<







C^
ya






.,Q €S





! , ,

^D







10.5
4 6 8 10 12 14
PH
• SR2-AFA - A OSR2-AFA - B
ASR2-AFA-C
Ash - Fac. A. (NO+SNCR[-
I- +FF)

1000000
100000 •
10000 "
^j 1000
0) .nn .
" 37.F
< m -
1U
1 •
.1
ML
— MDL
d)
Scrubbe
iHA
D t





|


f °







L








^Sx-w
ES>
AM







ImCK
^T

— F




a fcfc






K





9.1
4 6 8 10 12 14
PH
DSR2-DGD-A OSR2-DGD-B
ASR2-DGD-C

jrSludge- Fac. B. (NO+SCR[-]+ESP)
Figure 31.  Aluminum.  Examples of characteristic leaching behavior as a function of pH.
                                        60
-------
                                      Characterization of Coal Cumbustion Residues



=d 6.43in
D) l\/l/^l ' U
^ MCL
JD
W

.1 -
2
ML
— MDL
a) Fly;

gffi


_..

f*


...






a?«?


._.

on
OS


_..



T 	
j-l^.
I






10.3
4 6 8 10 12 14
PH
DSR2-DFA-A OSR2-DFA-B
ASR2-DFA-C
\sh - Fac. B. (NO+SNCR[-]+FF)

1000
100
u
D) MCL10
3: 5.44
JD
w

.1
ML
— MD
c)
ScrubberSli


&Ll


^^m • •


J 4


™ " "







•YnffT'
QS"'*


* ^^^

609V

'"T
— (•--
-j-



nA
[^





§
1





9.1
2 4 6 8 10 12 14
PH
DSR2-DGD-A OSR2-DGD-B
ASR2-DGD-C
idge- Fac. B. (NO+SCR[-]+ESP,MgLime

100
«
MCL1°
t 2-53
(-1 "I -
C/D
>

BB r




.1
2
ML
— MDL
b) Gypsu

1000
100
S MCL10 "
w 1-76
1

K










®
-.f....
•i--


*t
B



/a
1








6.9
4 6 8 10 12 14
PH
• SR2-QAU - A *SR2-QAU - B
m - Fac. Q. (FO+SCR[+
+ESP)


i-
^*-


"
2
ML
— MDL
d)
FSSL- Fa

_•


...







•»•



._.

AM



— 4.





1



1

"

1'2.2
4 6 8 10 12 14
PH
• SR2-DCC-A *SR2-DCC-B
ASR2-DCC-C
c. B. (NO+SCR[-]+ESP,MgLime)
Figure 32. Antimony. Examples of characteristic leaching behavior as a function of pH.
                                        61
-------
Characterization of Coal Combustion Residues II

1000 -
^ 46.8
D)
=2- MCL-in -
tn
* ,

fa




&





.1
2
ML
— MDL
a)
Fly Ash -F
1000 -
100 -
73, MCL1Q -
^_
in
<
0.545
0.1 -
ML
— MD
c)
ScrubberSli

&>n/


,









x&sl






on
tl






r%-
j. 	 .
j_ .


f*





10.3
4 6 8 10 12 14
PH
OSR2-DFA-A OSR2-DFA-B
ASR2-DFA-C
ac. B. (NO+SCR[-]+ESP,MgLime)


^A
0° ,
0 L


';
2
L
JC



] 0





i





*B]P
4





8>


— ej>
. . .




D ^^Al




&


9.1
4 6 8 10 12 14
PH
D SR2-DGD - A » SR2-DGD - B
ASR2-DGD -C

]ge - Fac. B. (NO+SCR[-]+ESP, Mg Lime)

10000
1UUU
, — , 1UU
^29.0
"*• MChn -
^
1 -
.1 4
ML
— MDL
b)
Fly Ash-

*%~






1 A.





















PAO






i
> ^22





L










10.1
4 6 8 10 12 14
PH
• SR2-BFA-A OSR2-BFA-B
ASR2-BFA-C
Fac. B. (NO+SCR[+]+ESP,MgLime)

10000
1000
inn -
, — , IUU
^5
=2- MOHn -
en
< 2.09
-
0.1 4
ML
— MDL
d)
FSSL- I

#





4











^,,
~5~LJ~





S





•.






_^J
1


1!2.2
4 6 8 10 12 14
PH
• SR2-DCC-A *SR2-DCC-B
ASR2-DCC-C
-ac. B. (NO+SCR[-]+ESP,MgLime)

Figure 33. Arsenic. Examples of characteristic leaching behavior as a function of pH.
                                         62
-------
                                      Characterization of Coal Cumbustion Residues

1 uuuu
MCL
-i nnn -
192
H nn -
I 1
•-1-. m -
CD 1U
m
1 .
n 1 -
^-
ML
— MDL
a)
FlyAsh

^1
4]






tSyB2






k






£5si2






*TS£






.^>a f
i





If





10.3
4 6 8 10 12 14
pH
DSR2-DFA-A OSR2-DFA-B
ASR2-DFA-C
- Fac. B. (NO+SCRH+ESP, Mg Lime)



MCL
1UUU
-i nn -

05
CD
I
OH
. 1 n
f
— MDL
c)
FSSL-
:
Sff
*




•^1





U





BT«^





—





-v




1
I 	




.2

I 4 6 8 10 12 14
PH
• SR2-DCC-A *SR2-DCC-B
ASR2-DCC-C
Fac. B. (NO+SCR[-]+ESP,MgLime)

10000 •
MCL
1000 •
113
100 '
O)
2; 10 '
CO
CD
1 '
0.1 '
ML
— MD
b)
ScrubberSk

&C
u




^^ • ^
2
dg

MCL

1UUU
[
:j 80.tru
CD
m

1
OH
2
ML
— MDL
d)
Gypsum
o r





~ * "

^^^C




^m • ^^^

Jv <2
" 5



^^^ "


i



_ L _
1






™ • ^^^

11.0
4 6 8 10 12 14
PH
• SR2-KGD-A OSR2-KGD-B

e - Fac. K. (NO+SCR[+]+ESP, Mg Lime)



-------
Characterization of Coal Combustion Residues II

100000
10000 -
3551
-i nnn -

ra 10°
CD 10
\
SSffl






j— • -
»Q






™ * ™
i







CDAAn
1






• ^^^ <
iOD







n\A/i=i
f*
l [^



T 	
1 	
• 11 i


1 f



• • ^^^

°'1 10.3
2 4 6 8 10 12 14
ML PH
— MDL
a)
FlyAsh
DSR2-DFA-A OSR2-DFA-B
ASR2-DFA-C
- Fac. B. (NO+SCRH+ESP, Mg Lime)

100000
_. ..40000 -
DWEtuuu
2214
1000
ra 10°
1U
1
0* _
. 1 n
f-
ML
— MDL
c)
Gypsum

*EJ—






-D




_.,

a-------
                                        Characterization of Coal Cumbustion Residues
      100
           ififfl
       10
  -T MCL
  O 0.7951
       0.1
                         A
          246
        ML
   —   MDL
                          10.3
                     8    10   12   14
                     PH
              DSR2-DFA-A    OSR2-DFA-B
              ASR2-DFA-C
 a)
    Fly Ash - Fac. B. (NO+SCR[-]+ESP, Mg Lime)
                                               100
                                                10
                                          ^  MCL
                                          O)

                                          TJ"    1
                                          O
                                              0.200
                                               0.1



	
1 1 1


0 L

, ,


CZ




'D0af
	
• i i


>
_.
-------
Characterization of Coal Combustion Residues II

1UUUU
1UUU
132
MCllDO -
_i
D)
^ -in -
1 — • 1U
o
H _
1

(>
	 1—



DJ
*>



&
>
. . —


9.1
4 6 8 10 12 14
PH
DSR2-DGD-A OSR2-DGD-B
ASR2-DGD-C

Ige- Fac. B. (NO+SCR[-]+ESP,MgLime)

1UUUU
851 100° -
„ MCllDO -
_i
D)
=*- -in -
• — • 1U
o
1
HJ

~^b~K


	 	 _
.1
2
ML
— MDL









	 j


• — •

&&&••*.


— . .

9 |**>W


— • —

A







• —

16.1
4 6 8 10 12 14
PH
• SR2-BFA-A *SR2-BFA-B
ASR2-BFA-C

b)
Fly Ash - Fac. B. (NO+SCR[+]+ESP, Mg Lime)
10000 -
1000 -
228
MCW -
_l
D)
^ -in -
L_
o
1 -
0.1 -
ML
— MD
d)
ScrubberSli

!
"tfl--


! 	
2
L
jd

	




•-




H*S-.


• —

P-^-fl-


— •

D ta


— • —

B







• —

lb.1
4 6 8 10 12 14
PH
D SR2-BGD - A O SR2-BGD - B
ASR2-BGD -C

ge - Fac. B. (NO+SCR[+]+ESP, Mg Lime)
Figure 37.  Chromium. Examples of characteristic leaching behavior as a function of pH.
                                        66
-------
                                      Characterization of Coal Cumbustion Residues


1UUU
MC!rnn
_i
S 11.2ln .


WM
•— ' 1U TW^T1^
0 1 °*
1 [

.1 -r
2
ML
— MDL
a)
FSSL- F



ct









.
*
• — •



&Q3
— . .


n c
"QT^
— • —




• —

12.2
4 6 8 10 12 14
PH
• SR2-DCC-A *SR2-DCC-B
ASR2-DCC-C
:ac. B. (NO+SCR[-]+ESP,MgLime)

10000
1000
MCI -inn

_l
73)
^ -in -
1 — • 10
0 2.87
0 1 -

&CD

	
_ . _

Dn

—
. . _



••



•
DDD
—5
"!"


OD

_ . .


o
s° ft

_ . _




• • —


246 7.28 10 12 14
PH
ML
°)r
Gypsum
• SR2-NAU - A 0 SR2-NAU - B
(Gyp-U) - Fac. N. (FO+SCR[+]+ESP)

10000
715 1°°°
MCW
_i
D)
=2- -in
1 — • 10
o
1
0.1
ML
— Mt
b)
FSSL





f-
DL
-1
:
^smM


!_ _
^1




•- ••M


— • —

0£f/


	 . .
"• I


— • —
'-


• • —

80
4 6 8 10 12 14
PH
• SR2-BCC - A * SR2-BCC - B
ASR2-BCC-C
:ac. B. (NO+SCR[+]+ESP,MgLime)

10000
-i nnn -
1 000
MCI -inn -
IT
D) 1n .
^- 10
O
0.235

?"»
D

r~ • ~

0.1 -M
2
ML
— MDL
d)
Gypsum


<





>
0

..



D
0
-^


D
D
y\
	 •


,/tf1

— . _.
4 6 7'1 8nU 10 12
pH




• —



14
• SR2-NAW-A OSR2-NAW-B
(Gyp-W) - Fac. N. (FO+SCR[+ 4
•ESP)

Figure 38.  Chromium. Examples of characteristic leaching behavior as a function of pH.
                                        67
-------
Characterization of Coal Combustion Residues II

1000
100
- m -
0) 1°
0
0 .
1
0.255
H -1 -
ffi





 10 -
0 1.65
1 '
.1 H
i-
ML
— MDL
d)
Gypsum

3 0


_ . -

DOC




£





13
— i




n&of
— .



t •
— . _




• • —


> 4 6 7§ 10 12 14
•pH
CISR2-OAU -A OSR2-OAU - B

(Gyp-U) - Fac. O. (FO+SCR[+]+ESP)
Figure 39. Cobalt. Examples of characteristic leaching behavior as a function of pH.
                                        68
-------
                                      Characterization of Coal Cumbustion Residues

1UUU
100
IT MCL
ra 10 -
JD
D.
•
0.339

•
fy


Zm
0.1 4—
2
ML
— MDL
a)
FlyA

1000
H nn -
IUU
_i MCL
ra 10 -
JD
D.
0.569
0-\ _

~ • ^



I
...



5
"



JSyt



PA^



ii0. _
. . .


?i
. . —

10.5
4 6 8 10 12 14
pH
• SR2-AFA - A * SR2-AFA - B
ASR2-AFA-C
>h - Fac. A. (NO+SNCR[+]+FF)




*
— •
1 1 1
2
ML
— MDL
c)
FSSL- Fa



• H



A



757!



1 i i



i i i


'•
i i i


8.4
4 6 8 10 12 14
PH
• SR2-ACC - A * SR2-ACC - B
ASR2-ACC-C
c. A. (NO+SCR[+]+ESP, Mg Lime)


1000
100 T
U MCL
ra 10 '
JD
CL
0.354


^
O
^
0.1 I —
2
ML
— MDL
b)
Scrubber!

1000
H nn -
IUU
U MCL
ra 10 -
JD
D.
1
°'140 01 ^-

• • ™


D

~ • ™



0



^}S.



3^



	 B



i.



• —

6.8
4 6 8 10 12 14
PH
d SR2-AGD - A O SR2-AGD - B
A SR2-AGD - C
Sludge- Fac. A. (NO+SNCR[+]+FF)


j
"
	
i i i
2
ML
— MDL
d)
Gypsum (



_^SC"




D
P-



a?



— -j



B, , P



'



i i i


7.5
4 6 8 10 12 14
PH
• SR2-OAU - A 0 SR2-OAU - B
Gyp-U) - Fac. O. (FO+SCR[+]+ESP)

Figure 40. Lead.  Examples of characteristic leaching behavior as a function of pH.
                                         69
-------
Characterization of Coal Combustion Residues II

10000
587
DWEL
, — , 100
D)
10
5



!





f







.1
2
ML
— MDL
a)
Fly/S

1000
DWEL
100 •
=d in 9-in -
0) IU-Z10
=L
0
5



^r







H





°5







p
S^t;







"n










7.3
4 6 8 10 12 14
PH
D SR2-CGD - A O SR2-CGD - B
ASR2-CGD-C

c)
ScrubberSludge- Fac. A. (NO+SNCR[-]+FF)

10000
1956
1000
nwFi

. — . 1UU
o 10
5
H _
I



•

i
S



2
ML
— MDL
b)
FlyA
1000 •
DWEL
135 10Q
U
D) 10 '
=L
0
5
0.1 •
ML
— MD
d)
ScrubberSh



ODA
S





3JA





f>Q i





i 	
j














10.3
4 6 8 10 12 14
PH
OSR2-DFA-A OSR2-DFA-B
ASR2-DFA-C
sh - Fac. B. (NO+SCRH+FF)



«TA





2
L
jd
: o i





t<33E&b&
m ____. ,_{^


"



a fi&i





3








9.1
4 6 8 10 12 14
PH
OSR2-DGD-A OSR2-DGD-B
ASR2-DGD -C

ge - Fac. B. (NO+SCR[-]+ESP, Mg Lime)
Figure 41. Molybdenum. Examples of characteristic leaching behavior as a function of pH.
                                        70
-------
                                      Characterization of Coal Cumbustion Residues

1UUUU
1UUU
241
DWEL
100 -
15)
o 10
S.
A _
I





-0


_ . -
.1
2
ML
— MDL
a)
FSSL- Fa

10000
1000
DWEL
H nn -
•— p IUU
5 18.8
o 10
5

. 1 n
ML
— MDL
c)
Gypsum


•




•S
UJ




^





^
-1 	




•





.<• —





8.4
4 6 8 10 12 14
PH
• SR2-ACC-A *SR2-ACC-B
ASR2-ACC-C
c. A. (NO+SCR[+]+ESP, Mg Lime)




! 	
B


I
(



___
oC
D




..
f





-B-qj






DO**'






& c!







	



4 6 T8 10 12 14
''TbH
• SR2-OAU -A OSR2-OAU - B
Gyp-U) - Fac. O. (FO+SCR[+]+ESP)


1UUUU
1UUU
DWEL
138
100 -
15>
o 10
5
I



Hi U

-


_ . -
.1
2
ML
— MDL
b)
FSSL- Fc

10000
1000
DWEL
H nn -
IUU
_i
S 14.3 j
• — i 1U
0
5
\
. \ n
ML
— MDL
d)
Gypsum


D-









a£_n





AC





•i





12.2
4 6 8 10 12 14
PH
• SR2-DCC-A *SR2-DCC-B
ASR2-DCC-C
c. B. (NO+SCR[-]+ESP, MgLime)




-*r
^.



>
(



ftjc






&






-« i
j.

i



> °






-------
Characterization of Coal Combustion Residues II

1000
100 -
MCL
0)
1 "


j, n
*



.1
2
ML
— MDL
a)
Fly Ash -F

1000
100
MCL
21 9

=d 10 '
D)
1 "
0-1 .




%&





i




A.J
^




loQ
%






ftttl
T 	



A
5'



10.3
4 6 8 10 12 14
PH
DSR2-DFA-A OSR2-DFA-B
ASR2-DFA-C

ac. B. (NO+SCR[-]+ESP, MgLime)

&







2
ML
c)
Scrubber SI L

h
J 0






A
••




A
— fita






jfflflx

1
1
T
1
1


D fi&lS










9.1
4 6 8 10 12 14
PH
DSR2-DGD-A OSR2-DGD-B
ASR2-DGD-C

dge - Fac. B. (NO+SCR[-]+ESP, Mg Lime)

1000
123
100 -
MCL
0)
0)
1 "



0
4



.1
2
ML
— MDL
b)
Fly Ash -F
1000 •
100 •
MCL
5* 10 '
D)
V 2.31
0.1 '
ML
— MD
d)
ScrubberSli


M»





i




^
:



— ffpj
Cj -fT~


r

0 «












9.2
4 6 8 10 12 14
PH
• SR2-KFA - A 0 SR2-KFA - B
ac. K. (NO+SCR[+]+ESP, MgLime)


-#D

:^.^

2
L
id



SiSiSi




is


BSrQ_

*.Si*.Si,



a
^ c n
-.I..!-.**




• n. B '








ib.1
4 6 8 10 12 14
PH
DSR2-BGD-A OSR2-BGD-B
ASR2-BGD -C

ge- Fac. B. (NO+SCR[+]+ESP, MgLime)
Figure 43. Selenium.  Examples of characteristic leaching behavior as a function of pH.
                                         72
-------
                                      Characterization of Coal Cumbustion Residues

1000
-i nn -
MCL
16 3
— i -in -
~~ 10
0)

CO -1 -
1
.1 -
ML2
— MDL
a)
FSSL-

m






>
J












^n






<2
A t






D
S






1




4 6 8 10 122'2 14
PH
• SR2-DCC-A *SR2-DCC-B
ASR2-DCC-C

Fac. B. (NO+SCR[-]+ESP,MgLime)

10000
1000
F_

15) 18.5
-*- 10
0)
co
0-1 _


&CD

,.____



2
ML
— MDL
c)
Gypsum I

CD

___




<

..




^R

~%1






&n




1


o






	


7.2
4 6 8 10 12 14
PH
• SR2-NAU - A 0 SR2-NAU - B
Gyp-U) - Fac. N. (FO+SCR[+]+ESP)


1000
1 nn -
MCL
22.6
— i -in -
~~ 10
0)
0)
w * .
1
.1 •
ML :
— MDL
b)
FSSL- F
3K

•— — — —



• •

	





••




• ^
__J*





V
nn





V
•





1




8.2
I 4 6 8 10 12 14
PH
• SR2-KCC-A *SR2-KCC-B
:ac. K. (NO+SCR[+]+ESP,MgLime)

10000
1000
325
•i nn -
MCI
D)
.-1-. 10
0)
CO
1
n -1 -
> »c







° E







B












j.



> 0





___£
<9 5














°'1 H 6.9
2 4 6 8 10 12 14
- ML PH
— Mm
d)
Gypsum
• SR2-QAU - A 0 SR2-QAU - B
(Gyp-U) -Fac.Q. (FO+SCR[+]+ESP)

Figure 44. Selenium.  Examples of characteristic leaching behavior as a function of pH.
                                         73
-------
Characterization of Coal Combustion Residues II

1000
100
5* -in -
o> 10
F MCL
0.773 n
. 1 T
ML
— MDL
a)
Fly Ash-
sate



i=.-.-.=
Son/




\





SA
 10
i — MPI


.1 '
f-
ML
— MDL
c)
FSSL- F
'.
^>
^
SSi.


^ " ™

JS

-





S>___
a>-n—




Aca



~~~~"
DA>D


1 *"
4 6 8 10 1;
PH

]
1
•]




2
> 14
• SR2-DCC-A *SR2-DCC-B
ASR2-DCC-C
ac. B. (NO+SCR[-]+ESP, MgLime)


1000
100
38.0
5* -in -
o> 10
F MCL
A _
I
. 1 T
ML
— MDL
b)
Fly Ash-
0




_..
ta
o











]
n J





s-f
i

~~i '
rr
to














9.2
! 4 6 8 10 12 14
PH
• SR2-KFA-A *SR2-KFA-B
Fac. K. (NO+SCR[+]+ESP, MgLime)

1000
100
5" -in -
D) 10
— 2.98
F MCL
\
.1 -
f-
ML
— MDL
d)
FSSL- F


">J

^ " ™


L_"




— .




•.JL*




psp
i



• •




i




i




! 4 6 8 10 12 14
PH
• SR2-KCC - A * SR2-KCC - B
ac. K. (NO+SCR[+]+ESP, MgLime)

Figure 45. Thallium. Examples of characteristic leaching behavior as a function of pH.
                                        74
-------
                                       Characterization of Coal Cumbustion Residues
3.3.2. Comparisons of the Ranges of Constituent Concentrations from Laboratory Testing
       with Measurements of Field Samples and the EPA Risk Report Database
Figure 46 through Figure 59 present comparisons of the range of constituent concentrations
observed in laboratory extracts from testing as a function of pH and LS (SR002.1 and SR003.1)
over the pH range from 5.4 to 12.4 and LS ratios from 0.5 to 10. This pH range represents the 5th
and  95th  percentiles  of pH observed  in  field samples  from  CCR  landfills  and  surface
impoundments, as discussed in Section 2.6. For laboratory leaching test extracts, the presented
data represent the observed minimum, natural pH, and maximum concentration, considering all
results from both test methods. Including  results from  testing as a function of LS  allows
consideration of potentially higher concentrations observed for initial releases that may occur at
low LS ratios in the field. The MCL or DWEL is included in each figure as a dashed horizontal
line to provide a reference value. However, the concentration ranges indicated in the figures  as
results of this  study  are direct measurements  of laboratory  extracts  and do not  consider
attenuation that may occur in the field. Ranges of field observations are included for comparison
as derived from the EPRI database, considering only observations from disposal sites associated
with facilities that have wet FGD scrubbers.  The 5th, median, and 95th percentile of field data is
presented for surface impoundments ["Surface Imp. (EPRI)"] and landfills ["Landfill (EPRI)"].
Surface impoundment  data are compared with scrubber sludge results because scrubber sludges
are most likely to be disposed in this manner (see Section 1). Landfill data are compared with
FSS and  FSSL because these blended materials are the likely to be disposed in landfills. Also
included  for comparison  is the 5th, median, and 95th percentile of the database used to carry out
human and ecological health risk evaluations in the EPA Risk Report (EPA, 2007) ("CCW Ash,"
"CCW FGD,"  and "CCW Ash and Coal Waste"  referring to monofilled fly ash, disposed FGD
scrubber  sludge, and combined CCR disposal, respectively).
pH.   The natural pH  of the fly ash samples evaluated in this report was alkaline24,  scrubber
sludge samples were neutral to alkaline,  gypsum samples were neutral and FSS samples were
mildly alkaline (pH ~8) to very alkaline (pH>ll), most likely depending on the amount of lime
added.
Mercury.  Laboratory extract concentration ranges  for  two of the  scrubber sludge samples
(Facility B) and four of the FSS samples (facilities B, K, M) exceeded the MCL for mercury. The
mercury  concentration ranges indicate that  the greatest leaching concentrations are expected
from scrubber  sludge and blending with fly ash and lime to produce FSS does not substantially
decrease, and may increase, mercury leaching.  All natural pH samples were less than the MCL,
most by more than an  order of magnitude. All fly ash  and gypsum data were less than the MCL,
regardless of pH. Mercury field data were very sparse.
Aluminum. There was no reference limit available for aluminum. The range of laboratory
extract concentrations  from scrubber sludge samples agreed well  with field observations. The
range of  field observations for landfills tended to be similar to somewhat lower than the values
observed for laboratory extracts. However, the range used in the EPA Risk Report (EPA, 2007)
had an upper bound approximately one order of magnitude greater than the field data and the
laboratory extracts.
24 Some fly ash samples reported on in Sanchez et al. (2006) were acidic.


                                          75
-------
Characterization of Coal Combustion Residues II


Antimony.  Fly ash and FSS had the highest concentrations of antimony in laboratory extracts.
The range of field observations  for surface impoundments  (EPRI) was much greater than for
laboratory extracts  of scrubber  sludge, but also likely reflects co-disposal  of fly ash with
scrubber sludge in surface impoundments. If the field data  includes co-disposal data, then the
concentration range reported for field observations is  entirely  consistent with  the laboratory
testing. The range of field observation for landfills (EPRI) was lower than observed in laboratory
extracts.  This comparison  suggests the potential for attenuation or immobilization under field
conditions, many  of which may be reducing in contrast to the oxidizing conditions used in the
laboratory testing. For gypsum, all natural pH results were less than the MCL.
Arsenic.  Leachable arsenic appears  to be distributed between fly ash and  scrubber sludge.
Results for Facility A (fly ash, scrubber sludge, and FSS), Facility B (scrubber sludge and FSS)
and Facility M (FSS) suggest that NOx  controls increase the teachability  of arsenic at  the
material's natural pH. Results from field observations indicate narrower ranges than laboratory
testing. Ranges used in the EPA Risk report (EPA, 2007) appear to be much higher than the
laboratory testing results, except for Facility M. All results for gypsum were less than the MCL.
Barium. Laboratory testing results indicate a much broader range of concentrations than field
observations. Two samples of FSS, both with NOx controls off (Facility B and Facility M), had
much greater laboratory extract  concentrations than the other samples. All natural  pH results
were less than the MCL for fly ash, scrubber sludge and gypsum.
Boron.   Most notable for  boron is  a reduction  of approximately  an  order  of magnitude in
teachable boron from gypsum as a consequence of washing (facilities N, O). There is no clear
trend  amongst  the  material  types  for boron.  Laboratory results  are  consistent  with field
observations. All gypsum natural  pH results were less than the DWEL.
Cadmium.   Cadmium concentrations in laboratory  extracts were generally  lower  for  the
scrubber sludge  than for the  other materials. For scrubber sludge, cadmium  concentrations
observed in laboratory extracts were less than the concentrations reported for field observations
for surface impoundments.  For all cases,  cadmium concentrations in laboratory extracts were
consistent with field  observations for landfills.  In  addition,  the measured  concentrations in
laboratory extracts from this study and reported for field results are approximately an order of
magnitude less than the upper bound reported for CCW and coal  waste in the Risk Report (EPA
2007).
Chromium. The range of field observations appears low in comparison to the laboratory testing
results. The  increase in chromium leaching, apparently as a consequence of NOx controls, is
evident  for facilities A, B  and M. Six cases exceed the MCL by  greater than one order of
magnitude. Test results for all of the gypsum  samples are well below the  MCL.  The field
observations for both surface impoundments and landfills are up to two orders of magnitude less
than the laboratory testing results.
Cobalt.  The use  of NOx controls appears  to increase cobalt leaching from fly  ash based results
for facilities A and  B.  The  data  range used by the EPA risk report (EPA, 2007) for combined
management  of ash and  coal  waste is one to  two orders  of magnitude  greater than  the
observations for laboratory extracts and field observations.
                                           76
-------
                                       Characterization of Coal Cumbustion Residues II


Lead.  Laboratory test results indicate concentration ranges generally lower than or consistent
with field observations for surface impoundments and landfills and much lower than the values
used in the EPA risk report (EPA, 2007). All fly ash and gypsum samples were less than the
MCL.
Molybdenum. Leachate molybdenum concentrations exceeding the DWEL by up to two orders
of magnitude  were observed  for fly ash  and FSS.  Leachate molybdenum concentrations
generally less than the DWEL were observed for gypsum.
Selenium.  Similar ranges of selenium concentrations are expected for all materials.
Thallium.  Laboratory test results indicate  a concentration range in excess of two  orders of
magnitude for all materials and the observed concentration can exceed the MCL for thallium by
more than  one  order  of magnitude.  Washed  gypsum had significantly  lower  extract
concentrations of thallium than unwashed gypsum.












Nat nv































Nat Ov



















Iflfli ;
Fly Ash






















pn|-ror| nv


































N 3t Ox
































_
3 C) ^ C) e> LJJ S f 3 > S i
-i < Q, ca ^ " < 5 < 5 < •=
— — o_ 2 "^ O Q- C
LLi-L1-Li-Li-ro ro^rou,"3
t LJ_ ^3 n 03 LJ- I
3 U- LJ.
ScrubberSludge
Gypsum
5"
1
2
J
T3
1_

o o H o c
8^8^













J g c
j < <
d S ;
< <- CD m ^ 2 -
. — *
££££££,_








Landfill[EPRI]
CCW FGD[EPA]
& Coal Waste [EPA]

:ixated ScrubberSludge ^
Figure 46. Natural pH (pH in distilled water at LS=10) observed in SR02 extracts.
                                          77
-------
Characterization of Coal Combustion Residues II
10.000
_ 1.000
l>
D)
1 0.100
0.010
0.001 -
MCL = 2 M9/L
Max
Min
^o wn p H


Nat. Ox.


4 I
t'l|l
I
Nat. Ox.



III..'

_ + _ + + ~ ^ + _ + + „




Forced Ox.




«,
^


g
ffii IHISj !!
Fly Ash | ScrubberSludge

<
3 s
4 >

> ^



D
f ?§ f
§ g tS
y 6 s y
u. ra ^- u.
Gypsum
Nat. Ox. | . Ox.


••
4 >
< »
4 .
jy CT H CT CT 9
o o " o o <
O <£ Q cQ ^ ^
< <£ CQ cQ ^ 2
^ ra ^ ra ra ra



(




*


Fac. M (MAS) +
Landfill [EPRI]
CCW FGD [EPA]
&Coal Waste [EPAl
Fixated ScrubberSludge
<











"S> -
< :



Max
Min
*own pH

Nat. Ox.
4
Nat. Ox.
i




Forced Ox.

111 <• I-
' ' 1 1 *
r



" < <





4



L"L"° ^^^^^1 o g ^
1
> t


If
1





r 5-
c g
- £
Q S
t s
Q- O
Fly Ash ScrubberSludge Gypsum
Nat. Ox. I.Ox.

' 11,"
'V f







' + '++' +
^ CT ^ CT CT 9 c?
^ o u o o ^ <
y, ^ G, co^ ^ ^, ^
< ^ CD CQ ^ ^ ^
U (J U (J (J (J

f
Fixated ScrubberSludge



• .
•


Landfill [EPRI]
:W FGD [EPA]
1 Waste [EPA]
° (3
in

Figure 47 and Figure 48.  Mercury and Aluminum.  Comparison of maximum, minimum and
natural pH concentrations observed in SR02 and SR03 extracts over the pH domain 5.4< pH<
12.4. (key: - = NOx control off; + = NOx control on; U = unwashed gypsum; W = washed
gypsum; Nat. Ox.  = natural oxidation; Forced Ox. =  forced oxidation; I.Ox.  = inhibited
oxidation).
                                        78
-------
                                      Characterization of Coal Cumbustion Residues
1,000.0
100.0
J) 10.0
l/>
1.0
0.1
MCL = 6 M9/L
Max
Min
*own pH


Nat. Ox. Nat. Ox. Forced Ox.
••.hit UL L

_ .. -u-— -: - - |_
* ' I
Hill
+ ' + +  g Z> Z>
<<£<<£; g a g a a a- + + + + + +
y,


1
+ + + +
o o o o o g oo
0 0 JJ 0 0 < <
cri < S, CD ^ ^ ^
-------
Characterization of Coal Combustion Residues II



nj
CD mn -


MCL = 2000 |J<
Max
Min
•own pH
Nat. Ox.


-tjj
4 •







Nat. Ox.




J
ll
I
4



1* ]

»

fill!
Surf ace Imp. [EPRI]

Forced Ox.


, M i
<* Ti

zi ;
s ^ g 5 ^
S >• 3" >• S" S
1 < o < 2 a
.2 .O
u • u • y u
co u co u (0 co
l_l_ TO ii CO LJ- i|_
1 1 1 1
Fly Ash ScrubberSludge
Nat. Ox. . Ox.
.__!__•__.
p



ir, ' .,1
i i

S-J cT H CT CT 9 

< > 4 . •
4 '
4 >


+ + + +
^^O^T^O ^cJ^cJucJ
CJ -CJ -^CJ L^^L^1^1^1^^
COUcOU,^CO u- U-U-Ll-LL
I i CO |j_ CO U- i i
1 1 1 1
Fly Ash ScrubberSludge
Gypsum Fixated ScrubberSludge


Landfill [EPRI]
W FGD [EPA]
1 Waste [EPA]
!_> CO
°3
in

Figure 51 and Figure 52.  Barium and Boron.  Comparison of maximum, minimum and natural
pH concentrations observed in SR02  and SR03 extracts over the pH domain 5.4< pH<  12.4.
(key: - = NOx control off; + = NOx control on; U = unwashed gypsum; W = washed gypsum;
Nat. Ox. = natural oxidation; Forced Ox. = forced oxidation; I.Ox. = inhibited oxidation).
                                        80
-------
                                     Characterization of Coal Cumbustion Residues




•o


MCL - 5 |jc

Max
Min
*own pH








t\





h



4

<
L
C
<
L




Jat



<

? <
iL<
c <
j
u




Ox



> 4

+
fe £
t c
TS .

Fl\








i E
Q c
J
u

f A





<


+
? <
J_ L
E 5
Q ^
•o

sh





4


f •"
L b
i J
a .
2 r
L c






»


I
L
L£
/)
I
5>




Nat. Ox.


4 >
1 1
Ihll

1 + ' + + =*
-— • v -— ££
Q Q 9 Q Q 0.
^ O O O L"-1
CO ^ CO ^ ^ g
•§
| ScrubberSludge


Forced Ox.

, ,

rttu

3~ f *5 ^ S 3
1. i S. § BS
. ^ .O
co o Eo o w co
1 i CO I i CO LJ_ i i
u- Li-
Gypsum


Nat. Ox. | . Ox.
1
. |_ i
r
\[m\

ft G H G G 9 oo'
X O X U O S <
B < B CD ^ ^, ^
•* < m m ^ S 2
,ro CO ,ro CO CO CO in

Fixated ScrubberSludge





1 1
'

ndfill[EPRI]
FGD [EPA]
JO 5,
O
0 c
c
<








t
L
L£
i;
SI
T5
•^
>
T5
3
a
/)
t




















10,000.0 •
1,000.0 '

|>
fi 10.0 •







Nat. Ox.
i,

4

»
4



I
4


4







Nat. Ox.

* 1



Forced Ox.


1 ,
^^ T T
4 !

I


• 4





Nat. Ox. |
T I
4 '

4 j
1 r



.Ox.



1








»







+ ++^ '+ ++= ZlSZlSZlZl +'++'+ =^^
<<'<<'<'Q- Qa9aao- ^ + ^ + ^ ^ OO-OQ-Q-Q^ c
p;LL4rLi_Li_trj ^CDCDCDLU 5^^^^Q^ P O x O O 5 "^ L
ii < B m. x. jz P_  < % < < ° -------
Characterization of Coal Combustion Residues II



S l
o
o



Max
Min
»ownpH







°- 1.00 '


MCL = 15 M9/L
Max
Min
*own pH


Nat. Ox.


} , t
< > 4> < •
IflHf
LJ- LJ- LJ- O
Fly Ash



Nat. Ox.

f~

M
I'lll

_ + _ + +5.
f« u y u u >
0
Fly Ash


Nat. Ox.

1 '
4 >
< > ' » < >
8 O ^ O O L.U
^
^
| ScrubberSludge



Nat. Ox.


"
4 « .. "

+ ' + + ^
-—v -~^ C^
Q Q ° Q Q D-
^ (D " U U LJ£
^ si a. CD, ^
< < m CD *: §"
£ ^ £ % % g
^
(/)
| ScrubberSludge


Forced Ox. Nat. Ox. .Ox. T
1

m,.J i •.. )
4 •
+
II!
^ LJ- ^ LJ- ^ O
°3
Gypsum Fixated ScrubberSludge ^



ForcedOx. Nat. Ox. I.Ox.
4 '
_L — ,

i L
i I •
liiij r u 1

3g^g^3 +•++ + g<<
Ss-Ss-SS o8"oo<< utiiy
<:5<-?<:<- ii
-------
                                      Characterization of Coal Cumbustion Residues





o



DWEL= 200 ug/
Max
Min
»own pH




"3
o
(ft .
10.0 ;
MCL = 50 ug/L
Max
Min
*own pH

Nat. Ox.
1 (M
M




_ + _ + + 5.
< < < < < Q.
o|a ||^
0
Fly Ash



Nat. Ox.
4 >

, r p
4 •

<"<-<"<-<- CL
^~ LL. Ll_ Ll_ M^.
!«!««=>
U- LL U- LL LL O

Fly Ash

Nat. Ox.

. |__L.L_.
" r*^
1 1
4 •


+ + =.
Q Q ° Q Q D-
« CJ3 ^ U U u
y. < S- CQ ^ "
5
| ScrubberSludge



Nat. Ox.


t' '
1 1
™ Sd £ Sd Sd g
U- LL L"- LL LL co

ScrubberSludge

Forced Ox.



E
m

^ § ^ § ^ ^
i ?i i i i
i. < a § t s
.2 .O
£ o % d ra ^
LL ra LL ra LL LL
Gypsum



Forced Ox.
< >

< »

+ + + + ? +
LL LL
Gypsum

Nat. Ox. 1. Ox.
1 '
4 I
r^4~4 ,



' + •++• +
8 o y o o s <
^ LL U- LL LL LL LL
Fixated ScrubberSludge



Nat. Ox. .Ox.

4 .
< •
4 >
* ' V

o 77 ^ c7 c3" f^

Fixated ScrubberSludge


1 .
to
_ 1



LV < <
III
0 5






< >


a < <
n D- D.
-LJ, tii tii
= Q 0)
"- O to
"D LL CO
§ g g
O CD
0 5
1
Figure 57 and Figure 58. Molybdenum and Selenium.  Comparison of maximum, minimum and
natural pH concentrations observed in SR02 and SR03 extracts over the pH domain 5.4< pH<
12.4.  (key: - = NOx control off; + = NOx control on; U = unwashed gypsum; W = washed
gypsum; Nat. Ox.  = natural oxidation;  Forced Ox.  =  forced oxidation; I.Ox.  =  inhibited
oxidation).
                                        83
-------
Characterization of Coal Combustion Residues II
1,0
1
MCL = 2 u
Max
Min
*own pH




10.0 '
1.0 '
3/L



Nat. Ox.

4

»


—
4


4
4



»





Nat. Ox.

4





4
1
ft
<







»

Forced Ox.
I
I
I:


I
P t
L
Nat. Ox. |
1 1
IJ i;

.Ox.
1
' 1


ififff iiiiii Piiiji
^ LI- Li-

Fly Ash
| ScrubberSludge
Gypsum
Fixated ScrubberSludge




t
andfill[EPRI]
V FGD[EPA]
Waste [EPA]
ccv
Ash & Coal

Figure  59.   Thallium.  Comparison of maximum, minimum  and natural  pH concentrations
observed  in  SR02   and  SR03  extracts  over  the   pH  domain   5.4<  pH<   12.4.
(key: -  = NOx control off; + = NOx control on; U = unwashed gypsum; W  = washed gypsum;
Nat. Ox. = natural oxidation; Forced Ox. = forced oxidation; I.Ox. = inhibited oxidation).
                                        84
-------
                                        Characterization of Coal Cumbustion Residues II


4. SUMMARY OF RESULTS, CONCLUSIONS AND RECOMMENDATIONS

The following sections present conclusions from the results presented in this report.
Tables 8 through  11 summarize the results obtained from this study for fly ash, FGD gypsum,
scrubber sludge, and FSS, respectively. The set of 23 CCRs evaluated in this report reflects 84
and 74 percent, respectively, of the current and future facility configuration types with acid gas
scrubbers based on generating capacity, but only  a limited number  of facilities within each
configuration type. Each table provides the following attributes, and associated ranges, related to
each material type and constituent examined:
    1.  Total content (mg/kg, dw) from acid digestion.
   2.  The minimum  and maximum elemental concentrations measured in laboratory leaching
       test extracts over the domain of 5.4< pH< 12.4 from leaching evaluation as a function of
       pH at LS=10 mL/g (SR002.1) and as a function of 0.5< LS< 10 mL/g dw (SR003.1). This
       range is intended to represent the potential  range of leachate concentrations expected to
       be observed in the field from  management of each of the material types in monofilled
       management conditions. Concentration ranges for individual samples of each material
       type are compared in Section 3.3.2.
   3.  The minimum  and maximum elemental concentrations measured in laboratory leaching
       test extracts when extracted with deionized water only ("natural pH") and 0.5< LS< 10
       mL/g dw (SR003.1). The resulting pH range is also indicated.
   4.  The MCL or DWEL and  TC  (as available) for each  constituent to provide reference
       concentrations for evaluation of the concentration results summarized as described above.
       However, the expected leachate concentration ranges  derived directly  from laboratory
       testing and probabilistic assessments do not  include any dilution and attenuation that may
       occur prior to  impacting water resources. Previous studies have indicated dilution and
       attenuation factors of as low  as 2  to 10 on a national basis or as high as  8,000 at a
       particular site25. Thus, comparisons with the MCL,  DWEL or TC  for any constituent
       must be done with caution.
   5.  Variability in extract concentration as a function  of pH based on results from laboratory
       leaching testing  (SR002.1). Classification  of variability is  as  follows:   (a) Low =
       concentration range < 1 order  of magnitude, (b) Med. = concentration range of  1 to 2
       orders of magnitude, (c) High = concentration range of >2  orders of magnitude.

In addition, results are emphasized through coding as follows:
    1.  Expected concentration values that exceed  either the MCL or DWEL  for the given
       constituent are in red bold typeface.
   2.  Constituents are underlined  in the column heading (e.g., Cd in Table 9) when one of the
       expected concentration ranges exceeds either the MCL or DWEL.
25 See Section 3.3.


                                           85
-------
Characterization of Coal Combustion Residues II
Based on the results of testing and evaluations in this study, the following conclusions are drawn:
    1.  For each CCR type the following constituents exceeded either the maximum contaminant
       level (MCL) or drinking water equivalent level  (DWEL) in at  least one laboratory
       leaching test condition over the range  of pH and LS ratios considered, and therefore
       potentially  may present  unacceptable  environmental risks under some management
       scenarios. These cases warrant more detailed evaluation, including  consideration of site-
       specific conditions.
          a.  Fly ash - antimony, arsenic, boron, cadmium, chromium, molybdenum, selenium
              and thallium.
          b.  FGD gypsum - boron, cadmium, molybdenum, selenium and thallium.
          c.  Scrubber  sludge  -  mercury,  antimony,  arsenic,  boron,   chromium,  lead,
              molybdenum, selenium and thallium.
          d.  Fixated scrubber sludge  - mercury, antimony, arsenic barium, boron, cadmium,
              chromium, lead, molybdenum, selenium and thallium.
          However, (i) typically, evaluation results from only a subset of samples of a given
          material  type exceeded the indicated  criteria, (ii) never did the full range reported
          exceed the indicated threshold, and (iii) this analysis does not account for additional
          dilution and attenuation processes that may occur under field management scenarios.
          These results  suggest that (i)  consideration  of dilution and attenuation  factors for
          specific  management scenarios  may  indicate  that release concentrations may be
          higher than exposure concentrations, and that release concentrations above the MCL
          or DWEL may not result in exposure concentrations above those levels; (ii) linear
          partition coefficients (Kds) are not appropriate for representing source term release
          from  CCRs for a range of constituents  and materials; and,  (iii) evaluation  of
          individual CCR sources may indicate that the environmental compatibility of specific
          types of CCRs with general  management  scenarios  will depend on the  source
          (reflected through leaching characteristics) of the material.
    2.  Leaching of individual  constituents  may  vary  over several  orders of magnitude,
       depending on the conditions of the management scenario. Thus, these results can be used
       to suggest design conditions that would  reduce or minimize constituent release (e.g., pH,
       and other conditions).
    3.  Leaching concentrations do not  correlate with  total   content  except for   specific
       constituents  in selected materials where the constituent (a) is weakly retained,  and (b)
       leaching concentrations have a low variability relative to pH. Thus, total content is not a
       good indicator of leaching.
    4.  Results of this study suggest  that it appears that Cr teachability is associated with the use
       of post-combustion NOx controls.  This is based on a limited set of paired samples from
       the  same facility operating with and with SCR  or SNCR in use.  This finding will be
       further evaluated as additional data are collected.
    5.  The systematic leaching behavior of COPCs observed in the range  of samples evaluated
       suggests that the  geochemical mechanisms  controlling leaching can  be discerned and

                                           86
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                                 Characterization of Coal Cumbustion Residues
quantified using geochemical speciation modeling, which in turn, can serve as the basis
for evaluating and improving design of CCR management scenarios. Development of
generalized geochemical speciation models  for the materials  evaluated in this study is
recommended.
Ranges  of concentrations of some constituents in laboratory  leaching test extracts  and
field  data included  in  this study  suggest  applicable concentration ranges  for  risk
evaluation are different from the concentration ranges used in  a recent report by USEPA
(EPA, 2007). The new information reported here will help provide a more up-to-date and
comprehensive dataset for future risk assessments.
                                    87
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Characterization of Coal Combustion Residues II
TableS. Fly Ash. Summary of results.

Total in Material
(mg/kg)
Hg
0.04 -
0.6
Sb

3 - 15
As

70-90
Leaching test and assessment results
Cone. Range
for
5.4-------
                                                                      Characterization of Coal Cumbustion Residues
Table 9. FGD Gypsum. Summary of results.


Total in

Material
(mg/kg)
Hg


001 -

0.5
Sb



2-6

As



2-4

Leaching test and assessment results
Cone. Range
for

5.4-------
Characterization of Coal Combustion Residues II
Table 10.  Scrubber Sludge.  Summary of results.

Total in Material
(mg/kg)
Ss
0.04-
0.6
Sb
4- 15
As
4-40
Leaching test and assessment results
Cone. Range
for
5.4-------
                                                                        Characterization of Coal Cumbustion Residues
Table 11. Fixated Scrubber Sludge.  Summary of results.

Total in Material
(mg/kg)
Ss
0.02 -
1.0
Sb

5-20
As

3-70
Leaching test and assessment results
Cone. Range
for
5.4
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Characterization of Coal Combustion Residues II


5. REFERENCES

ACAA  (American Coal Ash Association), 2007. 2006 Coal Combustion Product (CCP)
Production and Use  Survey. http://www.acaa-usa.org/CCPSurveyShort.htm (accessed  May
2008).
ASTM,  2002. Method D 6784-02, "Standard Test Method for Elemental, Oxidized, Particle-
Bound, and Total Mercury in Flue Gas Generated from Coal-Fired Stationary Sources (Ontario-
Hydro Method)." American Society for Testing and Materials, 2002.
Clean Air Mercury Rule.  Code of Federal Regulations, 70 FR 28606; May 18, 2005.
Clean Air Interstate Rule. Code of Federal Regulations, 70 FR 25162; May 12, 2005.
DOE-EIA (Official Energy Statistics from the U.S.  Government  -  Energy Information
Administration),   2007.   Annual  Energy  Outlook  2007   with   Projections  to  2030.
http://www.eia.doe.gov/oiaf/aeo/index.html  (accessed November 2007).
Duong, D. Do.,  1998. Adsorption Analysis: Equilibria and Kinetics, London: Imperial College
Press, 1998, 892 p.
EPA, 1988. Report to Congress - Wastes from the Combustion of Coal by Electric Utility Power
Plants, EPA/530-SW-88-002. Washington,  DC: U.S. Environmental Protection Agency, Office
of Solid Waste and Emergency Response, 1988.
EPA, 1996. Method 3052,  "Microwave Assisted Acid Digestion of Siliceous and Organically
Based Matrices." Test Methods for Evaluating Solid Waste, Physical/Chemical Methods (SW-
846). U.S. Environmental Protection Agency,  1996.
EPA, 1998a. Method 7470A, "Mercury in Liquid Waste (Manual Cold-Vapor Technique)." Test
Methods  for   Evaluating  Solid   Waste,  Physical/Chemical  Methods   (SW-846).  U.S.
Environmental Protection Agency, 1998.
EPA, 1998b. Method  7473, "Mercury in  Solids and  Solutions by Thermal Decomposition,
Amalgamation, and Atomic Absorption Spectrophotometry." Test Methods for Evaluating Solid
Waste, Physical/Chemical Methods (SW-846). U.S. Environmental Protection Agency, 1998.
EPA, 1999.  Report to  Congress-Wastes from  the Combustion of Fossil  Fuels:  Volume 2-
Methods,  Findings  and Recommendations,  EPA  530-R-99-010.  Washington,  DC:  U.S.
Environmental Protection Agency, Office of Solid Waste and Emergency Response, 1999.
EPA, 2000.  Characterization and evaluation of landfill leachate,  Draft Report.  68-W6-0068.
U.S. Environmental Protection Agency, September 2000.
Kilgroe, J., C. Sedman,  R.  Srivastava, J.  Ryan, C.W. Lee, S. Thorneloe,  2001.  Control of
Mercury Emissions from Coal-Fired Electric Utility Boilers:  Interim Report, EPA-600/R-01-
109, Dec. 2001.
EPA, 2002.  Characterization and Management of Residues from Coal-Fired Power Plants,
Interim Report, EPA-600/R-02-083. U.S. Environmental Protection Agency, December 2002.
EPA, 2003.  Technical Support Document  for the Assessment of Detection and Quantitation
Approaches.       U.S.   Environmental    Protection    Agency,    2003.    Available   at
http://epa.gov/waterscience/methods/det/index.html. (accessed June 2008).
                                         92
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                                       Characterization of Coal Cumbustion Residues II


EPA, 2005. Control of Mercury Emissions from Coal Fired Electric Utility Boilers: An Update.
Air Pollution Prevention and Control Division, National Risk Management Research Laboratory,
Office of Research and Development, U.S. Environmental Protection Agency, Research Triangle
Park, NC, Feb 18, 2005. http://www.epa.gov/ttn/atw/utility/
ord_whtpaper_hgcontroltech_oar-2002-0056-6141.pdf (accessed May 5, 2005).
EPA, 2006. 2006 Edition of the Drinking Water Standards and Health Advisories.  EPA 822-R-
06-013 (updated August, 2006).   Office  of Water, U.S. Environmental Protection Agency.
Washington, DC.

EPA, 2007.  Human and Ecological Risk Assessment of Coal Combustion Wastes.   Docket #
EPA-HQ-RCRA-2006-0796; Docket Item# EPA-HQ-RCRA-2006-0796-0009. Released as part
of     notice      of      data      availability      on      August      29,      2007;
http://www.epa.gov/epaoswer/other/fossil/noda07.htm.
EPRI, 2005. Personal communication  of Electric Power Research Institute (EPRI) leaching
database (as of June 2005); summary information from K. Ladwig to D. Kosson.
EPRI, 2006, Characterization of Field Leachates at Coal Combustion Product Management
Sites: Arsenic, Selenium,  Chromium,  and Mercury Speciation,  EPRI Report Number 1012578.
Electric  Power  Research Institute  (EPRI), Palo  Alto, CA and U.S.  Department of Energy,
Pittsburgh, PA, 2006.
Hensel, B., 2006. Sampling and Analysis Plan for Plant 14090, EPRI SAP1674. Electric Power
Research Institute (EPRI), 2006.

Hutson, N.D., 2008.  Mercury Capture on Fly Ash and Sorbents: The Effects of Coal Properties
and Combustion Conditions, Water Air SoilPollut: Focus (2008) 8:323-331.

Kilgroe, J., C.  Sedman, R.  Srivastava,  J. Ryan, C.W. Lee, S. Thorneloe.  Control of Mercury
Emissions from Coal-Fired Electric Utility Boilers:  Interim Report, EPA-600/R-01-109, Dec.
2001.
Kosson, D. S., H. A. van der Sloot, F. Sanchez, and A. C. Garrabrants, 2002. An Integrated
Framework for Evaluating  Leaching  in  Waste  management and  Utilization of  Secondary
materials. Environmental Engineering Science 19(3): 159-204 (2002).
Laudal, D.L., J.S. Thompson, C.A. Wocken (2004) Selective Catalytic Reduction Mercury Field
Sampling Project, EPA-600/R-04-147, November 2004.
Ladwig, K. Personal communication, Nov.  15, 2007.
MTI  (McDermott  Technology,  Inc.),  2001.   Mercury   Emissions  Predictions,   http://
www.mtiresearch.com/aecdp/mercury.htmltfCoal%20Analyses%20and%20Mercury%20Emissio
ns%20Predictions (accessed November 2002).
Munro, L. J., K. J. Johnson, and K. D. Jordan,  2001.  An  interatomic potential for mercury
dimmer. Journal of Chemical Physics 114(13): 5545-5551 (2001).
Rudzinski, W., W. A. Steele, and G. Zgrablich, 1997. Equilibria and dynamics of gas adsorption
on heterogeneous solid surfaces, Amsterdam: Elsevier, 1997.
Ruthven, D. M., 1984. Principles of Adsorption and Adsorption Processes, New York: Wiley,
1984, 433 p.
                                         93
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Characterization of Coal Combustion Residues II


Pavlish, J. H., E. A. Sondreal, M. D. Mann, E. S. Olson, K. C. Galbreath, D. L. Laudal, and S. A
Benson, 2003. Status Review of Mercury Control Options for Coal-Fired Power Plants. Fuel
Processing Technology 82: 89-165 (2003).
SAB  (EPA Science Advisory Board, Environmental Engineering Committee), 2003.  "TCLP
Consultation  Summary." Presented at the Science Advisory Board  (SAB)  Environmental
Engineering Committee consultation with U. S. Environmental Protection Agency., Washington,
D.C., June 17-18,2003.
Sanchez, F.,  and D. S. Kosson, 2005. Probabilistic approach for estimating the release  of
contaminants under field management scenarios. Waste Management 25(5), 643-472 (2005).
Sanchez, F., R.  Keeney, D.  S. Kosson, and R. Delapp, 2006. Characterization of Mercury-
Enriched Coal Combustion  Residues from Electric Utilities  Using  Enhanced Sorbents for
Mercury Control, EPA-600/R-06/008. Prepared for the U.S. Environmental Protection Agency -
Air Pollution Prevention and Control Division, Contract No. EP-C-04-023, Work Assignment 1-
31, February 2006.  www.epa.gov/nrmrl/pubs/600r06008/600r06008.pdf
Srivastava, R.K., W. Jozewicz, 2001. Flue Gas Desulfurization: The State of the Art.  Journal
of Air and Waste Management 51, 1676-1688.
Srivastava, R.K., N. Hutson, B. Martin, F. Princiotta,  J. Staudt, 2006.  Control  of Mercury
Emissions from Coal-Fired Electric Utility Boilers, Environmental Science & Technology,  ¥7,
1385.
Thorneloe,  S., 2003. "Application of Leaching  Protocol  to Mercury-Enriched Coal  Combustion
Residues", Presentation to the U. S. Environmental Protection Agency  (EPA) Science Advisory
Board (SAB), Environmental Engineering Committee, Washington, D.C., June 17, 2003.
Thorneloe,  S., 2006. Evaluating Life-Cycle Environmental  Tradeoffs from the Management of
Coal  Combustion Residues  Containing Mercury and  Other Metals, Thesis for Masters  of
Environmental Management,  Nicholas  School  of the Environment and  Earth Sciences, Duke
University, May 2006.
Thorneloe,  S., D. Kosson, F.  Sanchez, B. Khan, P. Kariher, 2008.  Improved Leach Testing for
Evaluating  the Fate of  Mercury and Other Metals from  Management of Coal  Combustion
Residues,  Proceedings  for the  Global Waste Management  Symposium,  Copper Mountain
Conference Center, Colorado, USA, Sept 7-10, 2008.
Vidic, R.D., 2002.  Combined Theoretical and Experimental Investigation of Mechanisms and
Kinetics of Vapor-Phase Mercury uptake by Carbonaceous Surfaces, Final Report. Grant No.
DE-FG26-98FT40119 to U.  S.  Department of Energy (DOE), National Energy  Technology
Laboratory, 2002.
Wang, J., Wang, T., Mallhi, H., Liu, Y., Ban, H. and Ladwig, K., 2007.  The role of ammonia on
mercury leaching from coal fly ash.  Chemosphere 69:1586-1592.
                                          94
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&EPA
QAPP for the Characterization of
Coal Combustion Residues

Appendix A. Quality Assurance Project Plan
Category III / Technology Development
Final

Contract No. EP-C-04-023
Work Assignment No. 4-26

May 2008
-------
 PetefKanfier
 ARCADIS U.S., Inc
 Work Assignment Leader
                          A.
                                                     Date
Laura Beach Nessley
ARCADIS U.S., Inc.
Quality Assurance Officer
                                                     Date
Susan Thorneloe
U.S. Environmental Protection Agency
Work Assignment Manager
                                                     Date
Andy Miller                              ~~~          Date
U.S. Environmental Protection Agency
Acting Chief, Atmospheric Protection Branch,
                   ")
Robert Wright               //
U.S. Environmental Protection Agency
Quality Assurance Representative
                                                     Date
                                                                            Prepared for
                                                                            Susan Thorneloe
                                                                            U.S. Environmental Protection Agency
                                                                            National Risk Management Research Laboratory
                                                                            Air Pollution Prevention and Control Division
                                                                            Atmospheric Protection Branch
                                                                            Research Triangle Park, NC 27711

                                                                            Prepared by
                                                                            ARCADIS U.S., Inc.
                                                                            4915 Prospectus Drive
                                                                            Suite F
                                                                            Durham
                                                                            North Carolina 27713
                                                                            Tel 919 544 4535
                                                                            Fax 919 544 5690

                                                                            Our Ref
                                                                            RN990234.0026

                                                                            Date:
                                                                            May 2008
                                                                           QAPP for the Characterization of Coal
                                                                           Combustion Residues
                                                                           Quality Assurance Project Plan
                                                                           Category III / Technology Development
                                                                           Final
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                                                                                      Date: April 2008
                                                                                      Page: i
List of Tables                                                                                       iii

List of Figures                                                                                      iii

Distribution List                                                                                     iv

1.  Project Objectives and Organization                                                             1
      1.1     Purpose                                                                                  1
      1.2     Project Objectives                                                                         2

2.  Project Organization                                                                            4

3.  Experimental Approach                                                                         7
      3.1     Task I: QAPP Development                                                                 7
      3.2     Task II: Thermal Stability                                                                    7
      3.3     Task III: Application of Leaching Framework to Evaluate Leaching Potential of Mercury-Enriched
             Coal Combustion Residues and Cement Kiln Dust                                              7

4.  Sampling Procedures                                                                          10
      4.1     Sample Custody Procedures                                                               10
      4.2     CCR, and Reference Fly Ash Samples                                                       10
             4.2.1   Physical and Chemical Characterization Samples                                       11
             4.2.2   Leaching Study Samples                                                            11
      4.3     Leachate Collection                                                                       12
             4.3.1   Tier 1 Screening Tests                                                             13
             4.3.2   Tier 2 Solubility and Release as a Function of pH and L/S Ratio                           13

5.  Testing and Measurement Protocols                                                            15
      5.1     Physical Characterization                                                                  15
             5.1.1   Surface Area and Pore Size Distribution                                               15
             5.1.2   pH and Conductivity                                                               15
             5.1.3   Moisture Content and Loss on Ignition (LOI)                                           16
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                                                                                    Project No.: RN990234.0026
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                                                                                    Date: April 2008
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      5.2    Chemical Characterization                                                                16
            5.2.1   Dissolved Organic Carbon / Dissolved Inorganic Carobn (DOC/DIC) and Elemental
                   Carbon / Organic Carbon (EC/OC)                                                   16
            5.2.2   Mercury (CVAA)                                                                 17
            5.2.3   Other Metals (ICP)                                                               17
            5.2.4   Anions Analysis by 1C                                                             18
            5.2.5   X-Ray Fluorescence (XRF) and Neutron Activation Analysis (NAA)                        18

6.  QA/QC Checks                                                                               20
      6.1    Data Quality Indicator Goals                                                               20
      6.2    QC Sample Types                                                                       21

7.  Data Reduction, Validation, and Reporting                                                     22

8.  Assessments                                                                                 23

9.  Appendicies                                                                                  24

10. References                                                                                   25
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List of Tables
Table 3-1.    Summary of testing under task III to be performed for detailed characterization of CCRs
Table 4-1.    NIST 1633B SRM Certified Values
Table 5-1.    MDL and MLQ of Total Organic Carbon Analyzer
Table 6-1.    Data Quality Indicator Goals
Table 8-1.    PEA Parameters and Ranges
11
17
20
23
List of Figures
Figure 2-1.    Project Organizational Chart
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Distribution List

Copies of this plan and all revisions will be initially sent to the following individuals. It is the responsibility of
the U.S. Environmental Protection Agency (EPA) Work Assignment Manager and of the ARCADIS, U.S.,
Inc. (ARCADIS) Work Assignment Leader to make copies of the plan available to all field personnel.

Susan Thorneloe, EPA Work Assignment Manager.jDffice of Research and Development, National Risk
Management Research Laboratory, Air Pollution Prevention and Control Division, Research Triangle Park,
NC.

Phone:(919)541-2709

Robert Wright, EPA Quality Assurance Representative. Office of Research and Development, National
Risk Management Research Laboratory, Air Pollution Prevention and Control Division, Research Triangle
Park, NC.

Phone:(919)541-4502

Peter Kariher,  ARCADIS Work Assignment Leader. Research Triangle Park, NC.

Phone:(919)541-5740

Laura Nessley, ARCADIS Quality Assurance Officer. Research Triangle Park, NC.

Phone: (919) 544-4535x258
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1.   Project Objectives and Organization

1.1  Purpose

In December 2000, EPA determined that regulations are needed to control the risks of mercury (Hg)
emissions from coal-fired power plants. A number of Hg control options are currently being evaluated
through bench-scale and  full-scale demonstrations. For each of the technologies that appears to have
commercial application, the resulting residues are to be evaluated to determine any potential cross-media
impacts through either waste management of these residues or use in commercial applications. Coal
combustion residues (CCRs) include bottom ashes, fly ashes, and scrubber sludges or synthetic gypsum
from flue gas desulfurization (FGD) systems. The questions to be addressed through this research include:

•   What are the changes to CCRs resulting from application of control technology at coal-fired power plants
    including changes in  pH, metals content, and other parameters that may influence environmental
    release?

•   For CCRs that are land disposed, the questions to be addressed  include:

           o   Will any of these changes result in an increase in the potential for leaching of mercury (Hg)
               and  other metals such as arsenic (As), selenium (Se), lead  (Pb), cadmium (Cd), cobalt
               (Co), aluminum (Al), barium (Ba), molybdenum (Mo), tin (Sb), thalium (Th), and chromium
               (Cr) from disposal of CCRs in impoundments, monofills, and minefills?

           o   What is the fate of Hg and other metals from CCRs that are land disposed?

•   For CCRs that are used in commercial applications, the questions to be addressed include:

           o   Will any of the changes to CCRs from application of control technologies at coal-fired power
               plants impact their use in commercial applications?

           o   What is the fate of Hg and other metals in CCRs when used in commercial applications?

           o   What is the extent of Hg, As, Pb, Se, Cd, Co, Al, Ba, Mo, Sb, Th, and Cr release during high
               temperature manufacturing processes used to produce cement clinkers, asphalt,  and
               wallboard?

           o   Are Hg and other pollutants such as As, Se, Pb, Cd,  Co, Al, Ba,  Mo, Sb, Th, and Cr present
               in CCRs that are used in commercial applications such as highway construction or
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               beneficial use scenarios subject to conditions that would result in their release to the
               environment?

EPA's Air Pollution Prevention and Control Division (APPCD) through an on-site laboratory support contract
with ARCADIS is to conduct a comprehensive study on the fate of mercury (Hg), arsenic (As), selenium
(Se), lead (Pb), cadmium (Cd), cobalt (Co), aluminum (Al), barium, (Ba), molybdenum (Mo), antimony (Sb),
thalium (Th), and chromium (Cr) in CCRs. This research will  be conducted in three tasks. Task I will focus on
updating the QAPP to clearly define the project scope and procedures. Task II will focus on completing the
report on the evaluating the potential release of Hg and other heavy metals from a cement kiln operation.
Task III will cover the evaluation of CCRs potential to leach Hg and other heavy metals during disposal or
beneficial use scenarios. The scope of this QAPP covers Task I through Task III.

1.2  Project Objectives

EPA's Office of Solid Waste (OSW) has been asked to provide general guidance on appropriate testing to
evaluate the release potential of Hg and other metallic contaminants (As, Se, Pb, Cd, Co, Al, Ba, Mo, Sb,
Th, and Cr) from CCRs via leaching, run-off, and volatilization when disposed in landfills and incorporated
into commercial products using high/low temperature commercial processes. This evaluation in projected
disposal and reuse situations (different waste management scenarios; see Section  1.1) will both help assess
the likely suitability of new or modified wastes for reuse, and  ensure that Hg, As, Se, Pb, Cd, Co, Al, Ba, Mo,
Sb, Th, and Cr removed from stack emissions are  not subsequently released to the environment in
significant amounts as  a result of CCR reuse or disposal practices.

The primary objective of this project is to generate  a comprehensive database that will enable EPA/OSWto
(1) evaluate changes in CCRs resulting from the implementation of different Hg control technologies (see
Section 3.1), and (2) assess environmental releases of these toxic metals during CCR management
practices including land disposal and commercial applications. OSW will be using the results to determine
needs in regard to future policies for managing CCRs whose characteristics are changing as a result of the
MACT under development for coal fired power plants. OAR will be using the data to determine the potential
for cross-media impacts and potential changes to disposal and reuse  practices which impact the economics
of potential regulations for coal-fired power plants.  The data will also be used to address questions raised by
Congress and others regarding establishing the net benefit of potential requirements for reducing emissions
from coal-fired power plants.

Data on the chemical stability of these metals (leaching tests) will be generated using the EPA/OSW
recommended methods (see Reply to comments on EPA/OSWs Proposed Approach to Environmental
Assessment of CCRs Discussed  March 5, 2002 - Appendix A) developed by Dr. David Kosson and Dr.
Florence Sanchez of Vanderbilt University titled An Integrated Framework for Evaluating Leaching in Waste
Management and Utilization of Secondary Materials (Kosson et al., 2002, Environmental Engineering
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Science, Volume 19, Numbers). The ability of these EPA/OSW methods to assess leaching of the metals of
interest will be further demonstrated with the use of a NIST standard reference material (SRM) with certified
amounts of trace metals. Using this comprehensive database, EPA/OSW will determine the feasibility of the
application of the above methods to CCRs and they will assess the environmental impacts of different types
of CCRs' waste management practices.

A secondary objective of this project is to modify and develop a QA/QC framework for the proposed leaching
assessment approach developed by Kosson et al. The reference fly ash may be an appropriate candidate
fora method QC sample. These activities will  be carried out in cooperation with Drs. Kosson and Sanchez
during implementation of the proposed  methods (see Task II, Section 3.2).
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2.  Project Organization

The organizational chart for this project is shown in Figure 2-1. The roles and responsibilities of the project
personnel are discussed in the following paragraphs. In addition, contact information is also provided.

EPA Work Assignment Manager, Susan Thorneloe: The EPA WA Manager is responsible for
communicating the scope of work, data quality objectives and deliverables required for this work
assignment. The EPA WA Manager is also responsible for providing ARCADIS with the various types of
CCRs to be characterized.

Phone:(919)541-2709
E-mail: thorneloe.susan@epamail.epa.qov

EPA QA Representative, Robert Wright: The EPA QA Representative will be responsible for reviewing and
approving this QAPP. This project has been assigned a QA category III and may be audited by EPA QA. Mr.
Wright is responsible for coordinating any EPA audits.

Phone (919) 541-4502
E-mail: wriqht.bob@epamail.epa.gov

ARCADIS Work Assignment Leader, Peter Kariher: The ARCADIS WA Leader is responsible for preparing
project deliverables and managing the work assignment. He will ensure the project meets scheduled
milestones and stays within budgetary constraints agreed upon by EPA. The WA Leader is also responsible
for communicating any delays in scheduling or changes in cost to the EPA WA Manager as soon as
possible.

Phone (919) 541-5740
E-mail: kariher.peter@epamail.epa.gov

ARCADIS Inorganic Laboratory Manager, Peter Kariher. In addition to being the work assignment leader,
Peter Kariher is  also responsible for the operation of EPA's in-house Inorganic Laboratory. Mr. Kariher will
review and validate all analytical data reports and ensure that the leaching studies are performed properly.
He will also operate the mercury analyzer and ion-chromatograph. For the leaching studies and mercury and
metals analyses, Mr. Kariher will be supported by one chemist: Eric Morris and one technician: John Foley.

Mr. Morris will perform HF extractions of solid CCR and SRM samples and also be responsible for mercury
analysis of samples by CVAA. John Foley will perform the leaching tests.  Mr. Kariher and Mr. Morris will
submit the remaining HF digestates to the subcontract analytical laboratory, Test America-Savannah for
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ICP/MS analysis of the other target metals. Mr. Kariherwill also be responsible for assisting Drs. Kosson
and Sanchez in the development of appropriate QA/QC procedures for the leaching assessment methods.

Phone (919) 541-5740
E-mail: kariher.peter@epamail.epa.gov

Test America-Savannah Analytical Manager, Kathryn Smith: Ms.  Smith will review and validate the ICP/MS
results and report them to Mr. Kariher.

Phone (912) 354-7858
E-mail: kathye.smith@testamericainc.com

ARCADIS Designated QA Officer, Laura Nessley: The ARCADIS QA Manager, Laura Nessley, has been
assigned QA responsibilities for this work assignment. Ms. Nessley will be responsible for reviewing this
QAPP prior to submission to EPA QA for review. Ms. Nessley will also ensure the QAPP is implemented by
project personnel by performing internal assessments. All QA/QC related problems will be reported directly
to the ARCADIS WAL, Peter Kariher.

Phone: (919) 544-2260 ext. 258
E-mail: lnessley@arcadis-us.com

Vanderbilt University, Methods Development, Professors David Kosson and Florence Sanchez: Dr. Kosson
in cooperation with Dr. Florence Sanchez developed the leachability methods being evaluated on this
project. He will be available to consult regarding method optimization and development of QA/QC
procedures. Dr. Kosson and Dr. Sanchez will be on-site in the early stages of the project to assist in setting
up the procedures.

Dr. Kosson
Phone:(615)322-1064
E-mail: David.Kosson@vanderbilt.edu

Dr. Sanchez
Phone: (615)322-5135
E-mail: Florence.Sanchez@vanderbilt.edu

ARCADIS Project Manager, Johannes Lee: The ARCADIS Project Manager, Johannes Lee, has been
assigned financial, contractual and managerial responsibilities for this work assignment. Mr. Lee will be
responsible for communications with the EPA project officer, the oversight of financial status, and fulfilling
contractual requirements.
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Phone: (919) 544-2260 ext. 269
E-mail: ljee@arcadis-us.com

ARCADIS Safety Officer, Jerry Revis: The ARCADIS Safety Officer, Jerry Revis, has been assigned the
safety supervisor responsibilities for this work assignment. Mr. Revis will be responsible for reviewing safety
plans, performing periodic safety inspections, communicating with the EPA safety office, and oversight of
safety operations.

Phone: (919) 544-2260 ext. 243
E-mail: irevis@arcadis-us.com
              Bob Wright, EPA
Susan Thorneloe, EPA
                                        Johannes Lee, ARCADIS
                   Libby Nessley, ARCADIS
                                        Peter Karihe

Jerry Revis,
ARCADIS
                                                 •, ARCADIS
   David Kosson, Vanderbilt
 Florence Sanchez, Vanderbilt
                             Eric Morris, ARCADIS
            John Foley, ARCADIS
Kathryn Smith, Test America
Figure 2-1.    Project Organizational Chart
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3.  Experimental Approach

3.1  Task I: QAPP Development

The purpose of this task is to develop and modify the existing QAPP (QA ID number 02028) developed
during WA 2-26 to comply with the requirements of the NRMRL QA requirements and definitions.

3.2  Task II: Thermal Stability

This task covers the work to be performed to modify, edit, and complete the report on the thermal stability
studies titled "Characterization of Coal Combustion Residues"

3.3  Task III: Application of Leaching Framework to Evaluate Leaching Potential of Mercury-Enriched Coal
    Combustion Residues and Cement Kiln Dust

This task will investigate the fate of Hg, As, Se, Pb, Cd, Co, Al, Ba, Mo, Sb, Th, and Cr during CCR
management practice of land disposal. Using the recently proposed test methods developed by Kosson et
al. in coordination with EPA's Office of Solid Waste, leaching studies were first conducted on a reference fly
ash. The reference fly ash is a high quantity fly ash that has been characterized by ICP/MS and CVAA
analyses. The ICP/MS and  CVAA analyses will be checked using the NIST SRM 1633b. NIST SRM 1633b
is a bituminous coal fly ash  that is fully described in Section 4.2.2. The results obtained from the reference fly
ash leaching studies were used to evaluate the performance of the method. Using a known standard in
place of the CCR material will also allow optimization of the proposed test methods. The quality control
procedures regarding the reference fly ash tests  are described in Section 6.0.

A summary of testing that will be carried out on the coal combustion residues is presented in Table 3-1 along
with the number of replicates, the material mass  required and the number of extracts that will be generated.
Detailed descriptions of the methods listed in Table 3-1 can be found  in the document titled Leaching Test
Methods - see Appendix A.

Leaching studies will be conducted on high priority CCRs that will allow estimating constituent release by
leaching for a range of conditions that are likely to occur during management practices. A separate test plan
for the leaching experiments under this task is  provided by its developers (Drs. Kosson and Sanchez). This
test plan, titled  "Draft (Revision #2), Sampling and Characterization Plan for Coal Combustion Residues from
Facilities with Enhanced Mercury Emissions Reduction Technology" (included  in Appendix A) together with
this QAPP will cover all the issues regarding Task III. Two levels of testing will  be performed. The first level
will provide detailed characterization of representative samples of CCRs that reflect each dominant CCR
chemistry with respect to mercury release. This will define the behavior of the general class of CCR
chemistry. This detailed characterization would establish  a baseline for comparison of subsequent test
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results. A summary of testing that will be carried out on the three dominant CCR chemistries (pH
dependence, US ratio dependence, and total composition) are presented in Table 3-2 along with the
number of replicates, the material mass required and the number of extracts that will be generated.

Table 3-1.   Summary of testing under task III to be performed for detailed characterization of CCRs

Test
pH01.1
(pH Titration Pre-Test)
Moisture content
SR002.13
SR003.1b
US=10mL/g
US = 5 mUg
US = 2 mUg
US = 1 mUg
US = 0.5 mUg
Method 3052 Total Digestion
+ Physical Characterization
Total

Number p
replicates
2
3
2
2
-
-
-
-
-
-
-

naterial /
aliquot
(g)
8
8
40
-
-
-
-
-
-
10
-
Mass
material /
test
replicates
(g)
8
16
440
430
40
40
50
100
200
10
-

Total mass
of material
required (g)
16
24
880
1290
-
-
-
-
-
20
2230

Number of analytical
samples
2
3
22
10
-
-
-
-
-
5
39
aAlkalinity, Solubility, and Release as a Function of pH
bSolubility and Release as a Function of Liquid
/ Solid Ratio
(US)


Residues collected before and after application of enhanced Hg control technologies will be examined to
evaluate the effect of the enhanced systems on the leaching behavior of CCRs.

Estimates of the extent of release of the metals of concern during management scenarios that include
percolation through the CCRs or infiltration flow around the CCRs (e.g., when compacted to low permeability
or otherwise expected to behave as a monolithic material) will be determined. These data will be used to
determine the risk of land disposal of the different CCRs. Mass balances for each metal will be determined
using the chemical characterization data obtained in Task III. Utilization of mass balance as a QA/QC tool is
described in section 6. Details of this QA/QC procedure are outlined in section 6. In addition to testing of the
CCRs as generated, CCRs as used in commercial products will be examined. Only commercial  uses for
which there is a potential for release of Hg during leaching will be considered. One commercial use of CCRs
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that may be of concern for Hg leaching is cement-based materials (i.e., concrete/grout, waste stabilization,
road base/subbase). A generic cement-based product made from samples representative of the major coal
fly ash categories will be examined. A second commercial use of CCRs that may be of concern is
incorporation in gypsum board. In this case leaching of Hg after disposal is of concern. This task will
consider the potential for Hg leaching after disposal from a representative  gypsum board product.
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4.  Sampling Procedures

The following subsections describe the sampling procedures to be used for each task. Whenever possible,
standard methods will be followed. In some cases, draft methods may be evaluated and implemented. Each
method to be used will be cited and any deviations from the methods will be documented.

4.1  Sample Custody Procedures

The following types of samples will be generated during these tests:

1.  "As-received" CCR samples before and after application of Hg control technologies, SRM and reference
    fly ash samples (solid samples) and treated CCR samples as used in commercial applications

2.  Post -leaching and post-thermal desorption CCR, reference fly ash samples and treated CCR samples
    (solid samples)

3.  Leachate samples (liquid samples)

Each sample generated will be analyzed in-house or by outside laboratories and chain-of-custody
procedures will be required. CCRs will be logged as they are received by the ARCADIS WAL, Mr. Peter
Kariher. Information regarding where each CCR originated and any other descriptive information available
will be recorded in a dedicated laboratory notebook by Mr. Kariher. A 200 g grab sample will be taken from
each "as-received" CCR and processed for physical and chemical characterization. All samples will be
properly contained and identified with a unique sample  ID and sample label. Sample labels at a minimum will
contain the sample ID, date sampled, and initials of the analyst responsible for preparing the sample. Chain-
of-custody forms will be generated for all samples prior to transfer for analysis.

Handling of CCR samples for the leaching tests (Task II) is described in detail by the leaching procedure
provided by its developers. This procedure is included in Appendix A.

4.2  CCR, and Reference Fly Ash Samples

As mentioned, the focus of this program is to obtain information on the leachability and stability of Hg, As,
Se,  Pb, Cd, Co, Al, Ba, Mo, Sb, Th, and Cr in CCRs. Chemical modifications are being implemented in wet
scrubbers to  enhance the Hg capture. The scrubber sludge from these facilities will be impacted by these
new control technologies. The scrubber sludge samples from these facilities will be included in this test
program.
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The Hg control testing facilities will be identified and their test reports will be obtained and amended to this
QAPP. The test reports will include information on the history/origin of each CCR sample, facility process
description, CCR type, sampling location, sampling time and method, coal type, operating condition, and
sample storage condition. Section 4.1 describes the sampling custody procedure.

4.2.1   Physical and Chemical Characterization Samples

"As received" CCR will be well mixed prior to taking samples for physical characterization. Mixing of the sub-
samples collected at the site will be done using a riffle splitter. To ensure a good homogeneity of the final
composite sample that will be used for the study, the first two composite samples exiting the splitter will be
reintroduced at the top of the splitter. This procedure should be repeated at least 6 times. At the end, the two
resulting homogeneous composite samples will be combined in the same bucket and stored until laboratory
testing. A 200 g representative sample will be taken from the homogenized "as received" CCR and
subjected to physical characterization measurements. Samples will also be taken of any CCRs that undergo
size-reduction techniques (if size reduction is needed for testing purposes). The reference fly ash samples
will be processed in the same manner as the CCRs. They will be tracked by lot number and will not require
size-reduction.

4.2.2  Leaching Study Samples

CCRs used for leaching studies may undergo size reduction to acquire an adequate sample for testing. The
size reduction method is outlined in the leaching test methods (see Appendix A). If "as-received" CCRs are
altered in anyway prior to leaching studies, a representative sample will be submitted for physical and
chemical characterization. SRM samples will not require size reduction. The NIST 1633B SRM is a
bituminous coal fly ash that has been sieved through  a nominal sieve opening of 90 urn and blended to
assure homogeneity. The certified values for the constituent elements are given in Table 4-1. The reference
fly ash will also be certified using ICP/MS and CVAA.

Table 4-1.   NIST 1633B SRM Certified Values
Element
Arsenic
Barium
Cadmium
Chromium
Copper
Lead
Manganese
Concentration (mg/kg)
136.2 + 2.6
709 + 27
0.784 + 0.006
198.2 + 4.7
112.8 + 2.6
68.2 + 1.1
131.8 + 1.7
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  Mercury                  0.141 +0.019
   Nickel                    120.6 + 1.8
  Selenium                  10.26 + 0.17
  Strontium                   1041+14
  Thorium                   25.7 + 1.3
  Uranium                   8.79 + 0.36
 Vanadium                   295.7 + 3.6
4.3  Leachate Collection

The proposed test method described in the publication titled An Integrated Framework for Evaluating
Leaching in Waste Management and Utilization of Secondary Materials (Kosson, et al., 2002) will be used to
conduct leaching studies. This publication along with the referenced procedures is provided in Appendix A.
There are three tiers to this test method:

•   Tier 1) Screening based assessment (availability)

•   Tier 2) Equilibrium-based assessment over a range of pH and Liquid/solid (US) ratios

•   Tier 3) Mass transfer based  assessment

The Tier 1 screening test provides an indication of the maximum potential for release under the limits of
anticipated environmental conditions expressed on a mg contaminant leached per kg waste basis. Tier 2
defines the release potential as a function of liquid-to-solid (L/S) ratio and pH. Tier 3  uses information on L/S
equilibrium in conjunction with mass transfer rate information. As mentioned previously, prior to testing CCR,
a reference fly ash will be used to demonstrate the effectiveness of the proposed test methods. Procedures
for each tier are discussed in the following subsections.

If needed, prior to tier testing, the "as-received" CCR will be size reduced using the procedure PS001.1
Particle Size Reduction to minimize mass transfer rate limitation through larger particles. The pH will be
then tested using the method pHOOLO pH Titration Pretest. These methods can be found in the Leaching
Test Methods (Appendix A).
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4.3.1  Tier 1 Screening Tests

Test Method AV002.1 Availability at pH 7.5 with EDTA (found in the Leaching Test Methods in Appendix
A) will be used to perform the screening test. This method measures availability in relation to the release of
anions at an endpoint pH of 7.5+0.5 and cations under enhanced liquid-phase solubility due to complexation
with the chelating agent. Constituent availability is determined by a single challenge of an aliquot of the
reference fly ash or size reduced CCR material to dilute acid or base in Dl water with the chelating agent,
ethylenediaminetetraacetic acid (EDTA). Extracts are tumbled end-over-end at 28+2 rpm at room
temperature fora contact time of 24 hours. At the end of the 24-hour period, the leachate pH value of the
extraction  is measured. The retained extract is filtered through a 0.45 u.m polypropylene filtration membrane
and the sample is stored at 4°C until analysis.

The results from this test are used to determine the maximum quantity, or the fraction of the total constituent
content, of inorganic constituents (Hg, As, Se, Pb, and Cd) in a solid matrix that potentially can be  released
from the solid material in the presence of a strong chelating agent. The chelated availability, or mobile
fraction, can be considered (1) the thermodynamic driving force for mass transport through the solid
material, or (2) the potential long-term constituent release. Also, a mass balance based on the total
constituent concentration provides the fraction of a constituent that may be chemically bound, or immobile in
geologically stable mineral phases.

4.3.2  Tier 2 Solubility and Release as a Function of pH and US Ratio

Test Method SR002.1 Alkalinity, Solubility and Release as a Function of pH is the method to be used for
Tier 2 pH Screening. This procedure is  included in the leaching test methods (Appendix A). The protocol
consists of 11 parallel extractions of particle size  reduced material at a liquid-to-solid ratio of 10 ml
extractant per gram of dry sample. An acid or base addition schedule is formulated for 11 extracts  with final
solution pH values between 3 and 12, through addition of aliquots of HNO3 orKOH as needed. The exact
pH schedule is adjusted based on the nature of the CCR; however, the range of pH values must include the
natural pH of the matrix, which may extend the pH domain. The extraction schedule and the range of tested
pHs are outlined in the developers' leaching test plan, "Draft (Revision #2), Sampling and Characterization
Plan for Coal Combustion Residues from Facilities with Enhanced Mercury Emissions Reduction
Technology" (see Appendix A).

If large particles are present in the CCR material, the material being evaluated is particle size reduced to 2
mm by sieving to remove any large pebbles present. A mortar and pestle may be used to break up clumps
of material. A 40 g dry sample of the reference fly ash or size reduced CCR is  used for these tests. Using
the schedule, equivalents  of acid or base are added to a combination of deionized water and the reference
fly ash or particle size reduced CCR. The final liquid-to-solid (L/S) ratio is 10 ml extractant per gram of
sample, which  includes Dl water, the added acid  or base, and the amount of moisture that is inherent to the
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waste matrix as determined by moisture content analysis. The 11 extractions are tumbled in an end-over-
end fashion at 28 rpm for a contact time of 24 hrs. Following gross separation of the solid and liquid phases
by centrifuging for 15 minutes, leachate pH measurements are recorded and the phases are separated by
pressure filtration through 0.45 |j,m polypropylene filtration membranes. Analytical samples of the leachates
are collected and preserved as appropriate for chemical analysis. For metal analysis, leachates are
preserved by acidification with HNO3 to a pH <2 and stored at 4 °C until analysis. For anion analysis,
leachates are stored at 4°C until analysis. Mercury samples are prepared with 87 ml of leachate, 3 ml of
nitric, 5 ml: of 5% KMnO4, and 5 ml of 10% hydroxylamaine hydrochloride to clear the solution before
analysis.

Test method SR003.1 Solubility and Release as a Function of L/S Ratio is the method to be used for Tier
2 US ratio screening. This method is included in the leaching test methods (Appendix A). The protocol
consists of five parallel batch extractions over a range of L/S ratios (0.5,1, 2, 5, and 10 mL/g dry material)
using the particle size reduced CCR and Dl water as the extractant. Extractions are conducted at room
temperature in leak-proof vessels that are tumbled at 28+2 rpm for 24 hours. Solid and liquid phases are
separated by centrifuging for 15  minutes, and then pH and conductivity measurements are taken. The  liquid
is further separated by pressure  filtration using a 0.45 |j,m polypropylene filter membrane. Leachates are
collected for each of the 5 L/S ratios and preserved as appropriate for chemical analysis. For metal analysis,
leachates are preserved  by acidification with HNO3 to a  pH <2 and stored at 4 °C until analysis. For anion
analysis, leachates are stored at 4 °C until analysis. The range of tested L/S ratios is outlined in the leaching
test plan, "Draft (Revision #2), Sampling and Characterization Plan for Coal Combustion Residues from
Facilities with Enhanced  Mercury Emissions Reduction Technology" (Appendix A).
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5.  Testing and Measurement Protocols

Whenever possible, standard methods will be used to perform required measurements. Standard methods
are cited in each applicable section. Where standard methods are not available, operating procedures will be
written to describe activities. In situations where method development is ongoing, activities and method
changes will be thoroughly documented in dedicated laboratory notebooks.

5.1  Physical Characterization

5.1.1  Surface Area and Pore Size Distribution

A Quantachrome Autosorb-1 C-M/S chemisorption mass-spectrometer Surface Area Analyzer will be used
to perform Brunauer, Emmett, and Teller (BET) method surface area, pore volume, and pore size
distribution analysis on each as-received and size reduced CCR. A 200 mg sample is degassed at 200 °C
for at least one hour in the sample preparation manifold. Samples are then moved to the analysis manifold,
which has a known volume. Total  gas volume in the analysis manifold and sample tube is calculated from
the pressure change after release of an N2 gas from the analysis manifold known volume. Report forms are
automatically  generated after each completed analysis. The instrument uses successive dosings of N2 while
measuring pressure. Standards of known surface area are run with each batch of samples as a QC check.
Detailed instructions for the operation of this instrument are included in the Mercury Facility Manual.

5.1.2  pH and  Conductivity

pH and conductivity will be measured on all aqueous extracts. Conductivity is a measure of the ability of an
aqueous solution to carry an electric current. This ability is dependent upon the presence of ions; on their
total concentration, mobility, and variance; and  on the temperature of the measurement.

pH of the leachates will be measured using a combined pH electrode. A 2-point calibration will be done
using pH buffer solutions. The pH  meter will be accurate and reproducible to 0.1 pH units with a range of 0
to 14.

Conductivity of the  leachates will be measured  using a standard conductivity probe. The conductivity probe
will be calibrated using appropriate standard conductivity solutions for the conductivity range of concern.
Conductivity meters are typically accurate to +1% and have a precision of +1%. The procedure to measure
pH and conductivity will be as follows:

Following a gross separation of the solid and  liquid phases by centrifugation or settling, a minimum volume
of the supernatant to measure the solution pH and conductivity will be taken and poured in a test tube. The
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remaining liquid will be separated by pressure filtration and filtrates will be appropriately labeled, preserved,
and stored for subsequent chemical analysis.

5.1.3  Moisture Content and Loss on Ignition (LOI)

Moisture content of the "as received" CCR, the reference fly ash and SRM samples will be determined using
ASTM D 2216-92. This procedure supersedes the method indicated in the leaching procedure (see
Appendix A). This method, however, is not applicable to the materials containing gypsum (calcium sulfate
dihydrate or other compounds having significant amounts of hydrated water), since this material slowly
dehydrates at the standard drying temperature (110°C). This slow dehydration results in the formation of
another compound (calcium sulfate hemihydrate) which is not normally present in natural material. ASTM
method  C 22-83 will be used to determine the moisture content of materials containing gypsum.

Loss on ignition (LOI) is performed by placing dried samples in a furnace at 650 °C for 1 hour and
measuring the mass lost during the combustion.

5.2  Chemical Characterization

5.2.1  Dissolved  Organic Carbon / Dissolved Inorganic Carobn (DOC/DIC) and Elemental Carbon / Organic Carbon
      (EC/OC)

Analyses of total dissolved organic carbon and dissolved inorganic carbon are performed on a Shimadzu
model TOC-V CPH/CPN combustion catalytic oxidation NDIR analyzer. Five-point calibration curves, for
both inorganic (1C) and non-purgeable organic carbon (NPOC) analyses, are generated for an analytical
range between 5 ppm and  100 ppm and are accepted with a correlation coefficient of at least 0.995.
Reagent grade potassium hydrogen phthalate is used as the NPOC standard and sodium hydrogen
carbonate is used as the 1C standard. An analytical blank and check standard at approximately 10 ppm are
run every 10 samples. The standard is required to be within 15% of the specified value. A new calibration
curve is generated if the check standard measurement does not meet specification. A volume of
approximately 16 mL  of undiluted sample is loaded for analysis.  Inorganic carbon analysis is performed first
for the analytical blank and standard and then the samples.  Total carbon (non-purgeable organic carbon)
analysis follows with addition of 2M hydrochloric acid to a pH of 2 and a sparge gas flow rate of 50 mL/min.
Method  detection limit (MDL) and minimum level of quantification (MLQ) are shown in Table 5-1.
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Table 5-1.   MDLand MLQof Total Organic Carbon Analyzer

                            MDL (ppm)             MLQ (ppm)
          1C                    0.07                   0.20
        NPOC                  0.09                   0.20
Elemental carbon and organic carbon are determined using a Sunset Laboratory Carbon Aerosol Analysis
Lab Instrument in E-581 A. This method is defined in NIOSH 5040. This equipment uses a furnace to heat
the sample and combust the carbon to carbon dioxide. The carbon dioxide is reduced to methane and a FID
is used to quantify the carbon emitted as the sample is heated from ambient to 870 °C over four heating
steps. Samples are prepared by weighing 3 grams of the CCR into a 500 mL Nalgene high-density
polyethylene bottle. A 37 mm tared pre-baked quartz filter is loaded into a 2.5 urn particulate sampler and
attached to the bottle. The particulate sampler is connected to a vacuum source and a rotometerto control
the flow at 4 liters per minute. The CCR material is aspirated onto the quartz filter for 5 minutes and the filter
is reweighed to determine the mass loading. Duplicate filters are prepared for each material. Three analyses
are performed on each filter. Blank filters are  provided to determine background levels.

5.2.2  Mercury (CVAA)

Mercury analysis of each extract and leachate will be carried out by Cold Vapor Atomic Absorption (CVAA)
Spectrometry according to EPA SW846 Method 7470A Mercury in Liquid Waste (Manual Cold Vapor
Technique). Samples are treated with potassium permanganate to reduce possible sulfide interferences. A
Perkin Elmer FIMS 100 Flow Injection  Mercury System is the instrument to be used for this analysis.  The
instrument is calibrated with  known standards ranging from 0.25 to 10 u.g/L mercury. The detection limit for
mercury in aqueous samples is 0.05 u.g/L.

5.2.3  Other Metals (ICP)

Analysis for As, Se, Pb, Cd, Co, Al, Ba, Mo, Sb, Th, and Crwill be performed on a  ICP-MS using SW-846
Method 6020. Metals and estimated instrument detection limits are listed in the method. The ICP will be
profiled and calibrated for the target compounds and specific instrument detection limits will be determined.
Mixed calibration standards will be  prepared at least 5  levels. Each target compound will also be analyzed
separately to determine possible spectral interference or the presence of impurities. Two types of blanks will
be run with each  batch of samples. A calibration blank is used to establish the analytical curve and the
method blank is used to identify possible contamination from varying amounts of the acids used in the
sample processing. Additional daily QC checks  include an Initial Calibration Verification (ICV) and a
Continuing Calibration Verification (CCV). The ICV is prepared by combining target elements from a
standard source different than that  of the calibration standard and at a concentration within the linear
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working range of the instrument. The CCV is prepared in the same acid matrix using the same standards
used for calibration at a concentration near the mid-point of the calibration curve. A calibration blank and a
CCV or ICV are analyzed after every tenth sample and at the end of each batch of samples. The CCV and
ICV results must verify that the instrument is within 10% of the initial calibration with an RSD < 5% from
replicate integrations. Procedures to incorporate the analysis of a MS/MSD for these CCR samples will be
evaluated.

These analyses will be performed at two different ICP-MS facilities. The first facility is Test America
Laboratories in Savannah, Ga. This laboratory uses a Agilent ICP-MS with octopole reaction system (ORS)
and will measure the metal species for the total content. The second facility is Vanderbilt University
(Department of Civil and Environmental Engineering). This laboratory uses a Perkin Elmer model ELAN
DRC II. Vanderbilt University is responsible for measuring the metals content in the leachates. Standard
analysis mode is used for Pb and DRC mode is used for analysis of As and Se.

5.2.4  Anions Analysis by 1C

Aqueous concentrations of anions (fluoride, chloride, nitrate, sulfate, sulfides, carbonate and phosphate) will
be determined using ion chromatography  (1C). Standard methods (i.e., USEPA guideline SW-846) will be
used. These analyses are performed using a Dionex HPLC system and a conductivity detector. Equipment
used in the instrument includes a ATC-3 anion trap column, AS-11G 4-mm guard column, and a AS-11
analytical column.  The system uses a sodium hydroxide gradient elution at 1  mL/min to resolve the peaks.

5.2.5  X-Ray Fluorescence (XRF) and Neutron Activation Analysis (NAA)

For the twelve target metals, XRF analysis will be performed on each CCR to provide additional information
on the CCR material.  This information will be useful in  supplementing and/or validating CVAA and ICP
results and calculating mass balances. XRF is capable of detection limits in the u.g range. If levels are in the
ng range, XRF analysis will not be useful.  Considering the  high detection limit of the XRF, this method will be
used only as a second validation method or a "referee" method. Details of XRF analysis are included in the
Mercury Facility Manual.

Neutron activation analysis (NAA) is an established analytical technique  with elemental analysis
applications. This method is not currently being used but it will be considered in this test program. NAA is
different from AA or inductively coupled plasma mass spectrometry (ICP-MS) because it is based on nuclear
instead of electronic properties. Neutron activation analysis is a sensitive multi-element analytical method for
the accurate and precise determination of elemental concentrations in unknown materials. Sensitivities are
sufficient to measure certain elements at the nanogram level and below, although the method is well suited
for the determination of major and minor elemental components as well.  The method is based on the
detection and measurement of characteristic gamma rays emitted from radioactive isotopes produced in the
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sample upon irradiation with neutrons. Depending on the source of the neutrons, their energies and the
treatment of the samples, the technique takes on several differing forms. It is generally referred to as INAA
(instrumental neutron activation analysis) for the purely instrumental version of the technique. RNAA
(radiochemical neutron activation analysis) is the acronym used if radiochemistry is used to separate the
isotope of interest before counting. FNAA (fast neutron activation analysis) is the form of the technique if
higher energy neutrons,  usually from an accelerator based neutron generator, are used.
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6.  QA/QC Checks

6.1  Data Quality Indicator Goals

Data quality indicator goals for critical measurements in terms of accuracy, precision and completeness are
shown in Table 6-1.

Table 6-1.   Data Quality Indicator Goals

As, Se,

Anions,





Measurement
Pb, Cd, Co, Al, Ba, Mo, Sb, Th,
and Cr Concentration
Hg Concentration
Sulfate, Carbonates, Chlorides
pH, conductivity, ORP
Carbon Content
Surface Area BET
Loss on Ignition (LOI)
Moisture
Method
ICP-MS/6020
CVAA/7470A
IC/SW-846
Electrode
DIC/DOC EC/OC
ASTM D6556-07
ASTM D7348-07
ASTM D2216-92
ASTM C22-83
Accuracy
10%
10%
10%
2%
10%
5%
2%
N/A
Precision
10%
10%
10%
2%
10%
5%
2%
10%
Completeness
>90%
>90%
>90%
100%
>90%
>90%
100%
N/A
N/A: Not Applicable (see Appendix B)
Accuracy will be determined by calculating the percent bias from a known standard. Precision will be
calculated as relative percent difference (RPD) between duplicate values and relative standard deviation
(RSD) for parameters that have more than two replicates. Completeness is defined as the percentage of
measurements that meet DQI goals of the total number measurements taken.

Mass balance calculations will also be used as a data quality indicator. Different mass balance recovery
methods will be examined. The reference fly ash sample will be used to develop and validate an appropriate
mass balance recovery method. Mass balance will be determined by using the metals concentrations
determined by analysis of the "as-received" reference fly ash as the total. Results from successive leaching
samples and analysis of any solid residues will be combined to determine recoveries.

One approach that will be considered is the  use of either total digestion (Method 3052B) or Neutron
Activation Analysis (NAA) for the analysis of solid residues.

The mass balance recovery will only be performed on 3  pH points and one low L/S ratio. Uncertainty
analysis will be considered for each mass balance. The selection of the target pH values will be dependent
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on the natural pH of the material. If the natural pH is <5, then natural pH, 7 and 9 will be selected as the
target pH values. If the natural pH ranges between 5 and 9, then 5, 7 and 9 will be selected as the target pH
values, and if the natural pH is >9, then 5, 7 and natural pH will selected as the target pH values. In addition,
an extraction at the natural pH of the material and an L/S ratio of 1 mL/g will be carried out. At least 4
replicates per extract will be run. In the case where the mass balance will be performed using total digestion
or NAA, at least 3 representative samples per residue will be analyzed.

6.2  QC Sample Types

Types of QC samples used in this project will include blanks, spiked samples, replicates, and mass balance
tests on the reference fly ash and the SRM. For physical characterization testing, duplicate samples of the
CCR, reference fly ash and SRM will be processed through each  analysis. Duplicates must agree within
+10% to be considered acceptable.  For the leaching studies, an objective of this project is to determine the
appropriate types of QC samples to  incorporate in the proposed leaching methods. This will be
accomplished by subjecting the reference fly ash to the leaching procedure and determining the metals'
mass balances by analyzing the leaching solution and the post-leachate solids. Initially, mass balances of
70-130% will be considered as an acceptable QC of the leaching  procedure. Further statistical analysis on
available data will be performed to narrow down the range of acceptable mass balances. This method
development will be thoroughly documented in  a dedicated laboratory notebook. Leaching of the reference
fly ash samples may also be used as method controls during testing of CCR samples. For the fixed-bed
reactor testing, one in every five tests will be run in duplicate. Duplicate results from the reactor testing are
expected to agree within 20% to be  considered valid. Identical to the leaching procedure, the use of the
reference fly ash as a baseline QC sample will also be implemented during TPD tests (initial mass balances
of 70-130%). Required QC samples for metals and mercury sampling trains are detailed in EPA Method 29
and the Ontario Hydro Methods (Appendix B). QC samples required for ICP, CVAA, 1C analysis are detailed
in Methods 3052B, 7470A, and SW-846 respectively.
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7.  Data Reduction, Validation, and Reporting

Chemical (ICP, CVAA, TGA, XRF, 1C, NAA) and physical (surface area, pore size distribution and density)
characterization data are reduced and reports are generated automatically by the instrument software. The
primary analyst will review 100% of the report for completeness and to ensure that quality control checks
meet established criteria. If QC checks do not meet acceptance criteria, sample analysis must be repeated.
A secondary review will be performed by the Inorganic Laboratory Manager to validate the analytical report.
If appropriate, certain chemical characterization data will be compared to the XRF and NAA analyses. In
addition, the designated QA Officer will review at least 10% of the raw data for completeness. Analytical data
will be summarized in periodic reports to the ARCADIS WAL. The procedures for reduction, validation and
reporting of the leaching experiments (Task II) are outlined in Appendix A. ARCADIS WAL is responsible for
the implementation of these procedures. ARCADIS and Vanderbilt University will be responsible for
publishing results and reports. QA/QC activities will be mentioned in any published materials. A data quality
report will be provided in the final report of this investigation.
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8.  Assessments

Assessments and audits are an integral part of a quality system. This project is assigned a QA Category III
and, while desirable, does not require planned technical systems and performance evaluation audits. EPA
will determine external or third-party audit activities. Internal assessments will be performed by project
personnel to ensure acquired data meet data quality indicator goals established in Section 6. The ARCADIS
Designated QA Officer will perform at least one internal technical systems audit (TSA) to ensure that this
QAPP is implemented and methods are performed according to the documented  procedures. This audit will
occur during the early stages of the project to ensure any necessary corrective actions are implemented
before large amounts of data are collected.

There are currently no planned performance evaluation audits but Table 8-1 lists the measurement
parameters and expected ranges should EPA determine a PEA should be provided.
Table 8-1.

As, Se,
PEA Parameters and Ranges
Analyte or Measurement
Pb, Cd, Co, Al, Ba, Mo, Sb, Th, and Cr
Hg
PH

Method
ICP-MS/3052/6020
CVAA/7470A
Electrode

Expected Range
1-100 |jg/ml_
0.25to10ug/L
0-14
In addition to the internal TSA, the ARCADIS Designated QA Officer will perform an internal data quality
audit on at least 10% of the reported data. Reported results will be verified by performing calculations using
raw data and information recorded in laboratory notebooks.
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9.  Appendices
Vanderbilt Leaching Procedures
Vanderbilt Leaching Test Plan
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                                DRAFT (Revision # 2)


      SAMPLING AND CHARACTERIZATION PLAN FOR COAL COMBUSTION
      RESIDUES FROM FACILITIES WITH ENHANCED MERCURY EMISSIONS
                            REDUCTION TECHNOLOGY
Objectives
       The specific objectives of this proposal are to:
1.   Evaluate a new leaching test framework for assessing the effect of new mercury emission
    controls on the leaching behavior of coal combustion residues (CCRs); and,
2.   Use test results in conjunction with release models and site-specific information to estimate
    the long-term release of mercury and other inorganic contaminants of potential concern.

Background
       In December 2000, EPA announced its intent to regulate mercury emissions from coal-
fired electric utility stream generating plants. The burning of coal in electric utility boilers
generates residual materials including fly ash, bottom ash, boiler slag, and wet flue gas
desulfurization (FGD) scrubber solids and sludges. These residual materials are collectively
referred to as "coal combustion residues" (CCRs). Currently, ca. 70% of CCRs are land disposed
(in a monofill or surface impoundment) and  the other 30% are reused or recycled for commercial
uses such as production of wallboard, cement, and asphalt (USEPA 2002). Changes in Hg
control technology requirements for coal-fired electric utility power plants will cause changes in
the dominant chemistries of fly ash and wet FGD scrubber solids and sludges. Within this
framework, EPA/OSW has  been asked to provide guidance on appropriate testing for evaluating
the CCRs resulting from the new mercury control technologies.
       The main technologies proposed to retrofit Hg control are  summarized in Table 1. These
technologies can  be placed in four broad categories that reflect different dominant CCR
chemistries:
       •   Coal ash injection;
       •   Powdered activated carbon injection;
       •   Calcium based sorbent injection; and,
       •   Oxidizing agent (EDTA or gaseous H2S) injection.
       The primary commercial applications/uses of CCRs are summarized in Table 2.
Commercial uses constitute approximately 30% of all CCRs produced. The other 70% are land-
disposed.
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Table 1. Retrofit Hg control technologies.
Existing pollution air
control
Retrofit Hg control
Pilot or Full scale
Coal type
C-S ESP (70%)
Injection of Sorbent
-   Coal Ash injection + Spray cooling
-   Powdered Activated Carbon (PAC) + Spray cooling
                                    TM
                         (DarcoFGD'™ Carbon)
   PSCO
   PSE&G Hudson
   Generating Station
   AECDP Phase III studies
   Wisconsin Electric
   Pleasant Prairie facilities
   Brayton Point
-  Low sulfur bituminous coal

-  Ohio bituminous coal
-  PRB subbituminous coal

-  Low sulfur bituminous coal
                       -  Calcium-based sorbent + Spray cooling
                                                   PAC more effective sorbent than limestone
FF
Injection of Sorbent
-   Coal Ash injection + Spray cooling
-   Powdered Activated Carbon (PAC) + Spray cooling
                                                                                                    -  Low sulfur bituminous coal
                                    TM
                         (DarcoFGD ""Carbon)
C-SESP + FGD(12%)
-  PAC injection + Injection of oxidizing agent (EDTA,
   Gaseous H2S)
-  PAC injection + Catalysts (SNRC or SCR)	
FF + FGD
-  PAC injection + Injection of oxidizing agent (EDTA,
   Gaseous H2S)
-  PAC injection + Catalysts (SNRC or SCR)	
C-S ESP + SDA
-  Injection of Sorbent: calcium-based sorbents
Lower level of Hg than FF + SDA
C-S ESP + CFA
-  Injection of Sorbent: dry powdered lime
FF + SDA
FF + CFA (5%)
   Injection of Sorbent: calcium-based sorbents
   Injection of Sorbent
-  180 MWe boiler
-  55 MWe boiler
-  Eastern bituminous coal
H-S ESP
H-S ESP + FGD
   PAC + Spray cooling + PFF (Polishing Fabric Filter)
   PAC + PFF
C-S ESP       Cold side (downstream of the air heater) Electrostatic Precipitator— Post combustion particulate matter control technology
FF            Fabric Filter- Post combustion particulate matter control technology
FGD          Flue Gas Desulfurization - Post combustion SC>2 control technology
SDA          Spray Dryer Adsorber - Post combustion SO2 control technology             (4.6%)
CFA          Vertical Duct Absorber - Post combustion SC>2 control technology
SNCR         Selective non-catalytic reduction - Post combustion NOX control technology     (3.8%)
SCR          Selective catalytic reduction - Post combustion NOX control technology
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Table 2. Primary commercial use of OCRs.
                                 Fly Ash
            FGD
            Comments
Concrete/Grout
Waste Stabilization

Structural fills

Mining applications


Raw feed for cement clinker

Road base/Subbase


Flow/able fill
Other

Mineral filler



Soil modification

Agriculture

Snow and ice control

Blasting grit/roofing granules

Wallboard
49%
9.3%
15%

7.3%


6.1%

5.9%


4.1%
2.2%

0.8%
6.5%
0.4%
13%

5.2%


0%

0.4%


0%
4.1%

0%
0.4%
0.1%
0%
0%
0%
0%
1 .8%
0%
0%
69%
CCRs undergo carbon separation
or high temperature combustion
prior to use
Backfill to promote vegetation
growth or serve as soil cover
CCRs mixed with lime and
aggregates to form a road base

Fluid mixtures of cementitious
material, water, coal fly ash,
aggregates and sometimes
chemical admixtures
Broad range of industrial products
(asphalt, plastics, metal alloys,
fertilizers, carpet backing, etc.)
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Testing Overview
       This experimental program focuses on characterization of leaching from coal combustion
residues (CCRs) that are produced from the typical emissions control technology anticipated to
be used to reduce mercury emissions in response to stricter regulatory requirements. This
program focuses on residue types that are anticipated to be produced in high-volume (i.e.,
representative of a significant fraction of the overall CCR streams). Two levels of testing are
recommended. The first level would focus on detailed characterization of a representative sample
of CCR that reflects each dominant CCR chemistry with respect to mercury release. This will
define the behavior of the general class of CCR chemistry. This detailed characterization would
establish a baseline for comparison of subsequent test results. The second level would provide
screening evaluation of additional samples anticipated to be representative of each dominant
CCR chemistry. The second level screening would be used to determine if the CCR being tested
exhibits the same leaching  behavior as the general class of CCRs, which is assumed to have the
same dominant chemistry.  If the leaching behavior is found to be significantly different than
anticipated, then more complete characterization  can be completed.
       Residues collected before and after application of Hg control technologies will be
examined to evaluate the effect of the enhanced systems on the leaching behavior of CCRs.

Coal flv ash (CFA)
       Two types of CFAs will be evaluated under this project: a class C coal fly ash (CFA-C)
and a class F coal fly ash (CFA-F). For CFA-C, representative samples from facilities burning a
subbituminous coal and a lignite coal will be examined. For CFA-F, representative samples from
a facility burning a bituminous coal will be examined.
       Because numerous different technologies can be found for air pollution control and
retrofit  Hg control, only the  technologies  anticipated to result in different CFA chemistry will be
considered as the major categories. For example, fabric filters (FF) and cold side electrostatic
precipitators (C-S ESP) used as post combustion, particulate matter control technologies are not
expected to produce CFAs with significantly different dominant chemistry, even though
differences in particulate removal efficiency and Hg concentrations are expected. Similarly, semi-
dry and dry technique injections (i.e., spray dryer adsorber and dry powdered lime) used as  post
combustion,  SO2 control technology are  expected to  produce similar leaching chemistries
compared to wet techniques that are based on calcium injection.
       As a result, four primary techniques of retrofit Hg controls to existing air pollution control
systems will  be considered as the primary CFA sources:
       (i)  C-S ESP (cold side electrostatic precipitator) or FF (fabric filter) with coal ash  recycle;
       (ii)  C-S ESP or FF with powdered activated  carbon (PAC) injection;
       (iii)  C-S ESP or FF with calcium based sorbent; and,
       (iv) C-S ESP or FF + FGD (flue gas desulfurization) with PAC and  injection of oxidizing
           agent (EDTA or gaseous H2S).
       It is anticipated that not all technology types will be employed at facilities burning both
types of coal. The source of the CFAs to be tested will be selected in collaboration with EPRI and
EPA/OSW.
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FGD residues.
       The residues that result from FGD wet scrubbing processes used for post combustion,
SO2 control technologies, are a slurry containing 5 to 10% solids. The majority of the solid
material is calcium sulfite, calcium sulfate, or calcium carbonate with the percentage of each
being determined by the coal type, process conditions, and the specific FGD technology used
(USEPA 2002). The different wet collector systems are not expected to produce FGD residues
with significantly different chemistry, even though the upstream air pollution control efficiency (i.e.,
particulate removal) may affect the Hg content.
       It is therefore recommended to carry out a detailed characterization on a representative
sample of FGD residues collected before and after application of enhanced Hg control
technologies and carry out screening evaluation on additional samples.
       The source of the FGD residues to be tested will be selected in collaboration with EPRI
and EPA/OSW.

Commercial applications
       In addition to testing of the CCRs as generated, CCRs as used in commercial  products
will be examined. Only commercial uses for which there is a potential for release of Hg during
leaching will be considered. For example high temperature processes (e.g., cement
manufacturing, asphalt manufacturing, or wallboard manufacturing) are expected to result in
revolatilization of mercury and are unlikely to be of concern in terms of leaching. As the primary
commercial uses of CCRs that may be of concern for Hg leaching are cement-based materials
(i.e., concrete/grout, waste stabilization, road base/subbase), it is recommended to test generic
cement-based materials made of samples representative of the  major CFA categories.
Formulation of the generic materials will be decided in collaboration with EPA/OSW. A fractional
factorial statistical design (facility technology and  coal type combusted as the primary factors) is
anticipated for detailed characterization testing of these cement-based materials.

CFA Sample and Testing

Currently Available Test Facilities
       A multiple-site, full-scale field test program is currently being conducted under
DOE/NETL cooperative agreement. This program aims to obtain performance and  cost data for
using activated carbon (PAC) injection to reduce Hg emissions from existing coal-fired electric
utility power plants equipped only with ESP or FF for post-combustion air pollution controls
(USEPA 2001). Four  power plant facilities are participating: (i) the Alabama Power Gaston facility,
(ii) the Wisconsin Electric Pleasant Prairie facility, (iii) the PG&E NEC Salem Harbor facility and
(iv) the Brayton Point facility. Characteristics of each site (i.e., coal type, baseline technology and
tested enhanced system) are briefly described below.

Alabama Power Gaston facility
       The Alabama Power Gaston facility burns various low-sulfur bituminous coals  (foreign
coals) and is equipped with a hot-side ESP (H-S ESP). As part of the DOE/NETL test program, a
fabric filter (FF) was installed after the H-S ESP and powdered activated carbon (PAC) injection
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was used for Hg control technology. Testing at this site of the performance of the Hg control
technology was conducted in the Spring of 2001. During the testing, samples after the H-S ESP
and after the FF with PAC injection were taken and stored on site. However, no information
concerning sample compositing and storage conditions is available1.

Wisconsin Electric Pleasant Prairie facility
       The Wisconsin Electric Pleasant Prairie facility burns PRB subbituminous coals (low
sulfur) and uses a cold-side ESP for PM control. As part of the DOE/NETL test program,
powdered activated carbon (PAC) injection was used for Hg control technology. Testing at this
site of the performance of the Hg control technology has  been completed. Two levels of carbon
rate have been tested: a high carbon rate and a regular carbon  rate.

PG&E NEG Salem Harbor facility
       The PG&E NEG Salem Harbor facility burns low-sulfur  bituminous coals from South
America. This facility is equipped with cold-side ESP for PM control and uses ammonia injection
for NOX control. As part of the DOE/NETL test program, powdered activated carbon (PAC)
injection for Hg control technology will be tested late Spring or Summer 2002.
       The CFA currently collected (i.e., before application of Hg control technology) contains
ca. 25% carbon.

Brayton Point facility
       The Brayton Point facility burns low-sulfur bituminous coals and is  equipped with cold-
side ESP for PM control. As part of the DOE/NETL test program, powdered activated carbon
(PAC) injection for Hg control technology will be tested late Spring or Summer 2002.

Recommended Cases and Levels of Testing
       Three dominant CFA chemistries can be identified among the facilities proposed.

       The Alabama Power Gaston facility and the Brayton Point facility should result in CCRs
with the same dominant chemistry. The use of fabric filters (FF) compared  to cold side
electrostatic precipitators (C-S ESP) as post combustion  particulate  matter control technologies is
not expected to show significant differences in CFA chemistry, even though differences in
particulate removal efficiency and Hg concentrations are  expected. These two facilities burn the
same type of coals (i.e., low-sulfur bituminous coals) and utilize the same retrofit Hg control
technology (PAC injection). It is therefore recommended to perform a detailed characterization on
the CFA of the Brayton Point facility and do screening tests on the CFA of the Alabama Power
Gaston facility2.
1 USEPA will pursue obtaining available information on sampling and sample preservation.
2 Depending on the storage conditions of the CFA samples taken during Spring 2001 from the
Alabama Power Gaston facility, detailed characterization may be carried out on the CFA from this
facility instead of the CFA from the Brayton Point facility. In that case, screening test will be
carried out on the CFA from the Brayton Point facility. USEPA will verify the conditions of the CFA
samples stored at the Alabama Power Gaston facility.
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       The Wisconsin Electric Pleasant Prairie facility is expected to have a different CFA
chemistry due to the use of a different coal type (i.e., PRB subbituminous coal). It is
recommended to perform a detailed characterization of the CFA from this facility. Although the
performance for two levels of carbon rate injection (i.e., regular and high) were tested, the
detailed characterization will only be carried out on samples obtained using the regular carbon
rate injection. Screening tests will be carried out on samples obtained using the high carbon rate
injection.

       The PG&E NEC Salem Harbor facility is also expected to have a different CCR chemistry
due to the injection of ammonia for NOX control. It is also recommended to perform a detailed
characterization of the CFA from this facility.

       The recommended cases and levels are summarized in Table 3.
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Table 3. Recommended cases and levels of testing for CFA.
Cases* Facility
1** Brayton
Point
facility



Alabama
Power
Gaston
facility


2 Wisconsin
Electric
Pleasant
Prairie
facility



3 PG&E
NEC
Salem
Harbor
facility


Coal type
Low-sulfur
bituminous
coals



Various low-
sulfur
bituminous
coals


PRB
subbituminous
coals




Low-sulfur
bituminous
coals



Technology Hg retrofit
technology
CS-ESP PAC
injection



H-S ESP FF + PAC
injection


C-S ESP PAC
injection -
Regular
carbon rate



PAC
injection -
High carbon
rate
ESP + PAC
ammonia injection
injection



Sample type
CFA before
implementation
of Hg retrofit
CFA with
enhanced
system
CFA before
implementation
of Hg retrofit
CFA with
enhanced
system
CFA before
implementation
of Hg retrofit
CFA with
enhanced
system
CFA with
enhanced
system
CFA before
implementation
of Hg retrofit
CFA with
enhanced
system
Level of testing
recommended
Detailed
characterization
Or
Screening
Detailed
characterization
Or
Screening
Screening
Or
Detailed
characterization
Screening
Or
Detailed
characterization
Detailed
characterization
Detailed
characterization

Screening
Detailed
characterization
Detailed
characterization

* Based on identified dominant CFA chemistries.
** Depending on the storage conditions of the CFA samples taken during Spring 2001 from the
Alabama Power Gaston facility, detailed characterization may be carried out on the CFA from this
facility instead of the CFA from the Brayton Point facility. In that case, screening test will be
carried out on the CFA from the Brayton Point facility. USEPA will verify the conditions of the CFA
samples stored at the Alabama Power Gaston facility.
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Draft proposal - Vanderbilt University                                            03/05/2002

Detailed Characterization for Representative CFA Chemistries
       Detailed characterization corresponding to Tier 2b (equilibrium characterization) and 3b
(mass transfer rate characterization) of the leaching framework will be carried out on
representative CFA samples from each of the three recommended facility before and after
application of the Hg control technology. Detailed characterization will consist of the following
analyses:
       •   Total elemental analysis including mercury, carbon, sulfur and metals;
       •   Material alkalinity/acidity, constituent solubility and release as a function of pH
           (SR002.1);
       •   Constituent solubility and release as a function of liquid-to-solid ratio (SR003.1); and,
       •   Compacted granular mass transfer leaching rate (MT002.1).
       It is recommended that SR002.1, SR003.1 and MT002.1 be carried out in duplicate on
each sample. It is also recommended to extend the leaching schedule of the MT002.1 for
additional extractions up to a cumulative leaching time of ca. 30 days to provide more information
about long-term material behavior. Extracts generated from each leaching test will be analyzed
for pH, conductivity, total mercury, other metals of interest (i.e., Se, As, Pb and Cd) and principal
constituents (i.e., Fe, S, Ca, Cl and C). Aqueous mercury  and sulfur speciation analyses will be
carried out on three leachate samples (acidic, neutral, alkaline) from SR002.1 for each material
tested. TDS will also be analyzed for the samples without acid or alkali addition from SR002.1.

Screening Level Analysis of Additional Samples
       Screening level testing will be carried out on additional CFA samples from the other
facilities that are expected to have the same dominant leaching chemistry as the samples used
for detailed characterization. Screening level testing corresponding to Tier2a and 3a of the
leaching framework will include:
       •   The use of three extractions to define release at acidic, neutral and alkali pH
           conditions with consideration of the material's natural pH at LS=10 mL/g (i.e.,
           abbreviated version of the SR002.1  protocol);
       •   One extraction at the natural pH of the material and LS of 0.5 mL/g (i.e., abbreviated
           version of the SR003.1 protocol); and,
       •   A four points, 5 day  compacted granular leach test (i.e., abbreviate version of the
           MT002.1 protocol).
       It is recommended that screening testing be carried out in triplicate on each sample.
Extracts generated from each leaching test will be analyzed for pH, conductivity, total mercury,
other metals of interest (i.e., Se, As, Pb and Cd) and principal constituents (i.e., Fe, S, Ca, Cl and
C).

Sampling Requirements
       Two 10 kg  homogenized samples from each facility are required to perform the complete
study. The first sample taken before application of the Hg  control technology will serve as a
baseline for comparison with the second sample taken after application of the Hg control
technology.
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Sample collection
       The sample collection requirements provided below are based on recommendations
made by the International Ash Working Group (IAWG) (IAWG 1997)3.
       CFA samples will be obtained immediately after production. Generally, the most
appropriate location for sampling is from the transport system that conveys the material from the
particulate collection device to storage silos. Grab samples of the entire width of the conveyor belt
or conveyor discharge chute will be gathered  using either a clean trowel or bucket.
       One sample will consist of a total quantity of 10 kg of CFA that will be obtained over a
period of 5 days. Four sub-samples of ca. 0.5 kg each will be collected each day for a total of 20
sub-samples.
       Each sub-sample will be stored in sealed dry bottle labeled with the date and time the
sub-sample was collected.

Compositing of samples
       All 20 sub-samples will be combined in a single container. The sample will be thoroughly
mixed to create the homogeneous composite  sample. The sample will then be sealed and stored
in a dry atmosphere until laboratory testing. Individual samples for each test will be taken as grab
samples from the composite sample.


FGD Sample and Testing
       The source of the  FGD material is to be determined. Sample collection and compositing
should be as described for other CCRs (see above). Detailed characterization will be completed
on one composite sample  each with and without application of enhanced mercury emissions
control from the same facility.

Cement-based Product sample and Testing
       Generic cement-based materials made of CFA from the three identified facilities will be
tested. Formulation of the generic materials will  be decided in collaboration with EPA/OSW.
Detailed characterization will be carried out on the resulting materials.

Quality Control
       A detailed quality assurance plan will  be developed by each testing laboratory in
accordance with standard  USEPA guidelines. The quality assurance plan will include testing of
standard reference materials, use of spikes during leaching tests and analytical procedures,
testing replication, replicate sample analysis, and other quality assurance procedures as
considered appropriate.
3 These sampling recommendations may need to be modified to provide conformance with
practical sampling at the facilities being evaluated (e.g., pneumatic conveyance) and based on
already obtained samples.
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Physical and Chemical Analyses
       The specific surface area and pore size distribution of the CFAs examined will be
measured using nitrogen adsorption (i.e., BET analysis) to provide insight into the elemental Hg
absorption capacity.

       Metals content in solid phases will be determined using NAA and x-ray fluorescence
(XRF). pH and conductivity will be measured on all aqueous extracts. Mercury analysis of each
leachate will be carried out by CVAA according to USEPA procedure SW846-7470A. Aqueous
concentrations of metals (i.e., Se, As, Pb and Cd) and principal constituents (Fe, S, Ca and C)
will be determined using inductively coupled plasma mass spectrometry (ICP-MS). Aqueous
concentrations of anions (chloride, sulfate, sulfides, nitrate) will be determined using ion
chromatography (1C). Standard methods (i.e., USEPA guideline SW-846) will be used.

Data Management and Interpretation
       All data generated will be maintained in Excel spreadsheet tables and plotted in
accordance with the specific leaching procedure. For each material type, results from detailed
characterization will  be compared to results from short tests and consistency between  all leaching
tests will be evaluated. Integration of test results will occur by calculation of estimated constituent
fluxes and cumulative release over 100 years using site-specific information (infiltration rate,
precipitation frequency, fill geometry, fill density, fill pH) and the appropriate leaching mode
controlling release (equilibrium or mass transfer). Distribution of 100-year release estimates will
be provided using stochastic analysis.
References
IAWG (1997). Municipal Solid Waste Incinerator Residues. Amsterdam, Elsevier Science
       Publishers.
USEPA (2001). Control of mercury emissions from coal-fired electric utility boilers: Interim report,
       National Risk Management Research Laboratory Research Triangle Park.
USEPA (2002). Characterization and management of residues from coal-fired power plants.
       Washington DC, Office of Research and Development, USEPA.
                                                                                      11
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Appendix A - Summary of Testing Protocols (Kosson, et al, 2001)
SR002.1 (Alkalinity, Solubility and Release as a Function of pH)
        The objectives of this testing is to determine the acid/base titration buffering capacity of
the tested material and the liquid-solid partitioning equilibrium of the "constituents of potential
concern" (COPCs). This protocol consists of 11 parallel extractions of particle size reduced
material at a liquid-to-solid ratio of 10 ml extractant /g dry sample. An acid or base addition
schedule is formulated for eleven extracts with final solution pH values between 3 and 12,
through addition of aliquots of HNO3 or KOH as needed. The exact schedule is adjusted based
on the nature of the material;  however, the range of pH values includes the natural  pH of the
matrix that may extend the pH domain (e.g., for very alkaline or acidic materials). Using the
schedule, the equivalents of acid or base are added to a combination of deionized (Dl) water and
the particle size reduced material. The final liquid-solid (LS) ratio is 10 ml extractant/g dry sample
which includes Dl water, the added acid or base,  and the amount of moisture that is inherent to
the waste matrix as determined by moisture content analysis. The eleven extractions  are tumbled
in an end-over-end fashion at 28±2 rpm. Contact  time is a function of the selected maximum
particle size, with an extraction period  of 48 hr for the base case of 2 mm maximum particle size.
Following gross separation of the solid and liquid  phases by centrifugation or settling, leachate pH
measurements are taken and the phases are separated by vacuum  filtration  through 0.45-um
polypropylene filtration membranes. Analytical samples of the leachates are  collected and
preserved as appropriate for chemical analysis. The acid and base neutralization behavior of the
materials is evaluated by plotting the pH of each extract as a function of equivalents of acid or
base added per gram  of dry solid. Equivalents of  base are presented as opposite sign of acid
equivalents. Concentration of constituents of interest for each extract is plotted as a function of
extract final pH to provide liquid-solid partitioning  equilibrium as a function of pH.
        The abbreviated version of the SR002.1-A (Alkalinity, Solubility and Release as a
Function of pH) protocol consists of three  parallel extractions of particle size  reduced  material at a
liquid-to-solid ratio of 10 ml extractant/g dry sample. The selection of the target pH values is
dependent on the natural pH of the material. If the natural pH  is <5, then natural pH, 7 and 9 are
selected as the target pH values. If the natural pH ranges between 5 and 9, then 5, 7  and 9 are
selected as the target pH values, and if the natural pH is >9, then 5, 7 and natural pH are
selected as the target pH values.

SR003.1 (Solubility and Release as a Function of LS Ratio)
        The objective  of this test is to determine the effect of low liquid-to-solid ratio on liquid-
solid partitioning equilibrium when the solution phase is controlled by the tested material. This is
used to approximate initial pore-water conditions  and initial leachate compositions in many
percolation scenarios  (e.g., monofills). This protocol consists of five  parallel batch extractions
over a range of LS ratios (i.e., 10,  5, 2, 1, and  0.5 ml/g dry material), using deionized (Dl) water
as the extractant with  aliquots of material that  has been particle size reduced. The mass of
material used for the test varies with the particle size of the material. All extractions are
                                                                                        12
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conducted at room temperature (20±2°C) in leak-proof vessels that are tumbled in an end-over-
end fashion at 28±2  rpm. Contact time is a function of the selected maximum particle size, with
an extraction period  of 48 hr for the base case of 2 mm maximum particle size. Following gross
separation of the solid and liquid phases by centrifugation or settling, leachate pH and
conductivity  measurements are taken and the phases are separated by a combination of
pressure and vacuum filtration using  0.45-um polypropylene filter membrane. The five leachates
are collected, and preserved as appropriate for chemical analysis.
       The  abbreviated version, SR003.1-A (Solubility and Release as a Function of LS Ratio)
protocol consists of two parallel extractions of particle size reduced material using Dl water at
liquid-to-solid ratio of 10 and 0.5 ml extractant /g dry sample, respectively.  The extraction at LS
of 10 mL/g may be the same sample as used in SR002.1-Ato reduce the required number of
analyses.

MT002.1 (Mass Transfer Rates in Compacted Granular Materials')
       The  objective of this test is to measure the rate of COPC release from compacted
granular materials under mass transfer-controlled release conditions. This protocol consists  of
tank leaching of continuously water-saturated compacted granular material with intermittent
renewal of the leaching solution. An unconsolidated or granular material is compacted into molds
at optimum moisture content using a  modified Proctor compactive effort. A  10-cm diameter
cylindrical mold is used and the sample is packed to a depth of 7 cm. The mold and sample  are
immersed in deionized water such that only the surface area of the top face of the sample
contacted the leaching medium, without mixing. The leachant is refreshed with an equal volume
of demineralized  water using a liquid to surface area ratio of 10 mL/cm2 (i.e., LS ratio of 10 cm) at
cumulative times of 2, 5 and 8 hours, 1, 2, 4 and 8 days. This schedule results in seven leachates
with leaching intervals of 2, 3, 3, 16 hours, 1, 2 and 4 days. The solution pH and conductivity for
each leachate is  measured for each time interval. A leachate sample is prepared for chemical
analysis by vacuum  filtration through a 0.45-um-pore size polypropylene filtration membrane and
preservation as appropriate. Leachate concentrations are plotted as a function of time along with
the analytical detection limit and the equilibrium concentration determined from SR002.1 at the
extract pH for quality control. Cumulative release and flux as a function of time for each
constituent of interest are plotted and used to estimate mass transfer parameters (i.e., observed
diffusivity).
       The  abbreviated version, MT002.1-A (Mass Transfer Rates in Compacted Granular
Materials) protocol consists of 4 extractions in a 5 days period.
                                                                                      13
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ENVIRONMENTAL ENGINEERING SCIENCE
Volume 19, Number 3, 2002
© Mary Ann Liebert, Inc.
  An Integrated Framework  for Evaluating  Leaching  in Waste

        Management and  Utilization  of Secondary Materials



            D.S. Kosson,1'* H.A. van der Sloot,2 F. Sanchez,1 and A.C. Garrabrants1

                        1 Department of Civil and Environmental Engineering
                                      Vanderbilt University
                                          Nashville,  TN
                          2The Netherlands Energy Research Foundation
                                     Petten, The Netherlands



                                          ABSTRACT

A framework for the evaluation of inorganic constituent leaching from wastes and secondary materials is
presented. The framework is based on the measurement of intrinsic  leaching properties of the material in
conjunction with mathematical modeling to estimate release under field management scenarios. Site-spe-
cific and default scenarios are considered, which may be selected based on the evaluation context. A tiered
approach is provided to allow the end user to  balance between the specificity of the release estimate, the
amount of testing knowledge required, a priori knowledge, and resources required to complete an evalu-
ation. Detailed test methodologies are provided for a suite of laboratory leaching tests.

Key words: leaching; metals; waste; soil; utilization; beneficial use; secondary materials; disposal; land-
fill; risk assessment; test  methods

              INTRODUCTION                 implementing this portion of RCRA, the USEPA  asks,
                                                  "Would this waste pose unacceptable environmental haz-
LBACHING TESTS are used as tools to estimate the re-   ards if disposed under a plausible, regulatorily defined,
    lease potential of constituents from waste materials   mismanagement scenario?"  This scenario typically rep-
over a range of possible waste management activities, in-   resents "worst-case" management (i.e., the estimated
eluding during recycling or reuse, for assessing  the effi-   highest risk, plausible, legal management option), and
cacy of waste treatment processes, and after  disposal,   wastes posing such unacceptable environmental hazards
They may also be used to develop end points for  reme-   warrant classification and regulation as hazardous wastes.
diation of contaminated soils and the source term for en-   In developing the Toxicity Characteristic regulation (40
vironmental risk  characterization.  (In  this   context,   CFR 261.24), the USEPA defined the plausible, worst-
"source term" refers to representation of constituent re-   case mismanagement scenario for evaluating industrial
lease from a waste or contaminated soil that is used in   waste as codisposal in a municipal solid waste (MSW)
subsequent  fate and  transport modeling for exposure   landfill. The assumption of this mismanagement scenario,
evaluation in risk  assessment.) The Resource Conserva-   in turn, resulted in the development of the Extraction Pro-
tion and Recovery Act (RCRA) requires the USEPA to   cedure Toxicity test and its successor, the Toxicity Char-
classify wastes as either hazardous or nonhazardous. In   acteristic Leaching Procedure (TCLP; see 45 FR 33084,

  *Correspondingauthor: VU Station B-35 1831, Nashville, TN 37235. Phone: 615-322-1064;Faj: 615-322-3365;E-mail: David.
Kosson@Vanderbilt.edu

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160
                                   KOSSON ETAL.
May 19,1980, and 55 FR 11798, March 29,1990), which
attempts to replicate some key leaching factors typical of
MSW landfills.
  The TCLP has come under criticism because of over-
broad application of the test (and underlying assumption
of MSW codisposal) in evaluating and regulating wastes,
and some technical specifications of the methodology.
The Science  Advisory Board of USEPA reviewed the
leaching  evaluation framework being employed by the
agency in 1991 and 1999 (USEPA, 1991, 1999). In the
1999 review, the Science Advisory Board stated:

   The current state of the science supports, even en-
   courages,  the development and use of  different
   leach tests for different applications. To be most
   scientifically  supportable,  a  leaching  protocol
   should be both accurate and reasonably related to
   conditions governing leachability under  actual
   waste  disposal conditions.
and
   The multiple uses of TCLP may require the devel-
   opment of multiple leaching tests. The result may
   be a more flexible,  case-specific,  tiered testing
   scheme or a suite of related tests incorporating the
   most important parameters affecting leaching. Ap-
   plying the improved procedure(s) to the worst-case
   scenario likely to be encountered in the field could
   ameliorate many problems associated with current
   procedures. Although the Committee recognizes
   that these modifications may be more cumbersome
   to implement, this  type of protocol would better
   predict leachability.

  The  Science Advisory Board also criticized the TCLP
protocol on the basis of several technical considerations,
including the test's consideration of leaching kinetics, liq-
uid-to-solid ratio, pH, potential for colloid formation, par-
ticle size reduction, aging, volatile losses, and comingling
of the tested material with other wastes (i.e., codisposal).
  In response, this paper offers an alternative framework
for  evaluation of waste leaching potential that responds
to many of the criticisms of the TCLP. It provides a tiered,
flexible framework capable of incorporating a range of
site conditions that affect waste leaching, and so can es-
timate  leaching potential under conditions more repre-
sentative of actual waste management. The paper also ad-
dresses practical implementation  of the framework in
different applications, and an example application of this
approach for evaluating alternative treatment processes
for  mercury contaminated soils is presented in a com-
panion paper (Sanchez et al., 2002c). The leach testing
protocols used in the framework also address technical
concerns with the TCLP. The test protocols provided here
are designed only for application to inorganic species;
however, the concepts presented for the integrated frame-
work are general, with application to both inorganic and
organic species. Applicable test  methods for organic
species are the subject of future development. Complete
technical specifications for the protocols are provided in
the Appendix.
IS THE RIGHT  QUESTION BEING ASKED?

  In evaluating the leaching potential of wastes based
on a single, plausible worst-case mismanagement sce-
nario via TCLP, the USEPA seeks to provide environ-
mental protection for unregulated wastes.  However,
wastes are managed in many different settings, and un-
der a range of conditions that affect waste leaching. The
reliance of the USEPA on a single, plausible worst-case,
management scenario for leach testing may be generally
protective, but often at the cost of over regulation. It has
also proven to be inadequately protective in some cases
(see discussion of spent aluminum potliner regulation at
62 FR 41005, July 31, 1997, and 62 FR 63458, Decem-
ber 1, 1997). Although reliance on  a  single waste man-
agement scenario as the basis for leach testing may sim-
plify implementation  of RCRA, many  of the wastes
evaluated using TCLP have little if  any possibility of
codisposal with MSW; assessment of the release poten-
tial of wastes as actually managed is needed to better
understand the hazards posed by waste. Neither the
TCLP nor any other test performed under a single set of
conditions can provide an accurate  assessment of waste
hazards for all wastes.
  From an  environmental protection perspective (and
setting aside the particular requirements  of RCRA), the
goal of leaching testing is to answer the question "What
is the potential for  toxic constituent release from  this
waste by leaching (and therefore the risk) under the se-
lected management option?" For environmentally sound
waste management,  the following questions result from
different perspectives:

1.  From the waste generator's perspective—which waste
   management options are acceptable for a waste?
2.  From the waste management facility's perspective—
   which wastes are suitable for disposal in a specific
   disposal facility?
3.  From the potential end-user's perspective—is this sec-
   ondary material acceptable for use in commerce (e.g.,
   as a construction material)?
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INTEGRATED FRAMEWORK FOR EVALUATING LEACHING
                                                161
  The framework for answering these questions should
be  consistent across  many  applications, ranging from
multiple waste disposal scenarios to determination of the
environmental acceptability of materials that may be sub-
ject to leaching (e.g., construction materials). At the same
time, the framework should be flexible enough to  con-
sider regional and facility-specific differences in factors
affecting leaching (e.g., precipitation, facility design). A
methodology guideline (ENV 12920, 1996) developed
under European standardization initiatives recommends
that the management scenario be a central consideration
in the testing and evaluation of waste  for disposal and
beneficial use of secondary materials. This methodology
is an extension of the approach in the Building Materi-
als  Decree established in The Netherlands (Building Ma-
terials Decree, 1995).
  The answers to the questions posed above require sev-
eral interrelated assessments including (a) the release rate
and total amount over a defined time interval of poten-
tially hazardous constituents from the waste, (b) attenu-
ation of the constituents of concern as they migrate from
the waste, through  groundwater,  to the receptor being
considered, (c) exposure of the receptor, and (d) the tox-
icity of each specific constituent. Considerable effort has
resulted in accurate assessment techniques and data for
evaluating contaminant transport through the environ-
ment (and attenuation), and toxicity for a large number
of constituents.
  In contrast to the detailed research on constituent fate,
transport, and risk following release, estimation of con-
stituent release by leaching most  often assumes (a) the
total content present is available for release, or (b) the
contaminant concentration in the leachate will be equal
to that measured during a single batch extraction and is
constant with time (this assumption is  often referred to
as the "infinite source" assumption), or (c) the fraction
of the contaminant extracted during a batch extraction is
equal  to the fraction that  will leach  (USEPA, 1986;
Goumans et al., 1991). These approaches frequently re-
sult in grossly inaccurate estimation of actual  release
(both over- and underestimation). Inaccurate release es-
timation, in turn, forces disposal of materials that are suit-
able for beneficial use, mandates remediation of soils to
levels  beyond that necessary for environmental protec-
tion, unnecessarily depletes disposal capacity, or results
in groundwater contamination  (if release is underesti-
mated). In addition, treatment  processes, that  may be
proven to reduce  the extracted concentration for a regu-
latory  test (TCLP), have resulted in increased release
when compared to management scenarios without treat-
ment (Garrabrants, 1998). Thus, methodologies that re-
sult in a more accurate estimate of contaminant leaching
may both improve  environmental protection  through
more efficient use of resources and be economically ben-
eficial.
  In general, leaching tests can be classified into the fol-
lowing categories (Environment Canada, 1990): (a) tests
designed to simulate contaminant release under a specific
environmental scenario (e.g., synthetic acid rain leach test
or TCLP), (b) sequential chemical extraction tests, or (c)
tests which assess fundamental leaching parameters.
  Tests that are designed to simulate release under spe-
cific environmental scenarios are limited because they
most often do not provide information  on release under
environmental scenarios  different  from the one being
simulated. This type of limitation has led to widespread
misuse and misinterpretation of TCLP  results.  Reliance
on simulation-based testing also results  in treatment pro-
cesses that are designed to "pass the  test" rather  than to
improve waste characteristics or reduce leaching under
actual use or disposal scenarios. For instance, it is com-
mon practice to include waste  treatment additives  to
buffer the TCLP leachant at a pH resulting in minimum
release  of  target  constituents. However,  when the
buffered material is landfilled, the landfill leachate pH
may be dominated either by the material buffering ca-
pacity (monofill scenarios) or by other sources  (codis-
posal scenarios). In either case, the  release scenario may
differ significantly from conditions simulated by the test-
ing protocol, and unpredicted leaching behavior may oc-
cur.
  Sequential chemical extraction tests  evaluate  release
based on  extraction of the  waste  with a series  of in-
creasingly more aggressive  extractants. The sequential
extraction approach, originally compiled by Tessier et al.
(1979),  has been adapted by others  (Frazer and Lum,
1983). These adapted approaches have limitations  that re-
quire case-by-case  evaluation (Khebohian and  Bauer,
1987; Nirel and Morel, 1990). In  addition, the  opera-
tionally defined  nature  of  sequential extraction ap-
proaches make generalized application  in a waste man-
agement framework difficult.
  In addition, geochemical speciation modeling also can
provide useful insights into leaching behavior, as it pro-
vides information on possible solubility controlling min-
eral phases (Meima et al., 1999; van  der Sloot, 1999;
Crannell et al., 2000), the role of sorption processes with
Fe,  Mn, and Al phases (Meima and Comans, 1998,1999),
and complexation with dissolved organic matter (Keizer
and van Riemsdijk, 1998; Kinniburgh  et  al., 1999; van
der Sloot, personal communication 2002). However, geo-
chemical modeling  often requires  detailed solid phase
identification that is either impractical or not possible for
complex materials, and needed solubility and adsorption
parameters may be  unavailable. Although the  informa-
tion it provides can be used effectively in waste man-
                                                               ENVIRON ENG SCI, VOL. 19, NO. 3, 2002
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162
                                   KOSSON ETAL.
agement,  geochemical modeling often  only  provides
qualitative or semiquantitative results, and is not a tool
for regulatory control.
  The alternative framework described below was de-
signed to assess intrinsic waste leaching parameters,
thereby providing a sound basis for estimation of release
potential in a range of different potential waste manage-
ment scenarios. It provides a basis either for choosing ac-
ceptable  management or  disposal from among several
possible  options or for judging whether a preselected
management or disposal option, is, in fact, environmen-
tally sound and appropriate.
  AN ALTERNATIVE FRAMEWORK FOR
        EVALUATION OF LEACHING

  Waste testing should provide information about po-
tential contaminant release from a waste in  the context
of the anticipated disposal or utilization conditions. Thus,
testing should reflect the range of conditions (e.g., pH,
water contact, etc.) that will be present in the waste and
at its interface with its surroundings during the long term,
which may be significantly different than the properties
of the material immediately following production. [Ex-
amples where the material as produced has different con-
stituent release behavior than that during utilization are:
(1) concrete pillars immersed in surface water where re-
lease reflects the neutral pH of surface water rather than
the alkali pH of Portland cement concrete (van der Sloot,
2000); (2)  stabilized coal fly ash  exposed to seawater
showing surface sealing (Hockley  and van der  Sloot,
1991); (3) MSWI bottom ash used in road-base applica-
tion being neutralized with a few years of field exposure
(Schreurs et al., 2000);  and (4) use of steel slag in coastal
protection applications where V and Cr leaching is re-
duced by the natural formation of ferric oxide coatings
in the utilization environment (Comans et al., 1991).]
  The goals of a revised framework for evaluation of
contaminant leaching should be to: (a) provide conserv-
ative  (in this paper,  "conservative" estimates of release
implies that the actual release will be less than or equal
to the estimated release during the management scenario
considered.), but realistic estimates of contaminant leach-
ing for a broad range of waste types, constituents of con-
cern,  environmental conditions, and  management op-
tions; (b) utilize testing strategies that can be carried out
using standard laboratory practices in reasonable time
frames (e.g., several hours to several days, depending on
requirements); (c) provide for release estimates that con-
sider  site-specific  conditions; (d)  encourage improve-
ments in waste management practices; (e) provide flexi-
bility to allow level  of evaluation (and hence degree of
overconservatism) to be based  on the user's  require-
ments; (f) evolve in response to new information and take
advantage of prior information; and (g) be cost effective.
(For most cases, more detailed waste characterization re-
sults in more accurate estimates of actual contaminant re-
lease, providing safety margins by reducing the degree
of overestimated release. However, more detailed char-
acterization requires additional  testing cost  and time,
which  may not be justified because of either the limited
amount of waste to be managed, time constraints, or other
reasons.)
  In concert with these goals, evaluation of constituent
release can be approached by a series of steps: (1) define
management scenarios and mechanisms occurring in the
scenarios (e.g., rainfall  infiltration) that  control  con-
stituent release; (2) measure intrinsic leaching parame-
ters for the waste or material being evaluated (over a
range of  leaching conditions); (3) use release models in-
corporating measured leaching parameters (correspond-
ing to anticipated management conditions) to estimate re-
lease fluxes and long-term cumulative release; and (4)
compare  release estimates to acceptance criteria. Man-
agement  scenarios can either be default scenarios that are
designed to be conservative or incorporate site-specific
information to  provide  more accurate estimates of re-
lease. In  CEN TC 292,  such a scenario-based approach
has been described as an experimental standard (ENV
12920, 1996). This standard describes steps very similar
to those identified above. [CEN/TC 292 is the European
Standardization Organization (CEN)  technical commit-
tee dealing with characterization  of waste (established in
1993). For additional information, see www.cenorm.be
on the Internet.]
  The controlling release mechanisms most often can be
described in terms  of either equilibrium  controlled or
mass-transfer rate controlled. Equilibrium controlled re-
lease occurs for slow percolation  through porous or gran-
ular materials. Mass transfer rate controlled release oc-
curs when flow is predominantly  at the exterior boundary
of monolithic materials or percolation is very rapid rela-
tive to mass transfer rate of constituent release to the per-
colating water. Intrinsic leaching parameters that are to
be measured using  laboratory testing are:  constituent
availability, constituent partitioning  at equilibrium be-
tween  aqueous and solid phases as a function of pH and
liquid-to-solid(LS) ratio, acid and base neutralization ca-
pacities (ANC and BNC), and constituent mass transfer
rates.  Definition of management scenarios and applica-
tion of intrinsic parameters, release models and decision
criteria are discussed in later sections of this paper.
  To achieve the desired framework  goals and series of
evaluation  steps,  a  three-tiered testing program is  pro-
posed (Fig. 1). An analogous, tiered approach, developed
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INTEGRATED FRAMEWORK FOR EVALUATING LEACHING
                                                 163
/ MATERIAL \
\ WASTE, SOIL OR PRODUCT j


i


! MA NAGEM E MT SCE NARIO \
/ • Specific disposal or \
\ ulilization scenario /
\ - Default cases /
(
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TIER 2
TIER 3

1
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) ( Default (see text)
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(Material specific)
, !
BmpieiKj. u,sinj
TierSC
MASS
p TRANSFER RATE
Quality Contrul
jMalerial specific]
omplience testirg— '
LEVEL C
                            Figure 1.   Alternative framework for evaluation of leaching.
with input from the authors of this paper, has been rec-
ommended by Eighmy and Chesner for evaluation of sec-
ondary  materials  for  use in  highway  construction
(Eighmy and Chesner, 2001). In the framework presented
in this paper, each successive tier provides leaching data
that is more  specific to the material being tested and pos-
sible leaching conditions than the previous tier. Individ-
ual leaching tests are designed to provide data on intrin-
sic leaching parameters for a waste or secondary material.
Results from multiple tests, used in combination with ei-
ther  default management scenario assumptions (more
conservative, but with simpler implementation) or site-
specific information, provide more accurate release as-
sessments. However, the results of a single test (e.g., the
first  tier availability test) can be used as the most con-
servative approach for management decisions when time
or economic considerations do not justify more detailed
evaluations.
  Three tiers of assessment can be defined to efficiently
address the above waste management questions and  cri-
teria: Tier 1—screening based assessment (availability);
Tier 2—equilibrium based  assessment (over a range of
pH and LS conditions); and Tier 3—Mass transfer based
assessment.
  Progressing from Tier 1  through Tier 3  provides in-
creasingly more realistic and tailored, and less conserv-
ative, estimates of release, but also requires more exten-
sive testing.
  Tier 1 is a screening test that provides an assessment
of the maximum potential for release under the limits of
anticipated environmental conditions, without consider-
ation of the time frame for release to occur. This concept
of maximum potential release is often  referred to as
"availability." In practical application, availability is op-
erationally defined using a selected test method. Leach-
ing potential is expressed on a mass basis (e.g., mg X
leached/kg waste). The basis for this bounding analysis
would be testing under extraction conditions that maxi-
mize release within practical considerations (see further
discussion below). Tier 2 testing is based on defining liq-
uid-solid equilibrium as  a function of pH and LS (i.e.,
chemical retention in the matrix). Tier 3 testing uses in-
formation on liquid-solid equilibrium in conjunction with
mass transfer rate information (i.e., physical retention of
constituents in addition to chemical retention in the ma-
trix). Both Tier 2 and Tier 3 testing may use either de-
fault or site-specific management assumptions (e.g., in-
filtration rates, fill depth)  to estimate release as a function
of time. For a scenario, leachate concentrations based on
equilibrium  will always be greater than or equal to those
based on mass transfer rate. Thus, equilibrium release es-
timates (Tier 2) may be a conservative approximation in
                                                                ENVIRON ENG SCI, VOL. 19, NO.  3, 2002
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164
                                    KOSSON ETAL.
the absence of mass transfer rate information (Tier 3).
(Extrapolation of laboratory mass transfer tests results to
field conditions requires careful consideration of the ex-
ternal surface area for water contact and the potential for
external stresses.)
  For Tier 2 and Tier 3 assessments, three levels of test-
ing (Levels A, B, or  C)  are defined. Each of the three
levels of testing may be used, depending on the amount
of previous knowledge (test data) of the waste, or the de-
gree of site-specific tailoring desired. Level A (in either
Tier 2 or 3) uses concise or  simplified tests. The basis
for Tier 2A would be measurement of the leaching char-
acteristics at conditions that bound the range of antici-
pated field scenarios for equilibrium (e.g., use of three
extractions to define release at acidic, neutral, and alkali
pH conditions with consideration of the material's nat-
ural pH at LS = 10 mL/g). The basis for Tier 3A testing
would be a coarse estimate of release rates (e.g., a four-
point, 5-day monolithic leach test).  The data from these
tests would be used in conjunction with default manage-
ment scenario bounding conditions, and simplified re-
lease models, to provide a conservative assessment in the
absence of more detailed knowledge. Example applica-
tions of Level A testing (in either Tier 2 or 3) include for
routine disposal of wastes that may fail Tier 1 testing,
simplified evaluations for disposal or utilization that can
be justified based on more conservative assumptions, and
verification that a material being tested exhibits charac-
teristics similar to a class of materials that has previously
been more extensively characterized (e.g., Level B, see
below).
  Level  B testing provides detailed characterization of
the waste or secondary raw material.  The basis for Tier
2B  testing would be definition of equilibrium over the
full range  of relevant pH and LS  conditions (i.e., pH
2-13, and LS 0.5-10  mL/g).  The maximum release ob-
served under these conditions also is functionally equiv-
alent to the availability measured in Tier 1, although the
specific values may differ based  on  the method of deter-
mination. The basis for Tier 3B testing would be a more
complete definition of mass transfer rates (e.g., 10 data
points over 60 days) and verification of material integrity
(e.g., strength after leaching). These more detailed data
can be used in conjunction with either default or site-spe-
cific management scenario assumptions, and either sim-
plified or advanced release models.  For example, results
from Level B testing in conjunction with default scenar-
ios and simplified release models can provide the basis
for comparison of treatment processes.  Results  from
Level B testing used in conjunction with site-specific in-
formation and advanced models provide the most realis-
tic and least conservative assessment. Level B testing
would only be carried out initially for a material or class
of materials generated in large quantities, and thereafter
only if significant changes in material characteristics are
indicated by periodic Level A testing. Level B testing
provides insight into the critical components for a given
material, thus providing the basis for selection of a re-
duced set of parameters for subsequent testing. After
completion of Level B testing, Level A testing can be
used to answer the question, "Does the material currently
being tested have the same characteristics  of the mate-
rial that was  previously characterized in  more detail
(Level B)?" The frequency of testing can be related to
the degree of agreement with the level B testing. Good
performance is then rewarded by reduction in  test fre-
quency. A deviation then requires initially more frequent
testing to verify the deviation, and if necessary, a return
to the level B testing to evaluate the cause.  Additional
examples  of application  of Level  B  testing include
monofill disposal of special wastes and approvals for ben-
eficial use of secondary materials.
  Level C provides the most simplified testing for qual-
ity control purposes, and relies on measurement of a few
key indicators of waste characteristics, as  identified in
the level B testing. An example of Level C testing would
consist of titration of a sample to a designated pH with
measurement of the concentration of a limited number of
constituents in the resulting single extract. Specific Level
C testing requirements would be defined on a case  spe-
cific basis. Level C should only be used after  Level B
testing has initially been completed to provide a context
for quality control. One application of Level C testing
would be the routine (e.g., daily, weekly  or monthly)
evaluation of incinerator ash prior to disposal.
  A feedback loop is provided between Tier 2C and Tier
2A within the framework (Fig. 1). This loop is provided
to indicate that Tier 2A testing can be used  on a random
basis  to provide further assurance of attainment of regu-
latory objectives when much more simplified testing is
allowed on a routine basis (Tier 2C). In this case, the Tier
2A testing is compared with the more complete Tier 2B
characterization testing to verify that the batch  of mate-
rial being tested has not deviated significantly from the
material that was originally characterized, and serves as
the baseline assessment. A similar approach may be used
when quality control testing is based on mass transfer rate
testing (Tier 3C) rather than equilibrium testing (Tier 2C).
  Although the  above framework provides the specific
basis  only  for evaluation of inorganic constituents, an
analogous set of test conditions can be described for eval-
uation of organic constituents. Additional considerations
for organic constituents would include (a)  the potential
for mobility of a nonaqueous phase liquid, (b) the fact
that pH dependence of aqueous partitioning is usually
limited to the indirect (although important) effect of pH
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INTEGRATED FRAMEWORK FOR EVALUATING LEACHING
                                                165
on dissolved organic carbon levels from humic or simi-
lar substances, and (c) availability for many organic con-
stituents is limited, and may require  a more complex
modeling approach.
    DECISION MAKING BASED ON THE
        EVALUATION FRAMEWORK

  Application of laboratory testing results to  environ-
mental decision making requires linking the laboratory
data to environmental end points of concern (protection
of human health and environment). This is done through
data or models that represent environmental processes,
including groundwater transport of released constituents,
exposure to humans or animals via drinking water, and
the  toxicity of the released constituents of concern.
  This linkage was established for the TCLP based on
assuming the test results yielded a leachate constituent
concentration that reflected anticipated field leachate that
would be produced during disposal in the bounding sce-
nario. This leachate constituent concentration, in turn,
would be reduced through natural groundwater attenua-
tion processes as it moved through the groundwater (e.g.,
dilution and adsorption) before reaching a drinking wa-
ter well. This "concentration-based approach" implicitly
assumes an infinite source of the constituents of concern,
and does not account  for either the anticipated changes
in release over time (including exhaustion of the source)
or the potential for cumulative effects of release over
time. Furthermore,  this  approach considers  only the
leaching behavior of the material; it does not consider the
management context (e.g., disposal vs. utilization, design
of the management scenario, geographic location). Thus,
the  concentration-based approach  establishes a leachate
concentration (as measured in the TCLP), below which
no  significant impact  to drinking  water is anticipated.
This approach also  can be misleading if the test condi-
tions do not reasonably reflect the field conditions (e.g.,
with respect to pH and LS ratio).
  The proposed alternative is a performance or "impact-
based approach." This approach focuses on the release
flux of potentially toxic constituents over a defined time
interval. Thus, the  management scenario  is evaluated
based on a source term that incorporates consideration of
system design, net infiltration, and the leaching charac-
teristics of the material. Basing assessment and decisions
on estimated release allows consideration of the waste as
containing a finite amount of the constituent of interest,
the  time course of release, and the ability to adapt test-
ing results to a range of management scenarios. The mea-
sure of release would be the mass of constituent released
per affected area  over time  (i.e., release flux). Knowl-
edge of the release flux would allow more accurate as-
sessment of impact to water resources (e.g.,  groundwa-
ter or surface water) by defining the mass input of con-
stituent to the receiving body over time. Results of this
impact-based approach can provide direct input into sub-
sequent risk assessment for decision making, either based
on site-specific analysis or using a generalized set of de-
fault assumptions.


Management scenarios
  Waste management  or utilization scenarios must be
used to link laboratory assessment results to  impact as-
sessment. Defining scenarios for this purpose requires the
leaching mode controlling release (equilibrium or mass
transfer), the  site-specific LS ratio, the field pH, and a
time frame for assessment. Values describing a  specific
waste management facility or a hypothetical default sce-
nario could be used. Using these site conditions with lab-
oratory measures of constituent solubility as a function
of pH and LS ratio, a simple release model can be used
to estimate the cumulative mass  of the constituent re-
leased over the time frame for a percolation/equilibrium
scenario. Including laboratory measurement of  mass
transfer rates allows for application of simple release
models for mass transfer rate controlled management sce-
narios (e.g., monolithic materials).
  For  a hypothetical default landfill disposal scenario,
parameter values may be based on national data for dif-
ferent landfill types, or defined as a policy matter. Val-
ues for field pH  and LS ratio may be either measured at
an actual site or estimated for the site. Measuring field
pH requires collecting  landfill leachate or landfill pore
water and measuring the pH before contact with the air
begins to alter the  pH. LS ratio serves as the surrogate
parameter for time. Good agreement has been obtained
between laboratory test data and landfill leachate based
on LS (van der Sloot, 2001). Measuring field LS ratio in-
volves measuring the volume of leachate collected (an-
nually) from the landfill, and comparing it with the esti-
mated waste volume in the landfill, or the landfill design
capacity. As an alternative to measuring the LS  ratio, it
may be estimated, based on defining the geometry for the
management  scenario  and  local  environmental condi-
tions. Parameters for defining the management scenario
include fill geometry (relating waste mass to impacted
area), net infiltration rates (defining amount of water con-
tact), and time frame. For example, a default disposal sce-
nario may be  a fill height of  10m, 20 cm infiltration per
year and 100 years  (alternatively, the total mass of waste
and footprint area may be specified). The selection of the
default management scenario is ultimately a considera-
tion of typical waste management practices and  of soci-
                                                               ENVIRON ENG SCI, VOL. 19, NO. 3, 2002
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166
                                   KOSSON ETAL.
etal value judgments reflected in the regulatory develop-
ment process.
  For  discussion purposes,  a  100-year interval is sug-
gested as a  hypothetical assessment period, although
other time frames could be used. (The authors have found
100 years to be a useful period for release estimates. This
period is typically longer than a lifetime but short enough
to be comprehendible. In addition, for many cases, a ma-
jor fraction of the long-term release is anticipated to oc-
cur during a period less than this interval.) For compar-
ison of treated wastes, a cube 1 meter on edge is assumed.
Laboratory test results  are presented primarily as release
per unit mass of waste tested (e.g., mg X/kg waste), but
also are presented and  used on a concentration basis for
Tier 2  testing.


Environmental considerations
  Release estimates for most  cases assume that condi-
tions influencing release are  controlled by the waste ma-
terial and associated design  conditions; however, prop-
erties of surrounding materials may dominate the release
conditions  in some scenarios. These  external  stresses
(e.g., pH or redox gradients, carbonation, comingling
effects) can lead to substantial deviation from material-
driven leaching behavior.  For instance, caution must be
used if large pH or redox gradients exist between the
waste  and  the surrounding  environment or within the
waste matrix. The solubility of many inorganic species
may be strongly a function  of pH (e.g., Pb, Cd,  Ba) or
significantly altered by redox conditions  (e.g., Cr, Se,
As). Large gradients in pH or redox potential can result
in precipitation or rapid dissolution phenomena for some
elements as concentration gradients within the material
or at the material boundary redistribute over long time
intervals (van der Sloot etal, 1994; Sanchez, 1996). The
release of highly  soluble species (e.g., Na, K, Cl) is not
considered a strong function of leachate conditions.
  Redox gradients  and reducing conditions may result
from material characteristics, biological activity,  or ex-
ternal inputs. Materials with inherent reducing properties
include several types of industrial slag, fresh sediment,
and degrading organic  matter. Testing of these materials
under air-exposed conditions may lead to  unrepresenta-
tive answers for the situation to be evaluated. For an ap-
propriate assessment of reducing materials, testing and re-
lease modeling that considers conditions imposed  by
external factors,  rather than  by the waste  itself, will be
necessary. This is still an underdevelopedarea of research.
  For most alkaline wastes, the most prevalent interface
reaction is absorption of carbon dioxide. Carbonation of
waste  materials  results in the formation  of carbonate
species and neutralization of alkaline buffering capacity.
For Portland cement-based matrices, the conversion of
calcium hydroxide to calcium carbonate has been noted
to reduce pore water pH towards 8 (Garrabrants, 2001;
Sanchez, 2002a). Thus, if pH-dependent species are a
concern, carbonation of the matrix can play a significant
role in predicting long-term release.
   Currently, the proposed approach does not consider the
impact of comingling  different types of wastes during
disposal other than the impact of resulting changes in pH.
In cases where a pH gradient appears to be the most sig-
nificant factor, release estimates can be accomplished us-
ing advanced modeling approaches in conjunction with
characterization data interpolated from the concentration
as a function of pH as defined under Tier 2. Test meth-
ods and release models to assess the impact of material
aging under carbonation and reducing conditions are un-
der development (NVN 7438, 2000; Garrabrants, 2001;
Sanchez  et al, 2001). Experimental work is in progress
to evaluate  waste-waste  interaction  by   quantifying
buffering of pH, dissolved organic carbon, and leaching
from waste mixtures (van der Sloot et al, 2001a, 200Ib).
        TEST METHODS FOR USE IN
              THE FRAMEWORK

Criteria for equilibrium test methods
  Important considerations for the design of equilibrium
test methods are  (a) the relationships between particle
size, sample size, and contact time; (b) definition of an
appropriate LS ratio; (c) selection of the acid or alkali for
pH modification; and (d) practical mechanical limits. Ex-
perimental observations with several wastes have  indi-
cated that use of a maximum particle size of 2 mm and
contact time of 48 h results in a reasonable measurement
of equilibrium  (Garrabrants, 1998). If diffusion is as-
sumed to  be the  rate controlling mechanism, the  rela-
tionships between particle size and contact time required
to approach equilibrium can be approximated as diffu-
sion from  a sphere into a finite bath (Crank, 1975).  Crit-
ical parameters are the fraction of constituent released at
equilibrium, observed diffusivity, particle diameter, and
contact time. The ratio between the fraction of constituent
released at a given time and the fraction of the constituent
released at equilibrium can be considered an index of the
approach to equilibrium. Results of simulations using this
modeling approach are consistent with approaching equi-
librium after 48 h  for  observed diffusivities less  than
10~14 m2/s (Garrabrants, 1998).
  Equilibration times for different particle size systems,
assuming  all  other properties remain constant (e.g., ob-
served diffusivity, liquid-solid ratio, fractional release at
-------
INTEGRATED FRAMEWORK FOR EVALUATING LEACHING
                                                      167
Table 1.  Specifications for the base case and suggested alternative conditions for equilibrium extractions.

Minimum
Minimum
Container

sample size (g)
contact time (hr)
size (mL)

Base case
2
40
48
250
Maximum particle

0.3
20
18
500
size [mm]
Suggested alternates
5
80
168(7
1,000



days)
equilibrium), can be evaluated using a dimensionless time
parameter:
                         Dobs-t
                     T =
(1)
where T is the dimensionless time parameter [ —]; t is the
contact time [s]; r is the particle radius [m]; and, Dobs is
the observed diffusivity [m2/s].
  Based on this approach, achieving a condition equiv-
alent to the 2 mm/48 h case, a particle size of 5 mm would
require extraction for 12.5 days; for a particle size of 9
mm, 40.5 days would be required. However, most mate-
rials undergoing testing would be sized reduced  or natu-
rally have a particle size distribution with the  maximum
particle size specified. Thus, a maximum particle size of
2 mm with a 48-h minimum contact time is specified as
a base case, with alternative conditions suggested con-
sidering both equivalent approaches to equilibrium and
practical limitations  (Table  1).  Demonstration of ap-
proximating equilibrium conditions for the material be-
ing tested is recommended before using alternative con-
tact times.
  Selection of sample sizes assumes testing of represen-
tative aliquots of the material being  evaluated.  For the
base case with a maximum particle size of 2 mm, a sam-
ple size of 40 g (equivalent dry weight) is recommended
when carrying out an extraction at an LS ratio of 10 mL/g.
Heterogeneous materials and materials with a larger par-
ticle size will require either testing of larger aliquots or
homogenization and particle size reduction prior to sub-
sampling for testing.  A discussion and example  of sam-
pling of heterogeneous materials and particle size reduc-
tion followed  by subsampling for   leaching  tests  is
provided elsewhere (IAWG, 1997).
  For many test methods, an LS ratio of 10  mL/g has
been selected  to provide adequate extract volumes for
subsequent filtration  and analysis while using standard
size extraction containers (i.e., 500 mL). This liquid-to-
LS  ratio also provides  for reasonable  approach to equi-
librium based on theoretical considerations.  Typically,
use of an LS ratio of 10 mL/g provides solubility-con-
trolled equilibrium over the range of pH relevant for ex-
trapolation to the field. The resulting solution concentra-
tion is generally only weakly dependent on LS ratio be-
tween LS ratio of 10 and 2 mL/g. LS ratio dependence
may be verified using an  extraction at lower LS (see
methods below).
  In the experimental methods, pH adjustments are made
using aliquots of nitric acid or potassium hydroxide. Ni-
tric acid was chosen to minimize the potential for pre-
cipitation (e.g., such as occurring with sulfuric  acid),
complexation  (e.g., with  organic acids or hydrochloric
acid), or analytical interferences. It is also recognized that
nitric acid is oxidizing, which is a conservative selection
due to the solubility behavior of metal hydroxyl species
(e.g., Pb(OH)3~, Cd(OH)3~) and the potential for oxi-
dizing conditions during management. However, oxyan-
ions (e.g., chromate) exhibit maximum release at near
neutral to slightly alkaline  conditions that typically are
achievable without significant acid additions. Testing for
release under reducing conditions requires the develop-
ment of additional  test methods because consideration
must be given to acid selection, sample handling, and es-
tablishment of reproducible reducing conditions. Potas-
sium hydroxide was selected to avoid interference with
the use of sodium ion as an inert tracer  in some applica-
tions; however, sodium hydroxide may be substituted for
cases in which potassium characterization is a concern.
  During extraction, complete mixing should be insured
by end-over-end mixing. In all cases, it is desired to test
the material with the minimum amount of manipulation
or modification needed prior to extraction. Thus, it is
preferable to avoid sample drying before testing, although
this can be acceptable when nonvolatile constituents are
of primary interest and it is  necessary to achieve particle
size reduction.
           RECOMMENDED TEST METHODS

        The following test methods are recommended for use
      in the proposed tiered  leaching framework. The general
                                                               ENVIRON ENG SCI, VOL. 19, NO. 3, 2002
-------
168
                                   KOSSON ETAL.
purpose, approach, and application of these test methods
are shown in Table 2.  Detailed protocols for these test
methods are presented as Appendix A.

Tier 1—screening tests
  An ideal screening test would result in a conservative
estimate of release over the broad range  of anticipated
environmental conditions. In addition, this screening test
would require only a single extraction that could be com-
pleted in less than 24 h. However, this ideal scenario is
impossible to achieve. Several approaches to measuring
"availability" or maximum leaching potential have been
developed or considered. One approach is a two step se-
quential extraction procedure with particle size <300
Aim, LS = 100 mL/g and control at pH 8 and 4 (NEN
7341, 1994). Another approach uses EDTA to chelate
metals of interest in solution at near neutral pH during a
single extraction (Garrabrants and Kosson, 2000). Either
of these approaches can be used as a screening test, but
both approaches have practical limitations relative to im-
plementation. The NEN 7341 requires a  small particle
size, two extractions, and pH control. The  approach  of
Garrabrants  and Kosson (2000) requires  a pretitration,
and can  have some difficulties in controlling the pH. This
approach also has been criticized as providing a release
estimate that may be too conservative. (NEN is the na-
tional Dutch standardization organization, where a stan-
dardization committee has been addressing the develop-
ment of leaching tests  for  construction materials and
waste materials since 1983.  For additional  information,
see www.nen.nl on the Internet.)

Tier 2—solubility and release as a function of pH
  The objectives of this testing is to determine the
acid/base titration buffering capacity of the  tested mate-
rial and the  liquid-solid partitioning equilibrium of the
"constituents of potential concern" (COPCs). For wastes
with high levels of COPCs, the liquid-solid partitioning
equilibriumis determinedby aqueous solubility as a func-
tion of pH. For low levels of COPCs, equilibrium may
be dominatedby adsorption processes. However, the con-
current release  of other constituents (e.g., dissolved or-
ganic carbon, other ions) will also impact the results by
modifying the  solution characteristics of the aqueous
phase. [For example, the dissolution of organic carbon
from a waste has  been shown to increase the solubility
of copper in municipal solid waste incinerator (MSWI)
bottom ash and several  metals in matrices containing or-
ganic matter (van der  Sloot, personal communication,
2002).]  The two approaches that have been considered
for achieving the  objective of measuring  solubility and
release as a function of pH are (a) static (controlled) pH
testing at multiple pH values through use of a pH con-
troller at desired set points (van der Sloot et al., 1997),
and (b)  a series of parallel extractions of multiple sam-
ple aliquots using a range of additions of acid or alkali
to achieve the desired range of end point pH values (En-
vironment Canada and  Alberta Environmental Center,
1986; Kosson et al., 1996; Kosson and van der Sloot,
1997; prEN14429, 2001).  Both testing approaches have
been shown to provide similar results (van der Sloot and
Hoede,   1997), including determination of  both  the
acid/base titration buffering capacities of the tested ma-
terial  and the characteristic behavior of the constituents
of potential concern. The static pH approach has the ad-
vantage of being able to achieve desired pH end points
with a high degree of accuracy. The parallel extraction
approach has the advantage of mechanical simplicity. The
range of pH examined should include the extreme values
of pH anticipated under field conditions and the pH when
controlled by the tested material (i.e., "natural" or "own"
pH). Thus, although the recommended method below
provides a full characteristic behavior curve (i.e., for Tier
2, level B testing), an abbreviated version based on three
analysis points may be used for simplified testing (i.e.,
for Tier  2A). The recommended method below  is  also
analogous  to  CEN   TC  292  Characterization   of
Waste-Leaching Behavior Test-pH Dependence Test
with Initial Acid/Base Addition (prEN14429, 2001).

   SR002.1 (alkalinity, solubility and release as a func-
tion ofpH). This protocol consists of 11 parallel extrac-
tions of particle size reduced material at a liquid-to-solid
ratio of 10 mL extractant/g dry sample. An acid or base
addition schedule is formulated for 11 extracts with final
solution pH values between  3 and 12, through addition
of aliquots of HNOs or KOH as needed. The exact sched-
ule is adjusted based on the nature of the material; how-
ever, the range of pH values  includes the natural pH of
the matrix that may extend the pH domain (e.g., for very
alkaline  or acidic materials). Using the schedule,  the
equivalents of acid or base are added to a combination
of deionized (DI) water and the particle size reduced ma-
terial. The final liquid-solid (LS) ratio is 10 mL extrac-
tant/g dry sample which includes DI water, the added acid
or base, and the amount of moisture that is inherent to
the waste matrix as determined by moisture content anal-
ysis. The 11 extractions are tumbled in an end-over-end
fashion at 28 ± 2 rpm.  Contact time is a function of the
selected maximum particle size, with an extraction pe-
riod of 48 h for the base case of 2 mm maximum parti-
cle size. Following gross separation  of the solid and liq-
uid phases by  centrifugation or  settling,  leachate  pH
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INTEGRATED FRAMEWORK FOR EVALUATING LEACHING
                                                                                      169
Table 2.  Comparison of recommended leaching protocols and applications.
Tier   Test name
Purpose
Methodology
Output
Application
       AV001.1    To determine the
                      potentially
                      extractable content
                      of constituents
                      under
                      environmental
                      conditions.
       AV002.1    To determine the
                      potentially
                      extractable content
                      of constituents
                      under
                      environmental
                      conditions.
       SR002.1    To obtain solubility
                      and release data as
                      a function of
                      leachate pH
       SR003.1    To estimate pore
                      water conditions by
                      obtaining solubility
                      and release data as
                      a function of LS
                      ratio.
       MT001.1    To determine mass
                      transfer parameters.
                   To estimate rate of
                      release under
                      continuously
                      saturated conditions.
       MT002.1    To determine mass
                      transfer parameters.
                   To estimate rate of
                      release under
                      continuously
                      saturated conditions.
                 Parallel extractions at
                   pH 4 and 8 in DI
                   water; Liquid-to-
                   solid (LS) ratio of
                   100 mL/g; contact
                   time dependent on
                   particle size.
                 Single extraction
                   using 50 mM
                   EDTA; LS ratio of
                   100 mL/g; contact
                   time dependent on
                   particle size

                 Multiple parallel
                   extractions using DI
                   water and HNO3 or
                   KOH; LS ratio of
                   10 mL/g; contact
                   time dependent on
                   particle size.

                 Multiple parallel
                   extractions using DI
                   water; LS ratios of
                   0.5 to 10 mL/g;
                   contact time
                   dependent on
                   particle size.

                 Semidynamic tank
                   leaching of
                   monolithic material;
                   Liquid-to-surface-
                   area ratio of 10
                   [mL/cm2]
                 Semidynamic tank
                   leaching of
                   compacted granular
                   material; Liquid-to-
                   surface-area ratio of
                   10 [mL/cm2]
                   Availability at pH 4.
                   Availability at pH 8.
                   Availability in EDTA.
                    Material-specific
                      acid/base titration
                      curve.
                    Solubility and release
                      as a function of pH.
                    Solubility and release
                      as a function of LS
                      ratio.
                    Observed constituent
                      diffusivity.
                    Rate and cumulative
                      release of
                      constituent release
                      under continuously
                      saturated
                      conditions.

                    Observed constituent
                      diffusivity.
                    Rate and cumulative
                      release of
                      constituent release
                      under continuously
                      saturated
                      conditions.
                Screening: conservative
                   release estimate.
                Characterization: realistic
                   source term for
                   modeling mass
                   transport-controlled
                   release.
                Screening: conservative
                   release estimate.
                Characterization: realistic
                   source term for
                   modeling mass
                   transport-controlled
                   release.
                Characterization: detailed
                   behavior of COPC as a
                   function of pH.
                Compliance: abbreviated
                   protocol to indicate
                   consistency with
                   previous
                   characterization.
                Characterization: detailed
                   behavior of COPC as a
                   function of LS ratio.
                Compliance: abbreviated
                   protocol to indicate
                   consistency with
                   previous
                   characterization.
                Characterization: detailed
                   leaching mechanisms
                   and rate of release
                   under mass-controlled
                   leaching scenario.
                Compliance: abbreviated
                   to indicate consistency
                   with previous
                   characterization.
                Characterization: detailed
                   leaching mechanisms
                   and rate of release
                   under mass-controlled
                   leaching scenario.
                Compliance: abbreviated
                   to indicate consistency
                   with previous
                   characterization.
                                                                     ENVIRON ENG SCI,  VOL. 19, NO. 3, 2002
-------
170
                                                 KOSSON ET AL.
measurements are taken, and the phases are separated by
vacuum filtration through 0.45-^m polypropylene filtra-
tion membranes. Analytical samples of the leachates are
collected and preserved as appropriate for chemical anal-
ysis. The acid and base neutralization behavior of the ma-
terials is evaluated by plotting the pH of each extract as
a function of equivalents of acid or base added per gram
of dry solid. Equivalents of base are presented as oppo-
site  sign  of acid equivalents.  Concentration of  con-
stituents of interest for each extract is plotted as a func-
tion of extract final pH to provide liquid-solidpartitioning
equilibrium as a function of pH. Figure 2 (a)  and (b)
shows   conceptual  output  from  the  recommended
SR002.1 protocol with the recognition that a broad range
of behaviors  is possible. In Fig. 3(a), the output data of
the SR002.1 protocol for a cementitious synthetic waste
matrix (Garrabrants, 2001) is compared to the total ele-
mental content and constituent availability (Tier 1  value).
  The abbreviated version of the SR002.1-A (Alkalinity,
Solubility, and Release as a Function  of pH) protocol con-
sists of three parallel extractions of particle size reduced
             material at a liquid-to-solid ratio of 10 mL extractant/g
             dry sample. The selection of the target pH values is de-
             pendent on the natural pH of the material. If the natural
             pH is  <5, then natural pH, 7 and 9, are selected as the
             target pH values. If the natural pH ranges between 5 and
             9, then 5, 7, and 9 are selected as the target pH values,
             and if the natural pH is >9, then 5, 7, and natural pH are
             selected as the target pH values.

             Tier 2—solubility  and release as a function
             of LS ratio
                The objective of this test is to determine the effect of
             low  liquid-to-solid ratio on  liquid-solid partitioning
             equilibrium when the solution phase is controlled by the
             tested material.  This is used to approximate initial pore-
             water  conditions and initial leachate compositions in
             many percolation scenarios (e.g., monofills). This objec-
             tive  is accomplished by  a series of parallel extractions
             using multiple aliquots of the tested material at different
             LS ratio with deionized water to achieve the desired range
                                                                        Cation ic
                                                                        Ampholcrit
                                                                       — Oxyanionic
                                                                        Highly Soluble
                      -2
                           0246
                             Acid Added [meq/gttry]
                             6       8      10
                                Leachale pH
                   13 ••
              I    12
              CL,
                   11 • •
                   10
-Matrix Ah
. Matrix B
                            246
                              LSRatio[mL/gdry]
                                                   10
Figure 2.  Conceptual data obtained using equilibrium-based testing protocols: (a) titration curve (SR002.1), (b) constituent re-
lease as a function of pH (SR002.1), (c) pH as a function of LS ratio (SR003.1), and (d) constituent concentration as a function
of LS ratio (SR003.1).
-------
INTEGRATED FRAMEWORK FOR EVALUATING LEACHING
                                                171
10000 lnn

Lead Release [mg/k|
s
§ 0
2 2 „ Sj

•<,. ~
•---> '
*
, 	

s

: • Re
, 	 fa
i Tt
, . ,_^JJ;



v


	 i 	 	
* *
*»
lease f(PH)
ail(pH4) .
tiii :
f
*
<*


I ,.
U 0 1
0.01 -
n nn i
i • SR002.1 Concf(pH) 1
! A SROQ3.L Concl{LS)

A
: *f
• IT
•y
**
* •
*^ . .



2 4 6 8 10 12 14 S 10 12 14
^ Leachate pH b) Leach ate pH
Figure 3.  Actual data obtained using equilibrium-based testing protocols from a cementitious synthetic waste: (a) lead release
as a function of pH compared to lead availability and total lead content, and (b) comparison of SR002.1 and SR003.1  concen-
tration data.
of conditions. When necessary, results can be extrapo-
lated to lower LS ratio than readily achieved under typ-
ical laboratory conditions. The range of LS ratio exam-
ined should include the condition used for solubility and
release as a function of pH testing (i.e., LS = 10 mL/g)
and the lowest LS practically achievable that approaches
typical pore water solutions (i.e., LS = 0.5 mL/g). Thus,
although the recommended method below provides a full
characteristic behavior curve (i.e., for Tier 2, level B test-
ing), an abbreviated version based on two analysis points
may be used for simplified testing (i.e., for Tier 2A). [The
abbreviated methods for testing solubility as a function
of pH  (three points) and solubility as a function of LS
(two points)  include one  common point in both tests.
Thus, for integrated testing under Tier 2,  four analysis
points are recommended.]
  For some materials, LS <2 mL/g may be difficult to
achieve with sufficient quantity of eluate for analysis due
to limitations of solid-liquid separation. In addition, the
formation of leachate colloids can result in overestima-
tion of release for some metals and organic contaminants.
Use of a column test is an alternative to use of batch test-
ing for measuring release as function of LS. A column
test (prEN14405, 2001), similar to  the Dutch standard
column test  (NEN 7343, 1995), has  been developed
within  the European Standardization Organization CEN.
  SR003.1 (solubility and release as a function ofLS ra-
tio). This protocol consists of five parallel batch extrac-
tions over a range of LS ratios (i.e., 10, 5, 2,  1, and 0.5
mL/g dry material), using DI water as the extractant with
aliquots of material that has been particle size reduced.
The mass of material used for the test varies with the par-
ticle size of the material. All extractions are conducted
at room temperature (20 ± 2°C) in leak-proof vessels that
are tumbled in an end-over-end fashion at 28 ± 2 rpm.
Contact time is a function of the selected maximum par-
ticle size, with an extraction period of 48 h for the  base
case of 2 mm maximum particle size.  Following gross
separation of the solid and liquid phases by centrifuga-
tion or settling, leachate pH and conductivity measure-
ments are taken, and the phases are separated by a com-
bination of pressure and vacuum filtration using 0.45-^m
polypropylene filter membrane.  The five leachates are
collected, and preserved as appropriate for chemical anal-
ysis. Figure 2 (c) and (d) shows conceptual output from
the recommended SR003.1 protocol with the recognition
that a broad range of behaviors is possible.  In Fig. 3(b),
the output data of equilibrium-based protocols (SR002.1
and SR003.1) are compared for a cementitious synthetic
waste matrix (Garrabrants, 2001).
  The abbreviated  version, SR003.1-A (Solubility and
Release as a Function of LS Ratio) protocol consists of
two parallel extractions of particle size reduced material
using DI water at liquid-to-solid ratio of 10 and 0.5 mL
extractant /g dry sample, respectively. The extraction at
an LS ratio of 10 mL/g may be the same sample as used
in SR002.1-A to reduce the required number of analyses.


Tier 3—mass transfer rate (monolithic and
compacted granular materials)
  The objective of mass transfer rate tests is to measure
the rate of COPC release from a monolithic material (e.g.,
solidified waste form or concrete  matrix) or a compacted
granular material. Results of these tests are to estimate
intrinsic mass transfer parameters (e.g., observed diffu-
sivities for COPCs) that are then used in conjunction with
other testing results and assessment models to estimate
                                                               ENVIRON ENG SCI, VOL.  19, NO. 3, 2002
-------
172
                                   KOSSON ETAL.
release. Results of these tests reflect both physical and
chemical interactions within the tested matrix, thus re-
quiring additional test results for integrated assessment.
Although the recommended methods are  derivatives of
ANS  16.1 (ANS, 1986), a leachability index is not as-
sumed nor used as a decision criterion. The recommended
methods below are also analogous to NEN 7345 (NEN
7345,1994) and methods under developmentby CEN TC
292.

  MT001.1 (mass transfer rates in monolithic materials).
This protocol consists of tank leaching of continuously
water-saturated monolithic material  with periodic re-
newal of the leaching solution. The vessel and sample di-
mensions are chosen so that the sample is fully immersed
in the leaching solution. Cylinders of 2-cm minimum di-
ameter and 4-cm  minimum height  or 4-cm minimum
cubes are contacted with DI water using a liquid-to-sur-
face area ratio of 10 mL of DI  water for every cm2 of
exposed solid surface area. Larger cylinder sizes are rec-
ommended for treated materials  that have a particle size
greater than 2 mm prior to solidification. Typically, the
cylinder diameter and height or cube dimension should
be at least 10 times the maximum particle size of the ma-
terial contained therein. Leaching solution is exchanged
with fresh DI water at predetermined cumulative times
of 2, 5, and 8 h,  1, 2, 4, and 8 days. [This schedule may
be extended for  additional extractions to provide more
information about longer term release. The recommended
schedule extension would be additional cumulative times
of 14 days, 21 days, 28 days, and every 4 weeks there-
after as desired. Alternately, the  duration of the test may
be shortened (e.g., cumulative time of 4 days) for com-
pliance testing.] This schedule results in seven leachates
with leaching intervals of 2, 3,  3 and 16  h, 1,2, and 4
days. At the completion of each  contact period, the mass
of the monolithic  sample after  being freely drained is
recorded to monitor the amount of leachant absorbed into
the  solid matrix. The  solution pH and conductivity for
each  leachate  is measured  for  each  time  interval. A
leachate sample is prepared for chemical analysis by vac-
uum filtration through  a 0.45-^m pore size polypropy-
lene filtration membrane and preservation as appropriate.
Leachate concentrations are plotted as a function of time
along with the analytical detection limit and the equilib-
rium concentration determined from SR002.1 at the ex-
tract pH for quality control to ensure that release was not
limited by saturation of the leachate. Cumulative release
and flux as a function of time for each constituent of in-
terest are plotted and used to estimate mass transfer pa-
rameters (i.e., observed diffusivity). Figure 4 shows sam-
ple  output data from the MT001.1 test for a  solidified
waste matrix (van  der Sloot, 1999). The solubility data
shown in the figure corresponds to data derived from
SR002.1.

  MT002.1 (mass transfer rates in compacted granular
materials). This protocol consists of tank leaching of con-
tinuously water-saturated compacted granular  material
with intermittent renewal of the leaching solution. This
test is used when a  granular material is expected to be-
have as a monolith  because of compaction during field
placement. An  unconsolidated or  granular material is
compacted into molds at optimum  moisture content us-
ing a modified Proctor compactive effort (NEN 7347,
1997). A 10-cm diameter cylindrical mold is used and
the sample is packed to a depth of  7 cm. The mold and
sample are immersed in deionized  water such that only
the surface area of the top face of the sample contact the
leaching medium, without  mixing. The leachant is re-
freshed with an equal volume of deionized water using a
liquid to surface area ratio  of 10  mL/cm2 (i.e.,  LS ratio
of 10 cm) at cumulative times of 2, 5, and 8 h, 1, 2, 4,
and 8 days. This schedule results in seven leachates with
leaching intervals of 2, 3, 3, and  16 h, 1, 2, and 4 days.
The solution pH and conductivity for each leachate is
measured for each time interval. A leachate sample is
prepared for chemical analysis  by  vacuum filtration
through  a 0.45-^m pore size polypropylene filtration
membrane and preservation as appropriate. Leachate con-
centrations are plotted as a  function of time along with
the analytical detection limit and the equilibrium con-
centration determined from SR002.1 at the extract pH for
quality control. Cumulative release and flux  as a func-
tion of time for each constituent of interest are plotted
and used to  estimate mass transfer  parameters (i.e., ob-
served diffusivity).
    RELEASE ASSESSMENT ESTIMATES

  Release estimates may be obtained for site-specific and
management scenario-specific cases  when appropriate
environmental data (e.g., precipitation frequency  and
amounts) and design information (e.g., placement geom-
etry, infiltration rates) are available. For  many situations,
site-specific information either may not  be readily avail-
able or may not be necessary (e.g., as in the case when
the intent  of testing is only to provide uniform side-by-
side comparisons of treatment processes). For these sit-
uations, default scenarios may be defined; an application
of this approach  is provided in the companion paper
(Sanchez et al., 2002c). These default scenarios are for
illustrative purposes only, and  other parameter values
may be more appropriate for different management sce-
narios and geographic locations.
-------
INTEGRATED FRAMEWORK FOR EVALUATING LEACHING
                                                                                                         173
                   7.5	
                             20      40     60
                                 Time (days)
                                                   80
                                                                      20      40      60
                                                                           Time (days)
                  160
                             20      40      60
                                Time (days)
                                                                         1         10
                                                                          Time (days)
Figure 4.  Actual data obtained using MT001.1 protocol from a stabilized waste (van der Sloot, 1999): (a) leachate pH as a
function of cumulative time, (b) comparison of leachate barium concentration (MT001.1) and barium solubility as a function of
pH (SR002.1), (c) cumulative release of barium as a function of cumulative time, and (d) barium flux as a function of mean cu-
mulative time.
Percolation-controlled scenario
  Percolation-controlled  release  occurs  when  water
flows through a permeable fill with low infiltration rate
and low liquid-to-solid ratio (Fig. 5). In this case, local
equilibrium at field pH is assumed to be limiting release.
The information required to estimate constituent release
during this scenario is the (a) field geometry, (b) field
density, (c) anticipated infiltration rate, (d)  anticipated
field pH,  (e) anticipated site-specific liquid-to-solid ra-
tio, and (f) constituent solubility at the anticipated field
pH. The anticipated site-specific liquid-to-solid (LSsite)
ratio represents the cumulative liquid-to-solid ratio that
can be expected to contact the fill over the estimated time
period. It is based on the infiltration rate, the contact time,
the fill density, and the fill geometry, and can be  deter-
mined according to (Hjelmar, 1990; Kosson etal., 1996):
                 LSsite = 10
                                                  (2)
                                                        ratio  (L/kg);  inf is  the  anticipated  infiltration rate
                                                        (cm/year); fyear is the estimated time period (year); p is
                                                        the fill density (kg/m3); //gn is the fill depth (m); and 10
                                                        is a conversion factor (10 L/cm-m2).
                                                          Over an interval of 100 years or longer, LSsne values
                                                        greater than  10 mL/g may be obtained for cases that have
                                                        relatively high rates of infiltration or limited placement
                                                        depth (Kosson et al, 1996; Schreurs et al, 2000).  How-
                                                        ever, for many disposal scenarios, the observed LSs-Ae has
                                                        been less than 2 L/kg over a period of ca. 10 years, and
                                                        for an isolated landfill site with  reduced infiltration, it
                                                        may take 1,000 years to reach LSs-Ae of  1 L/kg (Johnson
                                                        et al, 1998, 1999; Hjelmar et al, 2001).
                                                          An estimate  of the cumulative mass release per unit
                                                        mass  of material can  then be  obtained using the antici-
                                                        pated site-specific LS ratio and the constituent solubility
                                                        at the anticipated field pH  (Sfieid pe) according to:
                                                                                           pH)
                                                                                                          (3)
where, LSsne is the anticipated site-specific liquid-to-solid   where,.
                                                                      is the cumulative mass of the constituent
                                                                 ENVIRON ENG SCI, VOL. 19, NO.  3, 2002
-------
174
                                    KOSSON ETAL.
  Scenario characteristics
   - Granular or highly permeable material  ,
   - Low infiltration rate
   - Low liquid-solid ratios [mL/g]
                                   Site information
                                    - Infiltration rate inf
                                    - Fill density    p
                                    - Fill geometry   // M
                                    - Field pH
       Local equilibrium at field pH is rate limiting

         Figure 5.  Release scenario: percolation.
released (mass basis) at time fyear (mg/kg); and Sfieid pH
is the constituent solubility (mg/L)  at the pH value cor-
responding to field pH.

Mass transfer-controlled scenario
  Mass transfer-controlled scenario occurs when infil-
trating water is diverted around a low permeability fill or
prevented from percolating through the fill due to an im-
permeable overlay (Fig. 6) or adjacent high permeability
channels. In this case, mass transport within the solid ma-
trix is rate limiting. The information required to estimate
constituent release during such scenario are the (a)  field
geometry, (b) field density, (c) initial leachable content,
and (d) observed diffusivity of the species of concern.
  The mechanisms of release under mass transfer  con-
trol can be quite complex and constituent specific. The
rate of COPC diffusion through the material can be re-
tarded by surface reactions or precipitation of insoluble
compounds. Alternately, mass transport may be enhanced
by species complexation or mineral  phase dissolution.
Numerical techniques often are required to fully describe
release under complex mechanistic  conditions. Sophisti-
cated models have been  developed, or are  under devel-
opment, to account for dissolution^recipitation phenom-
ena (Batchelor,  1990, 1992, 1998; Cheng and Bishop,
1990; Hinsenveld, 1992; Batchelor and Wu, 1993;  Hin-
senveld and Bishop, 1996; Moszkowicz et al., 1996,
1997, 1998; Sanchez, 1996; Baker and Bishop,  1997),
sorption/desorption phenomena,  and material  hetero-
geneity (Sanchez et al, 2002b).

  Fickian diffusion model. The Fickian diffusion model,
based on Pick's second law, assumes  that the species of
interest is initially present throughout the homogeneous
porous medium at uniform concentration and considers
that mass transfer takes place in response to concentra-
tion gradients in  the pore water solution of the porous
medium.  The assumptions  and release estimation  ap-
proach shown here is most  appropriate for release sce-
narios for which  only highly soluble species are  a con-
cern or for which external stresses (e.g., pH gradients,
carbonation, redox changes) are not significant.
  In the classical representation of the diffusion model,
two coupled parameters characterize the magnitude and
rate of the release: CQ, the initial leachable content (e.g.,
available release  potential, total elemental content) and
Z30bs, the observed diffusivity of the species in the porous
medium. (The value used for the initial leachable content
and the determined observed diffusivity are coupled pa-
rameters such that the same set of parameters obtained
from experimental data must be used in determining long-
term release estimates.) When the species of concern is
not depleted over the time period of interest, the  cumu-
lative mass release can be described by a one-dimensional
semi-infinite geometry. Depletion is considered to occur
when more than 20% of the total leachable content has
been released  (de Groot, 1993).
  For a one-dimensional geometry, an analytical solu-
tion for Fickian diffusion is provided by Crank (1975),
with the simplifying assumption of zero concentration at
the solid-liquid interface (i.e., case of a sufficient water
renewal; infinite bath assumption):
                            /nobs. f\
              Marea = 2-p-Cof —~

where M(area is the cumulative mass of the constituent re-
leased (surface area basis) at time t (mg/m2)]; Q,  is  the
initial leachable content (i.e., available  or total elemen-
tal content) (mg/kg); p is the sample density (kg/m3); t
is the time interval (s); and, Dobs is the observed diffu-
sivity of the species of concern (m2/s).
                             - Low permeability material
                             - High infiltration rate
                             - High liquid-surface area ratios
Site information
 - Fill density
 - Fill geometry S, V
 - Fill porosity
   Mass transport within solid matrix is rate limiting

 Figure 6.  Release scenario: diffusion-controlled scenario.
-------
INTEGRATED FRAMEWORK FOR EVALUATING LEACHING
                                                                                                 175
  The test conditions for the MT series protocols (i.e.,
MT001.1  and MT002.1) are designed to ensure a non-
depleting matrix and approximate the zero-concentration
boundary, although field conditions may not satisfy these
simplifications for many cases, and the resulting release
estimate may overestimate release. Therefore, other mod-
eling approaches may be required to more accurately ex-
trapolate to field conditions.
  In release  scenarios  for which COPC depletion does
not occur  and Fickian diffusion is considered the domi-
nant release mechanism, the mass release is proportional
to release  time by a t112 relationship. After a log trans-
form, Equation (4) becomes:
log
                                      + |log t   (5)
                                        2
  Thus, the logarithm of the cumulative release plotted
vs. the logarithm of time is expected to be a straight line
with a slope of 0.5. Often, initial release as observed from
laboratory testing reflects wash off or dissolution of sur-
face-associated constituents. The apparent constituent re-
lease then may be followed by diffusion-controlled re-
lease. Mass release over this initial time when surface
phenomena are observed would result in a line with a
slope greater than 0.5. In these cases, only the data points
reflecting diffusion-controlled release are  used to esti-
mate observed diffusivity. The initial release should be
verified to be insignificant in relation to the long-term
field estimate of release  (see Sanchez et al, 2002c, for an
illustration of this phenomena).

  Estimation of observed diffusivity. Under the assump-
tions of the Fickian diffusion model, an observed diffu-
sivity can be determined for each leaching interval where
the  slope is 0.5 ± 0.15 by (de Groot and van der Sloot,
1992):
          £>?bs = Til
                                           (6)
                    2-p-C0(Vti - Vt
where D,-obs is the observed diffusivity of the species of
concern for leaching interval i (m2/s); Ma'rea  is the mass
released (surface area basis) during  leaching interval i
(mg/m2); f; is the contact time after  leaching interval i
(s); and, f,--i is the contact time after leaching interval
i - 1 (s).
  The overall observed diffusivity is then determined by
taking the average of the interval observed diffusivities.

  Release estimates. An estimate of the cumulative mass
release for the management scenario can then be obtained
using the analytical solution [Equation (4)] over the an-
ticipated assessment interval. When  COPC  release per
                                                 unit mass of material is desired, conversion based on ma-
                                                 terial field geometry can be applied to Equation (4).
                                                                    = 2-Qr--
                                                                           V
                                                                                 77
                                                 (7)
                                                 where, Mmass is the cumulative mass of the constituent
                                                 released (mass basis) at time t (mg/kg); S is the fill sur-
                                                 face area (m2); and V is the fill volume (m3).
                                                   In the case where initial surface wash-off is considered
                                                 to provide significant contribution to the release predic-
                                                 tion (i.e., >5% of cumulative release), release from ini-
                                                 tial surface wash-off is added to release estimate from
                                                 diffusion-controlled phenomena. An estimate of the cu-
                                                 mulative mass release can then be obtained using:
                                                             = fl/fwash-off. '
                                                               Jwarea     v
                                                                                        V
                                                                                              TT
                                                                                                   1/2
                                                                                                        (8)
where, Myr||h"off is the mass of constituent released (sur-
face area basis) from surface wash-off (mg/m2).
  When depletion of the COPC is anticipated to occur
over the release interval, three-dimensional analysis us-
ing finite body models may be required to estimate cu-
mulative release.  Analytical solutions may be found for
different geometries in mass transport literature (Crank,
1975) or simplifying assumptions may be applied to val-
idate the above ID approach  (Kosson et al, 1996). Al-
ternately, numerical methods may be used to solve the
Fickian diffusion equation in three dimensions (Barna,
1994).
  The above estimates represent a conservative approach
for most mass transfer-controlled release scenarios where
significant external stresses are not present. A zero sur-
face concentration assumes a maximum gradient, or driv-
ing force, for mass transport (infinite bath assumption).
In the case of slow water flow past the surface or small
liquid-to-surface area ratios, accumulation of the COPC
concentration in the leachate reduces the concentration
gradient and limits leachate concentration to the mass of
COPC in equilibrium with the solid phase. Thus, the up-
per bound (or maximum concentration) for mass trans-
fer-controlled release  should be estimated using release
estimates obtained from equilibrium assumptions  (e.g.,
Tier 2 testing in conjunction with percolation controlled
release).


Other modeling considerations
  Mass transport modeling  approaches (Garrabrants,
2001; Garrabrants et al,  2002; Sanchez et  al,  2001;
Tiruta-Barna et al, 2002)  are under development to ad-
dress environmental conditions that are more likely to be
encountered in the field such as intermittent wetting under
                                                                ENVIRON ENG SCI, VOL. 19, NO. 3, 2002
-------
176
                                   KOSSON ETAL.
varied environmental conditions (i.e., relative humidity
and CC>2 content). Additional modeling also has been
done to relate column test results to field leaching through
application of geochemical speciation (Dijkstra et al.,
2002). These models can provide more accurate release
estimates, but typically require additional information
(experimental and field) and greater expertise for use. The
simple modeling approach provided here is intended to
be a conservative, first-order approximation that will re-
sult in overestimation of actual release for most cases.
       EXAMPLE APPLICATIONS OF
              THE FRAMEWORK

  Important potential applications of the leaching frame-
work defined here include (a) the comparative assessment
of waste treatment processes, such as for determinations
of equivalent treatment under RCRA; (b) estimating en-
vironmental impacts from utilization of secondary mate-
rials in construction  applications; or  (c) estimating re-
leases from large scale waste monofills. For these cases,
Tier 2B and Tier 3B testing is recommended for initial
evaluation. An example of this application is provided in
the  accompanying paper (Sanchez et al., 2002c). Subse-
quently, Tier 2A testing can be used to establish consis-
tency between the materials initially tested and other sim-
ilar materials.
       ECONOMIC CONSIDERATIONS

  The more extensive testing recommended in the pro-
posed framework will obviously increase initial testing
costs. However, these initial costs should be  offset by
several factors. First, detailed characterization of a  ma-
terial is only necessary initially to define its characteris-
tic leaching properties, and only for materials that are
produced  in relatively large  quantities. Subsequently,
much less testing is needed to verify that new samples
conform to the previously established properties. Second,
cost  savings should be realized through the framework
by enabling alternative management strategies that are
not possible under the current rigid system. Treatment
processes evaluated under this system will be better tar-
geted to reducing leaching under field scenarios. Reduced
treatment costs may be achieved in many cases (how-
ever, treatment costs may increase in cases where treat-
ment processes were only effective at meeting TCLP, but
were ineffective at reducing leaching in the field to  lev-
els consistent with risk-based end points). In addition, the
potential for environmental damage and future liability
will  be reduced because of the closer  relationship be-
tween testing and field performance. Costs for Tier 1 and
Tier 2A testing should be of the same order of magni-
tude as current TCLP testing. Reductions in costs are an-
ticipated as the  methods become commercialized and
data interpretation is automated.
                 CONCLUSIONS

  The proposed framework presents an approach to eval-
uate the leaching potential of wastes over a range of val-
ues for parameters that have a significant impact on con-
stituent leaching  (e.g., pH,  LS,  and waste form) and
considering the management scenario. This approach pre-
sents the potential to estimate leaching much  more ac-
curately (than many currently used leach tests), relative
to field leaching, when conditions for leach test data are
matched with field conditions. The greater accuracy of
the  proposed approach makes it a useful tool for exam-
ining waste and assessing the environmental soundness
of a range of waste management options as well  as for
assessing the effectiveness of proposed waste  treatment
methods. In  addition, the proposed framework provides
flexibility to the end user to select the extent  of testing
based on the level of information needed, and readily per-
mits the incorporation of new testing methods and release
models as they are developed for specific applications.
Appropriately used in waste regulatory programs, this ap-
proach could make those programs substantially more
cost-effective and protective of  the environment. The
flexibility of the proposed approach allows for develop-
ment of the framework to provide a greater degree of tai-
loring to site conditions, to account for the effects of other
waste leaching parameters critical to a particular site. Re-
liance on a tiered approach to testing can also make this
approach more  economical for  smaller waste  volumes
and therefore more broadly feasible.
ACKNOWLEDGEMENT AND DISCLAIMER

  Primary support for this research was provided by the
USEPA Northeast Hazardous Substances Research Cen-
ter and the USEPA Office of Solid Waste. Limited sup-
port also was provided by (1) The Consortium for Risk
Evaluation  with  Stakeholder  Involvement  (CRESP)
through U.S.  Department of Energy Grants DE-FG26-
OONT 40938  and DE-FG02-OOER63022.AOOO, and (2)
EU DG Research funded projects. The authors gratefully
acknowledge  the  thoughtful feedback  from Mr.  Greg
Helms (USEPA), and Dr. Charles W. Powers (Institute
for Responsible Management) during the development of
this manuscript, and the technical support of Ms. Teresa
-------
INTEGRATED FRAMEWORK FOR EVALUATING LEACHING
                                                  177
Kosson during the development of the test methods. The
authors also gratefully acknowledge the thoughtful com-
ments and feedback of the anonymous reviewers and the
assistance of the Editor, Dr. D. Grasso, lead author of the
USEPA  Science Advisory Board  Review  (1999) for
which this paper is primarily in response. The view points
expressed in this paper are solely the responsibility of the
authors and do  not necessarily reflect the view or en-
dorsement of the USEPA.
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180                                                                                      KOSSONSTAL.

                                              APPENDIX

                     A.I. AV002.1 (AVAILABILITY AT PH 7.5 WITH EDTA)

1. Scope
1.1. This test method measures the maximum quantity, or mobile fraction of the total content, of inorganic con-
    stituents in a solid matrix that potentially can be released into solution. An extraction fluid of 50 mM  ethyl-
    enediamine-tetraacetic acid (EDTA) is used to chelate metals of interest in solution at near neutral pH during a
    single extraction.
1.2. This is a candidate screening protocol (Tier 1).
1.3. This test method is not intended for the release characterization of organic constituents.

2. Cited Protocols
2.1. ASTM (1980) "Standard Method for Water (Moisture) Content of Soil, Rock, and Soil-Aggregate Mixtures D
    2261-80," Philadelphia, PA: American Society for Testing and Materials.
2.2. pHOOl.O (pH Titration Pretest).
2.3. AW001.0  (Acid Washing of Laboratory Equipment).
2.4. PS001.1 (Particle Size Reduction).

3. Summary of the Test Method
  Constituent availability is determined by a single challenge of an aliquot of the solid matrix to dilute acid or base
in deionized (DI) water with a chelating agent (Garrabrants and Kosson, 2000). A solution of 50 mM ethylenedi-
amine-tetraacetic acid (EDTA) in DI water is  used to minimize liquid phase solubility limitations for cationic con-
stituents with very low solubility (i.e., Pb, Cu, Cd). For most materials, this test is conducted on material that has
been particle size <2 mm and a minimum sample mass of 8 g dry sample is used. (The particle size, sample mass,
and contact time shown here represent a typical base case scenario. Alternate sample masses and contact times are
required for materials where particle size reduction to <2 mm is either impractical or unnecessary  (see accompa-
nying text).  In all extractions, a liquid-to-solid (LS) ratio of 100 mL extractant/g dry sample and a contact time of
48 h are used  to reduce mass transfer rate limitations. Extracts are tumbled in  an end-over-end fashion at 28 ± 2
rpm at room temperature (20 ± 2°C). After the appropriate contact time, the leachate  pH value  of the extraction is
measured. The retained extract is filtered through 0.45-^m pore size polypropylene filtration membranes, and the
analytical sample is saved for subsequent chemical analysis.
  The required end point pH value for the optimized extraction of cations and anions is 7.5 ± 0.5. The final spec-
ified pH value is obtained by addition of a predetermined equivalent of acid or base  prior to the beginning  of the
extraction. The amount of acid or  base  required to obtain the final end point pH value is specified by a titration
pretest of the material that follows the "pHOOl .0 (pH Titration Pretest)" protocol with the modifications that the titra-
tion solution is 50-mM EDTA solution rather than DI water. The required pH range for this pretest is limited to pH
values 5 through 8. Because "AV002.1 (availability at pH 7.5 with EDTA)" is a batch extraction procedure used for
materials that may be heterogeneous in acid neutralization capacity,  extractions at the limiting values of 7.0 and 8.0
are recommended in addition to the pH target  value extraction. The leachate with a pH value closest to 7.5 is saved
for chemical analysis while the others are discarded.

4. Significance and Use
  The results from this test are used to determine the maximum quantity, or the fraction of the total constituent con-
tent, of inorganic constituents in a  solid  matrix that potentially can be released from the solid material in the pres-
ence of a strong chelating agent such as  EDTA. The chelated availability, or mobile fraction, can be considered (1)
the thermodynamic driving force for mass transport through the solid material  or  (2) the potential long-term con-
stituent release. Also, a mass balance  based on the total constituent concentration provides the fraction of a con-
stituent that may be chemically bound,  or immobile in geologically stable mineral phases. The availability  repre-
sents a potential for constituent release, not an actual release measurement. This procedure measures availability in
relation to the release of anions at an end point pH of 7.5 ±  0.5 and cations under enhanced liquid-phase solubility
due to complexation with the chelating agent.
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INTEGRATED FRAMEWORK FOR EVALUATING LEACHING                                       181

5. Apparatus
5.1. Extraction Vessel—a wide-mouth container, constructed of high-density polyethylene that does not preclude
    headspace (e.g., Nalgene #3120-9500 or equivalent). The vessel must have a leak-proof seal that can sustain the
    required end-over-end tumbling. The container must be of sufficient volume to accommodate both a minimum
    solid sample and a leachant volume based on a LS ratio of 100 mL extractant/g dry sample. If centrifugation is
    to be used for gross phase separation, the extraction vessel should be  capable of withstanding centrifugation at
    4000 rpm for a minimum of  10 min.
5.2. Extraction Apparatus—rotary tumbler capable of rotating the extraction vessels in an end-over-end fashion at
    constant speed of 28 ± 2 rpm (e.g., Analytical Testing, Werrington, PA, or equivalent).
5.3. Filtration Apparatus—pressure or vacuum filtering apparatus (e.g., Nalgene #300-4000, or equivalent).
5.4. Filtration Membranes—0.45-^m  pore size polypropylene filtration membrane (e.g., Gelman Sciences GH
    Polypro #66548, Fisher Scientific, or equivalent).
5.5. pH Meter—standard, two point calibration pH meter (e.g., Accumet 20, Fisher Scientific, or equivalent).
5.6. Adjustable Pipetter—Oxford Benchmate series or equivalent with disposable  tips (delivery range will depend
    on material neutralization capacity and acid  strength).
5.7. Centrifuge (optional)—e.g., RC5C, Sorvall Instruments, Wilmington, DE, or equivalent.

6. Reagents and Materials
6.1. Reagent-Grade Water—deionized (DI) water must be used as the major extractant in this procedure. DI water
    with a resistivity of 18.2 MH can be provided by commercially available water deionization systems (e.g., Milli-
    Q Plus, Millipore Corp., Bedford,  MA, or equivalent).
6.2. 50 mM EDTA Solution—prepared by dissolving 18.61 g of disodium ethylenediamine-tetraacetate dihydrate—
    CioHi4N2O8Na2'2H2O (Sigma Chemical, St. Louis, MO, or equivalent) in  1 L of DI water.
6.3. 2 N Nitric Acid Solution—prepared by diluting Tracemetal Grade Nitric Acid (Fisher Scientific or equivalent)
    with deionized water.
6.4. 1 N Potassium Hydroxide Solution—reagent Grade (Fisher Scientific  or equivalent).

7. Acid Washing Procedure
  Because  the concentrations of  inorganic constituents in leachates may be very low (i.e., <10 /ug/L), all labora-
tory equipment that comes in contact with the material, the extraction fluid, or the leachant must be rinsed with 10%
nitric acid followed by three rinses with DI water to remove residual inorganic deposits following "AW001.0 (Acid
Washing of Laboratory Equipment)."

8. Initial Sample Preparation
8.1. Particle Size  Reduction—depending on the  nature of the material, a sufficient mass  of the material should be
    particle size reduced to <2 mm using  "PS001.1 (Particle Size Reduction)" protocol.
8.2. Solids  Content Determination—it  is necessary to know the solids content  of the material being tested  so that
    appropriate adjustments can be made to conduct the test under the specified LS ratio. Prior to the initiation of
    the test, a moisture content determination of the "as-received" material must be conducted using ASTM Method
    D 2261-80, "Standard Method for Laboratory Determination of Water  (Moisture) Content of Soil, Rock, and
    Soil-Aggregate Mixtures." The solids content is calculated as the  mass of the dried sample divided by the mass
    of "as received"  material as in  the following equation:

                                               SC = —d-a                                          (Al-1)
                                                     A*rec
where SC is the solids content (g dry/g); M^ly is the dry sample mass (g  dry),  and Mrec  is the mass of the  "as re-
ceived" material (g).

9. AV002.1 Procedure
  The AV002.1 protocol may  be conducted only after the required equivalents of acid or base  to reach the three
specified extraction pH values are determined. The three extraction pH values should include the pH target value

                                                              ENVIRON ENG SCI, VOL. 19, NO. 3, 2002
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182                                                                                      KOSSONSTAL.

Table Al-1.  Example schedule of acid addition and 50-mM EDTA makeup for a dry equivalent sample mass of 8 g dry and
a dry basis moisture content of 0.1 mL/g dry for the "AV002.1 (Availability at pH 7.5 with EDTA)" protocol.


Extract no.
1 — limit
2 — target
3— limit
End point
solution
pH
7.0
7.5
8.0
Equivalents of
acid to add
(mEq/g dry)
1.05
0.93
0.63
Volume of 2 N
HNO3
(mL)
4.20
3.48
2.52
Volume of
moisture in
sample (mL)
0.8
0.8
0.8
Volume of 50
mM EDTA
makeup (mL)
795.00
795.72
796.68
(i.e., 7.5) plus the two-pH limiting values (i.e., 7.0 and 8.0). Additionally, the volume of 50-mM EDTA solution re-
quired to obtain a total LS ratio of 100 mL/g dry material should be calculated. Table Al-1 shows an example sched-
ule of HNC>3 additions following the pHOOl.O protocol for a dry equivalent sample mass of 8 g (<2 mm particle
size) and a dry-basis moisture content of 10% (i.e., 0.1 mL/g dry)

 9.1. Place the minimum dry equivalent sample mass (i.e., 8 g dry) into each of three high-density polyethylene bot-
     tles. Label each bottle with one of the above target pH values. The required equivalent mass of "as-received"
     material can be calculated following Equation (Al-4) if the solids content is known.

                                               Mrec = ^f                                         (Al-4)

     where Mrec is the the mass of the  "as received" material (g), M^Ty is the dry equivalent sample mass (i.e., 8 g
     dry for particle size <2 mm (g dry), and SC is the solids content of the material (g  dry/g).
 9.2. Add the appropriate makeup volume of 50-mM EDTA solution to each bottle as specified in a schedule of acid
     and base additions (e.g., Table Al-1).
 9.3. Add the appropriate volume of 2  N HNOs or 1  N KOH required to achieve the end point pH values to each
     bottle with an automatic pipetter.  Volumes of acid or base are specified by the predetermined schedule (e.g.,
     Table Al-1).
 9.4. Tighten the leak-proof lid for each bottle and tumble the three extracts in an end-over-end fashion at a speed
     of 28 ± 2 rpm at room temperature (20 ± 2°C).
 9.5. At the end of the equilibration period, remove the extraction vessels from the rotary tumbler.
 9.6. Clarify the leachates by allowing the bottles to stand for 15 min. Alternately, centrifuge the bottles at 4000 ±
      100 rpm for 10 ± 2 minutes.
 9.7. Decant a minimum volume of clear, unpreserved supernatant from each bottle into suitable vessel to measure
     final solution pH.
 9.8. Save the leachate with a  pH value that is both within the target pH range (i.e., 7.5 ± 0.5) and closest  to the
     target pH value (i.e., 7.5). The other extracts are discarded.
 9.9. Separate the solid and liquid phases of the saved extract by vacuum filtration through a 0.45-^m pore size
     polypropylene filtration membrane. The  filtration apparatus may be exchanged for a clean apparatus as often
     as necessary until all liquid has been filtered.
9.10. Collect, preserve, and store the amount of leachate required for chemical analysis.

10. AV002.1 Interpretation
  After chemical analysis, the chelated availability can be determined for  each "constituent of potential concern"
(COPC). This availability can be calculated on a dry sample mass basis by multiplying the constituent  concentra-
tion in the leachate by the test-specific LS ratio as shown in Equation (Al-5).

                                                            LS                                    (Al-5)
where AVL^DiA is the constituent availability using 50-mM EDTA (mg/kg dry), CEDTA is the constituent concen-
tration using 50 mM EDTA (mg/L), and LS is the test liquid to solid ratio (i.e., 100) (L/kg).
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INTEGRATED FRAMEWORK FOR EVALUATING LEACHING                                       183

11. References
GARRABRANTS, A.C., and KOSSON, D.S. (2000). Use of a chelating agent to determine the metal availability
for leaching from soils and wastes. Waste Manage. Res. 20(2-3), 155-165.
    A.2. SR002.1 (ALKALINITY, SOLUBILITY AND RELEASE AS A FUNCTION OF PH)

1. Scope
1.1. This test method provides the acid/base titration buffering capacity of the tested material and the liquid-solid
    partitioning equilibrium of the "constituents of potential concern" (COPC) as a function of pH at a liquid-to-
    solid (LS) ratio of 10-mL extractant/g dry sample.
1.2. This is a characterization protocol (Tier 2b) designed to obtain detailed leachability information.
1.3. This test method is not intended for the determination of the solubility profile of organic constituents.

2. Cited Protocols
2.1. ASTM (1980) "Standard Method for Water (Moisture) Content of Soil, Rock, and Soil-Aggregate Mixtures D
    2261-80," Philadelphia, PA: American Society for Testing and Materials.
2.2. pHOOl.O (pH Titration Pretest).
2.3. AW001.0 (Acid Washing of Laboratory Equipment).
2.4. PS001.1  (Particle Size Reduction).

3. Summary of the Test Method
Based on the information obtained in the "pHOOl.O (pH Titration Pretest)" protocol,  an acid or base addition sched-
ule is formulated for 11 extracts with final solution pH values between 3 and 12, via addition of HNOa or KOH ali-
quots. The exact schedule is adjusted based on the nature of the material; however, the range of pH values must in-
clude the natural pH of the matrix, which may extend the pH  domain (e.g., for very alkaline or acidic materials).
(Natural pH is defined as the pH,  which is obtained when the  designated amount of material is contacted with DI
water for the designated period of time.) Depending on the natural pH and buffering capacity of the material being
tested, HNO3, and/or KOH may be required to achieve the target pH values. Additionally, if potassium is a COPC,
NaOH may be substituted for KOH in this protocol.
  Using the schedule, the equivalents of acid or base are added to a  combination of deionized (DI) water and the
particle size reduced material. The material is particle size reduced to <2 mm, and a sample size of 40 g dry sam-
ple is used. [The particle size, sample mass, and contact time shown here represent a typical base case scenario. Al-
ternate sample masses and contact times are required for materials where particle size reduction to <2 mm is either
impractical or unnecessary (see accompanying test).] The final liquid-to-solid (LS) ratio is 10 mL extractant/g dry
sample, which includes DI water, the added acid or base, and the amount of moisture that is inherent to the waste
matrix as determined by moisture content analysis. The 11 extractions are tumbled in an end-over-end fashion at
28 ± 2 rpm for a  contact time  of 48 h. Following gross  separation  of the solid and liquid phases by centrifugation
or settling, leachate pH measurements are taken and the phases are separated by vacuum filtration through 0.45-^m
polypropylene filtration membranes. Analytical samples  of the  leachates are collected and preserved as appropriate
for chemical analysis.

4. Significance and Use
The SR002.1 protocol can be used (1) to create a material-specific titration curve  of the acid or base neutralization
capacity of the material in contact with varying equivalents of acid or base at a liquid-to-solid ratio of 10 mL/g dry,
and (2) to characterize the liquid-solid partitioning equilibrium behavior of COPCs as a function of pH between the
pH values of 3 and 12 at a liquid to solid ratio of 10 mL/g dry.
  This protocol was modified from the Acid Neutralization Capacity Test (Environment Canada and Alberta Envi-
ronmental Center 1986) for use with  materials having  little acid neutralization capacity (e.g., soils or industrial
wastes). Size-reduced material and low LS ratio ensure that thermodynamic equilibrium between solid and liquid
                                                              ENVIRON ENG SCI, VOL. 19, NO. 3, 2002
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184                                                                                      KOSSONSTAL.

phases is obtained within the duration of the protocol for most low solubility constituents (e.g., Pb, As, Cu, Cd). In
the case of highly soluble species (e.g., Na, K, Cl), which do not reach saturation prior to complete solubilization of
the species from the solid phase, this protocol can be used to measure the release of the available fraction of the to-
tal constituent content.

5. Apparatus
5.1. Extraction Vessel—a wide-mouth container constructed of high-density polyethylene that does not preclude head-
    space (e.g., Nalgene #3140-0250 or equivalent). The vessel must have a leak-proof seal that can sustain the end-
    over-end tumbling and centrifugation required. The container must be of sufficient volume to accommodate both
    the solid sample and a leachant volume based on a LS ratio of 10 mL extractant/g dry sample. Because cen-
    trifugation may be required for gross phase separation, the extraction vessel should be capable of withstanding
    centrifugation at 4,000 rpm for a minimum of 10 min.
5.2. Extraction Apparatus—rotary tumbler capable of rotating the extraction vessels in an end-over-end fashion at a
    constant speed of 28 ± 2 rpm (e.g., Analytical Testing, Werrington, PA, or equivalent).
5.3. Filtration Apparatus—pressure  or vacuum filtering apparatus (e.g., Nalgene #300-4000 or equivalent).
5.4. Filtration Membranes—0.45-^m pore size polypropylene filtration membrane (e.g., Gelman Sciences GH
    Polypro #66548, Fisher Scientific, or equivalent).
5.5. pH Meter—standard, two point  calibration pH meter (e.g., Accumet 20, Fisher Scientific, or equivalent).
5.6. Adjustable Pipetter—Oxford Benchmate series or equivalent with  disposable tips (delivery range will depend
    on material neutralization capacity and  acid strength).
5.7. Centrifuge (recommended)—e.g., RC5C, Sorvall Instruments, Wilmington, DE, or equivalent.

6. Reagents  and Materials
6.1. Reagent Grade Water—deionized water must be used as the major extractant in this procedure. Deionized wa-
    ter with a resistivity of 18.2 MH can be provided by commercially available  water deionization systems (e.g.,
    Milli-Q Plus, Millipore Corp., Bedford, MA, or  equivalent).
6.2. 2 N Nitric Acid Solution—prepared by diluting Tracemetal Grade Nitric Acid (Fisher Scientific, or equivalent)
    with deionized water.
6.3. 1 N Potassium Hydroxide Solution—reagent Grade (Fisher Scientific, or equivalent).

7. Acid  Washing Procedure
  Because the concentrations of inorganic constituents in leachates may be very low (i.e.,  < 10 /ug/L), all laboratory
equipment that comes in contact with the material, the extraction fluid,  or the leachant must be rinsed with 10% ni-
tric acid followed by three rinses with DI water to remove residual inorganic deposits following "AW001.0 (Acid
Washing of Laboratory Equipment)."

8. Initial Sample Preparation
8.1. Particle Size Reduction—depending on the nature of the material, a sufficient mass  of the material should be
    particle size reduced to <2 mm using "PS001.1  (Particle Size Reduction)" protocol.
8.2. Solids Content Determination—it is necessary to know the solids  content of the material being tested  so that
    appropriate adjustments can be made to conduct the test under a specified LS ratio.  Prior to the initiation of the
    test, a moisture content determination of the "as-received" material must be conducted using ASTM Method D
    2261-80,  "Standard Method for Laboratory Determination of Water (Moisture) Content of Soil, Rock, and
    Soil-Aggregate Mixtures." The  solids content is  calculated as the mass of the dried sample divided by the mass
    of "as-received" material following Equation (A2-1).

                                               SC = —^                                         (A2-1)
                                                     Mrec
    where SC is the solids content (g dry/g), M^ly is the  dry sample mass (g dry), and Mrec is the mass of the "as-
    received" material (g).
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INTEGRATED FRAMEWORK FOR EVALUATING LEACHING
                                                               185
Table A2-1.  Example schedule for acid addition for 40 g dry equivalent mass samples and a moisture content (dry basis) of
0.1 mL/g dry for the "SR002.1 (Alkalinity, Solubility and Release as a Function of pH)" protocol.
Extract
no.
1
2
3
4
5
End point
solution pH
12.0
11.0
10.0
9.0
8.0
Equivalents of
acid to add
(mEq/g)
-1.10
-0.75
-0.58
-0.15
-0.09
Volume of 2 N
HNO3 or 1 N
KOH (ml)
44.0
30.0
23.2
6.0
3.6
Volume of
moisture in
sample (mL)
4.0
4.0
4.0
4.0
4.0
Volume of DI
water makeup
(mL)
352.0
366.0
372.8
390.0
392.4
                 Natural
0.00
0.0
4.0
396.0
7
8
9
10
11
6.0
5.0
4.0
3.0
2.0
0.08
0.12
0.90
1.80
3.10
1.6
2.4
18.0
36.0
62.0
4.0
4.0
4.0
4.0
4.0
394.4
393.6
378.0
360.0
334.0
9. SR002.1 Procedure
  The SR002.1 protocol may be conducted only after the equivalents of acid or base required to span the desired
pH range are determined from a material specific titration curve as generated by "pHOO 1.0 (pH Titration Pretest)"
or equivalent. Because the pretest provides information for acid and base additions at LS of 100 mL/g dry sample,
the pH response for the SR002.1 protocol at an LS ratio of 10 mL/g dry sample will be approximate. The variabil-
ity in end point pH, however, is consistent with the objective of this protocol (i.e., to measure constituent solubility
and release over a broad pH range with end points of approximately pH 3 and 12). Table A2-1 shows the example
schedule of acid or base additions and DI water make up volume for the SR002.1 protocol generated from the titra-
tion information shown in  Figure 1 using 40 dry g of sample with a moisture content (dry basis) of 0.1 mL/g dry.

9.1. Place  the minimum dry equivalent mass (i.e., 40 g dry sample) into each of eleven high-density polyethylene
    bottles. The equivalent mass of "as-received" material can be calculated if the solids content is known follow-
    ing Equation (A2-4).
               MLVL dry
          rec =	
                SC
                                                                                                   (A2-4)
    where Mrec is the mass of the "as-received" material (g), M^ly is the dry equivalent sample mass [i.e., 8 g dry
    for particle size <2 mm (g dry)], and SC is the solids content of the material (g dry/g).
9.2. Label each bottle with the extraction number or acid addition and add the volume of DI water specified in the
    schedule for LS ratio makeup (e.g., Table A2-1).
9.3. Add the appropriate volume of acid or base to each extraction using an adjustable pipetter. The required vol-
    ume of acid or base is specified in the schedule for acid addition (e.g., Table A2-1).
9.4. Tighten the leak-proof lid on each bottle and tumble all extracts in an end-over-end fashion at a speed of 28 ±
    2 rpm at room temperature (20 ± 2°C) for 48 h.
9.5 At the conclusion of the agitation period, remove the extraction vessels from the rotary tumbler and clarify the
   leachates by allowing the  bottles to stand for 15 min. Alternately, centrifuge the bottles at 4000 ± 100 rpm for
   10 ± 2 min.
9.6. Decant a minimum volume of clear, unpreserved supernatant from  each extraction to measure and record the
    solution pH.
9.7. For each extraction, separate the solid from the remaining liquid by vacuum filtration through a 0.45-^m pore
                                                               ENVIRON ENG SCI, VOL. 19, NO. 3, 2002
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186
KOSSON ET AL.
    size polypropylene filtration membrane. The filtration apparatus may be exchanged for a clean apparatus as of-
    ten as necessary until all liquid has been filtered.
9.8. Collect, preserve, and store the amount of leachate required for chemical analysis.

10. SR002.1 Interpretation
10.1. pH Titration Curve—the material response to acid or base addition at LS of 10 mL/g dry can be interpreted if
     a pH titration curve is  generated. Plot the pH of the sample analyzed as a function of the equivalents of acid
     or base added per dry gram of material. For materials where both acid and base were required, equivalents of
     base can be presented as opposite sign of acid equivalents (i.e., 5 mEq/g  of KOH would correspond to  — 5
     mEq/gofHN03).
10.2. "Liquid-SolidPartitioning " (LSP) Curve—after chemical analysis has been conducted, a constituent LSP curve
     can be generated for each constituent of concern. The constituent concentration in the liquid phase of each ex-
     tract is plotted as a function of solution pH. The curve indicates the equilibrium concentration of the constituent
     of interest at LS  of 10 mL/g  over a pH range. Additionally, the  constituent LSP behavior with pH is indica-
     tive of specific  constituents speciation in  the solid matrix. Figure A2-1 illustrates typical LSP curve behaviors
     for cationic, amphoteric, and  oxyanionic  constituents as a function of pH.

  The  shape of the LSP curve (i.e., general location of maxima/minima) is controlled by the equilibrium between
liquid phase constituent (e.g., Pb+2) and solid phase species [e.g., Pb(OH)2 or Pb3(PC>4)2) as a function of pH. Also,
leachate ionic strength and the presence of complexing (e.g., acetate or chloride ions) or coprecipitating (sulfate or
carbonate ions) agents in the leachant solution can influence the LSP curvature and magnitude (Kosson et al., 1996).
  At very low pH, the matrix often is broken  down by the aggressive leachant and the measured constituent solu-
bility approaches a limiting value (as shown in Fig. A2-1). Because much of the nonsilica-based matrix can be di-
gested  at pH values =2, the  corresponding release in this pH range  can represent either the release of the total con-
stituent content or  the release of  only an operationally defined "available fraction" of the total content. To correlate
the release in  this  pH range to total element analyses, a release-based curve can be developed by multiplying the
measured release concentration at each pH value by the LS ratio in L/kg.

11. References
KOSSON, D.S., VAN DER SLOOT, H.A., and EIGHMY, T.T. (1996). An approach for estimating of contaminant release dur-
  ing utilization and disposal of municipal waste combustion residues./. Hazard. Mater. 47, 43-75.
                                                          &
                                                    LcachatepH
    Figure A2-1.  LSP curves of cationic, amphoteric, oxyanionic, and highly soluble species from the SR002.1 protocol.
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INTEGRATED FRAMEWORK FOR EVALUATING LEACHING                                        187

         A.3. SR003.1 (SOLUBILITY AND RELEASE AS A FUNCTION OF LS RATIO)

1. Scope
1.1. This test method is used to determine the effect of low liquid-to-solid ratio on liquid-solid partitioning equilib-
    rium when the solution phase is controlled by the tested material. This is used to approximate initial pore wa-
    ter conditions and initial leachate compositions in many percolation scenarios (e.g., monofills). In this test, the
    pH and redox conditions are dictated by the sample matrix. The solubility as a function of liquid to solid (LS)
    ratio can be determined for all "constituents of potential concern" (COPCs) over a range of LS ratios from 10
    to 0.5 mL/g dry material.
1.2. This is a characterization protocol (Tier 2b) designed to obtain detailed leachability information.
1.3. This test method is not intended for the characterization of the release of organic constituents.

2. Cited Protocols
2.1. ASTM (1980) "Standard Method for Water (Moisture) Content of Soil, Rock, and Soil-Aggregate Mixtures D
    2261-80," Philadelphia, PA: American Society for Testing and Materials.
2.2. AW001.0 (Acid Washing of Laboratory Equipment).
2.3. PS001.1 (Particle Size Reduction).

3. Summary of the Test Method
  This protocol consists of five parallel batch extractions over a range of LS ratios (i.e., 10, 5, 2, 1, and 0.5 mL/g
dry material), using DI water as the extractant with minimum 40 g  dry sample aliquots of material that have been
particle size reduced to <2 mm. [The particle  size, sample masses, and contact time shown here represent a typical
base case scenario. Alternate sample masses and contact times are required for materials where particle size reduc-
tion to <2 mm is either impractical or unnecessary (see accompanying text).] Additional material may be required
at low LS ratio to provide leachate yield sufficient for analytical methods (Table A3-1). All extractions  are tumbled
in an end-over-end fashion at 28 ± 2 rpm at room temperature (20  ± 2°C) in leak-proof vessels for 48 h. Follow-
ing gross separation of the solid and liquid phases by centrifugation or settling, leachate pH and conductivity mea-
surements are taken. The bulk phases are separated by a combination of pressure and vacuum filtration using 0.45-
fjLm polypropylene filter membrane. In  all, five leachates are collected, and preserved as appropriate for chemical
analysis.

4. Significance and Use
  The SR003.1 protocol can be used to provide an estimate of constituent concentration as the extraction LS ratio
approaches the bulk porosity of the material. The solution filling the pores of the material (i.e., pore water) locally
approaches thermodynamic equilibrium with the different constituents of the material of concern. The resulting pore
water solution may be saturated with material constituents, which can result in deviations from ideal dilute solution
behavior and activity coefficients significantly different from unity. Estimation of the activity coefficient within the
pore water is necessary for accurate estimation of constituent concentration within the pore water and coupled mass
transfer rates for leaching. Thus, the use of decreasing LS ratio allows for experimentally approaching the compo-
sition of  the pore water solution of the  material of concern and determining the change in pH and species concen-
tration in comparison to that measured at an LS ratio  of 10 mL/g dry as  used in the "SR002.1  (Alkalinity, Solubil-
ity and Release as a Function of pH)" protocol.

5. Apparatus
5.1. Extraction Vessel—a wide-mouth container constructed of plastic, that does not preclude headspace (e.g., Nal-
    gene #3140-0250 or equivalent). The vessel must have a leak-proof seal that can sustain the end-over-end tum-

Table A3-1.   Minimum dry equivalent mass as a function of LS ratio recommended for the SR003.2 protocol.

LS 10 mL/g               LS 5 mL/g               LS 2 mL/g               LS 1 mL/g               LS 0.5 mL/g

40 g                        40 g                     50 g                   100 g                   200 g


                                                               ENVIRON ENG SCI, VOL. 19, NO. 3,  2002
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188                                                                                      KOSSONSTAL.

    bling and centrifugation required. The container must be of sufficient volume to accommodate both a minimum
    solid sample mass and a leachant volume based on a maximum LS ratio of 10-mL extractant/g dry sample. The
    extraction vessel should be capable of withstanding centrifugation at 4000 rpm for minimum of 10 min.
5.2. Extraction Apparatus—rotary tumbler capable of rotating the extraction vessels in an end-over-end fashion at
    constant speed of 28 ± 2  rpm (e.g., Analytical Testing, Werrington, PA, or equivalent).
5.3. Filtration Apparatus—filtering apparatus (e.g., Nalgene #300-4000, or equivalent) capable of pressure and vac-
    uum filtration.
5.4. Filtration Membranes—0.45-^m pore  size polypropylene filtration membrane (e.g.,  Gelman  Sciences GH
    Polypro #66548, Fisher Scientific, or equivalent).
5.5. pH Meter—standard, two point calibration pH meter (e.g., Accumet 20, Fisher Scientific, or equivalent).
5.6. Graduated Cylinder—determined by particle size and LS ratio, polymethylpentene (e.g., Nalgene #3663-0100,
    or equivalent) volume.
5.7. Centrifuge—e.g., RC5C, Sorvall  Instruments, Wilmington, DE, or equivalent.

6. Reagents and Materials
6.1. Reagent Grade Water—deionized water must be used as the major extractant in this procedure. Deionized wa-
    ter with a resistivity of 18.2 MH can be provided by commercially available water deionization  systems (e.g.,
    Milli-Q Plus, Millipore Corp., Bedford, MA, or equivalent).

7. Acid  Washing Procedure
  Because the concentrations of inorganic constituents in leachates may be very low (i.e.,  < 10 /ug/L), all laboratory
equipment that comes in contact with the material, the extraction fluid, or the leachant must be rinsed with 10% ni-
tric acid  followed by three rinses with DI water to remove residual inorganic deposits following AW001.0 (Acid
Washing of Laboratory Equipment).

8. Initial Sample Preparation
8.1. Particle Size Reduction—depending on the nature of the material, a sufficient mass  of the material should be
    particle size reduced to <2 mm using "PS001.1 (Particle Size Reduction)" protocol.
8.2. Solids Content Determination—it is necessary to know the solids content of the material being  tested so that
    appropriate adjustments can be made to conduct the test under a specified LS ratio. Prior to the initiation of the
    test,  a moisture content determination of the "as-received" material must be conducted using ASTM Method D
    2261-80, "Standard Method for  Laboratory Determination of Water (Moisture) Content  of Soil, Rock, and
    Soil-Aggregate Mixtures." The solids content is calculated as the mass of the dried sample divided by the mass
    of "as received" material following Equation (A3-1).

                                               SC =  —dj^                                          (A3-1)
                                                     -™rec
    where SC is the solids content (g dry/g), M^Ty is the dry sample mass [g dry], and Mrec is the mass of the "as-
    received" material (g).

9. SR003.1 Procedure
9.1. Place the minimum dry equivalent mass required for each LS ratio (Table A3-1) into each of five high-density
    polyethylene bottles. The equivalent mass of "as-received" material can  be  calculated if the solids content is
    known following Equation (A3-2).

                                                      M-^dry                                         / A o /-\\
                                                rec = —-^                                         (A3-2)
                                                      o C*
    where Mrec is the mass of the "as-received" material (g), M^ly is the dry equivalent sample mass (see Table A3-
    1) (g dry), and SC is the solids content  of the material (g dry/g).
9.2. Measure out the appropriate volume of DI water in a graduate cylinder for each of the following LS ratios—
    10, 5, 2, 1, and 0.5  mL/g dry equivalent mass. For a dry material, this volume will be the mass  of the aliquot
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INTEGRATED FRAMEWORK FOR EVALUATING LEACHING                                       189

    multiplied by the desired LS ratio. However, if the material has high moisture content (e.g., >5%), the volume
    of water contained in the sample should be subtracted from the volume of DI water to be added.
9.3. Add the DI water to the solid material and tighten the leak-proof lid.
9.4. Tighten the leak-proof lid on each bottle and tumble all extracts in an end-over-end fashion at a speed of 28 ±
    2 rpm at room temperature (20 ± 2°C) for 48 h.
9.5. Remove the extraction vessel  from the rotary tumbler at the conclusion of the agitation period.
9.6. Clarify the leachates by allowing the bottles to stand for 15 min. Alternately, centrifuge the bottles at 4000 ±
    100 rpm for 10 ± 2 minutes.
9.7. Decant a minimum volume of clear, unpreserved supernatant to measure the solution pH.
9.8. Separate the solid from the remaining liquid by a combination of pressure and vacuum filtration through a 0.45-
    ^im pore size polypropylene filtration membrane. A nonreactive gas (e.g., nitrogen or argon) should be used for
    pressure filtration. The  filtration apparatus may be exchanged for a clean apparatus as often as necessary until
    all liquid has been filtered.
9.9. Collect, preserve, and store the amount of leachate required for chemical analysis.

10. SR003.1 Interpretation
  The filtered extracts are analyzed for common ionic strength-contributing cations (i.e., sodium, potassium, cal-
cium) and any other constituents of interest. Conductivity, pH, and concentrations of constituents of concern as a
function of the liquid to solid ratio then are extrapolated to the liquid to solid ratio for the pore water within the ma-
trix. The liquid-to-solid ratio for the pore water is defined by the porosity of the matrix as:

                                                LS = ——                                          (A3-3)
                                                     Pdry
where LS is the liquid-to-solid ratio on a dry basis (mL/g dry), e is the porosity (cm3/cm3) estimated by measuring
the water absorption capacity of the matrix, and pdry is the density on a dry basis (g dry/cm3).
  The resulting concentrations of sodium, potassium, and hydroxide (i.e., pH) then are used to estimate the pore wa-
ter ionic  strength and activity coefficients.
          A.4. MT001.1 (MASS TRANSFER RATES IN MONOLITHIC MATERIALS)

1. Scope
1.1. This protocol assesses the release rate of "constituents of potential concern" (COPCs) from monolithic materi-
    als under mass transfer-controlled release conditions. These conditions occur when the mode of water contact
    with the solid material results in a flow around a structure with low permeability (e.g., cement treated wastes,
    capped granular fills, or compacted granular material).
1.2. This test method is not intended for the characterization of the release behavior of organic constituents.

2. Cited Protocols
2.1. ASTM (1980) "Standard Method for Water (Moisture) Content of Soil, Rock, and  Soil-Aggregate Mixtures D
    2261-80," Philadelphia, PA: American Society for Testing and Materials.
2.2. U.S. Army Corps of Engineers (1970) Engineering Manual. "Engineering and Design: Laboratory Soils Test-
    ing." EM 1110-2-1906, Washington, DC: Office of the Chief of Engineers.
2.3. AW001.0  (Acid Washing of Laboratory Equipment).

3. Summary of the Test Method
  The MT001.1 (Mass Transfer Rates in Monolithic Materials) protocol consists of tank leaching of continuously
water-saturated monolithic material with periodic renewal of the leaching solution.  The vessel and sample dimen-
sions are chosen so that the sample is fully immersed in the leaching solution. Cylinders of 2-cm minimum diame-
ter and 4-cm minimum height or 4-cm minimum cubes are contacted with DI water using a liquid to surface area
ratio of  10 mL of DI water for every cm2 of exposed solid surface area. Leaching solution is exchanged with fresh

                                                               ENVIRON ENG SCI, VOL.  19, NO. 3, 2002
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                                                      KOSSON ET AL.
DI water at predetermined cumulative times of 2, 5 and 8 h, 1, 2, 4, and 8 days. (This schedule may be extended
for additional extractions to provide more information about longer term release. The recommended schedule ex-
tension would be additional cumulative times 14 days, 21 days, 28 days, and every 4 weeks thereafter as desired.)
This schedule results in seven leachates with leaching intervals of 2, 3, 3, and 16 h, 1,2, and 4 days. At the com-
pletion of each contact period, the mass of the monolithic sample after being freely drained is recorded to  monitor
the amount of leachant absorbed into the solid matrix. The solution pH and  conductivity for the leachate is mea-
sured for each time interval. A leachate sample is prepared for chemical analysis by vacuum filtration through a
0.45-/jan pore size polypropylene filtration membrane and preservation as appropriate. Leachate concentrations are
plotted as a function of time along with the analytical detection limit and the  equilibrium concentration determined
from SR002.1 protocol at the extract pH for quality control. Cumulative release and flux as a function of  time for
each constituent of interest are plotted and used to estimate  mass transfer parameters (i.e., observed diffusivity).

4. Significance and  Use
  The objective of the MT001.1 protocol is to measure the  rate of COPC release from a monolithic material (e.g.,
solidified waste form or concrete matrix) under leaching conditions where the rate of mass transfer through the solid
phase controls constituent release. These conditions simulate mechanisms that occur when water (e.g., infiltration
or groundwater)  is  diverted to flow around a relatively impermeable material (e.g., solidified waste forms, road base
material, or capped granular fills). Results of this test are used to estimate intrinsic mass transfer parameters (e.g.,
observed diffusivities for COPCs) that are then used in conjunction with other testing results and assessment mod-
els to estimate release. Results of the MT001.1 protocol reflect both physical and chemical interactions within the
tested matrix, thus requiring additional test results for integrated assessment. Although the recommended method is
derivative of ANS  16.1 (ANS 1986), a leachability index is  not assumed nor  used as a decision criterion.

5. Apparatus
5.1. Extraction Vessel—a polypropylene container with an opening large enough so that the monolith can be easily
    removed and replaced. The container must also have an air-tight cover to minimize the exposure to carbon diox-
    ide, which can lead to carbonate formation in some highly alkaline matrices.
5.2. Monolith Holder—a mesh or structured holder constructed of an inert material to leachate constituents and acid
    washing liquids. At least 98% of the monolith surface area should be exposed to the leachant. Also, the holder
    must orient  the monolith in the center of the leaching vessel so that there is an approximately equal amount of
    leachant opposing every surface. A schematic of one such design for 10-cm diameter by 10-cm cylindrical sam-
    ples is presented in Figure A4-1. The dimension of this apparatus may be scaled as appropriate for sample size.
5.3. Filtration Apparatus—pressure or vacuum filtering apparatus (e.g., Nalgene #300-4000, or equivalent).
|K 	 fl5M|ldipa| ,^1
red IF ih -a-ar. tti-ud
ttllDttfl WOCfc


^^^
1Qcm*a. X 10on
Moiwinr.c Sanip^
h.

                              L
                            '-I.—:
.J
                                    Cn-m
                                                       U-Smm
                                                                      3 tm
                                                                                   mi ml* 'jlln
                                                                     11 or-
                                                           cm 4i.
Figure A4-1.  Design schematic for monolithic sample holder for MT001.1 (Mass Transfer in Monolithic Materials) protocol.
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INTEGRATED FRAMEWORK FOR EVALUATING LEACHING                                        191

5.4. Filtration Membranes—0.45-^m pore size polypropylene filtration membrane (e.g., Gelman Sciences GH
    Polypro, Fisher Scientific #66548, or equivalent).
5.5. pH Meter—standard, two point calibration pH meter (e.g., Accumet 20, Fisher Scientific, or equivalent).
5.6. Beaker—100-mL borosilicate glass (e.g., Fisher Brand, or equivalent).

6. Reagents and Materials
6.1 Reagent Grade Water—deionized water must be used as the major extractant in this procedure. Deionized wa-
   ter with  a resistivity of 18.2 MH can be provided by commercially available water deionization systems (e.g.,
   Milli-Q Plus, Millipore Corp., Bedford, MA, or equivalent).

7. Acid Washing Procedure
  Because the concentrations of inorganic constituents in leachates may be very low (i.e., <10 /ug/L), all labora-
tory equipment that comes in contact with the material, the extraction fluid, or the leachant must be rinsed with 10%
nitric acid followed by three rinses with DI water to remove residual inorganic deposits following AW001.0 (Acid
Washing of Laboratory Equipment).

8. Initial Sample Preparation
8.1. Preparation of Monolithic Samples—the surface area of the monolithic sample must be known to estimate con-
    stituent  release from the test sample in the  MT001.1 protocol. A representative sample of existing monolithic
    materials must be obtained by coring or some other nondestructive method. Cylinders of 2-cm minimum diam-
    eter and 4-cm minimum height or 4-cm minimum cubes are recommended.
8.2. Moisture Determination—it is necessary to know the moisture content of  the material being tested so that the
    release of constituents can be normalized to the dry equivalent mass of the monolith. This adds flexibility to the
    leaching characterization  approach by allowing for  comparison among treatment options of varying moisture
    contents. Because moisture content procedures tend to alter the chemical  and physical properties of the solid
    phase, an additional sample must be prepared in exactly the same manner as the test sample to use for moisture
    determination. Alternately, determination of moisture content may be taken using material samples segregated
    during gross particle size reduction following the "PS001.0 (Particle Size  Reduction to <300 /urn, <2 mm or
    <5 mm)" protocol. Moisture determination of the solid matrix must be conducted using ASTM Method D 2261-
    80, "Standard Method for Laboratory  Determination of Water (Moisture) Content of Soil, Rock, and Soil-Ag-
    gregate Mixtures."

9. MT001.0 Procedure
  This protocol is a dynamic tank leaching procedure with leachant exchanges at cumulative leaching times of 2, 5,
and 8 h, 1, 2, 4, and 8 days. This schedule results in seven leachates with leaching intervals of 2, 3, 3,  and 16 h, 1,
2, and 4 days. The leachant is DI water and the pH of each leachate is measured.
9.1. Specimen Measurements
    9.1.1.  Measure and record the dimensions (i.e., diameter and height for a cylinder; length, width, and depth for
           a parallelepiped) of the monolithic specimen for surface area calculation.
    9.1.2.  Measure and record the mass of the specimen. This value is monitored for each leachant exchange.
    9.1.3.  Place the specimen in the  monolith holder, if a holder is used.
    9.1.4.  Measure and record the mass or the specimen and holder, if applicable.
9.2. Leachant Exchange
    9.2.1.  Place the mesh (if a mesh is used instead or a holder), in a clean leaching vessel.
    9.2.2.  Fill the clean leaching vessel with the required volume of DI water using a liquid to  surface area ratio
           of 10 mL of DI water for  every cm2 of exposed solid surface area.
    9.2.3.  Gently place the specimen or the specimen and holder in the leaching vessel so that the leachant is evenly
           distributed around the specimen. Submersion should be gentle enough that the physical  integrity of the
           monolith is  maintained and wash-off is minimized.
    9.2.4.  Cover the leaching vessel  with the air-tight lid.

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192                                                                                       KOSSONSTAL.

    9.2.5.  By repeating Steps 9.2.1-9.2.2 at the end of the leaching interval, prepare a fresh leachantin anew leach-
           ing vessel.
    9.2.6.  Remove the specimen or the specimen and holder from the vessel. Drain the liquid from the surface of
           the specimen  into the leachate for approximately 20 s.
    9.2.7.  Measure and  record the mass of the specimen or the mass of the specimen and holder. The difference
           in mass between measurements is an indication of the potential sorption  of leachant by the matrix. In
           the case where a holder is used, moisture will condense on the holder as the leaching intervals increase
           in duration and sample sorption may not be evident.
    9.2.8.  Place the specimen or the specimen and holder into the clean leaching vessel of new leachant prepared
           in Step 9.2.2.
    9.2.9.  Cover the clean leaching vessel with the air-tight lid.
    9.2.10. Decant 25-50 mL  of leachate into a 100-mL beaker.
    9.2.11. Measure and  record the pH of the decanted leachate.
    9.2.12. Filter the remaining leachate through a 0.45-^m polypropylene membrane.
    9.2.13. Collect and preserved enough leachate for chemical analysis.
    9.2.14. Repeat the  leachate exchange procedure (Steps 9.2.1-9.2.14) until all seven leachants are collected.

10. MT001.0 Interpretation
10.1. Mass Transfer Coefficients—interpretation of the release of constituents using the "MT001.0 (Mass Transfer
     Rates in Monolithic  Materials)" protocol is illustrated using the bulk diffusion model. Other models that may also
     be used to determine mass transfer coefficients and tortuosity values include the Shrinking Unreacted Core model
     (Hinsenveld and Bishop, 1996) and the Coupled Dissolution-Diffusion model (Sanchez, 1996). These models in-
     corporate chemical release parameters into the model to better estimate release mechanisms and predictions.
       At the conclusion  of the MT001.0 protocol, the interval mass released is calculated for each leaching interval as:

                                                Mti =
                                                       A

     where Mtt is the mass released during leaching interval i (mg/m2), Q is the constituent concentration in inter-
     val i (mg/L), V{ is the leachant volume in interval i (L), and A is the specimen surface area exposed to the
     leachant (m2).
       An observed diffusivity of COPCs can be determined using the logarithm of the cumulative release plotted
     vs. the logarithm of time. In the case of a diffusion-control mechanism, this plot is expected to be a straight
     line with a slope of 0.5. An observed diffusivity can then be determined for each leaching interval where the
     slope is 0.5 ± 0.15 by (de Groot and van der Sloot, 1992):

                                             /          M'i           \2
                                                                                                    (A4-2)
                                             y 2 p CQ

     where D°bs is the observed diffusivity of the species of concern for leaching interval i (m2/s), Mti is the mass
     released during leaching interval i (mg/m2), f; is the contact time after leaching interval i (s), f,--i  is the con-
     tact time after leaching interval i — 1 (s), Q is the Initial leachable content (i.e., available release potential)
     (mg/kg), and p is the sample density (kg/m3).
       The overall observed diffusivity is then determined by taking the average of the interval observed diffusiv-
     ities.  Only those interval mass transfer coefficients corresponding to leaching intervals with slopes between
     0.35 and 0.65 are included in the overall average mass transfer coefficient (IAWG, 1997).

10.2. Matrix Tortuosity—tortuosity is a measure of the physical retention in the matrix and is a matrix-specific prop-
     erty. The matrix tortuosity reflects the extended path length of a diffusing ion in the pore structure of a matrix
     relative to a straight path through the matrix. Typically, the mass transfer release of noninteractive components,
     or tracers, is  measured and observed interval mass transfer coefficients are compared  to the tracer  molecular
     diffusivity in aqueous solutions as shown in Equation (A4-4).
                                                     rjmol
                                                 T = —r-                                           (A4-4)
                                                      obs                                           v     '
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INTEGRATED FRAMEWORK FOR EVALUATING LEACHING                                        193

     where T is the the matrix physical retention, or tortuosity ( —), Dm°l is the molecular diffusion coefficient in
     aqueous solution (m2/s), and Dobs is the observed diffusion coefficient in the matrix (m2/s).
        Sodium or chloride is normally selected as tracer elements under the assumption that these elements do not
     react with the matrix being evaluated. The matrix tortuosity should be calculated as the average of interval tor-
     tuosity values subject to the same interval slope criteria (0.35—0.65) pertaining to  mass transfer coefficients.

11. References
DE GROOT, G.J., and VAN DER SLOOT, H.A.  (1992). Determination of leaching characteristics of waste materials leading to
  environmental product certification. In: T.M. Gillam and C.C. Wiles, Eds., Solidification and Stabilization of Hazardous, Ra-
  dioactive, and Mixed  Wastes, 2nd Volume, ASTM STP 1123. Philadelphia, PA: American Society for Testing and Materials,
  pp. 149-170.
HINSENVELD, M., and BISHOP, P.L. (1996). Use of the shrinking core/exposure model to describe the teachability from ce-
  ment stabilized wastes. In T.M. Gilliam and C.C. Wiles, Eds., Stabilization and Solidification of Hazardous, Radioactive, and
  Mixed Wastes, 3rd Volume, ASTM STP 1240, Philadelphia, PA: American Society for Testing and Materials.
IAWG. (1997). Municipal Solid Waste Incinerator Residues. Amsterdam: Elsevier Science Publishers.
KOSSON, D.S., KOSSON, T.T., and VAN DER SLOOT, H. (1993). Evaluationof solidification/stabilization treatment processes
  for municipal waste combustion residues. EPA  Cooperative Agreement #CR 818178-01-0. Cincinnati, OH: U.S. Environmen-
  tal Protection Agency.
SANCHEZ, F. (1996). Etude de la lixiviation de milieux poreux con tenant des especes solubles: Application au cas des dechets
  solidifies par liants hydrauliques. Doctoral Thesis, Lyon, France: Institut National des Sciences Appliquees de Lyon.


             A.5. MT002.1 (MASS TRANSFER RATE IN  GRANULAR MATERIALS)

1. Scope
1.1. This protocol assesses the release rate of "constituents of potential concern" (COPCs) from compacted granu-
    lar matrices under mass transfer-controlled release conditions. These conditions occur when the mode of water
    contact with  the solid material results in a flow around a material structure (e.g., capped granular fills,  or low
    permeability  compacted granular material).
1.2. This test method  is not intended for the  characterization of the release behavior of organic constituents.

2. Cited Protocols
2.1. ASTM (1978) "D 1557. Standard Method for Moisture-Density Relations of Soils and Soil-Aggregate Mixtures
    Using  10 Ib.  Rammer and 18 in. Drop," Philadelphia, PA: American Society for Testing and Materials.
2.2. ASTM (1980) "D 2261-80. Standard Method for Water (Moisture) Content of Soil, Rock, and Soil-Aggregate
    Mixtures," Philadelphia, PA: American Society for Testing and Materials.
2.4. U.S. Army Corps of Engineers (1970) Engineering  Manual. "Engineering and Design: Laboratory Soils Test-
    ing." EM 1110-2-1906, Washington, DC: Office of the Chief of Engineers
2.5. AW001.0 (Acid Washing of Laboratory Equipment).

3. Summary of the Test Method
  The MT002.0 (Mass Transfer Rates in Compacted Granular Materials) consists of tank leaching of continuously
water-saturated compacted granular material with intermittent renewal of the leaching solution. This test is used when
a granular material is  expected to behave as a monolith  because of compaction during field placement. An uncon-
solidated or granular material, size-reduced to <2 mm is compacted into molds using modified Proctor Compactive
Effort (ASTM Method D 1557 "Standard Method for Moisture-Density Relations of Soils and Soil-Aggregate Mix-
ture using 10 Ib. Rammer and 18 in. Drop"). (The particle size reduction and cylindrical matrix diameter specified
represents a base  case scenario. Change in the particle size specification requires alteration of the compacted sam-
ple diameter for a cylindrical matrix such that the matrix diameter is 10 times the maximum particle diameter.) A
10-cm diameter cylindrical mold is used, and the sample is packed to a depth of 10 cm. The mold and sample are
immersed in DI such  that only the surface area of the top face of the sample contacted the leaching medium. The

                                                               ENVIRON  ENG SCI, VOL. 19, NO. 3, 2002
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194
KOSSON ET AL.
leachant is refreshed with an equal volume of DI using a liquid to surface area ratio of 10 mL/cm2 (i.e., LS of 10
cm) at cumulative times of 2, 5, and 8 h, 1,2, 4, and 8 days. (This schedule may be extended for additional extrac-
tions to provide more information about longer term release. The recommended schedule extension would be addi-
tional cumulative times  14 days, 21 days, 28 days, and every 4 weeks thereafter as desired.) This schedule results
in seven leachates with leaching intervals of 2, 3,  3, and 16 hours, 1, 2, and 4 days. The  solution pH and conduc-
tivity for the leachate is measured for each time interval. A leachate sample is prepared  for chemical analysis by
vacuum filtration through a 0.45-^m pore size polypropylene filtration membrane and preservation as appropriate.
Leachate concentrations are plotted as a function of time along with the analytical detection limit and the  equilib-
rium concentration determined from SR002.1 protocol at the extract pH for purposes of quality control. Cumulative
release and flux as a function of time for each constituent of interest are plotted and used  to estimate mass  transfer
parameters (i.e., observed diffusivity).

4. Significance and Use
   The objective of the MT002.1 protocol is to measure the rate of COPC release from compacted granular materi-
als under leaching conditions where the rate of mass transfer through the solid phase can control constituent release.
These conditions simulate mechanisms that occur when water (e.g., infiltration or groundwater)  is diverted to flow
around a relatively impermeable material (e.g., compacted granular fills). Results of this test are used to estimate in-
trinsic mass  transfer parameters (e.g., observed diffusivities for COPCs) that are then used  in conjunction with other
testing results and assessment models to estimate release.

5. Apparatus
5.1. Extraction Vessel—a polypropylene container with an opening large enough so that the monolith can be easily
    removed and replaced (e.g., Cole-Farmer #AP-06083-15 or equivalent). The container must also have an air-
    tight cover to minimize the exposure to carbon dioxide, which can lead to carbonate formation in some highly
    alkaline matrices.
5.2. Specimen Mold—a 10-cm diameter by 10-cm high cylindrical mold constructed of an inert material to leachate
    constituents and acid washing liquids (e.g., MA Industries, Inc., Peachtree City, GA, or equivalent). It must be
    constructed so that the exposed surface area of the test specimen is only one circular face of the mold. If nec-
    essary, 3-mm diameter drain holes may be cut  into the mold to aid in drainage of leachate from the mold. These
    holes should be  placed at least 10 cm above the  bottom of the mold. A schematic of one such  design is pre-
    sented in Figure A5-1.
5.3. Filtration Apparatus—pressure or vacuum filtering apparatus (e.g., Nalgene #300-4000 or equivalent).
5.4. Filtration Membranes—0.45-^m pore size polypropylene filtration membrane (e.g.,  Gelman  Sciences GH
    Polypro #66548, Fisher Scientific,  or equivalent).
5.5. pH Meter—standard, two point calibration pH meter (e.g., Accumet 20, Fisher Scientific, or equivalent).
5.6. Beaker—100 mL, borosilicate glass (e.g., Fisherbrand or equivalent).
                                    Dffllns9*j^'
                                    Hates   *
  Figure A5-1.  Design schematic for compacted sample mold for MT002.1 (Mass Transfer in Granular Materials) protocol.
-------
INTEGRATED FRAMEWORK FOR EVALUATING LEACHING                                       195

6. Reagents and Materials
6.1. Reagent Grade Water—deionized water must be used as the major extractant in this procedure. Deionized wa-
    ter with a resistivity of 18.2 MH can be provided by commercially available water deionization systems (e.g.,
    Milli-Q Plus, Millipore Corp., Bedford, MA, or equivalent).

7. Acid Washing Procedure
  Because the concentrations of inorganic constituents in leachates may be very low (i.e.,  <10 /ug/L), all labora-
tory equipment that comes in contact with the material, the extraction fluid, or the leachant must be rinsed with 10%
nitric acid followed by three rinses with DI water to remove residual inorganic deposits following "AW001.0 (Acid
Washing of Laboratory Equipment)."

8. Initial Sample Preparation
8.1. Optimum Moisture Content—optimum moisture content refers to the amount of moisture [fractional mass of
    water (g water/g dry material)] in the granular sample that is present at the optimum packing density (g dry ma-
    terial/cm3). This density is defined and the determination described in ASTM Method D 1557 "Standard Method
    for Moisture-Density Relations of Soils and Soil-Aggregate Mixtures Using 10 Ib. Rammer and 18 in. Drop."
    Modifications of this standard method are used as described below. The optimum moisture content of the ma-
    terial is determined using a preliminary test consisting of determining the dry density of the compacted mater-
    ial as a function of varying water contents. For this purpose, ca. 100 g of "as-received" material compacted in
    a 4.8-cm diameter mold are used. Three consecutive layers of materials are compacted 25 times using a 1 kg (2
    Ib) hammer and 45 cm (18 in) drop [modifications of the Proctor Compactive Effort  (ASTM D 1557 "Standard
    Method for Moisture-Density Relations of Soils and Soil-Aggregate Mixtures Using 10 Ib. Rammer and 18 in.
    Drop")]. The height and weight of the resulting compacted material is measured. A  known amount of water is
    then added and mixed with the same material sample and the same procedure as for the "as-received" material
    is followed. This step is repeated several times, and then a curve  of the dry density vs. the water  content, ex-
    pressed as a percent of the dry mass of material, is drawn. This curve is parabolic, with the maximum indicat-
    ing the optimum water content. It is important that the granular material be compacted at optimum moisture
    content to obtain packing densities that approximate field conditions.
8.2. Moisture Determination—prior to the initiation of the test, a moisture determination of the compacted granular
    matrix must be conducted using ASTM Method D  2261-80, "Standard Method for Laboratory Determination
    of Water (Moisture) Content of Soil, Rock, and Soil-Aggregate Mixtures." The moisture content determination
    also may be conducted on the unconsolidated bulk material used for  the compaction at the optimum moisture
    content.

9. MT002.1 Procedure
  The MT002.1 procedure is a dynamic tank leaching procedure with leachant exchanges at predetermined cumu-
lative times of 2, 5, and 8 h,  1,2, 4, and 8 days. This  schedule results  in seven leachates with leaching intervals of
2, 3, 3, and 16 h, 1, 2, and 4 days. The leachant is DI water and the pH of each leachate is recorded.

9.1. Preparation of Test Specimens
    9.1.1.  Measure and record the mass of a clean sample mold.
    9.1.2.  Using the method described below, compact the granular material  at its optimum moisture  content into
           the mold to a minimum height of 10 cm.  It is recommended that the compacted height be  slightly un-
           der the drainage holes for best drainage of the sample.
           Compaction technique: three consecutive layers of material are compacted 25 times using a 1 kg (2 Ib)
           hammer and 45-cm (18 in) drop [modifications of the Proctor Compactive Effort (ASTM D  1557 "Stan-
           dard Method for Moisture-Density Relations of Soils and Soil-Aggregate Mixtures Using  10 Ib. Ram-
           mer and 18 in. Drop")].
    9.1.3.  Measure and record  the mass of the sample mold and compacted sample. The  difference in this mea-
           surement and the empty mold mass (Step 9.1.1) is recorded as  the mass of granular material at optimum
           moisture. This value is monitored at the end of each leaching interval as an indication of  the mass of
           leachant that is sorbed into the matrix.

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196                                                                                       KOSSONSTAL.

    9.1.4.  Measure and record the height of the compacted matrix by measuring the outer height of the mold to
           the rim and subtracting the inside depth from the rim to the matrix.
9.2. Leachant Exchange
    9.2.1.  Fill a clean leaching vessel with  1000 mL of DI water.
    9.2.2.  At the beginning of the first leaching interval, there is no recovered leachate. The sample and mold are
           gently placed in the leaching vessel so that the leachant is evenly distributed around the sample. Sub-
           mersion should be gentle enough that the physical integrity of the monolith is maintained.
    9.2.3.  Cover the leaching vessel with the air-tight lid.
    9.2.4.  At the end of the leaching interval, prepare a fresh leachant in a new leaching vessel (Step 9.2.1).
    9.2.5.  Remove the sample and mold from the vessel. Drain the leachate from the surface of the specimen into
           the leachate for approximately 20 s.
    9.2.6.  Measure and record the mass of the sample and mold. The  difference in mass between interval mea-
           surements is an indication of the potential sorption of leachant by the matrix.
    9.2.7.  Place the sample and holder into the clean leaching vessel of new leachant.
    9.2.8.  Cover the clean leaching vessel with the air-tight lid.
    9.2.9.  Decant 25-50 mL  of leachate into a 100-mL beaker.
    9.2.10. Measure and record the pH of the decanted leachate.
    9.2.11. Filter at least 500 mL of the remaining leachate through a 0.45-mm polypropylene membrane. After fil-
           tration, the remaining leachate is discarded.
    9.2.12. Collect and preserved enough leachate for chemical analysis.
    9.2.13. Repeat the leachate exchange procedure (Steps 9.2.1-9.2.12) until all seven leachants are collected.


10. MT002.1 Interpretation
10.1. Mass Transfer Coefficients — interpretation of the release of constituents using the MT002.0 (Mass  Transfer
     Rates in Granular Materials) protocol is illustrated using the bulk diffusion model. Other models that may also
     be used to determine mass transfer coefficients and tortuosity values include the Shrinking Unreacted Core
     model (Hinsenveld and Bishop, 1996)  and the Coupled Dissolution/Diffusion model (Sanchez, 1996). These
     models incorporate chemical release parameters into the model to better estimate release mechanisms and pre-
     dictions.
       At the conclusion of the MT001.0 protocol, the interval mass released is calculated for each leaching interval as:
                                                Mt =    L                                          (A5.1}
     where Mt{ is the mass released during leaching interval i (mg/m2); Q is the constituent concentration in inter-
     val i  (mg/L), V{ is the leachant volume in interval i (L), and A is the specimen surface area exposed to the
     leachant (m2).
       An observed diffusivity of COPCs can be determined using the logarithm of the cumulative release plotted
     vs.  the logarithm of time. In  the case of a diffusion-control mechanism, this plot is expected to be a straight
     line with a slope of 0.5. An observed diffusivity can then be determined for each leaching interval where the
     slope is 0.5 ± 0.15 by (de Groot and van der Sloot, 1992):
                                                   o-                                        (A5-2)
     where Z)°bs is the observed diffusivity of the species of concern for leaching interval i (m2/s), Mti is the mass
     released during leaching interval i (mg/m2), t{ is the contact time after leaching interval i (s),  t{ - i  is the con-
     tact time after leaching interval i — 1 (s), Q is the Initial leachable content (i.e., available release potential)
     (mg/kg), and p is the sample density (kg/m3).
       The overall observed diffusivity is then determined by taking the average of the interval observed diffusiv-
     ities.  Only those interval mass transfer coefficients corresponding to leaching intervals with slopes between
     0.35 and 0.65 are included in the overall average mass transfer coefficient (IAWG, 1997).

10.2. Matrix Tortuosity — tortuosity is a measure of the physical retention in the matrix and is a matrix-specific prop-
     erty. The matrix tortuosity reflects the extended path length of a diffusing ion in the pore structure of a matrix
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INTEGRATED FRAMEWORK FOR EVALUATING LEACHING                                         197

     relative to a straight path through the matrix. Typically, the mass transfer release of noninteractive compo-
     nents, or tracers, is measured and observed interval mass transfer coefficients are compared to the tracer mo-
     lecular diffusivity in aqueous solutions as shown in Equation (A4-4).
                                                      rjmol
                                                 T = —r-                                            (A5-3)
                                                      £,obs                                            ^     >

     where T is the the matrix physical retention, or tortuosity ( —), Z)mo1 is the molecular diffusion coefficient in
     aqueous solution (m2/s), and D°bs is the the observed diffusion coefficient in the matrix (m2/s).
        Sodium or chloride is normally selected as tracer elements under the assumption that these elements do not
     react with the matrix being evaluated. The matrix tortuosity should be calculated as the average of interval tor-
     tuosity values subject to the same interval slope criteria (0.35-0.65) pertaining to mass transfer coefficients.

11. References

DE FROOT, G.J., and VAN DER SLOOT, H.A. (1992). Determination of leaching characteristics of waste materials leading to
  environmental product certification. In: T.M. Giliam and C.C. Wiles, Eds., Solidification and Stabilization of Hazardous, Ra-
  dioactive, and Mixed Wastes,  2nd Volume, ASTM STP 1123. Philadelphia, PA: American Society for Testing and Materials,
  pp. 149-170.
HINESENVELD, M., and BISHOP, P.L. (1996). Use of the shrinking core/exposure model to describe the teachability from ce-
  ment stabilized wastes." In T.M. Gilliam and C.C. Wiles, Eds., Stabilization and Solidification of Hazardous, Radioactive, and
  Mixed Wastes, 3rd Volume, ASTM STP 1240, Philadelphia, PA: American Society for Testing and Materials.
IAWG. (1997). Municipal Solid  Waste Incinerator Residues. Amsterdam: Elsevier Science Publishers.
SANCHEZ, F. (1996). Etude de  la lixiviation de milieux poreux contenantdes especes solubles: Application au cas des dechets
  solidifies par liants hydrauliques. Doctoral Thesis, Lyon, France: Institut National des Sciences Appliquees de Lyon.
                             A.6. pHOOl.O (PH TITRATION PRETEST)

1. Scope
1.1. This protocol is used to generate a material-specific pH titration curve of a solid material at a liquid-solid (LS)
    ratio of 100 mL/g dry sample. This titration curve is used to formulate an acid and base addition schedule for
    the "SR002.1 (Alkalinity, Solubility and Release as a Function of pH)" protocol.
1.2. This protocol is not intended for determination of pH titration data for organic matrices.

2. Cited Protocols
2.1. ASTM (1980) "D 2261-80 Standard Method for Determination of Water (Moisture) Content of Rock, Soil and
    Soil-Aggregates mixtures," Philadelphia, PA: American Society for Testing and Materials.
2.2. SR002.1 (Alkalinity, Solubility and Release as a Function of pH).
2.3. AW001.0 (Acid Washing for Laboratory Equipment).
2.4. PS001.1 (Particle Size Reduction).

3. Summary of the Method
  This protocol is used to obtain a material-specific titration curve between the pH values of 2 and  12. From this
titration curve, the required equivalents of acid or base to obtain endpoint pH values are determined for addition to
DI water extractions in the "SR002.1 (Alkalinity, Solubility and Release as a Function of pH)"  protocol. All proce-
dures are conducted at room temperature (20 ± 2°C) and at a LS ratio of 100 mL/g dry sample  on material that has
been size reduced to <2 mm using "PS001.1 (Particle Size Reduction)"protocol. In the pHOOl.O protocol, a mini-
mum equivalent sample mass of 8 g dry sample is used. The natural pH of the appropriate sample mass of aliquot
of material in DI water at an LS ratio of 100 mL/g dry sample is measured in a borosilicate glass beaker using a pH
meter. (Natural pH is defined as the pH, which  is obtained when the designated amount of material is contacted with
DI water for the designated period of time.) The natural pH of the material is used to determine if acid (base) is re-
quired to lower (raise) the solution pH in order to cover the range from pH 3 to 12.

                                                                ENVIRON ENG  SCI, VOL. 19, NO. 3, 2002
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198                                                                                      KOSSONSTAL.

  Next, a series of 100- to 500-^L aliquots of acid are added to this beaker containing the minimum sample mass
(i.e., 8 g dry equivalent mass) and DI water at a LS ratio of 100 mL/g. Nitric acid is used to lower the solution pH.
The volume of acid added will depend on the buffering capacity of the material. For each addition, the solution pH
is measured after 20-30 min of stirring using a magnetic stirrer followed by 5 min of settling. The cumulative acid
addition and the solution pH are monitored for each addition until the desired acidic pH range is covered. The ali-
quot addition procedure is repeated on a new sample aliquot using 100- to 500-^L aliquots of base, if required, un-
til the entire pH range from values of 3 to 12 is covered. The use of potassium hydroxide or sodium hydroxide to
raise the solution pH should be based on consideration of the constituents of interest (i.e., if potassium is a con-
stituent of concern, NaOH must be used in the titration).
  From the data collected by addition of acid and/or base, a titration curve showing the pH response as a function
of the equivalents of acid or base added per dry  gram of sample is generated. Equivalents of base are presented as
negative equivalents of acid  (i.e., 1 mEq/g dry KOH equals  — 1 mEq/g dry HNOa).  A schedule  of volumetric acid
or base additions and extraction media makeup volumes is created for the SR002.1 (Alkalinity,  Solubility and Re-
lease as a Function of pH) protocol.

4. Significance and Use
  Because the release of inorganic constituents is often controlled by liquid phase pH, the end  point pH (i.e., the
pH of the leachate after the desired contact time) is a critical parameter, which must be controlled, in many leach-
ing protocols. The final pH of the liquid phase is a result of the neutralization,  or titration, of the alkalinity in the
material by an acid or a base. In batch extraction procedures designed to challenge the material  at specific pH tar-
get values (e.g., SR002.1 protocol), leachate pH may be controlled by the addition of predetermined  equivalents of
acid  or base according to the acid/base addition schedule and material-specific titration curve as provided by pHOO 1.0
(pH Titration Pretest).

5. Apparatus
5.1. Beaker—400 mL borosilicate glass (e.g., Fisher Brand, or equivalent).
5.2. Magnetic Stirring Bar—25 mm X 9.5 mm dia. Teflon coated (e.g., Fisherbrand #09-311-9,  or equivalent).
5.3. Magnetic Stirrer—e.g., Barnstead/Thermolyne S46725,  or equivalent.
5.6. Adjustable Pipetter—100-1,000 fjiL Oxford Benchmate, or equivalent, with disposable tips.

6. Reagents
6.1. Reagent Grade Water—DI water must be used as the major extractant in this procedure. DI water with a re-
    sistivity of 18.2 MH can be provided by commercially available water deionization systems (e.g., Milli-Q Plus,
    Millipore Corp., Bedford, MA, or equivalent).
6.2. 2 N Nitric Acid Solution—prepared by diluting Tracemetal Grade Nitric Acid (e.g., Fisher Scientific, or equiv-
    alent) with deionized water.
6.3. 1 N Potassium Hydroxide Solution—Reagent grade (e.g., Fisher Scientific, or equivalent).

7. Acid Washing Procedure
  Because the concentrations of inorganic constituents in leachates may be very low  (i.e., <10 /u.g/L), all labora-
tory equipment that comes in contact with the material, the extraction fluid, or the leachant must be rinsed with 10%
nitric acid followed by  three rinses with DI water to remove residual inorganic deposits following AW001.0 (Acid
Washing of Laboratory Equipment).

8. pHOOl.O Procedure
  The pHOOl.O protocol consists of three sections used to (1) measure the natural pH of a size reduced material in
DI water at a LS ratio of 100 mL/g dry sample,  (2) determine the pH titration behavior of the material to addition
of 2 N nitric acid or 1 N potassium hydroxide (NaOH optional), and (3) generate a schedule of acid and/or base ad-
ditions to achieve desired pH endpoints for use in the RU-SR002.1 protocol. A detailed procedure for each part of
the pretest follows.
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INTEGRATED FRAMEWORK FOR EVALUATING LEACHING                                       199

8.1. Natural pH of Solid Materials
8.1.1. Place the minimum dry equivalent mass (i.e., 8 g dry sample) into an appropriate beaker. The equivalent mass
      of "as-received" material can be calculated if the solids content is known following Equation (A6-1).
      where Mrec is the mass of the "as-received" material (g), Mdry is the dry equivalent sample mass [i.e., 8 g dry
      sample) (g dry)], and SC is the solids content of the material (g dry/g).
8.1.2. Using a graduated cylinder, measure out the appropriate volume of DI water based on a LS of 100 mL/g dry
      sample and add it to the beaker. Also, add a magnetic stirring bar to the beaker.
8.1.3. Agitate the slurry with a magnetic stirrer at medium speed for 5 min.
8.1.5. Make three pH measurements reading within 30 to 60 sec after the transfer and record the average.
8.1.6. Based on the mean natural pH value, determine if acid, base, or a combination of the two is required to cover
      the range of pH from 2 to 12. For example, if the material has a natural pH of 12.4  (e.g., a material treated
      by solidification/stabilization), then only acid would be needed. However, if a soil with a natural pH of 6.7 is
      to be tested, both reagents are required. Acid is used to lower the solution pH and base is used to raise the
      solution pH.

8.2. pH Titration
8.2. 1. To the slurry formed in Section 8.1, add a minimum aliquot of 100 /uL of 2 N nitric acid and mix for a min-
      imum of 20 min at medium speed using a magnetic stirrer. In the case where only base is required to raise
      the solution pH, follow Steps 8.2.1 through 8.2.3 substituting "base" for "acid."
8.2.2. Allow the suspension to settle for 5 min and perform a pH measurement of the solution.
8.2.3. Record the cumulative volume of acid and the corresponding solution pH.
8.2.4. Repeat the process (Steps 8.2.1 and 8.2.3) using 100-^L increment additions of the 2 N acid, recording each
      addition and the subsequent pH measurement until the appropriate pH range is obtained. If it is anticipated
      that the material has a high amount of acid neutralization capacity, larger aliquots (e.g., 250 /uL) may be added
      as long as the pH shift after completed mixing is less than three pH units.
8.2.5. If necessary, repeat Section  8.1 and Steps 8.2.1 through 8.2.4 using 1  N KOH solution to obtain a required
      pH range (typically between pH values of approximately 2 and 12).

9. Data Interpretation
  The data from the pHOOl.O protocol must be analyzed in terms of the  solution pH resulting from the cumulative
addition of equivalents of acid or base normalized for a gram  of dry sample. The following example data (Table
A6-1) which may result from this pretest using 2 N HNOa and 1 N KOH for a material with  near-neutral natural
pH and medium buffering capacity is used for illustrative purposes only. Equivalents and volumes of base are pre-
sented as negative values of acid (i.e., 1 mEq of base equals — 1 mEq of acid and 1 mL of base equals — 1 mL  of
acid). If the natural pH of the material is near or above 12.0, the pretest would result in data determined only by ad-
dition of HNO3.
  Using the solution pH response to cumulative acid and base addition, a material-specific titration curve similar to
Fig. A6-1  can be generated for an LS ratio of 100 mL/g dry sample. Extrapolation of this titration curve to achieve
target pH endpoints with other LS  ratios (e.g., in SR002.1 protocol) will  result in an approximate pH response.

9.1. SR002.1 Protocol Schedule
  If a material-specific titration curve is not available, the "pHOOl.O (pH Titration Pretest)" protocol must be con-
ducted to determine the approximate equivalents of acid or base needed  to achieve final pH end points for extrac-
tions ranging from pH 3 to  pH 12. The required equivalents of acid or base  are  determined by creating a titration
curve for the material, between these target pH values, and reading the equivalents from the curve that correspond
to the target pH values. The pH response to acid and base additions as determined by this method will be approxi-
mate due to the large difference in  LS ratio (i.e., LS of 100 mL/g dry  for pHOOl.O and LS of 10 mL/g dry for
SR002.1).

                                                              ENVIRON ENG SCI,  VOL.  19, NO.  3, 2002
-------
200
                                        KOSSON ET AL.
                      Table A6-1.  Example pH 001.0 (pH Titration Pretest) results for a sample
                      mass of 8 g dry sample.
                      Volume of 2 NUNO3 or
                      1 N KOH Added (^L)
Equivalents of acid
 added [mEq/g]a
Solution pH
-6,400
-4,800
-4,000
-3,200
-2,400
-1,600
-800
0
400
1,000
1,600
2,000
3,000
4,000
6,000
-0.80
-0.60
-0.50
-0.40
-0.30
-0.20
-0.10
0.00
0.10
0.25
0.40
0.50
0.75
1.00
1.50
12.5
12.1
11.8
11.2
10.3
8.8
7.9
6.8
5.7
4.9
4.3
3.9
3.4
2.8
2.1
                        a2 N HNO3 = 2 mEq/mL for the 8-g sample; therefore, 1,000 /iL HNO3
                      = 1 mL  HNO3  = 0.25 mEq HNO3/g. Dry 1 N KOH =  1 mEq/mL for the
                      8-g sample; therefore, 1,000 /un KOH = 1 KOH = 0.125 mEq KOH/g.
9.1.1. Determine the equivalents of HNOs or KOH per dry gram of material required to reach all of the 11 desired
      end point pH values between 3 and 12 from the titration curve shown in Fig. A6-1. For each target pH, a hor-
      izontal line is drawn from the desired pH value to the titration curve. Then a vertical line is drawn from the
      titration curve to the equivalents of acid that are required to obtain this pH value. In this manner, the equiv-
      alents of acid or base required for all target end point pH values can be determined.
9.1.2. Convert the acid or base addition for each target pH from mEq/g dry sample to a volume addition of 2 N ni-
      tric acid  or 1  N base using Equation (A6-2).
14 •
12


4.
2 -
0^






-0.58
meq/g ,
V
\



' i
>
k
V^
°"^~-a_^
0.00
, meq/g
-2.0 -1.0 0.0 1.0
Acid Added [meq/g]

meq/g
2.0 3.0
Figure A6-1.  Example "pHOOl.O (pH Titration Pretest)" data showing schedule point selection for "SR002.1 (Alkalinity, Sol-
ubility and Release as a Function of pH)".
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INTEGRATED FRAMEWORK FOR EVALUATING LEACHING
                                                              201
Table A6-2.  Example schedule for acid addition for 40 g dry equivalent mass samples and a moisture content (dry basis) of
0.1 mL/g dry for the "SR002.1 (Alkalinity, Solubility and Release as a Function of pH)" protocol.
Extract
no.
1
2
3
4
5
End point
solution pH
12.0
11.0
10.0
9.0
8.0
Equivalents of
acid to add
(mEq/g)
-1.10
-0.75
-0.58
-0.15
-0.09
Volume of 2 N
HNO3 or 1 N
KOH (ml)
44.0
30.0
23.2
6.0
3.6
Volume of
moisture in
sample (mL)
4.0
4.0
4.0
4.0
4.0
Volume of DI
water makeup
(mL)
352.0
366.0
372.8
390.0
392.4
                Natural
0.00
0.0
4.0
396.0
7
8
9
10
11
6.0
5.0
4.0
3.0
2.0
0.08
0.12
0.90
1.80
3.10
1.6
2.4
18.0
36.0
62.0
4.0
4.0
4.0
4.0
4.0
394.4
393.6
378.0
360.0
334.0
                                            va/b =
           _ Aeq-Mdrv
               Na/b
                                       (A6-2)
      where Va/h is the volume of acid or base to be added (mL), Aeq is the amount of acid or base expressed in
      equivalents (mEq/g dry), Mdry is the dry equivalent sample mass (i.e., 8) (g dry), and NO/I, is the normality of
      the acid (i.e., 2) or base (i.e., 1) (mEq/mL).
9.1.3. Calculate the volume of makeup DI water required to provide an LS of 10 mL of extractant per gram of dry
      solid sample. If the material has high moisture content, the volume of water contained within the sample should
      be subtracted from the total required leachant. For example, 40  g dry equivalent mass sample with a dry-ba-
      sis moisture content of 10% (i.e., 0.1 mL/g dry) and requiring an addition of 15 mL of 2 N Nitric Acid would
      also require 381 mL of DI water as a makeup volume according to the following equation:
                                                - Va/b - (Mdry-MCd basis)
                                                           (A6-3)
      where VDI is the volume of DI water makeup (mL), Mdry is the mass of dry solid sample (i.e., 20) (g dry), LS
      is the test liquid to solid ratio (i.e., 10) (mL/g dry), Va/i, is the volume of acid or base from the titration curve
      (mL), and MCd basis is the moisture content on a dry mass  basis (mL water/g dry) from ASTM D 2261-80.
        Table A6-2 shows the example schedule of acid or base additions and DI water make up volume for the
      SR002.1 protocol generated from the titration information  shown in Fig. A6-1 using 40 dry g of sample with
      a moisture content (dry  basis) of 0.1 mL/g dry.
                           A.7. PS001.1 (PARTICLE SIZE REDUCTION)
1. Scope
1.1 This protocol is used to size reduce a solid material to a particle size of either <300 /urn, <2 mm, or <5 mm
for subsequent characterization.

2. Cited Protocols
2.1. ASTM (1980) "Standard Method for Water (Moisture) Content of Soil, Rock, and Soil-Aggregate Mixtures D
    2261-80," Philadelphia, PA: American Society for Testing and Materials.
                                                              ENVIRON ENG SCI, VOL. 19, NO. 3, 2002
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202                                                                                       KOSSONSTAL.

2.2. AW001.0 (Acid Washing of Laboratory Equipment).
2.3. SR002.1 (Alkalinity, Solubility and Release as a Function of pH).
2.4. SR003.1 (Solubility and Release as a Function of LS Ratio).

3. Summary of the Protocol
  Depending on the nature of the solid samples, all solid samples to be subjected to equilibrium-based leaching pro-
tocols (e.g., SROOx.l series protocols) must be particle size reduced to <300 /urn, <2 mm, or <5 mm to minimize
mass transfer rate limitation through larger particles.
  Particle size reduction to 5 mm or 2 mm should be accomplished by crushing with a rock hammer in a thick (i.e.,
4-8 mil), sealed plastic bag followed by sieving through either a  5 mm or 2 mm polyester sieve. Alternatively, a
laboratory size jaw crusher can be used for particle size reduction  to <2 mm or <5 mm.
  Prior to particle size reduction to <300 /urn, desiccation to a maximum moisture content of 15% (w/w) may be
necessary for materials with naturally high moisture contents. Particle size reduction then is conducted in a closed
vessel using a ball mill with an appropriate aggregate or other equivalent grinding apparatus (e.g., mortar and pes-
tle or centrifugal grinder). Milling is immediately followed by separation of the <300 /urn fraction through a 300-
fjira (50 mesh) sieve. The jar milling/sieving process is repeated on the fraction that does not pass the sieve until a
minimum of 85% of the initial material mass has been size reduced and collected. The milled product is stored in
an air-tight polyethylene vessel until required for leach testing.

4. Significance and Use
  Large particle sizes may limit the release of constituents in extraction protocols used to measure constituent sol-
ubility or release at low liquid-to-solid (LS) ratios (i.e., SR002.1 and SR003.1). Testing protocols such as these are
designed reach  equilibrium between  solid and liquid phases within reasonable test duration for material leaching
characterization. Application of these protocols to materials of larger particle will necessitate longer contact time to
obtain equilibrium between solid and liquid phases.

5. Apparatus
5.1.  Reduction Apparatus—jar mill (e.g., U.S. Stoneware #764 AVM) with an appropriate grinding media  (e.g.,
     zirconia pellets, Fisher Scientific, or equivalent) or other apparatus suitable for size reducing solid materials.
5.2.  Mill Jar Vessel—ceramic jar (e.g., Fisher Scientific #08-382C) or polyethylene bottle (e.g., Nalgene #2120-
     0005) with air-tight lid or equivalent.
5.3.  Rock Hammer—e.g., Stanley Steelmaster SB24 or equivalent.
5.4.  Scalable Plastic Bag—e.g., Ziploc Brand Freezer Bags, or equivalent.
5.5.  Jaw Crusher—e.g., ASC Scientific Laboratory Size Jaw Crusher.
5.6.  Mortar—e.g.,  Coors #60319, or equivalent.
5.7.  Pestle—e.g., Coors #60320, or equivalent.
5.8.  Desiccator—e.g., Fisherbrand #08-615B, or equivalent.
5.9.  Desiccant—8 mesh indicating SiC>2 desiccant (e.g., EM Science, Gibbstown, NJ,  or equivalent).
5.10. Sieve—5 mm high-density polyethylene U.S. standard sieve with polyester mesh.
5.11. Sieve—2 mm (10 mesh) high-density polyethylene U.S. standard sieve with polyester mesh  (e.g., Cole Farmer
     #AP-06785-20, or equivalent).
5.12. Sieve—300 /urn (50  mesh) stainless steel U.S. standard sieve with stainless steel mesh [A  plastic body/mesh
     (e.g.,  polyethylene^olyester)  is recommend if available at a 300 /urn (50 mesh)  opening.] (e.g., Fisherbrand
     #04-881-10T, or equivalent).
5.13. Storage Vessel—wide-mouth, polyethylene bottle with an air-tight lid (e.g., Nalgene #3120-9500, or equiva-
     lent).

6. Acid Washing  Procedure
  To minimize cross contamination of replicates or samples, all laboratory equipment that comes in contact with the
material must be rinsed with 10% nitric acid followed by DI water to remove residual deposits following the "AWOO1.0
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INTEGRATED FRAMEWORK FOR EVALUATING LEACHING                                        203

(Acid Washing of Laboratory Equipment)" protocol. For the "PS001.1  (Particle Size Reduction)" protocol, it is
mandatory that equipment is acid washed between material types and recommended between replicates.

7. Particle Size Reduction Procedure
7.1.  For particle size reduction to  <5 mm or <2 mm, an initial mass of sample should be placed in a thick, seal-
     able plastic bag on a hard surface.
7.2.  With a rock hammer, crush the monolithic or large granular material into smaller units. If the integrity of the
     plastic bag is compromised during  size reduction, the material may be transferred into a new bag.
7.3.  As an alternative method, laboratory size jaw crusher can be used for particle size reduction to <5 mm or <2
     mm.
7.4.  When the material seems to be of a uniform particle size, sieve the material through a 5-mm sieve or a 2-mm
     sieve, retaining both the fraction that passes and the fraction that does not pass the sieve.
7.5.  Return the fraction that does not pass the sieve into the plastic bag for continued size reduction.
7.6.  Repeat Steps 1.2-1A until greater than 85% of the initial material mass has been reduced to either <5 mm or
     <2 mm. Place the entire sample mass into an air-tight vessel until a moisture content analysis is conducted.
7.7.  Determine the moisture content of  the material using ASTM method D 2261-80 "Standard Method for Labo-
     ratory Determination of Water (Moisture) Content of Soil, Rock, and Soil-Aggregate Mixtures."
7.8.  For further particle size reduction to <300 /urn, desiccation may be necessary if the moisture content of the
     material is greater than 15% (w/w).  If no desiccation is required, continue particle size reduction with Step 7.8.
7.9.  Place the solid material in a porcelain milling jar or plastic milling vessel that is approximately half filled with
     milling media. The total volume of media and sample  should be less than 2/3 of the bottle volume.
7.10. Place the vessel on the ball mill and tumble it until  the material breaks into  smaller units. The duration of
     milling will vary depending on material properties. If the sample does not break down, grinding with a mor-
     tar and pestle followed by jar milling may be required.
7.11. Sieve the material through a 300-^m (50  mesh) sieve, collecting the particles that pass the sieve in an appro-
     priate storage container.
7.12. Return the grinding media and the  fraction  that does not pass the sieve to the milling jar for additional parti-
     cle size reduction. Alternately, continue to reduce the particle size using the mortar and pestle.
7.13. Repeat the milling/sieving process (Steps 7.9-7.12) until a minimum of 85% of the original mass has been par-
     ticle size reduced to  less  than 300 /urn.
7.14. Store the size-reduced  material in an air-tight container to  prevent contamination through exchange with the
     environment. Store in a cool, dark,  and dry place until use.
               A.8. AW001.0 (ACID WASHING OF LABORATORY EQUIPMENT)

1. Scope
1.1. This procedure is used to prepare laboratory equipment for use in inorganic extraction tests.

2. Summary of the Protocol
  Because concentrations of inorganic constituents in leachates may be very low  (i.e., <10 /ug/L), all laboratory
equipment that is exposed to the material, the extraction fluid, or the leachant must be rinsed with 10% nitric acid
followed by DI water to remove residual deposits. This equipment includes supplies, utensils and containers or any
surface that will come into direct contact with the material. After removing loose debris with soap and tap water, all
contacting surfaces are rinsed with 10% nitric acid then triple rinsed with DI water. The equipment is  dried and
stored in such a manner as to minimize contamination with trace  metals. When the equipment is used, no further
preparation is required.

3. Reagents and Materials
3.1. Cleaning Brush—soft, nondamaging brush (e.g., Fisher Scientific, or equivalent).
3.2. Detergent—e.g., Sparkleen, Fisher Scientific,  or equivalent.

                                                               ENVIRON ENG SCI, VOL. 19, NO. 3, 2002
-------
204                                                                                       KOSSONSTAL.

3.3. Reagent Grade Water—DI water with a resistivity of 18.2 MO can be provided by commercially available deion-
    ization systems (e.g., Milli-Q Plus, Millipore, Bedford, MA, or equivalent).
3.4. 70% (v/v) Nitric Acid—made by dilution of Tracemetal Grade nitric acid (e.g., Fisher Scientific, or equivalent)
    with DI water.

4. Acid Washing Procedure
4.1. Rinse loose debris from the surface of the object using tap water.
4.2. Wash the object thoroughly using a brush, soap, and water. Triple rinse with tap water.
4.3. Using a designated laboratory squirt bottle, apply a steady stream of 10% nitric acid solution to completely cover
    all contacting surfaces. Repeat the application of the 10% nitric acid three times.
4.4. Triple rinse all surfaces with DI water.
4.5. Dry the object by using direct sunlight, ovens, or forced drafts of warm air. Take care to limit exposure to air-
    borne particulates or any source of contamination.
4.6. Objects that are  not for immediately use must be covered or stored in an  area where exposure to airborne par-
    ticulates or any other source of contamination can be minimized. Alternately, all equipment can be triple dipped
    into a polyethylene crock (Cole-Parmer #AP-06724-60, or equivalent) containing a 10% nitric acid bath with a
    dipping basket (e.g., Cole-Parmer #AP-06717-50, or equivalent).  For this approach, however,  frequent moni-
    toring of the  metals concentration and renewal of the bath solution are required to minimize the possibility of
    depositing metals onto equipment surfaces.

5. Safety
  Caution should be taken when working with either the full  strength or 10% nitric acid solutions. At a minimum
of safety precautions, the use of acid resistant gloves and  eye protection are required. All equipment should be rinsed
over a tank constructed of an inert material (e.g., polyethylene tank, Nalgene #14100-0015, or equivalent).
-------
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-------
                                                                               Project No.: RN990234.0026
                                                                               Revision: 0
                                                                               Date: April 2008
                                                                               Page:25
10. References

ASTM, 1983. Method C 22-83, "Standard Specification for Gypsum".

ASTM, 1992. Method D 2216-92, "Standard Test Method for Laboratory Determination of Water (Moisture)
Content of Soil and Rock".

ASTM, 2002. Method D 6784-02, "Standard Test Method for Elemental, Oxidized, Particle-Bound, and Total
Mercury in Flue Gas Generated from Coal-Fired Stationary Sources (Ontario-Hydro Method)".

EPA, 1996a. Method 3052 "Microwave Assisted Acid Digestion of Siliceous and Organically Based
Matrices". Test Methods for Evaluating Solid Waste, Physical/Chemical Methods (SW-846).

EPA, 1996b. Method 6010 "Inductively Coupled Plasma-Atomic Emission Spectrometry". Test Methods for
Evaluating Solid Waste, Physical/Chemical Methods (SW-846).

EPA, 1996c . Method 29 "Determination of Metals Emissions from Stationary Sources." Code of Federal
Regulations, Title 40, Part 60, Appendix A, April 1996.

EPA, 1998. Method 7470A "Mercury in Liquid Waste (Manual Cold-Vapor Technique)". Test Methods for
Evaluating Solid Waste, Physical/Chemical Methods (SW-846).

EPA, 2002a. Characterization and Management of Residues from Coal-Fired Power Plants, Interim Report.
EPA-600/R-02, 083, December 2002.

EPA, 2002b. Reply to comments on EPA/OSWs Proposed Approach to Environmental Assessment of
CCRs. Discussed March 5, 2002.

Kosson, D.S.,  van derSloot, H.A., Sanchez, F. and Garrabrants, A.C., 2002a. An Integrated Framework for
Evaluating Leaching in Waste Management and Utilization of Secondary Materials. Environmental
Engineering Science 19 (3): 159-204.

Kosson, D.S.,  and Sanchez, F., 2002b. Draft (Revision #2), Sampling and Characterization Plan for Coal
Combustion Residues from Facilities with Enhanced Mercury Emissions Reduction Technology. May 2002.
-------
                        Appendix B
         Total Elemental Content by Digestion
Fly Ash	B-1



Scrubber Sludge	B-2



Gypsum	B-3



Fixated Scrubber Sludge (FSS)	B-4



Fixated Scrubber Sludge with Lime (FSSL)	B-5
-------
Total Elemental Content by Digestion

Sample ID:
Mercury ng/g
Arsenic u.g/g
Cadmium u.g/g
Lead u.g/g
Selenium u.g/g
Cobalt u.g/g
Aluminum u.g/g
Barium u.g/g
Molybdenum u.g/g
Antimony u.g/g
Thallium u.g/g
Chromium u.g/g
Fly Ash
Fac. A
CFA AFA
379 602
88 71
1.0 1.3
69 81
21.9 25.6
49.1 54.7
138,280 127,065
1,361 1,016
14.5 16.9
8.2 13.7
3.2 3.8
151 152
Fac. B
DFA BFA
114 88
90 82
0.7 0.9
36 47
2.9 2.5
21.0 23.5
105,917 109,365
1,360 1,461
10.9 10.7
2.8 3.6
4.5 4.7
169 192
Fac. K
KFA
42
85
1.0
93
4.8
38.1
123,248
585
22.9
6.0
13.0
124
-------
Total Elemental Content by Digestion

Sample ID:
Mercury ng/g
Arsenic u.g/g
Cadmium u.g/g
Lead u.g/g
Selenium u.g/g
Cobalt u.g/g
Aluminum u.g/g
Barium u.g/g
Molybdenum u.g/g
Antimony u.g/g
Thallium u.g/g
Chromium u.g/g
Scrubber Sludge
Fac. A
CGD AGO
432 45
3.6 7.3
0.3 0.4
2.5 4.8
2.1 3.0
1.0 3.4
7,969 12,746
82.2 146.9
8.9 18.7
3.9 9.4
2.4 3.7
9.2 12.0
Fac. B
DGD BGD
303 613
10.0 22.7
0.6 1.5
11.0 13.1
1.8 2.9
1.5 42.3
12,729 198,116
76.4 2,426.4
14.2 27.0
8.8 7.8
3.5 11.9
20.6 342.7
Fac. K
KGD
573
40.9
0.8
26.1
4.2
13.4
40,256
243.1
25.8
13.3
4.6
49.4
-------
Total Elemental Content by Digestion

Sample ID:
Mercury ng/g
Arsenic u.g/g
Cadmium u.g/g
Lead u.g/g
Selenium u.g/g
Cobalt u.g/g
Aluminum u.g/g
Barium u.g/g
Molybdenum u.g/g
Antimony u.g/g
Thallium u.g/g
Chromium u.g/g
Gyp-U & Gyp-W
Fac. N
NAU NAW
537.8 53.7
2.3 3.5
0.5 0.4
2.4 5.5
2.8 2.6
2.7 2.6
8,030 9,836
57.1 52.8
4.0 3.7
2.4 2.1
0.7 0.7
9.1 18.0
Fac. O
OAU OAW
392.0 38.5
1.6 3.8
0.3 0.4
0.9 11.5
2.3 2.3
2.9 3.3
456 11,584
3.2 51.7
3.1 4.6
1.6 1.9
0.6 0.6
17.1 8.3
Fac. P
PAD (U)
9.9
2.6
0.3
3.3
19.3
3.5
12,653
52.8
2.4
2.6
0.6
5.7
Fac. Q
QAU
505.8
1.8
0.3
2.4
28.2
1.1
3,187
55.9
11.5
5.8
2.3
8.7
-------
Total Elemental Content by Digestion



Sample ID:
Mercury
Arsenic
Cadmium
Lead
Selenium
Cobalt
Aluminum
Barium
Molybdenum
Antimony
Thallium
Chromium
ng/g
M-g/g
M-g/g
M-g/g
Mg/g
Mg/g
Mg/g
Mg/g
Mg/g
Mg/g
Mg/g
Mg/g
FSS
Fac. A
CCC
386.9
71.5
0.7
54.5
22.8
39.6
106,542
1,065.2
11.1
5.7
2.5
119.0
ACC
513.2
55.7
1.2
64.3
20.1
45.2
114,004
712.8
14.4
9.7
3.4
129.7
-------
Total Elemental Content by Digestion

Sample ID:
Mercury ng/g
Arsenic u.g/g
Cadmium u.g/g
Lead u.g/g
Selenium u.g/g
Cobalt u.g/g
Aluminum u.g/g
Barium u.g/g
Molybdenum u.g/g
Antimony u.g/g
Thallium u.g/g
Chromium u.g/g
FSSL
Fac. B
DCC BCC
203.2 411.8
16.3 4.3
0.8 0.9
9.7 5.7
2.0 2.4
6.4 2.4
35,131 29,359
370.1 100.3
8.6 26.3
4.7 13.6
0.8 6.4
53.2 35.0
Fac. K
KCC
1,039.1
3.3
1.0
3.7
3.9
1.7
30,627
76.6
31.2
16.9
7.9
39.4
Fac. M
MAD MAS
229.7 355.4
44.1 42.0
1.6 1.4
67.9 95.1
2.0 3.9
20.3 22.2
46,483 44,919
232.1 262.0
22.1 18.2
6.0 9.6
4.2 3.3
53.9 52.7
-------
                          Appendix C


      Elemental Total Content (by XRF), Carbon,
       Loss on Ignition and  Specific Surface Area

Nomenclature
BDL = below detection limit
BRL = below reportable limit (20 mg/kg)
CV = coefficient of variation (%)
EC = elemental carbon
OC = organic carbon
S.A. = specific surface area (BET isotherm by gas adsorption)
TC = total carbon
LOI = loss on ignition
n = number of sample aliquots analyzed
o = standard deviation based on n analyses
Notes
   1.  All elemental and carbon analysis results reported on a dry weight basis.
   2. Moisture content reported is for "as received" samples.
-------
Fly Ash
Sample ID:

Analyte

Al
As
Ba
Br
Ca
Cd
Ce
Cl
Co
Cr
Cu
F
Fe
Ga
Ge
K
La
Mg
Mn
Mo
Na
Nb
Ni
P
Pb
Rb
Sc
Se
Si
Sr
S
Ti
V
W
Y
Zn
Zr
EC (%)
OC (%)
TC (%)
LOI (%)
S.A. (m2/g)
Moisture (%)

Detection
Limit
(mg/kg)
160
380
84
200
1,000
640
220
46
24
28
14
820
340
16
14
48
54
100
32
26
76
18
48
40
34
16
500
16
18
920
16
30
38
36
18
14
24






CFA

Mean n a CV
(mg/kg) (mg/kg) (%)
130,222 2 36 0.0
BDL 2
1,260 2 7 0.6
BDL 2
36,640 2 72 0.2
BRL 2
BDL 2
6,202 2 47 0.8
65 2 3 5.0
177 2 35 19.9
181 2 2 1.0
BRL 2
52,876 2 108 0.2
50 2 2 3.6
BRL 2
21,293 2 144 0.7
BDL 2
9,465 2 75 0.8
527 2 1 0.2
BRL 2
3,684 2 57 1.6
32 2 15 45.7
105 2 8 7.2
1,395 2 11 0.8
67 2 16 24.2
134 2 8 5.9
BDL 2
27 2 4 16.0
234,602 2 539 0.2
1,176 2 4 0.3
3,999 2 180 4.5
9,460 2 54 0.6
294 2 10 3.4
BDL 2
90 2 7 7.9
128 2 3 2.3
318 2 16 5.1
3.6 2 0.32 8.9
0.1 2 0.06 60.0
3.69 2 0.26 7.0

2.57 1
18.9 3 0.1 0.529
AFA

Mean n a CV
(mg/kg) (mg/kg) (%)
124,986 2 193 0.2
BDL 2
1,044 2 12 1.1
BDL 2
38,531 2 425 1.1
BRL 2
BDL 2
5,918 2 104 1.8
72 2 10 14.0
197 2 4 2.0
211 2 2 0.9
BRL 2
51,065 2 463 0.9
51 2 1 1.5
BRL 2
18,241 2 77 0.4
127 2 31 24.4
9,115 2 0 0.0
323 2 6 1.9
26 2 12 45.2
4,099 2 27 0.7
32 2 5 14.6
126 2 9 7.3
1,335 2 12 0.9
73 2 11 14.9
115 2 2 1.7
BDL 2
29 2 2 8.0
212,998 2 232 0.1
1,007 2 2 0.2
3,973 2 27 0.7
8,372 2 62 0.7
360 2 2 0.4
BRL 2
93 2 3 3.3
140 2 4 2.8
282 2 13 4.5
9.03 2 1.59 17.6
0.11 2 0.02 18.2
9.15 2 1.61 17.6

13.89 1
18.6 3 0.05 0.269
-------
Fly Ash
Sample ID:
Analyte

Al
As
Ba
Br
Ca
Cd
Ce
Cl
Co
Cr
Cu
F
Fe
Ga
Ge
K
La
Mg
Mn
Mo
Na
Nb
Ni
P
Pb
Rb
Sc
Se
Si
Sr
S
Ti
V
W
Y
Zn
Zr
EC (%)
OC (%)
TC (%)
LOI (%)
S.A. (m2/g)
Moisture (%)
DFA
Mean
(mg/kg)
115,447
BDL
1,283
BRL
32,621
BRL
BRL
310
24
228
60
BRL
116,523
37
BRL
19,630
BDL
8,120
255
BRL
6,955
BRL
57
1,787
BDL
120
BRL
BRL
222,181
1,040
5,370
5,984
196
BRL
54
133
213
1.38
0.03
1.46

2.37
11
n

2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2

1
3
a
(mg/kg)
111

11

37


0
20
0
2

668
5

74

74
15

7

3
26

1


148
4
89
67
9

10
15
15
0.11
0.01
0.18


0.4
CV
(%)
0.1

0.9

0.1


0.1
80.6
0.2
3.7

0.6
14.1

0.4

0.9
5.8

0.1

4.6
1.5

1.2


0.1
0.4
1.7
1.1
4.5

18.0
11.5
7.1
8.0
33.3
12.3


3.636
BFA
Mean
(mg/kg)
112,215
BDL
1,325
BRL
35,238
BRL
BRL
455
26
245
57
BRL
111,577
32
23
20,284
BDL
8,991
262
BRL
7,498
22
75
2,435
BDL
134
BRL
BRL
219,739
1,150
7,358
6,166
194
BRL
33
145
217
1.51
0.43
1.93

5.74
11.6
n

3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
2
2
2

1
3
a
(mg/kg)
352

10

411


59
4
14
5

1,514
4
5
52

62
7

147
5
7
21

1


659
16
173
65
10

4
4
7
0.43
0.27
0.7


0.4
CV
(%)
0.3

0.8

1.2


13.0
16.1
5.7
9.2

1.4
13.7
23.6
0.3

0.7
2.8

2.0
21.4
9.4
0.9

0.6


0.3
1.4
2.4
1.0
5.1

12.0
2.9
3.1
28.5
62.8
36.3


3.448
-------
Fly Ash
Sample ID:
Analyte

Al
As
Ba
Br
Ca
Cd
Ce
Cl
Co
Cr
Cu
F
Fe
Ga
Ge
K
La
Mg
Mn
Mo
Na
Nb
Ni
P
Pb
Rb
Sc
Se
Si
Sr
S
Ti
V
W
Y
Zn
Zr
EC (%)
OC (%)
TC (%)
LOI (%)
S.A. (m2/g)
Moisture (%)
KFA
Mean
(mg/kg)
124,250
BDL
582
BRL
14,150
BRL
BDL
BDL
BRL
160
92
BRL
161,175
37
29
15,800
80
5,898
230
31
2,588
BRL
148
1,083
54
94
BRL
BRL
213,325
BDL
2,980
6,208
228
86
78
179
196
0.08
0.13
0.21
1.59

0.3
n

2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
1

3
a
(mg/kg)
2,051

36

71




22
1

5,975
10
1
71
10
39
13
5
32

9
53
17
3


1,874

212
25
10
5
1
2
10
0.03
0.01
0.03


0.3
CV
(%)
1.7

6.3

0.5




13.7
0.8

3.7
27.1
2.4
0.4
12.8
0.7
5.7
14.9
1.2

6.0
4.9
32.2
3.0


0.9

7.1
0.4
4.5
6.1
0.9
1.0
5.2
37.5
7.7
14.3


100
-------
Gypsum (Unwashed, Gyp-U)
Gypsum (Washed, Gyp-W)
Sample ID:

Analyte

Al
As
Ba
Br
Ca
Cd
Ce
Cl
Co
Cr
Cu
F
Fe
Ga
Ge
K
La
Mg
Mn
Mo
Na
Nb
Ni
P
Pb
Rb
Sc
Se
Si
Sr
S
Ti
V
W
Y
Zn
Zr
EC (%)
OC (%)
TC (%)
LOI (%)
S.A. (m2/g)
Moisture (%)

Detection
Limit
(mg/kg)
160
380
84
200
1,000
640
220
46
24
28
14
820
340
16
14
48
54
100
32
26
76
18
48
40
34
16
500
16
18
920
16
30
38
36
18
14
24






NAU

Mean n a CV
(mg/kg) (mg/kg) (%)
345 3 38 10.9
BRL 3
BDL 3
BRL 3
299,167 3 1,168 0.4
BRL 3
BRL 3
1,327 3 101 7.6
BRL 3
BRL 3
33 3 9 26.2
BDL 3
1,433 3 38 2.6
BRL 3
BRL 3
BRL 3
BDL 3
549 3 13 2.4
BRL 3
BRL 3
281 3 37 13.1
BRL 3
233 3 12 5.2
417 3 14 3.4
BRL 3
BRL 3
BDL 3
BRL 3
3,000 3 235 7.8
BDL 3
225,233 3 850 0.4
31 3 20 63.8
BRL 3
223 3 14 6.4
BRL 3
BRL 3
BRL 3
BDL 3
0.55 3 0.06 10.9
0.55 3 0.06 10.9
9.20 1
9.92 1
27.8 3 0.01 0.04
NAW

Mean n a CV
(mg/kg) (mg/kg) (%)
197 3 85 43.3
BRL 3
BDL 3
BRL 3
290,200 3 400 0.1
BRL 3
BRL 3
BRL 3
BRL 3
BRL 3
26 3 16 62.4
BDL 3
1,297 3 21 1.6
BRL 3
BRL 3
BRL 3
BDL 3
360 3 8 2.2
BRL 3
BRL 3
196 3 7 3.6
BRL 3
222 3 9 4.1
380 3 12 3.0
BRL 3
BRL 3
BDL 3
BRL 3
2,703 3 51 1.9
BDL 3
231,633 3 153 0.1
BDL 3
BRL 3
159 3 6 3.6
BRL 3
BRL 3
BRL 3
BDL 3
0.51 3 0.02 3.9
0.51 3 0.02 3.9
2.10 1
3.88 1
28 3 0.1 0.357
-------
Gypsum (Unwashed, Gyp-U)
Gypsum (Washed, Gyp-W)
Sample ID:
Analyte

Al
As
Ba
Br
Ca
Cd
Ce
Cl
Co
Cr
Cu
F
Fe
Ga
Ge
K
La
Mg
Mn
Mo
Na
Nb
Ni
P
Pb
Rb
Sc
Se
Si
Sr
S
Ti
V
W
Y
Zn
Zr
EC (%)
OC (%)
TC (%)
LOI (%)
S.A. (m2/g)
Moisture (%)
OAU
Mean
(mg/kg)
1,074
BRL
BDL
BRL
285,567
BRL
BDL
644
BRL
BRL
26
BRL
1,763
BRL
BRL
375
BDL
2,903
33
BRL
272
BRL
225
BRL
BRL
BRL
BDL
BRL
4,220
BDL
220,267
98
BRL
181
BRL
BRL
BRL
0.43
2.5
2.93
20.4
7.58
21.3
n

3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
2
2
2
1
1
3
a CV
(mg/kg) (%)
192 17.9



1,050 0.4


9 1.4


16 59.1

64 3.6


31 8.2

286 9.8
19 58.3

20 7.3

12 5.5





266 6.3

839 0.4
12 12.3

28 15.5



0.56 130.2
0.45 18.0
0.11 3.8


6.4 30.05
OAW
Mean
n
(mg/kg)

BRL
BDL
BRL

BRL
BRL
BRL
BRL
BRL

BRL

BRL
BRL

BRL


BRL

BRL

BRL
BRL
BRL
BDL
BRL

BDL




BRL
BRL
BRL






927



284,500





29

1,720


330

2,073
48

209

207





3,907

224,467
78
59
147



0.05
2.31
2.36
3.91
3.39
21.3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
2
2
0

1
3
a
(mg/kg)
142



557





16

26


25

101
21

33

32





106

493
14
25
35



0.07
0.06
0


1.3
CV
(%)
15.3



0.2





56.8

1.5


7.6

4.9
43.8

15.7

15.7





2.7

0.2
18.2
42.8
23.4



140.0
2.6
0.0


6.103
-------
Gypsum (Unwashed, Gyp-U)
Sample ID:
Analyte

Al
As
Ba
Br
Ca
Cd
Ce
Cl
Co
Cr
Cu
F
Fe
Ga
Ge
K
La
Mg
Mn
Mo
Na
Nb
Ni
P
Pb
Rb
Sc
Se
Si
Sr
S
Ti
V
W
Y
Zn
Zr
EC (%)
OC (%)
TC (%)
LOI (%)
S.A. (m2/g)
Moisture (%)
PAD (U)
Mean
(mg/kg)
1,257
BRL
BDL
BRL
300,500
BRL
BRL
147
BRL
BRL
99
1,952
1,637
BRL
BRL
471
BDL
769
158
BRL
287
BRL
545
224
BRL
BRL
BDL
BRL
2,497
BDL
225,050
58
BRL
428
BRL
BRL
BRL
BDL
0.12
0.12
2.75

18.3
n

3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
1

3
a
(mg/kg)
172



557


35


11
116
95


28

40
9

28

27
17




223

624
19

25




0.03
0.03


1.6
CV
(%)
14



0


24


11
5.9
5.8


5.9

5.2
5.5

9.6

4.9
7.7




8.9

0.3
32.7

5.8




25
25


8.743
QAU
Mean
(mg/kg)
4,817
BRL
BDL
BRL
301,100
BRL
BRL
1,130
BRL
BRL
114
6,122
1,503
BRL
BRL
501
BDL
10,053
72
BRL
1,553
BRL
566
417
BRL
BRL
BDL
22
11,433
BDL
202,117
192
BDL
465
BRL
BRL
BRL
0.03
0.87
0.91
6.12

24.4
n

3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
1

3
a
(mg/kg)
242



800


44


9
586
10


8

703
8

57

12
5



1
506

1,032
19

24



0
0.12
0.12


4.2
CV
(%)
5.03



0.27


3.93


7.70
9.6
0.7


1.5

7.0
10.8

3.7

2.2
1.1



2.6
4.4

0.5
9.7

5.1



0
13.79
13.19


17.21
-------
Scrubber Sludge (ScS)
Sample ID:

Analyte

Al
As
Ba
Br
Ca
Cd
Ce
Cl
Co
Cr
Cu
F
Fe
Ga
Ge
K
La
Mg
Mn
Mo
Na
Nb
Ni
P
Pb
Rb
Sc
Se
Si
Sr
S
Ti
V
W
Y
Zn
Zr
EC (%)
OC (%)
TC (%)
LOI (%)
S.A. (m2/g)
Moisture (%)

Detection
Limit
(mg/kg)
160
380
84
200
1,000
640
220
46
24
28
14
820
340
16
14
48
54
100
32
26
76
18
48
40
34
16
500
16
18
920
16
30
38
36
18
14
24






CGD

Mean n a CV
(mg/kg) (mg/kg) (%)
5,609 3 530 9.4
BRL 3
192 3 16 8.2
BDL 3
348,533 3 735 0.2
BRL 3
BRL 3
8,073 3 589 7.3
BRL 3
BRL 3
BRL 3
3,432 3 994 29.0
3,581 3 106 3.0
BRL 3
BRL 3
1,465 3 68 4.7
BDL 3
3,760 3 326 8.7
160 3 5 2.9
BRL 3
908 3 82 9.0
BRL 3
BRL 3
393 3 24 6.1
BRL 3
BRL 3
BDL 3
32 3 2 6.5
12,486 3 529 4.2
BDL 3
177,098 3 703 0.4
258 3 17 6.6
BRL 3
BDL 3
BRL 3
BRL 3
BRL 3
0.27 2 0.03 11.11
0.12 2 0.03 25
0.39 2 0.06 15.38

16.63
22.2 3 5 22.52
AGO

Mean n a CV
(mg/kg) (mg/kg) (%)
8,687 2 142 1.6
BRL 2
189 2 38 20.3
BDL 2
327,840 2 0 0.0
BRL 2
BRL 2
8,537 2 212 2.5
BRL 2
BDL 2
BRL 2
1,966 2 366 18.6
6,295 2 21 0.3
BRL 2
BRL 2
2,463 2 12 0.5
BRL 2
9,888 2 358 3.6
159 2 4 2.6
BRL 2
1,572 2 33 2.1
BRL 2
BRL 2
468 2 10 2.2
BRL 2
BRL 2
BDL 2
BRL 2
25,103 2 1,540 6.1
BDL 2
169,806 2 499 0.3
354 2 22 6.1
BRL 2
BRL 2
BRL 2
BRL 2
BRL 2
0.1 2 0.07 70.0
0.35 2 0.02 5.7
0.45 2 0.05 11.1

14.47
19.4 3 0.4 2.062
-------
Scrubber Sludge (ScS)
Sample ID:
Analyte

Al
As
Ba
Br
Ca
Cd
Ce
Cl
Co
Cr
Cu
F
Fe
Ga
Ge
K
La
Mg
Mn
Mo
Na
Nb
Ni
P
Pb
Rb
Sc
Se
Si
Sr
S
Ti
V
W
Y
Zn
Zr
EC (%)
OC (%)
TC (%)
LOI (%)
S.A. (m2/g)
Moisture (%)
DGD
Mean
(mg/kg)
2,378
BRL
BDL
BDL
339,697
BRL
BDL
5,025
BRL
BDL
BRL
BRL
3,368
BRL
BRL
534
BDL
15,882
44
BRL
572
BRL
BRL
87
BRL
BRL
BDL
BRL
7,168
BDL
184,853
209
BRL
BRL
BRL
BRL
BRL
0.3
0.14
0.44

17.54
48.8
n a CV
(mg/kg) (%)
2 136 5.7
2
2
2
2 310 0.1
2
2
2 124 2.5
2
2
2
2
2 16 0.5
2
2
2 3 0.7
2
2 116 0.7
2 14 32.5
2
2 19 3.3
2
2
2 2 1.8
2
2
2
2
2 198 2.8
2
2 194 0.1
2 2 0.7
2
2
2
2
2
2 0.04 13.3
2 0.05 35.7
2 0.01 2.3


3 1.3 2.664
BCD
Mean
(mg/kg)
20,836
BRL
417
BDL
287,766
BRL
BDL
4,003
BRL
95
21
BRL
35,445
BRL
BRL
4,377
BDL
11,606
96
BRL
1,753
BRL
BRL
388
BRL
29
BDL
BRL
41,890
BDL
147,870
1,622
46
BRL
BRL
45
63
0.93
0.22
1.15

22.69
43.3
n

2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2


3
a CV
(mg/kg) (%)
1,274 6.1

6 1.4

1,854 0.6


8 0.2

31 33.0
8 40.9

618 1.7


19 0.4

116 1.0
2 2.0

116 6.6


0 0.0

19 65.5


1,699 4.1

1,120 0.8
54 3.3
14 29.9


0 0.9
5 7.3
0.05 5.4
0.01 4.5
0.04 3.5


0.1 0.231
-------
Scrubber Sludge (ScS)
Sample ID:
Analyte

Al
As
Ba
Br
Ca
Cd
Ce
Cl
Co
Cr
Cu
F
Fe
Ga
Ge
K
La
Mg
Mn
Mo
Na
Nb
Ni
P
Pb
Rb
Sc
Se
Si
Sr
S
Ti
V
W
Y
Zn
Zr
EC (%)
OC (%)
TC (%)
LOI (%)
S.A. (m2/g)
Moisture (%)
KGD
Mean
(mg/kg)
24,950
BRL
213
BRL
249,725
BRL
BRL
1,900
BRL
43
31
BRL
36,100
BRL
BRL
3,745
BDL
11,525
89
BRL
810
BRL
77
238
BRL
21
BDL
BRL
32,100
BDL
178,225
1,558
48
68
20
62
58
0.22
0.49
0.71
8.63

45.3
n

2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
1

3
a
(mg/kg)
1,697

7

4,632


205

6
4

2,121


318

106
17

65

1
19

5


1,838

1,945
117
5
7
5
10
5
0.19
0.29
0.48


0.4
CV
(%)
6.8

3.3

1.9


10.8

13.2
11.4

5.9


8.5

0.9
19.5

8.0

1.8
7.9

25.6


5.7

1.1
7.5
9.6
9.8
24.7
16.1
7.9
86.4
59.2
67.6


0.883
-------
Fixated Stabilized Sludge (FSS)
Sample ID:

Analyte

Al
As
Ba
Br
Ca
Cd
Ce
Cl
Co
Cr
Cu
F
Fe
Ga
Ge
K
La
Mg
Mn
Mo
Na
Nb
Ni
P
Pb
Rb
Sc
Se
Si
Sr
S
Ti
V
W
Y
Zn
Zr
EC (%)
OC (%)
TC (%)
LOI (%)
S.A. (m2/g)
Moisture (%)

Detection
Limit
(mg/kg)
160
380
84
200
1,000
640
220
46
24
28
14
820
340
16
14
48
54
100
32
26
76
18
48
40
34
16
500
16
18
920
16
30
38
36
18
14
24






CCC

Mean n a CV
(mg/kg) (mg/kg) (%)
111,012 2 3,421 3.1
BDL 2
1,144 2 11 1.0
BDL 2
78,145 2 4,908 6.3
BRL 2
BDL 2
5,403 2 41 0.8
53 2 8 14.8
168 2 23 13.7
162 2 4 2.3
BRL 2
46,513 2 37 0.1
45 2 1 3.3
BRL 2
18,116 2 335 1.8
94 2 6 6.7
9,034 2 297 3.3
474 2 17 3.5
BRL 2
3,521 2 86 2.4
BRL 2
98 2 3 3.0
1,167 2 7 0.6
59 2 2 3.2
107 2 1 0.7
BDL 2
31 2 2 6.0
195,178 2 5,466 2.8
1,051 2 8 0.8
34,418 2 4,946 14.4
8,282 2 30 0.4
257 2 17 6.7
BDL 2
65 2 3 4.6
104 2 2 2.2
259 2 3 1.1
3.93 2 0.47 12.0
0.05 2 0 0.0
3.98 2 0.47 11.8

4.93 1
17.2 3 1.4 8.1
ACC

Mean n a CV
(mg/kg) (mg/kg) (%)
102,335 2 334 0.3
BDL 2
962 2 58 6.0
BDL 2
81,978 2 37 0.0
BRL 2
BDL 2
7,933 2 1,291 16.3
63 2 9 14.1
141 2 19 13.7
164 2 12 7.5
BRL 2
44,675 2 260 0.6
44 2 4 9.3
BRL 2
16,028 2 37 0.2
105 2 3 2.8
10,254 2 56 0.5
320 2 3 0.9
BRL 2
3,421 2 74 2.2
21 2 2 10.6
100 2 6 6.0
1,060 2 28 2.7
54 2 4 7.6
90 2 3 3.7
BDL 2
26 2 2 7.1
170,986 2 297 0.2
BDL 2
38,799 2 482 1.2
7,012 2 26 0.4
282 2 15 5.3
BRL 2
76 2 10 13.7
104 2 9 8.5
221 2 12 5.2
8.73 2 1.03 11.8
0.57 2 0.46 80.7
9.3 2 0.58 6.2

10.22 1
25.8 3 0.1 0.4
-------
Fixated Stabilized Sludge with Lime (FSSL)
Sample ID:
Analyte

Al
As
Ba
Br
Ca
Cd
Ce
Cl
Co
Cr
Cu
F
Fe
Ga
Ge
K
La
Mg
Mn
Mo
Na
Nb
Ni
P
Pb
Rb
Sc
Se
Si
Sr
S
Ti
V
W
Y
Zn
Zr
EC (%)
OC (%)
TC (%)
LOI (%)
S.A. (m2/g)
Moisture (%)
DCC
Mean
(mg/kg)
16,929
BRL
333
BDL
304,718
BRL
BRL
6,261
BRL
48
BRL
BRL
17,223
BRL
BRL
3,910
BRL
15,511
74
BRL
1,498
BRL
BRL
275
BRL
28
BDL
BRL
33,135
BDL
158,777
1,343
46
BRL
BRL
42
46
0.91
0.17
1.08

3.46
38.9
n

2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2

1
3
a
(mg/kg)
113

9

1,740


140

11


227


15

76
12

30


20

5


38

3,820
8
3


7
4
0.17
0.12
0.05


0.5
CV
(%)
0.7

2.6

0.6


2.2

22.7


1.3


0.4

0.5
16.3

2.0


7.3

16.3


0.1

2.4
0.6
7.4


17.1
9.1
18.7
70.6
4.6


1.3
BCC
Mean
(mg/kg)
4,953
BDL
158
BDL
327,010
BRL
BRL
4,433
BRL
45
BRL
BRL
10,682
BRL
BRL
1,055
BDL
11,553
52
BDL
762
BRL
BRL
112
BRL
BRL
BDL
BRL
11,681
BDL
183,273
441
BRL
BRL
BRL
25
BRL
0.49
0.17
0.66

14.49
42.3
n

2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2

1
3
a
(mg/kg)
423

9

288


444

12


308


2

259
9

37


16




571

452
21



2

0.04
0.04
0.07


0.1
CV
(%)
8.5

5.7

0.1


10.0

26.5


2.9


0.2

2.2
17.5

4.9


14.3




4.9

0.2
4.7



8.3

8.2
23.5
10.6


0.2
-------
Fixated Stabilized Sludge with Lime (FSSL)
Sample ID:
Analyte

Al
As
Ba
Br
Ca
Cd
Ce
Cl
Co
Cr
Cu
F
Fe
Ga
Ge
K
La
Mg
Mn
Mo
Na
Nb
Ni
P
Pb
Rb
Sc
Se
Si
Sr
S
Ti
V
W
Y
Zn
Zr
EC (%)
OC (%)
TC (%)
LOI (%)
S.A. (m2/g)
Moisture (%)
KCC
Mean
(mg/kg)
1,628
BRL
BDL
BRL
291,100
BRL
BDL
812
BRL
BRL
BRL
BRL
938
BRL
BRL
165
BDL
9,933
BRL
BRL
355
BRL
51
BRL
BRL
BRL
BDL
BRL
5,075
BDL
220,400
79
BRL
66
BRL
BRL
BRL
0.26
0.58
0.85
5.63

51.4
n a CV
(mg/kg) (%)
2 11 0.7
2
2
2
2 0 0.0
2
2
2 44 5.4
2
2
2
2
2 11 1.1
2
2
2 5 2.8
2
2 81 0.8
2
2
2 26 7.4
2
2 5 9.1
2
2
2
2
2
2 64 1.3
2
2 141 0.1
2 19 23.8
2
2 35 52.8
2
2
2
3 0.15 57.7
3 0.32 55.2
3 0.44 51.8
1

3 0.5 0.973














































-------
Fixated Stabilized Sludge with Lime (FSSL)
Sample ID:
Analyte

Al
As
Ba
Br
Ca
Cd
Ce
Cl
Co
Cr
Cu
F
Fe
Ga
Ge
K
La
Mg
Mn
Mo
Na
Nb
Ni
P
Pb
Rb
Sc
Se
Si
Sr
S
Ti
V
W
Y
Zn
Zr
EC (%)
OC (%)
TC (%)
LOI (%)
S.A. (m2/g)
Moisture (%)
MAD
Mean
(mg/kg)
38,380
BDL
187
BRL
230,470
BRL
BDL
3,105
BRL
65
95
BRL
66,275
BRL
42
9,468
63
8,241
174
BDL
2,340
BRL
334
316
61
68
BDL
BRL
60,300
BDL
171,105
2,643
136
215
32
171
128
0.34
0.96
1.30
5.79
7.36
32.1
n

10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
3
3

1
1
3
a
(mg/kg)
1,036

19

1,157


449

12
14

487

8
111
23
89
7

574

10
17
12
4


1,345

2,703
28
10
39
7
14
10
0.02
0.36
0.34


0.2
CV
(%)
2.7

10.0

0.5


14.5

18.4
14.7

0.7

18.3
1.2
36.9
1.1
4.1

24.5

3.0
5.5
19.1
6.1


2.2

1.6
1.1
7.3
18.3
20.8
8.2
7.9
6.2
38.0
26.1


0.6
MAS
Mean
(mg/kg)
32,200
BRL
183
BRL
207,367
BRL
BDL
873
BDL
55
90
BRL
46,767
BRL
36
7,290
57
4,540
121
BDL
6,220
BRL
300
229
60
43
BDL
BRL
50,800
BDL
173,800
2,103
119
193
23
149
102
0
0.75
0.75
3.69

27.2
n

3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
2
2
2
1

3
a
(mg/kg)
721

15

3,408


71

15
10

603

2
111
25
30
8

122

16
26
26
10


1,249

1,552
38
28
27
8
13
9
0
0.01
0.01


1
CV
(%)
2.2

8.0

1.6


8.1

27.2
11.2

1.3

5.7
1.5
43.8
0.7
6.3

2.0

5.3
11.1
42.6
22.8


2.5

0.9
1.8
23.7
13.7
35.7
8.7
8.4

1.3
1.3


3.7
-------
             Appendix D

           pH Titration and
Constituent Leaching as a Function of pH
          (SR002 test results)
Fly Ash Comparisons
pH titration
Mercury
Aluminum
Antimony
Arsenic
Barium
Boron
Cadmium
Chromium
Cobalt
Lead
Molybdenum
Selenium
Thallium
Gypsum Comparisons
pH titration
Mercury
Aluminum
Antimony
Arsenic
Barium
Boron
Cadmium
Chromium
Cobalt
Lead
Molybdenum
Selenium
Thallium
D-1
D-2
D-3
D-4
D-5
D-6
D-7
D-8
D-9
D-10
D-11
D-1 2
D-1 3
D-1 4
D-1 5
D-1 6
D-1 7
D-1 8
D-1 9
D-20
D-21
D-22
D-23
D-24
D-25
D-26
D-27
D-28
D-29
D-30
-------
Scrubber Sludge Comparisons
pH titration
Mercury
Aluminum
Antimony
Arsenic
Barium
Boron
Cadmium
Chromium
Cobalt
Lead
Molybdenum
Selenium
Thallium
Fixated Stabilized Sludge Comparisons
pH titration
Mercury
Aluminum
Antimony
Arsenic
Barium
Boron
Cadmium
Chromium
Cobalt
Lead
Molybdenum
Selenium
Thallium
Table of Outliers
D-31
D-32
D-33
D-34
D-35
D-36
D-37
D-38
D-39
D-40
D-41
D-42
D-43
D-44
D-45
D-46
D-47
D-49
D-51
D-53
D-55
D-57
D-59
D-61
D-63
D-65
D-67
D-69
D-71
D-73
D-75
-------
         Fly Ash Comparisons (FA)
Facility A
Coal: low sulfur bituminous
ARC: NO+SNCR+FF
Facility B
Coal: low sulfur bituminous
ARC: NO+SCR+ESP(CS) [Mg lime]

Facility K
Coal: sub- bituminous
ARC: NO+SCR+ESP(CS) [Mg lime]
CFA
(SNCROff)

AFA
(SNCROn)
DFA
(SCR Off)

BFA
(SCR On)
  KFA
(SCR On)
-------
Fly Ash Comparisons




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14
-------
   Gypsum (Gyp-U, Gyp-W) Comparisons
Facility N
Coal: bituminous
ARC: FO+SCR+ESP(CS)


Facility O
Coal: bituminous
ARC: FO+SCR+ESP(CS)


Facility P
Coal: bituminous
ARC: FO+ SCR & SNCR +ESP(CS)


Facility Q   	
Coal: sub-bituminous
ARC: FO+SCR+ESP(CS)
Gyp-U
NAU
(unwashed)

OAU
(unwashed)




Gyp-W
NAW
(washed)

OAW
(washed)
 PAD (U)
(unwashed)
  QAU
(unwashed)
-------
Gypsum Comparison
Gyp-U
14
19
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14
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-------
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-------
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ASR2-CGD-C


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14
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14


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14
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14
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ASR2-BGD-C


14
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14
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     1000 -E

      100


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 ^2.44
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      0.1


  	ML
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10   12    14
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            ASR2-CGD-C
                                                 1000
                                                  100
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                                                          A SR2-AGD - C
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                                                          ASR2-BGD-C
1000
100

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14
-------
Fixated Scrubber Sludge (FSS, FSSL) Comparisons
FSS: Fly Ash + Scrubber Sludge (FA+ScS)
 Facility A (FSS)
 Coal: low sulfur bituminous
 ARC: NO+SNCR+FF
ccc
(S NCR Off)

ACC
(SNCROn)
page break
FSSL: Fly Ash + Scrubber Sludge + Lime (FA+ScS+lime)
 Facility B (FSSL)
 Coal: low sulfur bituminous
 ARC: NO+SCR+ESP(CS) [Mg lime]

 Facility K (FSSL)
 Coal: sub-bituminous
 ARC: NO+SCR+ESP(CS) [Mg lime]


 Facility M (FSSL)
 Coal: bituminous
 ARC: IO+SCR+ESP(CS)
DCC
(SCR Off)

BCC
(SCR On)
 KCC
(SCR On)
MAD
(SCR Off)

MAS
(SCR On)
-------
Fixated Scrubber Sludge Comparisons




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19
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-------
Fixated Scrubber Sludge Comparisons

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122 19
m
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ASR2-DCC-C



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            ASR2-MAD-C
                                                14
                                             11.6
                                                10
        -2-10123456
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-------
Off
On
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4 6 8 10 12
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ASR2-CCC-C


14
100
10
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14
100
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ASR2-BCC-C


14
100
10
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14
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14
-------
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14
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A SR2-ACC - C


14
-------
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mnnnnn
mnnnn
mnnn
• — • mnn
i! 100 -
^ Q c-i 1 n H

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A 4 6 8 10 W
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ASR2-DCC-C


14
mnnnnn
mnnnn
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3- 100 -
< 10

1 J
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80
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pH
OSR2-BCC-A OSR2-BCC-B
ASR2-BCC-C


14
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14
mnnnnn
mnnnn
mnnn
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3- 100 -
< 10

1 J
0 1
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OSR2-MAD-A OSR2-MAD - B
ASR2-MAD-C


14
mnnnnn
mnnnn
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i! 100 -
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1 J
0 1
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pH
0 S R2-MAS - A 0 S R2-MAS - B


14
-------
Off
On
mnn
100
zr
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CO
0 1
	 ML
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100
4 6 8 10 12
pH
0 SR2-CCC - A 0 SR2-CCC - B
A SR2-CCC - C


14
1000
100
56.3
U
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w
0 1
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A SR2-ACC - C


14
-------
Off
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100
u
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SMCL "
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ASR2-DCC-C


14
1000
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ASR2-BCC-C


14
1000
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14
1000
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-------
Off
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518.8
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A SR2-CCC - C


14

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4 6 8'4 10 12 14
pH
a SR2-ACC - A 0 SR2-ACC - B
A SR2-ACC - C


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ASR2-DCC-C



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ASR2-BCC-C



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ASR2-MAD-C


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14
OSR2-CCC-A OSR2-CCC-B
ASR2-CCC-C


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0 S R2-ACC - A OS R2-ACC - B
ASR2-ACC-C


-------
Off
On
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SR002.1 Outliers resulting from inconsistency in pH determination.

Material

AFA
BFA
KFA
AGO
AGO
AGO
AGO
AGO
AGO
AGO
BCD
NAU
BCC
BCC
MAD
SR002.1
Material
CFA
CFA
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AFA
CGD
CGD
CGD
DGD
NAW
NAW
Test
Position

T08
T08
T05
T01
T02
T03
T04
T05
T06
T07
T09
T06
T03
T04
T11

Replicate

A
C
B
C
C
C
C
C
C
C
B
B
C
C
C
Cone. [gq/LI
pH Hg Al
S.I. ug/L ug/L
8.40 0.245 7570
8.36 0.01 1210
5.05 0.02 721
1.35 0.01 52800
1.65 0.01 43800
1.85 0.03 39700
2.03 0.03 34800
2.32 0.01 24700
2.58 0.01 22000
3.76 0.02 9580
7.61 0.025 2440
4.12 0.002 341
2.71 1.49 3780
3.74 1.74 808
3.63 8.23 74546

Sb
ug/L
31.4
6.17
34.9
61.3
20.6
16.1
9.55
5.01
4.15
3.65
2.79
0.971
6.02
4.73
75.6
Outliers resulting from inconsistency in concentration
Replicate
A
A
A
B
B
B
C
C
A
B
Element
Cd
Co
Co
Cd
Sb
Mo
Cd
Cr
As
Pb
pH[S.I.]Conc. [ug/L]
3.32 72.9
9.00 6.73
7.92 0.730
11.6 4.22
5.23 11.1
5.23 9.42
8.98 1.17
9.03 24.3
7.25 10.2
5.39 9.32












As
ug/L
57.9
29.3
114
243
129
13.3
9.26
7.16
6.11
6.12
5.54
0.55
69.1
28.4
4317

Ba
ug/L
312
142
226
80.0
93.7
83.8
70.4
69.7
61.8
37.2
162
65.9
188
83.8
2725

B Cd
ug/L ug/L
557 0.608
7532 1.190
37652 1 .478
7185 2.0
7859 2.0
8154 1.93
7103 1.77
7266 1 .750
7647 1.700
6632 1 .660
583 0.200
2164 0.200
8435 7.360
7121 9.410
26299 4.81

Cr
ug/L
1310
873
6
900
882
869
848
732
787
719
220
6
703
712
26

Co
ug/L
8.4
7.0
1.8
106
90.3
85.0
79.0
81.9
77.0
63.2
0.26
1.4
168.0
83.8
190

Pb
ug/L
0
0
0
64
35
8
3
0
0
0
0
0
1
1
8

Mo
ug/L
877
1874
2071
117
61.9
7.9
0.4
0.4
4.1
21.6
61.4
14.5
77
103
697

Se
ug/L
83
14
40.9
119
68
37
20
25
21
20
3
17.0
61
47
873

Tl
ug/L
3.33
1.94
87.9
8.65
7.96
6.56
7.38
7.45
6.50
7.15
4.15
4.36
9.91
7.07
182
measurements.



































































































-------
             Appendix E

               pH and
Constituent Leaching as a Function of LS
         (SR003 test results)
Fly Ash Comparisons
pH titration
Mercury
Aluminum
Antimony
Arsenic
Barium
Boron
Cadmium
Chromium
Cobalt
Lead
Molybdenum
Selenium
Thallium
Gypsum Comparisons
pH titration
Mercury
Aluminum
Antimony
Arsenic
Barium
Boron
Cadmium
Chromium
Cobalt
Lead
Molybdenum
Selenium
Thallium
E-1
E-2
E-3
E-4
E-5
E-6
E-7
E-8
E-9
E-10
E-11
E-1 2
E-1 3
E-1 4
E-1 5
E-1 6
E-1 7
E-1 8
E-1 9
E-20
E-21
E-22
E-23
E-24
E-25
E-26
E-27
E-28
E-29
E-30
-------
Scrubber Sludge Comparisons
pH titration
Mercury
Aluminum
Antimony
Arsenic
Barium
Boron
Cadmium
Chromium
Cobalt
Lead
Molybdenum
Selenium
Thallium
Fixated Stabilized Sludge Comparisons
pH titration
Mercury
Aluminum
Antimony
Arsenic
Barium
Boron
Cadmium
Chromium
Cobalt
Lead
Molybdenum
Selenium
Thallium
Table of Outliers
E-31
E-32
E-33
E-34
E-35
E-36
E-37
E-38
E-39
E-40
E-41
E-42
E-43
E-44
E-45
E-46
E-47
E-49
E-51
E-53
E-55
E-57
E-59
E-61
E-63
E-65
E-67
E-69
E-71
E-73
E-75
-------
         Fly Ash Comparisons (FA)
Facility A
Coal: low sulfur bituminous
ARC: NO+SNCR+FF
Facility B
Coal: low sulfur bituminous
ARC: NO+SCR+ESP(CS) [Mg lime]

Facility K
Coal: sub- bituminous
ARC: NO+SCR+ESP(CS) [Mg lime]
CFA
(SNCROff)

AFA
(SNCROn)
DFA
(SCR Off)

BFA
(SCR On)
  KFA
(SCR On)
-------
Fly Ash Comparisons




Off
On

19
in
I R
Q. °
R
/
9
c


ft I
B '




I




^8^











I





b





2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-CFA - A 0 SR3-CFA - B
A SR3-CFA - C



19
m
1 8-
R
/
9
C

/
^



i
>
]




a











\
s.




9





2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-AFA - A 0 SR3-AFA - B
A SR3-AFA - C



19
1 n
I R
Q. °
R
A
9
C

a° t





\





6











i
E




\
]




2 4 6 8 10 12
LS ratio [mL/g]
OSR3-DFA-A OSR3-DFA-B
ASR3-DFA-C



19
1 n
I R
Q. °
R
A
9
C


ax *





\





a






















2 4 6 8 10 12
LS ratio [mL/g]
nSR3-BFA-A OSR3-BFA-B
ASR3-BFA-C



19
m
X ft
Q. b
R
/
9
c


OB t





8





3











(





J




2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-KFA - A 0 SR3-KFA - B


-------
Off
On
0 s
MPI 9 -H
HP 15
i rb
^.
ai
n 5
n H
C
	 ML
	 'MDL




O— J




n



















A


2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-CFA - A 0 SR3-CFA - B
A SR3-CFA - C


0 ^
MPI 9 -H
HP 15
i rb
^.
ai
n 5
n H
C
	 ML
	 'MDL




_l& I




* 	




6














R


2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-AFA - A 0 SR3-AFA - B
A SR3-AFA - C


0 S
MPI 9 -H
HP 15
i rb
^.
^1
n 5
n H
C
	 ML
	 >MDL




A
A
•B^ I




a




A









i




•


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-DFA-A OSR3-DFA-B
ASR3-DFA-C


0 ^
MPI 9 -H
HP 15
i rb
^.
^1
n 5
n H
C
	 ML
	 >MDL




_nj± ]




s




DD














ja


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-BFA-A OSR3-BFA-B
ASR3-BFA-C


0 ^
MPI 9 -H
HP 15
i rb
^.
^1
n 5
n H
C
	 ML
	 'MDL




5&_i




«




_pq









•




I


2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-KFA - A 0 SR3-KFA - B


-------
Off
On
4nnn


3000 -
"^nn
01 onnn
7? i^nn
1000 -
500
n H
C
	 ML
— 'MDL



t
D






k























C




]
t
£


1



2 4 6 8 10
LS ratio [mL/g]
0 SR3-CFA - A 0 SR3-CFA - B
A SR3-CFA - C


12

-lonnn
16000 -
14000 -
i9nnn
=d mnnn
D) IUUUU
— snnn
**• Rnnn

4000 -
ZUUU
n
C
	 ML
	 >MDL







?
*



]




ft

















1
f


<




5


^




2 4 6 8 10
LS ratio [mL/g]
OSR3-AFA-A OSR3-AFA-B
ASR3-AFA-C


12
^nnn
2500 -
9nnn
n1
01 i^nn
"^ mnn
^nn
n H
C
	 ML
	 >MDL


6
fi
1





!


&



















>

T
2 4 6 8 10
LS ratio [mL/g]
OSR3-DFA-A OSR3-DFA-B
ASR3-DFA-C


12

ocinn

2000 -
T 1500
^)
^.
mnn
^nn
n H
C
	 ML
— >MDL

-n —
&
A j


ei





A
D
0









E





)



2 4 6 8 10
LS ratio [mL/g]
OSR3-BFA-A OSR3-BFA-B
ASR3-BFA-C


12

°nnnn
isnnn
iRnnn
14000 -
T 19000 -
S 10000 -
snnn
Rnnn
4nnn
9nnn
n
C
	 ML
	 >MDL




|
ijl
nn












n
^\



















^
I


















2 4 6 8 10
LS ratio [mL/g]
OSR3-KFA-A OSR3-KFA-B


12
-------
Off
On
Of^

20 -
U 15 _
0)
^.
_o m
w 1U
MCL c
n j
c
	 ML
	 'MDL



R :

^_ .



3

^^ H



a
§

^^ ,





. ^^





• ^^
5
A



• ^_


2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-CFA - A 0 SR3-CFA - B
A SR3-CFA - C


^n
25 -
9n
H 15 -
_Q
w -in -
MPI
MOL 5 t
n '
c
	 ML
	 >MDL
"





^J _





^_ m



B


^_ ,






. ^_






_ ^_



a


_ ^

i
2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-AFA - A 0 SR3-AFA - B
A SR3-AFA - C


Q
7 _
MPI R

^ 4 -

OT 3 -
2 -
1 _
n -















•AA'£~~ "
0
	 ML
— >MDL





— p —

— •







• —







- —

5
3





- —


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-DFA-A OSR3-DFA-B
ASR3-DFA-C





=d 15 -
0)
S1 10 -
W
MCL
0
0
c
	 ML
	 >MDL

i

A

^_ .

\



^^ H



—8-

^^ ,





. ^^





• ^^





• ^_


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-BFA-A OSR3-BFA-B
ASR3-BFA-C


Rn
^n
4n
H 30 -
J3
OT on
m
MPI

0 -T
C
	 ML
	 >MDL
D
So J





\







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/













2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-KFA - A 0 SR3-KFA - B


-------
Off
On
°5
90
U 15 -
0)
^.
01 MPI 10^
<
c
0 -
C
	 ML
— 'MDL
o
2



— -

\



— -
D
A
0


— i





- —





- —


A


- —


2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-CFA - A 0 SR3-CFA - B
A SR3-CFA - C


^n
A^\
A(\
1.*
U 30
3 25-
(/) 9n
15
MPI 1 n -
5 _
n
C
	 ML
	 >MDL








* 4
•*--,-*-








»
^-SfT-








0
¥*[&,• i









- -, *(&* '









-, -*^'
^

D
£






v ,-•*-


2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-AFA - A 0 SR3-AFA - B
A SR3-AFA - C


Rn
70-
Rn
• — • ^n
D) ,.«
J? ?n -
9f"l

MCL 10 -
-
C
	 ML
	 >MDL
a
H







S








0














I







D


&





2 4 6 8 10 12
LS ratio [mL/g]
OSR3-DFA-A OSR3-DFA-B
ASR3-DFA-C


fin
5n
dn
5 30 -
MDL
A
8
3


^^^ _ .


I





6

















n
5




2 4 6 8 10 12
LS ratio [mL/g]
OSR3-BFA-A OSR3-BFA-B
ASR3-BFA-C


fln
yn
Rn
• — • ^n
D) ,.«
J? 30 -
9n
MPI 10-

0 -I
C
	 ML
	 >MDL
DO A
7






>







n














1
t






5








2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-KFA - A 0 SR3-KFA - B


-------
Off
On
7500


2500 -
5"MCi)oo -
-g, ZUUU
•— ' 1500
CD
innn
500 -
n H
C
	 ML
	 'MDL

A
LJ





° I
,

\






O
A
D




















a
A

2 4 6 8 10
LS ratio [mL/g]
0 SR3-CFA - A 0 SR3-CFA - B
A SR3-CFA - C


12

AOOO
3500 -
3000 -
1 — • 9500
d IV/ir-l
^g,MCL
2> OOOO -
to 1500
mnn

n H
C
	 ML
	 >MDL
A
O
— 0—






ft












A

























0
2 4 6 8 10
LS ratio [mL/g]
0 SR3-AFA - A 0 SR3-AFA - B
A SR3-AFA - C


12

of^nn
MPI 9nnn -,
U 1500
D)
m mnn
CD
500
0 H
C
	 ML
	 'MDL




D6 t




4




D















*
2 4 6 8 10
LS ratio [mL/g]
OSR3-DFA-A OSR3-DFA-B
ASR3-DFA-C


12

°500
MPI 9000 -H
U 1500
D)
m mnn
CO
500
0 H
C
	 ML
	 'MDL




A_6 1




S




A















a
2 4 6 8 10
LS ratio [mL/g]
OSR3-BFA-A OSR3-BFA-B
ASR3-BFA-C



12

°500
MPI 9000 ^
U 1500
D)
m mnn
CO
500
0 H
C
	 ML
	 'MDL




Qu [




J




0









(





!
2 4 6 8 10
LS ratio [mL/g]
0 SR3-KFA - A 0 SR3-KFA - B


12

-------
Off
On
snnn
nwFi 7000 -.
ROOO
^ooo
"01 /ooo
m?ooo
9nnn
mnn
n H
c
	 ML
	 'MDL






i






i
isX^






D
^fc.























&

2 4 6 8 10
LS ratio [mL/g]
0 SR3-CFA - A 0 SR3-CFA - B
A SR3-CFA - C


12

Rnnn
nwFiynnn -*
Rnnn
^nnn
"3> dnnn
m^nnn
9nnn
mnn
n H
C
	 ML
— >MDL














1*3—






n

























4 ^
2 4 6 8 10
LS ratio [mL/g]
0 SR3-AFA - A 0 SR3-AFA - B
A SR3-AFA - C


12

£000
DWEL7000 -
6000 -
^000

^_
9000
1000
0 H
c
	 ML
	 'MDL

0n
Q





Q










D
&























*



2 4 6 8 10
LS ratio [mL/g]
OSR3-DFA-A OSR3-DFA-B
ASR3-DFA-C


12

vnnnn


50000 -
U 4nnnn
D)
" 30000 -
m
9nnnn
...10000 -
DWEL
n
C
	 ML
	 >MDL

a

B ,






>
i







fi























2 4 6 8 10
LS ratio [mL/g]
OSR3-BFA-A OSR3-BFA-B
ASR3-BFA-C




12
onnnnn
ocnnnn
9nnnnn
n1
^) ic;nnnn
m mnnnn
c;nnnn
DWEL n '
c
	 ML
	 >MDL
O
n
Q
8





J






a












!





j

2 4 6 8 10 12
LS ratio [mL/g]
OSR3-KFA-A OSR3-KFA-B


-------
Off
On
p.
MPI ^
4 -
S 3-
T3
O 9 -
-1 _
n -




A
: |
— -
0
	 ML
	 >MDL




$
— -





-S .





• —





- —





s -


2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-CFA - A 0 SR3-CFA - B
A SR3-CFA - C


p.
MPI ^
4 -
S 3-
T3
O 9 -
-1 _
n -




: 8

i
— -
0
	 ML
	 >MDL




^
— -





a





- —





- —




A. m-m—
6 _


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-AFA-A OSR3-AFA-B
ASR3-AFA-C


m
Q
" 6
^MCI
-n A
O
9
n
C
	 ML
	 >MDL

S


1

_ _




^

-— -





a
— _ .






. —






• ^^H






S. _


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-DFA-A OSR3-DFA-B
ASR3-DFA-C


Of^
20-
HT 15
i 1b
^.
T! m
O
MPI ^ -
04
C
	 ML
	 >MDL
D
£
a
I



)





A














*


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-BFA-A OSR3-BFA-B
ASR3-BFA-C


m
0
" 6
^MCI
-n 4
O
9
n
C
	 ML
	 >MDL

5




^^H •

J




— -




3

— - .






. -—










....f ...
- J-,-

i
2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-KFA - A 0 SR3-KFA - B


-------
Off
On
1600

141)1) -
:j 1000 -
? ROO

O oUU
200 -
MCL •
C
	 ML
	 'MDL

O
A

1







I








B
v
























fl

2 4 6 8 10
LS ratio [mL/g]
0 SR3-CFA - A 0 SR3-CFA - B
A SR3-CFA - C


12

°000
1800 -

1400

^ IzUU
51 mnn
" 800 -
O
ROO
400
200 -
MCL Z™
C
	 ML
— >MDL
A

&




L















&





























A
u




2 4 6 8 10
LS ratio [mL/g]
0 SR3-AFA - A 0 SR3-AFA - B
A SR3-AFA - C


12

°000
1800 -

1400

^ IzUU
51 mnn
" 800 -
O
ROO
400

MCL 2°°
0 -f
C
	 ML
	 >MDL

6


A
fa

i









i










D






























	 13 	
2 4 6 8 10
LS ratio [mL/g]
OSR3-DFA-A OSR3-DFA-B
ASR3-DFA-C



12

4000

OOUU -
TOOO
H1 2500 -
51 9nnn

O luUL)
mnn
500 -
MPI r\ .
c
	 ML
	 >MDL
9


A
1







I








0

























&

2 4 6 8 10
LS ratio [mL/g]
OSR3-BFA-A OSR3-BFA-B
ASR3-BFA-C


12

1RO
140
190

_j MCL1 uu
^ RO -
/•^ Rn
yin
9n
n H
c
	 ML
	 >MDL

D
0
u

t







\








D
O























*



2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-KFA - A 0 SR3-KFA - B


-------
Off
On
0 s
2 -
U is
i 1-5
^.
0 1
o 1
.5 J
n
C
	 ML
	 'MDL

0
0
I




>



a

A















A
2 4 6 8 10
LS ratio [mL/g]
0 SR3-CFA - A 0 SR3-CFA - B
A SR3-CFA - C


12
1R
1R

14
19
- 10-
D) IU
" 0
o 8
O R
4 -
9
0
C
	 ML
	 >MDL
<>
6


\

«




^~i T




-I-P -




ft



1-P-, '








• ,^-P








-, 1-1-



n
fi



T ,^—

2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-AFA - A 0 SR3-AFA - B
A SR3-AFA - C


0 S
9
U 1 S
i 1-5
^.
0 1
o 1
n ^ -i
n
C
	 ML
	 >MDL




AA i




^




A















\
2 4 6 8 10
LS ratio [mL/g]
OSR3-DFA-A OSR3-DFA-B
ASR3-DFA-C



12
°n
1R
1R
14
U 1?
^l lz
T* m -
0 ft
0 6
yl
o
n '
C
	 ML
	 >MDL


A^



6?
O




^"i ¥





-I-P ,-
n

A
o





i-pi, •









• ,^-p









-, i-p-





&
&


¥ ,^—

2 4 6 8 10 12
LS ratio [mL/g]
OSR3-BFA-A OSR3-BFA-B
ASR3-BFA-C


"> ^
9
U 1 s
i 1-5
^.
0 1
o 1
n s

-T
C
	 ML
	 >MDL
O




































2 4 6 8 10
LS ratio [mL/g]
0 SR3-KFA - A 0 SR3-KFA - B


12
-------
Off
On
1fi
MPI
•\A
19
1 — • in
_l IU
5 8 -
;? R -
Q_ D
A
9
n j
C
	 ML
	 'MDL









^









*^« •









-^S -









. ^^









• ^^









# ^


2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-CFA - A 0 SR3-CFA - B
A SR3-CFA - C


1fi
MPI
14
19
1 — • m
_i iu
5 8 -
;? R -
Q_ D
A
9
n
C
	 ML
	 >MDL









—a. i









ill. _









•.1£',









, ^^









• ^^









A —


2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-AFA - A 0 SR3-AFA - B
A SR3-AFA - C


1R
MPI
14
19
1 — • m
_l IU
5 8 -
;? R -
Q_ D
4
9
0
C
	 ML
	 >MDL









-O^J









^^^ -









-^*i .









. ^^









• ^^









A- ^


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-DFA-A OSR3-DFA-B
ASR3-DFA-C


1R
MPI
14
19
1 — • m
_i iu
5 8 -
P R -
Q_ D
A
9
0
C
	 ML
	 >MDL








Aff.J









ill. _









•^'









. ^^









• ^^









A- ^


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-BFA-A OSR3-BFA-B
ASR3-BFA-C


1R
MPI
14
19
1 — • m
_i iu
5 s -
;? R -
Q_ D
4
9

-
C
	 ML
	 >MDL









-f&-<




















































!^7V — V 	 1 	 v 	 1 	 1 	 v 	 1
2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-KFA - A 0 SR3-KFA - B


-------
Off
On
onnnn

25000 -
9nnnn -
_i
5 ic;nnn -
0
s mnnn -
5000 -

DWEL 0 4
C
	 ML
	 'MDL
O









a g_





O



















2 4 6 8 10
LS ratio [mL/g]
0 SR3-CFA - A 0 SR3-CFA - B
A SR3-CFA - C


12

T^nn
3000 -
9c;nn
=d 9nnn
D) ^-UUU
3.
1—1 1500
innn

ODD -
DWEL
0 -f
C
	 ML
	 >MDL

&

!






s









—




















g

2 4 6 8 10
LS ratio [mL/g]
0 SR3-AFA - A 0 SR3-AFA - B
A SR3-AFA - C


12
Rnnn
7000 -
6000 -
T ^nnn
5 dnnn
° ?nnn
9nnn

1UUU -
DWEL n
C
	 ML
	 >MDL
a
o


Q

1







I








— D —



























2 4 6 8 10
LS ratio [mL/g]
OSR3-DFA-A OSR3-DFA-B
ASR3-DFA-C


12

i4nnn


10000 -
=d Rnnn
D) OUUU
^.
1 ' Rnnn
4nnn
2000 -
DWEL n
C
	 ML
	 >MDL

1


8
:






I







A






















2 4 6 8 10
LS ratio [mL/g]
OSR3-BFA-A OSR3-BFA-B
ASR3-BFA-C




12
^nnnn
-3c;nnn
-snnnn
•—? 9c;nnn
5 onnnn
° i^nnn
innnn
cnnri
DWEL 0
C
	 ML
	 >MDL
o
D


Q


















D























s
2 4 6 8 10
LS ratio [mL/g]
OSR3-KFA-A OSR3-KFA-B



12
-------
Off
On
fin

MCL o(J -
A_r\
S 30-
CD
OT on -
10 -

0 J
C
	 ML
	 'MDL

O
n
X





>






a
ft

















A




2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-CFA - A 0 SR3-CFA - B
A SR3-CFA - C


yn
60 -
MPI ^n -
=d dn
^) ^u
•— • 30
w
9n

ID -
0 -1
C
	 ML
	 >MDL

A
a
1






fc






/V
A





















6




2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-AFA - A 0 SR3-AFA - B
A SR3-AFA - C


fin
MPI ^n -H
4n
S 30-
0)
OT on
m

o 4
c
	 ML
	 >MDL

W

0
<





^





B











I
i




D
&


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-DFA-A OSR3-DFA-B
ASR3-DFA-C


190
inn
Rn
_i
"5 60 -
"MPI
w An -
9n

0 -T
C
	 ML
	 >MDL

B

%

:






i




























d


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-BFA-A OSR3-BFA-B
ASR3-BFA-C






n1
2.
(D
w 150 -
inn
MPI ^n -H
n H
C
	 ML
— >MDL
n
o

D
r
<







i










Q

















t









i


2 4 6 8 10
LS ratio [mL/g]
0 SR3-KFA - A 0 SR3-KFA - B


12
-------
Off
On
10
m
Q
^3) R _
ZL D
F 4 -
MCL 2 -
i
0 -
C
	 ML
	 'MDL
O




— _

y



— -

O



— .





. —





- —



H

- —


2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-CFA - A 0 SR3-CFA - B
A SR3-CFA - C


1R
14
19
m
-p 1U
"3) R
ZL °
rr R
A

MCL 2 -
n
C
	 ML
	 >MDL
A
It
n
':

1

__ _


\
>

D

__ _



A


D
__ ,







. __







_ __






ft


I
2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-AFA - A 0 SR3-AFA - B
A SR3-AFA - C


A
3.5 -
-3
"> ^
_, zo
D)MP| 9 -H
LT 1 S
1
n ^
n
C
	 ML
	 >MDL
D
%

a
u
i




]
\
t

A





n


__ .
A















_ __





\



>


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-DFA-A OSR3-DFA-B
ASR3-DFA-C


-10
10-
0

"3) R
=L D
H 4 _
MPI 9 -H
i
n
C
	 ML
	 >MDL
ft

5


_ _


J


__ _



D
&
— ,





. __











i

i
2 4 6 8 10 12
LS ratio [mL/g]
OSR3-BFA-A OSR3-BFA-B
ASR3-BFA-C


^nn
ocn
9nn
ZT
"01 i^n
^~ mn
^n
MPI n -i
C
	 ML
	 >MDL
A


1





3






Q

















\

2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-KFA - A 0 SR3-KFA - B


-------
   Gypsum (Gyp-U, Gyp-W) Comparisons
Facility N
Coal: bituminous
ARC: FO+SCR+ESP(CS)


Facility O
Coal: bituminous
ARC: FO+SCR+ESP(CS)


Facility P
Coal: bituminous
ARC: FO+ SCR & SNCR +ESP(CS)


Facility Q   	
Coal: sub-bituminous
ARC: FO+SCR+ESP(CS)
Gyp-U
NAU
(unwashed)

OAU
(unwashed)




Gyp-W
NAW
(washed)

OAW
(washed)
 PAD (U)
(unwashed)
  QAU
(unwashed)
-------
Gypsum Comparison




Gyp-U
14
19
in
I R
Q. °
R
4
9
C



D t





J





5











I





]



2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-NAU - A 0 SR3-NAU - B


14
19
m
I R
Q. °
R
A
9
C



0 5





\





B











E





]



2 4 6 8 10 12
LS ratio [mL/g]
OSR3-OAU-A OSR3-OAU-B


Gyp-W
14
19
m
I R
a. °
R
A
9
C




a 5




J
^ 	




o
D










S,





j



2 4 6 8 10 12
LS ratio [mL/g]
OSR3-PAD-A OSR3-PAD-B


14
19
m
I R
Q. °
R
A
9
C



a





5





D











\





J



2 4 6 8 10 12
LS ratio [mL/g]
OSR3-NAW-A OSR3-NAW-B


14
19
m
1 8-
R
/
9
C


n
i





3





0











I





>



2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-OAW - A 0 SR3-OAW - B


14
19
m
I R
Q. °
R
A
9
C



3




J
...



ft











R





i



2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-QAU - A 0 SR3-QAU - B


-------
Gyp-U
0 s
MPI 9 -
HP 15-
i 1-b
^.
ai
n 5
n H
C
	 ML
	 'MDL




.^. .



























2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-NAU - A 0 SR3-NAU - B


0 ^
MPI 9 -
HP 15
i 1-b
^.
^1
n 5
n H
C
	 ML
	 >MDL
































2 4 6 8 10 12
LS ratio [mL/g]
OSR3-OAU-A OSR3-OAU-B


Gyp-W
0 S
MPI 9
HP 1 5 -
0)
^.
a-i
n 5
n
C
	 ML
	 >MDL




— ^ t-




*




_a

















2 4 6 8 10 12
LS ratio [mL/g]
OSR3-NAW-A OSR3-NAW-B


0 ^
MPI 9
HP 1 5 -
0)
^.
^1
n 5
n
C
	 ML
	 >MDL




_ft_.



























2 4 6 8 10 12
LS ratio [mL/g]
0 S R3-OAW - A OS R3-OAW - B


0 ^
MPI 9 -
HP 15
i 1-b
^.
^1
n 5
n H
C
	 ML
	 'MDL




a ^




!l




_lfiL..

















2 4 6 8 10 12
LS ratio [mL/g]
OSR3-PAD-A OSR3-PAD-B


0 ^
MPI 9
HP 1 5 -
0)
^.
^1
n 5
n
C
	 ML
	 'MDL




_*>_r



























2 4 6 8 10 12
LS ratio [mL/g]
OSR3-QAU-A OSR3-QAU-B


-------
Gyp-U
4nn
?^n -
?nn -
"^n
01 9nn -
7? 1^0-
mn
^n -
n
c
	 ML
	 'MDL





t
a






a





0













L








J






2 4 6 8 10
LS ratio [mL/g]
0 SR3-NAU - A 0 SR3-NAU - B


12
A^n
Ann
T^n
?nn
=d 9^(1
0) ZOU
— Tin
< iKf) -
mn
^n
n
c
	 ML
	 >MDL



r



n
° ?
O








D
O
















A
















2 4 6 8 10
LS ratio [mL/g]
OSR3-OAU-A OSR3-OAU-B


12
Gyp-W
4nn
?^n
?nn
^^in
01 9nn
:< i^n
mn
^n
n H
c
	 ML
	 >MDL








i

Q








U












A

^












2 4 6 8 10
LS ratio [mL/g]
OSR3-NAW-A OSR3-NAW-B


12
mnn
onn
ann
ynn
"~T ROD
^ 500
"
<
9nn
inn
n H
C
	 ML
	 >MDL


a
o
r





>



]






O
D

















I
MDL
9 j






]






o



















s







2 4 6 8 10 12
LS ratio [mL/g]
OSR3-PAD-A OSR3-PAD-B


°nn
1 j?n
iRn
140
"T 190
01 mn
1 ' Rn
< ou
RO
4n
9n
n H
c
	 ML
	 >MDL




C

n 






n

o















n
S
















2 4 6 8 10
LS ratio [mL/g]
OSR3-QAU-A OSR3-QAU-B


12
                                       E-19
-------
Gyp-U
Q
7 _
MPI R

^ 4 -

co 3
9
1 _





E n

i v <


0 -r
0
	 ML
— >MDL


]


>







O




























— - i^ -i — v ~~ i- ~~u
2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-NAU - A 0 SR3-NAU - B


Q
7 _
MPI R

_i 5
"3> *
-° -3
co °
9
1 _




= ^T^

; C



0 -r
0
	 ML
	 'MDL


l^~

>



p



0

















*







s



•%» - i^ -i ~~ v ~~ r ^nj
2 4 6 8 10 12
LS ratio [mL/g]
OSR3-OAU-A OSR3-OAU-B


Gyp-W
7
MPI R
c
5" 4
^) ^
3.
1 — ' ^
J3 °
co
9
1





; °



]
— ^


0 -r
0
	 ML
	 >MDL





D
>W

























2 4 6 8 10 12
LS ratio [mL/g]
OSR3-NAW-A OSR3-NAW-B


Q
7
MPI R

^ 4 -

co 3
9
1



: 0

t
! o




0 -r
0
	 ML
	 'MDL


]

>




u



o
























....I...


— - i^ -i — v ~~ i- ^nj
2 4 6 8 10 12
LS ratio [mL/g]
0 S R3-OAW - A OS R3-OAW - B


7
MPI R -
c
5" 4
^) ^
3.
1 — ' ^
J3 °
co
9
1 _






'- ft

t

0 -r
0
	 ML
	 >MDL





J





O
D




















...A....


— - i^— -i ~~ v ~~ r ^^j- ~n
2 4 6 8 10 12
LS ratio [mL/g]
OSR3-PAD-A OSR3-PAD-B



19
m
51 s
^> °
1 — 'MPI R -,
CO
A
9
0,
c
	 ML
	 >MDL

D

i






\








o













c






J



2 4 6 8 10 12
LS ratio [mL/g]
OSR3-QAU-A OSR3-QAU-B


                                       E-20
-------
Gyp-U
19
MPI m ^
g
U
5 6 -
"<





>





,0, '





• —





" , ,1





]"



2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-NAU - A 0 SR3-NAU - B


19
MPI m ^
g
U
5 6 -
MDL


[
D
o <



]

X
— -




0
~ '





• 	




. . . .<




>




2 4 6 8 10 12
LS ratio [mL/g]
OSR3-OAU-A OSR3-OAU-B


Gyp-W
19
MPI m ^
g
U
5 6 -
w
< 4 -
9
i
n
C
	 ML
	 >MDL



4

~>"i



v

]





^, '





• —





" , ,<





>


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-NAW-A OSR3-NAW-B


19
MPI m ^
g
U
5 6 -
w
< 4 -
9
i
n
C
	 ML
	 >MDL



[
D
0 ,
— -



]
^
— -




O
~ '





• —





" , ,1





]"


2 4 6 8 10 12
LS ratio [mL/g]
0 S R3-OAW - A OS R3-OAW - B


19
MPI m ^
g
U
5 6 -
j?
< 4
9
i
n
C
	 ML
	 >MDL



&
t





i
— -



0
D
	 •





• 	





" , ,<





>



2 4 6 8 10 12
LS ratio [mL/g]
OSR3-PAD-A OSR3-PAD-B


19
MPI m ^
g
U
5 6 -
w
< 4 -
9
i
n
C
	 ML
	 >MDL

D
0 I
{

— -


]
>

— -



n
o
— '





• —





--





>_ _


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-QAU-A OSR3-QAU-B


                                        E-21
-------
Gyp-U
of^nn
MPI 9nnn
U 1500 -
D)
^.
ra 1000
CO
500
n
C
	 ML
	 'MDL




_^J




>




0









. . . r




i . .


2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-NAU - A 0 SR3-NAU - B


°500
MPI 9000
U 1500 -
D)
^.
ffl 1000
CO
500
n
C
	 ML
	 'MDL




—e~j




1




D









. . . ^




> . , .


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-OAU-A OSR3-OAU-B


Gyp-W
of^nn
MPI 9nnn -
U 1500
D)
^.
ra 1000
CO
500
0 H
C
	 ML
	 >MDL




—&U




i




n









. . i




! . , .


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-NAW-A OSR3-NAW-B


°500
MPI 9000 -
U 1500
D)
^.
ffl 1000
CO
500
0 H
C
	 ML
	 >MDL




__^s_<




> , .




o









. , . i




> . , .


2 4 6 8 10 12
LS ratio [mL/g]
0 S R3-OAW - A OS R3-OAW - B


of^nn
MPI 9nnn
U 1500 -
D)
^.
ra 1000
CO
500
n
C
	 ML
	 'MDL




_^>._<




V i .




n









i • i K




V . | .


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-PAD-A OSR3-PAD-B


of^nn
MPI 9nnn -
U 1500
D)
^.
ra 1000
CO
500
0 H
C
	 ML
	 'MDL




-&J




]




O









, , «




>


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-QAU-A OSR3-QAU-B


                                       E-22
-------
Gyp-U
1 pnnn
1 finnn
1 yinnn

^) mnnn


4nnn
9nnn
n H
c
	 ML
	 'MDL
| Q



'- t









a

































r_









i

) 2 4 6 8 10
LS ratio [mL/g]
0 SR3-NAU - A 0 SR3-NAU - B


12
Rnnnn
cnnnn


^_
m 9nnnn
mnnn
nwp .
n H
c
	 ML
	 'MDL



; t






a







ft























) 2 4 6 8 10
LS ratio [mL/g]
OSR3-OAU-A OSR3-OAU-B


12
Gyp-W
snnn
nwFi ynnn -
finnn
^nnn
"01 /nnn
m?nnn
9nnn
mnn
n H
c
	 ML
	 'MDL







— *1







t







n


























2 4 6 8 10 12
LS ratio [mL/g]
OSR3-NAW-A OSR3-NAW-B


Rnnn
nwFiynnn -
finnn
^nnn
"3> 4nnn
m^nnn
9nnn
mnn
n H
C
	 ML
— >MDL




0
(







J








n
















, ' J







^ ^_


2 4 6 8 10 12
LS ratio [mL/g]
0 S R3-OAW - A OS R3-OAW - B


flnnn
nwFi ynnn
Rnnn
^nnn
"01 /nnn
m?nnn
9nnn
mnn
n
c
	 ML
	 'MDL






Q <















8
















,_^i







>^. ,_^_


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-PAD-A OSR3-PAD-B


vnnnn
cnnnn
cnnnn
U /nnnn
D)
" 30000
m
9nnnn
mnnn
nwFi .
n H
c
	 ML
	 'MDL
D


E







i









a


























2 4 6 8 10
LS ratio [mL/g]
OSR3-QAU-A OSR3-QAU-B


12
                                       E-23
-------
Gyp-U
Q
7 _
R -

1 4-
~° 1 ~
o °
9
1 _


~- 0
i n



I



0
	 ML
	 'MDL




i









Q



























2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-NAU - A 0 SR3-NAU - B



MPI ^
4 -
S 3-
T3
O 9 -
-1 _



i 9




0
	 ML
	 'MDL


J







D











r





j



2 4 6 8 10 12
LS ratio [mL/g]
OSR3-OAU-A OSR3-OAU-B


Gyp-W
R
MPI ^
4
_l
5 3 -
T3
O 9 -
-1





; &

t

0
	 ML
	 'MDL




t





O
p





















2 4 6 8 10 12
LS ratio [mL/g]
OSR3-NAW-A OSR3-NAW-B


R
MPI ^
4
_l
5 3 -
T3
O 9 -
-1





: O

0
I

0
	 ML
	 >MDL




J






5




















2 4 6 8 10 12
LS ratio [mL/g]
0 S R3-OAW - A OS R3-OAW - B


R
MPI ^
4 -
S 3-
T3
O 9 -
-1 _







: 9
0
	 ML
	 'MDL
































2 4 6 8 10 12
LS ratio [mL/g]
OSR3-PAD-A OSR3-PAD-B


1R

19
• — • in
_i iu
"& 8 -
-0 R
0 MCL
yl
O
n -i
c
	 ML
	 'MDL

e
i








3




























[
<







]
>






2 4 6 8 10 12
LS ratio [mL/g]
OSR3-QAU-A OSR3-QAU-B


                                       E-24
-------
Gyp-U
190
MPI mn
8n -
_i
"§j en -
0 40 .
9n -
n
c
	 ML
	 'MDL





_JLJ





> , .





^A..











. , . r





i . .


2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-NAU - A 0 SR3-NAU - B


i">n
MPI mn
Rn
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0 40 _
9n
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	 ML
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3 ...


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-OAU-A OSR3-OAU-B


Gyp-W
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sn
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0 40 _
9n
n H
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	 ML
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-NAW-A OSR3-NAW-B


i">n
MPI mn -H
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0 40 _
9n
n H
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2 4 6 8 10 12
LS ratio [mL/g]
0 S R3-OAW - A OS R3-OAW - B


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0 40 _
20 -
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C
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-PAD-A OSR3-PAD-B


i^n
MPI mn -H
Rn
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0 40 _
9n
n H
c
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	 'MDL





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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-QAU-A OSR3-QAU-B


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Gyp-U
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2 4 6 8 10
LS ratio [mL/g]
0 SR3-NAU - A 0 SR3-NAU - B


12
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2 4 6 8 10
LS ratio [mL/g]
OSR3-NAW-A OSR3-NAW-B


12
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C
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2 4 6 8 10
LS ratio [mL/g]
0 S R3-OAW - A OS R3-OAW - B


12
1 R
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1 9
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D) I
^ 08
o °'8
O OR
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C
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-PAD-A OSR3-PAD-B


Rn
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4n
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0
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n H
C
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3







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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-QAU-A OSR3-QAU-B


                                       E-26
-------
Gyp-U
1fi
MPI

19
1 — • in
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5 8 -
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A
9
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2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-NAU - A 0 SR3-NAU - B


1fi
MPI

19
1 — • m
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5 8 -
;? R -
Q_ D
A
9
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> 4 6 8 10 12
LS ratio [mL/g]
OSR3-OAU-A OSR3-OAU-B


Gyp-W
1R
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19
1 — • m
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5 8 -
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4
9
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-NAW-A OSR3-NAW-B


1fi
MPI

19
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;? R -
Q_ D
4
9
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2 4 6 8 10 12
LS ratio [mL/g]
0 S R3-OAW - A OS R3-OAW - B


1R
MPI

19
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P R -
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-PAD-A OSR3-PAD-B


1fi
MPI

19
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9
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3


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-QAU-A OSR3-QAU-B


                                       E-27
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Gyp-U
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nwFi 9nn
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-NAU-A OSR3-NAU-B


°50
n\A/Fi 9nn
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O)
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O 100
50 -
n
c
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0

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2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-OAU - A 0 SR3-OAU - B


Gyp-W
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D)
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	 ML
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-NAW-A OSR3-NAW-B


250
nwFi 9nn ,
5" 150
D)
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50
0
C
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2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-OAW - A 0 SR3-OAW - B


950
n\A/FI 900
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50
n
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2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-PAD - A 0 SR3-PAD - B


450
400
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"DW%0 -
0 ZUU
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100
50
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2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-QAU - A 0 SR3-QAU - B


                                       E-28
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Gyp-U
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CD
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2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-NAU - A 0 SR3-NAU - B


Rnn
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9nn
mn
MPI
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-OAU-A OSR3-OAU-B


Gyp-W
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CD
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m
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-NAW-A OSR3-NAW-B


iRn
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190
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£ RO -
MPI
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2 4 6 8 10 12
LS ratio [mL/g]
0 S R3-OAW - A OS R3-OAW - B


mnn
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5 500 -

W 4UU
300
9nn
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C
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-PAD-A OSR3-PAD-B


T^OO
TOOO
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•— ' 1500
W
innn
500
MCL o J
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3

2 4 6 8 10 12
LS ratio [mL/g]
OSR3-QAU-A OSR3-QAU-B


                                       E-29
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Gyp-U
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1- ZU
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2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-NAU - A 0 SR3-NAU - B



19
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-OAU-A OSR3-OAU-B


Gyp-W
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1 ' -i
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-NAW-A OSR3-NAW-B


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2 4 6 8 10 12
LS ratio [mL/g]
0 S R3-OAW - A OS R3-OAW - B


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1 ' -i
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-PAD-A OSR3-PAD-B


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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-QAU-A OSR3-QAU-B


                                       E-30
-------
    Scrubber Sludge (ScS) Comparisons
Facility A
Coal: low sulfur bituminous
ARC: NO+SNCR+FF
Facility B
Coal: low sulfur bituminous
ARC: NO+SCR+ESP(CS) [Mg lime]


Facility K
Coal: sub- bituminous
ARC: NO+SCR+ESP(CS) [Mg lime]
  CGD
(SNCROff)
  AGO
(SNCROn)
  DGD
 (SCR Off)
  BGD
(SCR On)
           KGD
         (SCR On)
                      E-31
-------
Scrubber Sludge Comparisons




Off
On

19
m
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A
9
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2 4 6 8 10 12
LS ratio [mL/g]
nSR3-CGD-A OSR3-CGD-B
ASR3-CGD-C



19
m
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2 4 6 8 10 12
LS ratio [mL/g]
nSR3-AGD-A OSR3-AGD-B
A SR3-AGD - C



19
in
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Q. °
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9
C


Bl A
Aa




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2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-DGD-A OSR3-DGD-B
ASR3-DGD-C



19
m
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A
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2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-BGD-A OSR3-BGD-B
ASR3-BGD-C



19
m
I R
Q. °
R
A
9
C

J
8




3





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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-KGD-A OSR3-KGD-B


                                      E-32
-------
Off
On
0 s
MPI 9 -H
HP 15
i rb
^.
ai
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C
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-CGD-A OSR3-CGD-B
ASR3-CGD-C


0 S
MPI 9 -H
HP 15
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^.
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C
	 ML
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-AGD-A OSR3-AGD-B
A SR3-AGD - C


0 5
MPI 9 ^
HP 15
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C
	 ML
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2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-DGD-A OSR3-DGD-B
ASR3-DGD-C


"> 5
MPI 9 ^
HP 15
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^.
a-l
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0-
C
	 ML
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2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-BGD-A OSR3-BGD-B
ASR3-BGD-C


"> 5
MPI 9 ^
HP 15
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^.
^1
n 5
n H
C
	 ML
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-KGD-A OSR3-KGD-B


                                             E-33
-------
Off
On
nnn
snn

f(j(j
finn
=d 5nn
0) OUU
— Ann
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200 -
inn
n H
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2 4 6 8 10
LS ratio [mL/g]
OSR3-CGD-A OSR3-CGD-B
ASR3-CGD-C


12
°5nn
2000 -
T 1500
"oi
^.
mnn

500 -
n H
C
	 ML
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1 !




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2 4 6 8 10
LS ratio [mL/g]
OSR3-AGD-A OSR3-AGD-B
A SR3-AGD - C


12

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600 -
^
D)
3.
9nn

1UU -
n H
C
	 ML
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R


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2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-DGD-A OSR3-DGD-B
ASR3-DGD-C


^nnn

2500 -
9nnn
"^ 1500
-------
Off
On
7
MPI R -
5 .
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^.
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V)
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-CGD-A OSR3-CGD-B
ASR3-CGD-C


m
Q
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7
"MCL 6 -
H 5-

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9
1

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c
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A





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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-AGD-A OSR3-AGD-B
A SR3-AGD - C


7

c
"a 4 ~
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.Q ^
W
9
1 _




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0
	 ML
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2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-DGD-A OSR3-DGD-B
ASR3-DGD-C


7
MPI R -
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W
9
1 _
0-
c
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2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-BGD-A OSR3-BGD-B
ASR3-BGD-C


7
MPI R -
c
5" 4

w
9
1 _
n -






: 0 *
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0
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1
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-KGD-A OSR3-KGD-B


                                             E-35
-------
Off
On
19
MPI 1 n ^
g
U
5 6 -
w
< 4 _
9
i
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C
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A,


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-CGD-A OSR3-CGD-B
ASR3-CGD-C


19
MPI 1 n ^
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5 6 -
w
< 4 _
9
i
n
C
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-AGD-A OSR3-AGD-B
A SR3-AGD - C


19
MPI 1 n ^
g
U
5 6 -
< 4 _
9
i
n
C
	 ML
	 .MDL




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"A,


2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-DGD-A OSR3-DGD-B
ASR3-DGD-C


19
MPI 1 n ^
g
U
5 6 -
< 4 _
9
i
n
C
	 ML
	 .MDL

Q
0


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d


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—


A
6

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2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-BGD-A OSR3-BGD-B
ASR3-BGD-C


oci
9n
U 15
D)
^.
01 ^ylpl 1 n ^
<
C
n
C
	 ML
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Jt




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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-KGD-A OSR3-KGD-B


                                             E-36
-------
Off
On
c;nnnn
/cnnn
40000
35000 -
T 30000 -
"3> 95000 -
' — ' 90000
15000
10000
n\A/F I
UVVtLj-nnn

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c
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	 'MDL

8
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2 4 6 8 10
LS ratio [mL/g]
OSR3-CGD-A OSR3-CGD-B
ASR3-CGD-C


12

°50000
900000
T 150000
^)
3.
1 — ' 100000
50000
DWEL n '
C
	 ML
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-AGD-A OSR3-AGD-B
ASR3-AGD-C


70000

oUUUU -
50000 -
U 40000
D)
" 30000 -
CD
90000
,.-10000 -
DWEL
o
C
	 ML
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-DGD-A OSR3-DGD-B
ASR3-DGD-C


14
ROOO
DWEL7000 -
6000 -
5000


9000
1000
0 -
C
	 ML
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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-BGD-A OSR3-BGD-B
ASR3-BGD-C


14

snnn
nwFi ynnn -.
finnn
^nnn
"01 /nnn
m?nnn
9nnn
mnn
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c
	 ML
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D
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2 4 6 8 10
LS ratio [mL/g]
OSR3-KGD-A OSR3-KGD-B


12

                                             E-37
-------
Off
On

MPI 9000 -,
U 1500
D)
m mnn
CD
500
0 H
C
	 ML
	 'MDL




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2 4 6 8 10
LS ratio [mL/g]
OSR3-CGD-A OSR3-CGD-B
ASR3-CGD-C


12

°500
MPI 9000 -H
U 1500
D)
m mnn
CD
500
0 H
C
	 ML
	 'MDL




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A
2 4 6 8 10
LS ratio [mL/g]
OSR3-AGD-A OSR3-AGD-B
A SR3-AGD - C


12

°500
MPI 9000 ^
U 1500
D)
^.
ffl 1000
CO
500
0 H
C
	 ML
	 'MDL




n*




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B
2 4 6 8 10 12
LS ratio [mL/g]
OSR3-DGD-A OSR3-DGD-B
ASR3-DGD-C


14

°500
MPI 9000 ^
U 1500
D)
^.
ffl 1000
CO
500
0 H
C
	 ML
	 >MDL



6
B




6









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B
2 4 6 8 10 12
LS ratio [mL/g]
OSR3-BGD-A OSR3-BGD-B
ASR3-BGD-C


14

°500
MPI 9000 ^
U 1500
D)
m mnn
CO
500
0 H
C
	 ML
	 'MDL




D i
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2 4 6 8 10
LS ratio [mL/g]
OSR3-KGD-A OSR3-KGD-B


12

                                             E-38
-------
Off
On
p.
MPI ^
4 -
S 3-
T3
O 9 -
-1 _
n






•
0
	 ML
	 'MDL
H.
^m •
i i '





rr •





-a •





- —





- —





i —


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-CGD-A OSR3-CGD-B
ASR3-CGD-C


C.
MPI ^
4 -
S 3-
T3
O 9 -
-1 _
n





4





--r--
0
	 ML
	 >MDL





~!( '





• —





- —




D
5 —


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-AGD-A OSR3-AGD-B
ASR3-AGD-C


R
MPI ^
4 -
S 3-
T3
O 9 -
-1 _
0-
c
	 ML
	 >MDL






1
•ri
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SD
— o-






































I 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-DGD-A OSR3-DGD-B
ASR3-DGD-C


C.
MPI ^
4 -
S 3-
T3
O 9 -
-1 _
0-
c
	 ML
	 >MDL






i
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> 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-BGD-A OSR3-BGD-B
ASR3-BGD-C


R
MPI £.
4 -
S 3-
T3
O 9 -
-1 _
n -


n


4
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0
	 ML
	 'MDL





— -





0





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", , , <





> , , ,


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-KGD-A OSR3-KGD-B


                                             E-39
-------
Off
On
190
MPI 1 nn -H
sn
_i
"§j en -
0 40 _
9n
n -i
c
	 ML
	 'MDL





£ I





9





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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-CGD-A OSR3-CGD-B
ASR3-CGD-C


nnn
Rnn
vnn
Rnn
^ ^nn
0) OUU
— jinn
^ ?nn
9nn
MPI 1 nn -H
n H
C
	 ML
— >MDL
6








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A
B


























A
B







2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-AGD - A 0 SR3-AGD - B
A SR3-AGD - C


i">n
MPI 1 nn -H
Rn
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0 40 _
9n
n H
c
	 ML
	 >MDL





BO





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A
,B^.


2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-DGD-A OSR3-DGD-B
ASR3-DGD-C


nnn
Rnn
vnn
Rnn
^ ^nn
D) OUU
— jinn
^ ?nn
9nn
MPI 1 nn -H
n H
C
	 ML
— >MDL

4&








4

















1































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2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-BGD-A OSR3-BGD-B
ASR3-BGD-C


i°n
MPI 1 nn -H
sn
_i
"§j Rn -
0 40 _
9n
n -i
c
	 ML
	 >MDL





d





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3

















i


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-KGD-A OSR3-KGD-B


                                             E-40
-------
Off
On
m
Q
0
7
" 6 -
S 5-

o 4 -
0 3-
9
1

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c
	 ML
	 'MDL

ft
D


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$



— -







A

— .









• —









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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-CGD-A OSR3-CGD-B
ASR3-CGD-C


7D
Rn
50 -
" /in
•& 40~
^ 30 -
° 90
ZU
m

-T
C
	 ML
	 >MDL




D
A ,
0 I






*























A
Q






2 4 6 8 10 12
LS ratio [mL/g]
OSR3-AGD-A OSR3-AGD-B
A SR3-AGD - C


1 ">
1 -
n s
_i
^ OR
O
o n A
n 9
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c
	 ML
	 >MDL
A
a
A
a

^_ M





x—





m ^^





•AT ,•





^^ —





^^^






-, sr
2 4 6 8 10 12
LS ratio [mL/g]
OSR3-DGD-A OSR3-DGD-B
ASR3-DGD-C


14
n oci

0.2 -
HP 015
D)
^.
o n 1
O
One; ,
n
c
	 ML
	 >MDL




AA




A









^














A


2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-BGD-A OSR3-BGD-B
ASR3-BGD-C


"> c\
9
U 1 s
i 1-5
^.
0 1
o 1
Oc _,
n
c
	 ML
	 >MDL


D
t




^





0









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>
2 4 6 8 10
LS ratio [mL/g]
OSR3-KGD-A OSR3-KGD-B



12
                                              E-41
-------
Off
On
1fi
MPI
14
19
1 — • in
_l IU
5 8 -
;? R -
Q_ D
A
9
n j
C
	 ML
	 'MDL









=A^









a^. -









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A —


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-CGD-A OSR3-CGD-B
ASR3-CGD-C


1R
MPI
14
19
1 — • m
_l IU
5 8 -
;? R -
Q_ D
A
9
n
C
	 ML
	 >MDL









— B-









w. -









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, ^^









• ^^









A —


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-AGD-A OSR3-AGD-B
A SR3-AGD - C


1R
MPI
14
19
1 — • m
_l IU
5 8 -
P R -
Q_ D
A
9
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	 ML
	 >MDL








A





















































a


2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-DGD-A OSR3-DGD-B
ASR3-DGD-C


1R
MPI
14
19
1 — • m
_l IU
5 8 -
P R -
Q_ D
A
9
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C
	 ML
	 >MDL








D.A








n

















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2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-BGD-A OSR3-BGD-B
ASR3-BGD-C


^n
25-
9n
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SMPI -IE; .
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Q- m
c;

0 -T
C
	 ML
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5





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3











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i. . . .


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-KGD-A OSR3-KGD-B


                                             E-42
-------
Off
On



^ lot) -
D)
^.
o 100 -
50
0,
C
	 ML
	 'MDL


i
!




a





D














D


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-CGD-A OSR3-CGD-B
ASR3-CGD-C


Rnn
vnn
Rnn
U 500 -
5 400

^ 300 -
inn
0,
C
	 ML
	 'MDL
A






















6























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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-AGD-A OSR3-AGD-B
A SR3-AGD - C


14DD

1200 -
innn
^ 800 -
D) uuu
3.
o oUU
4nn
DWEL 200 -
n H
C
	 ML
	 'MDL
9

e








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6
2 4 6 8 10 12
LS ratio [mL/g]
OSR3-DGD-A OSR3-DGD-B
ASR3-DGD-C


14

A^n
400 -
T^n
?nn
_i
SDW! :
0 ZUU
S 1^0
inn

50 -
n H
C
	 ML
	 >MDL
&














H



















	

























E9



2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-BGD-A OSR3-BGD-B
ASR3-BGD-C


mnn
900 -
son
700
U ROO
5 500 -
o Ann
?nn
DWfS -
mn
n H
C
	 ML
	 'MDL


|









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A






























V
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2 4 6 8 10
LS ratio [mL/g]
OSR3-KGD-A OSR3-KGD-B


12

                                             E-43
-------
Off
On
fin
MPI ^n -H
An
S 30-
CD
OT on -
1 n
n H
c
	 ML
	 'MDL



A
<





i


















t





t


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-CGD-A OSR3-CGD-B
ASR3-CGD-C


fin
MPI ^n -H
4n
S 30-
(D
OT on
1 n
n H
c
	 ML
	 >MDL




g
<





4






Q










5





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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-AGD-A OSR3-AGD-B
A SR3-AGD - C


of^n

200 -
U 150
D)
^.
MDL

Ko
0
n
A
/




;





D
&









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2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-DGD-A OSR3-DGD-B
ASR3-DGD-C


fin
MCL 50 -
dn
S 30-
(D
OT on

10 -
n H
C
	 ML
	 >MDL




n°
,.





I





a











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^








2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-BGD-A OSR3-BGD-B
ASR3-BGD-C


fin
MPI ^n -H
4n
S 30-
0)
OT on
m
n H
c
	 ML
	 >MDL


a

i





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D
^

















,.f,.


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-KGD-A OSR3-KGD-B


                                             E-44
-------
Off
On

on
T 15 -
3.
1 — ' m
i- IU
C
MCL
0 4
C
	 ML
	 .MDL

V
0



:

*
D



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> 4 6 8 10 12
LS ratio [mL/g]
OSR3-CGD-A OSR3-CGD-B
A.SR3-CGD-C


50

T 30
D)
3.
1 — ' on
i- ^u
in
MCI
0 4
C
	 ML
	 .MDL


O
|

:
^


3





D














H

> 4 6 8 10 12
LS ratio [mL/g]
OSR3-AGD-A OSR3-AGD-B
A SR3-AGD - C


^n
oc
9n
"3) -ic.
=L lo
F 10 _
X
MCL
n -i
C
	 ML
	 .MDL
A
fi|







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4

n




















1*1




2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-DGD-A OSR3-DGD-B
ASR3-DGD-C


An
Ti
?n
'"^
31 2:D
"3> on
=L zu
LT I1!
in
c;

MCL j
C
	 ML
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|

A










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2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-BGD-A OSR3-BGD-B
ASR3-BGD-C


^n
Ti
?n
oc;
51 2:D
"3> on
=L zu
LT I1!
in
K.
MPI
n H
C
	 ML
	 .MDL
o
I

















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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-KGD-A OSR3-KGD-B


                                             E-45
-------
Fixated Scrubber Sludge (FSS, FSSL) Comparisons
FSS: Fly Ash + Scrubber Sludge (FA+ScS)
 Facility A (FSS)
 Coal: low sulfur bituminous
 ARC: NO+SNCR+FF
ccc
(S NCR Off)

ACC
(SNCROn)
page break
FSSL: Fly Ash + Scrubber Sludge + Lime (FA+ScS+lime)
 Facility B (FSSL)
 Coal: low sulfur bituminous
 ARC: NO+SCR+ESP(CS) [Mg lime]

 Facility K (FSSL)
 Coal: sub-bituminous
 ARC: NO+SCR+ESP(CS) [Mg lime]


 Facility M (FSSL)
 Coal: bituminous
 ARC: IO+SCR+ESP(CS)
DCC
(SCR Off)

BCC
(SCR On)
 KCC
(SCR On)
MAD
(SCR Off)

MAS
(SCR On)
                          E-46
-------
Fixated Scrubber Sludge Comparisons




Off
On

19
1 n
I 8
Q. b
R
/
9
c


*





S





A

















0





2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-CCC - A 0 SR3-CCC - B
A SR3-CCC - C



19
-i n
I R
Q. °
R
A
9
C


8





S





$

















A




2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-ACC - A 0 SR3-ACC - B
A SR3-ACC - C


                                      E-47
-------
Fixated Scrubber Sludge Comparisons




Off
On

19
in
I R
Q. °
R
/
9
c
A





a





f

















4






2 4 6 8 10 12
LS ratio [mL/g]
OSR3-DCC-A OSR3-DCC-B
ASR3-DCC-C



19
m
I R
0. °
R
/
9
c


A^
°0
D



A
O




|





^

















^
a



2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-BCC-A OSR3-BCC-B
ASR3-BCC-C



19
m
I R
Q. °
R
/
9
c


D I





^






a










1
<




]
>



2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-KCC - A 0 SR3-KCC - B



19
m
I R
a. °
R
4
9
C


Jt.
u





















r




>





2 4 6 8 10 12
LS ratio [mL/g]
D SR3-MAD - A 0 SR3-MAD - B
ASR3-MAD-C



12 -
m
I R
Q. °
R
A
9
C













Q











t





3





2 4 6 8 10 12
LS ratio [mL/g]
0 S R3-MAS - A 0 S R3-MAS - B


                                      E-48
-------
Off
On
0 s
MPI 9 -H
HP 15
i rb
^.
ai
n 5
n H
C
	 ML
	 'MDL




_fl \




3




A














A
n


2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-CCC - A 0 SR3-CCC - B
A SR3-CCC - C


0 S
MPI 9 -H
HP 15
i rb
^.
^1
n 5
n H
C
	 ML
	 >MDL





























J


2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-ACC - A 0 SR3-ACC - B
A SR3-ACC - C


                                             E-49
-------
Off
On
0 S
MPI 9 -H
IT IS
i 1-5
^.
ra 1
I
n 5
n H
C
	 ML
	 'MDL









H_




f\














	 A


2 4 6 8 10 12
LS ratio [mL/g]
OSR3-DCC-A OSR3-DCC-B
ASR3-DCC-C


"> 5
MPI 9 -H
IT 1*i
i 1-5
^.
m 1
I
n MDL




a£_




A




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f.


2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-BCC-A OSR3-BCC-B
ASR3-BCC-C


0 ^
MPI 9 -H
HP 15
i rb
^.
^1
n 5
n H
C
	 ML
	 >MDL




°-




3




A








<




>



2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-KCC - A 0 SR3-KCC - B


      2.5

MCL    2
 D)
 I
      0.5

        0
 ---- ML
 - 'MDL
                     4    6     8    10    12
                      LS ratio [mL/g]
             D SR3-MAD - A    O SR3-MAD - B

             ASR3-MAD-C
                                               MCL
 D)
 I
      0.5

        0
          0     2     4    6     8    10   12
 	ML             LS ratio [mL/g]
 — 'MDL  ,	.
             0 S R3-MAS - A    0 S R3-MAS - B
                                               E-50
-------
Off
On
7DD
finn


^ 4UU -
D)
" 300 -
9nn
mn
n j
C
	 ML
	 'MDL















o




















A
O
n





2 4 6 8 10
LS ratio [mL/g]
0 SR3-CCC - A 0 SR3-CCC - B
A SR3-CCC - C


12

9nnn
" 1500-
n.
^ 1UUU -
n H
C
	 ML
	 >MDL



0




a




A












D
A
0



2 4 6 8 10
LS ratio [mL/g]
0 SR3-ACC - A 0 SR3-ACC - B
A SR3-ACC - C


12

                                              E-51
-------
Off
On
10

10 -
0
Ij1
"3> R _
< A -
2 -
n
C
	 ML
	 .MDL





A"





A





t





• —





- —

V



- —

2 4 6 8 10 12
LS ratio [mL/g]
OSR3-DCC-A OSR3-DCC-B
ASR3-DCC-C


vnn
600 -

— i1 4nn
D)
•— ' 300
9nn

1UU -
n H
C
	 ML
	 .MDL


&°
nj






O














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2 4 6 8 10 12
LS ratio [mL/g]
OSR3-BCC-A OSR3-BCC-B
ASR3-BCC-C


14
iRnn
idnn
i9nn
innn
01 snn
7? finn
4nn
9nn
n H
C
	 ML
— .MDL

r

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5



j

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2 4 6 8 10
LS ratio [mL/g]
0 SR3-KCC - A 0 SR3-KCC - B


12

14DD


1000 -
— i1 finn
D)
•— ' 600
4nn
200
n H
C
	 ML
	 .MDL




O
i
A





\
I



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}
I
2 4 6 8 10
LS ratio [mL/g]
OSR3-MAD-A OSR3-MAD - B
ASR3-MAD-C


12

iRnnn
14000 -
12000 -
innnn

7? finnn


zuuu -
n H
C
	 ML
	 .MDL



(







1








n















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2 4 6 8 10
LS ratio [mL/g]
0 S R3-MAS - A 0 S R3-MAS - B



12
                                             E-52
-------
Off
On
-10

m
g

W 4 _

2 -






I








I







D













1
B
t






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TII
0 2 4 6 8 10 12
	 ML LS ratio [mL/g]
— .Mm


a SR3-CCC - A 0 SR3-CCC - B
A SR3-CCC - C



fin

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CO on

10 -
MPI







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Q |








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I I - -I ^— T ^^ I" ^ I
0 2 4 6 8 10 12
	 ML LS ratio [mL/g]
— .MDL


0 SR3-ACC - A 0 SR3-ACC - B
A SR3-ACC - C



                                             E-53
-------
Off
On
7


5 -
5" 4
^) ^
3.
1 — ' ^
.0 °
W
9
1 -

J
c
	 ML
	 'MDL





8 S,





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D
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nL_

_..j._...
2 4 6 8 10
LS ratio [mL/g]
OSR3-DCC-A OSR3-DCC-B
ASR3-DCC-C


12

1R
14 -
12 -
1 — • in
_l IU
5 8 -
-Q MPI R _
CO MOL D
A


-r
C
	 ML
	 >MDL

&








8








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3
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ft




2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-BCC-A OSR3-BCC-B
ASR3-BCC-C


7
MPI R -H
c
| 4-
1 — ' ^
.0 °
W
9
1

0 J
c
	 ML
	 >MDL



o
i






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D













i






^
T^T 	
\ • -i ~~ T ~~ r ^i • ~
2 4 6 8 10
LS ratio [mL/g]
0 SR3-KCC - A 0 SR3-KCC - B


12

7
MCL 6 -
c
5" 4

W
9

1 -
0 -
c
	 ML
	 >MDL






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\


2 4 6 8 10
LS ratio [mL/g]
OSR3-MAD-A OSR3-MAD-B
ASR3-MAD-C


12


25-
:j
^ 15 -
w 10 -
MCL ,-

-r
C
	 ML
	 'MDL

— O —

I





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D
O











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1




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2 4 6 8 10 12
LS ratio [mL/g]
0 S R3-MAS - A 0 S R3-MAS - B


                                             E-54
-------
Off
On
Of^
20 -
U 15 -
D)
^.
in MPI 10-.
<
-
n -
C
	 ML
	 'MDL

r



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— -

&
D



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• —





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o



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2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-CCC - A 0 SR3-CCC - B
A SR3-CCC - C


A*\
An

oo
?n
^ 25-
T_
" 9f"l
MDL



A
B




^^i ¥




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d








¥ i ^"


2 4 6 8 10 12
LS ratio [mL/g]
0 SR3-ACC - A 0 SR3-ACC - B
A SR3-ACC - C


                                             E-55
-------
Off
On
19
MPI 1 n ^
g
5"
™ 6 -
MDL


A
3

0

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0
R





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2 4 6 8 10 12 14
LS ratio [mL/g]
OSR3-BCC-A OSR3-BCC-B
ASR3-BCC-C


19
MPI 1 n ^
g
U
5 6 -
w
< 4 _
9
i
n
C
	 ML
	 >MDL




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3
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LS ratio [mL/g]
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2 4 6 8 10 12
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12

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MPI 9000 ^
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2 4 6 8 10
LS ratio [mL/g]
0 SR3-ACC - A 0 SR3-ACC - B
A SR3-ACC - C


12

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ynnn
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1000
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2 4 6 8 10
LS ratio [mL/g]
OSR3-DCC-A OSR3-DCC-B
ASR3-DCC-C


12


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2 4 6 8 10
LS ratio [mL/g]
0 SR3-KCC - A 0 SR3-KCC - B



12

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2 4 6 8 10
LS ratio [mL/g]
0 SR3-MAD - A 0 SR3-MAD - B
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12


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2 4 6 8 10
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12

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2 4 6 8 10
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0 SR3-CCC - A 0 SR3-CCC - B
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12

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2 4 6 8 10
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0 SR3-ACC - A 0 SR3-ACC - B
A SR3-ACC - C


12

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On
snnn
nwFi ynnn -.
Rnnn
5000 -

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2 4 6 8 10
LS ratio [mL/g]
OSR3-DCC-A OSR3-DCC-B
ASR3-DCC-C


12

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2 4 6 8 10 12 14
LS ratio [mL/g]
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ASR3-BCC-C


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2 4 6 8 10
LS ratio [mL/g]
OSR3-MAD-A OSR3-MAD - B
ASR3-MAD-C



12

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2 4 6 8 10
LS ratio [mL/g]
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12

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0 SR3-CCC - A 0 SR3-CCC - B
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12

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2 4 6 8 10
LS ratio [mL/g]
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12

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OSR3-DCC-A OSR3-DCC-B
ASR3-DCC-C


12

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2 4 6 8 10 12
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OSR3-BCC-A OSR3-BCC-B
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14

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LS ratio [mL/g]
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12

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12

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2 4 6 8 10 12
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14

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LS ratio [mL/g]
OSR3-MAD-A OSR3-MAD - B
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LS ratio [mL/g]
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2 4 6 8 10 12
LS ratio [mL/g]
0 S R3-MAS - A 0 S R3-MAS - B


                                             E-74
-------
SR003.1 outliers resulting from inconsistency in constituent concentration.
Material
AFA
KFA
KFA
KFA
KFA
KFA
CGD
CGD
CGD
Replicate
C
B
B
B
B
B
A
B
C
Element
Cr
As
As
Al
Al
Se
Sb
Sb
Sb
pH [S.I.]
10.7
9.21
9.27
9.27
9.21
9.21
7.19
7.23
7.23
Cone. [ug/L]
1870
2710
22.0
970
24474
15847
95.2
94.7
94.6
                                   E-75
-------
                          Appendix F
                          Curve Fits
Fly Ash
CFA                                                       F-1
AFA                                                       F-4
DFA                                                       F-7
BFA                                                      F-10
KFA                                                      F-13
Gypsum	
NAU                                                      F-16
NAW                                                     F-19
OAU                                                      F-22
OAW                                                     F-25
PAD                                                      F-28
QAU                                                      F-31

Scrubber Sludge
CGD
AGO
DGD
BCD
KGD
F-34
F-37
F-40
F-43
F-46
Fixated Scrubber Sludge	
CCC                                                      F-49
ACC                                                      F-52
DCC                                                      F-55
BCC                                                      F-58
KCC                                                      F-61
MAD                                                      F-64
MAS                                                      F-67
                                F-i
-------
Fac. A (NO+SNCR+FF) SNCR Off (CFA)
                                        Fly Ash
mnnnn -•
10000 -
1000-
IJ 100-
a 10 -
< 1 -
0.1 -
0.01 -
n nm .
f




mnnnn -•
10000 -
1000-
u 100-
3 10 -
m 1 -
0.1 -
0.01 -
n nm -
f




mnnnn -•
10000 -
1000-
ir 100-
a 10-
6 1-
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0.01 -
n nm -
f





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4


                                                       Arsenic
                                                       log
Number
of points
pH range of
validity
                                                          0.0007 PH5
                                                         -0.0217 pH4
                                                          0.2542 pH3
                                                         -1.2873 PH2
                                                          2.5649 pH
                                                          0.6438 pH°
                                                            0.89 R2
   33
         3-12.2
                                                       Boron
log (|jg/L) Number
of points
0.0006 PH5 33
-0.0201 pH4
0.2649 pH3
-1.6551 PH2
4.8871 pH
-1.3626 pH°
0.95 R2
pH range of
validity
3-12.2






                                                       Chromium
                                                       log
Number
of points
pH range of
validity
                                                         -0.0012 PH5
                                                          0.0540 pH4
                                                         -0.8972 pH3
                                                          7.1037 PH2
                                                        -26.4298 pH
                                                         38.7176 pH°
                                                            0.86 R2
   33
         3-12.2
                                          F-1
-------
Fac. A (NO+SNCR+FF) SNCR Off (CFA)
                                       Fly Ash
mnn -
100 -j
™0.1 -i
0.01 -j
n nm -
2





mnnnn -
10000 -
1000 -
5* 100-
O)
a 10-
0 ,.
0.1 -
0.01 -
0 001 •






mnnnn -
10000 -
1000-
5* 100-
Ji 10 -
W 1 '
0.1 -
0.01 -
n nm -







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4



                                                       Mercury
                                                       log
Number
of points
pH range of
validity
                                                          0.0002 PH5
                                                         -0.0066 pH4
                                                          0.0900 pH3
                                                         -0.5537 PH2
                                                          1.4875 pH
                                                         -2.8720 pH°
                                                            0.26 R2
   33
         3-12.2
                                                       Molybdenum
log (|jg/L) Number
of points
0.0000 PH5 33
0.0009 pH4
-0.0513 pH3
0.5414 PH2
-1.7120 pH
3.2458 pH°
0.89 R2
pH range of
validity
3-12.2






                                                      Antimony
                                                       log
Number
of points
pH range of
validity
                                                          0.0000 PH5
                                                          0.0046 pH4
                                                         -0.1459 pH3
                                                          1.6229 PH2
                                                         -7.4137 pH
                                                        13.63554 pH°
                                                            0.92 R2
   33
         3-12.2
                                          F-2
-------
Fac. A (NO+SNCR+FF) SNCR Off (CFA)
                                       Fly Ash
mnnnn -•
10000 -
1000 -
5* 100-
2 10-
w 1 -
0.1 -
0.01 -
0 001 "
f




mnnnn -•
10000 -
1000 -
5- 100-
S 10-
p 1 -
0.1 -
0.01 -
n nm .
f





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                                                     Selenium
                                                      log
Number
of points
pH range of
validity
                                                         0.0008 PH5
                                                        -0.0258 pH4
                                                         0.2999 pH3
                                                        -1.5228 PH2
                                                         3.1957 pH
                                                         0.3518 pH°
                                                           0.93 R2
   33
         3-12.2
                                                     Thallium
log (|jg/L) Number
of points
0.0000 PH5 33
0.0000 pH4
0.0044 pH3
-0.0749 PH2
0.2180 pH
2.0598 pH°
0.93 R2
pH range of
validity
3-12.2






                                         F-3
-------
Fac. A (NO+SCNR+FF) SNCR On (AFA)
                                        Fly Ash
mnnnn -•
10000 -
1000-
IJ 100-
a 10 -
< 1 -
0.1 -
0.01 -
n nm .
f




mnnnn -•
A nnnn
I UUUU •
1000-
u 100-
3 10 -
m 1 -
0.1 -
0.01 -
n nm -
f




mnnnn -•
10000 -
1000-
U 100-
a 10-
6 1-
0.1 -
0.01 -
n nm -
f




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                                                       Arsenic
                                                       log
Number
of points
pH range of
validity
                                                          0.0001 PH5
                                                         -0.0019 pH4
                                                          0.0015 pH3
                                                          0.1957 PH2
                                                         -1.4877 pH
                                                          5.5315 pH°
                                                            0.98 R2
   32
         2.7-12.4
                                                       Boron
log (|jg/L) Number
of points
0.0000 PH5 32
0.0021 pH4
-0.0734 pH3
0.7424 PH2
-2.9441 pH
8.0314 pH°
0.96 R2
pH range of
validity
2.7-12.4






                                                       Chromium
                                                       log
Number
of points
pH range of
validity
                                                          0.0001 PH5
                                                         -0.0018 pH4
                                                          0.0073 pH3
                                                          0.1298 PH2
                                                         -1.2375 pH
                                                          5.8813 pH°
                                                            0.88 R2
   32
         2.7-12.4
                                          F-4
-------
Fac. A (NO+SCNR+FF) SNCR On (AFA)
                                        Fly Ash
mnn -
100 -j
™0.1 -i
:
0.01 -j
n nm -
2





mnnnn -
10000 -
1000 -
5* 100-
O)
a 10-
0 ,.
0.1 -
0.01 -
0 001 •






mnnnn -
10000 -
1000-
5* 100-
Ji 10 -
w 1 '
0.1 -
0.01 -
n nm -






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                                                        Mercury
                                                        log (M9/L)
Number
of points
pH range of
validity
                                                           0.0000 PH5
                                                           0.0000 pH4
                                                          -0.0082 pH3
                                                           0.1383 PH2
                                                          -0.4587 pH
                                                          -1.6599 pH°
                                                             0.74 R2
   32
         2.7-12.4
                                                        Molybdenum
                                                        log (ug/L)
Number
of points
pH range of
validity
                                                           0.0000 PH5
                                                           0.0062 pH4
                                                          -0.1913 pH3
                                                           2.0426 PH2
                                                          -8.5610 pH
                                                          14.0167 pH°
                                                             0.87 R2
   32
         2.7-12.4
                                                        Antimony
                                                        log (ug/L)
Number
of points
pH range of
validity
                                                          -0.0004 PH5
                                                           0.0202 pH4
                                                          -0.3967 pH3
                                                           3.5282 PH2
                                                         -14.1597 pH
                                                         22.14925 pH°
                                                             0.96 R2
   32
         2.7-12.4
                                           F-5
-------
Fac. A (NO+SCNR+FF) SNCR On (AFA)
                                      Fly Ash
mnnnn -•
10000 -
1000 -
5* 100-
2 10-
w 1 -
0.1 -
0.01 -
0 001 "
f




mnnnn -•
10000 -
1000 -
5- 100-
S 10-
p 1 -
0.1 -
0.01 -
n nm .
*-





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PH
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4











4


                                                     Selenium
                                                      log
Number
of points
pH range of
validity
                                                        0.0000 PH5
                                                        0.0030 pH4
                                                        -0.0936 pH3
                                                        1.0106 PH2
                                                        -4.4104 pH
                                                        8.5268 pH°
                                                          0.81 R2
   32
         2.7-12.4
                                                     Thallium
log (|jg/L) Number
of points
0.0000 PH5 32
0.0001 pH4
0.0026 pH3
-0.0747 PH2
0.2849 pH
1.8297 pH°
0.98 R2
pH range of
validity
2.7-12.4






                                         F-6
-------
                                        Fly Ash
Fac. B (NO+SCR+ESP, Mg [lime]) SCR Off (DFA)
mnnnn -.
10000 -
1000-
IJ 100-
a 10 -
< 1 -
0.1 -
0.01 -
n nm .
2





mnnnn -•
10000 -
1000-
u 100-
S 10 -
m 1 -
0.1 -
0.01 -
0 001 "
f-





mnnnn -.
10000 -
1000 -
U 100 -
a 10-
6 1-
0.1 -
0.01 -
Onm -
2





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                                                       Arsenic
                                                       log
Number
of points
pH range of
validity
                                                          0.0005 PH5
                                                         -0.0163 pH4
                                                          0.1723 pH3
                                                         -0.7010 PH2
                                                          0.5740 pH
                                                          3.7495 pH°
                                                            0.96 R2
   33
         2.2-12.4
                                                       Boron
log (|jg/L) Number
of points
0.0003 PH5 33
-0.0089 pH4
0.1049 pH3
-0.5538 PH2
1.2873 pH
3.4258 pH°
0.99 R2
pH range of
validity
2.2-12.4






                                                       Chromium
                                                       log
Number
of points
pH range of
validity
                                                          0.0014 PH5
                                                         -0.0520 pH4
                                                          0.7206 pH3
                                                         -4.4699 PH2
                                                         11.7192 pH
                                                         -7.5446 pH°
                                                            0.88 R2
   33
         2.2-12.4
                                          F-7
-------
                                        Fly Ash
Fac. B (NO+SCR+ESP, Mg [lime]) SCR Off (DFA)
mnn -.
100-
^ 10 -
a 1-
O)
1 0.1 -
0.01 -
Onm -
f





mnnnn -•
10000 -
1000-
5* 100 -
2 10-
1 1-
0.1 -
0.01 -
Onm -






mnnnn -•
10000-
1000-
^ 100-
a 10 -
(f) 1 -
0.1 -
0.01 -
n nm -
f







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                                                        Mercury
                                                        log (M9/L)
Number
of points
pH range of
validity
                                                           0.0000 PH5
                                                           0.0000 pH4
                                                           0.0027 pH3
                                                          -0.0666 PH2
                                                           0.4908 pH
                                                          -2.5534 pH°
                                                             0.22 R2
   33
         2.2-12.4
                                                        Molybdenum
                                                        log (ug/L)
Number
of points
pH range of
validity
                                                          -0.0005 PH5
                                                           0.0201 pH4
                                                          -0.3388 pH3
                                                           2.6571 PH2
                                                          -9.2644 pH
                                                          13.3049 pH°
                                                             0.97 R2
   33
         2.2-12.4
                                                        Antimony
                                                        log (ug/L)
Number
of points
pH range of
validity
                                                           0.0000 PH5
                                                           0.0025 pH4
                                                          -0.0845 pH3
                                                           0.9524 PH2
                                                          -4.2521 pH
                                                         7.805926 pH°
                                                             0.95 R2
   33
         2.2-12.4
                                           F-8
-------
                                       Fly Ash
Fac. B (NO+SCR+ESP, Mg [lime]) SCR Off (DFA)
mnnnn -•
10000 -
1000-
U 100 -
a 10-
Q} A
c/3 i -
0.1 -
0.01 -
Onm -





mnnnn -•
10000 -
1000-
5- 100-
S 10-
P 1 -
0.1 -
0.01 -
n nm -
*-





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                                                     Selenium
                                                      log
Number
of points
pH range of
validity
                                                         0.0005 PH5
                                                        -0.0159 pH4
                                                         0.1723 pH3
                                                        -0.7590 PH2
                                                         1.1355 pH
                                                         1.5106 pH°
                                                           0.89 R2
   33
         2.2-12.4
                                                     Thallium
log (|jg/L) Number
of points
0.0000 PH5 33
0.0025 pH4
-0.0639 pH3
0.5195 pH2
-1.8617 pH
4.8676 pH°
0.96 R2
pH range of
validity
2.2-12.4






                                         F-9
-------
                                        Fly Ash
Fac. B (NO+SCR+ESP, Mg [lime]) SCR On (BFA)
mnnnn -
10000-
1000 -
^j 1 uu -
O)
=: 10 -
(/5 ^
< 1 -
0.1 -
0.01 -
Onm -





mnnnn -,
10000 -
1000-
:j 100-
3 10 -
m 1 -
0.1 -
0.01 -
n nm -
X




mnnnn -.
10000 -
1000-
U 100 -
1 10-
o 1-
0.1 -
0.01 -
Onm -
2



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-------
                                       Fly Ash
Fac. B (NO+SCR+ESP, Mg [lime])  SCR On (BFA)
mnn -•
100-
^ 10 -
O)
a 1 -
O)
1 0.1 -
0.01 -
0 001 "
f




mnnnn -•
10000 -
1000 -
5* 100 -
a 10-
i 1-
0.1 -
0.01 -
n nm -
f




mnnnn -•
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1000 -
:i 100 -
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a 10 -
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0.1 -
0.01 -
n nm -
f



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4


                                                      Mercury
                                                       log
Number
of points
pH range of
validity
                                                          0.0000 PH5
                                                         -0.0035 pH4
                                                          0.1116 pH3
                                                         -1.2349 PH2
                                                          5.4704 pH
                                                         -9.2383 pH°
                                                            0.65 R2
   32
         2.5-12
                                                      Molybdenum
log (|jg/L) Number
of points
0.0000 PH5 32
0.0035 pH4
-0.1122 pH3
1.2523 PH2
-5.4291 pH
9.6881 pH°
0.98 R2
pH range of
validity
2.5-12






                                                      Antimony
                                                       log
Number
of points
pH range of
validity
                                                          0.0000 PH5
                                                          0.0051 pH4
                                                         -0.1561 pH3
                                                          1.6647 PH2
                                                         -7.2346 pH
                                                        12.04581 pH°
                                                            0.93 R2
   32
         2.5-12
                                         F-11
-------
                                        Fly Ash
Fac. B (NO+SCR+ESP, Mg [lime]) SCR On (BFA)
mnnnn -.
10000 -
1000-
U 100 -
a 10-
Q} A
c/3 i •
0.1 -
0.01 -
Onm -
2




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10000 -
1000-
5- 100-
S 10-
P 1 -
0.1 -
0.01 -
n nm -
f





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4


                                                       Selenium
                                                        log (M9/L)
Number
of points
pH range of
validity
                                                           0.0000 PH5
                                                           0.0011 pH4
                                                          -0.0352 pH3
                                                           0.3974 PH2
                                                          -1.8915 pH
                                                           4.7830 pH°
                                                             0.96 R2
   32
         2.5-12
                                                       Thallium
                                                        log (ug/L)
Number
of points
pH range of
validity
                                                          -0.0005 PH5
                                                           0.0206 pH4
                                                          -0.3042 pH3
                                                           2.0105 PH2
                                                          -6.1262 pH
                                                           9.3522 pH°
                                                             0.98 R2
   32
         2.5-12
                                          F-12
-------
                                        Fly Ash
Fac. K (NO+SCR+ESP, Mg [lime]) SCR On (KFA)
mnnnn -•
10000 -
1000 -
T mn -
O)
=: 10 -
< 1 -
0.1 -
0.01 -
Onm -
f




mnnnn -•
10000 -
1000 -
:j 100 -
3 10-
m 1 -
0.1 -
0.01 -
n nm -
f




mnnnn -.
10000 -
1000-
u 100-
S 10-
o 1-
0.1 -
0.01 -
2




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4


                                                       Arsenic
                                                        log (M9/L)
Number
of points
pH range of
validity
                                                          0.0007 PH5
                                                          -0.0260 pH4
                                                          0.3592 pH3
                                                          -2.2619 PH2
                                                          6.0550 pH
                                                          -2.2275 pH°
                                                            0.93 R2
   21
         2.7-12
                                                       Boron
log (|jg/L) Number
of points
-0.0001 PH5 21
0.0027 pH4
-0.0392 pH3
0.2754 PH2
-0.9625 pH
5.9926 pH°
0.97 R2
pH range of
validity
2.7-12






                                                       Chromium
                                                        log (M9/L)
Number
of points
pH range of
validity
                                                          0.0022 PH5
                                                          -0.0798 pH4
                                                          1.0585 pH3
                                                          -6.2638 PH2
                                                          15.4466 pH
                                                          -9.7299 pH°
                                                            0.91 R2
   21
         2.7-12
                                          F-13
-------
                                        Fly Ash
Fac. K (NO+SCR+ESP, Mg [lime]) SCR On (KFA)
mnn -.
100-
1 1-
O)
1 0.1 -
0.01 -
0 001 •
f




mnnnn -•
10000 -
1000-
5* 100 -
2 10-
1 1-
0.1 -
0.01 -
Onm -





mnnnn -•
10000 -
1000-
U 100 -
2 10-
c/3 1 -
0.1 -
0.01 -
Onm -





o
on
45% 6 8 10 1295%1
PH
D SR2-KFA-A O SR2-KFA - B





o^cT0"' 
•**s


I 45% 6 8 10 1295%1
PH
D SR2-KFA-A O SR2-KFA - B






a^f^r^^^^



I 45% 6 8 10 1295%1
PH
D SR2-KFA-A O SR2-KFA - B




4










4











4


                                                        Mercury
                                                        log (M9/L)
Number
of points
pH range of
validity
                                                          -0.0008 PH5
                                                           0.0300 pH4
                                                          -0.4333 pH3
                                                           3.0046 PH2
                                                         -10.0046 pH
                                                          11.2021 pH°
                                                             0.39 R2
   21
         2.7-12
                                                        Molybdenum
                                                        log (ug/L)
Number
of points
pH range of
validity
                                                          -0.0015 PH5
                                                           0.0603 pH4
                                                          -0.9103 pH3
                                                           6.4725 PH2
                                                         -21.0404 pH
                                                          26.6266 pH°
                                                             0.93 R2
   21
         2.7-12
                                                        Antimony
                                                        log (ug/L)
Number
of points
pH range of
validity
                                                          -0.0006 PH5
                                                           0.0251 pH4
                                                          -0.3745 pH3
                                                           2.6459 PH2
                                                          -8.6433 pH
                                                         11.47399 pH°
                                                             0.93 R2
   21
         2.7-12
                                          F-14
-------
                                       Fly Ash
Fac. K (NO+SCR+ESP, Mg [lime]) SCR On (KFA)
mnnnn -.
10000 -
1000-
_i 100 -
a 10-
0.1 -
0.01 -
n nm -
f




mnnnn -.
10000 -
1000-
u 100-
S 10-
p 1 -
0.1 -
0.01 -
0 001 •
f





D^^^**~"


45% 6 8 10 1295%1
PH
D SR2-KFA-A O SR2-KFA - B





n^
-------
Fac. N (FO+SCR+ESP) SCR
Unwashed Gypsum (NAD)
Gypsum
mnnnn -•
10000 -
1000-
IJ 100-
a 10 -
< 1 -
0.1 -
0.01 -
n nm .
f




mnnnn -•
10000-
1000 -
U 100-
3 10-
m 1 -
0.1 -
0.01 -
0 001 •
f-




mnnnn -•
10000 -
1000-
n- 100-
a 10-
6 1-
0.1 -
0.01 -
n nm -
f






ken x>a
^k^i
^^i-
<&.
^^o^ ^^
^^nrn^0^*^^^



> 45% 6 8 10 1295%1
PH
D SR2-NAU-A O SR2-NAU - B









4












4












4


                                                      Arsenic
                                                      log
                             Number
                             of points
pH range of
validity
                                                         0.0000 PH5
                                                        -0.0020 pH4
                                                         0.0638 pH3
                                                        -0.6990 PH2
                                                         2.7201 pH
                                                        -1.8862 pH°
                                                           0.94 R2
                                21
                                     2.2-12
                                                      Boron
log (|jg/L) Number
of points
0.0000 PH5 21
-0.0011 PH4
0.0127 pH3
-0.0694 PH2
0.1363 pH
3.2687 pH°
0.59 R2
pH range of
validity
2.2-12






                                                      Chromium
                                                      log
                             Number
                             of points
pH range of
validity
                                                         0.0000 PH5
                                                        -0.0042 pH4
                                                         0.1188 pH3
                                                        -1.1260 PH2
                                                         3.8034 pH
                                                        -1.3307 pH°
                                                           0.93 R2
                                21
                                     2.2-12
                                         F-16
-------
Fac. N (FO+SCR+ESP) SCR
Unwashed Gypsum (NAD)
Gypsum
mnn -
100 -j
1 1-1
™0.1 -i
:
0.01 -j
n nm -
2





mnnnn -
10000 -
1000 -
5* 100-
O)
a 10-
0 ,.
0.1 -
0.01 -
0 001 "






mnnnn
10000
1000
IT 100
a 10
0.1
0.01
Onm






o n
-~\ D
n o oTtDCHO-n — D-GI °
45% 6 8 10 1295%1
PH
D SR2-NAU-A O SR2-NAU - B







>
-------
Fac. N (FO+SCR+ESP) SCR
Unwashed Gypsum (NAD)
Gypsum
mnnnn -•
10000 -
1000 -
5* 100-
2 10-
w 1 -
0.1 -
0.01 -
0 001 "
f




mnnnn -•
10000 -
1000 -
5- 100-
S 10-
p 1 -
0.1 -
0.01 -
n nm .
*-





^
-------
Fac. N (FO+SCR+ESP) SCR On
Washed Gypsum (NAW)
Gypsum
mnnnn -•
10000 -
1000-
IJ 100-
a 10 -
< 1 -
0.1 -
0.01 -
0 001 •
f-





mnnnn -•
10000 -
1000-
U 100-
3 10 -
m 1 -
0.1 -
0.01 -
n nm -
f





mnnnn -•
10000 -
1000-
U 100-
3 10-
6 1-
0.1 -
0.01 -
n nm -
f







"ETD — ^A
B^^**nxsn ** GKB


! 45% 6 8 10 1295%1
PH
D SR2-NAW-A O SR2-NAW- B






> iSun_— ^^^-QOJD—  45% 6 8 10 1295%1
PH
D SR2-NAW-A O SR2-NAW- B





i
ES

> 45% 6 8 10 1295%1
PH
D SR2-NAW-A O SR2-NAW-B









4













4










4



                                                      Arsenic
                                                       log
                             Number
                             of points
pH range of
validity
                                                         0.0000 PH5
                                                         0.0000 pH4
                                                         0.0104 pH3
                                                         -0.1919 PH2
                                                         0.8260 pH
                                                         0.3744 pH°
                                                           0.88 R2
                                21
                                      2.2-11.5
                                                      Boron
log (|jg/L) Number
of points
-0.0002 PH5 22
0.0072 pH4
-0.0896 pH3
0.5263 PH2
-1.4989 pH
3.5388 pH°
0.86 R2
pH range of
validity
2.2-11.5






                                                      Chromium
                                                       log
                             Number
                             of points
pH range of
validity
                                                         -0.0019 PH5
                                                         0.0582 pH4
                                                         -0.6380 pH3
                                                         3.1220 PH2
                                                         -7.2340 pH
                                                         8.9886 pH°
                                                           0.84 R2
                                22
                                      2.2-11.5
                                         F-19
-------
Fac. N (FO+SCR+ESP)  SCR On
Washed Gypsum (NAW)
Gypsum
mnn -
100 -j
™0.1 -i
:
0.01 -j
n nm -
2





mnnnn -
10000 -
1000 -
5* 100-
O)
a 10-
0 ,.
0.1 -
0.01 -
0 001 •






mnnnn -
10000 -
1000-
5* 100-
Ji 10 -
w 1 '
0.1 -
0.01 -
n nm -








BH3 fln-E&ga— QO-D— O-glC3
45% 6 8 10 1295%1
PH
D SR2-NAW-A O SR2-NAW- B







? ^_^__^^HS^t-^>°-<>~<^
~°


2 45% 6 8 10 1295%1
PH
D SR2-NAW-A O SR2-NAW-B








5o ° o ^j3-^-
-------
Fac. N (FO+SCR+ESP)  SCR On
Washed Gypsum (NAW)
Gypsum
mnnnn -•
10000 -
1000 -
«J 100-
2 10-
w 1 -
0.1 -
0.01 -
n nm .
f




mnnnn -•
10000 -
1000 -
5- 100-
S 10-
p 1 -
0.1 -
0.01 -
n nm .
*-





|UHJ" 
-------
Fac. O (FO+SCR+ESP) SCR On
Unwashed Gypsum (OAU)
Gypsum
mnnnn -•
10000 -
1000-
5- 100-
a 10 -
< 1 -
0.1 -
0.01 -
n nm .
f




mnnnn -•
10000 -,
1000-
u 100-
S 10 -
m 1 -
0.1 -
0.01 -
0 001 •
f




mnnnn -•
10000 -
1000-
U 100 -
1 10-
o 1-
0.1 -
0.01 -
n nm .
f






jfi
^ — u


! 45% 6 8 10 1295%1
PH
D SR2-OAU-A 0 SR2-OAU - B




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PH
D SR2-OAU-A 0 SR2-OAU-B






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o o o

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PH
D SR2-OAU-A 0 SR2-OAU-B









4











4









4


                                                     Arsenic
                                                      log
                             Number
                             of points
pH range of
validity
                                                         0.0000 PH5
                                                         0.0000 pH4
                                                        -0.0093 pH3
                                                         0.2381 PH2
                                                        -1.8904 pH
                                                         4.5126 pH°
                                                           0.83 R2
                                22
                                     2.1-12
                                                      Boron
log (|jg/L) Number
of points
0.0000 PH5 22
0.0011 pH4
-0.0156 pH3
0.1022 PH2
-0.3155 pH
4.1318 pH°
0.50 R2
pH range of
validity
2.1-12






                                                      Chromium
                                                      log
                             Number
                             of points
pH range of
validity
                                                         0.0000 PH5
                                                        -0.0017 pH4
                                                         0.0453 pH3
                                                        -0.3593 PH2
                                                         0.5531 pH
                                                         2.3144 pH°
                                                           0.64 R2
                                22
                                     2.1-12
                                         F-22
-------
Fac. O (FO+SCR+ESP) SCR On
Unwashed Gypsum (OAU)
Gypsum
1 _
^ 0.1-
3
O)
1 0.01 -
n nm .
2




mnnnn -•
10000 -
1000-
=r 100-
O) »
=> 10-
1 1-
0.1 -
0.01 -
n nm .
f




mnnnn -•
10000 -
1000 -
IT 100 -
O)
^ 10 -
-° i
w 1 -
0.1 -
0.01 -
n nm -
f



0 0
S O 	 DOLS2J K2 LJ UQ D U O
45% 6 8 10 1295%1
PH
D SR2-OAU-A 0 SR2-OAU - B





| ^^^^
I 45% 6 8 10 1295%1
PH
D SR2-OAU-A 0 SR2-OAU - B




^
D uoiiirnn no
I 45% 6 8 10 1295%1
PH
D SR2-OAU-A 0 SR2-OAU - B




4







4






4


                                                      Mercury
                                                      log (ug/L)
                             Number
                             of points
pH range of
validity
                                                         0.0000 PH5
                                                         0.0000 pH4
                                                         0.0000 pH3
                                                        -0.0019 pH2
                                                         0.0388 pH
                                                        -2.7933 pH°
                                                           0.06 R2
                                22
                                     2.1-12
                                                      Molybdenum
log (|jg/L) Number
of points
0.0000 PH5 22
0.0034 pH4
-0.1085 pH3
1.1949 PH2
-5.2283 pH
8.1256 pH°
0.94 R2
pH range of
validity
2.1-12






                                                      Antimony
                                                      log (ug/L)
                             Number
                             of points
pH range of
validity
                                                         0.0000 PH5
                                                         0.0010 pH4
                                                        -0.0339 pH3
                                                         0.4313 PH2
                                                        -2.2243 pH
                                                       3.611087 pH°
                                                           0.34 R2
                                22
                                     2.1-12
                                         F-23
-------
Fac. O (FO+SCR+ESP) SCR On
Unwashed Gypsum (OAU)
Gypsum
mnnnn -.
10000 -
1000-
^7 mn •"
a 10 -
(/) 1 ~
0.1 -
0.01 -
0 001 •
f




mnnnn -.
10000-
1000 -
U 100 -
O) dn
~i I U "
p 1 -
0.1 -
0.01 -
0 001 •










45% 6 8 10 1295%1
PH
D SR2-OAU-A 0 SR2-OAU - B








a o— no^b-Hg-^-no^Ha o


45% 6 8 10 1295%1
PH
D SR2-OAU-A 0 SR2-OAU-B








4












4


                                                    Selenium
                                                    log
                            Number
                            of points
pH range of
validity
                                                      -0.0001 PH5
                                                       0.0033 pH4
                                                      -0.0441 pH3
                                                       0.2748 PH2
                                                      -0.8016 pH
                                                       2.8887 pH°
                                                         0.68 R2
                               22
                                    2.1-12
                                                    Thallium
log (|jg/L) Number
of points
-0.0004 PH5 22
0.0129 pH4
-0.1587 pH3
0.9015 pH2
-2.3776 pH
2.7504 pH°
0.62 R2
pH range of
validity
2.1-12






                                       F-24
-------
Fac. O (FO+SCR+ESP) SCR On
Washed Gypsum (OAW)
Gypsum
mnnnn -•
10000 -
1000-
IJ 100,
a 10 -
< 1 •
0.1 -
0.01 -
0 001 •
f-




mnnnn -•
10000 -
1000 t
U 100-
3 10 -
m 1 -
0.1 -
0.01 -
n nm -
f




mnnnn -•
10000 -
1000-
U 100 J
a 10-
6 1-
0.1 -
0.01 -
n nm -
f











> 45% 6 8 10 1295%1
PH
D SR2-OAW-A 0 SR2-OAW-B





«ao
^SSi6Lm^o-<>--j:ShX>
W^ Q


I 45% 6 8 10 1295%1
PH
D SR2-OAW-A 0 SR2-OAW-B







4












4











4


                                                      Arsenic
                                                       log (M9/L)
                             Number
                             of points
pH range of
validity
                                                          0.0000 PH5
                                                          0.0023 pH4
                                                         -0.0634 pH3
                                                          0.6242 PH2
                                                         -2.7118 pH
                                                          4.9902 pH°
                                                            0.79 R2
                                22
                                      1.8-11.7
                                                      Boron
log (|jg/L) Number
of points
0.0000 PH5 22
0.0005 pH4
-0.0134 pH3
0.1401 PH2
-0.6948 pH
4.0303 pH°
0.86 R2
pH range of
validity
1.8-11.7






                                                      Chromium
                                                       log (ug/L)
                             Number
                             of points
pH range of
validity
                                                          0.0000 PH5
                                                         -0.0021 pH4
                                                          0.0570 pH3
                                                         -0.4850 PH2
                                                          1.1950 pH
                                                          1.3926 pH°
                                                            0.96 R2
                                22
                                      1.8-11.7
                                         F-25
-------
Fac. O (FO+SCR+ESP) SCR On
Washed Gypsum (OAW)
Gypsum

0.1 -
2 0.01 -
O)
1 C
0.001 -
n nnm -
t




mnnnn -•
10000 -
1000-
5" 100 -
2 10-
1 1-
0.1 -
0.01 -
Onm -





mnnnn -•
10000 -
1000 -
IJ 100 -
I 1°T
0.1 -
0.01 -
Onm -




n D
«n-n— rr~ assnreo — ns-o
> 45% Q 8 10 1295%1
PH
D SR2-OAW-A 0 SR2-OAW-B




^~
! 45% 6 8 10 1295%1
PH
D SR2-OAW-A 0 SR2-OAW-B




ED D
! 45% 6 8 10 1295%1
PH
D SR2-OAW-A 0 SR2-OAW-B




4






4






4


                                                      Mercury
                                                       log (ug/L)
                             Number
                             of points
pH range of
validity
                                                         -0.0004 PH5
                                                         0.0129 pH4
                                                         -0.1781 pH3
                                                         1.1504 PH2
                                                         -3.3958 pH
                                                         0.9725 pH°
                                                           0.20 R2
                                33
                                      1.8-11.7
                                                      Molybdenum
log (|jg/L) Number
of points
0.0000 PH5 22
0.0033 pH4
-0.1047 pH3
1.1514 PH2
-5.0399 pH
7.7425 pH°
0.90 R2
pH range of
validity
1.8-11.7






                                                      Antimony
                                                       log (ug/L)
                             Number
                             of points
pH range of
validity
                                                         -0.0005 PH5
                                                         0.0151 pH4
                                                         -0.1810 pH3
                                                         1.0337 PH2
                                                         -2.9866 pH
                                                       3.885143 pH°
                                                           0.61 R2
                                22
                                      1.8-11.7
                                         F-26
-------
Fac. O (FO+SCR+ESP)  SCR On
Washed Gypsum (OAW)
Gypsum
mnnnn -•
10000 J
1000 J
U 100 J
75>
a 10-
c/3 1 -
0.1 -
0.01 -
0 001 "
f-






mnnnn -•
10000-
1000-
u 100-
S 10-
P 1 C

0.1 -
0.01 -
0 001 "
f-





\
!
!

. '•iJi— 1 v — H-JQ-fyfry'v-l^rV* my>^^
!
!
!
!

! 45% 6 8 10 1295%1
PH
D SR2-OAW-A 0 SR2-OAW- B
!-•*








^> 0 x>
tnn — o — ncHin-o-QO — DCI— o



! 45% 6 8 10 1295%1
PH
D SR2-OAW-A 0 SR2-OAW- B
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4
















4




                                                    Selenium
                                                     log (ug/L)
                            Number
                            of points
pH range of
validity
                                                        0.0000 PH5
                                                        0.0002 pH4
                                                       -0.0038 pH3
                                                        0.0328 PH2
                                                       -0.1754 pH
                                                        2.0273 pH°
                                                          0.89 R2
                               22
                                     1.8-11.7
                                                    Thallium
log (|jg/L) Number
of points
0.0000 PH5 22
0.0008 pH4
-0.0259 pH3
0.3003 PH2
-1.4645 pH
2.0400 pH°
0.66 R2
pH range of
validity
1.8-11.7






                                        F-27
-------
Fac. P (FO+SCR,SNCR+ESP)
SCR,SNCR On
Unwashed Gypsum (PAD)
Gypsum
mnnnn -•
10000 -
1000-
IJ 100-
a 10 -
< 1 -
0.1 -
0.01 -
0 001 •
f-




mnnnn -•
10000 -
1000-
U 100-
3 10 -
m 1 -
0.1 -
0.01 -
n nm -
f




mnnnn -•
10000 -
1000-
U 100-
3 10-
6 1-
0.1 -
0.01 -
n nm -
f





b
^°^^-^<«


! 45% 6 8 10 1295%1
PH
D SR2-PAD (U) - A
0 SR2-PAD (U) - B





I r^^J_l_r^r^ „ ^gygr^0
t>^H=l~KaffiMC> °~




I 45% 6 8 10 1295%1
PH
D SR2-PAD (U) - A
0 SR2-PAD (U) - B






|— ^-^


I 45% 6 8 10 1295%1
PH
D SR2-PAD(U)-A
0 SR2-PAD(U)-B








4












4










4


                                                     Arsenic
                                                      log (M9/L)
                             Number
                             of points
pH range of
validity
                                                         0.0000 PH5
                                                         0.0002 pH4
                                                        -0.0097 pH3
                                                         0.1807 PH2
                                                        -1.5132 pH
                                                         4.4016 pH°
                                                           0.92 R2
                                22
                                     2.1-11.8
                                                     Boron
log (|jg/L) Number
of points
0.0000 PH5 22
0.0008 pH4
-0.0172 pH3
0.1359 PH2
-0.4408 pH
2.9850 pH°
0.97 R2
pH range of
validity
2.1-11.8






                                                     Chromium
                                                      log (M9/L)
                             Number
                             of points
pH range of
validity
                                                        -0.0006 PH5
                                                         0.0227 pH4
                                                        -0.3097 pH3
                                                         2.0477 PH2
                                                        -6.7078 pH
                                                         9.7534 pH°
                                                           0.78 R2
                                22
                                     2.1-11.8
                                         F-28
-------
Fac. P (FO+SCR,SNCR+ESP)
SCR,SNCR On
Unwashed Gypsum (PAD)
Gypsum
mnn -
100 -|
3.10-!
o) _. :
^ 1-!
o) i
^ 0.1 -|
Om - 1
n nm . _
2




mnnnn -
10000 -
1000 -
5* 100-
O)
=: 10 -
0 i
^ 1 '
0.1 -
0.01 -
n nm .





mnnnn -
10000 -
1000-
5* 100-
E 10-
S 1 -
0.1 -
0.01 -
n nm -




* o oo a
n o ^r-^ u^-u
> D
45% 6 8 10 1295%1
PH
D SR2-PAD(U)-A
0 SR2-PAD(U)-B




\^^
2 45% 6 8 10 1295%1
PH
D SR2-PAD(U)-A
0 SR2-PAD(U)-B




E>
i D— n A
| "-D-CO^- p^^' ^
2 45% 6 8 10 1295%1
PH
D SR2-PAD(U)-A
0 SR2-PAD(U)-B





4






4







4


                                                     Mercury
                                                      log (M9/L)
                            Number
                            of points
pH range of
validity
                                                        0.0005 PH5
                                                        -0.0162 pH4
                                                        0.2074 pH3
                                                        -1.2097 PH2
                                                        3.2019 pH
                                                        -5.0694 pH°
                                                          0.27 R2
                               22
                                     2.1-11.8
                                                     Molybdenum
log (|jg/L) Number
of points
0.0000 PH5 22
0.0022 pH4
-0.0681 pH3
0.7703 PH2
-3.5340 pH
5.6101 pH°
0.88 R2
pH range of
validity
2.1-11.8






                                                     Antimony
                                                      log (ug/L)
                            Number
                            of points
pH range of
validity
                                                        -0.0004 PH5
                                                        0.0138 pH4
                                                        -0.2091 pH3
                                                        1.5244 PH2
                                                        -5.3498 pH
                                                      7.144552 pH°
                                                          0.80 R2
                               22
                                     2.1-11.8
                                         F-29
-------
Fac. P (FO+SCR,SNCR+ESP)
SCR,SNCR On
Unwashed Gypsum (PAD)
Gypsum
mnnnn -•
10000 -
1000 -
5* 100-
2 10-
w 1 -
0.1 -
0.01 -
0 001 "
f





mnnnn -•
10000 -
1000 -
U 100-
§! 10-
p 1 -
0.1 -
0.01 -
n nm .
f






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0 SR2-PAD(U)-B








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PH
D SR2-PAD (U) - A
0 SR2-PAD(U)-B









4












4



                                                     Selenium
                                                      log
                            Number
                            of points
pH range of
validity
                                                        -0.0001 PH5
                                                        0.0050 pH4
                                                        -0.0688 pH3
                                                        0.4485 PH2
                                                        -1.3823 pH
                                                        3.9535 pH°
                                                          0.88 R2
                               22
                                     2.1-11.8
                                                     Thallium
                                                      log
                            Number
                            of points
pH range of
validity
                                                        0.0000 PH5
                                                        0.0000 pH4
                                                        0.0000 pH3
                                                        0.0000 PH2
                                                        0.0000 pH
                                                        -0.5017 pH°
                                                           1.00 R2
                               22
                                     2.1-11.8
                                         F-30
-------
Fac. Q (FO+SCR+ESP) SCR On
Unwashed Gypsum (QAU)
Gypsum
mnnnn -•
10000 -
1000-
IJ 100^
a 10 -
< 1 -
0.1 -
0.01 -
n nm .
f





mnnnn -•
10000 -
1000-
u 100-
3 10 -
m 1 -
0.1 -
0.01 -
n nm -
f





mnnnn -•
10000 -
1000^
IT 100-
a 10-
6 1-
0.1 -
0.01 -
n nm -
f






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fe U


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PH
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4













4



                                                      Arsenic
                                                      log
                             Number
                             of points
pH range of
validity
                                                         0.0000 PH5
                                                        -0.0019 pH4
                                                         0.0607 pH3
                                                        -0.6215 PH2
                                                         2.1356 pH
                                                        -0.1662 pH°
                                                           0.85 R2
                                22
                                      1.9-11.9
                                                      Boron
log (|jg/L) Number
of points
0.0001 PH5 22
-0.0025 pH4
0.0279 pH3
-0.1457 PH2
0.3297 pH
3.3723 pH°
0.75 R2
pH range of
validity
1.9-11.9






                                                      Chromium
                                                      log
                             Number
                             of points
pH range of
validity
                                                         0.0000 PH5
                                                        -0.0044 pH4
                                                         0.1254 pH3
                                                        -1.1736 PH2
                                                         3.8496 pH
                                                        -1.0618 pH°
                                                           0.94 R2
                                22
                                      1.9-11.9
                                         F-31
-------
Fac. Q (FO+SCR+ESP) SCR On
Unwashed Gypsum (QAU)
Gypsum
mnn -•
100 -
_ 10-
ra 0.1 -
0.01 -
0.001 -
Onnm -
*~




mnnnn -•
10000 -
1000-
=r 100-
2 10-
1 1-
0.1 -
0.01 -
0 001 •
f




mnnnn -•
10000-
1000 -
IJ 100 -
2 10-
w 1 -
0.1 -
0.01 -
n nm .






O O v*^^^^^^O O
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PH
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4










4











4


                                                      Mercury
                                                      log (ug/L)
                             Number
                             of points
pH range of
validity
                                                        -0.0023 PH5
                                                         0.0818 pH4
                                                        -1.0670 pH3
                                                         6.2937 PH2
                                                       -16.5299 pH
                                                        14.2041 pH°
                                                           0.59 R2
                                22
                                      1.9-11.9
                                                      Molybdenum
log (ug/L) Number
of points
-0.0001 PH5 22
0.0051 pH4
-0.0720 pH3
0.4890 PH2
-1.6134 pH
3.2477 pH°
0.84 R2
pH range of
validity
1.9-11.9






                                                      Antimony
                                                      log (ug/L)
                             Number
                             of points
pH range of
validity
                                                        -0.0005 PH5
                                                         0.0154 pH4
                                                        -0.1704 pH3
                                                         0.8347 PH2
                                                        -1.8753 pH
                                                       2.662904 pH°
                                                           0.92 R2
                                22
                                      1.9-11.9
                                         F-32
-------
Fac. Q (FO+SCR+ESP) SCR On
Unwashed Gypsum (QAU)
Gypsum
mnnnn -.
10000-
1000 -
U 100 -
a 10-
0} A
0.1 -
0.01 -
Onm -





mnnnn -.
10000 -
1000 -
U 100 -
O) .in
—3 \ \J ™
1- 1 -
0.1 -
0.01 -
n nm -
f




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4











4


                                                      Selenium
                                                       log
                             Number
                             of points
pH range of
validity
                                                         -0.0007 PH5
                                                         0.0228 pH4
                                                         -0.2646 pH3
                                                         1.3386 pH2
                                                         -3.0263 pH
                                                         6.1037 pH°
                                                           0.96 R2
                                22
                                      1.9-11.9
                                                      Thallium
                                                       log
                             Number
                             of points
pH range of
validity
                                                         0.0002 PH5
                                                         -0.0080 pH4
                                                         0.0968 pH3
                                                         -0.5440 PH2
                                                         1.3510 pH
                                                         -0.6419 pH°
                                                           0.59 R2
                                22
                                      1.9-11.9
                                         F-33
-------
                                   Scrubber Sludge
Fac. A (NO+SNCR+FF) SNCR Off (CGD)
mnnnn -•
10000 -
1000-
IJ 100-
a 10 -
< 1 -
0.1 -
0.01 -
n nm .
f




mnnnn -•
10000 -
1000-
u 100-
3 10 -
m 1 -
0.1 -
0.01 -
n nm -
f




mnnnn -•
10000 -
1000-
51 100-
S 10-
6 1-
0.1 -
0.01 -
n nm -
f





P
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PH
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4












4










4


                                                       Arsenic
                                                       log
Number
of points
pH range of
validity
                                                         -0.0008 PH5
                                                          0.0282 pH4
                                                         -0.3932 pH3
                                                          2.6545 PH2
                                                         -8.9610 pH
                                                         12.6001 pH°
                                                            0.94 R2
   33
         2.3-12.1
                                                       Boron
log (|jg/L) Number
of points
0.0000 PH5 33
0.0006 pH4
-0.0042 pH3
-0.0040 PH2
0.0982 pH
3.6570 pH°
0.87 R2
pH range of
validity
2.3-12.1






                                                       Chromium
                                                       log
Number
of points
pH range of
validity
                                                          0.0000 PH5
                                                          0.0004 pH4
                                                         -0.0162 pH3
                                                          0.2658 PH2
                                                         -1.8835 pH
                                                          5.4585 pH°
                                                            0.95 R2
   33
         2.3-12.1
                                          F-34
-------
                                    Scrubber Sludge
Fac. A (NO+SNCR+FF) SNCR Off (CGD)
mnn
100 -
uio-i
S i-i
O)
I0.1-!
0.01 -
2

A A

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PH
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100000
10000
1000
5* 100
O)
a 10
o ,.
0.1
0.01
0.001

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PH
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mnnnn
10000 -
1000-
U 100 -
a 10-
c/3 1 -
0.1 -
0.01 -
Onm -

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PH
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                                                        Mercury
                                                        log (M9/L)
Number
of points
pH range of
validity
                                                           0.0000 PH5
                                                           0.0009 pH4
                                                          -0.0238 pH3
                                                           0.2307 PH2
                                                          -0.9535 pH
                                                          -0.0940 pH°
                                                             0.54 R2
   33
         2.3-12.1
                                                        Molybdenum
                                                        log (ug/L)
Number
of points
pH range of
validity
                                                           0.0000 PH5
                                                           0.0054 pH4
                                                          -0.1725 pH3
                                                           1.9608 pH2
                                                          -9.0268 pH
                                                          14.2898 pH°
                                                             0.93 R2
   32
         2.3-12.1
                                                        Antimony
                                                        log (ug/L)
Number
of points
pH range of
validity
                                                           0.0000 PH5
                                                           0.0000 pH4
                                                          -0.0043 pH3
                                                           0.1264 PH2
                                                          -1.1171 pH
                                                         3.317181 pH°
                                                             0.59 R2
   32
         2.3-12.1
                                          F-35
-------
                                   Scrubber Sludge
Fac. A (NO+SNCR+FF) SNCR Off (CGD)
mnnnn -•
10000 -
1000 -
5* 100-
Ji 10 -
w 1 -
0.1 -
0.01 -
n nm .
f




mnnnn -•
10000 -
1000 -
U 100-
§! 10-
p 1 -
0.1 -
0.01 -
n nm .
f




3
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^ as —



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PH
D SR2-CGD - A O SR2-CGD - B







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4












4


                                                       Selenium
                                                        log
Number
of points
pH range of
validity
                                                          0.0000 PH5
                                                          0.0005 pH4
                                                          -0.0080 pH3
                                                          0.0404 PH2
                                                          -0.3208 pH
                                                          3.3561  pH°
                                                            0.67 R2
   33
         2.3-12.1
                                                       Thallium
                                                        log
Number
of points
pH range of
validity
                                                          0.0009 PH5
                                                          -0.0310 pH4
                                                          0.4015 pH3
                                                          -2.3150 PH2
                                                          5.7637 pH
                                                          -5.0217 pH°
                                                            0.81 R2
   33
         2.3-12.1
                                          F-36
-------
                                   Scrubber Sludge
Fac. A (NO+SNCR+FF) SNCR On (AGO)
mnnnn -•
10000 -
1000-
IJ 100-
a 10 -
< 1 -
0.1 -
0.01 -
n nm .
f




mnnnn -•
10000 1
1000-
u 100-
3 10 -
m 1 -
0.1 -
0.01 -
n nm -
f




mnnnn -•
10000 -
10001
U 100-
a 10-
6 1-
0.1 -
0.01 -
n nm -
f





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PH
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4












4












4


                                                      Arsenic
                                                       log
Number
of points
pH range of
validity
                                                         0.0000 PH5
                                                         0.0015 pH4
                                                        -0.0509 pH3
                                                         0.6228 PH2
                                                        -3.2804 pH
                                                         7.0788 pH°
                                                           0.98 R2
   26
         2.1-12
                                                      Boron
log (|jg/L) Number
of points
0.0000 PH5 26
-0.0013 pH4
0.0139 pH3
-0.0701 PH2
0.1629 pH
3.7266 pH°
0.85 R2
pH range of
validity
2.1-12






                                                      Chromium
                                                       log
Number
of points
pH range of
validity
                                                         0.0000 PH5
                                                         0.0000 pH4
                                                        -0.0004 pH3
                                                         0.0107 PH2
                                                        -0.0980 pH
                                                         3.0646 pH°
                                                           0.91 R2
   26
         2.1-12
                                         F-37
-------
                                   Scrubber Sludge
Fac. A (NO+SNCR+FF) SNCR On (AGO)
mnn
100 -
O) '
*• 0.1 -|
0.01 -p
n nm -
2





mnnnn -
10000 -
1000 -
5* 100-
O)
a 10-
0 ,.
0.1 -
0.01 -
n nm .






mnnnn -
10000 -
1000-
5* 100-
E 10 -
w 1 '
0.1 -
0.01 -
n nm -






1 D
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4












4












4



                                                      Mercury
                                                       log (M9/L)
Number
of points
pH range of
validity
                                                         0.0000 PH5
                                                         0.0000 pH4
                                                         0.0077 pH3
                                                         -0.1719 PH2
                                                         1.1303 pH
                                                         -4.0056 pH°
                                                           0.23 R2
   26
         2.1-12
                                                      Molybdenum
log (|jg/L) Number
of points
0.0000 PH5 26
0.0000 PH4
-0.0258 PH3
0.5797 PH2
-3.7633 pH
7.7685 pH°
0.66 R2
pH range of
validity
2.1-12






                                                      Antimony
                                                       log (M9/L)
Number
of points
pH range of
validity
                                                         0.0000 PH5
                                                         0.0000 pH4
                                                         -0.0061 pH3
                                                         0.1440 PH2
                                                         -1.1368 pH
                                                        3.56153 pH°
                                                           0.92 R2
   26
         2.1-12
                                         F-38
-------
                                  Scrubber Sludge
Fac. A (NO+SNCR+FF) SNCR On (AGO)
mnnnn -•
10000 -
1000 -
5* 100^
2 10-
w 1 '
0.1 -
0.01 -
0 001 "
f





mnnnn -•
10000 -
1000 -
U 100-
2 101
p 1 -
0.1 -
0.01 -
n nm .
f







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4













4



                                                    Selenium
                                                     log (M9/L)
Number
of points
pH range of
validity
                                                        0.0000 PH5
                                                        0.0013 pH4
                                                       -0.0371 pH3
                                                        0.3837 PH2
                                                       -1.7572 pH
                                                        4.3792 pH°
                                                          0.97 R2
   26
         2.1-12
                                                    Thallium
log (|jg/L) Number
of points
0.0000 PH5 26
0.0002 pH4
-0.0052 pH3
0.0493 PH2
-0.1977 pH
1.1598 pH°
0.93 R2
pH range of
validity
2.1-12






                                        F-39
-------
                                    Scrubber Sludge
Fac. B (NO+SCR+ESP, Mg[lime]) SCR Off (DGD)
mnnnn -•
10000 -
1000-
IJ 100-
a 10 -
< 1 -
0.1 -
0.01 -
n nm .
f




mnnnn -•
10000 -
1000-
5- 100-
a 10 •
m 1 -
0.1 -
0.01 -
n nm -
f




mnnnn -•
10000 -
1000-
U 100-
a 10-
6 1-
0.1 -
0.01 -
n nm -
f



--N_
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PH
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PH
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4







4







4


                                                       Arsenic
                                                        log (M9/L)
Number
of points
pH range of
validity
                                                          -0.0007 PH5
                                                           0.0289 pH4
                                                          -0.4547 pH3
                                                           3.3264 PH2
                                                         -11.5334 pH
                                                          17.0255 pH°
                                                             0.96 R2
   33
         2.7-12.2
                                                        Boron
                                                        log (M9/L)
Number
of points
pH range of
validity
                                                          -0.0003 PH5
                                                           0.0140 pH4
                                                          -0.2107 pH3
                                                           1.4581 PH2
                                                          -4.6569 pH
                                                           9.5595 pH°
                                                             0.93 R2
   33
         2.7-12.2
                                                        Chromium
                                                        log (M9/L)
Number
of points
pH range of
validity
                                                          -0.0003 PH5
                                                           0.0148 pH4
                                                          -0.2732 pH3
                                                           2.4523 PH2
                                                         -10.6275 pH
                                                          18.2067 pH°
                                                             0.72 R2
   32
         2.7-12.2
                                          F-40
-------
                                   Scrubber Sludge
Fac. B (NO+SCR+ESP, Mg[lime]) SCR Off (DGD)
mnn -
100 -j
3.10-!
o) _. :
^ 1-!
o) i
=1= 0.1 -|
:
0.01 -j
n nm -
2




mnnnn -
10000 -
1000 -
5* 100-
O)
=: 10 -
0 i
^ 1 '
0.1 -
0.01 -
n nm .





mnnnn -
10000 -
1000-
5* 100-
™ 10-
-0 -1
w 1 '
0.1 -
0.01 -
n nm -




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4







4







4


                                                      Mercury
                                                       log (M9/L)
Number
of points
pH range of
validity
                                                          0.0000 PH5
                                                          0.0000 pH4
                                                          0.0180 pH3
                                                         -0.3838 PH2
                                                          2.0983 pH
                                                         -2.2719 pH°
                                                            0.93 R2
   33
         2.7-12.2
                                                      Molybdenum
log (|jg/L) Number
of points
0.0000 PH5 33
0.0021 pH4
-0.0627 pH3
0.6193 pH2
-2.4187 pH
5.5281 pH°
0.94 R2
pH range of
validity
2.7-12.2






                                                      Antimony
                                                       log (ug/L)
Number
of points
pH range of
validity
                                                          0.0003 PH5
                                                         -0.0097 pH4
                                                          0.1189 pH3
                                                         -0.6819 pH2
                                                          1.8782 pH
                                                       -1.112199 pH°
                                                            0.94 R2
   33
         2.7-12.2
                                         F-41
-------
                                  Scrubber Sludge
Fac. B (NO+SCR+ESP, Mg[lime]) SCR Off (DGD)
mnnnn -•
10000 -
1000 -
5* 100-
2 10-
w 1 -
0.1 -
0.01 -
0 001 "
f




mnnnn -•
10000 -
1000 -
5- 100-
S 10-
p 1 -
0.1 -
0.01 -
n nm .
f





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PH
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PH
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4











4


                                                     Selenium
                                                     log
Number
of points
pH range of
validity
                                                        0.0000 PH5
                                                       -0.0009 pH4
                                                        0.0307 pH3
                                                       -0.3451 PH2
                                                        1.3992 pH
                                                        0.3267 pH°
                                                          0.95 R2
   33
         2.7-12.2
                                                     Thallium
log (|jg/L) Number
of points
0.0000 PH5 33
0.0011 pH4
-0.0312 pH3
0.3014 PH2
-1.3194 pH
3.5611 pH°
0.95 R2
pH range of
validity
2.7-12.2






                                        F-42
-------
                                   Scrubber Sludge
Fac. B (NO+SCR+ESP, Mg[lime]) SCR On (BCD)
mnnnn
10000
1000
:r 100
™ 10
(f) A
< 1
0.1
0.01
n nm





mnnnn -_

10000 -
1000-
5- 100-
3 10-
m 1 -
0.1 -
0.01 -
n nm .
2




mnnnn -
10000 -
1000-
_i 100 -
1 10-
o 1-
0.1 -
0.01 -
Onm -




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4







4







4


                                                      Arsenic
                                                       log
Number
of points
pH range of
validity
                                                          0.0000 PH5
                                                          0.0013 pH4
                                                         -0.0361 pH3
                                                          0.3327 PH2
                                                         -1.3737 pH
                                                          3.9930 pH°
                                                            0.91 R2
   32
         1.7-12.2
                                                      Boron
log (|jg/L) Number
of points
0.0000 PH5 32
0.0018 pH4
-0.0437 pH3
0.3214 PH2
-0.8458 pH
4.8877 pH°
0.87 R2
pH range of
validity
1.7-12.2






                                                      Chromium
                                                       log
Number
of points
pH range of
validity
                                                         -0.0001 PH5
                                                          0.0028 pH4
                                                         -0.0426 pH3
                                                          0.3031 PH2
                                                         -1.0111 pH
                                                          3.5726 pH°
                                                            0.83 R2
   32
         1.7-12.2
                                         F-43
-------
                                   Scrubber Sludge
Fac. B (NO+SCR+ESP, Mg[lime]) SCR On (BCD)
mnn -
100 -j
3.10-1
™0.1 -i
:
0.01 -j
n nm -
2





mnnnn -
10000 -
1000 -
5* 100-
O)
a 10-
0 ,.
0.1 -
0.01 -
0 001 •






mnnnn -
10000 -
1000-
5* 100-
§? m-
W 1 '
0.1 -
0.01 -
n nm -






V 	 ^
^\ J
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PH
D SR2-BGD-A O SR2-BGD - B





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2 45% 6 8 10 1295%1
PH
D SR2-BGD-A O SR2-BGD - B










2 45% 6 8 10 1295%1
PH
D SR2-BGD-A O SR2-BGD - B






4













4












4



                                                      Mercury
                                                       log (M9/L)
Number
of points
pH range of
validity
                                                          0.0000 PH5
                                                          0.0041 pH4
                                                         -0.1048 pH3
                                                          0.8589 PH2
                                                         -2.7065 pH
                                                          3.2775 pH°
                                                            0.85 R2
   32
         1.7-12.2
                                                      Molybdenum
log (|jg/L) Number
of points
0.0000 PH5 32
0.0013 pH4
-0.0361 pH3
0.3087 PH2
-0.9670 pH
3.2947 pH°
0.91 R2
pH range of
validity
1.7-12.2






                                                      Antimony
                                                       log (ug/L)
Number
of points
pH range of
validity
                                                          0.0000 PH5
                                                          0.0006 pH4
                                                         -0.0149 pH3
                                                          0.1154 PH2
                                                         -0.2702 pH
                                                       1.067545 pH°
                                                            0.94 R2
   32
         1.7-12.2
                                         F-44
-------
                                  Scrubber Sludge
Fac. B (NO+SCR+ESP, Mg[lime]) SCR On (BCD)
mnnnn -•
10000 -
1000 -
^T 100 -
2 10-
w 1 -
0.1 -
0.01 -
n nm .
f




mnnnn -•
10000 -
1000 -
5- 100-
S 10-
p 1 -
0.1 -
0.01 -
n nm .
f




AH •
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PH
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4











4


                                                     Selenium
                                                     log (M9/L)
Number
of points
pH range of
validity
                                                        0.0000 PH5
                                                        0.0014 pH4
                                                       -0.0365 pH3
                                                        0.2897 PH2
                                                       -0.9256 pH
                                                        2.9988 pH°
                                                          0.96 R2
   32
         1.7-12.2
                                                     Thallium
log (|jg/L) Number
of points
0.0000 PH5 32
0.0011 pH4
-0.0285 pH3
0.2481 PH2
-0.9482 pH
2.7381 pH°
0.93 R2
pH range of
validity
1.7-12.2






                                        F-45
-------
                                   Scrubber Sludge
Fac. K (NO+SCR+ESP, Mg[lime]) SCR On (KGD)
mnnnn -•
10000 -
1000-
IJ 100-
a 10-
< 1 -
0.1 -
0.01 -
0 001 •
f-




mnnnn -•
10000 -
1000-
U 100-
3 10 -
m 1 -
0.1 -
0.01 -
n nm -
f




mnnnn -•
10000 -
1000-
U 100-
a 10-
6 1-
0.1 -
0.01 -
n nm -
f




1
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4












4












4


                                                      Arsenic
                                                       log
Number
of points
pH range of
validity
                                                         0.0008 PH5
                                                         -0.0288 pH4
                                                         0.3902 pH3
                                                         -2.4595 PH2
                                                         6.8727 pH
                                                         -4.5315 pH°
                                                           0.84 R2
   22
         2.7-12
                                                      Boron
log (|jg/L) Number
of points
0.0000 PH5 22
0.0010 pH4
-0.0377 pH3
0.3655 PH2
-1.3944 pH
6.1779 pH°
0.98 R2
pH range of
validity
2.7-12






                                                      Chromium
                                                       log
Number
of points
pH range of
validity
                                                         -0.0008 PH5
                                                         0.0294 pH4
                                                         -0.4255 pH3
                                                         2.8848 PH2
                                                         -9.1563 pH
                                                        12.0589 pH°
                                                           0.75 R2
   22
         2.7-12
                                         F-46
-------
                                   Scrubber Sludge
Fac. K (NO+SCR+ESP, Mg[lime]) SCR On (KGD)
mnn -
100 -j
i10"!
™0.1 -i
:
0.01 -j
n nm -
2





mnnnn -
10000 -
1000 -
5* 100-
O)
a 10-
0 ,.
0.1 -
0.01 -
0 001 •






mnnnn -
10000 -
1000-
5* 100-
Ji 10 -
W 1 '
0.1 -
0.01 -
n nm -






DO
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4













4













4



                                                      Mercury
                                                       log (M9/L)
Number
of points
pH range of
validity
                                                         0.0000 PH5
                                                         0.0000 pH4
                                                         -0.0044 pH3
                                                         0.1094 PH2
                                                         -1.0400 pH
                                                         2.9254 pH°
                                                           0.78 R2
   22
         2.7-12
                                                      Molybdenum
log (|jg/L) Number
of points
0.0000 PH5 22
0.0008 pH4
-0.0228 pH3
0.2101 PH2
-0.6729 pH
2.7693 pH°
0.85 R2
pH range of
validity
2.7-12






                                                      Antimony
                                                       log (ug/L)
Number
of points
pH range of
validity
                                                         0.0005 PH5
                                                         -0.0166 pH4
                                                         0.1993 pH3
                                                         -1.1038 PH2
                                                         2.8331 pH
                                                       -1.752373 pH°
                                                           0.98 R2
   22
         2.7-12
                                         F-47
-------
                                  Scrubber Sludge
Fac. K (NO+SCR+ESP, Mg[lime]) SCR On (KGD)
mnnnn -•
10000 -
1000 -
5* 100-
2 10-
w 1 -
0.1 -
0.01 -
0 001 "
f




mnnnn -•
10000 -
1000 -
5- 100-
a 10 •
p 1 -
0.1 -
0.01 -
0 001 "
f




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4











4


                                                     Selenium
                                                     log (M9/L)
Number
of points
pH range of
validity
                                                        0.0000 PH5
                                                        0.0036 pH4
                                                       -0.1022 pH3
                                                        1.0035 pH2
                                                       -4.0949 pH
                                                        8.3748 pH°
                                                          0.94 R2
   22
         2.7-12
                                                     Thallium
log (|jg/L) Number
of points
0.0000 PH5 22
0.0016 pH4
-0.0437 pH3
0.4242 PH2
-1.7853 pH
4.8711 pH°
0.98 R2
pH range of
validity
2.7-12






                                        F-48
-------
                               Fixated Scrubber Sludge
Fac. A (NO+SNCR+FF) SNCR Off (CCC)
100000-j
10000 -
1000-
:j ioo-
a 10 -
< 1 -
0.1 -
0.01 -
0.001 -
f


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1000-
u 100-
3 10 -
m 1 -
0.1 -
0.01 -
0.001 -
f



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10000 -
1000-
U 100-
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0.1 -
0.01 -
0.001 -
f


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                                                       Arsenic
                                                       log (M9/L)
Number
of points
pH range of
validity
                                                          0.0003 PH5
                                                         -0.0081 pH4
                                                          0.0631 pH3
                                                          0.0312 PH2
                                                         -1.8668 pH
                                                          6.3883 pH°
                                                            0.98 R2
   33
         1.9-11.5
                                                       Boron
log (|jg/L) Number
of points
0.0008 PH5 33
-0.0269 pH4
0.3094 pH3
-1.6155 PH2
3.8231 pH
0.6614 pH°
1.00 R2
pH range of
validity
1.9-11.5






                                                       Chromium
                                                       log
Number
of points
pH range of
validity
                                                          0.0017 PH5
                                                         -0.0564 pH4
                                                          0.7047 pH3
                                                         -3.9089 PH2
                                                          9.0163 pH
                                                         -3.6696 pH°
                                                            0.88 R2
   33
         1.9-11.5
                                          F-49
-------
                           Fixated Scrubber Sludge
Fac. A (NO+SNCR+FF) SNCR Off (CCC)
mnn -•-
100 -
-i 10 -
3 1-
£ 0.1 -
0.01 -
n nm -
2

D £
V.


mnnnn
1000
i 10
o
5 0.1
n nm


D



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10000 -
1000 -
5* 100-
2 10-
0.1 -
0.01 -
0 001 -
t




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4


Mercury
log (ug/L) Number pH range of
of points validity
0.0000 pH5 33 1.9-11.5
0.0000 pH4
0.0019 pH3
-0.0361 pH2
0.2055 pH
-1.7725 pH°
0.03 R2





Molybdenum
log (ug/L) Number pH range of
of points validity
0.0000 pH5 33 1.9-11.5
0.0053 pH4
-0.1555 pH3
1.5875 PH2
-6.3484 pH
10.5137 pH°
0.96 R2





Antimony
log (ug/L) Number pH range of
of points validity
0.0021 pH5 33 1.9-11.5
-0.0679 pH4
0.8156 pH3
-4.3890 PH2
10.2486 pH
-5.912484 pH°
0.98 R2



                                   F-50
-------
                              Fixated Scrubber Sludge
Fac. A (NO+SNCR+FF) SNCR Off (CCC)
mnnnn -•
10000 -
1000 -
5* 100-
2 10-
w 1 -
0.1 -
0.01 -
0 001 "
f




mnnnn -•
10000 -
1000 -
U 100-
S 10-
p 1 -
0.1 -
0.01 -
n nm .
*-




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4












4


                                                     Selenium
                                                      log
Number
of points
pH range of
validity
                                                        0.0011 PH5
                                                       -0.0325 pH4
                                                        0.3377 pH3
                                                       -1.4414 PH2
                                                        2.1742 pH
                                                        1.8675 pH°
                                                          0.97 R2
   33
         1.9-11.5
                                                     Thallium
log (|jg/L) Number
of points
0.0000 PH5 33
0.0003 pH4
-0.0062 pH3
0.0259 PH2
-0.1507 pH
2.3981 pH°
0.99 R2
pH range of
validity
1.9-11.5






                                        F-51
-------
                               Fixated Scrubber Sludge
Fac. A (NO+SNCR+FF) SNCR On (ACC)
mnnnn -•
10000 -
1000-
IJ 100-
a 10 -
< 1 -
0.1 -
0.01 -
n nm .
f




mnnnn -•
10000 -
1000-
u 100-
3 10 -
m 1 -
0.1 -
0.01 -
n nm -
f




mnnnn -•
10000 -
1000-
ir 100-
a 10-
6 1-
0.1 -
0.01 -
n nm -
f




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4












4












4


                                                      Arsenic
                                                       log
Number
of points
pH range of
validity
                                                         0.0001  PH5
                                                         -0.0037  pH4
                                                         0.0437  pH3
                                                         -0.1810  PH2
                                                         -0.0615  pH
                                                         3.2076  pH°
                                                           0.95  R2
   33
         1.5-12.7
                                                      Boron
log (|jg/L) Number
of points
0.0000 PH5 33
0.0001 pH4
-0.0036 pH3
0.0234 PH2
-0.0328 pH
4.0439 pH°
0.98 R2
pH range of
validity
1.5-12.7






                                                      Chromium
                                                       log
Number
of points
pH range of
validity
                                                         0.0002 PH5
                                                         -0.0076 pH4
                                                         0.0983 pH3
                                                         -0.5438 PH2
                                                         1.1077 pH
                                                         2.7122 pH°
                                                           0.90 R2
   33
         1.5-12.7
                                         F-52
-------
                                Fixated Scrubber Sludge
Fac. A (NO+SNCR+FF) SNCR On (ACC)
mnn -
100 -j
3.10-!
™0.1 -i
s
0.01 -j
n nm -
2




mnnnn -
10000 -
1000 -
«J 100-
O)
a 10-
o ,.
0.1 -
0.01 -
n nm .





mnnnn -
10000 -
1000-
5* 100-
Ji 10 -
w 1 '
0.1 -
0.01 -
n nm -




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PH
D SR2-ACC-A 0 SR2-ACC - B




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4







4







4


                                                       Mercury
log (|jg/L)
Number
of points
                                                                              pH range of
                                                                              validity
                                                           0.0004 PH5
                                                          -0.0144 pH4
                                                           0.1766 pH3
                                                          -0.9344 PH2
                                                           2.0547 pH
                                                          -2.9787 pH°
                                                             0.51 R2
   33
         1.5-12.7
                                                       Molybdenum
                                                        log (ug/L)
Number
of points
                      pH range of
                      validity
                                                          -0.0001 PH5
                                                           0.0067 pH4
                                                          -0.1361 pH3
                                                           1.1943 PH2
                                                          -4.3249 pH
                                                           6.6694 pH°
                                                             0.84 R2
   33
         1.5-12.7
                                                       Antimony
                                                        log (ug/L)
Number
of points
                      pH range of
                      validity
                                                           0.0010 PH5
                                                          -0.0333 pH4
                                                           0.3801 pH3
                                                          -1.8693 PH2
                                                           3.6906 pH
                                                        -0.080232 pH°
                                                             0.95 R2
   33
         1.5-12.7
                                          F-53
-------
                              Fixated Scrubber Sludge
Fac. A (NO+SNCR+FF) SNCR On (ACC)
mnnnn -•
10000 -
1000 -
5* 100-
2 10-
w 1 -
0.1 -
0.01 -
0 001 "
f




mnnnn -•
10000 -
1000 -
5- 100-
S 10-
p 1 -
0.1 -
0.01 -
n nm .
f





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4











4


                                                     Selenium
                                                     log (M9/L)
Number
of points
pH range of
validity
                                                        0.0003 PH5
                                                       -0.0086 pH4
                                                        0.0873 pH3
                                                       -0.3386 PH2
                                                        0.2833 pH
                                                        2.6362 pH°
                                                          0.87 R2
   33
         1.5-12.7
                                                     Thallium
log (|jg/L) Number
of points
-0.0001 PH5 33
0.0033 pH4
-0.0348 pH3
0.1324 PH2
-0.2428 pH
2.2696 pH°
0.99 R2
pH range of
validity
1.5-12.7






                                        F-54
-------
                                Fixated Scrubber Sludge
Fac. B (NO+SCR+ESP, Mg[lime]) SCR Off (DCC)
mnnnn -•
10000 -
1000-
IJ 100-
a 10 -
< 1 -
0.1 -
0.01 -
n nm .
f




mnnnn -•
10000 -
1000-
u 100-
3 10 -
m 1 -
0.1 -
0.01 -
n nm -
f




mnnnn -•
10000 -
1000-
IJ 100-
S 10-
6 1-
0.1 -
0.01 -
n nm -
f




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PH
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4












4











4


                                                       Arsenic
                                                        log
Number
of points
pH range of
validity
                                                           0.0000 PH5
                                                          -0.0006 pH4
                                                           0.0181 pH3
                                                          -0.1961 PH2
                                                           0.7840 pH
                                                           1.4866 pH°
                                                             0.98 R2
   33
         2.2-12.3
                                                       Boron
                                                        log
Number
of points
pH range of
validity
                                                           0.0019 PH5
                                                          -0.0653 pH4
                                                           0.8304 pH3
                                                          -4.8343 PH2
                                                          12.8130 pH
                                                          -8.2699 pH°
                                                             0.79 R2
   33
         2.2-12.3
                                                       Chromium
                                                        log
Number
of points
pH range of
validity
                                                           0.0002 PH5
                                                          -0.0095 pH4
                                                           0.1347 pH3
                                                          -0.8525 PH2
                                                           2.2686 pH
                                                          -0.9643 pH°
                                                             0.41 R2
   33
         2.2-12.3
                                          F-55
-------
                               Fixated Scrubber Sludge
Fac. B (NO+SCR+ESP, Mg[lime]) SCR Off (DCC)
mnn -
100 -
o> ^
O)
=1= 0.1 -
0.01 -
n nm -
2





mnnnn -
10000 -
1000 -
=d 100-
O)
a 10-
0 ,.
0.1 -
0.01 -
0 001 •






mnnnn -
10000 -
1000-
5* 100-
E 10 -
W 1 '
0.1 -
0.01 -
n nm -






B^^sQ: o A
^~%^-^° J
n ^n^^
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PH
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4












4













4



                                                       Mercury
log (|jg/L)
Number
of points
                                                                             pH range of
                                                                             validity
                                                          0.0007 PH5
                                                         -0.0247 pH4
                                                          0.3313 pH3
                                                         -2.1029 PH2
                                                          6.0066 pH
                                                         -5.7078 pH°
                                                            0.80 R2
   33
         2.2-12.3
                                                       Molybdenum
log (|jg/L) Number
of points
0.0000 PH5 33
-0.0004 pH4
0.0084 pH3
-0.0629 PH2
0.1706 pH
2.3949 pH°
0.39 R2
pH range of
validity
2.2-12.3






                                                      Antimony
                                                       log
Number
of points
                      pH range of
                      validity
                                                          0.0008 PH5
                                                         -0.0256 pH4
                                                          0.3101 pH3
                                                         -1.7307 PH2
                                                          4.4146 pH
                                                       -2.870284 pH°
                                                            0.83 R2
   33
         2.2-12.3
                                         F-56
-------
                              Fixated Scrubber Sludge
Fac. B (NO+SCR+ESP, Mg[lime]) SCR Off (DCC)
mnnnn -•
10000 -
1000 -
T -i nn
^ i uu •
2 10-
w 1 -
0.1 -
0.01 -
0 001 "
f




mnnnn -•
10000 -
1000 -
5- 100-
S 10-
p 1 -
0.1 -
0.01 -
n nm .
*-




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PH
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PH
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4











4


                                                     Selenium
                                                      log
Number
of points
pH range of
validity
                                                        0.0001 PH5
                                                       -0.0039 pH4
                                                        0.0585 pH3
                                                       -0.4093 PH2
                                                        1.2933 pH
                                                        0.7895 pH°
                                                          0.96 R2
   33
         2.2-12.3
                                                     Thallium
log (|jg/L) Number
of points
0.0000 PH5 33
-0.0001 pH4
0.0065 pH3
-0.1025 PH2
0.4073 pH
1.1965 pH°
0.76 R2
pH range of
validity
2.2-12.3






                                        F-57
-------
                               Fixated Scrubber Sludge
Fac. B (NO+SCR+EPS, Mg[lime]) SCR On (BCC)
mnnnn -•
10000 -
1000-
IJ 100-
a 10 -
< 1 -
0.1 -
0.01 -
n nm .
f




mnnnn -•
10000 -
1000-
u 100-
3 10 -
m 1 -
0.1 -
0.01 -
n nm -
f




mnnnn -•
10000 -
1000 -
U 100-
a 10-
6 1-
0.1 -
0.01 -
n nm -
f





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4












4











4


                                                       Arsenic
                                                       log (M9/L)
Number
of points
pH range of
validity
                                                          0.0000 PH5
                                                          0.0010 pH4
                                                         -0.0302 pH3
                                                          0.3340 PH2
                                                         -1.7158 pH
                                                          5.0940 pH°
                                                            0.93 R2
   31
         2.7-12.1
                                                       Boron
log (|jg/L) Number
of points
0.0004 PH5 31
-0.0113 pH4
0.1346 pH3
-0.7389 PH2
1.8312 pH
2.2849 pH°
0.95 R2
pH range of
validity
2.7-12.1






                                                       Chromium
                                                       log (M9/L)
Number
of points
pH range of
validity
                                                          0.0000 PH5
                                                         -0.0017 pH4
                                                          0.0235 pH3
                                                         -0.1471 PH2
                                                          0.4192 pH
                                                          2.4198 pH°
                                                            0.12 R2
   31
         2.7-12.1
                                          F-58
-------
                           Fixated Scrubber Sludge
Fac. B (NO+SCR+EPS, Mg[lime]) SCR On (BCC)
mnn
100 -j
-r 10-j fc, 	 . _
— • "^rn ^\. n*
o) • A n _ 
-------
                              Fixated Scrubber Sludge
Fac. B (NO+SCR+EPS, Mg[lime]) SCR On (BCC)
mnnnn -•
10000 -
1000 -
5* 100-
E 10-
O) A
(f) 1 •
0.1 -
0.01 -
n nm .
f





mnnnn -•
10000 -
1000 -
U 100-
§! 10-
p 1 -
0.1 -
0.01 -
n nm .
f






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4



                                                     Selenium
                                                      log (M9/L)
Number
of points
pH range of
validity
                                                        0.0000 PH5
                                                        0.0000 pH4
                                                        0.0009 pH3
                                                        -0.0147 PH2
                                                        -0.0335 pH
                                                        2.1750 pH°
                                                          0.91 R2
   31
         2.7-12.1
                                                     Thallium
log (|jg/L) Number
of points
-0.0001 PH5 31
0.0049 pH4
-0.0652 pH3
0.4114 PH2
-1.3119 pH
2.6934 pH°
0.97 R2
pH range of
validity
2.7-12.1






                                        F-60
-------
                                Fixated Scrubber Sludge
Fac. K (NO+SCR+ESP, Mg[lime]) SCR On (KCC)
mnnnn -•
10000 -
1000-
IJ 100-
a 10 -
< 1 -
0.1 -
0.01 -
n nm .
f




mnnnn -•
10000 -
1000-
u 100-
3 10 -
m 1 -
0.1 -
0.01 -
n nm -
f




mnnnn -•
10000 -
1000-
U 100-
a 10-
6 1-
0.1 -
0.01 -
n nm -
f





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4












4


                                                       Arsenic
                                                        log
Number
of points
pH range of
validity
                                                          -0.0012 PH5
                                                           0.0477 pH4
                                                          -0.6894 pH3
                                                           4.6622 PH2
                                                         -14.8519 pH
                                                          18.8950 pH°
                                                             0.92 R2
   22
         2.5-12.5
                                                       Boron
                                                        log
Number
of points
pH range of
validity
                                                          -0.0004 PH5
                                                           0.0168 pH4
                                                          -0.2392 pH3
                                                           1.5605 pH2
                                                          -4.6725 pH
                                                           9.6267 pH°
                                                             0.92 R2
   22
         2.5-12.5
                                                       Chromium
                                                        log
Number
of points
pH range of
validity
                                                          -0.0002 PH5
                                                           0.0083 pH4
                                                          -0.1339 pH3
                                                           1.0025 PH2
                                                          -3.4268 pH
                                                           4.8410 pH°
                                                             0.19 R2
   22
         2.5-12.5
                                          F-61
-------
                                Fixated Scrubber Sludge
Fac. K (NO+SCR+ESP, Mg[lime]) SCR On (KCC)
mnn -
100 -j[

^ 1 - j
™0.1 -i
:
0.01 -|
n nm -
2


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10000 -
1000 -
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O)
a 10-
o ,.
0.1 -
0.01 -
0.001 -




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10000 -
1000-
5* 100-
Ji 10 -
W 1 '
0.1 -
0.01 -
0.001 -






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                                                       Mercury
log (|jg/L)
Number
of points
                                                                              pH range of
                                                                              validity
                                                           0.0000 PH5
                                                           0.0013 pH4
                                                          -0.0218 pH3
                                                           0.0379 PH2
                                                           0.2010 pH
                                                           1.1663 pH°
                                                             0.87 R2
   22
         2.5-12.5
                                                       Molybdenum
                                                        log
Number
of points
                      pH range of
                      validity
                                                          -0.0005 PH5
                                                           0.0183 pH4
                                                          -0.2789 pH3
                                                           2.0192 PH2
                                                          -6.8913 pH
                                                           9.9918 pH°
                                                             0.63 R2
   22
         2.5-12.5
                                                       Antimony
                                                        log (M9/L)
Number
of points
                      pH range of
                      validity
                                                           0.0002 PH5
                                                          -0.0056 pH4
                                                           0.0676 pH3
                                                          -0.3141 PH2
                                                           0.2986 pH
                                                        0.938777 pH°
                                                             0.30 R2
   22
         2.5-12.5
                                          F-62
-------
                              Fixated Scrubber Sludge
Fac. K (NO+SCR+ESP, Mg[lime]) SCR On (KCC)
mnnnn -•
10000 -
1000 -
5* 100-
2 10-
w 1 -
0.1 -
0.01 -
0 001 "
f




mnnnn -•
10000 -
1000 -
5- 100-
S 10-
p 1 -
0.1 -
0.01 -
n nm .
f





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PH
D SR2-KCC-A 0 SR2-KCC - B






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PH
D SR2-KCC-A 0 SR2-KCC - B








4











4


                                                     Selenium
                                                     log
           Number
           of points
pH range of
validity
-0.0006 pH5
 0.0217 pH4
-0.2981 pH3
 1.8987 PH2
-5.7054 pH
 8.6506 pH°
   0.91 R2
                                                                     22
                                                                           2.5-12.5
                                                     Thallium
log (|jg/L) Number
of points
-0.0001 PH5 22
0.0053 pH4
-0.0743 pH3
0.5009 PH2
-1.6510 pH
2.8022 pH°
0.84 R2
pH range of
validity
2.5-12.5






                                        F-63
-------
                               Fixated Scrubber Sludge
Fac. M (10+SCR+ESP) SCR Off (MAD)
mnnnn -•
10000 -
1000 -
IJ 100-
a 10 -
< 1 -
0.1 -
0.01 -
0 001 •
f-




mnnnn -•
10000 -
1000-
U 100-
3 10 -
m 1 -
0.1 -
0.01 -
n nm -
f




mnnnn -•
10000 -
1000-
U 100-
a 10-
6 1-
0.1 -
0.01 -
n nm -
f



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-------
                                Fixated Scrubber Sludge
Fac. M (10+SCR+ESP) SCR Off (MAD)
mnn -.
100-
10 -
""-" 1
O) '
a 0.1 -
1 0.01 -
0.001 -
n nnm .
2





mnnnn -•
10000 -
1000 -
5* 100-
a 10 -
i 1-
0.1 -
0.01 -
0 001 "
f





mnnnn -•
10000 -
1000-
5* 100-
2 10-
W 1 '
0.1 -
0.01 -
0 001 •
f





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4













4












4



                                                        Mercury
                                                        log (M9/L)
Number
of points
pH range of
validity
                                                           0.0000 PH5
                                                           0.0094 pH4
                                                          -0.2656 pH3
                                                           2.5452 PH2
                                                          -9.8769 pH
                                                          13.8468 pH°
                                                             0.86 R2
   32
         2.6-12.3
                                                        Molybdenum
                                                        log (ug/L)
Number
of points
pH range of
validity
                                                           0.0002 PH5
                                                          -0.0086 pH4
                                                           0.1230 pH3
                                                          -0.8221 PH2
                                                           2.6145 pH
                                                          -0.3740 pH°
                                                             0.63 R2
   32
         2.6-12.3
                                                        Antimony
                                                        log (ug/L)
Number
of points
pH range of
validity
                                                           0.0002 PH5
                                                          -0.0021 pH4
                                                          -0.0296 pH3
                                                           0.5450 PH2
                                                          -2.4967 pH
                                                         5.114599 pH°
                                                             0.92 R2
   32
         2.6-12.3
                                          F-65
-------
                               Fixated Scrubber Sludge
Fac. M (10+SCR+ESP) SCR Off (MAD)
mnnnn -•
10000 -
1000 -
5* 100-
2 10-
w 1 -
0.1 -
0.01 -
0 001 "
f




mnnnn -•
10000 -
1000 -
U 100-
§! 10-
p 1 -
0.1 -
0.01 -
n nm .
*-




_^^___ 
-------
                               Fixated Scrubber Sludge
Fac. M (10+SCR+ESP) SCR On (MAS)
mnnnn -•
10000 -
1000-
U 100-
3 10-
3 1-
0.1 -
0.01 -
n nm .
f-




mnnnn -•
10000 -
1000-
5- 100-
a 10 •
m 1 -
0.1 -
0.01 -
n nm -
f




mnnnn -•
10000 -
1000-
u 100-
1 10-
6 1-
0.1 -
0.01 -
n nm -
f



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PH
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4






4







4


                                                      Arsenic
                                                       log
Number
of points
pH range of
validity
                                                         -0.0006 PH5
                                                          0.0232 pH4
                                                         -0.3335 pH3
                                                          2.2147 PH2
                                                         -6.8466 pH
                                                         10.6171 pH°
                                                            0.81 R2
   22
         2.4-12
                                                       Boron
log (|jg/L) Number
of points
0.0000 PH5 22
-0.0016 pH4
0.0371 pH3
-0.3072 PH2
1.0561 pH
3.1828 pH°
0.98 R2
pH range of
validity
2.4-12






                                                      Chromium
                                                       log
Number
of points
pH range of
validity
                                                         -0.0006 PH5
                                                          0.0210 pH4
                                                         -0.2970 pH3
                                                          2.0580 PH2
                                                         -6.9467 pH
                                                          9.9484 pH°
                                                            0.46 R2
   22
         2.4-12
                                         F-67
-------
                               Fixated Scrubber Sludge
Fac. M (10+SCR+ESP) SCR On (MAS)
mnn -
100 -j
1 'l-f
™0.1 -i
:
0.01 -j
n nm -
2





mnnnn -
10000 -
1000 -
5* 100-
O)
a 10-
0 ,.
0.1 -
0.01 -
0 001 •






mnnnn -
10000 -
1000-
5* 100-
Ji 10 -
W 1 '
0.1 -
0.01 -
n nm -







° \P n*
>O6
00
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PH
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4













4













4



                                                      Mercury
                                                       log (M9/L)
Number
of points
pH range of
validity
                                                          0.0000 PH5
                                                          0.0080 pH4
                                                         -0.2237 pH3
                                                          2.1376 PH2
                                                         -8.2729 pH
                                                         11.3916 pH°
                                                            0.88 R2
   22
         2.4-12
                                                      Molybdenum
log (|jg/L) Number
of points
-0.0003 PH5 22
0.0119 pH4
-0.1732 pH3
1.1891 PH2
-3.7626 pH
7.1211 pH°
0.70 R2
pH range of
validity
2.4-12






                                                      Antimony
                                                       log (ug/L)
Number
of points
pH range of
validity
                                                          0.0000 PH5
                                                          0.0036 pH4
                                                         -0.0990 pH3
                                                          0.9322 PH2
                                                         -3.5290 pH
                                                       6.401426 pH°
                                                            0.82 R2
   22
         2.4-12
                                         F-68
-------
                               Fixated Scrubber Sludge
Fac. M (10+SCR+ESP) SCR On (MAS)
mnnnn -•
10000 -
1000 -
5* 100-
2 10-
0.1 -
0.01 -
0 001 "
f




mnnnn -•
10000 -
1000 -
U 100-
§> 10 -
p 1 -
0.1 -
0.01 -
n nm .
f





45% 6 8 10 1295%1
PH
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PH
D SR2-MAS-A O SR2-MAS - B




4








4


                                                       Selenium
                                                       log
Number
of points
pH range of
validity
                                                         -0.0005 PH5
                                                          0.0196 pH4
                                                         -0.2867 pH3
                                                          1.9611 PH2
                                                         -6.2502 pH
                                                          9.9506 pH°
                                                            0.91 R2
   22
         2.4-12
                                                       Thallium
                                                       log
Number
of points
pH range of
validity
                                                         -0.0004 PH5
                                                          0.0153 pH4
                                                         -0.2276 pH3
                                                          1.5530 pH2
                                                         -4.8966 pH
                                                          7.4317 pH°
                                                            0.96 R2
   22
         2.4-12
                                          F-69
-------
         APPENDIX G
Facility Process Flow Diagrams and
       Sampling Locations
-------
FACILITY A POWER STATION OVERVIEW
   Facility A Process Diagram and CCR Sampling Location
-------
                                              184 SSltL
DBA
Storage
      Facility N Process Diagram and CCR Sampling Location
-------