&fi6 .- SIMULATED COAL GAS MCFC POWER PLANT SYSTEM VERIFICATION Technical St&us Report for June 1998 For Work Performed Under DOE Contract No. DE-AC21-90MC27394 Presentedlo Contractor Reports Receipt Coordinator U.S. Department of Energy Morgantown Energy Technology Center 3610 Collins Ferry Road Morgantown, WV 26507 Presentedby J.A. Scroppo, Project Manager M-C Power Corporation 8040 South Madison Street Burr Ridge, IL 60521 Reviewedby: ~ Authorizedby: . 7/W T.G. Benja#in, Advanced Tec~ology Manager - .. -.,. ., ,.- .... . .. ; . .. -~ 3 ,. -. ., ,,.-, ,.:, --- <.9
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&fi6.-
SIMULATED COAL GAS MCFC POWER PLANT SYSTEM VERIFICATION
Technical St&us Report
for
June 1998
For Work Performed Under DOE Contract No. DE-AC21-90MC27394
Presentedlo
Contractor Reports Receipt CoordinatorU.S. Department of Energy
Morgantown Energy Technology Center3610 Collins Ferry RoadMorgantown, WV 26507
Presentedby
J.A. Scroppo, Project ManagerM-C Power Corporation
8040 South Madison StreetBurr Ridge, IL 60521
Reviewedby: ~ Authorizedby:.
7/W
T.G. Benja#in, Advanced Tec~ology Manager
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This Quarterly Technical Progress Report was prepared with the
support of the U.S. Department of Energy, under Cooperative
Agreement No. DE-FC21 -94MC31 175. However, any opinions,findings, conclusions, or recommendations expressed herein are
those of the authors and do not necessarily reflect the views ofthe DOE.
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DISCLAIMER
This report was prepared as an account of work sponsoredby an agency of the United States Government. Neitherthe United States Government nor any agency thereof, norany of their employees, make any warranty, express orimplied, or assumes any legal liability or responsibility forthe accuracy, completeness, or usefulness of anyinformation, apparatus, product, or process disclosed, orrepresents that its use would not infringe privately ownedrights. Reference herein to any specific commercialproduct, process, or service by trade name, trademark,manufacturer, or otherwise does not necessarily constituteor imply its endorsement, recommendation, or favoring bythe United States Government or any agency thereof. Theviews and opinions of authors expressed herein do notnecessarily state or reflect those of the United StatesGovernment or any agency thereof.
DISCLAIMER
Portions of this document may be illegible
in electronic image products. Images are
produced from the best available original
document.
TABLE OF CONTENTS
Executive Summary
Introduction
Laboratory and Field Work
Reports and Presentations
Outside Contacts
Administrative Aspects
Plan for the Next Quarter
Appendix A – Stabilization of Heavy Metal Containing Hazardous Wastes with
By-Products from Advanced Clean Coal Technology Systems
Appendix B – An Evaluation of the Long-Term Leaching Characteristics of Metalsfrom Solidified/Stabilized Wastes
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EXECUTIVE SUMMARY
During the thirteenth quarter of Phase 2, work continued on conducting scholarly work,
preparing for field work, preparing and giving one presentation, submitting. one manuscript, andmaking an additional outside contact.
Scholarly work
Jana M. Agostini, the graduate student assigned to this project from the Department ofCivil and Environmental Engineering, has concluded her work on evaluation of the long-term
stability of Phase 1 samples. On November 20 she submitted the final report on her M.S.
project, entitled “An Evaluation of the Long-Term Leaching Characteristics of Metals from
Solidified/Stabilized Wastes.” In her work she evaluated the long-term leaching characteristics
of six s/s waste samples. She found that cadmium and chromium remained tightly boundwithin the s/s matrix after two years. The leachability of lead and zinc from the s/s matrices
varied among the six samples after two years of curing.
r Field Work
The Mill Service Yukon Plant (MSYP)Department of Environmental Protection on
is awaiting-a response from the Pennsylvania
MSYP’S applications {1) for a minor permit
modification for the installation of a new silo and new storage pads and (2) for a revision to the
air permit to operate the bagnouse on the new silo.
Reuorts and 1’resentations
A presentation was made on “Autoclave Cellular Concrete Research at the University
of Pittsburgh: Physical and Environmental Properties” to the Coal Technology Group of thePittsburgh Section of the American Chemical Society.
A manuscript on “Stabilization of Heavy Metal Containing Hazardous Wastes with 13y-
Products from Advanced Clean Coal Technology Systems” was submitted to the editor of the
Journal of the Air & Waste Management Association.
Outside Contacts
Discussions by internet were held with Dr. Avinash Chandra, Chief Scientific Officer ofthe Centre for Energy Studies of IIT, Delhi, concerning a possible visit by him to the School of
Engineering Center for Environment and Energy here in Pittsburgh. Unfortunately, the additional
cost of the airfare, incurred in changing the airline ticket he held for the trip he was planning
to the United States, was prohibitive, and plans for a visit by Dr. Chandra to Pittsburgh on thistrip were canceled.
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s for the Next Quarter
During the quarter from December 30, 1998 through March 30, 1999, work on Task 1
of Phase 2 will continue. The principal investigator will maintain contact with MAX
Environmental Technologies, Inc., as it plans the installation of equipment at the Mill ServiceYukon Plant to conduct Phase 2 of the project.
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INTRODUCTION
This seventeenth quarterly report describes work done during the seventeenth three-
month period of the University of Pittsburgh’s project on the “Treatment of Metal-LadenHazardous Wastes with Advanced Clean Coal Technology By-Products~”
This report describes the activities of the project team during the reporting period. The
principal work has focussed upon new laboratory evaluation of samples from Phase 1,
discussions with MAX Environmental Technologies, Inc., on the field work of Phase 2, givinga presentation, submitting a manuscript and making and responding to one outside contact.
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LABORATORY AND FIELD WORK
Scholarlv Actlwtv. .
Jana M. Agostini, the graduate student assigned to this project from the Department ofCivil and Environmental Engineering, has concluded her work on evaluation of the long-termstability of Phase 1 samples. On November 20 she submitted the final report on her M.S.
project, entitled “An Evaluation of the Long-Term Leaching Characteristics of Metals fromSolidified/Stabilized Wastes.” Here is the abstract of the report:
Current hazardous waste treatment standards are based on the premise
that the leaching properties of stabilized/solidified (s/s) wastes do not
significantly change with time. However, numerous studies have examined the
mineralogical changes which occur in s/s wastes with time. Changes in the
mineralogy of the s/s matrix could cause changes in the microstructure, which
may influence the leachability of hazardous constituents in the s/s matrix. The
objective of this research was to evaluate the long-term leaching characteristicsof s/s waste samples (originally prepared during [Phase 1 of this project] at the
University of Pittsburgh) by analyzing the available s/s waste samples; and to
support such results with a review of the literature in this area. Six s/s wastesamples, remaining from [Phase 11, were examined to evaluate changes in theleachability of cadmium, chromium, lead and zinc as a result of aging. In order
to measure changes, the six original s/s waste samples were retested using theToxicity Characteristic Leaching Procedure (TCLP) and the Shake Extraction Test
(ASTM D 3987-85) after two years of curing. Cadmium, as measured in theTCLP Ieachates of the six samples, remained immobilized after-two years, as
expected based on the literature review. Chromium also remained tightly bound
within the s/s matric after two years, in agreement with previously published
results. The leachability of lead from the s/s matrices varied among the six
samples after two years of curing. This result is expected based on the noted
mechanisms for lead immobilization found in the literature. Similar to lead, the
concentration of zinc in the TCLP Ieachates of the two year old samples varied.
The varying results for zinc stabilization may be expected according to themechanisms desribed for zinc immobilization presented in the literature. Inaddition, the shake extraction test Ieachates contained lesser concentrations of
cadmium, chromium, lead and zinc than did the TCLP Ieachates for each of the
six s/s wastes examined. This result is expected since the shake extraction test. .used a less aggressive extraction fluid (near neutral pH) than does the TCLP.
The full report is reproduced in Appendix B.
The Mill Service Yukon Plant (MSYP) is awaiting a response from the PennsylvaniaDepartment of Environmental Protection on MSYP’S applications (1) for a minor permit
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modification for the installation of a new silo and new storage pads and (2) for a revision to the
air permit to operate the baghouse on the new silo.
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REPORTS AND PRESENTATIONS
On October 20 the co-principal investigator made a presentation on “Autoclave CellularConcrete Research at the University of Pittsburgh: Physical and Environmental Properties” tothe Coal Technology Group of the Pittsburgh Section of the Americari ‘Chemical Society.
On November 2 the co-principal investigator submitted a final version of a manuscript
“Stabilization of Heavy Metal Containing Hazardous Wastes with By-Products from AdvancedClean Coal Technology Systems” to the editor of the Journal of the Air& Waste ManagementAssociation. A copy of the manuscript is provided in Appendix A.
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OUTSIDE CONTACTS
Jndian lnsilute of Technoloav. Delhi
On October 10 Dr. Avinash Chandra, Chief Scientific Officer of the Centre for EnergyStudies of IIT, Delhi, suggested that his travel itinerary to the United States be modified to
allow lim to come to Pittsburgh from St. Louis, where he would be attending the IEEE IndustrialApplications Society Conference on October 14. He wished to come to Pittsburgh on October
15 to follow up on the exchange of correspondence between the School of Engineering Centerfor Environment and Energy (ECEE) and Prof. C. N. K. Bansal, Head of the Centre. He noted
that Prof. Bansal wishes to initiate some programs of mutual interest, which he hoped that Dr.
Chandra could discuss in person with the staff of ECEE. It was determined that, unfortunately,
the additional cost of the airfare, incurred in changing the airline ticket, was prohibitive, and
plans for a visit by Dr. Chandra to Pittsburgh on October 15 were canceled.
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ADMINISTRATIVE ASPECTS
This section provides the monthly highlights and closes by comparing progress with themilestone chart.
Swcial Act cmi
There were no special actions during this quarter.
Month Y HI ighliahti
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Here are the highlights of the thirteenth three-month period of the second phase of the
project.
Swte mber 30- Octobe r 30, 1998
● Presentation is given on autoclave cellular concrete to the Coal Technology
Group of the Pittsburgh Section of the American Chemical Society.
Octobe r 30- Novembe r 30, 1998
● Final manuscript describing Phase 1 is submitted to the Journa/of the Air &Waste Management Association.
● Graduate student presents her final report on long-term stability of six samples
from Phase 1.
November 30- December 30, 1998
NONE
an-son of Proaress w ith Milestone Chart
The following task for Phase 2 had been scheduled for completion during the first
quarter of Phase 2:
● Task 1 - Test Plan for Phase 2
Task 1 still was not completed during the thirteenth period of this phase. The decision in early
April 1996 by METC that an environmental assessment of the Phase 2 project at the Yukon
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plant of Mill Service, Inc. (MSI), would have to be conducted and the subsequent withdrawal
in late April 1996 by MSI from Phase 2 necessitated a search for a new subcontractor to host
and participate in the commercial test of Phase 2. MAX Environmental Technologies, Inc., hasrejoined the project team and is designing modifications at the Mill Service Yukon Plant (MSYP)
to enable it to enter this business area and carry out the field work on.this project. The testplan for Phase 2 will be prepared shortly before the permits are in place for the installation of
the equipment at MSYP for carrying out the demonstration.
Work has been suspended on two tasks from Phase 1:
● Task 4- Treatment of Metal-Laden Waste with CCT Solid By-Product
● Task 5- Data Analysis
The fourth by-product and the final three residues are no longer being actively sought.
When the Phase 2 testing program is initiated, consideration will be given to reestablishing this
activity.
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PLAN FOR THE NEXT QUARTER
During the quarter from December 30, 1998 through March 30, 1999, work on Task 1
of Phase 2 will continue. The principal investigator will maintain contact with MAX
Environmental Technologies, Inc., as it plans the installation of equipment at the Mill ServiceYukon Plant to conduct Phase 2 of the project.
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APPENDIX A
STABILIZATION OF HEAVY METAL CONTAININGHAZARDOUS WASTES WITH BY-PRODUCTS FROMADVANCED CLEAN COAL TECHNOLOGY SYSTEMS.-
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STABILIZATION OF HEAVY METAL CONTAINING HAZARDOUS WASTES WITHBY-PRODUCTS FROM ADVANCED CLEAN COAL TECHNOLOGY SYSTEMS
Jesse W. PrittsUnited StatesEnvironmentalProtection Agencywashingto~ Dc
Ronald D. Neufeld and JamesT. CobbUniversityof PittsburghPittsburgh PA
IMPLICATIONS
The 1990 Clean-Air-Act Amendmentsinstituteda reduction in atmospheric sulfhrdioxide
emissionsfrom coal-fired power plants.To meet these reductions, anew generationof advanced
coal combustion systems develop~ designedto be environmentallycleaner andmore eflicient.... .
thanconventional coal-burning processes. These systemseffectively remove sulfbrdioxide formed
duringcoal combustio~ preventingits releaseto the atmosphere.The disposal of residues
produced by these systems is becoming increasinglyproblematic. The waste management
community is actively searchingfor beneficialuses for these residues. One potentialapplicationis
the use of these materialsas treatmentchemicalsfor hazardouswastes.
ABSTRACT
The purpose of this investigationwas to evaluatethe success of residuesfkom advancedClean
Coal Technolo~ (CCT) systemsas stabiition agentsfor heavy metalcontaininghazardous
wastes. k the context examinedhere, Stabii[on refm to techniquesthatreduce the toxicity of
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a waste by converting the hazardousconstituentsto a less soluble, mobile, or toxic ford. Three
advanced CCT by-products were used: coal-waste-fired circulatingfluidti bed combustor
(CFBC) residue;pressurizedffuidd bed combustor (PFBC) residu~ and spraydrierresidue.. .
Seven metal-ladenhazardouswastes were treated: three contaminatedsoils; two airpollution
control dusts;wastewater treatmentplantsludge, and sandblastwaste. Each of the seven
hazardouswastes were treatedwith each of the three CCT by-products at dosages of 10%, 30Y0,
and 50°/0, by weight (by-productwaste). The treatmenteffectivenessof each mixturewas
evaluatedby the Toxicity CharacteristicLeaching Procedure (TCLP). Of the 63 mixtures
evaluat@ 21 produced non-hazardousresidues. Treatmenteffectivenesscan likelybe attributed
to mechanismssuch as precipitationand encapsulationdue to the formation of hydratedcalcium
silicates and calcium sutio-aluminates.Results indicatethatthese residueshave potentialbeneficial-----
uses to the hazardous waste treatmentmmmmity, possibly substitutingfor costly treatment
chemicals.
INTRODUCTION
The passage of the 1990 CleanAir Act Amendmentsprompted the development of a numberof
from the production of lead acid storage batteries.MunitionsSoil Contaminatedsoil from a munitionsdepot where’kad-containing
munitionswere stored.IndustrialSoil Contaminatedsoil from a city multi-useindustrialsite.WWT’P Soil Contaminatedsoil from sewage dryingbeds from a former hospital
wastewater treatmentplant site.BOF Dust Baghouse dust from a basic oxygen fimnacesteehnakingfacility.IncineratorDust Fly ashcollected by an electrostatic precipitatorat a municipalwaste
Basic Cement Chemistry as Applied in Stabilization/SolidificationProcesses ........................................................................................9
Mechanisms of Stabilization ..........................................................l2
6.0 SUMMARY AND Conclusions ...........................................................53
7.0 SUGGESTIONS FOR FUTURE RES~RCH ..........................................55
APPENDIX
APPENDIX
APPENDIX
APPENDIX
A CLEAN-COAL TECHNOLOGY BY-PRODUCTS ................57
B ORIGINAL DATA ................................................................6l
c USING THE PERKIN-ELMER 1IOOBAA SPECTROPHOTOMETER ............................................67
D QA PROJECT PLAN FOR “TREATMENT OFMETAL-lADEN HAZARDOUS WASTES WITHADVANCED CLEAN-COAL TECHNOLOGYBY-PRODUCTS” .................................................................74
REFERENCES NOT CITED .............................................................................lOO
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LIST OF FIGURES
Figure No. Page
1 Solubilities of Metal Hydroxides as a Function of pH ....................16
2 Eh-pl-i Diagram for Pati of the Cr-O-H System ..............................l9<+ [’
3 Eh-pH Diagram for Cadmium ........................................................2O.. ‘\
4 ‘ A Summary of Models for the Interaction of PriorityMetal Pollu~ants with Cement ..............................................23
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5“ Lead Co~centra~cm versus Time for TCLP Extracts ......................47
6 Lead Concentration versus Time for Shake ExtractionTest Extracts ..................................................................................48
7 Zinc Concentration versus Time for TCLP Extracts .......................5l
8 Zinc Concentration versus Time for Shake ExtractionTest Extracts ..................................................................................52
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Table No.
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B4
B5
B6
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LIST OF TABLES
Page
Mean Comparison of CCT By-Product Properties .........................66
Shake Extraction Test - ~nc Analysis ...........................................7l
TCLP Leachate Metal Concentration versusTCLP Leachate pH ........................................................................72
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NOMENCLATURE
The following is a listing of the various chemical compounds and mineral speciesdiscussed throughout this document.
Common Name Cement Chemistry Chemical FormulaNotation
Tricalcium silicate (alite)-\
Dicalcium silicate (belite). .
Tricalcium alti~inate . .
Tetracalcium aluminoferrite
Calcium silicate hydrate(tobermorite gel)
Calcium aluminoferrite hydrate
Tetracalcium aluminate hydrate. _
Ettringite
Calcium sulfate (anhydrite)
Calcium carbonate
Anhydrous lime (quicklime)
Hydrated lime (portlandite)
c31t “ 3CaO”SiOz
CJ4 2CaO”SiOz
C,A 3CaO”Alz0,
CdAF 4Cao”AlzO~”FezO~
3CaO”2Si02”3H20
3Ca0.A120~-FezO~. 12HZ0
3Ca0.AlzOa.Ca(OH)z”12H20
3Ca0.A120,.3CaS0,.32~0
CaSOd
CaCO~
CaO
Ca(OH)2
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i 1.0 INTRODUCTION
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Stabilization/Solidification (S/S) processes are effective in treating a variety
of waste materials ~forreuse or disposal. According to the US EPA, stabilization;;?/
refers to those technologies that reduce the hazardous potential of a waste by‘\
converting ‘the contaminants into their least soluble, mobile, or toxic form.. .>
I Solidification techniques are those which enc&ipsulatethe waste in a monolithic solid
I of high structural integrity.(lY The standard bulk material handling and mixing
equipment used in many s/s processes make the technology appear simple.
.-.1However, significant challenges arise when s/s processes are applied. The
I morphology and chemistry of s/s treated wastes are complex and, as yet, not well
understood.-.
IS/S is frequently the technology of choice for the treatment of soils and
! sludges containing one or more metal contaminants. According to current
regulations regarding hazardous wastes promulgated by the US EPA,
.Istabilization/solidification processes have been identified as the Best Demonstrated
I Available Technology (BDAT) for a variety of listed waste codes.(z) Presently, the
environmental acceptability of a hazardous waste is based upon the US EPAsIExtraction Procedure Toxicity Test (EP Tox) or the Toxicity Characteristic Leaching
.i Procedure (TCLP). A treated waste is deemed stable if the EP Tox or TCLP
*Parenthetical references placed superior to the line of text refer to thebibliography.
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Ieachate derived from it contains constituents in concentrations
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maximum contaminant levels (MCLS) stated in the regulation. However, the
question of whether the immobilized constituents remain immobilized with the
passage of time is hot well defined.;,>?/
in order to -determine the successful long-term performance of a
solidification/stabilization (s/s) process, many types of analyses, including physical
tests, leaching ahd extraction tests, chemical tests, biological tests and micro-
characterizations may be required. Currently, no one test or procedure can be
performed to determine the long-term performance of a s/s waste. Most often, a
combination of several tests is needed to gather information about the chemistry
and mineralogy of the treated waste.
As a basis for this study, six treated waste samples, which were developed
through a previous research project at the University of Pittsburgh (1995), were
analyzed using two different extraction procedures, the TCLP and the Shake.
Extraction Test (ASTM D 3987435). For the original research project, three different
lime-containing Clean Coal”Technology (CCT) fly ash by-products were used as the
s/s binders to treat seven different types of metal-laden hazardous wastes. As a
result of the previous research, many of the binder/waste mixtures passed the TCLP
and were deemed stabilized according to regulations. For this project, six of the
original s/s treated wastes, which initially passed the TCLP, were re-examined after
two years curing time to determine if the leachability of metals from the treated
waste had changed. In addition, the shake extraction test was performed on the
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samples in order to accumulate more information about the leachability of metals
from the treated waste samples.
Though other methods have been used to determine the long-term
performance of s/s &astes, the TCLP and Shake Extraction Test were used for this;,?/
study for the reasons discussed below... -%
● ‘ The previous research project at the University of Pittsburgh, from
“whichthe samples for this study were taken, used the above listed
extraction procedures. For reasons of consistency, these procedures
were repeated in this study.
● As discussed in Section 2.7.2 and 2.7.3 of this document, the
repetition of the TCLP on s/s wastes, after several years of curing,
has been used h several other long-term performance studies.
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BACKGROUND AND LITERATURE REVIEW
2.1 Solidification/StabilizationTechnologyOvewiew
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“Stabilization/solidification is normally a two step treatment process in which
the waste is’initiallychemically stabilized, to concentrate the hazardous components. .
in the waste into an insoluble form. Solidification occurs, due to a second set of.“
chemical reactions initiated by the addition of cementitious additives to the stabilized
waste.’’(3) In order to assure an adequate level of performance, it is essential to
understand the two key processes which are fundamental to the production of an
environmentally acceptable waste. The first process is the method for producing
a solid material, since this-is--essential for solidification. The second process is
responsible for the containment of the hazardous constituents of the waste within
the microstructure of the solidified material.(4) However, it should be noted that a
material need not be solidified in order to achieve stabilization of hazardous
constituents.
Containment of hazardous components is the most important characteristic
of solidified wastes, and has
chemically simple systems.
been extensively investigated, particularly for
Studies indicate that a number of retention
mechanisms operate, but it is not clear whether these make a significant
contribution to metal containment in commercially produced solidified materials.(5)
Stabilization/solidification technologies can be broadly categorized as either
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inorganic or organic systems, based on the nature of the solidification chemicals
used, not the waste composition. Inorganic systems are used for the chemical
fixation and solidification of complex wastes in order to produce a nontoxic,
environmentally safe product that can be used as landfill material. These processes~~/’
use inorganic reagents which react with certain waste components and ‘with.. ‘\
themselves’to form chemically and mechanically stable products. Organic systems. .
are not often+.used for industrial wastes except in the area of radioactive waste
solidification. These systems are sometimes hydrophobic in nature and therefore
create difficulty when mixed with water based wastes.(s)
2.1.1 Inorganic Processes
Inorganic processes
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are generally grouped into two categories: those that
use bulking agents, such as fly ash, and those that do not. Bulking agents are
those materials which, when added to the mixture, add to the total solids and
viscosity of the waste. These bulking agents may prevent the settling out of the
suspended waste components before solidification can occur and/or help produce
a solid with better physical properties. Bulking agents may either be inert, or may
have reactive capability or pozzolanic activity.
Pozzolans are materials that do not demonstrate cementing capabilities
when used alone, but in combination with other materials, such as Portland cement
or lime, will interact with these materials to form a cementitious product. The most
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important inorganic systems in use are: Portland cement, lime/fly ash, kiln dust,
inhibitors, which include boric acid, some inorganic salts and metal compounds in
I the waste, tend to slow the rate of setting effecting the hardening of the solidified
1. product. Conversely, chemical accelerators, such as lime or calcium chloride, work
+Jto speed the setting time of the solidified matrix. Controlling the effects of inhibitors
I and accelerators in s/s waste mixtures is essential in producing an environmentally
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2.2 Regulatory Background
The treatment and disposal of hazardous wastes are regulated primarily by
two federal laws and their amendments. The Resource Conservation and Recovery
Act (RCRA) of’1976, as amended k)ythe Hazardous and Solid Waste Amendments
(HSWA) of 1984, gives the US EPA the authority to regulate the disposal of
hazardous wastes and to set treatment standards. The second major regulation for
hazardous waste is the Comprehensive Environmental Response, Compensation
and Liability Act (C ERCLA) of 1980, as amended by the Superfund Amendments
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and Reauthorization Act (SARA) of 1986. CERCLA regulates the cleanup of spilled
materials and abandoned waste sites.
US EPA is responsible for establishing treatment standards for each type of
hazardous waste. The treatment standards are based on the Best Demonstrated;>?/
Available Technology (BDAT), rather than on risk-based or health-based\
standards. In order to”be deemed. ....
must: ., \ +% \
(1) offer the greatest reduction
the BDAT for a waste type, the technology
of toxicity, mobility, or volume of the waste;
(2) be demonstrated to work at the full-scale level, and;
(3) be commercially available.
Stabilization/solidification has been identified as the BDAT for a variety of waste
types containing both organitiand inorganic contaminants.
2.3 Basic Cement Chemistry as Applied in Solidification/Stabilization Processes
The most commonly used s/s processes utilize Portland cement, lime and/or
fly ash as the reagents. As discussed in later sections of this document, an
understanding of the interaction between the cementitious binder and the waste is
fundamental in characterizing the effectiveness of the s/s process. Thus, an
explanation of the petilnent cementitious reactions for the setthg of the SISwaste
is included herein.
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Cementitious reactions refer to the basic hydration reactions that occur when
cement clinker and water are mixed together, resulting in stiffening, hardening,
evolution of heat, and finally development of long-term strength. The hydrates
that form from the fpur principle compounds determine most of the characteristics& /J
of the hardened cement. The ptimary cement compounds include: tricalcium silikate.. :\
or alite (C$), dicalcium silicate or belite (CZS), tricalcium aluminate (CA) and
,,.tetracalcium aluminofewite (C4AIF).’ The mineral gypsum (CaSOq) is added to the
cement during the final cement grinding and functions to help slow the rate of
setting.
When cement and water are mixed together, the C$ hydrates and hardens
rapidly. This reaction is responsible for the initial set and early strength of the
material. Belite, or C2S, hydrates and hardens slowly, contributing to strength
increases beyond one week. The aluminates, C~A and CAAF, react, as shown
below to form calcium aluminate hydrates which provide some structure to the
system. The hydration of C$ liberates a large amount of heat during the first few
days of cement hydration and hardening, contributing slightly to early strength
development. Tetracalcium aluminoferrite is added to the cement clinkering
process to reduce the clinkering temperature and assist in the manufacture of
cement. C~AF hydrates quickly but contributes Iitile to the overall strength. The
basic cement hydration reactions are as follows:
*For brevity, this notation system represents calcium, silicon, aluminum, and ironoxides with C, S, A, and F, respectively. The subscripts denote the relative moleratios of each component, for example, 2CaOd5i02 is C2S.
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2(3CaO=SiOJ + 6H20 = 3CaO*2SiOz.3Hz0Tricalcium silicate (alite) Tobermorite get
2(2CaO”SiOz) + 4H20 = 3Ca0.2SiOz ●3HZ0Dicalcium silicate (belite) Tobermorite gel
Figure 4 A Summary of Models for the Interaction ofPriority Metal Pollutants with Cement
In addition to this study, research
present study is presented below.
2.5.1 Cadmium
specific to the four metals examined in the
Studies of cadmium uptake in cementitious systems indicate that cadmium
is tightly bound within the solidified matrix. Peon and Perry ’36)examined cadmium
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I1 stabilization in ordinary Portland cement/pulverized fuel ash (OPC/PFC) mixtures.
1 The authors reported that cadmium induced only moderate changes
)microstructure of the solidified matrix, and that x-ray diffractometry
in the
(XRD)
I examination confirmed the presence of the calcium hydroxide phase. Compressive~~,/
!strength testing revealed that the addition of Cd greatly reduced the strength of the
,. :\
1solidified p~oducts, however, leaching tests indicated that Cd was well retained by,.
the OPC/PFAI m@rix.(~7) .
I Cartiedge, et al.(38)examined the s/s of cadmium salts using Portland cement
1fixing agents. The study used TCLP leaching tests, conduction calorimetry, and
.’:1solid-state NMR as a function of time to investigate the behavior of cadmium salts
Iin cement-based solidification. According to the report, both cadmium hydroxide
I
(Cd(OH)2) and cadmium nitrate (Cd(N03),) caused a slight acceleration of cement
hydration. As cadmium nitrate was added to the mixture, cadmium hydroxide began
I to precipitate out of
Iprecipitation of calcium
solution as a solid,
hydroxide (Ca(OH)2).
providing nucleation sites for the
However, the study noted that other
J
than the “minor acceleration of silicate hydration, the Cd salts have little effect on
I the cement matrix.” Citing that cadmium and calcium ions have the same charge,
1
and nearly the same ionic radius, Cartledge, et al. suggest that the substitution of
cadmium for calcium in crystal lattices maybe a method of cadmium immobilization.
j In their study, however, the authors suggest that the mechanism for cadmium
Istabilization was microencapsulation of solid Cd(OH)2 within CSH gel and/or calcium
hydroxide, due to the presence of only small amounts of free Cd’+ in solution. The>
..
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authors assert that cadmium leaching is minimal because
accessible to water nor in a very soluble chemical form.”(39)
2.5.2 Chromium ~;,~,/
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25
it is “neither very
In aqueous systems, chromium is found in two valence states, Cr(Vl) and
Cr(lll). In a sfudyby Cocke and Mollah ‘40),the authors suggest that the aqueous
chemistry of Cr(lll) ions greatly influences the fixation of chromium. At higher pH
(above 8), as in the case of s/s systems, the Cr(OH)- ion may exist in appreciable
amounts. It was noted that these ions were not likely to be absorbed by the
negative silicate surfaces; and, like cadmium, the chromate ion may serve as a
nucleation site for the precipitation of hydrates, becoming dispersed in the bulk of
the solidified matrix.
A study by Kindness, et al. ’42)demonstrated that the mechanism of
chromium stabilization in blast furnace slag/cement (BFS/OPC) blends was through
reduction of Cr(Vl) to Cr(lll) by S2- (a constituent of slags), and subsequent
incorporation into the cement hydrates. Macias ’43)asserts that slags continue to
release S2- ions because of their slow hydration, thus inhibiting the chromium from
oxidizing back to the C~ speciation. In their article, Bonen and Sarkar ‘a) state
that the excellent retention of Cp+ is related to the formation of insoluble Cr(OH)~.
nHzO.
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2.5.3Lead
An early study by Thomas, et al. ’45)demonstrated that lead forms mixed
solids during cemen~ hydration, as supported by the authors’ titrations of lead nitrate;.,~,
against calcium hydroxide and calcium’sulfate. During the titrations, the pH end‘\
point fluctuated between 8.5 and 10, which Thomas explained in terms of
dissolution of “’the.first-formed solids and reprecipitation. Using NMR, Cartledge et
al. ’46)confirmed
reactions caused
the extreme retardation of the aluminate and silicate hydration
by lead salts in cementitious systems. The authors point out that
previous studies proposed that the retardation effect of lead salts is caused by the
rapid formation of a gelatinous coating of lead salts around the cement clinker
grains, thus preventing contacfbetween the grains and water. The study concluded
that as the pH of the cement system fluctuates during the hydration process, lead
salts undergo solubilization and reprecipitation, resulting in the presence of lead
salts on the surfaces of cement minerals. The authors assert that the Pb salts are
therefore readily accessible to leaching fluid.
These results were suppoited by the studies conducted by Cocke and Moilah
’47)which confirmed, using microscopic analyses, that lead compounds were
located on the outer surfaces of cement particles. The study also demonstrated
that lead was present in the less soluble silicate, carbonate, and hydroxide forms,
and not the more soluble oxide form.
27
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2.5.4 Zinc
Though zinc is not listed as a RCRA metal, it can be found at significant
concentrations in fiazardous waste streams. Cocke et al. ’48)have proposed that;,?/
zinc retards the hydration and setting of cement by precipitating an amorphous layer.-Y
of zinc hydroxide onto the surface of the cement clinker grains. The surface. .
compound wbs identified as CaZn2(OH)G Q 2H20, resulting from calcium aided
adsorption of the normally anionic zinc species at high pH. The study by Peon and
Perry ’49)confirms the notion that Zn greatly retards the hydration of cement. The
authors also state that the presence of zinc produces a significant change in the
pore structure through enhanced ettringite and monosulfate formation. It was also
noted that zinc caused substantial lowering of the pH of the system, and that the pH
of the system was not high enough to resolubilize the amphoteric Zn.
2.6 Metals Leachability as a Function of pH
The success of s/s treatment is expected to depend on the pH of the material
for metals that are immobilized as hydroxide, carbonate, sulfide, silicate, and
phosphate precipitates. However, none of the common leaching tests require pH
measurement and data to correlate pH to metal mobility are sparse. Recent studies
have attempted to correlate the final pH of the Ieachate with the mobility of metals
from s/s wastes.
I.
28
! In 1992, Jones, et al. ’51)performed a study in which the effects of waste
constituents on s/s waste leachability were evaluated. The authors plotted metal
concentration versus final Ieachate pH for s/s wastes that had been subjected to the1“1 EP leaching test {EPA Method 131 OA, SW 846). The authors noted that the
;.>9/amphoteric nature of cadmiuml volubility was evident since Cd concentrations~ .. ‘\
tincreased as the pH rose above 10.5. In addition, nickel concentrations in the. .
j:,,
Ieachate showed a ‘similar pH dependency, though less pronounced. Ni
I concentration increased approximately 2 orders of magnitude below pH 7.5.
-1 “Chromium concentrations decreased slightly with increasing Ieachate pH.
-1.,.>Trussel and Batchelor ’52)noted a correlation between pi-l and the leaching
I of metals from the s/s material in their 1996 article. The authors noted that the
Ilower the pH, the greater the-metal leaching. However, the degree to which this
correlation was observed varied for different metals. Cadmium and mercury were
1 shown to be highly leachable at acidic pH, whereas moderate mobilization was
/
noted for lead and chromium. In 1996, Erickson and Barth ’53)examined the
relationship between the degree of lead immobilization and Ieachate pH. The
I authors note the high volubility of lead at acidic and near neutral pH values. In
11I
addition, the authors suggest a pH range of minimum volubility for lead at pH 10.5-
12, and noted the amphoteric behavior of Pb in s/s materials.
29
2.7 Long-Term Performance of Stabilized/Solidified Wastes
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2.7.1 Methods for the Analysis of Long-Term Performance of Stabilized/SolidifiedWastes
.;:?/
In recent ye~{s, several studies have shown the failure of leaching tests
alone to p~ovide information on the durability of metals in stabilized/solidified
wastes. Wh~@ tiie TCLP has value for comparative and regulatory purposes, it
gives no information about the chemical interactions between the waste and the
binder. As well, numerous studies have verified that the TCLP does not accurately
simulate long-term leaching under varying environmental conditions. The
TCLP was designed to simulate the conditions that a waste would be exposed to
if placed in a sanitary land~ll. ‘The procedure assumes that acetic acid, produced
by microorganisms in the landfill, and leaching at about pH 5 would be the expected
conditions. However, many sh wastes are disposed of on-site, and thus are
exposed to site-specific conditions. The contents of this section should help to
elucidate the analytical methods, besides leaching tests, which can be employed
to describe and possibly predict the permanence of metals in stabilized/solidified
wastes.
Klich ’56)asserts that the need to incorporate the use of microscopy at ail
levels of resolution into the long-term durability studies of s/s wastes is fundamental
in gaining an understanding of the degradation mechanisms which effect leaching
of hazardous constituents. The methods of powder x-ray diffraction (XRD) analysis,
30
..
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optical petrography, scanning electron microscopy (SEM) combined with energy
dispersive spectroscopy (EDS), transmission electron microscopy (TEM), electron
probe microanalysis (EPMA), Fourier transform infrared spectroscopy (FTIR), and
x-ray photoelectron spectroscopy (XPS) are among the analytical tools used by
Klich and other researchers to
with the aging of s/s wastes.
>?/“
investigate the microstructural changes associated
Powder XRD aids in the identification of the dominant crystalline mineral
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constituents using their characteristic sets of diffraction spectra. XRD can be used
to confirm the presence or absence of specific mineral phases in the cementitious
material. Optical petrography allows the user to characterize the effects of
weathering in aged s/s wastes contaminated with metals. Petrographic microscope
techniques can be used to ‘evaluate geologic and soil materials. SEM is a
frequently used microscopic method because of its high spatial resolution, and
when combined with EDS, allows easy recognition and identification of metal
contaminants within the cement matrix. TEM is capable of even greater spatial
resolution, and selected area diffraction patterns are helpful in determining the
structure of crystals and the orientation of the crystal phases within the material.
EPMA is a non-destructive technique for chemically analyzing small areas of solid
samples, and is therefore useful in studying the containment of metals in cements.
FTIR is useful for molecular characterization, providing insight into the molecular
structure. FTIR has been used to investigate the hydration of cement, by monitoring
the changes in the vibrational spectra with time. XPS can provide qualitative and
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semi-quantitative information on the chemical state of elements using binding
energies of those elements. FTIR and XPS have been used recently to study the
effect of carbonization on s/s wastes.
.;,?./
2.7.2 Simulated Long-Term Performance Study Results
Sequentiator multiple extraction procedures have been employed to study
the long-term leaching characteristics of s/s wastes. US EPA developed the
Multiple Extraction Procedure (MEP, SW 846 Method 1320) to simulate the leaching
that a waste undergoes from repetitive extractions. This procedure serves to reveal
the highest concentration of each constituent that is likely to leach in a natural
environment. Based on this–type of assumption, other researchers have used
multiple or sequential leaching procedures, as described below, to evaluate long-
term leaching of metals from s/s wastes over a relatively short term.
In 1994, Lee, et al. ‘6*)presented a method for studying long-term metals
leachability in solidified wastes called the multiple toxicity characteristic leaching
procedure (MTCLP). In this procedure, the first extraction sequence uses the
TCLP, while the following 8 extraction sequences follow the TCLP, except that a
3.0) is used. The authors assert that the MTCLP can be used to simulate the
leaching of a waste subjected to repetitive precipitation of acid rain on a sanitary
landfill.
32
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Andres, et al. ’61)studied the long-term behavior of steel foundry wastes
stabilized with cement materials using a dynamic leaching test (DLT). The DLT was
adapted from the American Society Test ANS 16.1. A monolithic cylindrical sample
was immersed in djstilled water at a specified ratio of Ieachate volume to sample;:?,/
surface area. The Ieachant was renewed at frequent intewals and “the.. -\
concentration of metals was determined. The authors concluded that lead has
greater mobility than zinc, and that the mobility of zinc changed with differing s/s
matrices.
Webster and Loehr ’62)performed a study in which the long-term leaching of
metals from concrete products was analyzed using a sequential extraction
procedure employing both acidic extraction fluid and seawater. The authors
concluded that pH alone could not fully explain the leaching behavior of metals in
the concrete products. In addition, the authors noted that the severe environment
created during the acidic sequential extractions resulted in the leaching of
substantial amounts of alkalinity from the concrete, allowing the Ieachate pH to drop
below 4, where metals are highly soluble.
2.7.3 Long-Term Performance Study Results
A significant unresolved issue of stabilizatiordsolidification is how well the s/s
treated waste maintains its immobilization characteristics over time. The question
is not whether s/s wastes will eventually release their contaminants into the
.,
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33
I environment, but whether this release is environmentally acceptable. Since s/s
technologies for waste treatment have only been in use for a few decades, the
number and duration of research studies of particular s/s products must be based1
on the available sfioder-term field data, laboratory tests, and models of leachingf,?/
behavior... “\
Per~ et al.(ti) used the TCLP to study the long-term leaching behavior of four
Ii types of wast&s @ntaminated with metals or inorganic. The study showed that the
I effect of time on TCLP results was highly waste-dependent. For some of the
wastes, Ieachate concentrations remained stable with time, while in other wastes,
Jthe concentration of metals in the Ieachate increased. Similar results were obtained
by Akhter and Cartledge(65) and Cartledge(66), except that both increases and
decreases in metals Ieachabfity, as measured by the TCLP, were observed with
aging. In some cases, spectroscopic analysis was used to link these changes with
I changes in the chemical structure of the stabilized waste.
Badamchian, et al. ‘Gnperformed chemical and physical analyses to evaluate
the long-term effectiveness of the s/s of several wastes stabilized during US EPAs
Superfund Innovative Technology Evaluation (SITE) program. The TCLP results
‘1
from the study demonstrated that metals remained immobilized over the six-yearIperiod, for two of the SITE s/s technologies, and that the concentrations of TCLP-
Ieachable metals in all of the aged samples were below the RCRA threshold limits...1
I The second portion of this study, which was initiated to examine the mineralogical
changes in the wastes afler six years, was presented in Klich’s dissertation.@) The
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results of that portion of the study identified chemical weathering features and
mineralogical changes that were promoted by pervasive cracking at the macro-,
micro-, and submicroscopic scales. The cracking observed within the cement matrix
and within the wask aggregates allowed moisture, air, and groundwater to interact:?/’
with the treated waste constituents. The study confirmed that metals migrate from... ‘<
waste aggregates into the porous cement micromass overtime, and as discussed. .
previously, tfie manner in which the metal is immobilized within the cement
micromass is different for each metal. The author also asserts that the same
environmental issues that affect the durability of concrete must be considered when
evaluating the durability and performance of s/s wastes.
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3.0 PRfOR RESEARCH AT THE UNIVERSITY OF PllTSBURGHAND ORIGINAL SAMPLE PREPARATION
3.1 Prior Research at the University of Pittsburgh
In 1994, res~archers at the University of Pittsburgh’s Department of\
Chemical and Petroleum Engineering and Department of Civil and Environmental: +. ,,
Engineering began wo~kon the project titled, “Treatment of Metal-Laden Hazardous
Wastes with Advanced Clean-Coal Technology By-Products,” funded by the United
States Department of Energy. “Thegoals of the project, to be completed in two
phases, were to (1) perform stabilization/solidification treatability studies to
determine if Clean-Coal Technology (CCT) by-products were effective in.—
immobilizing the metals present in the various wastes according to the TCLP
(Phase 1 work), and (2) demonstrate the full-scale effectiveness of s/s of metal-
Iaden wastes using CCT by-products (Phase 2 work). To date, the Phase 1 studies
have been completed, confirming the effective stabilization/solidification of metals
in various hazardous waste streams using CCT by-products,
As previously mentioned, the s/s waste samples examined for the purposes
of this document were gathered from the original samples prepared during Phase
1 of the research project described above. The following sections briefly describe
the characteristics of the s/s reagents and the wastes used in the original study, and
the preparation of the resulting treated waste samples.
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3.2 Original Sample Preparation
Stabilization/Solidification Agents
;??/
The Clean Coal Technology (CCT) program refers to a Federally furided.-\
cooperative effort with selected electric utilities and others to demonstrate a new. .
generation of! innovative coal processes which are environmentally cleaner and
more efficient than conventional coal-burning processes (US DOE, 1991 ). The
resulting waste stream from the CCT processes is fly ash rich in lime. The
pozzoianic properties of the fly ash, coupled with the higher than normal lime
content make the CCT by-products attractive as s/s reagents. A brief description
of each of the CCT by-producls used in the original study, as well as the respective
CCT process, is included in Appendix A. In addition, further information on the CCT
by-products, as well as the results and conclusions of the Phase 1 study are
documented in the theses by Clifford and Prints.
The three CCT by-products used in the original study each originate from
slightly different CCT processes. Prior to the s/s activities, each of the CCT by-
products was characterized to determine its geochemical and reactive propetiies.
In addition, a comprehensive metals analysis of each of three CCT by-products was
performed prior to the start of the original project. The metals analyzed include the
eight RCRA metals (As, Ba, Cd, Cr, Pb, Iig, Se and Ag) and seven other metals
(Sb, Be, Cu, Ni, Tl, V and Zn) which may be regulated in the future. A total
37
I constituent analysis was performed to see which of these metals were present in
I each by-product and in what concentration. As well, a TCLP metals analysis wasI
)completed to determine the actual leachable metals concentrations in each of the
I CCT by-products. The results of this very thorough metals analysis demonstrated
! ;;>~,/
) that the CCT by-products were’ nc}tcharacteristically toxic in their own right, and”thatI .. -\
they would not contribute to the leachable metals concentrations in the subsequent.
\ treated
1
waste~mixtures.
3.2.2 Hazardous Waste Materials
The hazardous wastes chosen for the original study included three
contaminated soils. Metals””analysisof each of the wastes demonstrated that each
contained significant amounts of leachable lead, and was therefore characteristically
hazardous as defined by the US EPA. The “Munitions Soil”waste is a contaminated
soil from a former military munitions depot, where lead-containing munitions were
stored on site. The “Industrial Soil”waste is a contaminated soil from an industrial
site. The waste is a mixture of contaminated soil and debris from plant operations
in the area. The “Wastewater Treatment Plant (WWTP) Soil” is tainted soil from a
former hospital wastewater treatment plant, which used lead piping in the sewage’
distribution system.
38
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3.2.3 Treated Waste Mixtures
One of the goals of the Phase I work was to perform a treatability study using
different combinatio~s of CCT by-products with hazardous wastes. In so doing, the~~/
wastes were combined with the CCT by-products in the following ratios, 10YO,30Y0,.. .-\
50?40 (where 10% denotes a combination of 1 part CCT by-product with 9 parts,. .
waste) in an effort to determine which by-product dosage was most effective in.’
immobilizing the metals present in the waste. The number of CCT by-prod uctiwaste
combinations examined during the treatability study was extensive, however, only
a select number of the original treated waste samples were available for this long-
term study. The treated waste samples which were used in this study include:
Munitions Soil with 10O?40CFBC Residue, Munitions Soil with 50% PFBC Residue,
Munitions Soil with 50% Spray Dryer Residue, WWTP Soil with 50% PFBC
Residue, WWTP Soil with 50% CFBC Residue, and Industrial Soil with 50V0 PFBC
Time Current BDAT Future BDAT Munitions Soil WWTP Soil WWTP Soil Munitions Soil Munitions Soil Industrial Soil(days) Standard Standard WI 100% EPC WI 50% EPC WI 50% Tidd WI 50% Tidd WI 50% Consol WI 50% Tidd
L Sign in the logbmk It is on the bench by the instrument.~~,,/
2. Flip open cover for the limp holder. Check to see if a lamp(Cu) is in position. Ifnot place a lamp (CU) into the holder and rotate turet into the proper position (lampshines through sample compartment).
,.
3.Tum #ow~ switch on. It is located at the bottom left comer of instrument.
4. Wait for the computer to run the initialization test (a couple of minutes). Thecomputer screen will display the ElementSelectMode page &@re 1.) when done.
5.At the bottom of the screen, there are options listed in rectangles. They areactivated by the grey soft function keys located on the top row of the key pad (13gure
6).
6- Type in the date in the follow format, 951025, then press the DATE soft functionkey. .-
7. Place lamp into holder and turn the turet until in proper position (where the Culamp was). Next plug in lamp in either the HCL 1 or HCL 2 (If using a non-codedlamp an adapter must be used). Make sure the Lamp soft function key is set tothecorresponding lamp connection. The Lamp fimction key toggles between lamp 1 and2-
8. Type in the element number (If a non-coded lamp is used), then press theELEMENT soft key. Xfusing a coded lamp the computer will know what is there andwill display the “cookbook” parameters.
9. Type in the appropriate current (mA) and press the L.CURR soft key. Generally,this is 2 or 3 mA lower than the maximum current list on the lamp.
Settim? UD thesrm3roDhotometerandalismin$ztheIamD:
L Press the SETUP fimctionkey. The functionkeysarewhiteand arebated on theleft-handsideofthekeypad.
2.The computer wilI automatically setup the wavelength to be monitored for thespecific element chosen. Doubie check that it is the right wavelength. The monitorshouId look like Figure 2.
.. . ... .. . ...
69
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L Turn on the f% fm thehood behind you....
2.Turn on tie ai.r~The v&e is on the right side of the hood.
3. Turn on the acetylene (short tank). The pressure should be set to 13 psig (-rabove 15 psig).
4. Press tie F’IAklE key (red).
5. Watch the air gauge when the flame ignites.psig for proper operation-
6. Wait 20 min. for the sj%em to equilabte.
The linepressure should be 57-59
~edtin~ DUtitY and Sensitivim
1. Press the CONT fixriction key. &reen should look ~ figUre 3.
2. Place a beaker of D.L water onto the sample tray and insert sampling tube intoIiqui&
3. Pressthe A~O-ZERO softkey. The instrument is now zeroed. It should takeabout 10-20 m.h for the lamp and flame to stabilize.
4. Measure the absorbance of one of the standards. Use the one with theconcentration ckxest to the sensitm“- .ty check concenkadon listed in the AA manual.
5.Ifthesensitivelyisnothighenough, you may have to change the fuel mixture forthe flame. To do so, press the ATOM CONTR function key. The lab instructorwillshow you how. Press theMAIN KEYS soft key to returnto continuous mode.
6. Measure the absorbanceof the qual@ control sample. Compare the two resultsand determine the purity (and correct concentration) of the standard.
●
✌ ✎
✎
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3. If backgroundcorrectionis needed,pressthe BG CORR soft key.
4. Next align the lamp and maxhnke the energyout pu~ Tim lab instructorwillshow you how the first time.
5. Record the Iampeiemen~ energy, currenGand other Morn@on requestedin thelog book. --
Lkhtirw the ffiime:
L Turn on,the I%,, ●..
2.Turn on the air.
\
for the hood behind you.\
.The valve is on the tight side of the hood.
3.Turn on the acetyiene (short tank). The pressure shouId be set to 13 psig @everabove 15 psig).
4. press the FLAME key(red).
5. Watch the air gauge when the flame ignites. The line pressure should be 57-59psig for proper operation.
._
6. Wait 20 min. for the system to equilabxate.
Checkixw DUlitV and sensitiviw:
1. Press the CONT function key. Screen should look like figure 3.
2. Pi.ace a beaker of D.I. water onto the sample tray and insert sampling tube intoliquid.
3. Press the AUTO-ZERO soft key. The instrument is now zeroed. It should takeabout 10-20 min. for the lamp and flame tostabilize.
4. Measuretheabsorbanceof one of the standards. Use the one with theconcentrationclosest to the sensitivitycheck concentrationlisted in the M manual.
5. If the sen$tivi~ is not high enough, you may have to change the fuel mixtureforthe flame. To do so, press the ATOM CONTR function key. The lab instructorwillshow you how. Press theMAIN KEYS soft key to returnto continuous mode.
6. Measure theabsorbance of the quality control sample. Compare the two resultsand determinethe purity (and correct concentration) of the standard.
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X. Press tbe PROG tiedon key. Scteen should look like figure 4.
‘..3. &m&ntrationof tie standardsareenterednexL S1 isthefirststandard,S2 thesecond and v forrh. The number of decimal pkicesusedincateringtheconcentrationof thestandardswilldemminethenumbtiofdecimalpiacesdisplayedbytheoutput(i.e.5.00wilIgive2 decimalpiaceoutput).
5. Press the RUN fimction key. Screen should look W figure 5.
6. The &t soft key is-the AUTO-ZERO. Press this key at anytimeyouwanttozerotheSpectrophotometer.
7. Press the STD 14 soft &y. PIace the stan&rd On the sampletrayandputthesample tube into the Iiquid. Press the STD X soft key (X is the appropriate standardcuxently beingmeasured,k. 1,2 etc.)
8.. Rqx=t.forallslandards. When the last standaxd has been run a ealibxation curvewnll be pmted out..
9. Samplesshould be measuredinthefollowingordera.Qualitycontrolsampleb.Blankc- samples(max20)d-Spikedsamplee.Spikingsolution
10.Place sampleonkayandputsampietubeintoliquid.
11.-PressREAD functionkey(blue).
~. Repeatforeachsetof20 samples, s@xingwith a calibmtion ch~k. Always endwith a calibrationcheck.
72
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I300 mm
T485 mm
J-Clcl[mmmmacl
EalEzHza E EIEIEILwEHiia IzHzHElLl12ai3 la EIElGmEIcl IZ3EI EHma
among individual measnxremants of an identical sample
parameter. The precision for these studies will be
measured in term of the standard deviation(s) of
replicate neasuremen~<~;
and/or critical ~rge
R= = the
c) Completenesss:
of valid data
largest
n-l
(R=) :
of the K: - the smallest of the Xa
-Completeness is a measure of the amount
collected as compared to the amount
expected within the constraints of the operation and
sampling program. It is a function of two factors.
i) SampLes collected but not analyzed;
ii) Data
Since all
subjected
rejection
rejected following validation procedures.
samples collected are expected to be
to the intended analyses and since the data
rate is anticipated to be well. under 10%,
completeness will be s 90% for all analyses.
d) Representativeness: Representativeness is a measure of
the degree to which the data accurately and precisely
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represent
levels of
nature of
carefully
the systenr under study. TO
representativeness in these
81
attati accept~le
studies, the
the samples collected will be
e-uated with respect to homogeneity y anti
relationship to the conditions pertaining in the
landfill test cells. ““K addition, careful protocols .Of.. -\
sample collection, storage and presemation will be
+.,
e) Co~ajabiL~ty:
importance when
*alyses passes
times.
Comparability will be a factor of
the responsibility for specific
from one analyst to another or is given
to more than a single analyst. This factor will be
addressed by subjecting each anal.yst’s technique to a
care~~l statistical eva~uation using pure reference._
samples and spiked samples.
data assuring continuity and
derived.
6.0 SAMPLING AND SHIPPING PROCEDURES
From these evaluations
comparability will be “
E’aculty,graduate students, and project manager from Pitt
will visit the Yukon Plant of Mill Sezxrice. The graduate
students will obtain samples and prepare cylinders for
compressive test strength testing and leachate testing. Fo&y
cylinders will be prepared during each trip, comprising a SaIfLpk!
set. The cylihciers will be transpofied by ground vehicle to
Benedum Hall, University of Pittsburgh and an identification will
be number assigned to cylinders, and recorded in sample log book.
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7.0 CALIBRATION PROCEDURES
The calibration of aU laboratory equipment used
studies will be performed in accordance with stamdard
procedures as specified by tis&&nt manufactures or
in these
operational
by accepted
standard ~alyti.ca’~ methodologies and protocols as presented in
EPA manuals.. .
...
The calkiatio’n procedures in this effort will be those
specified in the analytical procedures list in Table 1 of this
Quality Assurance Puoject Plan.
All instrumental systems used will be fully calibrated in
accordance with the referenced methods (Table 1) at the beginning
of an analytical run. Recalibration will follow naturally as a._
consequence of the inclusion of quality control check standards
among the samples run.
Calibration standards will be obtained from commercial
sources or prepared using the highest quality prtiary standard
reagents. In all cases, manufactures’ lot numbers will be
recorded in the sample log book and referenced in all associated
analytical procedures-
8.0
8.01
ANALYTICAL PROCEDURES
All of the analytical methods used axe listed in Table 1.
Lea~te test.
Two leaching test procedures will be used;
1) TCLP, method 1310, SW-846
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2) ASTM, method D3987.
8.02 ~ - The EP extracts obtained from the TCLP and ASTM
leaching procedures will be digested in accordance will EPA SW-.
846 Method 3010 with the excep@on of As, Se and 13g. *senic,
Selium and Mercu~ will be digested\
in Table 1. ..
The me~al~ will be measured by
according the methods cited
atomic absorption
spectrometry using’ the methodology presented in Table 1. Direct
aspiration analyses will be performed on metals using a Perkin-
Elmer Model 11OOB AA spectrophotometer. Commercially available
certified standards
working standards.
method. Selium and
procedures found in
will be used to determine the purity of the
Mercury will be analyzed by the cold vapor
-“sSnic will be first analyzed by flame AA
the Perkin Elmer AA instruction manual.
Because the detection limits for these two metals is close to the
regulatory maxium concentrations for toxicity characteristic, the
hydride method will be substituted. The method described in a
Varian application note, “Some
Generator” will be followed.
9.0
9.01
DATA UCTION REPORTING
Metals
Studies with a Varian-76 Hydride
The metals will be analyzed in accordance with the
procedures outline above for other inorganic parameters. Metal
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concentrations will
The and metals
be reported in mg/L.
data will be repotied
84
to the principal
investigator. Results will be validated based on obsezwed and
expected trends and on internal QC checks. The data will also be-.
subject to validation during q,petings of the research team during
which all..results-xwill be reviewed.\
9.02 ReDo*ma.
and of Data
ALL fu&@ental analytical data collected (absorbance
readings, peak heights, etc.) will be recorded in
notebooks, and/or filed on, computer disks or hard
along with associated analytical information such
laboratory
copy output,
as calibration
data, reagent concentrations, and sample dilutions. These
analytical data will then be reduced to the ultimate reporting by
appropriate procedures’. ‘Internal calibrations, methods i= which
the instrument has been calibrated to yield data directly in
appropriate reporting units by use of one or more standards will
be used with the Atomic absorption spectroscopy of metals.
85
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Analysts: Data Storedin Computer for Pro- -------------- --—
cessing and Retrieval
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Validation ofMetals Data
II f RecommendationTeam Validation
of Data Management Group
Figure 4. Validation Sequence for Data
.
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i
ITABLE 3. EQUATIONS AND REPORTING UNITS FOR ANALYTICAL
PARAMETERS
b
86
Parameter: Metals # / Reporting Unit: mg/L
Method: ~ Direct Aspiration Flame AA
Reference: USEPA SW-846
Equation: “! .“Method 7000, Section 7 .4.2
xug/L in sample = A * (C + B) / C
Where;
A= mg/L of metal- in diluted aliquot from calibration curve;
B.fief
C.fief
deionized distilled water used for dilution;
sample aliquot
10.0 INTERNAL QUALITY CONTROL CHECKS
10.01 J$etala
Quality control procedures for metals will be consistent
with methodology presented. in EPA SW-846. In this regard, the
following strategies will be followed:
a) The AA spectrophotorneter will. be calibrated by use of
standards prepare in the lab which the purity has been
previously checked with a certified commercial standards.
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will
87
b) One sample in four (25%) will be run in replicate.
Agreement within 3 of the mean will be required on all
replicates.
c) For every five samples analyzed, a water blank and blank.
spiked with a known mixtzw= of =tals will be =a~yzed- The
percent recotiery will be calculated for each metal..
Recov’eriesshould be within 90-110%.
d) ‘“’;Fazlufe to attain the criteria in either steps (b) or
(c)above will’ be cause to repeat the entire set of metal
analyses.
PERFORMANCE AND SYSTEM AUDITS
In cooperation with the sponsor, a complete Syst- audit
be carried out as deemed appropriate by the sponsor.
The QA/QC strategy outlined previously will assure that
ongoing performance audits will be maintained.
12.0 PREVENTIVE MAINTENANCE PROCEDURES AND SCHEDULES
Preventive maintenance will be conducted on all instruments
at a minimum frequency as specified by the manufacturers of the
instrumentation. In addition, more frequent maintenance will be
conducted if
complete log
instrument.
the age, condition and level of use dictate. A
will be maintained of all such activity for each
Beyond a selection of standard electronic parts - resistors,
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88
capacitors, etc. - no extensive supply of replacement parts will
be kept on hand. The University of Pittsburgh’s location in a
major metropolitan area pexmits rapid emergency setice and
acquisition of replacement parts from local sources.<
Furthermore, a significant poq@ion of instrument se-ice will
entail simple replacement of circuit boards, parts which will not
be commonly kept on hand by instrument users, but which can be:,,
rapidly acqu+reti and installed. It is unlikely that any but the “
most extreme of instrument failures will entail a down-the of
more than 48 hours on any instrument.
13.0 SPECIFIC ROUTINE PROCEDURES USED TO ASSESS PRECISION, “
ACCUI#.CY AND COMPLETENESS
Since the volume bf--si~ples to be analyzed during the course
of the investigations precludes the analysis of replicates of all
samples, the following methodology will be used to monitor
precision and accuracy.
a) During the initial phases of the study, all analytical
methodology will be subjected to a statistical evaluation using
known standard samples. The object of this evaluation will be
the establishment of levels of precision and accuracy expected
for each method. The standard samples will be selected to cover
the ranges of values anticipated for the actual samples.
In all cases, the analyst whose responsibility will be the
routine measurement of the specific parameter under consideration
89..-
wiU conduct the analyses for this statistical evaluation.
b) CIXZtrOLdtartswill be ~~s~ f- ~ reFetit~=
-ysis of - acceptable ~~1 ~~ - me ~~1
criterion will be 3 units . The control chart will contain the
tistmmental re+oxlse plotted over time over time.>?/
c) Sticepr~sion &d accuracy will be subject to the .
technique of the specified analyst, any change in analyti.-l
personnelwill necessitate a re-etiuation of< +. -.
method and generation of a new contzml chart.
ene -al yst be allowed to use a cozz~=l chart
Once control charts are established, the
the analytical
In no case will
by another analyst.
routine inclusion
of spiked samples, contzol standards and sample replicates will
permit evaluation of means, ranges and relative standard
deviation which can he used b t~= to assess accuracy axd also
be compared by use of &t~tisticaL prOCedL-eS SuCh as me t tes~-
CompLeteness will be e-lusted by means of accurate S@le
loggbg and trackfig so that the ratio of acceptable analyses to
the number of samples drawn may be determined.
14.0 CORRECTIVE AC’I!ZONS
Corrective actions h response to obsemed deviations of
analytical methodology from speci:ied control criteriawill be
taken on the basis of the nature of the method.
a) Me-: h Routine inst.-ent maintenance and
cl.eani~g and preparation of new standards followed by
recaI.ibration should alleviate the bulk of problems in purely
instrumental techniques. Only k the most extreme
inte~ention of se~ice personnel be required.
b) ~: Since metaJ. analyses involve both
cases will the
an elaborate
●✎
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wet chemical technique (digestion) and instrumental method,
analytical probl~ may entail elements of both. The use of a
clean standard should serve to localize the
or instrument - after which the appropriate
will be taken. ‘ ;,?,/
~,. .’\
problem - digestion
corrective action
15.0 QUALITY ASS-C3T REPORTS TO MANAGEMENT..
Data aqses.,smeptwill be conducted by the project
investigators on a’continuing basis. The following reports will
be in fulfilling QA responsibilities:
a) A report will be made following performance audits.
This will be included in the subsequent progress report.”
b) A section describing all QA activities and results will
be included in the-final project report.
The Quality Assurance Reports will include the following
components, where appropriate.
a) Modification of the existing Quality Assurance Project
. . . Plan and rationale underlying such modifications.
b) Any limitations o:rconstraints on the applicability of
the data and proposals regarding their elimination.
c) The current status of quality assurance programs and
accomplishments and the status and outcome of corrective
actions taken.
d) The results of any quality assurance system or
performance evaluation audits undertaken with respect to the
.:,
191
analytical methodology.
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e) Updated assessments of the quality of the data in terms
of precision, bias, completeness, representativeness and
comparability, as appropriate..
f) Description of any p~~,gram of quality-related training
unciertaken in the course of research including the\
identification of the personnel involved and status and
outcomes .of these programs.
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16.0 REFERENCES
Test Methods for Evaluating SeLid Wastes, Physical/~-ical
Methods, U.S. EPA SW-.846, 1986 revision.
ASTM, Method D3987.
Model 11OOB Atomic Absorption Operator’s Manual, PerkinElmer, Release A2,,,Sept~er 1988.
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-_ BIBLIOGRAPHY
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
,,
94
IBIBLIOGRAPHY
Cullinane, M. J., and L. W. Jones. Stabilization/Solidification ofHazardous Waste. Cincinnati: U.S. Environmental Protection Agency(U.S. EPA) Hazardous Waste Engineering Research Laboratoy(HWERL), EPA/600/D-86/028, 1986.
Means, J. L., Smith, L. &,;Nehring, K. W., Brauning, S. E.,Gavaskar, A. R., Sass, B. M., ~les, C. C., and Mashni, C. l., The ~Am{ication of Solidification/Stabilization to Waste Materials, (Boca Raton,Florida: Lewis Publishers, 1995), p. 4.
. .
~heese~an, C. R., Sollars, C.J., and Perry, R., “Mechanisms ofMetal Containment Resulting from the Solidification of a CommerciallyProduced Stabilized Waste,” Stabilization and Solidification ofHazardous. Radioactive, and Mixed Wastes: 3rd Volume, ASTM STP1240, T. Michael Gilliam and Carlton C. Wiles, Eds., American Society forTesting and Materials, 1996.
Gilliam, T. M. And Spence, R. D., “Development of Cement-BasedGrouting Technology: A Perspective”, Proceedings of the FirstInternational Symposium on Cement Industry Solutions to WasteManagement, Caiga~,-Alberta, Canada, pp 45-53, October 7-9, 1992.
Conner, J. R., Chemical Fixation and Solidification of HazardousWastes (New York: Van Nostrand Reinhold, 1990), p. 25.
Ibid., p. 26.
Ibid., p. 27.
Ibid., p. 3.
Ibid., p. 202.
Ibid., p. 204.
Ibid., p. 205.
Ibid., p. 30.
Means, Op. Cit., p. 154.
Lea, F. M., The Chemistry of Cement and Concrete, 3rd Edition,(Chemical Publishing, New York, 1970).
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I 15. Adaska, W. S., ~resouthick, S. W. and West, P. B., “Solidificationand Stabilization of Wastes Using Potiland Cement,” Portland CementAssociation, (1994), p. 6-7.
16. Kosmatka, S. H. and Panarese, W. C., “Design and Control ofConcrete Mixtures,” EBOOOI, Portland Cement Association, 1990.
17. Adaska, Op. Cit., p. 7. ,Z,
18. LaGre~, M. D., Buckingham, P. L., and Evans, J. C., HazardousWaste Management (New York: McGraw-Hill, Inc., 1994), p. 648.
Means, Op. ‘Cit., p. 154.: .19.
20.
21.
22.
LaGrega; Op. Cit., p. 647.
IConner, Op. Cit., p. 31.
Bhatty, M. S. Y., “Fixation of Metallic Ions in Portland Cement,”Proceedings of the 4th National Conference on Hazardous Wastes andHazardous Materials, (Washington, D.C., 1987), p. 140-145.
23. U.S. Environmental Protection Agency. Federal Register: 52(155):29999 (August 12, 1987).
Klich, Ingrid, “Permanence of Metals Containment in Solidified andStabilized Wastes” (Ph.D. Dissertation, Texas A&M University, 1997).
Brookins, D. G., Eh-~H Diaarans for Geochemist, (Springer-Verlag, New York, 1988).
‘1 31.
.:!
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4
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32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
Dragun, J., “The Fate of Hazardous Materials in Soil,” HazardousMaterials Contr. (May/June 1988), p. 41-65.
Bhatty, Op. Cit., p, 141.
Klich, Op. Cit., p. ;33-42.
Cocke, D. L. and Mollah, M. Y. A., “The Chemistry and LeachingMechanisms of Hazardous Sut$~tances in CementitiousSol~dification/~tabilization Systems,” Chemistrv and Microstructure of”Solidified Waste Forms, edited by R. D. Spence ( Boca Raton, Florida:Lewis Publishers, 1993), p. 24.
...
Peon, C;”S. and Perry, R., “Studies of Zinc, Cadmium, and MercuryStabilization in OPC/PFA Mixtures,” Materials Research SocietvSvposium Proceedings, Vol. 86, (1987), p. 76.
Ibid., p. 76.
Cartledge, F. E., Butler, L.G, Chalasani, D., Eaton, H.C., Frey, F.P., Herrara, E., Tittlebaum, M. E. and Yang, S., “ImmobilizationMechanisms in Solidification/Stabilization of Cd and Pb Salts UsingPortland Cement Fixing Agents,” Environmental Science and Technology,vol. 24, No. 6 (1990), p. 871.
Ibid., p. 871.
Cocke, Op. Cit., p. 202.
Cocke, Op. Cit., p. 202.
Kindness, A., Macias, A., and Glasser, F.P., “immobilization ofChromium in Cement Matrices,” Waste Management, Vol. 14, No. 1,(1994), p. 11.
Macias, A., Kindness, A., and Glasser, F. P., “Impact of CarbonDioxide on the Immobilization Potential of Cemented Wastes: Chromium,”Cement and Concrete Research, Vol. 27, (1997), p. 224.
Bonen, D. and Sarkar, S. L., “The Present State-of-the-Art ofImmobilization of Hazardous Heavy Metals in Cement-Based Materials,”Advances in Cement and Concrete, (ASCE, New York, 1994), p. 488.
.
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45.
46.
47.
48.
49.
50.
51.
52.
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I....
53.
54.
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97
Thomas, N. L., Jameson, D. A., and Double, D. D., Cement andConcrete Research, Vol. 11, (1981), p. 143-153.
Cartledge, Op. Cit., p. 872.
Cocke, Op. Cit., p. 213.
Cocke, Op. Cit., p. 233.,P,
, Peon, Qp. Cit., p. 74-75.
Erickson, P., .M. and Barth, E. F.,’’Evaluation of ContaminantLeachability Factors by Comparison of Treatability Study Data for MultipleSolidified/Stabiflzed Materials,” Stabilization and Solidification ofHazardous. Radioactive. and Mixed Wastes: 3rd Volume. ASTM STP1240, edited by T. M. Gilliam and C. C. Wiles, American Society forTesting and Materials, (1996), p. 429-441.
Jones, L. W., Bricks, R. M., and Cullinane, M. J.,”Effects ofSelected Waste Constituents on Solidified/Stabilized Waste Leachability,”Stabilization and Solidification of Hazardous. Radioactive, and MixedWastes, 2nd Volume. ASTM STP 1123, edited by T. M. Gilliam and C. C.Wiles, American Society for Testing and Materials, (Philadelphia, PA,1992), p. 193-203. -
Trussel, S. and Batchelor, B., “Chemical Characterization of PoreWater of a Solidified Hazardous Waste,” 3rd ASTM InternationalSymposium of Stabilization/Solidification of Hazardous. Radioactive andMixed Wastes, edited by T. M. Gilliam, American Society for Testing andMaterials, (Williamsburg, VA, 1993), p. 20-21.
Erickson, Op. Cit., p. 438.
Ortego, O. E., Barroeta, Y., Cartledge, F. K, and Akhter, H.,“Leaching Effects on Silicate Polymerization -An FTIR and 29Si NMRStudy of Lead and Zinc in Portland Cement,” Environmental Science andTechnology , Vol. 25, No. 6, (1991), p. 1171-1174.
Butler, L. G., Cartledge, F. K., Eaton, H. C., and Tittlebaum, M. E.,“Microscopic and NMR Spectroscopic Characterization of Cement-Solidified Hazardous Wastes,” Chemistry and Microstructure of SolidifiedWaste Forms, edited by R. D. Spence, (Lewis Publishers, Boca Raton,Florida, 1993), p. 151-168.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
— n .,
●
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98
Bonen, D. and Sarkar, S. L., “The Effects of SimulatedEnvironmental Attack on Immobilization of Heavy Metals Doped inCement-Based Materials,” Journal of Hazardous Materials, Vol. 40,(1995), p. 321-335.
Hassett, D. J., “Leaching Characterization Using the SyntheticGroundwater Leaching Procedure (SGLP),” American EnvironmentalLaboratory, Vol. 8, (1996), p. 1,-$,
. Klich, Op. Cit., p. 159.\
Mollah, M. Y. A., Hess, T. R., Tsai, Y-N., and Cocke, D. L., “AnFTIR a~d ~PS !,nvestigations of the Effects of Carbonization on theSolidification/Stabilization of Cement Based Systems - Portland Type Vwith Zinc,” Cem’ent and Concrete Research, Vol. 23, (1993), p. 773.
Lee, C-H., Wang, IH-C., Lin, C-M., Yang, G. C. C., “A Long-TermLeachability Study of Solidified Wastes by the Multiple ToxicityCharacteristic Leaching F]rocedure,” Journal of Hazardous Materials, Vol.38, (1994), p. 65-74.
Andres, A., Ortiz, l., Viguri, J. R., and Iraben, A.,”Long-TermBehaviour of Toxic Metals in Stabilized Steel Foundry Dusts,” Journal ofHazardous Materials, Voll. 40, (1995), p. 35-41.
Webster, M. T. and Loehr, R. C., “Long-Term Leaching of Metalsfrom Concrete Products,” Journal of Environmental Enaineerinq, August1996, p. 720.
Means, Op. Cit., p. 33.
Perry, K. J., Prange, N. E., and Garvey, W. F., “Long-TermLeaching Performance for Commercially Stabilized Waste,” T. M. andWiles, C.C, eds., Stabilization and Solidification of Hazardous.Radioactive, and Mixed Wastes, edited by T. M. Wiles and C. C. Wiles(Philadelphia, Pennsylvania: American Society for Testing and Materials,1992), p. 242-251.
Akhter, H. and Cartlege, F. K, 1991. “First Evidence that LongCure Times in Cement/Fly Ash Solidification/Stabilization Can Result inReversal- of Hydration and Polymerization in the Matrix ApparentlyCaused by Arsenic Salts.” Pre-print of extended abstract presented to theDivision of Environmental Chemistry of the American Chemical Society,New York, August 25-30, 1991.
99
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66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
Caftlege, F. K., 1992. “Solidification/Stabilization of ArsenicCompounds.” Presented at US EPA Workshop on Arsenic and Mercury:Removal, Recovery, Treatment and Disposal, Arlington, Virginia, August9. EPA/600/R-92/l 05. US Environmental Protection Agency.
Badamchian, B., Brock, C. L., Klich, l., and Hubbard, J.,“Evaluation of Long-Term Effectiveness of Solidified and StabilizedWastes,n Proceedirms Superfund XVI: Environmental Conference andExhibition for the Hazardous ~aterials/Hazardous Waste Management
-t (wa*in9ton! D-C-* I 995)} P. 599-608.\
Klich, Op. Cit., p. iv....
~li~h, Op. Cit., p. 156.
Clifford, B. V., “A Microscopic Evaluation of the Stabilization of aHazardous Sandblast Waste with Clean-Coal Technology By-Products”(unpublished M. S. thesis, School of Engineering, University of Pittsburgh,1996).
Pritts, J. W., “Stabilization and Solidification of Metal-LadenHazardous Wastes with Advanced Clean-Coal Technology By-Products”(unpublished M.S. thesis, School of Engineering, University of Pittsburgh,1996).
Schreiber, E., “Using the Perkin-Elmer 1100 BAASpectrophotometer” (document prepared using instrument manual,School of Engineering, University of Pittsburgh, undated).
Bonen, Op. Cit., p. 335.
Thomas, Op. Cit., p. 153.
Cartledge, Op. Cit., p. 73.
Cocke, Op. Cit., p. 220.
Cocke, Op. Cit., p. 223.
Peon, Op. Cit., p. 74.
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REFERENCES NOT CITED
Assmann, D. And Brodda, B.-G., “Fixation of Residues from Special HazardousWaste Incinerators for Shallow Land Disposal,” Stabilization and “Solidification of Hazardous. Radioactive. and Mixed Wastes, 2nd Volume,ASTM STP 1123, T.M. Gilliarn,~yd C. C. VMles, Eds., American Societyfor Testing and Materials, Philadelphia, 1992, pp. 90-102.
.. :\
Bangart, R.’L. and Tokar, M., “Low-Level Radioactive Waste Disposal in theUnited States,” Stabilization and Solidification of Hazardous. Radioactive,and M~ed+.Wastes, 2nd Volume, ASTM STP 1123, T.M. Gilliam and C. C.Wiles, “Eds.,American Society for Testing and Materials, Philadelphia,1992, pp. 3-11.
Boehmer, A. M., Gillins, R. L., and Larsen, M. M., “Stabilization of Mixed Wasteat the Idaho National Engineering Laboratory,” Environmental As~ects ofStabilization and Solidification of Hazardous and Radioactive Waste,ASTM STP 1033, P. L. Cote and T.M. Gilliam, Eds., American Society forTesting and Materials, Philadelphia, 1996, pp. 343-357.
Buckley, L. P., Tosello, N. B.,--and Woods, B. L., “Leaching Low-LevelRadioactive Waste in Simulated Disposal Conditions,” EnvironmentalAspects of Stabilization and Solidification of Hazardous and RadioactiveWaste, ASTM STP 1033, P. L. Cote and T.M. Gilliam, Eds., AmericanSociety for Testing and Materials, Philadelphia, 1996, pp. 330-342.
Darnell, G. R., ‘Sulfur Polymer Cement, a Final Waste Form for Radioactive andHazardous Wastes,” Stabilization and Solidification of Hazardous.Radioactive. and Mixed \/Vastes, 3rd Volume, ASTM STP 1240, T.M.Gilliam and C. C. Wiles, lEds., American Society for Testing and Materials,Philadelphia, 1996, pp. 272.
de Groot, G. J., Wijkstra, J., Hoede, D., and van der Sloot, H. A., “LeachingCharacteristics of Selected Elements from Coal Fly Ash as a Function ofthe Acidity of the Contact Solution and the Liquid/Solid Ratio,”Environmental Aspects of Stabilization and Solidification of Hazardousand Radioactive Waste, ASTM STP 1033, P. L. Cote and T.M. Gilliam,Eds., American Society for Testing and Materials, Philadelphia, 1996, pp.170-183.
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Dermatas, D. And Meng, X., “Stabilization/Solidification (S/S) of Heavy MetalContaminated Soils by Means of a Quicklime Based TreatmentApproach,” Stabilization and Solidification of Hazardous, Radioactivexand Mixed Wastes, 3rd Volume, ASTM STP 1240, T.M. Gilliam and C. C.Wiles, Eds., American Society for Testing and Materials, Philadelphia,1996, pp. 499.
Fuhrmann, M. and Colombo, P., ‘tLea,@ing-induced Concentration Profiles in theSolid Phase of Cement,” Environmental Aspects of Stabilization and ‘Solidification of Hazardous and Radioactive Waste, ASTM STP 1033, P.L. Cole and T.M. Gilliam, Eds., American Society for Testing andMaterials, Philadelphia, 1996, pp. 302-314....,+..1
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