EPA/-530-SW-87-028A
EPA
United States
Environmental Protection
Agencv
Office of Solid Waste
and Emergency Response
Wasnington, DC 20460
EPA. 530-SW-87 (
Octooer 1987
Solid W«n
Characterization of MWC Ashes
and Leachates from MSW Landfills,
Monofills, and Co-Disposal Sites
SummaryVolume I of VII
-------
R-33-6-7-1
FINAL
CHARACTERIZATION OF MUNICIPAL WASTE COMBUSTOR ASHES
AND LEACHATES FROM
MUNICIPAL SOLID WASTE LANDFILLS, MONOFILLS, AND
CODISPOSAL SITES
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
f' OFFICE OF SOLID WASTE
WASHINGTON, D.C.
CONTRACT NO. 68-01-7310
WORK ASSIGNMENT NO. 04
EPA Contract Officer EPA Project Officer
Jon R. Perry Gerry Dorian
Prepared by
NUS CORPORATION
OCTOBER 1987
. * U.S. Environmental Protection Agem
Region 5, Library (5PL-16)
£')'-. "'."-"horn Street, Room 1070
CLio. , , .: 60604
-------
CHARACTERIZATION OF MUNICIPAL WASTE
COMBUSTOR ASHES AND LEACHATES FROM
MUNICIPAL SOLID WASTE LANDFILLS,
MONOFILLS, AND CODISPOSAL SITES
Principal Investigators
Wesley L Bradford, Ph. D.
Senior Scientist
Versar. Inc
Haia K. Roffman, Ph.D.
Manager of Chemistry, Toxicology,
and Risk Assessment Department
and Director of Technical Quality
Waste Management Services Group
NUS Corporation
This report has undergone internal review by the United States Environmental
Protection Agency and has been subjected to peer review as well.
Peer Reviewers
Frank J. Roethel, Ph.D.
Research Professor
Marine Sciences Research Center
Waste Management Institute
SUNY
Stoneybrook, New York
Steven E. Sawell
Physical Scientist
Currently under contract to
Environment Canada
managing the Ash Contaminant
Leachate Ability Project for the
National Incineration Testing
and Evaluation Program (NITEP)
Ontario, Canada
Jan Sykora, Ph.D.
Associate Professor
University of Pittsburgh
Graduate School of Public Health
Department of Industrial and
Environmental Health Sciences
Pittsburgh, Pennsylvania
-------
TABLE OF CONTENTS
EXECUTIVE SUMMARY ES-1
1.0 INTRODUCTION 1-1
1.1 BACKGROUND 1-1
1.1.1 Federal Regulation of Wastes 1-1
1.1.2 Concern Regarding Leachates 1-2
1.1.3 Municipal Waste Incineration 1-3
1.2 OBJECTIVES 1-3
, 1.3 -SCOPE OF WORK/APPROACH 1-6
1.4 SUMMARY REPORT 1-7
1 1.5 DATA LIMITATIONS 1-8
1.6 ACRONYMS AND DEFINITIONS 1-10
i
t 2.0 CHEMICAL CHARACTERIZATION OF MWC ASHES 2-1
2.1 INORGANIC CONSTITUENT CONTENT IN MWC ASHES 2-1
' 2.2 ORGANIC COMPOUNDS FOUND IN MWC ASHES 2-19
2.3 RANGES OF PCDDS, PCDFS, AND PCBS IN MWC ASHES 2-21
3.0 CONVENTIONAL PARAMETERS IN LEACHATES FROM MSW
DISPOSAL SITES, CODISPOSAL SITES, AND MONOFILLS 3-1
i
4.0 INORGANIC CONTENT IN LEACHATES FROM MSW DISPOSAL
I SITES, CODISPOSAL SITES. AND MONOFILLS AS WELL AS IN EXTRACTS .. 4-1
4.1 INORGANIC CONTENT IN ACTUALM.EACHATES 4-1
4.2 INORGANIC CONTENT IN EXTRACTS FROM MWC ASHES 4-8
i - 4.2.1 Extraction Procedure (EP) 4-9
i 4.2.2 Toxicity Characteristic Leaching Procedure (TCLP) 4-10
4.2.3 Monofilled Waste Extraction Procedure (MWEP) 4-12
4.2.4 Inorganic Concentrations in Extracts from
MWC Ashes 4-13
i
5.0 ORGANICS IN LEACHATES FROM MSW DISPOSAL SITES,
CODISPOSAL SITES. AND MONOFILLS AS WELL AS IN EXTRACTS 5-1
, 5.1 ORGANICS IN LEACHATES FROM MSW
AND CODISPOSAL SITES 5-1
5.2 ORGANICS IN LEACHATES FROM MONOFILLS 5-5
5.3 ORGANICS IN EXTRACTS FROM MWC ASHES 5-5
6.0 PCDDs AND PCDFs IN LEACHATES AND EXTRACTS 6-1
7.0 CONCLUSIONS 7-1
8.0 REFERENCES 8-1
-------
TABLE OF CONTENTS - Continued
ADDITIONAL VOLUMES TO FOLLOW
VOLUME II CHARACTERIZATION OF MUNICIPAL LANDFILL LEACHATES -
A LITERATURE REVIEW, SEPTEMBER 1987
VOLUME III ADDENDUM TO CHARACTERIZATION OF MUNICIPAL LANDFILL
LEACHATES - A LITERATURE REVIEW, SEPTEMBER 1987
VOLUME IV CHARACTERIZATION OF MUNICIPAL WASTE COMBUSTION
RESIDUES AND THEIR LEACHATES - A LITERATURE REVIEW,
SEPTEMBER 1987
VOLUME V CHARACTERIZATION OF MUNICIPAL WASTE COMBUSTOR
RESIDUES, APRIL 1987
VOLUME VI CHARACTERIZATION OF LEACHATES FROM MUNICIPAL WASTE
DISPOSAL SITES AND CODISPOSAL SITES, SEPTEMBER 1987
VOLUME VII ADDENDUM TO MONOFILL REPORT, SEPTEMBER 1987
r
III
-------
TABLES
NUMBER PAGE
-' r ES-1 Summary for PCDD and PCDF Values in Ashes ES-5
ES-2 Summary of Metal Content in Ashes ES-6
ES-3 Cadmium and Lead in Extracts and Leachates ES-7
ES-4 Summary of PCDD and PCDF Values in Leachates and Extracts ES-8
1-1 Summary of MSW Incinerator Statistics 1-4
1-2 Make-Up of Composite Samples Taken by Versar and Number
, of Composite Samples Analyzed at the Four Facilities 1-11
2-1 Materials Disposed into the Municipal Waste Stream 2-2
1 2-2 Ranges of Concentrations of Inorganic Constituents
in Fly Ash, Combined Ash, and Bottom Ash from
1 Municipal Waste Incinerators in ug/g (ppm) 2-3
j 2-3 Ash Monofill Characteristics 2-8
2-4 Municipal Waste Combustor Design and Operating Characteristics . 2-9
t 2-5 Total Metals Data for Solid Samples, Versar Study 2-11
f 2-6 Ranges of Concentrations of Organics in Fly and Bottom Ash
from Municipal Waste Incinerators in ng/g (ppb) 2-20
2-7 Ranges of Concentrations of PCDDs,PCDFs, and PCBs
in Fly Ash from Municipal Waste Incinerators in ng/g (ppb) 2-22
2-8 PCDD and PCDF in Solid Samples-Versar Study 2-23
3-1 Conventional Contaminant Concentration Ranges in
T Leachates from Municipal Disposal and Codisposal Sites 3-2
3-2 Characteristics of Municipal Solid Waste
Disposal Sites Selected for NUS Study 3-3
I' 3-3 Characteristics of Selected Codisposal
! (MSW and MWC Ash) Sites 3-4
1 3-4 Conventional Parameters in Leachates from
Monofills and in Quench Waters 3-6
4-1 Inorganic Concentration Ranges in Leachates from
* Municipal Disposal and Codisposal Sites in mg/l (ppm) 4-2
4-2 Ranges of Leachate Concentrations of Inorganic
1 Constituents from Monofills in mg/l (ppm) 4-3
j 4-3 Inorganic Constituents in Leachates from
Codisposal Sites (NUS) in mg/l (ppm) 4-6
4-4 Inorganic Constituents in Leachates
from Monofills (Versar) in mg/l (ppm) 4-7
1 4-5 Ranges of Inorganic Concentrations in Leachates
Produced by SW-924, EP, and TCLP Leaching
Procedures from Fly Ash, in mg/l (ppm) 4-14
4-6 Ranges of Inorganic Concentrations in Extracts
produced by SW-924, EP, and TCLP Leaching
Procedures from Combined Ash in mg/l (ppm) 4-16
4-7 Extractable Metals Data for Three Laboratory
Leaching Procedures, Versar Study 4-20
4-8 Inorganic Content in NY Ashes and in EPToxicity,
TCLP, and SW-924 Extracts, in ppm 4-24
4-9 Inorganic Content in NC Ash and in EP Toxicity,
TCLP, and SW-924 Extracts in ppm 4-25
IV
-------
TABLES - Continued
NUMBER PAGE
5-1 Concentrations of Organic Constituents in Leachate
from Municipal Waste Landfills in ug/l(ppb) 5-2
5-2 Contaminant Concentrations from Leachate of Municipal
Landfills and Codisposal Sites in mg/l (ppm) 5-4
5-3 Ranges of Leachate Concentrations of Organics
from Municipal Solid Waste Incinerator Residues (Monofiils)
Determined from Leachate Field Samples in mg/l (ppm) 5-6
5-4 Organic Constituents in Field Water Samples 5-7
5-5 Ranges of Extract Concentrations of Organic Constituents
from Municipal Waste Incinerator Bottom Ash for
Three Leaching Procedures in mg/l (ppm) 5-11
5-6 Ranges of Extract Concentrations of Organic Constituents
from Municipal Waste Incinerator Combined Fly and
Bottom Ash for Three Leaching Procedures in mg/l (ppm) 5-12
5-7 Ranges of Extract Concentrations of Organic Constituents
From Municipal Waste Incinerator Fly Ash for Three Leaching
Extraction Procedures in mg/l (ppm) 5-13
6-1 Chlorinated Dioxin and Chlorinated Dibenzofuran
Levels in Ashes and Leachates from Monofiils 6-2
6-2 Chlorinated Dioxin and Chlorinated Dibenzofuran
Levels in Ash and Leachates from the NC Codisposal Landfill 6-11
-------
FIGURES
NUMBER PAGE
2-1 Concentrations of Metals in Fly Ash Sampled by
Versar at Facilities A, B,C, and Din mg/kg (ppm) 2-14
2-2 Concentrations of Metals in Bottom Ash
from Facility B in mg/kg (ppm) 2-15
2-3 Concentrations of Metals in Combined
Bottom and Fly Ash Sampled at Versar at
Facilities A, C, and D in mg/kg (ppm) 2-16
2-4 Concentrations of Metals in One Landfill Composite
Sample Collected by Versar at Facility C and
Facility D in mg/kg (parts per million) 2-17
2-5 Concentrations of Dioxin Homologs in Fly Ash from the Four
Facilities Sampled by Versar in ng/g (parts per billion) 2-29
2-6 Concentrations of Furan Homologs in Fly Ash from the
Four Facilities Sampled by Versar in ng/g (parts per billion) 2-30
2-7 Concentrations of Dioxiniand Furan Homologs
in Bottom Ash from Facility B Sampled by Versar
in ng/g (parts per billion) 2-31
2-8 Concentrations of Dioxin Homologs in Combined
Bottom Ash and Fly Ash from Three Facilities
Sampled by Versar in ng/g (parts per billion) 2-32
2-9 Concentrations of Furan Homologs in Combined
Bottom Ash and Fly Ash from the Three Facilities
Sampled by Versar in ng/g (parts per billion) 2-33
2-10 Concentrations of Dioxin and Furan Homologs
in Landfill Composites From the Two Facilities
Sampled by Versar in ng/g (parts per billion) 2-37
6-1 Concentrations of Dioxin Homologs in Field
Leachates from the Three Facilities Sampled by
Versar in ng/l (parts per billion) 6-7
6-2 Concentrations of Furans in Field Leachates from
the Three Facilities Sampled by Versar ng/l (parts per trillion) 6-8
6-3 Concentrations of Dioxin Homologs in Quench Water from
the four Facilities Sampled by Versar in ng/l (parts per trillion) 6-9
6-4 Concentrations of Furan Homologs in Quench Water from
the Four Facilities Sampled by Versar in ng/l (parts per trillion) 6-10
VI
-------
ACRONYMS AND DEFINITIONS
BNA
BOD
CAS
CB
CERCLA
COD
Codisposal
CP
OWE
EP
EPA
ESP
HSWA
HWC
LF
MCL
Monofill
MSW
MW
MWC
MWEP
ND
NPDES
PAHs
PCBs
Base-neutral and Acid Extractables
Biological Oxygen Demand
Chemical Abstract Service
Chlorobiphenyl
Comprehensive Environmental Response, Compensation, and
Liability Act
Chemical Oxygen Demand
Disposal together of municipal solid wastes and municipal solid waste
combustion ashes
Chlorinated Phenols
Deionized Water Extraction Test Method
Extraction Procedure
U.S. Environmental Protection Agency
Electrostatic Precipitator
Hazardous and Solid Waste Amendments
Hazardous Waste Combustion
Landfill
Maximum Contaminant Level
A landfill that contains only solid waste combustion ashes and
residues
Municipal Solid Waste
Monitoring Well
Municipal Waste Combustion
Monofilled Waste Extraction Procedure, also known as SW-924
Not Detected
National Pollutant Discharge Elimination System
Polynuclear Aromatic Hydrocarbons
Polychlorinated Biphenyls
VII
-------
ACRONYMS AND DEFINITIONS
PAGE TWO
PCDDs
PCDFs
POTW
RCRA
RDF
RPD
SS
SW-924
TCLP
TDS
TEF
TNK
TOC
TSCA
Polychlorinated dibenzo-p-dioxins
Polychlorinated dibenzofurans
Publically Owned Treatment Works
Resource Conservation and Recovery Act
Refuse Derived Fuel
Relative Percent Difference
Suspended Solids
Deionized Water Extraction Test Method
Toxic Characteristics Leaching Procedure Test Method
Total Dissolved Solids
Toxic Equivalency Factors
Total Nitrogen Kjeldahl
Total Organic Carbon
Toxic Substances Control Act
VIII
-------
EXECUTIVE SUMMARY
The Hazardous and Solid Waste Amendments (HSWA) to RCRA, which were signed
into law on November 8,1984, require that the EPA address the issue of Subtitle D.
The EPA is to determine whether the existing Subtitle D, nonhazardous, Criteria
(40 CFR Part 257) are adequate to protect human health and the environment from
groundwater contamination and to recommend whether additional authorities are
needed to enforce the Criteria. The agency is to present its conclusions in a report
to Congress by Novembers, 1987. Additionally, the EPA must revise the Criteria by
March 31, 1988, for facilities that may receive hazardous household waste or waste
from small-quantity generators.
Recently, there has been a move toward reduction of waste volume because of a
steady decrease in space available for municipal solid waste disposal. Both
government and the public have been concerned about identifying and
implementing alternatives for reducing waste volume. Incineration of solid waste is
one of the primary alternatives pursued for waste reduction. However, questions
have been raised about the potential environmental effects of this alternative.
Incineration produces ashes, which must be managed. Effective management
includes consideration of produced leachates. Ashes are generally contained within
the disposal site area. Municipal Waste Combustor (MWC) ash, by the nature of its
origin, consists predominantly of silicon oxide (SiO2), i.e., glass. Additional
components within the ash matrix are aluminum oxide; iron oxide; calcium oxide;
magnesium oxide; sodium oxide; potassium oxide; titanium oxide; and sulfate,
chloride and phosphate ions. When disposed in municipal waste landfills
(codisposal landfills) some of these constituents may leach. Certain inorganics
(metals) and organics, including dioxins, are of particular concern.
Because of the metal and organic content of MWC ashes, questions have been
raised about whether tighter control over ash disposal is necessary. Data that
chemically characterize MWC residues can be used to determine whether an
alternative management strategy is needed and, if a strategy is needed, what
structure it should have.
ES-1
-------
To assist the EPA in data collection in support of regulatory decisions,
NUS Corporation and Versar, Incorporated, have conducted several studies that are
herein combined into one report entitled "Characterization of Municipal Waste
Combustor Ashes and Leachates from Municipal Solid Waste Landfills, Monofills,
and Codisposal Sites." The main objective of these projects was to assist EPA in
developing data to evaluate the potential health and environmental effects of
leachate from municipal landfills, codisposal landfills, and monofills.
As part of these projects, NUS conducted a study of the available literature from the
United States, Canada, Japan, and Europe to collect baseline data on municipal
waste landfills, codisposal landfills, and monofills. The baseline data included
ranges of concentrations of organics and inorganics in fly ash, bottom ash, and
combined ash. Next, four municipal waste disposal sites, two codisposal sites, and
four incinerator sites were chosen for field studies.
NUS collected 3 samples of leachate from each of four selected municipal waste
disposal sites (for a total of 12 samples) plus 1 duplicate sample. NUS also collected
3 samples of leachate from each of two selected codisposal sites for a total of
6 samples. In addition, NUS collected 2 samples of fresh ashes that were being
delivered to the codisposal site for disposal. Versar sampled leachate, waste
combustion ashes, and quench water from four incinerators and their companion
monofills. In total, Versar collected 12 composite samples of combined bottom/fly
ash, 5 composite samples of bottom ash (limited to one facility), 20 composite
samples of fly ash, 10 samples of quench water, 9 samples of leachate, and
2 composite samples of disposed ash.
Leachate and quench water samples were analyzed for metals; for organics,
including PCBs, polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated
dibenzo-furans (PCDFs); and for selected conventional parameters, including pH,
specific conductance, chemical oxygen demand, and ammonia-nitrogen, etc.
Ash samples were analyzed for metals and organics, including PCBs, base-neutral
acid extractables (BNAs), PCDDs, and PCDFs. The ashes were subjected to simulated
leachability tests in the laboratory, which included the three most commonly
applied leaching tests- the Extraction Procedure (EP) toxicity test, the Toxicity
Characteristics Leaching Procedure (TCLP) toxicity test, and the Monofilled Waste
ES-2
-------
Extraction Procedure (SW-924) test. The laboratory-produced leachates or extracts
, were then analyzed for inorganic constituents (metals), semi-volatile compounds,
. . andthehomologsof PCDDsand PCDFs.
i
Because of the nature of the sites sampled, the limited number of sites sampled, the
relatively small number of samples collected at each site, and the types of samples
collected, the data obtained from these studies and presented here are not
necessarily representative of all municipal waste combustion facilities or ash fills. In
particular, the monofills evaluated were designed and became operational in the
1970s and early 1980s and are not likely to accurately represent the performance of
the current generation of monofills. Monofills currently being put into operation
generally include more extensive controls and more precise management than
those included in this study.
The four MSW and the two codisposal sites selected for sampling by NUS were sites
that do not accept industrial waste and which became operational only after RCRA
regulations come into effect. Therefore, they represent "best case scenarios" of the
*' waste industry. A limited number of incinerator sites (i.e., four) were sampled and a
limited number of samples were taken at each of these sites. (See Table 1-2 for
i complete sampling information.)
*; -^
In addition, MWC ashes are extremely heterogeneous in nature and collecting
j representative "laboratory scale" ash samples is extremely difficult. For this reason,
ashes collected from the combustors (the Versar study) were grab sampled at
1 predesignated intervals and then composited to a single sample. This compositing
was intended to "smooth out" the great heterogeneity of the ashes. However, in
reality, the variability of obtained results between days, shifts, and units within the
same facility is extremely great. The differences between facilities are even greater.
This indicates that the variability in operating characteristics, facility design, and
feed material composition have a significant effect on the resultant MWC residue
quality. The great variability was observed for metals, organics, PCDDs, and PCDFs.
Of the residue fractions, i.e., fly ash, bottom ash and combined bottom and fly ash,
the fly ash, because of its finer particles, contains higher concentrations of toxic
metals, PCBs, PCDDs, and PCDFs. The bottom ash contains the lowest concentrations
of these constituents and the combined ash levels fall in between the bottom ash
ES-3
-------
and the fly ash. Combining the ash fractions effectively dilutes the total metals
concentrations of the fly ash. Unlike the metals, the semivolatile compounds, i.e.,
naphthalene, phthalates, phenanthrene, seem to concentrate in the bottom ash.
Concentrations of 2,3,7,8-TCDD in fly ash solids ranged from 0.07 to 3.9 ppb, as
indicated in Table ES-1. Concentrations in bottom ash samples ranged from below
detectable limits to 0.01 ppb.
Metal content in leachates was lower than metal content in ashes (see Tables ES-2
and ES-3). The metal content in actual leachate collected from the codisposal sites
and from the monofills was always lower than in test leachates (EP, TCLP, or
SW-924) (see Table ES-3). (Note: The table references values for lead and cadmium
only since these metals were the ones that occasionally exceeded the maximum
allowable limits.) The actual leachates were always below the EP Toxicity Maximum
Allowable Limit. However, one ash sample collected from one of the two codisposal
sites exceeded the EP Toxicity Maximum Allowable Limit of 5 mg/l (parts per million
[ppm]) for lead when subjected to all three test methods, and the second ash sample
exceeded this limit when subjected to the TCLP test method.
None of the leaching procedures extracted base neutral compounds or PCBs. The EP
and SW-924 extracted the higher homologs of PCDDs and PCDFs in very small
quantities. (A homolog refers to the number of chlorine atoms on the organic
structure, but not the position of those atoms; there are eight homologs of PCDD
and eight homologs of PCDF. The higher the homolog the more chlorine atoms on
the structure). The TCLP failed to extract any of the PCDDs or the PCDFs. The
concentrations of PCBs, PCDDs, PCDFs, and semivolatile compounds were negligible
in the actual leachate samples and in the laboratory-prepared leachate samples (see
Table ES-4). Therefore, these compounds appear to be relatively immobile in the
natural environment. Since the leachate samples were not filtered prior to analysis,
the extremely low (parts per trillion) levels of these compounds detected in these
leachates reflect total values, i.e., values in the water and in the suspended solids.
All leachate samples, those collected by Versarand those collected by NUS, were
ES-4
-------
TABLE ES-1
SUMMARY FOR PCDO AND PCDF VALUES IN ASHES
(All units of ashes in ng/g or parts per billion)
Fly Ash, Versar
Combined Fly Ash
and Bottom Ash,
Versar
Bottom Ash, Versar
Landfill Composite,
Versar
Combined Ash, NUS
Total COO
0-12.018(22)*
6.2-350(12)
0.27-40.25 (5)
20.7-28.8(2)
0.55-14.67(2)
Total CDF
5.52-3,187(22)
12.34-480.4(12)
0.16-15.9(5)
14.41-27.31(2)
1.24-6.21 (2)
2,3,7,8-TCDD
0.07-3.9 (22)
0.02-0.78(12)
<0.04-0.01 (5)
0.07-0.15(2)
0(2)
2,3,7,8-TCDF
0.66-26 (2)
0.41-12(12)
0.02-0.3 (5)
0.51-1.3(2)
0.07-0.11(2)
= Number in ( ) indicates number of samples
ES-5
-------
TABLE ES-2
SUMMARY OF METAL CONTENT IN ASHES
(All Units in ppm)
Parameter
Cadmium
Chromium
Copper
Iron
Lead
Manganese
Nickel
Zinc
Arsenic
Selenium
Mercury
No. of Samples
Versar Fly Ash
107-475
48-105
484-2,380
5.960-22,300
2,830-14,400
320-1,410
52-245
3,460-38,800
16-149
2.5-15.6
0.94-35
20
Versar Bottom
Ash
1.1-43
24-105
581-10,700
12,000-115,000
1,380-3,930
430-1,520
17-90
914-12,400
2.2-24.6
2.5
0.12-0.36
5
Versar
Combined Ash
7.8-45
12-332
193-5,900
2,100-95,100
259-13,200
110-3,130
13-556
545-46,000
2.9-22.8
0.25-2.5
0.11-8.7
15
Versar Landfill
Composite
8.7-30
52-85
402-1,190
19,600-60,600
709-1,210
445-572
51-120
2,050-4,740
6.0-14.8
<2.5-<5
0.25-0.57
2
NUS Landfill
Composite
8.6-14.8
28.2-55.2
226-5,100
11,900-18,900
630-3,240
352-508
144-498
1,510-3,750
11.4-19.6
<5
0.1-3.8
2
ES-6
-------
TABLE ES-3
CADMIUM AND LEAD IN EXTRACTS AND LEACHATES
(Units in ppm)
VERSAR
Fly Ash
EPToxicity
TCLP
SW-924Fluid#1
SW-924 Fluid #2
Combined Fly Ash and Bottom Ash
EP Toxicity
TCLP
SW-924 Fluid #1
SW-924 Fluid #2
Bottom Ash
EPToxicity
TCLP
SW-924 Fluid #1
SW-924 Fluid #2
Cd
6.02-18
0.015-17.2
0.005-0.122
0.005-0.033
0.06-0.827
0.025-3.32
0.005
0.005
0.388
0.418
<0.0t
<0.01
Pb
4.72-25.2
0.0025-15.2
0.025-0.128
0.025-0.148
2.09-34
0.655-30.1
0.025-0.063
0.025
34
30.1
<0.05
<0.05
No. of Samples
6
6
3
3
3
3
3
3
1
1
1
1
Actual Leachates Monofills
0.0025-0.044
0.025-2.92
9
NUS
Combined Ash
EPToxicity
TCLP
SW-924 Fluid #1
0.195-0.275
0.155-0.275
<0.02
48.8-3.17
9.58-240
75.4
2
2
1
Actual Leachates Codisposal Sites
0.006-0.011
0.010-0.027
6
ES-7
-------
TABLE ES-4
»
SUMMARY OF PCOD AND PCDF VALUES IN LEACHATES AND EXTRACTS
(All units in ng/l or parts per trillion)
VERSAR STUDY
Quench Water, Versar
Field Leachates, Versar
Groundwater, Versar
TCLP, extract of Fly
Ash, Versar
TCLP, extract of
Bottom Ash, Versar
TCLP, extract of
Bottom /Fly Ash,
Versar
Field Leachates, NUS
TCLP Combined Ashes,
NUS
EP-Toxicity, NUS
SW-924, NUS
Total CDD
0.06-2.550 (9)
0.06-543 (8)
0(4)
0-0.188(4)
0.91(1)
0(3)
0.38-15.9(2)
0(2)
0.033-0.052 (2)
0.035(1)
Total CDF
0.06-4,338(9)
0.1-823(8)
0(4)
0-0.049 (4)
0.054(1)
0(3)
0.14-0.21(2)
0(2)
0-0.012(2)
0(1)
2,3,7,8-TCDD
0.035-17(9)
0.025-1.6(8)
0(4)
0(4)
0(1)
0(3)
0(2)
0(2)
0(2)
0(1)
2,3,7,8-TCDF
0.03-110(9)
0.025-1 1 (8)
0(4)
0(4)
0(1)
0(3)
0(2)
0(2)
0(2)
0(1)
Number in ( ) indicates number of samples
ES-8
-------
turbid and thus contained suspended solids. The suspended solids are probably the
main contributor of these contaminants to the total reported values.
Of the three extraction tests, ashes subjected to the SW-924 were found to have
values that correspond most closely to those of actual leachates collected from
monofills. The TCLP procedure using extracting fluid number one produces extracts
that follow the SW-924 in meeting actual leachate values. The EP toxicity is the
most aggressive in extracting chemical constituents of ashes and produces extracts
most unlike field leachates. The TCLP procedure using extracting fluid number two
seems to counteract such treatment processes as in-stack lime-treatment, which is
used to collect the fine particles and thus prevent them from exiting the stacks. It
requires the acidification with a pH of 2.88 of wastes that exhibit very basic
characteristics. This acidification releases "fixed" metals from the treated ash.
In general, there are no discernible differences between the quality of leachates
from the codisposal sites sampled in this study (which came into operation
following adoption of RCRA requirements and which do not accept industrial
waste) and those leachates from the municipal disposal sites. This indicates that the
neutral (pH 6.98 to 7.82) generated leachates do not promote leaching of metals
from the MWC ashes. On the contrary, they can provide dilution.
The pH in leachates from monofills, as reported in the literature, ranged between
8.04 and 8.3, and in leachates from the monofills sampled by Versar, ranged
between 7.44 and 8.58. The pH in leachates from the two codisposal sites collected,
by NUS ranged from 7.2 to 7.3. The neutral to basic pH conditions in the municipal
solid waste (MSW) facilities, the codisposal sites, and the monofills indicate an
environment in which the solubilities of metals are limited.
Bacterial activities appear to be under way at all the sampled sites. The pH of the
monofill leachates ranged between 7.44 and 8.58. These slightly to moderately
basic waters can sustain bacteria, especially since they contained TOC levels that
indicate sufficient sources of nutrition. Such bacteria can play a vital role in shaping
the water quality of the monofill leachate. The presence of ammonia (although at
very low levels) is evidence of anaerobic bacterial activity.
ES-9
-------
Additional data are needed in several areas. The data base for the general
} characterization and toxic characteristics of codisposal sites and monofills is very
limited. While the data base for metal levels in extracts from ashes is large, data on
the relationship between ashes and leachates in codisposal sites and monofills is
almost absent. In addition, levels of PCDDs and PCDFs in leachates from municipal
waste disposal sites should be determined. A recent Canadian Government
publication claims that PCDDs and PCDFs have been found in raw municipal solid
waste. Further studies in this area are recommended.
t
Levels of PCDDs and PCDFs in leachates from codisposal sites and levels of
semi-volatile compounds in leachates from monofills should be established and
evaluated. It also appears that several systematic studies are necessary to
characterize discharges from the MSW incineration cycle and to expand the existing
data base, in particular, in the area of comparison between simulated and actual
leachate tests.
In summary, in general the data from the EPA-sponsored studies (NUS and Versar)
J ' were consistent with the data in the literature. Key findings of the project are as
I- follows:
r
* Ash data showed dioxins/furans and metals content.
Compared to monofills, leachate from MSW and codisposal facilities
contained somewhat lower concentrations of metals but considerably
! higher concentrations of organic compounds, especially Volatile Organic
Compounds (VOCs).
* Leaching tests did not simulate the environment, and results differed
among tests. Differences in EP, TCLP, and distilled water dearly indicated
« that acid environments enhance leachability. Contrary to earlier studies,
combined ash failed the EP test for lead nearly as often as did fly ash alone.
(A limited number of ash samples from each facility were collected;
additional analyses may be necessary.)
- t
pH from monofills, codisposal facilities, and new MSW landfills did not
differ significantly.
ES-10
-------
It is important to remember that these data are based on samples collected from a
small number of sites. Additional studies may be necessary in the future.
ES-11
-------
1.0 INTRODUCTION
This report, "Characterization of Municipal Waste Combustor Ashes and Leachates
from Municipal Solid Waste Disposal Sites, Monofills, and Codisposal Sites," has
been prepared for the United States Environmental Protection Agency (EPA) in
response to Work Assignment No. 4 under Contract No. 68-01 -7310.
1.1 BACKGROUND
1.1.1 Federal Regulation of Wastes
In 1979, under authority of Sections 1008(a)(3) and 4004(a) of Subtitle D of the
Resource Conservation and Recovery Act (RCRA), EPA promulgated "Criteria" for
determining whether specific Subtitle D (nonhazardous waste) disposal facilities
and practices pose a reasonable probability of adverse effects to human health or to
.. the environment (40CFR Part 257). Major provisions of the Criteria include
| prohibitions concerning adverse effects to endangered species, discharges to
surface water, and discharges to groundwater. Those facilities that violate the
Criteria are considered "open dumps" and are prohibited under RCRA.
* EPA also promulgated guidelines for the development of State Solid Waste
J Management Plans (40 CFR Part 256) in 1979. These guidelines required that states
I seeking EPA Subtitle D grant funds be given the authority to prohibit, close, and
» upgrade open dumps. These grant funds were available from 1977 to 1981; state
participation in this program was voluntary. Except for approval of the state plans
, and disbursement of grant funds, EPA had no direct implementation authority.
Thus, Subtitle D has basically been a state-administered program.
Federal funding of State Subtitle D activities was terminated after 1981. Since then,
the focus of EPA's efforts under RCRA has been on the Subtitle C (hazardous waste)
provisions. As a result, EPA has little current information regarding the status of
state nonhazardous waste programs and the Subtitle D facilities themselves.
1-1
-------
The Hazardous and Solid Waste Amendments (HSWA) to RCRA, signed into law on
1 Novembers, 1984, require EPA to submit a report to Congress by November 8, 1987,
addressing whether the Subtitle D Criteria (40 CFR Part 257) are adequate to protect
human health and the environment from groundwater contamination and
recommending whether additional authorities are needed to enforce the Criteria.
Further, EPA must revise the Criteria by March 31,1988, for facilities that may
receive hazardous household waste or small quantity generator waste. These
revisions are to include groundwater monitoring, location restrictions, and
corrective action, as appropriate.
Within 18 months of the promulgation of the revised Criteria, each state must
develop a permit program or other system of prior approval to ensure that each
facility eligible to receive hazardous household waste or small quantity generator
waste is in compliance with the Criteria. The HSWA envision Subtitle D to continue
to be state implemented. However, if the states fail to enforce the Criteria, EPA
may intervene.
!" 1.1.2 Concern Regarding Leachates
/
f Data available in the literature regarding the chemical composition of leachates
, generated by municipal disposal facilities have raised concerns about the chemical
composition of leachate generated from municipal waste landfills. These concerns
center on the detection of certain toxic inorganics (mainly metals) and organic
constituents in the leachates generated from municipal Subtitle D facilities, and on
the lack of available data for a comprehensive and defensible evaluation of the
effects of these leachates on human health and the environment.
At the same time, there has been a steady decrease in space available for municipal
solid waste (MSW) disposal. Therefore, there is an increased concern by local, state,
and Federal governments, as well as by the public, for identifying and implementing
alternatives for reducing the volume of MSW by means that are compatible with
environmental, economic, and social factors.
1-2
-------
1.1.3 Municipal Waste Incineration
f
Incineration of municipal solid waste to reduce waste volume and to produce
energy is currently being considered as an important alternative. However, there is
concern about the effects of leachates from ash disposal landfills on human health
and the environment. Certain organics and heavy metals are of particular concern.
The potential for increasing MWC emissions to the air and increasing the volume of
4
produced leachates to water resources, has alerted regulators and the public to the
need to assess the actual public health and environmental effects of MWC ashes.
For this purpose, EPA has retained the services of NUS and Versar to assist EPA in
developing data to assess the effects of MWC ashes. Table 1-1 provides a summary
of municipal solid waste incinerator statistics.
1.2 OBJECTIVES
The principal objective of NUS' part of the project was to assist EPA in developing
! ' data to evaluate the potential health and environmental effects of leachate from
<
municipal landfills and codisposal sites. To meet this objective, a number of tasks
l: with more precise objectives were developed. These objectives were
i
To conduct a study of the available literature to present baseline data on
t the chemical characteristics of leachates generated from municipal waste
landfills, codisposal landfills, and monofills.
To conduct a literature study regarding the chemical composition of MWC
ashes.
To provide information from that review on the range of concentrations of
organicsand inorganics in MWC fly ash, bottom ash, and combined ash.
To select four municipal waste disposal sites and sample their leachates
(minimum of three samples per site).
1-3
-------
TABLE 1-1
SUMMARY OF MSW INCINERATOR STATISTICS*
Total facilities operating number
With heat recovery
Total MSW Managed (Ton/Day)
Total Ash Generated (Ton/Day)
a. Ash Disposed
b. Dry-weight Basis
c. Bottom Ash as Disposed
d. Fly Ash as Disposed
e. Com bi ned Ash as Di sposed
Number of Facilities
a. Disposal Method
1. Onsite Landfill
2. Off site Landfill
3. Other/Unknown
b. Type of Landfill
1. Monofill
2. Codisposal
3. Other/Unknown/Not LF
Ash Disposed of:
a. Disposal Method
1. Onsite Landfill
2. Off site Landfill
3. Other/Unknown
b. Type of Landfill
1. Monofiil
2. Codisposal
3. Other/Unknown/Not LF
Total
102
55
33,541
7,547
5,191
2,930
361
4,255
23
73
6
36
41
25
22.78%
77.22%
0.00%
35.50%
17.45%
46.57%
Modular
51
31
5,296
1,943
965
1,630
143
169
12
36
3
16
19
16
3.37%
96.63%
0.00%
25.97%
46.14%
27.89%
Conventional
48
24
26,018
5,374
4,027
1,175
114
4,085
9
36
3
18
21
9
28.61%
71.39%
0.00%
38.30%
5.70%
55.32%
RDF
3
NA
2,227
231
199
125
105
0
2
1
0
2
1
0
50.39%
49.61%
0.00%
50.39%
49.61%
0.00%
Source: Engineering Science
RDF = Refuse Derived Fuel
LF = Landfill
* Note: These statistics were developed independently of those in EPA's recent MWC study;
however, trends in the two studies are generally consistent.
1-4
-------
To select two codisposal sites (MSW disposal sites in which municipal
incinerator ashes are also disposed) and sample their leachates (minimum
of three samples per site).
To sample MWC ashes as they are arriving at the two selected codisposal
sites.
To analyze all collected leachate samples for conventional parameters (i.e.,
ammonia, BOD, COD, etc.) and the compounds on the RCRA Appendix IX
list by qualified, experienced, and competent laboratories.
To subject the collected MWC ashes to the three most commonly applied
leaching tests: the EP toxicity test, the TCLP toxicity test, and the
SW-924test.
To analyze the laboratory-produced leachates (extracts) for inorganic
constituents (metals), semi-volatile compounds, and hornologs of
polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated
dibenzofurans (PCDFs).
To analyze the ashes and the leachates collected from the codisposal
facilities for hornologs of polychlorinated dibenzo-p-dioxins (PCDDs) and
polychlorinated dibenzofurans (PCDFs).
To sample the four incinerators sampled by Versar and to analyze the
samples for conventional parameters including pH, specific conductance,
COD, and ammonia-nitrogen.
To compare analytical chemical results obtained for the collected leachate
samples from the codisposal sites to those obtained for the extracts.
To compare the analytical chemical results obtained from the collected
leachate samples and the extracts to results obtained for leachate collected
from hazardous'waste sites.
1-5
-------
The mai n objectives of the Versar study were
To collect MWC ashes, both separately and combined: fly ash from air
emission control equipment and bottom ash, and combined fly ash and
bottom ash from four different monofilled landfills.
To collect process quench water, leachates, and groundwater from
monofilled landfills containing solid residues.
To analyze ashes, leachates, and quench water for inorganics (metals),
organics, and dioxins.
To subject collected ashes to the EP, TCLP, and the SW-924 extraction
procedures and analyze extracts for metals, organics.and dioxins.
The overall objective of this entire project was to provide data to assess the
potential health and environmental effects which result from MWC ash disposal in
municipal landfills or in monofilled landfills and to assess the availability of
management tools to reduce or minimize such potential effects.
1.3 SCOPE OF WORK/APPROACH
Several tasks were conducted to effectively meet the objectives of this project.
First, a literature review of the environmental effects of municipal waste
disposal sites was conducted. The data from this review were presented in
two NUS reports:
- Characterization of Municipal Landfill Leachates - A Literature Review,
September 1987 (Volume II of this report).
- Addendum to Characterization of Municipal Landfill Leachates - A
Literature Review. September 1987 (Volume III of this report).
1-6
-------
Next, a literature review was conducted of the environmental effects of
municipal waste combustion residues and their leachates. This effort
resulted in the following NUS report:
- Characterization of Municipal Waste Combustion Residues and their
Leachates- A Literature Review, September 1987 (Volume IV of this
report).
Versar then conducted a characterization study of municipal combustor
residues. As part of the study, four incinerators and associated monofills
were sampled for their ashes, quench waters, and leachates. This study is
presented in the following report:
- Characterization of Municipal Waste Combustor Residues, April 1987
(Volume V of this report).
Next, NUS conducted a characterization of leachates from four municipal
waste disposal sites and two codisposal sites This study resulted in the
following NUS report:
- Characterization of Leachates from Municipal Waste Disposal Sites and
Codisposal Sites. September 1987 (Volume VI of this report).
Finally, NUS revisited the incinerators sampled by Versar to sample for pH,
specific conductance, COD, and ammonia-nitrogen, and to obtain
additional facility information. This study resulted in the following NUS
report:
- Addendum to Monofill Report. September 1987 (Volume VII of this
report).
1.4 SUMMARY REPORT
This report is a summary' report and is not intended to repeat data presented in the
other volumes, but rather to discuss findings based on the data presented in detail
in Volumes II through VII.
1-7
-------
This report focuses primarily on issues related to ash characteristics. A large body of
literature has been developed concerning the potential effects of combustion
properties and flue-gas-cleaning devices on both air emissions and residues.
Although some of the findings of this report may relate to such issues, the report is
not intended to address those subjects in depth.
Section 2.0 of this report summarizes the available information regarding the
4
chemical characteristics of all ashes: fly ash, bottom ash, and combined ashes. The
characterization includes available data regarding inorganic constituents (including
metals), organics, polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-
dioxins(PCDDs), and polychlorinated dibenzofurans(PCDFs).
Section 3.0 reports the available information regarding major chemical constituents
(i.e., Total Dissolved Solids (TDS), Total Suspended Solids (TSS), pH, sulfate, chloride,
nitrate, nitrite, phosphate) in municipal landfills, codisposal landfills, and monofills.
Section 4.0 reports the inorganic content (including metals) in leachates from
monofills, codisposal landfills, and municipal landfills and in extracts from the
different ashes. Similarly, Section 5.0 summarizes findings of the organic content
and PCBs in leachates from the three different types of landfills and in extracts. In
Section 6.0, levels of polychlorinated dibenzo-p-dioxins and polychlorinated
dibenzofurans in extracts and in monofill leachates are detailed. Section 7.0
provides a discussion of the results reported in Sections 2.0 through 6.0, and
Section 8.0 lists the cited references.
1.5 DATA LIMITATIONS
Data obtained from the literature (Volumes II through IV) have inherent limitations
that must be considered. These limitations include many unknowns such as
sampling procedures, analytical methodologies, quality assurance and quality
control (QA/QC) procedures employed in the field and in the laboratory,
information regarding the type of wastes disposed of at the facility, etc.
In contrast to these limitations of the data obtained from the literature, the data
obtained from the EPA-sponsored studies (Volume V and Volume VI) are reliable
because these studies adhered to stringent QA/QC protocols, employed the most
1-8
-------
acceptable analytical methodologies, and provided descriptions of the sampled
facilities. Data obtained through these two EPA-sponsored studies are of
acceptable accuracy and precision. For this reason, information obtained from the
literature is reported here, but the main emphasis and the majority of the
conclusions drawn originate from data obtained from these two EPA-sponsored
studies.
The NUS sampling data used in this study originated from only four municipal
facilities and only two codisposal facilities, none of which accepted industrial waste.
All four facilities went into operation after RCRA was promulgated. Three grab
leachate samples were collected from each disposal facility. In addition, from each
codisposal facility, two grab samples of fresh incinerator ash brought in for disposal
were collected. For these reasons, this data are by no means representative of the
solid waste industry in general.
The Versar sampling data used in this report originated from only four incinerators
and associated monofilled landfills. No well purging occurred prior to groundwater
sampling by Versar, except for Facility C At Facility C, the well was purged with five
standing volumes prior to sample collection. According to EPA protocols, well
purging prior to sampling is required so that samples represent the water quality of
the aquifer, not the quality of water standing in the wells. All groundwater samples
were "grab" samples.
Table 1-2 provides a listing of the make-up of the composite samples and the
number of composite samples analyzed at the four facility studied by Versar. MSW
ashes are extremely heterogeneous in nature and collecting representative
"laboratory scale" ash samples is extremely difficult, almost impossible, For this
reason, compositing of samples collected at known time intervals may somewhat
overcome this difficulty.
Combustion facilities sampled are not state-of-the-art facilities. Poor combustion at
these facilities may lead to higher levels of organics in ashes than at new facilities.
In addition, air pollution control devices at these facilities sampled may not capture
as high a level of metals and organics as are captured by air pollution control devices
at newer facilities. The monofills sampled are also not state-of-the-art facilities.
1-9
-------
This doesn't affect data; however, controls at new monofills are likely to be
substantially greater.
None of the liquid samples collected by either NUS or Versar were filtered in the
field or in the laboratory prior to analysis. All leachate samples collected by NUS
and Versar were all turbid indicating the presence of fine particles. In addition,
samples designated for metal analyses were acidified in the field without filtration.
Thus, all chemical analyses reported by NUS and Versar represent total values levels
in the liquid phase and in the fine particles suspended in the liquid.
1.6 ACRONYMS AND DEFINITIONS
To assist readers of this report, a list of commonly used acronyms and definitions of
some specialized terms is included in each volume, except Volume V. This list can be
found following the Table of Contents of each volume.
1-10
-------
TAiLE 1-2
MAKEUP OF COMPOSITE SAMPLES TAKEN BY VERSAR AND
NUMBER OF COMPOSITE SAMPLES ANALYZED AT THE FOUR FACILITIES
futility A
taulilyR
facility C
tatillly (1
Bottom/Fly Aih
grab samples - or*
pei houi
Toul ol 3 composite
samples
None
0 giab samples - one
pei houi
Total ol S composite
samples
grab samples - ana
every 40 minutes loi
6 hours
1 otal of 4 composite
samples
Bottom Ash
None
4 gi ab samples
Total ol S composite
samples
None
None
fly Ash
Bgiab samples -one
per hour
total off composite
samples
4 grab samples
lolalolS composite
samples
grab samples each
of Ihieeli actions
(line, medium.
coaise)
,'
loUlolS composite
samples
91 ab samples one
every 40 minutes lor
(hows
Total ol 5 composite
samples
Quench Water
1 giab sample liom
each unit
total ol 2 samples
1 g< ab sample Irom
each unit
Total ol 1 samples
1 grab sample liom
each unit
lolalol 2 samples
I giab sample
Total ol 3 samples
Leachate
None
1 grab sample from
each location
Tola! ot 3 samples
e 1 grab sample liom
each location
Total ol 3 samples
1 grab sample liom
each location
Total ot 3 samples
Landfill Disposed
Ash
Mone
None
50. 2-loot coie
sections Irom
landfill perimeter
e Total ol J composite
sample
50. 2-foot coie
sections liom
landfill perimeter
e Total oM composite
sample
-------
2.0 CHEMICAL CHARACTERIZATION OF MWC ASHES
The incineration of municipal solid waste (MSW) results in municipal waste
combustor (MWC) ashes: fly ash and bottom ash. In assessing the chemical
characteristics, these ashes are characterized individually, or combined. Disposal is
usually in a combined form. Table 2-1 contains a summary of MSW stream data
statistics, as of 1986 (Engineering Science, 1986). These materials constitute the
"feed" into incinerators and once incinerated, yield MWC ashes.
Data on the chemical characteristics of ashes have been generated by industry
because of two main regulatory requirements: (1) assessment of potential effects
on air quality and (2) assessment of the quality of extracts generated via regulatory
procedures (i.e., EP-toxicity and TCLP) and experimental extraction procedures, (i.e.,
deionized water, column leaching, etc.) and the assessment of the effects these
extracts may have on surface and groundwater resources.
The chemical characteristics of MWC ashes have been determined in terms of
inorganic constituents (including metals) and organics, including polychlorinated
biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated
dibenzofurans (PCDFs).
2.1 INORGANIC CONSTITUENT CONTENT IN MWC ASHES
Table 2-2 lists the ranges of inorganic constituents detected by the different studies,
including the EPA-sponsored Versar study (Volume V of this report), of fly ashes,
bottom ashes, and combined ashes. The data in this table dearly demonstrate that
inorganic constituents are generally more concentrated in the smaller particles of
fly ash than in the larger particles, which generally constitute the bottom ash. The
combined ash content generally falls in between. Exceptions to this trend were
exhibited by copper and iron, which were detected at higher concentrations in
bottom ash than in fly ash. Canadian and German studies also verify this trend.
- *
The "volatilization-condensation" reaction mechanism, may have a significant
effect on the leachability of inorganics from ashes. According to this mechanism
2-1
-------
TABLE 2-1
MATERIALS DISPOSED INTO THE MUNICIPAL WASTE STREAM
(In Millions of Tons and Percent)
Materials
Paper and Paperboard
Glass
Metals
Plastics
Rubber and Leather
Textiles
Wood
Other
Pood Wastes
Yard Wastes
Miscellaneous Inorganic Wastes
TOTAL
1970
Tons
36.5
12.5
13.5
3.0
3.0
2.2
4.0
-
12.7
21.0
1.8
110.3
%
33.1
11.3
12.2
2.7
2.7
2.0
3.6
0.1
11.5
19.0
1.6
100.0
1984
Tons
49.4
12.9
12.8
9.6
3.3
2.8
5.1
0.1
10.8
23.8
2.4
133.0
%
37.1
9.7
9.6
7.2
2.5
2.1
3.8
0.1
8.1
17.9
1.8
100.0
2000
Tons
65.1
12.1
14.3
15.5
3.8
3.5
6.1
0.1
10.8
24.4
3.1
158.8
%
41.0
7.6
9.0
9.8
2.4
2.2
3.8
0.1
6.8
15.3
2.0
100.0
Source: PCR Engineering, 1986
2-2
-------
TABLE 2-2
RANGES OF CONCENTRATIONS OF INORGANIC CONSTITUENTS
IN FLY ASH, COMBINED ASH, AND BOTTOM ASH
FROM MUNICIPAL WASTE INCINERATORS IN ug/g (ppm)
Parameter
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Silver
Aluminum
Antimony
Beryllium
Bismuth
Boron
Bromine
Calcium
Cesium
Cobalt
Copper
Iron
Lithium
Magnesium
Manganese
Molybdenum
Nickel
Fly Ash
15-750
88-9,000
< 5-2,2 10
21-1,900
200-26,600
0.9-35
0.48-15.6
ND-700
5,300-176,000
139-760
ND-<4
36-<100
35-5,654
21-250
13.960-270,000
2,100-12,000
2.3-1,670
187-2,380
900-87,000
7.9-34
2,150-21,000
171-8,500
9.2-700
9.9-1,966
Combined Bottom
and Fly Ash
2.9-50
79-2,700
0.18-100
12-1,500
31-36,600
0.05-17.5
0.10-50
0.05-93.4
5,000-60,000
<120-<260
NO. 1-2.4
.
24-174
4,100-85,000
1.7-91
40-5,900
690-133,500
6.9-37
700-16,000
14-3,130
2.4-290
13-12,910
Bottom Ash
1.3-24.6
47-2,000
1.1-46
13-520
110-5,000
ND-1.9
ND-2.5
ND-38
5,400-53,400
ND-<0.44
ND
85
5,900-69,500
3-62
80-10,700
1,000-133,500
7-19
880-10,100
50-3,100
29
9-226
2-3
-------
TABLE 2-2
RANGES OF CONCENTRATIONS OF INORGANIC CONSTITUENTS
IN FLY ASH, COMBINED ASH, AND BOTTOM ASH
FROM MUNICIPAL WASTE INCINERATORS IN ug/g (ppm)
PAGE TWO
Parameter
Phosphorus
Potassium
Silicon
Sodium
Strontium
Tin
Titanium
Vanadium
Yttrium
Zinc
Gold
Chloride
Country
Fly Ash
2,900-9,300
11,000-65,800
1,783-266,000
9, 780-49,500
98-1,100
300-12,500
< 50-42,000
22-166
2-380
2,800-152,000
0.16-100
1,160-11,200
USA, Canada
Combined Bottom
and Fly Ash
290-5,000
290-12,000
1,100-33,300
12-640
13-380
1,000-28,000
13-150
0.55-8.3
92-46,000
USA
Bottom Ash
3,400-17,800
920-13,133
1,333-188,300
1,800-33,300
81-240
40-800
3,067-11,400
53
200-12,400
USA, Canada
ND - Not detected at the detection limit
Blank - Not reported, not analyzed for
Source: Literature (Volume IV) and Versar Study (Volume V)
2-4
-------
theory, it is suggested that during combustion, metals became deposited on fly ash
particles as metal oxides, hydroxides and/or salts by means of the volatilization-
condensation reaction mechanism. According to this mechanism, which is highly
dependent on combustion conditions, the majority of metals do not occur as cations
on the ash particles but rather as coatings of metal oxides, hydroxides, and
chlorides.
The primary factor that determines whether a metal will occur in the particle matrix
or will be surface deposited is its boiling point. The "volatilization condensation"
mechanism occurs when inorganic constituents such as cadmium and lead volatilize
in the high-temperature combustion zone and then condensate at lower
temperatures onto the surfaces of the less volatile metals that stay in the matrix,
such as manganese, silicon, and aluminum (Cahill and Newland, 1982). The
condensation occurs in the form of the metal oxides, hydroxides, and chlorides,
which later dissolve in the presence of water. Although these metals may be
present in a relatively nonsoluble form in the original waste, in the incinerator they
are oxidized, and in the oxidized form they adhere to the surfaces of the small
fly-ash particles. They are relatively more soluble in aqueous and acid solutions in
this ionic form, particularly if they have oxidized on small particles.
In support of this mechanism, Klein etal. (1975) have classified the elements found
in coal ash into four classes. Despite the major differences between coal ashes and
MWC ashes, general trends can be observed. The four classes discussed by Klein
et al. (1975) are as follows.
Class I Al, Ba, Be, Ca, Co, Fe, K, Mg, Mn, Si, Sr, Ti, - non-volatizing elements
which stay in matrix.
Class II As, Cd, Cu, Ga, Pb, Sb, Zn, Se, - volatizing elements which become
oxides on particle surfaces.
Class III Hg, Cl, and Br, - volatile elements that remain essentially in the gas
phase; and do not condense on ash.
i
Class IV Cr, Cs, Ni, U, V, - unclassified elements exhibiting properties of
either Class I or Class II.
2-5
-------
The Class III elements CI, Hg, F and Br are highly volatile, and are present as gases at
all times during the combustion process. For this reason, mercury levels are very low
in MWC ashes. However, some newer MWC incinerators include pollution-control
equipment designed to condense these elements onto the fly ash.
Class I elements, having boiling points above the oven temperatures, are not
volatilized in the combustion zone. Instead, they form a melt of uniform
composition that becomes the matrix. Class I elements remain in the condensed
state and exhibit minimal surface deposition.
Class II elements are volatilized during combustion and have little opportunity to
become incorporated in the bottom ash. These elements, including cadmium, and
lead, condense or become absorbed onto the fly ash particle surface as the flue gas
cools.
Following are boiling points of some possible inorganic species during combustion,
according to Cahill and Newland (1982).
Species Boiling or Subliming
<1,550°C
Cd, CdO, CdS
Cr(CO)6, CrCI3, Cr2S3
PbCI2, PbO, PbS
Species Boiling or Subliming
>1,550°C
Cr, Cr203
Cu, CuO
Mn, MnO, MnO2
Pb
This topic is further discussed in Section 4.0.
Several studies (for particulars, see Volume IV) describe the fly ash characteristics by
particle size. The data generated by these studies further demonstrate that the
respirable (less than 5 microns in size), smaller particles contain higher levels of
inorganic constituents (including metals).
t
The data given in Table 2-2 indicate that concentrations of several inorganic
constituents regulated under RCRA were as follows: Arsenic values ranged
2-6
-------
between 15 and 750 ug/g (ppm) in fly ash, 2.9 and 50 ug/g (ppm) in combined ash,
and 1.3 and 24.6 ug/g (ppm) in bottom ash; lead values ranged between 200 and
26,600 ug/g (ppm) in fly ash, between 31 and 36,600 ug/g (ppm) in combined ash,
and between 110 and 5,000 ug/g (ppm) in bottom ash; cadmium values ranged
between <5and 2,210 ug/g (ppm) in fly ash; 0.18 and 100 ug/g (ppm) in combined
ash, and 1.1 and 46 ug/g (ppm) in bottom ash; values of chromium ranged between
21 and 1,900 ug/g (ppm) in fly ash, 12 and 1,500 ug/g (ppm) in combined ash, and
13 and 520 ug/g (ppm) in bottom ash. For purposes of evaluating impacts on
groundwater,' the concentrations in leachate are most useful and, hence, various
leaching and leachate studies were performed.
The wide range in concentrations may result from differences in the sampling,
analytical, and QA/QC procedures employed. It also reflects differences in the
incinerated wastes, in the operating conditions of the incinerator, and in the
pollution control equipment employed at the incinerator. Different pollution
equipment types remove different sizes of particles, and as a result, different levels
of inorganics, including metals in the removed ashes. The fabric filter dust
collectors (baghouses), which have a higher efficiency of removing smaller particles,
would thus contain higher levels of inorganics. Similarly, pollution control
technologies employed to remove the respirable (less than 5 microns in size), finer
particles, with the use of additives such as lime, would also result in ashes
containing higher levels of inorganics.
To better define the levels of inorganic constituents (including metals) in ashes, the
individual analyses conducted in the course of the properly designed,
EPA-sponsored, Versar study are worth reviewing here. The entire Versar Report is
presented in Volume V of this report.
Samples of fly ash, bottom ash, and combined bottom and fly ash collected from
four incinerator facilities, as described in detail in Volume V, were analyzed for
Cadmium (Cd), Chromium (Cr), Copper (Cu), Iron (Fe), Lead (Pb), Manganese (Mn),
Nickel (Ni), Zinc (Zn), Arsenic (As), Selenium (Se), and Mercury (Hg). To better
understand the data obtained by the Versar study, Table 2-3 describes the ash
characteristics of their associated monofills and Table 2-4 describes the municipal
waste combustor design. For confidentiality the facilities are designated as A
through D, as are the monofills. Facility A sends the MWC ashes to Monofill A,
2-7
-------
TARLE 2-3
ASH MONOFIU CHARACTERISTICS
facility
A
B
C
O
Year > of
Operation
1982 198 /
1981 1987
1970 198;
Pott 1480
1987
Com butt or
Hetidue
Disposed
60 IPO
130
155
90
Other lypeiotWtite Disposed
lire*, cotnti iKtMM dcbiM. and
noncombostiblei
large ilcmt and construe lion debris
MoiKOmbusttble items
Tires and noncombutlittlei
teachate
Collection
Sytlrm
Non«
None
None
Oiawel (not
lunclioning)
Covet
Daily UMltovei;
1 loot (lay Iwial
-------
TABLE 2-4
MUNICIPAL WASTE COMBUSTOR DESIGN AND
OPERATING CHARACTERISTICS
1 .11 lllly
A
n
c
D
1 at ilily 1 y|N?
HflixMie/elifiljy leinvviy
tiilllimiom lei-il. wdln
wall, lulaiy liln
I nciyy letowciy
tllllllllUOUS ll'l'll WVdlCI
vMall. tid»fliny 91 die
t iinl.imom l.-i-J.
11*1 IJIIIH dliiuj ijlale.
lulaiy k tin
t lU'iCjy lei nwfiy
iiMilinuiius lueil wdlvi
wall if< IIIIIH dlinij «>.
ISH
ISI'
ISI*
VWMIO
Cum^tonliun*
%Kt;iidenlidl
V.tom/lnJuil
SO
no
JO
so
so
so
III I'lf lldlllllllllj
Hcinuve laige iili|eilt
\tfpdule ijla\\. Him aiul
aluminum lui n-« yi If
Ktmove Urge dpplianic^ anil
sliieil lues
Reinnvt lanje items
Hemovu tiit'l anil lai^i*
MuiuoiiibuidUe inaienals
felyile lennus itu-lals ,n
snap puniMliiallysliiiMlanil
bum hiei
IJD
HSP = I Icclroslalic precipitation
Rosed on opeutoi estimate
-------
Facility B sends the ashes to Monofill B, and so forth. The results obtained by Versar
for these metal levels in the ash samples are listed in Table 2-5. The composite
samples collected from the landfill had been subjected to weathering, whereas the
bottom and fly ash samples collected at the incinerators were fresh samples. Thus,
the landfill samples reflect the effects of mixing the different ashes as well as
weathering effects.
Figures 2-1 through 2-3 depict graphically the levels of selected metals found in fly
ash, bottom ash, and combined ash respectively in each of the facilities sampled by
Versar. Each bar in these three graphs represents the concentration of the specific
metal in each individual sample. Each sample consists of a composite of several grab
samples collected at an individual unit at an individual shift as listed in Table 1-2 and
in the notes on the individual figures.
Figure 2-4 depicts graphically the levels of selected metals detected in the landfill
composite samples collected from the two monofills sampled by Versar.
Review of the fly-ash data in Table 2-5 and Figures 2-1 through 2-3 indicated that
the variability between shifts and/or units at any given facility was relatively small
without any dominant trends, except that at Facility B, Unit 4 generally had higher
metal concentrations than Unit 3. The variability between facilities was relatively
large compared to that between shifts and units. In general, Facility B had the
highest metal concentration (for 5 out of the 11 metals), whereas Facility C had the
lowest metal concentration (for 6 out of the 11 metals). The predominant metals
were iron and zinc, which were followed closely by lead, while the least prevalent
metal was selenium.
A review of the metals data for the combined bottom/fly ash and bottom ash
showed that the variability between shifts and units was relatively high, although
no significant trends were observed. The variability between the facilities was very
high, with the standard deviation generally exceeding the average metal
concentrations. Facility B had the highest concentration of metals (the highest or
second highest concentrations for 10 out of 11 metals), whereas Facility A had the
lowest concentration of-metals (the lowest or second lowest concentrations for
9 out of the 11 metals). The predominant metals were iron, zinc, lead, and copper.
2-10
-------
TABLE 2-5
TOTAL METALS DATA FOR SOLID SAMPLES, VERSAR STUDY
Fir ASM
id!
A
A
A
A
A
8
1
1
8
1
C
C
c
c
c
0
0
0
0
0
SMC K
Ity Description
Unit 1. 9/26. AN
Unit 1. 9/26. AH. Quo
Unit 1. 9/26. PH
Unit 2. 9/26. AH
unit 2. 9/26. PH
FACILITY A AVERAGE
STANDARD DEVIATION
Unit 3. 9/28. AH
Unit 3. 9/28. AH. Oup
unit 3. 9/29. PH
Unit 4. 9/28. AN
Unit 4. 9/29, PH
FACILITY 8 AVERAGE
STANOAAO OEVIAriOH
Unit 2. 9/28. PH
:- unit 2. -9/29. PH
unit 2. 9/29. PH. Oup
Unit 2. 9/30. AH
Unit 2. 9/30. PH
FACILITY C AVERAGE
STAMOAftO DEVIATION
Unit 1-2. 10/3. AH
Unit 1-2. 10/3. AH. Oup
unit 1-2. 10/3. PH
Unit 1-2. 10/4. AH
Unit 1-2, 10/4, PH
FACILITY 0 AVERAGE
STAKOAUO DEVIATION
TOTAL NUMBER
NINIHUH
HAJUWH
OVERALL AVERAGE
STANDARD DEVIATION
Cd
g/kg
193
186
215
222
138
190.8
29.6
322
316
251
381
475
349.0
75.3
107
191
157
223
188
173.2
39.1
259
172
286
210
206
226.6
40.6
20
107
475
235
-.85
Cr
g/kg
79
66
67
66
76
70.3
5.6
105
98
74
97
100
94.8
10.8
' 76
54
52
48
49
55.8
10.3
77
67
93
89
90
83.2
9.8
20
48
105
78.2
17.2
Cu
g/kg
2380
2040
1870
1250
1040
1716
499
745
724
586
912
854
765
112
1050
531
556
484
485
62X
216
516
518
597
486
510
525
38
20
484
2380
907
550
Ft
flAg
17400
15000
9730
20200
15900
15646
3444
9900
9350
5960
16200
22300
12742
5812
9030
8200
8450
15700
14400
11356
3511
3320
7190
8790
8960
9170
8486
706
20
5960
22300
12058
4611
Pb
g/kg
5550
5400
5660
5480
6090
5636
243
7350
7270
5280
9230
14400
3706
3109
3260
3490
3130
3420
2830
3226
234
5450
4600
5770
4740
4430
4998
519
20
2830
14400
5642
2534
Hn
»Ag
1010
1020
1060
807
1090
997
99
895
399
824
1310
1070
998
176
320
388
382
341
353
357
25
857
751
1250
1410
1190
1092
248
20
320
1410
861
335
N1
8/kg
106
91
98
97
160
110
25
80
76
52
67
68
69
10
130
102
95
245
212
157
61
53
55
86
89
86
76
14
20
52
245
103
49
2n
g/kg
15700
14SOO
15100
17400
9480
14436
2660
32700
31800
23600
34000
38800
32130
4923
10200
10300
8460
10600
9940
9900
750
221CO
18600
23900
17600
17300
19900
2630
20
3460
38800
19104
3901
As
Q/kg
41.9
38.0
48.8
36.8
16.0
36.3
11.0
106
89.9
79.0
131
149
111.0
25.3
29.0
16.2
17.7
26.8
32.2
24.4
6.3
50.7
54.5
60.4
47.2
43.2
51.2
5.9
20
16
149
55.7
36.4
S«
g/kg
<5
<5
<5
-5
<5
2.5
0
< 10
4 ! Q
10.0
11.7
15.6
9.5
4.1
4.9
7.6
6.2
7.8
8.8
7.0
1.3
9.S
9.1
15.5
10.7
9.6
10.9
2.4
20
2.5
IS. 6
7.5
4.0
Hg
g/kg
27
23
35
25
24
26.8
4.3
9.3
6.0
12
19
21
13.9
5.2
1.3
5
4.0
3.5
1.4
3.0
1.5
1.8
2.0
1.4
0.94
1.0
1.4
0.4
20
0.94
35
U.3
10 7
2-11
-------
TABLE 2-5
TOTAL METALS DATA FOR SOLID SAMPLES, VERSAR STUDY
PAGE TWO
COHBIMD BOTTOM MO FLY ASH
Facility
SMPlt
Otscriotiofl
A unit 1. 9/25. AH
A unit 1. 9/26. H»
A unit 2. 9/26. AN
A unit 2. 9/26. AH. Oup
A unit 2. 9/26. f*
FACILITY A AVERAGE
STANDARD DEVIATION
C unit 2. 9/28, PM
C unit 2. 9/29, PN
C Unit 2. 9/30. AN
C Unit 2. 9/30. AH. Oup
C unit 2. 9/30. PH
FACUITY C AVERAGE
STANDARD DEVIATION
9 I/nit 1-2. 10/3. AH
0 unit 1-2. 10/3, PN
0 unit 1-2. 10/4. AH
0 unit 1-2. 10/4, AM. Oup
0 Jnit 1-2. 10/4, PH
FACILITY 0 AVERAGE
STANDARD DEVIATION
TOTAL NUH8ER
MINIMUM
MAXIMUM
OVERALL AVERAGE
STANDARD DEVIATION
Cd
j/"g
17
13
17
IS
37
19.3
8.7
7.3
10
24
27
20
17.8
7.6
45
18
17
18
23
24.2
10.6
IS
7.8
45
20. S
9.5
Cr
*/kfl
25
19
12
16
12
16.8
4.9
22
332
19 .
26
37
87.2
122.6
33
28
31
36
43
35.2
5.3
IS
12
332
46.4
76.9
Cu
*/*«
452
317
369
377
193
3S6
86
329
5900
3420
608
5900
3231
2432
424
1060
289
728
524
60S
269
15
193
5900
1397
1921
F<
/kg
5130
6500
6650
9140
2100
5904
2300
5220
22300
5040
9720
16000
11656
6650
24500
8000
8590
95100
19000
31038
32638
15
2100
95100
16199
22073
Pfc
*A9
633
585
2200
1140
1670
1246
619
259
6950
1700
1060
13200
4634
4884
3410
319
571
'612
688
1220
1098
IS
259
13200
2366
3324
Nn
9/kfl
281
331
184
2S1
188
247
56
110
339
155
1810
254
534
643
462
797
3130
640
544
u:s
1014
15
110
3130
632
7S2
m
jAfl
21
30
22
24
13
22.0
5.5
44
556
42
38
93
154.5
201.7
37
25
26
119
32
57.8
37.0
15
13
556
78.1
131.0
2n
9A,
1810
1480
1730
3050
1980
2010
544
545
1520
1570
3250
2980
1973
1005
2950
1920
2400
46000
2390
11132
17437
IS
545
46000
5038
10971
AS
9/kfl
6.1
2.9
7.9
12.2
4.7
6.8
3.2
4
4.7
S.7
7
22.3
3.3
7.1
16.4
4.3
5.4
6.1
6.4
7.7
4.4
15
2.9
22.8
7.77
5.21
$
*A«
"0.5
«2.S
«5
«S
«o.s
1.4
1.9
1.4
<5.
<4.
-------
TABLE 2-5
TOTAL METALS DATA FOR SOLID SAMPLES, VERSAR STUDY
PAGE THREE
BOTTOM ASH
SMI It
Kility OMCHptlon
I unit : 9/28. AM
3 Unit 3. 9/29. «
9 unit 4. 9/28. AH
8 Unit 4. 9/28. AM. OuO
1 unit 4. 9/29. m
HO.
Avg.
Sw. Otv.
Cd
Cu
Ft
2.3
1.1
3.8
3.5
43
5
1.1
43
10.74
16.16
R< Zh As St
og/kg «g/kg «g/kg ag/kg
105 10700 12000 2920
24 7250 27100 1380
46 792 115000 2140
78 581 24100 3930
33 1720 17SOO 3630
5555
24 S81 12000 1380
105 10700 115000 3930
61.20 4209 39140 2800
29.67 4060 38290 942
1520
430
1010
938
538
5
430
1520
887
387
35
17
34
90
29
5
17
90
41.4
25.2
1930
914
2350
5760
12400
5
914
12400
4671
4194
3.
2..
S.
5,
24.
2.
24.
9.2C
8.M
I <5.
<5.
<5.
-5.
«5.
5
2.5
2.5
) 2.50
! 0.00
0.36
0.13
0.12
0.12
0.13
S
0.12
0.36
0.17
0.09
Description
Ptriwttr Coaootui
^criotter Conoositt
LANOflU OMPOSITE
Cd Cr Cu Ft .Ptt
ng/kg nj/kg Bj/kg mg/kg
Hn
N1 In As Se *q
ng/kg ng/kg irg/kg mg/kg mg/kg
8.7 85 1190 60600 709
30 52 402 19600 1210
572
455
120 4740
51 2050
6.fl <5 0.57
14.8 «2.S 0.25
2-13
-------
ricuM t-i
FLY ASH
My A)
Co.c~tr.tl.., tf MUll I* H» Jlh *-»«* * »
i raciiuitt n. . e. »« i» «»/»t («»
MHAIS
J
J
^"
tf
FLY ASH
citily B)
MC1ALS
i
a
»J
f,
l«00
FLY ASH
(FaciMy 0)
MtlAlS
»U: Uck tar
»f
IMIvlAul t*^»t« c*ll*l*
t«rl** UkM tfvrlMf ttal shift. *ic*ft f»r ncllllr Mich IM wty 4 u^lrt (Ukl* l-?|.
»f fr»fc
-------
FIBRE 2-2
Concentrations of fetals In Bottoi Ash f
Facility B In eg/kg (DDK)
4000 l
3000-
Q.
Q.
.2000-
1000-
Cd
BOTTOM ASH
(Facility B)
Mote: Each bar represents an Individual san?le collected fna an Individual unit during
an Individual shift. Each saiple consists of a co^Msite of four grab saaples taken
during that shift (Table 1-2).
2-15
-------
«.oitccni.r«ii""» ** ,*.*.- -
Sailed at Versar at Faculties A. C0 and D In *g/kg (pp>)
2300
MOO
I 1300
a
COMBINED BOTTOM ASH & FLY ASH
(Facility A)
300
Pb
METALS
4000
COMBINED BOTTOM ASH & FLY ASH
(Facility 0)
3000
tx
a
1000
C«
»>b
METALS
15000
COMBINED BOTTOM ASH & FLY ASH
(Facility C)
a.
a.
tp
ji
.10OOO
5000
ID
I
fM
ca
METALS
Mote: Each bar represents an Individual sample
collected froai an Individual wilt during an
Individual shift. Each sanle consists of a
composite of 8 grab saa^tes taken during the shift.
(fable 1-2)
-------
FIGURE 2-4
Concentrations of Metals in One Landfill Coaposite Saaple Collected by Versar
at Facility C and Facility 0 In ing/kg (parts per Million)
aoo
600
Q.
a
.400-
o<
JOO-
1500
-^ 1000
Q.
a
500-
Cd
LANDFILL COMPOSITE
(Facility C)
Cr
MCTALS
LANDFILt COMPOSITE
(Facility 0)
Cr
2-17
-------
Selenium was again the least prevalent. Selenium, a relatively volatile element, may
exhibit behavior which fits the Klein etal. (1975) Class III classification.
The landfill perimeter composite metals data, Figure 2-4, was similar to combined
bottom ash/fly ash data from the same facilities. Although there were some
exceptions, the landfill composite samples generally contained lower
concentrations of each metal than did their corresponding bottom/fly ash samples.
Again, this was expected because the landfill composite samples had been subjected
to weathering, which would leach some of the component metals. It is interesting
to note that although the metal concentrations were typically lower in the
weathered ash than in freshly generated ash, except for the lead concentration in
Facility C, considerable concentrations of metals remain in the weathered ash. This
fact suggests that a major portion of the metals in the ash may not be readily
mobile in the environment.
A comparison of the concentrations of metals in the fly ash to those in the combined
bottom/fly and bottom ash, indicates the following:
The variability between shifts, units, and facilities was substantially higher
for the combined and bottom ash than it was for the fly ash. In fact, the
variability between shifts and units for the bottom/fly and bottom ash was
greater than the variability between facilities for the fly ash. This
observation was expected because of the heterogeneous nature of the
bottom/fly and bottom ash based on the diverse range of particle sizes
compared to the more homogeneous nature of the fly ash. This
heterogeneity made it extremely difficult to collect representative,
comparable samples, as evidenced by the standard deviations.
The concentrations of cadmium, mercury, chromium, lead, nickel, zinc,
selenium, and arsenic were between 1.5 and 10 times higher in the fly ash
than in the bottom/fly or bottom ash.
The concentrations of copper and iron were approximately two times
higher in the bottom/fly and bottom ash than they were in the fly ash.
2-18
-------
The concentration of manganese was approximately equivalent for both
ash fractions.
The metal distribution in bottom ash or fly ash generally fit the Klein (1975)
metal classification, as described in Section 2.1.
2.2 ORGANIC COMPOUNDS FOUND IN MWC ASHES
Table 2-6 lists the ranges of organic compounds detected in MWC ashes as reported
by the different studies reported in the literature, including the EPA-sponsored
Versar study, (see Volume IV) The data presented in this table clearly demonstrate
the absence of one fraction of organic chemical compounds that are extremely
prevalent in hazardous wastes sites, namely, volatile compounds. Volatiles are not
expected to be present in materials that were combusted in incinerators at
temperatures much higher than the boiling points of these compounds. This point
is being raised because several recent studies (Plumb and Fitzsimmons, 1984; Plumb,
June 1985; Plumb, November 1985; and Plumb and Parolini, 1986) conducted on
hazardous waste sites recommend using volatile compounds as indicator
.
parameters for assessing leachate "problems" at hazardous waste sites. Such
indicators would not be appropriate for ash disposal sites.
Examination of the data provided in Table 2-6 indicates that polyaromatic
hydrocarbons (PAHs), phthalates, chlorobenzenes, and chlorophenols are the most
prevalent types of compounds found in MWC ashes. Like the inorganics in ashes,
the ranges of organics vary widely, covering several orders of magnitude.
Variations in combustion quality are likely to contribute to this variability, along
with several of the factors described in Section 2.1.
The organic compounds, except for PCBs, PCDDs, and PCDFs, were detected more
frequently in the larger particles of the bottom ash. A proper example is the
behavior of the phthalates. Based on the limited data reported in Table 2-6, the
phthalates seem to be concentrating in the bottom ash rather than the fly ash. For
example, butylbenzyl-phthalate was not detected (NO) in fly ash while present at
180 ng/g (ppb) in bottom ash; similarly di-n-butyl phthalate was not detected in fly
ash, while present at 360 ng/g (ppb) in bottom ash; bis(2-ethylhexyl) phthalate was
present in fly ash at 85 ng/g (ppb) while in bottom ash it was detected at
2-19
-------
TABLE 2-6
RANGES OF CONCENTRATIONS OF ORGANICS IN FLY
FROM MUNICIPAL WASTE INCINERATORS in
AND BOTTOM ASH
ng/g (ppb)
Constituent
Naphtnalene
Biphenyi
Acenaphthylene
Anthracene
Fluorene
Phenanthrene
Oi-n-butyl phthalate
Fluoranthene
Pyrene
Butyl benzyl phthalate
Chrysene
Bis(2-ethylhexyl)phthalate
Benzanthrene
Benzo(k)fluoranthene
Benzo(a)pyrene
Benzo(g,h,i)perylene
Oiethyl phthalate
Acenaphthene
Normal alkanes
Chlorobenzenes
Chlorophenols
Country
Range, Fly Ash
270-9,300
2-1,300
ND-3,500
1-500
0-100
21-7,600
NO
0-6,500
0-5,400
NO
0-690
85
0-300
ND-470
N 0-400
0-190
6,300
50,000
80-4,220
50.1-9,630
USA, Canada, Japan
and The Netherlands
Range, Bottom Ash
570-580
37-390
53
ND-150
500-540
360
110-230
1 50-220
130
ND-37
2,100
ND-51
NO-5
NO
28
17
0
USA and Canada
ND s Below detection limit
Blank = Not reported
Source: Literature (Volume IV) and Versar Study (Volume V)
2-20
-------
2,100 ng/g (ppb). However, diethyl phthalate was not detected in bottom ash but
was detected at 6,300 ng/g (ppb) in fly ash. It is possible that organics are left in the
bottom ash rather than in the fly ash. The fly ash is exposed to higher temperatures
m the incinerator, where these compounds are being pyrolized.
2.3 RANGES OF PCDDs, PCDFs, AND PC3s IN MWC ASHES
Ranges of PCDDs, PCDFs and PCBs in fly ash, bottom ash, and combined ash are
listed in Table 2-7. The data presented in this table clearly indicate that many
homologs of PCDDs and PCDFs as well as PCBs are found in MWC ashes. The levels
are higher in the smaller fly-ash particles than in the larger bottom-ash particles.
The levels in combined ashes fall in between. The higher concentrations in fly ash
may result because the smaller particles have larger surface area relative to the total
weight. These data may also imply that these compounds have a higher affinity for
smaller particles than for larger particles. Smaller particles offer greater surface
area for sorption, and the lower mass increases the concentration.
Table 2-8 lists levels of PCDDs and PCDFs in the different ash samples collected by
Versar (Volume V). Figures 2-5 through 2-9 depict graphically the levels of the total
PCDD and PCDF homologs in fly ash, bottom ash, and combined ash in each sampled
facility. Each bar represents the concentration of each homolog in each sample.
Each sample consists of a composite of several grab samples collected at an
individual unit at an individual shift. The number of samples in each composite
sample is given in Table 1-2 and in the notes given on each figure.
A review of the PCDD homolog concentrations in the fly ash (Figure 2-5) showed
that the variability of the homoiog concentrations between units and shift was
relatively small, and the variability of these concentrations between the facilities
was extremely large. Facility C had the highest concentration of total PCDDs, as well
as the highest concentration of each PCDD homoiog. Facility B had the second
highest concentration of each PCDD homolog, followed by Facility D and Facility A
which had the lowest concentration of each PCDD homolog. The hexa-CDD
homolog was the most prevalent at three of the four facilities (it was the third most
prevalent at Facility B), and the tetra-CDD homolog was the least prevalent at all
four facilities. Approximately 5 percent of the total tetra-CDDs was made up of the
2,3,7,8-TCDD isomer.
2-21
-------
TABLE 2-7
RANGES OF CONCENTRATIONS OF PCDDs. PCDFs, AND PCBs
IN FLY ASH FROM MUNICIPAL WASTE INCINERATORS in ng/g (ppb)
Constituent
MCDD
DCOO
T3CDO
T4CDD
PCDD
HCDO
H7CDO
OCDO
2,3,7,8-TCDD
Total PCDO
MCDF
DCDF
T3CDF
T4CDF
PCDF
HCDF
H7CDF
OCDF
2,3,7,8-TCDF
Total PCDF
Mono CB
OiCB
TnCB
Tetra CB
Penta CB
Hexa CB
-tepta CB
OctaCB
Nona CB
Oeca CB
Total PCS
Country
Range Fly Ash
2.0
0.4-200
1.1-82
ND-250
ND-722
ND-5,565
ND-3.030
ND-3,152
0.1-42
5.23-10.883
41
NO-90
0.7-550
NO-410
NO- 1,800
Tr-2,353
Tr-666
N 0-362
0.1-5.4
3.73-3,187
0.29-9.5
0.13-9.9
NO-25
0.5-42
0.87-225
0.45-65
NO-0.1
ND-1.2
NO
NO
ND-250
USA, Canada, West Germany
The Netherlands, Jaoan
Range Combined Ash
0.14-14
1.9-50
1 4-78
1 4-120
0.84-89
0.02-0.78
6.2-350
2.3-91
1.6-37
1.2-35
0.62-36
0.18-8.4
0.41-12
6.14-153.9
NO
0.126-1.35
0.35-14.3
16.5-16.5
ND
ND-32.15
USA
Range Bottom Ash
NO
ND
ND
< 0.04-0.65
ND-3
ND-2.3
ND-6.3
NO-29
< 0.04-0. 7
NO-110
1.1
0.63
ND
0.15-1.4
0.07-6.2
ND-2.5
ND-6.9
ND-3.7
ND.10
ND-65
NO-1.3
ND-5.5
NO-80
ND-47
ND-48
ND-39
ND
ND
ND
ND
ND-180
USA, Canada, Japan
NO s Below Detection Limit Blank a Not reported
Tr = 0.0 1
-------
TABLE 2-8
PCDO AND PCDF IN SOLJD SAMPLES - VERSAR STUDY
FLY ASH (DIOXIN HOMOLOGS)
Pltnt
A
A
A
A
A
a
3
a
a
a
c
c
c
c
c
c
c
0
0
0
0
0
Saaplt
Description
Unit 1. 9/26, AN
Unit 1, 9/26, AH, Oup
Unit 1, 9/26, PM
Unit 2. 9/26, AM
Unit 2. 9/26. PM
FACILITY A AVERAGE
STANDARD DEVIATION
Unit 3, 9/28. AM
Unit 3, 9/28. AM, Oup
Unit 3. 9/29. PM
Unit 4. 9/28. AM
Unit 4, 9/29, PM
FACILITY 8 AVERAGE
STANDARD DEVIATION
Unit 2. 9/28. PH
Unit 2. 9/29. PM
Unit 2. 9/29. PM. Oup
Unit 2. 9/30, AM
Unit 2. 9/30, PM
Unit 2, Coarse
Unit 2. Pint (ESP)
FACILTIY C AVERAGE
STANDARD DEVIATION
Unit 1-2. 10/3, AM
Unit 1-2, 10/3, AN, Oup
Unit 1-2. 10/3, PM
Unit 1-2. 10/4. AM
Unit 1-2, 10/4, PM
FACILITY 0 AVERAGE
STANDARD DEVIATION
TOTAL NUMBER
MINIMUM
MAXIMUM
OVERALL AVERAGE
STANDARD DEVIATION
2.3,7.8
TOO
("9/3)
0.093
0.11
0.13
0.24
0.22
0.16
0.06
0.38
0.38
0.63
0.24
0.13
0.35
0.17
2.2
1.5
2.1
2.4
1.5
<0.14
3.9
1.95
1.07
0.38
0.45
0.83
0.66
0.37
0.54
0.18
22
0.07
3.9
0.86
0.98
TETRA
-COO
("9/9)
2.3
2.3
4.7
5.2
6.6
4.32
1.58
12
11
18
6.5
7.0
10.90
4.15
27
31
33
43
18
<0.14
38
27.2
13.3
5.2
5.1
19
11
7.9
9.64
5.15
22
0.07
43
14.3
12.2
PENTA
-COO
(ng/9)
11
14
20
16
32
18.60
7.31
139
114
137
84
99
114.60
21.34
238
710
722
513
335
«0.02
980
500
309
54
46
91
61
45
59.4
16.8
22
0.01
980
203
270
HEXA
-COO
(ng/g)
20
20
35
18
24
23.40
6.12
126
123
322
207
209
197
73
697
5565
3946
1430
1052
<0.03
3400
2299
1880
105
103
106
89
49
90.4
21.6
22
0.015
5565
802
1475
HEFTA
-COO
(ng/g)
14
14
26
14
14
16.40
4.80
100
93
203
352
435
237
136
331
1759
3030
1751
1089
<0.06
4900
1837
1559
45
48
81
39
37
50.0
16.0
22
0.03
4900
653
1199
OCTA
-COO
(ng/g)
17
18
31
13
11
18.00
6.99
96
89
210
586
1363
469
482
393
2460
3152
2338
1433
<0.16
2700
1782
1116
44
48
113
35
37
55.4
29.2
22
0.08
3152
690
1017
TOTAL
-COO
(ng/g)
64.3
68.3
116.7
66.2
87.6
80.7
19.3
473
430
390
1235.5
2113
1028
617
1686
10525
10883
6075
3927
0
12018
6445
4441
253.2
250.1
410
235
175.9
265
77.7
22
0
12018
2363
3775
2-23
-------
TABLE 2-8
PCDD AND PCDF IN SOLID SAMPLES - VERSAR STUDY
PAGE TWO
'See
FLY ASH (FURAN HOMOLOGS)
Plant
A
A
A
A
A
8
B
B
8
a
C
C
C
C
C
'c
C
0
SMplt
Otscrlptlon
Unit 1. 9/26, AM
Unit 1, 9/26. AM. Oup
Unit 1. 9/26, PM
Unit 2. 9/26, AM
Unit 2. 9/26, PM
FACILITY A AVERAGE
STANDARD DEVIATION
Unit 3, 9/28. AM
Unit 3. 9/28. AM. Oup
Unit 3. 9/29. PM
Unit 4, 9/28. AM
Unit 4, 9/29, PM
FACILITY 8 AVERAGE
STANDARD DEVIATION
Unit 2. 9/28, PN
Unit 2. 9/29. PN
Unit 2. 9/29. PN. Oup
Unit 2. 9/30. AM
Unit 2. 9/30, PN
Unit 2. CMTM*
Unit 2. Pint (ESP)*
FACILITY C AVERAGE
STANDARD DEVIATION
Unit 1-2. 10/3. AM
2.3.7.8
Tcor
(ng/g)
0.66
26
13
13
0 Unit 1-2. 10/3. AM, Oup
0
0
0
text
Unit 1-2. 10/3. PM
Unit 1-2, 10/4, AM
Unit 1-2. 10/4. PM
FACILITY 0 AVERAGE
STANDARD DEVIATION . - ,
TOTAL NUMBER
MINIMUM
MAXIMUM
OVERALL AVERAGE
STANDARD DEVIATION
2
0.66
26
13.33
12.67
TETRA
-CDF
(ng/g)
20
23
34
52
89
43.6
25.3
91
97
107
48
59
80.4
22.8
61
164
169
130
73
3.8
110
102
55
36
36
93
70
53
57.6
21.7
22
3.8
169
73.6
43.2
PENTA
-cor
(ng/g)
7.1
10
15
16
32
16.0
8.6
64
65
61
37
46
54.6
11.1
56
221
226
153
93
1.5
310
152
100
32
27
47
32
27
33.0
7.3
22
1.5
310
71.8
80.0
2-24
HEXA
-CDF
(ng/g)
17
14
23
96
18
33.6
31.3
56
61
241
41
54
90.6.
75.5
54
336
2353
473
638
0.22
590
635
738
115
21
37
87
37
69.4
34.9
22
0.22
2353
246
496
HEPTA
-CDF
(ng/g)
14
12
22
44
9.9
20.4
12.5
40
40
19
49
63
42.2
14.3
10
32
77
666
610
«0.03
570
281
292
80
3.8
75
50
29
47.6
28.5
22
0.015
666
114
201
OCTA
-CDF
(ng/g)
2.1
2.3
4.0
1.4
2.0
2.4
0.9
8.1
8.3
21
11
34
16.5
9.9
24
60
362
108
175
«0.1S
170
128
114
4.9
5.6
9.3
3.1
3.7
5.4
2.4
22
0.075
362
46
86
TOTAL
-CDF
(ng/g)
60.2
61.3
98
209.4
150.9
116.0
57.2
259.1
271.3
449
186
256
284
87.6
205
813
3137
1530
1589
5.52
1750
1297
1001
267.9
93.4
311.3
242.1
149.7
213
79.9
22
5.52
3187
552
76S
TCDO *
TCDF
(ng/g)
124.5
130.1
214.7
275.6
238.5
196.7
59.9
732.1
701.3
1339
1421.5
2369
1313
606
1891
11338
14070
7605'
5516
5.52
13768
7742
5187
521.1
343.5
721.3
477.1
325.6
478
143
22
5.52
14070
2915
4436
-------
TABLE 2-8
PCDD AND PCDF IN SOUD SAMPLES - VERSAR STUDY
PAGE THREE
COMBINED BOTTOM ASH AND FLY ASH (DIOXIN HOMOLOGS)
2.3.7,8 TETRA PEMTA HEM HCTTA OCTA TOTAL
Soplt TCOO -COD -COO -COO -COO -COO -COO
PUnt Otserlptlon (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g)
A Unit 1. 9/26. AN 0.02 1.5 2.7 1.9 1.7 0.89 8.69
A Unit 1. 9/26. PN
A Unit 2. 9/26. AN
A Unit 2. 9/26. m
FACILITY A AVERAGE
STANDARD DEVIATION
C Unit 2. 9/28. PH
C Unit 2. 9/29. PN
C Unit 2. 9/30. AN
C Unit 2. 9/30. AN. Oup
C Unit 2. 9/30. PN
FACILITY C AVERAGE
STANDARD DEVIATION
0 Unit 1-2. 10/3. AN
0 Unit 1-2. 10/3. PN
0 Unit 1-2, 10/4, AN
0 Unit 1-2. 10/4, PN
FACILITY 0 AVERAGE
STANDARD DEVIATION
TOTAL NUMBER
MINIMUM
NAXINUN
OVERALL AVERAGE
STANDARD DEVIATION
0.07
0.33
0.14
0.14
0.12
0.13
O.S2
0.78
<0.31
0.36
0.28
0.07
<0.08
«fl.2S
0.04
0.07
0.04
12
0.02
0.78
0.21
0.24
2.2
13
$.57
5.26
2.2
2
14
13
1.3
6.50
S.73
1.3
0.46
«0.28
1.1
0.75
0.47
12
0.14
14
4. 35
5.23
3.2
19
8.30
7.57
11
11
47
50
10
25.8
18.6
4
2.3
1.9
2.6
2.70
0.79
12
1.9
50
13.7
16.3
2
11
4.97
4.27
13
18
67
78
11
37.4
29.0
3.4
1.4
1.5
1.8
2.03
0.81
12
1.4
78
17.5
25.3
1.5
8.2
3.80
3.11
15
31
120
120
22
61.6
48.0
3.3
1.4
1.5
1.6
1.95
0.78
12
1.4
120
27.3
42.5
0.84
3.7
1.81
1.34
7.7
18
89
89
18
44.3
36.7
2.6
1.4
1.3
1.2
1.63
0.57
12
0.84
89
19.5
31.7
9.74
54.9
24.44
21.54
48.9
80
337
350
S2.3
176
137
14.6
6.96
6.2
8.3
9.02
3.31
12
6.2
350
82.3
119
2-25
-------
TABLE 2-8
PCDD AND PCDF IN SOLID SAMPLES - VERSAR STUDY
PAGE FOUR
COMBINED BOTTOM ASH AND FLY ASH (FURAN HOMOLOGS)
2.3,7.8 TETRA PEMTA HCXA HEFTA OCTA TOTAL TCDO »
TCDF -CDF -CTF -CDf -Of -Of -CDF TCDF
Hint Owcrlptlon ((19/9) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g)
A Unit 1. 9/26. AN 0.38 6.3 2.S 1.3 0.62 0.18 10.9 19.59
A Unit 1. 9/29, PN
A Unit 2. 9/26. AN
A Unit 2. 9/26. m
FACILITY A AVERAfiE
STANDARD DEVIATION
C Unit 2. 9/28. «t
C Unit 2. 9/29. PN
C Unit 2. 9/30. AN
C Unit 2. 9/30. AN. Duo
C Unit 2, 9/30. m
FACILITY C AVERAGE
STANDARD DEVIATION
0 Unit 1-2. 10/3. AN
0 Unit 1-2. 10/3. PN
0 Unit 1-2. 10/4, AH
0 Unit 1.2. 10/4. PN
FACILITY 0 AVERACE
STANOARO DEVIATION
TOTAL NUNBEK
NIWMUN
NM1HUN
OVERALL AVERACE
STANOARO DEVIATION
2.4
12
5.09
4.92
0.8
0.89
2.9
3.8
O.SS
1.79
1.31
0.76
0.44
0.41
0.62
0.56
0.14
12
0.41
12
2.20
3.14
20
91
39.10
37.12
5
4.7
20
24
3.4
11.42
8. 75
5.1
3.1
2.3
3.4
3.48
1.02
12
2.3
91
15.69
23.90
6.7
37
15.40
15.37
S.2
5.5
20
27
4.8
12.50
9.23
4.7
2
1.6
2.2
2.63
1.22
12
1.6
37
9.93
11.10
3.2
18
7.50
7.47
6.4
11
24
3S
6.3
16.54
11.27
4.1
1.3
1.2
1.8
2.10
1.18
12
1.2
35
9.47
10.3S
1.2
6.6
2.81
2.69
4.8
8
27
36
8.2
16.80
12.39
2.6
0.81
0.83
1.1
1.34
0.74
12
0.62
36
8.1S
10.95
0.28
1.3
0.59
0.51
1.4
1.8
6.7
8.4
2.1
4.08
2.89
0.59
0.27
0.21
0.23
0.33
0.15
12
0.18
8.4
1.96
2.61
31.38
153.9
65.4
63.1
22.8
31
97.7
130.4
24.8
61.34
44.34
17.09
7.48
6.14
8.73
9.86
4.27
12
6.14
153.9
45.2
49.5
41.12
208.8
89.8
84.6
71.7
111
434.7
480.4
87.1
237
181
31.69
14.44
12.34
17.03
18.88
7.58
12
12.34
480.4
127
157
2-26
-------
TABLE 2-8
PCDD AND PCDF IN SOLID SAMPLES - VERSAR STUDY
PAGE FIVE
BOTTOM ASH (DIOX1N HOMOLOGS)
2.3.7,8 TETtt PENTA KOA HEFTA OCA TOTAL
TOO -Tffff *COO *COO -COD ~Hlff *COO
Plwit Otserlptlon (ng/g) (1^/9) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g)
I Unit 3. 9/28. AN
-------
TABLE 2-8
PCDD AND PCDF IN SOLID SAMPLES - VERSAR STUDY
PAGE SIX
LANDFILL COMPOSITE (DIOXIN HOMOLOGS)
M«nt Description
C PtHatttr Co^esIt*
0 Nrlattir Co*ostt*
2.3.7.8 rrnu PCHTA HGCA KFTA OCTA TOTAL
TCDO -COD -COO -COO -COD -^TTP -CDO
(ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g)
0.07
0.1S
1.2
2.S
S.7
6
6.8
4.1
9
4.2
6.1
3.9
28.8
20.7
LANDFILL COMPOSITE (FURAN HOMOLOGS)
Plant Description
C P«r1ntttr Co^oslU
0 Ptrimtttr Composite
2.3,7,8 TFTRA PCJITA HOA HEFTA OCTA TOTAL TCOO »
TCDF .CDF -CDF -CDF -CDF -CDF -CDF TCDF
(ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g)
0.51
1.3
2.4
11
3.9
7.7
4
5.3
3.3
2.7
0.81
0.61
14.41
27.31
43.21
48.01
2-28
-------
name i-s
»f tUit* NoMlOft lit r\j Itik frt» the Four
Sw»l«4 kjr Icrur In *«/v (p*rti per kill Ian)
o>
OOXIN HOMOtOCS
DtOXIN MOUOLOCS
I
1000
FLY ASH
(Facililx B)
FLY ASH
Mly 0)
fct»: tick b»r fMrvuoti « lndl«l«wl t«vle coll»cU4 fr» *n lndlvl*Ml wit AirliM * ln4l«l*Ml tklft. tick
llHy I «*fck conllitt «
It candttt «f t
u^lti (!*> l-
Ulcn
UMt tklfl.
-------
rieuM »-«
CMcentntlont »f F«r»« lte"ol«l» l» O/ *ik fn» the roar ricllltlts
ky »tr»«r In iif/f fart* >«r kill Mi)
FLY ASH
(f OCtflly A)
FLY ASH
(Facility C)
HOMOLOCS
FURAN HOUOLOGS
230
FLY ASH
(Facilily B)
FLY ASH
(Facrtily 0)
O
m
i
fM
HOMOiOCS
FURAN HOMOIOGS
oU: bck tar rr»rt**nt« »n lf»4UI*ul
Mplc conilits *f cwpeilU «f frik
few frvk u^ilct (Uklt 1-7).
fnm «n In4l*l*u1 Milt 4vrlM in li«ll«ld««1 skirt. t»tk
lti Ukcn *irl*« tint tfclfl. Mccpt for facility I hick cmtlsted of
-------
Concentrations of Dioxin and Ftiran ifowotogs In Bottoa Ash fro»
Facility B Sailed by Versar in ng/g (parts per billion}
BOTTOM ASH
(Facility B)
OIOXIN HOMOLOGS
BOTTOM ASH
(Facility B)
rn
i
rsi
o
a
a
1
I
I
fc
I
Hote: Each bar represents an individual
sample collected fro» an Individual unit
during an individual shift. Each staple
consists of ca^raslte of four grab samples
taken during that shift.
fURAN HOMOIOCS
-------
COMBINED BOHOM ASH & FLY ASH
(Focility A)
4V
IS
ji
o»
*..
^
I
rl
1
1
!
^
1
Jj
1 ? ? ? ? ?
3 I 1 i S fi
DIOXIN HOMOLOGS
130
o 100
a
a
COMBINED BOHOM ASH 8c FLY ASH
(Facility C)
r>'
*
W
I
DIOXIN HOMOLOGS
COMBINED DOTIOM ASH &. FLY ASH
(Facility D)
DIOXIN HOMOLOGS
IN
m
i
rM
Hole: Each bar represents an Individual sample
collected fra an Individual unit during an
Individual shift. Each sample consists of
co^mslte of 8 grab sampled taken at
approxlMtely equal Intervals during that shift.
-------
COMBINED BOTTOM ASH & FLY ASH
(Facility A)
toe
M
40
to-
_^ J
i
& * & & 5
M M i
§
. s
FURAN HOMOLOCS
COMBINED BOTTOM ASH & FLY ASH
(Facility C)
ruRAN HOMOLOCS
COMBINED B01IOM ASH & FLY ASH
(Facility 0)
FURAN HOMOLOGS
m
ro
i
fM
Note: Each bar represents an Individual
saajile collected fro* an Individual unit
durlno an Individual shift. Each stele
cons Its of a composite of 8 frab sables
taken
-------
finally, one significant trend was noted. As the total PCDDs increased, the
abundance of the hexa- through octa-chlonnated classes increased dispro-
portionately (i.e., when the total PCDD concentration was less than 500 ng/g (ppb),
the hexa- through octa-chlonnated classes accounted for 70 percent of the total
PCDD concentration; however, when the total PCDD concentrations exceeded
500 ng/g (ppb), the hexa- through octa-chlorinated classes accounted for 90 percent
of the total PCDD concentration).
At Facility C, two discrete fly-ash fractions were analyzed for PCDDs (see Table 2-8).
The first of these, the coarse fly ash (i.e., economizer ash), did not contain any
detectable PCDDs. However, the second of these fractions, the fine fly ash (i.e.,
electrostatic precipitator ash), contained the highest PCDD concentrations of any fly
ash sample that was analyzed in the coarse of the Versar Study. This was expected
because the PCDD compounds adhere more strongly to finer particles.
A review of the PCDF homolog concentrations in the fly ash, Figure 2-6, again
showed that the variability between the shift and units was relatively small,
whereas the concentration variability between facilities was extremely large (i.e.,
the concentrations standard deviations for the homologs exceeded the average
homolog concentrations). Facility C had the highest concentrations of total PCDFs,
as well as the highest concentrations of each PCDF homolog, followed by Facility B,
Facility D, and Facility A, which had the lowest concentration of each PCDF
homolog. The hexa-CDF homolog was the most prevalent at three facilities, and the
second most prevalent at the fourth facility. Similarly, the octa-CDF homolog was
the least prevalent at three facilities, and the second least prevalent at the fourth
facility. The tetra-CDF homolog was generally the second most prevalent, with the
exception of Facility C, where it was the least prevalent. As was the case for the
PCDDs, the hexa- through octa-chlorinated classes of PCDFs increased dispro-
portionately as the total PCDFs increased.
As was the case for the PCDDs, two discrete fly ash fractions from Facility C were
analyzed for PCDFs (see Table 2-8). Again, the coarse fly-ash fraction contained a
minimal quantity of PCDFs, but the fine fly-ash fraction exhibited the highest
concentrations of PCDF-homologs found in any fly-ash sample. This was again
anticipated because the PCDF compounds, acting similarly to the PCDD compounds,
adhere more strongly to the finer fly-ash particles.
2-34
-------
Comparison of PCDD with PCDF levels in the fly ash indicated that the total
concentrations of PCDDs and PCDFs followed the same sequence of abundance
among the facilities (i.e., the total concentrations of both PCDDs and PCDFs
increased in the order: Facility A - Facility D - Facility B - Facility C; the production
of the hexa-chlorinated classes of PCDDs and PCDFs was favored at each of four
facilities; the penta- and/or hepta-chlorinated classes of both PCDD and PCDF were
never the most or least abundant. Also, there was no correlation between the
relative abundances (i.e., percentage) of PCDD or PCDF homologs in the total
PCDD/PCDF concentrations.
A review of the PCDD homolog concentrations in the combined bottom/fly ash
(Figure 2-8) and bottom ash (Figure 2-7) showed that the variability between shifts
and units was relatively small compared to the variability between facilities.
Facility C combined-ash samples had the highest concentrations of individual PCDD
homologs as well as total PCDDs. The samples from Facility A had the second
highest PCDD concentrations, followed by the samples from Facilities D and B,
sequentially. There were no notable trends for the relative abundances of the
individual PCDD homologs. For example, the penta-CDD homolog was the most
abundant for Facilities A and D, while the octa-CDD and hepta-CDD homologs.
predominated at Facilities B and C, respectively. Similarly, the least abundant
homolog was tetra-CDD for Facilities B, C, and D; however, the octa-CDD homolog,
which was the most abundant at Facility B, was the least abundant at Facility A. The
2,3,7,8-TCDD isomer concentrations were very low for all four facilities, usually
being only slightly above the detection limit.
A review of the PCDF homolog concentrations in the combined bottom/fly ash
(Figure 2-9) and bottom ash (Figure 2-7) samples indicated that the variability
between shifts and units was relatively large, and that the variability between
facilities was extremely large.
The combined-ash samples from Facilities A and C had the highest concentrations of
PCDFs. The octa-CDF homolog was the least prevalent for three of the facilities;
however, it was the second most abundant homolog for Facility B. This difference
may be attributed to the Facility B sample, which consisted exclusively of bottom
ash, whereas the samples from the other three facilities consisted of combined
2-35
-------
bottom/fly ash. The tetra- and hepta-CDF homologs predominated, each being the
most abundant homolog at two facilities. The concentrations of the penta- and
hexa-CDF homologs were approximately equal; these homologs were never the
most or least abundant at any facility. The 2,3,7,8-TCDF isomer accounted for 15 to
20 percent of the total tetra-CDF homologs.
Comparison of the PCDD and PCDF concentrations in the combined and bottom ash
indicates the following observation. The facilities that had the higher
concentrations of PCDDs had the highest concentrations of PCDFs, and this was also
true for the facilities with the lowest concentrations. There was no apparent
correlation or trend between the relative abundances of PCDDs or PCDFs in the total
PCDD/PCDF concentrations.
A review of the landfill composite sample results for PCDDs (Figure 2-10) showed
that Facilities C and D were approximately equal. The tetra-CDD homolog was the
least abundant at both facilities, and the hepta-CDD and penta-CDD homologs were
the most abundant. The tetra-CDDs at each facility were approximately 6 percent
2,3,7,8-TCDD.
The PCDF results of the landfill composite sa,mples (Figure 2-10) srjowed that
Facility D contained higher concentrations than Facility C. The octa-CDF homolog
was the least prevalent at each facility, and the hexa-CDF and tetra-CDF homologs
were the most prevalent at both facilities. There did not appear to be any trend
concerning the concentrations of 2,3,7,8-TCDF, or the relative abundances of PCDD
or PCDF in the total PCDD/PCDF concentrations.
Comparison of the PCDD and PCDF results of the combined bottom/fly ash
(Figures 2-8 and 2-9; Table 2-8) with the landfill perimeter composite samples from
Facilities C and D (Figure 2-10 and Table 2-8) indicate that the combined ash from
Facility C contained six times more PCDDs and four times more PCDFs than the
landfill composite. Conversely, at Facility D, the landfill composite sample
contained two times more PCDDs and five times more PCDFs than the combined ash
samples. The reason for this occurrence may be that the landfill composite samples
at Facility C may have been biased by bottom ash, whereas the landfill composite
sample at Facility D may have been biased by fly ash, which contained significantly
more PCDDs and PCDFs than the bottom or combined ash.
2-36
-------
!-)
C«KMtr«tl«i« «f
TM FKllttUi
LANDFILL COMPOSITE
ifclx C)
F«ran Nnvlafi In landfill
r **rur In »t/fl (f*rt> ftr
^**
1
Inm Um
LANDFILL COMPOSITE
cMilr C)
B
OIOWN HOMOLOGS
HOMOLOGS
CO
f
fM
I4
LANDFILL COMPOSITE
(Facility 0)
i 10
5
LANDFILL COMPOSITE
cWIx 0)
OOXIN HOMOIOGS
FUflAN HOMOLOCS
tote: Utk ca^oilte M*1c cwultt** *f 50 t-foot c»r»
Ukc« frw lt»
latUn (T*kl* 1-7)
-------
Upon comparing the PCDD and PCDF results of the fly ash with the combined
bottom/fly ash or bottom ash, the following observations were noted. First, the
variability between facilities for both fly ash and combined/bottom ash PCDD and
PCDF concentrations is extremely high. This may be a consequence of differences
the feed material, incinerator conditions, and plant designs at the four facilities or it
may be a consequence of sampling variability. Second, the variabilities between
shifts and units for both PCDDs and PCDFs in the combined/bottom ash are greater
than the corresponding variabilities for the fly ash. This discrepancy is probably
caused by the relatively higher heterogeneity of the combined/bottom ash
compared to the relatively higher homogeneity of the fly ash. Third, the fly ash from
three facilities contained from 3 to 40 times more PCDDs than the combined ash,
and the fly ash from Facility B contained 120 times more PCDDs than the facility's
bottom ash. This indicates that the PCDDs are associated with the fine fly-ash
particles and that PCDD concentrations in the bottom ash are minimal. Therefore,
the difference between the PCDD concentrations in the fly ash and combined ash is
probably caused by a bottom-ash dilution effect. Similarly, the fly ash from three
facilities contained from 2 to 25 times more PCDFs than the combined ash, and the
.
fly ash from Facility B contained 75 times more PCDFs than the facility's bottom ash.
Therefore, the difference between PCDF concentration in the combined ash and fly
ash is probably a result of the dilution effect from the bottom ash. Fourth, the
tetra-CDD homologs are the least prevalent in both the fly ash and the
combined/bottom ash, whereas the hexa-through octa-chlorinated classes of PCDDs
are the most prevalent. This suggests that the typical incinerator conditions favor
the production of the more highly chlorinated PCDD species. However, for both the
fly ash and combined/bottom ash, the tetra- through hexa-PCDFs are more
abundant than the hexa through octa. This may suggest that the same incinerator
conditions that favor the formation of the higher PCDDs also favor the formation of
the lower PCDFs.
The toxicity of the individual PCDD and PCDF homologs varies greatly. The tetra
homologs are more toxic than the others, and of the tetra, the 2,3,7,8-TCDD is the
most toxic. In a recent March 1987 publication of the Risk Assessment Forum of the
U.S. EPA: Interim Procedures for Estimating Risks Associated with Exposures to
Mixtures of Chlorinate Dibenzo-p-Dioxins and Dibenzofurans (CDDs and CDFs)
(Bellin and Barnes, 1987), and distributed in a draft form by Lee M. Thomas in
2-38
-------
January 7,1987, a methodology of converting the concentrations of PCDD and PCDF
homologs to 2,3,7,8-TCDD is given. This methodology, which determines the
"Toxicity Equivalence Factors" (TEF), was used to determine the individual TEFs for
ashes and their natural and simulated leachates. This is further discussed and
reported in the applicable tables presented in Section 6.0 of this report.
According to recently obtained information from Canadian studies (Sawell, 1987)
dioxin entering the incinerator is actually destroyed by the incinerator. However,
during incineration, new dioxins are formed from chlorinated organic compounds
that can produce dioxins. These Canadian studies report that incinerators are net
destroyers of dioxins.
2-39
-------
3.0 CONVENTIONAL PARAMETERS IN LEACHATES
FROM MSW DISPOSAL SITES, CODISPOSAL SITES, AND MONOFILLS
Table 3-1 lists ranges of conventional parameters (i.e., pH, specific conductance,
total dissolved solids, ammonia-nitrogen, sulfate, nitrate-nitrogen, COD, BOD,
TOC, etc.) in leachates collected from MSW sites, as reported in the literature and as
found by the NUS study. Results obtained from the EPA-sponsored study,
conducted by NUS, are given in the last two columns: ranges of the six samples
collected from the two codisposal sites are given in the last column, and of the
» thirteen samples collected from the four MSW sites, in the column next to the last.
J The study is described in detail in Volume VI of this report and the literature
, information is reported in Volumes II and III of this report.
i
The NUS-selected MSW and codisposal sites were carefully chosen (as described in
Section 2.0 of Volume VI) to include only sites constructed after RCRA regulations
came into effect and sites that do not accept industrial wastes. The selected
codisposal sites accept in excess of 25 percent of their waste in the form of MWC
ashes.
To better understand the data obtained by the NUS study, Table 3-2 lists the
characteristics of the four selected municipal solid waste disposal sites and Table 3-3
lists the characteristics of the two selected codisposal sites.
The data presented in Table 3-1 indicate a great variation in levels of each of the
analyzed parameters. The variability in the data reported in the literature ranges
over several orders of magnitude. For example, pH ranges from acidic (3.7) to
basic (8.5). The behavior of the other parameters is similar. Values of BOD, COD,
and TOC are high, as expected, ranging from not detected (NO) to 720,000 mg/l
(ppm) for BOD; ND to 750,000 mg/l (ppm) for COD; and from ND to 30,500 mg/l
(ppm) for TOC. Nitrate-nitrogen values, for which there is a drinking water
a standard of 10 mg/l (ppm), ranged from ND to 1,300 mg/l (ppm).
3-1
-------
TABLE 3-1
to
i
NJ
CONVENTIONAL CONTAMINANT CONCENTRATION MANGES IN LEACHATES
FROM MUNICIPAL DISPOSAL AND CODtSPOSAL SITES
pH
IDS
BOO
IOC
G«Mg«0972)
3785
0-20.650
042.276
62.615
954.610
022.800
342.600
1 1.826
01.416
0 1,106
01.300
1 154
OeW«Ut
11977)
3765
0-20.650
56444.900
2.61016.600
133.360
4069.520
25626.000
0-22.600
4 7-2.467
II. SSI
02 1029
0130
6585
M«liy/Ciou
0975)
3715
3109.500
10051.000
1001.200
2,200720.000
3.2605.730
351.700
472.350
201.370
0 2 845
2 4 550
4518
03 136
Ctmeron
(1978)
3785
020.900
042.300
955.000
09.000
022.800
342.800
02 13
01.826
04>I3
01.106
0 154
Wiuontin
Hcpofl
(20uUt)
^M
589
NO I5.0SO
58450.430
2 140.900
48072.500
NO 195.000
6 6 97.900
NO 30.500
52225.000
2 11.375
0074
NO 1.850
23.320
NO 234
5obolka
Report
(44 nut)
S480
1.90025.873
1.400 16.120
28 2.835
721.600
44050.450
5-6.884
0 8 9.380
1205.475
0 12 0 790
8500
473938
113 1.200
45-782
0 SO 95
All concentrations in mo/I except pH (std units) and Sp. Cond (umhos/cm).
NUS
MunKip*!
(4SiUt)
69878
2.71031.800
32926
300 > 10.000
1.0008.700
1382.680
6703.000
5701.600
73660
53580
<0102
02-38
MIS CodiipoMl
(2 SiUt)
7273
1.9307.9/0
452.220
1.300 3.900
438 1.310
9002.200
<20S7
190450
160410
10 70
7
09723
NO = Not detected
-------
TAILE 3-2
CHARACTERISTICS OF MUMCIPAL SOUD WASTE DISPOSAL SITES SELECTED FOR NUS STUDY
facility
K
Fl
SM
Vl>
Opened tot
Opeialion
198)
ilotuie
1998
May 19/S
Closure
-1992
1976
January
1980
fapatily
(yards'/year)
80.000
21.000
1 S»IO*
480.000
(7S tons/day)
Geographic Profile
186 acres in lotting hilh. areas.
range liom iiual agricultural
lo leudenlial. toil it glacial
and moraine, mostly highly
permeable sandy UN
1 20 acre vie m forested aiea;
unit ai« medium- lo Ime-
grained tandl. undetlam by
ultylo clay-Irk* und
58 a«bi»
DetdAramalt
Sludge
Method ol
MMemeiit
AieafiM
Sequential
trench
method
fiench and
aieaM
Mamp
Method
liner
S loot thick (lay
pe>ma*Miiy
7 « 10 Mo
4HO'cmA«O
6-inch Ilink
benlonte potymw
anduMl
(permeability
» > 10 '<»*<)
None - naluially
lined with clay and
mudtlone
None
laachate C ylleclion/
IrealmentSyilvin
6inchpciloialedPVC
?ipes mgravel tienchvi.
hauled to K3IW
6 inchperloialedPVC
pipvt m gravel trenches.
pumped lo sealed pool.
vapoi ated and hauled to
POTW
Collected HI trenches.
pumped to lagoon, stored
in winter, spr ay irrigated
on acl|a< ent land in
summer
Collection reteivou on
downgradienl side ol liH.
htachaie is sprayed back
over UndliUaree
Cover
>atly 6 inches ol
soil
final 2 led ul
com|Mi letl i lay
sod and 6 tmlu-t «'
topsoil
Daily * indies ul
soil
Final Hi' dies <>
benlnrute 'ml mn
Daily S inches ol
MMl.
Final Hvtlul
clay lo#soil
Daily t> mclies nl
weathiiied tliale
Final 1 Ice lol
compacted lopio.l
Ul
I
Ul
-------
fr-E
i
H
>
£
? S
* r
§*
s
- r
&
1 B-
i
£
ffj
it!
Optucdloi
OpCfllKMI
i
*
S
1
|
ft
n
-------
Leachates collected from the NUS-selected sites, both the MSW and the codisposal
sites, contained the same parameters, reported by other studies (Table 3-1) but at
lower levels. For example, the pH in the NUS municipal leachate samples were
neutral to slightly basic ranging between 6.98 and 7.8 and, in the codisposal
leachate samples, the pH was slightly basic ranging between 7.2 and 7.3; COD levels
ranged between 1,000 and 8,700 mg/l (ppm) in the MSW leachates and 1,300 and
3,900 mg/l (ppm) in the codisposal leachates; nitrate-nitrogen values were all well
below the maximum contaminant level (MCL) of 10 mg/l (ppm). They ranged
between <0.1 and 0.2 mg/l (ppm) in the MSW leachates and <0.1 and
0.7 mg/l (ppm) in the codisposal leachates.
Generally, there was no difference between the leachates collected from the four-
MSW sites and the two codisposal sites. The ranges overlapped, and as stated
previously, fell well within the ranges of other MSW leachates.
There are two main reasons why leachates collected for this EPA-sponsored NUS
study were relatively "cleaner:"
The selected sites were all constructed in the post-RCRA era. Thus, these
sites are not likely to contain hazardous wastes other than those from
small-quantity generators.
The selected sites do not accept industrial wastes.
During the week of June 2nd through June 6th 1987, the four monofills sampled by
Versar in 1986, which had not originally been sampled for conventional parameters,
were resampled by NUS for pH, specific conductance, COD, and ammonia-nitrogen.
The facilities were resampled for leachates and quench waters at the same location
points where the original samples had been collected. Results are summarized in
Table 3-4. The original sampling effort is described in Volume V of this report and
the results of the NUS effort are described in the form of a trip report in Volume VII
of this report. Volume VII also contains pertinent information regarding the
facility's operating practices, as obtained in June of 1987.
i
Comparison of the limited monofill data available and listed in Table 3-4 with the
data given in Table 3-1 indicates that, as expected, ammonia-nitrogen and COD
3-5
-------
TABLE 3-4
CONVENTIONAL PARAMETERS IN LEACHATES PROM MONOFILLS
AND IN QUENCH WATERS
Parameter
pH, pH Units
Specific Conductance
COO, mg/l (ppm)
NHj-N. mg/l (ppm)
Temperature. °C
Facil
Leachate
-
-
-
-
-
tyA
Quench
Water
11 91
4,900
38
0.7
36.3
Facility 3
Leachate
7 44
4.200
10,000
1,200
30
33.3
Quench
Water
5.68
9,100
470
4.1
408
Facility 0
Leacnate
3.12
9.300
340
36
293
Quench
Water
11 73
< 10.000
320
45
31 5
Specific conductance in umhos/cm
No leachate collection system
3-6
-------
levels in the monofill leachates were much lower than in the MSW disposal and
codisposal leachates. However, levels of specific conductance, which provide a
measure of total dissolved solids, were similar to the values obtained for the MSW
and the codisposal sites. The pH of leachates from the monofiil were, as expected,
on the basic side (7.44-8.58) and the quench waters, except for Facility C (5.68), were
even more basic (11.73-12.09).
The presence of ammonia-nitrogen in the monofill samples, although in very small
concentrations, suggests the presence of anaerobic bacteria. Given adequate time
and carbonaceous substrate, which serve as nutrients for the bacteria, significant
microbial activity will take place.
3-7
-------
TABLE 4-1
INORGANIC CONCENTRATION RANGES IN IE ACHATES
FROM MUNICIPAL DISPOSAL AND COOISPOS AL SITES IN mg/1 (ppm)
Trace Element
Aluminum
Arsenic
Barium -
Beryllium
Boron
Cadmium
Calcium
Total Chromium
Copper
Cyanide
Iron
lead
Magnesium
Manganese
Mercury
Molybendum
Nickel
Potassium
Sodium
Titanium .
Vanadium
Zinc
No of Samples
George
(1972)
54080
N099
0 2 5500
NO 50
165-15600
006 MOO
2 8 3770
NO 7700
NO 1000
Chian/
DeWallo
09/7)
003 17
607200
NO 9 9
0-2820
<0 10-20
17 15600
009125
283770
NO 7700
ND370
Meiry /Cross
(1975)
2402570
0.12-1700
64 547
13
28-3800
853800
003 135
Cameron
(1978)
NO 122
ND-116
NO 54
NO 03
NO 3 73
NO 0 19
54000
NO 33 4
NO- 10
NO 0 1 1
0 2-5500
NO SO
165 15600
006-1400
NO 0064
NO 052
NO 01 08
2 8 3770
NO 7700
NO 50
NO 14
NO 1000
Wisconsin
Repoit
(20 sites)
ND8S
ND702
NO- 12. 5
ND036
0867-13
NO 04
200 2500
NO 5 6
NO 4 06
NO 6
NO- 1500
NO- 14 2
NO 780
NO 31 1
NO 001
001-143
ND-75
NO 2.800
126010
le
limit
50
10
50
--
-
50
02
-
-
NO = Not delected at the detection limit
Blank = Not Reported
Source: Literature (Volumes II and III) and NUS Study (Volume VI)
-------
TABLE 4-2
RANGES OF LEACHATE CONCENTRATIONS OF INORGANIC CONSTITUENTS
FROM MONOFILLS in mg/l (ppm)
Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Silver
Aluminum
Beryllium
Boron
Calcium
Cobalt
Copper
Iron
Lithium
Magnesium
Manganese
Molybdenum
Nickel
Potassium
Sodium
Strontium
Tin
Concentration
0.005-0.218
1.0
ND-0.044
0.006-1.53
0.012-2.92
0.001-0.008
0.0025-0.037
0.07
21
0.022-24
0.168-121
0.103-4.57
ND-0.412
21.5
200-4,000
EP Toxicity
Maximum
Allowable Limit
5.0
100.0
1.0
5.0
5.0
0.2
1.0
5.0
-.
Primary Drinking
Water Standard
0.050
1.000
0.010
0.050
0.050
0.002
0.010
0.050
4-3
-------
TABLE 4-2
RANGES OF LEACHATE CONCENTRATIONS OF INORGANIC CONSTITUENTS
FROM MONOFILLS in mg/l (ppm)
PAGE TWO
Constituent
Titanium
Vanadium
Yttrium
Zinc
Chloride
Sulfate
pH
TDS
Country
Concentration
NO -3.3
1,803-18,500
94
8.04-8.3
11,300-28,900
EP Toxicity
Maximum
Allowable Limit
Primary Drinking
Water Standard
NO = Below Detected Limit
Blank = Not Reported
Source: Literature (Volume IV) and Versar Study (Volume V)
4-4
-------
level ranges of three studies exceeded the 5.0mg/i (ppm) EP Toxicity Maximum
Allowable Limit of lead.
The municipal and codisposal sites selected by NUS for sampling generated
leachates (last two columns of Table 4-1) of similar inorganic content, but at much
lower concentrations that those reported in the literature. The two main possible
reasons for this occurrence, as discussed in Section 3.0, are the fact that the NUS
sampled sites began operation after RCRA requirements came in effect, and that
these sites do not accept industrial waste for disposal.
Data presented in Table 4-2 regarding the inorganic content in leachates collected
from monofills indicate that all EP Toxicity Maximum Allowable Limits were met.
The pH in the monofills was basic, as expected, ranging between 8.04 and 8.3.
Comparison between data listed in Tables 4-1 and 4-2 indicates that the high range
of metals of concern in leachates from monofills is lower than the high ranges in
MSW facilities as reported in the literature for the following elements: arsenic,
barium, beryllium, cadmium, chromium, iron, lead, mangane?"1, mercury,
potassium, sodium, and zinc.
Tables 4-3 and 4-4 list the concentrations of the inorganic parameters (including
metals) in the individual codisposal sites (Volume VI) and the individual monofill
sites (Volume V), respectively. Samples collected by Versar and by NUS were grab
samples. Samples were not filtered in the field prior to acidification for
preservation purposes. Thus, the results reported in Tables4-3 and 4-4 represent
total values, i.e., the values found in the aqueous phase and the values found in the
fine particles suspended in the leachate samples.
4-5
-------
TABLE 4-3
INORGANIC CONSTITUENTS IN FIELD LEACHATES FROM COOISPOSAL SITES (NUS) IN mg/l (ppm)
Inorganic
Constituent
Arsenic .
Cadmium
Chromium
Copper
Iron
Lead
Manganese
Mercury
Nickel
Selenium
Zinc
pH. pi (Units
NY 01
0010
00)1
0009
0 18
938
0018
11 3
NO
023
NO
1 21
7.2
NY 02
0008
0.009
0011
020
924
0010
11 2
ND
023
NO
1 21
72
NY-03
0012
0006
0013
019
938
0022
11.3
ND
024
ND
1 21
7.2
NCOI
0044
ND
ND
ND
21 1
0026
1 31
ND
0.13
ND
O.IS
7.3
NC02
0046
ND
0005
ND
104
0027
1.48
ND
0 14
ND
009
73
NC03
0044
ND
0008
ND
209
0018
1 29
ND
ND
ND
0 12
73
Range
0 008- 0 046
00060011
00050013
ND020
209 104
00100.027
1 29-11.3
ND
0 13-0.24
ND
009 1 21
727 3
EPToxicity
Maximum
Allowable
Limit
50
to
50
...
...
SO
02
...
1 0
...
...
Primary Drinking
Water Standards
0050
0010
0050
...
...
0050
...
0002
...
0010
...
en
ND = Below detection limit
Source. NUS Study (Vomume
-------
lAiU 4-4
INOHGANICi CONSIIIUINIi IO« HUD UACHAHi (MOM MONOHUi (VtRSAR) IN my/l (ppm)
InoKj.mu
Crmviilm>ni
Ai \riiM
f Jdiimim
LlirointufM
Cit|i|u*i
ll*W»
Itfjd
Mill tij.iitf^r
Mvrtuf y
N,,ktl
Svlciuum
/nit
f.«iliiylu<.ili(>
U(Jb9
)9«
/
0 758 i 1 4
0 0?S i 92
001) 4 >/
< 0 0002 0 OOttO
^OOIS04I2
u
1 0
'.0
bO
02
10
Pi (limy
DniUi'lij
Wulcr
SliMUljIl
ooto
Illllll
0 U'.il
OHIO
OUU2
OOIU
Suunu Vcnjl Study (Volume V)
-------
4.2 INORGANIC CONTENT IN EXTRACTS FROM MWC ASHES
Many extraction procedures have been suggested by industry, academia, technical
organizations, and regulatory agencies. The main objective of such leaching tests is
to simulate natural leaching conditions in the absence of actual field leachate
composition data. The data obtained from these tests usually serve as input for
designing landfills and leachate treatment facilities. For this purpose, the tests are
intended to be conservative, because a facility that is overtreating wastes is always
preferred to a facility that is undertreating wastes.
Two extraction procedures have regulatory significance; the leaching characteristics
from these methods are used to classify a waste as "hazardous" or "nonhazardous"
under the Resource Conservation and Recovery Act (RCRA). These two procedures
are the present Extraction Procedure (EP) and the proposed Toxicity Characteristic
Leaching Procedure (TCLP).
Since the EP toxicity and the TCLP procedures are required by regulatory agencies, a
significant amount of data has been generated for these procedures. Data for any
of the other procedures are not readily available in the published literature except
for one procedure in which leaching is being done with distilled water. Thus, in
addition to the two regulatory procedures, the Monofilled Waste Extraction
Procedure (MWEP) (also known as SW-924), in which distilled water is used, has
been used in the two EPA-sponsored studies (Versar, Volume V of this report, and
NUS, Volume VI of this report). Data reported in the literature for distilled or
deionized water extraction was referred to throughout this section as data
obtained through method SW-924, although all such data may not have been
obtained through this specific method. Following are summary conditions for these
three extraction procedures:
4-8
-------
SUMMARY CONDITIONS FOR EP, TCLP, and MWEP METHODS
Conditions
Liquid: Solid Ratio
Extraction Medium
pH Control
Extraction Time
Agitation Method
Temperature Control
Particle Size
Number of Extractions
EPa
20:1
0.5N acetic acid
5
24 hours
Tumbler
20-40»C
< 9.5 mm
1
TCLPb
20:1
0. 1 N acetate buffer
5 or 3
18 hours
Tumbler @ 30 ± 2 rpm
22 1 3'C
< 9.5 mm
1
MWEPc
10:1 per extraction
Oistilled/deionized
water
None
18 hours per extraction
Tumbler
25 ± 1°C
< 9.5mmg
4. sequentially**
a EP-Extraction Procedures (40 CFR 261, Appendix 11), 1980.
b TCLP - Toxicity Characteristic Leaching Procedure (Revised 40 CFR 261, Appendix II). 1986.
c MWEP - Monofilled Waste Extraction Procedure (A Procedure for Estimating Monofilled Solid
Waste Leachate Composition. Technical Resource Document SW-924. 2nd Edition).
d For the Versar and NUS projects, a modified MWEP method was used with only one or two
sequential extractions.
The following three subsections describe the details of these procedures. This
information is important in order to understand the differences in concentration
levels of individual constituents leached by the different methods, and more
importantly, the reasons the leaching procedures are extracting significantly higher
levels of certain pollutants than occur in the natural leachate.
4.2.1 Extraction Procedure (EP)
The EP method was developed to classify a solid waste as hazardous or
nonhazardous, based on predetermined hazard levels for 14 specific constituents.
Therefore, the analytical results from the EP-prepared ash residues may be used to
formulate regulatory strategies and to evaluate the adequacy of current disposal
practices. For solid residue samples that contain no filterable liquid (i.e., contain
only surface and interstitial moisture), the EP method is performed as follows:
1. Obtain a representative TOO gram sample of residue.
2. Crush material to < 9.5 mm, if necessary.
4-9
-------
3. Place sized solid residue in extractor vessel.
4. Add amount of deionized water equal to 16 times the weight of the solid
residue.
5. Begin agitation and measure pH.
a. If pH is > 5.0, adjust to 5.0 ± 0.2 with 0.5N acetic acid.
b. If pH is <, 5.0, no adjustment is necessary.
6. Continue monitoring pH at specified intervals, adjusting pH, as required in
5a, for 6 hours. The maximum amount of acid added should not exceed
four times the mass of the extracted residue.
7. Agitate mixture for a total of 24 hours between 20-40"C
a. If at the end of 24 hours the pH is > 5.2, adjust to 5.0 ± 0.2 and
continue agitation for an additional 4 hours.
b. If pH is <. 5.2, no additional agitation is necessary.
8. Add required amount of deionized water to equal 20:1 ratio, accounting
for volume of acid added, and filter mixture using a 0.45 um membrane
filter.
9. Analyze or preserve filtrate (i.e., laboratory leachate) as required.
If the residue sample contains filterable liquid, the sample is first separated into its
component phases, and the above procedure is performed on the solid phase.
Then, the initial filtrate and solid extract are combined for analysis.
4.2.2 Toxicitv Characteristic Leaching Procedure (TCLP)
The TCLP method was developed by the EPA to replace the EP as the hazardous
waste classification criteria under RCRA; however, the TCLP method has not yet
legally replaced the EP method. The TCLP classification criteria are based on all
Appendix IX constituents, including volatiles, whereas the EP classifications are
based on predetermined hazard levels for only the 14 specific contaminants of the
Primary Drinking Water Standards.
4-10
-------
When the residue sample contains no filterable liquid, the TCLP method is
performed as follows:
1. Obtain a representative 100 gram sample of residue.
2. Crush material to < 9.5 mm, if necessary, and place residue in extraction
vessel.
3. Determine appropriate extraction medium:
a. Weigh out 5 grams subsample of residue; reduce particle size to < 1 mm,
if required; place sample in a 500 ml beaker.
b. Add 96.5 ml of distilled/deionized water (ASTM Type II).
c. Stir sample vigorously for 5 minutes with magnetic stirrer.
d. Measure pH.and, if pH is <.5, use Extraction Fluid #1.
e. If pH > 5, add 3.5 ml 1.) N HCI; slurry for 30 seconds; heat to 50°C for 10
minutes.
f. Allow mixture to cool to room temperature and measure pH.
-,
g. If pH <, 5, use Extraction Fluid #1, and if pH > 5, use Extraction
Fluid #2.
4. Add amount of extraction fluid selected in Step 3 equal to 20 times the
weight of the solid residue.
5. Close extraction vessel, and agitate in rotary extractor device at 30 ± 2 rpm
for 18 hours, maintaining the temperature at 22 ± 3°C.
6. Filter material through a 0.6 to 0.8 um glass fiber filter.
7. Analyze or preserve filtrate as required.
If the residue sample contains filterable liquid, the sample is first separated into its
component phases, and the above procedure is carried out on the solid phase.
Then, if the initial filtrate and solid extract are compatible (i.e., will not form
multiple phases or precipitates on combination), they are analyzed separately, and
the results are mathematically combined to yield the total leachable composition.
4-11
-------
Since the pH of the waste determines the nature of the extraction fluid used, either
Extraction Fluid #1 or #2, it is important to define the TCLP definition of these
Fluids:
Extraction Fluid #1 is made by combining 64.3 ml of 1.0 N NaOH and 5.7 ml
glacial acetic acid to the appropriate volume of water and diluting to a
volume of one liter. The pH of this fluid should be 4.93 ± 0.02
Extraction Fluid #2 is made by diluting 5.7 ml glacial acetic acid with ASTM
Type 2 water to a volume of one liter. The pH of this fluid should be
2.88 ± 0.02.
4.2.3 Monofilled Waste Extraction Procedure (MWEP)
The MWEP method was developed to estimate the quantity of potentially leachable
constituents in a given solid waste and to measure the concentration of these
constituents in extracts. The procedure includes a sequential four-step batch
extraction, which produces data that can be used to construct an aqueous
extraction profile for each of the constituents. For the EPA-sponsored studies-the
NUS and Versar studies (Volume V and Volume VI of this Report)--a modified MWEP
method with only two sequential batch extraction was used. Unlike the EP and
TCLP methods, the MWEP has no regulatory significance.
The modified MWEP method is performed as follows:
1. Obtain subsample and determine percent solids.
2. Obtain representative sample equal to 100 grams dry weight and place in
extraction vessel.
3. Add appropriate amount of dtstilled/deionized water to give a 10:1
liquid-to-solid weight ratio, taking into account the moisture determined
in step 1.
4-12
-------
4. Extract (i.e., agitate using a tumbler) the mixture for 18 hours at a
temperature of 25 ± 1°C.
5. Filter mixture through a 0.45 urn nitrocellulose membrane filter (for
inorganic analyses) or a 0 .6 - 0.8 urn glass fiber filter (for organic analyses).
6. Retain filtrate for subsequent analysis. Place in properly cleaned sample
container and preserve as required.
7. Place filter cake (i.e., solid residue) back into extraction vessel and add
1 liter of fresh distilled/deionized water.
8. Repeat steps 4 through 6.
9. Analyze the two sequential extracts separately.
Data obtained from the literature, which indicated extraction with deionized
water, was considered to have been extracted in a manner similar to this procedure.
4.2.4 Inorganic Concentrations in Extracts from MWC Ashes
Table 4-5 lists ranges of inorganic parameters (including metals) detected in extracts
produced by the deionized water extraction procedure (SW-924), EP and TCLP from
MWC fly ash; Table4-6 lists levels of inorganic parameters (including metals)
observed in such leachates produced from combined (fly and bottom) ashes as
reported in the literature and by the Versar Study. The reviewed literature
(Volume IV of this report) did not contain similar leachate information for bottom
ashes. This is probably because bottom ashes contain much lower levels of
inorganics than fly ashes and than combined ashes, as discussed in Section 2.0 and as
illustrated in Table 2-2. Thus, the assessment of the leachability of inorganics from
bottom ashes is not as significant. For comparison purposes, the EP Toxicity
Maximum Allowable Limit and the Primary Drinking Water Standards are included
in the last two columns of each table.
i
Only one published reference included data from the TCLP extractions by Fluid #1
and Fluid #2. These values are listed in Tables 4-5 and 4-6. Examination of the data
4-13
-------
TABLE 4-5
RANGES OF IMORGAWC CONCENTRATIONS IN LEACHATES
PRODUCED IV SW 924. EP. AND TCIP LEACHING PROCEDURES FROM FLY ASH. IN mg/l (ppm)
Constituent
Arsenic
iaiium
Cadmium
Chromium
Lead
Mercury
Selenium
Silver
Aluminum
Beryllium
Boron
Calcium
Cobalt
Copper
Iron
Lithium
Magnesium
Ranges of
Concentrations
SW-924
0005-0005
0 19-1 68
ND-33
00025 176
0 150.000
0 00002-0 02
0 0025-0 108
0 02 0 05
0.09-0.25
001 001
NO 2100
8964620
NDO 12
00025-1.240
00025-0 167
027038
003376
Ranges of
Concentrations
EPToxkity
0 002-0 OS
0067-228
0025-18
00025 0 135
0019-5335
NO 0007
0 003-0 085
0001-0051
0 159 188
0 005 0.005
1 53 6.53
1.150-5.810
0 025-0 1 14
0033-10.6
0.0025-0.49
02610.455
0093-149
Ranges of
TCLP
0 005 0 1 1 1
0015 172
0 0025-0.544
0025-152
0 004 0 004
000250025
000250201
0.0025 190
Ranges of Concentrations - TCLP
fluid *1
038 1 48
003-188
002-012
6 10268
002007
021-160
001 001
1 36 7 3
1,450-5.390
0030.14
0.02-1470
003017
0 25 0 55
006 171
fluid tl
05-1 86
003-203
0 02-0 03
53366
0 02-0 08
0 09 0 09
001-001
1 79-594
1,2105,070
0.03 0 06
002-108
0 03 0 03
0 28 0 53
004-1090
EP liiNicity
Maximum
Allovwable
Limit
50
1000
10
50
50
02
1.0
50
Primary
Drinking
Water
Standards
0050
1 000
0010
0050
0050
0002
0010
0050
I
^
-------
TABLE 4-5
RANGES OF INORGANIC CONCENTRATIONS IN LEACIIATES
PRODUCED BY SW-924. EP. AND TOP LEACHING PROCEDURES FROM FLY ASH. IN mg/l (ppm)
PAGE TWO
Constituent
Manganese
Molybdenum
Nickel
Potassium
Sodium
Strontium
Tin
Titanium
Vanadium
Yttrium
Zinc
Ranges oi
Concentratipns
SW924
0 0005 0 052
0 220 34
ND-420
702 2530
587-971
26-17.7
009009
0.05-0.05
0 02 0.02
005005
0.005-4 15
Ranges of
Concentrations
EPToxicity
0 005 8 03
010-0.229
0 09 2 9
6162.170
506821
35-16
0 09-0 09
0 05 0 OS
00150015
0.05005
336-768
Ranges of
TCLP
0049 14 7
00075-1 52
0151-746
Ranges of Concentrations - TCLP
Fluid II
001-7 19
0 100 28
0 09 2 48
574 2.390
474922
397 146
0 09 0 09
005-005
0 02-0 02
0 05 0 05
227-885
Fluid f 2
0.01-328
0 10031
0 09 0 63
/OB2.780
1.950 2,500
34 1730
0 09-0 09
005005
002002
0 05 0 05
384621
EP Toxicity
Maximum
Allowable
limit
Primary
Drinking
Water
Standards
en
NO - Below detection limit
Blank - Not reported
Source: Literature (Volume VI) and Versar Study (Volume V)
-------
TABLE 4-6
RANGES OF INORGANIC CONCENTRATIONS IN EXTRACTS PRODUCED BY SW-924. EP. AND TCLP
LEACHING PROCEDURES FROM COMBINED ASH. IN mg/l (ppm)
Constituent
Arsenic *
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Silver
Aluminum
Beryllium
Boron
Calcium
Cobalt
Copper
Iron
Lithium
Ranges of
Concentrations
SW-924
0.005005
0 150.39
0005003
0 0025-0 02
0025-2.98
001-0 1
00025005
ND-0.05
0 17 294
NO 0 01
0.1-0.22
122-536
001 003
000250 19
000250038
001 005
Ranges of
Concentrations
EP Toxicity
0005-0.1
0027-63
001 394
0 0059-0 46
0.02-34
NO-60
00020.10
0001-0 10
31.9-438
0 005-0.005
1 23233
77-1,740
0 050-0 057
0039-1 19
4.5-143
0063-0093
Ranges of
TCLP
0.005-0037
0.025-3.32
0.025 0 439
0 655 30 1
0 004-0.004
0 0025 0 025
.'
000250019
0828606
Ranges ol Concentrations - TCLP
Fluid 41
0.01-003
0.10-32
003-1 9
0 2-0 32
0947
0 OS 0 06
001 001
0 02-0 04
308328
0.01-001
253289
1.930 1.990
0 05-0 05
005009
183 230
009-0.10
Fluid *2
001-0 10
0 05 0 63
001-047
001-0 16
0.05 6 10
NOO 10
001-005
001-005
0 09-0.09
001-001
1.75-1 77
362-1.430
0 03-0 03
0 02-0 02
2 18633
0 06 0 06
EP Toxicity
Maximum
Allowable
Limit
50
100.0
10
50
50
02
1 0
50
Primary
Drinking
Water
Standard
0050
1 00
0010
0050
0050
0002
0010
0.050
£>.
cn
-------
TABLE 4-6
RANGES OF INORGANIC CONCENTRATIONS IN EXTRACTS
PRODUCED BY SW-924. EP. AND TOP LEACHING PROCEDURES FROM COMBINED ASM. IN mg/l (ppm)
PAGE TWO
Constituent
Magnesium
Manganese
Molybdenum
Nickel
Potassium
Sodium
Strontium
Tin
Titanium
Vanadium
Yttrium
Zinc
Chloride
Sullate
Ranges of
Concentrations
SW-924
ND-0.19
ND-0 01
0070.1
0 0075 0 09
85.2-120
68385.3
0583.19
0.02-009
001005
0 02-0 03
001 005
00015096
209-644
156571
Ranges of
Concentrations
EP Toxicity
228427
36624
0.100 10
0241-2.03
10 154
899-100
2.45-4.9
0 09 0.09
005005
00150015
0 05-0 05
38 5-726
78952
85 1.150
Ranges of
Concentrations
TCLP
42-119
0 346-0.805
233373
Ranges of Concentrations - TCLP
Fluid #1
41 7 41 8
7.04-747
o too to
0.33041
106 111
103-110
5.345.47
0.090.09
005-008
005006
0 OS 0 05
72283.2
Fluid #2
0 14279
322334
0 100 10
009009
86.5-939
1.410-1.500
394401
009009
0 05 0 05
002002
0 OS 0 OS
23.5-32
302625
260-1.450
EP Toxicity
Maximum
Allowable
Limit
Primary
Drinking
Water
Standards
^i
NO - Below detection limit
Blank - Not reported
Source: Literature (Volume IV) and Versar (Volume 0
-------
listed in Tables 4-5 and 4-6 indicates that the EP Toxicity Maximum Allowable Limit
is not met by the high range values of cadmium and lead extracted by the EP and
the TCLP tests from fly ash and combined ash. Arsenic, barium, selenium, and silver
values obtained by any of the tests from either fly ash or combined ash met the EP
Toxicity Maximum Allowable Limit. Mercury extracted from fly ash by every one of
the extraction procedures met the EP Toxicity Maximum Allowable Limit. Only one
mercury value (6.0 mg/l) ppm obtained by the EP toxicity test from combined ash did
not meet the EP Toxicity Maximum Allowable Limit. This suggests that the single
high mercury value (6.0 mg/l) was probably an anomaly. Similarly, one chromium
value, obtained when extracting fly ash with deionized water, did not meet the EP
Toxicity Maximum Allowable Limit.
The study conducted by Cahill and Newland (1982) was designed to compare
efficiencies of metal extraction from municipal incinerator ashes. In this study, also
cited and discussed in Section 2.0 of this report, batch extractions were performed
for two metals, cadmium and manganese, from refuse ash using deionized water,
0.1 N HCl, 1.0 N HO, and 6.0 N HCI. The results of this part of the Cahill and Newland
study indicated that increased amounts of cadmium and manganese were leached
-
with increasing acidity. These two metals were chosen because of their different
presumed mechanism of ash deposition during combustion (see Section 2.0 for
discussion of the volatilization-condensation reaction mechanism). Cadmium
exhibits surface predominance, whereas manganese exhibits matrix predominance.
The metals most likely to be leached are those that occur principally as surface
deposited metals. Elements with lower boiling points typically exhibit higher
extractability, whereas elements with higher boiling points show lower
extractability. A "volatilization condensation" mechanism occurs when metals,
such as cadmium and lead, volatilize in the high-temperature combustion zone of
the incinerator and then condense at lower temperatures onto the surfaces of less
volatile metals such as manganese, silicon, and aluminum. The data presented in
Tables 4-5 and 4-6 confirm these conclusions. The condensation of these metals
occurs in the oxide form which is relatively soluble in water and acids. Thus,
although these metals may be present in the raw waste in relatively insoluble forms,
after the oxidation in trie incinerator to a combination of oxides and metal salts,
their solubility in water and acids increases. Cadmium and lead are extracted by the
4-18
-------
deionized water, and the acid solutions used by the EP and TCLP, to a much higher
degree than any of the other metals.
A better understanding of these three different leaching procedures and their
actual correlation with the reality of metal leaching from MWC ashes can be
obtained by reviewing the following paragraphs, which summarize the data
obtained from the two EPA-sponsored studies, the Versar and NUS studies
(described in detail in Volume V and Volume VI of this report).
In the Versar study, leachates prepared by EP, TCLP, and SW-924 were analyzed for
the following metals: cadmium, (Cd), chromium (Cr), copper (Cu), iron (Fe), lead
(Pb), manganese (Mn), nickel (Ni), zinc (Zn), arsenic (As), selenium (Se), and mercury
(Hg). The results of these analyses are tabulated by sample matrix, facility, and
leachate procedure in Table 4-7. The MWEP method yielded two extracts from each
laboratory extract composite sample. These extracts are listed in Table 4-7 as EX1
(i.e., Extraction 1) and EX2 (i.e., Extraction 2).
Tables 2-3 and 2-4 respectively list the characteristics of the sampled incinerators
and the sampled monofills. A review of Table 4-7 indicates the following:
The variability between extraction procedures and sample matrices appears
to be much greater than the variability between facilities.
Zinc, iron, lead, and manganese were present in the highest concentrations
in the extracts, whereas mercury was not present in any of the extracts.
A comparison between the different extraction procedures as provided by Table 4-7
indicates the following:
The EP and TCLP extraction methods were much more aggressive than the
MWEP for leaching every metal, except selenium. In fact, the MWEP
method was the only extraction procedure that leached selenium. Data
obtained from the literature (Volume IV), Tables 4-5 and 4-6, indicate that
deionized water leached metals.
4-19
-------
TABLE 4-7
EXTRACTABLE METALS DATA FOR
THREE LABORATORY LEACHING PROCEDURES, VERSAR STUDY
LMCtUtt
Srolt
Jroctdur* F«ci lity NitrU
EP To*
rap
SW24-X1
SW24-EX2
EP To*
Tap
SW24-EX1
SW24-EJ2
EP Tox
Tap
5W24-CI1
SW24-O2
EP Toi
rap
S*924-£X1
W24-JX2
EP To,
£P To,
Tap
rap
a"24.£Xl
S*924.£X1
!l«24-£«
*924-£X2
0 To»
TOP
"'24.£ji
*24.£X2
C» To,
ra.p
*W4-£xi
*«««
»T0,
W To,
OP
* TCLP
&o**"?Xl
j]!!4"**1
***S
A
A
A
A
C
c
c
c
0
0
0
0
B
B
B
B
A
A
*
A
A
A
A
A
8
B
8
B
;
C
C
c
0
0
a
3
0
0
0
0
BottM/Fly
BettOM/Fly
SOttM/Fly
BottOB/Fly
BOttoWFly
SottOB/Fly
BottON/Fly
BOttOO/Fly
Bottom/Fly
SottOMVFly
Bottom/Fly
8otto«/F]y
Bottai
Sot to*
Bottom
Bottom
.My
Fly (Oup.)
Fly
Fly (Oup.;
Fly
Fly (Oup.)
Fly
Fly (Oup.)
Fly
Fly
F'y
Fly
Fly
Fly
Fly
Fly
Fly
Fly (Oup.)
My
Fly (Dup.)
Fly
F'.y (Oup.J
Fly
Fly (Quo.)
Cd
9/1
0.327
0.683
-0.01
-0.01
0.060
3.32
-0.01
-0.01
0.649
0.325
-0.01
-0.31
0.388
0.418
<0.01
-0.01
6.02
7.72
0.015
0.032
-0.015
-0.01
-0.01
-4.01
18.0
17.2
-0.01
0.033
7.89
8.36
0.122
-0.01
8.60
9.18
10.3
3.90
0.015
"<0.01
<0.31
<0.31
Cr Cu F«
J/L og/L ag/L
0.016 1.19 4.50
0.096 0.019 60. S
-0.005 <0.005 -0.005
-0.005 -0.005 -0.005
0.0059 0.039 143
-0.005 0.0076 23.4
-0.005 0.023 0.038
-4.005 -0.005 0.015
0.033 0.051 66.4
-0.005 -0.005 0.828
0.005 0.070 -0.005
-0.005 0.009 0.01
3.150 0.127 21.0
0.439 0.018 52.8
-O.OOS 0.0089 -0.005
-O.OOS -O.OOS 0.024
'-O.OOS 0.045 -0.005
-O.OOS 3.254 0.007
0.136 -0.005 190
-0.005 O.:i6 -4.005
0.010 0.027 0.167
-O.OOS 0.089 -4.005
-0.005 0.009 0.057
-0.005 -4.005 -4.005
-0.005 0.171 0.060
-0.005 0.078 0.019
0.0086 -0.005 -0.305
0.01 0.012 0.118
0.038 1.62 0.490
0.129 0.201 34.2
3.3060 0.045 3.067
-0.005 -O.OOS -0.005
-O.OOS 0.041 0.012
-0.005 0.131 0.3074
0.487 0.013 12.3
0.544 0.0059 15.3
0.071 3.0052 <0.305
3.114 0.0051 -0.005
0.115 -0.005 -0.005
0.15 -0.005 -0.305
Pb
1/1
20.3
16.3
-o.os
-0.05
2.39
7.30
0.063
-0.05
7.26
0.65S
-O.OS
-0.05
34.3
30.1
-0.35
-4.35
4.72
10.3
0.962
-------
TABLE 4-7
EXTRACTABLE METALS DATA FOR
THREE LABORATORY LEACHING PROCEDURES, VERSAR STUDY
PAGE TWO
LMcnatt Sana It
ProctOurt Typ«
1? fox Confcined
tottoM/
fly AsA
TCIP COM into
8otto»/
Fly Ash
SH 924 Caaintd
utrict 1 Bottom/
Fly Asfl
S* 924 Cottlrtd
Eitric: 2 Bottom/
Fly ASH
Sf Te« ?iy Asn
TO.P F !y Asft
* 924 riy A,n
Strict :
* «4 Fiy Mft
'"let 2
January
Statistics
Mtn.
HU.
Av,.
Std OM
Nin.
««x.
Avc.
Std 0«v
Hin.
NU.
Av,.
Std Otv
Htn.
«4x.
Avq.
Std Otv
Mm.
K4X.
Avc.
Scd 0«v
H'n.
H«x.
Avc.
Std Otv
Hin.
Wx.
AVC.
Std 3tv
Hin.
w*.
Avg.
Std Otv
Cd
flg/L
0.06
0.32?
9.481
0.289
0.025
3.32
1.111
1.296
9.005
9.905
9.005
0.000
O.OOS
9.005
0.005
0.000
6.32
13
9.553
3.395
0.015
17.2
7.468
5.006
9.006
9.122
0.027
0.043
0.005
0.033
0.010
0.010
Cr
BA
0.0059
0.15
O.OS1
O.OM
0.0025
0.439
0.135
0.180
0.0025
0.005
0.003
0.001
0.0025
0.0025
0.003
0.000
0.0025
0.038
0.003
0.013
0.0025
0.544
0.217
0.218
0.0025
0.114
0.03S
0.042
0.002S
0.15
0.047
0.061
Cu
H/l
0.039
1.19
0.353
0.48S
0.0025
0.019
0.012
0.007
0.0025
0.07
0.028
0.02S
0.0025
0.009
0.004
0.003
0.041
1.52
0.377
0.561
0.0025
0.201
0.970
0.072
0.0025
0.989
0.029
0.931
3.0025
0.912
0.005
9.904
Ft
«gA
4.5
143
SI. 725
53.677
0.828
60.6
34.407
23.338
0.0025
0.038
0.011
0.915
.0.0025
0.024
0.013
0.308
0.0025
0.49
0.096
0.177
0.0025
190
42.004
67.172
0.3025
0.167
0.941
9.0S1
9.0025
3.118
0.031
0.344
J>6
nj/L
2.09
34
16.038
12.419
0.655
30.1
13.589
11.032
9.025
9.063
0.035
0.016
0.025
0.025
0.025
0.000
4.72
25.2
16.237
6.654
0.025
15.2
8.216
6.029
0.025
0.128
0.044
0.038
0.02S
9.148
0.953
9.046
ttfl
JA
3.6
6.24
4.525
1.014
4.2
11.9
7.525
2.775
0.0005
0.9021
0.001
0.001
0.9005
0.3012
0.001
0.000
2.71
3.33
6.058
1.337
0.049
14.7
7.013
S.315
9.0005
0.014
0.005
0.004
0.0005
9.0052
0.002
9.002
N1
«gA
0.241
0.415
0.311
0.071
0.346
0.805
0.549
0.168
0.0075
0.0075
0.008
0.000
0.0075
0.0075
0.008
0.000
0.137
1.92
0.570
0.611
0.0075
1.52
0.521
0.498
0
0.022
0.009
0.307
0.0075
0.0075
0.008
0.300
Zn
ngVL
38.5
726
221. ISO
291.610
23.3
373
133.825
139.706
0.0015
0.067
0.018
0.028
0.0031
0.051
0.019
0.020
186
726
404.000
171.624
9.151
746
361.459
271.582
0.926
1.22
0.256
3.435
0.0015
1.2
0.221
0.439
AS
nj/L
O.OOS
O.OOS
9. DOS
9.000
O.OOS
0.037
0.017
0.013
O.OOS
O.OOS
O.OOS
0.000
O.OOS
O.OOS
O.OOS
9.000
O.OOS
O.OOS
0.005
0.000
O.OOS
0.111
0.045
0.040
0.005
O.OOS
O.OOS
0.000
O.OOS
O.OOS
0.005
0.000
UM C*
no jv
*/l «q/L
0.904 9.025
0.004 3.025
0.004 9.025
0.000 0.000
0.004 0.002S
0.004 0.025
0.004 0.019
0.000 0.010
0.01 0.0025
0.01 0.025
0.010 0.011
0.000 0.009
0.01 9.0025
0.01 0.9025
0.010 0.003
0.000 0.000
0.004 0.025
0.004 0.025
0.004 0.025
0.000 0.000
0.004 0.0025
0.004 0.325
0.004 3.01?
0.000 0.009
9.01 0.0025
0.02 0.108
0.012 0.039
0.004 0.034
0.01 0.0025
0.01 0.0125
0.010 0.009
0.000 0.005
4-21
-------
TABLE 4-7
EXTRACTABLE METALS DATA FOR
THREE LABORATORY LEACHING PROCEDURES, VERSAR STUDY
PAGE THREE
LEGEND:
EP TOX - EP TQXICin extraction procedure
TO.P TOTAL CHARACTERISTIC LEACHATE PROCEDURE
SW 924 Procedure for «st1»»t1ng «onof111ed solid waste leacnate conswsition
SW 924 EX1 First utract using SW 924 procedure
SW 924 EX2 Second txtract (on tim sam taoDle) using SW 924 procedure
Bottom/Fly coitineC bottom ash and fly ash
Fly - Fly «n
Bottoa - BottM asn
Quo. Duplicate (split) of tht previous saiple
Source: Versar Study (Volume V)
4-22
-------
The EP method appeared to extract copper and zinc more vigorously than
the TCLP method, whereas the TCLP method extracted chromium, iron,
manganese, nickel, and arsenic more aggressively than the EP method. In
fact, the TCLP method was the only one to extract arsenic. The extraction
efficiencies of EP and TCLP were approximately equal for cadmium, lead,
and zinc.
The concentrations of metals in SW-924-EX1 were generally greater than
those in SW-924-EX2.
In the NUS Study, two fresh ash samples were collected from two codisposal
facilities as they were arriving for disposal (NY and NC). These ashes were leached
by the same methods as the Versar Study. Results for these two ashes samples are
reported in detail in Volume VI of this report and in Tables 4-8 and 4-9, respectively.
For comparison, the EP Toxicity Maximum Allowable Limit and the Primary Drinking
Water Standards are given in the last two columns of each table.
Examination of the data presented in these two tables indicates that all EP Toxicity
Maximum Allowable Limits were met except for lead. In one ash sample (NC), the
EP Toxicity Maximum Allowable Limit of 5 mg/l (ppm) was not met by any of the
three leaching methods, and in fact, exceeded it many folds. The lead levels were
49 mg/l (ppm) (EP), 240 mg/l (ppm) (TCLP), and 75 mg/l (ppm) (SW-924). For the
second ash (NY) sample, the EP toxicity leachate for lead was only 3.17 mg/l (ppm).
Comparison of the aggressiveness of the leaching process between the EP and the
TCLP indicates that for one ash (NC) sample, the TCLP leached consistently higher
levels of metals, while for the second ash (NY) sample, the EP toxicity leaching
procedures leached higher levels of cadmium and barium.
Comparison between inorganics in actual leachates from codisposal sites and
monofills (Section 4.1) and in extracts produced by leaching procedures (Section 4.2)
indicates that the levels of inorganic constituents, including metals in actual natural
leachates were always lower than in leachates produced in the laboratory. The
actual leachates always met the EP Toxicity Maximum Allowable Limits. The
test-generated leachates, as discussed previously in this section, did not meet the EP
Toxicity Maximum Allowable Limit for lead.
4-23
-------
TABLE 4-8
INORGANIC CONTENT IN NY ASHES
AND IN EP TOXIQTY, TCLP, AND SW-924
EXTRACTS. IN PPM
Contaminant
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Manganese
Mercury
Nickel
Selenium
Zinc
Barium
Silver
Ash
11.4
14.8
55.2
226
18,900
630
508
0.10
144
<5
1,510
-
-
EPToxicity
<0.02
0.195
<0.02
NO
NO
3.17
NO
<0.02
NO
<0.05
NO
0.832
<0.02
TCLP
0.203
0.155
0.270
NO
NO
9.58
NO
< 0.002
NO
<0.025
NO
0.633
<0.02
SW-924
Insufficient
Sample
EP Toxicity
Maximum
Allowable
Limit
5.0
1.0
5.0
5.0
0.2
1.0
100
5.0
Primary
Drinking
Water
Standards
0.050
0.010
0.050
0.050
0.002
0.010
0.100
0.050
NO - Below the detection limit
Source: NUS Study (Volume VI)
4-24
-------
TABLE 4-9
INORGANIC CONTENT IN NCASH
AND IN EP TOXIdTY. TCLP. AND SW-924
EXTRACTS, IN PPM
Contaminant
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Manganese
Mercury
Nickel
Selenium
Zinc
Barium
Silver
Ash
19.6
8.6
28.2
5,100
11,900
3,240
352
3.8
498
<5
3,750
NO
NO
EPToxicity
0.049
0.275
0.043
NO
NO
48.8
NO
<0.002
NO
<0.05
NO
0.820
<0.02
TCLP
0.169
0.384
<0.1
NO
NO
240
NO
0.044
NO
<0.025
NO
0.924
<0.1
SW-924
0.026
<0.02
<0.02
NO
NO
75.4
NO
< 0.002
NO
< 0.005
NO
3.29
<0.02
EP Toxicity
Maximum
Allowable
Limit
5.0
1.0
5.0
5.0
0.2
1.0
100.0
5.0
Primary
Drinking
Water
Standards
0.050
0.010
0.050
0.050
0.002
0.010
0.100
0.050
NO Selow the detection limit
Source: NUS Study (Volume VI)
4-25
-------
Actual leachates from many MSW disposal sites, as reported in the literature and
discussed as summarized in Table 4-1, also periodically did not meet the EPToxicity
Maximum Allowable Limit.
A recently published, EPA-sponsored study (SAIC) describes the collection of
leachates from thirteen carefully selected hazardous waste disposal sites.
Inorganics detected in the leachates from these hazardous waste sites were at much
higher concentrations than in the leachates collected from the four municipal waste
disposal sites, from the two NUS study codisposal sites (Volume VI), and from the
Versar study monofills (Volume V).
4-26
-------
5.0 ORGANICS IN LEACHATES FROM MSW DISPOSAL SITES,
CODISPOSAL SITES, AND MONOFILLS AS WELL AS IN EXTRACTS
5.1 ORGANICS IN LEACHATES FROM MSW AND CODISPOSAL SITES
Tables 5-1 and 5-2 list ranges of organic compounds found in leachates collected
from MSW disposal sites, as reported in the literature (Volumes II and III of this
report). For comparison, the results obtained from the NUS study, where thirteen
leachate samples collected from four MSW disposal sites and six leachate samples
collected from two codisposal sites were analyzed for the entire list of Appendix IX
compounds, are given in the last two columns of each table. The data presented in
the last two columns were extracted from Volume VI of this report.
Examination of the data presented in these two tables indkates that numerous
organic compounds, including many known or suspected carcinogens, are found in
leachates from MSW disposal sites as reported in the literature.
The NUS sampling data used in this study originated from four MSW facilities and
two codisposal facilities, none of which accepted industrial waste. All six facilities
went into operation after RCRA was promulgated. For this reason, these data are
by no means representative of MSW landfills in general.
The sites sampled by NUS, both the MSW and the codisposal sites, contained fewer
compounds, and the compounds detected were present at significantly lower
concentrations. Two probable reasons for this occurrence are that the selected sites
were all constructed after RCRA regulations were enacted and that the selected
sites do not accept industrial wastes for disposal.
Organic compound levels in leachates from the NUS-selected municipal disposal
sites do not differ significantly from those collected from the codisposal sites.
5-1
-------
TABLE 5-1
CONCENTRATIONS OF ORGANIC CONSTITUENTS
IN LEACHATE FROM MUNICIPAL WASTE LANDFILLS, IN yg/l (ppb)
Constituent
Acetone
Benzene
Bromomethane
1-3utanol
Carbon tetrachloride
Chlorobenzene
Chloroethane
Bis(2-Chloroethoxy)methane
Chloroform
Chlorom«than«
Delta BHC
Dibromomethane
1.,4-Dichiorobenzene
Dichlorodifluoromethane
1,1-Dichloroethane
1 ,2-Oichloroethane
Gs-1,2-0ichloroeth«n*
Trans- 1,2-Dichloroethene
Dichloromethane
1 ,2-Dichloropropane
Di ethyl phthalate
Dimethyl phthalate
Di-n-butyl phthalate
Endrin
Ethyl acetate
Range*
140-11,000
2-6,080
10-170
50-360
2-398
2-237
5-860
2-2S
2-1,300
10-170
0-5
5-25
2-37
1 0-450 ~
2-6,300
0-11,000
4-190
4-2,760
2-3,300
2-100
2-330
4-55
4-150
0-1
5-50
NUS Municipal
4-4,600
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND-16
ND
ND
ND
ND-230
ND
ND
ND-23
ND
ND
NUS Codisposal
ND- 1,500
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND-250
ND
5-2
-------
TABLE 5-1
CONCENTRATIONS OF ORGANIC CONSTITUENTS
IN LEACHATE FROM MUNICIPAL WASTE LANDFILLS, IN ug/l (ppb)
PAGE TWO
Constituent
Ethyl benzene
8is(2-ethylhexyl) phthalate
lsophor»ne
Methyl ethyl ketone
Methyl isobutyl ketone
Naphthalene
Nitrobenzene
4-Nitrophenol
Pentachlorophenol
Phenol
2-Propanol
1 , 1 ,2.2-Tetrachloroethane
Tetrachloroethene
Tetrahydrofuran
Toluene
Toxaphene
1,1,1-Trichloroethane
1 , 1 ,2-Trichloroethane
Trichloroethene
Trichlorofluoromethane
Vinyl chloride
m-Xylene
p-Xylene + o-Xylene
Range*
5-4,900
6-150
10-16,000
110-28,000
10-660
4-68
2-120
17-40
3-470
10-28.800
94-10,000
7-210
2-620
5-260
2-3,200
0-5
0-2,400
2-500
1-1,120
4-100
0-110
21-79
12-50
NUS Municipal
NO
ND
NO
290-12.000
NO
ND
NO
ND
ND
ND-2,100
NO
ND
ND
ND
ND-1,100
ND-16
ND
ND
ND
ND-230
ND
ND
ND-23
NUS Codisposal
ND-15
ND
ND
ND-2,200
ND
ND
ND
NO
ND
ND-2.100
' "NO
ND
ND
ND
ND-120
ND
ND
NO
ND
ND
ND
ND
ND-290
*Source: Sobotka and Wisconsin Studies described and referenced in Literature
Reviews Volumes II and III.
ND a Below detection limit
5-3
-------
TABLE 5-2
CONTAMINANT CONCENTRATIONS FROM
LEACHATE OF MUNICIPAL LANDFILLS AND CODISPOSAL SITES
(Concentration in mg/l) (ppm)
Parameter
Benzene^)
Butanol<*>
Chlorobenzene
Cis-l,2-0ichloroethylene
1 , 1-0ichloroethane<*>
1,2-Oichloroethane
1 ,2-Dichlorobenzene
1 ,4-Oichlorobenzene<*>
Dichloromethane<*>
1 ,2-Dichloropropane
EthanoK*)
Ethyl Acetate
Ethyl Benzene
Methyl Ethyl Ketone
Methyl Isobutyl Ketone
1-Propanol
2-PropanoKa>
Tetrachloroethylene
Tetrahydrofuran
Toluene
Trans- 1 ,2-Oichloroethylene<»)
Trichloro«thane<*>
Trichloroethylene<*>
Xylene
Lyon*
Municipal
Landfill
0.036
25
0.046
0.019
0.200
0.002
110.
0.290
0.015
0.650
0.087
37.
41.
0.280
0.180
0.0038
0.0076
0.043
0.092
Meeker-
Municipal
Landfill
0.270
0.120
0.060
0.190
0.035
0.032
0.064
0.013
0.018 "
0.820
9.8
0.410
0.076
1.9
0.140
0.390
0.017
0.043
0.32
Rochester"
Municipal
Landfill
0.54
10.
0.47
0.026
0.006
0.010
0.014
1.3
0.081
23.
0.130
0.250
27.
0.710
11.
26.
0.250
0.430
0.6
0.088
0.125
0.198
NUS
Municipal
Sites
ND-0.004
ND-0.016
NO
ND-12.0
ND-1.1
NO
NUS
Codisposal
Sites
NO
NO
ND-0.015
ND-2.2
ND-0.12
ND-0.29
* Source: Texas A&M University Report discussed and described in Volume I
(a) s Potential carcinogens
NO = Below detection l
5-4
-------
5.2 ORGANICS IN LEACHATES FROM MONOF1LLS
Volume V of this report, the Versar Study, reported levels of organics in leachates
collected from monofills. Table 5-3 summarizes the findings of this report in terms
of compounds and concentrations. The number of times each compound was
detected has also been reported in this table. Analyses were carried out for TOC,
organic scan, and BNAs.
The quench water collected at each of the four sampled facilities contained a larger
number of organic compounds and at significantly higher concentrations. The
quench water contained phenol; 2-methyl phenol; 4-methyl phenol; dimethyl
phenol; benzoicacid; naphthalene; acenaphthalene; phenantrene; butyl phthalate
fluoranthene; pyrene; bis(ethylhexyl)phthalate; methyl butanoic acid;
1,2,4-trithiolane; 2-hydroxy benzoic acid; 4-hydroxy-4-methyl-2-pentanone; 1H;
3H-naphtho (1,8-cd) pyran-1,3-dion; 3-hydroxy-2methyl 4H pyran-4-one; hexanoic
acid; methyl pentanoic acid; benzaldehyde; methyl pentanediol;
5-(hydroxymethyl)-2-2-furancarboxaldehyde; benzene propanoic acid; tetra
decanoic acid; 2,2,4-trimethyl 1,3-purine dione; benzene acetic acid; and decanoic
acid. Table 5-4 summarizes the levels of these organics in quench water, field
leachates, and groundwater samples collected by Versar at monofills.
5.3 ORGANICS IN EXTRACTS FROM MWC ASHES
The EPA-sponsored Versar and NUS studies reported organic compounds in extracts
generated in the laboratory by the EP, TCLP, or any other tests. These are reported
in detail in Volumes V a'nd VI of this report.
The ashes collected by NUS were leached by Versar in the same manner the Versar
collected samples were leached. Analyses were conducted by Versar, as well. The
Versar study has produced leachates which contained some base-neutral and acid
extractables, as reported in Tables 5-5 through 5-7. The NUS ashes produced
extracts that did not contain any of the base-neutral and acid extractable (BNA)
compounds above the detection limits.
5-5
-------
TABLE 5-3
RANGES OF LEACHATE CONCENTRATIONS OF ORGANICS FROM
MUNICIPAL SOLID WASTE INCINERATOR RESIDUES (MONORLLS)
DETERMINED FROM ACTUAL LEACHATE FIELD SAMPLES IN mg/l (ppm)
Constituents
Ethyl Hexyl Phthalate'
Dimethyl Propane Diol2
Biphenyl
Hexa Tiepane3
Thiolane4
Benzaldehyde
Sulfonylbis sulfur
Number of Samples
Range of
Concentration
NO -0.08
ND-0.120
ND-0.051
ND -0.082
ND - 0.400
ND - 0.008
ND- 0.011
9
Number of
Times Found*
4 out of 9
4 out of 9
2 out of 9
1 out of 9
2 out of 9
1 out of 9
1 out of 9
ND = Below Detection Limit
Source: Versar Study (Volume V)
1
2
3
4
Bis(2-ethyl HexyOphthalate (CAS 117-81-7)
2,2-Dinethyl-1,3-propanediat (CAS 126-30-7)
Hexathiepane (CAS 17233-71-5)
1,2,4-Trithiolane (CAS 289-16-7)
*Above Detection Limit
5-6
-------
TABLE 5-4
ORGANIC CONSTITUENTS IN FIELD WATER SAMPLES
FltlD IEAO4ATES
Ethyl Olmttnyl
Plant
a
8
9
c
c
c
0
3
0
Plant
a
a
a
c
c
c
0
0
0
Sample
Description
East Side
Northeast Corner
North Side
Northwest Corner
Northeast Corner
North Side
Southeast Corner
Northeast Corner
Northeast Corner, Quo
NO.
Kin.
Max.
Avg.
Std. Oev.
Saoole
Description
East Side
Northeast Corner
North Side
Northwest Corner
Northeast Corner
North Side
Southern Corner
Northeast Corner
Northeast Corner. Oup
NO.
Mln.
.>
-------
TABLE 5-4
ORGANIC CONSTITUENTS IN FIELD WATER SAMPLES
PAGE TWO
QUENCH HATES
Plant
A
A
a
9 '
a
c
c
0
3
0
Plant
A
A
8
8
8
C
C
0
0
0
$4*0 le
Description
Unit 2. 9/28
Unit 1. 9/28
Unit 3. 9/28
jntt 4. 9/28. Quo
Unit 4, 9/28
Unit 2. 9/26
Jntt 2. 9/30
Unit 2. 10/3
Unit 2. 10/3. Oup
Jntt 2. 10/4
M.
Mtn.
W»*.
Avg.
Sto. Oev.
Sarnie
Description
Unit 2. 9/28
Unit 1. 9/25
Unit 3. 9/28
Unit 4. 9/28. Oup
Unit 4. 9/28
unit 2. 9/28
Unit 2. 9/30
Unit 2. 10/3
unit 2. 10/3. Quo
Unit 2. 10/4
NO.
*1n.
*u.
Avg.
Stfl. 3ev.
TOC
(9/1)
94.5
26.9
77.3
421.0
418.5
3.2
29.2
165.9
153.3
1228.3
10
3.2
1228
261.5
352.4
Actnapn.
tnyiene
208968
(ug/L)
J
1
S
$
5.0
o.'o
Organic
Scan
<«/!)
<0.25
-0.25
<0.2S
<0.2S
<0.2S
12.3
<0.25
<0.25
<0.2S
j
0.125
12.3
1.48
3.13
Pnenan-
tnrtne
85018
(ug/L)
5
I
9
$
5.3
3.3
BHA
Ptats
Found
(HO.)
29
8
23
20
20
5
25
25
25
9
S
29
20.0
7.7
Butyl
Pntnalate
84742
(ug/L)
3
1
3
3
3.0
0.9
Phenol
108952
(ug/L)
65
170
380
380
60
71
640
7
50
540
252.3
205.2
Fluor.
antnene
206440
(ug/L)
S
1
S
6
8.9
0.3
<-n»oiyi
gnenol
95487
(ug/L)
8
17
40
44
7
7
86
7
5
86
29.6
27.3
Pyrtne
129000
(ug/L)
5
1
S
S
5.0
0.0
«-««uiyi
pnenol
106445
(ug/L)
92
94
23
3
23
94
69.7
33.0
Ethyl
Hexyl
Phtnalate
117817
(ug/L)
3
1
3
3
8.0
0.0
pnenol
10S679
(ug/L)
44
1
44
44
44.0
0.0
Netnyl
Sutanotc
Add
116530
(ug/L)
33
1
33
33
33.0
9.0
MIUO1C
Acid
65850
(ug/L)
36
260
300
2100
2100
S70
900
3800
8
36
3800
1258.3
1219.0
Molecular
Sulfur
10544500
(ug/L)
29
130
2
29
130
?9.5
S3. 5
mpnini-
iene
91203
(ug/L)
3
1
8
a
9.0
0.0
.^
Th 10 lane
289167
(ug/L)
23
1
23
23
23.0
0.3
5-8
-------
TABLE 5-4
ORGANIC CONSTITUENTS IN FIELD WATER SAMPLES
PAGE THREE
Plant
A
A
9
a
9
C
C
0
0
0
QUENCH MTEX
SMI a
Oa»cr(pt1on
Unit 2. 9/26
Unit 1. 9/26
Unit 3. 9/28
unit 4, 9/28. Quo
Unit 4. 9/28
Unit 2. 9/28
Unit 2. 9/30
unit 2. 10/3
unit 2. 10/3. Dup
unit 2. 10/4
10.
run.
lax.
Avg.
Stl. Oav.
2-Hydroi Hydroxy
ftmmnif Itofflvl
Acid Pantanon*
69727 30717
(ug/U («g/L)
40 26
50
42
3 I
40 26
SO 26
44.3 26.0
4.3 0.0
Pyran Hydroxy
lagntho Natnyl
01 on* Pyranona
81845 118718
(ug/l) (ug/L)
6 U
130
1 2
6 U
6 130
6.0 70.5
0.0 59.5
Hvdro
Pyranon*
542280
(ug/L)
u
1
11
11
11.0
0.0
Maxanolc
Acid
142821
(ug/U
22
10
30
sa
37
45
SI
920
8
10
920
148.6
292.7
Matnyl
Panunoic
Acid
646071
(ug/L)
i;
34
38
3
17
as
63.0
32.6
Sant-
aldanyd*
100527
(«g/L)
22
1
22
22
22.0
0.3
Hatftyl
Pentana-
d1o!
144194
(ug/L)
17
1
17
17
17.0
0.0
Plant
A
A
3
8
a
c
c
0
0
0
SMDla
Catenation
Unit 2. 9/28
Unit 1. 9/28
Unit 3. 9/28
Unit «, 9/28. Oup
Unit 4. 9/28
Unit 2. 9/28
Unit 2. 9/30
Unit 2. 10/3
Unit 2. 10/3. Oup
unit 2. 10/4
Furan Struana. Tatrm natty I
CarMi- Procanolc Oacanole Purina
aldaflyd* A
-------
TABLE 5-4
ORGANIC CONSTITUENTS IN FIELD WATER SAMPLES
PAGE FOUR
Plant
A
8
C
C
C
C
GBOUNOMTO
Saoplt
Otjcnption
»2
13
117
M
Production
No.
din.
Ma*.
Aug.
Std.
TOC
(«9/l)
3.4
2.7
30.9
75.1
97.4
2.9
S
2
97.4
43.75
41.56
Organic
Scan
(«B/D
«0.2S
«0.23
«0.25
«fl.2S
<0.2S
<0.25
Ethyl
MA Htzyl
Peaks Phtlwlatt
round U7817 Unknowns
(No.) (ug/L) (*)
IMTE:
of organic eonstltutnti abbrtviatad:
"XAS nucMrs providtd «ltn comtltuant nans
5-10
-------
TABLE 5-5
RANGES OF EXTRACT CONCENTRATIONS OF ORGANIC CONSTITUENTS
FROM MUNICIPAL WASTE INCINERATOR BOTTOM ASH
FOR THREE LEACHING PROCEDURES (in mg/l) (ppm)
Constituents
Naphthalene
Methyl Naphthalene
Dimethyl Prodiol'
Methyoxy Ethane*
Phenol
E. Dim Dioxane3
BisOxy Ethanol4
Oleyl Alcohols
Ethoxy Ethanol 6
Cycloocta Oecone7
M. Furan Dione*
BenzoicAcid
Range of Concentrations
Deionized Water
Extraction Procedure
First Extraction
ND
NO
ND
ND-0.010
ND- 0.028
ND
ND
ND
ND
ND-0.150
ND- 0.006
ND- 0.046
Second Extraction
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Extraction
Procedure
ND
ND
ND
ND-0.012
ND
ND
ND
ND
ND
ND
ND
ND
Toxic Characteristic
Leaching Procedure
ND
ND
ND
ND- 0.022
ND
ND
ND
ND
ND
ND
ND
ND
ND = Below Detection Limit
1 2,2-dimethyl-1,3-propanediool (CAS 126-30-7)
2 1-methoxy-2-(methoxmethoxy) Ethane (9C1) (CAS 77498-88-7)
3 5-ethyl-2,2-dimethyl-1,3-Dioxane(9C1) (CAS 25796-26-3)
4 2,2-[1,2-«thanediglibis (oxy) bix-bis] Ethanol (CAS 112-27-6)
5 (2)-9 Octadecen-1 -01 (CAS 143-28-2)
6 2-(2-(ethenyloxy)ethonxy)-£thanol (CAS 929-37-3)
7 1,4,7,10,13,16-Hexaoxacyclooctodecane (CAS 17455-13-9)
8 3,4-dimethyl-2,5-Furadione (9C1) (CAS 766-39-2)
5-11
-------
TABLE 5-6
RANGES OF EXTRACT CONCENTRATIONS OF ORGANIC CONSTITUENTS
FROM MUNICIPAL WASTE INCINERATOR COMBINED FLY AND BOTTOM ASH
FOR THREE LEACHING PROCEDURES IN mg/l (ppm)
Constituents
Naphthalene
Methyl Naphthalene
Oleyl AlcohoP
Methyoxy Ethane*
Methoxy Ethanol
Dimethyl Propdiol3
Phenol
Bis Oxy Ethanol4
Ethoxy Ethanol 5
Cycloocta Decone6
M. Furan Dione7
E. Dim Oioxane3
Benz, Di Carboxy A
Range of Concentrations
Deioni zed Water
Extraction Procedure
First Extraction
NO
NO -0.080
NO -0.088
NO
NO
ND-0.160
NO
NO -0.096
ND-0.310
NO -0.580
NO
ND-0.510
NO
Second Extraction
NO
NO
NO
ND
NO -0.006
ND-O.UO
ND- 0.033
ND- 0.018 "
ND- 0.390
ND- 1.2
ND
NO
ND- 0.002
Extraction
Procedure
Test
ND-a
ND-18
ND
ND
NO
ND-0.190
ND
ND
ND
ND
ND
ND
ND
Toxic Characteristic
Leaching Procedure
ND
ND
ND
ND
ND-0.013
ND-O.UO
ND
ND
ND
ND
ND
ND
ND
ND s Below Detection Limit
Source: Versar Study (Volume V)
1 (2)-9 Octadecen -1 -01 (CAS 143-28-2)
2 1 -Methoxy -2- (methoxy methoxy) Ethane (9C1) (CAS 74498-88-7)
3 2.2-Di methyl-1,3-Propanedial (CAS 162-30-7)
4 2,2-{1,2-Etharediylbis(oxy) bis-] ethanol (CAS 112-27-6)
5 (2)-9 Octadecer-1-01 (CAS 143-28-2)
6 1,4,7,10,13,16-Hexaoxa cycloocta decane (CAS 17455-13-9)
7 3,4-Dimethyl-2,5-Furadione (9C1) (CAS 766-39-2)
8 5-Ethyi-2,2-dimethyl-1,3-Oioxane(9C1) (CAS 25796-26-3)
5-12
-------
TABLE 5-7
RANGES OF EXTRACT CONCENTRATIONS OF ORGANIC CONSTITUENTS
FROM MUNICIPAL WASTE INCINERATOR FLY ASH
FOR THREE LEACHING EXTRACTION PROCEDURES in mg/l (ppm)
Constituents
Naphthalene
Methyl Naphthalene
Dimethyl Prodiol1
Methyoxy Ethane^
Methoxy Ethanol
Range of Concentrations
Deionized Water Extraction
Procedure
First Extract! on
NO
NO
NO
NO
NO
Second Extraction
NO
NO
NO
ND
NO
Extraction
Procedure Test
ND
ND
ND
ND
ND
Toxic Characteristic
Leaching Procedure
ND
ND
ND
ND-0.01
ND-0.01
ND s Below Detection Limit
Source: Versar Study (Volume V)
1 2.2-dimethyl-1,3-propanedial (CAS 125-30-7)
2 l-methoxy-2-(methoxy methoxy) Ethane (9CI) CAS 74498-88-7)
5-13
-------
Examination of the Versar data reported in Tables 5-5 through 5-7 indicates that the
results for the EP-prepared extracts showed that similar BNAs were detected in
samples from each facility with approximately equal concentrations. Furthermore,
every EP extract that had a quantifiable SNA-contained diethylphthalate, which was
the predominant BNA. Phthalate esters, such as diethyl phthalate, are common
plasticizers. This fact was also noted in the laboratory leachate blank samples and
therefore may represent a background interference. The BNAs appeared to be
slightly more abundant in the bottom/fly ash than in the fly ash. This is consistent
with the observation that phthalate compounds were detected in the Versar-
sampled bottom ash samples rather than fly ash samples (see Section 2.0).
A review of the TCLP-prepared leachate results showed the same trends described
above for the EP-prepared extracts.
The results presented in Tables 5-3 through 5-7 for the SW-924 extracts showed that
there was not a predominant BNA compound, that the bottom/fly ash and bottom
ash contained slightly more leachable BNAs than the fly ash, and that there was
essentially no difference between the first and second SW-924 extractions.
Upon comparing the results from the three different leaching procedures, the
following observations were noted. First, the TCLP method appears to be more
efficient for extracting BNAs than the EP method. However, for the compounds
that were extracted by both procedures (e.g., diethylphthalate), the concentrations
were approximately equal. Second, the extraction efficiency for SW-924 procedure
appears to lie between the EP and TCLP methods. However, SW-924 procedures
extracted totally different classes of BNA constituents than the EP and TCLP
methods. Finally, for all three procedures, the combined bottom/fly ash and bottom
ash contained sightly more BNAs than their corresponding fly ash. This fact
suggests that the BNA compounds are associated with the coarser, heavier bottom
ash materials or may be completely destroyed as the fly ash passes through
high-temperature zones in the incinerator.
5-14
-------
6.0 PCDDs AND PCDFs IN LEACHATES AND EXTRACTS
As discussed in Section 2.3, MWC ashes contain a variety of PCDD and PCDF
homologs. Since the tetra homologs for both PCDDs and PCDFs are more toxic (the
tetra 2,3,7,8 is the known most toxic), the EPA (1987) has developed an interim
procedure of estimating the risk associated with exposure to mixtures of PCDDs and
PCDFs by using the Toxicity Equivalency Factors (TEF), which essentially convert
concentrations of each homolog to a 2,3,7,8-TCDD equivalent, based on toxicity.
Table 6-1 lists levels of PCDD and PCDF homologs found in fly ash, bottom ash,
combined ashes, TCLP-generated leachates, actual field-collected leachates and
quench waters as reported in the Versar Report (Volume V of this report) for the
four facilities sampled in the course of the Versar Study. The 2,3,7,8-TCDD
equivalents were calculated and reported in the bottom of each column, assuming
conservatively that the total individual homologs consist entirely of the 2, 3, 7, 8 of
that particular homolog. For example, for calculating the TEF of penta-CDD, the
total penta CDD was assumed to consist entirely of 2,3,7,8 penta CDD. Since the
acceptable level of 2,3,7,8-TCDD is 1 part per billion (ppb), the 2,3,7,8-TCDD
equivalents are calculated in this unit (ug/kg for solids and ug/l for liquids).
A review of the PCDD and PCDF concentrations in the TCLP-prepared leachates
showed that the extracted concentrations of PCDDs and PCDFs were approximately
equal. Only hepta-CDD and octa-CDD homologs were detected in two fly ash
leachates (Facilities A and B), and only the octa-CDD homolog was detected in one
bottom ash leachate (Facility B). Similarly, the hepta-CDF and octa-CDF homologs
were detected in one fly ash leachate (Facility B), whereas only the hepta-CDF
homolog was detected in the Facility A fly ash leachate. The octa-CDF homolog was
detected in only one bottom ash leachate (Facility B). Because the solid samples
contained significantly more PCDD and PCDF homologs than the TCLP-prepared
leachates, these observations indicate that the TCLP method is inefficient for
extracting (i.e., leaching) PCDD and PCDF compounds in a waste ash matrix.
6-1
-------
TABLE 6-1
CHLORINATED DIOXIN AND CHLORINATED DIBENZOFURAN LEVELS
IN ASHES AND LEACHATES FROM MONOFILLS
en
i
NJ
Compound
MONOFILLA
2.3.7.8TCDD
TOTAL TCDD
TOTAL PCDD
TOTAL HXCDO
TOTAL HpCDO
TOTALOCDO
TOTAL Dioxin
2,3,7.8TCDF
TOTAL TCDF
TOTAL PCDF
TOTAL HXCDF
TOTAL HpCDF
TOTAL OCOF
TOTAL Furan
2.3.7.8TCDD
Equivalency
fug/kg or ug/0
Fly Ash
(ng/g)
0093024
2366
11 32
1835
1426
11 31
64.3 1167
-
2089
7.1-32
1496
9944
1440
6022094
21 50
Fly/Bottom
Ash (ng/g)
002033
15 13
2.7 19
19 11
1.7 8.2
084 37
86954.9
088 12
6391
2537
13 18
06266
0 18 1 3
109 1539
3524
TCLP Leachates (ng/l>
Bottom/Fly
<0038
<0038
<0023
<0018
<0028
<0035
0
<0031
<0031
.<0013
<0008
<0013
<0060
0
0000
Fly
<0056
<0056
< 0.056
<0026
Oil
0078
0188
<0 120
<0120
<0019
<0015
0049
<0081
0049
0000
Quench
Water
(ng/l)
<0.08 <008
012
082 4
066 2
058 19
043098
259 1088
0.27-2.1
1.7-12
0.91-6.1
0.51-3.1
0.36-1.2
027027
402 2477
0001 0005
-------
en
TABLE 6-1
CHLORINATED DIOXIN AND CHLORINATED DIBENZOFURAN LEVELS
IN ASHES AND LEACHATES FROM MONOFILLS
PAGE TWO
Compound
MONOFILL B
2.3.7.8TCDD
TOTAL TCDD
TOTAL PCDD
TOTAL HXCDD
TOTAL HpCDD
TOTAL OCDD
TOTAL Dioxin
2.3.7.8TCDF
TOTAL TCDF
TOTAL PCDF
TOTAL HXCDF
TOTAL HpCDF
TOTAL OCDF
TOTAL Furan
2.3.7.8TCDD
Equivalency
(pg/kg or pg/l)
Fly Ash
(ng/g)
0 13063
65 18
84 139
123 322
93435
89 1,363
4302.113
-
48 107
3765
41 241
1963
81 34
186271.3
106527
Bottom
Ash (ng/g)
<004001
<004065
<001 2
<0002 2 3
<00963
<0 1629
<0 27 4025
002 03 '
006 1.3
002 1.5
002-25
003 -6.9
<004 37
0.16 159
00047.7
TCLP Leachates (ng/l)
Bottom Ash
<0076
<0076
<0027
<0015
<0 120
0091
0091
<0040
<0040
<0013
<0022
<0043
0054
0054
0000
Fly Ash
<0072
<0072
<0040
<0027
0036
Oil
0.146
<0052
<0052
<0026
<0020
0063
089
0 152
0000
Field
Leachate
(ng/l)
<006028
<00666
<005 25
<002 22
000921
0 14 14
0 149886
<0.05-37
<00522
<0.02-17
<001 16
00594
0.05-1.9
0.1 663
0000 0037
Quench
Water
(ng/l)
<007 <007
<007-<007
<0.03-<0.05
<001 <004
<003005
0060 13
0060 18
<006 <008
<006 <008
<001-<004
<001 <002
<002 004
<015 <030
0004
0000 0000
-------
TABLE 6-1
CHLORINATED OIOXIN AND CHLORINATED OIBENZOFURAN LEVELS
IN ASHES AND LEACHATES FROM MONOFILLS
PAGE THREE
Compound
MONOFILLC
2.3.7.8TCDD
TOTAL TCDD
TOTAL PCDD
TOTAL HXCDD
TOTAL HpCDD
TOTAL OCDD
TOTAL Dioxin
2.3.7.8TCDF
TOTAL TCDF
TOTAL PCDF
TOTAL HXCDF
TOTAL HpCDF
TOTAL OCDF
TOTAL Furan
2.3.7.8TCDD
Equivalency
(iig/kgor pg/1)
Fly Ash
(ng/g)
<014 39
<0.14-43
< 002 980
<0035,565
< 006 4.900
<0.163,152
0-12,018
0.66 26
38 169
1.5310
0222.353
<003666
<0 15 362
552-3.187
0 22 780
Bottom/Fly
Ash (ng/g)
0.12078
1 3-14
1050
11-78
15 120
7.7-89
48.9-350
0.55 38
3424
4827
6.3 35
4836
1.484
228 130.4
62-33
Landfill
Composite
(ng/g)
007
12
5.7
68
9
6.1
288
051
24
3.9
4
33
081
1441
3.7
TCLP Leachates (ng/l)
Bottom Fly
<0065
<0065
<0067
<0022
<0049
<0 100
0
<0064
<0064
<0020
<0020
<0024
<0 130
0
0000
Fly
<0094
<0094
<0042
<0019
<0079
<0.130
0
<0077
<0077
<0026
<0014
<0030
<0.100
0
0000
Field
Leachate
(ng/l)
<005 1 6
<005 28
<00393
<002 130
<002 172
006 120
0.06-543
<008 11
<00865
<002 64
<001 76
<00360
004 15
004280
0.000 0 062
Quench
Water
. (ng/D
<0.17 <081
<017059
0.2659
1110
1.5-19
1.2-12
4064749
0 14055
09824
0.764
061 62
05265
025 1 4
3.12-20.5
0 000 0 004
Ok
-------
TABLE 6-1 /
CHLORINATED DIOXIN AND CHLORINATED DIBENZOFURAN LEVELS
IN ASHES AND LEACHATES FROM MONOFILLS
PAGE FOUR
Compound
MONOFILL D
2.3.7.8TCDD
1 OTAL TCDD
TOTAL PCDD
TOTAL HXCDD
TOTAL HpCDD
TOTAL OCDD
TOTAL Dioxin
2,3,7.8 TCDF
TOTAL TCDF
TOTAL PCDF
TOTAL HXCDF
TOTAL HpCDF
TOTAL OCDF
TOTAL Furan
2.3.7.81CDD
Equivalency
(jig/kg or ng/0
Fly Ash
(ng/g)
0 37 0 83
5.1 19
4691
49 106
3781
35 113
175.92532
-
3693
2747
21 115
3880
3198
9343118
28-57
Bottom/Fly
Ash (ng/g)
004007
<0.28 1 3
1.94
1.4 34
1433
1226
6.2 146
0.41 0.76
2351
1647
1241
081 26
021-059
6 14 1709
13-28
Landfill
fomnrktittf*
(ng/g)
0.15
25
6
4.1
42
39
207
1.3
11
7.7
53
27
061
2731
4.3
TCLP Leachaies (ng/l)
Bottom Fly
<0230
<0230
<0060
<0.044
<0 100
<0230
0
<0200
<0200
<0042
<0025
<0035
<0260
0
0000
Fly
<0071
<0071
<0048
<0022
<0038
<0 140
0
<0048
<0048
<0016
<0013
<0020
<0015
0
0000
Field
Leachate
(ng/l)
<0.22 <0.26
0 13027
<022 04
2.1-2.2
8.2 8.8
23 25
3393 36 17
0.370.4
2.93
2.3-2.4
19-19
1213
081 084
921-934
0.000 0001
Quench
Water
(ng/l)
1 17
24 700
80650
72 500
77450
53 330
306 2,550
14 110
91 640
83560
81 490
59 310
1675
330 2,075
0055 0427
en
-------
Furthermore, they indicate that only the highly chlorinated PCDD and PCDF species
(i.e., hepta- and octa-) tended to be extracted by TCLP.
The field leachate sample results indicate that only minute quantities in the part per
trillion levels of PCDDs (Figure 6-1) and PCDFs (Figure 6-2) were identified. This
suggests that PCDDs and PCDFs are not mobile in the natural environment through
aqueous transport pathways unless significant microbial activity produces organic
acids or similar compounds which have the potential to make dioxins mobile
(Sawell, 1987).
The PCDD results for the quench water (Figure 6-3) showed that the variability
between shifts and units was relatively small compared to the variability between
facilities. This suggests that the different combustion conditions and feed materials
at each facility contributes to this variability. The quench water samples from
Facility D contained the highest PCDD concentrations. There did not appear to be
any correlations for the least or most abundant homologs, or for the 2,3,7,8-TCDD
isomer.
A review of the PCDF concentrations in the quench water (Figure 6-4) again showed
that the variability between shifts and units was relatively small compared to the
variability between facilities. The quench water from Facility D contained the
highest PCDF concentrations. Again, there did not appear to be any trends for the
least or most abundant homologs, or for the 2,3,7,8-TCDF isomer.
It should be noted that neither the quench water samples nor the field leachates
samples were filtered prior to analysis. All of these samples appeared turbid, and
thus contained suspended particulates. The analyses of these samples report total
values, i.e., levels in the water samples and levels in the suspended solids. The
variation in results reported for these samples may originate from differences in the
amounts of solids found in these samples.
Due to the low solubility of these compounds in water, the reported values are
probably mostly values of the suspended particulates.
. i
Table 6-2 lists the concentrations of PCDD and PCDF homologs detected in the ashes
disposed of in the two codisposal sites (NC and NY) sampled by NUS (Volume IV of
6-6
-------
K § 8 S
1X7 J TOO «
TUTU-COO gjj
' - 5
o
' '1
2
§
PCHTA-CSO
HOW-COO
MCPTA-COO
^<3
o
.
9&ssasss9sss>ssssss8&sa
OCTA-COO -
s m
oS
~x
>
o
5
X
2
§
l/l
8 a
TOO .
PtHTA-COO - I
HOW-COO
HCFTA-COO
OCTA-COO - 8
s m
o O
^ I
33
:§
?!
8f
S"
;i
»
* n
!J
y
II
M
i
O
o
x
Z
o
l/t
"9/1 (ppt)
^ ^ M
o w> 3
2.3.7.8 TCOO -
TTKA-COO
PENTA-COO -
HOU-COO
MC^TA-COO
S?
o
n
6-7
"« >
-------
ojr
FIELD LEACHATE
(Facility B)
I
_i^
-v T
5 5
6 S
FURAN HOMOLOCS
FIELD LEACHATE
(Focility C)
FIELD LEACHATE
(Facility 0)
FURAN HOMOLOGS
Note: tach bar repn-sents an Individual
frai an Individual unit.
collect*d
oo
to
HOMOLOGS
-------
itntlvu »t »!«! No»l«t* «
»«rwr In
tram Mw MOT
QUENCH WATER
(Fadkly A)
QUENCH WATER
(FociMy C)
DlOXM HOMCX.OGS
OOXIN MOUOUXJS
\o
QUENCH WATER
B)
»00
§
QUENCH WATER
(Facility D)
HOMOtOGS
OOXIN HOMOIOCS
U: bcb Wr
M In4l«l*«1 f»k M^
-------
13
a.
ex
».
5
QUENCH WATER
(Facility A)
QUENCH WATER
(Facility C)
FURAN HOMOLOGS
FURAN HOMOLOGS
QUENCH WATER
(Facility 8)
BOO
00
'400
200
fs"
QUENCH WATER
(Facility D)
1
I.
I.
FURAN HOMOLOGS
Note: Each bar represents an Individual grab sample.
FURAN MOMOLOCS
-------
TABLE 6-2
CHLORINATED DIOX1N AND CHLORINATED DIBENZOFURAN LEVELS
IN ASH AND LEACHATES FROM THE NC CODISPOSAL LANDFILL
Compound
2.3,7,8-TCDD
TOTAL TCDO
TOTAL PCDD
TOTAI, HXCDD
TOTAL HpCDD
TOTAL OCDD
2.3,7,8-TCDF
TOTAL TCDF
TOTAL PCDF
TOTAL HXCDF
TOTAL HpCDF
TOTAL OCDF
2,3.7,8-TCDO
Equivalents ppb
(ug/kg or ug/l)
Ash
(ng/g)
Ppb
NO
0.03
0.10
0.1
0.18
O.U
0.07
0.56
0.29
0.19
0.11
0.02
0.27
Leachates (ng/l)
parts per trill ion
Actual
NO
NO
NO
0.130
0.770
15
ND
NO
0.035
0.035
0.085
0.054
0.001
TCLP
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.000
SW924
NO
ND
ND
ND
ND
0.035
ND
ND
ND
ND
ND
ND
0.000
EP-Tox
ND
ND
ND
ND
0.021
0.031
ND
ND
NO
ND
0.012
ND
0.000
ND 3 Below detection limit
Source: NUS Study (Volume VI)
6-11
-------
TABLE 6-2
CHLORINATED OIOXIN AND CHLORINATED DIBENZOFURAN LEVELS IN ASH
AND LEACHATES FROM THE NY CODISPOSAL LANDFILL
PAGE TWO
Compound
2.3:7.8-TCDD
TOTAL TCDD
TOTAL PCDO
TOTAL HXCDD
TOTAL HpCDD
TOTAL OCDD
2,3,7,8-TCDF
TOTAL TCDF
TOTAL PCDF
TOTAL HXCDF
TOTAL HpCDF
TOTAL OCDF
2,3,7.8-TCDD
Equivalents
(ug/kg or ug/l)
Ash
(ng/g, ppb)
ND
0.02
0.12
0.43
4.2
9.9
0.11
0.46
0.54
1.2
2.2
1.7
4.4
leachates (ng/l)
parts per trill ion
Actual
ND
ND
ND
0.047
0.120
0.210
ND
ND
0.028
0.041
0.043-
0.023
0.000
TCLP
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
0.000
EP-Tox
ND
ND
ND
ND
ND
0.033
ND
ND
NO
ND
NO
ND
0.000
ND a Below detection limit
Source: NUS Study (Volume VI)
6-12
-------
this report). PCDO and PCDF homolog concentrations in actual leachate samples, as
well as in leachates generated by the EP, TCLP, and SW-924 methods are also given
m these tables. Calculated 2,3,7,8-TCDO equivalents are included in the bottom of
each column.
Review of the data presented in Table 6-2 indicates the following:
2,3,7,8-TCDO, the most carcinogenic homolog known, was not detected in
the ashes, the actual leachates, or the extracts.
The ashes contained ng/g (ppb) levels of total tetra, penta, hexa, hepta,
and octa PCDDs and PCDFs.
The NY ashes were a product of incomplete combustion, the beginning of
the burn. As would be expected, the concentrations of most homoiogs are
somewhat higher in these ashes.
Extracts produced by the the TCLP procedure did not contain any of the
PCDD or PCDF homoiogs.
SW-924 was run on only one ash sample. This leaching procedure produced
only 0.035 ng/l (parts per trillion) of the octa dioxin homolog. According to
the EPA "Toxicitv Equivalency Factors" (TEF) by which the individual
homolog toxicity is converted to 2,3,7,8-TCDD equivalency, the multiplying
factor for this octa homolog is 0.00. In other words, the octa homolog is
treated as having no carcinogenic potential.
The EP toxicity leaching procedures produced for one ash, 0.033 ng/l of the
dioxin octa and for the second ash, 0.031 ng/l (part per trillion) of the
dioxin octa, and 0.021 ng/l (part per trillion) of the dioxin hepta homoiogs.
The TEF for HpCDD is 0.001, which represents a very low level of
carcinogenicity compared to 2,3,7,8-TCDD.
The actual leachates collected at both codisposal sites contained very low
concentrations of HXCDD, HpCD, OCDD, PCDF, HXCDF, HpCDF, and OCDF.
6-13
-------
Although the ashes from one site exhibited higher concentrations of most
homologs because of incomplete combustion, the leachate did not exhibit
the same trend. The leachates reflected previously disposed ashes present
at the site rather than the analyzed ashes.
The leachates from the two codisposal sites did not contain any tetra
homologs.
Wastes from MSW facilities have not been routinely subjected to the
expensive testing for PCDDs or PCDFs. Neither have leachates from MSW
facilities. However, according to a recent Canadian Government
Publication, Ontario Ministry of the Environment: PCDDs and PCDFs:
Scientific Criteria Document for Standard Development. No. 4-84,
September 1985, dioxins and dibenzofurans were detected in actual solid
waste found in municipal waste disposal sites. Such waste, the bulk of the
codisposal site material, could contribute PCDDs and PCDFs to the leachates
produced by these codisposal sites.
Canadian studies suggest that incinerators, on a mass balance basis, are net
destroyers of dioxins (Sawell, 1987).
6-14
-------
7.0 CONCLUSIONS
The main conclusions of the information obtained through the literature reviewed
for this study and from the two EPA-sponsored studies are reported in this section.
The main conclusions for the MSW and codisposal study (the NUS study) are as
follows:
Conventional Parameters
Water-quality parameters detected in the thirteen leachate samples
collected at these four municipal waste sites were within the range of those
reported in the literature for other sites. However, they dici not show as
much variation as does the published literature. The ranges reported in the
literature are very wide for most parameters, covering several orders of
magnitude; the pH ranged from acidic(3.7) to basic (8.5); The BOD, COD,
and TOC values ranged from not determined (ND) to 720,000, 750,000 and
30,500 mg/l, respectively. The levels in leachates from the four sites
sampled by NUS were at least one order of magnitude lower for BOD, COD,
and TOC than values reported in the literature, and the pH was neutral to
slightly basic, ranging from 6.98 to 7.8.
Generally, there was no dear difference between the general water quality
parameters of the thirteen leachate samples collected from the four
municipal disposal sites and the six leachate samples collected from the two
codisposal sites.
Bacteria seem to be able to play an important part in the final water-
quality characteristics of field leachates, as evidenced by the presence of
ammonia in monofill leachates. The presence of 438 to 1,310 ppm of TOC
and the 1,300 to 3,900 ppm of COD in the collected samples is indicative of
substrate which' may provide nutrients for bacteria. Both oxidizing and
reducing bacteria can affect the quality of leachates in monofills.
7-1
-------
Inorganics
Concentrations of inorganic parameters (including metals) detected in
leachates from the four municipal disposal sites were similar to levels
reported in the literature for leachates from other municipal disposal sites.
However, the higher levels of the metals reported in the literature
exceeded the EP Toxicity Maximum Allowable Limit. Leachates from the
four facilities sampled always met the EP Toxicity Maximum Allowable
Limit. These four facilities were all constructed after the RCRA regulations
were enacted, and these facilities do not accept industrial hazardous
wastes.
In general, there is no clear difference between the metal content in
leachates from the codisposal sites and from the municipal disposal sites.
This indicates that the neutral (pH 6.98 to 7.82) MSW-generated leachates
do not promote leaching of metals from the MWC ashes. On the contrary,
in the facilities we tested, they can provide dilution.
The metal content in actual leachates collected from the codisposal sites
was always lowerthan in test leachates (EP, TCLP, or SW-924). Jhe actual
leachates always met the EP Toxicity Maximum Allowable Limit; one ash
sample exceeded the EP Toxicity Maximum Allowable Limit of 5 mg/l for
lead when subjected to any of the three test methods.
A recently published, EPA-sponsored study, "Composition of Leachates
from Actual Hazardous Waste Sites." describes the collection of leachates
from 13 carefully selected hazardous waste disposal sites. The metals
detected in leachates from the hazardous waste sites were at much higher
concentrations than in the leachates collected from the four municipal
waste disposal sites and from the two codisposal sites.
The pH in leachates from monofills, as reported in the literature, ranged
between 8.04 and 8.3 and, in leachates from the monofills sampled by
Versar, the range was between 7.44 and 8.58. The slightly lower pH values
in leachates from the codisposal sites (7.2 to 7.3) may imply that the ashes
have a somewhat neutralizing effect on the leachates generated by
7-2
-------
municipal wastes. This may reflect a high initial wash-off of calcium-based
compounds in the ash.
Orqanics
^^^
Very few organic compounds, of the huge list of organics on Appendix IX,
were detected in the leachates from either the municipal waste disposal
sites or the codisposal sites. Only 11 volatile compounds, 4 semi-volatile
compounds, and 5 pesticides were detected in these leachates.
Concentrations of these compounds were very low. The volatile
compounds cannot originate from the MWC ashes because volatiles are
driven off at much lower temperatures than those in an incinerator.
There is no noticeable difference in the number of organic compounds, or
in the detected levels, between the leachates collected from the codisposal
sites and the municipal disposal sites.
Leachates generated by EP, TCLP, or SW-924 from ashes collected from the
codisposal sites did not generate detectable semi-volatile compounds
or PCBs.
In the recently published, EPA-sponsored study in which leachates from
13 carefully selected actual hazardous waste sites were analyzed for the
same compounds, leachates from these hazardous sites contained
42 organic acids, 43 oxygenated/heteroatomic hydrocarbons, 39 halogen-
ated hydrocarbons, 26 organic bases, 32 aromatic hydrocarbons, and
8 aliphatic hydrocarbons. The levels of these detected compounds ranged
from several parts per billion (ppb) to many thousands of parts per million
(ppm).
The leachates from the four municipal waste disposal sites were not
analyzed for PCDDs or PCDFs. Only the actual leachates from the
codisposal sites, the ashes from these sites, and the artificially generated
leachates were- analyzed for PCDDs and PCDFs. None of the analyzed
samples contained 2,3,7,8-TCDD, which is the most toxic homolog known.
The ashes contained ppb levels of total tetra, penta, hexa, and octa. The
7-3
-------
TCLP procedure did not produce any PCDDs or PCDFs; the EP toxicity
procedure and SW-924 produced part-per-trillion (ppt) levels of the octa
and hepta homologs. The actual leachates contained part-per-trillion (ppt)
levels of octa, hepta, and hexa levels of PCDDs and octa, hepta, hexa, and
penta of PCDFs. Even when assuming conservatively that each total
homolog type consisted of only the appropriate 2,3,7,8 homolog, the
2,3,7,8-TCDD equivalents were 0.00 ug/l. The ash at one site (NY), which
was from the beginning of a run and did not go through complete
combustion, contained somewhat higher PCDD and PCDF levels than the
second site (NC) ash. A recent government of Canada publication claims
that PCDDs are PCDFs are present in raw municipal waste. Before any
conclusions are drawn regarding PCDD and PCDF levels in leachates from
codisposal sites , leachates from raw municipal waste disposal sites should
be analyzed for PCDDs and PCDFs as well.
The main conclusions from the monofiil study (the Versar Study) are as follows for
residue values:
The variability of the contaminant concentrations between days, shifts, and
units at any of the four sampled .facilities was significant, a fact which
indicates that slight changes in the incinerator feed material (i.e., the raw
refuse) and /or the operating parameters significantly affected the quality
of MWC residue. The variability of the contaminant concentrations
between these facilities was extremely large (i.e., the standard deviations
of the concentrations exceeded the average concentrations). This suggests
that the variability of operating characteristics, facility design, and feed
material composition between facilities has a significant impact on the
resultant MWC residue quality. It may also imply that, despite compositing
the analyzed samples, the heterogenetic nature of the ashes generally
precludes obtaining representative "laboratory size" samples.
In general, the weight ratio of bottom ash to fly ash was approximately 3 to
1 for the four facilities in this study. This ratio appears to be high and may
reflect less than ideal operating conditions at the facilities sampled.
Generally, fly ash makes up 10 to 20 percent of the total (Sawell, 1987).
7-4
-------
The quench water at all four facilities was discharged to the local
wastewater treatment plant. Based on the analytical results for the quench
water samples, this appears to be a suitable disposal technique.
Generally, there did not appear to be a correlation between the operating
characteristics of the sampled facilities and the metals concentrations in the
residues. The variation in metal composition within each facility, each unit,
and each shift is greater than the variation between the different units.
The fly ash contained higher concentrations of all metals except copper and
iron than the bottom ash. Therefore, combining the ash fractions
effectively diluted the total metals concentrations of the fly ash.
The fly ash consistently contained higher concentrations of PCBs, PCDDs,
and PCDFs than the combined ash or bottom ash. However, the combined
ash and bottom ash had higher concentrations of semi-volatiles than the fly
ash.
The contaminant concentrations of the disposed ash (i.e., the landfill
perimeter composites) and the combined ash were not significantly
different except for lead in one of two sampled facilities.
The PCB concentrations were less than the 50 ppm limit established by the
Toxic Substances Control Act (TSCA) for all solid samples. Therefore, the
solid residues would not be classified as hazardous materials, based solely
on their PCB content.
In 27 percent of the fly ash samples, the 2,3,7,8-TCDD concentration
exceeded the limit of 1.0 ppb established by the National Center for
Disease Control for safe soil ingestion levels. This limit was not exceeded by
any of the combined ash or bottom ash samples.
Forthe Monofill Data:
Actual leachates from all sampled facilities met the EP Toxicity Maximum
Allowable Limit.
7-5
-------
The concentrations of metals in the groundwater samples did not exceed
the Primary or Secondary Drinking Water Standards. Some groundwater
samples were not properly obtained and wells sampled were not located
downgradient from the disposal facility in all cases.
Based on chemical analysis of collected leachates, it can be assumed that
bacterial activities were present in all sampled sites. The pH of the monofill
leachates ranged between 7.44 and 8.58. These slightly to moderately
basic waters can sustain bacteria, especially since the TOC levels ranged
between 59 and 536mg/l (ppm). Such bacteria can play a vital role in
shaping the water quality of the monofill leachate. The presence of
ammonia is evidence of anaerobic bacteria activity. The ammonia-nitrogen
level ranged between 1.2 and 36 mg/l (ppm). For comparison purposes, the
pH levels in the four NUS sampled MSW facilities ranged between 6.98
and 7.8; in the two codisposai sites, the range was between 7.2 and 7.3.
The ammonia-nitrogen levels in the MSW leachates ranged between 53
and 580 mg/l (ppm); in the codisposai sites they ranged between 160 and
410 mg/l (ppm). The TOC levels in the MSW leachates ranged between 138
, and 2,680 mg/l (ppm); in the codisposai site leachates between 436 and
1,310 mg/l (ppm). These data indicate that the leachates from these MSW
codisposai landfills and monofills do not differ significantly in pH. The pH
of the MSW facilities was neutral to slightly basic. The TOC levels and the
ammonia levels indicate that anaerobic bacteria activities are taking place
at all facilities.
The neutral to basic pH conditions in the MSW facilities, the codisposai
sites, and the monofills indicate an environment in which the solubilities of
the RCRA-regulated metals are limited.
The concentrations of PCBs, PCDDs, PCDFs, and semi-volatile compounds
were negligible in the actual leachate samples and in the laboratory-
prepared extracts. Therefore, these compounds appear to be relatively
immobile in the natural environment.
7-6
-------
the quality of leachates with time at a monofill where no new ashes are
being brought in.
Based on the limited, available data base it appears that codisposal of ashes
and MSW may reduce the leached level of the conventional pollutants, the
level of PCDOs and PCDFs and the levels of several metals. In the monofills
the 2,3,7,8-TCDD equivalents ranged between 0.000 and 0.062 ug/l (ppb),
while in the the codisposal sites the range was between 0.000 and
0.00} ug/l (ppb). Similarly, the levels of metals were lower in co-disposal
facilities than in monofills. In the sampled codisposal sites, lead ranged
between 0.01 and 0.27 mg/l (ppm); in the monofills the range was between
0.012 and 2.92 mg/l (ppm); cadmium levels in the codisposal sites ranged
between not determined (ND) and 0.011 mg/l (ppm), while in the monofills
the range was between ND and 0.044 mg/l (ppm). Similar differences are
evident for each metal analyzed. Additional studies to determine the
quality of leachates from codisposal sites and monofills could increase the
confidence in this conclusion. However, because these lower
concentrations appear to be primarily the result of dilution, the total mass
of leached metals is likely to be substantially the same in monofills and
co-disposal facilities handling the same quantity of,ash. Furthermore, a
co-disposal facility would have to be much larger than a monofill to handle
an equivalent quantity of ash; thus, management practices that could be
used at a monofill may not be feasible at a co-disposal facility.
The rate of metal release from acidic fly ash may be reduced when the
acidic fly ashes are mixed with the more basic bottom ashes for disposal in
monofills. More studies are needed to verify this conclusion.
7-8
-------
For the Leaching Results:
i
The EP Toxicity Maximum Allowable Limit for cadmium was exceeded by
100 percent of the EP-prepared fly ash extracts. However, the cadmium EP
Toxicity Maximum Allowable Limit was not exceeded by any of the
EP-prepared combined ash or bottom ash extracts.
j
The EP Toxicity Maximum Allowable Limit for lead was exceeded by
1 83 percent of the EP-prepared fly ash extracts and by 75 percent of the
EP-prepared combined ash or bottom ash extracts.
1
The EP and TCLP methods were more aggressive than the MWEP (SW-924)
methods for extracting metals. The EP method appeared to be slightly
more efficient than the TCLP method for leaching lead; however, the TCLP
method appeared to be slightly more efficient than the EP method for
extracting arsenic, chromium, and manganese. The extraction efficiencies
of the EP and TCLP methods were approximately equal for the other
metals. None of the laboratory leaching procedures were efficient for
extracting organic base neutral compounds and PCBs.
The TCLP was ineffective for extracting the organic constituents including
PCDDs, PCDF, and semi-volatile compounds.
Comparison of actual leachate data with the EP, TCLP, and SW-924 data
indicates that the SW-924 results most closely represent the actual data,
1 followed by the TCLP using extracting Fluid No. 1. The EP toxic procedure
extracted significantly higher levels of metals than were found in the actual
1 leachate.
i The fact that the analyzed quench waters contained higher levels of
inorganics, PCDDs, and PCDFs than the actual leachates, and that the first
leachate produced by SW-924 contained consistently higher levels of
contaminants than the second leachate, implies that the leaching of
contaminants from ashes should be decreasing with time, depending on
the pH environment and other factors. This can be verified by monitoring
7-7
-------
8.0 REFERENCES
. Bellin, J. S., and D. G. Barnes, 1987. Interim Procedures for Estimating Risks
Associated with Exposures to Mixtures of Chlorinated Dibenzo-p-Dioxins and
Dibenzofurans (CDDs and CDFs). EPA, Risk Assessment Forum.
i
Cahill, C. A., and L W. Newland, 1982. "Comparative Efficiencies of Tract Metal
' Extraction from Municipal Incinerator Ashes." International Journal of
: Environmental Analytical Chemistry. Vol. 11, pp. 227-239.
i
i Cameron, R. D., 1978. "The Effects of Solid Waste Landfill Leachates on Receiving
Waters." Journal American Well Water Association. March 1978, pp. 173-176.
Chian E. S. K., and F. B. DeWalle, 1977 Evaluation of Leachate Treatment. Volume I.
Characterization of Leachate. EPA-600/2-77-186b.
Engineering Science, 1986. Summary of MSW Incinerator Ash Survey: USEPA,
Hazardous Waste Branch, Contract No. 68-02-3888, Work. Assignment No. 43,
October 1986.
EPA, (U.S. Environmental Protection Agency), 1987. Risk Assessment Forum, Interim
Procedures for Estimating Risks Associcated with Exposures to Mixtures of
Chlorinated Dibenzo-p-Dioxins and -Dibenzofurans (CDDs and CDFs).
EPA/625/3/87/012, March 1987.
i
George J. A., 1972. Sanitary Landfill, Gas and Leachate Control, the National
A Perspective. EPA, Office of Solid Waste Management Programs.
Klein, D. H., A. W. Andren, J. A. Carter, J. B. Emery, C. Feldman, W. Fulderson,
W. S. Lyon, J. C. Ogle, Y. Talmi, R. I. van Hook, and N. Bolton, 1975. Environmental
Science and Technology. Vol 9, (9).
Metry, A. A., and F. L.- Cross, 1975. Leachate Control and Treatment Vol. 7,
Environmental Monograph Series. Technomic Publishing Company, Westport, Ct.
8-1
-------
Ontario, Canada, Ministry of the Environment. 1985. Polychlorinated Dibenzo-o-
Dioxins (PCDDs) and Polvchlorinated Dibenzofurans (PCDFs). Scientific Criteria
Document for Standard Development No. 4-8u. September, 1985.
Plumb, R. H., Jr., and C. K. Fitzsimmons, 1984. "Performance Evaluation of RCRA
Indicator Parameters." Proceedings - First Canadian/American Conference on
Hvdroqeoloqy.
Plumb, R. H., Jr., 1985. "Volatile Organic Scans: Implications for Groundwater
Monitoring." Proceedings of the Petroleum Hydrocarbons and Organic Chemicals
in Groundwater-Prevention, Detection, and Restoration-Conference. Lockheed
Engineering and Management Services Company, Inc., Las Vegas, Nevada.
Plumb, R. H., Jr., 1985. "Disposal Site Monitoring Data: Observations and Strategy
Implications." Proceedings-Second Canadian/American Conference on
Hydroqeoloqy.
Plumb, R. H., and J. R. Parolini, 1986. Organic Contamination of Groundwater Near
Hazardous Waste Disposal Sites: A Synoptic Overview. Lockheed Engineering and
Management Services Co., Las Vegas, Nevada.
PCR Engineering, 1986. Characterization of Municipal Solid Waste in the United
States I960 2000. USEPA/OWPE Contract No. 68-01-7037, prepared by Franklin
Associates for PRC, July 25,1986.
Sawell, S., 1987. Personal Communication between S. Sawell, Environment Canada,
Ontario, Canada, and Haia Roffman, NUS Corporation.
Science AppJications International Corporation (SAIC), no date. Composition of
Leachates from Actual Hazardous Waste Sites. Prepared for EPA, Contract
No. 68-03-3113, Work Assignment 39-7.
Sobotka & Co., Inc., 1986. Case History Data. Compiled and reported in July 1986
report to USEPA Economic Analysis Branch of the Office of Solid Waste.
8-2
-------
j,as A&M University (Brown K. W., and K. C, Donnelly), no date. The Occurrence
yd Concentration of Organic Chemicals in Hazardous and Municipal Waste Landfill
.eachate.
Wisconsin Bureau of Solid Waste Management, (P. M. McGinley and P. Met), 1984.
Formation Characteristics. Treatment and Disposal of Leachate from Municipal Solid
Waste landfills. A Wisconsin Department of Natural Resources Special Report,
August 1984.
r P f
U.S. Environmental Protection Agency
"- gion 5, Library (5PL-16)
, <^0 S. Dearborn Sti-eet, Room 1670
Chicago, IL 60604
------- | |