Emissions of Metals Chromium and Nickel Species and Organics from Municipal Wastewater Sludge Incinerators. Volume VI Site 8 Emission Test Report


EPA/600/R-92/003f
March 1992
EMISSIONS OF METALS, CHROMIUM AND NICKEL SPECIES, AND ORGANICS
FROM MUNICIPAL WASTEWATER SLUDGE INCINERATORS
VOLUME VI: SITE 8 EMISSION TEST REPORT
Prepared by:
Robin R. Segall
Entropy Environmentalists, Inc.
Research Triangle Park, North Carolina 27709
William G. DeWees
DEECO, Inc.
Cary, North Carolina 27519
F. Michael Lewis
Mountain View, California 94040
EPA Contract No. 68-CO-0027
Work Assignment No. .0-5
Technical Managers:
Harry E. Bostian, Ph.D.
Risk Reduction Engineering Laboratory
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
Eugene P. Crumpler
Office of Water
U.S. Environmental Protection Agency
Washington, D.C. 20460
RISK REDUCTION ENGINEERING LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268

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DISCLAIMER
This material has been funded wholly or in part by the United States
Environmental Protection Agency's Risk Reduction Engineering Laboratory and Office
of Water (OW) under contract numbers 68-02-4442, Work Assignment No. 81; Contract
No. 68-02-4462, Work Assignment No. 90-108; and Contract No. 68-C0-0027, Work
Assignment No. 0-5. It has been subjected to the Agency's review and it has been
approved for publication as an EPA document. Mention of trade names or commercial
products does not constitute an endorsement or recommendation for use.
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FOREWORD
Today's rapidly developing and changing technologies and industrial products and
practices frequently carry with them the increased generation of materials that, if
improperly dealt with, can threaten both public health and the environment. The U.S.
Environmental Protection Agency is charged by Congress with protecting the Nation's
land, air, and water resources. Under a mandate of national environmental laws, the
agency strives to formulate and implement actions leading to a compatible balance
between human activities and the ability of natural systems to support and nurture life.
These laws direct the EPA to perform research to define our environmental problems,
measure the impacts, and search for solutions.
The Risk Reduction Engineering Laboratory is responsible for planning,
implementing, and managing research, development, and demonstration programs to
provide an authoritative, defensible engineering basis in support of the policies,
programs, and regulations of the EPA with respect to drinking water, wastewater,
pesticides, toxic substances, solid and hazardous wastes, and Superfund-related activities.
This publication is one of the products of that research and provides a vital
communication link between the research and the user community.
The problem of disposing of primary and secondary sludge generated at municipal
wastewater treatment facilities is one of growing concern. Sludge of this type may
contain toxics such as heavy metals and various organic species. Viable sludge disposal
options include methods of land disposal or incineration. In determining the
environmental hazards associated with incineration, the Risk Reduction Engineering
Laboratory and the Office of Water have sponsored a program to monitor the emissions
of metals and organics from a series of municipal wastewater sludge incinerators. The
following document presents the final results from the Site 8 emissions test program.
E. Timothy Oppelt, Director
Risk Reduction Engineering Laboratory
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ABSTRACT
The U.S. Environmental Protection Agency (EPA) Office of Water (OW) has
drafted risk-based sludge regulations under Section 405d of the Clean Water Act and
EPA's Risk Reduction Engineering Laboratory (RREL) has been assisting OW in the
collection of supporting data for the proposed regulations. Proposed regulations and a
solicitation for public comment was published in the Federal Register on February 6,
1989. Final regulations are scheduled for publication in the Federal Register in January
1992. Because of the associated cancer risk, there is particular concern regarding
chromium and nickel species in the emissions from sludge incineration.
An RREL/OW research program was implemented to determine the ratios of •
hexavalent to total chromium and nickel subsulfide to total nickel in sewage sludge
incinerator emissions under varied incinerator operating conditions. Site 8, a fluidized
bed incinerator, had good combustion conditions as indicated by low levels of CO and
THC emissions when compared to a multiple hearth incinerator. This report presents
the test results from the third of five incinerator test sites. Four incinerators tested
under a previous project conducted by Radian Corporation are included in the Site
numbering convention used. Thus, the third site in the series tested under the present
project, covered "by this report, is referred to as Site 8.
Secondary objectives of the Site 8 test program included comparing the results for
chromium and nickel subspecies determined by different analytical procedures, gathering
data on other metals and inorganic/organic gases in the incinerator emissions, and
assessing pollutant removal efficiencies by measuring emissions at both the inlet and
outlet to the venturi/impingement tray scrubber control system, and at the outlet of a
pilot-scale wet electrostatic precipitator installed for this test program.
The Site 8 facility is a 24.1 million gallons per day (MGD) secondary biological
treatment plant with a 0.1 MGD septage handling facility. The wastewater influent
comes from predominantly (90%) domestic sources. The treatment facility serves a
population of approximately 175,000.
The incinerator tested was a fluidized-bed incinerator manufactured by Nichols.
The incinerator is designed to burn 1000 pounds per hour at 25% solids of a blended
primary/secondary sludge mixture. Particulate emissions from the incinerator are
controlled by a variable throat venturi scrubber that operates at a pressure drop of about
31 in of water. For the testing program, a pilot-scale wet electrostatic precipitator was
added and sampling was conducted downstream of this system.
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It was anticipated that the nickel subsulfide emissions from a fluidized-bed
incinerator would constitute less than 1% of the total nickel emissions. A wet chemical
analysis indicated that within the analytical detection limit (less than 10% of the total
nickel), no nickel subsulfide was present in the samples. Samples were also analyzed by
X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine
sturcture (EXAFS); no nickel subsulfide was detected within the instrumental detection
limit of 10% of the total nickel.
It was anticipated that the hexavalent chromium emissions from a fluidized-bed
incinerator would constitute less than 1% of the total chromium emissions. A wet
chemical analysis indicated that within the analytical detection limit (less than 1% of the
total chromium), no hexavalent chromium was present in the samples.
Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans
(PCDFs) and semivolatile and volatile organic compounds were also measured. The
total PCDD and PCDF emissions averaged 0.7 and 1.7 nanograms per dry standard cubic
meter (ng/dscm), respectively. Of the semivolatile organics compounds measured, only
1,4-dichlorobenzene (at 21 mg/dscm), naphthalene (at 8.5 mg/dscm), and bis(2-
ethyl)phthalate (at 7.1 mg/dscm) were detected for all three sample runs. Benzyl
alcohol, 1,2-dichlorobenzene, and benzoic acid were detected for at least one of the
three sample runs. Eight of the target volatile organics compound were detected for all
three test runs; they averaged: methylene chloride (110 mg/dscm), chloroform (17
mg/dscm), 1,1,1-trichloroethane (at 6.8 mg/dscm), trichloroethene (at 5.2 mg/dscm),
benzene (6.2 mg/dscm), tetrachloroethene (9.4 mg/dscm), toluene (7.7 mg/dscm), and
ethylbenzene (2,6 mg/dscm).
This report was submitted in fulfillment of Work Assignments under Contract
Nos. 68-02-4442, 68-02-4462, and 68-C0-0027 from the Risk Reduction Engineering
Laboratory under the sponsorship of the U.S. Environmental Protection Agency.
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TABLE OF CONTENTS
Section	Page
Disclaimer	ii
Foreword	 iii
Abstract	 iv
List of Figures	ix
List of Tables	xi
Acknowledgement 	xii
1.0 Introduction		1-1
2.0 Site 8 Test Summary		2-1
2.1	Testing program design		2-1
2.2	Test program results 		2-4
2.2.1	Test program	 2-4
2.2.2	Particulate'/metals results summary 		 2-8
2.2.3	Hexavalent chromium results		 2-8
2.2.4	Nickel speciation	2-12
2.2.5	PCDD/PCDF, Semivolatile and Volatile Organic Compounds . . 2-12
2.2.6	Carbon Monoxide and Total Hydrocarbons and CEMs	2-13
2.2.7	Conclusions	2-13
3.0 Process Description and Operation	 3-1
3.1 Facility description 		3-1
32 Incinerator and pollution control system 		3-2
3.3	Incinerator operating conditions during testing		3-5
4.0 Test Results	^		4-1
4.1	Flue gas conditions 	 4-2
4.1.1	Inlet flue gas conditions		4-2
4.1.2	Midpoint flue gas conditions 		4-5
4.1.3	Wet ESP outlet ESP flue gas conditions		4-5
4.2	Particulate/metals results 		4-5
4.2.1	Control device inlet results 	 4-6
4.2.2	Midpoint (Venturi/tray scrubber outlet) results 	 4-9
4.2.3	Wet ESP outlet results 	4-11
4.2.4	Control device removal efficiencies for metals and particulate . . 4-11
4.2.5	Sludge feed results 	4-12
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Table of contents (continued)
Section	Page
4.2.6	Scrubber water results	4-15
4.2.7	Metal emission factors	4-15
4.3	Hexavalent chromium results . .	4-18
4.3.1	Control device inlet results 	4-21
4.3.2	Midpoint results 	4-21
4.3.3	ESP outlet results 	4-22
4.4	Nickel speciation results 	4-22
4.5	Dioxin/furan and semivolatile organic results	4-24
4.6	Volatile organic results 	4-24
4.7	Continuous emission monitoring results	4-28
4.8	Conclusions from Site 8 test 	4-34
5.0 Sampling Locations and Procedures	 5-1
5.1	Emission sampling locations 	 5-1
5.1.1	Inlet to the control system		5-1
5.1.2	Midpoint		5-4
5.1.3	Outlet of the Wet ESP 		5-6
5.2	Sampling procedures		5-6
5.2.1	Total metals	 5-6
5.2.2	Nickel/nickel subsulfide 	5-11
5.2.3	Chromium and hexavalent chromium (recirculating train) . . . 5-16
5.2.4	Chromium and hexavalent chromium (impinger train)	5-20
5.2.5	Semivolatile Organic and PCDD/PCDF 	5-20
5.2.6	Volatile organic sampling train (VOST) . 	5-26
5.2.7	Continuous emissions monitoring	5-31
5.2.7.1	Sample and data acquisitions 	5-31
5.2.7.2	Carbon monoxide/carbon dioxide analysis	5-32
5.2.7.3	Oxygen analysis 	5-32
5.2.7.4	Nitrogen oxides (NO,) analysis	5-32
5.2.7.5	Sulfur dioxide (S02) analysis	5-33
5.2.7.6	Total hydrocarbon analysis	5-33
5.2.8	EPA Methods 1,2,3, and 4	5-33
5.2.8.1	Volumetric gas flow rate determination	5-33
5.2.8.2	Flue gas molecular weight determination 	5-34
5.2.8.3	Flue gas moisture determination	5-34
5.2.9	Process samples 	5-35
5.3	Process data 	5-35
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Table of contents (continued)
Section	Page
6.0 Analytical Procedures 	 6-1
6.1	Chromium speciation and analyses	 6-1
6.1.1	IC/PCR analysis for hexavalent chromium		6-4
6.1.2	ICAP analysis for total chromium 		6-4
6.1.3	XANES analysis for chromium speciation 		6-5
6.2	Nickel speciation and analysis 		6-6
6.2.1	XANES analysis for nickel speciation 	 6-6
6.2.2	NiPERA method for nickel speciation	 6-6
6.3	Multiple metals analysis	 6-9
6.3.1	Flue gas samples	6-10
6.3.2	Dewatered sludge samples	6-10
6.3.3	Scrubber water samples	6-12
6.4	Semivolatile organic analysis 	6-12
6.5	Volatile organic analysis 	6-16
6.6	Sludge sample analyses 	6-16
7.0 Quality Assurance and Quality Control 	 7-1
7.1	QA/QC program objectives	 7-1
7.2	Flue gas sampling and analysis QC results	 7-5
7.2.1	General flue gas sampling quality control 	 7-5
7.2.2	Sampling and analysis for particulate matter/total metals and
nickel/nickel subsulfide	 7-7
7.2.2.1	Sampling operations	 7-7
7.2.2.2	Sample analysis 	 7-7
7.2.3	Total chromium and hexavalent chromium sampling
and analysis 	7-10
7.23.1 Sampling operations 	7-10
7.2.3.2 Sample analysis	7-10
7.2.4	Continuous emissions monitoring	7-12
7.3	Metals analysis of process samples	7-15
References	 8-1
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LIST OF FIGURES
Number	Page
3-1 Schematic of Site 8 process and control equipment	 3-4
5-1 Process diagram with sampling locations	 5-2
5-2 Inlet sampling location	 5-3
5-3 Midpoint sampling location 	 5-5
5-4 ESP outlet sampling location	 5-7
5-5 Schematic of multiple metals/particulate sampling train	 5-8
5-6 Sample recovery procedures for multiple metals train	5-10
5-7 Schematic of nickel/nickel subsulfide sampling train		5-12
5-8 Schematic of sample recovery procedures for nickel train	5-15
5-9 Schematic of recirculating reagent impinger train for hexavalent chromium . . 5-17
5-10 Sample recovery scheme for hexavalent chromium
recirculating impinger train 	5-19
5-11 Schematic of inlet impinger sampling train for hexavalent chromium	5-21
5-12 Sample recovery scheme for hexavalent chromium impinger train	5-23
5-13 MM5 train for sampling semivolatile organics and PCDD/PCDF	5-25
5-14 Semivolatile organics train sample recovery scheme 	5-27
5-15	Schematic of volatile organic sampling train	5-29
6-1	Analytical protocol for quadruplicate recirculatory hexavalent chromium
sampling at midpoint and outlet locations	 6-3
6-2 Analytical protocol for paired nickel sampling at the scrubber inlet
sampling location	 6-7
6-3 Analytical protocol for paired nickel sampling at the scrubber
outlet sampling location	 6-8
6-4 Sample preparation and analysis scheme for multiple metals trains	6-11
6-5 Extraction schematic for semivolatile organic samples	6-13
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LIST OF TABLES
Number	Page
2-1 Summary of sampling and analytical methods by test location: Site 8 . . . . 2-2,2-3
2-2 Specific elements and compounds of interest 	 2-5
2-3 Summary of sampling and analytical methods	 2-6
2-4 Summary of inlet, midpoint, and ESP outlet flue gas conditions: Site 8 .... 2-7
2-5 Metals and particulate emissions and collection efficiency of the
venturi/tray scrubber: Site 8	 2-9
2-6 Metals and particulate emissions and collection efficiency
of the wet ESP: Site 8	2-10
2-7	Summary of hexavalent and total chromium result: Site 8	2-11
3-1	Incinerator design information	 3-3
3-2	Summary of incinerator operating conditions at Site 8 	 3-6
4-1	Summary of inlet, midpoint, and ESP outlet flue gas conditions; Site 8 .... 4-3
4-2 Summary of inlet and outlet continuous emission measurements: Site 8 .... 4-4
4-3 Metals and particulate emissions and collection efficiency of the
venturi/tray scrubber: Site 8	 4-7
4-4 Metals and particulate emissions and collection efficiency
of the wet ESP: Site 8 	 4-8
4-5 Summary of metal concentrations in fly ash 	4-10
4-6 Input rate of metals in sewage sludge	4-13
4-7 Results for proximate and ultimate analyses of sludge samples	4-14
4-8 Discharge rate of metals in scrubber water	'	4-16
4-9 Rate of metals to and from incinerator 	4-17
4-10 Inlet and outlet metal emission factors	4-17
4-11 Ratio of metal to particulate 	4-19
4-12 Summary of hexavalent and total chromium results: Site 8	4-20
4-13 Summary of nickel species emissions: Site 8 	4-23
4-14 PCDD/PCDF emissions summary 	4-25
4-15 Semivolatile emissions summary	4-26,4-27
4-16 Volatile organics emissions summary 	4-29
4-17 Summary of inlet and midpoint continuous emission monitoring
results (10-min averages)	4-30,4-31,4-32
4-18 Summary of inlet and midpoint continuous emission monitoring
results (5-min averages)	4-33
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LIST OF TABLES (Continued)
Number	Page
5-1	Metals glassware cleaning procedures	 5-9
5-2	Sample recovery components for multiple metals train	 5-9
5-3	Nickel/nickel subsulfide glassware cleaning procedures	5-14
5-4	Sample recovery components for the nickel/nickel subsulfide train	5-14
5-5	Cr+*/Cr teflon/glass components cleaning procedures	5-18
5-6	Sample recovery components for the Cr+6/Cr recirculating reagent
impinger sampling train	5-18
5-7	Cr/Cr+* glassware cleaning procedures	5-22
5-8	Sample recovery components for Cr/Cr+* impinger train 	5-22
5-9	Semivolatile organics glassware cleaning procedure 	5-26
5-10	Sample recovery components for semivolatile organics train	5-28
5-11	Process monitoring data	5-36
6-1	Summary of sampling and analytical methods	 6-2
7-1	Precision, accuracy and completeness objectives	 7-4
7-2	Isokinetics and leak check summary; Site 8, multi-metal, nickel and
semivolatile trains, midpoint and outlet locations	 7-8
7-3 QC results for reagent blanks and audit sample for multi-metal and nickel
sampling trains 	 7-9
7-4 Isokinetics and leak check summary; Site 8, hexavalent chromium sampling,
midpoint and outlet locations		 . 7-11
7-5 Recoveries of 5ICr+* spike 	7-13
7-6 Summary of CEM drift checks	7-14
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ACKNOWLEDGEMENTS
The authors gratefully acknowledge the following invaluable contributions to the
fforts described in this report: Dr. Joseph E. Knoll of the Quality Assurance Division of
EPA for advice and assistance on hexavalent chromium sampling and analysis, Dr.
Vladimar Zatka of Zatka Chemical Consulting Company for advice and analytical work
on nickel speciation, Dr. Nolan F. Mangelson of Brigham Young University for
instrumental analysis of chromium and nickel species, Dr. Kate K. Luk of Research
Triangle Institute for metals analysis, Dr. James R. Holtzclaw of General Engineering
Laboratories for ICP/MS analysis of hexavalent and total chromium, Dr. Yves Tondeur
of Triangle Laboratories for trace organic analysis, and Dr. Scott C. Steinsberger,
formerly of Entropy Environmentalists, Inc. for his tireless effort and ingenuity in
developing new methodologies.
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1.0 INTRODUCTION
The U.S. Environmental Protection Agency (EPA) Office of Water (OW) has
been developing new regulations for sewage sludge incinerators and EPA's Risk
Reduction Engineering Laboratory (RREL) has been assisting OW in the collection of
supporting data. There is particular concern regarding chromium and nickel species in
the emissions from incineration of municipal wastewater sludge because of the associated
cancer risk. OW has drafted risk-based sludge regulations under Section 405d of the
Clean Water Act which have been published for comment in the Federal Register.
Volume 54, No. 23, February 6, 1989. Final regulations are scheduled for publication in
the Federal Register in January 1992.
The draft regulations are based on the risk incurred by the "most exposed
individual11 (MEI). The MEI approach involves calculating the risk associated with an
individual residing for seventy years at the point of maximum ground level concentration
of the emissions just outside the incinerator facility property line. EPA's proposal for
regulating sewage sludge incinerators is based on ensuring that the increased ambient air
concentrations of metal pollutants emitted from sludge incinerators are below the
ambient air human health criteria. The increased ambient air concentrations for four
carcinogenic metals, arsenic, chromium, cadmium, and nickel, are expressed as annual
averages. The concentrations are identified in the proposed regulations as Risk Specific
Concentrations (RSC). Both nickel and chromium emissions from sludge incinerators
presented a specific problem in establishing RSCs, because unknown portions of the
emissions of these metals are in forms which are harmful to human health. In
performing the risk calculations, EPA assumed that 1% of the emissions of chromium
from the sludge incinerators is in the most toxic form, hexavalent
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chromium. For nickel, EPA assumed that 100% of the nickel emissions are in the most
toxic form, nickel subsulfide.
Chromium is likely to be emitted in either the highly carcinogenic hexavalent state
(Cr+6) or in the noncarcinogenic trivalent state (Cr+3). Trivalent chromium has not been
shown to be carcinogenic and is toxic only at levels higher than those normally found in
sewage sludge incinerator emissions. Although hexavalent chromium (as the most
oxidized form) could be reasonably expected to result from combustion processes,
investigators speculate that most of the chromium is likely to be emitted in the trivalent
state.1 This is because hexavalent chromium is highly reactive, and thus likely to react
with reducing agents to form trivalent chromium.
Studies have been conducted to determine the potential for chromium in sewage
sludge to be converted to the hexavalent form. Analysis of laboratory combusted sludges
dosed with various levels of lime and ferric chloride revealed that the hexavalent to total
chromium ratio increased with lime dosage.1 One-hundred percent conversion of
chromium to hexavalent chromium was observed in several of the tests.1 These tests
indicate that when lime and ferric chloride are used as sludge conditioners, high ratios of
hexavalent to total chromium may be formed under certain incinerator operating
conditions.
EPA has previously sponsored emission testing studies for measurement of
hexavalent chromium at two sludge incinerators.2*3 For one site, the hexavalent
chromium concentrations were below the analytical detection limit; for the other site, a
hexavalent-to-total chromium ratio of 13% was calculated. The 1% value chosen for the
draft regulations jnay seem low. This is the result, however, of weighting various values
to give the most credible ones more influence. With this approach, lower values were
assigned a stronger contribution. The lack of a substantial data base on hexavalent
chromium emissions prompted the following statement in the EPA's Technical Support
Document for the Incineration of Sewage Sludge: "EPA plans to perform additional tests
of sewage sludge incinerator emissions for hexavalent chromium before this proposed
rule is finalized. The additional data should allow the Agency to better understand how
hexavalent chromium is generated in sewage sludge incinerators." As previously stated,
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EPA assumed that 100% of the nickel emissions are in the subsulfide form to calculate
an RSC. Since the Agency had no nickel subsulfide emission data from sewage sludge
incinerators, it took the most conservative approach in conducting the nickel risk analysis
and assumed that all emitted nickel compounds cause the same health effects as nickel
subsulfide. Again, the Technical Support Document stated: MAs additional data become
available on the form of chromium and nickel emissions from combustion sources, the
Agency will consider what changes, if any, would be appropriate for these proposed
regulations."
There were no published EPA emission measurement test methods for the
sampling and analysis of hexavalent chromium or nickel subsulfide. In addition, very
little data exist on the conditions that may cause their formation.
The primary objective of the Site 8 test program was to determine the ratio of
hexavalent-to-total chromium and the ratio of nickel subsulfide-to-total nickel for a
typical sewage sludge incinerator under low excess air and short ash residence time as
typically provided by fluidized-bed incinerator combustion. Low excess air and a short
residence time of the ash in the furnace are not favorable conditions for the formation of
hexavalent chromium; low excess air is favorable for the formation of nickel subsulfide.
OW has established seven secondary objectives also beneficial to the overall test
program.
(1) Implement sampling and analytical procedures for chromium and nickel in
municipal sewage sludge incinerator uncontrolled flue gas emissions and
controlled stack emissions.
(2) Compare the ratios of emissions of (1) hexavalent-to-total chromium and
(2) nickel subsulfide-to-total nickel for various types of incinerators and for
different operating conditions.
(3) Compare the analytical results of emissions of chromium and nickel
subspecies determined by different analytical procedures.
(4) Gather data on additional metals and inorganic and organic gaseous
components (as cited in the Federal Register. Volume 54, No. 23, February
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6, 1989) in uncontrolled and controlled incinerator emissions to obtain
background data on the effect of operating conditions on these emissions.
(5) Evaluate wet electrostatic precipitators as retrofit control systems to help
existing facilities meet the new sewage sludge emission regulations.
Continuous emissions monitoring of oxygen (02), carbon dioxide (C02), carbon
monoxide (CO), sulfur dioxide (S02), and oxides of nitrogen (NO,) at the control system
inlet and CO and total hydrocarbons (THC) at the control system outlet stack were used
to establish process and control equipment operation during the manual testing and to
provide additional emissions data.
This report presents the results for Site 8 the fourth test program in a series of
five completed for this portion of RREL's research program (Sites 5, 6, 7, 8, and 9).
Four incinerators tested under a previous project conducted by Radian Corporation are
included in the Site numbering convention used. This report is organized in two
volumes. The Emission Report is contained in Volume VI, while the Appendices are
included in Volume VII.
The following sections present detailed descriptions of the testing and results from
the Site 8 program. Section 2.0 presents a summary of the results. Section 3.0 presents
the process description and process operating conditions. Section 4.0 provides a detailed
discussion of the sampling and analytical results. Section 5.0 describes the sampling
location and procedures and Section 6.0 describes the analytical procedures. The quality
assurance/quality control activities and results are presented in Section 7.0.
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2.0 SITE 8 TEST SUMMARY
2.1 TESTING PROGRAM DESIGN
The emphasis of testing at Site 8 was to determine the effect of low excess air on
the conversion of total chromium and total nickel in the sludge to hexavalent chromium
and nickel subsulfide in the emissions. The following criteria were considered in
selecting this test site: adequate levels of chromium and nickel in the sludge, suitable
sampling locations, a fluidized-bed incineration process, a venturi scrubber capable of
achieving medium to high pressure drops, and a site not previously tested for RREL.
Also considered in selecting Site 8 was the presence of a pilot-scale wet electrostatic
precipitator (wet ESP).
Low excess air in the furnace presents conditions which are not favorable for the
formation of hexavalent chromium, and are favorable for the formation of nickel
subsulfide. In addition to speciation of chromium and nickel emissions, sampling was
also conducted for trace metals, polychlorinated dibenzo-p-dioxins and polychlorinated
dibenzofurans (PCDDs/PCDFs), semivolatile organic compounds, and volatile organic
compounds. Continuous emissions monitoring (CEM) techniques were used to measure
O* C02, CO, S02, and NOx at the control system inlet and 02, C02, CO, S02, NOx, and
THC at the control system outlet stack. The monitoring data were used principally to
determine process and control equipment operating conditions during the chromium and
nickel speciation tests.
The emission testing at Site 8 was conducted from January 9 to January 12, 1990.
The test program sampling matrix is shown in Table 2-1. Sampling was conducted at the
inlet and outlet (hereafter referred to as the midpoint) of the venturi/impingement tray
scrubber used to control the incinerator emissions and at the outlet of a pilot-scale wet
ESP temporarily applied to the system (hereafter referred to as the outlet). Certain inlet
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TABLE 2-1. SUMMARY OF SAMPLING AND ANALYTICAL METHODS BY TEST LOCATION: SITE 8
N)
i
N)
Sampling
Location
Sample
Type
Sampling
Method
No. of
Runs
Analysis
Parameter
Analysis
Method
Out let
Combustion gas
RC train (EPA
Draft MHtl )*
3 paired-train
Cr*fl, total Cr
Ion chromatography with po«
chromatography (IC/PCR), gi
ICP/AAS, I CP/MS, XANES


EPA Draft Mi Htdb
3 paired-train
Ni subsulfide,
total Ni
EPA Draft Mtd, XANES,
ICP/AAS


EPA Draft Multi-
metal Htd
3 paired-train
PM, Cr, Ni, As,
Pb, Cd, Be, Hg
ICP/AAS


MM5 (SW-846 Htd
0010)
3
PCDD/PCOF,
semivolatiles
HRGC/HRMS (SW-846 Mtds
8290 & 8270*)


Methods 3 & 4

o2/co2/h,o
Orsat, Gravimetric


CEM
•
«
02
CO,
CO
S02
NO„
Electrocatalytic cell
NO IR
GFC
IR
Chemiluminescence
Midpoint
Combustion gas
RC train (EPA
Draft Mtd)*
6 quad-train
Cr*a, total Cr
IC/PCR, gamma counter,
ICP/AAS, I CP/MS, XANES


EPA Draft Ni Mtdb
6 paired-train
Ni subsulfide,
total Ni
EPA Draft Mtd, XANES,
ICP/AAS


EPA Draft Multi-
metal Mtd
6 paired-train
PM, Cr, Ni, As,
Pb, Cd, Be, Hg
ICP/AAS


MM5 (SW-846 Mtd
0010)
3
PCOD/PCOF,
semivolatiles
HRGC/HRMS (SW-846 Mtds
8290 & 8270)c


VOST (SU-846 Mtd
0030)
3
Volatile organics
GC/HS (SW-846 Mtds
5040 & 8240)


Methods 3 & 4

02/C02/H20
Orsat, Gravimetric
(Continued)

-------
TABLE 2-1. (Continued)
Sanpling	Sample	Sampling	No. of	Analysis	Analysis
Location	Type	Method	Runs	Parameter	Method
Inlet Combustion gas
RC train (EPA
Draft Mtd)'
6 quad-train
Cr'4
, total Cr
IC/PCR, garrma counter,
ICP/AAS, I CP/MS, XANES

EPA Draft Mi Mtd"
6 paired-train
Ni subsulfide,
total Ni
EPA Draft Mtd, XANES,
ICP/AAS

EPA Draft Multi-
metal Mtd
6 paired-train
PM,
Pb,
Cr, Ni, As,
Cd, Be, Hg
ICP/AAS

Methods 3 & 4

Oj/COj/^O
Orsat, Gravimetric

CEH
0
O,
CO,
CO
SO,
NO,

Electrocatalytic cell
NDIR
GFC
IR
Chemi luninescence
Scrubber Liquid
Water Inlet
Integrated grab
h
Cr.
Cd,
Ni, As, Pb,
Be, Hg
ICP/AAS
Scrubber Liquid
Water Outlet
Integrated grab
h
Cr,
Ni, As, Pb,
ICP/AAS
Cd, Be, Hg
Incinerator Bottom Ash
Ash Discharge
Grab
J
Cr,
Cd,
Ni, As, Pb,
Be, Hg
ICP/AAS
Incinerator Sludge
Feed
Grab
h
Cr, Ni, As, Pb,
Cd, Be, Hg
Moisture
Proximate & ulti-
mate analyses
Heating value
ICP/AAS
ASTM D3174
ASTM D3174, D3175, D3178,
D3179, D2361, D3177
ASTM 03176
Recirculating train for hexavalent chromiun at midpoint and outlet and impinger train for inlet.
"Method 5-type sampling train for nickel.
'Plus SW-846 Methods 3540, 3550, 3510, and/or 3520 for sample preparation and cleanup.
">iethod-5 type sampling train for chromiun.
'Collect integrated samples simultaneously with manual sampling at each location.
'Conducted using RC, Hi, Hultimetal, MM5, and impinger trains.
"During manual sampling at inlet and outlet locations.
"Two aliquots taken during each test period.
JOne sample taken during each test period.
*Taken at 30-minute intervals during test period starting 30 minutes prior.

-------
and outlet flue gas conditions (see Table 2-1) were monitored continuously to ensure
that acceptable incinerator operating conditions existed during the manual sampling.
The specific elements and compounds of interest for the emission testing are
presented in Table 2-2. A summary of the sampling and analytical methods used to
conduct the testing are presented in Table 2-3.
Three test runs were conducted at the inlet, the midpoint, and the outlet sampling
locations at Site 8 for arsenic, beryllium, cadmium, chromium, lead, and nickel. The
particulate emissions were also determined using the multiple metals sampling train.
Composite sludge feed samples and scrubber water inlet and outlet samples were taken
during each test day. The sampling and analytical methods are described in detail in
Sections 5.0 and 6.0, respectively.
2.2 TEST PROGRAM RESULTS
This section summarizes the test results for the Site 8 test program. The
emissions results and associated emission factors are highlighted in this section; the run
by run data, as well as the process sample results are detailed in Section 4.0. The test
program schedule is presented in Section 2.2.1. Particulate and metal results are
summarized in Section 2.2.2, hexavalent chromium results are summarized in Section
2.2.3; nickel speciation results are summarized in Section 2.2.4; PCDD/PCDF,
semivolatile, and volatile organic compound results are summarized in Section 2.2.5, and
total hydrocarbon (THC) and carbon monoxide (CO) results are summarized in Section
2.2.6. Conclusions are presented in Section 2.2.7.
2.2.1 Test Program
The Site 8 sampling locations, run numbers, and sample times are summarized in
Table 2-4. Testing was conducted during normal (steady-state) operation.
2-4

-------
TABLE 2-2. SPECIFIC ELEMENTS AND COMPOUNDS OF INTEREST
I. Metal Speciation	11. Total Metals6 III. Combustion Gases and
Criteria Pollutants
A. Trivalent Chromium4
A.
Arsenic
A.
o2
B. Hexavalent Chromium*
B.
Beryllium
B.
C02
C. Soluble Nickelb
C.
Cadmium
C.
CO
D. Sulfidic Nickel1*
D.
Chromium
D.
so2
E. Oxidic Nickel"
E.
Lead
E.
NO,

F.
Mercury
F.
THC

G.
Nickel


IV. PCDDs/PCDFS
PCDDs
A.
Mono-CDD
B.
Di-CDD
C.
Tri-CDD
D.
2378-TCDD
E.
Other TCDD
F.
12 378-PCDD
G.
Other PCDD
H.
123478-HxCDD
I.
123678-HxCDD
J.
12 3789-HxCDD
K.
Other HxCDD
L.
12 34678-HpCDD
M.
Other HpCDD
N.
Octa-CDD
PCDFs
O.	Mono-CDF
P.	Di-CDF
Q.	Tri-CDF
R.	2378-TCDF
S.	Other TCDF
T.	12378-PCDF
U.	2 378-PCDF
V.	Other-PCDF
W.	12 3478—HxCDF
X.	12 3678-HxCDF
Y.	2 34678-HxCDF
Z.	123789-HxCDF
AA.	Other HxCDF
BB.	1234678—HpCDF
CC.	1234789-HpCDF
DD.	Other HpCDF
EE.	Octa-CDF
Semivolatile Oraanics
VI.
Volatile Oraanics
A.
Bis (2-ethylhexyl)phthalate
A.
Acrylonitrile
B.
1,2-Dichlorobenzene
B.
Benzene
C.
1,3-Dichlorobenzene
C.
Carbon tetrachloride
D.
1,4-Dichlorobenzene
D.
Chlorobenzene
E.
Phenol
E.
Chloroform
F.
Naphthalene
F.
1,2-dichloroethane


G.
Trans1,2-dichloroethane


H.
Ethylbenzene


I.
Methylene chloride


J.
Tetrachloroethane


K.
Toluene


L.
1,1,1-Trichloroethane


M.
Trichloroethane


N.
Vinyl chloride
•Hexavalent chromium is generally soluble in water; however, in the trivalent
form, it is generally insoluble. This causes problems in determining the
amount of total chromium in stack emissions. The chromium subspecies are of
interest to OW since their rate of conversion fluctuates, thus giving
unreliable estimates of total chromium emissions.
^Nickel subspecies are of interest to OW for the same reasons described for
chromium emissions.
cThese metals are of specific interest to OW. They were analyzed by ICAP;
chromium and nickel were also analyzed also by XANES.
2-5

-------
TABLE 2-3. SUMMARY OF SAMPLING AND ANALYTICAL METHODS
Sampling Location
Parameter
Sampling Method
Analysis Method
Inlet to the
• Total chromium,
EPA Draft 4b
IC/PCR, gamma
Control Device
Cr + e
Cr+e Methods
counter,XANES,

ICAP/AA

• Total nickel,
EPA Draft®
EPA Draft Method,

nickel
Ni Method
XANES, ICP/AA

subsulfide

• Particulates,
EPA Draft
ICAP/AA

metalsd
MMtl Method

® O2 / CO21 CO,
3A, 10, 7E
3A, 10, 7E

NOx, S02,
and 6C
and 6C

• Fixed gases
Method 3
Orsat

-------
TABLE 2-4. SUMMARY OF INLET, MIDPOINT, AND ESP OUTLET FLUE GAS CONDITIONS; SITE 8
Run No. &
Condition
Sampling Test
Location Date Run Time
Flue Gas Conditions
Temp Moisture Oxygen Air Flow
(°F) (% H20) (% dry) (dscf/min)
Run 4
Normal
Midpoint 1/09/90 12:00-14:00
ESP Outlet 12:00-14:00
91.7 6.7 8.0 3260
76.2 3.9 8.0 1182
Run 5
Normal
Inlet 1/09/90 15:00-15:30
Midpoint 14:15-16:15
ESP Outlet 14:3 0-16:30
905 38 8.1 3185
89.3 6.8 8.1 3185
75.6 2.4 8.1 1393
Run 7
Normal
Inlet 1/10/90 11:15-11:45
Midpoint 10:45-12:45
ESP Outlet 10:45-12:45
1160 40 10 2820
91.4 6.7 7.5 2820
81.9 3.2 7.6 1313
Run 6
Normal
Midpoint 1/10/90 14:15-16:15
ESP Outlet 14:3 0-16:30
92.6 8.1 7.4 2878
79.2 3.6 7.4 1336
Run 9
Normal
Inlet 1/11/90 09:3 0-10:00
Midpoint 09:15-11:15
ESP Outlet 09:15-11:15
1180 37 7.9 2870
103 9.0 8.0 2870
93.2 4.9 8.0 1626
Run 8
Normal
Inlet 1/11/90 14:30-15:15
Midpoint 12:55-14:55
ESP Outlet 12:55-14:55
1170 36 7.7 3170
106 8.9 7.7 3170
91.5 NDa 7.7 1582
Run 10
Normal
Inlet 1/12/90 09:50-10:35
Midpoint 09:30-11:30
1180 41 8.0 2690
88.4 6.7 8.0 2690
aNot determined
-------
2.2.2 Particulate/Metals Results
Test runs 5, 7, 9, and 10 were conducted to determine control system collection
efficiency for the metals of interest: arsenic (As), beryllium (Be), cadmium (Cd),
chromium (Cr), lead (Pb), nickel (Ni), and mercury (Hg). Runs 7, 9, and 10 were used
to determine the collection efficiency of the venturi scrubber/impingement tray control
system, and runs 5, 7, and 9 were used to determine the collection efficiency of metals
for the wet ESP. The metals and particulate emissions were determined using the
multiple metals (MMtl) sampling system. The emissions results and collection
efficiencies of the venturi scrubber/impingement tray scrubber for metals and particulate
are shown in Table 2-5 on a concentration basis and mass emission rate basis. The
removal efficiency of the pilot scale wet ESP for particulates and metals are shown in
Table 2-6 along with the results on a concentration and mass emission basis. Note: The
mercury results are not shown because EPA recently determined that mercury
precipitates in the MMtl sampling train impinger solution. New digestion procedures
have been added to the method to recovery the mercury in the precipitate. Therefore,
the results for mercury in this study are considered invalid and are not reported.
2.2.3 Hexavalent Chromium Results
The hexavalent chromium samples from the Method 5-type trains used to conduct
the inlet sampling and some of the outlet recirculating train samples were analyzed by
General Engineering Laboratory in Charleston, SC. Due to background interferences
and the extremely low levels of the native hexavalent chromium, no reportable data was
obtained. The remaining samples were analyzed by ion chromatography (IC) with a
post-column colorimetric reaction (PCR) specific for hexavalent chromium. IC was also
used to separate the hexavalent chromium isotope from the trivalent isotope prior to
gamma emission counting. All samples analyzed by IC/PCR were also analyzed for total
chromium by inductively-coupled argon plasmography (ICP). The results for the
hexavalent chromium samples are presented in Table 2-7.
2-8
-------
TABLE 2-5. METALS AND PARTICULATE EMISSIONS AND COLLECTION EFFICIENCY
OF THE VENTURI/TRAY SCRUBBER: SITE 8
Run No. / Location
As
fig/m3
mg/hr
Be
jtg/m3 mg/hr
Cd
M9/m3 mg/hr
Cr
pg/m3 mg/hr
Pb
pg/m3 reg/hr
N
Kg/n3
Mg/hr
Particulate
mg/n»3 g/hr
RUN 7D - INLET
161
786
42
207
152
741
2790
13600
2200
10700
1170
5690
19500
95100
RUN 7D - MIDPOINT
<0.9
<5.0
0.02
0.08
0.50
2.46
3.27
16.0
4.75
23.2
2.52
12.3
2.94
14.3
COLLECTION
EFFICIENCY (X)
>99.44"

99.96

99.68

99.88

99.78

99.99

RUN 90 - INLET
244
1200
28
139
183
899
2680
13200
2590
12800
1480
7290
20900
103000
RUN 90 - MIDPOINT
<1.0
<5.0
<.03
<.12
0.30
1.46
2.33
11.5
0.77
3.78
1.33
6.57
4.81
23.7
COLLECTION
EFFICIENCY (X)
>99.59

>99.89

99.84

99.91

99.70

99.91

99.99

RUN 10D - INLET
212
977
40
186
296
1360
3500
16200
3510
16200
2310
10700
23700
109000
RUN 1OD - MIDPOINT
<1.0
<5.0
0.01
0.03
0.13
0.62
1.58
7.26
0.41
1.88
0.88
4.04
3.60
16.6
COLLECTION
EFFICIENCY (X)
>99.53

99.98

99.95

99.96

99.99

99.96

99.99

INLET - Average
206
988
37
177
210
1000
2990
14300
2760
13200
1650
7880
21400
102000
MIDPOINT - Average
<1.0
<5.0
<.02
<.08
0.31
1.51
2.39
11.6
1.98
9.62
1.58
7.64
3.78
18.2
EFFICIENCY
Average (X)
>99.52

>99.95

99.82

99.92

99.91

99.89

99.99

'The collection efficiency is based on the concentration results, because the flowrate at wet ESP outlet was less than that at the
midpoint.
-------
TABLE 2-6. METALS AND PARTICULATE EMISSIONS AND COLLECTION EFFICIENCY
OF THE WET ESP: SITE 8
Run No./Location
As
llQ/nS
mg/hr
Be
Mg/m3
mg/hr
Cd
Mfl/m3
mg/hr
Cr
M9/m3
mg/hr
Pb
Mg/m3
mg/hr
Ni
Mfl/m3
mg/hr
Particulate
mg/m3 g/hr
RUN 50 - MIDPOINT
<0.9
<4.a
0.01
0.08
0.56
3.08
1.40
7.63
1.81
9.89
1.58
8.64
6.28
34.3
RUN 5A - ESP OUTLET
<0.9
<2.1
0.00
0.00
0.05
0.13
0.40
0.97
<.10
<.2
<.2
<.5
1.16
2.77
RUN 5B - ESP OUTLET
<0.9
<2.1
-.01"
0.00
0.08
0.20
0.93
2.22
<.10
<.2
0.20
0.49
2.05
4.90
COLLECTION
EFFICIENCY (X)
UAbc

>95

RUN 7D - MIDPOINT
<1.0
<5.0
0.02
0.08
0.50
2.46
3.27
16.0
4.75
23.2
2.52
12.3
2.94
14.3
RUN 7A - ESP OUTLET
0.93
2.10
<.04
<.09
0.19
0.43
0.85
1.92
0.04
0.09
0.84
1.89
0.30
0.67
RUN 78 - ESP OUTLET
<0.9
<2.1
<.04
<.09
0.28
0.63
0.99
2.22
0.25
0.57
0.96
2.16
0.74
1.66
COLLECTION
EFFICIENCY (X>
NA

MIDPOINT - Average
<1.0
<4.9
0.02
0.08
0.53
2.77
2.34
11.8
3.28
16.5
2.05
10.5
4.61
24.3
ESP OUTLET - Average
<0.9
<2.1
<.04
<.09
0.15
0.35
0.79
1.83
<.12
<.26
<.55
<1.26
1.06
2.5
EFFICIENCY-Average(X)
NA

>96

RUN 9D - MIDPOINT
<1.0
<5.0
<.03
<.12
0.30
1.46
2.33
11.5
0.77
3.78
1.33
6.57
4.81
23.7
RUN 9A - ESP OUTLET*
<0.8
<2.3
<.03
<.10
0.26
0.73
1.22
3.42
<.10
<.2
2.13
5.95
4.33
12.1
RUN 98 - ESP OUTLET
1.37
3.82
<.03
<.10
3.60
10.0
3.44
9.59
0.15
0.42
0.85
2.36
2.68
7.5
COLLECTION
EFFICIENCY (X)
NA

-540

>84

-11

'Negative numbers indicate sample value was less than blank value.
'Value was less than the detection limit
'The collection efficiency is based on concentration, because the flowrate through wet ESP was less than at the midpoint.
dUet ESP was operated above the design flowrate and results not included in average.
-------
TABLE 2-7. SUMMARY OF HEXAVALENT AND TOTAL CHROMIUM RESULT:SITE 8
Sample
Identity
Native
Hex Cr
(ug/dscm)
Recovery of
Isotope Spikes (%)
51Cr+6 53Cr+6
Total
Chromium
(ug/dscm)
Ratio
Cr+6/Cr
(%)
Run 4B-IN
Run 4C-IN
Run 4D-IN
NA
< 11
< 11
NA
40.0
25.0
96500
72100
b
< 0.01
< 0.02
Run 4A-MID
Run 4B-MID
Run 4C-MID
Run 4D-MID
NA
< 0.02
0.01
0-02
NA
63.4
10.7
9.5
3.0
1.4
1.7
< 0.5
0.7
1.1
Run 4A-ESP
Run 4B-ESP
NA
0. 03
85.9 NA
78.2
1.1
2.5
Run 6A-IN
Run 6B-IN
NA
< 7.5
48.3 NA
66.1
31200
< 0.02
Run 6A-MID
Run 6B-MID
Run 6C-MID
Run 6D-MID
< 0.02
NA
0.02
< 0.02
62.3
NA
52.8
62.2
1.5
1.9
2.9
1.5
< 1.2
0.6
< 1.1
Run 6A-ESP
Run 6B-ESP
NA
< 0.02
92.6 NA
85.1
1.4
0.8
< 0.4
Run 8A-IN
Run 8B-IN
NA
9.9
82.8 NA
79.5
3800
0.3
Run 8A-MID
Run 8B-MID
Run 8C-MID
Run 8D-MID
NA
< 0.02
< 0.02
< 0.01
NA
79.3
73.6
74.0
1.2
1.5
1.3
< 1.3
< 1.2
< 1.1
Run 8A-ESP
Run 8B-ESP
NA
< 0.01
81.4 NA
65.6
0.9
1.0
< 1.3
aNA - Not available.
b— - Could not be calculated due to lack of data.
Note: Problems were encountered in the inlet hexavalent
chromium analysis and the midpoint and outlet total
chromium analysis.
2-11
-------
2,2.4 Nickel Speciation
The nickel speciation runs were conducted simultaneously with the particulate/metals
train runs. Nickel subsulfide cannot be measured directly at the levels encountered in
these emissions. A wet chemical technique was used to measure sulfidic nickel, the
combination of both nickel sulfide and nickel subsulfide. Sulfidic nickel was detected in
only one of the midpoint samples analyzed, and its presence is suspected to be an
artifact caused by sampling as sulfidic nickel was not detected in any of the inlet samples
analyzed. Because of the extremely low weight of sample collected for the outlet
samples no attempt was made to conduct nickel speciation. Based on the limit of
detection for the midpoint, the nickel subsulfide constitutes less than 14% of the total
nickel emissions (excluding the one possible outlier). Considering the limit of detection
for the inlet samples, the nickel subsulfide constitutes less than 10% of the total nickel
emissions.
2.2.5 PCDD/PCDF. Semivolatile and Volatile Organic Compounds
The trace organic sample was conducted in the normal discharge stack for the
venturi/impingement tray scrubber, which is the same emission as the midpoint location.
The total polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans
(PCDFs) emissions averaged 0.7 and 1.7 nanogram per dry standard cubic meter
(ng/dscm), respectively. Of the semivolatile organics compounds measured, only 1,4-
dichlorobenzene (at 21 mg/dscm), naphthalene (at 8.5 mg/dscm), and bis(2-
ethyl)phthalate (at 7.1 mg/dscm) were detected for all three sample runs. Benzyl
alcohol, 1,2-dichlorobenzene, and benzoic acid were detected for at least one of the
three sample runs. Eight of the target volatile organics compound were detected for all
three test runs; they averaged: methylene chloride (110 mg/dscm), chloroform (17
mg/dscm), 1,1,1-trichloroethane (at 6.8 mg/dscm), trichloroethene (at 5.2 mg/dscm),
benzene (6.2 mg/dscm), tetrachloroethene (9.4 mg/dscm), toluene (7.7 mg/dscm), and
ethylbenzene (2.6 mg/dscm).
2-12
-------
2.2.6 Carbon Monoxide and Total Hydrocarbons and CEMs
EPA is evaluating monitoring CO and THC emissions as a surrogate indicator of
organic emissions. Since the emissions of CO and THC were consistently low, they do
not provide spread to establish a correlation. Continuous emissions monitoring (CEM)
of oxygen, carbon dioxide, and oxides of nitrogen were also conducted at the inlet and
outlet (midpoint) of the venturi/ impingement tray scrubber. The scrubber system
demonstrated a collection efficiencies of about 93% and 72% for sulfur dioxide and
oxides of nitrogen, respectively.
2.2.7 Conclusions
From the perspective of method development and data quality, the test program
conclusions are:
1. The ratio of hexavalent chromium to total chromium in the emissions was
very low (despite relatively high total chromium levels), probably due to the
short sludge retention time in the fluidized bed incinerator and the absence
of alkaline material in the sludge.
2. The ratio of nickel subsulfide to total nickel in the emissions was extremely
low, with the nickel sulfide/subsulfide species measured at the inlet and
midpoint being less than the detection limit.
3. Compared to Site 3, a fluidized bed incinerator where the only semi-volatile
organic compound detected was bis(2-ethylhexyl)phthalate, several additional
semivolatiles were found in the emissions at Site 8. These were 1,2-
dichlorobenzene, 1,4-dichlorobenzene, benzyl alcohol, benzoic acid, and
naphthalene.
4. The volatile organic compound emission results for Site 8 were consistent
with the results for Site 3 (another fluidized-bed incinerator). Carbon
tetrachloride and chlorobenzene, reported in the emissions at Site 3, were not
found in the emissions from Site 8.
2-13
-------
3.0 PROCESS DESCRIPTION AND OPERATION
3.1 FACILITY DESCRIPTION
The Site 8 facility is a 24.1 million gallons per day (MGD) secondary biological
treatment plant with a 0.1 MGD septage handling facility. The wastewater influent
comes from predominantly (90%) domestic sources. The treatment facility serves a
population of approximately 175,000.
Septage flows are combined with incoming wastewater subsequent to both streams
being screened and degritted. The screening and grit from both streams are hauled to
the County Landfill.
The primary treatment process begins in two 110 ft diameter circular primary
clarifiers. The primary sludge is then pumped to two gravity thickeners for further
thickening, and the gravity thickened sludge is pumped to blend tanks where it is mixed
with waste biological sludge. The primary sludge accounts for 40 to 50% of the sludge
solids volume. The waste biological sludge accounts for the remaining 50 to 60% of the
sludge solids volume.
The secondary treatment system involves two side-by-side three-pass biological
reactors configured to operate in any process mode; this facility normally uses the
+
reaeration mode. Aeration is supplied by fine bubble dome diffusers. The effluent
biological sludge is further thickened by dissolved air flotation thickening and pumped to
the blend tank and mixed with the primary sludge.
The clear supernate that overflows the secondary clarifiers is chlorinated and
discharged into the river.
All 22 tons per day of sludge solids are dewatered by two belt presses to a
concentration of 22 to 25% solids. Approximately 15 to 17 tons of solids are dewatered
by one press and fed to'the fluidized bed incinerator. The air pollution control system
3-1
-------
associated with this incinerator consists of a water injection venturi and an impingement
tray scrubber. The remaining 5 to 7 tons of solids are lime stabilized and hauled to out-
of-state landfill. Site 8 sludge is generically classified for any type of land application.
Also, Site 8 is consistently in compliance with Regulation Permit Requirements for
exhaust gas stack emissions and plant effluent water discharge.
3.2 INCINERATOR AND POLLUTION CONTROL SYSTEM
The incinerator tested was a fluid bed incinerator originally manufacturer by
Dorr-Oliver but recently upgraded by Niro under the direction of Consulting Engineer
Services to include a heat exchanger and a warm windbox (nominal temperature 600 -
700 °F). As part of the upgrade, the incinerator was tested and found to be in
compliance with Federal and State regulations. However, severe erosion problems
occurred in the venturi scrubber. Modifications were made in the water rates and
piping. A second test conducted just prior to the EPA study indicated that a significant
improvement in scrubber performance had been achieved. While these scrubber
modifications improved the overall performance of the incinerator, they made testing of
the wet ESP somewhat more difficult because of the extremely low emissions from the
improved scrubbing system.
The fluid bed has a freeboard inside diameter of 11 ft 0 in and a freeboard height
of 15 ft 0 in. The fluidized sand bed has an average depth of 5 ft. During normal
operation, the fluidizing air rates varies from 3,200 - 3,400 scfm. The average bed
temperature is 1350 °F and the freeboard is 1,500 °F. The incinerator design
information is presented in Table 3.1 and a diagram of the process and control
equipment is presented in Figure 3.1.
Sludge is fed into the incinerator by means of a positive displacement pump which
results in an extremely uniform feed rate as indicated in Appendix A of Volume VII.
During the test program, the wet cake feed rate averaged 4,966 lbm/hr and the oil usage
was 24.66 gph. Deviations from these values were generally insignificant over the entire
-------
TABLE 3-1. INCINERATOR DESIGN INFORMATION
Design Parameter Value
Incinerator
Original Manufacturer Dorr-Oliver
Upgrade Manufacturer Nitro
Inside Diameter of Freeboard 22 ft 0 in
Height of Freeboard 15 ft 0 in
Depth of Fluidized Bed 5 ft 0 in
Maximum Design Sludge Feed Rate, dtpd 14.3
Fluidizing air blower, scfm 3,200 - 3,400
Excess Air, % 02 7.5 - 8.5
Auxiliary Fuel Oil
Operating Period 24 hr/day, 7 day/wk
Pollution Control System
Normal
Venturi, gpm 80
Tray Scrubber, gpm 280
Average Venturi pressure drop, in w.c. 31
Sludge Feed
Solids, % 20 - 22
Combustible solids, % 65 - 70
Heating Value, BTU/lb 10,900
3-3
-------
Heat
Exchanger
Sand
Feed,
Fluidized
Sand
Fluidized
Air _^z~
Sludge
i Inlet
Fluidized Bed
Incinerator
Figure 3
Exhaust
Stack
MM5 + VOST
Sampling
Port
Inlet
Sample
Port
Roof
Midpoint
Sample
Point
Water & „ i
Ash
Wet ESP
Sampling
Port
/
\

iCOIX
De-
mister
I.D.
Fan
Water &
Ash
i-O1—1
Water &
Ash
Venturi /
Tray Scrubber
Wet
Electrostaic
Precipitator
Schematic of Site 8 process and control equipment.
-------
test program. Combustion in this system was excellent with CO emissions averaging 7
ppm and the THC averaging 3 ppm. Typical flue gas oxygen measured at the fluid bed
exhaust varied between 7.5% and 8.5%. Sand make up averaged 25 lb/hr.
Air pollution control is a fixed throat venturi scrubber, modified as indicated
above, followed by a three plate tray scrubber. The average venturi scrubber pressure
drop during the testing period was approximately 31 in w.c. The scrubber water is
tertiary-treated, non-chlorinated plant effluent used once through.
As indicated above, the positive displacement feed pumps provided an extremely
uniform feed rate to the furnace and therefore operating conditions remained essentially
unchanged during the entire testing program.
3.3 INCINERATOR OPERATING CONDITIONS DURING TESTING
Incinerator operating data were monitored by F. Michael Lewis and recorded by
Site 8 staff. All testing was conducted during steady-state conditions. Mike Lewis was
responsible for suspending sampling if the operating parameters remained outside
specified operating ranges for more than 15 minutes.
A summary of the general operating conditions for each test run is contained in
Table 3-2, All runs were consisted representative of steady-state operations.
3-5
-------
TABLE 3-2. SUMMARY OF INCINERATOR OPERATING CONDITIONS AT SITE 8
Run
Wind
Temperatures (°F)
1 Bed Freeboard
Neat Exchanger
Flow Rates
Venturi Tray
Fluidizing Air
Fuel
Sludge
Solids Feed Rate
Pressures
Venturi
No.
Box

Inlet
Outlet
(gpnO
(9pm)
(scfm)
(gpnO
(X)
(dry tons/hr)
(AP)
4
640
1355
1500
1530
1160
80
260
3050
26
24
16
31
5
640
1360
1500
1520
1160
80
260
3000
23
24
17
31
6
640
1360
1510
1540
1170
80
260
3050
25
21
15
34
7
640
1340
1500
1530
1170
80
250
3050
26
21
15
33
8
640
1350
1510
1540
1170
80
160
3000
22
22
15
34
9
640
1370
1520
1540
1170
80
160
2950
17
22
15
33
10
630
1390
1520
1540
1170
80
240
2950
18
24
1B
32
-------
4.0 TEST RESULTS
The results of the emission tests performed at Site 8 from January 9 to January
12, 1990 are presented in this section. Site 8 is a fluidized-bed incinerator equipped with
a venturi scrubber/impingement tray scrubber combination to control emissions. This
site was selected for testing principally because (1) a measurable amount of total
chromium and total nickel was present in the sludge and (2) the facility had a pilot-scale
wet electrostatic precipitator on-site for evaluation. The primary objectives of this test
program were to (1) determine the effect of low excess air on the conversion of total
chromium and total nickel in the sludge to hexavalent chromium and nickel subsulfide in
the emissions and (2) evaluate the wet electrostatic precipitator (ESP) for use as a
retrofit control system for existing facilities. All testing was conducted during steady-
state normal incinerator operations.
In addition to the presentation of the results, variability and outliers in the data
are discussed in this section. The incinerator operating conditions and other process
parameters are discussed in relation to the results; however, a complete statistical
analysis of the emission results relating to the operating conditions is not included in this
report.
Results are presented in metric units with English units provided in parentheses
where appropriate. Flue gas results are presented as measured and normalized to an
equivalent 7% 02 concentration. Mass emission rates are also presented for each of the
parameters. In addition, emission factors relating stack emissions to sludge feed
composition and rates are presented where appropriate. Supporting data for the results
presented in this section are included in the appendices in Volume VII.
4-1
-------
4.1 FLUE GAS CONDITIONS
The uncontrolled emissions from the fluidized-bed incinerator were tested in the
bend of an elbow from the incinerator to the venturi scrubber. Because of the extremely
high temperatures and pressures at this location, the flue gas flow rate was not measured
directly. Since the control equipment was a closed system, the flue gas flow rate
(corrected to dry standard conditions) measured after the control system was assumed to
be the same as before the control system. The uncontrolled emissions testing location is
referred to as the "inlet" location. The location used to sample emissions controlled by
the venturi scrubber/impingement tray scrubber, which are the emissions normally
discharged to the atmosphere, is referred to as the "midpoint" location. Downstream of
the midpoint location, a duct was installed to divert about one half of the flue gas to the
pilot-scale wet ESP. The downstream sampling location from the wet ESP is referred to
as the "ESP outlet". A summary of the Site 8 inlet, midpoint, and ESP outlet flue gas
conditions is presented in Table 4-1, along with the run numbers, test dates, and run
times. A summary of inlet and outlet continuous monitoring measurements is presented
in Table 4-2.
4.1.1 Inlet Flue Gas Conditions
The flue gas volumetric flow rates at the inlet location during Runs 5, 7, 8, 9, and
10 were fairly consistent averaging 83.3 dry standard cubic meters per minute
(dscm/min), [2950 dry standard cubic feet per minute (dscf/min)], for normal operating
condition. The inlet flue gas flow rate was calculated by using the midpoint location flue
gas flow rate and correcting to standard conditions. The average flue gas temperature
for Runs 5, 7, 8, 9 and 10 was 603°C (1117°F) under normal operating conditions with
moisture and oxygen contents of 38% and 8.4%. The average CO concentrations were
10 ppm uncorreted and 11 ppm corrected to 7% 02, respectively, under normal operating
conditions.
4-2
-------
TABLE 4-1. SUMMARY OF INLET, MIDPOINT, AND ESP OUTLET FLUE GAS CONDITIONS; SITE 8
Run No. &
Condition
Sampling Test
Location Date Run Time
Flue Gas Conditions
Temper Moisture Oxygen Air Flow
(°F) (% H20) (% dry) (dscf/min)
Run 4
Normal
Midpoint 1/09/90 12:00-14:00
ESP Outlet 12:00-14:00
91.7 6.7 8.0 3260
76.2 3.9 8.0 1182
Run 5
Normal
Inlet 1/09/90 15:00-15:30
Midpoint 14:15-16:15
ESP Outlet 14:3 0-16:30
905 38 8.1 3185
89.3 6.8 8.1 3185
75.6 2.4 8.1 1393
Run 7
Normal
Inlet 1/10/90 11:15-11:45
Midpoint 10:45-12:45
ESP Outlet 10:45-12:45
1160 40 10 2820
91.4 6.7 7.5 2820
81.9 3.2 7.6 1313
Run 6
Normal
Midpoint 1/10/90 14:15-16:15
ESP Outlet 14:30-16:30
92.6 8.1 7.4 2878
79.2 3.6 7.4 1336
Run 9
Normal
Inlet 1/11/90 09:30-10:00
Midpoint 09:15-11:15
ESP Outlet 09:15-11:15
1180 37 7.9 2870
103 9.0 8.0 2870
93.2 4.9 8.0 1626
Run 8
Normal
Inlet 1/11/90 14:30-15:15
Midpoint 12:55-14:55
ESP Outlet 12:55-14:55
1170 36 7.7 3170
106 8.9 7.7 3170
91.5 NDa 7.7 1582
Run 10
Normal
Inlet 1/12/90 09:50-10:35
Midpoint 09:30-11:30
1180 41 8.0 2690
88.4 6.7 8.0 2690
aNot determined
-------
TABLE 4-2. SUMMARY OF INLET AND OUTLET CONTINUOUS EMISSION
MEASUREMENTS: SITE 8

Diluent
(X dry)
Pollutant Gases (actual ppro dry and/or corrected to 7X 02)
Run No./
Sarnpl ing

Carbon
Sulfur
Oioxide
Nitrogen Oxide
Carbon
Monoxide
Cold THC
Condition
Location
Oxygen
Dioxide
Actual
S7X 02
Actual
97X 02
Actual
37X 02
Actual
Run 4
Inlet
7.94

376
403
95
102
9
10

Normal
Midpoint
7.99
10.5
24
26
24
26
6
7
2
Run 5
Inlet
8.09

347
377
96
104
9
10

Normal
Midpoint
8.11
10.3
26
28
25
27
6
7
3
Run 7
Inlet
7.49

158
164
80
83
12
13

Normal
Midpoint
7.56
10.9
25
26
27
29
9
9
3
Run 6
Inlet
7.62

334
351
87
91
10
11

Normal
Midpoint
7.74
10.8
28
29
25
26
7
7
3
Run 9
Inlet
7.92

419
450
115
123
9
10

Normal
Midpoint
7.99
10.7
26
28
25
27
7
8
3
Run 8
Inlet
7.66

302
318
106
112
10
11

Normal
Midpoint
7.75
10.7
35
37
31
33
7
7
5
Run 10
Inlet
8.02

322
347
73
79

. .*

Normal
Midpoint
8.03
*
24
26
21
23

_ .*
. .*
* - Computer malfunction did not allow time to bring all monitors on-line.
-------
4.1.2 Midpoint Flue Gas Conditions
The flue gas volumetric flow rates at the midpoint sampling site for Runs 4, 5, 6,
7, 8, 9, and 10 ranged from 76.2 dscm/min to 92.3 dscm/min under normal operating
conditions and averaged 84.4 dscm/min (2980 dscf/min). The flue gas temperatures
averaged 34.8°C (94.6°F) with average moisture, oxygen, and carbon dioxide contents of
7.6%, 7.8%, and 10.7%, respectively. The CEM results for the midpoint were considered
the same as for the ESP outlet location since the wet ESP was a closed system.
4.1.3 Wet ESP Outlet Flue Gas Conditions
The flue gas volumetric flow rates at the wet ESP outlet sampling site for Runs 4,
5, 6, 7, 8, and 9 ranged from 33.5 dscm/min to 46.0 dscm/min under normal operating
conditions and averaged 39.8 dscm/min (1400 dscf/min). For Runs 4, 5, 6, and 7, the
wet ESP was operated at the design flow rate about 1350 dscfm. This rate represented
about 45% of the flue gas flow rate exiting the venturi/impingement tray scrubber
system. For Runs 8 and 9, the flue gas flow rate through the wet ESP was increased
above design and averaged 1600 dscfm, about 54% of the rate exiting the
venturi/impingement tray scrubber system.
A flexible duct was used to connect the emission discharge stack from the
venturi/impingement tray scrubber system to the inlet of the wet ESP. This duct exited
outside the building and provided some additional cooling of the stack gas prior to
entering the wet ESP. The average flue gas temperatures at the outlet was 28.3°C
(82.9°F) with moisture, oxygen, and carbon dioxide content of 7.6%, 7.8%, and 10.7%,
respectively.
4.2 PARTICULATE/METALS RESULTS
Particulate/metals emissions were determined using the draft EPA method
"Methodology for the Determination of Trace Metals Emissions in Exhaust Gases for
4-5
-------
Stationary Source Combustion Processes" (reproduced in Volume VII: Site 8 Test
Report, Appendices).
Four runs (Runs 5, 7, 9, and 10) were conducted to determine control system
collection efficiency for the metals of interest: arsenic (As), beryllium (Be), cadmium
(Cd), chromium (Cr), lead (Pb), nickel (Ni) and mercury (Hg). Note: The mercuiy
results are not shown because EPA recently determined that mercuiy precipitates in the
MMtl sampling train impinger solution. New digestion procedures have been added to
the method to recoveiy the mercuiy in the precipitate. Therefore, the results for
mercuiy in this study are considered invalid and are not reported. Runs 7, 9, and 10
were used to determine the collection efficiency of the venturi scrubber/impingement
tray control system, and Runs 5, 7, and 9 were used to determine the collection efficiency
of the wet ESP. The particulate emissions were determined using the multiple metals
sampling system. The emission results and collection efficiencies of the venturi
scrubber/impingement tray scrubber for metals and particulate are shown in Table 4-3
on a concentration basis and mass emission rate basis. The removal efficiency of the
pilot scale wet ESP for particulates and metals are shown in Table 4-4 along with the
results on a concentration and mass emission basis. These results represent average
emissions from a fluidized-bed sludge incinerator during typical operations (steady-state
conditions).
Research Triangle Institute (RTT) analyzed all the total metals samples. A
reagent blank was collected to assess background contamination levels of each target
metal. A complete discussion of Quality Assurance/Quality Control procedures and
results is presented in Section 7.0.
4.2.1 Control Device Inlet Results
The flue gas metals and particulate concentrations at the control device inlet are
shown in Table 4-3 for uncontrolled emissions (Runs 7, 9, and 10) and represent
metals/particulate emissions during normal furnace operations. The concentration of
metals (/tg/g) in the fly ash was determined based on analysis of the fly ash catch from
4-6
-------
TABLE 4-3. METALS AND PARTICULATE EMISSIONS AND COLLECTION EFFICIENCY
OF THE VENTURI/TRAY SCRUBBER: SITE 8
Run No. / Location
As
pg/m3 mg/hr
Be
M9/m3
mg/hr
Cd
lig/mS mg/hr
Cr
pg/m3 mg/hr
Pb
pg/m3 mg/hr
Ni
Mfl/m3
mg/hr
Particulate
mg/n3 g/hr
RUN 7D - INLET
161
786
42
207
152
741
2790
13600
2200
10700
1170
5690
19500
95100
RUN 7D - MIDPOINT
<0.9
<5.0
0.02
0.08
0.50
2.46
3.27
16.0
4.75
23.2
2.52
12.3
2.94
14.3
COLLECTION
EFFICIENCY(X)
>99.44*

99.96

99.68

99.88

99.78

99.99

>99.89

99.84

99.91

99.70

99.91

99.99

RUN 100 - INLET
212
977
40
186
296
1360
3500
16200
3510
16200
2310
10700
23700
109000
RUN 100 - MIDPOINT
<1.0
<5.0
0.01
0.03
0.13
0.62
1.58
7.26
0.41
1.88
0.88
4.04
3.60
16.6
COLLECTION
EFFICIENCY(X)
>99.53

99.98

99.95

99.96

99.99

99.96

99.99

INLET • Average
206
988
37
177
210
1000
2990
14300
2760
13200
1650
7880
21400
102000
MIDPOINT - Average
<1.0
<5.0
<.02
<.08
0.31
1.51
2.39
11.6
1.98
9.62
1.58
7.64
3.78
18.2
EFFICIENCY-Average(X)
>99.52

>99.95

99.82

99.92

99.91

99.89

99.99

'The collection efficiency is based on the concentration results, because the flowrate at wet ESP outlet was less than that at the
midpoint.
-------
TABLE 4-4. METALS AND PARTICULATE EMISSIONS AND COLLECTION EFFICIENCY
OF THE WET ESP: SITE 8
Run No./Location
As
£9/m3
mg/hr
Be
|ig/m3
mg/hr
Cd
#ig/m3
mg/hr
Cr
#ig/m3
mg/hr
Pb
#ig/n3
mg/hr
Ni
jig/m3
mg/hr
Particulate
mg/m3 g/hr
RUN 5D - MIDPOINT
<0.9
<4.8
0.01
0.08
0.56
3.08
1.40
7.63
1.81
9.89
1.58
8.64
6.28
34.3
RUN 5A - ESP OUTLET
<0.9
<2.1
0.00
0.00
0.05
0.13
0.40
0.97
<.10
<.2
<.2
<.5
1.16
2.77
RUN 5B - ESP OUTLET
<0.9
<2.1
-.01*
0.00
0.08
0.20
0.93
2.22
<.10
<.2
0.20
0.49
2.05
4.90
COLLECTION
EFFICIENCY(X)
NA°-C

>95

RUN 70 • MIDPOINT
<1.0
<5.0
0.02
0.08
0.50
2.46
3.27
16.0
4.75
23.2
2.52
12.3
2.94
14.3
RUN 7A - ESP OUTLET
0.93
2.10
<.04
<.09
0.19
0.43
0.85
1.92
0.04
0.09
0.84
1.89
0.30
0.67
RUN 7B - ESP OUTLET
<0.9
<2.1
<.04
<.09
0.28
0.63
0.99
2.22
0.25
0.57
0.96
2.16
0.74
1.66
COLLECTION
EFFICIENCY(X)
NA

>96

RUN 90 - MIDPOINT
<1.0
<5.0
<.03
<.12
0.30
1.46
2.33
11.5
0.77
3.78
1.33
6.57
4.81
23.7
RUN 9A - ESP OUTLET"
<0.8
<2.3
<.03
<.10
0.26
0.73
1.22
3.42
<.10
<.2
2.13
5.95
4.33
12.1
RUN 9B - ESP OUTLET
1.37
3.82
<.03
<.10
3.60
10.0
3.44
9.59
0.15
0.42
0.85
2.36
2.68
7.5
COLLECTION
EFFICIENCY(X)
NA

-540

>84

-11

Beryllium
Cadmium
Chromium
Lead
Nickel
5D-MID
2.4
90
220
290
250
5A-ESP
5B-ESP
NAb
NA
46
41
350
450
NA
NA
NA
100
7D-IN
2.2
7.8
140
110
60
7D-MID
5.8
170
1100 1600
860
7A-ESP
7B-ESP
NA
NA
640
380
2800
1300
140
340
2800
1300
9D-IN
1.4
8.8
130
120
71
9D-MID
NA
60
490
160
280
9A-ESP
9B-ESP
NA
NA
60
1300
280
1300
NA
57
490
320
10D-IN
1.7
12
150
150
97
10D-MID
2.0
37
440
110
240
aArsenic was below the limit of detection in all midpoint runs,
inlet values were less than 25 Mg/g and outlet less than 695
M9/g-
Below the level of detection, less than indicated detection
limit.
4-10
-------
location runs averaged: arsenic - <5 mg/hr, beryllium - <0.1 mg/hr, cadmium - 1.9
mg/hr, chromium - 10.6 mg/hr, lead - 9.7 mg/hr, and nickel - 7.9 mg/hr. The particulate
mass averaged 22.2 g/hr.
For each midpoint sampling run, the micrograms of each target metal collected
was divided by the grams of particulate collected to provide the concentration of that
metal in the fly ash. The results are presented in Table 4-5.
4.2.3 Wet ESP Outlet Results
The flue gas metal and particulate concentrations at the wet ESP outlet are shown
in Table 4-4. The average values for Runs 5, 7, and 9 represent metals emissions during
normal furnace operations. For Runs 5 and 7, the wet ESP was operated at its design
flue gas flow rate. For Run 9, the wet ESP was operated above its design flue gas flow
rate and did not shown a significant collection efficiency. Therefore, the averages shown
include only Runs 5 and 7. Arsenic emissions were at or below the level of detection,
which was about 1 /ig/dscm for all Wet ESP outlet sampling runs. The beryllium
emissions were at or below the level of detection, which was about 0.04 /ig/dscm for all
outlet runs. Lead was below the detection limit for all runs and averaged <0.1 /ig/dscm.
All the other metal were detected for all test runs and averaged: cadmium - 0.15
/ig/dscm, chromium - 0.8 /ig/dscm, and nickel 0.6 /ig/dscm. The particulate
concentrations averaged 1.1 mg/dscm.
The mass emission rates are not summarized because the Wet ESP was handling
only about one half of the total flow from the venturi/impingement tray scrubber.
4.2.4 Control Device Removal Efficiencies for Metals and Particulate
The pollutant removal (collection) efficiencies reported for the venturi
scrubber/impingement tray scrubber were based on the emission concentration, see
Table 4-4. The efficiencies for the Wet ESP cannot be based on the mass emission rates
since the Wet ESP handles less than half of the emissions. The venturi/impingement
4-11
-------
tray scrubber removal efficiencies measured for the particulate and target metals
averaged: particulate - 99.99%, arsenic - >99.52% (midpoint samples were below the
level of detection), beryllium - > 99.95% (midpoint sample values were at or below the
limit of detection), cadmium - 99.82%, chromium - 99.92%, lead - 99.91%, and nickel -
99.89%.
The wet ESP pollutant removal efficiencies measured for the particulate and
target metal runs averaged: particulate - 78%, arsenic - all midpoint and outlet samples
were below the level of detection, beryllium - all midpoint and outlet sample values were
at or below the limit of detection, cadmium - 71%, chromium - 62%, lead - >96%, and
nickel - >81%. It should be noted that the midpoint emissions were extremely low
making additional collection of particulates and metals by the wet ESP extremely
difficult.
4.2.5 Sludge Feed Results
A composite sludge feed sample was collected over the duration of each test day
and included two test runs for the first three days. The metal feed rates based on the
concentration of metals in the sludge and the sludge feed rates are presented in
Table 4-6. The mass feed rates of metals in the sludge were fairly consistent and
averaged: arsenic - not detected (< 34 g/hr), beryllium - 0.27 g/hr, cadmium - 2.2 g/hr,
chromium - 30 g/hr, lead - 39 g/hr, and nickel - 19 g/hr.
The results of the sludge proximate and ultimate analyses are presented in
Table 4-7. All of these results were fairly consistent from run-to-run with the exception
of the moisture content on Run 4. The results for the metals runs (Runs 5, 6, 8, 10, and
12) averaged: moisture - 80.29%, volatile matter - 68.44% (dry basis), fixed carbon -
8.46% (dry basis), ash - 23.10% (dry basis), sulfur - 0.77% (dry basis), carbon - 42.81%
(dry basis), hydrogen - 6.25% (dry basis), nitrogen - 4.32% (dry basis), oxygen - 22.75%
(dry basis), and BTU per pound - 8300 (dry basis).
4-12
-------
TABLE 4-6. INPUT RATE OF METALS IN SEWAGE SLUDGE

Metal
Input in
Sewage
Sludge
(g/hr)

Run No.
As
Be
Cd
Cr
Pb
Ni
Run 4/5
NDa
0.3
2.1
27
38
16
Run 6/7
ND
0.3
2.0
29
41
17
Run 8/9
ND
0.3
2.3
28
37
18
Run 10
ND
0.3
2.4
35
38
26
Average
ND
0.3
2.2
30
39
19
Detection
Limit*3
34
0.2
0.7
1
14
1
aND - Not detected.
bDetection Limit - Values represent the detection limit expressed
in g/hr.
4-13
-------
TABLE 4-7. RESULTS FOR PROXIMATE AND ULTIMATE ANALYSES OF SLUDGE SAMPLES

Dry
Basis
Analysis
(%)*

Run
No
Moisture
(%)
Volatile
Matter
Fixed
Carbon
Ash
S
C
H
N
0
Btu/lb
4/5
80.35
67.12
9.53
23.35
0.78
42.98
6.07
4.53
22.29
8424
6/7
81.42
68.14
9.16
22.70
0.79
43.07
6. 17
4.32
22.96
8462
8/9
79.97
69.26
7.98
22.76
0.75
42.87
6.36
4.28
22.98
8479
10
79.45
69.24
7.17
23.59
0.77
42.32
6.41
4. 15
22.76
7832
Avg.
80.29
68.44
•
8.46
23. 10
0.77
42.81
6.25
4.32
22.75
8300
aElemental analysis - S (Sulfur), C (Carbon), H (Hydrogen), N (Nitrogen), and O
(Oxygen)•
-------
4.2.6 Scrubber Water Results
Scrubber water influent and effluent samples were collected for all sampling runs.
The venturi scrubber water effluent samples had to be collected from the bottom of one
discharge pipe and the impingement tray scrubber water effluent samples were collected
from the bottom of another discharge pipe. The water effluent samples therefore may
not be representative of the discharge effluent. Due to the nature of the scrubber water
effluent sampling location, the results should be treated as an approximation. The mass
discharge rates of the metals collected in the scrubber are presented in Table 4-8. These
values represent the effluent concentration minus the influent concentration times the
scrubber water flow rate of 80 gal/min to the venturi scrubber and about 260 gal/min to
the impingement tray scrubber. The average values for the metals runs were: arsenic -
not detected (< 1.5 g/hr), beryllium - 0.26 g/hr, cadmium - 2.0 g/hr, chromium - 25 g/hr,
lead - 30 g/hr, and nickel - 17 g/hr.
The input of metals to the incinerator from the sludge, discharge of metals from
the incinerator at the inlet sampling site and the scrubber water discharge are presented
in Table 4-9. All of these results should be the same for each metal. The inlet sampling
site gave a significantly lower results then the other two mass balance measurements. It
is not known which of the values are correct.
4.2.7 Metal Emission Factors
One of the objectives of the overall sewage sludge incinerator test program was to
develop emission factors relating the stack emissions of the target compounds to the
sludge feed rate of these compounds. At Site 8, metal emissions testing was performed
at both the inlet and outlet of two control devices; therefore, uncontrolled and controlled
emissions can be related to the sludge feed composition. The ratios of uncontrolled
metal emissions (outlet of the incinerator and inlet to the control device) to the metal
feed rates in the sludge are presented in Table 4-10. These ratios were calculated based
4-15
-------
TABLE 4-8. DISCHARGE RATE OF METALS IN SCRUBBER WATER

Metal
Discharge
Emissions
in Scrubber
Water (g/hr)
Run No.
As
Be
Cd
Cr
Pb
Ni
Run 4/5
NDa
0.20
1.8
20
23
13
Run 6/7
ND
0.27
2.1
25
30
17
Run 8/9
ND
0.36
2.4
34
41
22
Run 10
ND
0.22
1.5
22
27
15
Average
ND
0.26
2.0
25
30
17
Detection
Limitb
1.5
0.01
0.03
0.05
0.6
0. 06
aND - Not detected.
bDetection Limit - Values represent the detection limit
expressed in g/hr.
4-16
-------
TABLE 4-9. RATE OF METALS TO AND FROM INCINERATOR

Metal
Emissions
to and
from
Incinerator
(9/hr)
Run No.
As
Be
Cd
Cr
Pb
Ni
Scrubber
Water
<1.5
0.26
2.0
25
30
16
Inlet
Sampling
1.0
0.18
1.0
14
13
7.9
Sludge
<34
0.27
2.2
30
39
19
TABLE 4-10. INLET AND OUTLET METAL EMISSION FACTORS
g metal at location/g metal in sludgea
Location
Be
Cd
Cr
Pb Ni
Inlet
0. 66b
0.46b
0.
48b 0 . 34b
0.4 0b

Midpoint
<0.00007
0.0009
0.0004
0.0002 0.0004
ESP Outlet
<0.00007
0.0003
0.0001
<0.00001 <0.0001
a - Arsenic was below detection limit in the sludge.
b < - Values should be 1.0. The difference is a result of
sampling and analytical error for the two sampling
locations
4-17
-------
on the metal concentrations at the inlet compared to the metals in the sludge. The
metal mass emission rates at the inlet location measured by manual sampling should be
identical to the metal mass emission rates from the incinerator measured in the sludge.
However since different sampling techniques were used and the metals concentration in
the sludge was extremely low, the differences in the results represent sampling and
analytical error. The metal factors averaged: arsenic - not detected, beryllium - 66%,
cadmium - 46%, chromium - 48%, lead - 34%, and nickel - 40%. The corresponding
control device outlets (midpoint and ESP) emission factors are also presented in Table
4-10. The metals at the midpoint location compared to the percent of metals feed to the
incinerator averaged: arsenic - not detected, beryllium - at or below detection (less than
0.007%), cadmium - 0.09%, chromium - 0.04%, lead - 0.02%, and nickel - 0.04%. The
wet ESP outlet metal emissions compared to the percent of metals feed to the
incinerator averaged: arsenic - not detected, beryllium - at or below the detection limit
(less than 0.007%), cadmium - 0.03%, chromium - 0.01%, lead - at or below the
detection limit (less than 0.001%), and nickel - at or below the detection limit (less than
0.01%). The controlled metal emission factors decrease in the same proportion as the
control device removal efficiencies as shown in Tables 4-3 and 4-4.
Another emission factor that can be calculated is the ratios of metals in terms of
/ig of metal measured in the emissions to grams of particulate. These emission factors
are presented in Table 4-11.
4.3 HEXAVALENT CHROMIUM RESULTS
The hexavalent chromium (Cr+6) samples collected were analyzed by ion
chromatography with a post column reaction (IC/PCR) specific for hexavalent
chromium. Ion chromatography was also used to separated slCr+< from 5lCr+3 for
gamma emission counting. Analysis for the total chromium was conducted using
inductively-coupled argon plasmography. The results for Cr+<, the isotope speciation,
and total chromium for Site 8 are presented in Table 4-12. The results for each
sampling location are discussed in the following subsections.
4-18
-------
TABLE 4-11. RATIO OF METAL TO PARTICULATE
Run No./
Location
Ratio of
Metal to
Particulate (ng
metal/g
particulate)
As
Be
Cd
Cr
Pb
Ni
5D-MID
NDa
2.4
90
222
288
252
5A-ESP
5B-ESP
ND
ND
ND
ND
46
41
348
454
ND
ND
ND
100
7D-IN
8
2 . 2
7.8
143
113
60
7D-MID
ND
5.8
172
1114
1617
858
7A-ESP
7B-ESP
ND
ND
ND
ND
637
378
2861
1337
138
343
2820
1303
9D-IN
12
1.4
8.8
128
124
71
9D-MID
ND
ND
61
485
159
277
9A-ESP
9B-ESP
ND
ND
ND
ND
60
1342
282
1283
ND
57
491
315
10D-IN
9
1.7
12
148
148
97
10D-MID
ND
2.0
37
438
114
243
ND - Below the limit of detection.
4-19
-------
TABLE 4-12. SUMMARY OF HEXAVALENT AND TOTAL CHROMIUM
RESULTS: SITE 8
Sample
Identity
Native
Hex Cr
(ng/dscm)
Recovery of
Isotope Spikes(%)
51Cr+6 53Cr+6
Total
Chromium
(^g/dscm)
Ratio
Cr+6/Cr
(%)
Hun 4B-IN
Run 4C-IN
Run 4D-IN
NA
< 11
< 11
NA
40.0
25.0
96500
72100
b
< 0.01
< 0.02
Run 4A-MID
Run 4B-MID
Run 4C-MID
Run 4D-MID
NA
< 0.02
0.01
0.02
NA
63.4
10.7
9.5
3.0
1.4
1.7
< 0.5
0.7
1.1
Run 4A-ESP
Run 4B-ESP
NA
0.03
85.9 NA
78.2
1.1
2.5
Run 6A-IN
Run 6B-IN
NA
< 7.5
48.3 NA
66.1
31200
< 0.02
Run 6A-MID
Run 6B-MID
Run 6C-MID
Run 6D-MID
< 0.02
NA
0.02
< 0.02
62.3
NA
52.8
62.2
1.5
1.9
2.9
1.5
< 1.2
0.6
< 1.1
Run 6A-ESP
Run 6B-ESP
NA
<0.02
92.6 NA
85. 1
1.4
0.8
< 0.4
Run 8A-IN
Run 8B-IN
NA
9.9
82.8 NA
79.5
3800
0.3
Run 8A-MID
Run 8B-MID
Run 8C-MID
Run 8D-MID
NA
< 0.02
< 0.02
< 0.01
NA
79.3
73. 6
74.0
1.2
1.5
1.3
< 1.3
< 1.2
< 1.1
Run 8A-ESP
Run 8B-ESP
NA
< 0.01
81.4 NA
65, 6
0.9
1.0
< 1.3
aNA - Not available.
b— - Could not be calculated due to lack of data.
Note: Problems were encountered in the inlet hexavalent
chromium analysis and the midpoint and outlet total
chromium analysis.
4-20
-------
Two samples from the inlet runs were also analyzed for hexavalent and total
chromium using X-ray absorption near-edge structure (XANES) and extended X-ray
absorption fine structure (EXAFS) by BYU. The hexavalent chromium was below the
instrument's detection limit for both inlet samples indicating a hexavalent to total
chromium ratio of less than 10% and 15% for Runs 8 and 11, respectively.
4.3.1 Control Device Inlet Results
The recirculating train design in use at the time of this test program could not be
employed at the inlet location due to the high temperature and particulate loading at
this location. Therefore, the inlet samples were captured directly in an impinger train
containing 1 N KOH. The presence of dissolved salts in some of the impinger samples
interfered with the preconcentration procedure resulting in higher detection limits. All
the inlet samples were analyzed by direct injection and the isotope speciation was not
affected. Cr+6 was detected in only one inlet sample (Run 8, train B). Recovery of the
5lCr+6 spike ranged from 25% to 83%. The variability in the isotope spike recoveries
and native Cr+* results may have been due to the sampling times employed that were
decreased during the test program due to the high particulate loading. The ratio of
hexavalent to total chromium was 0.3% for Run 8 and <0.02% for Runs 4 and 6.
4.3.2 Midpoint Results
At the midpoint location, quadruplicate recirculating trains were employed to
collect Cr+6 and total chromium. The emissions at the midpoint are representative of
the typical plant emissions. The Cr+6 concentrations at the midpoint ranged from <
0.01 ug/dscm to 0.02 ug/dscm. The 5lCr+< spike recovery ranged from 9.5% to 79%.
The 9.5% and 10.7% recoveries seen for trains C and D from Run 4 appear to be
outliers, since train B for the same run had a 63.4% recovery. The ratio of hexavalent to
total chromium ranged from <0.4% to <1.3%.
4-21
-------
4.3.3 ESP Outlet Results
Paired recirculating trains were employed to collect Cr+< and total chromium at
the outlet of the pilot-scale wet ESP. The Cr+< concentrations ranged from <0.01 to
0.03 ug/dscm. Recovery of the 5,Cr+< spike ranged from 65.6% to 92.6%. The ratio of
hexavalent to total chromium ranged from <0.4% to 2.5%.
4.4 NICKEL SPEC1ATION RESULTS
The major objective of the nickel speciation testing was to determine the percent
of the nickel emissions in the form of nickel subsulfide. It was anticipated that the
nickel subsulfide emissions from fluidized bed incinerators would constitute less than 1%
of the total nickel emissions, because these incinerators typically operate with high excess
air which is not favorable for the formation of nickel subsulfide. Dr. Vladimir Zatka,
the developer of the Nickel Producers Environmental Research Association (NiPERA)
nickel speciation method, conducted the sample analysis. This wet chemical analytical
method involves sequential leaching. The first leaching step removes all soluble nickel.
Peroxide is used to convert the nickel sulfides and subsulfides to soluble nickel sulfate
which is then leached in the second step. The third step leaches the metallic nickel
compounds and finally total digestion of the remaining sample typically yields 2the nickel
oxides. The results of the sequential leaching nickel analysis shown in Table 4-13
indicate that, within the detection limit of the wet chemical method, no nickel subsulfide
was present in the samples. Based on the detection limits, the nickel subsulfide to total
nickel ratio is less than 12% for the inlet emissions and less than 10% for the outlet
emissions.
BYU also analyzed samples from the same runs by XANES and EXAFS; no
nickel subsulfide was detected within the instrumental detection limit of 10% of the total
nickel.
4-22
-------
TABLE 4-13. SUMMARY OF NICKEL SPECIES EMISSIONS: SITE 8a

Nickel

Soluble

Sulfidicb
Oxidic
Total

Run
No.
^g/dscm
%Total
jig/dscm
%Total
jxg/dscm
%Total
jig/dscm
%Total
Midpoint
Run
5
0.32
52.6
<
0.065
< 10.5
0.29
47.4
0.61
100
Run
7
0.22
24 . 0

0.108
12 . 0C
0.58
64.0
0.90
100
Run
10
0. 17
35.7
<
0.069
< 14.3
0.31
64.3
0.52
100
Run
10d
0.26
50.0
<
0.074
< 14.3
0.26
50.0
0.48
100
Inlet
Run
8e
555
12.0
<
370
< 9.0
3546
88.0
4101
100
Run
8d
487
10.0
<
195
< 3.8
4672
90.0
5159
100
Run
10
301
4.0
<
301
< 3.9
7377
96.0
7678
100
aThese nickel speciation emissions represent the discharge emissions from the
incinerator and the outlet of the venturi scrubber/tray scrubber. It is not
known why these emissions are about one half of the emissions from the multiple
metal train,
bThe sulfidic nickel is a combination of the nickel sulfide and nickel
subsulfide.
cThis sample was damaged when probe heat was lost. Another sample from the same
run will be analyzed.
dRepresents a duplicate analysis.
eTo evaluate accuracy, a weighed portion of Run 8 was spiked with 2.0 ug Ni
as a soluble nickel salt. Of the added Ni, 1,8 ug was recovered for a 90%
recovery rate.
-------
4.5 DIOXIN/FURAN AND SEMIVOLATILE ORGANIC RESULTS
Sampling for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated
dibenzofurans (PCDFs), and other semivolatile organics was conducted in the discharge
stack from the venturi scrubber/impingement tray scrubber (emission are the same as
those measured at the midpoint location) under normal incinerator operating conditions.
Three two-hour runs were conducted using Modified Method 5 (MM5), SW-846 Method
0100 procedures, except that a final toluene rinse was performed and analyzed separately
for PCDD/PCDF.
The concentration of dioxins/furans detected in the flue gas are presented in
Table 4-14. The total PCDDs averaged 0.7 ng/dscm and the total PCDFs averaged 1.7
ng/dscm.
The concentration of the other semivolatile organic compounds detected in the
flue gas are shown in Table 4-15. Of the semivolatile organic compounds measured, only
three were above the minimum detection limit for all three runs; they averaged:
1,4-dichlorobenzene - 21 mg/dscm, naphthalene - 8.5 mg/dscm, and
bis(2-ethylhexyl)phthalate - 7.1 mg/dscm. Three other semivolatile organic compounds
were above the minimum detection limit for a least one test run and averaged: benzyl
alcohol - 5.6 mg/dscm, 1,2-dichlorobenzene - 2.1 mg/dscm, and benzoic acid - 24
mg/dscm.
4.6 VOLATILE ORGANIC RESULTS
Sampling for volatile organic compounds (VOCs, those organic compounds with
boiling points less than 150°C) was conducted at the same location as the semivolatile
organic sampling. Three one-hour runs were conducted under normal incinerator
operating conditions using the volatile organic sampling train (VOST). Each VOST run
utilized four pairs of Tenax/Tenax-charcoal traps which were exposed to approximately
20 liters of flue gas each.
4-24
-------
TABLE 4-14. PCDD/PCDF EMISSIONS SUMMARY
Run No.
Congener
4-OUT-MM5
6-OUT-MM5
8-OUT-MM5
Average
CDD

Concentration/
ng/dacm *

Total MCDD
NDb
ND
ND
ND
Total DCDD
ND
ND
ND
ND
Total TriCDD
1.91E-01
1.13E-02
ND
6.74E-02
2378-TCDD
2.23E-02
ND
ND
7.43E-03
Other TCDD
3.50E-01
1.02E-02
ND
1.20E-01
12378-PeCDD
1.84E-02
ND
ND
6.13E-03
Other PeCDD
1.54E-01
5.02E-03
ND
5.30E-02
123478-HxCDD
7.02E-03
ND
ND
2.34E-03
123678-HxCDD
1.40E-02
ND
ND
4.67E-03
123789-HxCDD
1.77E-02
ND
ND
5.90E-03
Other HxCDD
9.90E-02
8.43E-03
ND
3.58E-02
1234678-HpCDD
1.11E-01
1.99E-02
1.43E-02
4 - 84E-02
Other HpCDD
6.97E-02
0.00E+00
0.00E+00
2.32E-02
OCDD
7.10E-01
1.87E-01
1.81E-01
3.59E-01
Total CDD
1.76E+00
2.41E-01
1.96E-01
7.33E-01
CDF
Concentration, ng/dscm •

Total MCDF
ND
ND
ND
ND
Total DCDF
6.54E-03
2.08E-02
ND
9.11E-03
Total TriCDF
6.2 5E-01
1.22E-01
3.88E-03
2.50E-01
2378-TCDF
4.92E-02
5.56E-03
1.49E-03
1.88E-02
Other TCDF
1.39E+00
1.24E-01
7.17E-03
5.07E-01
12378-PeCDF
1.11E-01
ND
ND
3.70E-02
23478-PeCDF
6.47E-02
5.92E-03
ND
2.35E-02
Other PeCDF
1.04E+00
3.61E-02
8.22E-03
3.61E-01
123478—HxCDF
1.21E-01
1.20E-02
ND
4.43E-02
123678-HxCDF
6.01E-02
6~82E-03
ND
2.23E-02
234678—HxCDF
4.63E-02
6.10E-03
ND
1.75E-02
123789—HxCDF
4.12E-03
ND
ND
1.37E-03
Other HxCDF
3.94E-01
8.07E-03
ND
1.34E-01
1234678—HpCDF
1.86E-01
2.12E-02
6.72E-03
7.13E-02
1234789-HpCDF
3.00E-02
ND
ND
1.00E-02
Other HpCDF
1.52E-01
5.74E-03
5.53E-03
5.44E-02
OCDF
2.07E-01
8.82E-02
2.91E-02
1.08E-01
Total CDF
4.49E+00
4.63E-01
6.22E-02
1.67E+00
Total CDD/CDF
6.25E+00
7.04E-01
2.58E-01
2.40E+00
• =» 68 Deg. F — 29.92 inches Hg.
*ND = Reported as not detected or estimated maximum possible concentration;
both expressed as zero (0) in calculating totals and averages.
4-25
-------
TABLE 4-15. SEMIVOLATILE EMISSIONS SUMMARY
Run No-.
4-OUT-MM5 6-OUT-MM5 8-OUT-MM5 Average
Compound Concentration, /jg/dscm •
Phenol
NDb
ND
NO
ND
bis(2-Chloroethyl)ether
ND
NO
ND
NO
2-Chlorophenol
ND
NO
ND
ND
1,3-Dichlorobenzene
ND
NO
NO
NO
1,4-Dichlorobenzene
1.99E+04
3.01E+04
1.18E+04
2.06E+04
Benzyl alcohol
NO
1.32E+04
3.54E+03
5.58E+03
1,2-Dichlorobenzene
NO
6.15E+03
ND
2.05E+03
2-Methylphenol
NO
ND
ND
NO
bis(2-Chloroisopropy1)ether
ND
ND
ND
ND
4-Methylphenol
NO
ND
ND
ND
N-Nitroso-di-n-propylamine
ND
NO
ND
ND
Hexachloroethane
ND
ND
ND
ND
Nitrobenzene
ND
ND
ND
ND
Isophorone
ND
ND
ND
ND
2-Nitrophenol
ND
NO
ND
ND
2,4-Dimethylphenol
ND
NO
ND
ND
Benzoic acid
4.04E+04
NO
3.02E+04
2 -35E+04
bis(2-Chloroethoxy)methane
ND
NO
ND
ND
2,4-Dichlorophenol
ND
NO
ND
NO
1,2,4-Trichlorobenzene
ND
ND
ND
ND
Naphthalene
6.41E+03
1.50E+04
3.97E+03
8.46E+03
4-Chloroaniline
ND
NO
ND
ND
Hexachlorobutadiene
ND
ND
ND
NO
4-Chloro-3-methylphenol
ND
ND
ND
ND
2-Methylnaphthalene
ND
ND
NO
ND
Hexachlorocyclopentadiene
ND
ND
ND
ND
2,4,6-Trichlorophenol
ND
ND
ND
ND
2,4,5-Trichlorophenol
ND
ND
NO
NO
2-Chloronaphthalene
ND
ND
ND
ND
2-Nitroaniline
ND
ND
NO
NO
Dimethylphthalate
ND
ND
ND
ND
Acenaphthylene
ND
ND
ND
ND
3-Nitroaniline
ND
ND
ND
ND
Acenaphthene
ND
ND
NO
ND
2,4-Dinitrophenol
ND
ND
ND
ND
4-Nitrophenol
ND
ND
ND
ND
Oibenzofuran
ND
ND
ND
ND
2,4-Dinitrotoluene
ND
ND
ND
ND
2,6-Dinitrotoluene
ND
ND
NO
ND
Diethylphthalate
ND
ND
ND
ND
4-Chlorophenyl-phenylether
ND
ND
ND
ND
Fluorene
ND
ND
ND
ND
4-Nitroaniline
ND
ND
ND
ND
4f 6-Dinitro-2-methylphenol
ND
NO
ND
ND
N-Nitrosodiphenylamine(1)
ND
ND
ND
ND
4-Bromophenyl-phenylether
ND
ND
ND
ND
Hexachlorobenzene
ND .
ND
ND
ND
Pentachlorophenol
ND
ND
ND
NO
Phenanthrene
ND
NO
ND
ND
Anthracene
ND
ND
ND
ND
Di-n-butylphthalate
ND
ND
ND
ND
(Continued)
4-26
-------
TABLE 4-15. (Continued)
Compound
Run No.
4-OUT-MM5 6-OUT-MM5
Concentration, A*g/d
8-OUT-MM5
scm *
Average
Fluoranthene
ND
ND
ND
N
Pyrene
ND
ND
ND
ND
Butylbenzylphthalate
ND
ND
ND
ND
3,3'-Dichlorobenzidine
ND
ND
ND
ND
Benzo(a)anthracene
ND
ND
ND
ND
Chrysene
ND
ND
ND
ND
bis(2-EthylhexylJ phthalate
7.63E+03
1.03E+04
3.21E+03
7.05E+03
Di-n-octylphthalate
ND
ND
ND
ND
Benzo(b)fluoranthene
ND
ND
ND
ND
Benzo(k)fluoranthene
ND
ND
ND
ND
Benzo(a)pyrene
ND
ND
ND
ND
Indeno(1,2,3-cd)pyrene
ND
ND
ND
ND
Dibenz(a,h)anthracene
ND
ND
ND
ND
Benzo(g,h,ijperylene
ND
ND
ND
ND
• m 68 Deg. F — 29.92 inches Hg
bND * Reported as not detected or estimated values;both expressed as zero (0)
in calculating totals and averages.
4-27
-------
The concentration of the volatile organics in the flue gas are presented in Table
4-16. Five of the target compounds were below the analytical detection limit during all
three test runs; acrylonitrile, vinyl chloride, 1,2-dichloroethane, and chlorobenzene. The
detection limits for these compounds are shown in the detailed run data which are
presented in the Volume VII: Site 8 Draft Report, Appendices.
The other eight target compounds were detect in all three test runs and averaged:
methylene chloride - 110 mg/dscm, chloroform - 17 mg/dscm, 1,1,1-trichloroethane - 6.8
mg/dscm, Trichloroethene - 5.2 mg/dscm, Benzene - 6.2 mg/dscm, Tetrachloroethene -
9.4 mg/dscm, toluene - 7.7 mg/dscm, and ethylbenzene - 2.6 mg/dscm.
4.7 CONTINUOUS EMISSION MONITORING RESULTS
Continuous emissions monitoring (CEM) was performed at the inlet and midpoint
sampling locations at Site 8. The inlet CEM systems included oxygen (02), carbon
dioxide (C02), sulfur dioxide (S02), oxides of nitrogen (NOx), and carbon monoxide
(CO). The midpoint CEMSs included oxygen (02), carbon dioxide (C02), sulfur dioxide
(S02), oxides of nitrogen (NOJ, carbon monoxide (CO) and total hydrocarbons (THC).
The CEM probes were located upstream of the manual sampling locations. All
measurements were made on a dry basis. The averages of the CEM data on a run-by-
run basis are presented in Table 4-2. The one-minute averages for each compound for
all the runs are included in Appendix E of Volume VII: Site 8 Draft Report,
Appendices. To provide an indication of how the monitored emissions changed with
time, the 10-minute averages are presented in Tables 4-17 and 4-18. The indicated time
(i.e., 12:10) is the time at the end of the 10-min average. Runs 3, 4, 5, 6, 7 and 13
represent normal furnace operating conditions.
EPA is evaluating CO and THC monitoring as a surrogate indicator of organic
emissions. Since the emissions of CO and THC were consistently low, they do not
provide spread to establish a correlation.
4-28
-------
TABLE 4-16. VOLATILE ORGANICS EMISSIONS SUMMARY
VOC Run No.
4-OUT-VOST 6-OUT-VOST
Concentration, ng/dscm •
8-OUT-VOST
Average
Acrylonitrile
Vinyl Chloride
NDb ND
ND ND
ND
ND
ND
ND
Methylene Chloride (m/z ® 86]
1 1.44E+05 4.45E+04
1.35E+05
1.08E+05
Chloroform
1.17E+04 1.41E+04
2.45E+04
1.68E+04
1,2-Dichloroethane
ND ND
ND
ND
lf1,1-Trichloroethane
6.76E+03 6.96E+03
6.55E+03
6.77E+03
Carbon Tetrachloride
ND ND
ND
ND
Trichloroethene
1.67E+03 6.71E+03
7.34E+03
5.24E+03
Benzene
4.52E+03 9.06E+03
4.96E+03
6.18E+03
Tetrachloroethene
5.20E+03 1.66E+04
6.40E+03
9.40E+03
Toluene
4.14E+03 1.48E+04
3.95E+03
7.66E+03
Chlorobenzene
ND ND
ND
ND
Ethylbenzene
1.29E+03 4.40E+03
—¦ ¦ —
2.22E+03
2.64E+03
• = 68 Deg. F — 29.92 inches Hg
= Reported as not detected or estimated values;both expressed as zero (0)
in calculating totals and averages.
4-29
-------
TABLE 4-17. SUMMARY OF INLET AND MIDPOINT CONTINUOUS EMISSION MONITORING RESULTS
(10-min averages)

Inlet
Location

Outlet Location
Time
02
CO
S02
NOx
02
CO 2
CO
S02
NOX
THC
24 hr.
%
ppm
ppm
ppm
%
%
ppm
ppm
ppm
ppm

Run 4 -
January
9, 1990

12:10
7.80
9.4
440.7
94.9
7.97
10.49
6.9
97.3
23.5
2.5
12:20
7.78
8.4
483.3
87.7
7 .96
10.49
6.0
98.3
23.2
2.2
12:30
7.85
8.9
497.6
91.5
8.03
10.43
6.4
102.2
23.4
2.2
12:40
8.01
9.0
485.0
94.6
8.13
10.35
6.4
105.8
23.7
2.5
12:50
8.01
9.1
479 .4
96.9
8.04
10.43
6.5
107.5
24.4
2.6
13:00
8. 10
9.2
487.1
96.7
8.12
10.36
6.5
107.6
24.2
2.5
13:10
7.90
8.8
486.3
95.3
7.93
10.52
6.1
106.1
24.4
2.5
13:20
7.85
9.2
481.3
97.7
7.87
10.56
6.4
107.6
24.8
2.4
13:30
7.83
8.8
467.6
92.9
7.87
10.57
6.0
105.2
24.9
2.2
13:40
8.03
9.7
452 .8
101.2
8.01
10.45
6.6
109.4
25.4
2.6
13:50
7.86
8.9
430.8
94.0
7.75
10.65
5.9
106.0
25.0
2.2
14:00
8.26
10.0
426.1
99.0
8.16
10.34
6.7
114.0
25.7
2.6

Run 5 -
January
9, 1990

17:00
7.74
8.6
403.5
87.9
7.88
10.52
6.3
108.4
23.0
2.7
17:10
7.76
10. 0
439.6
97.7
7.87
10.53
7.5
113.2
25.2
3.0
17:20
8.67
9.6
436.5
100.9
8.77
9.74
7.5
113.6
27.0
3.8
17:30
8.04
8.9
470.3
92.2
8. 16
10.29
6.7
111.3
23.2
3.1
17:40
7.86
8.7
471.6
90.5
7.95
10.44
6.5
108.9
22.8
2.7
17:50
8.63
10.7
465.0
112.0
8.58
9.93
8.3
121.4
26.3
3.9
18:00
8.35
9.9
455.2
107.3
8.32
10. 12
7.8
114.7
26.4
4.1
18:10
8.21
8.8
448.8
94.4
8. 18
10.23
6.9
110.2
24.7
3.4
18.20
8.12
9.1
445.8
95.6
8.09
10.30
7.2
109.7
24.9
3.4
18.30
8.00
9.0
440.7
93.6
7.96
10.38
7.0
109.6
24.4
3.4
18:40
7.84
8.9
428.3
90.8
7.80
10.54
6.9
109.1
24.4
3.4
18:50
7.80
8.7
418.9
87.0
7.75
10.58
6.7
110.4
24.3
3.2
19:00
7. 66
8.6
404.8
84.4
7. 62
10.69
6.5
109.7
24.2
3.0
-------
TABLE 4-17. (Continued)

Inlet
Location

Outlet
Location

Time
02
CO
S02
NOX
02
C02
CO
S02
NOX
THC
24 hr.
%
ppm
ppm
ppm
%
%
ppm
ppm
ppm
ppm

Run 7 January
10, 1990

10:55
7.01
12.7
278.1
82.8
7. 17
11.28
10.8
101.3
21.7
2.7
11:05
7.09
9.0
286.2
74. 1
7. 11
11.30
6.9
103.5
21.3
2.1
11:15
10.28
8.4
212.7
109.2
10.27
8.60
6.9
93.4
59.3
4.2
11:25
6.86
13.3
275.5
73. 0
6.82
11. 51
11.3
100.9
22.5
2.4
11:35
6.78
19.4
293.7
84.7
6.74
11.56
16.8
112.0
26.6
3.3
11:45
7.71
11.0
251.6
80.3
7. 65
10.82
8.2
116.0
25.4
3.2
11:55
7.34
9.9
254.5
73. 1
7.39
11.05
7.3
111.0
23.4
2.8
12:05
7.41
10.4
243.1
74.9
7.54
10.93
7.6
111. 5
24.4
2.9
12:15
7.30
11.8
240.6
78.0
7.43
11.01
8.7
113.6
25.5
3.1
12:25
7.39
12.7
236.2
80.3
7.51
10.95
9.5
115. 6
26.6
3.5
12:35
7.34
11.2
233.5
76.2
7.47
10.99
8.1
115.5
25.2
3.2
12*45
7.40
11.4
229.7
75.9
7.54
10.94
8.3
115.7
25.6
3.2

Run 6 -
January
10, 1990

14:45
7.27
11.0
488.3
91.6
7.42
11.05
8.6
125.7
27.1
3.7
14:55
7.49
10.7
507.4
100.5
7 . 62
10.88
8.3
127.0
26.2
3.3
15:05
7. 50
10.7
504.6
98.5
7. 63
10.86
8.2
126.4
26.1
3.4
15:15
7.56
9.4
506. 6
92.6
7. 69
10.81
7.1
124.5
24.8
3.2
15:25
7.65
9.2
503.8
90.7
7.77
10.75
6.9
124.8
24.2
2.9
15:35
7.98
8.3
475.9
83.5
8.10
10.49
6.0
121.0
23.3
2.6
15:45
7.92
8.1
459.4
79.2
8. 01
10.56
5.8
112 .4
22.3
2.2
15:55
7.81
8.5
412.3
77. 1
7.90
10.66
6.0
117.8
23.0
2.3
16:05
7.84
8.1
337.4
71.9
7.92
10.64
5.7
119.5
22.8
2.3
16:15
7.85
7.9
264.9
66.8
7.94
10.63
5.6
117.6
23.0
2.3
(Continued)
-------
TABLE 4-17. (Continued)

Inlet
Location

Outlet Location
Time
02
CO
S02
NOx
02
C02
CO
S02
NOx
THC
24 hr.
%
ppm
ppm
ppm
%
%
ppm
ppm
ppm
ppm

Run 9 -
January
11, 1990

9:25
8.17
9.4
496.4
107.4
8.18
10.54
7.1
111.4
24.3
3.0
9:35
7.92
8.7
523.2
104.5
7.88
10.76
6.5
107.6
23.7
2.1
9:45
7.76
8.8
537.9
106.0
7.73
10.87
6.5
108.0
24.3
2 . 0
9:55
7.71
8.9
536.7
108.8
7.67
10.92
6.4
109.7
24.4
2.1
10: 05
7.95
9.8
528.2
120.1
7.94
10.72
7.1
113.8
25.5
2.9
10: 15
7.75
9.5
525. 1
117.3
7.89
10.75
6.7
113.1
24.8
2.2
10:25
7 . 88
9.2
521. 5
118.1
8.02
10.63
6.5
115.1
24.8
2.4
10:35
7.95
9.2
522.4
117.3
8.09
10.57
6.5
114.7
24.9
2.5
10:45
7.91
9.1
524.9
115.9
8.04
10. 61
6.5
115.6
24.9
2.4
10: 55
7.85
9.1
522. 5
118. 1
7.99
10.66
6 . 6
115.9
25.1
2.4
11:05
7.99
9.6
511.0
116.9
8.11
10. 56
7.0
118.7
25.8
2.3
11:15
8.15
10.5
469.8
132.8
8.29
10.44
7.8
124. 1
27.6
3.8

Run 8 -
January
11, 1990

13:05
7. 15
10. 1
464.0
103.0
7.27
11. 11
7.5
148. 1
29.9
3.7
13:15
7.50
10.1
441. 3
103.7
7.64
10.84
7.5
151.8
30.5
4.5
13:25
7.42
9.8
431.7
102 . 1
7.56
10.90
7.2
152.8
29.9
4.1
13:35
7.41
10.0
451.0
104.3
7.54
10.91
7.3
154.7
30.4
4.1
13:45
7.36
10.3
497.2
109. 1
7.49
10.95
7.6
155.5
30.9
4.4
13:55
7.36
10.0
539.3
112.2
7.46
10.97
7.4
155,6
30.7
4.1
14:06
7.35
10.0
529. 1
117.1
7.49
10.94
7.4
155. 5
30.9
4.2
14:17
7.37
10.1
496.9
115.3
7.50
10.97
7.4
156.0
30.9
4.2
14:48
8.85
9.9
270.3
102.3
8.80
9.75
7.7
143.6
33.5
6.9
14:58
8.29
8.3
253.8
84.8
8.24
10.21
6.2
138.5
28.9
4.6
15:08
7.46
7.5
265. 3
74.0
7.39
10.89
5.3
136.9
27.0
2.8
15:18
7.36
8.8
290. 6
78.7
7.29
10.99
6.3
144.0
29.3
3.2
15:28
7.24
9.2
286. 8
82 . 0
7.31
10.96
6. 6
132.6
28.9
3.2
-------
TABLE 4-18. SUMMARY OF INLET AND MIDPOINT CONTINUOUS EMISSION MONITORING RESULTS
(5-min averages)

Inlet
Location

Outlet Location
Time
02
CO
S02
NOx
02
CO 2
CO
S02
NOx
THC
24
hr.
%
ppm
ppm
ppm
%
%
ppm
ppm
ppm
ppm

Run 10 -
January
12,
1990

10
00
8. 12
N/A
272.4
73.5
8. 12
N/A
N/A
88.1
21.0
N/A
10
05
8 . 76
N/A
234.4
25.0
8.78
N/A
N/A
95.9
18.6
N/A
10
10
7.80
N/A
288.3
70. 1
7.91
N/A
N/A
90.5
20.5
N/A
10
15
7.07
N/A
343.2
28.2
7.05
N/A
N/A
101.1
20.5
N/A
10
20
7.90
N/A
334.2
64.6
7.90
N/A
N/A
97.6
20.8
N/A
10
25
8.08
N/A
367. 1
27.7
8. 09
N/A
N/A
101.9
18.4
N/A
10
30
7.96
N/A
388.0
79.2
7.95
N/A
N/A
103.8
21.5
N/A
10
35
8.08
N/A
392.6
28.5
8. 12
N/A
N/A
101.9
18.2
N/A
10
40
8. 10
N/A
406.0
82.0
8. 09
N/A
N/A
105.0
21.6
N/A
10
45
7.99
N/A
417.2
82.7
7.99
N/A
N/A
104.8
21.6
N/A
10
50
8.23
N/A
422.7
8 5.0
8.21
N/A
N/A
106.8
22.0
N/A
10
55
8.21
N/A
434.6
86.4
8.20
N/A
N/A
108.4
21.6
N/A
11
00
8.11
N/A
446.4
86.1
8. 10
N/A
N/A
108.1
21.3
N/A
11
05
8. 17
N/A
453.6
86.0
8. 16
N/A
N/A
109.0
21.3
N/A
11
10
8.11
N/A
467.5
88.4
8. 11
N/A
N/A
105. 1
21.6
N/A
11
15
8.00
N/A
483.4
89.3
8.00
N/A
N/A
104.9
21.6
N/A
11
20
8.01
N/A
480.5
89. 1
8.00
N/A
N/A
104.4
22.0
N/A
11
25
7.93
N/A
501. 1
87.1
7.92
N/A
N/A
107. 1
21.6
N/A
11
30
7.92
N/A
501.8
81.1
7.91
N/A
N/A
105.8
21.6
N/A
11
35
7.94
N/A
506. 4
88.4
7.93
N/A
N/A
106. 1
21.9
N/A
11
40
7.90
N/A
505.6
90.2
7.94
N/A
N/A
116.6
23.0
N/A
-------
4.8 CONCLUSIONS FROM SITE 8 TEST
From the perspective of method development and data quality, the test program
conclusions are:,
1. The ratio of hexavalent chromium to total chromium in the emissions was
very low (despite relatively high total chromium levels), probably due to
the short sludge retention time in the fluidized bed incinerator and the
absence of alkaline material in the sludge.
2. The ratio of nickel subsulfide to total nickel in the emissions was extremely
low, with the nickel sulfide/subsulfide species measured at the inlet and
midpoint being less than the detection limit.
3. Compared to Site 3, a fluidized bed incinerator where the only semi-
volatile organic compound detected was bis(2-ethylhexyl)phthalate, several
additional semivolatiles were found in the emissions at Site 8. These were
1,2-dichlorobenzene, 1,4-dichlorobenzene, benzyl alcohol, benzoic acid, and
naphthalene.
4. The volatile organic compound emission results for Site 8 were consistent
with the results for Site 3 (another fluidized-bed incinerator). Carbon
tetrachloride and chlorobenzene, reported in the emissions at Site 3, were
not found in the emissions from Site 8.
4-34
-------
5.0 SAMPLING LOCATIONS AND PROCEDURES
Sampling procedures used during the Site 8 program are briefly described in this
section. Standard EPA methods or draft EPA procedures were used for all sampling.
Emission sampling locations are discussed in Section 5.1, and methods and procedures
are discussed in Section 5.2.
5.1 EMISSION SAMPLING LOCATIONS
Emission sampling was conducted at: (1) the inlet to the installed control system
(incinerator discharge), (2) the outlet stack of the installed control system consisting of a
venturi scrubber/impingement tray scrubber and inlet to the pilot-scale wet ESP
(midpoint), and (3) the outlet of the pilot-scale wet ESP. The particulars for each of
these sampling locations are described below.
5.1.1 Inlet to the Control System
The sampling location for the inlet to the control system is shown in Figures 5-1
(Point 1) and Figure 5-2. The flue gas at this point was coming directly from the
incinerator at a temperature of about 1,000°F (538°C). As shown, the ducting exits the
furnace horizontally, turns, and goes down vertically into the venturi scrubber. As in the
majority of incinerators, the duct is not long enough to provide a uniform flow pattern
and meet the EPA Method 1 criteria. The exact direction of the flow at the sampling
point was determined using a directional probe and the "Alternative Measurement Site
Selection Procedure" in EPA Method 1, Section 2.5 (40 CFR 60, July 1, 1990); the
sampling train nozzles were directed into the flow for testing. Since the objective of the
5-1
-------
Sand
Feed
i
N)
Fluidized
Sand
Fluidized
Air_^r
Heat
Exchanger
ZD
Sludge
Inlet
Fluidized Bed
Incinerator
Exhaust
Stack
MM5 + VOST
Sampling
Port
Inlet
Sample
Port
Roof
Midpoint
Sample
Point
Water & .. 1
Ash
Water &
Ash
Wet ESP
Sampling
Port
trzr.rj,
De
mister
Venturi /
Tray Scrubber
Water &
Ash
Wet
Electrostaic
Precipitator
Figure 5-1. Process diagram with sampling locations.
-------
7' 1-5/16'
26" I.D.
3' 3
Figure 5-2. Inlet sampling location.
5-3
-------
program was to determine the ratios of nickel subsulfide to total nickel and hexavalent
chromium to total chromium rather than the absolute concentration of these emissions,
and four samples were collected simultaneously at the same point, the sampling location
was considered adequate for this test.
A 4-in sample port was installed at this location for the manual testing and a
1-in sample port was installed for extraction of the continuous emission monitoring
samples. Because of the likelihood of poor gas velocity distribution, and the fact that
additional ports would have been detrimental to the refractory lining of the duct, the
standard flue gas volumetric flow rate was not determined at the inlet location. The
standard flue gas volumetric flow rate from the outlet location corrected using the inlet
and outlet oxygen concentration was used to calculate flow rates and emission for these
locations.
5.1.2 Midpoint
The midpoint sampling locations are shown in Figures 5-1 (Points 2 and 3) and
Figure 5-3. The midpoint emissions were typical of this plant. A slipstream was diverted
to the pilot-scale wet ESP. The flue gas temperature at this point is typically about
100°F (38°C). Sample Point 2 was located in the vertical, circular stack which had one 6
in sampling port for the quadruplicate train sampling. Prior to testing, a velocity traverse
was conducted to determine the flue gas flow rate. Testing was then conducted at a
single point of average velocity. The single point of average velocity was then used to
determine the flue gas flow rate for that test run.
Sampling for volatile and semi-volatile organics was performed at sample Point 3.
The semi-volatile organic sampling was conducted by traversing the stack through two 4
in sampling ports orientated 90° apart. Volatile organic sampling was performed at a
single point in the stack.
5-4
-------
LD.
THERMOCOUPLE
SECTION K-K
TO
STACK
TO
WET ESP
THERMOCOUPLE
SCRUBBER
Figure 5-3. Midpoint sampling location.
5-5
-------
5.1.3 Outlet of the Wet ESP
The sampling location at the outlet of the pilot-scale wet ESP is shown in Figures
5-1 (Point 4) and Figure 5-4. The flue gas at this point has passed through the venturi
scrubber/impingement tray scrubber and the ESP. The flue gas temperature at this
point is typically about 100°F (38°). The sampling point is located in a vertical, circular
stack which has two ports at 90° apart. Prior to testing, a velocity traverse was conducted
to determine the flue gas flow rate at this location. Testing was then conducted at a
single point of average velocity. The pressure data collected at the single point was used
to determine the flue gas flow rate for the test run.
5.2 SAMPLING PROCEDURES
5.2.1 Total Metals
Sampling for total metals at the inlet, midpoint, and outlet locations followed the
procedures in the draft EPA method, "Methodology for the Determination of Trace
Metals Emissions in Exhaust Gases from Stationary Source Combustion Processes.*1 A
diagram of the multiple metals sampling train used in this test program is shown in
Figure 5-5 and a copy of the draft method is reproduced in Appendix B found in Volume
VII: Site 8 Test Report, Appendices. The sampling train and procedures used are
similar to those for EPA Method 5 (40 CFR Part 60) with the following exceptions:
• A glass or quartz nozzle and probe liner are used;
• a Teflon filter support is used;
• a low metals background quartz fiber filter is used;
• 5% nitric acid/10% hydrogen peroxide solution replaced water in the
impingers;
• the glassware is cleaned according to the procedure in Table 5-1; and
• the sample is recovered as shown in Table 5-2 and Figure 5-6.
5-6
-------
1
> 2 ft.
o
A
Demister
Wet ESP
B i
14" Diameter
2 Axes
8 Points/ Axis
16 Total Points
8 ft.
Figure 5-4. ESP outlet sampling location.
5-7
-------
AH glass sample exposed surface to here.
(Except when T©Hon filler support Is used
L/l
i
CO
Thermocouple CherJ,
*y Valve
Thermometer
Glass
Filter
Holder
Tnermocoupl

Glass
Glass probe liner
Probe

Implngers with
Absorbing Solutions
Heated Area
Reverse-Type
Pilot Tube
Pltot
Manometer
i
Empty (Optional Knockout)
5% HNO 3 710% H £ O 2
4%KkViO 4/10%H2SO4
Bypass
Valve
Vacuum
Line
Vacuum
Gauge
Thermocouples
Or I ce
Main
Valve
Dry Gas
Melor
Figure 5-5. Schematic of multiple metals/particulate sampling train.
-------
TABLE 5-1. METALS GLASSWARE CLEANING PROCEDURES
NOTE: Use disposable gloves and adequate ventilation.
1. Soak all glassware in hot, soapy water (Alconox).
2. Rinse with tap water, three times.
3. Rinse with deionized water, three times.
4. Soak in 10% HN03 for 10 hours.
5. Rinse with deionized water, three times.
6. Cap glassware with Teflon tape.
7. Leave cleaned glassware capped until field assembly.
TABLE 5-2. SAMPLE RECOVERY COMPONENTS FOR MULTIPLE
METALS TRAIN
Component Code Item
1 AR Acetone rinse of probe liner, nozzle, and front
half of filter housing
2 PR-HNO3 0.1 N nitric acid rinse of probe liner, nozzle,
and front half of filter housing
3 F Filter
4 BH HN03/H202 impinger contents and 0.1 N nitric
acid rinse of impingers 1, 2, 3, connecting
glassware, and back half of filter housing
5-9
-------
Probe Liner
and Nozzle
Rinse with
Brush line
with non-
metallic
brush and
rinse with
acetone
Check liner
to see if
particulate
removed: if
not repeat
step above
Rinse three
times with
0.1 N
nitric acid
Front Half of
Filter Housing
FiIter
Brush with
nonmetalIic
brush and
rinse with
acetone
Rinse three
times with
0.1 N
nitric acid
T
F
(3)1
Carefully
remove fiIter
from support
with Teflon-
coated tweezer
and place in
petri dish
Brush loose
particulate
onto fiIter
Seal petri
dish with
tape
AR
(2)
F
(1)
Filter Support
and Back Half
of Filter
Housing
Rinse
three
times
with
0.1 N

nitric acid
1st Impinger
(Empty at
beginning
of test)
Measure
impinger
contents
Empty
contents
into
container
Rinse three
times with
0.1 N
nitric acid
BH
(4)
2nd & 3rd
Impingers
(HN03/H202)
Last Impinger
Weigh for
moisture
Measure
impinger
contents
Discard
contents
into
container
Rinse three
times with
0.1 N
nitric acid
SF
(6)
* Number in parentheses indicates container number.
Figure 5-6. Sample recovery procedures for multiple metals train.
5-10
-------
For the inlet sampling system, the nozzle and probe liner were quartz glass and
the filter holder was borosilicate glass with a Teflon filter support. For the midpoint and
outlet sampling systems, the nozzle, probe liner, and filter holder were borosilicate glass.
At both midpoint and outlet, Teflon frits were used to support the filters. Probes and
filter holder were heated to 248°F _+_ 25°F to prevent moisture condensation. High purity
quartz fiber filters without organic binder and with a 99.95% collection efficiency for 0.3
micron dioctyl phthalate (DOP) smoke particles were used.
The samples were collected over a 30- or 45-minute period at the inlet sampling
site and over a 2-hr period at the midpoint and outlet locations. The high moisture
content at the inlet location required the use of an extra large (2 L) Knockout impinger
to allow operation of the train for a 1-hr sampling period. Sampling for total metals was
conducted simultaneously with the nickel sampling. Four sampling trains (quadruplicate
trains) were operated simultaneously. One sample was intended for total metals analysis,
two for nickel speciation, and the fourth was collected as a backup in the event of system
failure during sampling.
Total metals samples were analyzed by inductively-coupled argon plasma
spectroscopy and atomic absorption spectroscopy for total Cr, Ni, As, Pb, Cd, and Be.
These samples were handled and shipped according to the draft method.
5.2.2 Nickel/Nickel Subsulfide
Sampling for nickel/nickel subsulfide at the inlet, midpoint, and outlet locations
followed the draft EPA method, "Methodology for the Determination of Nickel
Compound Emissions from Stationary Sources." A diagram of the nickel sampling train
is shown in Figure 5-7 and the method description is presented in Appendix B found in
Volume VII: Site 8 Test Report, Appendices. The sampling train and procedures are
identical to those of EPA Method 5 (40 CFR Part 60) with the following exceptions:
• A glass or quartz nozzle and probe liner are used;
• a low metals background quartz fiber filter is used;
5-11
-------

Glass
Filter Holder
<-ri
to
Thermocouple
Glass Nozzle
Glass Probe
Reverse -Type]
Pilot Tube
Thermocouple Check
Valve
Thermometer
Quartz
Filter
Heated Area
Impingers
Ice Bath
Pltot
Manometer
Silica Gel
Water
Bypass
Valve
vacuum
Line
vacuum
Thermocouples
Or ce
Dry Gas
Meter
Figure 5-7. Schematic of nickel/nickel subsulfide sampling train.
-------
• the glassware is cleaned according to the procedure in Table 5-3; and
• the sample is recovered as shown in Table 5-4 and Figure 5-8.
For the inlet sampling system, the nozzle and probe liner were quartz glass and
the filter holder was borosilicate glass. For the midpoint and outlet sampling system, the
nozzle, probe liner, and filter holder were borosilicate glass. Although not required, a
Teflon frit was used to support the filters. The probe and filter holder were heated to
248°F _±_ 25°F to prevent moisture condensation. High purity quartz fiber filters without
organic binder and with a 99.95% collection efficiency for 0.3 micron dioctyl phthalate
(DOP) smoke particles were used.
The nickel speciation sampling trains were operated simultaneously with the
multiple metal train under both operating conditions.
A representative filter from each operational condition at the midpoint sampling
location and an aliquot of the samples for the inlet location were sent for analyses by
XANES and EXAFS by Brigham Young University (BYU). The outlet samples were
not analyzed due to the lack of material. These filter samples were placed on dry ice
immediately after recovery. The remaining inlet and outlet filters were analyzed by Dr.
Vladimir Zatka. The inlet location samples were recovered and stored dry because of
the large volume of sample. For the outlet samples, the acetone probe rinse was vacuum
filtered through the filter. The acetone filtrate was archived with the exception of one of
the 12 daily samples; this filtrate sample was analyzed for total nickel to demonstrate
that the nickel compounds are not soluble in acetone. Each day the filters to be
analyzed by Dr. Zatka were stored in a desiccator under a dry nitrogen atmosphere and
%
sent to Dr. Zatka at the conclusion of each run condition. The dry nitrogen atmosphere
was used because past experience has shown that oxidation of nickel compounds can
occur over a several week period.
5-13
-------
TABLE 5-3. NICKEL/NICKEL SUBSULFIDE GLASSWARE CLEANING
PROCEDURES
NOTE: Use disposable gloves and adequate ventilation.
1. Soak all glassware in hot, soapy water (Alconox).
2. Rinse with tap water, three times.
3. Rinse with deionized water, three times.
4. Soak in 10% HN03 for 10 hours.
5. Rinse with deionized water, three times.
6. Cap glassware with Teflon tape.
7. Leave cleaned glassware capped until field assembly.
TABLE 5-4. SAMPLE RECOVERY COMPONENTS FOR THE NICKEL/NICKEL
SUBSULFIDE TRAIN
Component Code Item
1 AR Acetone rinses of probe liner, nozzle and front
half of filter housing
2 F Filter*
* The samples sent to BYU were immediately placed on dry ice.
The samples sent to RTI were placed in a desiccator and stored under a dry nitrogen
atmosphere.
5-14
-------
FiIter and
Cyclone
Particulate
Matter
(Fraction F)
Acetone
Front Half
Rinse
(Fraction AR)
0.1 M Nitric
Front Half
Rinse
(Discarded)
Back Half
Components
(Discarded)
Label sample
Combine rinses in
sample container
Store and ship
with dry ice
for analysis
For BYU sample,
seal in petri dish
with Teflon tape
Recover filter
and cyclone sample
dry with brush
Recover silica
gel, weigh, and
discard
For Zatka sample,
place in vacuum
fiItration device
Filter acetone
rinses through
particulate
Rinse back half
components with
0.1 N HN03 and
discard
Recover impinger
solution, measure
volume and discard
solution
Recover acetone
and store in labeled
container. Analyze
1 for every 8 samples
Recover particulate
into labeled petri
dish and store in
desiccator under
dry nitrogen until
analysis
Brush and rinse
nozzle, probe,
cyclone, and
front half of
fiIter holder 3
times with acetone
Brush and rinse
nozzle, probe,
cyclone, and
front half of
fiIter holder 3
times with 0.1 N
nitric solution
and discard
Figure 5-8. Schematic of sample recovery procedures for nickel train.
5-15
-------
5.2.3 Chromium and Hexavalent Chromium (Recirculating Train)
Sampling for hexavalent and total chromium (Cr+
-------
GLASS
IMPINGERS

i
TEFLON
IMPINGERS
TEFLON
LINES
ASPRATOR
150 ml
0.1N NaOH
100 ml
0.1 N NaOH
EMPTY
100 ml
0.1N HNOj
SILICA
GEL
RECIRCULATING
LIQUID
ICE BATH
TO
METHOD 5-TYPE
METERBOX
NOZZLE
Figure 5-9. Schematic of recirculating reagent impinger train for hexavalent chromium.
-------
TABLE 5-5. Cr'/Cr TEFLON/GLASS COMPONENTS CLEANING PROCEDURES
NOTE: Use disposable gloves and adequate ventilation.
1. Soak all components in hot, soapy water (Alconox).
2. Rinse with tap water, three times.
3. Rinse with deionized water, three times.
4. Soak in 10% HN03 for 10 hours.
5. Rinse with deionized water, three times.
6. Cap Teflon/glassware with Teflon tape.
7. Leave cleaned Teflon/glassware capped until field assembly.
TABLE 5-6. SAMPLE RECOVERY COMPONENTS FOR THE Cr+
-------
Weigh
Discard
Silica Gel
Filter
FiItrate
Filter Solution through
0.45 jun Teflon Filter
DI H20 Rinse All Components and
Combine with Impinger Solutions
Recover Teflon Impingers Together and
Measure Volume
Nitrogen Purge of Train
Nozzle, Aspirator, Recirculation and
Sample Lines, Teflon Knockout Impinger,
Teflon Impingers containing 0.1 N KOH
Container 3 Container 1 Container 4
Component F Component IMP Component SG
Nitric Acid Rinse All Components
Recover contents of nitric impinger
Container 2
Component NR
Figure 5-10. Sample recovery scheme for hexavalent chromium recirculating impinger
train.
5-19
-------
was stored and transported cold. The Teflon filters and nitric acid rinse samples
analyzed for total chromium did not require any special handling procedures. Filters and
nitric rinse portions were shipped to the respective laboratories for analysis.
5.2.4 Chromium and Hexavalent Chromium (Impinger Train)
The Cr+fi/Cr sampling at the inlet was conducted for all runs without recirculation
of the impinger reagent, due to the high temperature and particulate loading at this
location. The gas sample and particulate matter was collected directly in the impinger
reagent, a solution of 1 N KOH. A diagram of the sampling train is shown in Figure
5-11. This procedure involves the use of the EPA Method 5 sampling train with the
following modifications:
• The train does not have a filter section;
• a quartz nozzle and probe liner are used;
• the glassware is cleaned according to the procedure in Table 5-7; and
• the sample is recovered as shown in Table 5-8 and Figure 5-12.
The sampling train nozzle and probe liner were made of quartz glass and the
impinger train was made of borosilicate glass. The probe was heated to 248°F _+. 25°F to
prevent moisture condensation.
All inlet location hexavalent chromium sampling was conducted using the
impinger train. The sample train preparation and sample recovery procedures were
generally the same as described for the midpoint and outlet hexavalent chromium
sampling.
5.2.5 Semivolatile Organic and PCDD/PCDF
Sampling for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated
dibenzofurans (PCDFs), and other semivolatile organics was conducted at Point 3 (see
5-20
-------
Thermocouple Check
T Valve
Thermocouple
Glass Nozzle
Glass Probe 1
Reverse-Type
Pltot Tube
•Ice Bath
80% IPA / 20% 2N NaOH
or
0.5 M Phosphate Buffer
Silica Gel
Vacuum
Une
Vacuum
Gauge
Thermocouples
Orifice
Main
Valve
AJr-Tight
Pump
\ Dry Gas /
\ Meter /
Figure 5-11, Schematic of inlet impinger sampling train for hexavalent chromium.
-------
TABLE 5-7. Cr/Cr+< GLASSWARE CLEANING PROCEDURES
NOTE: Use disposable gloves and adequate ventilation.
1. Soak all glassware in hot, soapy water (Alconox).
2. Rinse with tap water, three times.
3. Rinse with deionized water, three times.
4. Soak in 10% HN03 for 10 hours.
5. Rinse with deionized water, three times.
6. Cap glassware with Teflon tape.
7. Leave cleaned glassware remained capped until field assembly.
TABLE 5-8. SAMPLE RECOVERY COMPONENTS FOR Cr/Cr+< IMPINGER
SAMPLING TRAIN
Component Code Item
1 I KOH impinger filtrate and rinse of impinger
train
2 NR 0.1 N nitric acid rinses of impinger train
3 F Filter (low metal quartz filter)
5-22
-------
Label sampI
Label sample
Store and ship
to laboratory
Store and ship
to laboratory
Combine rinses in
sample container
Carbine filtrate
in sample
container
Rinse impinger
train with 0.1 N
nitric acid
Recover impinger
contents and
filter. Rinse
impinger train
with 0.1 N KOH
& fiIter sample
Nitrogen Purge of Train
Figure 5-12. Sample recovery scheme for hexavalent chromium impinger train.
5-23
-------
Figure 5-1) at the midpoint sampling location. Three 2-hr runs were conducted
employing the Modified Method 5 (MM5) train of SW-846 Method 0010, except that a
final toluene rinse was conducted and analyzed separately for PCDD/PCDF. A
schematic of the MM5 sampling train is shown in Figure 5-13 and a copy of Method
0010 is reproduced in Volume VII: Site 8 Emission Test Report, Appendices.
The sampling train consisted of a heat-traced probe with a nickel-plated, stainless
steel button hook nozzle, and attached thermocouple and pitot tube. The glass probe
was maintained at a temperature of 250°F 25°F. After the probe, the gas passed
through a heated glass fiber filter (Reeve Angel 934 AH), a water-cooled condenser, and
then through a sorbent module containing approximately 25 g of XAD-2 resin. The
XAD module was followed by a series of four impingers. The XAD inlet temperature
was monitored to ensure that the temperature of the flue gas sample entering the
module was maintained below 20°C. The first impinger, acting as a condensate reservoir
connected to the outlet of the XAD module, was modified with a short stem so that the
sample gas did not bubble through the collected condensate. The first and fourth
impingers were empty, the second and third contained 100 ml of distilled water, and the
fifth contained a known weight of silica gel. The impingers were weighed prior to
assembling the sample train to permit gravimetric moisture determination. All sample-
exposed surfaces within the train were glass or Teflon; no sealant greases were used.
The impingers were followed by a pump, a dry gas meter, and a calibrated orifice meter.
The glassware was cleaned according to the procedure in Table 5-9.
Sampling was conducted isokinetically (+. 10%) with readings of flue gas
parameters recorded at traverse points selected according to EPA Method 1. Leak-
checks on the MM5 sampling train were performed before and after each sampling run
and for any port change. In the event that any portion of the train was disassembled and
reassembled (i.e., due to filter or resin changes), leak-checks were performed. The
sample train leak-checks and leakage rate (where applicable) were documented on the
field test data sheet for each respective run.
Blanks of reagents, XAD modules, and filters were collected.
5-24
-------
Nozzle
Temperature
Indicator
Pi tot tube
Probe
Thermocouple
1.9-2.5 cm
I .9-2.5 cm

mm*
Heated Probe
Thermocouple (behind)
Stack Wall
S Type
Pitot Tube
(thermocouple^
Magnehelic Gauges
ing Water
Thermometer
©
(Thermometer)-^
¦<-^5orbent Trap^ tT
Meter
Ice Bath
Console
Hi

tmptu
(Optional KO) Water Water
Silica Gel
Flow Control valves
Thermometer pjnP
F
Vacuum
Gauge
Calibrated orfice
Coarse
Yacuum
Dry Gas
Meter
Magnehelic Gauges
Figure 5-13. MM5 train for sampling semivolatile organics and PCDD/PCDF.
5-25
-------
TABLE 5-9. SEMIVOLATTLE ORGANICS GLASSWARE CLEANING
PROCEDURE
1. Soak all glassware in hot, soapy water (Alconox)
2. Rinse with tap water, three times
3. Rinse with deionized water, three times
4. Bake at 450°F for 2 hours*
5. Rinse with acetone, three times
6. Rinse with pesticide grade hexane, three times
7. Cap glassware with clean glass plugs or hexane-rinsed
aluminum foil
'Step 4 not used for probe lines or non-glass (e.g., Teflon, nylon) components
which cannot withstand 450°F.
Following completion of each test run, the MM5 trains were transported to a
sample recovery area on-site, out of the sunlight. Sample recovery procedures are
outlined in Figure 5-14 and Table 5-10. Acetone followed by hexane was used to
conduct the initial rinses of the sampling train. These rinses were followed by a final
toluene rinse (three times) which was analyzed for PCDD/PCDF only.
All MM5 samples were stored on ice until they were delivered to Triangle
Laboratories for analysis.
5.2.6 Volatile Organic Sampling Train (VOST)
Sampling for volatile organic compounds (VOCs, organic compounds with boiling
points less than 100°C) was conducted at the midpoint (outlet to the venturi
scrubber/impingement tray scrubber). Three 1-hr runs were conducted under normal
incinerator operating conditions using the volatile organic sampling train (VOST) (see
Figure 5-15) in accordance with SW-846 Method 0030, which is reproduced in Volume
VII: Site 8 Emission Test Report, Appendices.
5-26
-------
NOZZLE. CYCIONE AND XAD CONDENSER. FILTER SUPPORTS.
FH FILTER HOUSWG * PROBE IINER * FILTER MODULE BH F1TER HOUSING * IdPlNGCflS SlICA GEL
BRUSH/RINSE
WITH ACETONE
(3.)
BRUSH/fWSE WITH
HEXANE
(3i)
ATTACH 250 ml
FLASK TO BALL
JOINT
BRUSH/RINSE
WITH ACETONE
<3x)
5UAL NSPECTION
EMPTY FLASK
Lr\
t
N)
-J
BRUSH/RINSE WITH
HEXANE
(3*)
EMPTY FLASK
VISUAL INSPECTION
REMOVE WITH
TVYEEZEHS TO
PRECLEANEO
ALUMINUM FOIL
BRUSH LOOSE
PARTICULATE
ONTO riLTER
REMOVE
AND CAP
RUSE
WITH ACETONE
(3x)
MEASURE
VOLUME
GW
EMPTY CONTENTS
NIO SAMPIE
CONTAINER
WEIGH
DISCARD
RINSE WITH
HEXANE
(3x)
RNS£ WTH
Dl WATER
(3«)
TRANSPORT N
ORIGINAL GLASS
PETRI DISH
WRAP THE
MODULE IN
ALUMINUM FOL
PR
SM
CH
* Final toluene rinse (3x).
Figure 5-14. Semivolatile organics train sample recovery scheme.
-------
TABLE 5-10. SAMPLE RECOVERY COMPONENTS FOR SEMIVOLATILE
ORGANICS TRAIN
Component Code Item
1 F Filter(s)
2 PR Acetone and hexane rinses of
nozzle, probe, transfer line,
cyclone (if used), and
front half of filter holder
3 CR Acetone and hexane rinses of back
half of filter holder,
filter support, and condenser
4 IR 1st through 4th impinger
contents and DI HzO rinses
5 SM XAD-2 resin
6 TR Final toluene rinse of train
7 SG Silica gel
5-28
-------
HEAT
SAMPLE
3 • WAY
VALVE

_r
ICE WATER
CONDENSER
ICE WATER
CONDENSER
TENAX / CHARCOAL
CARTRIDGE
TENAX
CARTRIDGE
VALVE
DRY
GAS METER
SILICA GEL
DRYING
TUBE
ROTAMETER
CONDENSING
IMPINGER
PUMP
Figure 5-15. Schematic of volatile organic sampling train.
-------
The VOST consisted of a glass-lined probe with a glass wool plug to remove
particulate matter, followed by an assembly of condensers and organic resin traps as
illustrated in Figure 5-15. Samples were collected using paired Tenax and Tenax/
charcoal cartridges, with each cartridge preceded by a condensing module. The first
condenser cooled the gas stream and condensed the water vapor present. The flue gas
and condensed moisture then passed through a cartridge containing 1.5 g of Tenax resin
(60-80 mesh). The condensate was collected in an impinger which was continually
purged by the gas stream. The second condenser and cartridge containing
Tenax/charcoal served as a backup for low volume breakthrough compounds. Following
the second cartridge was a silica gel drying tube for residual moisture removal. The
sampling train was operated at a flow rate of 1.0 L/min and the total collection volume
did not exceed 20 standard liters.
The system was leak-checked by closing the valve at the inlet to the first
condenser and evacuating the system to 10 in Hg. The system was then isolated and the
leak rate noted. The leak rate was less than 1 in Hg after one minute. The train
was returned to atmospheric pressure by purging through a charcoal tube. The leak
checks were conducted before and after each pair of VOST tubes were collected. The
recovery activities for the VOST included:
• Leak check system as required;
• cap the VOST cartridges;
• place the cartridges in their original glass culture tubes with glass wool to
absorb shock;
• measure the volume of the condensate impinger with a precleaned
graduated cylinder (after final pair of tubes collected for the run);
• transfer the measured condensate volumes to 40 mJ VOA vials and diluting
the volume with DI water to decrease headspace and reduce the possibility
of revolatilization of the compounds; and
• reduce reactivity by storing all samples at 4°C.
5-30
-------
The samples collected during each VOST run consisted of two pair of sorbent
tube (Tenax cartridge, a Tenax/charcoal cartridge), and the condensate (captured by the
midget impinger, archived).
Gas sample temperatures were monitored at the outlet of the sample probe and
the inlet to the Tenax cartridge using thermocouples. The gas temperature through the
probe was maintained above 150°C to prevent the premature condensation of the volatile
components. The temperature of the gas through the resin cartridges was maintained at
less than 20°C.
5.2.7 Continuous Emissions Monitoring
Continuous emission monitoring systems (CEMSs) were used at the control device
inlet and midpoint to measure concentrations of CO, C02, 02, NO,, and S02; CO and
total hydrocarbons (THC as propane) were monitored at the stack outlet location. The
primary intent of the continuous monitoring effort was to: (1) determine concentrations
of these compounds, and (2) provide a real-time indication of combustion conditions.
The continuous monitoring systems were calibrated daily, but no attempt was made to
certify the monitors using the EPA instrumental test methods. The monitoring systems
used to determine CO, C02, 02, NO„ S02, and THC are discussed in the following
sections.
5.2.7.1 Sample and Data Acquisition - Sample gas was drawn through a sample gas
conditioner consisting of an ice bath and knockout trap to remove moisture and thus
provide a dry gas stream for analysis. Sample gas from the gas conditioner was pumped
through a sample manifold at a flow rate which exceeded the total sample requirements
of the various gas analyzers. The manifold was used to provide slip stream sample flows
to each analyzer. A separate gas conditioning system and sample line was used for the
inlet and outlet sampling locations.
To maximize representativeness of the CEM measurements, all gases for
calibration were introduced at the inlet of the sample line. The instruments were
5-31
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calibrated prior to each test run. At the end of each test run, a post-test calibration was
performed. If instrument drift exceeded 2% of the span value for a pollutant, the
corresponding data were adjusted linearly to account for the drift. Data from the
analyzers was collected and recorded using a microprocessor data acquisition/reduction
system. A hard copy of the reduced data (engineering units) was printed at the end of
each sample run and the raw data were stored on the computer hard drive and on floppy
disks.
5.2.7.2 Carbon Monoxide/Carbon Dioxide Analysis - TECO Model 48 analyzers were
used to measure CO concentrations in the flue gas. The TECO Model 48 is a gas filter
correlation (GFC) analyzer. It measures the concentration of CO by infrared adsorption
at a characteristic wavelength. Fuji 3300 analyzers were used to determine C02
concentration. The Fuji 3300 is a non-dispersive infrared (NDIR) analyzer.
5.2.7.3 Oxygen Analysis - Teledyne Model 320P-4 02 analyzers were used to
continuously measure flue gas oxygen concentrations. The Teledyne analyzer uses an
electro-chemical cell to produce a linearized voltage signal that is proportional to the
ratio of oxygen concentration of a reference gas (ambient air) and the oxygen
concentration of the sample.
52.7.4 Nitrogen Oxides (NOJ Analysis - TECO Model 10 analyzers were used for NO,
measurement. This instrument determines NOx concentrations by converting all nitrogen
oxides present in the sample to nitric oxides and then reacting the nitric oxide with
ozone. The reaction produces a chemiluminescence proportional to the NOx
concentration in the sample. The chemiluminescence is measured using a high-sensitivity
photomultiplier. Also, during the time between the manual sampling runs, the ratio of
NO to N02 was determined. This ratio is of interest because NOz can be effectively
removed by the venturi scrubber.
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5.2.7.5 Sulfur Dioxide (S02) Analysis - Sulfur dioxide in the flue gas was measured using
Maihak UNOR 6N analyzers. This instrument measures S02 on the basis of infrared
adsorption.
5.2.7.6 Total Hydrocarbon Analysis - A Beckman 400A analyzer was used to measure
total hydrocarbons (THC) as propane in the flue gas. This instrument is a continuous
flame ionization analyzer (FIA). The detector is a burner where a regulated flow of
sample gas passes through a flame sustained by regulated amounts of air and hydrogen.
Hydrocarbons passing through the flame undergo a complex ionization that produces
electrons that are detected by polarized electrodes. The THC analyzer was calibrated
using propane standards, and the THC concentrations were reported in parts per million
by volume (ppmv) as propane.
5.2.8 EPA Methods 1. 2. 3. and 4
The methods used to determine the flue gas moisture content, molecular weight,
and volumetric flow rate are described in the following sections.
5.2.8.1 Volumetric Gas Flow Rate Determination - The volumetric gas flow rate at the
pilot-scale wet ESP outlet location was determined during this program using procedures
described in EPA Method 2. Based on this method, the volumetric gas flow rate is
determined by measuring the cross-sectional area of the stack and the average velocity of
the flue gas. The average flue gas velocity is calculated from the average pitot tube
pressure (delta P), the average flue gas temperature, the wet molecular weight, and the
absolute static pressure. Temperature and delta P profile data was obtained by
traversing the midpoint stack prior to the each test run. The number of sampling points
required to measure the average gas velocity was determined using the procedures in
EPA Method 1. The number of sampling points and their distances from the duct wall
are a function of the proximity of the sampling location to the nearest upstream and
downstream flow disturbance.
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Temperature and pressure profile data was measured at each of the sampling
points using an S-type pitot tube. A calibrated aneroid barometer was used to obtain
barometric pressure readings each day. The static gas pressures at the inlet and outlet
locations were measured by disconnecting one side of the S-type pitot and then rotating
the pitot so that it was perpendicular to the gas flow.
The standard flue gas flow rate at the inlet location was not measured; but was
calculated by correcting the standard flue gas flow rate measured at the outlet using the
difference between the inlet and outlet oxygen concentrations. This calculation corrects
for the dilution air from the shaft cooling which enters the duct between the inlet and
outlet locations. Isokinetic sampling was achieved by measuring the pitot tube pressure
(delta P) at a single point at regular intervals during sampling. The MM5 sampling
system was traversed according to Method 5. The isokinetic calculations were performed
using these measured values.
5.2.8.2 Flue Gas Molecular Weight Determination - The integrated sampling technique
described in EPA Method 3 was used to obtain composite flue gas samples at the
midpoint and outlet locations for fixed gas (02, C02) analysis. A small diaphragm pump
and a stainless steel probe were used to extract a single-point flue gas sample which was
collected in a Tedlar bag. Moisture was removed from the gas sample by a water-cooled
condenser so that the fixed gas analysis is on a dry basis.
The composition of the gas sample was determined using an Orsat analyzer only
when there was problems with the CEMs. When using the Orsat, if more than six passes
were required to obtain a constant (<_ 0.3 percent difference, absolute) reading for
either 02 or CO2, the appropriate absorbing solution was replaced. The S02
concentration was well below the level at which correction of the C02 concentration is
required (5,000 ppm).
5.2.8.3 Flue Gas Moisture Determination - The moisture content of the flue gas was
determined using the methodology described in EPA Method 4. Based on this method,
a known volume of particulate-free gas was pulled through a chilled impinger train. The
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quantity of condensed water was determined gravimetrically and then related to the
volume of gas sampled to determine the moisture content.
During this project, the moisture content of the flue gas was determined
simultaneously with the operation of the manual sampling trains. The volume of solution
in the impingers was determined before and after sampling. The volume increase in
water was then related to the volume of gas sampled to calculate the moisture content.
5.2.9 Process Samples
Samples of sludge feed and scrubber outlet water (effluent) were collected during
the flue gas sampling. These process samples were composites of grab samples collected
at regular intervals and combined after each run was completed. All process samples
were stored in 500-mI polyethylene sample containers prepared according to EPA
Protocol C.
The volume of each sludge feed grab sample was approximately 250-ml. The grab
samples were combined and homogenized in a plastic bucket using a mortar mixer for at
least 10 min. From the homogenized mixture, two 500-ml portions were taken and saved
for metals analysis, proximate and ultimate analyses, and analyses of moisture content
and heating value.
Scrubber water samples consisted of the composite of two equal size grab samples
collected from the venturi scrubber discharge and the impingement tray scrubber
discharge, respectively during each run. These samples were thoroughly mixed before
aliquots were taken for analysis.
5.3 PROCESS DATA
Incinerator and control system operating parameters were monitored during all
manual test runs to characterize the system operations. The parameters monitored are
presented in Table 5-11.
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TABLE 5-11. PROCESS MONITORING DATA
Parameter
Frequency of
Readings
Source of Readings
Incinerator Operating Data
Wind Box Temperatures
Bed Temperatures
Freeboard Temperatures
Heat Exchanger Inlet Temp
Heat Exchanger Outlet Temp
Incinerator Outlet Oz
Auxiliary fuel usage
Sludge Feed Rate
Sludge Feed Characteristics
Moisture (wt %)
Volatiles (wt %)
Heating Value
Scrubber System Operating Data
Differential Pressure (in. H20)
Scrubber Inlet Temp (°F)
Scrubber Outlet Temp (°F)
60 minutes
60 minutes
60 minutes
60 minutes
60 minutes
Continuous
As used
60 Minutes
Once per run
Once per run
Once per run
60 minutes
60 minutes
60 minutes
Plant operating log
Plant operating log
Plant operating log
Plant operating log
Plant operating log
Entropy CEMSs
Plant operating log
Plant operating log
Entropy analysis
Entropy analysis
Entropy analysis
Plant operating log
Plant operating log
Plant operating log
5-36
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6.0 ANALYTICAL PROCEDURES
The laboratory activities for this program focused on (1) analytical procedures
designed to speciate chromium based on their valency state and nickel based on the
compound, and (2) analysis of selected samples for concentration of arsenic, beryllium,
cadmium, chromium, lead, nickel, and mercury. Note: The mercury results are not
shown because EPA recently determined that mercury precipitates in the MMtl sampling
train impinger solution. New digestion procedures have been added to the method to
recovery the mercury in the precipitate. Therefore, the results for mercury in this study
are considered invalid and are not reported.
The sample matrices included flue gas samples, sludge samples, bottom ash
samples, and scrubber water samples. Sludge samples were also subjected to moisture,
proximate and ultimate analyses, and heating value determination. A summary of the
analytical methods employed is provided in Table 6-1. Each of these methods are
described briefly in the sections below and detailed procedures are included in Volume
VII, Appendices.
6.1 CHROMIUM SPECIATION AND ANALYSES
Several analytical procedures were employed to speciate chromium compounds in
the samples to determine the ratio of hexavalent chromium (Cr+*) to total chromium
(Cr). Since the hexavalent chromium analytical results using ICP/MS analysis and a
S3Cr+6 spike provided no reportable results, this analytical techniques is shown in the
tables and figures but will not be discussed.
Flow diagrams of the analytical protocol for the quadruplicate recirculatory
hexavalent chromium sampling train are shown in Figure 6-1. Samples from this train
6-1
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TABLE 6-1. SUMMARY OF SAMPLING AND ANALYTICAL METHODS
Sample Type
Parameter
Analysis Method
Flue Gas
Total chromium, Cr+<4,b
IC/PCR, gamma counter
ICAP/AAS, ICP/MS, XANES
Total nickel,
nickel subsulfidesc
EPA Draft Method,
ICAP/AAS, XANES
• Particulates, metals*
Gravimetric, ICAP/AAS
Solid/Liquid • Feed sludge
• Scrubber water:
inlet d
outlet —d
Bottom ash d
"Recirculating reagent impinger train for hexavalent chromium at the midpoint and ESP
outlet locations, with 0.1 N KOH impinger solution.
bMethod 5-type impinger train for chromium at the inlet location, with 1 N KOH
impinger solution.
'Method 5-type sampling train for nickel.
dMetals analysis included chromium, nickel, arsenic, lead, cadmium, beryllium, and
mercury (Note: The mercury results not reported due problems with the draft
EPA Method).
The sludge samples were analyzed for same metals as the scrubber water plus moisture,
proximate and ultimate analyses.
6-2
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- Resi
FiItrete
Fi Urate
Acid Digest
Total Cr
Analysis
Cr and 53Cr
Analysis
by I CP/MS
IC/PCR Analysis
for Cr+6
[C/PCR Analysis
for Cr+6
Gamma Count
of Residue
for 51Cr
Gamma Count
of Residue
for 51Cr
Filter through
0.45 Micron
Teflon filter
Filter through
0.45 Micron
Teflon filter
1 Combination
of Residue and
HN03 Solutions
for Total Cr
Preconcentrate
for 53Cr+6
Analysis by I CP/MS
Recirculatory
Sampling Train
Impinger Sol.
and 0.1. Rinse
Recirculatory
Sampling Train
Impinger Sol.
and D.I. Rinse
Ganrna Count
of IC Fractions
for Speciation
of 51Cr
Recirculatory
Sampling Train
HN03 Impinger
and Train Rinse
Recirculatory
Sampling Train
HN03 Impinger
and Train Rinse
Recirculatory Train A
with 53Cr*6 Spike
Recirculatory Trains B, C, and D
with 5lCr*6
Figure 6-1. Analytical protocol for quadruplicate recirculatory
hexavalent chromium sampling at midpoint and outlet locations.
6-3
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were analyzed for Cr+6 using ion chromatography with a Cr+6-specific post column
reaction (IC/PCR) by Entropy and for total Cr using inductively-coupled argon plasma
emission spectroscopy (ICAP) Research Triangle Institute (RTI). Entropy also
performed gamma emission measurements of labeled hexavalent chromium (s1Cr+<)
spiked into the impinger reagents to monitor conversion of chromium species that may
occur during sampling, sample handling, and sample preparation.
6.1.1 IC/PCR Analysis for Hexavalent Chromium
The IC/PCR analysis for Cr+< was performed by Entropy on the recirculatory
(RC) impinger train samples. Samples consisted of alkaline impinger solutions from the
recirculatory impinger train.
Entropy performed on-site filtration of the alkaline impinger samples employing
an all-Teflon pressure filtration device and Teflon membrane filters with a 0.45 micron
pore size (see Figure 6-1). The filtrates was analyzed for Cr+6 by the IC/PCR method.
To determine the ratio of the soluble SICr+3 and 5lCr+6 species, 0.5 ml fractions of the
IC/PCR discharge were collected at regular time intervals during the IC/PCR analysis,
and the gamma emissions measured for each fraction. For samples with the slCr spike,
the gamma emissions from the filter residue and the HN03 rinses were measured before
combining them for digestion and total Cr analysis.
The IC/PCR system was calibrated with a series of three Cr+* standard solutions
with concentrations ranging from 1.0-to-100 ng/ml, prepared fresh daily from a working
standard. The laboratory verified the concentration of their working standard solution by
ICP analysis or ICP/MS analysis for total Cr. A calibration check sample was analyzed
with every ten samples.
6.1.2 ICP Analysis for Total Chromium
Residue samples from the filtration of the alkaline impinger solution for the
recirculation trains were analyzed with the corresponding HN03 rinses for total
6-4
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chromium (see Figure 6-1). Where appropriate, an aliquot of HN03 rinses was first
measured for gamma emissions prior to the sample being reduced to near dryness. It
was then combined with the residue sample for HNO3/HF digestion and analyzed for
total chromium using ICP by RTL
Sludge samples, bottom ash samples, and scrubber water samples were analyzed
for total Cr during the ICAP analysis for the other target metals, as described in
Subsections 6.3.2, 6.3.3, and 6.3.4, respectively.
6.1.3 XANES Analysis for Chromium Speciation
X-ray absorption near-edge structure (XANES) spectroscopy was employed to
determine the chemical state of an element without chemical pretreatment which may
alter the chemical state. XANES spectroscopy requires a high intensity X-ray source
provided by synchrotron radiation. For this test program, Brigham Young University
(BYU) arranged for access to the Brookhaven synchrotron. Eight-hour irradiation times
were required to obtain spectra for chromium samples in the 300-to-1000 ug/g
concentration range. The irradiation was performed at an electron energy of 3.0 GeV
with a current of approximately 50 mA. The X-ray beam is monochromatized with a
double crystal silicon spectrometer and a 1-mm (vertical dimension) entrance slit which,
with this configuration, produces a resolution of approximately 0.4 eV at the vanadium K
edge at 5.465 KeV.
An aliquot of the bulk inlet sample and filter sample from the nickel sampling
train were placed in the sample chamber at an angle 45 degrees to the X-ray beam, and
the sample chamber was purged with helium. The sample spectra was measured by the
fluorescence extended X-ray absorbance fine structure technique with a fluorescence
detector.
Reference spectra were obtained from standards with known ratios of Cr+6 to
total Cr. A separate report of this analysis prepared by BYU is presented in Volume
VII: Site 8 Test Report, Appendices.
6-5
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6.2 NICKEL SPECIATION AND ANALYSIS
Two different procedures were employed to speciate nickel compounds in samples
to determine the ratio of nickel subsulfide (Ni3S2) to total nickel (Ni). The first
procedure, XANES analysis, was performed by BYU. The second procedure performed
by Dr. Vladimir Zatka, employed the Nickel Producers Environmental Research
Association (NiPERA) method. The analytical protocol for the inlet sampling location
and outlet location are presented in Figure 6-2 and Figure 6-3, respectively.
6.2.1 XANES Analysis for Nickel Speciation
XANES spectroscopy was employed by BYU to determine the ratio of Ni3S2 to
total Ni. The analytical procedures were identical to those described in Subsection 6.1.4
for chromium speciation, with the exception that reference spectra was determined on
standards with known ratios of Ni3S2 to total Ni. The detection limit for Ni3S2 by
XANES was reported to be 5% of the total nickel.
6.2.2 NiPERA Method for Nickel Speciation
The NiPERA sequential leaching method was employed by Dr. Vladimir Zatka to
determine the ratio of sulfidic nickel species, Ni3S2 and nickel sulfide (NiS), to total Ni.
The NiPERA method is not capable of speciating between Ni3S2 and NiS. The NiPERA
method involved two sequential leachings of the solid sample with a series of solutions
with increasing oxidation strength. The leaching procedure was performed in a Teflon
vacuum filtration device fitted with a cellulose membrane filter with a 0.2 micron pore
size. The water soluble Ni species was leached during the first step and the sulfidic Ni
species was leached during the second step. Four nickel phase groups are determined:
6-6
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Freeze with Dry Ice
Store Desiccated
under Dry N2
Store Oesiccated
under Dry N2
Determine Particulate
Mass by Draft Protocol
Ship to Zatka for
Nickel Speciation by
NiPERA Method
Archive sample fort
Nickel Speciation by
NiPERA Method
Ship Frozen to BYU
for Nickel Speciation
by XANES Method
ICAP Screen for Target
Metals (As, Be, Cd, Cr
Pb, Ni, and H9)
(Contained Front and
Back Half Analysis)
AREAL Multi-Metal
Sampling Train D
Particulate Matter
(Filter, Probe Rinse
and Cyclone Catch)
Method 5-Type
Sampling Train C
Particulate Matter
(Filter, Probe Rinse
and Cyclone Catch)
Method 5-Type
Sampling Train B
Particulate Matter
(FiIter and Dry
Cyclone Catch)
Method 5-Type
Sampling Train A
Figure 6-2. Analytical protocol for paired nickel sampling at the scrubber inlet
sampling location.
6-7
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Filter and
Cyclone
Particulate
Matter
(Fraction F)
Acetone
Front Half
Rinse
(Fraction AR)
0.1 N Nitric
Front Half
Rinse
(Discarded)
Back Half
Components
(Discarded)
Recover silica
gel, weigh, and
discard
Filter acetone
rinses through
Combine rinses in
sample container
For BYU sample,
seal in petri dish
with Teflon tape
Recover filter
and cyclone sample
dry with brush
For Zatka sample
place in vacuum
filtration device
vol
Recover impinger
solution, measure
me and discard
solution
Rinse back half
components with
0.1 N HN03 and
discard
Brush and rinse
nozzle, probe,
cyclone, and
front half of
fiIter holder 3
times with 0.1 N
nitric solution
and discard
Brush and rinse
nozzle, probe,
cyclone, and
front half of
fiIter holder 3
imes with acetone
particulate
Store and ship
with dry ice
for analysis
Recover particulate
into labeled petri
dish and store in
desiccator under
dry nitrogen until
analysis
Recover acetone
and store in labeled
container. Analyze
1 for every 8 samples
Figure 6-3. Analytical protocol for paired nickel sampling at the scrubber
outlet sampling location.
6-8
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Nickel Groups
1) soluble nickel
2) sulfidic nickel
3) metallic nickel
4) oxidic nickel
Types of Nickel
water soluble nickel salts;
Leaching Solution
0,1M ammonium acetate
besides Ni3S2 and NiS, also dissolved peroxide-citrate
are arsenides NiAs and Ni„As8> and
selenide NiSe;
free or alloyed with iron (ferronickel); methanol-bromine
refractory nickel oxide; nitric/perchloric acid
For this test program, the first and second leach solutions were collected
separately. The leached residue was digested prior to Ni analysis following the SW-846,
Method 3050.
The three Ni subsamples were analyzed for total Ni by atomic absorption (AA)
analysis. The AA was calibrated with a series of seven Ni standard solutions ranging in
concentration from 0.5-to-20 ug/ml. An interference check sample was analyzed prior to
sample analysis, and a calibration check sample was analyzed with every 10 samples. A
reagent blank was carried through the procedure and analyzed with the actual samples.
6.3 MULTIPLE METALS ANALYSIS
Analysis of flue gas samples, dewatered sludge samples, incinerator bottom ash,
and scrubber water samples for the target metals; arsenic (As), beryllium (Be), cadmium
(Cd), chromium (Cr), lead (Pb), and nickel (Ni), employed matrix-specific preparation
and digestion followed by ICAP analysis. All prepared sample solutions were initially
archived for possible reanalysis for As and Pb by graphite furnace atomic absorption
spectroscopy (GFAAS), however, reanalysis was not required.
6-9
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6.3.1 Flue Gas Samples
Flue gas samples were analyzed for the target metals following the procedures
described in the draft AREAL procedure. A copy of the draft method is provided in
Volume VII: Site 8 Test Report, Appendices, and an analytical flow chart in Figure 6-4.
For each train, the particulate mass concentration was determined gravimetrically from
the front half portion of the sampling train. The particulate matter was then subjected
to microwave HN03/HF digestion in a pressure relief vessel. The combined nitric
acid/hydrogen peroxide impinger solution and nitric acid rinse was reduced to near
dryness and digested with HN03. The front and back half digestates were combined
prior to ICP analysis for As, Be, Cd, Cr, Pb, and Ni. A portion of the digestate was
archived for reanalysis by GFAAS for As and Pb, if they were not detected by ICP;
however, this did not prove necessary.
The ICP was calibrated with two series of five standard solutions containing the
target metals ranging in concentration from 0 to 100 ug/ml (depending on the element).
Cr and Ni were in one series of solutions and As, Be, Cd, and Pb were in the second
series of solutions. An interference check sample was analyzed prior to sample analysis,
and a calibration check sample was analyzed with every 10 samples. A reagent blank
was carried through the procedure and analyzed with the field samples.
6.3.2 Dewatered Sludge Samples
The dewatered sludge samples were analyzed for the target metals after
determination of their moisture and ash content, heating value, and proximate and
ultimate analyses following ASTM Methods D3174, D3175, D3177, D3178, D3179, and
D2361 (not reproduced in Appendices because they are standard methods). A dried
portion of the sludge sample was subjected to microwave HN03/HF digestion in a
pressure relief vessel identical to the flue gas particulate samples described above. This
digestion procedure was chosen because it provided comparison of the metals in the
sludge with the flue gas samples and the bottom ash samples (see below). The digestion
6-10
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Container 2
HNQ3 Probe Rinse
(Labeled FK)
Acidify to pH2
with cooc. HM03
Reduce volune to
near dryness and
digest with HF and
conc. HN03 using
microwave digestion
Container 1
Acetone Probe Rinse
(Labeled AR)
Reduce to dryness
in a tared beaker
Determine residue
weight in beaker
Solubilize residue
with conc. HN03
Container 3
FiIter
(Labeled F)
Desiccate
to
constant t
weight
Detemine fiIter
particulate weight
Divide into 0.5 g
sections and digest
with conc. HF and
HN03 using pressure
relief microwave
digestion procedure
Container 4
Knockout &
HN03/H202 Impingers
(Labeled BH)
Acidify half
of remaining
sairple to pH
of 2 with
conc. HN03
Fraction 2A
Reduce volume
to near
dryness and
digest with
HN03 and H202
Analyze for
As and Pb by GFAAS
(Not conducted)
Filter and dilute
to known volune
Fraction 1
Analyze by ICP for
target metals .
Fraction 1A
Figure 6-4. Sample preparation and analysis scheme for multiple metals trains.
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solution was analyzed by ICAP following the procedures described for the flue gas
samples and archived for possible GFAAS analysis, however, no GFAAS analyses were
required.
6.3.3 Scrubber Water Samples
Portions of the inlet and outlet scrubber water samples were acidified with HN03
and reduced to near dryness on a hot plate. Because the venturi scrubber discharge
water samples had a high solids content, the solids were subjected to the microwave
HNO3/HF digestion described above. The digested solutions were analyzed by ICP for
all the target metals except Hg following the procedures described for the flue gas
samples, A portion of the solution was archived for possible GFAAS analysis, however,
no GFAAS analyses were required.
6.4 SEMIVOLATILE ORGANIC ANALYSIS
The semivolatile organic train (MM5) samples were analyzed for PCDD/PCDF
using SW-846 Method 8290 and for other semivolatile organic compounds using a
combination of SW-846 Methods 3540, 3550, 3510, 3520, and 8270. The analysis of
semivolatile organic compounds by GC/MS is a highly specialized procedure involving a
complex series of extraction and clean-up procedures. These procedures are outlined for
the target semivolatile organic compounds in Figure 6-5. The actual analysis by GC/MS
requires highly trained individuals and computerized data acquisition and data
interpretation. The protocol to be followed for analysis of the trace organic samples
contains analytical criteria for confirmation of 2, 3, 7, 8-TCDD, quantification
procedures, and QA/QC requirements for analytical data, which are described below.
To monitor the extraction, clean-up, and analysis of the semivolatile organic
samples, labeled internal standards were added to the field samples and laboratory
blanks, and performance audit sample prior to extraction. One set of labeled internal
standards was added in all the Soxhlet extraction steps. A second set of the labeled
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PR CR SM F IR
Concentrate
Liquid/ Liquid
Extraction w/ MeCl
Place in
Soxhlett
Spike
Extraction
v* MeCl2
Extraction
w/ Toluene
Combine
Split 1:1
Split 1:1
Combine
Concentrate
Analyze Aliquot
for Semrvolatiles;
Archive Remaining Extract
Solids
Toluene
Rinse
Extract A
(MeC!2)
Extract C
(MeCi2)
Extract D
(MeQ2)
Extract E
(MeG2 /Toluene)
XAD Resin Trap
and Filter
Impinger Contents
and Dl H2 O Rinses
Acetone/Hexane Rinses of
Probe Uner, Nozzle, and
Front HaJf of Filter Housing
Combined with Acetone/Hexane
Rinses of Condenser and
Back Half of Filter Housing
Concentrate
Hexane Exchange for
MeC!2 /Toluene
Extract G
PCDD/PCDF
Cleanup
Extract H
Analyze Aliquot
for PCDD/PCDF;
Archive Remaining Extract
Figure 6-5. Extraction schematic for semivolatile organic samples.
6-13
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internal standards was added to impinger samples from the MM5 train during extraction,
but the recoveries of the standards were not used to adjust the results. Internal standard
recoveries should typically be in the range of 50% to 150%. Since these surrogates can
be used to adjust the results for native compounds, low recoveries do not invalidate the
data, but do result in higher than desired detection limits. The surrogates and the target
recoveries are shown below.
PCDD/PCDF Labeled Surrogates
• I3Cir2,3,7,8-TCDD
• °Cu-lf2,3,7,8-PeCDD
• l3Cirl,2,3,6,7,8-HxCDD
13C12-lt2t3,4,6,7,8-HpCDD
l3CI2-OCDD
l3C12-2,3,7,8-TCDF
Chlorobenzene and PCB Labeled Internal Standards
• l3C6-1,2,4,5 Tetrachlorobenzene
• l3C«-Hexachlorobenzene
• l3C|2-Pentachlorobiphenyl
• I3C,2-Octachlorobiphenyl
Chlorophenol Labeled Internal Standards
• i3(V3,4 Dichlorophenol
• l3C4-2,'4,5 Trichlorophenol
• l3C6-Pentachlorophenol
Polvaromatic Hydrocarbon Labeled Internal Standards
• dlO - Acenaphthene
• dlO - Anthracene
• dlO - Pyrene
6-14
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• D12 - Benzo(a)Anthracene
• dl2 - Benzo(a)Pyrene
• dl4 - Bidenzo(a,h) Anthracene
• dl2 - Benzo(g,h,i)Perylene
Corrective action for internal standard recoveries outside the specified limits can
require re-extracting sample residues and reanalysis. Sample residues were retained as a
precaution.
A second criterion for validating analytical data was a demonstration that the
extraction and cleanup system was free of contamination. Method blanks and matrix
blanks were analyzed.
The following analytical criteria were used for confirmation of the target trace
organic compounds:
• Retention time of specific trace organic isomers;
• retention time window of respective trace organic series of isomers based
on standard mixtures;
• chlorine isotope ratio of molecular ions of respective trace organic isomers
within jL 20% of the values determined from the external standards; and
• responses of respective trace organic masses greater than 2.5 times the
signal-to-noise ratio.
Once the trace organic compounds have been identified and confirmed by the
procedures described above, the compounds were quantified by comparison of the
response factors of the sample analytes to the response factors of known amounts of
native trace organic compound external standards. The recoveries of the internal
standards, added to the Soxhlet extraction step, were used to adjust the results of the
corresponding native CDD/CDPs (i.e., I3CU-TCDD recovery will be used to adjust
results for all native TCDD's and TCDFs).
6-15
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6.5 VOLATILE ORGANIC ANALYSIS
Volatile organic components in the gaseous streams were analyzed in samples
collected from each VOST run. The samples collected from each VOST run consisted
of four pairs of a Tenax cartridge and a Tenax/charcoal backup cartridge. Two pairs of
Tenax tube samples were analyzed for volatile organics using the thermal desorption
GC/MS procedures specified in Methods 5040 and 8240 of SW-846. The organic
contents of each set of Tenax and Tenax/charcoal traps were thermally desorbed onto an
analytical trap. The compounds were then thermally desorbed off the trap into the
GC/MS. Helium was the carrier gas in all cases.
The major QC procedures included GC/MS tuning, calibration system
performance checks, and analysis of QC check samples. During actual sample analysis, a
reagent blank, a matrix spike, and a matrix spike duplicate were analyzed with each
batch of samples (up to a maximum of 20 samples/batch). The criteria for acceptable
performance for the QC measures described above are compound-specific and can be
found in SW-846 Method 8240.
6.6 SLUDGE SAMPLE ANALYSES
Dewatered sludge samples were subjected to moisture analysis and proximate and
ultimate analyses. Ultimate and proximate analyses were combinations
of measurements performed with the following ASTM procedures; ash by ASTM D3174,
volatile matter by ASTM D3175, carbon and hydrogen by ASTM D3178, nitrogen by
ASTM D3179, chlorine by ASTM D2361, and sulfur by D3177. The heating value was
calculated from the carbon and hydrogen content determined by ASTM D3178. The
metals analysis of the sludge samples was described in Section 6.3.2.
6-16
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7.0 QUALITY ASSURANCE AND QUALITY CONTROL
This section discusses the quality assurance and quality control (QA/QC)
activities implemented for the sewage sludge incineration test program and the QA/QC
results for the Site 8 test. The objectives of and basic activities for the QA/QC program
are briefly discussed in the section below. Summaries of the QC data and QA audit data
are presented in Sections 7.2 through 7.4.
7.1 QA/QC PROGRAM OBJECTIVES
For any environmental measurement, a degree of uncertainty exists in the data
generated due inherent limitations of the measurement system employed. To assess the
quality of the data and to establish limitations on the ultimate use of the data, a
comprehensive QA/QC program was implemented for this test effort. The objective of
the QA/QC program was to produce complete, representative, and comparable data of
known quality.
The terms used to define the QA/QC objectives established for the test program
are defined as follows:
(1) Data Quality: The total of features and characteristics of a product (measurement
data) that determine its ability to satisfy a given purpose. These characteristics
are defined as follows:
• Precision - A measure of mutual agreement among individual
measurements of the same property, usually under prescribed similar
7-1
-------
conditions. Precision is best expressed in terms of the standard deviation
(or the relative standard deviation). Various measures of precision exist
depending upon the prescribed conditions.
• Accuracy - The degree of agreement of a measurement (or an average of
measurements of the same parameter), X, with an accepted reference or
true value, T, usually expressed as the difference between two values, X-T,
or the difference as a percentage of the reference or true value, 100 (X-
T)/T, and sometimes expressed as a ratio, X/T. Accuracy is a measure of
the bias in a system.
• Completeness - A measure of the amount of valid data obtained from a
measurement system compared with the amount that was expected to be
obtained.
• Comparability - A measure of the confidence with which one data set can
be compared with another.
• Representativeness - The degree to which data accurately and precisely
represent a characteristic of a population, variations of a parameter at a
sampling point, or an environmental condition.
(2) Quality Control: The overall system of activities whose purpose is to provide a
quality product or service: for example, the routine application of procedures for
obtaining prescribed standards of performance in the monitoring and
measurement process.
(3) Quality Assurance: A system of activities whose purpose is to provide assurance
that the overall quality control is in fact being done effectively.
7-2
-------
It is the total integrated program for assuring the reliability of monitoring
and measurement data.
• It is the system for integrating the quality planning, quality assessment, and
quality improvement efforts of various groups in an organization to enable
operations to meet user requirements at an economical level. In pollution
measurement systems, quality assurance is concerned with the activities
that have an important effect on the quality of the pollutant measurements,
as well as the establishment of methods and techniques to measure the
quality of the pollution measurements. The more authoritative usage
differentiates between "quality assurance" and "quality control," where
quality assurance is the "system of activities to provide assurance that the
quality control system is performing adequately."
To meet these objectives, a thorough Quality Assurance Project Plan (QAPP),
integrated with the sampling and analysis plan, was prepared. All elements of the QAPP
were implemented during the sampling and analytical phases of the sewage sludge
incinerator test program for Site 8. In the QAPP, the specific EPA methods, other
standard test methods, and state-of-the-art sampling/analytical procedures to be
employed and QC activities performed were described.
The QAPP emphasized: (1) adherence to the prescribed sampling procedures, (2)
careful documentation of sample collection and analytical data, (3) the use of chain-of-
custody records, (4) adherence to prescribed analytical procedures, and (5)
implementation of independent systems audits and performance audits. These QA/QC
activities provide a mechanism to control data quality within acceptable limits and
provide the necessary information to assess the quality of the data.
The data, quality objectives for the measurement parameters are presented in
Table 7-1. These data quality objectives are for analysis of the samples collected during
emission testing at the individual sites. Where possible, the precision and accuracy
7-3
-------
TABLE 7-1. PRECISION, ACCURACY AND COMPLETENESS OBJECTIVES
Parameter
Total particulate (EPA Method 5)
Nickel/metals distribution in particulate
Cr+* distribution in particulate
Flue gas total metal
Flue gas volatile organics (VOST)
Flue gas semi-volatile organics (MM5)
Flue gas PCDD/PCDF (MM5)
Continuous Emission Monitoring
(02, C02) CO, THC, NOw SO:)
Feed sludge: Metals/Cr/Ni
Velocity/volumetric flow rate (Methods 1&2)
Fixed gases/molecular weight (Method 3)
Moisture (EPA Method 4)
Flue gas temperature (thermocouple)
Scrubber Water Influent and Effluent:
Metals/Cr/Ni
Precision* Accuracy1 Completeness1
(%)
(%)
(%)
± 11
± 10
90
50c
NA
90
50*
NA
90
NA
NA
90
± 50d
± 50"
90
± 50d
± 50d
90
± 50d
± 50d
90
± 20e
± 20f
90
NA
NA
90
± 6
± 10
95
± 10f
± 20"
90
± 20
± 10
90
± 2°F
± 5°F
90
NA
NA
90
'When possible, precision and accuracy based on collaborative tests results.
"Valid data percentage of total tests conducted.
CEPA collaborative test data not available.
Analytical phase only.
•Percent difference for duplicate analyses, where
Percent = First Value - Second Value x 100
Difference 0.5 (First + Second Values)
Coefficient of variation (CV) determined from daily analyses of a control
sample, where
% CV = Standard Deviation x 100
Mean
Relative error (%) derived from audit analyses, where
Percent = Measured Value - Theoretical Value x 100
Error Theoretical Value
NA = Not applicable. For precision, because multiple samples not to be taken
or analyzed; for accuracy, because audit samples not available.
7-4
-------
objectives for the measurement parameters were obtained from the specified methods or
from EPA collaborative tests. This type of data was not available for the determination
of metals in the flue gas and solid samples.
7.2 FLUE GAS SAMPLING AND ANALYSIS QC RESULTS
Quality control activities for flue gas sampling included: (1) equipment
calibrations, (2) glassware and equipment cleaning, (3) procedural checks during
sampling and sample recovery, (4) sample custody procedures, (5) procedural checks
during sample analysis, and (6) the use of labeled recovery and internal standards, field
blanks, laboratory blanks, QC check samples, matrix spikes, and duplicate analyses. The
QC results for these activities are discussed in this section, with activities generally
applicable to all the flue gas sampling methods discussed in Section 7.2.1 and method
specific results discussed separately in Sections 7.2.2 and 7.2.3.
7.2.1 General Flue Gas Sampling Quality Control
For all of the flue gas sampling methods, pre-test calibrations were performed on
the sampling nozzles, pitot tubes, temperature sensors, and analytical balances. Both
pre- and post-test calibrations were performed on all dry gas meters employed during
flue gas sampling. All equipment met the criteria specified in the QAPP for this
program. The post-test calibrations for all dry gas meters employed during sampling
were within the specified 5% agreement with the pre-test calibrations.
All sampling train glassware and Teflon components, sample containers, and
sampling tools were precleaned initially with soap and water followed by a DI water
rinse and 0.1 N nitric acid rinse, and a final DI water rinse. During on-site testing, all
sampling train glassware was capped with Parafilm or Teflon tape prior to and
immediately after each test run. A clean, dust-free environment was maintained on-site
for sampling train assembly and sample recovery.
7-5
-------
QC activities during flue gas sampling included:
• Visual equipment inspection;
• collection of sample train blanks;
• ensuring the proper location and number of traverse points;
• conducting pre-test and post-test pitot tube and sample train leak
checks;
• maintaining proper temperature at the sample probe (if applicable),
filter housing, and impinger train outlet;
• maintaining isokinetic sampling rates; and
• recording all data on preformatted field data sheets and noting any
unusual occurrences on a test log sheet.
Leak check and isokinetic calculation results are presented separately for each
method in the sections that follow. The QC criterion for leak checks was a rate less than
or equal to 0.02 cubic feet per minute (cfm) at 15 in Hg vacuum for the pre-test check
and, for the post-test check less than 0.02 cfm, at the highest vacuum encountered during
sampling. For isokinetic sampling, the QC criterion was to have the average sampling
rate within 10% of isokinetic.
Detailed procedures for sample recovery, specific for each method and described
in the QAPP, were followed. Graphic flow charts of each procedure were readily
available in the recovery area.
Sample custody procedures employed for all flue gas samples and process samples
emphasized proper labeling and preparation of chain-of-custody records for transfer of
the samples to the different laboratories involved in the test program. Pre-printed labels
were prepared with a unique alphanumeric code for each sample collected or generated
during sample recovery. Samples were also logged in a master logbook. Samples were
stored and shipped to the laboratories following the method-specific procedures. Upon
receipt of the samples, each laboratory logged the samples into their own sample custody
system and stored the samples under the prescribed conditions.
7-6
-------
7.2.2 Sampling and Analysis for Particulate Matter/Total Metals and Nickel/Nickel
Subsulfide
Sampling and analysis for particulate matter and total metals followed the draft
EPA method, "Methodology for the Determination of Trace Metals Emissions in
Exhaust Gases from Stationary Source Combustion Processes." Sampling for nickel and
nickel subsulfide followed EPA Method 5 for sample collection and the NiPERA wet
chemical method and XANES instrumental method for sample analyses. Quadruplicate
sampling trains were employed with two sampling trains used to collect samples for
nickel speciation (Trains A, and B) and a two train used to collect particulate
matter/total metals sample (Train C and D). The results of the QC operations during
sampling and analysis are presented in the following sections.
7.2.2.1 Sampling Operations - Isokinetic calculation and leak check results for the
midpoint and ESP outlet sampling location are summarized in Table 7-2. All of the
sampling trains operated at the midpoint and outlet locations met the QC criteria for
isokinetic sampling of 90-to-110%. Nine of the 28 sampling trains operated at the
midpoint for collection of particulate matter/total metals and nickel/nickel subsulfide
samples were less than 90% isokinetic. However, all of these runs were within 6% of the
allowable.
The post-test leak check results for all 21 midpoint and outlet sampling trains met
the QC criteria.
At the inlet sampling location, isokinetic sampling was not performed due to the
duct configuration. The post-test leak check results for all 11 inlet sampling trains met
the QC criteria.
7.2.2.2 Sample Analysis - Analytical results for the metals laboratory blanks and the
audit sample are presented in Table 7-3. Chromium was found in the front half reagent
blank, but the quantity was less than those found in the field samples. An average value
of 1.9 ug was used to correct the field sample results, as well as the audit sample result.
-------
TABLE 7-2. ISOKINETICS AND LEAK CHECK SUMMARY; SITE 8, MULTI-
METAL, NICKEL AND SEMIVOLATILE TRAINS,
MIDPOINT AND OUTLET LOCATIONS
Run
Train
Location
Isokinetic
Leak Rate
Vacuum
No.
No.

(%)
(cfm)
(in. Hg)
4
MM5
Midpoint
102.4
0.006
15
5
B
Midpoint
96.0
0.007
10
5
C
Midpoint
100.5
0.004
10
5
D
Midpoint
109.9
0.020
10
5
A
Outlet
100.6
0.012
10
5
B
Outlet
100.9
0.013
10
6
MM5
Midpoint
97.5
0.004
15
7
A
Midpoint
93.4
0.001
10
7
B
Midpoint
101.4
0.004
10
7
C
Midpoint
97.2
0.001
10
7
D
Midpoint
104.4
0.001
•10
7
A
Outlet
963
0.005
10
7
B
Outlet
99.3
0.006
10
8
MM5
Midpoint
104.1
0.011
15
9
A
Midpoint
100.6
0.001
10
9
B
Midpoint
101.1
0.004
10
9
C
Midpoint
98.9
0.001
10
9
D
Midpoint
103.8
0.001
10
9
A
Outlet
93.8
0.012
10
9
B
Outlet
97.2
0.014
10
11
A
Midpoint
100.9
0.002
10
11
B
Midpoint
104.8
0.002
10
11
C
Midpoint
99.8
0.008
15
11
D
Midpoint
103.8
0.004
15
7-8
-------
TABLE 7-3. QC RESULTS FOR REAGENT BLANKS AND AUDIT SAMPLE FOR
MULTI-METAL AND NICKEL SAMPLING TRAINS
Reagent Blanks Audit Sample
Metal Front Half Back Half Found" Actual Error
(#»g) 0»g) 0»g) (#«g) %
Arsenic
<3.0
<0.6
11.7
9.6
21.9
Beryllium
NDb
ND
4.9
4.85
3.1
Cadmium
ND
ND
9.8
10.0
-2.0
Chromium
1.9
ND
10.1
10.3
-6.7
Lead
ND
ND
55.4
50.4
9.9
Nickel
ND
ND
26.2
25.2
4.0
"Blank corrected by front half blank values.
bNot Detected.
-------
Calibration check samples were analyzed with every ten samples. The results for
the calibration check samples were all within 10% of the expected value.
The audit sample results ranged from -8.7 to 21.9% of the true audit value. The
audit sample analyzed, a quartz glass filter with spiked metals, was provided by EPA's
Quality Assurance Division in Research Triangle Park, NC.
7.2.3 Total Chromium and Hexavalent Chromium Sampling and Analysis
Sampling and analysis for total chromium (Cr) and hexavalent chromium (Cr+*)
were performed following the procedures in the draft EPA method, "Determination of
Hexavalent Chromium from Stationary Sources." The QC activities for the Cr/Cr+6
testing performed at Site 8 are discussed in the following sections.
7.2.3.1 Sampling Operations - Isokinetic and leak check results for the chromium
sampling at the midpoint and outlet sampling location are summarized in Table 7-4.
Four of the 12 sampling trains operated at the midpoint for collection of Cr/Cr+6
samples were less than 90% isokinetic. Since the midpoint sampling location was down
stream of a venturi scrubber which tends to emit small particles, the non-isokinetic
sampling should not have caused a significant bias.
The post-test leak check results for all the midpoint and outlet sampling trains
met the QC criteria.
At the inlet sampling location, isokinetic sampling was not performed due to the
duct configuration. The post-test leak check results for all inlet sampling trains met the
QC criteria.
7.2.3.2 Sample Analysis - Neither Cr or Cr+6 were detected in any of the reagent blanks
submitted for analysis. All analyses for Cr+6were performed in duplicate with the
percent deviation of duplicate samples ranging from 0.7% to 7.9% for the reported
7-10
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TABLE 7-4. ISOKINETICS AND LEAK CHECK SUMMARY; SITE 8,
HEXAVALENT CHROMIUM SAMPLING, MIDPOINT AND OUTLET
LOCATIONS
Run
Train
Location
Isokinetics
Leak Rate
Vacuum
No.
No.

(%)
(cfm)
(in. Hg)
4
A
Midpoint
87.5
0.002
15
4
B
Midpoint
86.5
0.010
15
4
C
Midpoint
86.0
0.014
15
4
D
Midpoint
83.1
0.010
15
4
A
Outlet
104.1
0.004
10
4
B
Outlet
98.1
0.007
10
6
A
Midpoint
98.8
0.001
10
6
B
Midpoint
102.5
0.001
10
6
C
Midpoint
99.9
0.001
10
6
D
Midpoint
108.8
0.001
10
6
A
Outlet
97.7
0.011
10
6
B
Outlet
95.8
0.009
10
8
A
Midpoint
100.7
0.001
10
8
B
Midpoint
99.5
0.001
10
8
C
Midpoint
98.4
0.001
10
8
D
Midpoint
105.7
0.001
10
8
A
Outlet
91.1
0.013
11
8
B
Outlet
90.9
0.009
11
7-11
-------
values. The Cr+6 calibration curve was linear from 0.566 ppb to 1.77 ppb, with a
maximum percent deviation of -11.1%,
To determine the extent of Cr+< conversion that occurred during sampling, a
radioactively-labeled Cr+6 spike, slCr+<, was added to the absorbing solution in each
sampling train prior to sampling. The 5lCr+6 spike was recovered and analyzed by ion
chromatography with a post column reaction (IC/PCR). Fractions of IC discharge were
collected at regular time intervals and counted in a gamma counter, along with the filter
and rinse samples. The 5lCr+6 recoveries are shown in Table 7-5. They ranged from
25.0 to 82.8% for the inlet samples, 52.8% to 79.3% (excluding outliers for trains C and
D from Run 4) for the midpoint samples, and 65.6% to 85.9% for the outlet samples.
7.2.4 Continuous Emission Monitoring
Continuous emission monitoring (CEM) was performed at the scrubber inlet and
midpoint for 02, C02, CO, S02, and NO,. Total hydrocarbons were also monitored at
the midpoint using a conditioned (cold) sample. Instrument calibrations were performed
at the beginning of each test day and at the conclusion of each test day. Instrument drift
checks, the comparison of the post-test measurement of zero and span gases to the pre-
test values, were performed each day and are summarized in Table 7-6. All CEM data
were drift corrected assuming linear drift.
The drift values for both the zero and span were within 5% for all CEMS. Four
different levels of calibration gases were used for 02, C02, CO, S02, and NOx, and three
calibration gases were used in the direct calibration check. Two calibration gases were
used for the drift test after each day, and no performance audit was conducted. All the
data meets the span and zero drift requirements of Method 3A, 6C, 7E, 10, and 25A.
7-12
-------
4
4
4
4
4
4
4
6
6
6
6
6
6
6
8
8
8
8
8
8
8
TABLE 7-5. RECOVERIES OF 5lCr+4 SPIKE
Train

"Cr+< Spike
No.
Location
(% of tot
C
Inlet
40.0
D
Inlet
25.0
B
Midpoint
63.4
C
Midpoint
10.7
D
Midpoint
9.5
A
Outlet
85.9
B
Outlet
78.2
A
Inlet
48.3
B
Inlet
66.1
A
Midpoint
62.3
C
Midpoint
52.8
D
Midpoint
62.2
A
Outlet
92.6
B
Outlet
85.1
A
Inlet
82.8
B
Inlet
79.5
B
Midpoint
79.3
C
Midpoint
73.6
D
Midpoint
74.0
A
Outlet
81.4
B
Outlet
65.6
7-13
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TABLE 7-6. SUMMARY OF CEM DRIFT CHECKS
Instrument Zero and Span Drift (percent of span)
02 C02 CO S02 NOx Cold THC
Date
01/09/91
01/10/90
01/11/90
01/12/90
CEM
Location
Inlet
Midpoint
Inlet
Midpoint
Inlet
Midpoint
Inlet
Midpoint
Zero Span
0.2 -1.0
0,2 1.1
0.2 -0.6
0.4 -0.4
0.2 -0.4
0.3 -0.3
0.3 -0.3
0.4 0.2
Zero Span
NA NA
0.6 0,2
NA NA
0.5 0.2
NA NA
0.5 -0.3
NA NA
NA NA
Zero Span
0.1 -0.3
-0.1 -0.3
0.1 -0.2
0.0 -0.3
0.1 -0.6
0.0 -0.6
NA NA
NA NA
Zero Span
1.3 0.2
1.6 -0.5
0.7 -0.1
2.1 1.4
1.2 -0.8
1.2 -0.4
0.2 -0.1
0.6 -0.8
Zero Span
0.4 -2.1
0.1 -1.8
0.3 -3.5
0.1 -3.2
0.5 0.3
0.1 3.5
0.2 1.3
0.0 -1.1
Zero Span
NA NA
0.8 0.8
NA NA
0.3 0.3
NA NA
-0.1 -0.3
NA NA
NA NA
NA = Not available. On 01/12/90, the computer malfunctioned on the last day of
testing and there was not sufficient time to conduct the post test zero and
span.
-------
7.3 METALS ANALYSIS OF PROCESS SAMPLES
Samples of sludge feed and scrubber effluent water were collected during each
test run. These process samples were grab samples collected at regular intervals, and
combined after each test to form composite samples. Quality control indicators for
metals analysis of the process samples are method blanks and calibration checks during
analysis.
None of the six target metals were detected in the method blanks for the sludge
feed and scrubber effluent samples.
Calibration check samples were analyzed with every ten samples. The results for
the calibration check samples for the sludge feed and the scrubber water samples were
all within 10% of the expected value.
7-15
-------
REFERENCES
1. Drees, L.M. Effect of Lime and Other Precipitants or Sludge Conditioners on
Conversion of Chromium to the Hexavalent State When Sludge is Incinerated. Final
Report. EPA Contract No. 68-03-3346, WA 05. 1988.
2. Majiam, T.T. Kasakura, N. Naruse and M. Hiraoka. 1977. Studies of Pvrolvsis
Process of Sewage Sludge. Prog. Wat. Tech. Vol. 9, 381-396. Great Britain: Pergamon
Press.
3. Umashima, T., M. Naruse and T. Nasakura. 1975. Behavior of Cr+6 in Incinerator
Process of Sewage Sludge. Paper presented at the 12th Annual Meeting of the
Association of Japan Sewage Works.
8-1
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before compter'
1. REPORT NO. 2.
EPA/600/R-92/003f
3 PB92-151601
4. title ano subtitle
EMISSIONS OF METALS, CHROMIUM AND NICKEL SPECIES, AND
ORGANICS FROM MUNICIPAL WASTEWATER SLUDGE INCINERATORS
VOLUME VI! SITE 8 EMISSION TEST REPORT
S. REPORT 0ATE
March 1992
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
William G. DeWees, Robin R. Segall
F. Michael Lewis
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME ANO ADDRESS
Entropy Environmentalists, Inc.
Research Triangle Park
North Carolina, 27709
10. PROGRAM ELEMENT NO.
B101
11. CONTRACT/GRANT NO.
Contract No. 68-CO-0027
Work Assignment: No. 0-5
12. SPONSORING AGENCY NAME AND AOORESS
Risk Reduction Engineering Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, OH 45268
13. TYPE OF REPORT ANO PERI00 COvEREO
Final Report 1989 - 91
14. SPONSORING AGENCY CODE
EPA/600/14
15. SUPPLEMENTARY NOTES
EPA Technical Contact: Dr. Harry E. Bostian, (513) 569-7619, FTS: 684-7619
16. A9STRACT
The Site 8 facility is a 24.1 million gallons per day (MGD) secondary biological
treatment plant with a 0.1 MGD septage handling facility. The wastewater influent
comes from predominantly (90 percent) domestic sources. The treatment facility
serves a population of approximately 175,000. All 22 tons per day of sludge solids
are dewatered by two belt presses to a concentration of 22 to 25 percent solids.
Approximately 15 to 17 tons of solids are dewatered by one press and fed to the
fluidized bed incinerator. The air pollution control system associated with this
incinerator consists of a water injection venturi, and an impingement tray scrubber-
A pilot-scale wet eletrostatic precipitator had been installed and was tested. The
ratio of hexavalent chromium to total chromium in the emissions was very low (despite
relatively high total chromium levels), probably due to the short sludge retention
time in the fluidized bed incinerator and the absence of alkaline material in the
sludge. The ratio of nickel subsulfide to total nickel in the emissions was
extremely low, with the nickel sulfide/subsulfide species measured at the inlet and
midpoint being less than the detection limit. Compared to Site 3, a fluidized bed
incinerator where the only- semi-volatile organic compound detected was bis(2-
ethylhexylJphthalate, several additional semivolatiles were found in the emissions at
Site 8. These were 1,2-dichlorobenzene, 1,4-dichlorobenzene, benzyl alcohol, benzoic
acid, and naphthalene. The volatile organic compound emission results for Site 8
were consistent with the results for Site 3 (an other fluidized—bed incinerator).
Carbon tetrachloride and chlorobenzene, reported in the emissions at Site 3, were not
found in the emissions from Site 8.
17. KEY WORDS ANO OOCUMENT ANALYSIS
a. DESCRIPTORS
b.IDENTIFIERS/OPEN ENOEO TERMS
C. COSATl Field/Croup
Wastewater, sludge disposal,
incinerators, combustion products
Emissions
chromium compounds
nickel compounds
total hydrocarbons
dioxin/furans
organic compounds

18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report}
IJNrT.ASRTFTFn
21. NO. OF PAGES
138
20. SECURITY CLASS (This page)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (R*v. 4-77) previous coition ispbsolete
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