Emissions of Metals Chromium and Nickel Species and Organics from Municipal Wastewater Sludge Incinerators. Volume VIII Site 9 Emission Test Report


EPA/600/R-92/003h
March 1992
EMISSIONS OF METALS, CHROMIUM AND NICKEL SPECIES, AND ORGANICS
FROM MUNICIPAL WASTEWATER SLUDGE INCINERATORS
VOLUME Vni: SITE 9 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 under Contract No. 68-02-4442, Work Assignment No. 81; Contract No. 68-02-
4462, Work Assignment No. 90-108; and Contract No. 68-CO-0027, Work Assignment No.
0-5. It has been subject 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 endorsement or recommendation for use.
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FOREWORD
Today's rapidly developing and changing technologies and industrial products and
practices frequently cany 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 9 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 were 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/OWRS 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 9, a multiple
hearth incinerator, was tested under normal combustion conditions and improved
combustion conditions. This report presents the test results from the fifth of five
incinerator test sites. Four incinerators tested under a previous project conducted by
Radian Corporation are included in the Site numbering convention used.
Secondary objectives of the Site 9 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
full scale wet electrostatic precipitator installed just prior to the test program.
Site 9, a dewatering and incineration facility located in a municipal wastewater
treatment plant, is operated and managed by a private firm. The hydraulic portion of
the plant is owned and operated by the city in which it is located. The facility is a
secondary plant designed for a 15 million gallon per day (MGD) wastewater flow. The
privatized solids handling portion of the facility is a regional site that also handles both
primary and secondary thickened sludges brought in from surrounding communities.
Site 9 includes a seven (7) hearth, multiple hearth furnace (MHF) built by Nichols
Engineering in 1974. The furnace flue gas leaves the furnace through a horizontal
breaching and then goes down into an adjustable throat venturi scrubber with a nominal
pressure drop of 20 in water column (w.c.). After leaving the venturi, the gases pass
upward through a three (3) plate tray scrubber with a Chevron mist eliminator. A 10 ft x
10 ft, upflow, wet electrostatic precipitator, manufactured by Beltran Associates, Inc., was
installed during the first week of testing.
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It was anticipated that the nickel subsulfide emissions from a multiple hearth
incinerator not using lime for conditioning would constitute less than 1% of the total
nickel emissions. A wet chemical analysis indicated that within the analytical detection
limit (< 10% of the total nickel), no nickel subsulfide was present in the samples.
It was anticipated that the hexavalent chromium emissions from a multiple hearth
incinerator not using lime for sludge conditioning would constitute less than 1% of the
total chromium emissions. A wet chemical analysis indicated that about 10% of the total
chromium emissions exiting the venturi/impingement tray scrubber during both normal
and improved combustion conditions was hexavalent chromium.
Polychlorinated dibenzodioxins and furans (PCDDs/PCDFs) and semivolatile and
volatile organic compounds were also measured. The total PCDD's and total PCDF's,
respectively, were 20.2 and 81.9 ng/dscm at the outlet of venturi/impingement tray
scrubber (midpoint sampling location) and 3.2 and 12.4 ng/dscm at the outlet of the wet
ESP during normal incinerator operation. During improved incinerator operation, the
total PCDD's and total PCDF's, respectively, were 1.6 and 7.1 ng/dscm at the midpoint
and 0.65 and 2.1 ng/dscm at the outlet Several semivolatile organic compounds were
detected at the midpoint and outlet locations during runs at both normal and improved
incinerator operation. The concentrations and number of semivolatile compounds
measured were typically less under improved incinerator operating conditions.
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	x
List of Tables	xi
Acknowledgement 	
1.0 Introduction				1-1
2.0 Site 9 Test Summary		2- i
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
223 Hexavalent chromium results	 2-8
2.2.4	Nickel speciation	 2-13
2.2.5	PCDD/PCDF, Semivolatile and Volatile Organic Compounds 2-13
22.6 Volatile Organic Results	 2-15
2.2.7	Continuous Emission Monitoring results 	2-16
2.2.8	Conclusions	 2-16
3.0 Process Description and Operation	 3-1
3.1 Facility description 		3-1
32	Incinerator and pollution control system 		3-1
33	Incinerator operating conditions during testing		3-4
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		4-6
4.13 Outlet flue gas conditions 		4-6
42 Particulate/metal results	 4-6
4.2.1	Control device inlet results 	 4-7
4.2.2	Midpoint (Venturi/tray scrubber outlet) results	4-10
423 Wet ESP outlet results 	4-12
4.2.4 Removal efficiency of control device for metals and particulate 4-13
42JS Sludge feed results 	4-13
vi i

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Section
Table of contents (continued)
Page
4.2.6	Scrubber water results	4-16
4.2.7	Bottom Ash Results 	4-16
42.8	Metal emission factors 	4-20
A3 Hexavalent chromium results	4-20
4.3.1 Control device inlet results	4-22
432 Midpoint results 	4-22
4.3.3	ESP outlet results	4-25
4.4	Nickel speciation results 	4-25
4.5	Dioxin/furan and semivolatile organic results	4-26
4.6	Volatile organic results 	4-31
4.7	Continuous emission monitoring results	4-33
4.8	Conclusions from Site 9 test 	4-38
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
5.13 Outlet of the Wet ESP 	 5-4
52	Sampling procedures	 5-7
5.2.1	Total metals	 5-7
5.2.2	Nickel/nickel subsulfide 	5-11
5.23 Chromium and hexavalent chromium (recirculating train) .... 5-15
5.2.4	Chromium and hexavalent chromium (impinger train)	5-17
5.2.5	Semivolatile Organic and PCDD/PCDF 	5-20
5.2.6	Volatile organic sampling train (VOST)	5-28
52.7 Continuous emissions monitoring	5-30
5.2.7.1 Sample and data acquisition	5-31
52.72 Carbon monoxide/carbon dioxide analysis	5-31
5.2.7.3	Oxygen analysis 			5-31
5.2.7.4	Nitrogen oxides (NOJ analysis	5-31
5.2.7.5	Sulfur dioxide (SO,) analysis	5-32
5.2.7.6	Total hydrocarbon analysis	5-32
5.2.8	EPA Methods 1,23, and 4	5-32
5.2.8.1	Volumetric gas flow rate determination 	5-32
5.2.8.2	Flue gas molecular weight determination 	5-33
5.2.8.3	Flue gas moisture determination	5-33
52.9	Process samples	5-34
53	Process data 		5-34
viii

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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
6.2	Nickel speciation and analysis 		6-5
6.3	Multiple metals analysis		6-6
6.3.1 Flue gas samples		6-6
632	Dewatered sludge samples	 6-8
633	Scrubber water samples	 6-8
63.4 Bottom ash samples 	 6-8
6.4	Semivolatile organic analysis 	 6-9
6.5	Volatile organic analysis 	6-12
6.6	Sludge sample analyses 	6-13
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	 7-4
7.2.1	General flue gas sampling quality control 	 7-4
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
12.22 Sample analysis 	7-10
7.23 Sampling and analysis for total chromium and
hexavalent chromium 	7-10
123.1	Sampling operations	7-10
123.2	Sample analysis 	7-13
7.2.4 PCDD/PCDFs, semivolativle organic, and volatile organic
compound sampling and analysis	7-13
7.2.4.1	Dioxin/Furan results 	7-13
7.2.4.2	Semivolatile organic compounds	7-13
7.2.4.3	Volatile organic compounds 		7-17
125 Continuous emission monitoring 	7-20
73 Process sample analysis QC results 	7-20
7.3.1 Metals analysis of process samples	7-22
7.4 External technical systems review	7-22
References	 8-1
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LIST OF FIGURES
Number	Page
3-1 Schematic of Site 9 furnace and pollution control systems	 3-3
3-2 Schematic of MHF during normal opertion mode	 3-6
3-3 Plot of sludge weight meter readings for normal operations 	 3-7
3-4 Hearth temperatures during normal operations	 3-8
3-5 Schematic of MHF during improved combustion conditions 	 3-9
3-6 Plot of sludge weight meter readings during improved combustion
conditions 	3-10
3-7 Hearth temperatures during improved combustion conditions	3-11
3-8 Comparison of breaching temperatures for normal and improved modes of
operation	3-12
3-9	Comparison of venturi pressure drops for normal and improved modes of
operation	3-13
4-1	Hydrocarbon emissions versur carbon monoxide emissions	4-37
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	 5-6
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	5-14
5-9	Schematic of recirculating reagent impinger train for hexavalent chromium .. 5-16
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	5-24
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 train hexavalent chromium
sampling at midpoint and outlet locations	 6-3
6-2 Sample preparation and analysis scheme for multiple metals trains	 6-7
6-3 Extraction schematic for semivolatile organic samples	6-10
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Number
LIST OF TABLES
Page
2-1 Summary of sampling and analytical methods by test location: Site 9 .... 2-2,2-3
2-2 Specific elements and compounds of interest 	 2-5
2-3 Summary of inlet, midpoint, and ESP outlet flue gas conditions: Site 9 ... 2-6,2-7
2-4 Summary of Site 9 particulate and multiple metal emissions and collection
efficiency	2-9,2-10
2-5 Summary of midpoint and outlet Cr+< and total chromium results	2-11,2-12
2-6	Summary of nickel species emissions: Site 9	2-14
3-1	Incinerator design information	 3-2
4-1	Summary of inlet, midpoint, and ESP outlet flue gas conditions; Site 9 .. 4-3,4-4
4-2 Summary of inlet and outlet continuous emission measurements: Site 9 .... 4-5
4-3 Summary of Site 9 particulate and multiple metal emissions and collection
efficiency	4-8,4-9
4-4 Summary of metal concentrations in fly ash 	4-11
4-5 Input rate of metals in sewage sludge	4-14
4-6 Results for proximate and ultimate analyses of sludge samples	4-15
4-7 Discharge rate of metals in scrubber water	4-17
4-8 Discharge rate of metals in bottom ash 	4-18
4-9 Rate of metals to and from incinerator 	4-19
4-10. Metals emission factors 		 4-21
4-11 Summary of midpoint and outlet Cr+< and total chromium results	4-23,4-24
4-12 Summary of nickel species emissions: Site 9 	4-27
4-13 PCDD/PCDF emissions summary for midpoint and outlet locations	4-28
4-14 Semivolatile emissions summary for outlet and
midpoint locations	4-29,4-30
4-15 Volatile organics emissions summary	4-32
4-16	Summary of inlet and midpoint continuous emission monitoring results (15-min
averages)	 4-34,4-35,4-36
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	5-13
5-4 Sample recovery components for the nickel/nickel subsulfide train	 5-13
5-5 Cr+'/Cr teflon/glass components cleaning procedures	5-18
5-6 Sample recovery components for the Cr+4/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 sampling train	5-22
5-9 Semivolatile organics glassware cleaning procedure 	5-26
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LIST OF TABLES (continued)
Number	Page
5-10 Sample recovery components for semivolatile organics train	5-26
5-11	Process monitoring data	5-35
6-1	Summary of analytical methods 	 6-2
7-1	Precision, accuracy and completeness objectives	 7-5
7-2	Isokinetics and leak check summary; Site 9, multi-metal and
nickel trains	7-8,7-9
7-3 QC results for reagent blanks and audit sample for multi-metal and nickel
sampling trains 	7-11
7-4 Isokinetics and leak check summary; Site 9, hexavalent chromium sampling
trains at midpoint and outlet locations	7-12
7-5 Recoveries of nCr+< surrogate	7-14
7-6 Summary of dioxin/furan recoveries	7-15
7-7 Dioxin/furan audit results 	7-16
7-8 Summary of semivolatile organic compound recoveries	7-18
7-9 Summary of volatile organic compound recoveries 	7-19
7-10 Summary of CEM drift checks	7-21
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ACKNOWLEDGEMENTS
The authors gratefully acknowledge the following invaluable contributions to the
efforts 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, Ms. Elizabeth J. Arar and Dr. Stephen Long of
Technology Applications, Inc. for IC/PCR and 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
individual" (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
chromium. For nickel, EPA assumed that 100% of the nickel emissions are in the most
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toxic form, nickel subsulfide.
Chromium is likely to be emitted in either the highly carcinogenic hexavalent state
(Cr+<) 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.® This speculation is based on hexavalent chromium being 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
trivalent 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.3,4 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 may 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

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generated in sewage sludge incinerators."
As previously stated, 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: "As 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 9 test program was to determine the ratios of
hexavalent-to-total chromium and nickel subsulfide-to-total nickel for a typical sewage
sludge incinerator under normal combustion conditions (higher concentrations of carbon
monoxide and total hydrocarbons) and improved combustion conditions (lower
concentrations of carbon monoxide and total hydrocarbons). A multiple hearth
incinerator was selected for testing to provide for a long residence time of the ash in the
furnace which is favorable for the formation of hexavalent chromium. A unit that did
not use lime conditioning of the sludge for filtration purposes was selected. The Site 6
testing program had evaluated the effect of lime on the conversion of hexavalent
chromium. The higher excess air typically associated with multiple hearth incinerators is
not favorable for the formation of nickel subsulfide.
OW established seven secondary objectives also beneficial to the overall test
program.
(1) Implement sampling and analytical procedures for chromium and nickel in
uncontrolled and controlled flue gas emissions from municipal sewage
sludge incinerator .
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(2)	Compare the ratios of emissions of (1) hexavalent-to-total chromium and
(2) nickel subsulfide-to-total nickel for various types of municipal sewage
sludge incinerators and for different operating conditions.
(3)	Compare the emission results for chromium and nickel subspecies
determined by different analytical procedures.
(4)	Gather data on other metals and inorganic and inorganic gaseous
components (as cited in the Federal Register. Volume 54, No. 23, February
6, 1989) in uncontrolled and controlled incinerator emissions to obtain
background data on the effect of operating conditions on these emissions.
(5)	Evaluate application of wet electrostatic precipitator as a retrofit control
system on existing facilities to meet the new sewage sludge emission
regulations.
Continuous emissions monitoring of oxygen (Oz), carbon dioxide (COj), carbon
monoxide (CO), sulfur dioxide (SOz), and oxides of nitrogen (NOx) 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 9, the fifth 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 VIII, while the Appendices are
included in Volume IX.
The following sections present detailed descriptions of the testing and results from
the Site 9 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 9 TEST SUMMARY
2.1 TESTING PROGRAM DESIGN
The emphasis of testing at Site 9 was to determine the effect of different
combustion conditions 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 multiple hearth 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 9 was the presence of a full-scale wet
electrostatic precipitator (wet ESP).
Multiple hearth incinerators are typically operated at a high excess air in the
furnace which presents conditions which are more favorable for the formation of
hexavalent chromium, and less 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* CO* CO,
SOz, and NOx at the control system inlet and O* CO, and THC at the control system
outlet stack to the atmosphere. 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 9 was conducted from May 30 to June 7, 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
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TABLE 2-1. SUMMARY OF SAMPLING AND ANALYTICAL METHODS BY TEST LOCATION: SITE 9
Sampling
location
Sanple
Type
Sampling
Method
Ho. of
Runs
Analysis
Parameter
Analysis
Method
Outlet
Combustion gas
•
RC train (EPA
Draft MMtl)*
6 quad-train
Cr", total Cr
1C/PCR, gamma counter,
ICP/AAS, 1CP/MS, XANES

EPA Draft Ni Mtd"
6 triple-train
Ni sulfides,
total Ni
EPA Draft Mtd, XAHES,
ICP/AAS

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

MM5 (SU-846 Mtd
0010)
3
PC0D/PCDF,
semivolatiles
HRGC/HRMS (SU-846 Mtds
8290 & 8270)'

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

Methods 3 t (

Oj/COj/HjO
Orsat, Gravimetric

CEM
•
0,
CO,
CO
THC
Electrocatalytic cell
NDIR
GFC
FID
Midpoint
Combustion gas
RC train (EPA
Draft Mtd)'
6 quad-train
Cr", total Cr
IC/PCR, gamma counter,
ICP/AAS, 1CP/MS, XANES

EPA Draft Ni Mt
-------
TABLE 2-1. (Continued)
Sampling
Location
Sample
Type
Sampling
Method
No. of
Runs
Analysis
Parameter
Analysis
Method
to
i
w
Inlet
Combustion gas
RC train (EPA
Oraft Htd>*
EPA Draft Ni Htd*
EPA Draft Multi-
metal Mtd
Methods 3 14
CEM
6 quad-train
6 triple-train
6
Cr'
total Cr
Ni sulfides,
total Ni
PM, Cr, Ni, As,
Pb, Cd, Be, Hg
Oj/COj/HjO
CO,
SO,
NO.
IC/PCR, gamna counter,
ICP/AAS, ICP/MS, XANES
EPA Draft Mtd, XANES,
ICP/AAS
ICP/AAS
Orsat, Gravimetric
Electrocatalytic cell
NDIR
IR
Chemiluminescence
Scrubber Liquid
Integrated grab
h
Cr, Ni,
As,
Pb,
ICP/AAS
Hater Inlet

Cd, Be,
Hg

Scrubber Liquid
Integrated grab
h
Cr, Ni,
As,
Pb.
ICP/AAS
Hater Outlet

Cd. Be,
Hg

Incinerator Bottom Ash
Grab
1
Cr, Ni,
As,
Pb,
ICP/AAS
Ash Discharge

Cd,
Be,
Hg

Incinerator Sludge
Feed
Grab
Cr, Ni, As, Pb,
Cd, Be, Hg
Moisture
Proximate t ulti-
mate analyses
Heating value
ICP/AAS
ASTM 03174
ASTM D3174, D3175, 03178,
03179, D2361, D3177
ASTM D3178
"Recirculating train for hexavalent chromium at m<4>olnt and outlet and Impinger train for inlet.
'Method 5-type sampling train for nickel.
'Plus SU-846 Methods 3540, 3SS0, 3S10, and/or 3S20 for sample preparation and cleanup.
'Collect integrated samples simultaneously with manual sampling at each location; samples were analyzed when
no CEM data available.
'Conducted using RC, Ni, Multimetal, MMS, and impinger trains.
"During manual sampling at inlet and outlet locations.
"Two aliquots taken during each test period,
tone sample taken during each test period.
'Taken at 30-minute intervals during test period starting 30 minutes prior.
-------
scrubber used to control the incinerator emissions and at the outlet of a full-scale wet
ESP (hereafter referred to as the "outlet") recently added to the system. Certain inlet
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.
Six test runs were conducted at the inlet, the midpoint, and the outlet sampling
locations at Site 9 for particulate, arsenic, beryllium, raHrmnm chromium, lead, nickel,
mercury, hexavalent chromium. Dioxin/furan and semivolatile organic compound testing
was conducted at the midpoint and outlet Volatile organic compound sampling was
conducted at the outlet only. Composite sludge feed samples, bottom ash 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 9 test program. The
emission 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 22.1. Particulate and metal results are
summarized in Section 222, hexavalent chromium results are summarized in Section
223; nickel speciation results are summarized in Section 2.2.4; PCDD/PCDF,
semivolatile, and volatile organic compound results are summarized in Section 225, and
total hydrocarbon (THC) and carbon monoxide (CO) monitoring results are summarized
in Section 22.6. Conclusions are presented in Section 22.7.
22.1 Test Program
The Site 9 sampling locations, run numbers, and sample times are summarized in
Table 2-3. Test runs numbered 2, 3, 4, and 5 were conducted during normal furnace
2-4
-------
TABLE 2-2. SPECIFIC ELEMENTS AND COMPOUNDS OF INTEREST
I. Metal Soeciation II. Total Metalac III. Combustion Gases and
Criteria Pollutants
A. Trivalent Chromium*
A.
Arsenic
A.
°2
B. Hexavalent Chromium*
B.
Beryllium
B.
co2
C. Soluble Nickel"
C.
Cadmium
C.
CO
D. Sulfidic Nickel"
D.
Chromium
D.
so.
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.
12378-PCDD
G.
Other PCDD
H.
123478-HxCDD
I.
123678-HxCDD
J.
123789-HxCDD
K.
Other HxCDD
L.
1234678-HpCDD
M.
Other HpCOD
N.
Octa-CDD
PCDFa
0. Mono-CDF
P. Di-CDF
Q. Tri-CDF
R. 2378-TCDF
S. Other TCDF
T. 12378-PCDF
0. 2378-PCDF
V. Other-PCDF
W. 123478-HxCDF
X. 123678-HxCDF
Y. 234678-HxCDF
Z. 123789-HxCDF
AA. Other HxCOF
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
aHexavalent chromium is generally soluble in water; however, in the trivalent
form, it ia generally insoluble. This causes problems in determining the
amount of total chroaium 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 OH for the same reasons described for
chromium emissions.
'These metals are of specific interest to OH. They were analyzed by ICAP;
chromium and nickel were also analyzed also by XANES.
2-5
-------
TABLE 2-3. SUMMARY OF INLET, MIDPOINT, AND ESP OUTLET FLUE GAS CONDITIONS: SITE 9
Run No./
Pollutant/
Sampling
Test

Temp
Moisture
Oxygen
Flow Rate
Condition
Location
Date
Run Time
(OF)
(%h2o)
(%dry)
(dscm/min)
Run 2
Inlet
5/30/90
12:30-14:30
775
21.3
12.00
14908
Metals
Midpoint
Aborted due
to water droplet carryover

Normal
Outlet
5/30/90
12:30-14:30
114
3.9
14.51
19636
Run 3
Inlet
6/02/90
18:30-20:30
707
7.2
14.10
14004
Cr+6/Cr
Midpoint
Midpoint location was being relocated during this run
Normal
Outlet
6/02/90
19:35-21:50
123
2.0
15.72
18384
Run 4
Inlet
6/04/90
12:05-13:05
944
26.9
14.10
13982
Metals
Midpoint
Invalidated
due to water droplet
carryover

Normal
Outlet
6/04/90
12:18-13:18
132
8.0
15.72
18284
Run 5
Inlet
6/03/90
15:00-16:15
818
15.8
11.24
12109
Cr+6/Cr
Midpoint
6/03/90
15:00-17:00
81
3.3
11.24
12109
Normal
Outlet
6/03/90
15:00-17:00
136
3.7
13.71
16269
Run 8
Inlet
6/05/90
12:15-14:15
1229
24.1
10.17
13898
Cr+6/Cr
Midpoint
6/05/90
12:15-14:15
84
6.3
10.17
13898
Improved
Outlet
6/05/90
12:15-14:15
158
1.9
(12.25)*
17240
Run 9
Inlet
6/05/90
18:50-20:50
1327
27.7
10.61
13342
Metals
Midpoint
6/05/90
18:50-20:50
91
3.3
10.61
13342
Improved
Outlet
6/05/90
18:50-20:50
157
4.3
(12.48)
16305
Run 10
Inlet
6/06/90
12:30-13:30
1228
20.7
10.78
14309
cr+6/Cr
Midpoint
6/06/90
11:30-13:20
92
4.2
10.78
14309
Improved
Outlet
6/06/90
11:30-13:20
164
3.3
(12.6)
17468
(Continued)
-------
TABLE 2-3. (Continued)
Run No./
Pollutant/
Sampling
Test

Temp
Moisture
Oxygen
Flow Rate
Condition
Location
Date
Run Time
(°F)
(%H20)
(%dry)
(dscm/min)
Run 11
Inlet
6/06/90
16:15-17:45
1250
28.7
10.76
14339
Metals
Midpoint
6/06/90
15:45-17:45
92
4.3
10.76
14339
Improved
Outlet
6/06/90
15:45-17:45
147
4.9
(12.53)
17371
Run 12
Inlet
6/07/90
10:00-12:00
1317
29.5
9.97
13085
Metals
Midpoint
6/07/90
10:15-12:15
92
4.7
9.97
13085
Improved
Outlet
6/07/90
10:15-12:15
148
3.5
(12.29)
16611
Run 13
Inlet
6/07/90
16:20-18:00
1271
32.9
9.64
13091
Metals
Midpoint
6/07/90
16:00-18:00
98
4.9
9.64
13091
Improved
Outlet
6/07/90
16:00-18:00
154
5.2
(12.16)
16866
* Oxygen values shown in parentheses were calculated based on C02 CEM.
-------
combustion conditions. Test runs numbered 8, 9, 10, 11, 12, and 13 were conducted
during periods of improved furnace combustion conditions.
222 Particulate /Metals Results
Test runs 2, 4, 9, 11, 12, and 13 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). The metals and
particulate emissions were determined using EPA's Draft multiple metals (MMtl)
method. The particulate and metals emission results on a concentration and maw rate
basis as well as the collection efficiencies of the venturi scrubber/impingement tray
scrubber and the full scale wet ESP are shown in Table 2-4 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.
2.23 Hexavalent Chromium Results
The hexavalent chromium (Cr+<) samples collected were analyzed by ion
chromatography with a post column reaction (IC/PCR). The ion chromatograph was
used to separate nCr+< (a sampling train spike) from 51Cr+3 for gamma emission counting
and the post column reaction provided Cr'"-specific results. The results for Cr*', the
isotope speciation, and total chromium for Site 9 are presented in Table 2-5. In sample
train D of each quadruplicate train sampling system, the sampling reagent was spiked
with a stable hexavalent chromium isotope, nCr+<. The samples were to be analyzed by
Technology Applications, Inc. using IC/PCR for hexavalent chromium and IC/mass
spectroscopy (MS) to determine the amounts of °Cr+< (sampling train isotopic spike)
and nCr+< (most abundant native hexavalent chromium isotope). However, the
2-8
-------
TABLE 2-4. SUMMARY OF SITE 9 PARTICULATE AND MULTIPLE METAL EMISSIONS
AND COLLECTION EFFICIENCY
Run No.
As
M/«3 g/hr
Cd
M/m3 g/hr
Cr
M/«3 g/hr
Pb
»g/m3 g/hr
Nl
»g/«3 g/hr
Particulate
mg/n3 g/hr
Normal Combustion Conditions
OUT-2
MID-2 (Aborted)
IN-2
X Scrubber re*al
39.8 1.3
*1.2 1.0
N/A
157 5.1
200 5.1
0
157 5.3
142 3.6
0
1088 35.1
1*68 37.2
5
22.2 0.73
275 7.0
89
52.7 1761
451 11433
85
OUT-*
MID-4 (Invalid)
IN-*
X Total removal
<30 <0.9
20.* 0.*7
N/A
21.9 0.68
150 3.5
80
6.3 0.19
113 2.6
93
103 3.2
857 19.8
84
5.8 0.18
201 *.7
96
23.1 717
319 7380
90
(Continued)
Note: (let ESP Mas shut off during Run 2 and mi Malfunctioning during It in 4.
-------
TABLE 2-4. (Continued)
Run No.

As
Cd
Cr
Pb

Particulate

»g/m3
g/hr
M/mJ
g/hr
M/m3
g/hr
M/«0
g/hr
Mg/ntf
g/hr
mg/m3
g/hr
Improved Combustion Condition
OUT-9
<30
<0.9
3.7
0.10
2.75
0.08
37.9
1.05
2.42
0.07
4.2
115
X ESP Removal
N/A

NlD-9
71.6
1.6
167
3.8
37.9
0.86
1415
32.1
22.3
0.50
44.9
1017
X Scrubber Rental
N/A

IN-9
48.9
1.1
361
8.2
335
7.6
3483
78.9
638
14.5
883
20007
X Total Removal
N/A

99.54

99.42

OUT-11
<30
<0.9
5.8
0.17
3.2
0.09
51.0
1.50
1.58
0.05
4.1
122
X ESP Removal
N/A

HID-11
61.8
1.5
155
3.8
38.0
0.93
1111
27.1
25.2
0.61
46.4
1130
X Scrubber Remal
N/A

1M-11
<30
<0.9
264
6.4
329
8.0
2545
62.0
819
20.0
1200
29183
X Total Removal
N/A

99.77

99.58

OUT-12
<30
<0.9
<0.4
<0.01
1.73
0.05
16.6
0.47
2.45
0.04
3.5
99
X ESP Removal
N/A

>99.7

NID-12
66.6
1.5
187
4.3
32.1
0.71
1151
25.6
32.1
0.71
49.6
1102
X Scrubber Remal
N/A

IN-12
62.6
1.4
339
7.5
316
7.0
2520
56.0
769
17.1
856
19039
X Total Removal
N/A

>99.8

99.30

99.16

99.78

99.48

OUT-13
<30
<0.9
<0.4
<0.01
3.5
0.12
67.1
2.0
2.40
0.08
7.1
204
X ESP Removal
N/A

>99.7

HID-13
62.6
1.4
191
4.2
22.1
0.45
1401
31.1
28.5
0.61
50.0
1431
X Scrubber Remal
N/A

IN-13
69.4
1.6
319
7.1
184
4.0
2440
54.2
427
9.5
465
13294
X Total Removal
N/A

>99.8

99.2

OUTLET average
<30
<0.9
<2.6
<0.07
2.8
0.09
43.2
1.26
2.20
0.06
4.7
135
X ESP Removal
N/A

>98

MIDPOINT average
65.7
1.5
175
4.0
32.5
0.73
1270
29.0
27.0
0.61
47.7
1070
X Scrubber Remal
N/A

INLET average
52.7
<1.3
321
7.3
291
6.7
2750
62.8
663
15.3
851
20400
X Total Removal
N/A

>99

99.6

99.3

-------
TABLE 2-5. SUMMARY OF MIDPOINT AND OUTLET Cr+6 AND TOTAL CHROMIUM RESULTS
Date
Run No.,
Sample
Fractions
cr+6
Cr+6
Cr+6 to
and
Train, &
Cr*6
Total Cr
Conversion
Total Cr Total Cr
Time
Location
(ug)
("9)
(%)
(ug/M3)
(ug/M3)
(%)
6/2/90
3-A-MID
1.8
15.1
4.5
1.4
11.8
11.7
from 20:33
3-B-MID
1.9
15.3
1.9
1.3
10.7
12.4
to 20:45
3-C-MID
3.1
16.2
40.4
2.3
12.4
18.9

3-D-MID
2.3
22.4
99.9

INVALIDATED

Average

15.6
1.7
11.6
14.5
6/2/90
3-A-OUT
1.9
6.0
5.4
0.8
2.6
32.3
from 19:33
3-B-OUT
1.7
9.1
6.4
0.8
4.0
18.8
to 21:48
3-C-OUT
1.6
7.6
23.6
0.7
3.2
20.7

3-D-OUT
ND
11.0
95.0

INVALIDATED
Average

11.8
0.7
3.2
23.0
6/3/90
5-A-MID
3.3
23.3
8.1
2.5
17.2
14.3
from 14:47
5-B-MID
1.1
29.4
15.0
0.6
15.2
3.7
to 16:47
5-C-MID
2.8
30.7
24.4
1.4
15.3
9.2

5-D-MID
ND
30.6
99.3

INVALIDATED

Average

15.8
1.5
15.9
9.3
6/3/90
5-A-OUT
1.9
65.6
11.0
1.0
33. 9b
2.9
from 14:55
5-B-OUT
3.2
6.9
8.4
1.6
3.6
45.8
to 16:55
5-C-OUT
3.1
8.0
10.4
1.5
3.9
38.5

5-D-OUT
3.3
10.9
94.9

INVALIDATED

Average

9.9
1.4
3.7
36.7
6/5/90
8-A-MID
1.8
31.3
1.9
1.0
17.5
5.9
from 12:21
8-B-MID
2.5
34.8
2.0
1.3
18.3
7.2
to 14:21
8-C-MID
1.5
7.6
28.3
0.9
4.2 20.4

8-D-MID
ND
36.3
99.3

INVALIDATED

Average

10.7
1.1
17.9
6.0
(Continued)
-------
TABLE 2-5. (Continued)
Date
Run No.,
Sample
Fractions
Cr+6
Cr+6
Cr+6 to
and
Train, &
Cr 6 Total Cr
Conversion
Total Cr Total Ci
Time
Location
(ug)
(ug)
(%)
(ug/M3)
(ug/M3) (%)
6/5/90
8-A-OUT
0.8
3.2
6.5
0.4
1.6 24.9
from 12:15
8-B-OUT
1.2
3.7
7.4
0.6
1.8 32.8
to 14:15
8-C-OUT
3.0
4.4
12.4
1.5
2.2 67.6

8-D-OUT
ND
36.3
100.0

INVALIDATED
Average

8.8
0.8
1.7 47.9
6/5/90
9-MID

69.5

37.9
18:50-20:50
9-OUT

4.2

2.7
6/6/90
10-A-MID
1.9
23.5
1.6
1.2
14.5 8.1
from 11:35
10-B-MID
3.0
26.2
1.6
1.8
15.3 11.5
to 13:19
10-C-MID
2.5
24.9
21.3
1.4
14.6 9.9

10-D-MID
ND
27.9
100.0

INVALIDATED
Average

8.2
1.5
14.9 9.8
6/6/90
10-A-OUT
1.2
3.7
5.0
0.8
2.3 33.7
from 11:30
10-B-OUT
1.2
3.4
5.4
0.8
2.1 36.3
to 13:20
10-C-OUT
ND
8.3
92.3

INVALIDATED

10-D-OUT
1.2
2.9
4.6
0.8
1.9 40.9
Average

5.0
0.8
2.1 37.0
6/6/90
11-MID

72.5

38.0
15:45-17:45
11-OUT

4.0

3.2
aValues for invalidated runs not included in averages.
bOutlier not included in average.
-------
impinger solutions (sample) from these trains became acidic during testing, thereby
eliminating the possibility of evaluating the IC/PCR and IC/MS analytical approach.
No reason could be determined for this event. The samples were invalidated and no
analytical results are shown.
2.2.4 Nickel Speciation
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 multiple hearth 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
method involves sequential leaching. The results of the sequential leaching nickel
analysis shown in Table 2-6 indicate that, within the detection limit of the method, no
nickel subsulfide was present in the samples. Based on the detection limits, the ratio of
nickel subsulfide (actually sulfidic nickel) to total nickel in the inlet emissions is less than
2%, and less than 1% in the midpoint emissions. The outlet samples did not contain
sufficient material to conduct the nickel speciation analysis.
At the midpoint, the total nickel emissions measured using the nickel speciation
train agreed well with the total nickel emissions measured using the multiple metals
train. At the inlet, the nickel speciation train yielded total nickel emissions about twice
as high as the multiple metals train. The cause for this difference is not known.
2.2.5 PCDD/PCDF. Semivolatile and Volatile Organic Compounds
Sampling for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated
dibenzofurans (PCDFs), and other semivolatile organics was conducted at the midpoint
and outlet sampling locations. Two two-hour runs were conducted at each location, with
2-13
-------
TABLE 2-6. SUMMARY OF NICKEL SPECIES EMISSIONS: SITE 9
Run No.
Soluble
Hq/m3 %
Sulfidicb
fig/m3 %
Metallic
fig/m3 %
Oxidic
/ig/m3 %
Total
Hg/m3
Midpoint
Run 4Ca
Run 9C
Run lie
Run 12C
Run 13C
10.0 51.1
22.7 92.2
24.2 91.4
30.7 95.5
24.6 95.5
2.2 11.4
<0.1 <0.5
<0.1 <0.4
<0.1 <0.3
<0.1 <0.4
<0.4 <2.3
<0.1 <0.5
<0.1 <0.4
<0.1 <0.3
<0.1 <0.4
7.3 37.5
1.9 7.8
2.3 8.6
1.4 4.5
1.2 4.5
19.6
24.6
26. 4
32.1
25.8
INLET
Run 4C
Run 9C
Run 11C
Run 12C
Run 13C
77.0 18.1
201.0 19.2
449.1 20.5
415.6 30.4
358.5 55.8
<9.1 <2.1
<11.2 <1.1
<26.4 <1.2
<18.5 <1.4
10.5 1.6
<9.1 <2.1
<11.2 <1.1
<26.4 <1.2
<18.5 <1.4
<10.5 <1.6
330.6 77.8
826.4 78.7
1690.9 77.1
914.3 66.9
263.6 41.0
425.1
1049.5
2192.6
1366.6
643.1
aNote: Run 4 at the midpoint was considered invalid due to water droplet
carryover.
^he sulfidic nickel is a combination of nickel sulfide and nickel
subsulfide.
-------
one run conducted during normal incinerator operations (Run 7 A) and one during
improved incinerator operations (Run 7C). These flue gas samples were collected using
the Modified Method 5 (MM5) train and SW-846 Method 0010, except that a final
toluene rinse was performed and analyzed separately for PCDD/PCDF.
The concentrations of dioxin/furan compounds detected in the flue gas are
presented in Chapter 4. The total PCDD and total PCDF concentrations, respectively,
were 20.2 and 81.9 ng/dscm at the midpoint and 3.2 and 12.4 ng/dscm at the outlet
under the normal incinerator operation. During improved incinerator operation, the
total PCDD and total PCDF concentrations, respectively, were reduced to 1.6 and 7.1
ng/dscm at the midpoint and 0.65 and 2.1 ng/dscm at the outlet.
The concentrations of the semivolatile organic compounds detected in the flue gas
are also presented in Chapter 4. A number semivolatile compounds were measured at
levels above the minimum detection limit at the midpoint and outlet under normal and
improved incinerator operations. The concentrations and number of semivolatile
compounds detected were typically less under the improved incinerator combustion
conditions. For the normal combustion conditions, eleven semivolatile compounds were
detected for both runs: 1,4-dichlorobenzene, benzyl alcohol, 1,2-dichlorobenzene,
2-nitrophenol, benzoic acid, 1,2,4-trichlorobenzene, naphthalene, 2-methylnaphthalene,
dibenzofuran, phenanthrene, and bis(2-ethylhexyl)phthalate. For the improved
combustion conditions, five semivolatile compounds were detected for both runs: phenol,
benzyl alcohol, 4-methylphenol, benzoic acid, and 4-nitrophenol. The presence of
bis(2-ethylhexyl)phthalate is likely sample contamination.
2.2.6 Volatile Organic Results
Sampling for volatile organic compounds (VOCs, those organic compounds with
boiling points less than 150°C) was conducted at the outlet of the wet ESP. Three one-
hour runs were conducted under normal incinerator operating conditions using the
volatile organic sampling train (VOST). Each VOST sampling run utilized four pairs of
Tenax/Tenax-charcoal cartridges which were exposed to approximately 20 L of flue gas.
2-15
-------
The concentration of the volatile organics in the flue gas are presented in Chapter
4. Two of the target compounds were below the minimum detection limit during all
three test runs: 1,2-dichloroethane and carbon tetrachloride. Vinyl chloride was
measured in only two of the cartridge pairs. The detection limits of these compounds
are shown in the detailed run data which is presented in the Volume IX: Site 9 Draft
Report, Appendices.
The other ten target compounds were detected for all three test runs and
averaged: aciylonitrile - 1060 ug/dscm, methylene chloride - 383 ug/dscm, chloroform -
24.1 ug/dscm, 1,1,1-trichloroethane - 17.5 ug/dscm, trichloroethene - 24.6 ug/dscm,
benzene - 6390 ug/dscm, tetrachloroethene - 29.0 ug/dscm, toluene - 4080 ug/dscm,
chlorobenzene 55.5 ug/dscm, and ethylbenzene - 100 ug/dscm.
2.2.7 Continuous Emission Monitoring Results
Continuous emission monitoring (CEM) was performed at the inlet and outlet
sampling locations at Site 9. The inlet CEM systems included oxygen (02), carbon
dioxide (C02), sulfur dioxide (S02) and oxides of nitrogen (NOJ. The outlet CEMSs
included oxygen (02), carbon dioxide (C02), carbon monoxide (CO), and total
hydrocarbons (THC).
EPA is evaluating CO and THC monitoring as a surrogate indicator of organic
emissions. The average CO concentration from each run was plotted versus the THC
concentration from each run. The correlation was good, with a correlation factor of r =
0.93.
2.2.8 Conclusions
From the perspective of methods development and data quality, the conclusions
that may be drawn from the Site 9 testing are:
1. The ratio of nickel subsulfide to total nickel in the emission at Site 9 is
2-16
-------
extremely low, with the sulfidic nickel species being measured at less than
detection limit (about 1 to 2% of the total nickel).
2. The ratio of hexavalent chromium to total chromium in the emissions at
Site 9 was significantly higher that had been anticipated. Site 9 was
selected because it does not use lime for sludge conditioning for filtration
purposes. The high hexavalent chromium to total chromium ratio was
discussed with facility representatives and it was determined that some of
the sludge that is trucked in contains lime. Also some lime is used at the
facility. The sludge solids were determined to contain 2 to 3 % lime by
weight. This percentage of lime is less that would be used for sludge
conditioning, but it is higher than would be anticipated in a facility that did
not use lime for sludge conditioning. This may be the reason for the
higher than anticipated ratio.
3. Only two semivolatile organic compounds, benzyl alcohol and benzoic acid,
were found under normal and improved combustion conditions at Site 9.
This number was less than at Site 2, a multiple hearth incinerator, where
seven semi-volatile compounds, phenol, naphthalene, bis(2-
ethylhexyl)phthalate, 1,2,-dichlorobenzene, 1,3,-dichlorobenzene, 1,4,-
dichlorobenzene, and 2-nitrophenol were detected. Several additional
compounds were found in the emissions for the normal or improved
combustion conditions at Site 9; these compounds were
1,4-dichlorobenzene, 1,2-dichlorobenzene, 2-nitrophenol,
1,2,4-Trichlorobenzene, naphthalene, 2-methylnaphthalene, dibenzofuran,
phenanthrene, bis(2-ethylhexyl)phthalate, phenol, 4-methylphenol, and
4-nitrophenol.
4. The volatile organic compounds detected in the Site 9 multiple hearth
incinerator emissions were similar to the compounds reported for Sites 1,
2, and 4 (other multiple hearth incinerator tested). Carbon tetrachloride,
reported in the emissions at the other three sites, were not found in the
emissions from Site 9.
2-17
-------
3.0 PROCESS DESCRIPTION AND OPERATION
3.1 FACILITY DESCRIPTION
Under a lease agreement, the Site 9 dewatering and incineration facility, located
in a municipal wastewater treatment plant, is operated and managed by a private firm.
The hydraulic portion of the plant is owned and operated by the city.
The facility is a secondary plant designed for 15 million gallons per day (MGD) of
wastewater flow. Preliminary and primary treatment processes consist of two bar screens
followed by comminutors, a grit chamber, and two circular primary tanks. Secondary
treatment consists of an activated sludge process using diffused air aeration, and three
circular, secondary settling tanks for clarification. The final process, disinfection, is
accomplished by chlorination in two serpentine contact tanks.
The privatized solids handling portion of the facility is a regional site that handles
both primary and secondary thickened sludges brought in from surrounding communities.
Approximately 90% of the total solids incinerated at the facility are generated off-site
and trucked in to holding tanks.
3.2 INCINERATOR AND AIR POLLUTION CONTROL SYSTEM
The sludge incinerator at Site 9 is a seven (7) hearth, multiple hearth furnace
(MHF) built by Nichols Engineering in 1974. The original furnace design information is
shown in Table 3-1. A schematic of the multiple hearth furnace and associated air
pollution control equipment is presented in Figure 3-1.
The sludge dewatering system was completely rebuilt when the plant was
privatized. At the present time, the sludge is polymer conditioned and dewatered by two
3-1
-------
TABLE 3-1. INCINERATOR DESIGN INFORMATION
Design Parameter
Value
Incinerator
Manufacturer
Outside Diameter
Number of Hearths
Recommended Sludge Feed Rate
Exhaust Gas Volume (fan rating)
Excess Air
Oxygen: Furnace Exhaust
Auxiliary Fuel
Operating Period
Nichols
25 ft - 9 in.
7
20,000 lb/hr (wet)
21,000 acfm @ 120 °F
50 % - 100 %
7 % - 13 %
Oil/Gas
24 hr/day, 365 day/year
Pollution Control System
Venturi
Tray Scrubber
Wet Electrostatic Precipitator (Beltran Associates, Inc.)
490 gpm
1,200 gpm
18 dc kilovolts, 440 dc
milliamperes
Sludge Feed
Moisture
Solids
Combustible Solids
Ash
Heating Value
74-78 % by wt
22-26 % by wt (wet basis)
75 % by wt. (dry basis)
20 % by wt. (dry basis)
8500 Btu/lb
3-2
-------
Outlet Stack
Shaft
Cooling Air
Midpoint
Sampling Location
Outlet Slack
Sampling Location
Dewatered
Sludge '
Sciubber
Water Inlet
Wet
ESP
Inlet to Control,
System Sampling
Location
ID.
Fan
Venturl *
Sciubber
Separator/
Subcooler
Flooded
Elbow
Bottom Ash
•r©
Figure 3-1. Schematic of Site 9 furnace and air pollution control systems.
-------
belt presses and then deposited onto a series of inclined and horizontal conveyor belts
for feeding into the incinerator. A conveyor weight scale is installed on the inclined
conveyor. Sludge enters the incinerator through two top hearth drop chutes. There are
four (4) gas-oil fired auxiliary fuel burners located on each of hearths #1, #3, #5, and
#7 (numbered from top to bottom). The burners on hearth #1, are extremely oversized
and were intended to be able to raise the exhaust temperature to MOOT, if desired.
However, due to excessive auxiliary fuel consumption, these top hearth burners are not
used during normal operation.
The furnace flue gas leaves the furnace through a horizontal breaching and then
goes down into an adjustable throat venturi scrubber with a nominal pressure drop of 20
in. w.c.. After leaving the venturi, the gases pass upward through a three (3) plate tray
scrubber with a Chevron mist eliminator. A 10 ft x 10 ft, upflow, wet electrostatic
precipitator, manufacturer by Beltran Associates, was completed the first week of testing.
3.3 INCINERATOR OPERATING CONDITIONS DURING TESTING
During the testing period, the plant oxygen analyzer, installed with the sample line
in the top hearth, was not functioning. Incidents where opacity readings were greater
than 20% opacity occurred several times each day. When the testing contractor installed
an oxygen sample line in the exhaust breaching, it was quickly determined that the
primary cause of smoking was insufficient oxygen (less than 3% - 4%) during those
periods when the burning rate in the MHF was undergoing wide swings. For the
improved combustion conditions, breaching oxygen, measured with the testing EPA's
oxygen analyzer, was controlled by varying the forced combustion air flow rate.
All of the process variables, burner firing rates, forced combustion air rate,
venturi pressure drop, furnace draft, etc., were essentially manually controlled by
changing settings in the central control room. None of the loops were run in automatic
control. The skill level of the furnace operators was significantly higher than found in
many municipal plants. The general operating guideline for normal plant operation was
no opacity readings over 20% with minimum auxiliary fuel consumption.
3-4
-------
Figure 3-2 shows a schematic of the MHF with the hearth temperature ranges
(+/- Std. Dev.) under normal operation on May 30, 1990. Figure 3-3 is a plot of the
corresponding weight meter readings over time with a least squares line fit through the
data indicating an average wet feed rate of 7,482 lb/hr. Figure 3-4 presents the hearth
temperatures on hearths #1 - #5. The wide variations in the individual hearth
temperatures are readily apparent.
Figure 3-5 shows a schematic of the MHF under the "improved" operating
conditions with the hearth temperature ranges (+/- Std. Dev.) as operated on June 8,
1990. Figure 3-6 is a plot of the corresponding weight meter readings over time with a
least squares line fit through the data indicating an average wet feed rate of 7,460 lb/hr
which is almost the same as under normal operation. Figure 3-7 indicates the hearth
temperatures on hearths #1 - #5. Under this mode of operation, temperature variations
in the individual hearth temperatures were .significantly reduced.
Figure 3-8 shows a comparison of the breaching (furnace exit duct) temperatures
for the "normal" and "improved" modes of operation. During the "improved" mode of
operation, the adjustable throat in the venturi scrubber was used to control the furnace
draft, thereby taking maximum advantage of the capacity of the I.D. fan to remove
particulates with a higher pressure drop across the venturi. Figure 3-9 shows a
comparison of the venturi scrubber pressure drops.
Given the configurations of the sludge feed system, and the location and capacity
of the auxiliary fuel burners, in order to achieve the higher hearth temperatures required
to minimize CO and THC concentrations, it was necessary to fire the burners in hearths
#3 and #5 at their maximum firing rate, even though combustion was taking place. As a
result, large clinkers were formed necessitating the stopping of the rabble arms to clear
the hearth. Had it been possible to feed the sludge directly onto hearth #2, the burning
profile would have better matched the placement of the burners and this problem could
have been mitigated. Increasing the feed rate would have also moved the burning zone
down; however, at the high combustion air rates required, coupled with excessive in
leakage through the sludge feed ports which were not equipped with flap gate feeders,
water was carried out of the tray scrubber.
-------
SLUDGE FEED
Burner OFF
—I\J —
Not Used
Burner OFF
-l\l-
Burner ON
-l-l-
Burner OFF
—i\i—
I
To I.D. Fan Discharge
(No Recycling Ducting)
^ Shaft Cooling Air
i
1
J
Hearth #1
Drying
Hearth #2
Drying
Hearth #3
Drying
Hearth #4
Begin Burning
Hearth #5
(Combustion)
Hearth #6
Fixed Carbon Burnout
Hearth #7
Ash Cooling
FLUE GAS
EXHAUST
Hearth Temperature
No.
Range, °F
1
720 - 930
2
860 - 1215
3
1165 - 1360
4
1200 - 1380
5
770 - 1095
6
525 - 855
7
250 - 400
Forced
— l-l
Combustion
Air
ASH DISCHARGE
Figure 3-2. Schematic of MHF during normal combustion conditions
(original operating mode).
3-6
-------
190 p
180 -
170 -
160 -
150 -
140 -
130 -
120 -
110 -
100 -
90 -
80 -
70 -
60 -
50 -
40 -
30 -
20 -
10 -
0 -
-10 L
SITE #9 - ORIGINAL OPERATING MODE
AVG. WET SLUDGE FEED RATE = 7,482 Lbm./Hr.
HOURS FROM 7:00 A.M., 5/30/90
¦ DATA LEAST SQUARES FIT
Figure 3-3. Plot of sludge weight meter readings for normal operations
-------
u>
I
00
u.
d)
0)
Q
UJ
DC
ZDlo
h-X>
g§
M
cc
a
i
SITE #9 - ORIGINAL OPERATING MODE
LEGENDS = HEARTH NUMBER
H-1
HOURS FROM 7:00 A.M., 5/30/90
o H-2 a H-3 x H-4
H-5
Figure 3-4. Hearth temperatures during normal operations.
-------
SLUDGE FEED
Burner OFF
-i\i
Not Used
Burner ON
-i-i-
Burner ON
-i-i-
Burner OFF
—i\i—
To I.D. Fan Discharge
(No Recycling Ducting)
^ Shaft Cooling Air
i
L
r
Hearth #1
Drying
Hearth #2
Drying
Hearth #3
Begin Burning
Hearth #4
(Combustion)
Hearth #7
Ash Cooling
t ASH DISCHARGE
Hearth #5
Fixed Carbon Burnout
Hearth #6
Ash Cooling
FLUE GAS
EXHAUST
Hearth Temperature
No.
Range,
°F
1
1125
. 1155
2
1310
. 1375
3
1170
. 1220
4
1210
- 1250
5
460
- 555
6
420
- 490
7
445
- 525
Forced
1-
Combustion
Air
Figure 3-5. Schematic of MHF during improved combustion conditions.
3-9
-------
I
o
Q
111
111
LL
111
0—s
§•8
I c
>°
i£
13
O
SITE #9 - IMPROVED OPERATING MODE
AVG. WET SLUDGE FEED RATE = 7,460 Lbm./Hr.
HOURS FROM 8:00 A.M., S/8/90
DATA LEAST SQUARES FIT
Figure 3-6. Plot of sludge weight meter readings during improved combustion conditions.
-------
OJ
O)
d)
D
Ui
DC
Si
£0
X
fe
iS
1.60
1.50
1.40
1.30
1.20
1.10
1.00
0.90
0.80
0.70
0.60
0.50
0.40
SITE #9 - IMPROVED OPERATING MODE
LEGENDS = HEARTH NUMBER
X X X
H-1
HOURS FROM 7:00 A.M., 5/30/90
o H-2 a H-3 x H-4
H-5
Figure 3-7. Hearth temperatures during improved combustion conditions.
-------
u>
N)
O)
Q)
Q
uJ
CC
D
Ui(5
a. w
<3°
z
I
o
UJ
lil
CC
CO
1.40
SITE #9
ORIGINAL 5/30/90; IMPROVED 6/8/90
0.60
07:06 AM I 11:06 AM I 03:06 PM I 07:o6pM I 11:o6pM I 03:o6aM I
09:00 AM 01:00 PM 05:00 PM 09:06 PM 01:00 AM 05:00
TIME AT DAY OF TEST
ORIGINAL o IMPROVED
AM
Figure 3-8. Comparison of breaching temperatures for normal and improved modes of operation.
-------
SITE #9
ORIGINAL 5/30/90; IMPROVED 6/8/90
TIME AT DAY OF TEST
¦ ORIGINAL o IMPROVED
Figure 3-9. Comparison of venturi pressure drops for normal and improved modes of operation.
-------
4.0 TEST RESULTS
The results of the emission tests performed at Site 9 from May 30 to June 7, 1990
are presented in this section. Site 9 is a multiple hearth incinerator equipped with a
venturi scrubber/impingement tray scrubber combination and a wet electrostatic
precipitator 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 was just completing installation of a full-scale wet electrostatic
precipitator (ESP) which could be evaluated. The primary objectives of this test
program were to (1) determine the effect of combustion conditions at a multiple hearth
incinerator not using lime conditioning on the conversion of total chromium and total
nickel in the sludge to hexavalent chromium and nickel subsulfide emissions and (2)
evaluate the wet ESP for use as a retrofit control system for existing facilities. Testing
was conducted during normal furnace combustion conditions and improved furnace
combustion conditions. The two test conditions are referred to as "normal" and
"improved" combustion conditions.
In addition to the presentation of the results, variability and outliers in the data
are discussed. 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 1% 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 IX.
4-1
-------
4.1 FLUE GAS CONDITIONS
The uncontrolled emissions from the multiple hearth incinerator were tested in
the breaching from the incinerator leading to the venturi scrubber. Because of the
extremely high temperatures and short length of ducting, the gas velocity used to
establish isokinetic sampling rates was measured at only the single sample point location.
The reported inlet flue gas flow rate (corrected to diy standard conditions) was
calculated from that measured at the outlet to the control systems with corrections made
for dilution from the shaft cooling air entering the stack prior to the outlet sampling site.
The correction was made using the differences in oxygen concentrations at each location.
The uncontrolled emissions testing location is referred to as the "inlet" location (see
Point 1 in Figure 5-1). The emissions controlled by the venturi scrubber and
impingement tray scrubber, which consitituted the discharge emissions to the atmosphere
prior to the installation of the wet ESP, is referred to as the "midpoint" location (see
Point 3 in Figure 5-1). The wet ESP was installed downstream of the midpoint location
and the sampling location in the discharge stack of the wet ESP is referred to as the
"outlet" location (see Point 2 in Figure 5-1). A summary of the Site 9 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 emissions
monitoring measurements is present in Table 4-2.
4.1.1 Inlet Flue Gas Conditions
The flue gas volumetric flow rates at the inlet location during Runs 2, 3, 4, 5, 8, 9,
10, 11, 12, and 13 were not measured directly. Rather the inlet flue gas flow rates were
calculated by correcting the measured outlet flue gas flow rate for dilution air with the
difference between the outlet and inlet oxygen concentrations. The average inlet flue gas
temperature for Runs 2, 3, 4, 5, 8, 9, 10, 11, 12, and 13 was 5868C (1087°F) under normal
operating conditions with moisture and oxygen contents of 23.8% and 13.7%,
respectively.
4-2
-------
TABLE 4-1. SUMMARY OF INLET, MIDPOINT, AND ESP OUTLET FLUE GAS CONDITIONS; SITE 9
Run No.,
Pollutant Sampling
& Condition Location
Test
Date
Run Time
Temp
(OF)
Moisture
(%H20)
Oxygen Flow Rate
(%dry) (dscm/min)
Run 2
Metals
Normal
Inlet
Midpoint
Outlet
5/30/90
Aborted -
5/30/90
12:30-14:30 775 21.3 12.00
Due to water droplets carryover at sampling
12:30-14:30 114 3.9 14.51
14908
location
19636
Run 3
Cr+6/Cr
Normal
Inlet
Midpoint
Outlet
6/02/90
Midpoint
6/02/90
18:30-20:30 707 7.2 14.10
location was being relocated during this run
19:35-21:50 123 2.0 15.72
14004
18384
Run 4
Metals
Norma1
Inlet
Midpoint
Outlet
6/04/90 12:05-13:05
Run is considered invalid
6/04/90 12:18-13:18
944
due to
132
26.9 14.10 13982
water droplet carryover
8.0 15.72 18284
Run 5
Cr+6/Cr
Normal
Inlet
Midpoint
Outlet
6/03/90
6/03/90
6/03/90
15:00-16:15
15:00-17:00
15:00-17:00
818
81
136
15.8
3.3
3.7
11.24
11.24
13 .71
12109
12109
16269
Run 8
Cr+6/Cr
Improved
Inlet
Midpoint
Outlet
6/05/90
6/05/90
6/05/90
12:15-14:15
12:15-14:15
12:15-14:15
1229
84
158
24.1
6.3
1.9
10.17
10.17
(12.25)*
13898
13898
17240
Run 9
Metals
Improved
Inlet
Midpoint
Outlet
6/05/90
6/05/90
6/05/90
18:50-20:50
18:50-20:50
18:50-20:50
1327
91
157
27.7
3.3
4.3
10.61
10.61
(12.48)
13342
13342
16305
Run 10
Cr+6/Cr
Improved
Inlet
Midpoint
Outlet
6/06/90
6/06/90
6/06/90
12:30-13:30
11:30-13:20
11:30-13:20
1228
92
164
20.7
4.2
3.3
10.78
10.78
(12.6)
14309
14309
17468
(Continued)
-------
TABLE 4-1. (Continued)
Run Ho.

Pollutant
Sampling
Test

Temp
Moisture
Oxygen
Flow Rate
Condition
Location
Date
Run Time
(OF)
(%H20)
(%dry)
(dscm/min)
Run 11
Inlet
6/06/90
16:15-17:45
1250
28.7
10.76
14339
Metals
Midpoint
6/06/90
15:45-17:45
92
4.3
10.76
14339
Improved
Outlet
6/06/90
15:45-17:45
147
4.9
(12.53)
17371
Run 12
Inlet
6/07/90
10:00-12:00
1317
29.5
9.97
13085
Metals
Midpoint
6/07/90
10:15-12:15
92
4.7
9.97
13085
Improved
Outlet
6/07/90
10:15-12:15
148
3.5
(12.29)
16611
Run 13
Inlet
6/07/90
16:20-18:00
1271
32.9
9.64
13091
Metals
Midpoint
6/07/90
16:00-18:00
98
4.9
9.64
13091
Improved
Outlet
6/07/90
16:00-18:00
154
5.2
(12.16)
16866
* - Oxygen values shown in parentheses were calculated based on C02 CEMs values.
-------
TABLE 4-2. SUMMARY OF INLET AND OUTLET CONTINUOUS EMISSION MONITORING
MEASUREMENTS: SITE 9
Flue Gas Conditions
Diluent (X dry)
Run No./
Sampling
Temp.
Moisture
Flow Ratea

Carbon
Sulfur Dioxide
Nitrogen Oxides
Carbon Monoxide
Cold THC
Condition
Location
(Of)
(XH20)
(dscf/min)
Oxygen
Dioxide
Actual
87* 02
Actual
87* 02
Actual
an 02
Actual
Run 2
Inlet
775
21.3
14908
12.00
6.77
285
488
162
278

Normal
Outlet
114
3.9
19636
14.51
-*
--

648
1343
40.7
Run 3
Inlet
707
7.2
14004
14.10
5.39
246
496
122
246
..

Normal
Outlet
123
2.0
18384
15.72
--

1026
2305
38.6
Run 4
Inlet
944
26.9
13982
14.10
4.94
206
415
157
316

Normal
Outlet
132
8.0
18284
15.70

••
1147
2536
102
Run 5
Inlet
818
15.8
12109
11.24
7.17
315
506
185
396
..

Normal
Outlet
136
3.7
16269
13.71

--
--
1338
2621
141
Run 8
Inlet
1229
24.1
13898
10.17
7.90
262
401
211
323

Improved
Outlet
1S8
1.9
17240
(12.2S)b
5.82
--

--
304
532
7.7
Run 9
Inlet
1327
27.7
13342
10.61
7.69
251
381
214
324
..
..

Improved
Outlet
157
4.3
16305
(12.48)
5.82

**
307
548
6.5
Run 10
Inlet
1228
20.7
14309
10.78
7.48
258
398
214
330
--
..

Improved
Outlet
164
3.3
17468
(12.61)
5.65

368
663
7.0
Run 11
Inlet
1250
28.7
14339
10.76
7.43
288
443
213
327
..

Improved
Outlet
147
4.9
17371
(12.53)
5.66

--
--
--
372
666
7.5
Run 12
Inlet
1317
29.46
13085
9.97
8.20
263
374
241
343

Improved
Outlet
148
4.72
16611
(12.29)
5.88
--

303
533
5.7
Run 13
Inlet
1271
32.97
13091
9.64
8.S3
324
446
17V
246

Improved
Outlet
154
5.17
16866
(12.16)
6.01
--
--
--
--
251
437
4.9
Pollutant Gases (actual ppm and/or corrected to 7X 02)
I
Ln
'Inlet flourates were calculated by mathematically adjusting outlet flourate for oxygen,
'oxygen values in parentheses were calculated based on C02 values.
-------
4.1.2 Midpoint Flue Gas Conditions
The flue gas volumetric flow rates at the midpoint sampling site for Runs 2, 3, 4,
5, 8, 9, 10, 11, 12, and 13 ranged from 400 dscm/min to 531 dscm/min and averaged 444
dscm/min (15678 dscf/min) under normal operating conditions. The flue gas average
temperatures were 30.7°C (87.9T) with moisture, oxygen, and carbon dioxide content of
5.9%, 14.1%, and 5.0%, respectively. The CEMs results for the inlet and midpoint
would be the same on a dry basis because the venturi/impingement tray scrubber is a
closed system
4.1.3 Outlet Flue Gas Conditions
The flue gas volumetric flow rates at the wet ESP outlet sampling site for Runs 2,
3, 4, 5, 8, 9, 10, 11, 12, and 13 ranged from 461 dscm/min to 556 dscm/min and averaged
494 dscm/min (17443 dscf/min) under normal operating conditions. The flue gas
average temperature was 62°C (143°F) with moisture, oxygen, and carbon dioxide
contents of 4.2%, 14.1%, and 5.0%, respectively.
4.2 PARTICULATE/METAL RESULTS
Particulate/metal emissions were determined using the draft EPA method
procedure for "Methodology for the Determination of Metals Emissions in Exhaust
Gases from Hazardous Waste Incineration and Similiar Combustion Processes"
(reproduced in Volume IX: Site 9 Test Report, Appendices).
Six runs (Runs 2, 4, 9, 11, 12, and 13) were conducted to determine control system
collection efficiency for the multiple metals: arsenic (As), beryllium (Be), rariminm (Cd),
chromium (Cr), lead (Pb), nickel (Ni) and mercury (Hg). 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 recoveiy the mercury in the precipitate. Therefore, the results for mercury in
4-6
-------
this study are considered invalid and are not reported. Runs 2, 4, 9, 11, 12, and 13 were
used to determine the metals collection efficiency of the venturi scrubber/impingement
tray control system, Runs 9, 11, 12, and 13 were used to determine the metals collection
efficiency for the wet ESP; and Run 2 was used to determine if the midpoint and outlet
locations gave the same results with the wet ESP turned off. During Runs 2 and 4, the
air flow rate through the impingement tray scrubber was too high and cause water
droplet carryover at the midpoint sampling location. The midpoint location was moved
downstream after Run 2 and the flue gas flow rate through the system was reduced after
Run 4.
The particulate emissions were determined using the multiple metals sampling
system. The particulate and metals emission results and collection efficiencies for the
venturi scrubber/impingement tray scrubber and wet ESP are shown in Table 4-3 on a
concentration basis and mass emission rate basis. These results represent average
emissions from a multiple hearth sludge incinerators during normal combustion
conditions and improved combustion conditions.
Research Triangle Institute (RH) 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 uncontrolled flue gas metals and particulate emission concentrations
measured at the control device inlet are shown in Table 4-3. Runs 2 and 4 represent
metals/particulate emissions during normal combustion conditions. Runs 9, 11, 12, and
13 represent metals/particulate emissions during improved combustion conditions. The
average concentrations of metals in the uncontrolled emissions from the incinerator
during improved combustion conditions in terms of ng of metal per dry standard cubic
meter of flue gas (/cg/dscm) for Runs 9, 11, 12, and 13 is are: arsenic - 53 fig/dscm,
beryllium - 1.4 Mg/dscm, cadmium - 320 /ig/dscm, chromium - 290 >cg/dscm, lead - 2750
4-7
-------
TABLE 4.3. SUMMARY OF SITE 9 PARTICULATE AND MULTIPLE METAL EMISSIONS
AND COLLECTION EFFICIENCY
Run No.
As
M/*3 g/hr
Cd
»g/m3 g/hr
Cr
ng/m3 g/hr
Pb
*B/«3 g/hr
Ni
*0/«*3 g/hr
Particulate
Mg/m3 g/hr
Normal Confaustion Conditions
OUT-2
HID-2 (Aborted)
IN-2
X Scrubber rental
39.8 1.3
41.2 1.0
N/A
157 5.1
200 5.1
0
157 5.3
H2 3.6
0
1088 35.1
1468 37.2
5
22.2 0.73
275 7.0
89
52.7 1761
451 11433
85
OUT-*
MID-4 (Invalid)
IN*
X Total removal
<30 <0.9
20.4 0.47
N/A
21.9 0.68
150 3.5
80
6.3 0.19
113 2.6
93
103 3.2
857 19.8
84
5.8 0.18
201 4.7
96
23.1 717
319 7380
90
(Continued)
Note: Wet ESP mi shut off during Run 2 and was Malfunctioning during Run 4.
-------
TABLE 4-3. (Continued)
Run No.

As
Cd
Cr
Pb

Particulate

M/mS
g/hr
(ig/mJ
g/hr
$g/mS
g/hr
M/«3
g/hr
H9/mi
g/hr
mg/m3
g/hr
Improved Conixistion Conditions
OUT-9
<30
<0.9
3.7
0.10
2.75
0.08
37.9
1.05
2.42
0.07
4.2
115
X ESP Removal
N/A

HIO-9
71.6
1.6
167
3.8
37.9
0.86
1415
32.1
22.3
0.50
44.9
1017
X Scrti>ter Rom I
N/A

IN-9
48.9
1.1
361
8.2
335
7.6
3483
78.9
638
14.5
883
20007
X Total Rcawval
N/A

99.54

99.42

OUT-11
<30
<0.9
5.8
0.17
3.2
0.09
51.0
1.50
1.58
0.05
4.1
122
X ESP Rcawval
N/A

HID-11
61.8
1.5
155
3.8
38.0
0.93
1111
27.1
25.2
0.61
46.4
1130
X Scrutator Rental
N/A

IH-11
<30
<0.9
264
6.4
329
8.0
2545
62.0
819
20.0
1200
29183
X Total Re«noval
N/A

99.77

99.58

OUT-12
<30
<0.9
<0.4
<0.01
1.73
0.05
16.6
0.47
2.45
0.04
3.5
99
X ESP Roaoval
N/A

>99.7

HID-12
66.6
1.5
187
4.3
32.1
0.71
1151
25.6
32.1
0.71
49.6
1102
X Scrubber Rental
N/A

IN-12
62.6
1.4
339
7.5
316
7.0
2520
56.0
769
17.1
856
19039
X Total Rcatoval
N/A

>99:8

99.30

99.16

99.78

99.48

OUT-13
<30
<0.9
<0.4
<0.01
3.5
0.12
67.1
2.0
2.40
0.08
7.1
204
X ESP Rcawval
N/A

>99.7

NIO-13
62.6
1.4
191
4.2
22.1
0.45
1401
31.1
28.5
0.61
50.0
1431
X Scrti&er Reoal
N/A

IN-13
69.4
1.6
319
7.1
184
4.0
2440
54.2
427
9.5
465
13294
X Total Reawval
N/A

>99.8

99.2

<30
<0.9
<2.6
<0.07
2.8
0.09
43.2
1.26
2.20
0.06
4.7
135
X ESP Rmoval
N/A

>98

MIDPOINT average
65.7
1.5
175
4.0
32.5
0.73
1270
29.0
27.0
0.61
47.7
1070
X Scri±ber Rental
N/A

INLET average
52.7
<1.3
321
7.3
291
6.7
2750
62.8
663
15.3
851
20400
X Total Removal
N/A

>99

99.6

99.3

-------
Mg/dscm, and nickel - 660 /tg/dscm. The particulate concentration averaged 850
mg/dscm.
The flue gas metal and particulate mass emission rates at the control device inlet
are shown in Table 4-3. Because the inlet sampling site had to be installed in the short
length of duct (breaching between the incinerator and the venturi scrubber), the mass
emission rate (g/hr) were calculated using the flue gas flow rate measured at the
midpoint location. The metal mass emissions rates for the inlet runs during improved
combustion conditions averaged: arsenic - < 1.3 g/hr, beryllium - < 0.03 g/hr, cadmium -
7.3 g/hr, chromium - 6.7 g/hr, lead - 63 g/hr, and nickel - 15 g/hr. The particulate mass
emission rates averaged 20.4 kg/hr.
For each inlet sampling run, the mass of each target metal collected was divided
by the mass of particulate collected to yield the concentration of metal in the fly ash.
The results are presented in Table 4-4.
4.22 Midpoint Location (Venturi /Trav Scrubber Outlet) Results
The flue gas metals and particulate concentrations at the midpoint
(venturi/impingement tray scrubber outlet or wet ESP inlet) are shown in Tables 4-3.
The average values for Runs 9, 11, 12, and 13 represent metals emissions entering the
wet ESP during improved furnace combustion conditions. For Rim 2, the wet ESP was
shut off to determine if the midpoint and outlet results were the same with the wet ESP
off-line. During Runs 2 and 4, the flue gas flow rate through the impingement tray
scrubber was too high resulting in water droplet carryover at the midpoint sampling
location. The midpoint location was subsequently relocated further from the
impingement tray scrubber discharge and the flow rate was reduced. For Rim 4, the new
midpoint sampling location was used. However, during this run, the flow rate again
increased, resulting in water droplet carryover and invalidating the midpoint results. The
concentration of metals at the midpoint location for the improved combustion conditions
averaged: arsenic - 65.7 /ig/dscm, beryllium - < 0.2 /ig/dscm, cadmium - 175 /ig/dscm,
chromium - 33 /tg/dscm, lead 1270 /ig/dscm, and nickel 27 /tg/dscm. The particulate
4-10
-------
TABLE 4-4. SUMMARY OF METAL CONCENTRATIONS IN FLY ASH
Location
and Run No.
Metals Concentration in Fly Asha
(mg metal/g particulate)
Beryllium
Cadmium
Chromium
Lead
Nickel
Inlet 2
Midpoint 2
0.002
NAb
0.4
3.0
0.3
3.0
3.3
21
0.6
0.4
Inlet 4
Outlet 4
0.0004
NA
0.5
1.0
0.4
0.3
2.7
4.5
0.6
0.3
Inlet 9
Midpoint 9
Outlet 9
0. 002
NA
NA
0.4
3.7
0.9
0.4
0.8
0.6
4.0
32
9.0
0.7
0.5
0.6
Inlet 11
Midpoint 11
Outlet 11
0. 002
NA
NA
0.2
3.3
1.4
0.3
0.8
0.8
2.1
24
12
0.7
0.5
0.4
Inlet 12
Midpoint 12
Outlet 12
0.002
NA
NA
0.4
3.8
NA
0.4
0.7
0.5
2.9
23
4.7
0.9
0.6
0.7
Inlet 13
Midpoint 13
Outlet 13
0.002
NA
NA
0.7
3.8
NA
0.4
0.4
0.5
5.3
28
9.4
0.9
0.6
0.3
Inlet Avg.
Midpoint Avg
Outlet Avg.
0.002
NA
NA
0.4
3.5
NA
0.3
1.2
0.4
3.2
25
6.6
0.8
0.5
0.4
aArsenic was below the limit of detection in all midpoint runs,
inlet values were less than 0.025 mg/g and outlet less than 0.7
mg/g.
DBelow the level of detection, less than indicated detection
limit.
4-11
-------
concentrations averaged 48 mg/dscm. The flue gas metal and particulate mass emission
rates at the control device inlet are shown in Table 4-3. The metal mass emissions rates
at the midpoint under improved combustion conditions averaged: arsenic - 1.5 g/hr,
beryllium - <0.01 g/hr, cadmium - 4 g/hr, chromium - 0.7 g/hr, lead - 29 g/hr, and
nickel - 0.6 g/hr. The particulate mass averaged 1.07 kg/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. These results are presented in Table 4-4.
4.2.3 Wet ESP Outlet Results
The flue gas metals and particulate concentrations at the wet ESP outlet are
shown in Table 4-3. The average values for Runs 9, 11, 12, and 13 represent metals
emissions during improved combustion conditions. The wet ESP was not operated
during Run 2. For the improved combustions conditions, arsenic emissions were at or
below the level of detection, which was about 30 pg/dscm for all outlet sampling runs.
The beryllium emissions were at or below the level of detection, which was about 02
Mg/dscm for all outlet runs. All the other metals were detected for all test runs and
averaged: cadmium - <2.6 /tg/dscm, chromium - 2.8 /tg/dscm, lead - 43 /ig/dscm, and
nickel 2.2 jig/dscm. The particulate concentrations averaged 4.7 mg/dscm. The flue gas
metal and particulate mass emission rates at the ESP outlet are shown in Table 4-3. The
metal mass emissions rates for all outlet testing averaged: arsenic - < 0.9 g/hr,
beryllium - <0.1 g/hr, cadmium - <0.7 g/hr, chromium - 2.8 g/hr, lead - 12 g/hr, and
nickel - 0.6 g/hr. The particulate mass averaged 135 g/hr.
For each outlet sampling run, the milligrams of each target metal collected was
divided by the grams of particulate collected to provide the concentration of that metal
in the fly ash. These results are presented in Table 4-4.
4-12
-------
4.2.4 Removal Efficiency of Control Device for Metals and Particulate
The pollutant removal (collection) efficiencies reported for the venturi
scrubber/impingement tray scrubber and the wet ESP were calculated based on the mass
emission rate, see Table 4-3. The venturi/impingement tray scrubber pollutant removal
efficiencies measured for the particulate and target metal runs during improved
combustion conditions averaged: particulate - 95%, arsenic - none, beryllium - all
midpoint samples were below the level of detection, cadmium - 45%, chromium - 89%,
lead - 54%, and nickel - 96%.
The wet ESP pollutant removal efficiencies calculated for the particulate and
target metal runs under improved combustion conditions averaged: particulate - 87%,
arsenic - all outlet samples were below the level of detection, beryllium - all midpoint
and outlet sample values were at or below the limit of detection, cadmium - >98%,
chromium - 88%, lead - 96%, and nickel - 90%.
The combined removal efficiencies demonstrated by the scrubbers/wet ESP under
improved combustion conditions averaged: particulate - 993%, arsenic - all outlet
samples were below the level of detection, beryllium - all midpoint and outlet sample
values were below the limit of detection, cadmium - >99%, chromium - 99%, lead -
98%, and nickel - 99.6%.
4.2.5 Sludge Feed Results
A composite sludge feed sample was made from grab samples collected over the
duration of each run. The metal feed rates based on the concentration of metals in the
sludge and the sludge feed rates are presented in Table 4-5. The mass feed rates of
metals in the sludge were fairly consistent and for the improved combustion conditions
averaged: arsenic - not detected (<100 g/hr), beryllium - <0.8 g/hr, cadmium - 8.1
g/hr, chromium - 82 g/hr, lead - 210 g/hr, and nickel - 150 g/hr.
The results of the sludge proximate and ultimate analyses are presented in Table
4-6. All of these results were fairly consistent from run-to-run. The sludge analyses
4-13
-------
TABLE 4-5. INPUT RATE OF METALS IN SEWAGE SLUDGE
Metal Input in Sewage Sludge (g/hr)
Run
No.

As
Be
Cd
Cr
Pb
Ni

Normal
Combustion

Run
3

ND
ND
7.6
68
168
110
Run
4

160
0.77
11
79
200
120
Run
5

ND
ND
7.2
80
200
130
Improved Combustion
Run
8

ND
ND
8.9
92
310
140
Run
9

ND
ND
8.3
87
190
130
Run
10

160
0.83
11
90
230
160
Run
11

120
ND
8.2
82
220
160
Run
12

130
ND
8.1
85
210
170
Run
13

ND
3.0
8.0
76
210
150
All

<100
<0.8
8.7
82
220
140
Average

Runs
9,
10
<100
<0.8
8.1
82
210
150
11,
12 &
13

aND - Not detected.
bDetection Limit - Values represent the detection limit expressed
in g/hr.
4-14
-------
TABLE 4-6. RESULTS FOR PROXIMATE AND ULTIMATE ANALYSES OF SLUDGE SAMPLES

Dry
Basis Analysis
(%)a

Run
No.
Moisture
(%)
Volatile
Matter
Fixed
Carbon
Ash
S
C
H
N
O
Btu/lb
3
80.29
59.74
12.74
27.79
1.27
45.16
5.78
4.10
15.90
8723
4
77.57
65.92
8.09
25.99
0.88
43.53
6.24
4.63
18.74
8369
5
79.59
62.98
10.09
26.93
0.85
42.67
6.49
4.66
18.40
8351
8/9
76.95
66.03
9.16
24.81
0.85
45.17
6.38
4.95
17.83
8348
10/11
78.00
66.10
8.86
25.04
0.95
44.02
6.23
5.25
18.51
8688
12/13
79.15
66.88
8.34
24.78
0.89
44.62
6.31
5.08
18.32
8768
Avg.
78.59
64.61
9.55
25.89
0.95
44.20
6.24
4.77
17.95
8541
aElemental analysis - S (Sulfur), C (Carbon), H (Hydrogen), N (Nitrogen), and O
(Oxygen).
-------
results averaged: moisture - 78.59%, volatile matter - 64.61% (dry basis), fixed carbon -
9.55% (dry basis), ash - 25.89% (dry basis), sulfur - 0.95% (dry basis), carbon - 44.20%
(dry basis), hydrogen - 624% (dry basis), nitrogen - 4.77% (dry basis), oxygen - 17.95%
(dry basis), and BTU per pound - 8500 (dry basis).
4.2.6 Scrubber Water Results
Venturi and impingement tray scrubber water influent and effluent samples were
collected for all sampling runs. The scrubbers influent was colleted from a water feed
line to the scrubbers. The venturi scrubber effluent samples had to be collected from
the bottom of the tank near the discharge pipe and the impingement tray scrubber water
effluent samples were collected from the bottom of the tank near the other discharge
pipe. The water effluent samples therefore may not be representative of the discharge
effluent. Therefore, the results should be treated as an approximation. The mass
discharge rates of the metals collected in the scrubber are presented in Table 4-7. These
values represent the effluent concentration minus the influent concentration times the
scrubber water flow rate of 490 gal/min to the venturi scrubber and about 1200 gal/min
to the impingement tray scrubber. The average discharge values for the metals runs
during improved combustion conditions were: arsenic - 1.8 g/hr, beryllium - 0.05 g/hr,
cadmium - 9 g/hr, chromium - 11 g/hr, lead - 89 g/hr, and nickel - 35 g/hr.
4.2.7 Bottom Ash Results
Incinerator bottom ash samples were collected from the hopper at the conclusion
of each sample run. The bottom ash metal concentration results are shown in Table 4-8.
The bottom ash metal concentrations were converted to metal mass flow rates.
First, the bottom ash flow rates were determined using the percent ash values from the
proximate analyses (in Table 4-6) multiplied by the appropriate sludge feed rates to yield
total ash production rate. Then the average particulate emission rate measured at the
4-16
-------
TABLE 4-7. DISCHARGE RATE OF METALS IN SCRUBBER WATER

Metal Discharge Emissions
in Scrubber Water
(g/hr)
Run No.
As Be Cd
Cr Pb
Ni
Normal Combustion Conditions
Run 3
0.00
0.00
2.0
0.57
12
1.0
Run 4
0.00
0.02
10
10
80
17
Run 5
1.85
0.03
7.5
8.5
47
18

Improved Combustion
Conditions

Run 8
3 .21
0.05
17
8.9
120
30
Run 9
1.31
0.02
3.0
0.5
36
5.0
Run 10
2.02
0.12
9.0
9.5
120
32
Run 11
2.21
0.09
10
7.4
130
39
Run 12
2.18
0.08
12
30
110
73
Run 13
1.62
0.03
9.0
5.2
82
24
Average of
1.60
0.04
9.0
8.9
82
27
Runs 3-13

Average of
1.83
0.05
9.0
11
89
35
Runs 8-13

4-17
-------
TABLE 4-8 DISCHARGE RATE OF METALS IN BOTTOM ASH

Metal Discharge
Emissions
in Bottom Ash
(g/hr)
Run
No.
As
Be
Cd
Cr
Pb
Ni

Normal
Combustion

Run
3
7.0
0.34
1.1
54
120
100
Run
4
6.3
0.36
2.2
70
180
130
Run
5
7.9
0.33
1.7
57
140
110

Improved
Combustion

Run
8
0.0
0.34
4.4
64
140
110
Run
9
12
0.38
1.2
64
140
120
Run
10
6.7
0.35
1.0
61
160
140
Run
11
5.6
0.35
1.1
61
160
130
Run
12
8.1
0.34
1.5
58
150
140
Run
13
7.1
0.32
1.5
54
130
120
All

6.8
0.34
1.7
60
150
120
Average

Runs 9, 10
8.4
0.35
1.3
59
150
130
11,
12 & 13

4-18
-------
inlet location were subtracted from the total ash rates to give the bottom ash flow rate
for each run. The average ash flow rate was 4.6 tons/day. This average is, at best, a
rough estimate. The metals mass flow rates for the bottom ash are the product of the
metals concentration in the bottom ash times the ash flow rate. These are presented in
Table 4-8 and for the Runs 9, 10, 11, 12, and 13 and averaged: arsenic - 1.8 g/hr,
beryllium - 0.05 g/hr, cadmium - 9 g/hr, chromium 11 g/hr, lead 89 g/hr, and nickel - 35
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
summarized in Table 4-9.
TABLE 4-9. RATE OF METALS TO AND FROM INCINERATOR
Sampling
Location
Metal
Emissions to
and from
Incinerator
(g/hr)

As
Be
Cd
Cr
Pb
Ni
Sludge
Feed
<100
<0.8
8.1
82
210
150
Bottom
Ash
8.4
0.35
1.3
59
150
130
Inlet
Sampling
<1.3
<0.1
7.3
6.7
63
15
Scrubber
Water
<1.8
<0.1
8.5
11
89
35
4-19
-------
4.2.8 Metals 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 9, metal emissions testing was performed
at both the inlet and outlet of the control device; therefore, uncontrolled and controlled
emissions can be related to the sludge feed composition. The ratios of uncontrolled
metal emissions (outlet of the incinerator or inlet to the control device) to the metal
feed rates in the sludge are presented in Table 4-10. These ratios were calculated based
on the metals emissions measured at each location compared to the metals content of
the sludge. The uncontrolled metal emission factors (percentage of metals fed to
incinerator in the sludge) during improved combustion conditions averaged: arsenic • at
or below detection in sludge, beryllium - at or below detection in sludge, cadmium -
83%, chromium - 82%, lead - 30%, and nickel - 10%. The control device outlets
(midpoint and ESP outlet) emission factors are also presented in table 4-10. The metals
at the midpoint location in terms of percentage of metals fed to the incinerator emitted
to the wet ESP under improved combustion conditions averaged: arsenic - at or below
detection in sludge, beryllium - at or below detection in sludge, cadmium - 4%,
chromium - 8.9%, lead - 14%, and nickel - 4.1%. For the wet ESP metal emissions to
the atmosphere averaged: arsenic -at or below detection in sludge, beryllium - at or
below detection in sludge, cadmium - < 0.86%, chromium - 0.11%, lead - 0.6%, and
nickel - 0.04%. The controlled metal emission factors decrease in the same proportion
as the control device removal efficiencies.
43 HEXAVALENT CHROMIUM RESULTS
The hexavalent chromium (Cr+<) samples collected were analyzed by ion
chromatography coupled with a post column reaction (IC/PCR). The ion chromatograph
was used to separate the nCr+< from "Cr*3 for gamma emission counting and the post
column reaction provided Cr+<-specific results. The results for Cr+<, the isotope
4-20
-------
TABLE 4-10. METALS EMISSION FACTORS
Location/
Combustion
Condition
g metal
at location/g metal
in sludge*
Cd
Cr
Pb
Ni
Inlet
Improved
0.83
0.082
0.30
0.10
Midpoint
Improved
0.040
0.0089
0.14
0.0041
Outlet
Improved
<0.0086
0.0011
0.0060
0.00040
^he normal combustion conditions had too many upsets and
malfunctions to consider results as representative for evaluation
of the air pollution control equipment. Arsenic and beryllium
were at or below the analytical detection limit in the sludge
samples.
4-21
-------
speciation, and total chromium for Site 9 are presented in Table 4-11. Sampling train D
of each quadruplicate-train was spiked with a stable hexavalent chromium isotope, 0Cr+4.
The samples were to be analyzed by Technology Applications, Inc. using IC/PCR for
hexavalent chromium and IC/mass spectroscopy (MS) to determine the amounts of
labeled hexavalent chromium (°Cr*4) and the most common native hexavalent chromium
isotope (S2Cr+4). However, the impinger solutions (sample) from these trains became
acidic during testing, thereby eliminating the possibility of evaluating the IC/PCR and
IC/MS analytical approach. No reason could be determined for this event. The
samples were invalidated and no analytical results are shown. The results for each
sampling location are discussed separately in the following subsections.
4.3.1 Control Device Inlet Results
The inlet Cr+4/Cr samples were collected utilizing a high temperature (quartz
glass probe not Teflon) recirculating train because of temperature constraints on Teflon.
The inlet samples could not be analyzed for hexavalent chromium due to the presence of
dissolved salts which interfered with the post column reaction. The samples were
analyzed by direct injection into the IC to perform the isotope speciation. The
recoveries of nCr+* spiked in the trains before sampling ranged from 87% to 113%.
4.3.2 Midpoint Results
At the midpoint location, quadruplicate recirculating trains were employed to
collect Cr+< and total Cr. One train from each run contained a spike of two hexavalent
chromium isotopes (°Cr+t and "Cr*4). These samples were invalidated due the sample
becoming acidic during testing which caused unacceptably high conversion of the
hexavalent chromium and spikes. The other three trains were spiked with nCr+< and
remained alkaline during testing. The emissions measured at the midpoint are
representative of the plant emissions prior to installation of the wet ESP. The Cr+4
concentrations at the midpoint ranged from 0.6 ug/dscm to 2.5 ug/dscm and averaged
4-22
-------
TABLE 4.11. SUMMARY OF MIDPOINT AND OUTLET Cr+6 AND TOTAL CHROMIUM RESULTS
Date
Run No.,
Sample
Fractions
Cr+6
Cr+6
Ratio of
and
Train, &
Cr*5 Total Cr
Conversion
Total Cr Cr+6/Cr
Time
Location
(ug)
(ug)
(%)
(ug/M3)
(ug/M3)
(*)
6/2/90
3-A-MID
1.8
15.1
4.5
1.4
11.8
11.7
from 20:33
3-B-MID
1.9
15.3
1.9
1.3
10.7
12.4
to 20:45
3-C-MID
3.1
16.2
40.4
2.3
12.4
18.9

3-D-MID
2.3
22.4
99.9

INVALIDATED

Average

15.6
1.7
11.6
14.5
6/2/90
3-A-OUT
1.9
6.0
5.4
0.8
2.6
32.3
from 19:33
3-B-OUT
1.7
9.1
6.4
0.8
4.0
18.8
to 21:48
3-C-OUT
1.6
7.6
23.6
0.7
3.2
20.7

3-D-OUT
ND
11.0
95.0

INVALIDATED
Average

11.8
0.7
3.2
23.0
6/3/90
5-A-MID
3.3
23.3
8.1
2.5
17.2
14.3
from 14:47
5-B-MID
1.1
29.4
15.0
0.6
15.2
3.7
to 16:47
5-C-MID
2.8
30.7
24.4
1.4
15.3
9.2

5-D-MID
ND
30.6
99.3

INVALIDATED
Average

15.8
1.5
15.9
9.3
6/3/90
5-A-OUT
1.9
65.6
11.0
1.0
33.9b
2.9
from 14:55
5-B-OUT
3.2
6.9
8.4
1.6
3.6
45.8
to 16:55
5-C-OUT
3.1
8.0
10.4
1.5
3.9
38.5

5-D-OUT
3.3
10.9
94.9

INVALIDATED

Average

9.9
1.4
3.7
36.7
6/5/90
8-A-MID
1.8
31.3
1.9
1.0
17.5
5.9
from 12:21
8-B-MID
2.5
34.8
2.0
1.3
18.3
7.2
to 14:21
8-C-MID
1.5
7.6
28.3
0.9
4. 2b
20.4

8-D-MID
ND
36.3
99.3

INVALIDATED

Average

10.7
1.1
17.9
6.0
(Continued)
-------
TABLE 4.11. (Continued)
Date
Run No.,
Sample Fractions
Cr+6
Ratio of
and
Train, &
Cr 6 Total Cr
Conversion
Cr+6 Total Cr Cr+6 to
Time
Location
(ug) (ug)
(*)
(ug/M3) (ug/M3) Total Cr
6/5/90
8-A-OUT
0.8 3.2
6.5
0.4 1.6 24.9
from 12:15
8-B-OUT
1.2 3.7
7.4
0.6 1.8 32.8
to 14:15
8-C-OUT
3.0 4.4
12.4
1.5 2.2 67.6

8-D-OUT
ND 36.3
100.0
INVALIDATED
Average

8.8
0.8 1.7 47.9
6/5/90
9-MID
69.5

37.9
18:50-20:50
9-OUT
4.2

2.7
6/6/90
10-A-MID
1.9 23.5
1.6
1.2 14.5 8.1
from 11:35
10-B-MID
3.0 26.2
1.6
1.8 15.3 11.5
to 13:19
10-C-MID
2.5 24.9
21.3
1.4 14.6 9.9

10-D-MID
ND 27.9
100.0
INVALIDATED
Average

8.2
1.5 14.9 9.8
6/6/90
10-A-OUT
1.2 3.7
5.0
0.8 2.3 33.7
from 11:30
10-B-OUT
1.2 3.4
5.4
0.8 2.1 36.3
to 13:20
10-C-OUT
ND 8.3
92.3
INVALIDATED

10-D-OUT
1.2 2.9
4.6
0.8 1.9 40.9
Average

5.0
0.8 2.1 37.0
6/6/90
11-MID
72.5

38.0
15:45-17:45
11-OUT
4.0

3.2
aValues for invalidated runs not included in averages.
bOutlier not included in average.
-------
1.5 ug/dscm. The 51Cr+< spike recoveries ranged from 61% to 98% and averaged 87%.
The ratio of Cr+< to total Cr ranged from 3.7% to 20.4% and averaged 9.9%.
433 ESP Outlet Results
At the wet ESP outlet location, quadruplicate recirculating trains were employed
to collect Cr+< and total chromium. One train from each run contained a spike of two
hexavalent chromium isotopes (°Cr+< and ^Cr"1"®). These samples were invalidated due
the sample becoming acidic during testing which caused unacceptably high conversion of
the hexavalent chromium and spikes. The other three trains were spiked with "Cr"1"® and
remained alkaline during testing. The Cr+< concentrations ranged from 0.4 to 1.6
ug/dscm and averaged 0.9 ug/dscm. Recoveries of the ^Cr*' spike ranged from 76% to
95% and averaged 91%. The ratio of Cr+< to total Cr in the emissions ranged from
2.9% to 67% and averaged 36%. The increase in the ratio of Cr+< to total Cr as
compared to the midpoint results likely indicates that the wet ESP was more efficient in
collecting the trivalent chromium than the hexavalent chromium.
4.4 NICKEL SPECIATTON 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 multiple hearth 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
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
4-25
-------
compounds, and finally total digestion of the remaining sample typically yields the nickel
oxides.
The results of the NiPERA analysis shown in Table 4-12 indicate that, within the
detection limit of the method, no nickel subsulfide was present in the samples. Based on
the detection limits, the ratio of nickel subsulfide to total nickel in the inlet emissions is
less than 2% and in the midpoint emissions is less than 1%. The outlet samples did not
contain sufficient material to conduct nickel speciation analysis.
At the midpoint, the total nickel emissions measured using the nickel speciation
train agreed well with the total nickel emissions measured using the multiple metals
train. At the inlet, the nickel speciation train yeilded total nickel emissions about twice
as high as the multiple metals train. The cause for this difference is not known.
4.5 DIOXIN/FURAN AND SEMTVOLATILE ORGANIC RESULTS
Sampling for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated
dibenzofurans (PCDFs), and other semivolatile organics was conducted at the midpoint
location and outlet location. Two two-hour runs were conducted at each location, with
one run conducted during normal incinerator operationd (Run 7A) and one run during
improved incinerator operation (Run 7C). These flue gas samples were collected using
the Modified Method 5 (MM5) train and the procedures of SW-846 Method 0100, except
that a final toluene rinse was performed and analyzed separately for PCDD/PCDF.
The concentrations of dioxin/furan compounds detected in the flue gas are shown
in Table 4-13. The total PCDD and total PCDF concentration, respectively, were 20.2
and 81.9 ng/dscm at the midpoint and 3.2 and 12.4 ng/dscm at the outlet under the
normal incineration operations. During improved incinerator operations, the total
PCDD and PCDF concentrations, respectively, decreased to 1.6 and 7.1 ng/dscm at the
midpoint and 0.65 and 2.1 ng/dscm at the outlet
The concentrations of semivolatile organic compounds detected in the flue gas are
shown in Table 4-14. A number of semivolatile compounds were measured at levels
above the minimum detection limit at both the midpoint and outlet locations under runs
4-26
-------
TABLE 4-12. SUMMARY OF NICKEL SPECIES EMISSIONS: SITE 9
Run No.
Soluble
Hq/m3 %
Sulfidicb
Hg/m3 %
Metallic
/jg/m3 %
Oxidic
/jg/m3 %
Total
Hg/m3
Midpoint
Run 4Ca
Run 9C
Run 11C
Run 12C
Run 13C
10.0 51.1
22.7 92.2
24.2 91.4
30.7 95.5
24.6 95.5
2.2 11.4
<0.1 <0.5
<0.1 <0.4
<0.1 <0.3
<0.1 <0.4
<0.4 <2.3
<0.1 <0.5
<0.1 <0.4
<0.1 <0.3
<0.1 <0.4
7.3 37.5
1.9 7.8
2.3 8.6
1.4 4.5
1.2 4.5
19.6
24.6
26.4
32.1
25.8
INLET
Run 4C
Run 9C
Run 11C
Run 12C
Run 13C
77.0 18.1
201.0 19.2
449.1 20.5
415.6 30.4
358.5 55.8
<9.1 <2.1
<11.2 <1.1
<26.4 <1.2
<18.5 <1.4
10.5 1.6
<9.1 <2.1
<11.2 <1.1
<26.4 <1.2
<18.5 <1.4
<10.5 <1.6
330.6 77.8
826.4 78.7
1690.9 77.1
914.3 66.9
263.6 41.0
425.1
1049.5
2192.6
1366.6
643.1
aNote: Run 4 at the midpoint was considered invalid due to water droplet
carryover.
bThe sulfidic nickel is a combination of nickel sulfide and nickel
subsulfide.
-------
TABLE 4-13. PCDD/PCDF EMISSIONS SUMMARY FOR MIDPOINT
AND OUTLET LOCATIONS
Concentration (ng/ds cm1)
Isomer
OUT-MM5-7A
MID-MM5-7A
OUT-MM5-7C
MID-Mi
Total MCDD
4.08
16.7
NDb 0.
IS
Total DCDD
2.17
8.82
26.4
32.7
Total TriCDD
4.64
26.6
0.86
0.97
2378-TCDD
ND
ND
ND
ND
Other TCDD
1.14
7.02
0.15
0.14
12378—PeCDD
ND
ND
ND
ND
Other PeCDD
0.05
0.22
ND
ND
123478-HxCDD
ND
ND
ND
ND
123678-HxCDD
ND
ND
ND
ND
123789-HxCDD
0.03
ND
ND
ND
Other HxCDD
0.13
0.48
ND
0.04
1234678-HpCDD
0.29
1.73
ND
ND
Other HpCDD
0.25
1.50
0.05
ND
OCDD
1.35
9.24
0.48
1.45
Total CDD
14.1
72.3
27.9
35.5
Total Tetra-

Octa CDD
3.2
20.2
0.7
1.6
Total MCDF
23.0
299
ND
5.61
Total DCDF
29.2
186
3.54
13.0
Total TriCDF
11.5
56.1
3.76
4.34
2378-TCDF
1.39
7.76
0.28
1.12
Other TCDF
.55
28.9
0.10
3.19
12378—PeCDF
0.25
1.69
0.03
0.01
23478-PeCDF
1.17
7.25
0.12
0.44
Other PeCDF
.62
27.1
0.58
1.87
123478-HxCDF
0.26
1.79
0.02
ND
123678—HxCDF
0.09
0.38
ND
0.04
234678-HxCDF
0.19
1.14
ND
0.06
123789-HxCDF
ND
ND
ND
ND
Other HxCDF
0.51
3.12
0.04
0.17
1234678-HpCDF
0.11
ND
0.03
0.06
1234789-HpCDF
0.01
ND
ND
ND
Other HpCDF
0.08
0.60
0.01
0.02
OCDF
0.06
1.67
ND
ND
Total CDF 76.1 623 9.4 30.0
Total Tetra-
Octa CDD 12.4 81.9 2.1 7.1
Total CDD/CDF
Total Tetra-
Octa CDD/CDF
* = 68 Deg. F and 29.92 inches Hg.
"ND = Reported as not detected or estimated maximum possible concentration;
both expressed as zero (0) in calculating totals and averages.
90.2
15.6
696
102
37.3
2.8
65.5
8.7
4-28
-------
TABLE 4-14. SEMIVOLATILE ORGANIC EMISSIONS SUMMARY FOR OUTLET
AND MIDPOINT LOCATIONS
Concentration (pg/dscm*)
Analyte
Phenol
bis(2-Chloroethy1)ether
2-Chlorophenol
1.3-Dichlorobenzene
1.4-Dichlorobenzene
Benzyl alcohol
1,2-Dichlorobenzene
2-Methylphenol
bis(2-Chloroisopropyl)ether
4-Methylphenol
N-Nitroso-di-n-propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2,4-Dimethylphenol
Benzoic acid
bis(2-Chloroethoxy)methane
2,4-Dichlorophenol
1.2.4-Trichlorobenzene
Naphthalene
4-Chloroaniline
Hexachlorobutadiene
4-Chloro-3-methylphenol
2-Methylnaphthalene
Hexachlorocyclopentadiene
2,4,6-Trichlorophenol
2.4.5-Trichlorophenol
2-Chloronaphthalene
2-Nitroaniline
Dimethylphthalate
Acenaphthylene
3-Nitroaniline
Acenaphthene
2,4-Dinitrophenol
4-Nitrophenol
Dibenzofuran
2,4-Dinitrotoluene
2,6-Dinitrotoluene
D iethylphthalate
4-Chlorophenyl-phenylether
OUT-MM5-7A
MID—MM5-7
OUT-MM5-7C
MID-MM5-7
NDb
ND
176
162
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
30.8
33.4
ND
ND
800
1120
4100
3930
25.6
26.7
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
21.2
20.6
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
196
284
43.1
76.4
ND
ND
ND
ND
2850
3220
5090
4240
ND
ND
ND
ND
ND
ND
ND
ND
699
768
ND
ND
976
864
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
43.4
45.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
97.4
1440
45.2
44.7
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
(Continued)
4-29
-------
TABLE 4-14. (Continued)
Concentration (/ig/dscm*)
Analyte OUT-MM5-7A MID-MM5-7 OUT-MM5-7C MID-MM5-7C
Fluorene
ND
ND
ND
ND
4-Nitroaniline
ND
ND
ND
ND
4,6-Dinitro-2-methylphenol
ND
ND
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
ND
Phenanthrene
44.9
33.4
13.7
ND
Anthracene
ND
ND
ND
ND
Di-n-butylphthalate
ND
ND
ND
ND
Fluoranthene
ND
13.3
ND
ND
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-Ethylhexyl)phthalate
29.2
26.1
ND
71.6'
Di-n-octylphthalate
ND
ND
ND
ND
Benzo(b)£luoranthene
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
D ibenz(a,h)anthracene
ND
ND
ND
ND
Benzo(g,h,i)perylene
ND
ND
ND
ND
• 68 Deg. f — 29.92 inches Hg.
"ND = Reported as not detected or estimated values; both expressed as zero (0)
in calculating totals and averages.
cLikely the result of sample contamination.
4-30
-------
both normal and improved incinerator operations. The concentrations and number of
the semivolatile compounds detected were t ically less under the improved combustion
conditions. For the normal combustion conditions, eleven semivolatile compounds were
detected for both runs: 1,4-dichlorobenzene, benzyl alcohol, 1,2-dichlorobenzene,
2-nitrophenol, benzoic acid, 1,2,4-trichlorobenzene, naphthalene, 2-methylnaphthalene,
dibenzofuran, phenanthrene, and bis(2-ethylhexyl)phthalate. For the improved
combustion conditions five semivolatile compounds were detected for both sample runs:
phenol, benzyl alcohol, 4-methylphenol, benzoic acid, and 4-nitrophenol.
Bis(2-ethylhexyl)phthalate was found in the sample blank and the sample results are
likely a result of sample contamination.
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 outlet of the wet ESP. Three one-
hour runs were conducted under normal incinerator operating conditions using the
volatile organic sampling train (VOST). Each VOST sampling run utilized four pairs of
Tenax/Tenax-charcoal cartridges which were exposed to approximately 20 L of flue gas
each.
Runs 7-O-V-l, 7-0-V-2, and 7-0-V-3 contained benzene and toluene at levels
which gave saturated spectra. A secondary ion of each was used for quantitation in
order to better estimate the true amount of these compounds. Benzene was quantitated
on the m/z = 50 ion. Toluene was quatitated on the m/z = 65 ion. The calibration
data for these secondary ions is included with the initial calibration data for the analysis.
All samples, except for field blanks, contained on or more analytes at levels high than
the 0.1 to 1.0 (Lg range of the analysis. Benzene and toluene as noted in Table 4-15
exceeded 1.0 /ig and are considered estimated, not absolute, values.
The concentration of the volatile organics in the flue gas are presented in Table
4-15. Two of the target compounds were below the minimum detection limit during all
three test runs: 1,2-dichloroethane and carbon tetrachloride. Vinyl chloride was
4-31
-------
TABLE 4-15. VOLATILE ORGANICS EMISSIONS SUMMARY
FOR OUTLET LOCATION
Concentration (/ig/dscma)
Analyte
H
1
>
1
0
1
t-<
7-0-V-2
7—0—V-3
Average
Acrylonitrile
1400
1110
670
1060
Vinyl Chloride
ND13
143
55.7
66.2
Methylene Chloride
84.2
16.1
14.7
38.3
Chloroform
24.0
23.8
24.4
24.1
1,2-Dichloroethane
ND
ND
ND
ND
1,1,1-Trichloroethane
23 .4
22.2
6.9
17.5
Carbon Tetrachloride
ND
ND
ND
ND
Trichloroethene
22.4
27.5
23.9
24.6
Benzenec
10400
5090
3670
6390
Tetrachloroethene
21.0
33.8
32.1
29.0
Toluenec
5940
3720
2590
4080
Chlorobenzene
34.6
79.8
52.1
55.5
Ethylbenzene
137
107
57.1
100
1 = 68 Deg. F and 29.92 inches Hg
bND = Reported as not detected or estimated values; both
expressed as zero (0) in calculating totals and averages.
cBenzene and Toluene should be considered as estimated amounts
since they saturated the detector on the primary ion and had to
be read on the secondary ion.
4-32
-------
measured in only two of the tube pairs. The detection limits of these compounds are
shown in the detailed run data which is presented in the Volume IX: Site 9 Draft
Report, Appendices.
The other ten target compounds were detected for all three test runs and
averaged: acrylonitrile - 1060 ug/dscm, methylene chloride - 383 ug/dscm, chloroform -
24.1 ug/dscm, 1,1,1-trichloroethane - 17.5 ug/dscm, trichloroethene - 24.6 ug/dscm,
benzene - 6390 ug/dscm, tetrachloroethene - 29.0 ug/dscm, toluene - 4080 ug/dscm,
chlorobenzene 55.5 ug/dscm, and ethylbenzene -100 ug/dscm.
4.7 CONTINUOUS EMISSION MONITORING RESULTS
Continuous emission monitoring (CEM) was performed at the inlet and outlet
sampling locations at Site 9. The inlet CEM systems (CEMs) monitored oxygen (02),
carbon dioxide (C02), sulfur dioxide (S02), and oxides of nitrogen (NOJ. The outlet
CEMSs monitored oxygen (02), carbon dioxide (C02), carbon monoxide (CO), and total
hydrocarbons (THC). The CEMs 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 were presented in Table 4-2. The one-minute averages for each
compound for all the runs are included in Appendix E of Volume IX: Site 9 Draft
Report, Appendices. To provide an indication of how the monitored emissions changed
with time, the 15-minute averages are presented in Table 4-16. The indicated time (i.e.,
12:30) is the time at the end of the 15-min average. Runs 3, 4, and 5 represent normal
furnace combustion conditions. Runs 9, 10, 11, 12, and 13 represent improved furnace
combustion conditions.
EPA is evaluating CO and THC monitoring as a surrogate indicator of organic
emissions. The average CO concentration from each run was plotted versus the THC
concentration from each run. The correlation was good as shown in Figure 4-1, with a
correlation factor of r = 0.93.
4-33
-------
TABLE 4-16. SUMMARY OF INLET AND OUTLET CEM RESULTS
(15-min averages)

Inlet
Location

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

Run 2 -
May 30,
1990

12:30
16.45
3.03
107.5
107.6
17.57
_a
1301
59.6
12:45
13.25
5.28
118.5
137.9
17.65
-
835
32.4
13:00
5.11
12.21
603.8
132.7
12.94
-
1155
483.7
13:15
13.89
5.45
211.8
156.9
15.45
-
610
30.9
13:30
12.57
6.21
243.6
132.0
14.60
-
601
18.8
13:45
13.54
5.62
237.9
117.5
15.24
-
737
21.6
14:00
13.16
5.96
274.4
118.0
15.18
-
911
27.8
14:15
15.51
4.00
187.5
126.4
16.83
-
1259
54.2
14:30
14.32
3.82
198.6
125.5
16.54
-
1505
62.8
14:45
12.74
5.39
123.1
152.5
14.88
—
1532
71.0

Run 3 -
June 2,
1990

18:45
11.38
8.25
359.1
160.1
13.53
—
559
15.5
19:00
15.17
4.33
229.0
140.9
16.47
-
1072
31.4
19:15
16.11
4.04
158.3
112.8
17.09
-
1373
58.8
19:30
16.85
3.18
—.b
—
15.83
-
1073
36.9
19:45
13.11
5.97
259.0
120.9
14.92
-
904
34.1
20:00
10.83
8.01
419.2
121.4
13.24
-
799
23.6
20:15
14.78
4.63
198.3
116.9
16.10
-
767
23.6
20:30
15.54
3.82
159.4
110.0
16.73
-
1202
47.1
20:45
13.98
5.14
234.0
122.9
15.66
-
1062
40.7
21:00
12.65
6.31
298.1
122.1
14.68
-
904
32.0
21:15
13.32
5.83
284.1
123.1
15.05
-
869
25.3
21.30
15.21
4.18
203.8
120.4
16.47
-
1237
53.0
21:45
15.94
3.61
171.4
111.3
16.96
—
1296
60.9

Run 4 -
June 4,
1990
12:30
9.28
8.76
394.2
192.6
12.55
5.90
1875
287.0
12:45
11.15
7.71
372.3
252.9
13.28
5.76
1175
135.6
13: 00
17.42
2.27
86.7
113.7
18.12
1.79
1333
83.8
13:15
16.92
2.52
68.8
94.6
17.7
1.93
1184
92.7
(Continued)
4-34
-------
TABLE 4-16. (Continued)

Inlet
Location

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

Run 5 -
June 3,
1990

15:00
16.21
3.11
81.0
116.4
17.14
_a
1616
104.4
15:15
16.50
2.65
43.3
89.6
17.52
-
1382
120.4
15:30
8.64
8.68
303.9
171.4
12.25
-
1844
466.0
15:45
9.01
9.19
450.1
225.7
11.99
-
1662
455.5
16:00
12.15
6.44
249.2
185.9
14.40
-
1399
54.6
16:15
11.83
6.81
315.5
184.5
14.00
-
1615
81.5
16:30
10.20
8.09
390.6
183.4
12.82
-
1866
159.4
It :45
7.76
10.03
492.9
220.1
11.32
-
1876
234.9
17:00
11.86
7.12
367.9
242.8
14.00
—
1194
45.0
Run 8 - June 5, 1990
12:15
10.03
8.15
282.1
225.3
8.91°
5.98
314
7.3
12:30
10.76
7.48
248.2
228.4
10.08
5.70
326
7.8
12:45
11.39
6.91
215.3
213.1
10.70
5.33
397
9.7
13:00
10.26
7.86
249.6
212.0
9.19
5.88
343
9.1
13:15
9.86
8.13
274.1
202.4
9.56
5.95
338
8.4
13:30
9.81
8.15
275.1
202.2
9.74
5.89
328
7.8
13:45
9.31
8.59
299.1
206.5
9.39
6.18
280
6.7
14:00
9.74
8.27
279.9
218.9
9.67
6.00
248
5.8
14:15
10.56
7.58
246.5
219.1
10.49
5.61
303
7.0

Run 9 -
June 5,
1990

19:00
10.60
7.67
246.0
215.3
10.06°
5.73
347
7.0
19:15
10.46
7.81
260.5
212.5
9.40
5.87
323
6.8
19:30
10.63
7.63
240.0
194.8
8.86
5.97
300
6.8
19:45
10.82
7.57
216.8
167.6
9.22
5.92
286
6.4
20:00
11.76
7.35
3.2
1.7
10.09
5.74
314
6.2
20:15
12.80
7.26
2.1
1.5
9.18
5.93
291
6.1
20:30
10.94
7.75
200.2
205.7
9.59
5.80
286
6.1
20:45
10.16
8.10
275.0
225.4
9.50
5.96
274
5.9

Run 10 -
June 6,
1990

12:30
10.65
7.62
266.2
198.3
6.34c
5.69
352
6.9
12:45
11.75
6.62
227.5
183.5
8.36
5.09
476
8.8
13:00
10.38
7.78
268.4
201.0
7.46
5.82
377
7.2
13:15
10.77
7.46
252.6
209.3
7.35
5.69
345
6.3
13:30
10.06
8.00
271.5
214.9
6.51
6.03
296
5.8
(Continued)
4-35
-------
TABLE 4-16. (Continued)

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

Run 11 -
June 6,
1990

15:45
11.04
7.17
276.8
204.4
6.96c
5.52
433
8.6
16:00
11.12
7.07
271.6
207.6
7.42
5.45
412
8.3
16:15
11.17
7.03
269.4
207.8
7.60
5.42
410
8.2
16:30
11.01
7.18
277.3
214.7
7.60
5.52
380
7.7
16:45
11.11
7.09
274.4
204.7
7.04
5.42
418
8.2
17:00
10.76
7.42
283.5
213 .9
6.72
5.61
366
7.5
17:15
9.89
8.23
327.1
223.4
5.53
6.20
284
6.3
17:30
10.66
7.53
292.4
213.8
7.25
5.72
356
6.8
17:45
10.34
7.84
307.5
216.5
6.30
5.93
352
6.8

Run 12 -
June 30,
1990

10:00
10.54
7.75
245.7
228.6
9.53c
5.59
323
5.7
10:15
9.85
8.30
271.4
215.0
9.38
5.88
376
6.5
10:30
9.40
8.71
297.9
240.7
8.23
6.23
263
5.3
10:45
10.40
7.82
242.6
233.4
9.69
5.59
324
5.8
11:00
9.81
8.36
268.6
215.5
8.69
5.97
291
5.5
11:15
10.12
8.09
253.1
226.8
9.34
5.79
310
5.7
11:30
9.74
8.41
268.9
220.3
8.91
6.00
290
5.5
11:45
10.38
7.82
245.4
225.7
9.38
5.67
320
6.4
12:00
10.00
8.17
260.4
242.1
9.46
5.85
323
5.8
12:15
9.93
8.24
263.4
245.7
12.10
5.90
307
5.5

Run 13 -
June 7,
1990

16:00
9.37
8.72
318.7
175.6
8.74c
6.14
267
5.4
16:15
9.65
8.50
308.4
176.0
9.18
5.97
269
5.2
16:30
9.59
8.54
320.0
171.6
9.56
5.97
279
5.2
16:45
9.43
8.70
326.8
182.2
8.21
6.15
242
4.9
17:00
9.75
8.42
309.4
184.2
8.17
5.96
246
4.9
17.15
9.61
8.53
325.7
180.6
8.60
6.00
242
4.8
17:30
9.70
8.47
324.2
179.6
9.28
5.93
249
4.8
17:45
9.69
8.51
332.9
181.7
8.65
6.03
237
4.8
18:00
9.62
8.56
340.2
181.5
9.24
6.04
247
5.0
aC02 Monitor not installed for these runs.
bFlow rate problem through the sample system.
cThe percentage of oxygen emissions for Runs 8, 9, 10, 11, 12 and
13 is from hearth. The oxygen monitor probe was moved to a top
hearth location to help control furnace for improved combustion
conditions.
4-36
-------
t
-4
150
140
130
120
110
100
90
E
Q.
Q. 80
Q 70
60
50
40
30
20
10
0
-10
-

Run 5 ¦
-

Run 4 ¦
-
r = 0.93

-
Run 3 «r
Run 2 ¦
" Runs 8,9,10,11^
¦ 3^
and 13

V
1 1 1 1 1 1 1 1 1 1 1 1 1
0.8
(Thousands)
0.2 0.4 0.6
CO, ppm
Figure 4-1. Hydrocarbon emissions versus carbon monoxide emissions.
1.2
1.4
-------
4.8 CONCLUSIONS FROM SITE 9 TEST
From the perspective of methods development and data quality, the conclusions
that may be drawn from the Site 9 testing are:
1. The ratio of sulfidic nickel to total nickel in the emissions from Site 9 is
extremely low, with the reduced nickel species being measured at less than
detection limit (about 1 to 2% of the total nickel).
2. The ratio of hexavalent chromium to total chromium was significantly
higher than had been anticipated. The facility was selected because it does
not use lime for sludge conditioning. The high hexavalent chromium to
total chromium ratio was discussed with facility representatives and it was
determined that some of the sludge that is trucked in contains lime. Also
some lime is used at the facility. The sludge solids were determined to
contain 2 to 3% lime by weight. This percentage of lime in less than
would be used for sludge conditioning, but it is higher than would be
anticipated in a facility that did not use lime for sludge conditioning. This
may be the reason that for the higher than anticipated ratio.
3. Compared to Site 2, a multiple hearth incinerator where seven semi-
volatile compounds, phenol, naphthalene, bis(2-ethylhexyl)phthalate, 1,2,-
dichlorobenzene, 1,3,-dichlorobenzene, 1,4,-dichlorobenzene, and 2-
nitrophenol were detected, only two compounds, benzyl alcohol and
benzoic acid were found under normal and improved combustion
conditions at Site 9. Several additional compounds were found in the
emissions for the normal or improved combustion conditions at Site 9;
these compounds were 1,4-dichlorobenzene, 1,2-dichlorobenzene,
2-nitrophenol, 1,2,4-Trichlorobenzene, naphthalene, 2-methylnaphthalene,
dibenzofuran, phenanthrene, bis(2-ethylhexyl)phthalate, phenol,
4-methylphenol, and 4-nitrophenol.
4-38
-------
4. The volatile organic compounds detected in the Site 9 multiple hearth
incinerator emissions were similar to the compounds reported for Sites 1,
2, and 4 (other multiple hearth incinerator tested). Carbon tetrachloride,
reported in the emissions at the other three sites, were not found in the
emissions from Site 9.
4-39
-------
5.0 SAMPLING LOCATIONS AND PROCEDURES
Sampling procedures used during the Site 9 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 wet ESP (midpoint), and (3)
the outlet of the 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 Figure 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
-------
Outlet Stack
Shall
Cooling Air
Midpoint
Sampling Location
Outlet Stack
Sampling Location
Dewatered
Sludge '
Scrubber
Water Inlet
Wet
ESP
Inlet lo Control,,
System Sampling
Location
ID.
Fan
Venturl <
Scrubber
Separator/
Subcooler
Flooded
Elbow
Bottom Ash
Figure 5-1. Process diagram with sampling locations.
-------
Lfl
i
OJ
r Sample Port
o
To Venturi
I
6" Sample Port
o
T
4*
INCINERATOR
Figure 5-2. Inlet sampling location.
-------
program was to determine the ratios of nickel subsulfide to total nickel and hexavalent
chromium to total chromium in the emissions, rather than the absolute concentration of
these species, and four samples were collected simultaneously at the same point, the
sampling location was considered adequate for this test
A 6-in sampling port was installed at this location for the manual testing and a
1-in sampling 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
concentrations for this location.
5.1.2 Midpoint
The midpoint sampling location is shown in Figure 5-1 (Point 3) and Figure 5-3.
The midpoint emissions were typical of the facility's atmospheric discharge emissions
prior to the installation of the wet ESP. The flue gas temperature at this point is
typically about 100°F (38°C). Sample Point 3 was located in the horizontal, circular stack
which had one 4-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.
5.13 Outlet of the Wet ESP
The sampling location at the outlet of the wet ESP is shown in Figure 5-1 (Point
2) 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°C). Sample Point 2 was located in a vertical, circular
5-4
-------
44* DIAMETER
BUTTERFLY
VALVE
TO
WET
ESP
WALL
FROM
SCRUBBER
SYSTEM
Figure 5-3. Midpoint sampling location.
5-5
-------
41*
n
FLOW
N
*
41"
DIAMETER
1824"
2 AXES
12 POINTS/AXIS
24 TOTAL POINTS
O
A
•V
swrnnN N-N

TWO
36* * SAMPLING
N PORTS
196.3"
SILENCER
FROM
WET ESP
Figure 5-4. ESP outlet sampling location.
5-6
-------
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.
52 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." 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
IX: Site 9 Draft 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 first
two impingers and KMn04 in the third impinger;
• 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.
For the inlet sampling system, the nozzle and probe liner were made of quartz
glass and the filter holder was made of borosilicate glass with a Teflon filter support.
For the midpoint and outlet sampling systems, the nozzle, probe liner, and filter holder
were made of borosilicate glass. At both midpoint and outlet, Teflon frits were used to
support the filters. The probes and filter holders were heated to 248°F _+ 25°F to prevent
5-7
-------
All glut lampl* exposed surface lo here.
(Except when Tellon lillei support Is used ]
Thermometer
Glass
Filler
Holdef
Thermocouple ch#rk
"T Valve
Glass
Piobe
Implnoers with
Absorbing Solutions
Ice Bath
Pilot
Manomater
i
00
Silica Gal
Empty (Optional Knockout)
6% HNO a /IOX Ho O
4HKMlO 4/l0KH2SO4
Vacuum
Una —
Orlllce
Main
Valve
Dry Gas
Meter ,
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% HNOj 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
3
4
AR
PR-HNO,
BH
KMnO,
Acetone rinse of probe liner, nozzle, and front
half of filter housing
0.1 N nitric acid rinse of probe liner, nozzle,
and front half of filter housing
Filter
HN03/H202 impinger contents and 0.1 N nitric
acid rinse of impingers 1, 2, 3, connecting
glassware, and back half of filter housing
KMn04 impinger contents, and KMnO« and
HC1 rinse of impingers 4, 5, and connecting
glassware
5-9
-------
u«
I
~—»
o
Probe Liner
and Nozzle
acetone
I
Brush line
with non-
metal lie
brush and
rinse with
acetone
Check liner
to see if
particulate
removed: if
not repeat
step above
Front Half of
Filter Housing
Filter
Rinse with trusti with
nonmetallic
brush and
rinse with
acetone
Rinse three
times with
0.1 N
nitric acid
Rinse three
times with
0.1 N
nitric acid
~r
<3>*
Carefully
remove filter
from support
with Teflon-
coated tweezer
and place in
petri dish
Brush loose
particulate
onto filter
Seal petri
dish with
tape
AR F
(2) (1)
Filter Support
and Back Half
of Filter
Housing
Rinse three
times with
0.1 H
nitric acid
1st Infringer
(Empty at
beginning
of test)
Empty
contents
into
container
Rinse three
times with
0.1 N
nitric acid
¦H
(O
2nd ( 3rd
Infringers
(HN03/H202)
Empty
contents
into
container
Rinse three
times with
0.1 H
nitric acid
4th I 5th
Infringers
(Acidified
KMn04)
Last Implnger

Measure
infringer
contents

Empty
contents
into
container
Rinse three
times with
permanganate
reagent
Remove any
residue with
8 N HCl sol'n
Ueigt
mois
for
ture

Disci
ird
KMnO,
(5)
SF
(6)
* Number in parentheses indicates container number.
Figure 5-6. Sample recovery procedures for multiple metals train.
-------
moisture condensation. High purity quartz fiber filters without organic binder and with a
99.95% collection efficiency for 03 micron dioctyl phthalate (DOP) smoke particles were
used.
The samples were collected over a 30- or 45-min period at the inlet sampling
location 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 2-hr sampling period. Sampling for total metals was
conducted simultaneously with the nickel sampling. Four sampling trains were operated
simultaneously (quadruplicate trains). One of the four samples was intended for total
metals analysis, two for nickel speciation, and the fourth was collected as a backup in the
event of failure of one of the other three trains.
Total metals samples were analyzed by Research Triangle Institute (RTT) using
inductively-coupled argon plasma spectroscopy and atomic absorption spectroscopy for
total Cr, Ni, As, Pb, Cd, and Be. Theses 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 IX: Site 9 Draft 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;
• 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.
5-11
-------
Glatt
Filter Holdar
Tharmocoupla
Glai* Nozzla ,
Olaia Proba
RavauaTypaJ
Pilot Tuba
Tharmocoupla Chack
Valva
Haalad Araa
Implngara
Vacuum
Una
Tnarmocouptai
Figure 5-7. Schematic of nickel/nickel subsulfide sampling train.
-------
TABLE 5-3. NICKEL/NICKEL SUBSULFEDE 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
SUBSULFTDE TRAIN
Component
Code
Item
1
AR
Acetone rinses of probe liner, nozzle and front

half of filter housing
2
F
Filter
One of three samples sent to Dr. Zatka were placed in a desiccator and stored under a
dry nitrogen atmosphere. The remaining two samples were archived in a dry-cool area
for possible further analysis.
5-13
-------
Filter and
Cyclone
Particulate
Natter
(Fraction F)
Acetone
Front Half
Rinse
(Fraction AS)
0.1 N Nitric
Front Half
Rinse
(Oiscarded)
Back Half
Coaponents
(Discarded)
Label SwapIe
Archive in cool
dry area
Coafcine rinses in
staple container
Recover silica
gel, weigh, and
discard
Recover filter
and cyclone sample
dry with brush
For Zatka sample,
place in vacuus
filtration device*
Filter acetone
rinses through
particulate
Rinse back half
c exponents with
0.1 N Nitric ai
discard
voli
Recover inpinger
solution. Measure
¦w 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 wider
dry nitrogen until
analysis
Brush and rinse
nozzle, probe,
cyclone, and
front half of
filter holder 3
lines with acetone
Brush and rinse
nozzle, probe,
cyclone, and
front half of
filter holder 3
tines with 0.1 N
nitric solution
and discard
* Note: Inlet samples were not acetone rinsed.
Figure 5-8. Schematic of sample recovery procedures for nickel train.
5-14
-------
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.
Three nickel speciation sampling trains were operated simultaneously with one
multiple metal train under both operating conditions. Of three samples collected at each
the inlet and midpoint sampling points, one was analyzed by Dr. Vladimir Zatka and the
remaining two samples were archived in a cool dry location for possible future analysis.
The inlet location samples were recovered and stored dry because of the large volume of
sample. For the midpoint samples, the acetone probe rinse was vacuum filtered through
the filter. The acetone filtrate was archived. The outlet location samples were not
analyzed because of the extremely low amount of sample collected. 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 test. The dry nitrogen atmosphere was used
because past experience has shown that oxidation of nickel compounds can occur over a
several week period.
5.2.3 Chromium and Hexavalent Chromium (Recirculating Train)
Sampling for hexavalent and total chromium (Cr+
-------
GLASS

N02ZLE
i
o\
TEFLON
T-UNON
1
METHOD 5-TYPE
METERBOX
RECIRCULATING
LOUD
IMPINGER
TEFLON MP NGERS
TEFLON
LINES
PERISTALTIC
PUMP
150 ml
O.INKOH
SLICA :
75 ml
0.1 N KOH
75 ml
0.1 N KOH
EMPTY
WATER AND ICE BATH
Figure 5-9. Schematic of recirculating reagent impinger train for hexavalent chromium.
-------
• The train does not have a filter section;
• the reagents are continuously recirculated from the first impinger back to
the nozzle to provide a flow of reagents through the probe,and thus
preventing hexavalent chromium in the probe drying out and possibly
converting to another valence state;
• 0.1 N KOH replaces water in the impingers;
• the entire surface exposed to sample is constructed of Teflon and/or glass;
• the Teflon and/or glass components are cleaned according to the
procedure in Table 5-5; and
• the sample is recovered as shown in Table 5-6 and Figure 5-10.
The quadruplicate sampling systems were operated isokinetically during the 2-hr
runs conducted at the midpoint and outlet locations.
All the sampling trains were charged using a common stock of impinger solution
that was spiked with radioactively-labelled chromium to serve as a recovery standard for
conversion of hexavalent chromium in the samples. To verify the spike concentration,
and as a check for contamination, control samples of the stock solution were analyzed
with the field samples.
Immediately after sample recovery, each combined impinger solution/rinse sample
was pressure filtered through a separate 0.45 micron Teflon filter. The filtrates were
stored and transported cold to Entropy Laboratory. 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+
-------
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+
-------
Ueigh
Discard
Silica Gel
Filter
Filtrate
Filter Solution through
0.45 jm Teflon Filter
01 H20 Rinse All Components and
Caffeine with Inpinger Solutions
Recover Teflon Inpingers Together and
Measure Volune
Nitrogen Purge of Train
Nozzle, Aspirator, Recirculation and
Saaple Lines, Teflon Knockout Iapinger,
Teflon I^pingers containing 0.1 N KOH
Container 3 Container 1 Container 4
Component F Component IMP Conponent SG
Nitric Acid Rinse All Components
Recover contents of nitric inpinger
Container 2
Conponent NR
Figure 5-10. Sample recovery scheme for hexavalent chromium recirculating impinger
train.
5-19
-------
solution of 1 N KOH. A diagram of the sampling train is shown in Figure 5-11. The
procedure used followed EPA Method 5 with the following modifications:
• The sampling 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 Organics and PCDD/PCDF
Sampling for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated
dibenzofurans (PCDFs), and other semivolatile organics was conducted at Points 2 and 3
(see Figure 5-1) at the outlet and midpoint sampling locations, respectively. Three 2-hr
runs were conducted employing the procedures and 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 DC: Site 9 Draft 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 leaving the probe, the sample
gas passed through a heated glass fiber filter (Reeve Angel 934 AH), a water-cooled
5-20
-------
Quartz-Glass
Probe Uner/
Button-Hook Nozzle
Peristaltic
1/8" Tenon Una
(Reaching to rear ol
bullon-hook nozzle)
Temperature
Sensor
Thermometer
Im ptngers
Reverse-Type
Pilot Tube
Check
Valve
Phot
Manometer
or
Dillerenllal
Pressure
Gauge(s)
Empty *~ Silica ~
Gel
tOOmL
2-Liter
Implnger
Ice Bath
Bypass
Valve
Vacuum
Gauge
Vacuum
Line
n
Orifice
Main
Valve
Dry Gas
Meier
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 capped until field assembly.
TABLE 5-8. SAMPLE RECOVERY COMPONENTS FOR Cr/Cr+< IMPINGER
SAMPLING TRAIN
Component Code Item
1
IMP
IN KOH impinger catch and rinse of impinger

train
2
NR
0.1 N nitric acid rinse of probe liner, nozzle,

and impinger train
3
F
Filter*
The combined impinger catch/DI water rinse sample was pressure-filtered on-site
through a 0.45 micron Teflon filter immediately after sample recovery. The impinger
catch/DI water rinse samples were shipped to Entropy for next day analysis. After
Entropy's analysis, the impinger catch/DI rinse samples were sent to General
Engineering Laboratories for additional analysis.
5-22
-------
Filter
Label sample
Label sample
Store and ship
to laboratory
Store and ship
to laboratory
Conbine rinses in
sanple container
Conbine filtrate
in sanple
container
Rinse inpinger
train with 0.1 N
nitric acid
Recover iapinoer
contents and
filter. Rinse
inpinger train
with 0.1 N KOH
& filter sanple
through 0.45 jun
Teflon filter
Nitrogen Purge of Train
Figure 5-12. Sample recovery scheme for hexavalent chromium impinger train.
5-23
-------
Temperature
Indicator
B
Pitot tube
1.9-2.5 cm
Nozzle
Probe
Thermocouple
1.9-2.5 cm
Heated Probe
Thermocouple (behind)
Stack Wall
"5" Type
Pitot Tube
(thermocouple)^
Magnehelic Gauges
I (Cooling Water)
Thermometer
©
(Thermometer)-^
¦«-(Sorpent Trap)
To
Meter
Console

(OotWKO) Water Water
Silica Gel
Calibrated orfice•
Flow Control Valves
Thermometer
=£
*
r

Dry Ges
Meter
vacuum
Gauge
Vacuum
Magnehelic Gauges
Figure 5-13. MM5 train for sampling semivolatile organics and PCDD/PCDF.
5-24
-------
condenser, and then through a sorbent module containing approximately 25 g of XAD-2
resin. The XAD module was followed by a series of five 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. Tfc
first and fourth impingers were empty, the second and third contained 100 ml of distille _
water, and the fifth contained a known weight of silica gel. The impingers were weighed
prior to assembling the sampling train to permit gravimetric moisture determination. All
sample-exposed surfaces within the train were made of 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
sampling 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.
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.
5-25
-------
TABLE 5-9. SEMTVOLATTLE 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.
8. Leave cleaned glassware capped until field assembly.
'Step 4 not used for probe lines or non-glass (e.g., Teflon, nylon) components
which cannot withstand 450°F.
TABLE 5-10. SAMPLE RECOVERY COMPONENTS FOR SEMTVOLATTLE
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 H20 rinses
5
SM
XAD-2 resin
6
TR
Final toluene rinse of train
7
SG
Silica gel
5-26
-------
NOZZLE, CYCLONE AND
ni FILTER HOUSING'
PROBE LINEn *

BRUSH/RINSE
WITH ACETONE
(3.)
BRUSHWNS6 WITH
HEXANE
(3.)
5UAL. NSPECTION
AnACH 250 ml
FLASK TO BALL
JOINT
BRUSH/RINSE
WITH ACETONE
0«)
EMPTY FLASK
BRUSH/RINSE WITH
HEXANE
(3>)
EMPTY FLASK
FILTER
REMOVE WITH
TWEEZERS 10
PRECLEANED
ALUMINUM FOIL
BRUSH LOOSE
PARTICULATE
ONTO FILTER
TRANSPORT N
ORIGINAL GLASS
PETRI DISH
XAD
MODULE
REMOVE
AND CAP
CONDENSER. FILTER SUPPORTS.
BH FILTER HOUSING*
MPWGERS SILICA GEL
RINSE
WITH ACETONE
<3«)
niNSE WITH
HEXANE
<3«)
MEASURE
VOLUME
GAM
EMPTY CONTENTS
INTO SAMPLE
CONTAINER
RINSE WTH
Dl WATER
(3.)
WEIGH
DISCARD
WRAP THE
MODULE N
ALUMINUM FOL
VISUAL NSPECTCN
PR
SM
CH
* Fln«l lokxiw rinsa (3>). . , .
Figure 5-14. Semivolatile organics tram sample recovery scheme.
-------
52.6 Volatile Organic Sampling Train CVOST>
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
IX: Site 9 Draft Emission Test Report, Appendices.
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 grams 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 1 min 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-checking system as required;
• capping the VOST cartridges;
5-28
-------
MEAT
SAMPLE
I'llODE
3 • WAY
VALVE
ICE WATER
CONDENSER
L/l
i
N>
VO
ICE WATER
CONDENSER
TENAX / CHARCOAL
CARTRIDGE
0
VALVE
DRY
GAS METER
SILICA GEl
DRYING
TUBE
ROTAMETER
TENAX
CARTRIDGE
CONDENSING
IMPINGER
Figure 5-15. Schematic of volatile organic sampling train.
-------
• placing the cartridges in their original glass culture tubes with glass wool to
absorb shock;
• measuring the volume of the condensate impinger with a precleaned
graduated cylinder (after final pair of tubes collected for the run);
• transferring the measured condensate volumes to 40 ml VOA vials and
diluting the volume with DI water to decrease headspace and reduce the
possibility of revolatilization of the compounds; and
• reducing reactivity by storing all samples at 4°C.
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.
The samples collected during each VOST run consisted of two pairs of sorbent
tube (Tenax cartridge, Tenax/charcoal cartridge), and the condensate (captured by the
midget impinger, archived).
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, CO,, O* 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, CO,, O* NO„ SO* and THC are discussed in the following
sections.
5-30
-------
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
to 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
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
electrochemical 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.
5.2.7.4 Nitrogen Oxides (NOx) Analysis - TECO Model 10 analyzers were used for NO,
5-31
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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 NO,
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 NOj was determined. This ratio is of interest because N02 can be effectively
removed by a venturi scrubber.
52.15 Sulfur Dioxide (SO]) Analysis - Sulfur dioxide in the flue gas was measured using
Maihak UNOR 6N analyzers. This instrument measures S02 on the basis of infrared
adsorption.
52.1.6 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
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.
5-32
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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 were obtained by traversing the 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 disturbance.
The standard flue gas flow rate at the inlet and midpoint locations were not
measured; but were 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 enters the duct between
the midpoint 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 was 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 (<_ 03% difference, absolute) reading for either 02
or C02, the appropriate absorbing solution was replaced. The S02 concentration was
well below the level at which correction of the C02 is required (5,000 ppm).
5.2.8.3 Flue Gas Moisture Determination - The moisture content of the flue gas at each
sampling location was determined using the methodology described in EPA Method 4.
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Based on this method, a known volume of particulate-free gas was pulled through a
chilled impinger train. The 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
52.9 Process Samples
Samples of sludge feed, bottom ash, and venturi and impingement tray 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-ml 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.
53 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
Frequency of
Parameter
Readings
Source of Readings
Incinerator Operatine Data

Wind Box Temperatures
60 minutes
Plant operating log
Bed Temperatures
60 minutes
Plant operating log
Freeboard Temperatures
60 minutes
Plant operating log
Heat Exchanger Inlet Temp
60 minutes
Plant operating log
Heat Exchanger Outlet Temp
60 minutes
Plant operating log
Incinerator Outlet 02
Continuous
Entropy CEMSs
Auxiliary fuel usage
As used
Plant operating log
Sludge Feed Rate
60 Minutes
Plant operating log
Sludge Feed Characteristics

Moisture (wt %)
Once per run
Entropy analysis
Volatiles (wt %)
Once per run
Entropy analysis
Heating Value
Once per run
Entropy analysis
Scrubber Svstem Operating Data

Differential Pressure (in. H20)
60 minutes
Plant operating log
Scrubber Inlet Temp (*F)
60 minutes
Plant operating log
Scrubber Outlet Temp (#F)
60 minutes
Plant operating log
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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 valency states and nickel based on family of
compounds, and (2) analysis of selected samples for arsenic, beryllium, paHminni
chromium, lead, nickel, and mercury. The sample matrices included flue gas, samples,
sludge, bottom ash, and scrubber water. The 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 reproduced in
Volume DC, Appendices.
6.1 CHROMIUM SPECIATION AND ANALYSES
Several analytical procedures were employed to speciate chromium in the samples
to determine the ratio of hexavalent chromium (Cr+<) to total chromium (Cr). Since the
hexavalent chromium analysis using a °Cr+< spike and IC/MS provided no reportable
results due sampling problems, 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
were analyzed for Cr+< using ion chromatography with a Cr+<-specific post column
reaction (IC/PCR) by Entropy and for total Cr using inductively-coupled argon plasma
emission spectroscopy (ICAP) by RTT. Entropy also performed gamma emission
counting of labeled hexavalent chromium (slCr+<) spiked into the impinger reagents to
6-1
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TABLE 6-1. SUMMARY OF ANALYTICAL METHODS
Sample Type
Parameter
Analysis Method
Flue Gas
• Total chromium, Cr+fcJ> IC/PCR, gamma counter,
ICAP/AAS, ICP/MS, XANES
• Total nickel,
nickel subsulfides'
EPA Draft Method,
ICAP/AAS, XANES
Particulates, metalsd Gravimetric, ICAP/AAS
Solids/Liquid:
Feed sludge
Scrubber water:
Venturi
Impingement/tray
Bottom ash
• Metals
• Moisture
ICAP/AAS,
ASTM D3D174, D3175, D3178,
D3179, D2361, D3177*
ICAP/AASd
ICAP/AASd
ICAP/AASd
'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 to possible 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
Filtrate
Filtrate
Acid Digest
Total Cr
Analysis
Cr and S3Cr
Analysis
by !CP/MS
IC/PCR Analysis
for Cr+6
IC/PCR Analysis
for Cr+4
Ga*M Ccxnt
of Residue
for 51Cr
GaaM Count
of Residue
for 51Cr
Filter through
0.45 Micron
Teflon filter
Filter through
0.45 Micron
Teflon-filter
1 Combination
of Residue and
HM03 Solution
for Total Cr
Preconcentrate
for 53Cr+4
Analysis by ICP/MS
Recirculatory
Sampling Train
Inpinger Sol.
and D.I. Rinse
Reci rculatory
Sampling Train
Inpinger Sol.
and D.I. Rinse
GaaM Count
of IC Fractioi
for Speciatioi
of 51Cr
Recirculatory
Sapling Train
HN03 Rinse
Recirculatory Train A
with 53Cr+6 Spike
Recirculatory Trains B, C
with 51Cr»6
Figure 6-1. Analytical protocol for quadruplicate recirculatory train hexavalent
chromium sampling at midpoint and outlet locations.
6-3
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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+< by the IC/PCR method.
To determine the ratio of the soluble nCr+3 and nCr+* 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 51 Cr spike,
the gamma emissions from the filter residue and the HNO} 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.
6.1.2 TCP Analysis for Total Chromium
Residue samples from the filtration of the alkaline impinger solution for the
recirculatory trains were analyzed with the corresponding HN03 rinses for total
chromium (see Figure 6-1). Where appropriate, aliquots of the HN03 rinses plus the
Teflon filter were first measured for gamma emissions. Then the rinse sample was
reduced to near dryness and combined with the filter residue sample, subjected to
HNOj/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 63.2, 6.33, and 6.3.4, respectively.
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6.2 NICKEL SPECIATION AND ANALYSIS
To speciate nickel compounds in samples to determine the ratio of nickel
subsulfide (NijSj) to total nickel (Ni), Dr. Vladimir Zatka employed the Nickel
Producers Environmental Research Association (NiPERA) method. Hie NiPERA
sequential leaching method determines the ratio of sulfidic nickel species, nickel
subsulfide (Ni3S2) and nickel sulfide (NiS), to total NL It is not capable of speciating
between Ni3Sj and NiS. Individual nickel phases are extracted out from the solid sample
by sequential leachings using a series of solutions with increasing oxidation strength.
Four nickel phase groups are determined:
Nickel Groups Types of Nickel
1) soluble nickel
2) sulfidic nickel
3) metallic nickel
4) oxidic nickel
water soluble nickel salts;
besides Ni3S2 and NiS, also dissolved
are arsenides NiAs and Ni„As* and
selenide NiSe;
free or alloyed with iron (ferronickel);
refractory nickel oxide;
Leaching Solution
0.1M ammonium acetate
peroxide-citrate
methanol-bromine
nitric/perchloric acid
Three sequential leachings procedures were performed. Each utilized a 47 mm
all-Teflon vacuum filter holder fitted with a regenerated cellulose filter with a 02 micron
pore size. Each leach solution was collected separately. The leached final residue and
filters were wet-ashed with nitric and perchloric acids to have the oxidic nickel phase
determined.
The three nickel subsamples were analyzed for total nickel by atomic absorption
spectroscopy (AAS). Hie AAS was calibrated with a series of seven nickel 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 sample preparation
procedure and analyzed with the field samples.
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63 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), nickel (Ni) and mercury (Hg), employed matrix-specific
preparation and digestion followed by ICAP analysis. Note: The mercwy 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
recoveiy the mercury in the precipitate. Therefore, the results for mercury in this study
are considered invalid and are not reported. 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.
6.3.1 Flue Gas Samples
Flue gas samples were analyzed for the target metals following the procedures
described in the draft method. A copy of the draft method is provided in Volume IX:
Site 9 Draft Test Report, Appendices, and an analytical flow chart is shown in Figure 6-
2. For each train, the particulate mass concentration was determined gravimetrically for
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 of the impingers was
reduced to near dryness and digested with HN03. Finally, the front and back half
digestates were combined and analyzed for As, Be, Cd, Cr, Pb, and Ni by ICP. 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,
6-6
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Container 2
HN03 Probe Rinse
(Labeled FH)
Container 1
Acetone Probe Rinse
(Labeled AR)
Container 3
Filter
(Labeled F>
Container 4 Container 5
Knockout I Peruana anate Iopingerx
KH03/HZ02 lapingers (Labeled KHnO«)

Acidify to pH2
with cone. HH03
Determine residue
weight in beaker
Solubilize reaidue
with cone. HN03
Reduce to dryneM
in a tared beaker
Determine filter
particulate weight
Reduce volim
to near
dryneM and
digest with
KN03 and H202
Acidify half
of reaeinino
sople to pH
of 2 with
conc. HIKS
Fraction 2A
Digest with cone.
HF and HN03 using
pressure relief
¦icrowave digestion
procedure
Reduce voluae to
near dryness and
digest with HF and
conc. HMOS using
aicrouave digestion
Digest with acid
at 95* for 2 hr
and analyze
for Hg by CVAAS
Fraction 3
Analyze for
As and Pto by 6FAAS
(Hot conducted)
Filter
to known voli
Fraction 1
dilute
Analyze by 1CP for
target aetata
Fraction 1A
Figure 6-4. Sample preparation and analysis scheme for multiple metals trains.
6-7
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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.
632 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 HNO}/HF digestion in a
pressure relief vessel identical to the flue gas particulate samples described above. This
digestion procedure was chosen to provide for comparison of the metals in the sludge
with the flue gas samples and the bottom ash samples (see below). The digestion
solution was analyzed by ICAP following the procedures described for the flue gas
samples and archived for possible GFAAS analysis; however, GFAAS analyses were not
required.
633 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 digestion solutions were analyzed by ICP for
all the target metals except Hg following the procedures described for the flue gas
samples.
63.4 Bottom Ash Samples
Incinerator bottom ash samples were analyzed for the target metals including Hg
after determination of the moisture content following ASTM D3174. The procedures
6-8
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used are the same as described above for the sludge samples.
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 6-3. 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-TCDF, 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 and the recoveries of these
standards were used to adjust the results. A second set of the labeled 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 values 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 specific internal standards are shown below.
PCDD/PCDF Labeled Internal Standards
BCu-23,7,8-TCDD
BCu-lA3,7,8-PeCDD
BC12-lA3,6,7,8-HxCDD
uC15-lr23»4,6,7,8-HpCDD
"Qj-OCDD
6-9
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PR CR SM F IR
Concentrate
Spike
Liquid/Liquid
Extraction wtf Me CI
Place in
Soxhlett
Extraction
v*Mea2
Extraction
w/ Toluene
Split 1:1
Split 1:1
Analyze Aliquot
for Semivoiatiies;
Archive Remaining Extract
Solids
Toluene
Rinse
Extract B
(Toluene)
ExtraaC
(Mea2)
ExtractA
(MeC^
ExnctO
(MeQ2)
ExiractE
(MeCtg /Toluene)
Acetone/Hexane Rinses of
Probe Liner, Nozzle, and
Front Half of FSter Housing
Combined with Acatone/Hexane
Rinse* of Condenser and
Back Half of FHter Housing
XAO Resin Trap
andRter
Concentrate
Hexane Exchange for
MeCfe /Toluene
ExtractG
PCDD/PCDF
Cleanup
Extract H
Analyze ASquot
for PCDDVPCDF;
Archive Remaining Extract
Figure 6-3. Extraction schematic for semivolatile organic samples.
6-10
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• uCu-W,8-TCDF
Chlorobenzene and PCB Labeled Internal Standards
• uCr 1,2,4,5 Tetrachlorobenzene
• "Cj-Hexachlorobenzene
• DCu-Pentachlorobiphenyl
• uCu-Octachlorobiphenyl
Chlnrnphenol Labeled Internal Standards
• "Cj-3,4 Dichlorophenol
• uC<-2,4,5 Trichlorophenol
• uC«-Pentachlorophenol
Polvaromatic Hydrocarbon Labeled Internal Standards
• dlO - Acenaphthene
• dlO - Anthracene
• dlO - Pyrene
• D12 - Benzo(a)Anthracene
• dl2 - Benzo(a)Pyrene
• dl4 - Didenzo(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;
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• chlorine isotope ratio of molecular ions of respective trace organic isomers
within _+ 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 were 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/CDF's (i.e., uCu-2,3,7,8-TCDD recovery was used to adjust
results for all native TCDD's and TCDF's).
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 Tenax and Tenax/charcoal backup cartridges. Two pairs of the Tenax
cartridge samples from each run were analyzed for volatile organics using the procedures
specified in Methods 5040 and 8240 of SW-846. The organic contents of each pair of
Tenax and Tenax/charcoal cartridges were thermally desorbed onto an analytical trap.
The compounds were then thermally desorbed off the trap into a 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.
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6.6 SLUDGE SAMPLE ANALYSES
Dewatered sludge samples were subjected to the following: metals analysis and
proximate and ultimate analyses. Ultimate and proximate analyses involved a
combination 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 632.
6-13
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7.0 QUALITY ASSURANCE AND QUALITY CONTROL
This section discusses the internal quality assurance and quality control (QA/QC)
program implemented for the sewage sludge incineration test program by Entropy and its
subcontractors and the QA/QC results for the Site 9 test internal program. RREL,
through its EPA Quality Assurance Contract conducted a Technical Systems review of
the field test and most of the base laboratories in the program. The objectives of and
basic activities for the QA/QC program are briefly discussed in the section below.
Summaries of the internal QC data and QA audit data are presented in Sections 7.2
through 7.3. The external Technical Systems Review is discussed Section 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 systems 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. 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 9. The QAPP described the specific EPA
methods, other standard test methods, and state-of-the-art sampling/analytical
procedures to be employed and QC activities performed.
The terms used to define the QA/QC objectives established for the test program
are defined as follows:
7-1
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(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
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, is 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 under correct normal conditions.
• 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
7-2
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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.
• 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."
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
efforts provided a mechanism to control data quality within acceptable limits and 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 for
7-3
-------
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 include: (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 surrogates, 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
122 and 7.23.
7.2.1 General Flue Gas Sampling Quality Control
For all of the manual 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 the 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 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.
7-4
-------
TABLE 7-1. PRECISION, ACCURACY AND COMPLETENESS OBJECTIVES
Parameter Precision" Accuracy* Completeness1*
(%) (%) (%)
Total particulate (EPA Method 5)
± 11
± 10
90
Nickel/metals distribution in particulate
50®
NA
90
Cr+< distribution in particulate
50®
NA
90
Flue gas total metal
NA
NA
90
Flue gas volatile organics (VOST)
± 50"
± 50"
90
Flue gas semi-volatile organics (MM5)
± 50"
± 50"
90
Flue gas PCDD/PCDF (MM5)
± 50"
± 50"
90
Continuous Emission Monitoring

± 20'

(02, C02, CO, THC, NO„ S02)
± 20e
90
Feed sludge: Metals/Cr/Ni
NA
NA
90
Velocity/volumetric flow rate (Methods 1&2)
± 6
± 10
95
Fixed gases/molecular weight (Method 3)
± l(f
± 20*
90
Moisture (EPA Method 4)
± 20
± 10
90
Flue gas temperature (thermocouple)
± 2°F
± 5"F
90
Scrubber Water Influent and Effluent:

Metals/Cr/Ni
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
X CV = Standard Deviation x 100
Mean
'Relative error (X) 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.
7-5
-------
QC activities during flue gas sampling included:
• Visual equipment inspection;
• collection of sampling 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, where applicable; 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 cfm at 15 in Hg vacuum for the pre-test check and, for the post-test
check, 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. Each sample
container was sealed with a custody seal to ensure sample integrity. 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 method
for sample analysis. Quadruplicate sampling trains were employed with three sampling
trains used to collect samples for nickel speciation (Trains A, B, and C) and a single
train used to collect a particulate matter/total metals sample (Train 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 inlet,
midpoint, and outlet sampling locations are summarized in Table 7-2. Most of the
sampling trains operated at the midpoint and outlet locations met the QC criteria for
isokinetic sampling of 90-to-110%. One of the 24 sampling trains operated at the wet
ESP outlet for collection of particulate matter/total metals and nickel/nickel subsulfide
samples was less than 90% isokinetic. However, this was one of three trains used to
collect nickel samples. All the sampling trains (Train A) operated to collect the
particulate matter/total metals at the wet ESP outlet met the isokinetic criterion. Four
of the 19 trains operated at the midpoint were below the isokinetic criteria. All four
trains were from Run 4 and were invalidated.
The post-test leak-check results for all 43 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 22 of 23 inlet sampling trains
met the QC criteria, with exception having a 0.025 cfm leak. This leak was not
sufficient to invalidate the sample, particularly since only the ratio of the metals in the
particulate was of interest.
7-7
-------
TABLE 7-2. ISOKINETICS AND LEAK-CHECK SUMMARY: SITE 9,
MULTI-METAL AND NICKEL TRAINS
Run
Train
Location
Percent
Leak Rate
Vacuum
No.
No.

Isokinetics
(cfm)
(in. Hg)
2
B
Inlet
98.1
0.010
10
2
C
Inlet
93.0
0.008
10
2
D
Inlet
93.7
0.011
10
2
A
Outlet
98.1
0.008
15
2
B
Outlet
98.8
0.008
15
2
C
Outlet
97.3
0.008
15
2
D
Outlet
83.9
0.007
15
4
A
Inlet
114.6
0.016
3
4
B
Inlet
100.5
0.009
2
4
C
Inlet
119.1
0.011
3
4
0
Inlet
101.3
0.013
5
4
A
Midpoint
76.6
0.003
10
4
B
Midpoint
80.2
0.001
10
4
C
Midpoint
62.8
0.001
10
4
D
Midpoint
63.9
0.001
10
4
A
Outlet
102.5
0.001
8
4
B
Outlet
103.9
0.001
5
4
C
Outlet
100.8
0.002
15
4
D
Outlet
100.3
0.002
15
9
A
Inlet
167.4
0.016
5
9
B
Inlet
165.9
0.017
5
9
C
Inlet
158.2
0.019
5
9
0
Inlet
149.4
0.013
5
9
A
Midpoint
101.4
0.004
10
9
B
Midpoint
106.1
0.001
10
9
C
Midpoint
106.9
0.001
10
9
0
Midpoint
105.0
0.001
10
9
A
Outlet
103.3
0.008
15
9
B
Outlet
103.5
0.007
15
9
C
Outlet
101.9
0.007
15
9
D
Outlet
100.0
0.009
15
(Continued)
7-8
-------
TABLE 7-2. (Continued)
Run
Train
Location
Percent
Leak Rate
Vacuum
No.
No.

Isokinetics
(cfm)
(in. Hg)
11
A
Inlet
157.7
0.012
5
11
B
Inlet
162.2
0.013
4
11
C
Inlet
150.7
0.011
4
11
D
Inlet
147.7
0.009
6
11
A
Midpoint
102.2
0.002
9
11
B
Midpoint
108.2
0.001
8
11
C
Midpoint
103.6
0.001
9
11
D
Midpoint
105.6
0.001
8
11
A
Outlet
103.9
0.006
5
11
B
Outlet
104.7
0.009
5
11
C
Outlet
102.4
0.007
5
11
D
Outlet
100.8
0.008
5
12
A
Inlet
169.9
0.013
6
12
B
Inlet
166.7
0.014
5
12
C
Inlet
166.0
0.015
5
12
D
Inlet
164.2
0.025
6
12
A
Midpoint
100.7
0.004
10
12
B
Midpoint
105.5
0.001
10
12
D
Midpoint
104.2
0.001
10
12
A
Outlet
103.4
0.012
15
12
B
Outlet
103.3
0.014
15
12
C
Outlet
102.2
0.011
5
12
0
Outlet
101.5
0.009
5
13
A
Inlet
193.9
0.015
6
13
B
Inlet
208.5
0.007
5
13
C
Inlet
181.0
0.011
6
13
D
Inlet
181.4
0.014
8
13
A
Midpoint
101.2
0.003
10
13
B
Midpoint
105.7
0.001
10
13
C
Midpoint
106.9
0.001
10
13
0
Midpoint
104.1
0.001
10
13
A
Outlet
105.9
0.008
5
13
B
Outlet
104.1
0.009
5
13
C
Outlet
95.3
0.009
5
13
0
Outlet
102.7
0.008
5
7-9
-------
7.2.2.2 Sample Analysis - Analytical results for the reagent blanks and the audit sample
for metals testing are presented in Table 7-3. Chromium was found in the front half
reagent blank, but the quantity was significantly less than that found in the field samples.
An average value of 1.9 ng was used to correct the field sample results, as well as the
audit sample result.
Calibration check samples were analyzed with every ten field samples. The results
for the calibration check samples were all within 10% of the expected value.
The audit samples results ranged from -8.7 to 21.9% of the true audit value. The
audit sample analyzed was provided by EPA's Quality Assurance Division in Research
Triangle Park, NC.
7.23 Sampling and Analysis for Total Chromium and Hexavalent Chromium
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+<
testing performed at Site 9 are discussed in the following sections.
7.23.1 Sampling Operations - Isokinetic and leak-check results for the chromium
sampling at the midpoint and outlet sampling locations are summarized in Table 7-4.
The corresponding data for the inlet trains are not shown since the samples could not be
analyzed for native hexavalent chromium. Two of the twelve sampling trains operated at
the midpoint for collection of Cr/Cr+< samples were less than 90% isokinetic and one
train was over 110% isokinetic. Two of the twelve trains operated at the wet ESP outlet
were below 90% isokinetic. The outlet sampling location was downstream of the venturi
scrubber which would only allow passage of the smaller particles; therefore, 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.
7-10
-------
TABLE 7-3. QC RESULTS FOR REAGENT BLANKS AND AUDIT SAMPLES
FOR MULTI-METAL AND NICKEL SAMPLING TRAINS

Reagent Blanks
Audit Sample
Percent
Metal
Front Half
Back Half
Found
Actual
Error

(pg)
iP9)
(w)
(pg)
(%)
Arsenic
<16
<16
9.2
9.6
-3.7
Beryl Hum
<0.1
<0.1
4.6
4.85
-5.4
Cadmium
<0.2
<0.2
10.7
10.0
7.0
Chromium
<0.7
<0.7
12.4
10.3
20
Lead
<6.1
<6.1
53.4
50.4
6.1
Nickel
<1.3
<1.3
26.6
25.2
5.8
7-11
-------
TABLE 7-4. ISOKINETICS AND LEAK CHECK SUMMARY; SITE 9,
HEXAVALENT CHROMIUM SAMPLING TRAINS AT MIDPOINT
AND OUTLET LOCATIONS
Run
Train
Location
Percent
Leak Rate
Vacuum
No.
No.

Isokinetics
(cfm)
(in. Hg)
3
A
Midpoint
82.5
0.001
10
3
B
Midpoint
99.1
0.002
10
3
C
Midpoint
93.0
0.001
10
3
A
Outlet
89.8
0.001
15
3
B
Outlet
86.8
0.001
15
3
C
Outlet
92.5
0.001
15
5
A
Midpoint
69.9
0.001
10
5
B
Midpoint
99.4
0.002
10
5
C
Midpoint
105.8
0.001
10
5
A
Outlet
91.0
0.000
15
5
B
Outlet
106.9
0.000
15
5
C
Outlet
97.4
0.000
10
8
A
Midpoint
100.7
0.001
7
8
B
Midpoint
111.8
0.002
7
8
C
Midpoint
105.5
0.001
7
8
A
Outlet
99.2
0.004
8
8
B
Outlet
100.6
0.008
9
8
C
Outlet
99.8
0.012
8
10
A
Midpoint
98.9
0.005
10
10
B
Midpoint
104.6
0.005
10
10
C
Midpoint
102.9
0.001
10
10
A
Outlet
100.9
0.008
15
10
B
Outlet
101.7
0.009
15
10
D
Outlet
92.8
0.012
15
7-12
-------
7.2.3.2 Sample Analysis - Neither Cr or Cr+< were detected in any of the reagent blanks
submitted for analysis. All analyses for Cr+< were performed in duplicate with the
percent deviation of duplicate samples ranging from 0.7% to 4.0% for the reported
values. The Cr+< preconcentration curve was linear from 0.400 ppb to 6.0 ppb, with a
maximum deviation of 4.5%.
To determine the extent of Cr+< conversion that occurred during sampling, a
radioactive Cr+* surrogate, "Cr"1"*, was added to the absorbing solution in each train prior
to sampling. The "Cr"1"' spike was recovered and analyzed by IC/PCR. The IC
discharge was collected in timed fractions which were counted in a gamma counter,
along with the filter and HN03 rinse samples. The "Cr"1"' surrogate recoveries are shown
in Table 7-5. They ranged from 59.6% to 98.1% for the midpoint and outlet samples.
7.2.4 PCDD/PCDFs. Semivolatile Organic, and Volatile Organic Compound Samplir?
and Analysis
7.2.4.1 Dioxin/Furan Results - 1,2,3,4,6,8-HpCDD and OCDD were found in the HI
blank. The concentrations found are not greater than one-third the calculated method
quantitation limit for the associated samples. Blank contamination levels of one-third or
less are acceptable. All samples were spiked with surrogate, alternate, and internal
recovery standards, with the exception of the audit sample which was not spiked with a
surrogate. As shown in Table 7-6, all recoveries were in the range of 47 to 133% which
would be considered as acceptable for this program. An audit was conducted on the
dioxin/furan analysis. EPA audit sample no. 2176 was obtained from EPA's Quality
Assurance Division. As shown in Table 7-7, the audit results are acceptable.
7.2.42 Semivolatile Organic Compounds - Because of the high level of organics in the
samples, the sample had to be diluted to ensure that the target compounds were in the
analytical range. The extracts were run with a five and one-half minute solvent delay in
order to avoid damage to the filament caused by the large solvent front on the samples.
7-13
-------
TABLE 7-5. RECOVERIES OF SICr+< SURROGATE
Run
No.
Train
No.
Location
"Cr** Surrogate Recoveries
( % of total)
3
A
Midpoint
95.5
3
B
Midpoint
98.1
3
C
Midpoint
59.6
3
A
Outlet
94.6
3
B
Outlet
93.6
3
C
Outlet
76.4
5
A
Midpoint
91.9
5
B
Midpoint
85.0
5
C
Midpoint
75.6
5
A
Outlet
89.0
5
B
Outlet
91.6
5
C
Outlet
89.6
8
A
Midpoint
98.1
8
B
Midpoint
98.0
8
C
Midpoint
61.7
8
A
Outlet
93.5
8
B
Outlet
92.6
8
C
Outlet
87.6
10
A
Midpoint
98.4
10
B
Midpoint
98.4
10
C
Midpoint
78.7
10
A
Outlet
95.0
10
B
Outlet
94.6
10
C
Outlet
95.4
7-14
-------
TABLE 7-6. SUMMARY OF DIOXIN/FURAN RECOVERIES

Recovery
of Surrogate, Alternate, and
Internal
Standards

TLI blank
Audit
7A-OUT
7A-MID
7C-OUT
7C-MID
Name
(%)
(%)
(%)
(%)
(%)
(%)

Surrogate
Recovery

37C1-TCDD
116
HA*
118
119
112
118
13C12-PeCDF 234
115
NA
111
109
115
112
13C12-HXCDF 478
103
HA
114
126
112
112
13C12-HXCDD 478
90
NA
107
112
102
104
13C12-HpCDF 789
109
HA
133
122
129
113
Alternate Standards Recovery
13C12-HXCDF 789
71
76
65
65
75
80
13C12-HXCDF 234
82
97
71
74
82
93
Internal Standards Recovery
13C12-2378-TCDF
74
71
77
72
73
84
13C12-2378-TCDD
80
80
86
74
83
90
13C12-PeDCF 123
88
63
91
59
80
81
13C12-PeCDD 123
128
73
112
67
109
104
13C12-HXCDF 678
69
77
64
64
75
84
13C12-HXCDD 678
86
76
74
75
86
92
13C12-HpCDD 678
72
84
67
57
81
87
13C12-HpCDF 678
89
92
85
68
103
100
13C12-OCDD
54
47
59
43
79
70
*NA - Audit sample was not spiked with surrogate recovery standard.
-------
TABLE 7-7. DIOXIN/FURAN AUDIT RESULTS
U. S. EPA QAD DIOXIN/FURAN AUDIT FORM
AUDITOR: T. Logan AGENCY: EPA/QAD
AUDITEE ID Num: 2176 AGENCY TELE NO.: 541-2580
AUDITEE COMPANY: Entropy/Triangle AUDITEE ADDRESS: RTP, NC
AUDIT SAMPLE NO.: 143

DATE AUDIT SAMPLE RECEIVED:
6/14/90
DATE ANALYZED: 7/11 /90

CONFIRMATION ANALYSIS USED:
yes
AUDITEE'S NAME: Bill DeWees
SIGNATURE:

Compound
Auditee Result
Compound
Auditee Resi

(ng/sample)

(ng/sample)
2378-TCDD
1.20
2378-TCDF
1.50
Other TCDD
16.40
Other TCDF
51.50
12378-PCDD
2.70
12378-PCDF
3.20
Other PCDD
28.00
23478-PCDF
5.80
123478-HxCDD
6.90
Other PCDF
49.90
123678-HxCDD
6.00
123478-HxCDF
17.40
123789-HxCDD
14.60
123678-HxCDF
7.90
Other HxCDD
51.10
123789-HxCDF
8.10
1234678-HpCDD
34.40
234678-HXCDF
0.20
Other HpCDD
34.00
Other HxCDF
44.90
OCDD
71.10
1234678-HpCDF
28.10

1234789-HpCDF
1.00

Other HpCDF
16.30

OCDF
11.90
The results of the above performance audit sample will be calculated as follows:
RESULTS OF THE POLYCHLORINATED DIBENZODIOXINS (CDD)
1) 2 of the 11 different CDD are outside the 90% confidence intervals.
2) 0 of the 11 different CDD are outside 50% of the 90% confidence intervals.
RESULTS OF THE POLYCHLORINATED DIBENZOFURANS (CDF)
3) 8 of the 14 different CDF are outside the 90% confidence intervals.
4) 4 of the 14 different CDF are outside 50% of the 90% confidence intervals.
RESULTS BASED ON A 2,3,7,8-TCDD TOXIC EQUIVALENCY FACTORS
5) Based on the 2,3,7,8-TCDD toxic equivalency factors, the average percent error
outside the 90% confidence limits was 13.41% with an average bias of -2.68%.
7-16
-------
As shown in Table 7-8, no recovery data was therefore collected for the early eluting
surrogate 2-fluorophenol. The surrogate recoveries in the laboratory blank were very
good. The surrogate recoveries for 2-fluorobiphenyl, nitrobenzene-d5, and terphenyl-dM
were good in all samples. The recovery of phenol-dj was good in sample 7A-Out, but
the recovery of 2,4,6-tribromophenol was very low. The recoveries of phenol-dj and
2,4,6-tribromophenol were normal in sample 7A-Mid. The recoveries of these two acidic
surrogates were very high (approximately 180% for phenol-dj and 2,4,6-tribromophenol)
in samples 7C-Out and 7C-Mid. Because the recoveries of these surrogates look normal
in the laboratory blank and in most of the other samples this high recovery is most likely
due to a matrix effect No audit was conducted on the semivolatile organic sampling and
analysis.
7.2.4.3 Volatile Organic Compounds - As shown in Table 7-9, the recoveries for all
surrogates were normal in the two laboratory blanks and in the three field blanks. The
surrogate recoveries varied greatly in the VOST field samples, mainly due to the
extremely high levels of the target compounds. Several samples had no reported
recovery of l,2-dichloroethane-d4. This surrogate was lost due to the large amount of
methylene chloride in the samples. Elevated levels of the surrogate toluene-d, and
benzene-dg are due to large amounts of the unlabeled compounds present in the samples.
In sample 7A/1, there was no bromochloromethane found. This internal standard was
likely lost in the large methylene chloride peak that eluted in the same time window as
the analyte. All detected analytes were instead quantified against 1,4-difluorobenzene.
The response factors for these analytes are listed in chart enclosed in the case narrative
packet in Appendix C.
Samples 7A/1, 7A/2, 7A/3, 7B/1, 7B/2, 7B/3, 7C/1, 7C/2, and 7C/3 contained
benzene and toluene at levels which gave saturated spectra. A secondary ion of each
was used for quantitation in order to better estimate the true amount of these
compounds. Benzene was quantitated on the m/z = 50 ion. Toluene was quantitated
on the m/z = 65 ion. The calibration data for these secondary ions is included with the
initial calibration data for the analysis. All samples, except for field blanks, contained on
7-17
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TABLE 7-8. SUMMARY OF SEMIVOLATILE ORGANIC COMPOUND RECOVERIES
Recovery of Surrogate Standards at a Dilution Factor of 2

Blank
7A-OUT
7A-MID
7C-OUT
7C-MID
Name
(%)
(%)
(%)
(%)
(%)
Nitrobenzene-d5
55
128
116
100
134
2-Flourobiphenyl
74
106
108
104
98
Terphenyl-dl4
55
74
96
53
67
Phenol-d5
92
81
53
182
183
2-Flourophenol
0*
0*
0*
0*
0*
2,4,6,-Tribromophenol
100
4
54
471
476
*The MM5 extracts were run with a five and on-half minute solvent delay in order to
avoid damage to the filament caused by the large solvent front of the samples. No
data was therefore collected for the early eluting surrogate 2-flurophenol. This
surrogate is reported with a recovery of 0 percent.
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TABLE 7-9. SUMMARY OF VOLATILE ORGANIC COMPOUND RECOVERIES
Recovery of Surrogate Standards
Run
Toluene-d8
1,2,-Dichlorethene-d4
Benzene-d6
No.
(%)
(%)
(%)
7A/FB
126
93
115
7/2/FB
145
97
106
7/3/FB
136
96
100
VOSTBLK
127
82
107
VOSTBLK
138
91
105
7A/1
311
0
3410
7B/1
186
0
417
7C/1
181
0
1040
7A/2
188
0
430
7B/2
177
0
716
7C/2
148
149
754
7C/3
96
214
323
7B/3
99
183
236
7A/3
139
140
632
7-19
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or more analytes at levels high than the 0.1 to 1.0 jig range of the analysis. All amounts
listed on the quantitation reports that exceed 1.0 pg should be considered estimated, not
absolute, values.
7.2.5 Continuous Emission Monitoring
Continuous emission monitoring (CEM) was performed at the scrubber inlet and
scrubber outlet for 02, CO* CO, S02, and NOr Total hydrocarbons (THC) were also
monitored at the scrubber outlet on a conditioned (cold) sample. Instrument calibrations
were performed at the beginning and 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 7-10. All CEM data
were drift corrected assuming linear drift. Data from an instrument with drift exceeding
20% during a test period was invalidated.
The drift check results for both the zero and span were less than 5% for all
CEMs. Because the monitoring data were not intended for standard setting purposes,
four calibration gases each were used for Oj, CO* CO, SO* and NO, analyzers, and
three calibration gases were used in the direct calibration check. Two calibration gases
were used for the drift check at the end of each day, and no CEM performance audits
were conducted. This data meets drift requirements of Method 3A, 6C, 7E, and 25A.
7.3 PROCESS SAMPLE ANALYSIS QC RESULTS
Samples of sludge feed and scrubber effluent water were collected during each
test run. Grab samples of each type were collected at regular intervals and combined
after each test run to form composite samples. The QC results for the analyses
performed on these samples are presented in this section.
7-20
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TABLE 7-10. SUMMARY OF CEM DRIFT CHECKS
Instrument Zero and Span Drift (percent of span)
02 C02 CO S02 NOx Cold THC
Date
Location
Zero
Span
Zero
Span
Zero
Span
Zero
Span
Zero Span
Zero
Span
06/05/90
Inlet
0.2
-1.0
NA
NA
0.1
-0.3
1.3
0.2
0.4 -2.1
NA
NA

Outlet
0.2
1.1
0.6
0.2
-0.1
-0.3
1.6
-0.5
0.1 -1.8
0.8
0.8
01/06/90
Inlet
0.2
-0.6
NA
NA
0.1
-0.2
0.7
-0.1
0.3 -3.5
NA
NA

Outlet
0.4
-0.4
0.5
0.2
0.0
-0.3
2.1
1.4
0.1 -3.2
0.3
0.3
06/07/90
Inlet
0.2
-0.4
NA
NA
0.1
-0.6
1.2
-0.8
0.5 0.3
NA
NA

Outlet
0.3
-0.3
0.5
-0.3
0.0
-0.6
1.2
-0.4
0.1 3.5
-0.1
-0.3
06/08/90
Inlet
0.3
-0.3
NA
NA
NA
NA
0.2
-0.1
0.2 1.3
NA
NA

Outlet
0.4
0.2
NA
NA
NA
NA
0.6
-0.8
0.0 -1.1
NA
NA
NA = Not available
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7.3.1 Metals Analysis of Process Samples
Quality control procedures for analysis of metals in process samples were analysis
of method blanks and calibration check samples.
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.
Sludge and ash samples were spiked with various concentrations of As, Be, Cd,
Cr, Pb, and Ni. Percent recovery for these measurement spikes was 85% or better for
each spiked sample.
7.4 EXTERNAL TECHNICAL SYSTEMS REVIEW
RREL had its EPA Quality Assurance Contractor (PEI Associates in Cincinnati,
Ohio) conduct a Technical Systems Review (TSR) of the field test and the base
laboratories analyses. The Review Summary is contained in Volume IX: Site 9 Draft
Test Report, Appendices.
During the field TSR conducted on the afternoon of June 4 and morning of June
5, 1991, no deficiencies were noted with the sampling procedures. However, during the
period the audit was being conducted both the process and control equipment was upset
or malfunctioning. As noted in the report the first sample run that both the process and
control equipment functioned properly was the afternoon of June 5, 1990.
During the laboratory TSR, several minor concerns were noted. The conclusions
of the TSR were: "No concerns were noted that could compromise the quality of the
data generated from samples analyzed for this study at the three laboratories visited
during this TSR". Insufficient documentation of QA check was noted at the RTI
laboratory; however, this concern was considered minor because analysis of samples for
this project had not yet begun. Implementation of the QA check procedures and
documentation protocol specified in the methods selected for this project will ensure
7-22
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adequate documentation of data quality of samples analyzed at this facility. In general,
data generated from laboratory analyses preformed by the laboratories reviewed during
these TSRs should be adequate to meet the study objectives. A rating of satisfactory was
assigned to each laboratory visited.
7-23
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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
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before complet'
1. REPORT NO. 2.
EPA/600/R-92/003h
3 PB9 2-151620
4. TITLE AND SUBTITLE
EMISSIONS OF METALS, CHROMIUM AND NICKEL SPECIES, AND
ORGANICS FROM MUNICIPAL WASTEWATER SLUDGE INCINERATORS
VOLUME VIII: SITE 9 EMISSION TEST REPORT
5. REPORT OATE
March 1992
6. PERFORMING ORGANIZATION CODE
7. AUTHORISI
William G. DeWees, Robin R. Segall
F. Michael Lewis
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Entropy Environmentalists, Inc.
Research Triangle Park
North Carolina, 27709
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
Contract No. 68-CO-0027
Work Assignment No. 0-5
12. SPONSORING AGENCY NAME AND ADDRESS
Risk Reduction Engineering Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, OH 45268
13. TYPE OF REPORT AND PERIOD COVEREO
Final Report 1989 - 91
14. SPONSORING AGENCY CODE
EPA/600/14
IS. SUPPLEMENTARY NOTES
EPA Technical Contact: Dr. Harry E. Bostian, (513) 569-7619, FTS: 684-7619
16. A8STRACT
Site 9 is a secondary plant designed for 15 million gallons per day (MGD) of
wastewater flow. The sludge incinerator at Site 9 is a seven (7) hearth, multiple
hearth furnace (MHF) built by Nichols Engineering in 1974 controlled by an adjustablr
throat venturi scrubber with c. nominal pressure drop of 20 in. w.c.. After leaving
the venturi, the gases pass upward through a three (3) plate tray scrubber with a
Chevron mist eliminator. A 10 ft. x 10 ft., upflow, wet electrostatic precipitator,
manufacturer by Beltran Associates, Inc., was installed during the first week of
testing. The ratio of nickel subsulfide to total nickel in the emission at Site 9 it
extremely low, with the sulfidic nickel species being measured at less than deteetioi
limit (about 1 to 2 percent of the total nickel). The ratio of hexavalent chromium tc
total chromium in the emissions at Site 9 was significantly higher that had been
anticipated. Site 9 had only two semivolatile organic compounds detected under
normal and improved combustion conditions benzyl alcohol and benzoic acid. Several
additional compounds were found in the emissions for the normal or improved
combustion conditions at Site 9; these compounds were 1,4-dichlorobenzene,
1,2-dichlorobenzene, 2-nitrophenol, 1,2,4-Trichlorobenzene, naphthalene,
2-methylnaphthalene, dibenzofuran, phenanthrene, bis(2-ethylhexyl)phthalate, phenol,
4-methylphenol, and 4-nitrophenol. The volatile organic compounds detected in the
Site 9 multiple hearth incinerator emissions were similar to the compounds reported
for Sites 1, 2, and 4 (other multiple hearth incinerator tested). Carbon
tetrachloride and carbon tetrachloride, reported in the emissions at the other three
sites, were not found in the emissions from Site 9-..— —
17. KEY WOROS AND DOCUMENT ANALYSIS
a. descriptors
b.IDENTIFIERS/OPEN ENOEO TERMS
c. COSATi Field/Group
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)
UNCLASSIFIED
21. NO. OF PAGES
158
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220.1 (R.v. 4.77) previous coition is p
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