United States
Environmental Protection
Agency
EPA/600/R-07/043
April 2007
Test Measurements at
Five Municipal Solid Waste
Landfills with Landfill Gas
Control Technology
Final Report
-------
EPA/600/R-07/043
April 2007
Field Test Measurements at Five
Municipal Solid Waste Landfills with
Landfill Gas Control Technology
Final Report
Prepared for:
Susan A. Thorneloe
US Environmental Protection Agency
Office of Research and Development
Air Pollution Prevention and Control Division
National Risk Management Research Laboratory
Contract No. EP-C-04-023
Work Assignment 3-26
Prepared by:
ARCADIS G&M, Inc.
4915 Prospectus Drive, Suite F
Durham, North Carolina 27713
-------
Foreword
The U.S. Environmental Protection Agency (EPA) is charged by Congress with protecting the Nation's
land, air, and water resources. Under a mandate of national environmental laws, the Agency strives
to formulate and implement actions leading to a compatible balance between human activities and
the ability of natural systems to support and nurture life. To meet this mandate, EPA's research
program is providing data and technical support for solving environmental problems today and
building a science knowledge base necessary to manage our ecological resources wisely, understand
how pollutants affect our health, and prevent or reduce environmental risks in the future.
The National Risk Management Research Laboratory (NRMRL) is the Agency's center for
investigation of technological and management approaches for preventing and reducing risks from
pollution that threaten human health and the environment. The focus of the Laboratory's research
program is on methods and their cost-effectiveness for prevention and control of pollution to air, land,
water, and subsurface resources; protection of water quality in public water systems; remediation of
contaminated sites, sediments and ground water; prevention and control of indoor air pollution; and
restoration of ecosystems. NRMRL collaborates with both public and private sector partners to foster
technologies that reduce the cost of compliance and to anticipate emerging problems. NRMRL's
research provides solutions to environmental problems by: developing and promoting technologies
that protect and improve the environment; advancing scientific and engineering information to support
regulatory and policy decisions; and providing the technical support and information transfer to
ensure implementation of environmental regulations and strategies at the national, state, and
community levels.
This publication has been produced as part of the Laboratory's strategic long-term research plan. It is
published and made available by EPA's Office of Research and Development to assist the user
community and to link researchers with their clients.
Sally Gutierrez, Director
National Risk Management Research Laboratory
-------
Notice
The U.S. Environmental Protection Agency through its Office of Research and Development funded and
managed in the research described here under Contract No. EP-C-04-023 to Arcadis G&M, Inc. It has been
subjected to the Agency's review and has been approved for publication as an EPA document.
-------
Table of Contents
1. Introduction
1.1 Objective/Purpose and Intended Use of Project Results
1.2 Scope of Project
1.3 QA Considerations
1.3.1 PCDD/PCDF/PCB/PAH Measurements
1.3.2 Mercury Measurements
2. Landfill Descriptions
2.1 Characteristics of Landfills Selected for Field Tests
2.1.1 Landfill A
2.1.2 Landfill B
2.1.3 Landfill C
2.1.4 Landfill D
2.1.5 Landfill E
2.2 Description and Characteristics of Combustion Technology
2.2.1 Enclosed-Ground Flare (Landfills B and D)
2.2.1.1 LandfillB
2.2.1.2 Landfill D
2.2.2 1C Engine (Landfills A and C)
2.2.2.1 Landfill A
2.2.2.2 Landfill C
2.2.3 Boiler (Landfill E)
2.2.3.1 Landfill E
3. Test Operations
3.1 Sample Locations
3.2 Target Analytes
3.2.1 Raw Landfill Gas
1-1
1-3
1-3
1-4
1-4
1-5
2-1
2-1
2-1
2-2
2-2
2-2
2-2
2-3
2-3
2-3
2-3
2-3
2-3
2-4
2-4
2-4
3-1
3-1
3-2
3-2
IV
-------
Table of Contents
3.2.2 Control Technology Exit 3-4
3.3 Sampling and Analysis Methods 3-5
3.3.1 Raw Landfill Gas Sampling Analysis Methods 3-5
Where multiple organizations are listed, the letters A, B, C, D, and E in
parenthesis following the organization denotes the landfill site for
which the organization was the performing organization. 3-6
3.3.2 Control Technology Exit Sampling Analysis Methods 3-7
3.4 Field Test Sampling Operations Narrative 3-7
3.5 Variation from Test Methods or Planned Activities 3-8
3.5.1 Method Exceptions 3-8
3.5.1.1 Raw Landfill Gas 3-9
3.5.1.2 Control Device Exit 3-10
4. Test Results 4-1
4.1 Raw Landfill Gas 4-1
4.1.1 Landfill Gas Flow Rate and Temperature 4-1
4.1.2 Landfill Gas Constituent Concentrations 4-1
4.1.2.1 Major Constituents (CH4, CO2, O2) by Method 3C and
NMOCs by Method 25 4-2
4.1.2.2 Other Constituents 4-3
4.2 Control Equipment Stack 4-11
4.2.1 Gas Flow Rate and Temperature 4-11
4.2.2 Exhaust Gas Constituent Concentrations 4-12
4.2.2.1 CEM Constituents (O2, CO, CO2, SO2, NOX) 4-12
4.2.2.2 Other Constituents 4-13
5. Discussions of results 5-1
5.1 Comparison with AP-42 Default Values 5-1
5.2 Control Technology Assessment 5-2
5.3 Mercury Measurements 5-2
-------
Table of Contents
6. Data Quality Assessment 6-1
7. Conclusions 7-1
8. References 7-2
VI
-------
Table of Contents
Tables
Table 2-1. General Description of Tested Landfills 2-1
Table 3-1. Target Analytes for the Raw Landfill Gas Samples collected at the Gas Header 3-3
Table 3-2. Target Analytes for the Control Technology Exit Gas 3-5
Table 3-3. Testing Methods for Raw LFG 3-6
Table 3-4. Testing Methods for Control Technology Exit Gas 3-7
Table 4-1. Raw LFG Flow Rates 4-2
Table 4-2. Raw LFG Major Constituents 4-3
Table 4-3. Raw LFG Volatile Organic Compounds 4-4
Table 4-4. Raw LFG Hydrogen Sulfide 4-7
Table 4-5. Raw LFG Carbonyls 4-8
Table 4-6. Raw LFG Mercury Compounds 4-10
Table 4-7. Control Equipment Exit Stack Flow Rate and Temperature 4-12
Table 4-8. Control Equipment Exit O2, CO, CO2, SO2, NOX 4-13
Table 4-9. Control Equipment Exit Total Hydrocarbon 4-13
Table 4-10. Control Equipment Exit Dioxins and Furans Average Concentrationsa 4-15
Table 4-12. Control Equipment Exit HCI 4-18
Table 4-13. Control Equipment Exit Metal Emissions 4-18
Table 5-1. Comparison between LFG Constituent Concentrations and AP-42 Default Values 5-5
Table 6-1. Summary of Sampling and Analyses Exceptions 6-2
VII
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
1. Introduction
The purpose of this field test program is to generate data that may be used to update
EPA's factors for quantifying landfill gas emissions from municipal solid waste (MSW)
landfills. Because of health and environmental concerns, EPA issued in 1996 New
Source Performance Standards (NSPS) and Emission Guidelines (EGs) for new and
existing MSW landfills. These regulations are contained in 40 CFR Parts 51, 52, and
60, Standards of Performance for New Stationary Sources and Guidelines for Control
of Existing Sources: Municipal Solid Waste Landfills (U.S. EPA, 1996, 1991a, 1991b,
1991c). These regulations require that large landfills collect and control landfill gas
emissions.
Landfills are listed as a source for residual risk evaluation as part of EPA's Urban Air
Toxic Strategy. Landfills are also subject to New Source Review under Title V of the
Clean Air Act. The data being used for issuing air permits, developing estimates for
emission inventories and environmental or risk assessments, are obtained from EPA's
emission factors found in Chapter 2.4 of AP-42 (U.S. EPA, 1997). Factors for
evaluating uncontrolled emissions and also combustion by-products are included in
AP-42.
Much of the data used in developing the existing set of landfill gas emission factors in
AP-42 were collected in support of the NSPS and EGs. Therefore much of this data is
at least a decade old. Changes to the design and operation of MSW landfills have
occurred that are suspected to influence MSW landfill air emissions. In addition,
improvements in quality assurance (QA) and EPA test methods have occurred that
enable better detection limits and higher quality data.
Through a Cooperative Research and Development Agreement (CRADA 01/02 CR1
26CFX81 80401F), the U.S. Environmental Protection Agency (EPA) formed a
partnership with the Environmental Research and Education Foundation (EREF) to
collect comprehensive and up-to-date data at U.S. MSW landfills. Field testing was
conducted in two phases. The first phase helped finalize sampling and analytical
methods used for the raw landfill gas and combustion by-product emissions. The
second phase implemented the agreed upon methods using Category II QA project
plan that included on-site auditing of field tests. The field testing began in November
2002 and was completed in June 2005. EPA's Office of Research and Development
(ORD) worked in cooperation with industry partners and EPA's Office of Air Quality
Planning and Standards (OAQPS) in establishing scope, field sampling and analytical
protocols, and site selection. The field testing was conducted by ARCADIS G&M, Inc.
1-1
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
(ARCADIS), as contractor to the EPA National Risk Management Research laboratory
(NRMRL) Air Pollution Prevention and Control Division (APPCD), under several work
assignments as part of the Onsite Laboratory Support Contracts (68-C-99-201 and EP-
C-04-023).
Testing has been conducted in parallel to this field test program and is providing data
that evaluates potential fugitive emissions from landfills. Data has also been collected
to help quantify the emission differences between sites with and without leachate
recirculation (EPA-600/R-05/072). In addition, guidance has been developed for
evaluating the air pathway from older landfills (EPA-600/R-05/123a). The data from
this effort, field studies, and data collected from industry and state and local regulatory
agencies will be used in updating AP-42. Once updated factors are available, EPA's
Landfill Gas Emission Model (LandGEM) will be updated to reflect the newer
information (EPA-600/R-05/047). The revised emission factors for estimating
uncontrolled emissions and combustion by-products will be provided in a new release
of AP-42 including an updated background information document.
The site selection criteria for identifying potential sites for this study included: (1) no
enforcement actions associated with the site; (2) the site must be in compliance with
applicable EPA regulations (Clean Air Act and Resource Conservation Recovery Act);
(3) the site must have state-of-the-art combustion technology in place for landfill gas
control; and (4) the combustion technology must be representative of what is typical at
U.S. landfills. Because of the potential benefit from utilization of landfill methane, EPA
promotes landfill gas-to-energy projects through its Landfill Methane Outreach
Program (LMOP). (www.epa.gov/lmop') Updated statistics from LMOP indicate that
there are more than 400 landfill gas-to-energy projects in the U.S. (U.S. EPA, 2007).
There is also information providing distribution of energy recovery projects in the U.S.
(Thorneloe et al., 2000) This information was used in selecting the type and number of
combustion technologies to include in this study. Ideally it would be nice to include a
wider range of technologies but available funding limited the number to five facilities.
The technologies that were included in this evaluation were two enclosed flares, two
internal combustion (1C) engines, and one direct gas-fed boiler.
Sites that use leachate recirculation to accelerate waste decomposition were excluded
as potential candidate sites. It may be important in future studies to explore how
leachate recirculation may affect landfill gas emissions. However, this study did not
include sites that use leachate recirculation or other liquid additions to accelerate waste
decomposition.
1-2
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
1.1 Objective/Purpose and Intended Use of Project Results
The objective of this project was to collect and provide current data from U.S. MSW
landfills with state-of-the-art control technology used for reducing landfill gas (LFG)
emissions. Comprehensive testing was conducted of the raw landfill gas and the
combustion outlet exhaust. The data will be used to help develop emission factors for
use in updating EPA's AP-42 for estimating uncontrolled emissions from MSW landfills
and combustion by-product emissions. Pollutants of concern include methane (CH4),
volatile organic compounds (VOCs), persistent bioaccumulative toxics (PBTs) such as
mercury (Hg), and hazardous air pollutants (HAPs) such as benzene, vinyl chloride,
and methyl ethyl ketone. The data will also be used to supplement AP-42 and to
provide QA to data previously supplied by industry and others as part of the AP-42
update.
1.2 Scope of Project
The first phase of the project included two sites in the Northeast (Landfills A and B).
Input for Phase I was obtained from EREF and EPA's Office of Air Quality Planning
and Standards to identify appropriate sampling and analytical protocols and QA. Input
was also obtained to identify pollutants of concern for the raw landfill gas (collected
from the header pipe but upstream of gas pretreatment or condensate knockout) and
combustion by-product emissions. Prior to initiating Phase 2, a review was conducted
to determine changes needed to sampling and analytical protocol and QA. These
changes in sampling, analytical protocol and QA are listed in section 3.5. The second
phase included three sites located in the mid-west (Landfills C, D and E). Phase 1
testing took place from November 1 through Novembers, 2002. Phase 2 testing took
place from May 12 to May 16, 2004 for Landfills C and D, and from June 22 to June
23, 2005 at Landfill E.
The pollutants of interest for the raw (untreated) landfill gas included VOCs, non-
methane organic compounds (NMOCs), polycyclic aromatic hydrocarbons (PAHs),
polychlorinated biphenyls (PCBs), hydrogen sulfide (H2S), carbonyls (acetaldehyde,
formaldehyde), and Hg (total, elemental, and organo).
The pollutants of interest for combustion outlet exhaust included carbon monoxide
(CO), nitrogen oxides (NOX), sulfur dioxide (SO2), NMOCs as total hydrocarbons
(THCs), hydrogen chloride (HCI), total Hg, polychlorinated dibenzodioxins (PCDDs),
polychlorinated dibenzofurans (PCDFs), polycyclic aromatics hydrocarbons (PAHs),
and toxic heavy metals.
1-3
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
1.3 QA Considerations
This test program was conducted to meet Category II QA requirements. A generic QA
program plan (QAPP) was prepared for the field test project. In addition, a site-specific
QAPP was prepared for each field test.
This project set out to produce data that qualified to receive the "A" rating with respect
to the rating system described in Section 4.4.2 of the Procedures for Preparing
Emission Factor Documents (EPA-454/R-95-015). The cited EPA document provides a
clear description of the requirements for an "A" data quality rating:
"Tests are performed by using an EPA reference test method, or when not
applicable, a sound methodology. Tests are reported in enough detail for adequate
validation and raw data are provided that can be used to duplicate the emission
results presented in the report."
The Data Quality Objectives (DQOs) were specified in the Generic and Site-Specific
QAPPs. The extent to which this program achieved the DQOs was reported in detail in
each of the landfill test reports. Overall the DQOs were met except for a few limited
cases such as dimethyl mercury for landfills A and B. In addition there were issues
with PAH analysis which is discussed in more detail in this report. The issues that
were identified in Phase 1 were addressed in Phase 2 so that the DQOs were met as
explained in the individual reports. The list of changes made between Phases 1 and 2
is provided in Section 3.5 of this report.
As part of the QA process, an EPA QA representative conducted a Technical Systems
Audit (TSA) of the sampling operations during the Landfill C tests. The Audit Report
indicated that the sampling operations were in compliance with standard operating
procedures (SOPs) and methods.
The following two sections discuss the two groups of measurements that did not
produce the results as planned. All other measurements were conducted and produced
results as originally planned.
1.3.1 PCDD/PCDF/PCB/PAH Measurements
Method 23 was used to evaluate the concentrations of PAHs and PCBs in the raw LFG
for the two sites included in Phase 1 (Landfills A and B).
1-4
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
In order to achieve the desired low detection limits typically required of these target
analytes, the samples had to be greatly concentrated. The process of concentrating
the sample extracts produced recovery extracts that were extremely concentrated in
some other (not PAHs or PCBs) organic constituents. Those concentrations were
sufficiently high to cause instrumental interferences and prevented the extracts from
being analyzed to give the required low detection limits of the PAHs and PCBs target
analytes. Injection of these organic-rich extracts would have over-ranged and
corrupted the analytical instruments, necessitating major instrument repair and
cleaning.
In fact, commercial laboratories even declined to attempt to analyze these extracts.
The alternative of not concentrating the samples to avoid instrument over-ranging is
possible but would produce PAHs and PCBs method detection limits so high as to
render the measurements not meaningful. Therefore, during subsequent tests for
Landfills C, D and E, these samples were not included in the target list. However,
PAHs were analyzed in the combustion outlet exhaust.
1.3.2 Mercury Measurements
Landfills have been found to contain organo-mercury (Lindberg et al, 2005). Because
the available organo-mercury measurement and analysis methods are not established
EPA standard test methods, questions were raised about their application to landfill
gas given the range of constituents of potential interferences. Phase 1 conducted a
review of the protocol of these organo-mercury analysis methods and included QA
checks to help in the evaluation of the methods. For both Phase 1 sites (Landfills A and
B), unsatisfactory spike recoveries were obtained. ARCADIS in working with Frontier
Geosciences, the subcontractor laboratory, determined that reducing the sample
volume could result in more satisfactory spike recoveries. To help in improving
information on the precision of the protocol for organo-mercury, a second analytical
laboratory was contracted to compare results for one of the five landfills (i.e., Landfill
E). These results were reported in the Landfill E report.
During the course of the test program, after Phase 1 (Landfills A and B) was
completed, a review of mercury sampling and analysis was conducted including an
audit of Frontier Geosciences laboratory's mercury analysis operations. This resulted in
improving the procedures that were used in Phase 2. The conclusion is that organo-
mercury sampling and analysis can provide useful results and that refinements in the
protocols will improve the methods' applicability, accuracy, and precision.
1-5
-------
Lindberg et al, 2005 reported mercury measurement results from a total of nine
landfills. The methodology for sampling and analysis of total, di-methyl, and mono-
methyl used in these tests were very similar to the methodologies used at the five
landfills included in this report, although sample volumes were slightly different. The
range of total mercury in the Lindbergh report is from 10 to 11,500 ng/m3 while the
range of total mercury in this report is from 158 to 1330 ng/m3. Overall the
concentration of total Hg in the Lindbergh paper is much higher (as much as an order
of magnitude in some cases) than the total mercury concentrations included in this
report. The range of dimethyl mercury in the Lindbergh paper is from 4.5 to 99.8 ng/m3
while the range of dimethyl mercury in this report is from 6.5 to 77 ng/m3. Overall the
concentrations of dimethyl mercury reported in this report and the Lindberg paper are
similar. The range of monomethyl mercury in the Lindbergh paper is from ND to 39
ng/m3 while the range of monomethyl mercury in this report is from ND to 8.2 ng/m3.
Overall the concentration of monomethyl mercury in the Lindbergh paper is higher than
the monomethyl mercury concentrations included in this report.
Prestbo et al. (2003) determined total and dimethyl mercury concentrations in raw LFG
and found that dimethyl mercury comprised from 1 to 60 percent of the total mercury in
the LFG. Vasuki et al. (2003) measured total and dimethyl mercury concentrations in
Delaware LFGD and found that dimethyl mercury comprised about 8 percent of the
total LFG mercury. The percent mercury of the Vasuki et al (2003) paper is very
comparable with the data reported here for the five landfills tested, however, the
percent dimethyl mercury reported by Prestbo et al. (2003) appears to be very high by
as much as an order of magnitude. The discrepancy in the percent of dimethyl
mercury in LFG will be addressed in a follow-on study.
During the course of the test program, after Phase 1 (Landfills A and B) was
completed, ARCADIS' QA staff conducted an in-depth review of the mercury
measurement methodologies by conducting an audit of Frontier Geosciences
laboratory's mercury analysis operations. The results of that audit were included as a
part of the Phase 2 (Landfills C and D) test reports. The findings were that the mercury
measurement methods were capable of producing useable results, while the methods
were undergoing continuing refinements. Progress has been made steadily to improve
the methods' applicability, accuracy, and precision.
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
1-6
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
2. Landfill Descriptions
The five landfills included in this evaluation were MSW landfills with gas collection and
control technology. Two are located in the northeast and three were located in the mid-
west. All five are still operational (i.e., accepting waste). Characteristics of these
landfills are listed in Table 2-1.
Table 2-1. General Description of Tested Landfills
Year that Waste
Acceptance Began
Area/Waste Footprint
(acres)
Amount of waste
(tons)
Amount of waste
(cubic yards)
Facility estimated LFG
extraction rate
(standard cubic fee per
minute) a
Combustion Control
Technology
Field Test Dates
Landfill A
1972
56
2,700,000
in 2003
—
1700
Internal
Combustion
Engine
11 71/2002 to
11/2/2002
Landfill B
1967
40
4,000,000
in 2003
—
1500
Flare
11/4/2002 to
11/5/2002
Landfill C
1992
63
6,400,000
in 2004
1,580,000
in 2003
600
Internal
Combustion
Engine
5/1 2/2004 to
5/13/2004
Landfill D
1991
31
2,350,000
in 2004
421,639
400
Flare
5/1 5/2004 to
5/16/2004
Landfill E
1971
240
14,500,000
in 2005
—
4800
Boiler
6/22/2005 to
6/23/2005
a Extraction rate is what was collected, NOT production rate, and it is estimated
2.1 Characteristics of Landfills Selected for Field Tests
2.1.1 Landfill A
Landfill A is located in the Northeast and it began operation in 1972. Available
information provided by the landfill site operator indicated that the site had 2,700,000
tons of waste in place in 2003, over an area of 56 acres. The landfill used 3,375 feet of
horizontal collectors to collect the LFG. As of 2002, 29 vertical wells were in place to
extract landfill gas. The collected gas was piped to two reciprocating internal
combustion (RIC) engines. Any excess gas was flared. At this site, one of the two RIC
engines was selected for field testing. The engine tested was selected arbitrarily.
2-1
-------
2.1.2 Landfill B
Landfill B was located in the Northeast and began operation in 1967. Based on
information provided by the facility operator, the site had 4,000,000 tons of waste in
place, over an area of 40 acres in 2003. Approximately 2,500 feet of horizontal
collectors were used to collect landfill gas. Operators stated that 49 vertical wells were
used to extract landfill gas which is piped to an enclosed flare system.
2.1.3 Landfill C
Landfill C is located in the Midwest and began operation in 1992. Based on information
provided by the site operator, Landfill C has approximately 6,400,000 tons of waste in
place as of August 2004. Landfill gas is extracted using 54 vertical wells at a rate of
600 standard cubic feet per minute (scfm). The gas was piped to two Caterpillar 3560
engines. Excess gas was combusted in an enclosed flare.
2.1.4 Landfill D
Landfill D is located in the Midwest and began operation in 1991. Based on information
provided by the site operator, Landfill D has approximately 2,350,000 tons of waste in
place as of August 2004. The waste footprint covers an area of 31 acres. Landfill gas is
extracted using 21 vertical wells at a rate of 400 cubic feet per minute. Extracted gas is
piped to an enclosed flare.
2.1.5 Landfill E
Landfill E is located in the Midwest and began operation in 1971. As of June 2005, the
landfill has 14,500,000 tons of waste in place covering an area of 240 acres. The LFG
was extracted with 320 vertical wells and filtered, de-watered, compressed, and piped
to the end users. The flow rate of the landfill gas was 4,800 scfm. This site had a
number of innovative uses of landfill gas including producing steam for greenhouses,
providing fuel for a large industrial boiler (replacing fuel oil), providing fuel for an
asphalt plant, and the residual gas was flared. Demand and seasonal factors largely
determined the use pattern and the maximum and minimum usage rates.
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
2-2
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
2.2 Description and Characteristics of Combustion Technology
2.2.1 Enclosed-Ground Flare (Landfills B and D)
2.2.1.1 LandfillB
A Perennial Energy Enclosed Ground Flare Station, rated at a maximum LFG input
rate of 1500 scfm, was used to combust landfill gas at landfill B. A burner array and an
automatic louver system were designed to control gas and combustion air distribution.
Manufacturer information indicated that the flare was designed to obtain a minimum
residence time of 0.6 seconds at 1400 °F. The station included a condensate removal
device to prevent liquids from contacting the flare burners. The system also included a
flame arrester to prevent flame propagation into the LFG header pipe and collection
system. The unit was reported to be able to operate within a 5-to-1 turndown ratio [54.0
to 10.8 million British Thermal Units per hr (MMBtu/hr)]. The manufacturer also
reported minimal production of NOX and effective destruction of hydrocarbons.
2.2.12 Landfill D
The enclosed ground flare evaluated at Landfill D was a John Zink Model 72 rated at a
maximum LFG input rate of 695 scfm. A condensate removal system prevented liquids
from contacting the flare burners. A flame arrester prevented flame from propagating
from the burner array back into the LFG header pipe and collection system. A burner
array and an automatic louver system controlled gas and air distribution to achieve
effective combustion. The manufacturer claimed that the unit could be operated
satisfactorily within a 5-to-1 turndown ratio (from 20.9 to 4.0 MMBtu/hr). The system
was designed for a minimum residence time of 0.7 seconds at 1800 °F to combust
hydrocarbons with minimal production of NOX.
2.2.2 1C Engine (Landfills A and C)
2.2.2.-T Landfill A
Landfill A utilized a bank of four Caterpillar (CAT) generator sets for destruction of LFG
and generation of electricity. The engines were CAT 3412 four-stoke 1C engines,
adapted for landfill gas. The CAT 3412 was a spark-ignited (SI) V-12 engine with
displacement of 1649 cubic inches. The engine was turbocharged and after-cooled,
and had a cylinder bore diameter of 5.4 inches and a stroke of 6.0 inches. Engine #2
2-3
-------
was randomly selected and was tested. The engine was connected to a Caterpillar
SR4 Generator that was rated at 470 KW.
2.2.2.2 Landfill C
Landfill C utilized a bank of two Caterpillar generator-sets for destruction of LFG and
generation of electricity. The engines were CAT 3516 four-stoke engines, adapted for
LFG fuel. The CAT 3516 was a spark-ignition (SI) V-16 engine with 4210 cubic inches
displacement. The engine was turbocharged and after-cooled, and had a 6.7-inch
diameter cylinder bore and a 7.5-inch stroke. The engine drove a Caterpillar SR4
Generator that was rated at 800KW(at a 0.8 power factor). Engine #1 was randomly
selected and tested. The engine did not have pollution control equipment installed.
2.2.3 Boiler (Landfill E)
2.2.3.-T Landfill E
The tested boiler was a Combustion Engineering Model 33-7KT-10, A-Type Package
Boiler, rated at 80,000 pounds-per-hour of 250 psi steam. The boiler was fueled by the
collected LFG and produced base-load steam for an industrial facility. The boiler was
located on the industrial facility's property, located approximately three miles from
Landfill E.
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
2-4
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
3. Test Operations
The testing operations were conducted during spring through late fall (May through
early November), when ambient air temperatures were above freezing.
Sample collection and other testing operations typically required seven- to eight-person
sampling teams working for two full days. Prior to the sampling crew arriving at the
landfills, the host facility operator was asked to install the necessary sampling ports, if
these were not already present. In the case of Landfills C and D, excavation of soil was
needed to expose the underground raw LFG pipes.
Other than these modifications to allow sampling equipment access, facility
modification was not required or observed to have happened immediately prior to
these tests.
3.1 Sample Locations
Two kinds of samples were collected - the raw LFG and the exhaust gas from the
combustion-based emission control systems.
The raw LFG samples were collected from the LFG header pipe that connects the
landfill's network of collection pipes and wells. The sample ports were upstream of the
condensate removal unit, blower/compressor, and flow control or distribution
equipment. Hence, the collected samples are representative of the raw LFG in its
"natural" state.
During Phase 1 testing at Landfill A, a sample of condensate was collected from the
LFG pipe leading to the engines. That location was downstream of the condensate
removal unit and the condensate sample was not specified in the QAPPs. The sample
was judged to be extraneous to the test program and had unclear value. Analysis of
that sample was not useful without corresponding analysis of a vapor phase sample
collected at the same location. Therefore, that condensate sample was not analyzed
and similar samples were not collected during subsequent landfill tests.
For the tested engines and boiler, the exhaust gas samples were collected at their
stack as these control devices had distinct stack pipes. The tested enclosed flares did
not have distinct stacks as the whole flare unit served as the combustion unit and the
stack. For all tests, the sample locations were selected to allow for isokinetic sampling.
3-1
-------
3.2 Target Analytes
Through consultation between the CRADA partners and EPA's Office of Air Quality
Planning and Standards (OAQPS) and Landfill Methane Outreach Program (LMOP) in
the planning phase of the project, target analytes were selected. The list of analytes in
the raw landfill gas and combustion outlet was much more comprehensive than that
typical for performance tests of LFG control technology.
For organo-mercury compounds, standard EPA test methods were not available.
Methods that were developed through Frontier Associates were used. Using these
non-promulgated procedures required more effort in terms of quality assurance.
Measuring the range of constituents in LFG gas can be quite challenging when
compared to measuring other emission sources where there are fewer constituents to
analyze.
3.2.1 Raw Landfill Gas
Table 3-1 lists the target analytes for the raw LFG samples that were collected at the
gas header pipe. The list of target analytes for the raw LFG matched closely with the
constituents listed in AP-42 emission factors for landfills. In addition to these analytes,
the test included the "non-AP-42" compounds: carbonyls (formaldehyde and
acetaldehyde), polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls
(PCBs), speciated mercury (monomethyl, dimethyl, elemental, and total). These
constituents were of interest because of their status of being on the EPA list of HAPs.
Experience gained during Phase 1 testing revealed that the extracts of the PAH/PCB
samples contained excessive amounts of non-PAH organics. In order to make the
extracts safe to be injected into the gas chromatograph/mass spectrometer (GC/MS),
samples had to be diluted excessively. The high dilution made the method detection
levels forthe target PAHs too high, resulting in "non-detects" at the high detection
limits. The planned analysis method could not produce the desired results at the
needed detection levels. Therefore, these measurements were not included in Phase 2
testing.
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
3-2
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
Table 3-1. Target Analytes for the Raw Landfill Gas Samples collected at the Gas Header
Target Analytes in AP-42 List of Landfill Gas Constituents
Methane
Ethane
Propane
Butane
Pentane
Hexane
Carbonyl sulfide
Chlorodifiuoromethane
Chloromethane
Dichlorodifluoromethane
Dichlorofiuoromethane
Ethyl chloride
Fluorotrichloromethane
1,3-Butadiene
Acetone
Acetone
Acrylonitrile
Benzene
Bromodichloromethane
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chloroform
Dimethyl sulfide
Ethyl mercaptan
Ethylene dibromide
Ethylene dichloride
Methyl chloroform
Methyl isobutyl ketone
Methyl mercaptan
Methylene chloride
Propylene dichloride
t-1,2-Dichloroethene
Tetrachloroethene
Toluene
Trichloroethylene
Vinyl chloride
Vinylidene chloride
Ethanol
Methyl ethyl ketone
2-Propanol
1,4-Dichlorobenzene
Ethylbenzene
Xylenes
Non-methane organic
compounds
Hydrogen sulfide
Target Analytes Not Previously Included in AP-42
Acetaldehyde
Formaldehyde
Polycyclic aromatic
hydrocarbon a
Polychlorinated biphenyls a
Mercury
Organo-mercury compounds
Elemental
Total
Gases
Carbon dioxide
Oxygen
Moisture
3 These target analytes were part of Phase 1 testing. They were not included in Phase 2 testing
because of difficulties experienced by the analytical laboratory to analyze the overly organic-rich
sample extracts.
3-3
-------
The other analytes, oxygen (O2), carbon dioxide (CO2), and moisture, are not pollutants
but are of interest as they are useful indicators of the "quality" of the raw LFG. The
concentrations of nitrogen (N2) and O2 are also indicators of the extent of ambient air
infiltration into the LFG collection. Method 25C [for non-methane organic compound
(NMOC) determination] specifically recommends that these measurements be made to
determine the extent of potential air infiltration. Therefore, while measurements for
methane (CH4), CO2, O2, and N2 by Method 3C were not included in the original
QAPPs, these measurements were included and performed for all five landfill tests.
There was original interest in determining the concentration of the toxic heavy metals
lead (Pb), arsenic (As), cadmium (Cd), chromium (Cr), manganese (Mn), and nickel
(Ni) in the raw LFG. However, a method suitable for sampling the organics-rich raw
LFG and capable of detecting the suspected low concentrations of the toxic metals,
does not exist. Therefore measurement of the toxic heavy metals was not planned for
the raw LFG.
3.2.2 Control Technology Exit
Table 3-2 lists the target analytes for the control technology exit gas samples. The
focus of these analyses was to produce data that allowed for the assessment of the
efficacies of the three tested control technologies to destroy the constituents in the raw
LFG. They included O2, CO2, carbon monoxide (CO), nitrogen oxides (NOX), sulfur
dioxide (SO2), total hydrocarbons (THCs), hydrogen chloride (HCI), dioxins/furans,
PAHs, and the metals Pb, As, Cd, Cr, Mn, Ni and Hg.
Among the specified analytes, NMOC is the only one specified on the AP-42 list. The
VOCs analyzed individually for the raw LFG were not individually targeted for the
control technology exhaust gases because of the expected very low concentrations
there. This assumption turned out to be not true for 1C engines.
The gases O2 and CO2 were common combustion performance control parameters.
CO, NOX and SO2 are criteria pollutants, the formation of which is generally associated
with combustion processes.
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
3-4
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
Table 3-2. Target Analytes for the Control Technology Exit Gas
Target Analytes in AP-42 List of Landfill Gas Constituents
NMOCs
Target Analytes Not Previously Included in AP-42
Gases:
02
CO2
CO
NOx
SO2
HCI
PCDD/PCDF
PAHs
Metals:
Pb, As, Cd, Cr, Mn, Ni
Hg (total)
The emission reduction performance of hydrocarbons is determined using either
Method 25C or 25A. If the NMOC concentration is less than 50 ppm, then Method 25A
is recommended for use.
The remaining target analytes include HCI, PCDDs/PCDFs, PAHs, total Hg, and toxic
heavy metals (Pb, As, Cd, Cr, Mn, Ni). These analytes are also identified is EPA's list
of HAPs.
3.3 Sampling and Analysis Methods
3.3.1 Raw Landfill Gas Sampling Analysis Methods
Table 3-3 lists the sampling, analysis and measurement methods that were followed at
the raw LFG header pipe location. The table also included the name of the
organizations that performed the procedures. With the exception of the organic
mercury methods for mercury analysis, ARCADIS staff performed the field collection of
samples and associated data collection. Where multiple organizations are listed, the
3-5
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
Table 3-3. Testing Methods for Raw LFG
Procedure
EPA Method 1
EPA Method 2
EPA Method 3C
EPA Method 1 1
EPA Method 23
EPA Method 25C
EPA Method
40/TO-15
SW-846 Method
0100/TO-11
LUMEX instrument
Organic mercury
methods
Description
Selection of traverse points
Determination of gas velocity and volumetric
flow rate
Determination of CC>2, ChU, nitrogen (ISb), and
O2 in raw LFG
Determination of h^S
Determination of:
PCDDs/PCDFs by Method 8290,
PAHs by Method 8270
PCBs by Method 1668
Determination of raw LFG NMOCs
Determination of VOCs
Determination of carbonyls (formaldehyde,
acetaldehyde)
Determination of elemental mercury (Hg°)
Determination of:
monomethylmercury,
dimethylmercury, and
total mercury.
Organization Performing Analysis
ARCADIS G&M
ARCADIS G&M
Triangle Environmental Services
Oxford Laboratories (Landfills A, B,
C, D)
Enthalpy Analytical (Landfill E)
ALTA Analytical Perspectives
Triangle Environmental Services
Research Triangle Park
Laboratories
Resolution Analytics
ARCADIS G&M
Frontier Geosciences (Landfills A, B,
C, D, E)
Studio Geochimica (Landfill E)
letters A, B, C, D, and E in parenthesis following the organization denote the landfill
site for which the organization was the performing organization.
Where multiple organizations are listed, the letters A, B, C, D, and E in parenthesis following the
organization denotes the landfill site for which the organization was the performing organization.
3-6
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
3.3.2 Control Technology Exit Sampling Analysis Methods
Table 3-4 lists the sampling, analysis and measurement methods that were followed at
the control technology exit stack. As before, the table also included the name of the
organizations that performed the procedures. ARCADIS staff performed the field
collection of samples and associated data at this sampling location.
Table 3-4. Testing Methods for Control Technology Exit Gas
Procedure
EPA Method 1
EPA Method 2
EPA Method 3A
EPA Method 4
EPA Method 6C
EPA Method 7E
EPA Method 10
EPA Method 23
EPA Method 25A
EPA Method 26A
EPA Method 29
LUMEX instrument
Description
Selection of traverse points
Determination of stack gas velocity and
volumetric flow rate
Determination of 62 and CC>2 for flare stack
gas molecular weight calculations
Determination of stack gas moisture
Determination of SC>2
Determination of NOx
Determination of CO
Determination of:
PCDDs/PCDFs by Method 8290,
PAHs by Method 8270
PCBs by Method 1668
Determination of flare stack gas NMOCs, as
THCs when total organic concentration was
less than the 50 ppm Method 25C applicability
threshold
Determination of HCI
Determination of toxic heavy metals
Determination of elemental mercury (Hg°)
Organization Performing Analysis
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
ALTA Analytical Perspectives
ARCADIS G&M
Resolution Analytics
First Analytical Laboratories
ARCADIS G&M
3.4 Field Test Sampling Operations Narrative
As stated earlier, sampling typically required a sample team with seven or more
experienced samplers. Prior to the tests, site visits to each landfill were conducted to
3-7
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
gather necessary information for developing the quality assurance project plans and
making arrangements for the field tests. The ARCADIS field chief noted the availability
of sample ports and made arrangements with the host facility to have them installed if
suitable ports were absent. He confirmed that the necessary staging area was
available and that needed electrical utilities were accessible.
Two or more days before the scheduled tests, ARCADIS staff transported its field
sampling trailer to the site. The trailer carried the needed sampling instruments,
supplies, and emission monitors. Typically, one day of on-site preparation was needed
before the scheduled test began.
The actual sample collection required two full days. All measurements and samples
were collected in triplicate. The test samples and the required QA samples (field blanks
and spike samples) were prepared, recovered, and recorded on sample chain-of-
custody forms on site. The samples were transported back to ARCADIS' offices in
Durham, North Carolina, by ARCADIS' sampling truck-trailer. The sample custodian,
together with the sampling crew chief, made the arrangements to deliver the samples
to the subcontracted laboratories for analysis.
3.5 Variation from Test Methods or Planned Activities
The test program for the five landfills spanned over three and a half years. Results
from the earlier tests were used to guide the later tests. Some of the originally planned
test methods were substituted by other methods and are described in the following
sections.
3.5.1 Method Exceptions
Laboratory analytical procedures followed those prescribed by the specified methods,
with the following exceptions.
3-8
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
3.5.1.1 Raw Landfill Gas
Alternative method for the raw landfill gas samples included the following:
• Carbonyls were analyzed by EPA TO-11, instead of the originally selected Method
8315. Methods TO-11 and 8315 closely resemble each other.
• PAHs in the raw LFG were to be analyzed by SW-846 Method 8270 - The sample
extracts resulting from the raw LFG were found to contain excessive amounts of
non-PAH organics. In retrospect, this should have been expected as the LFG is
organic-rich (~40%). In order to make the extracts safe for injection into the gas
chromatograph mass spectrometer (GC/MS) (i.e., not cause instrument damage),
they have to be diluted significantly. The high dilution makes the method detection
levels for the target PAHs too high, resulting in "non-detects" at high detection
limits. The planned analysis method could not produce PAH concentrations at the
needed detection levels. The sample extracts are in storage and may be submitted
for analysis if a suitable method is available. These analyses were deleted from the
Landfills C, D, and E tests.
• PCBs in the raw LFG were analyzed by EPA Method 1668 (EPA 812/R-97-001) as
specified in the QAPP. However, similar to the difficulties experienced for the PAH
analysis, in order to make the extracts safe to be injected inject into the GC, they
have to be diluted excessively. The planned analysis method could not produce
the desired results at the needed detection levels. These analyses were deleted
from the Landfills C, D and E tests.
• NMOCs were analyzed by the GC/MS Method as described in EPA Publication
EPA/600-R-98/16.
• VOCs and CH4 were analyzed by EPA Method TO-15, with GC/MS and with
GC/flame ionization detector (FID).
• Method 3C for the analysis of CH4, CO2, O2, and N2 was added to support the
Method 25C analysis, as recommend by Method 25C.
• For Landfills C, D, and E, the sampling procedure for dimethylmercury was altered
by reducing the sample size volume on the Carbotrap from 10 L to 0.5 L.
3-9
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
3.5.1.2 Control Device Exit
Alternative method for the control device exit samples included the following:
• Method 25A was to evaluate organic compound concentrations in the combustion
outlet because of the low concentrations detected in Phase 1 sites. Method 25C is
applicable at concentrations of 50 ppmv or more. However, test results showed
that the 1C engines exhaust gases contained several hundred ppm of THCs.
Therefore, for any future field tests for 1C engines, Method 25C should be used to
quantify NMOCs rather than Method 25A.
• For Method 23 samples collected at Landfill C, analyses for PAHs were performed
by GARB Method 429 as opposed to Method 8270. However, these methods are
comparable. GARB Method 429 contains procedures for sampling, sample
recovery, clean-up, and analysis. Method 8270 is strictly an analytical method.
GARB Method 429 is specific to 19 PAHs, the target analytes of this portion of the
specified tests. The 19 PAHs are a subset of the 200+ target analytes listed for
Method 8270 for semivolatile organic compounds (SVOCs). Though specific
compounds called out for use in instrument performance verifications, internal
standard preparation, surrogate standards and continuing calibration
verifications/calibration checks are slightly different, both methods require them.
GARB Method 429 adds another level of QC with a required recovery standard.
Method performance and acceptance criteria for recoveries are better defined in
GARB Method 429 and meet or exceed those stated in Method 8270C. As long as
any additional compounds reported by the laboratory using GARB Method 429 are
included in the calibration standards and acceptable response factors are
demonstrated, using GARB Method 429 is essentially equivalent to using SW-846
Method 8270.
• As a result of examining the test results from Landfill A, which showed very low
concentrations of PCDDs/PCDFs/PAHs at the exit of an enclosed flare, no Method
23 sampling was conducted at Landfill D, also a site with an enclosed flare. A
decision was made to not sample for PCDDs/PCDFs at the exit of the enclosed
flare systems because the combustion gas temperature conditions found in the exit
of an enclosed flare system were not likely to allow the formation of
PCDDs/PCDFs. This also eliminated analysis of PAHs which uses the same
sample.
3-10
-------
4. Test Results
The following sections present data summaries of the measurements that were
planned and conducted. Section 4.1 and its subsections present data related to the
raw LFG. Section 4.2 and its subsections present data for the combustion exhaust
gases at the exit of the flares, engines, and boiler.
4.1 Raw Landfill Gas
4.1.1 Landfill Gas Flow Rate and Temperature
Table 4-1 presents information regarding the LFG flow rate for each landfill. The LFG
flowrate ranged from a low of 400 scfm for Landfill D to over 4000 scfm for Landfill E.
Landfill E was a much larger landfill as it was reported to have over 14 million tons of
waste in place, while Landfill D had about 2.4 million tons of waste.
The LFG header pipes at all the landfills did not have sufficiently long straight pipe
sections to allow ideal EPA Method 2 gas velocity measurements. Velocity
measurements were made under non-ideal conditions and were able to provide crude
estimates of the LFG flowrates. For the purpose of this study, the estimated LFG
flowrates were judged to be sufficiently accurate. For their intended use to estimate
pollutant emission rates, the added cost of needed improvement of the landfill gas
header piping system, and associated potential schedule delay, were not warranted.
Temperature of the LFG ranged from 54 to 71 °F. Landfill E, with the largest volume of
LFG, also had the highest measured LFG temperature.
4.1.2 Landfill Gas Constituent Concentrations
The principal focus of this test program was to determine the constituents that were
present in the raw LFG. The major constituents consist of CH4, CO2, N2, O2 and
moisture. These constituents were present in percent levels. Other constituents were
the various organic compounds which were present in ppm or lower concentrations.
Landfill gas also contained mercury including methyl- and dimethylmercury.
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
4-1
-------
Table 4-1. Raw LFG Flow Rates
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
Parameter
Facility flowrate readings
(scfm)
ARCADIS measured flow
rate by pitot probe (scfm)
LFG gas temperature
(°F)
Reported amount of waste
(ton)
Header pipe inner
diameter
(in)
Straight pipe upstream
(No. of pipe diameters)
Straight Pipe Downstream
(No. of pipe diameters)
Vacuum in header pipe,
Inches water column
(WC.)
Landfill A
1650-1700
J
1580 J
57
2,700,000
in 2003
12
o
~o
~4
34-35
Landfill B
1500 J
1745 J
62
4,000,000
in 2003
11
<2
<2
-
Landfill C
550-600 J
700 J
56
6,400,000
in 2004
14
>8
>8
21
Landfill D
400 J
380-850 J
54
2,350,000
in 2004
11
>8
>8
—
Landfill E
4340 J
3860 J
71
14,500,000
in 2005
16
<2
<2
-
J -Estimated value per EPA/G-8 guidance
4.1.2.1 Major Constituents (CH4, COa Cy by Method 3C and NMOCs by Method 25
Table 4-2 presents the concentrations of the major LFG constituent components and
NMOCs. The tabled provides the range and average for each of the constituent
concentrations.
The concentrations CH4, CO2, O2, N2, moisture and NMOCs varied over quite a wide
range between the landfills. In particular, Landfill D showed unusually high CH4 content
of more than 55 percent. Landfill B showed the lowest methane concentration, at just
below 40 percent.
4-2
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
Table 4-2. Raw LFG Major Constituents
Method
25C
Method
3C
Method
23
Constituent
Methane (% v/v)
Carbon Dioxide
(% v/v)
NMOC (ppm as
hexane)
Methane (% v/v)
Carbon Dioxide
(% v/v)
Oxygen (% v/v)
Nitrogen (%v/v)
Moisture (% v/v)
Range
Average
Range
Average
Range
Average
Range
Average
Range
Average
Range
Average
Range
Average
Range
Average
Landfill A
48.0-49.8
48.8
38.1-39.4
38.7
297-491
374
43.5-45.4
44.5
35.2-36.9
36.1
1.6-1.8
1.7
12.7-13.4
13.1
11.6-12.3
12.0
Landfill B
37.7-40.6
39.2
29.5-31.9
30.7
314-377
355
35.2-37.3
36.1
28.2-29.9
29.0
6.0-6.6
6.4
24.4-26.2
25.6
1.8-2.1
2.0
Landfill C
54.6-57.7
56.0
45.2-47.2
46.2
3650 - 9330
5870
47.4-49.1
48.0
35.4-36.9
35.9
1.4-1.9
1.6
13.5-18.9
15.9
NM
Landfill D
57.4-59.5
58.6
40.2-41.7
41.0
971 -1024
1006
54.3-55.6
55.1
37.6-38.5
38.1
0.01 -0.02
0.02
9.5-12.8
11.2
NM
Landfill E
46.7-50.9
49.5
33.3-36.3
35.3
194-288
233
46.8-51.7
49.5
30.2-31.9
31.3
2.1 -3.4
2.6
11.9-16.4
13.6
NM
NM - Not measured because moisture data were obtained by Method 23, which were not conducted during these tests.
All values are reported on an as-is basis, without correction for nitrogen-indicated potential air infiltration.
Data on the moisture in the LFG were only available for Landfills A and B because the
data is a computed output of the Method 23 sampling procedure. Method 23 samples
were collected for PAH and PCB analysis. This procedure was deleted from the test
program after experiences with Landfills A and B samples revealed that the analysis
could not be done. More explanation of this finding will be presented later in this report.
Without Method 23 sampling for Landfills C, D, E, no moisture data were collected.
4.1.2.2 Other Constituents
In addition to the major constituents, the other lower concentration constituents were of
interest because of their potential to cause adverse health effects. The following
sections summarize the results related to these compounds.
4-3
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
4.1.2.2.1 VOCs by Method 0040 with TO-15
Table 4-3 presents the average concentrations of the target volatile organic
compounds. The concentration data were obtained by summa canister samples
collected using Method 40 procedures. Analysis was performed by Method TO-15, with
gas chromatography and mass spectrometry (GC/MS). The alkanes (C2 through C6),
being present in much higher concentrations, were analyzed by GC flame ionization
detection (FID).
Table 4-3. Raw LFG Volatile Organic Compounds
Compound
By gas chromatography flame
ionization detector (GC/FID)
Ethane
Propane
Butane
Pentane
Hexane
By TO-15 gas
chromatography and mass
spectrometer (GC/MS)
Dichlorodifluoromethane (Freon
12)
1,2-Chloro-,1,2,2-
Tetrafluoroethane (CFC114)
Chloromethane
Vinyl chloride
1 ,3-Butadiene ((Vinylethylene)
Bromomethane (Methyl
Bromide)
Chloroethane (Ethyl Chloride)
Trichloromonofluoromethane
(CFC11)
Unit
Part
per
million
by vol
(ppmv)
ppmv
ppmv
ppmv
ppmv
Part
per
billion
by vol
(ppbv)
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
Method
Detection
Limit (NDL)
Range a
1
1
1
1
1
0.2
0.2
0.1
0.2
0.2
0.2
0.2
0.2
1
1
1
1
1
0.3
0.2
0.2
0.2
0.3
0.2
0.2
0.2
Average Concentration b
Landfill A
6.2
8.9
4.9
3.2
Not
Detected
(ND)
118
8
12
97
22
16
770
51
Landfill B
4.6
5.9
3.3
2.6
ND
468
44
72
410
89
46
1880
327
Landfill C
14.3
40.0
37.9
26.6
28.4
1600
127
1263
768
642
23
30400
504
Landfill D
5.6
30.5
ND
2.4
2.5
1240
110
232
1200
326
2.8
634
116
Landfill E
14
13.0
3.6
1
ND
232
15.3
ND
63
ND
ND
ND
8.1
4-4
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
Compound
1,1-Dichloroethene
1,1,2-Trichloro-1,2,2-
trifluoroethane (CFC113)
Carbon Disulfide
Ethanol
Isopropyl Alcohol (2-Propanol)
Methylene chloride
(Dichloromethane)
Dimethyl sulfide
Acetone
t-1 ,2-dichloroethene
Hexane
Methyl-t-butyl ether (MTBE)
1,1-Dichloroethane
Vinyl Acetate
cis-1 ,2-Dichloroethene
Cyclohexane
Chloroform
Ethyl Acetate
Carbon Tetrachloride
Tetrahydrofuran (Diethylene
Oxide)
1 ,1 ,1-Trichloroethane
2-Butanone (Methyl Ethyl
Ketone)
Heptane
Benzene
1,2-Dichloroethane
Trichloroethylene
(Trichloroethene)
1 ,2-Dichloropropane
Bromodichloromethane
1,4-Dioxane (1,4-Diethylene
Dioxide)
cis-1 ,3-Dichloropropene
Toluene (Methyl Benzene)
4-Methyl-2-pentanone (MIBK)
Unit
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
pppv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
Method
Detection
Limit (NDL)
Range a
0.2
0.2
0.2
0.2
0.2
0.1
20
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.3
0.2
0.2
0.2
20
0.3
0.3
0.3
0.3
0.4
0.5
0.3
0.3
0.3
0.3
0.5
0.4
0.5
0.3
0.2
0.2
0.3
0.2
0.3
0.2
0.2
0.2
0.3
0.2
Average Concentration b
Landfill A
1.7
2.0
14.4
19.7 J
114 J
997
ND
328
2.7
2470 J
54.4
33.4
242
74.1
165
40
1830
0.8
1180
4.9
273
242
73
1.0
28.0
0.8
2.6
1.9
0.2
1330
1070
Landfill B
8
11
134
202
356
169
ND
1610
9
1950
177
178
686
292
734
190
2310
5
882
31
1430
918
251
5
103
5
10
9.4
1.4
6770
886
Landfill C
55
39
157
172
1280
5350
68
11700
42
4940
257
423
24
1640
3300
744
1420
ND
1170
ND
4570
2860
1630
37
515
ND
ND
7
ND
23300
2170
Landfill D
21
19
93
394
6630
1110
ND
12800
53
3980
39
591
44
1780
2270
485
4600
38
2060
ND
8070
3580
1200
22
418
ND
ND
12
4
30300
ND
Landfill E
ND J
ND
339
ND J
2360 J
3050
ND
15500
ND
597 J
ND
ND
111
163
ND
ND
ND
ND
ND
ND
2490
331
887
ND
93.9
ND
ND
ND
ND
7950
ND
4-5
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
Compound
t-1 ,3-Dichloropropene
Tetrachloroethylene
(Perchloroethylene)
1 ,1 ,2-Trichloroethane
Dibromochloromethane
1,2-Dibromoethane (Ethylene
dibromide)
2-Hexanone (Methyl Butyl
Ketone)
Methyl Mercaptan
(Methanethiol)
Ethylbenzene
Chlorobenzene
m/p-Xylene (Dimethyl Benzene)
o-Xylene (Dimethyl Benzene)
Styrene (Vinylbenzene)
Tribromomethane (Bromoform)
1 ,1 ,2,2-Tetrachloroethane
1-Ethyl-4-methylbenzene (4-
Ethyl Toluene) see Note c
1 ,3,5-Trimethylbenzene see
Note c
1 ,2,4-Trimethylbenzene
1 ,4-Dichlorobenzene
1 ,3-Dichlorobenzene
Benzyl Chloride
1,2-Dichlorobenzene
1,1,2,3,4,4-Hexachloro-1,3-
butadiene
1 ,2,4-Trichlorobenzene
Acrylonitrile
Dichlorofluoromethane
(Freon21)
Chlorodifluoromethane
(Freon 22)
Ethyl Mercaptan (Ethanediol)
Carbonyl Sulfide (Carbon
oxysulfide)
Unit
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
Method
Detection
Limit (NDL)
Range a
0.2
0.2
0.2
0.2
0.2
0.2
20
0.2
0.2
0.2
0.2
0.1
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
20
20
20
20
20
0.2
0.3
0.2
0.2
0.2
0.2
20
0.3
0.2
0.65
0.3
0.2
0.3
0.2
0.2
0.2
0.3
0.3
0.3
0.2
0.3
0.2
0.3
20
20
20
20
20
Average Concentration b
Landfill A
0.3
42.1
7.6
ND
1.1
557
ND
575
195
3730 J
300
29.5
0.4
29.9
79.3 J
79.3 J
193
43.4
0.5
6.3
1.9
1.2
1.0
ND
ND
ND
ND
ND
Landfill B
3
176
39
16
7
441
ND
2800
229 J
3980
1410
222
ND
ND
386 J
386 J
949
255
2.03
20
0.4
5
5
ND
ND
ND
ND
ND
Landfill C
33
1690
445
9
21
ND
ND
5890
833
9200
3660
1270
16
ND
894 J
894 J
1510
328
394
ND
ND
ND
ND
ND
ND
ND
ND
ND
Landfill D
8
1020
ND
16
ND
ND
ND
8120
21
13600
5410
1180
9
ND
976 J
976 J
2190
686
650
ND
31
ND
ND
ND
ND
ND
ND
ND
Landfill E
ND
125
ND
ND
ND
ND
ND
ND
135
9000 J
3100
420
ND
ND
2510
1040
2640
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
4-6
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
ND - Constituent not detected at the stated method detection limits
a - Method detection limits provided by analytical laboratory
b - In computing averages, when all measurements are ND, the average is reported as ND. When one or
more measurement is above detection, the ND measurement is treated as 50% of the stated MDL. Though
not applicable here, the method further specifies that If MDL is not reported, a ND measurement is treated
as zero.
c -1 -Ethyl-4-methylbenzene (4-Ethyl Toluene) and 1,3,5-Trimethylbenzene co-eluted from the GC and also
have the same quantitation ions, thus making them indistinguishable. Therefore, the reported values
represent the combined concentrations of these two compounds.
J - Estimated value per EPA QA/G-8 guidance
4.1.2.2.2 Hydrogen Sulfide (H2S) by Method 11
Table 4-4 present the concentrations of hydrogen sulfide measured with Method 11.
H2S concentrations ranged from a low average concentration of 13 ppmv in Landfill A
to a high average concentration of 322 ppmv for Landfill E.
Table 4-4. Raw LFG Hydrogen Sulfide
(mg/m3)
(ppmv)
Range
Average
Range
Average
Landfill A
10.7-26.1
18.5
7.6-18.4
13.0
Landfill B
26.4-36.1
32.3
18.7-25.6
22.9
Landfill C
26.8-110.0
78.3
19.0-78.0
55.5
Landfill D
32.1-185.6
102.6
22.7-132
72.7
Landfill E
413-519
458 J
291 - 366
322 J
J Estimated value per EPA QA/G-8 guidance
4.1.2.2.3 Carbonyls by Method 0100 & 8315A
Table 4-5 presents the concentrations of formaldehyde and acetaldehyde. Notably,
acetaldehyde was uniformly present at a higher concentration than formaldehyde.
Formaldehyde was present in the single-digit to low-tens of ug/m3. Acetaldehyde was
present at concentration several times higher than formaldehyde.
4-7
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
Table 4-5. Raw LFG Carbonyls
Formaldehyde
Acetaldehyde
(Mg/m3)
(X10'3
ppmv)
(pg/m3)
(X10'3
ppmv)
Range
Average
Range
Average
Range
Average
Range
Average
Landfill A
2.3-5.0
4.1
1.8-4.1
3.3
18.9-67.8
45.7
10.3-37.0
24.9
Landfill B
3.3-4.1
3.6 J
2.65-3.30
2.90 J
21.9-35.0
27.0
12.0-19.2
14.8
Landfill C
26.9-46.6
33.9
22.7-37.3
27.2
114-495
242
62.4-27.0
132
Landfill D
16.0-39.0
25.0
12.9-31.5
20.1
72 - 534
348
39 - 293
191
Landfill E
8.1-11.8
9.6
6.5-9.6
7.8
27.9-151
92.4
15.3-82.8
50.6
4.1.2.2.4 PAHs by Method 0010 with 8270
As discussed previously in Section 3.5.1.1, attempts to analyze the PAH
concentrations in the raw LFG were unsuccessful.
4.1.2.2.5 PCBs by Method 0010 with 1668
As discussed previously in Section 3.5.1.1, attempts to analyze the PCB
concentrations in the raw LFG were unsuccessful.
4.1.2.2.6 Mercury
Mercury comes in various forms. It can be bound to particulates or in a gaseous
form. Gaseous mercury species is either organic or inorganic. Organic mercury or
methyl mercury is more toxic and regarded as a priority for determining the potential
release from U.S. landfills. Previous testing has identified both methyl and dimethyl
mercury in landfills.
Metallic, or elemental mercury, is an inorganic form used in products such as electrical
switches, fluorescent bulbs, and thermometers. It is a liquid and can evaporate into the
air as a gas. Inorganic mercury compounds take the form of mercury salts. Oxidized
mercury (sometimes called ionic or reactive gaseous mercury (RGM) is found
predominantly in water-soluble forms and may be deposited at a range of distances
from sources depending on a variety of factors including topographic and
meteorological conditions downwind of a source. Once mercury is deposited into
bodies of water like lakes or streams, it can be converted to methyl mercury through
microbial decomposition in soils and sediments. In this form, it is taken up by tiny
aquatic plants and animals. Fish that eat these organisms build up methylmercury in
4-8
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
their bodies. As ever-bigger fish eat smaller ones, the methylmercury is concentrated
further up the food chain which is referred to as "bioaccumulation".
Table 4-6 summarizes the results of the mercury measurements which include ograno-
mercury (i.e., dimethyl and monomethyl), elemental mercury, and total gaseous
mercury. Total mercury and organo-mercury were sampled and analyzed by the
Organic mercury method. Elemental mercury was measured by the LUMEX
instrument. Oxidized mercury was not analyzed directly but can be determined by
subtracting elemental and organo-mercury from total mercury.
The dimethyl mercury data for Landfills A and B did not meet data quality objectives
and the results were rejected due to low spike recoveries. During the Landfill A and B
tests, total sample volumes collected for dimethyl mercury on the Carbotrap were
approximately 10 L. The analysis of these samples resulted in poor recovery of spiked
dimethyl mercury. According to the researchers of the analytical laboratory, the poor
spike recoveries could be attributed to the migration of the spiked material during
sampling. The extent of material migration was believed to be highly dependent on
sample volume. Therefore spike recoveries in this instance could be improved by
reducing the sample volume.
For Landfills C, D, and E, the sampling procedure for dimethyl mercury was altered by
reducing the sample size volume on the Carbotrap from 10 L to 0.5 L. The modified
procedure resulted in much improved spike recoveries. The details of the mercury
measurement methods and method development experiences were included in the
Landfill C, and D reports, which are provided in appendices to this document.
Most of the mercury found was in the elemental state. The concentrations of the
organic forms of the mercury were about two orders of magnitude lower than the total
and elemental mercury concentrations. The results are comparable to those reported
by Lindberg et al. in 2005 for twelve landfills, although the total amount of mercury
reported in Lindberg et. al. 2005 is as much as one order of magnitude greater than the
total mercury reported here. In the Lindberg study, total gaseous Hg ranged from 10 to
12000 ng/m3. Dimethyl mercury ranged from 4.5 to 77 ng/m3 and monomethyl mercury
ranged from non-detect to 39 ng/m3.
Total mercury concentration averages ranged from 204 to 1460 ng/m3. Of these
amounts, elemental mercury was the highest component, with its averaged values
ranging from 58 to 440 ng/m3. Dimethyl mercury was the next most prevalent. After
discarding the Landfills A and B data because it did not meet data quality objectives,
dimethyl mercury averaged concentrations ranged from 15 to 53 ng/m3 approximately.
4-9
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
Monomethyl mercury was present at the lowest concentration, ranging from less than 1
to 5.4 ng/m3
Using the total mercury measurements as the basis, the sum of the elemental,
monomethyl and dimethyl mercury species contributed to about 28 to 49 percent of the
total mercury measured. It is suspected that the majority of the remaining mercury is
in the oxidized form.
Table 4-6. Raw LFG Mercury Compounds
Total
Dimethyl
Monomethyl
Elemental
(ng/m3)
(X10'6ppmv)
(ng/m3)
(X1 0"6 ppmv)
(ng/m3)
(X10'6ppmv)
(ng/m3)
(X1 0"6 ppmv)
Range
Average
Range
Average
Range
Average
Range
Average
Range
Average
Range
Average
Range
Average
Range
Average
Landfill A
601-676
632
72.4-81.4
76.1
R
R
ND-1.2
0.4
ND-0.13
0.04
280 - 325
308
33.7-39.1
37.1
Landfill B
158-234
204
17.7-26.2
22.8
R
R
1.1-1.3
1.2
0.12-0.15
0.13
53-61
58
6.4-7.3
7.0
Landfill C
423 - 427
425
50.9-51.4
51.2
6.5-20.9
14.8
0.7-2.2
1.5
3.1-5.4
3.9
0.35-0.60
0.44
90-103
99
10.8-12.4
11.9
Landfill D
723 - 751
740
87.0-90.4
89.1
49.7-53.1
51.0
5.2-5.6
5.3
2.40-2.64
2.47
0.264-0.296
0.278
265 - 290
278
31.9-34.9
33.5
Landfill E
1330-1650
1460a
149-184
163.5 a
17.4-99.8
52.5 a
1.82-10.5
5.5 a
3.4-8.2
5.4 a
0.380-0.920
0.61
437 - 445
440
52.6-53.6
53.0
R - Data rejected because spike recovery for these measurements were below acceptable range
ND - Constituent not detected at the detection limit of 0.63 ng/m3
a - Values are averages of Frontier and Geochimica results
4-10
-------
4.1.2.2.7 Metals by Method 29
The standard Method 29 is the reference method to determine trace concentrations of
the toxic metals. However, the method was designed for sample streams that are not
rich in organic constituents because it uses a strong oxidizer, potassium permanganate
solution, to capture the metals. The concern with applying this method to LFG was that
the potassium permanganate might react violently with the organic constituents in the
LFG. If that happened, the measurement would be invalidated and analysis might also
pose safety risk to the sampling personnel. Therefore, it was not included in the test
program.
4.2 Control Equipment Stack
The following subsections present the results obtained from measurements made at
the control equipment stack.
4.2.1 Gas Flow Rate and Temperature
Table 4-7 presents the exhaust gas flowrates and their temperatures at the stack of the
five control devices. The flowrates were obtained by velocity traverse measurements
performed according to EPA Method 2. The flowrates reflected the size of the control
equipment and ranged from 1310 scfm for the Landfill A engine to more then 28000
scfm for the Landfill E boiler.
The enclosed flares had the highest temperatures, at about 1400 °F. This was
consistent with the nature of the process. Flares do not have active heat utilization and
removal. The measured temperatures were lower than the expected flame
temperatures because of the introduction of dilution air.
The boiler in Landfill E had the lowest exit temperature at about 480 °F. The observed
temperature was consistent with typical boiler operations. The two reciprocating 1C
engines resulted in exhaust temperature around 735 °F for Landfill A's Caterpillar 3412
and 1000 °F for Landfill C's Caterpillar 3516. The Caterpillar 3516 was more than twice
the size of the Caterpillar 3412.
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
4-11
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
Table 4-7. Control Equipment Exit Stack Flow Rate and Temperature
Control
Technology
Unit Model
Size or
Capacity
LFG Flowrate
into Equipment
(scfm)a
Exit Flowrate
(dscfm)
Exit Gas
Temperature
(°F)
Range
Average
Range
Average
Landfill A
Reciprocating 1C
Engine
Caterpillar 341 2
1649 cu. in
displacement,
470KW
150
1290-1340
1310
732 - 738
735
Landfill B
Enclosed Flare
Perennial
Energy
10.8 to 54
MMBtu/hr
1500
19700-22000
20700
1359-1419
1389
Landfill C
Reciprocating 1C
Engine
Caterpillar 351 6
4210 cu. in
displacement,
800KW
300
1890-2000
1950
997-1038
1016
Landfill D
Enclosed
Ground Flare
John Zink Model
72
4.0 to 20.9
MMBtu/hr
400
7830 - 8290
8080
1412-1446
1437
Landfill E
Boiler
Combustion
Engineering 33-
7KT-10AType
80,000 Ib/hr 250
psi steam
2430
26820 - 30400
28690
476 - 488
479
a -This is a crude estimate based on the measured exit flow rate, the measured exit oxygen
concentration and the major constituent analysis of the LFG.
4.2.2 Exhaust Gas Constituent Concentrations
The following sections present the concentration and emission rates of the combustion
products O2, CO2, CO, SO2, NOX, THCs, HCI, dioxin /furans, PAHs, and toxic heavy
metals.
4.2.2.1 OEM Constituents (O2, CO, CO2, SOZ NOX)
Table 4-8 presents the average concentrations of O2, CO, CO2, SO2, and NOX found in
the control devices' exhaust gases. For the most part, they are unremarkable, except
for the very apparent and substantially higher concentrations of CO, THC and NOX that
are produced by the engines. The boiler was by far the most efficient combustion
device as it produced the lowest concentrations of CO and THCs. The flares tended to
produce more CO, especially if the more highly diluted flare exhaust gas was
accounted for. In addition to producing higher concentrations of CO and THC, the
engines also produced significantly higher concentrations of NOX. The Landfill C
engine, in particular, produced about 2700 ppm of NOX, an alarmingly high level by any
measure.
4-12
-------
Table 4-8. Control Equipment Exit O2, CO, CO2, SO2, NOX
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
O2 (% v/v)
CO2 (% v/v)
Moisture
(% v/v)
CO (ppmv)
SO2 (ppmv)
NOx(ppmv)
Remarks
Range
Average
Range
Average
Range
Average
Range
Average
Range
Average
Range
Average
Landfill A
7.4-7.6
7.5
12.8-13.2
12.9
11.3-12.5
12.1
549 - 570
560
29-39
34
142-183
166
Landfill B
12.5-16.1
14.9
2.9-4.8
4.2
5.8-7.3
6.5
11-13
10
3-8
6
10-12
11
0.6 sec at
1400 °F
Landfill C
2.3-3.2
2.7
15.6-16.5
16.3
16.2-18.3
17.0
556 - 585
568
-ND
ND
2280-3150
2730
Landfill D
13.5-13.5
13.5
6.3-6.4
6.4
7.9-10.3
8.4
69-92
80
ND
ND
7.7-9.7
8.5
Landfill E
7.2-7.9
7.5
12.1 -12.5
12.3
11.6-14.1
12.6
ND-14
9
41-68
55
3-21
13
ND - Constituent not detected at the detection limit of 2.0 ppmv
4.2.2.2 Other Constituents
4.2.2.2.1 THCs by Method 25A
Table 4-9 presents the concentrations of organic materials found in the control device
exhaust gases. The measurement was made with a continuous emission monitor, in
Table 4-9. Control Equipment Exit Total Hydrocarbon
As Propane,
(Ppmv)
As Hexane,
(Ppmv)
Range
Average
Range
Average
Landfill A
645 - 786
730
323 - 393
365
Landfill B
ND-6
4
ND-3
2
Landfill C
893 - 994
940
447 - 497
470
Landfill D
31.3-35.6
34.1
15.7-17.8
17.1
Landfill E
ND
ND
ND
ND
ND - Constituent not detected at the detection limit of 1.0 ppmv
4-13
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
accordance with Method 25A. Hydrocarbons concentrations were low for Landfill E's
boiler, fluctuating near the bottom of the instruments zero point. They were also very
low for Landfill B's flare. Landfill D's flare had a bit more THC in its stack gas, at about
17 ppm hexane. In contrast, both 1C engines produced exhaust gases that contained
more than 350 ppm of hexane-equivalent hydrocarbons.
The purpose of this measurement was to determine the amount of hydrocarbons in the
exhaust gases. Method 25A is suitable for this purpose. Moreover, identification and
quantitation of individual organic compounds were not objectives of this test program.
For future field tests, when there is a requirement to identify organic constituent
species in engine exhausts, we would recommend using EPA Method 40, which is well
suited to identify and quantify volatile organic compounds.
This project included measurements for PCDD/PCDFs and PAHs in the stack gases
and these data are presented later in this report.
4.2.2.2.2 Dioxin/Furans by Method 23 with 8290
Combustion processes with chlorinated compounds have the potential of producing
polychlorinated dioxins and furans (PCDD/PCDF). This is particularly relevant if the
combustion is not efficient and if the combustion products are allowed to cool down
slowly where they can come into contact with a particle-laden surface.
Sampling for PCDD/PCDFs was performed for all landfills except for Landfill D, which
used an enclosed flare. The decision to exclude Landfill D was based on two
considerations. Tests at Landfill B where enclosed flare was used resulted in
PCDD/PCDF data that were mostly below detection limits. Further, these findings were
consistent with the understanding that the flare exit gases could not possibly be cooled
to reach temperatures that were favorable to dioxin formation. Given the high cost of
sampling and analysis for PCDD/OCDF, it was decided not to conduct PCDD/PCDFs
at the second enclosed flare site.
Table 4-10 presents the PCDD/PCDF concentrations. As can be seen, PCDD/PCDFs
were mostly below detection limits, except for Landfill E. The boiler in Landfill E is a
device that is understood to have the potential to present the conditions that favors
PCDD/PCDF formation, which was confirmed.
4.2.2.2.3 PAHs by Method 0010 with 8270
Table 4-11 presents the concentrations of PAHs in the combustion stack gases.
Consistent with the THC data presented earlier, the 1C engines resulted in the highest
4-14
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
concentrations of PAHs. In an attempt to provide a means of comparing the control
technologies, Table 4-11 included a normalized PAH emission factor expressed as the
amount of PAHs emitted per cu. ft. of LFG combusted. As shown, the 1C engine at
Landfill C was found to emit the highest amount of PAHs at 0.01 mg/cu. ft. LFG. In
contrast, the boiler at Landfill E and the flare at Landfill B were both found to emit 0.003
mg/cu. ft. LFG.
4.2.2.2.4 HCI by Method 26A
Table 4-12 presents the HCI concentrations at the control device stacks. They ranged
from about 0.9 to 14 ppmv (1.4 to 21 mg/m3).
4.2.2.2.5 Metals by Method 29
Table 4-13 presents the metals found in the control equipment stack. The flares and
the engines have low emission rates compared to the boiler. The reason for the
generally higher metal emissions from the boiler is not understood.
Table 4-10. Control Equipment Exit Dioxins and Furans Average Concentrationsa
Concentration
(x10'3 ng/dscm)
Number of Samples
Contributing to Average
Dioxins
2,3,7,8-TCDD
Other TCDD
1,2,3,7,8-PeCDD
Other PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
Other HxCDD
1,2,3,4,6,7,8-HpCDD
Other HpCDD
1,2,3,4,6,7,8,9-OCDD
Total CDD
Furans
2,3,7,8-TCDF
Other TCDF
1,2,3,7,8-PeCDF
Landfill A
1
ND
22.0
ND
3.4
ND
ND
ND
0.2393
ND
0
ND
<33.8
ND
46.6
ND
Landfill B
1
ND
11.3
ND
13.6
ND
ND
ND
4.1
ND
2.4
ND
<34.7
0.5867
0.0088
1.1
Landfill C
3
ND
8.2
ND
3.4
ND
ND
ND
1.2
ND
0
3.7
ND
ND
0.75
ND
Landfill E
3
0.926
75.5
2.6
76.6
3.3
6.2
4.5
71.1
28.0
28.5
43.6
341
5.8
176
9.2
4-15
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
Concentration
(x10'3 ng/dscm)
Number of Samples
Contributing to Average
Dioxins
2,3,4,7,8-PeCDF
Other PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
Other HxCDF
1,2,3,4,6,7,8-HpCDF
1, 2,3,4,7 ,8,9-HpCDF
Other HpCDF
1,2,3,4,6,7,8,9-OCDF
Total CDF
Total CDD/CDF
Landfill A
1
ND
3.4
ND
ND
ND
ND
1.3
ND
ND
0
ND
13.9
<47.6
Landfill B
1
1.0
110
1.1
0.166
0.194
0.218
34.7
0.158
0.215
4.6
1.1
156
190
Landfill C
3
ND
0
ND
ND
ND
ND
0
ND
ND
0
ND
ND
ND
Landfill E
3
12.8
119
11.8
11.6
11.8
3.1
59.4
29.6
3.8
10.8
11.1
300
640
a - Landfill D was not measured for PCDD/PCDFs.
ND - Constituent not detected.
< - indicates that the concentration of the constituent is less than the listed value. In all cases the
number reported is rounded up to the nearest tenth.
4-16
-------
Table 4-11. Control Equipment Exit Averaged PAH Emissions '
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
Concentration (ng/dscm)
Number of Samples
Contributing to Average
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(g,h,i)perylene
Benzo(k)fluoranthene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
lndeno(1 ,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
2-Methylnaphthalene
Benzo(e)Pyrene
Perylene
Total PAH
Estimated LFG Inlet flow
Rate (scfm)
Measured Exit Gas Flow
Rate, average (scfm)
Total Emission Rate,
(mg/ft3 LFG)
Landfill A
1C
Reciprocating
Engine
1
521
731
116
41
3.2
22
15
6.4
144
3.2
154
950
6.6
17,900
1,900
175
7,580
17
3.1
30,300
150J
1,310
0.007
Landfill B
Enclosed Flare
1
16.2
3.1
8.3
2.5
1.1
3.1
2.5
1.0
2.5
0.3
22.4
319
1.2
4,060
12
18
3460
2.5
0.4
7,930
1500
20,700
0.003
Landfill C
1C
Reciprocating
Engine
3
555
1,510
372
62.2
3.1
45.3
6.1
10.8
165
2.9
361
707
8.3
43,000
2,670
290
6,700
30.8
1.0
56,500
300
1,950
0.010
Landfill E
Boiler
3
49.3
10.2
33.6
302
233
659
248
240
512
63.3
1400
74.5
277
785
1,200
832
650
355
40.3
7,960
2430
28,700
0.003
3 - Landfill D was not measured for PAHs.
J Estimated value per EPA QA/G-8 guidance
4-17
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
Table 4-12. Control Equipment Exit HCI
(mg/m3)
(ppmv)
(Ib/hr)
Range
Average
Range
Average
Range
Average
Landfill A
4.1-4.4
4.3
2.7-2.8
2.7
0.0197-0.0213
0.0203
Landfill B
1.4-2.1
1.7
0.9-1.4
1.1
0.11-0.16
0.13
Landfill C
13.8-20.6
18.0
9.1-14.3
12.0
0.103-0.163
0.136
Landfill D
2.0-2.2
2.2
1.3-1.3
1.3
0.06-0.06
0.06
Landfill E
2.0-2.4
2.1
1.3-1.6
1.4
0.21-0.26
0.23
Table 4-13. Control Equipment Exit Metal Emissions
Estimated
LFG Inlet
flow Rate
Arsenic
Cadmium
Chromium
Lead
Manganese
Mercury
Nickel
(scfm)
ug/dscm
X10'6 Ib/hr
X1Q-9lb/scfLFG
ug/dscm
X10'6 Ib/hr
X10'9lb/scfLFG
ug/dscm
X10'6 Ib/hr
X10'9lb/scfLFG
ug/dscm
X10'6 Ib/hr
X10'9lb/scfLFG
ug/dscm
X10'6 Ib/hr
X10'9lb/scfLFG
ug/dscm
X10'6 Ib/hr
X10'9lb/scfLFG
ug/dscm
X10'6 Ib/hr
X10'9lb/scfLFG
Landfill A
-150
3.0
15
1.7
0.37
1.8
0.2
8.5
41.4
0.46
6.1
29.5
3.2
13.5
66.2
7.4
ND
ND
ND
9.5
47
5.2
Landfill B
1500
0.70
66
0.7
0.18
14.5
0.16
1.7
132
147
0.65
52
0.6
8.3
660
7.3
ND
ND
ND
1.8
140
1.6
Landfill C
300
3.13
22.6
1.3
0.574
4.1
0.23
4.4
31.6
1.8
0.52
3.7
0.21
5.4
38.5
2.1
ND
ND
ND
18
126
7.0
Landfill D
400
4.7
142
5.91
0.209
6.3
0.26
4.1
122
5.1
ND
ND
ND
7.9
236
9.8
ND
ND
ND
4.8
144
6.0
Landfill E
2430
2.3
221
1.5
1.2
135
0.93
10
1,200
8.2
6.0
649
4.5
4.0
439
3.0
0.46
50
0.23
47
5300
36.4
4-18
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
This page intentionally left blank
4-19
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
5. Discussions of results
5.1 Comparison with AP-42 Default Values
Table 5-1 provides a comparison of the field test results of the five landfills to existing
AP-42 values for landfill gas. The table also identifies the test method and detection
limit for each constituent evaluated in the raw landfill gas. Of the forty-four AP-42
values, twenty-nine constituents were found to have average concentrations that are
half or lower than their corresponding AP-42 for all five landfills. Twelve of these
twenty-nine constituents were present at average concentrations that were no more
than one-tenth of the AP-42 values. These twelve compounds are:
1,1,1-trichloroethane; 1,1,2,2-tetrachloroethane; 1,2-dichloroethane; 1,2-
dichloropropane; isopropyl alcohol; bromodichloromethane; dichlorodifluoromethane;
ethane; ethanol; t-1,2-dichloroethene; trichloroethylene; and vinyl chloride. For
acrylonitrile, non-detects were reported for each of the five landfills.
For sixteen constituents, at least one landfill has a concentration greater than the
existing AP-42 value. The concentrations that are greater than the existing AP-42
values for at least on of the five landfills are highlighted in the table. These compounds
were: acetone, carbon tetrachloride, chlorobenzene, chloroethane, chloroform,
chloromethane, dichlorobenzene (1,4; 1,3; and 1,2), ethylbenzene, 1,2-dibromethane,
hexane, hydrogen sulfide, methyl ethyl ketone, pentane, and nonmethane organic
compounds. Four compounds were present at average concentrations at least three
times their AP-42 default values [i.e., carbon tetrachloride (3.6x), chloroethane (6.7x),
chloroform (12x), and 1,2-dibromoethane (10x)].
Twenty six compounds were found to be present in concentrations that are similar to
the AP-42 default values, i.e. their averaged concentrations were between 50 to 300%
the AP-42 default values. These compounds were: 1,1-dichloroethane; 1,1-
dichloroethene; acetone; butane; carbon disulfide; chlorobenzene; chloromethane; 1,4-
dichlorobenzene; 1,3-dichlorobenzene; 1,2-dichlorobenzene; methylene chloride;
ethylbenzene; trichloromonofluoromethane; hexane; hydrogen sulfide; mercury (total);
2-butanone; 2-hexanone; pentane; tetrachloroethylene; propane; m/p-xylene; o-xylene;
benzene; NMOC as Hexane; and toluene.
These data will be of help in providing: (1) QA of industry-supplied data; (2) filling data
gaps in the existing sets of LFG emission factors; and (3) updating existing emission
factors within AP-42. The inclusion of these data will undergo protocols for AP-42
emission factor development including addressing uncertainty and data quality.
5-1
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
5.2 Control Technology Assessment
Among the three tested control technologies (i.e., enclosed ground flare, 1C engine and
boiler) the boiler was the one capable of destroying the LFG most effectively, as
evidenced by the very low concentrations of organic compounds that exited the boiler
stack. However, the boiler does have a higher affinity to form PCDDs and PCDFs than
the flares or the engines. A more detailed review of the PCDD/PCDF data may be
warranted to assess the potential impacts of the levels of these compounds that were
formed.
1C engines do not appear to destroy landfill gas constituents as effectively as boilers or
flares. This could be due to tuning or maintenance of the engine. Also, engines are
typically operated to minimize NOx and CO emissions which will result in decreasing
NMOC destruction efficiency. In assessing potential impacts from use of 1C engines
for landfill gas control, pollution prevention tradeoffs can be considered from offsetting
power generation at a coal-fired electric utility (EPA-600/R-95-089). Often electricity
from 1C engines powered on landfill gas is used to help meet peak load energy
demands.
Enclosed ground flares are simple devices and are easier to maintain and operate as
compared to a boiler or 1C engine. They do not have the benefits of 1C engines or
boilers in offsetting fossil fuel use and providing methane for utilization. However, the
two enclosed flares evaluated in this project were found to effectively control
hydrocarbons and organic constituents.
5.3 Mercury Measurements
The technology of sampling and analyzing for mercury species is progressing steadily.
The current state of technology requires very specific knowledge that does not transfer
readily. The development of a method that can be promulgated as an EPA standard
procedure would be helpful in future research with mercury emissions.
This not withstanding, mercury measurement technology appears to be on the cusp of
becoming more "main-stream." Mercury's inclusion in future research studies should
be considered favorably, especially if the per-sample cost will go down because of
maturing of the technique and increased competition in the market place. However, the
use of independent standards is recommended for primary standard verification, spike
recoveries and blanks to provide quality assurance of the results.
5-2
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
Technical Systems Audits (TSAs) were conducted for the organo-mercury sampling
and analysis since this is not a standard EPA test method. One potential source of
error in any analysis is due to the standards used to calibrate the instrumentation.
Several issues were noted concerning the calibration standards. The first issue was
the apparent inability to verify the concentrations of the standards used to calibrate the
instrumentation used to measure MMHg and DMHg. The lack of an independent
standard to verify the primary standard is a cause of concern because any
inaccuracies in the primary standard will be promulgated throughout the analyses. It is
recommended that Frontier Geosciences or any other laboratory conducting organo-
mercury analyses identify stable standards for use as an independent verification of the
primary standard.
A second issue concerned how the calibration standards were stored. No expiration
dates were available for either the MMHg and DMHg standard materials. All standards
have a limited "shelf life" and should not be used after they have expired. It was not
clear if records were kept to prevent use of expired standards. It is recommended that
this become part of the standard operating procedures (SOPs) to prevent use of
standards that have degraded overtime.
A third issue was raised regarding how the standards were stored. The QA officer
found the MMHg analytical standard stored in a clear Teflon bottle, un-refrigerated in
front of a large window. The work plan had requested that samples and standards be
kept refrigerated and away from light.
The QA officer also recommended that standard practice should include retaining an
aliquot of spike solution or spiked traps when sending media to a field project.
The QA officer also noted several potential issues associated with the oragno-mercury
analyses. One area of concern was the instability of the MMHg instrument. The
analyst responsible for MMHg analysis indicated that it was common to have to
recalibrate and reanalyze samples. One suggestion to improve the robustness of
MMHg analysis is the inclusion of analytical spikes. Additionally calibration verification
samples should be analyzed frequently to ensure that the calibration is still acceptable,
i.e. the instrument has not drifted. Data validation of MMHg analyses must include
verification of the initial calibration, spike recoveries and calibration stability. Another
area of concern is the practice of forcing the calibration curve through zero. This
procedure is not consistent with most EPA-promulgated methods. Retention times
during MMHg analysis should be carefully monitored. This is critical given that
identification of MMHg is determined by retention times or relative retention times.
5-3
-------
Careful monitoring of retention times must become part of MMHg analysis. The final
observation made by the ARCADIS QA officer was that the digestate dilution technique
was not acceptably performed. The glassware used to bring the digested samples to
volume was not calibrated to Class A or Class B glassware. Furthermore the
glassware used was not compared against calibrated glassware. Inaccurate dilution of
the digestates is a common source of error in analysis where dilution is required. It is
recommended that Frontier Geosciences or any other lab performing these analyses
should modify their procedures to ensure accurate dilution of samples. This can be
done using calibrated glassware or by using a calibrated balance to determine the
dilution gravimetrically.
In addition to the TSA, an internal performance audit was performed by the ARCADIS
QA officer. Audit samples for THg, MMHg and DMHg were prepared by Cebam
Analytical located in Seattle, Washington. These audit samples were analyzed by
Frontier Geosciences as described in the report titled Determination of Total, Dimethyl,
and Monomethyl Mercury in Raw Landfill Gass at Pinconning and Montrose Michigan.
These results are present in Tables 5-3, 5-4, and 5-5. In summary the results met the
MQOs for recovery and the RPD between duplicate samples was also acceptable.
However, the recovery MQO of 50-150 percent makes it nearly impossible to
reasonably close a mass balance around Mercury. The measurement of the MMHg
audit samples showed the worst recoveries of the various Hg species, indicating that
MMHg analyses are more than likely the least robust of the analyses. Inclusion of the
suggestions listed above should increase the accuracy and precession of THg, MMHg,
and DMHg analyses. Mercury measurements from landfill gas are still in development,
but improvements have been made.
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
5-4
-------
Final Report
Field Test Measurements at
MSW Landfills with Combustion
Control Technology for Landfill
Gas Emissions
Table 5-1. Comparison between LFG Constituent Concentrations and AP-42 Default Values
Method
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M^O
M^O
Compound
1,1,1 -Trichloroethane
1 , 1 ,2,2-Tetrachloroethane
1,1-Dichloroethane
(Ethylidene Dichloride)
1,1-dichloroethene
1,2-Dichloroethane
1 ,2-Dichloropropane
Isopropyl alcohol
(2-Propanol)
Acetone
Acrylontrile
Bromodichloromethane
Butane
Carbon Disulfide
Carbon Tetrachloride
Ethyl Mercaptan (Ethanediol)
Carbonyl Sulfide (Carbon
Oxysulfide)
Chlorobenzene
Chloroethane
(Ethyl Chloride)
Chloroform
Chloromethane
CAS
Number
71-55-6
79-34-5
75-34-3
75-35^
107-06-2
78-87-5
67-63-0
67-64-1
107-13-1
75-27-4
106-97-8
75-15-0
56-23-5
75-08-1
463-58-1
108-90-7
75-00-3
67-66-3
74-87-3
Formula
Weight
133.42
167.85
98.96
96.94
98.96
112.98
60.11
58.08
53.06
163.83
58.12
76.13
153.84
62.13
60.07
112.56
64.52
119.39
50.49
Concentration (ppmv)
Default
Value
0.48
1.11
2.35
0.20
0.41
0.18
50.10
7.01
6.33
3.13
5.03
0.58
0.004
2.28
0.49
0.25
1.25
0.03
1.21
Landfill
A
0.005
0.0290
0.033
0.002
0.001
0.001
0.114
0.33
ND
0.003
4.87
0.014
0.00083
ND
ND
0.195
0.77
0.040
0.012
Landfill
B
0.031
ND
0.178
0.008
0.005
0.005
0.356
1.61
ND
0.01
3.3
0.134
0.005
ND
ND
0.229
1.88
0.19
0.072
Landfill
C
ND
ND
0.423
0.055
0.037
ND
1.280
11.7
ND
ND
37.9
0.157
ND
ND
ND
0.833
30.4
0.744
1.26
Landfill
D
ND
ND
0.591
0.021
0.022
ND
6.63
12.8
ND
ND
ND
0.093
0.038
ND
ND
0.021
0.63
0.485
0.232
Landfill
E
ND
ND
ND
ND
ND
ND
2.36
15.5
ND
ND
3.6
0.34
ND
ND
ND
0.135
ND
ND
ND
Detection
Limit
0.0003
0.0002
0.0003
0.0002
0.0003
0.0003
0.0002
0.0003
0.02
0.0002
1
0.0002
0.0005
0.02
0.02
0.0002
0.0002
0.0003
0.0001
5-5
-------
Final Report
Field Test Measurements at
MSW Landfills with Combustion
Control Technology for Landfill
Gas Emissions
Method
M-40
IVMO
IVMO
M-40
M-40
M-40
M-40
M-40
M^O
M-40
M-40
M-40
M^O
M-11
Methods
101A&
324
M-40
M-40
Compound
1 ,4-Dichlorobenzene
1,3-Dichlorobenzene
1,2-Dichlorobenzene
Dichlorodifluoromethane
(Freon 12)
Dichlorofluoro methane
(Freon 21)
Methylene Chloride
(Dichloromethane)
Dimethyl Sulfide (Methyl
Sulfide)
Ethane
Ethanol
Ethylbenzene
1,2-Dibromoethane
(Ethylene dibromide)
Trichloromonofluoromethane
(Fluorotrichloromethane) (F11)
Hexane
Hydrogen Sulfide
Mercury (Total)
2-Butanone
(Methyl Ethyl Ketone)
2-Hexanone
(Methyl Butyl Ketone)
CAS
Number
106-46-7
541-73-1
95-50-1
75-71-8
75-43^
75-09-2
75-18-3
74-84-0
64-17-5
100-41-4
106-93^
75-69-4
110-54-3
7783-06-4
78-93-3
591-78-6
Formula
Weight
147.00
147.00
147.01
120.91
102.92
84.94
62.13
30.07
46.08
106.16
187.88
137.38
86.18
34.08
215.63
72.10
100.16
Concentration (ppmv)
Default
Value
0.21
0.21
0.21
15.70
2.62
14.30
7.82
889
27.20
4.61
0.001
0.76
6.57
35.50
253.0E-6
7.09
1.87
Landfill
A
0.043
0.00047
0.0019
0.118
ND
0.997
ND
6.2
0.020
0.58
0.001
0.051
ND
13.1
300. E-6
0.27
0.557
Landfill
B
0.255
0.00203
0.0004
0.468
ND
0.169
ND
4.6
0.202
2.80
0.007
0.327
ND
22.9
22.8E-6
1.43
0.441
Landfill
C
0.328
0.394
ND
1.60
ND
5.35
0.68
14.3
0.172
5.89
0.021
0.504
4.94
55.5
51.2E-6
4.57
ND
Landfill
D
0.686
0.650
0.031
1.24
ND
1.11
ND
5.6
0.394
8.12
ND
0.116
3.98
72.7
89.1 E-6
8.07
ND
Landfill
E
ND
ND
ND
0.232
ND
3.05
ND
13.5
0.0002
ND
ND
0.0082
0.597
322 J
163E-6
2.49
ND
Detection
Limit
0.0003
0.0002
0.0003
0.0003
0.02
0.0001
0.02
1
0.0002
0.0003
0.0002
0.0002
0.0003
NR
6. E-6
0.0003
0.0002
5-6
-------
Final Report
Field Test Measurements at
MSW Landfills with Combustion
Control Technology for Landfill
Gas Emissions
Method
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-25C
M-40
Compound
Methyl Mercaptan
(Methanethiol)
Pentane
Tetrachloroethylene
(Perchloroethylene)
Propane
t-1,2-Dichloroethene
Trichloroethylene
(Trichloroethene)
Vinyl Chloride
m/p-Xylene
(Dimethyl Benzene)
o-Xylene
(Dimethyl Benzene)
Benzene
(No-disposal or Unknown)
NMOC as Hexane
(No-codispoal or Unknown)
Toluene
(Methyl Benzene)
(No or Unknown)
CAS
Number
74-93-1
109-66-0
127-18-4
74-98-6
156-60-5
79-01-6
75-01^
1330-20-7
95-47-6
71-43-2
108-88-3
Formula
Weight
48.11
72.15
165.83
44.09
96.94
131.38
62.50
106.16
106.16
78.11
86.17
92.13
Concentration (ppmv)
Default
Value
2.49
3.29
3.73
11.10
2.84
2.82
7.34
12.10
12.10
1.91
595.00
39.30
Landfill
A
ND
3.20
0.042
8.9
0.003
0.028
0.097
3.73
0.30
0.073
373
1.33
Landfill
B
ND
2.60
0.176
5.9
0.009
0.103
0.41
3.98
1.41
0.251
355
6.77
Landfill
C
ND
26.6
1.69
40.0
0.042
0.515
0.768
9.21
3.66
1.63
5870
23.3
Landfill
D
ND
2.37
1.02
30.5
0.053
0.418
1.20
13.6
5.41
1.20
1006
30.3
Landfill
E
ND
1.30
0.125
13.0
ND
0.094
0.0634
9.00
3.10
0.887
233
7.95
Detection
Limit
0.02
1
0.0003
1
0.0003
0.0002
0.0002
0.00065
0.0003
0.0002
NR
0.0003
ND - Constituent not detected at the stated method detection limits
NR - Constituent detection limit not reported by laboratory
5-7
-------
Final Report
Field Test Measurements at
MSW Landfills with Combustion
Control Technology for Landfill
Gas Emissions
5-8
-------
Final Report
Field Test Measurements
at MSW Landfills with
Combustion Control
Technology for Landfill Gas
Emissions
6. Data Quality Assessment
Detailed assessments of this project's performance in terms of quality are included in
the individual landfill test reports. With a few exceptions, the project was able to meet
the Measurement Quality Objectives (MQOs) established in the QAPPs.
Table 6-1 shows a comprehensive overview of measurements that, for various
reasons, did not meet the specified MQOs.
6-1
-------
Final Report
Field Test Measurements at
MSW Landfills with Combustion
Control Technology for Landfill
Gas Emissions
Table 6-1. Summary of Sampling and Analyses Exceptions
Method
EPA Method 1
EPA Method 2
EPA Method 3A
EPA Method 3C
EPA Method 4
EPA Method 6C
EPA Method 7E
EPA Method 10
EPA Method 1 1
Measurement
Selection of traverse points
Determination of stack gas
velocity and volumetric flow
rate
Determination of stack gas
O2 and CO2 for stack gas
molecular weight
calculations
Determination of CC>2, ChU,
N2, and O2 in raw LFG
Determination of stack gas
moisture
Determination of stack gas
SO2
Determination of stack gas
NOX
Determination of stack gas
CO
Determination of raw LFG
H2S
Quality Assurance Observations
Landfill A
Nl
Nl
CEM calibration and
drift check exceeded
criteria slightly.
Nl
Nl
CEM calibration and
drift check exceeded
criteria slightly.
CEM calibration and
drift check exceeded
criteria slightly.
Nl
Nl
Landfill B
Nl
Nl
CEM calibration and
drift check exceeded
criteria slightly
Nl
Nl
Drift and system bias
checks exceeded
criteria
Drift check exceeded
criteria
Nl
Nl
Landfill C
Nl
Nl
Nl
Nl
Nl
Nl
Nl
Nl
Exceeded hold time.
Landfill D
Nl
Nl
Nl
Nl
Nl
Nl
1 drift check was at 3.3%
Nl
Exceeded hold time.
Landfill E
Nl
Nl
Nl
Nl
Nl
Nl
Nl
Nl
Did not do QAPP-
specified spike.
However method does
not specify spike to be
required. Data was
flagged.
6-2
-------
Final Report
Field Test Measurements at
MSW Landfills with Combustion
Control Technology for Landfill
Gas Emissions
Method
EPA Method 23
EPA Method 23
EPA Method 23
EPA Method 25A
Measurement
Determination of LFG
PAHs by Method 8270
PCBs by Method 1668
Determination of stack gas
dioxins/furans by Method
8290
Determination of stack gas
PAHs by Method 8270
Determination of flare stack
gas NMOCs, as THCs
Quality Assurance Observations
Landfill A
Extracts too
concentrated for
analysis. No data
was produced
1 of 3 samples
analyzed. Did not
meet 90% completion
goal
1 of 3 samples
analyzed. Did not
meet 90% completion
goal
Nl
Landfill B
Extracts too
concentrated for
analysis. No data was
produced
Exceeded hold time.
Detected some targets
in blank. Data were
notated.
1 of 3 samples
analyzed. Did not meet
90% completion goal.
Exceeded hold time.
Detected some targets
in blank. Data were
notated.
1 of 3 samples
analyzed. Did not meet
90% completion goal.
Drift check exceeded
criteria
Landfill C
Not a specified
measurement
Nl
Detected targets in
blank.
Data reported and
flagged.
Recovery of di2-
perylene was low
Relevant data were
flagged.
Nl
Landfill D
Not a specified
measurement
Not a specified
measurement
Not a specified
measurement
Nl
Landfill E
Not a specified
measurement
Nl
Detected targets in
blank.
Data reported and
flagged.
Nl
6-3
-------
Final Report
Field Test Measurements at
MSW Landfills with Combustion
Control Technology for Landfill
Gas Emissions
Method
EPA Method 25C
EPA Method 26A
EPA Method 29
EPA Method
40/TO-15
SW-846 Method
0100/TO-11
Measurement
Determination of raw LFG
NMOCs
Determination of stack gas
HCI
Determination of stack gas
metals
Determination of raw LFG
VOCs
Determination of raw LFG
carbonyls (formaldehyde,
acetaldehyde)
Quality Assurance Observations
Landfill A
Exceeded hold time.
Detected 2 ppmv
hexane in field blank.
Nl
Nl
Detected low
concentrations of a
few targets infield
blank
Spike recovery
exceeded criteria for
ethanol and m/p
Xylene.
RSD for hexane and
isopropyl alcohol
exceeded criteria.
Affected data were
flagged
Formaldehyde levels
in samples are near
the MDL. Results are
flagged as estimates
"J"
Landfill B
Exceeded hold time.
Detected 8.5 ppmv
hexane in field blank.
Nl
Nl
Detected low
concentrations of a few
targets in field blank,
Spike recovery for
chlorobenzene
exceeded criteria.
RSD for Methylene
chloride exceeded
criteria.
Affected data were
flagged
Detected 0.07|jg
formaldehyde in field
blank
Landfill C
Nl
Nl
Nickel CCV at 10.6 and
14.0%
Detected low
concentrations of a few
targets in field blank.
Data were flagged.
Nl
Landfill D
N2 and O2 exceeded
threshold.
Data flagged
Nl
Nickel CCV at 10.6 and
14.0%
Detected low
concentrations of a few
targets in field blank.
Cyclohexane RSD
41.2%
Heptane RSD 57.4%
Data were flagged.
Nl
Landfill E
Exceeded hold time
Detected 3 ppmv
hexane in field blank.
1 sample had N2 and
O2 exceeded threshold.
Nl
Nickel CCV at 10.6 and
12.2%
Detected low
concentrations of a few
targets in field blank.
Ethanol spike recovery
2.4%, m/p-xylene
recovery 230%
Isopropyl alcohol RSD
56.3%
Hexane RSD 40.7%
Nl
6-4
-------
Final Report
Field Test Measurements at
MSW Landfills with Combustion
Control Technology for Landfill
Gas Emissions
Method
LUMEX instrument
Organic mercury
methods (Frontier)
Organic mercury
methods (Frontier)
Organic mercury
methods (Frontier)
Organic mercury
methods
(Geochimica)
Organic mercury
methods
(Geochimica)
Organic mercury
methods
(Geochimica)
Measurement
Determination of raw LFG
Hg°
Determination of raw LFG
monomethyl mercury.
Determination of raw LFG
dimethyl mercury
Determination of raw LFG
total mercury.
Determination of raw LFG
monomethyl mercury.
Determination of raw LFG
dimethyl mercury
Determination of raw LFG
total mercury.
Quality Assurance Observations
Landfill A
Nl
Exceeded 14-day
hold time
RSD exceeded
criteria
Exceeded 14-day
hold time
Spike recovery less
than 40%. Data
rejected.
Exceeded 14-day
hold time
Not a specified
measurement
Not a specified
measurement
Not a specified
measurement
Landfill B
Nl
Exceeded 14-day hold
time
RSD exceeded criteria
Exceeded 14-day hold
time
Spike recovery less
than 40%. Data
rejected.
Exceeded 14-day hold
time
Not a specified
measurement
Not a specified
measurement
Not a specified
measurement
Landfill C
Nl
Exceeded 14-day hold
time.
1 of 6 samples was
damaged.
Nl
Exceeded 14-day hold
time
Not a specified
measurement
Not a specified
measurement
Not a specified
measurement
Landfill D
Nl
Nl
Nl
Exceeded 14-day hold
time
Not a specified
measurement
Not a specified
measurement
Not a specified
measurement
Landfill E
Sampled at compressor
exit
Exceeded 14-day hold
time
Exceeded 14-day hold
time
Exceeded 14-day hold
time
Nl
Nl
Nl
Nl - No issues or QA exceptions
6-5
-------
Final Report
Field Test Measurements at
MSW Landfills with Combustion
Control Technology for Landfill
Gas Emissions
This page intentionally left blank
6-6
-------
7. Conclusions
The test data collected during this test program provides updated information
concerning the constituents in landfill gas and combustion by-products from five MSW
landfills. Ideally, it would be preferable to have collected data from a wider range of
landfills covering different gas control technology, geographic areas, landfill size and
age, and variations in waste composition. The data are considered useful in providing
a detailed and comprehensive set of data. It also helps in evaluating how
representative data are that have been supplied by industry, state and local regulatory
authorities, and others.
The average concentrations of constituents in landfill gas for the five landfills were half
or lower of their corresponding AP-42 values. For sixteen constituents, at least one
landfill had an average concentration greater than the existing AP-42 value. The
details of the sampling at each site are provided in the appendices to this report.
Limitations in the data include lack of data from a wider range of combustion
technology. Also, the field test measurements did not include wet or bioreactor landfills.
Not clear if there will be an increase in air toxics resulting from increased levels of
metals due to leachate recirculation and addition of sewage sludge or other liquid
additions. Also, this study did not include turbines since they are not as widely used as
boilers, 1C engines, and flares. With increasing use of micro-turbines, it would be
helpful to have data on combustion by-product emissions to compare to other
technologies in use.
With respect to project QA, while a few of the measurements presented some
challenges, the project succeeded in producing a comprehensive data set. Therefore,
this project met its data quality objective of "performing tests by using EPA reference
test methods, or when not applicable, sound methodology and that tests are reported
in enough detail for adequate validation and raw data are provided that can be used to
duplicate the emission results presented in the report."
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
7-1
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
8. References
Modrak, M. T.; Hashmonay, R. A.; Kagann, R. Measurement of Fugitive Emissions at a
Region I Landfill; EPA-600/R-04-001; Prepared for the National Risk Management
Research Laboratory of EPA's Office of Research and Development, Research
Triangle Park, NC. January 2004. Available at:
http://www.epa.gov/appcdwww/apb/EPA-600-R-04-001.pdf.
Modrak, M. T.; Hashmonay, R. A.; Varma R.; Kagann, R. Evaluation of Fugitive
Emissions at a Brownfield Landfill in Ft. Collins, Colorado Using Ground-Based Optical
Remote Sensing Technology; EPA-600/R-05/042; Prepared for the National Risk
Management Research Laboratory of EPA's Office of Research and Development,
Research Triangle Park, NC. March 2005. Available at:
http://www.epa.gov/ORD/NRMRL/pubs/600r05042/600r05042.htm
Modrak, M. T.; Hashmonay, R. A.; Varma R.; Kagann, R. Evaluation of Fugitive
Emissions at a Brownfield Landfill in Colorado Springs, Colorado Using Ground-Based
Optical Remote Sensing Technology; EPA-600/R-05/041; Prepared for the National
Risk Management Research Laboratory of EPA's Office of Research and
Development, Research Triangle Park, NC. March 2005. Available at:
http://www.epa.gov/ORD/NRMRL/pubs/600r05041/600r05041.htm
Thoma, E. D., R. C. Shores, E. L. Thompson, D. B. Harris, S. A. Thorneloe, R. M.
Varma, R. A. Hashmonay, M. T. Modrak, D. F. Natschke, and H. A. Gamble. Open
Path Tunable Diode Laser Absorption Spectroscopy for Acquisition of Fugitive
Emission Flux Data; Journal of Air and Waste Management Association. (55), 658-668
(2005).
Thorneloe, S.; A. Roquetta, J. Pacey, and C. Bottero, Database of Landfill-Gas-to-
Energy Projects in the United States, MSW Management, March/April 2000, pages
29-37.
Thorneloe, S.; S. Roe, R. Strait, L. Goodroad, J. Cosulich, and J. Pacey, Emerging
and Innovative Technologies for Landfill Gas Control and Utilization. Sardinia 99,
Seventh International Waste Management and Landfill Symposium, Published in
Proceedings, Volume II, Pages 611-616, October 4-8, 1999.
Thorneloe, S.; A. Roqueta, J. Pacey, C. Bottero. Database of Landfill Gas to Energy
Projects in the United States; Sardinia 99, Seventh International Waste Management
and Landfill Symposium, Published in Proceedings, Volume II, Pages 525-533,
October 4-8, 1999.
7-2
-------
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
Thorneloe, S.A., Emerging Technologies for Landfill Gas Control and Utilization,
Invited speaker at the Solid Waste Association of North America's (SWANA's) 21st
Annual Landfill Gas Symposium, March 1998. Published in proceedings.
Thorneloe, S.A.; M. A. Barlaz, R. Peer, L. C. Huff, L. Davis, and J. Mangino. Global
Methane Emissions from Waste Management. S.A. Thorneloe, M. A. Barlaz, R. Peer,
L. C. Huff, L. Davis, and J. Mangino. Published in Atmospheric Methane: Sources,
Sinks, and Role in Global Change, NATO ASI Series, Vol. 13,1993.
U.S. EPA, Map of U.S. Landfill Gas to Energy Projects, Office of Air and Radiation,
Jan 2007, http://www.epa.gov/lmop/docs/map.pdf.
U.S. EPA, Guidance for Evaluating Landfill Gas Emissions from Closed or
Abandoned Facilities (EPA-600/R-05/123a). Prepared for the National Risk
Management Research Laboratory of EPA's Office of Research and Development,
Research Triangle Park, NC. Available at:
http://www.epa.gov/ORD/NRMRL/pubs/600r05123/600r05123.pdf.
U.S. EPA, Landfill Gas Emissions Model (LandGEM) Version 3.02 User's Guide,
Prepared for EPA's National Risk Management Research Laboratory, EPA-600/R-
05/047, Prepared for the National Risk Management Research Laboratory of EPA's
Office of Research and Development, Research Triangle Park, NC. April 2005.
Software and User's Manual available at:
http://www.epa.aov/ORD/NRMRL/pubs/600r05047/600r05047.htm
U.S. EPA, First-Order Kinetic Gas Generation Model Parameters for Wet Landfills
(EPA/600/R-05/072, June 2005). Prepared for the National Risk Management
Research Laboratory of EPA's Office of Research and Development, Research
Triangle Park, NC. Available at:
http://www.epa.gov/ORD/NRMRL/pubs/600r05072/600r05072.htm
U.S. EPA, Emerging Technologies for the Management and Utilization of Landfill Gas,
EPA-600/R-98-021, Prepared for the National Risk Management Research Laboratory
of EPA's Office of Research and Development, Research Triangle Park, NC. February
1998.
U.S. EPA, Compilation of Air Pollutant Emission Factors (AP-42), Volume 1: Stationary
Point and Area Sources, 5th ed., Chapter 2.4: Municipal Solid Waste Landfills. EPA,
Office of Air Quality Planning and Standards. Research Triangle Park, NC, 1997.
http://www.epa.gov/ttn/chief/ap42/ch02/final/c02s04.pdf.
U.S. EPA, Standards of Performance for New Stationary Sources and Guidelines for
Control of Existing Sources: Municipal Solid Waste Landfills, final rule. Federal
Register, 61 FR 9905, March 12, 1996.
7-3
-------
U.S. EPA, Landfill Gas Energy Utilization: Discussion of Technical and Non-Technical
Issues, Solutions, and Trends, EPA-600/R-95-035, Prepared for the National Risk
Management Research Laboratory of EPA's Office of Research and Development,
Research Triangle Park, NC. March 1995.
Final Report
Field Test Measurements
at Five MSW Landfills with
Landfill Gas Control
Technology
U.S. EPA, Methodologies for Quantifying Pollution Prevention Benefits from Landfill
Gas Control and Utilization, EPA-600/R-95-089, Prepared for the National Risk
Management Research Laboratory of EPA's Office of Research and Development,
Research Triangle Park, NC. July 1995.
U.S. EPA, Landfill Gas Energy Utilization: Technology Options and Case Studies,
EPA-600/R-92-116, Prepared for the National Risk Management Research Laboratory
of EPA's Office of Research and Development, Research Triangle Park, NC. June
1992.
U.S. EPA, Analysis of Factors Affecting Methane Gas Recovery from Six Landfills,
EPA-600/2-9I-055, Prepared for the National Risk Management Research Laboratory
of EPA's Office of Research and Development, Research Triangle Park, NC.
September 1991.
U.S. EPA, 1991 a. Air Emissions from Municipal Solid Waste Landfills. Background
Information for Proposed Standards and Guidelines, EPA-450/3-90-011 a (NTIS PB91 -
197061), U.S. Environmental Protection Agency, Research Triangle Park, NC.
U.S. EPA, 1991 b. Standards of Performance for New Stationary Sources and
Guidelines for Control of Existing Sources: Municipal Solid Waste Landfills, proposed
rule. Federal Register, 56 FR 24468, May 30.
U.S. EPA, 1991 c. Regulatory Package for New Source Performance Standards and
lll(d) Guidelines for Municipal Solid Waste Air Emissions, Public Docket No. A-88-09
(proposed May 1991). U.S. Environmental Protection Agency, Research Triangle Park,
NC.
7-4
-------
Field Test Measurements at Five Municipal Solid Waste
Landfills with Landfill Gas Control Technology
Appendix A
SOURCE TEST REPORT
FOR LANDFILL A
This report presents the results of a field test conducted at Landfill A that is
located in the northeastern U.S. Testing took place on November 1 and 2, 2002.
-------
Table of Contents
Acronym List vii
1. Introduction 1-1
2. Landfill Facility Descriptions 2-1
2.1 Landfill Gas (LFG) Destruction Process Description and Operation 2-1
2.2 Control Equipment Description 2-1
2.3 Excess Landfill Gas (LFG) Flare 2-1
2.4 Sampling Locations 2-1
2.4.1 Raw Landfill Gas (LFG) Header Pipe 2-2
2.4.2 Engine #2 Stack 2-3
3. Test Operations 3-1
3.1 Test Team 3-1
3.2 Test Log 3-1
3.2.1 Planned Test Sample Matrices 3-1
3.2.2 Raw Landfill Gas (LFG) (Inlet) 3-3
3.2.3 Engine Stack 3-5
3.3 Field Test Changes and Deviations from QAPP Specifications 3-8
3.3.1 Variation from Test Methods and/or Planned Activities 3-8
3.3.2 Application of Test Methods 3-9
3.3.3 Test Method Exceptions 3-11
4. Presentation of Test Results 4-1
4.1 Raw Landfill Gas (LFG) Results 4-1
4.1.1 Raw Landfill Gas (LFG) Flow Rate and Temperature 4-1
4.1.2 Raw Landfill Gas (LFG) Constituents 4-1
4.2 Engine Stack Results 4-10
4.2.1 Engine Stack Gas Flow Rate and Temperature 4-10
-------
Table of Contents
4.2.2 Engine Stack Gas Constituents 4-10
4.2.3 Hydrogen Chloride (HCI) Emission Results 4-20
4.3 Comparison with AP-42 Default Values 4-22
5. Quality Assurance/Quality Control 5-1
5.1 Assessment of Measurement Quality Objectives 5-1
5.1.1 Continuous Emissions Monitors (CEMs) 5-1
5.1.2 Carbonyls (TO-11) 5-2
5.1.3 Hydrogen Sulfide (H2S) (EPA Method 11) 5-3
5.1.4 Dioxins and Furans (PCDD/PCDFs) (EPA Method 23/0011) 5-4
5.1.5 Polycyclic Aomatic Hydrocarbons (PAHs) (EPA Method 23/0011) 5-5
5.1.6 Polychlorinated Biphenyls (PCBs) 5-6
5.1.7 Non-Methane Organic Compounds (NMOCs) (Method 25C) 5-6
5.1.8 Hydrogen Chloride (HCI) (EPA Method 26A) 5-7
5.1.9 Metals (EPA Method 29) 5-7
5.1.10 Organo-Mercury (Hg) and Total Mercury (Hg) (Frontier) 5-8
5.1.11 Volatile Organic Compounds (VOCs) and Methane (CH4) (Method
TO-15) 5-10
5.2 Audits 5-11
-------
Table of Contents
Tables
Table 3-1. ARCADIS Test Team Members and Responsibilities 3-1
Table 3-2. Target Analytes for the Raw Landfill Gas and Sample Condensate
Collected at the Gas Header 3-2
Table 3-3. Target Analytes for the Engine Stack Gas Stream 3-3
Table 3-4. Raw Landfill Gas Sample Log and Collection Times 3-4
Table 3-5. Engine Stack Test Sample Log and Collection Times 3-7
Table 3-6. Test Methods and Performing Organizations 3-10
Table 4-1. Raw Landfill Gas VOC Concentrations 4-2
Table 4-2. Raw Landfill Gas Non-Methane Organic Compound (NMOC)
Concentrations 4-6
Table 4-3. Raw Landfill Gas Hydrogen Sulfide Concentrations 4-6
Table 4-4. Raw Landfill Gas Carbonyls Concentrations 4-7
Table 4-5. Raw Landfill Gas Total Mercury Concentrations 4-8
Table 4-6. Raw Landfill Gas Dimethyl Mercury Concentrations 4-9
Table 4-7. Raw Landfill Gas Monomethyl Mercury Concentrations 4-9
Table 4-8. Raw Landfill Gas Elemental Mercury Concentrations 4-10
Table 4-9. Engine Stack Gas Operating Conditions Measured during Sampling 4-11
Table 4-10. Engine Stack Combustion Product Concentrations. 4-14
Table4-11. Engine StackTHC Concentrations 4-14
Table 4-12. Engine Stack Dioxins and Furans Emissions 4-16
Table 4-13. Engine Stack Dioxins and Furans Toxicity Equivalent Emissions 4-17
Table 4-14. Engine Stack Polycyclic Aromatic Hydrocarbons Emissions 4-19
Table 4-15. Engine Stack Hydrogen Chloride Emissions 4-20
Table 4-16. Engine Stack Metal Emissions 4-21
Table 4-17. Engine Stack CO, SO2, NOX Concentrations 4-22
Table 4-18. Comparison of Raw Landfill Gas Constituent Concentrations with AP-42
Default Values 4-26
Table 4-19. Raw Landfill Gas Constituent Concentrations for Compounds without AP-42
Default Values 4-30
Table 5-1. CEM MQO Summary for Landfill A 5-2
-------
Table of Contents
Figures
Figure 2-1. Simplified Engine and Flare Process Flow Diagram and Sampling Points 2-2
Figure 2-2. Landfill Gas Collection Pipe 2-3
Figure 2-3. Engine/Generator Set #2 2-3
Figure 2-4. Engine Stack Dimension and Sampling Traverse Locations 2-4
Figure 3-1. Sampling Operations at the Raw Landfill Gas Inlet 3-3
Figure 3-2. Engine #2 Stack and Sampling Scaffold 3-6
Figure 4-1. Engine Stack Oxygen and Carbon Dioxide Concentrations 4-13
Figure 4-2. Engine Stack Total Hydrocarbon Concentrations 4-15
Figure 4-3. Engine Stack Carbon Monoxide Concentrations 4-23
Figure 4-4. Engine Stack Sulfur Dioxide Concentrations 4-24
Figure 4-5. Engine Stack Nitric Oxide Concentrations 4-25
IV
-------
Table of Contents
Appendices
A. Method TO-15 (VOCs, TICs, C2, C3, C4, C5, C6)
B. Method 25C (CH4, CO2, NMOC)
C. Method 3C (O2, N2, CH4, CO2)
D. Method TO-11 (Formaldehyde, Acetaldehyde)
E. Organic mercury Method (Mercury, Total, Monomethyl, Dimethyl)
F. LUMEX (Elemental Mercury)
G. Hydrogen Sulfide
H. Continuous Emission Monitor (Data and Charts)
I. Method 23 (PAH)
J. Method 23 (PCDD/PCDF)
K. Method 23 (PAH, PCDD/PCDF)
L Method 29 (Metals)
M. Method 26A(HCI)
P. Raw Field Data Records
Q. CEM Calibration Records and Span Gas Certification
R. Sampling Control Meter Boxes Calibration Record
-------
Table of Contents
This page intentionally left blank
VI
-------
Table of Contents
Acronym List
%D
AP-42
APPCD
ARCADIS
As
AS
CCVs
Cd
CEMS
CH4
C12
CO
CO2
Cr
DMHg
EPA
ES
FID
GC
GC/FID
GC/MS
HC1
Hg
H2S
1C
ICVs
LFG
MDL
Percent drift
Compilation of Air Pollutant Emission Factors
Air Pollution Prevention Control Division
ARCADIS G&M, Inc.
Arsenic
Alternative standard
Continuing calibration verification samples
Cadmium
Continuous emission monitoring system
Methane
Chlorine
Carbon monoxide
Carbon dioxide
Chromium
Dimethyl mercury
US Environmental Protection Agency
Extraction standard
Flame ionization detector
Gas chromatograph
Gas chromatograph/flame ionization detector
Gas chromatograph/mass spectrometer
Hydrogen chloride
Mercury
Hydrogen sulfide
Internal combustion
Internal calibration verification samples
Landfill gas
Method Detection Limit
VII
-------
Table of Contents
MMHg
Mn
MQOs
MSW
N2
Ni
NMOCs
NOX
O2
PAHs
Pb
PCBs
QA
QAPP
QC
RF
RPD
RRF
RSD
RTP
SO2
ss
TCDD/TCDFs
THCs
TICs
TSR
VOCs
WC
Monomethyl mercury
Manganese
Measurement quality objectives
Municipal solid waste
Nitrogen
Nickel
Non-methane organic compounds
Nitrogen oxides
Oxygen
Polynuclear aromatic hydrocarbons
Lead
Polychlorinated biphenyls
Quality Assurance
Quality Assurance Project Plan
Quality control
Response factor
Relative percent difference
Relative response factors
Relative standard deviation
Research Triangle Park
Sulfur dioxide
Sampling standards
Dioxins/furans
Total hydrocarbons
Tentatively identified compounds
Technical system review
Volatile organic compounds
Water column
VIM
-------
Source Test
Report for Landfill A
1. Introduction
Large municipal solid waste landfills are subject to Clean Air Act regulations because
of concerns related to their emissions and their potential adverse effects to human
health and the environment. Landfills are listed as a source of air toxics in the Urban
Air Toxics Strategy for future evaluation of residual risk. Existing emission factors for
landfill gas (LFG) were largely developed using data from the 1980s and early 1990s.
A database was developed summarizing data from approximately 1,200 landfills, along
with emissions information from the literature, and test reports prepared by state and
local government agencies and industry. These data were summarized in Compilation
of Air Pollutant Emission Factors (AP-42), Chapter 2.4. The final rule and guidelines
are contained in 40 CFR Parts 51, 52, and 60, Standards of Performance for New
Stationary Sources and Guidelines for Control of Existing Sources: Municipal Solid
Waste Landfills.
The overall purpose of this testing program was to generate data that may be used to
update AP-42 and include data that reflect current waste management operating
practices.
This report presents the results of a field test conducted at Landfill A that is located in
the northeastern U.S. Testing took place on November 1 and 2, 2002.
The site uses four internal combustion engine/electric generator sets to reclaim the
energy content in the LFG. A standby enclosed flare is used for the destruction of any
excess LFG. A more detailed description of the engine system is presented in Section
2. The specific purpose of the testing program was to determine the concentrations of
constituents in the raw LFG and emissions from the stack of one of the engines. The
constituents of interest in the raw LFG were volatile organic compounds (VOCs), non-
methane organic compounds (NMOCs), hydrogen sulfide (H2S), carbonyls
(acetaldehyde and formaldehyde), polycyclic aromatic hydrocarbons (PAHs),
poly chlorinated biphenyls (PCBs), and mercury (Hg) compounds. The pollutants of
interest for the treated LFG, in this case at the engine stack, were carbon monoxide
(CO), nitrogen oxides (NOX), sulfur dioxide (SO2), NMOCs as total hydrocarbons
(THCs), hydrogen chloride (HC1), dioxins/furans (PCDD/PCDFs), PAHs, total Hg, and
metals.
ARCADIS G&M, Inc. (ARCADIS), as contractor to the US Environmental Protection
Agency's (EPA) Air Pollution Prevention Control Division (APPCD), performed this
work underwork Assignment 4-1 of the Onsite Laboratory Support Contract (68-C-
1-1
-------
Source Test
Report for Landfill A
99-201). The testing activities followed the specifications of the approved "Site-
Specific Quality Assurance Project Plan for the Field Evaluations of Landfill Gas
Control Technologies - Landfill A ". This report was prepared under Work Assignment
2-26 of the continuing Onsite Laboratory Support Contract (EP-C-04-023).
1-2
-------
Source Test
Report for Landfill A
2. Landfill Facility Descriptions
Available information indicated that the site began operation in 1972. By 2003,
Landfill A had 2,700,000 tons of waste placed over an area of 56 acres. The landfill
used 3,375 feet of horizontal collectors to collect the LFG. The gases generated in the
landfill were extracted with 29 vertical wells. The collected LFG was piped to the
engine and enclosed flare system where it was combusted.
2.1 Landfill Gas (LFG) Destruction Process Description and Operation
Figure 2-1 shows a simplified process schematic of the engine and flare system at
Landfill A. The landfill utilizes a bank of four engine generator sets for destruction of
LFG and generation of electricity. The engines are Caterpillar 3412 four-stoke internal
combustion (1C) engines, adapted for LFG. The Caterpillar 3412 is a spark-ignited V-
12 engine with displacement of 1649 cubic inches. The engine is turbocharged and
after-cooled, and has a cylinder bore diameter of 5.4 inches and a stroke of 6.0 inches.
Engine #2 was tested and was connected to a Caterpillar SR4 Generator that is rated at
470KW.
2.2 Control Equipment Description
The engines did not have pollution control equipment installed.
2.3 Excess Landfill Gas (LFG) Flare
A Perennial Energy Enclosed Ground Flare Station, rated at maximum LFG input rate
of 1500 scfrn, received and destroyed excess LFG not needed by the four engines. The
enclosed flare was not part of the test program. Measurement of emissions from the
landfill flare system was the focus of testing at two other landfills, as an integral part of
the research program.
A condensate removal system prevents liquids from entering into the engine and flare
burners. A flame arrester prevents flame from propagating from the burner array back
into the LFG collection and flow control system.
2.4 Sampling Locations
Gas sampling was conducted at the raw LFG pipe that fed the engines and flare, and at
Engine #2 stack, as depicted in Figure 2-1.
2-1
-------
Source Test
Report for Landfill A
Figure 2-1. Simplified Engine and Flare Process Flow Diagram and Sampling Points
2.4.1 Raw Landfill Gas (LFG) Header Pipe
Raw LFG samples were collected from the header pipe as it emerged from the ground
and upstream of any processing units. Figure 2-2 shows the raw LFG inlet pipe. The
pipe was 12 inches in diameter as it emerged vertically from the ground and turned 90
degrees to run horizontally towards the LFG control-and-process system. At the
sampling point, which was about 8 feet after the bend, four %" gas taps were installed
on the top of the horizontal pipe, at approximately 6-inch spacing. Through these ports,
gases were withdrawn to obtain the test samples.
Comparing the physical arrangement of this header pipe with requirements of standard
sampling methodologies indicated that the header configuration rendered isokinetic
sampling at the gas collection pipe impossible. Therefore, isokinetic sampling was not
attempted at this location. Further discussions on this topic are presented in Section
3.3.1.1.
2-2
-------
Source Test
Report for Landfill A
Figure 2-2. Landfill Gas Collection Pipe
2.4.2 Engine #2 Stack
Engine #2 is shown in Figure 2-3. The exhaust gas of the engine was ducted outside of
the engine room via a pipe. The engine stack is 8.25 inches in diameter and has two 4-
inch sampling ports installed 90 degrees apart. Figure 2-4 is a schematic of the engine
stack and includes the locations of the sample traverse points. Isokinetic sampling was
possible at this location and was followed.
Figure 2-3. Engine/Generator Set #2
2-3
-------
Source Test
Report for Landfill A
Sampling
Ports
O
26"
Stack Cross Section
Traverse Points
Point# Distance
1 21"
3.25'
2.36"
3.20"
4.44"
7.S1"
9.05"
9.39"
Figure 2-4. Engine Stack Dimension and Sampling Traverse Locations
2-4
-------
Source Test
Report for Landfill A
3. Test Operations
As stated previously, the purpose of the sampling program was to determine the
concentrations of the target analytes in the raw LFG at the header pipe and emissions
from the engine stack.
3.1 Test Team
The tests were conducted by a team of seven individuals. In addition, ARCADIS'
Quality Assurance (QA) Officer conducted an internal technical system review (TSR)
during this test. The Work Assignment Leader provided general oversight. The team
members and their primary duties are listed in Table 3-1.
Table 3-1. ARCADIS Test Team Members and Responsibilities
Role
Test Engineer
Technician
Technician
Technician
Test engineer
Technician
Test engineer
Quality Assurance Officer
Work Assignment Leader
Primary Duty
Chief
CEM operator
Sample train preparation and recovery
Sample train operator at raw LFG inlet pipe
Sample train operator at stack
Sample train operator at stack
Mercury measurements
QA Technical Systems Review (Internal)
Observer and general over-sight
3.2 Test Log
3.2.1 Planned Test Sample Matrices
The list of target samples to be collected and measurements to be conducted are
specified in the Quality Assurance Project Plan (QAPP) dated October 29 2002. These
are reiterated here for completeness. Table 3-2 lists the target compounds of interest for
the raw LFG samples. Table 3-3 lists the target compounds of interest for the treated
gas, collected from the engine stack.
3-1
-------
Source Test
Report for Landfill A
Table 3-2. Target Analytes for the Raw Landfill Gas and Sample Condensate Collected at
the Gas Header
Volatile compounds
Methane
Ethane
Propane
Butane
Pentane
Hexane
Carbonyl sulfide
Chlorodifluoromethane
Chloromethane
Dichlorodifluoromethane
Dichlorofluoromethane
Ethyl chloride
Fluorotrichloromethane
1,3-Butadiene
Acetone
Acrylonitrile
Benzene
Bromodichloromethane
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chloroform
Dimethyl sulfide
Ethyl mercaptan
Volatile compounds
(continued)
Ethylene dibromide
Ethylene dichloride
Methyl chloroform
Methyl isobutyl ketone
Methylene chloride
Propylene dichloride
t-1,2-Dichloroethene
Tetrachloroethene
Toluene
Trichlorethylene
Vinyl chloride
Vinylidene chloride
Ethanol
Methyl ethyl ketone
2-Propanol
1,4-Dichlorobenzene
Ethylbenzene
Xylenes
Non-methane organic carbons
Reduced sulfur compounds
Hydrogen sulfide
Carbonyls
Acetaldehyde
Formaldehyde
Polycyclic aromatic
hydrocarbons
Polychlorinated biphenyls
Mercury
Organo-mercury compounds
Total
Elemental
Gases
Carbon dioxide
Oxygen
Moisture
3-2
-------
Source Test
Report for Landfill A
Table 3-3. Target Analytes for the Engine Stack Gas Stream
Gases
Oxygen
Carbon dioxide
Carbon monoxide
Nitrogen oxide
Sulfur dioxide
Total hydrocarbons
Non-methane organic compounds
Hydrogen chloride
Dioxins/Furans (PCDD/PCDFs)
Polycyclic Aromatic Hydrocarbons (PAHs)
Mercury
Total
Metals
Lead, arsenic, cadmium, chromium,
manganese, nickel
3.2.2 Raw Landfill Gas (LFG) (Inlet)
Sample collection took two days to complete. Figure 3-1 shows the sampling team in
action at this sample location. Table 3-4 lists the samples that were collected from the
raw LFG pipe.
Figure 3-1. Sampling Operations at the Raw Landfill Gas Inlet
3-3
-------
Source Test
Report for Landfill A
Table 3-4. Raw Landfill Gas Sample Log and Collection Times
Sampling
Method
Run Number
EPA Method 40 (TO-15, 25C, 3C)
A-Pre-M40-1 10202-01
A-Pre-M40-1 10202-02
A-Pre-M40-1 10202-03
EPA Method 23
A-Pre-M23-1 101 02-01
A-Pre-M23-1 101 02-02
A-Pre-M23-1 101 02-03
EPA Method 01 00
A-Pre-M01 00-1 10202-01
A-Pre-M01 00-1 10202-02
A-Pre-M01 00-1 10202-03
EPA Method 1 1
A-Pre-M001 1-1 10202-01
A-Pre-M001 1-1 10202-02
A-Pre-M001 1-1 10202-03
_umex Instrument
A-Pre-EM-1 10202-01
A-Pre-EM-1 10202-02
A-Pre-EM-1 10202-03
=rontier
A-Pre-TGM-110102-FB01
A-Pre-TGM-1 101 02-01
A-Pre-TGM-1 101 02-02
A-Pre-TGM-1 101 02-03
=rontier
A-Pre-MMM-110202-SP01
A-Pre-MMM-110202-FB01
A-Pre-MMM-1 10202-01
Analyte(s)
VOCs/NMOCs/O2/CO2,N2
VOCs/NMOCs/O2/CO2,N2
VOCs/NMOCs/O2/CO2,N2
PAHs, PCBs
PAHs, PCBs
PAHs, PCBs
Carbonyls
Carbonyls
Carbonyls
H2S
H2S
H2S
Elemental Hg a
Elemental Hg a
Elemental Hg a
Total gaseous Hg
Total gaseous Hg
Total gaseous Hg
Total gaseous Hg
Monomethyl Hg
Monomethyl Hg
Monomethyl Hg
Sample
Class
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Field Blank
Test
Test
Test
Spike
Field Blank
Test
Date
11/02/02
11/02/02
11/02/02
11/01/02
11/01/02
11/01/02
11/02/02
11/02/02
11/02/02
11/02/02
11/02/02
11/02/02
11/02/02
11/02/02
11/02/02
11/01/02
11/01/02
11/01/02
11/01/02
11/02/02
11/02/02
11/02/02
Run Period
10:30-10:58
11:40-12:18
12:37-13:09
11:05-14:08
11:05-14:05
15:46-18:46
11:23-11:53
12:10-12:40
13:03-13:33
14:33-14:43
15:40-15:50
16:25-16:35
14:49-16:00
14:49-16:00
14:49-16:00
14:45
11:20-11:55
12:26-13:03
13:49-14:23
15:50-14:24
13:30-13:35
10:15-10:44
3-4
-------
Source Test
Report for Landfill A
Sampling
Method
Run Number
A-Pre-MMM-1 10202-02
A-Pre-MMM-1 10202-03
Frontier
A-Pre-DMM-110202-SP01
A-Pre-DMM-110202-FB01
A-Pre-DMM-1 10202-01
A-Pre-DMM-1 10202-02
A-Pre-DMM-1 10202-03
Analyte(s)
Monomethyl Hg
Monomethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Sample
Class
Test
Test
Spike
Field Blank
Test
Test
Test
Date
11/02/02
11/02/02
11/02/02
11/02/02
11/02/02
11/02/02
11/02/02
Run Period
11:08-11:40
12:13-12:45
08:46-09:12
08:10-08:15
15:19-15:44
16:31 -17:00
17:26-17:55
Represents average of 3 readings, each of 30-second duration
3.2.3 Engine Stack
Sampling at the engine stack was conducted by accessing the sampling ports with the
aid of a scaffold. Figure 3-2 shows the engine and the sampling scaffold platform.
The engine stack was sampled for NMOCs (as THCs), PCDDs/PCDFs, PAHs, HC1,
lead (Pb), arsenic (As), cadmium (Cd), chromium (Cr), manganese (Mn), nickel (Ni),
total Hg, SO2, NOX, CO, carbon dioxide (CO2), and oxygen (O2). Table 3-5 lists the
test samples that were collected from the engine stack.
The engine stack cross-section was divided into 6 equal areas according to EPA
Method 1. Sampling at the engine stack was conducted at isokinetic conditions. Sample
collection times for the Method 26 HC1 train and the Method 29 metals train were 60-
minutes. Run time for the Method 23 PCDDs/PCDFs trains was 180 minutes. Run time
for continuous emission monitoring system (CEMS) parameters (SO2, NOX, CO, O2,
CO2, and THCs) varied.
3-5
-------
Source Test
Report for Landfill A
Figure 3-2. Engine #2 Stack and Sampling Scaffold
3-6
-------
Source Test
Report for Landfill A
Table 3-5. Engine Stack Test Sample Log and Collection Times
Sampling
Method
Run Number
EPA Method 3A (CEM)
A-Post-M3A-1 101 02-01
A-Post-M3A-1 101 02-02
A-Post-M3A-1 10202-03
EPA Method 3A (CEM)
A-Post-M3A-1 101 02-01
A-Post-M3A-1 101 02-02
A-Post-M3A-1 10202-03
EPA Method 10 (CEM)
A-Post-M10-110102-01
A-Post-M 10-1 101 02-02
A-Post-M 10-1 10202-03
EPA Method 7E (CEM)
A-Post-M7E-1 101 02-01
A-Post-M7E-1 101 02-02
A-Post-M7E-1 10202-03
EPA Method 6C (CEM)
A-Post-M6C-1 101 02-01
A-Post-M6C-1 101 02-02
A-Post-M6C-1 10202-03
EPA Method 25A (CEM)
A-Post-M25A-1 101 02-01
A-Post-M25A-1 101 02-02
A-Post-M25A-1 10202-03
Lumex Instrument
A-Post-EM-1 10202-01
A-Post-EM-1 10202-02
Analyte(s)
02
02
02
CO2
CO2
CO2
CO
CO
CO
NOx
NOX
NOX
SO2
SO2
SO2
NMOCs (THC)
NMOCs (THC)
NMOCs (THC)
Elemental Hg a
Elemental Hg a
Sample
Class
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Date
11/01/02
11/01/02
11/02/02
11/01/02
11/01/02
11/02/02
11/01/02
11/01/02
11/02/02
11/01/02
11/01/02
11/02/02
11/01/02
11/01/02
11/02/02
11/01/02
11/01/02
11/02/02
11/02/02
11/02/02
Run Period
12:03-14:50
16:42-19:00
09:50-15:20
12:03-14:50
16:42-19:00
09:50-15:20
12:03-14:50
16:42-19:00
09:50-15:20
12:03-14:50
16:42-19:00
09:50-15:20
12:03-14:50
16:42-19:00
09:50-15:20
12:03-14:50
16:42-19:00
09:50-15:20
14:49-16:00
14:49-16:00
3-7
-------
Source Test
Report for Landfill A
Sampling
Method
Run Number
EPA Method 26
A-Post-M26-1 101 02-01
A-Post-M26-1 101 02-02
A-Post-M26-1 10202-03
EPA Method 23
A-Post-M23-1 101 02-01
A-Post-M23-1 101 02-02
A-Post-M23-1 10202-03
EPA Method 29
A-Post-M29-1 101 02-01
A-Post-M29-1 101 02-02
A-Post-M29-1 10202-03
Analyte(s)
HCI
HCI
HCI
Dioxins/furans, PAHs
Dioxins/furans, PAHs
Dioxins/furans, PAHs
Metals
Metals
Metals
Sample
Class
Test
Test
Test
Test
Test
Test
Test
Test
Test
Date
11/01/02
11/01/02
11/02/02
11/01/02
11/01/02
11/02/02
11/01/02
11/01/02
11/02/02
Run Period
15:32-16:57
15:34-16:59
13:10-14:17
11:09-13:30
11:12-14:33
09:01 -12:14
17:42-18:55
17:44-18:57
13:13-14:21
Represents 3 readings, each 30 seconds in duration
3.3 Field Test Changes and Deviations from QAPP Specifications
3.3.1 Variation from Test Methods and/or Planned Activities
3.3.1.1 Sampling at the Raw Landfill Gas (LFG) Pipe
Because of the configuration of the raw LFG inlet pipe, isokinetic sampling at this
location was not possible and hence was not attempted. The gas collection pipe is 12
inches in diameter (see Figure 2-2). Isokinetic sampling requires a 4-inch port to
accommodate the sampling probe. During the pre-test site survey, facility could only
install %-inch sampling ports on the gas pipe because of safety concerns. Therefore,
collecting the samples isokinetically was not possible.
Isokinetic sampling would be of value if collecting particulate samples were needed.
Little particulate matter was expected in the raw LFG pipe and this speculation was
corroborated by the observation that the glass fiber filters on several of the sampling
trains did not reveal the presence of particulates.
3-8
-------
Source Test
Report for Landfill A
3.3.1.2 Landfill Gas (LFG) Inlet Pipe Condensate Sample
The facility used a condensate knock-out vessel to separate the condensate from the
gas stream. During these tests, the condensate drain valve was in the "closed" position.
According to the site operator, that was the typical operation configuration for the unit.
There were not provisions to withdraw a condensate sample from the knock-out vessel.
However, the pipe that delivers the raw LFG to the engines runs along the outside of
the engine room. A condensate drain pipe with a valve was in place. A sample of the
condensate was collected at that location and placed in archive storage so that it would
be available if analysis were deemed necessary. The condensate sample was not
analyzed.
3.3.1.3 Landfill Gas (LFG) Flow Rate Measurement
Gas flow as indicated by the LFG flow control station was recorded. However, the
accuracy of these measurements could not be verified because of the inability to
measure gas velocity accurately. The test team was able to make crude velocity
measurements by inserting a velocity probe part-way into the gas pipe. The accuracies
of these measurements are uncertain, even though they appear to agree with the
facility's flow control station readings.
3.3.2 Application of Test Methods
The sampling and, where applicable, analytical methods used in this test program
follow those specified in the QAPP. Table 3-6 lists the applicable measurement and
analysis methods and their corresponding performing organizations.
3-9
-------
Source Test
Report for Landfill A
Table 3-6. Test Methods and Performing Organizations
Procedure
EPA Method 1
EPA Method 2
EPA Method 3A
EPA Method 3C
EPA Method 4
EPA Method 6C
EPA Method 7E
EPA Method 10
EPA Method 1 1
EPA Method 23
EPA Method 25A
EPA Method 25C
EPA Method 26A
EPA Method 29
EPA Method 40/TO-1 5
SW-846 Method 0100/TO-1 1
LUMEX instrument
Organic mercury methods
Description
Selection of traverse points
Determination of stack gas velocity and
volumetric flow rate
Determination of stack gas O2 and CO2 for
flare stack gas molecular weight
calculations
Determination of CC>2, ChU, N2, and O2 in
raw LFG
Determination of stack gas moisture
Determination of stack gas SO2
Determination of stack gas NOX
Determination of stack gas CO
Determination of raw LFG H2S
Determination of stack gas
Dioxins/furans by Method 8290
PAHs by Method 8270
PCBs by Method 1668
Determination of flare stack gas NMOCs,
as THCs when total organic concentration
is less than the 50 ppm Method 25C
applicability threshold
Determination of raw LFG NMOCs
Determination of stack gas HCI
Determination of stack gas metals
Determination of raw LFG VOCs
Determination of raw LFG carbonyls
(formaldehyde, acetaldehyde)
Determination of raw LFG Hg°
Determination of raw LFG:
Monomethyl mercury
Dimethyl mercury
Total mercury.
Organization Performing Analysis
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
Triangle Environmental Services
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
Oxford Laboratories
ALTA Analytical Perspectives
ARCADIS G&M
Triangle Environmental Services
Resolution Analytics
First Analytical Laboratories
Research Triangle Park Laboratories
Resolution Analytics
ARCADIS G&M
Frontier Geosciences
3-10
-------
Source Test
Report for Landfill A
3.3.3 Test Method Exceptions
Laboratory analytical procedures followed those prescribed by the specified methods,
with the following exceptions:
RawLFG
• Carbonyls were analyzed by Method TO-11 instead of SW-846 Method 8315.
(Method TO-11 and Method 8315 closely resemble each other.)
• Polycyclic aromatic hydrocarbons (PAHs) were analyzed by SW-846 Method
8270 as specified in the QAPP. However, the sample extracts were found to
contain excessive amounts of non-PAH organics. In order to make the extracts safe
to be injected into the gas chromatograph/mass spectrometer (GC/MS), samples
had to be diluted excessively. The high dilution made the method detection levels
for the target PAHs too high, resulting in "non-detects" at the high detection limits.
The planned analysis method could not produce the desired results at the needed
detection levels. At the time of report writing, alternative analysis method had not
been identified. The sample extracts are in storage and may be submitted for
analysis if a suitable method becomes available.
• Polychlorinated biphenyls (PCBs) were analyzed by EPA Method 1668 (EPA
812/R-97-001) as specified in the QAPP. However, similar to the difficulties
experienced for the PAH analysis, in order to make the extracts safe to be injected
inject into the gas chromatograph (GC), they had to be diluted excessively. The
planned analysis method could not produce the desired results at the needed
detection levels.
• For raw LFG inlet samples, VOCs were analyzed by EPA Method TO-15.
Methane (CFL,) was analyzed by GC/FID and additionally by Method 3C.
Engine Stack
• Non-methane organic compounds (NMOCs) - Method 25A was used instead of the
specifically applicable Method 25 C.
3-11
-------
Source Test
Report for Landfill A
This page intentionally left blank
3-12
-------
Source Test
Report for Landfill A
4. Presentation of Test Results
Testing took place at Landfill A on November 1-2, 2002. Results of the testing are
presented in this section. Detailed test results are included in the Appendices for close
examination by the reader. The following subsections provide concise summaries of
the test results.
4.1 Raw Landfill Gas (LFG) Results
As depicted in Figure 2-2, sampling was conducted by extracting samples from the
four %-inch ports installed in the raw LFG pipe.
4.1.1 Raw Landfill Gas (LFG) Flow Rate and Temperature
4.1.1.1 Direct Measurements
The facility process system has a flow measurement system that displays the flow rate
on an instrument panel meter. The panel meter read between 1650 and 1700 scfm.
The small size of the sampling ports precluded the proper measurement of the velocity
profile all the way across the gas pipe. Nonetheless, measurements with a velocity
probe ranged from 1935 ft/minto 2075 ft/min. At these velocities, and with pipe inside
diameter of 12 inches, the volumetric flow rate was estimated to be about 1580 cu
ft/min. Vacuum at the raw LFG pipe was 34 to 35 inch water column (WC).
A direct measurement with thermocouples showed the raw LFG temperature was 57°F.
4.1.1.2 Landfill Gas (LFG) Flow Rate Combined Estimate
The raw LFG flow rate was based on two independent measurements: 1650 to 1700
scfm by the facility's flow rate indicator and 1580 scfm by the crude pitot probe
measurement. This resulted in an estimated average of 1640 scfm.
4.1.2 Raw Landfill Gas (LFG) Constituents
The concentrations of the constituents of interest in the raw LFG are presented in the
following Subsections 4.1.2.1 through 4.1.2.5. Following the presentation of the
constituent concentrations, Section 4.3 summarizes the data and presents a comparison
4-1
-------
Source Test
Report for Landfill A
with the AP-42 default emission concentration values. The section also presents the
estimated mass flow rates of the constituents at the raw LFG pipe.
In computing averages, when all measurements are "non-detect" (ND), the average is
reported as ND. When one or more measurement is above detection, the ND
measurement is treated as 50 percent of the stated method detection limit (MDL). If
MDL is not reported, a ND measurement is treated as zero.
4.1.2.1 Volatile Organic Compounds (VOCs)
Concentrations of VOCs were obtained by collecting summa canister samples using
Method 40 procedures. Analysis was performed by Method TO-15, with gas
chromatography and mass spectrometry (GC/MS). The alkanes (C2 through C6), being
present in much higher concentrations, were analyzed by GC flame ionization
detection (FID) on the same summa canister samples.
Table 4-1 lists the results of these analyses. Tentatively identified compounds (TICs)
can be seen in the Research Triangle Park (RTF) Laboratory reports in Appendix A.
Table 4-1. Raw Landfill Gas VOC Concentrations
Compound
Unit
MDL
Concentration
Run 1
Run 2
Run 3
Average a
Bv GC/FID
Ethane
Propane
Butane
Pentane
Hexane
ppmv
ppmv
ppmv
ppmv
ppmv
1
1
1
1
1
5.9
8.5
4.4
3.2
ND
6.5
9.0
4.7
2.7
ND
6.1
9.3
5.5
3.7
ND
6.2
8.9
4.9
3.2
ND
Bv TO-15 GC/MS
Dichlorodifluoromethane (Freon 12)
1,2-Chloro-,1,2,2-Tetrafluoroethane
(CFC114)
Chloromethane
Vinyl chloride
1,3-Butadiene (Vinylethylene)
ppbv
ppbv
ppbv
ppbv
ppbv
0.2
0.2
0.2
0.2
0.2
126
8.2
ND
101
24
132
8.0
36
103
22
96
7.1
ND
87
20
118
7.8
12
97
22
4-2
-------
Source Test
Report for Landfill A
Compound
Bromomethane (Methyl Bromide) c
Chloroethane (Ethyl Chloride)
Trichloromonofluoromethane
(CFC11)
1,1-Dichloroethene
1 , 1 ,2-Trichloro-1 ,2,2-trifluoroethane
(CFC113)
Carbon Disulfide
Ethanol d
Isopropyl Alcohol (2-Propanol) e
Methylene chloride
(Dichloromethane) c
Acetone c
t-1,2-dichloroethene
Hexane8
Methyl-t-butyl ether (MTBE)
1,1-Dichloroethane
Vinyl Acetate
cis-1 ,2-Dichloroethene
Cyclohexane
Chloroform
Ethyl Acetate
Carbon Tetrachloride
Tetrahydrofuran (Diethylene Oxide)
1,1,1-Trichloroethane
2-Butanone (Methyl Ethyl Ketone)
Heptane
Benzene
1,2-Dichloroethane
Trichloroethylene (Trichloroethene)
Unit
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
MDL
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
Concentration
Run 1
5.7
951
60
1.7
2.2
15.9
23.4 J
145 J
871
381
2.9
2270 J
60.6
17.8
435
79.9
177
44.0
ND
1.3
980
5.6
289
262
79.3
1.1
31.1
Run 2
5.7
1100
51
1.7
2.1
11.8
20.1 J
160 J
1070
325
2.6
2370 J
52.4
57.0
265
69.7
167
36.6
2670
1.1
1070
4.9
249
238
70.2
0.9
26.2
Run 3
35.6
256
43
1.6
1.8
15.6
15.7 J
36.1 J
1050
278
2.6
2780 J
50.2
25.5
27
72.7
151
38.7
2810
ND
1510
4.3
281
225
69.6
1.1
26.6
Average a
15.6
770
51
1.7
2.0
14.4
19.7J
114J
997
328
2.7
2470 J
54.4
33.4
242
74.1
165
39.8
1830
0.8
1180
4.9
273
242
73.0
1.0
28.0
4-3
-------
Source Test
Report for Landfill A
Compound
1 ,2-Dichloropropane
Bromodichloromethane
1,4-Dioxane (1,4-Diethylene
Dioxide)
cis-1 ,3-Dichloropropene
Toluene (Methyl Benzene)
4-Methyl-2-pentanone (MIBK)
t-1 ,3-Dichloropropene
Tetrachloroethylene
(Perch loroethylene)
1,1,2-Trichloroethane
Dibromochloromethane
1,2-Dibromoethane (Ethylene
dibromide)
2-Hexanone (Methyl Butyl Ketone)
Ethylbenzene
Chlorobenzene
m/p-Xylene (Dimethyl Benzene) d
o-Xylene (Dimethyl Benzene)
Styrene (Vinylbenzene)
Tribromomethane (Bromoform)
1 , 1 ,2,2-Tetrachloroethane
1-Ethyl-4-methylbenzene b
(4-Ethyl Toluene)
1,3,5-Trimethylbenzene b
1 ,2,4-Trimethylbenzene
1 ,4-Dichlorobenzene
1,3-Dichlorobenzene
Benzyl Chloride
1 ,2-Dichlorobenzene
Unit
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
MDL
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
Concentration
Run 1
0.8
3.6
3.1
ND
680
1250
0.6
45.1
7.5
ND
0.8
380
612
74.4
3200 J
312
41.5
1.1
49.1
81.9 J
81.9 J
199
44.5
0.6
3.8
2.8
Run 2
0.7
2.2
2.6
ND
1620
1320
0.2
40.0
7.5
ND
0.7
494
545
64.8
3540 J
290
38.2
ND
ND
77.4 J
77.4 J
186
42.3
0.7
4.5
2.7
Run 3
0.8
2.1
ND
0.5
1670
650
ND
41.1
7.9
ND
1.7
796
570
445
4450 J
298
8.8
ND
40.4
78.6 J
78.6 J
194
43.2
ND
10.5
ND
Average a
0.8
2.6
1.9
0.2
1330
1070
0.3
42.1
7.6
ND
1.1
557
575
195
3730 J
300
29.5
0.4
29.9
79.3 J
79.3 J
193
43.4
0.5
6.3
1.9
4-4
-------
Source Test
Report for Landfill A
Compound
1,1,2,3,4,4-Hexachloro-1,3-
butadiene
1 ,2,4-Trichlorobenzene
Acrylontrile
Dichlorofluoromethane (Freon 21)
Chlorodiflouromethane (Freon 22)
Ethyl Mercaptan (Ethanediol)
Carbonyl Sulfide (Carbon
oxysulfide)
Unit
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
MDL
0.2
0.2
20
20
20
20
20
Concentration
Run 1
1.1
0.5
ND
ND
ND
ND
ND
Run 2
1.3
1.3
ND
ND
ND
ND
ND
Run 3
1.3
1.2
ND
ND
ND
ND
ND
Average a
1.2
1.0
ND
ND
ND
ND
ND
ND - Constituent not detected at the stated detection limits
J - Value is categorized as an estimate per EPA QA/G-8 guidance
a In computing averages, when all measurements are ND, the average is reported as ND. When
one or more measurement is above detection, the ND measurement is treated as 50 percent of
the stated MDL. If MDL is not reported, a ND measurement is treated as zero.
b 1-Ethyl-4-methylbenzene (4-Ethyl Toluene) and 1,3,5-Trimethylbenzene co-eluted from the GC
and also have the same quantitation ions, thus making them indistinguishable. Therefore, the
reported values represent the combined concentrations of these two compounds.
c Analyte detected in blank sample: acetone = 3.3 ppbv, methylene chloride = 1.4 ppbv,
bromomethane = 1.03 ppbv
d Spike recovery: ethanol = 2-4 percent, m/p-xylene = 230 percent
e RSD: isopropyl alcohol - 56.3 percent, hexane = 40.7 percent
4.1.2.2 Non-methane Organic Compounds (NMOCs)
Non-methane organic compounds (NMOCs) in the raw LFG were analyzed by Method
25C on the Method 40 samples. The NMOC concentrations in the raw LFG are
presented in Table 4-2. This table also includes concentrations of CFL,, CO2, O2, and
nitrogen (N2) that are results obtained as part of the NMOC analyses. The moisture
concentration data were obtained from the Method 23 PAH/PCB sample train
measurements.
The other analytes, oxygen (O2), carbon dioxide (CO2), and moisture, are not pollutants
but are of interest as they are useful indicators of the "quality" of the raw LFG. The
concentrations of nitrogen (N2) and O2 are also indicators of the extent of ambient air
infiltration into the LFG collection. Method 25 C for NMOC determination specifically
4-5
-------
Source Test
Report for Landfill A
recommends that these measurements be made to determine potential air infiltration.
Therefore, while measurements for methane (CHO, CO2, O2, and N2 by Method 3C
were not included in the original QAPP, these measurements were included and
performed.
Table 4-2. Raw Landfill Gas Non-Methane Organic Compound (NMOC) Concentrations
Run 1
Run 2
Run 3
Average
NMOC
(ppmv as
Hexane)
Method 25C
297
334
492
374
CH4
(% v/v)
Method 25C
48.0
48.7
49.8
48.8
Method 3C
43.5
44.5
45.4
44.5
CO2
(% v/v)
Method 25C
38.1
38.6
39.4
38.7
Method 3C
35.2
36.1
36.9
36.1
02
(%v/v)
Method 3C
1.6
1.8
1.7
1.7
N2
(% v/v)
Method 3C
12.7
13.4
13.1
13.1
Moisture
(% v/v)
Method 23
12.3
12.0
11.6
12.0
Concentrations are reported without correction for nitrogen.
Method 25C analysis hold time was up to 51 days. Method specified hold time was 30 days.
4.12.3 Hydrogen Sulfide (H2S)
Raw LFG pipe H2S concentrations were obtained by collecting and analyzing the
samples in accordance with EPA Method 11. These results are presented in Table 4-3.
Table 4-3. Raw Landfill Gas Hydrogen Sulfide Concentrations
Run 1
Run 2
Run 3
Average
H2S Concentration
(mg/m3)
26.1
18.7
10.7
18.5
(ppmv)
18.4
13.2
7.6
13.0
4.12.4 Carbonyls
The target carbonyl compounds, formaldehyde and acetaldehyde, were analyzed by
Method TO-11 on samples collected by EPA Method 0100. The analysis results are
presented in Table 4-4.
4-6
-------
Source Test
Report for Landfill A
Table 4-4. Raw Landfill Gas Carbonyls Concentrations
MDL
Run 1
Run 2
Run 3
Average
Formaldehyde a
(Mg/m3)
2.1
2.3 J
5.0 J
5.0 J
4.1 J
(x10~3 ppmv)
1.7
1.8 J
4.0 J
4.0 J
3.3 J
Acetaldehyde
(Mg/m3)
4.2
18.9
67.8
50.3
45.7
(x10~3 ppmv)
2.3
10.3
37.0
27.4
24.9
' Measured formaldehyde values were near MDL
4.12.5 Mercury (Hg)
Mercury (Hg) can exist in several forms. This test program focused on the elemental,
monomethyl, and dimethyl forms of Hg, and total Hg. Elemental Hg was measured
with the LUMEX instrument. Organic monomethyl Hg, dimethyl Hg, and total Hg
were sampled and analyzed using the organic mercury method.
4.1.2.5.1 Total Mercury (Hg) Samples
To collect the total Hg samples, an iodated charcoal trap was used as a sorbent. A
backup tube was also present to assess any breakthrough. The sorbent tube was heated
to above the dew point of the gas stream to prevent condensation on the sorbent. A
silica gel impinger was used to collect and quantify the water vapor from the stream. A
diaphragm air pump was used to pull samples through the train and collect the samples.
A dry gas meter capable of measuring the volume in 10 ml increments was used to
monitor and quantify the volume of gas sampled.
Table 4-5 presents the total Hg concentrations in the raw LFG. They ranged from 601
to 676 ng/m3 with an average of 632 ng/m3. Spike recovery for total Hg samples was
95 percent.
4-7
-------
Source Test
Report for Landfill A
Table 4-5. Raw Landfill Gas Total Mercury Concentrations
MDL
Run 1
Run 2
Run 3
Average
Total Mercury Concentration
(ng/m3)
50
676
618
601
632
(x10's ppm)
6.0
81.4
74.4
72.4
76.1
Sample hold time exceeded 14 days
4.1.2.5.2 Dimethyl Mercury (Hg) Samples
To collect the dimethyl Hg sample, a Carbotrap was used as a sorbent. A backup tube
was also present to assess any breakthrough. A third iodated carbon trap was also
present to collect any elemental Hg present. The sorbent tube was heated to above the
dew point of the gas stream to prevent condensation on the sorbent. A silica gel
impinger was used to collect and quantify the water vapor from the stream. A
diaphragm air pump was used to pull sample through the train and collect the sample.
A dry gas meter capable of measuring the volume in 10 ml increments was used to
monitor and quantify the volume of gas sampled.
Table 4-6 presents the dimethyl Hg concentrations in the raw LFG. The analyzed
concentrations ranged from 5.1 to 8.2 ng/m3 with an average of 7.1 ng/m3. However,
spike recovery for the dimethyl Hg traps was only 41 percent, well below normally
acceptable levels. The spiked traps, without being exposed to the raw LFG, had
recoveries from 68 to 98 percent with an average of 83 percent. Recoveries were low in
the spiked traps possibly because of the presence of an unknown interfering compound
either destroying or masking the detection of the dimethyl Hg. For this reason,
dimethyl Hg concentrations data were flagged with "R" to indicate that the data were
rejected. Further development of this procedure was being undertaken by Frontier
Geosciences. More studies are needed to develop an acceptable method to determine
the actual dimethyl Hg concentrations more accurately.
4-8
-------
Source Test
Report for Landfill A
Table 4-6. Raw Landfill Gas Dimethyl Mercury Concentrations
MDL
Run 1
Run 2
Run 3
Average
Dimethyl Mercury Concentration
(ng/m3)
0.5
5.1 R
8.0 R
8.2 R
7.1 R
(xlO"6 ppmv)
0.05
0.53 R
1.8 R
1.9 R
0.74 R
Sample hold time exceeded 14 days
Spike recoveries were 0-5 percent
R - Results are rejected due to serious deficiencies per EPA QA/G-8 guidance
4.1.2.5.3 Monomethyl Mercury (Hg) Samples
To collect the sample, a set of three impingers filled with 0.001 M HC1 was used to
collect the monomethyl Hg. An empty forth impinger was used to knockout any
impinger solution carryover to the pump and meter system. A diaphragm air pump was
used to pull the sample through the train and collect the sample. A dry gas meter
capable of measuring the volume in 10 ml increments was used to monitor and
quantify the volume of gas sampled.
As shown in Table 4-7, monomethyl Hg concentrations in the raw LFG ranged from
non-detectto 1.2 ng/m3. Spike recovery for the monomethyl Hg sample was 70
percent.
Table 4-7. Raw Landfill Gas Monomethyl Mercury Concentrations
MDL
Run 1
Run 2
Run 3
Average
Monomethyl Mercury Concentration
(ng/m3)
0.13
ND
ND
1.2
0.4
(x10~6 ppmv)
0.014
ND
ND
0.13
0.04
Sample hold time exceeded 14 days
Relative standard deviation (RSD) of replicate sample exceeded ±30 percent
4-9
-------
Source Test
Report for Landfill A
4.1.2.5.4 Elemental Mercury (Hg)
Elemental Hg was determined by the LUMEX instrument and the results are presented
in Table 4-8.
Table 4-8. Raw Landfill Gas Elemental Mercury Concentrations
Run 1
Run 2
Run 3
Average
Concentration a
Background b
(ng/m3)
0.001
0.001
0.000
0.001
(xlO^ppmv)
0
0
0
0
Gas Pipe
(ng/m3)
280
325
320
308
(x10~6 ppmv)
33.7
39.1
38.5
37.1
'Average of three readings, each of 30-second duration
b Background measurement was made by sampling ambient air drawn through ice-chilled empty
impinger
4.2 Engine Stack Results
The engine stack was sampled for NMOCs (as THCs), PCDD/PCDFs, PAHs, HC1,
metals (Pb, As, Cd, Cr, Mn, Ni, total Hg), SO2, NOX, CO, CO2, and O2. The stack cross
section was divided into 6 equal areas according to EPA Method 1. Sampling run time
for HC1 and metals was 60 minutes. Run time for PCDD/PCDFs sampling was 180
minutes. Run time for CEMS parameters (SO2, NOX, CO, O2, CO2, and THCs) varied.
4.2.1 Engine Stack Gas Flow Rate and Temperature
Sampling at the engine stack was conducted at isokinetic conditions. The procedures
provided stack gas velocity distribution across the engine stack and reliable
measurements of stack gas flow rates. Table 4-9 lists the volumetric flow rates and
temperatures at the engine stack measured during the various sampling runs.
4.2.2 Engine Stack Gas Constituents
The concentrations of the constituents of interest in the engine stack are presented in
the following Subsections 4.2.2.1 through 4.2.2.7.
4-10
-------
Source Test
Report for Landfill A
Table 4-9. Engine Stack Gas Operating Conditions Measured during Sampling
Run Number
A-Post-M26-1 101 02-01
A-Post-M26-1 101 02-02
A-Post-M26-1 10202-03
A-Post-M29-1 101 02-01
A-Post-M29-1 101 02-02
A-Post-M29-1 10202-03
A-Post-M23-1 101 02-01
A-Post-M23-1 101 02-02
A-Post-M23-1 10202-03
Average
Date
11/01/02
11/01/02
11/02/02
11/01/02
11/01/02
11/02/02
11/01/02
11/01/02
11/02/02
Time
15:32-16:57
15:34-16:59
13:10-14:17
17:42-18:55
17:44-18:57
13:13-11:21
11:09-13:30
11:12-14:33
09:01-12:14
Average
Stack Temp
(°F)
732
732
734
737
737
734
738
738
733
735
Carbon
Dioxide
(%)a
12.8
12.8
13.2
12.8
12.8
13.2
12.8
12.8
13.2
12.9
Oxygen
(%) b
7.5
7.5
7.4
7.5
7.5
7.4
7.5
7.5
7.4
7.5
Moisture
(%)
12.3
12.3
12.5
11.9
11.3
12.4
12.3
12.0
11.6
12.1
Velocity
(actual ft/sec)
149
149
154
150
150
154
150
150
154
151
Volumetric
Flow Rate
(acfm)
3330
3330
3430
3340
3340
3430
3350
3350
3430
3370
Volumetric
Flow Rate
(dscfm)
1290
1290
1330
1300
1310
1330
1290
1300
1340
1310
Engine stack cross-section flow area is 0.37 sq. ft.
a Calibration bias = 2.2 - 3.3%, System bias = 1.1- 4.3%, Drift = 2.2 - 5.4%
b Calibration bias = 0 - 3.3%, System bias = 0 - 2.2%, Drift = 2.2 - 3.3%
4-11
-------
Source Test Report
for Landfill A
4.2.2.1 Engine Stack Oxygen and Carbon Dioxide
Oxygen (O2) and CO2 concentrations provide an overall indication of the combustion
process. Figure 4-1 shows the O2and CO2 concentrations measured by the CEMs
during the two days of testing. The plotted data included the CEM responses to the
instrument zeroing and calibration periods on November 1, 2002. The end-of-test
calibration data were included on the November 2, 2003 plot. These periods manifest
as the peaking and bottoming of the recorded values. Table 4-10 presents the daily
averages of O2and CO2 concentrations.
4.2.2.2 Engine Stack Total Hydrocarbon (THC) Concentrations
Engine stack THC concentrations were measured by EPA Method 25A that used a
CEMs. At the engine stack, hydrocarbon (including NMOCs) concentrations were
found to be below 50 ppmv. The low concentrations rendered Method 25C, the method
designed specifically for NMOC measurement, unsuitable to be applied at this
location.
Instead, EPA Method 25 A produced concentrations of all hydrocarbons that respond to
FID analysis. Real-time continuous instrument responses are shown in Figure 4-2. The
time-averaged concentrations are presented in Table 4-11. As can be seen, the
concentrations of THC ranged from 323 to 393 ppmv as hexane.
4.2.2.3 Engine Stack Dioxin/Furan (PCDD/PCDFs) Emissions
Three EPA Method 23 sampling runs were performed. As a cost-saving measure, only
the samples from one run (Run 3) were analyzed. Samples from runs 1 and 2 have been
extracted and are being held in the laboratory and are available for possible future
analysis, if deemed necessary.
Table 4-12 presents the engine stack PCDD/PCDF-emissions data. Table 4-13 presents
the same data, but expressed in terms of Toxicity Equivalent emissions.
4.2.2.4 Engine Stack Polycyclic Aromatic Hydrocarbon (PAH) Emissions
The concentrations of PAHs were obtained by analyzing a Method 23 sample using
Method 8270. As a cost-saving measure, only the sample from Run 3 was analyzed.
Two additional samples were collected and extracted but not analyzed. The PAH
concentrations in the Run 3 sample are presented in Table 4-14.
4-12
-------
Source Test Report
for Landfill A
Engine Stack Oxygen & Carbon Dioxide 11/1/02
14
12
10
06:00
8:24
10:48 13:12
Time
14
12
10
§ 8
•a
Engine Stack Oxygen & Carbon Dioxide 11/2/02
TT
Oxygen
Carbon Dioxide
Sampling Period
16:48
18:00
Figure 4-1. Engine Stack Oxygen and Carbon Dioxide Concentrations
4-13
-------
Source Test Report
for Landfill A
Table 4-10. Engine Stack Combustion Product Concentrations.
Run 1
Run 2
Run 3
Average
02
(%v)a
7.4
7.6
7.4
7.5
CO2
(%v)b
12.7
12.8
13.2
12.9
' Calibration bias = 2.2 - 3.3%, System bias = 1.1- 4.3%, Drift = 2.2 - 5.4%
' Calibration bias = 0 - 3.3%, System bias = 0 - 2.2%, Drift = 2.2 - 3.3%
Table 4-11. Engine Stack THC Concentrations
Run 1
Run 2
Run 3
Average
THC
(ppmdv as
propane)
759
786
645
730
THC
(ppmdv as
hexane)
380
393
323
365
Calibration bias = 0 - 3.8%, System bias = 0 - 3.8%, Drift = 0 - 3.3%
4-14
-------
Source Test Report
for Landfill A
mnn -,
Qnn
800 -
ynn
^700
Q
Efinn
Q.
£.
c ^nn
TO
§ 4UU
u
c
,9 ^nn
9nn
-inn
Engine Stack Total Hydrocarbon 11/1/02
Sampling Period
I OIQI nyurocQiDon
06:00
^ll
Tjw
rkkMtM
Tb
L
08:24 10:48 13:12 15:36 18:00 20:24
Time
Engine Stack Total Hydrocarbon 11/2/02
Sampling Period
Total Hydrocarbon
12:00
13:12
14:24 Time 15:36
16:48
18:00
Figure 4-2. Engine Stack Total Hydrocarbon Concentrations
4-15
-------
Source Test Report
for Landfill A
Table 4-12. Engine Stack Dioxins and Furans Emissions
Analyte
A-POST-M23-1 10202-03
Concentration
(x10~3 ng/dscm)
Emission Rate
(x10-9g/hr)
(x10'12lb/hr)
Dioxins
2,3,7,8-TCDD
Other TCDD
1,2,3,7,8-PeCDD
Other PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
Other HxCDD
1,2,3,4,6,7,8-HpCDD
Other HpCDD
1,2,3,4,6,7,8,9-OCDD
Total ODD
<0.48
22.0
<0.37
3.4
<1.2
<1.1
<1.2
0.239
<1.8
0.0
<2.0
<33.8
<1.1
50.1
<0.84
7.6
<2.8
<2.6
<2.6
0.545
<4.1
0.0
<4.6
<77.0
<2.4
110.5
<1.8
16.9
<6.1
<5.7
<5.8
1.2
<9.1
0.0
<10.2
<170
Furans
2,3,7,8-TCDF
Other TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
Other PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
Other HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
Other HpCDF
1,2,3,4,6,7,8,9-OCDF
Total CDF
Total CDD/CDF
<0.70
46.6
<0.64
<0.59
3.4
<1.3
<1.3
<1.3
<0.28
1.3
<1.5
<0.16
0.0
<1.3
13.9
<47.6
<1.6
106
<1.5
<1.4
7.7
<3.0
<3.0
<3.0
<0.65
3.0
<3.4
<0.36
0.0
<3.0
138
<214.8
<3.5
234
<3.2
<3.0
16.9
<6.7
<6.7
<6.7
<1.4
6.6
<7.6
<0.80
0.0
<6.6
304
<473.6
Two additional samples were collected, extracted and held in the laboratory for possible future
analyses: A-POST-M23-110102-01 and A-POST-M23-110102-02
"<" denotes the measurement was non-detect. The value following the "<" sign is the detection
limit.
4-16
-------
Source Test Report for
Landfill A
Table 4-13. Engine Stack Dioxins and Furans Toxicity Equivalent Emissions
Pollutant
Dioxins
2,3,7,8-TCDD
Other TCDD
1,2,3,7,8-PeCDD
Other PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
Other HxCDD
1,2,3,4,6,7,8-HpCDD
Other HpCDD
1,2,3,4,6,7,8,9-OCDD
Total ODD
A-POST-M23-1 1 0202-03
Concentration
(x10~3 ng/dscm)
Emission Rate
(xlO^g/hr)
(x10'12 Ib/hr)
1989 Toxicity
Equivalency
Factor
Toxicity Equivalent
Emissions
Concentration
(x10^ ng/dscm)
Emission Rate
(xlO^g/hr)
(x10'12 Ib/hr)
<0.48
22.0
<0.37
3.4
<1.2
<1.1
<1.2
0.239
<1.8
0.0
<2.0
<33.8
<1.1
50.1
<0.84
7.6
<2.8
<2.6
<2.6
0.545
<4.1
0.0
<4.6
77.0
<2.4
111
<1.8
17
<6.1
<5.7
<5.8
1.2
<9.1
0.0
<10.2
170
1
—
0.5
—
0.1
0.1
0.1
—
0.01
—
0.001
—
<0.48
NA
<0.18
NA
<0.12
<0.11
<0.12
NA
<0.018
NA
<0.0020
<1.0
<1.1
NA
<0.42
NA
<0.28
<0.26
<0.26
NA
<0.041
NA
<0.0046
2.4
<2.4
NA
<0.92
NA
<0.61
<0.57
<0.58
NA
<0.091
NA
<0.0102
5.2
Furans
2,3,7,8-TCDF
Other TCDF
1,2,3,7,8-PeCDF
<0.70
46.6
<0.64
<1.6
106
<1.5
<3.5
234
<3.2
0.1
—
0.05
<0.070
NA
<0.032
<0.16
NA
<0.073
<0.35
NA
<0.16
4-17
-------
Source Test Report for
Landfill A
Pollutant
2,3,4,7,8-PeCDF
Other PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
Other HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
Other HpCDF
1,2,3,4,6,7,8,9-OCDF
Total CDF
Total CDD/CDF
A-POST-M23-1 1 0202-03
Concentration
(x10'3 ng/dscm)
<0.59
3.4
<1.3
<1.3
<1.3
<0.28
1.3
<1.5
<0.16
0.0
<1.3
<13.9
<47.6
Emission Rate
(xlO^g/hr)
<1.4
7.7
<3.0
<3.0
<3.0
<0.65
3.0
<3.4
<0.36
0.0
<3.0
<138
<216
(x10'12 Ib/hr)
<3.0
17
<6.7
<6.7
<6.7
<1.4
6.6
<7.6
<0.80
0.0
<6.6
<304
<474
1989 Toxicity
Equivalency
Factor
0.5
—
0.1
0.1
0.1
0.1
—
0.01
0.01
—
0.001
—
—
Toxicity Equivalent
Emissions
Concentration
(xlO"3 ng/dscm)
<0.30
NA
<0.13
<0.13
<0.13
<0.028
NA
<0.015
<0.0016
NA
<0.0013
<0.844
<1.9
Emission Rate
(x10^g/hr)
<0.68
NA
<0.30
<0.30
<0.30
<0.065
NA
<0.034
<0.0036
NA
<0.0030
<1.9
<4.3
(x10'12 Ib/hr)
<1.5
NA
<0.67
<0.67
<0.67
<0.14
NA
<0.076
<0.008
NA
<0.0066
<4.2
<9.5
NA - Not applicable because no Toxicity Equivalent Factor is available
"<" denotes the measurement was non-detect. The value following the "<" sign is the detection limit.
4-18
-------
Source Testing
Final Report
Landfill A, Revision 3
Table 4-14. Engine Stack Polycyclic Aromatic Hydrocarbons Emissions
Analyte
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(g,h,i)perylene
Benzo(k)fluoranthene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
lndeno(1 ,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
2-Methylnaphthalene
Benzo(e)Pyrene
Perylene
Formula
Weight
154.21
152.20
178.23
228.30
252.32
252.32
276.34
252.32
228.29
278.35
202.26
166.22
288.35
128.17
178.23
202.26
142.20
252.32
253.31
A-POST-M23-1 10202-03
Concentration
(x10~6 ppmv)
81.3
116
15.7
4.3
0.31
2.1
1.3
0.61
15.2
0.27
18.3
138
0.555
3400
256
20.8
1300
1.6
0.29
(ng/dscm)
521
731
116
41
3.2
22
15
6.4
144
3.2
154
950
6.6
17900
1900
175
7580
17
3.1
Emission Rate
(x10'6g/hr)
1200
1700
265
94
7.3
50
34
15
329
7.2
351
2200
15
40800
4300
400
17300
38
7.0
(xlO^lb/hr)
2.6
3.7
0.58
0.21
0.016
0.11
0.074
0.032
0.725
0.016
0.774
4.8
0.033
90
9.5
0.88
38
0.085
0.016
Two additional samples were collected, extracted and held in the laboratory for possible future
analyses: A-POST-M23-110102-01 and A-POST-M23-110102-02
Samples were extracted within method-specified 14-day hold time. The Run 3 sample extract was
analyzed 50 days after extraction. The method specified extract hold time to be 40 days.
4-19
-------
Source Testing
Final Report
Landfill A, Revision 3
4.2.3 Hydrogen Chloride (HCI) Emission Results
Engine stack HCI emissions results are presented in Table 4-15.
Table 4-15. Engine Stack Hydrogen Chloride Emissions
Run 1
Run 2
Run 3
Average
HCI Concentration
(ppmdv)
2.7
2.7
2.8
2.7
(mg/m3)
4.1
4.3
4.4
4.3
HCI Emission Rate
(Ib/hr)
0.0197
0.0200
0.0213
0.0203
(g/hr)
8.9
9.1
9.7
9.2
4.2.3.1 Metals Emissions Results
Toxic heavy metals in the engine stack gases were measured by Method 29.
Manganese was determined by inductively coupled plasma - mass spectroscopy (ICP-
MS). Arsenic (As), Cd, Cr, Pb, and Ni were determined by graphite furnace atomic
absorption spectroscopy (GFAAS). Mercury was determined by cold vapor (CV) AA
and was not detected in any of the samples. Table 4-16 presents the engine stack metals
emissions results.
Elemental mercury (Hg°) concentration was separately measured by the LUMEX
instrument and those results are also included in Table 4-16.
4-20
-------
Source Testing
Final Report
Landfill A, Revision 3
Table 4-16. Engine Stack Metal Emissions
Analyte
Arsenic
Cadmium
Chromium
Lead
Manganese
Nickel
Mercury
(Total by Method 29)
Mercury
(Elemental by LUMEX)
A-POST-M29-1 10102-01
Concentration
(jjg/dscm)
3.6
0.78
9.6
11.9
12.1
2.0
<1.7
Emission Rate
(x10^»
g/hr)
7.9
1.7
21
26.3
26.8
4.4
<0.004
(x10%/hr)
17.5
3.8
46.6
58.1
59.0
9.8
<8.2
RUN1
0.027
0.060
0.13
A-POST-M29-1 10102-02
Concentration
(jjg/dscm)
3.0
0.18
11.0
5.5
8.4
16.0
<1.6
Emission Rate
(x10^»
g/hr)
6.6
0.4
24
12
19
34.4
<0.004
(x10-«lb/hr)
15
0.87
53.7
27.1
41.0
78.2
<8.0
RUN 2
0.032
0.071
0.16
A-POST-M29-1 10202-03
Concentration
(pg/dscm)
2.3
0.144
4.8
0.69
19.8
11.1
<1.5
Emission Rate
(x10^»
g/hr)
5.2
0.3
11
1.5
44.7
25
<0.003
(x10-«lb/hr)
11.5
0.716
24.0
3.4
98.5
55.1
<7.6
RUN 3
NM
NM
NM
Average
Concentration
(pg/dscm)
3.0
0.367
8.5
6.1
13.5
9.5
ND
Emission Rate
(x10^»
g/hr)
6.6
0.8
18.8
13.4
30
21.3
ND
(x10%/hr)
14.5
1.8
41.4
29.5
66.2
46.9
ND
Average
0.030
0.066
0.14
4-21
-------
Source Test Report
for Landfill A
4.2.3.2 Gaseous Concentrations: Carbon Monoxide (CO), Sulfur Dioxide (SCy, and Nitrogen
Oxides (NOX)
Gaseous emissions were measured with CEMs and included CO, SO2 and NOX. These
results are summarized in Table 4-17. The detailed CEM measurement plots are shown
in Figures 4-3 through 4-5.
Table 4-17. Engine Stack CO, SO2, NOX Concentrations
Run 1
Run 2
Run 3
Average
Concentration (ppmdv)
CO
562
549
570
560
SO2
NM
39
29
34
NOX (as
NO)
172
142
183
166
NM = Not measured. Instrument was not ready.
4.3 Comparison with AP-42 Default Values
One of the major objectives of the test program was to expand on the database of LFG
constituent compounds and their concentrations. If warranted, these data may
contribute towards updating the AP-42 default values.
Table 4-18 presents the concentrations of LFG constituents to provide direct
comparisons with AP-42 default emission concentration values. Table 4-19 presents
the concentration of other constituents targeted by the various analyses but not listed in
AP-42. An expanded discussion and comparison is included in the overall project
summary report.
4-22
-------
Source Test Report
for Landfill A
finn
Q.
c
o
c
0)
o
c
,9 onn -
1 nn
Engine Stack Carbon Monoxide 1 1/1/02
n
Sampling Period
Carbon Monoxide
rfn
^
06: 00 08:24 1 0: 48 13:12 1 5:36 1 8: 00 20:24
Time
Engine Stack Carbon Monoxide 11/2/02
snn
Q.
^.
c
0
f ^nn
TO OUU
t
c
0)
U
c
o
Oonn
tfWW*<*~~^^^ n
|
H
[
Sampling Period
Carbon Monoxide
12:00 13:12 14:24 _. 15:36 16:48 18:00
Time
Figure 4-3. Engine Stack Carbon Monoxide Concentrations
4-23
-------
Source Test Report
for Landfill A
50 i
E30
O ^3
're
= 20
(3 15
10
06:00
Engine Stack Sulfur Dioxide 1 1/1/02
M
08:24
10:48
13:12
Time
15:36
18:00
20:24
12:00
Engine Stack Sulfur Dioxide 11/2/02
13:12
14:24 Time 15:36
16:48
18:00
Figure 4-4. Engine Stack Sulfur Dioxide Concentrations
4-24
-------
Source Test Report
for Landfill A
Engine Stack Nitric Oxide (NO) 11/1/02
08:24 10:48 13:12 15:36 18:00 20:24
06:00
140
120
Engine Stack Nitric Oxide (NO) 11/2/02
12:00
13:12 14:24 Tjme 15:36 16:48 18:00
Figure 4-5. Engine Stack Nitric Oxide Concentrations
4-25
-------
Source Test Report
for Landfill A
Table 4-18. Comparison of Raw Landfill Gas Constituent Concentrations with AP-42 Default Values
Method
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
No Test
M-40
No Test
M-40
M-40
M-40
M-40
Compound
1,1,1-Trichloroethane
1,1 ,2,2-Tetrachloroethane
1,1-Dichloroethane
(Ethylidene Bichloride)
1,1-dichloroethene
1 ,2-Dichloroethane
1 ,2-Dichloropropane
Isopropyl alcohol
(2-Propanol)
Acetone
Acrylontrile
Bromodichloromethane
Butane
Carbon Disulfide
Carbon Monoxide
Carbon Tetrachloride
Carbonyl Sulfide
(Carbon oxysulfide)
Chlorobenzene
Chlorodiflouromethane
(Freon 22)
Chloroethane
(Ethyl Chloride)
Chloroform
CAS
Number
71-55-6
79-34-5
75-34-3
75-35-4
107-06-2
78-87-5
67-63-0
67-64-1
107-13-1
75-27-4
106-97-8
75-15-0
630-08-0
56-23-5
463-58-1
108-90-7
75-45-6
75-00-3
67-66-3
Formula
Wt.
133.42
167.85
98.96
96.94
98.96
112.98
60.11
58.08
53.06
163.83
58.12
76.13
28.01
153.84
60.07
112.56
86.47
64.52
119.39
Default
Value
(ppmv)
0.48
1.11
2.35
0.20
0.41
0.18
50.10
7.01
6.33
3.13
5.03
0.58
141
0.004
0.49
0.25
1.30
1.25
0.03
Detection
Limit
(ppmv)
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
Measured
Average
(ppmv)
0.005
0.0297
0.033
0.002
0.001
0.001
0.114
0.33
ND
0.003
4.87
0.014
NM
0.00083
NM
0.195
ND
0.77
0.040
Concentration
in Inlet LFG
(x10~9 Ib/ft3)
1.7
12.9
8.6
0.420
0.264
0.227
17.7
49.2
ND
1.1
731
2.8
NM
0.33
NM
56.6
ND
128
12
(ug/m3)
27
206
140
6.7
4.2
3.6
283
788
ND
18
11700
46
NM
5.3
NM
907
ND
2060
200
Mass Flow Rate in
Inlet LFG Stream
(mg/hr)
73
554
368
18
11
9.8
759
2120
ND
48
31400
120
NM
14
NM
2440
ND
5520
530
(xlO"3 Ib/hr)
0.16
1.2
0.811
0.040
0.025
0.022
1.70
4.70
ND
0.10
69.3
0.269
NM
0.031
NM
5.40
ND
12.2
1.20
4-26
-------
Source Test Report
for Landfill A
Method
M-40
M-40
M-40
M-40
M-40
M-40
M-40
No Test
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-11
Organic
mercury
Compound
Chloromethane
1 ,4-Dichlorobenzene
1 ,3-Dichlorobenzene
1 ,2-Dichlorobenzene
Dichlorodifluoromethane
(Freon 12)
Dichlorofluoromethane
(Freon 21)
Methylene Chloride
(Dichloromethane)
Dimethyl Sulfide
(Methyl sulfide)
Ethane
Ethanol
Ethyl Mercaptan
(Ethanediol)
Ethylbenzene
1 ,2-Dibromoethane
(Ethylene dibromide)
Trichloromonofluoromethane
(Fluorotrichloromethane)
(F11)
Hexane
Hydrogen Sulfide
Mercury
(Dimethyl)
CAS
Number
74-87-3
106-46-7
541-73-1
95-50-1
75-71-8
75-43-4
75-09-2
75-18-3
74-84-0
64-17-5
75-08-1
100-41-4
106-93-4
75-69-4
110-54-3
7783-06-4
Formula
Wt.
50.49
147.00
147.00
147.01
120.91
102.92
84.94
62.13
30.07
46.08
62.13
106.16
187.88
137.38
86.18
34.08
230.66
Default
Value
(ppmv)
1.21
0.21
0.21
0.21
15.70
2.62
14.30
7.82
889
27.20
2.28
4.61
0.001
0.76
6.57
35.50
Not Listed
Detection
Limit
(ppmv)
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.020
0.0002
0.0002
0.0002
0.0002
0.05E-06
Measured
Average
(ppmv)
0.012
0.043
0.00047
0.00203
0.118
ND
0.997
NM
6.2
0.020
ND
0.58
0.001
0.051
2.47
13.1
R
Concentration
in Inlet LFG
(x10~9 Ib/ft3)
1.6
17
0.18
0.77
36.8
ND
219
NM
480
2.4
ND
160
0.5
18
550
1200
R
(ug/m3)
25
260
2.9
12
590
ND
3510
NM
7800
38
ND
2500
8.3
290
8810
18400
R
Mass Flow Rate in
Inlet LFG Stream
(mg/hr)
68
708
7.7
33
1580
ND
9410
NM
21000
100
ND
6800
22
790
23700
49500
R
(xlO"3 Ib/hr)
0.15
1.6
0.0169
0.0731
3.50
ND
20.8
NM
45.4
0.22
ND
15
0.049
1.7
52.1
109
R
4-27
-------
Source Test Report
for Landfill A
Method
LUMEX
Organic
mercury
Organic
mercury
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
Compound
Mercury
(Elemental)
Mercury
(Monomethyl)
Mercury
(Total)
2-Butanone
(Methyl Ethyl Ketone)
2-Hexanone
(Methyl Butyl Ketone)
Methyl Mercaptan
(Methanethiol)
Pentane
Tetrachloroethylene
(Perchloroethylene)
Propane
t-1 ,2-Dichloroethene
Trichloroethylene
(Trichloroethene)
Vinyl Chloride
m/p-Xylene
(Dimethyl Benzene)
o-Xylene
(Dimethyl Benzene)
Benzene
(Co-disposal)
CAS
Number
7439-97-6
78-93-3
591-78-6
74-93-1
109-66-0
127-18-4
74-98-6
156-60-5
79-01-6
75-01-4
1330-20-7
95-47-6
71-43-2
Formula
Wt.
200.61
215.62
215.63
72.10
100.16
48.11
72.15
165.83
44.09
96.94
131.38
62.50
106.16
106.16
78.11
Default
Value
(ppmv)
Not Listed
Not Listed
253.0E-6
7.09
1.87
2.49
3.29
3.73
11.10
2.84
2.82
7.34
12.10
12.10
11.10
Detection
Limit
(ppmv)
0.014E-06
6E-06
0.0002
0.0002
0.020
1
0.0002
1
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
Measured
Average
(ppmv)
37E-06
130E-09
300E-06
0.27
0.557
ND
3.20
0.042
8.9
0.003
0.028
0.097
3.73
0.30
0.073
Concentration
in Inlet LFG
(x10~9 Ib/ft3)
0.019
0.000073
0.17
51
144
ND
597
18
1000
0.7
9.5
15.7
1000
82
15
(ug/m3)
0.31
0.0012
2.7
820
2310
ND
9560
290
16000
11
150
251
16400
1300
240
Mass Flow Rate in
Inlet LFG Stream
(mg/hr)
0.83
0.0031
7.1
2200
6200
ND
25700
780
44000
29
410
674
44000
3500
634
(xlO"3 Ib/hr)
0.0018
0.0000069
0.016
4.8
14
ND
56.6
1.7
97
0.064
0.90
1.5
97
7.8
1.4
4-28
-------
Source Test Report
for Landfill A
Method
M-40
M-25C
M-25C
M-40
M-40
Compound
Benzene
(No-disposal or Unknown)
NMOC as Hexane
(Co-disposal)
NMOC as Hexane
(No-codispoal or Unknown)
Toluene
(Methyl Benzene) (Co-
disposal)
Toluene
(Methyl Benzene) (No or
Unknown)
CAS
Number
71-43-2
108-88-3
Formula
Wt.
78.11
86.17
92.13
Default
Value
(ppmv)
1.91
2420.00
595.00
165.00
39.30
Detection
Limit
(ppmv)
0.0002
0.0002
0.0002
Measured
Average
(ppmv)
0.073
373
373
1.33
1.33
Concentration
in Inlet LFG
(x10~9 Ib/ft3)
15
83100
83100
316
316
(ug/m3)
240
1330000
1330000
5050
5050
Mass Flow Rate in
Inlet LFG Stream
(mg/hr)
634
3570000
3570000
13600
13600
(xlO"3 Ib/hr)
1.4
79000
79000
29.9
29.9
ND - Non detected at the stated detection limit
R - Data were rejected because of serious deficiency in spike recovery
4-29
-------
Source Test Report
for Landfill A
Table 4-19. Raw Landfill Gas Constituent Concentrations for Compounds without AP-42 Default Values
Method
M-0100/
TO-11
M-0100/
TO-11
M-23
M-23
M-25C
M-25C
M-25C
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
Compound
Acetaldehyde
Formaldehyde
Dioxins/Furans
PAHs
Carbon Dioxide
Methane
Oxygen
1 , 1 ,2,3,4,4-Hexachloro-1 ,3-butadiene
1 , 1 ,2-Trichloro-1 ,2,2-trifluoroethane
(CFC113)
1,1,2-Trichloroethane
1 ,2,4-Trichlorobenzene
1 ,2,4-Trimethylbenzene
1 ,2-Chloro-, 1 ,2,2-Tetrafluoroethane
(CFC114)
1 ,3,5-Trimethylbenzene
1,3-Butadiene
(Vinylethylene)
1,4-Dioxane
(1,4-Diethylene Dioxide)
CAS
Number
75-07-0
50-00-0
124-38-9
74-82-8
7782-44-7
87-68-3
76-13-1
79-00-5
120-82-1
95-63-6
76-14-2
108-67-8
106-99-0
123-91-1
Formula
Wt.
44.05
30.03
44.01
16.04
32.00
260.76
187.38
133.42
181.46
120.19
170.92
120.19
54.09
88.10
Detection
Limit
(ppmv)
0.0023
0.0017
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
Measured
Average
(ppmv)
0.025
0.0033
NM
NM
387000
488000
17000
0.001
0.002
0.008
0.001
0.19
0.008
0.079
0.022
0.00203
Concentration
in Inlet LFG
(xKT9 Ib/ft3)
2.9
0.259
NM
NM
44.0E6
20.2E6
1.4E6
0.8
0.983
2.6
0.460
60.0
3.4
24.6
3.1
0.462
(ug/m3)
46
4.14
NM
NM
705E6
324E6
23E6
13.4
15.8
42
7.4
961
55
395
49
7.4
Mass Flow Rate
in Inlet LFG Stream
(mg/hr)
125
11.1
NM
NM
1.89E9
0.871 E9
0.061 E9
36.0
42.3
113
19.8
2580
148
1060
132
20
(x10'3 Ib/hr)
0.275
0.0245
NM
NM
4.17E6
1.92E6
0.133E6
0.0794
0.0932
0.249
0.0436
5.7
0.325
2.3
0.291
0.0438
4-30
-------
Source Test Report
for Landfill A
Method
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
Compound
1-Ethyl-4-methylbenzene
(4-Ethyl Toluene)
4-Methyl-2-pentanone
(MIBK)
Benzyl Chloride
(Chloromethyl Benzene)
Bromomethane
(Methyl bromide)
cis-1 ,2-Dichloroethene
cis-1 ,3-Dichloropropene
Cyclohexane
Dibromochloromethane
Ethyl Acetate
Heptane
Methyl-t-butyl Ether
(MTBE)
Styrene
(Vinylbenzene)
t-1 ,3-Dichloropropene
Tetrahydrofuran
(Diethylene Oxide)
Tribromo methane
(Bromoform)
Vinyl Acetate
CAS
Number
622-96-8
108-10-1
100-44-7
74-83-9
156-59-2
10061-01-5
110-82-7
124-48-1
141-78-6
142-82-5
1634-044
100-42-5
1006-02-6
109-99-9
75-25-2
108-05^
Formula
Wt.
120.20
100.16
126.58
94.95
96.94
110.98
84.16
208.29
88.10
100.20
88.15
104.14
110.98
72.10
252.77
86.09
Detection
Limit
(ppmv)
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
Measured
Average
(ppmv)
0.079
1.07
0.006
0.016
0.074
0.00023
0.165
ND
1.83
0.24
0.054
0.030
0.00032
1.18
0.000423
0.242
Concentration
in Inlet LFG
(xKT9 Ib/ft3)
24.6
278
2.0
3.8
18.6
0.065
35.9
ND
416
62.7
12.4
7.9
0.092
221
0.276
53.9
(ug/m3)
395
4450
33
62
297
1.0
575
ND
6660
1000
200
127
1.5
3540
4.43
864
Mass Flow Rate
in Inlet LFG Stream
(mg/hr)
1060
12000
88
165
798
2.8
1540
ND
17900
2700
530
342
3.9
9490
11.9
2350
(x10'3 Ib/hr)
2.3
26.3
0.19
0.36
1.8
0.0062
3.4
ND
39.4
5.9
1.2
0.753
0.0087
20.9
0.0262
5.1
4-31
-------
Source Test Report
for Landfill A
This page intentionally left blank
4-32
-------
Source Test Report
for Landfill A
5. Quality Assurance/Quality Control
This project produced data that qualified to receive the "A" rating with respect to the
rating system described in section 4.4.2 of the Procedures for preparing Emission
Factor Documents (EPA-454/R-95-015). The cited EPA document provides a clear
description of the requirements for an "A" data quality rating. Tests were performed by
using an EPA reference test method, or when not applicable, a sound methodology.
Tests were reported in enough detail for adequate validation and raw data were
provided that could be used to duplicate the emission results presented in this report.
Throughout the results sections of this report, notations and footnotes were included to
flag data that, for various reasons, did not meet their associated measurement quality
objectives.
5.1 Assessment of Measurement Quality Objectives
Measurement quality objectives (MQOs) were established for each critical
measurement and documented in the Site-Specific QAPPfor the Field Evaluation of
Landfill Gas Control Technologies-Landfill A. The following subsections assess MQOs
for each measurement to determine if goals were achieved. When applicable, data
validation elements performed on laboratory analytical reports are also included.
5.1.1 Continuous Emissions Monitors (CEMs)
The combustion gases O2, CO/CO2, SO2, NOX and THC were measured in the field
using CEMs. The following MQOs were established for CEM measurements for
Landfill A:
• Direct calibration bias: ±2 percent
• System bias checks: ±5 percent
• Zero and drift: ±3 percent
• Completeness: >90 percent
Direct calibrations were performed daily prior to testing with certified calibration gases
at zero and a minimum of two other concentrations (typically a mid-level concentration
and one point near the full-scale end of the instrument range). System bias checks were
5-1
-------
Source Test Report
for Landfill A
performed pre-test and post-test. Drift checks were performed daily post-test. Table 5-1
summarizes these quality control (QC) checks for all instruments. Not all MQOs were
met for all CEM measurements. However, if the calibration and drift check criteria
were relaxed to ±5 percent, then all MQO would have been met. The fact that the
original QAPP MQOs were not fully met did not affect the usability of these data. The
reported data were notated accordingly.
Table 5-1. CEM MQO Summary for Landfill A
Instrument and
Range
Servomex O2
Analyzer (0-21%)
Cal Analytical CO2
Analyzer (0-20%)
Cal Analytical CO
Analyzer (0-650
ppm)
Cal Analytical SO2
Analyzer (0-500
ppm)
TECO THC
Analyzer (0-1 000
ppm)
TECO NOX
Analyzer (0^000
ppm)
Direct Calibration
(±2% criteria)
Total
(#)
6
6
6
6
NAa
6
Bias
Range
(%)
0-3.3
2.2-3.3
0-1.7
0-3.0
NAa
0.6-7.1
Complete
(%)
17
17
100
67
NAa
50
System Bias Checks
(±5% criteria)
Total
(#)
3
3
3
3
3
3
Bias
Range
(%)
0-2.2
1.1 -4.3
0.2-1.2
1.02.8
0-3.8
0.6-4.7
Complete
(%)
100
100
100
100
100
100
Drift Checks
(±3% criteria)
Total
(#)
6
6
6
6
3
3
Bias
Range
(%)
2.2-3.3
2.2-5.4
1.2-1.7
0.4-2.8
0-3.3
1.4-7.1
Complete
(%)
100
83
100
67
67
67
The method called for calibration gases to be introduced at a point of the sampling system close to the sampling
probe for them to flow through the heated sample line. Calibration gases were not injected directly to the analyzer
5.1.2 Carbonyls(TO-11)
The following MQOs were established in the QAPP for this method:
• Recovery (formaldehyde): 50-150 percent
• Precision: ±20 percent relative standard deviation (RSD)
5-2
-------
Source Test Report
for Landfill A
• Completeness: >90 percent
Four samples (including three raw LFG samples and one field blank) were submitted to
Resolution Analytics for formaldehyde and acetaldehyde determination. Results were
reported in RFA# 992014. The report included information on instrument calibration
and internal QC checks. Samples collected on October 31 and November 2, 2002 were
received by the laboratory on November 14, 2002 and analyzed on November 22,
2002. This met the 30-day hold-time limitation.
Analytical detection limits were reported as 13 ppb for formaldehyde and 9 ppb for
acetaldehyde in the extract. With an extract volume of 5 ml and sample gas volume of
about 31 standard liters, the MDLs were 1.7 xlO"3 and 2.3 xlO"3 ppmv for
formaldehyde respectively.
The field blank did not have detectable levels of acetaldehyde and showed 0.073(ig
formaldehyde detected. To assess accuracy, an external performance evaluation audit
sample containing 0.25 ppm formaldehyde and acetaldehyde was analyzed with the
sample set. Recovery was 101.6 percent% for formaldehyde and 96.3 percent for
acetaldehyde, which meets the 50-150 percent MQO. One project sample was injected
in duplicate and the percent drift (%D) range for formaldehyde was 0.7 percent and for
acetaldehyde was 3.2 percent. All MQOs were met for this method for a completeness
of 100 percent.
The test samples produced very low detection responses for formaldehyde. Therefore,
even though the detected levels of formaldehyde were higher than formaldehyde's
MDL, the reported concentrations for formaldehyde should be flagged as estimates and
notated with a "J".
5.1.3 Hydrogen Sulfide (H2S) (EPA Method 11)
The following MQOs were established in the Landfill A QAPP for this method:
• Accuracy: ±5 percent bias
• Precision: ±5 percent relative standard deviation (RSD)
• Completeness: >90 percent
5-3
-------
Source Test Report
for Landfill A
Three collected samples, a reagent field blank, and two laboratory in-house reagent
blanks were submitted to Oxford Laboratories for H2S analysis by EPA Method 11.
The samples were collected on November 2, 2002, and submitted to the laboratory on
November 14, 2002. The results report was dated November 22, 2002. Therefore, the
analysis met the 30-day hold time criteria.
The field blank submitted did not have quantifiable concentrations of H2S. A
laboratory spike was performed and the recovery was 101 percent. The three test
samples produced results of similar concentrations. Duplicate analysis of the Rn#2
sample resulted in 1.7 percent relative standard deviation (RSD). All MQOs were met
for this method for a completeness of 100 percent.
5.1.4 Dioxins and Furans (PCDD/PCDFs) (EPA Method 23/0011)
The following MQOs were established in the QAPP for this method:
• Recovery: 50-150 percent
• Completeness: >90 percent
Four sample sets (including one set of reagent blank and sample train rinsates) were
submitted to ALTA Analytical Perspectives for PCDD/PCDF analysis. The samples
were collected on November 1, 2002, and delivered to the laboratory on November 14,
2002. The samples were extracted on November 20, 2002 and analyzed on November
27, 2002. That met the 14-day hold-time for extraction and 40-day hold time for
analysis.
The field blank did not have detectable levels of the target analytes. Detection limits for
the various congeners were in the single-digit picogram level. To assess accuracy, each
sample train was spiked with standard Method 23 spiking compounds and analysis of
the samples yielded extraction standard (ES) recovery from 84 to 99 percent. Recovery
of sampling standards (SS) ranged from 106 to 108 percent. These recoveries were
well within the 50-150 percent MQO.
Because a decision was made to analyze only one of the three sample extracts, the
completeness goal of 90% was not achieved. However, all other MQOs were met for
this method.
5-4
-------
Source Test Report
for Landfill A
5.1.5 Polycyclic Aomatic Hydrocarbons (PAHs) (EPA Method 23/0011)
5.1.5.1 Raw Landfill Gas (LFG) Samples
The Method 23 samples collected from the raw LFG could not be concentrated below
750 to 1000 (iL. The produced cleaned up extracts contained gasoline-like
hydrocarbons and prevented the preparation of final extracts for PAH analysis.
Therefore the MQOs for this sample group was 0 percent complete.
5.1.5.2 Engine Stack Samples
The following MQOs were established in the QAPP for this method:
• Recovery: 50-150 percent
• Completeness: >90 percent
Four samples (including one reagent blank) collected from the engine stack were
submitted to ALTA Analytical Perspectives for PAH analysis. The report included
information on instrument calibration and internal QC checks. Samples collected on
November 1, 2002 were received by the laboratory on November 14, 2002. These were
extracted on November 20, 2002 and analyzed on January 9, 2003. That met the 14-
day hold-time for extraction but missed the analysis 40-day hold time by 10 days. The
data were reported with the appropriate notations.
Analysis of the field blank yielded detectable but low levels of a few of the target
compounds with all PAH analytes totaling to 15762 ng. In contrast, the test samples
showed total PAH level of 113974 ng. Recovery of ES ranged from 65 to 124 percent.
Recoveries of SS, di0-fluorene and di4-terphenyl were not reported. Recovery of the
alternative standard (AS) dio-anthracene was 57.9 percent. The reported recoveries
were within the 50 to 150 percent MQO.
Because a decision was made to analyze only one of the three sample extracts, the
completeness goal of 90% was not achieved. However, all other MQOs were met for
this method.
5-5
-------
Source Test Report
for Landfill A
5.1.6 Polychlorinated Biphenyls (PCBs)
The same Method 23 samples collected from the raw LFG were earmarked for analysis
for PCBs. Since the cleaned up extracts could not be concentrated below 750 to
1000 (iL because of the presence of gasoline-like hydrocarbons, final extracts could not
be prepared for the planned PCB analysis. Therefore the MQO for this sample group
was 0 percent complete.
5.1.7 Non-Methane Organic Compounds (NMOCs) (Method 25C)
The following MQOs were established in the QAPP for Landfill A:
• Recovery: 50 to 150 percent
• Precision: ±30 percent RSD
• Completeness: >90 percent
Four canister samples (including a field blank) were submitted from Landfill A for
NMOC analysis by Method 25-C to Triangle Environmental Services. The samples
were collected on November 2, 2002, submitted on December 3, 2002, and analyzed
between December 3 and 23, 2002. Therefore the analysis did not meet the 30 day hold
time requirements. The apparent delay in sample delivery was partly attributed to the
fact that the same canisters had to be analyzed by RTP Laboratory for volatile organics
first. The impact of exceeding the prescribed 30-day hold time by up to 21 days is
unknown. The laboratory report included information on instrument calibration and
internal QC checks.
The only detected NMOC in the field blank was at 2 ppmv as hexane. Accuracy for the
method was assessed by evaluating results of response factor (RF) check samples that
were run prior to and following sample analysis. Acceptance criteria established by the
method is that the RF must be within 10 percent of the response factor from initial
calibration. All response factor checks ranged from 0.9 to 7.4 percent of the initial
calibration, well within the 10 percent acceptance criteria. The %D between the pre and
post-test checks were less than 2 percent, ranging from 0.5 to 1.2 percent. Samples
were run in triplicate and all %RSDs for samples were less than 3.4 percent.
All MQOs were met for this method for a completeness of 100 percent. The reported
data were notated for the hold time exceedance.
5-6
-------
Source Test Report
for Landfill A
5.1.8 Hydrogen Chloride (HCI) (EPA Method 26A)
The following MQOs were established in the QAPP for Landfill A:
• Accuracy: ±10 percent bias
• Precision: ±10 percent RSD
• Completeness: >90 percent
Four samples (including one field blank) were submitted to Resolution Analytics for
HCI and chlorine (C12) determination. The results were reported in RFA# 992014. The
report included information on instrument calibration and internal QC checks. Samples
were collected on October 31 and November 2, 2002. These were received by the
laboratory on November 14, 2002, and analyzed on November 27, 2002, which met the
4 week hold-time requirement. Analytical detection limits were reported as 0.41 ppm
HCI.
The field blank did not contain detectable levels of HCI. In-house audit samples were
analyzed with each respective group of field samples and the measured concentrations
fell within method criteria of 10 percent of their expected values.
A matrix spike was performed on Sample #1 (A POSST-01). A 0.8 ml sample was
spiked with 0.8 ml of standard (50 ppm chloride) and analyzed in duplicate. The
laboratory reported 97.1 percent recovery of the HCI spike with a 0.02 percent
deviation in duplicate injections. This meets the MQO of ±10 percent with very good
precision. Calculated bias for internal QC check was <2.2 percent. All MQOs were met
for 100 percent completeness.
5.1.9 Metals (EPA Method 29)
The following MQOs were established in the Landfill A QAPP for this method:
• Accuracy: ±25 percent bias
• Precision: ±20 percent RSD
• Completeness: >90 percent
5-7
-------
Source Test Report
for Landfill A
Four sets of Method 29 Multi-Metals trains (including one field blank) were submitted
to First Analytical Laboratories for As, Cd, Cr, Pb, Mn, Hg, and Ni determination.
Results were reported in Project #21110. The report included information on
instrument calibration and internal QC checks. Samples were collected on October 31
and November 2, 2002, received by the laboratory on November 12, 2002, and
analyzed on November 14, 2002, which met the 14 day hold-time requirement. Method
detection limits for each of the target metals were reported as follows:
• As = 5.0(ig/L
• Cd = 0.2(ig/L
• Cr = 5.0(ig/L
• Pb = 5.0(ig/L
• Mn = 5 (ig/L
• Ni = lOjig/L
• Hg = 0.2^g/L
Traces of Cr, Mn and Ni were found in the blanks, which is not unusual.
All samples were spiked prior to analysis. Spike recoveries ranged from 82 to 110
percent and were within the acceptable range of 75-125 percent. In addition to spiking
the samples, for each metal, internal calibration verification samples (ICVs) and
continuing calibration verification samples (CCVs) were performed. ICVs were run at
the beginning of each run set and CCVs were run at a frequency of one for every 10
samples. ICV and CCV measured values were all
-------
Source Test Report
for Landfill A
• Precision: ±20 percent RSD
• Completeness: >90 percent
Mercury (Hg) analysis was performed by Frontier Geosciences. Four total Hg samples
(including a field blank) were taken at Landfill A. Samples were collected on
November 1 and 2, 2002 and analyzed in December 2002. That analysis schedule
exceeded the 14-day hold-time specified in the QAPP. All other quality assurance
measures indicated that the analysis of the traps were under good control. All field
blanks were consistent with historical values and indicate the detection limit is likely to
be at or below the previous estimated value of 50 ng/m3. Spike recoveries were 95.4
and 95.2 percent and relative percent difference (RPD) between replicates was 6.2
percent, which meets MQOs and are therefore 100 percent complete.
Five monomethyl mercury (MMHg) samples (including a field blank and field spike)
were collected on November 2, 2002. These samples were analyzed December 2005
which exceeded the 14-day hold-time. Analysis of these samples was under good
control with acceptable distillation spike recoveries and distillation duplicates. All
CCV standards had acceptable recoveries. Field spike recovery was 75 percent and
matrix spike recovery was 122 percent, which meets MQOs. The only prominent
incoherency of the MMHg data from Landfill A is the disagreement among the
replicates. Samples 021102-01 and 021102-02 had measured concentrations below the
estimated method detection limit but sample 021102-03 was reported at a concentration
of 1.2 ng/m3. This does not meet the ±30 percent RSD criteria for replicate samples.
Possible explanations for the differences between replicates include variability in the
landfill gas concentration or undetected sampling or analytical error. The data were
notated accordingly.
Five dimethyl mercury (DMHg) samples (including a field blank and field spike) were
collected on November 1 and 2, 2002. These samples were analyzed in December 2002
and did not meet the 14-day hold-time. Field spike recoveries for all DMHg analysis
were consistently low 0-40 percent. Because of recovery issues, DMHg concentrations
are likely biased low and the degree of bias is likely significant. QA measures in place
support the following conclusions:
• Replicate samples taken at each site reported similar concentrations which
indicated that the properties of the DMHg sampling train and landfill gas were
consistent and biases was not attributable to trap media or landfill sample gas.
5-9
-------
Source Test Report
for Landfill A
• Continuous calibration verifications (CCVs) used during the analysis indicates that
the detection systems were measuring accurately.
• Dimethyl Hg (DMHg) field blanks indicated that the trap media, handling
procedures and analytical techniques did not contribute to the problems with
recovery.
• Trip spikes (traps spike in the laboratory, shipped to the field but not used for
sampling) indicated that the laboratory standards, trap media and trap handling
procedures do not create significant bias.
• Field spikes (traps spiked in the lab and used to collect a replicate sample)
indicated that some property or action during sampling either destroyed or evaded
the DMHg adsorbed to the Carbotrap
The RSD between the three replicate samples was 23.9 percent, which meets the MQO
of ±30 percent, but because recovery MQOs were not met for any of the field spikes,
DMHg analysis was 0 percent complete. The data were reported with the appropriate
notations.
5.1.11 Volatile Organic Compounds (VOCs) and Methane (CH4) (Method TO-15)
The following MQOs were established in the Landfill A QAPP for this method:
• Accuracy: 50-150 percent recovery
• Precision: ±30 percent RSD
• Completeness: >90 percent
Four SUMMA canisters (including one field blank) were submitted from Landfill A to
RTP Laboratories for VOC and CHt determination by EPA Method TO-15. Results
were reported in Project #347-02. Samples were collected on November 2, 2002 and
analysis was completed by November 27, 2002, which met the 30 day hold-time
requirement.
Analysis of the field blank found 3.3 ppbv of acetone, 1.4 ppbv of methylene chloride,
and 1.03 ppbv of bromomethane. Other targets were either found at <1 ppbv or not
detected at the MDL of 0.2 ppb.
5-10
-------
Source Test Report
for Landfill A
Accuracy was assessed using results of a 10 ppbv laboratory control sample containing
all target compounds. For all but two compounds, recoveries ranged from 60-150
percent, which met the established acceptance criteria of 50-150 percent. The recovery
reported for ethanol was 2.4 percent, and 230 percent for m/p-xylene. Results for these
two compounds should be flagged as estimated ("J").
Sample 062205-04 was spiked with 200 ppbv of chlorobenzene prior to dilution with
helium and analysis. The recovery of chlorobenzene was 89.5 percent.
Precision was demonstrated through multiple injections of standards at five
concentration levels. The RSD between the calculated relative response factors (RRF)
must be <30% with allowances that two may be >40 percent. The average RSD was
13.8 percent and method criteria were met for all compounds except isopropyl alcohol
with an RSD of 56.3 percent and hexane with an RSD of 40.7 percent. Results for these
compounds should be flagged as estimated ("J")- Valid data was received for all
SUMMA canisters submitted, and these analyses were considered to be 100 percent
complete.
5.2 Audits
This project was designated as QA Category II effort. Hence, audits were required. The
internal and external audits performed for this project were completed earlier and their
findings were included in a separate report for Landfill D of this project.
5-11
-------
Source Test Report
for Landfill A
This page intentionally left blank
5-12
-------
Field Test Measurements at Five Municipal Solid
Waste Landfills with Landfill Gas Control Technology
Final Report
Appendix B
SOURCE TEST REPORT
FOR LANDFILL B
-------
Table of Contents
Acronym List vii
1. Introduction 1-1
2. Landfill Facility Descriptions 2-1
2.1 Flare Process Description and Operation 2-1
2.2 Landfill Gas (LFG) Sampling Locations 2-1
2.2.1 Landfill Gas (LFG) Header Pipe 2-1
2.2.2 Flare Stack 2-2
3. Test Operations 3-1
3.1 Test Team 3-1
3.2 Test Log 3-1
3.2.1 Planned Test Sample Matrices 3-1
3.2.2 Landfill Gas (LFG) Pipe (Inlet) 3-1
3.2.3 Flare Stack 3-5
3.3 Field Test Changes and Deviations from Quality Assurance Project Plan
(QAPP) Specifications 3-8
3.3.1 Variation from Test Methods or Planned Activities 3-8
3.3.2 Application of Test Methods 3-9
3.3.3 Test Method Exceptions 3-11
4. Presentation of Test Results 4-1
4.1 Raw Landfill Gas (LFG) Pipe Results 4-1
4.1.1 Raw Landfill Gas (LFG) Flow Rate and Temperature 4-1
4.1.2 Raw Landfill Gas (LFG) Constituents 4-2
4.2 Flare Stack Results 4-10
4.2.1 Flare Stack Gas Flow Rate and Temperature 4-10
4.2.2 Hydrogen Chloride (HCI) Emission Results 4-24
4.3 Comparison with AP-42 Default Values 4-26
-------
Table of Contents
5. Quality Assurance/Quality Control 5-1
5.1 Assessment of Measurement Quality Objectives (MQOs) 5-1
5.1.1 Continuous Emissions Monitors (CEMs) 5-1
5.1.2 Carbonyls (Method TO-11) 5-2
5.1.3 Hydrogen Sulfide (H2S) (EPA Method 11) 5-3
5.1.4 Dioxins and Furans (PCDD/PCDFs) (EPA Method 23) 5-4
5.1.5 Polycyclic Aromatic Hydrocarbons (PAHs) (EPA Method 23/0011) 5-4
5.1.6 Polychlorinated Biphenyls (PCBs) 5-5
5.1.7 Non-Methane Organic Compounds (NMOCs) (Method 25C) 5-5
5.1.8 Hydrogen Chloride (HCI) (EPA Method 26A) 5-6
5.1.9 Metals (EPA Method 29) 5-7
5.1.10 Organo-mercury (Hg) and Total mercury (Hg) (Frontier) 5-8
5.1.11 Volatile Organic Compounds (VOCs) and Methane (CH4) (Method
TO-15) 5-9
5.2 Audits 5-10
-------
Table of Contents
Tables
Table 3-1. Test Team Members and Responsibilities 3-1
Table 3-2. Target Analytes for the Landfill Gas Stream and Sample Condensate
Collected at the Gas Header 3-2
Table 3-3. Target Analytes for the Flare Stack Outlet Gas Stream 3-3
Table 3-4. Landfill Gas Inlet Sample Log and Collection Times 3-4
Table 3-5. Flare Stack Test Sample Log and Collection Times 3-7
Table 3-6. Test Methods and Performing Organizations 3-10
Table 4-1. Raw Landfill Gas VOC Concentrations 4-3
Table 4-2. Raw Landfill Gas Non-Methane Organic Compound (NMOC)
Concentrations 4-6
Table 4-3. Raw Landfill Gas Hydrogen Sulfide (H2S) Concentrations 4-6
Table 4-4. Raw Landfill Gas Pipe Carbonyls Concentrations 4-7
Table 4-5. Raw Landfill Gas Total Mercury Concentrations 4-8
Table 4-6. Raw Landfill Gas Dimethyl Mercury Concentrations 4-9
Table 4-7. Raw Landfill Gas Monomethyl Mercury Concentrations 4-9
Table 4-8. Raw Landfill Gas Elemental Mercury Concentrations 4-10
Table 4-9. Flare Stack Gas Operating Conditions, Measured during Sampling 4-11
Table 4-10. Flare Stack Combustion Products Concentrations 4-13
Table 4-11. Flare Stack THC Concentrations 4-15
Table 4-12. Flare Stack Dioxins and Furans Emissions 4-16
Table 4-13. Flare Stack Dioxins and Furans Toxicity Equivalent Emissions 4-17
Table 4-14. Flare Stack Polycyclic Aromatic Hydrocarbons Emissions 4-19
Table 4-15. Flare Stack Hydrogen Chloride Emissions 4-24
Table 4-16. Flare Stack Metals Emissions 4-25
Table 4-17. Flare Stack CO, SO2, NOX Concentrations 4-26
Table 4-18. Comparison of Raw Landfill Gas Constituent Concentrations with AP-42
Default Values 4-27
Table 4-19. Raw Landfill Gas Constituent Concentrations for Compounds without AP-42
Default Values 4-31
Table 5-1. Continuous Emissions Monitor Measurement Quality Objectives Summary
for Landfill B 5-2
Table 5-2. VOC detected in Method 40 Blank Sample and Test Samples 5-11
-------
Table of Contents
Figures
Figure 2-1. Simplified Flare Process Flow Diagram and Sampling Points
Figure 2-2. Landfill Gas Collection Pipe
Figure 2-3. Enclosed Flare Unit Showing Stack Sampling Ports
Figure 2-4. Flare Stack Dimension and Sampling Traverse Locations
Figure 3-1. Sampling Operations at the Landfill Gas Pipe Inlet
Figure 3-2. Sampling Operations at the Enclosed Flare
Figure 3-3. Sampling Port with Probe in Place
Figure 4-1. Flare Stack Oxygen and Carbon Dioxide Concentrations
Figure 4-2. Flare Stack Total Hydrocarbons Concentrations
Figure 4-3. Flare Stack Carbon Monoxide Concentrations
Figure 4-4. Flare Stack Sulfur Dioxide Concentrations
Figure 4-5. Flare Stack Nitric Oxide Concentrations
Figure 4-6. Flare Stack Nitrogen Dioxide Concentrations
2-2
2-3
2-3
2-4
3-3
3-6
3-6
4-12
4-14
4-20
4-21
4-22
4-23
IV
-------
Table of Contents
Appendices
A. Method TO-15 (VOCs, TICs, C2, C3, C4, C5, C6)
B. Method 25C (CH4, CO2, NMOC)
C. Method 3C (O2, N2, CH4, CO2)
D. Method TO-11 (Formaldehyde, Acetaldehyde)
E. Organic mercury Method (Mercury, Total, Monomethyl, Dimethyl)
F. LUMEX (Elemental Mercury)
G. Hydrogen Sulfide
H. Continuous Emission Monitor (Data and Charts)
I. Method 23 (PAH)
J. Method 23 (PCDD/PCDF)
K. Method 23 (PAH, PCDD/PCDF)
L Method 29 (Metals)
M. Method 26A(HCI)
P. Raw Field Data Records
Q. CEM Calibration Records and Span Gas Certification
R. Sampling Control Meter Boxes Calibration Record
-------
Acronym List
This page intentionally left blank
VI
-------
Acronym List
Acronym List
%D
AP-42
APPCD
ARCADIS
As
AS
CCVs
Cd
CEMS
CH4
C12
CO
CO2
Cr
DMHg
EPA
ES
FID
GC
GC/FID
GC/MS
HC1
Hg
H2S
ICVs
LFG
MMHg
Mn
Percent drift
Compilation of Air Pollutant Emission Factors
Air Pollution Prevention Control Division
ARCADIS G&M, Inc.
Arsenic
Alternative standard
Continuing calibration verification samples
Cadmium
Continuous emission monitoring system
Methane
Chlorine
Carbon monoxide
Carbon dioxide
Chromium
Dimethyl mercury
US Environmental Protection Agency
Extraction standard
Flame ionization detector
Gas chromatograph
Gas chromatograph/flame ionization detector
Gas chromatograph/mass spectrometer
Hydrogen chloride
Mercury
Hydrogen sulfide
Internal calibration verification samples
Landfill gas
Monomethyl mercury
Manganese
VII
-------
Acronym List
MQOs Measurement quality objectives
MSW Municipal solid waste
N2 Nitrogen
Ni Nickel
NMOCs Non-methane organic compounds
NOX Nitrogen oxides
O2 Oxygen
PAHs Polynuclear aromatic hydrocarbons
Pb Lead
PCBs Polychlorinated biphenyls
QA Quality Assurance
QAPP Quality Assurance Project Plan
QC Quality control
RF Response factor
RPD Relative percent difference
RRF Relative response factors
RSD Relative standard deviation
RTP Research Triangle Park
SO2 Sulfur dioxide
SS Sampling standards
TCDD/TCDFs Dioxins/furans
THCs Total hydrocarbons
TICs Tentatively identified compounds
VOCs Volatile organic compounds
VIM
-------
Source Test
Report for Landfill B
1. Introduction
Large municipal solid waste (MSW) landfills are subject to Clean Air Act regulations
because of concerns related to their emissions and their potential adverse effects to human
health and the environment. Landfills are listed as a source of air toxics in the Urban Air
Toxics Strategy for future evaluation of residual risk. Existing emission factors for landfill
gas (LFG) were largely developed using data from the 1980s and early 1990s. A database
was developed summarizing data from approximately 1,200 landfills, along with emissions
information from literature, and from test reports prepared by state and local government
agencies and industry. These data were summarized in Compilation of Air Pollutant
Emission Factors (AP-42), Chapter 2.4. The final rule and guidelines are contained in 40
CFR Parts 51,52, and 60, Standards of Performance for New Stationary Sources and
Guidelines for Control of Existing Sources: Municipal Solid Waste Landfills.
The overall purpose of this testing program was to generate data that may be used to update
AP-42 and to include data that reflect current waste management operating practices.
This report presents the results of a field test conducted at the Landfill B located in the
northeast U.S. Testing took place on November 4 and 5, 2002.
The site used an enclosed flare for destruction of the LFG. A more detailed description of
the flare system is presented in Section 2. The specific purpose of the testing program was
to determine emissions from the LFG pipe feeding the enclosed flare and from the flare
stack. The pollutants of interest for the raw untreated LFG were volatile organic
compounds (VOCs), non-methane organic compounds (NMOCs), hydrogen sulfide (H2S),
carbonyls (acetaldehyde, formaldehyde), polycyclic aromatic hydrocarbons (PAHs),
polychlorinated biphenyls (PCBs), and mercury (Hg) compounds. The pollutants of interest
for the treated LFG, in this case at the enclosed flare stack, were carbon monoxide (CO),
nitrogen oxides (NOX), sulfur dioxide (SO2), NMOCs as total hydrocarbons (THCs),
hydrogen chloride (HC1), dioxins/furans (PCDD/PCDFs), PAHs, total Hg, and metals.
ARCADIS G&M, Inc. (ARCADIS), as contractor to the US Environmental Protection
Agency's (EPA) Air Pollution Prevention Control Division (APPCD), performed this work
underWork Assignment 4-1 of Onsite Laboratory Support Contract. The testing activities
followed the specifications of the approved "Site-Specific Quality Assurance Project Plan
for the Field Evaluations of Landfill Gas Control Technologies Landfill B " dated October
29, 2002.
1-1
-------
Source Test
Report for Landfill B
This page intentionally left blank
1-2
-------
Source Test
Report for Landfill B
2. Landfill Facility Descriptions
Available information indicated that Landfill B began operation in 1967. As of 2003,
the site had 4,000,000 tons of waste in place, over an area of 40 acres. Raw LFG was
collected through 2,500 feet of horizontal collectors. The gases generated in the landfill
were extracted with 49 vertical wells. All collected LFG was piped to the enclosed
flare system and combusted.
2.1 Flare Process Description and Operation
A Perennial Energy Enclosed Ground Flare Station, rated at maximum LFG input rate
of 1500 scfrn, received and destroyed the collected LFG. Figure 2-1 shows a simplified
process schematic of the flare system. A burner array and an automatic louvre system
controlled gas and combustion air distribution to achieve proper combustion. A
condensate removal system prevented liquids from entering into the flare burners. A
flame arrester prevented flame from propagating from the burner array back into the
LFG collection and flow control system. The unit could be operated satisfactorily
within a 5-to-l turndown ratio (from 54.0 to 10.8 MMBtu/hr). The system did not have
provisions for heat recovery.
According to manufacturer information, the Perennial Energy Enclosed Ground Flare
Station was designed to afford the combustion gases a minimum residence time of 0.6
seconds at 1400°F to insure thermal destruction of CO and hydrocarbons, with minimal
production of NOX. Specific information related to the system's ability to destroy or
reduce other potential pollutants was not available.
2.2 Landfill Gas (LFG) Sampling Locations
Gas sampling was conducted at the raw LFG pipe and at the Perennial Energy
Enclosed Ground Flare stack, as depicted in Figure 2-1.
2.2.1 Landfill Gas (LFG) Header Pipe
Raw LFG samples were collected from the header pipe at the point where it emerged
from the ground and upstream of any processing units. Figure 2-2 is a photograph of
the raw LFG pipe. The pipe was 11 inches in diameter as it emerged from the ground
and expanded to 14 inches in diameter before passing through a wall into the building
that housed the gas control-and-process system. At the sampling point, four %-inch gas
2-1
-------
Source Test
Report for Landfill B
taps were installed, and gases were withdrawn through these ports to obtain the test
samples.
Comparing the physical arrangement of this header pipe with requirements of standard
sampling methodologies indicated that the header configuration rendered isokinetic
sampling at the gas collection pipe impossible. Therefore, isokinetic sampling was not
attempted at this location. Further discussions on this topic are presented in Section
3.3.1.1.
2.2.2 Flare Stack
Figure 2-3 shows the flare stack and the arrangement of the sampling ports. The flare
stack was 118 inches in diameter and has four 4-inch sampling ports installed 90
degrees apart. Figure 2-4 is a schematic of the flare stack and includes the locations of
the sample traverse points. Isokinetic sampling was possible at this location.
Figure 2-1. Simplified Flare Process Flow Diagram and Sampling Points
2-2
-------
Figure 2-2. Landfill Gas Collection Pipe
Source Test
Report for Landfill B
Figure 2-3. Enclosed Flare Unit Showing Stack Sampling Ports
2-3
-------
Source Test
Report for Landfill B
Sampling
Ports
O
4
63"
Stack Cross Section
Traverse Points
Point* Distance
300"
118"
1
2
3
4
5
6
7
8
9
10
11
12
2.S"
7.9"
13,9"
20.9"
29.S"
42,0"
76.0"
68.5"
97.1"
104.1"
110.3"
115,5"
Figure 2-4. Flare Stack Dimension and Sampling Traverse Locations
2-4
-------
Source Test
Report for Landfill B
3. Test Operations
As stated previously, the purpose of the sampling program was to determine the
chemical constituents of raw LFG and flare stack emissions.
3.1 Test Team
The tests were conducted by a team of eight individuals and a representative of the
landfill company. The team members and their primary duties are listed in Table 3-1.
Table 3-1. Test Team Members and Responsibilities
Role
Test Engineer
Technician
Technician
Technician
Test engineer
Technician
Test engineer
Air Programs Manager
Primary Duty
Chief
CEM operator
Sample train preparation and recovery
Sample train operator at raw LFG inlet pipe
Sample train operator at stack
Sample train operator at stack
Mercury measurements
Observer
3.2 Test Log
3.2.1 Planned Test Sample Matrices
The target list of samples and measurements to be collected were specified in the
Quality Assurance Project Plan (QAPP) dated October 29, 2002. These are reiterated
here for completeness. Tables 3-2 lists the target compounds of interest for the raw
LFG. Table 3-3 lists the target compounds of interest for the treated gas at the flare
stack.
3.2.2 Landfill Gas (LFG) Pipe (Inlet)
Sample collection took two days to complete. Table 3-4 lists the samples that were
collected from the raw LFG pipe. Figure 3-1 is a photograph of the sampling team in
action at this sample location.
3-1
-------
Source Test
Report for Landfill B
Table 3-2. Target Analytes for the Landfill Gas Stream and Sample Condensate
Collected at the Gas Header
Volatile compounds
Methane
Ethane
Propane
Butane
Pentane
Hexane
Carbonyl sulfide
Chlorodifluoromethane
Chloromethane
Dichlorodifluoromethane
Dichlorofluoromethane
Ethyl chloride
Fluorotrichloromethane
1,3-Butadiene
Acetone
Acrylonitrile
Benzene
Bromodichloromethane
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chloroform
Dimethyl sulfide
Ethyl mercaptan
Volatile compounds
(continued)
Ethylene dibromide
Ethylene dichloride
Methyl chloroform
Methyl isobutyl ketone
Methylene chloride
Propylene dichloride
t-1,2-Dichloroethene
Tetrachloroethene
Toluene
Trichlorethylene
Vinyl chloride
Vinylidene chloride
Ethanol
Methyl ethyl ketone
2-Propanol
1,4-Dichlorobenzene
Ethylbenzene
Xylenes
Non-methane organic carbons
Reduced sulfur compounds
Hydrogen sulfide
Carbonyls
Acetaldehyde
Formaldehyde
Polycyclic aromatic
hydrocarbons
Polychlorinated biphenyls
Mercury
Organo-mercury compounds
Total
Elemental
Gases
Carbon dioxide
Oxygen
Moisture
3-2
-------
Source Test
Report for Landfill B
Table 3-3. Target Analytes for the Flare Stack Outlet Gas Stream
Gases
Oxygen
Carbon dioxide
Carbon monoxide
Nitrogen oxide
Sulfur dioxide
Total hydrocarbons
Non-methane organic compounds
Hydrogen chloride
Dioxins/Furans
PAHs
Mercury
Total
Metals
Lead, arsenic, cadmium, chromium,
manganese, nickel
Figure 3-1. Sampling Operations at the Landfill Gas Pipe Inlet
3-3
-------
Source Test
Report for Landfill B
Table 3-4. Landfill Gas Inlet Sample Log and Collection Times
Sampling
Method
Run Number
EPA Method 40 (TO-15, 25C, 3C)
B-Pre-M40-1 10402-01
B-Pre-M40-1 10402-02
B-Pre-M40-1 10402-03
EPA Method 23
B-Pre-M23-1 10402-01
B-Pre-M23-1 10402-02
B-Pre-M23-1 10502-03
EPA Method 01 00
B-Pre-M01 00-1 10502-01
B-Pre-M01 00-1 10502-02
B-Pre-M01 00-1 10502-03
EPA Method 1 1
B-Pre-M001 1-1 10502-01 a
B-Pre-M001 1-1 10502-02
B-Pre-M001 1-1 10502-03
B-Pre-M001 1-1 10502-04
Lumex Instrument
Frontier
B-Pre-EM-1 10502-01
B-Pre-EM-1 10502-02
B-Pre-EM-1 10502-03
B-Pre-TGM-110402-FB01
B-Pre-TGM-1 10402-01
B-Pre-TGM-1 10402-02
B-Pre-TGM-1 10402-03
Analyte(s)
VOCs/NMOCs/O2/CO2,N2
VOCs/NMOCs/O2/CO2,N2
VOCs/NMOCs/O2/CO2,N2
PAHs, PCBs
PAHs, PCBs
PAHs, PCBs
Carbonyls
Carbonyls
Carbonyls
H2S
H2S
H2S
H2S
Elemental Hgb
Elemental Hgb
Elemental Hgb
Total gaseous Hg
Total gaseous Hg
Total gaseous Hg
Total gaseous Hg
Sample
Class
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Field Blank
Test
Test
Test
Date
11/04/02
11/04/02
11/04/02
11/04/02
11/04/02
11/05/02
11/05/02
11/05/02
11/05/02
11/05/02
11/05/02
11/05/02
11/05/02
11/05/02
11/05/02
11/05/02
11/04/02
11/04/02
11/04/02
11/04/02
Run Period
11:02-11:16
12:13-12:24
13:21-13:34
12:41 -15:41
12:42-15:42
09:38-12:41
09:48-10:28
10:45-11:15
11:27-11:58
12:51-13:01
13:22-13:32
14:20-14:30
14:58-15:08
16:35-17:00
16:35-17:00
16:35-17:00
13:22-13:25
10:52-11:32
11:44-12:21
12:33-13:11
3-4
-------
Source Test
Report for Landfill B
Sampling
Method
Frontier
Frontier
Run Number
B-Pre-MMM-110502-SP01
B-Pre-MMM-110502-FB01
B-Pre-MMM-1 10502-01
B-Pre-MMM-1 10502-02
B-Pre-MMM-1 10502-03
B-Pre-DMM-110502-SP01
B-Pre-DMM-110502-FB01
B-Pre-DMM-1 10502-01
B-Pre-DMM-1 10502-02
B-Pre-DMM-1 10502-03
Analyte(s)
Monomethyl Hg
Monomethyl Hg
Monomethyl Hg
Monomethyl Hg
Monomethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Sample
Class
Spike
Field Blank
Test
Test
Test
Spike
Field Blank
Test
Test
Test
Date
11/05/02
11/05/02
11/05/02
11/05/02
11/05/02
11/05/02
11/05/02
11/05/02
11/05/02
11/05/02
Run Period
10:41 -11:07
8:30-8:35
08:43-08:58
09:22-09:46
10:02-10:27
15:40-16:02
16:15-16:20
13:42-14:07
14:22-14:50
15:00-15:28
' Did not purge train at end of run; run was repeated
' Represents average of 3 readings, each of 30-second duration
3.2.3 Flare Stack
Sampling at the flare stack was conducted by accessing the sampling ports with the aid
of a scaffold. Figure 3-2 shows the flare and the sampling scaffold platform. Figure 3-3
shows one of the sampling ports with a sampling probe in place during sample
collection.
3-5
-------
Figure 3-2. Sampling Operations at the Enclosed Flare
Source Test
Report for Landfill B
Figure 3-3. Sampling Port with Probe in Place
3-6
-------
Source Test
Report for Landfill B
The flare stack was sampled for NMOCs (as THCs), PCDD/PCDFs, PAHs, HC1,
metals (lead [Pb], arsenic [As], cadmium [Cd], chromium [Cr], manganese [Mn],
nickel [Ni]), total Hg, SO2, NOX, CO, carbon dioxide (CO2), and oxygen (O2). Table
3-5 lists the test samples that were collected from the flare stack.
The flare stack cross-section was divided into 24 equal areas according to EPA
Method 1. Sampling at the flare stack was conducted at isokinetic conditions. Sample
collection times for the Method 26 HC1 train and Method 29 metals train were 60-
minutes. Run time for the Method 23 PCDD/PCDFs trains was 180 minutes. Run time
for continuous emission monitoring system (CEM) parameters (SO2, NOX, CO, O2,
CO2, and THCs) varied due to the CEM sampling system developing problems
shortening the useable measurement periods
Table 3-5. Flare Stack Test Sample Log and Collection Times
Run Number
EPA Method 3A (CEM) b
B-Post-M3A-1 10402-01
B-Post-M3A-1 10502-02
EPA Method 3A (CEM) b
B-Post-M3A-1 10402-01
B-Post-M3A-1 10502-02
EPA Method 10 (CEM) b
B-Post-M 10-1 10402-01
B-Post-M 10-1 10502-02
EPA Method 7E (CEM) b
B-Post-M7E-1 10402-01
B-Post-M7E-1 10502-02
EPA Method 6C (CEM) b
B-Post-M6C-1 10402-01
B-Post-M6C-1 10502-02
EPA Method 25A (CEM) b
B-Post-M25A-1 10402-01
B-Post-M25A-1 10502-2
Analyte(s)
02
02
CO2
CO2
CO
CO
NOx
NOX
SO2
SO2
NMOCs (THC)
NMOCs (THC)
Sample
Class
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Date
11/04/02
11/05/02
11/04/02
11/05/02
11/04/02
11/05/02
11/04/02
11/05/02
11/04/02
11/05/02
11/04/02
11/05/02
Run Period
12:10-17:45
13:15-14:45
12:10-17:45
13:15-14:45
12:10-17:45
13:15-14:45
12:10-17:45
13:15-14:45
12:10-17:45
13:15-14:45
12:10-17:45
13:15-14:45
3-7
-------
Source Test
Report for Landfill B
Run Number
Lumex Instrument
B-Post-EM-1 10502-01
B-Post-EM-1 10502-02
B-Post-EM-1 10502-03
B-Post-EM-1 10502-04
EPA Method 26A
B-Post-M26-1 10402-01
B-Post-M26-1 10402-02
B-Post-M26-1 10502-03
EPA Method 23
B-Post-M23-1 10402-01
B-Post-M23-1 10402-02
B-Post-M23-1 10502-03
EPA Method 29
B-Post-M29-1 10402-01
B-Post-M29-1 10402-02
B-Post-M29-1 10502-03
Analyte(s)
Elemental Hg a
Elemental Hg a
Elemental Hg a
Elemental Hg a
HCI
HCI
HCI
Dioxins/furans, PAHs
Dioxins/furans, PAHs
Dioxins/furans, PAHs
Metals
Metals
Metals
Sample
Class
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Date
11/05/02
11/05/02
11/05/02
11/05/02
11/04/02
11/04/02
11/05/02
11/04/02
11/04/02
11/05/02
11/05/02
11/05/02
11/05/02
Run Period
16:10-16:35
16:10-16:35
16:10-16:35
16:10-16:35
17:05-18:19
17:07-18:21
14:03-15:15
12:30-15:39
12:31 -15:41
09:40-12:51
09:40-10:53
11:29-12:42
14:05-15:17
Represents average of 3 readings, each of 30-second duration
The CEM sampling system developed problems and cut short the useable measurement periods.
3.3 Field Test Changes and Deviations from Quality Assurance Project Plan (QAPP)
Specifications
3.3.1 Variation from Test Methods or Planned Activities
3.3.1.1 Sampling at the Landfill Gas (LFG) Inlet Pipe
Because of the configuration of the raw LFG inlet pipe, isokinetic sampling at this
location was not possible or attempted. The gas collection pipe was 11 inches in
diameter and had a continuous curvature (Figure 2-2). Furthermore, the pipe diameter
changed to 14 inches abruptly near the %-inch sampling port, most likely introducing
additional undesirable flow disturbances. As such, the pipe did not have sufficient
3-8
-------
Source Test
Report for Landfill B
straight lengths of pipe-run upstream and downstream of the sample ports. The lack of
straight-run pipe precluded accurate velocity measurements.
Isokinetic sampling would be of value if particulate sampling was needed. Little
particulate matter was expected in the raw LFG and this was confirmed by the
observation of glass fiber filters on several of the sampling trains that did not reveal
particulate catch.
3.3.1.2 Landfill Gas (LFG) Inlet Pipe Condensate Sample
The raw LFG inlet pipe condensate sample was not collected because it was not a part
of the QAPP-specified samples.
3.3.1.3 Landfill Gas (LFG) Flow Rate Measurement
LFG flow rates were recorded as indicated by the Perennial Energy Enclosed Ground
Flare Station control panel. The accuracy of the flow rates indicated measurement
could not be independently verified because of the inability to measure gas velocity
accurately, as discussed in the previous section. The test team was only able to make
crude velocity measurements by traversing the pipe using a standard pitot probe. The
accuracies of these measurements were uncertain, even though they appeared to be
similar to the facility's flow rate readings.
3.3.2 Application of Test Methods
The sampling and, where applicable, analytical methods used in this test program
follow those specified in the QAPP. Table 3-6 lists the applicable measurement and
analyses methods and their corresponding performing organizations.
3-9
-------
Source Test
Report for Landfill B
Table 3-6. Test Methods and Performing Organizations
Procedure
EPA Method 1
EPA Method 2
EPA Method 3A
EPA Method 3C
EPA Method 4
EPA Method 6C
EPA Method 7E
EPA Method 10
EPA Method 1 1
EPA Method 23
EPA Method 25A
EPA Method 25C
EPA Method 26A
EPA Method 29
EPA Method 40
SW-846 Method 0100/TO-11
LUMEX instrument
Organic mercury methods
Description
Selection of traverse points
Determination of stack gas velocity and
volumetric flow rate
Determination of oxygen (O2) and carbon
dioxide (CO2) for flare stack gas molecular
weight calculations
Determination of carbon dioxide (CO2),
methane (ChU), nitrogen (N2), and oxygen
(O2) in raw LFG
Determination of stack gas moisture
Determination of sulfur dioxide (SO2)
Determination of nitrogen oxides (NOX)
Determination of carbon monoxide (CO)
Determination of hydrogen sulfide (H2S)
Determination of dioxins/furans, PAHs, and
PCBs
Determination of flare stack gas NMOCs, as
THCs when total organic concentration was
less than the 50 ppm Method 25C
applicability threshold
Determination of raw LFG NMOCs
Determination of hydrogen chloride (HCI)
Determination of metals
Determination of VOCs
Determination of carbonyls (formaldehyde,
acetaldehyde)
Determination of elemental mercury (Hg°)
Determination of raw LFG:
Monomethyl mercury
Dimethyl mercury
Total mercury.
Organization Performing
Analysis
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
Triangle Environmental Services
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
Oxford Laboratories
ALTA Analytical Perspectives
ARCADIS G&M
Triangle Environmental Services
Resolution Analytics
First Analytical Laboratories
Research Triangle Park
Laboratories
Resolution Analytics
ARCADIS G&M
Frontier Geosciences
3-10
-------
Source Test
Report for Landfill B
3.3.3 Test Method Exceptions
Laboratory analytical procedures followed those prescribed by the specified methods,
with the following exceptions:
Raw Landfill at Inlet
• Carbonyls were analyzed by Method TO-11 instead of SW-846 Method 8315.
(Method TO-11 and Method 8315 closely resemble each other.)
• Polycyclic aromatic hydrocarbons (PAHs) were analyzed by SW-846 Method
8270. The sample extracts were found to contain excessive amounts of non-PAH
organics. In order to make the extracts safe to be injected into the gas
chromatograph/mass spectrometer (GC/MS), the sample had to be diluted
excessively. The high dilution made the method detection limit (MDL) for the
target PAHs too high, resulting in "non-detects" (ND) at the high detection limits.
The planned analysis method could not produce the desired results at the needed
detection levels. At the present time, an alternative analysis method was not
identified. The sample extracts are in storage and may be submitted for analysis if
a suitable method is available.
• Polychlorinated biphenyls (PCBs) were analyzed by EPA Method 1668 (EPA
812/R-97-001) as specified in the QAPP. However, similar to the difficulties
experienced for the PAH analysis, in order to make the extracts safe to be injected
inject into the gas chromatograph (GC), the sample had to be diluted excessively.
The planned analysis method could not produce the desired results at the needed
detection levels
• For raw LFG inlet samples, VOCs were analyzed by EPA Method TO-15.
Methane (CFL,) was analyzed by GC/FID and additionally by Method 3C.
Flare Stack
• Non-Methane Organic Compounds (NMOCs) - Method 25A was used instead of
the specifically applicable Method 25C. This was necessitated by the low overall
organic compound concentrations in the flare stack gas, which were significantly
below the Method 25C's applicability threshold minimum level of 50 ppmv.
3-11
-------
Source Test
Report for Landfill B
This page intentionally left blank
3-12
-------
Source Test
Report for Landfill B
4. Presentation of Test Results
Testing took place at the Landfill B on November 4-5, 2002. Results of the testing are
presented in this section, and detailed test results are included in the Appendices. The
following subsections provide concise summaries of the test results.
4.1 Raw Landfill Gas (LFG) Pipe Results
As shown in Figure 2-2, sampling was conducted by extracting samples via the four %-
inch ports installed in the raw LFG pipe.
4.1.1 Raw Landfill Gas (LFG) Flow Rate and Temperature
4.1.1.1 Direct Measurements
The facility process system had a flow measurement system, which displayed the flow
rate on an instrument panel meter. The panel meter read a constant 1496% scfin. The
"%" symbol in the display was indicative that the flow measurement system was over-
ranged.
The small size of the sampling ports and lack of an adequately long straight pipe run
upstream of the sampling ports precluded the proper measurement of the LFG velocity
profile within this pipe. Nonetheless, attempted measurements with a velocity probe
returned readings ranging from 1400 ft/min near the bottom (inside curve) of the pipe,
to 5000 ft/min near the top (outside curve) of the pipe. Approximating the velocity,
using the arithmetic average velocity of 3160 ft/min and pipe inside diameter of 10
inches, the volumetric flow rate was estimated to be about 1745 cu ft/min.
A direct measurement with thermocouples showed the raw LFG temperature to be
62°F.
4.1.1.2 Flow Rate Estimate by Stoichiometric Calculations
The volumetric flow rate of the raw LFG was estimated by using the measured
volumetric flow rate of the flare stack exhaust, the composition of the flare stack
exhaust gas (O2 and CO2 concentrations) and the composition of the raw LFG (organic
constituents, CO2, O2, nitrogen [N2], etc) to input into a Stoichiometric computation
algorithm. This approach resulted in an estimated raw LFG flow rate of about 1300
dscfm. A worksheet outlining the Stoichiometric calculations is shown in Appendix O.
4-1
-------
Source Test
Report for Landfill B
4.1.1.3 Landfill Gas (LFG) Flow Rate Combined Estimate
Based on the three independent sources of the flow rate estimates, 1496 scfin by the
facility's flow rate indicator, 1745 scfm by the crude pitot probe measurement, and
1300 scfm by stoichiometric calculation, a reasonable combined estimate is 1500 scfm.
Because the flow rate is an estimate, any mass emission rates calculated based on this
raw LFG flow rate will also be recognized as estimates.
4.1.2 Raw Landfill Gas (LFG) Constituents
The concentrations of the constituents of interest in the raw LFG are presented in the
following Subsections 4.1.2.1 through 4.1.2.5. Following the presentation of the
constituent concentrations, Section 4.3 summarizes the data and presents a comparison
with the AP-42 default values. This section also presents the estimated mass flow rates
of the constituents at the raw LFG pipe.
4.1.2.1 Volatile Organic Compounds (VOCs)
Concentrations of VOCs were obtained collecting summa canister samples using
Method 40 procedures. Analysis was performed by Method TO-15, with gas
chromatography and mass spectrometry (GC/MS). The alkanes (C2 through C6), being
present in much higher concentrations, were analyzed by GC flame ionization
detection (FID) on the same summa canister samples.
Table 4-1 lists the results of these analyses. Tentatively identified compounds (TICs)
can be seen in the Research Triangle Park (RTF) Laboratory reports in Appendix A.
4.1.2.2 Non-methane Organic Compounds (NMOCs)
Non-methane organic compounds (NMOCs) in the raw LFG were analyzed by Method
25C on the Method 40 samples. NMOC concentrations in the raw LFG are presented
in Table 4-2. This table also includes the concentrations of CFL, CO2 and O2, which are
results obtained as part of the NMOC analyses. The moisture concentration data were
obtained from the Method 23 PAFI/PCB sample train measurements.
The other analytes, oxygen (O2), carbon dioxide (CO2), and moisture, are not pollutants
but are of interest as they are useful indicators of the "quality" of the raw LFG. The
concentrations of nitrogen (N2) and O2 are also indicators of the extent of ambient air
infiltration into the LFG collection. Method 25C for NMOC determination specifically
4-2
-------
Source Test
Report for Landfill B
recommends that these measurements be made to determine potential air infiltration.
Therefore, while measurements for methane (CHO, CO2, O2, and N2 by Method 3C
were not included in the original QAPP, these measurements were included and
performed.
Table 4-1. Raw Landfill Gas VOC Concentrations
Compound
Bv GC/FID
Ethane
Propane
Butane
Pentane
Hexane
BvTO-15GC/MS
Dichlorodifluoromethane (Freon 12)
1 ,2-Chloro-, 1 ,2,2-Tetrafluoroethane
(CFC114)
Chloromethane
Vinyl chloride c
1,3-Butadiene (Vinylethylene) c
Bromomethane (Methyl Bromide) c
Chloroethane (Ethyl Chloride)
Trichloromonofluoromethane (CFC1 1 )
1,1-Dichloroethene
1 , 1 ,2-Trichloro-1 ,2,2-trifluoroethane
(CFC113)
Carbon Disulfide
Ethanol
Isopropyl Alcohol (2-Propanol) c
Methylene chloride (Dichloromethane) c
Acetone c
Unit
ppmv
ppmv
ppmv
ppmv
ppmv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
MDL
1
1
1
1
1
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
Concentration
Run 1
4.6
6.0
3.0
3.3
ND
648
58
ND
560
111
39
2660
417
10
14
155
261
206
163
1900
Run 2
4.4
5.7
2.9
2.1
ND
672
65
217
585
136
46
2820
488
12
17
214
314
848
156
2480
Run 3
4.9
5.9
4.1
2.4
ND
83
9
ND
86
21
52
157
77
2
3
32
31
14
186
440
Average a
4.6
5.9
3.3
2.6
ND
468
44
72
410
89
46
1880
327
8
11
134
202
356
169
1610
4-3
-------
Source Test
Report for Landfill B
Compound
t-1 ,2-dichloroethene
Hexane
Methyl-t-butyl ether (MTBE)
1,1-Dichloroethane
Vinyl Acetate
cis-1 ,2-Dichloroethene
Cyclohexane
Chloroform
Ethyl Acetate
Carbon Tetrachloride
Tetrahydrofuran (Diethylene Oxide)
1,1,1 -Trichloroethane
2-Butanone (Methyl Ethyl Ketone)
Heptane
Benzene c
1,2-Dichloroethane
Trichloroethylene (Trichloroethene)
1 ,2-Dichloropropane
Bromodichloromethane
1,4-Dioxane (1,4-Diethylene Dioxide)
cis-1 ,3-Dichloropropene
Toluene (Methyl Benzene) c
4-Methyl-2-pentanone (MIBK) c
t-1 ,3-Dichloropropene
Tetrachloroethylene (Perchloroethylene)
1,1,2-Trichloroethane
Dibromochloromethane
1,2-Dibromoethane (Ethylene dibromide)
2-Hexanone (Methyl Butyl Ketone)
Ethylbenzene
Chlorobenzene d
Unit
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
MDL
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
Concentration
Run 1
11
1700
221
231
598
346
862
205
2130
6
717
37
1600
1240
312
6.8
129
10
11
10
2
8300
946
4
219
50
47
15
ND
3430
98 J
Run 2
14
1770
254
282
1430
454
1160
325
2570
9
925
49
2210
1230
373
7
151
4
12
18
2
10200
1080
4
263
57
1
5
226
4190
60 J
Run 3
2
2370
54
20
28
76
185
41
2240
1
1000
7
484
282
69
1
28
2
7
ND
ND
1810
633
1
46
10
ND
1
1096
762
529 J
Average a
9
1950
177
178
686
292
734
190
2310
5
882
31
1430
918
251
5
103
5
10
9.4
1.4
6770
886
3
176
39
16
7
441
2800
229 J
4-4
-------
Source Test
Report for Landfill B
Compound
m/p-Xylene (Dimethyl Benzene)
o-Xylene (Dimethyl Benzene)
Styrene (Vinylbenzene)
Tribromomethane (Bromoform)
1 , 1 ,2,2-Tetrachloroethane
1-Ethyl-4-methylbenzene (4-Ethyl
Toluene) b
1,3,5-Trimethylbenzene b
1,2,4-Trimethylbenzene c
1,4-Dichlorobenzene c
1 ,3-Dichlorobenzene
Benzyl Chloride
1 ,2-Dichlorobenzene
1 , 1 ,2,3,4,4-Hexachloro-1 ,3-butadiene c
1,2,4-Trichlorobenzene c
Acrylontrile
Dichlorofluoromethane (Freon 21)
Chlorodiflouromethane (Freon 22)
Ethyl Mercaptan (Ethanediol)
Carbonyl Sulfide (Carbon oxysulfide)
Unit
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
MDL
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
20
20
20
20
20
Concentration
Run 1
3510
1710
265
ND
ND
476 J
476 J
1140
304
5
23
ND
8
7
ND
ND
ND
ND
ND
Run 2
3890
2160
345
ND
ND
578 J
578 J
1450
393
1
27
1
6
8
ND
ND
ND
ND
ND
Run 3
4530
373
55
ND
ND
103 J
103 J
255
66
ND
10
ND
2
ND
ND
ND
ND
ND
ND
Average a
3980
1410
222
ND
ND
386 J
386 J
949
255
2.03
20
0.4
5
5
ND
ND
ND
ND
ND
ND - Constituent not detected at the stated detection limits.
3 In computing averages, when all measurements are ND, the average is reported as ND. When one or
more measurement is above detection, the ND measurement is treated as 50 percent of the stated MDL.
If MDL is not reported, a ND measurement is treated as zero.
b 1-Ethyl-4-methylbenzene (4-Ethyl Toluene) and 1,3,5-Trimethylbenzene co-eluted from the GC and also
have the same quantitation ions, thus making them indistinguishable. Therefore, the reported values
represent the combined concentrations of these two compounds.
c Analyte detected in blank sampled 0.21 to 3.03 ppbv. See Table 5-2 for analyte-specific detected levels.
d Chlorobenzene spike recovery was 211 percent.
4-5
-------
Source Test
Report for Landfill B
Table 4-2. Raw Landfill Gas Non-Methane Organic Compound (NMOC) Concentrations
Run 1
Run 2
Run 3
Average
NMOC (ppmv
as Hexane)
Method
25C
377
314
374
355
CH4
(% v/v)
Method
25C
40.6
39.2
37.7
39.2
Method
3C
37.3
35.8
35.2
36.1
CO2
(% v/v)
Method
25C
31.9
30.7
29.5
30.7
Method
3C
29.9
28.8
28.2
29.0
02
(%v/v)
Method
3C
6.0
6.6
6.6
6.4
N2
(% v/v)
Method
3C
24.4
26.2
26.2
25.6
Moisture
(% v/v)
Method
23
2.1
1.8
2.1
2.0
Concentrations are reported without correction for nitrogen
Method 25C hold time was 49 days; 19 days longer than the specified 30 days
4.12.3 Hydrogen Sulfide (H2S)
Landfill gas (LFG) pipe H2S concentrations were obtained by collecting and analyzing
the samples in accordance with EPA Method 11. These analytical results are presented
in Table 4-3.
Table 4-3. Raw Landfill Gas Hydrogen Sulfide (H2S) Concentrations
Run1 a
Run 2
Run 3
Run 4
Average b
H2S Concentration
(mg/m3)
26.4
36.1
27.1
33.8
32.3
(ppmv)
18.7
25.6
19.2
24.0
22.9
a Did not purge at end of Run 1. Added Run 4 to complete set.
'Run 1 data was not included in averaged value
4.12.4 Carbonyls
The target carbonyl compounds, formaldehyde and acetaldehyde, were analyzed by
Method TO-11 on samples collected by EPA Method 0100. The analysis results are
presented in Table 4-4.
4-6
-------
Source Test
Report for Landfill B
Table 4-4. Raw Landfill Gas Pipe Carbonyls Concentrations
MDL
Run 1
Run 2
Run 3
Average
Formaldehyde a
(Mg/m3)
2
3.31 J
4.07 J
3.45 J
3.61 J
(x10~3 ppmv)
1.6
2.65 J
3.26 J
2.76 J
2.89 J
Acetaldehyde
(Mg/m3)
4
35.0
21.9
24.1
27.0
(x10~3 ppmv)
2.2
19.1
12.0
13.2
14.8
' Measured formaldehyde values were near MDL
4.12.5 Mercury (Hg)
Mercury (Hg) can exist in several forms. This test program focused on the elemental,
monomethyl, and dimethyl forms of Hg, and total Hg. Elemental Hg was measured
with the LUMEX instrument. Organic monomethyl Hg, dimethyl Hg and total Hg were
sampled and analyzed using the organic mercury method.
4.1.2.5.1 Total Mercury (Hg) Samples
To collect the total Hg samples, an iodated charcoal trap was used as a sorbent. A
backup tube was also present to assess any breakthrough. The sorbent tube was heated
to above the dew point of the gas stream to prevent condensation on the sorbent. A
silica gel impinger was used to collect and quantify the water vapor from the stream. A
diaphragm air pump was used to pull sample through the train and collect the sample.
A dry gas meter capable of measuring the volume in 10 ml increments was used to
monitor and quantify the volume of gas sampled.
Table 4-5 presents the total Hg concentrations in the raw LFG. They ranged from 158
to 234 ng/m3 with an average of 204 ng/m3. Spike recovery for total Hg samples was
95 percent.
4-7
-------
Source Test
Report for Landfill B
Table 4-5. Raw Landfill Gas Total Mercury Concentrations
MDL
Run 1
Run 2
Run 3
Average
Total Mercury Concentration
(ng/m3)
50
219
234
158
204
(x10's ppm)
6.0
24.5
26.2
17.7
22.8
Sample hold time exceeded 14 days
Hold times exceeded 14 days
4.1.2.5.2 Dimethyl Mercury (Hg) Samples
To collect the dimethyl Hg sample, a carbotrap was used with a sorbent. A backup tube
was also present to assess any breakthrough. A third iodated carbon trap was also
present to collect any elemental Hg present. The sorbent tube was heated to above the
dew point of the gas stream to prevent condensation on the sorbent. A silica gel
impinger was used to collect and quantify the water vapor from the stream. A
diaphragm air pump was used to pull sample through the train and collect the sample.
A dry gas meter capable of measuring the volume in 10 ml increments was used to
monitor and quantify the volume of gas sampled.
Table 4-6 presents the dimethyl Hg concentrations in the raw LFG. These ranged from
1.6 to 2.1 ng/m3 with an average of 1.9 ng/m3. Spike recoveries for the dimethyl Hg
traps ranged from 1.5 to 4.4 percent, well below normally acceptable levels. The
spiked traps, without being exposed to the raw LFG, had recoveries from 68 to 98
percent with an average of 83 percent. Recoveries were low in the spiked traps
possibly because of the presence of an unknown interfering compound either
destroying or masking the detection of the dimethyl Hg. For this reason, dimethyl Hg
concentrations data were flagged with "R" to indicate that the data were rejected.
Further development of this procedure is being undertaken by Frontier Geosciences.
More studies are needed to develop an acceptable method to more accurately determine
the actual dimethyl Hg concentrations.
4-8
-------
Source Test
Report for Landfill B
Table 4-6. Raw Landfill Gas Dimethyl Mercury Concentrations
MDL
Run 1
Run 2
Run 3
Average
Dimethyl Mercury Concentration
(ng/m3)
0.5
2.0 R
2.1 R
1.6 R
1.9 R
(x10~6 ppmv)
0.05
0.209 R
0.220 R
0.168 R
0.200 R
Sample hold times exceeded 14 days
Spike recoveries were 0-5 percent
R -The results are rejected due to serious deficiencies per EPA QA/G-8 guidance
4.1.2.5.3 Monomethyl Mercury (Hg) Samples
To collect the sample, a set of three impingers filled with 0.001 M HC1 was used to
collect the monomethyl Hg. An empty forth impinger was used to knockout any
impinger solution carryover to the pump and meter system. A diaphragm air pump was
used to pull sample through the train and collect the sample. A dry gas meter capable
of measuring the volume in 10 ml increments was used to monitor and quantify the
volume of gas sampled.
As shown in Table 4-7, monomethyl Hg concentrations in the raw LFG ranged from
1.1 to 1.3 ng/m3 with an average amount of 1.2 ng/m3. Spike recovery for the
monomethyl Hg sample was 70 percent.
Table 4-7. Raw Landfill Gas Monomethyl Mercury Concentrations
MDL
Run 1
Run 2
Run 3
Average
Monomethyl Mercury Concentration
(ng/m3)
0.13
1.3
1.1
1.1
1.2
(x10~6 ppmv)
0.014
0.146
0.123
0.123
0.134
Sample hold time exceeded 14 days
Relative standard deviation (RSD) of replicate sample exceeded ±30 percent
4-9
-------
Source Test
Report for Landfill B
4.1.2.5.4 Elemental Mercury (Hg)
Elemental mercury (Hg) was determined by the LUMEX instrument and the results are
presented in Table 4-8. Before any measurement was made, the LUMEX instrument
was zeroed. The background measurements were made by drawing a sample of
ambient air through and ice-chilled empty impinger and recording the LUMEX
instrument reading.
Table 4-8. Raw Landfill Gas Elemental Mercury Concentrations
Run 1
Run 2
Run 3
Average
Concentration a
Background b
(ng/m3)
0
0
0
0
(x10~6 ppmv)
0
0
0
0
Gas Pipe
(ng/m3)
61
53
60
58
(xlO"6 ppmv)
7.3
6.4
7.2
7.0
Average of three readings, each of 30-seconds duration
Background measurement was made by sampling ambient air drawn through ice-chilled empty
impinger
4.2 Flare Stack Results
The flare stack was sampled for NMOCs (as THCs), PCDD/PCDFs, PAHs, HC1, Pb,
As, Cd, Cr, Mn, Ni, total Hg, SO2, NOX, CO, CO2, and O2. The stack cross section was
divided into 24 equal areas according to EPA Method 1. Sampling run time for HC1
and metals was 60 minutes. Run time for PCDD/PCDFs sampling was 180 minutes.
Run time for CEMS parameters (SO2, NOX, CO, O2, CO2, and THCs) varied.
4.2.1 Flare Stack Gas Flow Rate and Temperature
Sampling at the flare stack was conducted at isokinetic conditions. The procedures
provided stack gas velocity distribution across the flare stack and reliable
measurements of stack gas flow rates. Table 4-9 lists the volumetric flow rates and
temperatures at the flare stack measured during the various sampling runs.
4-10
-------
Source Test
Report for Landfill B
Table 4-9. Flare Stack Gas Operating Conditions, Measured during Sampling
Run Number
B-POST-M26-1 10402-01
B-POST-M26-1 10402-02
B-POST-M26-1 10402-03
B-POST-M29-1 10502-01
B-POST-M29-1 10502-02
B-POST-M29-1 10502-03
B-POST-M23-1 10402-01
B-POST-M23-1 10402-02
B-POST-M23-1 10502-03
Average
Duration
11/4/0217:05-18:19
11/4/0217:07-18:21
11/5/0214:03-15:15
11/4/029:40-10:53
11/5/0211:29-12:42
11/5/0214:05-15:17
11/4/0212:30-15:39
11/4/0212:31-15:41
11/5/0209:40-12:51
Average
Stack
Temp
(°F)
1419
1418
1374
1359
1368
1380
1414
1411
1359
1389
Carbon
Dioxide
(%)
4.8
4.8
2.9
4.8
4.8
2.9
4.8
4.8
2.9
4.2
Oxygen
(%)
16.1
16.1
12.5
16.1
16.1
12.5
16.1
16.1
12.5
14.9
Moisture
(%)
7.3
6.6
5.8
6.1
6.1
6.7
7.0
6.5
6.2
6.5
Velocity
(actual
ft/sec)
17.0
16.9
16.9
17.5
16.7
17.0
16.4
16.4
17.6
16.9
Vol. Flow
Rate
(acfm)
77400
77000
77000
79900
76100
77500
74800
74500
80200
77200
Vol. Flow
Rate
(dscfm)
20200
20300
21000
21900
20800
20900
19700
19700
22000
20700
Flare stack cross-section flow area was 75.94 sq. ft.
4.2.1.1 Flare Stack Oxygen (O2) and Carbon Dioxide (CO2)
Oxygen (O2) and CO2 concentrations provide an overall indication of the combustion
process. Figure 4-1 shows the O2 and CO2 concentrations measured by the CEMs
during the two days of testing. The plotted data included the CEM responses to the
instrument zeroing and calibration periods. These periods manifest as the peaking and
bottoming of the recorded values. Table 4-10 presents the daily averages of O2 and
CO2 concentrations.
4-11
-------
Flare Stack Oxygen & Carbon Dioxide 11/4/02
08:00 09:12 10:24 11:36 12:48 14:00 15:12 16:24 17:36 18:48
Time
25 -,
Flare Stack Oxygen & Carbon Dioxide 11/5/02
07:00 08:12 09:24 10:36 11:48 13:00 14:12 15:24
Figure 4-1. Flare Stack Oxygen and Carbon Dioxide Concentrations
Source Test
Report for Landfill B
4-12
-------
Source Test
Report for Landfill B
Table 4-10. Flare Stack Combustion Products Concentrations
Run 1
Run 2
Average
02
(% v)
16.1
17.0
16.6
CO2
(% v)
4.8
4.2
4.5
CEM sampling system malfunctioned and reduced the amount of useable data
4.2.1.2 Flare Stack Total Hydrocarbon (THC) Emissions
Flare stack THC emissions were measured by EPA Method 25A, which used a CEM.
At the flare stack, hydrocarbon (including NMOCs) concentrations were found to be
below 50 ppmv. The low concentrations rendered Method 25 C, the method designed
specifically for NMOC measurement, unsuitable to be applied at this location.
In its place, EPA Method 25 A produced concentrations of all hydrocarbons that
respond to flame ionization detector (FID) analysis. Real-time continuous instrument
responses are shown in Figure 4-2. The time-averaged concentrations are presented in
Table 4-11. As can be seen, the concentrations of THCs were low and less than 10
ppmv. The duration of valid measurements made during the second test day (Run 2)
was limited because of the failure of the temperature controller that maintained the
temperature of the heated sample line. The sample line was overheated and out-gassed,
as evidenced by the wild fluctuations in measured hydrocarbons during most of the
early part of the day. Although towards the end of the test, the test team was able to
restore operation of the hydrocarbon measurement system, the hydrocarbon test results
during Run 2 need to be viewed with caution.
4-13
-------
Source Test
Report for Landfill B
Flare Stack Total Hydrocarbon 11/4/02
08:00 09:12 10:24 11:36 12:48 14:00 15:12 16:24 17:36 18:48
Time
Flare Stack Total Hydrocarbon 11/5/02
Sampling Period
Total Hydrocarbon
10:36 11:48
Time
13:00
14:12
15:24
Figure 4-2. Flare Stack Total Hydrocarbons Concentrations
4-14
-------
Source Test
Report for Landfill B
Table 4-11. Flare Stack THC Concentrations
Run 1
Run 2
Average
THC
(ppmdv as
propane)
6
1a
4
THC
(ppmdv as
hexane)
2
0.5
2
' Based on limited data near the end of test
4.2.1.3 Flare Stack Dioxin/Furan Emissions (PCDD/PCDFs)
Three EPA Method 23 sampling runs were performed. As a cost-saving measure, only
the samples from one run (Run 3) were analyzed. Samples from runs 1 and 2 have been
extracted and are being held in the laboratory for possible future analysis.
Table 4-12 presents the flare stack PCDD/PCDFs emissions data. Concentrations for
most targets were below their detection limit and these were denoted by the less than
("<") sign, followed by the detection concentration level of that target. The mass
emission rates were calculated based on the target concentrations and the exhaust gas
flow rates measured at the sampling location.
Table 4-13 presents the same data, but expressed in terms of Toxicity Equivalent
emissions.
4.2.1.4 Flare Stack Polycyclic Aromatic Hydrocarbon (PAH) Emissions
The concentrations of PAHs were obtained by Method 23 analyses. The results are
presented in Table 4-14.
4-15
-------
Source Test
Report for Landfill B
Table 4-12. Flare Stack Dioxins and Furans Emissions
Analyte
B-POST-M23-1 10502-03
Concentration
(x10~3 ng/dscm)
Emission Rate
(x10-9g/hr)
(x10'12 Ib/hr)
Dioxins
2,3,7,8-TCDD
Other TCDD
1,2,3,7,8-PeCDD
Other PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
Other HxCDD
1,2,3,4,6,7,8-HpCDD
Other HpCDD
1,2,3,4,6,7,8,9-OCDD
Total ODD
< 0.346
11.3
< 0.291
13.6
<0.504
< 0.468
< 0.477
4.1
< 0.254
2.4
< 0.983
34.7
<12.9
421
<10.9
507
<18.8
<17.4
<17.8
154
<9.5
88.8
<36.7
1300
28.5
929
23.9
1100
41.5
38.4
39.2
339
20.9
196
80.9
2900
Furans
2,3,7,8-TCDF
Other TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
Other PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
Other HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
Other HpCDF
1,2,3,4,6,7, 8, 9-OCDF
Total CDF
Total CDD/CDF
0.587
0.0088
1.1
1.0
110
1.1
0.166
0.194
0.218
34.7
0.158
0.215
4.6
1.1
156
190
21.9
8800
40.9
38.0
4100
42.7
6.2
7.2
8.1
1300
5.9
8.0
170
42.5
14600
15900
48.2
19400
90.3
83.7
9100
94.2
13.7
16.0
18.0
2900
13.0
17.7
375
93.7
32200
35000
Two additional samples were collected, extracted and held in the laboratory for possible future
analyses: B-POST-M23-110402-01 and B-POST-M23-110402-02
"<" denotes the measurement was non-detect. The value following the "<" sign is the detection
limit.
4-16
-------
Source Test Report
for Landfill B
Table 4-13. Flare Stack Dioxins and Furans Toxicity Equivalent Emissions
Pollutant
Concentration
(x10^ ng/dscm)
Emission Rate
(x10-°g/hr)
(x10'12lb/hr)
1989 Toxicity
Equivalency
Factor
Toxicity Equivalent
Emissions
Concentration
(xlO"3 ng/dscm)
Emission Rate
(xlQ-Vhr)
(x10'12 Ib/hr)
Dioxins
2,3,7,8-TCDD
Other TCDD
1,2,3,7,8-PeCDD
Other PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
Other HxCDD
1,2,3,4,6,7,8-HpCDD
Other HpCDD
1,2,3,4,6,7,8,9-OCDD
Total ODD
Furans
2,3,7,8-TCDF
Other TCDF
1,2,3,7,8-PeCDF
< 0.346
11.3
< 0.291
13.6
< 0.504
< 0.468
< 0.477
4.1
< 0.254
2.4
< 0.983
34.7
<12.9
421
<10.9
507
<18.8
<17.4
<17.8
154
<9.5
89
<36.7
1300
<28.5
929
<23.9
1100
<41.5
<38.4
<39.2
339
<20.9
196
<80.9
2900
1
—
0.5
—
0.1
0.1
0.1
—
0.01
—
0.001
—
< 0.346
NA
< 0.146
NA
< 0.0504
< 0.0468
< 0.0477
NA
< 0.00254
NA
< 0.000983
0.640
<12.9
NA
<5.4
NA
<1.9
<1.7
<1.8
NA
< 0.095
NA
< 0.0367
23.9
<28.5
NA
<12.0
NA
<4.2
<3.8
<3.9
NA
< 0.209
NA
< 0.0809
52.6
0.587
0.0088
1.1
21.9
8800
41
48.2
19400
90
0.1
—
0.05
0.0587
NA
0.055
2.2
NA
2.0
4.8
NA
4.5
4-17
-------
Source Test Report
for Landfill B
Pollutant
2,3,4,7,8-PeCDF
Other PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
Other HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
Other HpCDF
1,2,3,4,6,7,8,9-OCDF
Total CDF
Total CDD/CDF
Concentration
(x10^ ng/dscm)
1.0
110
1.1
0.166
0.194
0.218
34.7
0.158
0.215
4.6
1.1
155
190
Emission Rate
(xlO^g/hr)
38
4100
43
6.2
7.2
8.1
1300
5.9
8.0
170
43
14600
15900
(x10'12lb/hr)
84
9100
94
14
16
18
2900
13
18
375
94
32200
35000
1989 Toxicity
Equivalency
Factor
0.5
—
0.1
0.1
0.1
0.1
—
0.01
0.01
—
0.001
—
—
Toxicity Equivalent
Emissions
Concentration
(x10^ ng/dscm)
0.51
NA
0.11
0.0166
0.0194
0.0218
NA
0.00158
0.00215
NA
0.0011
0.800
1.4
Emission Rate
(xlO^g/hr)
19.0
NA
4.3
0.62
0.72
0.81
NA
0.059
0.080
NA
0.043
29.8
53.7
(x10'12 Ib/hr)
42
NA
9.4
1.4
1.6
1.8
NA
0.13
0.18
NA
0.094
65.8
118.4
In computing averages, when all measurements are ND, the average is reported as ND. When one or more measurement is above detection, the
ND measurement is treated as 50 percent of the stated MDL. If MDL is not reported, a ND measurement is treated as zero.
"<" denotes the measurement was non-detect. The value following the "<" sign is the detection limit.
4-18
-------
Source Test Report
for Landfill B
Table 4-14. Flare Stack Polycyclic Aromatic Hydrocarbons Emissions
Analyte
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(g,h,i)perylene
Benzo(k)fluoranthene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
lndeno(1 ,2,3-cd)pyrene
Naphthalene a
Phenanthrene
Pyrene
2-Methylnaphthalene
Benzo(e)Pyrene
Perylene
Formula
Weight
154.21
152.20
178.23
228.30
252.32
252.32
276.34
252.32
228.29
278.35
202.26
166.22
288.35
128.17
178.23
202.26
142.20
252.32
253.31
B-POST-M23-1 10502-03
Concentration
(x10~6 ppmv)
2.5
0.489
1.1
0.261
0.106
0.299
0.219
0.092
0.266
0.025
2.7
46.1
0.0969
761
1.5
2.1
585
0.238
0.0371
(ng/dscm)
16.2
3.1
8.3
2.5
1.1
3.1
2.5
1.0
2.5
0.3
22.4
319
1.2
4060
12
18
3460
2.5
0.4
Emission Rate
(x10'6g/hr)
604
115
308
92.3
41.5
117
94
36
94
11
837
11900
43
151000
430
670
129000
93
14.5
(xlO^lb/hr)
1.30
0.254
0.678
0.204
0.092
0.258
0.207
0.079
0.207
0.024
1.8
26.2
0.096
333
0.94
1.5
285
0.205
0.032
Two additional samples were collected, extracted and held in the laboratory for possible future
analyses: B-POST-M23-110402-01 and B-POST-M23-110402-02
Analysis hold time was 50 days. Method specified hold time is 40 days.
Spike recovery ranged from 57.9 to 124 percent
a - 1920 ng found in reagent blank. More than 60000 ng found in test sample
4-19
-------
Source Test Report
for Landfill B
60
50
§30
c
HI
g20
o
O
10
Flare Stack Carbon Monoxide 11/4/02
Sampling Period
-Carbon Monoxide
09:12 10:24
12:48 14:00
Time
15:12 16:24 17:36
18:48
60 -,
50
ration (ppm Dry)
oo ^
o o
c
HI
£20
o
o
10 -
0
07
Flare Stack Carbon Monoxide 11/5/02
t
I
I/1
LH
1
I
Sampling Period
Carbon Monoxide
rSJS
J 1
00 08:12 09:24 10:36 11:48 13:00
Time
14:12
^ — *
15:24
Figure 4-3. Flare Stack Carbon Monoxide Concentrations
4-20
-------
Source Test Report
for Landfill B
25 -,
20 -
Q
Concentration (ppm
o 01 o 01
8
Flare Stack Sulfur Dioxide 11/4/02
r
I
00 09:12
|
10:24
.~j S
Sampl ng Period
SO2
/^^VlArtwVv ^^
/ M*\*u^, rf
„ . jS W
vA-r
11:36 12:48 14:00 15:12
Time
V
16:24 17:36 18:48
Flare Stack Sulfur Dioxide 11/5/02
07:00 08:12 09:24
10:36 11:48
Time
13:00 14:12 15:24
Figure 4-4. Flare Stack Sulfur Dioxide Concentrations
4-21
-------
Source Test Report
for Landfill B
25 -,
20 -
Q
Q.
C
O
Concentrat
o 01 o
8
Flare Stack Nitric Oxide (NO) 11/4/02
I
00
Ll
1
Sampli
NO
ng Perod
I,
*
%AAtajLJ
..1,1
TKVNr F WTV WWW|rf^
09:12 10:24 11:36 12:48 14:00 15:12
Time
J
16:24 17:36 18:48
Flare Stack Nitric Oxide (NO) 11/5/02
Q
E ic;
1
c
o
•£ 1 n
HI
o
c
0
o
c;
*a
1
\
(
J
Sampling Period
NO
5,
Hurt!.
(
i PTI
i
kr
V
07:00 08:12 09:24 10:36 11:48 13:00 14:12 15:24
Time
Figure 4-5. Flare Stack Nitric Oxide Concentrations
4-22
-------
Source Test Report
for Landfill B
Q
E
Q_
c
o
TO
r10
0)
o
c
0
Oc
Flare Stack Nitrogen Dioxide (NO2) 1 1/4/02
Sampling Period
NO2
L_
n ii
08:00 09:12 10:24
11:
I
36 12:48 14:00 15:12
Time
16:24 17:36 18:48
25
20
r
c
o
•E10
u
o
c
o
o
Flare Stack Nitrogen Dioxide (NO2) 11/5/02
07:00 08:12 09:24 10:36 11:48 13:00 14:12 15:24
Time
Figure 4-6. Flare Stack Nitrogen Dioxide Concentrations
4-23
-------
Source Test Report
for Landfill B
4.2.2 Hydrogen Chloride (HCI) Emission Results
Flare stack HCI emissions results are presented in Table 4-15.
Table 4-15. Flare Stack Hydrogen Chloride Emissions
Run 1
Run 2
Run 3
Average
HCI Concentrations
(ppmdv)
1.4
1.0
0.9
1.1
(mg/m3)
2.1
1.5
1.4
1.7
HCI Emission Rate
(Ib/hr)
0.16
0.12
0.11
0.13
(g/hr)
72
52
48
57
4.2.2.1 Metals Emissions Results
Toxic heavy metals in the flare stack gases were measured by Method 29. Manganese
was determined by inductively coupled plasma- mass spectroscopy (ICP-MS).
Arsenic (As), Cd, Cr, Pb, and Ni were determined by graphite furnace atomic
absorption spectroscopy (GFAAS). Mercury was determined by cold vapor (CV) AA
and was not detected in any of the samples. Table 4-16 presents the flare stack metals
emissions results.
Mercury (Hg) concentration (elemental) was separately measured by the LUMEX
instrument and those results are also included in Table 4-16.
4-24
-------
Source Test Report
For Landfill B
Table 4-16. Flare Stack Metals Emissions
Analyte
Arsenic
Cadmium
Chromium
Lead
Manganese
Nickel
Mercury
(Total by
method 29)
Mercury
(Elemental
by LUMEX)
B-POST-M29-1 10502-01
Concentration
(jjg/dscm)
0.90
0.24
1.8
0.66
6.4
2.1
<3.9
Emission Rate
(x10^»
g/hr)
34
8.7
67
24.5
240
80
<0.14
(x10%/hr)
74
19
150
54
530
180
<320
RUN1
0.001
.036
0.079
B-POST-M29-1 10502-02
Concentration
(pg/dscm)
<0.80
0.065
1.4
0.62
5.2
1.6
<4.1
Emission Rate
(x10^»
g/hr)
< 0.028
2.3
5.1
22
180
56
<0.15
(x10-«lb/hr)
62
5.1
110
48
410
120
<320
RUN 2
0.004
0.14
0.32
B-POST-M29-1 10502-03
Concentration
(pg/dscm)
0.79
0.25
1.7
0.69
13
1.6
<4.1
Emission Rate
(x10^»
g/hr)
28
8.7
61.3
24.3
470
56
<0.15
(x10-«lb/hr)
62
19
140
54
1000
120
<320
RUN 3
0.005
0.18
0.40
Average
Concentration
(pg/dscm)
0.70
0.18
1.7
0.65
8.3
1.8
ND
Emission Rate
(x10^»
g/hr)
30
6.6
60
23.5
300
64
ND
(x10-«lb/hr)
66
14.5
132
52
660
140
ND
Average
0.0033
0.12
0.26
4-25
-------
Source Test Report
for Landfill B
4.2.2.2 Gaseous Emissions: Carbon Monoxide (CO), Sulfur Dioxide (SCy, and Nitrogen Oxides
(NOX)
Gaseous emissions measured with CEMs include CO, SO2, and NOX. These results are
presented in Table 4-17.
Table 4-17. Flare Stack CO, SO2, NOX Concentrations
Run 1
Run 2
Average
Concentration (ppmdv)
CO
11
13
10
S02a
8
3
6
NOX (as NO) b
10
12
11
System bias = 1-24 percent, Drift check =1-180 percent
Drift check = 0-13 percent
4.3 Comparison with AP-42 Default Values
One of the major objectives of the test program is to expand on the database of LFG
constituent compounds and their concentrations. If warranted, these data may
contribute towards updating the AP-42 default values.
Table 4-18 presents the concentrations of LFG constituents to provide direct
comparisons with AP-42 default values. Table 4-19 presents the concentration of other
constituents targeted by the various analyses but are not listed in AP-42. An expanded
discussion and comparison is included in the overall project summary report.
4-26
-------
Source Test Report
For Landfill B
Table 4-18. Comparison of Raw Landfill Gas Constituent Concentrations with AP-42 Default Values
Method
M40
M40
M40
M40
M40
M-40
M40
M-40
M-40
M40
M40
M40
No Test
M40
M40
M40
M40
M40
Compound
1,1,1-Trichloroe thane
1 ,1 ,2,2-Tetrachloroethane
1,1-Dichloroethane
Ethylidene Dichloride)
1,1-dichloroethene
1 ,2-Dichloroethane
1 ,2-Dichloropropane
Isopropyl alcohol
(2-Propanol)
Acetone
Acrylontrile
Bromodichloromethane
Butane
Carbon Disulfide
Carbon Monoxide
Carbon Tetrachloride
Carbonyl Sulfide
(Carbon oxysulfide)
Chlorobenzene
Chlorodiflouromethane
(Freon 22)
Chloroethane
(Ethyl Chloride)
CAS
Number
71-55-6
79-34-5
75-34-3
75-354
107-06-2
78-87-5
67-63-0
67-64-1
107-13-1
75-27-4
106-97-8
75-15-0
630-08-0
56-23-5
463-58-1
108-90-7
75-45-6
75-00-3
Formula
Wt.
133.42
167.85
98.96
96.94
98.96
112.98
60.11
58.08
53.06
163.83
58.12
76.13
28.01
153.84
60.07
112.56
86.47
64.52
Default
Value
(ppmv)
0.48
1.11
2.35
0.20
0.41
0.18
50.10
7.01
6.33
3.13
5.03
0.58
141.00
0.004
0.49
0.25
1.30
1.25
Detection
Limit
(ppmv)
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.020
0.0002
1
0.0002
0.0002
0.020
0.0002
0.020
0.0002
Measured
Average
(ppmv)
0.031
ND
0.178
0.008
0.005
0.005
0.356
1.61
ND
0.010
3.30
0.134
NM
0.005
ND
0.229
ND
1.88
Concentration
in Inlet LFG
(x10«lb/ft3)
10.7
ND
45.5
2.0
1.3
1.5
55.3
242
ND
4.2
496
26.4
NM
2.0
ND
66.6
ND
314
(|jg/m3)
171
ND
729
32
21
23
886
3870
ND
68
7940
422
NM
32
ND
1070
ND
5020
Mass Flow Rate in Inlet
LFG Stream
(mg/hr)
436
ND
1860
82
52
60
2260
9860
ND
170
20200
1080
NM
81
ND
2720
ND
12800
(xWib/hr)
0.962
ND
4.1
0.18
0.12
0.13
5.0
21.7
ND
0.381
44.6
2.4
NM
0.18
ND
6.0
ND
28.2
4-27
-------
Source Test Report
For Landfill B
Method
M-40
M40
M-40
M40
M40
M40
M-40
M40
No Test
M40
M40
M40
M40
M40
M-40
M-40
M-11
Compound
Chloroform
Chloromethane
1 ,2-Dichlorobenzene
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene
Dichlorodifluoromethane
(Freon 12)
Dichlorofluoromethane
(Freon 21)
Methylene Chloride
(Dichlorome thane)
Dimethyl Sulfide
(Methyl sulfide)
Ethane
Ethanol
Ethyl Mercaptan
(Ethanediol)
Ethylbenzene
1 ,2-Dibromoethane
(Ethylene dibromide)
Trichloromonofluoromethane
(Fluorotrichloromethane) (F11)
Hexane
Hydrogen Sulfide
CAS
Number
67-66-3
74-87-3
95-50-1
541-73-1
106-46-7
75-71-8
75-434
75-09-2
75-18-3
74-84-0
64-17-5
75-08-1
100-414
106-934
75-69-4
110-54-3
7783-064
Formula
Wt.
119.39
50.49
147.01
147.00
147.00
120.91
102.92
84.94
62.13
30.07
46.08
62.13
106.16
187.88
137.38
86.18
34.08
Default
Value
(ppmv)
0.03
1.21
0.21
0.21
0.21
15.70
2.62
14.30
7.82
889.00
27.20
2.28
4.61
0.001
0.76
6.57
35.50
Detection
Limit
(ppmv)
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.020
0.0002
1
0.0002
0.020
0.0002
0.0002
0.0002
0.0002
Measured
Average
(ppmv)
0.190
0.072
0.0004
0.00203
0.255
0.468
ND
0.169
NM
4.6
0.202
ND
2.80
0.007
0.327
1.95
22.9
Concentration
in Inlet LFG
(xWlb/ft3)
58.6
9.4
0.15
0.771
96.9
146
ND
37.1
NM
360
24.1
ND
767
3.4
116
434
0.0020
(Ijg/m3)
939
150
2.4
12.4
1550
2340
ND
594
NM
5730
385
ND
12300
55
1860
6950
32400
Mass Flow Rate in Inlet
LFG Stream
(mg/hr)
2390
390
6.2
31.5
3960
5970
ND
1510
NM
14600
980
ND
31300
140
4740
17700
82500
(x1&3lb/hr)
5.3
0.85
0.014
0.0694
8.7
13.2
ND
3.3
NM
32.2
2.2
ND
69.0
0.306
10.5
39.0
182
4-28
-------
Source Test Report
For Landfill B
Method
Organic
mercury
LUMEX
Organic
mercury
Organic
mercury
M-40
M-40
No Test
M-40
M-40
M-40
M-40
M-40
M-40
M40
M40
Compound
Mercury
(Dimethyl)
Mercury
(Elemental)
Mercury
(Monomethyl)
Mercury
(Total)
2-Butanone
(Methyl Ethyl Ketone)
2-Hexanone
(Methyl Butyl Ketone)
Methyl Mercaptan
(Methanethiol)
Pentane
Tetrachloroethylene
(Perchloroethylene)
Propane
t-1 ,2-Dichloroethene
Trichloroethylene
(Trichloroethene)
Vinyl Chloride
m/p-Xylene
(Dimethyl Benzene)
o-Xylene
(Dimethyl Benzene)
CAS
Number
7439-97-6
78-93-3
591-78-6
74-93-1
109-66-0
127-18-4
74-98-6
156-60-5
79-01-6
75-014
1330-20-7
95-47-6
Formula
Wt.
230.66
200.61
215.62
215.63
72.10
100.16
48.11
72.15
165.83
44.09
96.94
131.38
62.50
106.16
106.16
Default
Value
(ppmv)
Not
Listed
Not
Listed
Not
Listed
2.53E-04
7.09
1.87
2.49
3.29
3.73
11.10
2.84
2.82
7.34
12.10
12.10
Detection
Limit
(ppmv)
0.05E-06
0.014E-06
6E-06
0.0002
0.0002
1
0.0002
1
0.0002
0.0002
0.0002
0.0002
0.0002
Measured
Average
(ppmv)
R
7.0E-6
.134E-6
22.8E-6
1.43
0.441
NM
2.60
0.176
5.9
0.009
0.103
0.410
3.98
1.41
Concentration
in Inlet LFG
(xWlb/ft3)
R
0.0036
0.0000747
0.0127
267
114
NM
485
75.4
670
2.3
35.0
66.2
1100
388
(Ijg/m3)
R
0.058
0.00120
0.204
4280
1830
NM
7770
1210
10800
36
560
1060
17500
6210
Mass Flow Rate in Inlet
LFG Stream
(mg/hr)
R
0.15
0.00305
0.52
10900
4660
NM
19800
3080
27500
92
1430
2700
44600
15800
(x1&3lb/hr)
R
0.000326
0.0000067
0.00114
24.0
10.3
NM
43.6
6.8
60.5
0.20
3.1
6.0
98.2
34.9
4-29
-------
Source Test Report
For Landfill B
Method
M40
M40
M-25C
M-25C
M-40
M-40
Compound
Benzene
(Co-disposal)
Benzene
(No-disposal or Unknown)
NMOC as Hexane
(Co-disposal)
NMOC as Hexane
(No-codispoal or Unknown)
Toluene
(Methyl Benzen)
(Co-disposal)
Toluene
(Methyl Benzene)
(No or Unknown)
CAS
Number
71-43-2
71-43-2
108-88-3
Formula
Wt.
78.11
78.11
86.17
92.13
Default
Value
(ppmv)
11.10
1.91
2420.00
595
165.00
39.30
Detection
Limit
(ppmv)
0.0002
0.0002
0.0002
0.0002
Measured
Average
(ppmv)
0.251
0.251
355
355
6.77
6.77
Concentration
in Inlet LFG
(xWlb/ft3)
50.7
50.7
79100
79100
1600
1600
(Ijg/m3)
812
812
1270000
1270000
25800
25800
Mass Flow Rate in Inlet
LFG Stream
(mg/hr)
2070
2070
3230000
3230000
65800
65800
(x1&3lb/hr)
4.6
4.6
7.1
7.1
145
145
R - Data were rejected because of serious deficiency in spike recovery
4-30
-------
Source Test Report
For Landfill B
Table 4-19. Raw Landfill Gas Constituent Concentrations for Compounds without AP-42 Default Values
Method
M-0100
M-0100
M-23
M-23
M-25C
M-25C
M-25C
M40
M40
M40
M40
M40
M40
M40
M40
M40
M40
Compound
Acetaldehyde
Formaldehyde
Dioxins/Furans
PAHs
Carbon Dioxide
Methane
Oxygen
1 ,1 ,2,3,4 ,4-Hexachloro-1 ,3-butediene
1 ,1 ,2-Trichloro-1 ,2,2-trifluoroethane
(CFC113)
1,1,2-Trichloroethane
1 ,2,4-Trichlorobenzene
1 ,2,4-Trimethylbenzene
1 ,2-Chloro-,1 ,2,2-Tetrafluoroethane
(CFC114)
1 ,3,5-Trimethylbenzene
1 ,3-Butadiene
(Vinylethylene)
1 ,4-Dioxane
(1 ,4-Diethylene Dioxide)
1 -Ethyl-4-methylbenzene
(4-Ethyl Toluene)
CAS
Number
75-07-0
50-00-0
124-38-9
74-82-8
778244-7
87-68-3
76-13-1
79-00-5
120-82-1
95-63-6
76-14-2
108-67-8
106-99-0
123-91-1
622-96-8
Formula
Wt.
44.05
30.03
44.01
16.04
32.00
260.76
187.38
133.42
181.46
120.19
170.92
120.19
54.09
88.10
120.20
Detection
Limit
(ppmv)
0.0023
0.0017
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
Measured
Average
(ppmv)
0.015
0.0029
NM
NM
307000
392000
64000
0.005
0.011
0.039
0.00503
0.95
0.044
0.386
0.089
0.009
0.386
Concentration in Inlet LFG
(xlf^lb/ft3)
1.7
0.23
NM
NM
34900000
16300000
5300000
3.4
5.3
14
2.4
290
19
120
12
2.1
120
(MgAn3)
27
3.6
NM
NM
559000000
260000000
85000000
54
85
220
38
4700
310
1920
200
34
1920
Mass Flow Rate in Inlet LFG
Stream
(mg/hr)
69
9.3
NM
NM
1430000000
663000000
220000000
140
220
550
96
12000
790
4900
510
87
4900
(xKHIWhr)
0.15
0.020
NM
NM
3100000
1500000
476400
0.30
0.48
1.2
0.21
27
1.7
10.8
1.1
0.19
10.8
4-31
-------
Source Test Report
For Landfill B
Method
M40
M40
M40
M40
M40
M40
M40
M-40
M40
M40
M40
M40
M40
M40
M-40
Compound
4-Methyl-2-pentanone
(MIBK)
Benzyl Chloride
(Chloromethyl Benzene)
Bromomethane
(Methyl bromide)
cis-1 ,2-Dichloroethene
cis-1 ,3-Dichloropropene
Cyclohexane
Dibromochloromethane
Ethyl Acetate
Heptane
Methyl-t-butyl Ether
(MTBE)
Styrene
(Vinylbenzene)
t-1 ,3-Dichloropropene
Tetrahydrofuran
(Diethylene Oxide)
Tribromomethane
(Bromoform)
Vinyl Acetate
CAS
Number
108-10-1
10044-7
74-83-9
156-59-2
10061-01-5
110-82-7
124-48-1
141-78-6
142-82-5
1634-044
100-42-5
1006-02-6
109-99-9
75-25-2
108-05-4
Formula
Wt.
100.16
126.58
94.95
96.94
110.98
84.16
208.29
88.10
100.20
88.15
104.14
110.98
72.10
252.77
86.09
Detection
Limit
(ppmv)
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
0.0002
Measured
Average
(ppmv)
0.89
0.020
0.046
0.292
0.0014
0.734
0.0160
2.31
0.92
0.177
0.222
0.003
0.88
ND
0.686
Concentration in Inlet LFG
(xlf^lb/ft3)
230
6.5
11
73.2
0.39
160
8.6
526
240
40.3
59.8
0.86
164
ND
153
(MgMi3)
3700
110
180
1170
6.3
2560
138
8430
3800
646
957
14
2630
ND
2450
Mass Flow Rate in Inlet LFG
Stream
(mg/hr)
9400
270
460
2990
16
6520
352
21500
9700
1650
2440
35
6710
ND
6230
0(10* Ib/hr)
21
0.59
1.0
6.6
0.035
14.4
0.775
47.4
21
3.6
5.4
0.078
14.8
ND
13.7
4-32
-------
Source Test Report
for Landfill B
5. Quality Assurance/Quality Control
This project produced data that qualified to receive the "A" rating with respect to the
rating system described in section 4.4.2 of the Procedures for preparing Emission
Factor Documents (EPA-454/R-95-015). The cited EPA document provides a clear
description of the requirements for an "A" data quality rating. Tests were performed by
using an EPA reference test method, or when not applicable, a sound methodology.
Tests were reported in enough detail for adequate validation and raw data were
provided that could be used to duplicate the emission results presented in this report.
Throughout the results sections of this report, notations and footnotes were included to
flag data that, for various reasons, did not meet their associated measurement quality
objectives.
5.1 Assessment of Measurement Quality Objectives (MQOs)
Measurement quality objectives (MQOs) were established for each critical
measurement and documented in the Site-Specific QAPPfor the Field Evaluation of
Landfill Gas Control Technologies-Landfill B. The following subsections assess
MQOs for each measurement to determine if goals were achieved. When applicable,
data validation elements performed on laboratory analytical reports are also included.
5.1.1 Continuous Emissions Monitors (CEMs)
Combustion produced gases O2, CO, CO2, SO2, NOX and THC were measured in the
field using CEMs. The following MQOs were established for CEM measurements for
Landfill B:
• Direct calibration bias: ±2 percent
• System bias checks: ±5 percent
• Zero and drift: ±3 percent
• Completeness: >90 percent
Direct calibrations were performed daily prior to testing, with certified calibration
gases at zero and a minimum of two other concentrations (typically a mid-level
concentration and one point towards the full-scale end of the instrument range).
System bias checks were performed pre-test and post-test. Drift checks were
performed daily, post-test. Table 5-1 summarizes these quality control (QC) checks for
all instruments. Not all MQOs were met for all CEM measurements. The SO2 analyzer
5-1
-------
Source Test Report
for Landfill B
exhibited excessive bias (1 to 24 percent) and drift (1 to 180 percent). The NOX
instrument also exhibited slightly elevated drift (0 to 13 percent). The other
instruments performed well and within the QAPP-specified criteria. The fact that the
original QAPP MQOs were not fully met is not believed to affect the usability of these
data. Results that did not meet the specified MQOs were presented with the
appropriate notations.
Table 5-1. Continuous Emissions Monitor Measurement Quality Objectives Summary for
Landfill B
Instrument and
Range
Servomex O2
Analyzer (0-21%)
Cal Analytical CO2
Analyzer (0-20%)
Cal Analytical CO
Analyzer (0-650
ppm)
Cal Analytical SO2
Analyzer (0-500
ppm)
TECO NOX
Analyzer (0^000
ppm)
TECO THC
Analyzer (0-1 000
ppm)
Direct Calibration
(±2% criteria)
Total
(#)
6
6
8
8
6
NAa
Bias
Range
(%)
0-0
0-2.2
0-0
0.0-1.0
0-2
NAa
Complete
(%)
100
67
100
100
100
NAa
System Bias Checks
(±5% criteria)
Total
(#)
4
4
2
2
2
8
Bias
Range
(%)
0-3.3
0-3.3
0.7-2.0
1-24
1-3
0-3
Complete
(%)
100
100
100
50
100
100
Drift Checks
(±3% criteria)
Total
(#)
4
4
4
4
4
4
Bias
Range
(%)
0-3.3
0-2.2
0-1.1
1-180
0-13
1.1 -4
Complete
(%)
75
100
100
50
50
50
aThe method called for calibration gases to be introduced at a point of the sampling system close to the sampling
probe for them to flow through the heated sample line. Calibration gases were not injected directly to the analyzer
5.1.2 Carbonyls (Method TO-11)
The following MQOs were established in the QAPP for this method:
• Recovery (formaldehyde): 5 0-15 0 percent
• Precision: ±20 percent relative standard deviation (RSD)
5-2
-------
Source Test Report
for Landfill B
• Completeness: >90 percent
Four samples (including three raw LFG samples and one field blank) were submitted
to Resolution Analytics for formaldehyde and acetaldehyde determination. Results
were reported in RFA# 992014. The report included information on instrument
calibration and internal QC checks. Samples collected on November 4 and 5, 2002,
were received by the laboratory on November 14, 2002 and analyzed on November 22,
2002. That met the 30-day hold-time limitation. Analytical detection limits were
reported as 13 ppb for formaldehyde and 26 ppb for acetaldehyde in the sample
extracts. Based on a 5 ml extract, the detection limits were 65 ng for formaldehyde and
130 ng for acetaldehyde. Based on sample volumes ranging from 32 to 42 1 at standard
conditions, the MDLs were 1.3 ppb for formaldehyde and 1.7 ppb for acetaldehyde.
The field blank did not have detectable levels of acetaldehyde and showed 0.070(ig
formaldehyde detected. To assess accuracy, an external performance evaluation audit
sample containing 0.25 ppm formaldehyde and acetaldehyde was analyzed with the
sample set. Recovery was 101.6 percent for formaldehyde and 96.3 percent for
acetaldehyde, which meets the 50-150 percent MQO. One project sample was injected
in duplicate and the percent drift (%D) range for formaldehyde was 4.3 percent and for
acetaldehyde was 5.4 percent. All MQOs were met for this method for a completeness
of 100 percent.
5.1.3 Hydrogen Sulfide (H2S) (EPA Method 11)
The following MQOs were established in the Landfill B QAPP for this method:
• Accuracy: ±5 percent bias
• Precision: ±5 percent RSD
• Completeness: >90 percent
Eight samples (including three reagent blanks and one field blank) plus two laboratory
in-house reagent blanks were submitted to Oxford Laboratories for H2S analysis by
EPA Method 11. The samples were collected on November 5, 2002, submitted to the
laboratory on November 14, 2002, and the results report was dated November 22,
2002. Therefore the analysis met the 30-day hold time criteria.
The field blank submitted did not have quantifiable concentrations of H2S. A
laboratory spike was performed and the recovery was 101 percent. The three test
samples produced results of similar concentrations. Duplicate analysis of a sample
within the same batch of samples resulted in 1.7 percent RSD. Spike recovery for the
5-3
-------
Source Test Report
for Landfill B
Run #1 samples was 101 percent. All MQOs were met for this method for a
completeness of 100 percent.
5.1.4 Dioxins and Furans (PCDD/PCDFs) (EPA Method 23)
The following MQOs were established in the QAPP for this method:
• Recovery: 50-150 percent
• Completeness: >90 percent
Four sample sets (including one set of reagent blank and sample train rinsates) were
submitted to ALTA Analytical Perspectives for PCDD/PCDFs analysis. The samples
were collected on November 4, 2002, and delivered to the laboratory on November 14,
2002. The samples were extracted on November 20, 2002 and analyzed on November
27, 2002. This met the 14-day hold-time for extraction and 40-day hold time for
analysis.
The field blank did not have detectable levels of the target analytes. Detection limits
for the various congeners were in the single-digit picogram level. To assess accuracy,
each sample train was spiked with standard Method 23 spiking compounds and
analysis of the samples yielded extraction standard (ES) recovery from 84 to 99
percent. Recovery of sampling standards (SS) ranged from 106 to 108 percent. These
recoveries are well within the 50-150 percent MQO.
Because a decision was made to analyze only one of the three sample extracts, the
completeness goal of 90% was not achieved. However, all other MQOs were met for
this method.
5.1.5 Polycyclic Aromatic Hydrocarbons (PAHs) (EPA Method 23/0011)
5.1.5.1 Raw Landfill Gas (LFG) Samples
Three sets of samples were sent to ALTA Analytical Perspectives for PAH analysis.
The Method 23 samples collected from the raw LFG could not be concentrated below
750 to 1000 (iL. The produced cleaned-up extracts contained gasoline-like
hydrocarbons and prevented the preparation of final extracts of PAH analysis.
No results were reported. Therefore, the MQOs for this sample group were 0 percent
complete.
5-4
-------
Source Test Report
for Landfill B
5.1.5.2 Flare Stack Samples
The following MQOs were established in the QAPP for this method:
• Recovery: 50-150 percent
• Completeness: >90 percent
Four samples (including one reagent blank) collected from the flare stack were
submitted to ALTA Analytical Perspectives for PAH analysis. The report included
information on instrument calibration and internal QC checks. Samples collected on
November 4, 2002 were received by the laboratory on November 14, 2002. These
were extracted on November 20, 2002 and analyzed on January 9, 2003. This met the
14-day hold-time for extraction but missed the analysis 40-day hold time by 10 days.
The results were reported with notation of this hold-time exceedance.
Analysis of the field blank yielded detectable but low levels of a few of the target
compounds with all PAH analytes totaling to 15762 ng. In contrast, the test samples
showed total PAH level of 113974 ng. Recovery of ES ranged from 65 to 124 percent.
Recoveries of SS, di0-fluorene and di4-terphenyl were not reported. Recovery of the
alternative standard (AS) dio-anthracene was 57.9 percent. The reported recoveries
were within the 50 to 150 percent MQO.
Because a decision was made to analyze only one of the three sample extracts, the
completeness goal of 90% was not achieved. However, all other MQOs were met for
this method.
5.1.6 Polychlorinated Biphenyls (PCBs)
The same Method 23 samples collected from the raw LFG were earmarked for analysis
for PCBs. Since the cleaned up extracts could not be concentrated below 750 to
1000 (iL because of the presence of gasoline-like hydrocarbons, final extracts could
not be prepared for the planned PCB analysis. No PCBs results were reported.
Therefore the MQO for this sample group was 0 percent complete.
5.1.7 Non-Methane Organic Compounds (NMOCs) (Method 25C)
The following MQOs were established in the QAPP for Landfill B:
• Recovery: 50 to 150 percent
5-5
-------
Source Test Report
for Landfill B
• Precision: ±30 percent RSD
• Completeness: >90 percent
Four canister samples (including a field blank) were submitted from Landfill B for
NMOC analysis by Method 25-C to Triangle Environmental Services. The samples
were collected on November 4, 2002, submitted on December 3, 2002, and analyzed
between December 3 and 23, 2002. Therefore the analysis did not meet the 30 day
hold time requirements. The apparent delay in sample delivery was partly attributed to
the fact that the same canisters had to be analyzed by RTF Laboratory for volatile
organics first. The impact of exceeding the prescribed 30-day hold time by up to 19
days is unknown. The results were reported with a notation of the hold-time
exceedances.
The laboratory report included information on instrument calibration and internal QC
checks.
NMOC in the field blank was at 8.5 ppmv as hexane. Accuracy for the method was
assessed by evaluating results of response factor check samples that were run prior to
and following sample analysis. Acceptance criteria established by the method is that
the response factor (RF) must be within 10 percent of the response factor from initial
calibration. All response factor checks ranged from 0.9 to 7.4 percent of the initial
calibration, well within the 10 percent acceptance criteria. The %D between the pre
and post-test checks were less than 2 percent, ranging from 0.5 to 1.2 percent. Samples
were run in triplicate and all %RSD for samples were less than 3.4 percent.
All MQOs were met for this method for a completeness of 100 percent.
5.1.8 Hydrogen Chloride (HCI) (EPA Method 26A)
The following MQOs were established in the QAPP for Landfill B:
• Accuracy: ±10 percent bias
• Precision: ±10 percent RSD
• Completeness: >90 percent
Four samples (including one field blank) were submitted to Resolution Analytics for
HCI and chlorine (C12) determination. The results were reported in RFA# 992014. The
report included information on instrument calibration and internal QC checks. Samples
were collected on November 4, 2002. These were received by the laboratory on
5-6
-------
Source Test Report
for Landfill B
November 14, 2002, and analyzed on November 27, 2002, which met the 4 week hold-
time requirement. Analytical detection limits were reported as 0.41 ppm HC1.
The field blank did not contain detectable levels of HC1. In-house audit samples were
analyzed with each respective group of field samples and the measured concentrations
fell within method criteria of 10 percent of their expected values.
A matrix spike was performed on a sample (B POSST-01) that was apart of this
sample batch. An 0.8 ml sample was spiked with 0.8 ml of standard (50 ppm chloride)
and analyzed in duplicate. The laboratory reported 97.1 percent recovery of the HC1
spike with a 0.02 percent deviation in duplicate injections. This meets the MQO of ±10
percent with very good precision. Calculated bias for internal QC check was <2.2
percent. All MQOs were met for 100 percent completeness.
5.1.9 Metals (EPA Method 29)
The following MQOs were established in the Landfill B QAPP for this method:
• Accuracy: ±25 percent bias
• Precision: ±20 percent RSD
• Completeness: >90 percent
Four sets of Method 29 Multi-Metal trains (including one field blank) were submitted
to First Analytical Laboratories for As, Cd, Cr, Pb, Mn, Hg, and Ni determination.
Results were reported in Project #21110. The report included information on
instrument calibration and internal QC checks. Samples were collected on November 4
and 5, 2002, received by the laboratory on November 12, 2002, and analyzed on
November 14, 2002, which met the 14 day hold-time requirement. Method detection
limits for each of the target metals were reported as follows:
• As = 5.0 (ig/L
• Cd = 0.2(ig/L
• Cr = 5.0(ig/L
• Pb = 5.0(ig/L
• Mn =5 (ig/L
5-7
-------
Source Test Report
for Landfill B
• Ni = 10(ig/L
• Hg = 0.2ng/L
Traces of Cr, Mn and Ni were found in the blanks, which is not unusual.
All samples were spiked prior to analysis. Spike recoveries ranged from 82 to 110
percent and were within the acceptable range of 75-125 percent. In addition to spiking
the samples, for each metal, internal calibration verification samples (ICVs) and
continuing calibration verification samples (CCVs) were performed. ICVs were run at
the beginning of each run set and CCVs were run at a frequency of one for every 10
samples. ICV and CCV measured values were all 90 percent
Total Hg analysis was performed by Frontier Geosciences. Four total Hg samples
(including a field blank) were taken at Landfill B. Samples were collected on
November 4, 2002 and analyzed in December 2002. That analysis schedule exceeded
the 14-day hold-time specified in the QAPP. All other quality assurance measures
indicated that the analysis of the traps were under good control. All field blanks were
consistent with historical values and indicate the detection limit is likely to be at or
below the previous estimated value of 50 ng/m3. Spike recoveries were 95.4 and 95.2
percent; and relative percent difference (RPD) between replicates was 6.2 percent,
which meets MQOs and are therefore 100 percent complete. The exceedance of 14-day
hold times was noted in the reported results.
Five monomethyl Hg (MMHg) samples (including a field blank and field spike) were
collected on November 5, 2002. These samples were analyzed December 2005 which
exceeded the 14-day hold-time. Analysis of these samples was under good control with
acceptable distillation spike recoveries and distillation duplicates. All CCVs had
acceptable recoveries. Field spike recovery was 70 percent and matrix spike recovery
was 116 percent, which met MQOs. The exceedance of 14-day hold times was noted
in the reported results.
5-8
-------
Source Test Report
for Landfill B
Five dimethyl Hg (DMHg) samples (including a field blank and field spike) were
collected on November 4, 2002. Analysis of these samples took place in December
2002 and did not meet the 14-day hold-time. Field spike recoveries for all DMHg
analysis were consistently low 0-5 percent. With the extremely low recovery, DMHg
concentrations are considered biased low and the degree of bias is significant. QA
measures in place support the following conclusions:
• Replicate samples taken at each site report similar concentrations which indicated
that the properties of the DMHg sampling train and LFG were consistent and
biases were not attributable to trap media or landfill sample gas.
• Continuous calibration verifications (CCVs) used during the analysis indicated
that the detection systems were measuring accurately.
• Dimethyl Hg (DMHg) field blanks indicated that the trap media, handling
procedures, and analytical techniques did not contribute to the problems with
recovery.
• Trip spikes (traps spike in the laboratory, shipped to the field but not used for
sampling) indicated that the laboratory standards, trap media, and trap handling
procedures did not create significant bias.
• Field spikes (traps spiked in the laboratory and used to collect a replicate sample)
indicated that some property or action during sampling either destroyed or evaded
the DMHg adsorbed to the Carbotrap
The RSD between the three replicate samples was 23.9 percent, which meets the MQO
of ±30 percent, but because recovery MQOs were not met for any of the field spikes,
DMHg analysis was 0 percent complete. The exceedance of 14-day hold times was
noted in the reported results. The results were categorized as "R" to indicate that the
results were rejected due to serious deficiencies as per EPA QA/G-8 Guidance.
5.1.11 Volatile Organic Compounds (VOCs) and Methane (CH4) (Method TO-15)
The following MQOs were established in the Landfill B QAPP for this method:
• Accuracy: 50-150 percent recovery
• Precision: ±30 percent RSD
• Completeness: >90 percent
5-9
-------
Source Test Report
for Landfill B
Four SUMMA canisters (including one field blank) were submitted from Landfill B to
RTF Laboratories for VOC and CFL, determination by EPA Method TO-15. Results
were reported in Project #347-02. Samples were collected on November 2, 2002 and
analysis was completed by November 27, 2002, which met the 30 day hold-time
requirement.
Analysis of the field blank found 3.03 ppbv of acetone and 1.24 ppbv of methylene
chloride. Table 5-2 lists the compounds that were found above the detection limit of
0.2 ppbv. Other target analytes were not detected. The average test sample
concentrations were significantly higher than the concentrations in the blank sample.
Therefore, the presence of these analytes in the blank sample did not affect the
conclusions that were drawn from these VOC data. Nonethelss, the results were
reported with the appropriate notations.
The summa canister of the Run #3 sample was spiked to 213 ppbv of chlorobenzene.
The recovery of chlorobenzene was 211 percent and was outside of the established
criteria. This out-of-criteria spike recovery was noted in the reported results.
Precision was demonstrated through multiple injections of standards at five
concentration levels. The RSD between the calculated relative response factors (RRF)
must be <30 percent with allowances that two may be >40 percent. The average RSD
was 10.18 percent and method criteria were met for all compounds except methylene
chloride with an RSD of 37.9 percent. Results for this compound are flagged as
estimated, "J". Valid data was received for all SUMMA canisters submitted, and these
analyses were considered to be 100 percent complete.
5.2 Audits
This project was designated as Quality Assurance (QA) Category II effort. Hence,
audits were required. The internal and external audits performed for this project were
completed and their findings were included in a separate report for Landfill D of this
project.
5-10
-------
Source Test Report
for Landfill B
Table 5-2. VOC detected in Method 40 Blank Sample and Test Samples
Compound
Vinyl chloride
1 ,3-Butadiene
Bromomethane
Isopropyl alcohol
Methylene chloride
Acetone
Benzene
Toluene
4-Methyl-2-pentanone (MIBK)
1 ,2,4-trimethylbenzene
1 ,4-dichlorobenzene
1,1 ,2,3,4,4-hexachloro-l ,3-butadiene
1 ,2,4-trichlorobenzene
Concentration,
(ppbv)
0.27
0.41
0.92
0.26
1.24
3.03
0.21
0.21
0.25
0.22
0.21
0.5
0.34
Average
Concentration in
Test Samples
(ppbv)
410
89
45
356
169
1610
251
6770
886
949
255
5
5
5-11
-------
Source Test Report
for Landfill B
This page intentionally left blank
5-12
-------
Field Test Measurements at Five Municipal Solid
Waste Landfills with Landfill Gas Control Technology
Final Report
Appendix C
SOURCE TEST REPORT
FOR LANDFILL C
-------
Table of Contents
Acronym List vii
1. Introduction 1-1
2. Landfill Facility Descriptions 2-1
2.1 Landfill Gas (LFG) Destruction Process Description and Operation 2-1
2.2 Control Equipment Description 2-1
2.3 Excess Landfill Gas (LFG) Flare 2-1
2.4 Landfill Gas (LFG) Sampling Locations 2-1
2.4.1 Landfill Gas (LFG) Header Pipe 2-2
2.4.2 Engine #1 Stack 2-2
3. Test Operations 3-1
3.1 Test Team 3-1
3.2 Test Log 3-1
3.2.1 Planned Test Sample Matrices 3-1
3.2.2 Landfill Gas (LFG) Pipe (Inlet) 3-2
3.2.3 Engine Stack 3-5
3.3 Field Test Changes and Deviations from Quality Assurance Project Plan
(QAPP) Specifications 3-9
3.3.1 Variation from Test Methods or Planned Activities 3-9
3.3.2 Application of Test Methods 3-10
3.3.3 Test Method Exceptions 3-11
4. Presentation of Test Results 4-1
4.1 Raw Landfill Gas (LFG) Results 4-1
4.1.1 Raw Landfill Gas (LFG) Flow Rate and Temperature 4-1
4.1.2 Raw Landfill Gas (LFG) Constituents 4-2
4.2 Engine Stack Results 4-9
4.2.1 Engine Stack Gas Flow Rate and Temperature 4-9
-------
Table of Contents
4.2.2 Engine Stack Gas Constituents 4-11
4.3 Comparison with AP-42 Values 4-19
5. Quality Assurance/Quality Control (QA/QC) 5-1
5.1 Assessment of Measurement Quality Objectives 5-1
5.1.1 Continuous Emissions Monitors (CEMs) 5-1
5.1.2 Carbonyls (SW-846 Method 8315A) 5-3
5.1.3 Hydrogen Sulfide (H2S) (EPA Method 11) 5-3
5.1.4 Dioxins and Furans (PCDD/PCDFs) (EPA Method 23/0011) 5-4
5.1.5 Polycyclic Aromatic Hydrocarbons (PAHs) (CARB 429) 5-4
5.1.6 Non-Methane Organic Compounds (NMOCs) (Method 25C) 5-5
5.1.7 Hydrogen Chloride (HCI) (EPA Method 26A) 5-7
5.1.8 Metals (EPA Method 29) 5-7
5.1.9 Total Mercury (Hg) and Organo-mercury (Hg) (Frontier) 5-9
5.1.10 Volatile Organic Compounds (VOCs) and Methane (CH4) (Method
0040/MethodTO-15) 5-10
5.2 Audits 5-11
5.2.1 EPA Technical Systems Audit 5-11
5.2.2 Laboratory Audits 5-14
-------
Table of Contents
Tables
Table 3-1. Test Team Members and Responsibilities 3-1
Table 3-2. Target Analytes for the Raw Landfill Gas Stream 3-2
Table 3-3. Target Analytes for the Engine Stack Gas Stream 3-3
Table 3-4. Raw Landfill Gas Sample Log and Collection Times 3-4
Table 3-5. Engine Stack Test Sample Log and Collection Times 3-7
Table 3-6. Sampling Methods 3-10
Table 4-1. Raw Landfill Gas VOC Concentrations 4-2
Table 4-2. Raw Landfill Gas Non-Methane Organic Compound (NMOC)
Concentrations 4-5
Table 4-3. Raw Landfill Gas Hydrogen Sulfide (H2S) Concentrations 4-6
Table 4-4. Raw Landfill Gas Carbonyls Concentrations 4-6
Table 4-5. Raw Landfill Gas Total Mercury Concentrations 4-7
Table 4-6. Raw Landfill Gas Dimethyl Mercury Concentrations 4-8
Table 4-7. Raw Landfill Gas Monomethyl Mercury Concentrations 4-8
Table 4-8. Raw Landfill Gas Elemental Mercury Concentrations 4-9
Table 4-9. Engine Stack Gas Operating Conditions Measured during Sampling 4-10
Table 4-10. Engine Stack Combustion Product Concentrations 4-11
Table 4-11. Engine Stack THC Concentrations 4-14
Table 4-12. Engine Stack Dioxins and Furans Emissions 4-15
Table 4-13. Engine Stack Dioxins and Furans Toxicity Equivalent Emissions 4-17
Table 4-14. Engine Stack Polycyclic Aromatic Hydrocarbons Emissions 4-20
Table 4-15. Engine Stack Hydrogen Chloride (HCI) Emissions 4-21
Table 4-16. Engine Stack Metals Emissions 4-21
Table 4-17. Engine Stack CO, SO2, NOX Concentrations 4-22
Table 4-18. Comparison of Raw Landfill Gas Constituent Concentrations with AP-42
Values 4-25
Table 4-19. Raw Landfill Gas Constituent Concentrations for Compounds without AP-
42 Values 4-28
Table 5-1. Continuous Emissions Monitor (CEM) Measurement Quality Objectives
(MQO) Summary for Landfill C 5-2
Table 5-2. Amounts of Polycyclic Aromatic Hydrocarbons in Blank Samples and Test
Samples 5-6
Table 5-3. VOCs Identified in Field Blank 5-11
Table 5-3. Total Mercury PEA Results 5-18
-------
Table of Contents
Table 5-4.
Table 5-5.
MMHg PEA Results
DMHg PEA Results
5-18
5-19
Figures
Figure 2-1. Simplified Engine and Flare Process Flow Diagram and Sampling Points 2-2
Figure 2-2. Raw Landfill Gas Collection Pipe 2-3
Figure 2-3. Engine/Generator Set #1 2-3
Figure 2-4. Engine Stack Dimension and Sampling Traverse Locations 2-4
Figure 3-1. Sampling Operations at the Raw Landfill Gas Pipe Inlet 3-3
Figure 3-2. Engine #1 Stack and Sampling Scaffold 3-6
Figure4-1. Engine Stack Oxygen and Carbon Dioxide Concentrations 4-12
Figure 4-2. Engine Stack Total Hydrocarbon Concentrations 4-13
Figure 4-3. Engine Stack Carbon Monoxide Concentrations 4-22
Figure 4-4. Engine Stack Sulfur Dioxide Concentrations 4-23
Figure 4-5. Engine Stack Nitric Oxide Concentrations 4-24
IV
-------
Table of Contents
Appendices
A. Method TO-15 (VOCs, TICs, C2, C3, C4, C5, C6)
B. Method 25C (CH4, CO2, NMOC)
C. Method 3C (O2, N2, CH4, CO2)
D. Method TO-11 (Formaldehyde, Acetaldehyde)
E. Organic mercury Method (Mercury, Total, Monomethyl, Dimethyl)
F. LUMEX (Elemental Mercury)
G. Hydrogen Sulfide
H. Continuous Emission Monitor (Data and Charts)
I. Method 23 (PAH)
J. Method 23 (PCDD/PCDF)
K. Method 23 (PAH, PCDD/PCDF)
L Method 29 (Metals)
M. Method 26A(HCI)
N. Analyte Concentration and Mass Flow Rate Computation Worksheets
P. Raw Field Data Records
Q. CEM Calibration Records and Span Gas Certification
R. Sampling Control Meter Boxes Calibration Record
-------
Acronym List
This page intentionally left blank
VI
-------
Acronym List
Acronym List
%D
AP-42
APPCD
ARCADIS
As
CCVs
Cd
CEMS
CH4
C12
CO
CO2
Cr
DMHg
EF
EPA
ES
FID
Frontier
GC/MS
HC1
Hg
H2S
ICVs
LFG
MMHg
Mn
MQOs
Percent difference
Compilation of Air Pollutant Emission Factors
Air Pollution Prevention Control Division
ARCADIS G&M, Inc.
Arsenic
Continuing calibration verification samples
Cadmium
Continuous emission monitoring system
Methane
Chlorine
Carbon monoxide
Carbon dioxide
Chromium
Dimethyl mercury
Efficiency factor
US Environmental Protection Agency
Extraction standards
Flame ionization detector
Frontier Geosciences
Gas chromatograph/mass spectrometer
Hydrogen chloride
Mercury
Hydrogen sulfide
Internal calibration verification samples
Landfill gas
Monomethyl mercury
Manganese
Measurement quality objectives
VII
-------
Acronym List
MSW Municipal solid waste
Ni Nickel
NIST National Institute of Standards and Technology
NMOCs Non-methane organic compounds
NOX Nitrogen oxides
O2 Oxygen
PAHs Polynuclear aromatic hydrocarbons
Pb Lead
PEA Performance evaluation audit
QA Quality Assurance
QAPP Quality Assurance Project Plan
QC Quality control
RF Response factor
RPD Relative percent difference
RRF Relative response factors
RSD Relative standard deviation
RTP Research Triangle Park
SO2 Sulfur dioxide
SOPs Standard operating procedures
SVOC Semi-volatile organic compounds
TCDD/TCDFs Dioxins/furans
TEQ Toxicity Equivalent
THCs Total hydrocarbons
TICs Tentatively identified compounds
TSA Technical systems audit
VOCs Volatile organic compounds
VIM
-------
Source Test Report
for Landfill C
1. Introduction
Large municipal solid waste (MSW) landfills are subject to Clean Air Act regulations
because of concerns related to their emissions and their potential adverse effects to human
health and the environment. Landfills are listed as a source of air toxics in the Urban Air
Toxics Strategy for future evaluation of residual risk. Existing emission factors for landfill
gas (LFG) were largely developed using data from the 1980s and early 1990s. A database
was developed summarizing data from approximately 1,200 landfills, along with emissions
information from literature and test reports prepared by state and local government agencies
and industry. These data were summarized in Compilation of Air Pollutant Emission
Factors (AP-42), Chapter 2.4. The final rule and guidelines are contained in 40 CFR Parts
51, 52, and 60, Standards of Performance for New Stationary Sources and Guidelines for
Control of Existing Sources: Municipal Solid Waste Landfills.
The overall purpose of this testing program was to generate data to be used to update AP-42
and include data that reflect current waste management operating practices. This report
presents the results of a field test conducted at Landfill C. Testing took place on May 13
and 14, 2004.
The site uses two internal combustion engine/electric generator sets to reclaim the energy
content in the landfill gas. A standby enclosed flare is used for the destruction of any excess
landfill gases not consumed by the engine/generator-sets. A more detailed description of
the engine system is presented in Section 2. The specific purpose of the testing program
was to determine the gas concentrations in the landfill gas pipe leading to the engines and
the enclosed flare, and gas emissions from the stack of one of the engines. The pollutants of
interest for the raw untreated landfill gas were volatile organic compounds (VOCs), non-
methane organic compounds (NMOCs), hydrogen sulfide (H2S), carbonyls (acetaldehyde,
formaldehyde), and mercury (Hg) compounds. The pollutants of interest for the treated
LFG, in this case at the engine stack, were carbon monoxide (CO), nitrogen oxides (NOX),
sulfur dioxide (SO2), NMOCs as total hydrocarbons (THCs), hydrogen chloride (HC1),
dioxins/furans (PCDD/PCDFs), polycyclic aromatic hydrocarbons (PAHs), total Hg, and
metals.
ARCADIS G&M, Inc. (ARCADIS), as contractor to the US Environmental Protection
Agency's (EPA) Air Pollution Prevention and Control Division (APPCD), performed this
work under Work Assignment 0-27 of the Onsite Laboratory Support Contract. The testing
activities followed the specifications of the approved "Site-Specific Quality Assurance
Project Plan for the Field Evaluations of Landfill Gas Control Technologies Landfill C. "
1-1
-------
Source Test Report
for Landfill C
This page intentionally left blank
1-2
-------
Source Test Report
for Landfill C
2. Landfill Facility Descriptions
Landfill C is located in a midwestern industrial state and began operation in 1992.
Based on information provided by the site operator, Landfill C has approximately
6,400,000 tons of waste in place as of August 2004, covering an area of 63 acres.. The
LFG generated in the landfill was extracted with 54 vertical wells, at a rate of 600 cfrn.
All collected LFG was piped to the engines and enclosed flare system where it was
combusted.
2.1 Landfill Gas (LFG) Destruction Process Description and Operation
Figure 2-1 shows a simplified process schematic of the engine and flare system.
Landfill C utilizes a bank of two Caterpillar generator-sets for destruction of LFG and
generation of electricity. The engines were Caterpillar 3516 four-stoke spark ignition
(SI) engines, adapted for LFG fuel. The Caterpillar 3516 was a spark-ignited V-16
engine with 4210 cubic inches displacement. The engine was turbocharged and after-
cooled, and had a 6.7-inch diameter cylinder bore and a 7.5-inch stroke. A Caterpillar
SR4 Generator rated at 800KW (at a 0.8 power factor) was driven by the engine.
Engine #1 was selected arbitrarily and tested.
2.2 Control Equipment Description
The engines did not have pollution control equipment installed.
2.3 Excess Landfill Gas (LFG) Flare
A John Zink Enclosed Ground Flare Station received and destroyed any excess LFG
not needed by the two engines. The Enclosed Ground Flare was not part of this test
program.
A condensate removal system prevented liquids from entering into the engine and flare
burners. A flame arrester prevented flame from propagating from the flare burner array
back into the LFG collection and flow control system.
2.4 Landfill Gas (LFG) Sampling Locations
Gas sampling was conducted at the raw LFG pipe, which fed the engines and flare, and
at Engine #1 stack as shown in Figure 2-1.
2-1
-------
Source Test Report
for Landfill C
Figure 2-1. Simplified Engine and Flare Process Flow Diagram and Sampling Points
2.4.1 Landfill Gas (LFG) Header Pipe
Raw LFG samples were collected from the header pipe, which was exposed by
excavating the soil around it. The sample ports were upstream of any processing units.
Figure 2-2 is a photograph of the raw LFG inlet pipe. The pipe was 14 inches in
diameter. At the sampling point, four %" gas taps were installed on the top of the
horizontal pipe, at approximately 12-inch spacing. Through these ports, gases were
withdrawn to obtain the test samples.
2.4.2 Engine #1 Stack
A picture of Engine #1 is shown in Figure 2-3. The exhaust gas of the engine was
ducted outside of the engine room via a pipe. The engine stack was 10 inches in
diameter and had two 4-inch sampling ports installed 90 degrees apart. Figure 2-4 is a
schematic of the engine stack and includes the locations of the sample traverse points.
Isokinetic sampling was possible at this location and followed.
2-2
-------
Source Test Report
for Landfill C
Figure 2-2. Raw Landfill Gas Collection Pipe
Figure 2-3. Engine/Generator Set #1
2-3
-------
Stack Crass Section
Source Test Report
for Landfill C
ii'im.- lli:
Will
Sampling Ports
Traverse Points
Point # Distance, in,
i"
1.5"
3"
7"
8.5
9"
Figure 2-4. Engine Stack Dimension and Sampling Traverse Locations
2-4
-------
Source Test Report
for Landfill C
3. Test Operations
As stated previously, the purpose of the sampling program was to determine the
chemical composition of the raw LFG pipe and the emission from an engine stack.
3.1 Test Team
The tests were conducted by a team of seven individuals. The team members and their
primary duties are listed in Table 3-1.
Table 3-1. Test Team Members and Responsibilities
Role
Test Engineer
Test Engineer
Test Engineer
Test Engineer
Sampling Technician
Senior Chemist
Senior Chemist
Project Officer
Quality Assurance Officer
Quality Assurance Officer
Primary Duty
Field Supervisor
CEM operator
Sample train preparation and recovery
Sample train operator at raw LFG inlet pipe
Sample train operator at stack
Mercury measurements
Mercury measurements
Field Observer
QA Technical Systems Audit
QA Technical Audit Liaison and Oversight
3.2 Test Log
3.2.1 Planned Test Sample Matrices
The list of target samples to be collected and measurements to be conducted are
specified in the Quality Assurance Project Plan (QAPP) Revision 1 dated March 2004.
These are reiterated here for completeness. Table 3-2 lists the target compounds of
interest for the raw LFG, collected at the raw LFG pipe. Table 3-3 lists the target
compounds of interest for the treated gas, at the engine stack.
3-1
-------
Source Test Report
for Landfill C
Table 3-2. Target Analytes for the Raw Landfill Gas Stream
Volatile compounds
Methane
Ethane
Propane
Butane
Pentane
Hexane
Carbonyl sulfide
Chlorodifluoromethane
Chloromethane
Dichlorodifluoromethane
Dichlorofluoromethane
Ethyl chloride
Fluorotrichloromethane
1,3-Butadiene
Acetone
Acrylonitrile
Benzene
Bromodichloromethane
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chloroform
Dimethyl sulfide
Ethyl mercaptan
Volatile compounds
(continued)
Ethylene dibromide
Ethylene dichloride
Methyl chloroform
Methyl isobutyl ketone
Methylene chloride
Propylene dichloride
t-1,2-Dichloroethene
Tetrachloroethene
Toluene
Trichlorethylene
Vinyl chloride
Vinylidene chloride
Ethanol
Methyl ethyl ketone
2-Propanol
1,4-Dichlorobenzene
Ethylbenzene
Xylenes
Non-methane organic
compounds
Reduced sulfur compounds
Hydrogen sulfide
Carbonyls
Acetaldehyde
Formaldehyde
Mercury
Organo-mercury compounds
Total
Elemental
Gases
Carbon dioxide
Oxygen
3.2.2 Landfill Gas (LFG) Pipe (Inlet)
Sample collection took two days to complete. Table 3-4 lists the samples that were
collected from the raw LFG pipe. Figure 3-1 is a photograph of the sampling team in
action at this sample location.
3-2
-------
Source Test Report
for Landfill C
Table 3-3. Target Analytes for the Engine Stack Gas Stream
Gases
Oxygen
Carbon dioxide
Carbon monoxide
Nitrogen oxide
Sulfur dioxide
Total hydrocarbons
Non-methane organic compounds
Hydrogen chloride
Dioxins/Furans
Polycyclic aromatic hydrocarbons
Mercury
Total
Metals
Lead, arsenic, cadmium, chromium,
manganese, nickel
Figure 3-1. Sampling Operations at the Raw Landfill Gas Pipe Inlet
3-3
-------
Source Test Report
for Landfill C
Table 3-4. Raw Landfill Gas Sample Log and Collection Times
Sampling
Method
Run Number
EPA Method 40 (TO-15, 25C, 3C)
C-Pre-M40-051204-FB
C-Pre-M40-051 304-01
C-Pre-M40-05 1304-02
C-Pre-M40-05 1304-03
EPA Method 01 00
C-Pre-M01 00-051 304-FB
C-Pre-M01 00-051 304-01
C-Pre-M01 00-051 304-02
C-Pre-M01 00-051 304-03
EPA Method 1 1
C-Pre-M001 1-051 304-FB
C-Pre-M01 1-051 304-01
C-Pre-M01 1-051 304-02
C-Pre-M01 1-051 304-03
Lumex Instrument
C-Pre-EM-051 204-01
C-Pre-EM-051 304-02
C-Pre-EM-051 304-03
C-Pre-EM-051 304-04
Frontier
04051 3-BR-STM2Blk
C- 0521 04 -01
04051 3-BR-STM1
04051 3-BR-STM3
04051 3-BR-STM4
Frontier
04051 3-BR-MHg8
04051 3-BR-MHg7
Analyte(s)
VOCs/NMOCs/O2/CO2,N2
VOCs/NMOCs/O2/CO2,N2
VOCs/NMOCs/O2/CO2,N2
VOCs/NMOCs/O2/CO2,N2
Carbonyls
Carbonyls
Carbonyls
Carbonyls
H2S
H2S
H2S
H2S
Hg
Elemental Hga
Elemental Hga
Elemental Hga
Elemental Hga
Total gaseous Hg
Total gaseous Hg
Total gaseous Hg
Total gaseous Hg
Total gaseous Hg
Monomethyl Hg
Monomethyl Hg
Sample Class
Field Blank
Test
Test
Test
Field Blank
Test
Test
Test
Field Blank
Test
Test
Test
Test
Test
Test
Test
Field Blank
Blind Spike
Test
Test
Test
Field Spike
Blind Spike
Date
5/12/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/12/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
Run Period
13:06-14:03
09:36-10:32
12:44-13:35
15:00-15:59
13:04-13:24
13:22-13:54
14:34-15:06
15:25-15:56
Not recorded
09:50-11:01
11:13-11:24
11:55-12:06
14:29
11:28
14:56
17:20
12:10
Not recorded
09:40-10:49
11:43-12:45
13:13-14:08
17:02-17:47
15:32
3-4
-------
Source Test Report
for Landfill C
Sampling
Method
Run Number
04051 3-BR-MHg2
040513-BR-MHg1
04051 3-BR-MHg3
04051 3-BR-MHg4
04051 3-BR-MHg5
Frontier
ARCADIS DMM Spike #1
ARCADISDMMSpike#2
04051 3-BR-DMHg4
04051 3-BR-DMHg5
04051 3-BR-DMHg6
04051 3-BR-DMHg1
04051 3-BR-DMHg2
04051 3-BR-DMHg3
Analyte(s)
Monomethyl Hg
Monomethyl Hg
Monomethyl Hg
Monomethyl Hg
Monomethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Sample Class
Field Blank
Test
Test
Test
Test
Blind Spike
Blind Spike
Field Blank
Trip Spike
Trip Spike
Test
Test
Test
Date
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
5/13/04
Run Period
11:10
09:42-10:38
11:46-12:40
13:14-14:09
14:59-15:52
Not recorded
Not recorded
16:30
17:38-17:40
Not recorded
13:41-13:43
14:37-14:45
15:15-15:18
Represents average of 3 readings, each 30-seconds in duration
3.2.3 Engine Stack
Sampling at the engine stack was conducted by accessing the sampling ports with the
aid of a scaffold. Figure 3-2 shows the engine and the sampling scaffold platform.
The engine stack was sampled for NMOCs (as THCs), PCDD/PCDFs, PAHs, HC1,
metals (lead [Pb], arsenic [As], cadmium [Cd], chromium [Cr], manganese [Mn],
nickel [Ni]), total Hg, SO2, NOX, CO, carbon dioxide (CO2), and (O2). Table 3-5 lists
the test samples that were collected from the engine stack.
The engine stack cross-section was divided into 6 equal areas for sample collection
according to EPA Method 1. Sampling at the engine stack was conducted at isokinetic
conditions except for the Method 26A samples which were extracted proportionally.
Sample collection times for the Method 29 metals train were 60-minutes. Run time for
the Method 23 PCDD/PCDFs trains was 180 minutes. Run time for the Method 26A
HC1 trains and the continuous emissions monitoring system (CEMS) parameters (SO2,
NOX, CO, O2, CO2, and THCs) varied.
3-5
-------
Source Test Report
for Landfill C
Figure 3-2. Engine #1 Stack and Sampling Scaffold
3-6
-------
Source Test Report
for Landfill C
Table 3-5. Engine Stack Test Sample Log and Collection Times
Sampling
Method
Run Number
EPA Method 3A (CEM)
C-Post-M3A-05 1304-01
C-Post-M3A-05 1304-01
C-Post-M3A-05 1304-01
C-Post-M3A-05 1404-01
C-Post-M3A-05 1404-01
EPA Method 3A (CEM)
C-Post-M3A-05 1304-01
C-Post-M3A-05 1304-01
C-Post-M3A-05 1304-01
C-Post-M3A-05 1404-01
C-Post-M3A-05 1404-01
EPA Method 10 (CEM)
C-Post-M1 0-051 304-01
C-Post-M1 0-051 304-01
C-Post-M1 0-051 304-01
C-Post-M1 0-051404-01
C-Post-M1 0-051404-01
EPA Method 7E (CEM)
C-Post-M7E-051 304-01
C-Post-M7E-051 304-01
C-Post-M7E-051 304-01
C-Post-M7E-051404-01
C-Post-M7E-051404-01
EPA Method 6C (CEM)
C-Post-M6C-051 304-01
C-Post-M6C-051 304-01
C-Post-M6C-051 304-01
C-Post-M6C-051 404-01
Analyte(s)
02
02
02
02
02
CO2
CO2
CO2
CO2
CO2
CO
CO
CO
CO
CO
NOx
NOx
NOX
NOX
NOX
S02
S02
S02
S02
Sample
Class
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Date
5/13/04
5/13/04
5/13/04
5/14/04
5/14/04
5/13/04
5/13/04
5/13/04
5/14/04
5/14/04
5/13/04
5/13/04
5/13/04
5/14/04
5/14/04
5/13/04
5/13/04
5/13/04
5/14/04
5/14/04
5/13/04
5/13/04
5/13/04
5/14/04
Run Period
12:38-13:37
16:13-17:12
17:57-18:56
10:28-11:27
17:32-18:32
12:38-13:37
16:13-17:12
17:57-18:56
10:28-11:27
17:32-18:32
12:38-13:37
16:13-17:12
17:57-18:56
10:28-11:27
17:32-18:32
12:38-13:37
16:13-17:12
17:57-18:56
10:28-11:27
17:32-18:32
12:38-13:37
16:13-17:12
17:57-18:56
10:28-11:27
3-7
-------
Source Test Report
for Landfill C
Sampling
Method
Run Number
C-Post-M6C-051 404-01
EPA Method 25A(CEM)
C-Post-M25A-051 304-01
C-Post-M25A-051 304-01
C-Post-M25A-051 304-01
C-Post-M25A-051404-01
C-Post-M25A-051404-01
Lumex Instrument
C-Post-EM-051 304-01
C-Post-EM-051 304-02
C-Post-EM-051 304-03
EPA Method 26A
C-Post-M26-051404-FB
C-Post-M26-051 404-01
C-Post-M26-051 404-02
C-Post-M26-051 404-03
EPA Method 23
C-Post-M23-051304-FB
C-Post-M23-051 304-01
C-Post-M23-051 304-02
C-Post-M23-051 404-03
EPA Method 29
C-Post-M29-051404-FB
C-Post-M29-051 404-01
C-Post-M29-051 404-02
C-Post-M29-051 404-03
Analyte(s)
SO2
NMOCs (THC)
NMOCs (THC)
NMOCs (THC)
NMOCs (THC)
NMOCs (THC)
Elemental Hga
Elemental Hga
Elemental Hga
HCI
HCI
HCI
HCI
PCDD/PCDFs, PAHs
PCDD/PCDFs, PAHs
PCDD/PCDFs, PAHs
PCDD/PCDFs, PAHs
Metals
Metals
Metals
Metals
Sample
Class
Test
Test
Test
Test
Test
Test
Test
Test
Test
Field Blank
Test
Test
Test
Field Blank
Test
Test
Test
Field Blank
Test
Test
Test
Date
5/14/04
5/13/04
5/13/04
5/13/04
5/14/04
5/14/04
5/13/04
5/13/04
5/13/04
5/14/04
5/14/04
5/14/04
5/13/04
5/13/04
5/13/04
5/14/04
5/14/04
5/14/04
5/14/04
5/14/04
Run Period
17:32-18:32
12:38-13:37
16:13-17:12
17:57-18:56
10:28-11:27
17:32-18:32
11:13
14:38
17:40
Not recorded
15:41-16:13
17:11-18:01
18:26-19:06
16:30
12:09-15:19
15:54-19:15
15:27-18:52
Mot recorded
09:25-10:35
11:07-12:27
12:29-13:39
Represents 3 readings, each 30-seconds in duration
3-8
-------
Source Test Report
for Landfill C
3.3 Field Test Changes and Deviations from Quality Assurance Project Plan (QAPP)
Specifications
3.3.1 Variation from Test Methods or Planned Activities
3.3.1.1 Sampling at the Raw Landfill Gas (LFG) Pipe
There were not variations from test methods or planned activities on the raw LFG pipe.
3.3.1.2 Landfill Gas (LFG) Inlet Pipe Condensate Sample
A raw LFG pipe condensation sample was not specified in the plan and was not
collected.
3.3.1.3 Landfill Gas (LFG) Flow Rate Measurement
Gas flow as indicated by the LFG flow control station was recorded. The accuracy of
the flow rate measurement could not be independently verified because of the inability
to measure gas velocity accurately. Access to the raw LFG pipe was via %" ports,
which were too small for method-specified velocity probes. The test team was able to
make crude velocity measurements by inserting velocity probes part-way into the gas
pipe. The accuracies of these measurements were uncertain, but they appeared to be
similar to the facility's flow rate readings.
3.3.14 Engine #1 Stack
Unforeseen conditions necessitated two deviations from the QAPP-specified sampling
procedures.
One testing day was lost because of local electrical utility failure and engine problems.
In order to complete the tests within the remaining time and available funds, the HC1
test method was changed from EPA Method 26A, an isokinetic traversing procedure, to
EPA Method 26, a single-point proportional procedure. This change allowed HC1
sampling to be done simultaneously with the EPA Method 29 metals sampling train
because inter-train probe interference was avoided. Since isokinetic sampling is only
required for sampling particulate-laden gases, the absence of particulate matter in the
engine exhaust is believed to be an acceptable alternative non-ioskinetic sampling
method and would not result in sampling errors.
3-9
-------
Source Test Report
for Landfill C
Secondly, because of error in received information on the engine stack diameter (10-
inch actual instead of 12-inch reported previously), substituting EPA Method 1A for
EPA Method 1 for sampling traverse point determination was necessary. Consequently,
EPA Method 2C was substituted for EPA Method 2 for determination of engine stack
velocity. A second set of sampling ports was installed to accommodate this change.
3.3.2 Application of Test Methods
Except for the deviations outlined above and immediately following, the sampling and
analytical methods used in this test program followed those specified in the QAPP.
Sampling methods are shown in Table 3-6.
Table 3-6. Sampling Methods
Procedure
EPA Method 1 A
EPA Method 2C
EPA Method 3A
EPA Method 3C
EPA Method 4
EPA Method 6C
EPA Method 7E
EPA Method 10
EPA Method 1 1
EPA Method 23
EPA Method 25A
Description
Selection of engine stack traverse points
Determination of engine stack gas velocity
and volumetric flow rate
Determination of engine stack oxygen (O2)
and carbon dioxide (CO2) for gas molecular
weight calculations
Determination of raw LFG carbon dioxide
(CO2), methane (CH4), nitrogen (N2), and
oxygen (O2) in raw LFG
Determination of engine stack gas moisture
Determination of engine stack sulfur dioxide
(S02)
Determination of engine stack nitrogen
oxides (NOx)
Determination of engine stack carbon
monoxide (CO)
Determination of raw LFG hydrogen sulfide
(H2S)
Determination of engine stack:
PCDD/PCDFs by Method 8290
Polycyclic aromatic hydrocarbons
(PAHs) by Method 8270
Determination of engine stack gas non-
methane organic carbons (NMOCs) (as
THCs) when total organic concentration is
less than the 50 ppm Method 25C
applicability threshold
Organization Performing Analysis
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
Triangle Environmental Services
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
Oxford Laboratories
ALTA Analytical Perspectives
ARCADIS G&M
3-10
-------
Source Test Report
for Landfill C
Procedure
EPA Method 25C
EPA Method 26
EPA Method 29
EPA Method 40/TO-1 5
SW-846 Method 0100/TO-11
LUMEX instrument
Organic mercury methods
Description
Determination of raw LFG NMOCs
Determination of engine stack hydrogen
chloride (HCI)
Determination of engine stack metals
Determination of raw LFG volatile organic
carbons (VOCs)
Determination of raw LFG carbonyls
(formaldehyde, acetaldehyde)
Determination of raw LFG and engine stack
elemental mercury (Hg°)
Determination of raw LFG:
Monomethyl mercury
Dimethyl mercury
Total mercury
Organization Performing Analysis
Triangle Environmental Services
Resolution Analytics
First Analytical Laboratories
Research Triangle Park Laboratories
Resolution Analytics
ARCADIS G&M
Frontier Geosciences
3.3.3 Test Method Exceptions
Laboratory analytical procedures followed those prescribed by the specified methods,
with the following engine stack exceptions:
• Non-methane organic compounds (NMOCs) - Method 25A was used instead of the
specifically applicable Method 25C.
• Polycyclic aromatic hydrocarbons (PAH) were analyzed by CARB Method 429 as
opposed to Method 8270. However, these methods are comparable. CARB Method
429 contains procedures for sampling, sample recovery, clean-up, and analysis.
Method 8270 is strictly an analytical method. CARB Method 429 is specific to 19
PAHs, the target analytes of this portion of the specified tests The 19 PAHs are a
subset of the 200+ target analytes listed for Method 8270 for semi-volatile organic
compounds (SVOCs). Though specific compounds called out for use in instrument
performance verifications, internal standard preparation, surrogate standards, and
continuing calibration verifications/calibration checks are slightly different, both
methods require them. CARB Method 429 adds another level of quality control
(QC) with a required recovery standard. Method performance and acceptance
criteria for recoveries are better defined in CARB Method 429 and meet or exceed
those stated in Method 8270C. As long as any additional compounds reported by
the laboratory using CARB Method 429 are included in the calibration standards
3-11
-------
Source Test Report
for Landfill C
and acceptable response factors (RFs) are demonstrated, using CARB Method 429
is essentially equivalent to using SW-846 Method 8270.
3-12
-------
Source Test Report
for Landfill C
4. Presentation of Test Results
Testing took place at Landfill C on May 13-14, 2004. Results of the testing are
presented in this section. Detailed test results are included in the Appendices. The
following subsections provide concise summaries of the test results.
4.1 Raw Landfill Gas (LFG) Results
As depicted in Figure 2-2, sampling was conducted by extracting samples via the four
%-inch ports installed in the raw LFG pipe.
4.1.1 Raw Landfill Gas (LFG) Flow Rate and Temperature
4.1.1.1 Direct Measurements
The facility process system had a flow measurement system, which displayed the flow
rate on an instrument panel meter. The panel meter displayed the gas flow rate to both
engines only and was taken after gas drying. With both engines running, the meter read
between 547 and 598 scfm during the tests, averaging at 574 scfm. During several
periods when Engine # 2 was down and only Engine # 1 was running, the panel meter
indicated gas flow rate averaging at 299.5 scfm, within 2 percent deviation.
The small size of the sampling ports precluded full method-compliant measurement of
the velocity profile all the way across the inlet gas pipe. Nonetheless, measurements
with a velocity probe returned readings ranging from 634 ft/min to 824 ft/min (wet). At
these velocities and with pipe inside diameter of 14 inches, the volumetric flow rate
was estimated to be about 700 scfm. Vacuum at the raw LFG inlet gas stream was at
approximately 21 inch water column.
A direct measurement with thermocouples showed the raw LFG temperature to be
56°F.
4.1.1.2 Raw Landfill Gas (LFG) Flow Rate Combined Estimate
Based on the two independent sources of the flow rate estimates, 574 scfm by the
facility's flow rate indicator and 700 scfm by the crude pitot probe measurement, an
average value would be 637 scfm. Clearly, the value is only an estimate. Hence, any
mass emission rates calculated based on this raw LFG flow rate will also, by necessity,
have to be recognized as estimates.
4-1
-------
Source Test Report
for Landfill C
4.1.2 Raw Landfill Gas (LFG) Constituents
The concentrations of the constituents of interest in the raw LFG are presented in the
Subsections 4.1.2.1 through 4.1.2.5. Following the presentation of the constituent
concentrations, Section 4.3 summarizes the data and presents a comparison with the
AP-42 values. The section also presents the estimated mass flow rates of the
constituents at the raw LFG pipe.
4.1.2.1 Volatile Organic Compounds (VOCs)
Concentrations of VOCs were obtained collecting summa canister samples using
Method 40 procedures. Analysis was performed by Method TO-15, with gas
chromatography and mass spectrometry (GC/MS). The alkanes (C2 through C6), being
present in much higher concentrations, were analyzed by GC flame ionization
detection (FID) on the same summa canister samples.
Table 4-1 lists the results of these analyses. Tentatively identified compounds (TICs)
can be seen in the Research Triangle Park (RTF) Laboratory reports in Appendix A.
Table 4-1. Raw Landfill Gas VOC Concentrations
Compound
Bv GC/FID
Ethane
Propane
Butane
Pentane
Hexane
Bv TO-15 GC/MS
Dichlorodifluoromethane (Freon 12)
1,2-Chloro-,1,2,2-Tetrafluoroethane
(CFC114)
Chloromethane
Vinyl chloride
1,3-Butadiene ((Vinylethylene)
Bromomethane (Methyl Bromide)
Unit
ppmv
ppmv
ppmv
ppmv
ppmv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
MDL
1
1
1
1
1
0.3
0.2
0.1
0.2
0.3
0.2
Concentration
Run 1
15.5
39.6
23.9
26.4
28.4
2270
166
3790
6
891
6
Run 2
12.2
39.5
27.9
23.4
26.7
1820
149
ND
1620
709
57
Run 3
15.3
40.8
61.9
29.9
30.0
720
66
ND
679
325
7
Average a
14.3
40.0
37.9
26.6
28.4
1600
127
1263
768
642
23
4-2
-------
Source Test Report
for Landfill C
Compound
Chloroethane (Ethyl Chloride)
Trichloromonofluoromethane (CFC1 1)
1,1-Dichloroethene
1 , 1 ,2-Trichloro-1 ,2,2-trifluoroethane (CFC1 1 3)
Carbon Disulfide
Ethanol
Isopropyl Alcohol (2-Propanol)c
Methylene chloride (Dichloromethane)c
Acetone c
t-1,2-dichloroethene
Hexane
Methyl-t-butyl ether (MTBE)
1,1-Dichloroethane
Vinyl Acetate
cis-1 ,2-Dichloroethene
Cyclohexane
Chloroform
Ethyl Acetate
Carbon Tetrachloride
Tetrahydrofuran (Diethylene Oxide) c
1,1,1 -Trichloroethane
2-Butanone (Methyl Ethyl Ketone)c
Heptane0
Benzene
1,2-Dichloroethane
Trichloroethylene (Trichloroethene)
1 ,2-Dichloropropane
Bromodichloromethane
1,4-Dioxane (1,4-Diethylene Dioxide)
cis-1 ,3-Dichloropropene
Toluene (Methyl Benzene)0
4-Methyl-2-pentanone (MIBK)C
t-1 ,3-Dichloropropene
Unit
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
MDL
0.2
0.2
0.2
0.2
0.3
0.2
0.2
0.1
0.3
0.3
0.3
0.3
0.4
0.5
0.3
0.3
0.3
0.3
0.5
0.4
0.3
0.3
0.2
0.2
0.3
0.2
0.3
0.2
0.2
0.2
0.3
0.2
0.2
Concentration
Run 1
50000
721
79
53
197
225
2060
8010
17700
57
6180
405
ND
38
2240
4560
1000
1970
ND
1140
ND
7150
3510
2140
62
841
ND
ND
3
ND
27400
3280
40
Run 2
39200
572
62
44
180
222
1530
6750
14100
46
5480
337
660
3
1780
3700
825
ND
ND
545
ND
6550
3240
1790
49
674
ND
ND
7
ND
24700
2850
35
Run 3
2000
218
25
21
93
68
250
1280
3300
22
3150
28
608
30
900
1650
403
2290
ND
1830
ND
ND
1820
950
ND
31
ND
ND
10
ND
18000
390
23
Average a
30400
504
55
39
157
172
1280
5350
11700
42
4940
257
423
24
1640
3300
744
1420
ND
1170
ND
4570
2860
1630
37
515
ND
ND
7
ND
23300
2170
33
4-3
-------
Source Test Report
for Landfill C
Compound
Tetrachloroethylene (Perchloroethylene)c
1,1,2-Trichloroethanec
Dibromochloromethane
1,2-Dibromoethane (Ethylene dibromide)
2-Hexanone (Methyl Butyl Ketone)
Ethylbenzenec
Chlorobenzene
m/p-Xylene (Dimethyl Benzene)0
o-Xylene (Dimethyl Benzene)0
Styrene (Vinylbenzene)
Tribromomethane (Bromoform)
1 , 1 ,2,2-Tetrachloroethane
1-Ethyl-4-methylbenzene (4-Ethyl Toluene) b
1,3,5-Trimethylbenzene b
1 ,2,4-Trimethylbenzene c
1,4-Dichlorobenzene
1 ,3-Dichlorobenzene
Benzyl Chloride
1 ,2-Dichlorobenzene
1 , 1 ,2,3,4,4-Hexachloro-1 ,3-butadiene
1 ,2,4-Trichlorobenzene
Acrylonitrile
Chlorodiflouromethane (Freon 22)
Unit
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
MDL
0.3
0.2
0.2
0.2
0.2
0.3
0.2
0.65
0.3
0.1
0.3
0.2
0.2
0.2
0.3
0.3
0.2
0.2
0.3
0.2
0.3
20
20
Concentration
Run 1
2310
675
13
33
ND
7450
ND
12100
4760
1560
22
ND
791
791
1750
363
341
ND
ND
ND
ND
ND
ND
Run 2
1900
660
11
29
ND
6600
ND
11000
4020
1490
25
ND
804
804
1800
401
356
ND
ND
ND
ND
ND
ND
Run 3
860
ND
2
ND
ND
3630
2500
4500
2210
750
ND
ND
1090
1090
970
221
185
ND
ND
ND
ND
ND
ND
Average a
1690
445
9
21
ND
5890
833
9200
3660
1270
16
ND
894
894
1510
328
294
ND
ND
ND
ND
ND
ND
ND - Constituent not detected at the stated detection limits
a In computing averages, when all measurements are ND, the average is reported as ND. When
one or more measurement is above detection, the ND measurement is treated as 50 percent of
the stated MDL. If MDL is not reported, a ND measurement is treated as zero.
b 1-Ethyl-4-methylbenzene (4-Ethyl Toluene) and 1,3,5-Trimethylbenzene co-eluted from the GC
and also have the same quantitation ions, thus making them indistinguishable. Therefore, the
reported values represent the combined concentrations of these two compounds.
c Analyte detected in blank sampled 0.21 to 3.03 ppbv. See table 5-3 for analyte-specific detected
levels.
4-4
-------
Source Test Report
for Landfill C
4.1.2.2 Non-methane Organic Compounds (NMOCs)
Non-methane organic compounds (NMOCs) in the raw LFG were analyzed by Method
25C on the samples collected by Method 40. The NMOC concentrations in the raw
LFG are presented in Table 4-2. The table also includes concentrations of methane
(CFL,), CO2, and O2, which are results obtained as part of the NMOC analyses.
The other analytes, oxygen (O2), carbon dioxide (CO2), and moisture, are not pollutants
but are of interest as they are useful indicators of the "quality" of the raw LFG. The
concentrations of nitrogen (N2) and O2 are also indicators of the extent of ambient air
infiltration into the LFG collection. Method 25 C for NMOC determination specifically
recommends that these measurements be made to determine potential air infiltration.
Therefore, while measurements for methane (CFLJ, CO2, O2, and N2 by Method 3C
were not included in the original QAPP, these measurements were included and
performed.
There is good agreement between CFL, and CO2 values obtained from Method 25C and
Method 3C.
Table 4-2. Raw Landfill Gas Non-Methane Organic Compound (NMOC) Concentrations
Run 1
Run 2
Run 3
Average
NMOC (ppmv
as Hexane)
Method 25C
3650
4630
9330
5870
CH4
(% v/v)
Method 25C
57.7
54.6
55.7
56.0
Method 3C
49.1
47.4
47.5
48.0
CO2
(% v/v)
Method 25C
47.2
45.2
46.2
46.2
Method 3C
36.9
35.4
35.5
35.9
02
(%v/v)
Method 3C
1.4
1.5
1.9
1.6
N2
(% v/v)
Method 3C
13.5
15.3
18.9
15.9
Moisture
(% v/v)
Method 23
NM
NM
NM
NM
Concentrations are reported without correction for nitrogen
NM - not measured because Method 23 sampling train was not run. Data column is included to
retain format consistency with reports for Landfills A and B.
4.1.2.3 Hydrogen Sulfide (H2S)
Raw LFG pipe H2S concentrations were obtained by collecting and analyzing the
samples in accordance with EPA Method 11. These results are presented in Table 4-3.
4-5
-------
Source Test Report
for Landfill C
Table 4-3. Raw Landfill Gas Hydrogen Sulfide (H2S) Concentrations
Run 1
Run 2
Run 3
Average
h^S Concentration
(mg/m3)
98.0
26.8
110.0
78.3
(ppmv)
69.4
19.0
78.0
55.5
Sample hold times exceeded specified 30 days by 3 days
4.12.4 Carbonyls
The target carbonyl compounds, formaldehyde and acetaldehyde, were analyzed by
SW-846 Method 8315 on samples collected by EPA Method 0100. The analysis results
are presented in Table 4-4.
Table 4-4. Raw Landfill Gas Carbonyls Concentrations
MDL
Run 1
Run 2
Run 3
Average
Formaldehyde
(Mg/m3)
8.0
28.3
26.9
46.6
33.9
(x10~3ppmv)
6.4
22.7
21.5
37.3
27.2
Acetaldehyde
(Mg/m3)
8.3
118
114
495
242
(x10~3ppmv)
4.5
64.3
62.4
270
132
4.12.5 Mercury (Hg)
Mercury (Hg) can exist in several forms. This test program focused on the elemental,
monomethyl, and dimethyl forms of Hg, and total Hg. Elemental Hg was measured
with the LUMEX instrument. Organic monomethyl Hg, dimethyl Hg, and total Hg
were sampled and analyzed using the organic mercury method.
4.1.2.5.1 Total Mercury (Hg) Samples
To collect the total Hg samples, an iodated charcoal trap was used as a sorbent. A
backup tube was also present to assess any breakthrough. The sorbent tube was heated
4-6
-------
Source Test Report
for Landfill C
to above the dew point of the gas stream to prevent condensation on the sorbent. A
silica gel impinger was used to collect and quantify the water vapor from the stream. A
diaphragm air pump was used to pull a sample through the train and collect the sample.
A dry gas meter capable of measuring the volume in 10 ml increments was used to
monitor and quantify the volume of gas sampled.
Table 4-5 presents the total Hg concentrations in the raw LFG. They ranged from 423
to 427 ng/m3 with an average of 425 ng/m3.
Table 4-5. Raw Landfill Gas Total Mercury Concentrations
MDL
Run 1
Run 2
Run 3
Average
Total Mercury Concentration
(ng/m3)
50
425
427
423
425
(x10's ppm)
6.0
51.2
51.4
50.9
51.2
Sample hold time was 15 days, exceeding the 14-day specification
4.1.2.5.2 Dimethyl Mercury (Hg) Samples
To collect the dimethyl Hg sample, a Carbotrap was used as a sorbent. A backup tube
was also present to assess any breakthrough. A third iodated carbon trap was also
present to collect any elemental Hg present. The sorbent tube was heated to above the
dew point of the gas stream to prevent condensation on the sorbent. A silica gel
impinger was used to collect and quantify the water vapor from the stream. A
diaphragm air pump was used to pull sample through the train and collect the sample.
A dry gas meter capable of measuring the volume in 10 ml increments was used to
monitor and quantify the volume of gas sampled.
Table 4-6 presents the dimethyl Hg concentrations in the raw LFG. The analyzed
concentrations ranged from 6.5 to 20.9 ng/m3 with an average of 14.8 ng/m3.
4-7
-------
Source Test Report
for Landfill C
Table 4-6. Raw Landfill Gas Dimethyl Mercury Concentrations
MDL
Run 1
Run 2
Run 3
Average
Dimethyl Mercury Concentration
(ng/m3)
0.5
20.9
6.5
17.1
14.8
(x10~6 ppmv)
0.05
2.2
0.7
1.8
1.5
4.1.2.5.3 Monomethyl Mercury (Hg) Samples
To collect the sample, a set of three impingers filled with 0.001 M HC1 was used to
collect the monomethyl Hg. An empty forth impinger was used to knockout any
impinger solution carryover to the pump and meter system. A diaphragm air pump was
used to pull sample through the train and collect the sample. A dry gas meter capable
of measuring the volume in 10 ml increments was used to monitor and quantify the
volume of gas sampled.
As shown in Table 4-7, monomethyl Hg concentrations in the raw LFG ranged from
3.1 to 5.4 ng/m3.
Table 4-7. Raw Landfill Gas Monomethyl Mercury Concentrations
MDL
Run 1
Run 2
Run 3
Average
Monomethyl Mercury Concentration
(ng/m3)
0.13
5.4
3.1
3.3
3.9
(x10~6 ppmv)
0.014
0.60
0.35
0.37
0.44
Sample hold time was 15 days, exceeding the 14-day specification
4.1.2.5.4 Elemental Mercury (Hg)
Elemental Hg was determined by the LUMEX instrument and the results are presented
in Table 4-8. The analyzed concentrations ranged from 90 to 103 ng/m3.
4-8
-------
Source Test Report
for Landfill C
4.2 Engine Stack Results
The engine stack was sampled for NMOCs (as THCs), PCDD/PCDFs, PAHs, HC1, Pb,
As, Cd, Cr, Mn, Ni, total Hg, SO2, NOX, CO, CO2, and O2. The stack cross section was
divided into 12 equal areas according to EPA Method 1A. Sampling run time for
metals was 60 minutes. Run time for HC1 varied between 40 and 50 minutes. Run time
for PCDD/PCDFs sampling was 180 minutes. Run time for CEMS parameters (SO2,
NOX, CO, O2, CO2, and THCs) varied.
Table 4-8. Raw Landfill Gas Elemental Mercury Concentrations
Run 1
Run 2
Run 3
Run 4
Average
Concentration a
Background
(ng/m3)
NM
2
20
3
8
(xlO"6 ppmv)
NM
0.2
2.4
0.4
1.0
Raw Landfill Gas
(ng/m3)
101
103
103
90
99
(x10~6 ppmv)
12.2
12.4
12.4
10.8
11.9
NM - Not measured
a Average of three repetitions
4.2.1 Engine Stack Gas Flow Rate and Temperature
Sampling at the engine stack was conducted at isokinetic conditions with the exception
of EPA Method 26 (HC1), which was conducted at proportional extraction rates. The
procedures provided stack gas velocity distribution across the engine stack and reliable
measurements of stack gas flow rates. Table 4-9 lists the volumetric flow rates and
temperatures at the engine stack measured during the various sampling runs.
4-9
-------
Source Test
Report for Landfill C
Table 4-9. Engine Stack Gas Operating Conditions Measured during Sampling
Run Number
C-Post-M29-051 404-01
C-Post-M29-051 404-02
C-Post-M29-051 404-03
C-Post-M23-051 304-01
C-Post-M23-051 304-02
C-Post-M23-051 404-03
Average
Date
05/14/04
05/14/04
05/14/04
05/13/04
05/13/04
05/14/04
Time
09:25-10:35
11:07-12:27
12:29-13:39
12:09-15:19
15:54-19:15
15:27-18:52
Average
Stack Temp
(°F)
1015
1028
1038
1005
1009
997
1016
Carbon
Dioxide
(%)
16.5
16.5
16.5
15.6
16.1
16.4
16.3
Oxygen
(%)
2.3
2.3
2.3
3.2
3.0
2.9
2.7
Moisture
(%)
17.5
17.5
18.0
16.2
16.7
16.2
17.0
Velocity
(actual ft/sec)
195
200
195
200
191
200
197
Volumetric
Flow Rate
(acfm)
6390
6530
6390
6550
6260
6460
6430
Volumetric
Flow Rate
(dscfm)
1920
1950
1890
2000
1920
2000
1950
Engine stack cross-section flow area is 0.55 sq. ft.
4-10
-------
Source Test Report
For Landfill C
4.2.2 Engine Stack Gas Constituents
The concentrations of the constituents of interest in the engine stack are presented in
the following Subsections 4.2.2.1 through 4.2.2.7.
4.2.2. 1 Engine Stack Oxygen (Cy and Carbon Dioxide
Oxygen (O2) and CO2 concentrations provide an overall indication of the combustion
process. Figure 4-1 shows the O2 and CO2 concentrations measured by the CEMs
during the two days of testing. The plotted data excluded the CEM responses during
instrument zeroing and calibration periods. Table 4-10 presents the daily averages of
O2 and CO2 concentrations.
Table 4-10. Engine Stack Combustion Product Concentrations
Run 1
Run 2
Run 3
Run 4
Run 5
Run 6
Average
02
(% v)
2.3
2.3
2.3
3.2
3.0
2.9
2.7
CO2
(% v)
16.5
16.5
16.5
15.6
16.1
16.4
16.3
4-11
-------
Source Test Report
For Landfill C
g.
c
.o
13
'c
20
18
16
14
12
Engine Stack Oxygen & Carbon Dioxide 5/13/04
5 10
c
o
o
•Carbon Dioxide
- Oxygen
Sampling Period
^Jy^i.^^
12:00
13:12 14:24
15:36
Time
16:48
18:00
19:12
20
18
Engine Stack Oxygen & Carbon Dioxide 5/14/04
16 -
14 -
12 -
c
o
| 10 -
c
01
= 8 H
o
O
6 -
4 -
2 -
0
- Oxygen
•Carbon Dioxide
Sampling Period
E
10:04
11:16
12:28
13:40 14:52
Time
16:04
17:16 18:28
Figure 4-1. Engine Stack Oxygen and Carbon Dioxide Concentrations
4-12
-------
Source Test Report
For Landfill C
4.2.2.2 Engine Stack Total Hydrocarbon (THC) Concentrations
Engine stack THC emissions were measured by EPA Method 25A, which used a
CEMs. EPA Method 25 A produces concentrations of all hydrocarbons that respond to
flame ionization detector (FID) analysis; these hydrocarbons are regarded as the
NMOCs reported as propane. Real-time continuous instrument responses are shown in
Figure 4-2. The time-averaged concentrations are presented in Table 4-11. The
instantaneous concentrations of total hydrocarbons ranged from 300 to 450 ppmv as
hexane.
Engine Stack Total Hydrocarbon 5/13/04
1000
600
200
0
Sampling Period
-Total Hydrocarbon
12:00
13:12
14:24
15:36
Time
16:48
18:00
19:12
Figure 4-2. Engine Stack Total Hydrocarbon Concentrations
4-13
-------
Source Test Report
For Landfill C
Table 4-11. Engine Stack THC Concentrations
Run 1
Run 2
Run 3
Average
THC
(ppmdv as
propane)
934
893
994
940
THC
(ppmdv as
hexane)
467
447
497
470
4.2.2.3 Engine Stack Dioxin/Furan (PCDD/PCDFs) Concentrations
Table 4-12 presents the engine stack PCDD/PCDFs emissions data. In all but one case
(12346789-OCDD on Run 1) results were below the detection limits of the analytical
method. The detection limits for the individual congeners varied from 0.96 to 12.7
picograms per sample. Table 4-13 presents the same data, but expressed in terms of
Toxicity Equivalent (TEQ) emissions. The TEQs are expressed as if the detection
limits were the actual laboratory results, i.e., the worst case.
4-14
-------
Source Test Report
for Landfill C
Table 4-12. Engine Stack Dioxins and Furans Emissions
Analyte
C-M23-5130W1
Concentration
(x1(>3ng/dscm)
Emission Rate
(xWg/rir)
(x10-'2|b/hr)
C-M23-5130W2
Concentration
(x1(H ng/dscm)
Emission Rate
(xWg/hr)
(xK>'2|b/hr)
C-M23-51404-03
Concentration
(xlO3 ng/dscm)
Emission Rate
(xWg/hr)
(x10<2|b/hr)
Average
Concentration
(x1(H ng/dscm)
Emission Rate
(xWg/hr)
(x10-'2|b/hr)
Dioxins
2,3,7,8-TCDD
Other TCDD
1,2,3,7,8-PeCDD
Other PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
Other HxCDD
1,2,3,4,6,7,8-HpCDD
Other HpCDD
1,2,3,4,6,7,8,9-OCDD
Total CDD
<0.67
4.2
<0.39
0
<1.2
<1.2
<1.4
0
<2.5
0
7.6
<19.1
<2.3
14.3
<1.3
0
<4.0
<4.1
<4.7
0
<8.5
0
25.9
<65.1
<5.0
31.4
<3.0
0
<8.9
<9.0
<10.3
0
<18.7
0
57.1
<144
<0.56
12.4
<0.56
10.2
<1.5
<1.6
<1.8
3.6
<1.2
0
<2.7
<36.2
<1.8
40.3
<1.8
33.3
<4.9
<5.2
<6.0
11.7
<4.0
0
<8.9
<118
<4.0
89.0
<4.0
73.5
<10.9
<11.4
<13.2
25.8
<8.9
0
<19.6
<260
O.46
8.1
<0.94
0
<0.95
<0.99
<1.1
0
<1.2
0
<4.0
<17.7
<1.6
27.3
<3.2
0
<3.2
<3.3
<3.8
0
<3.9
0
<13.5
<59.9
<3.4
60.3
<7.1
0
<7.1
<7.4
<8.4
0
<8.6
0
<29.9
<132
ND
8.2
ND
3.4
ND
ND
ND
1.2
ND
0
3.7
ND
ND
27.3
ND
11.1
ND
ND
ND
3.9
ND
0
10.1
ND
ND
60.2
ND
24.5
ND
ND
ND
8.6
ND
0
22.3
ND
Furans
2,3,7,8-TCDF
Other TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
Other PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
<0.58
0
<1.0
<0.94
0
<0.24
<0.23
<0.26
<0.40
<2.0
0
<3.5
<3.2
0
<0.81
<0.78
<0.88
<1.4
<4.3
0
<7.7
<7.0
0
<1.8
<1.7
<1.9
<3.0
<0.83
2.3
<0.74
<0.70
0
O.44
<0.40
<0.45
<0.69
<2.7
7.4
<2.4
<2.3
0
<1.4
<1.3
<1.5
<2.3
<6.0
16.3
<5.3
<5.0
0
<3.1
<2.9
<3.2
<5.0
<1.0
0
<0.76
<0.68
0
<0.44
<0.42
<0.47
<0.72
<3.5
0
<2.6
<2.3
0
<1.5
<1.4
<1.6
<2.4
<7.8
0
<5.7
<5.1
0
<3.3
<3.2
<3.5
<5.4
ND
0.75
ND
ND
0
ND
ND
ND
ND
ND
2.5
ND
ND
0
ND
ND
ND
ND
ND
5.4
ND
ND
0
ND
ND
ND
ND
4-15
-------
Source Test Report
for Landfill C
Analyte
Other HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
Other HpCDF
1,2,3,4,6,7,8,9-OCDF
Total CDF
Total CDD/CDF
C-M23-5130W1
Concentration
(x1(>3ng/dscm)
0
<0.37
<0.64
0
<2.6
<7.3
<26.4
Emission Rate
(xWg/rir)
0
<1.3
<2.2
0
<9.0
<24.9
<90.0
(x10-'2|b/hr)
0
<2.8
<4.8
0
<19.8
<55.0
<198
C-M23-5130W2
Concentration
(x1(H ng/dscm)
0
<1.2
<0.66
0
<3.0
<9.2
<45.4
Emission Rate
(xWg/hr)
0
<4.1
<2.2
0
<9.9
<37.4
<155
(xK>'2|b/hr)
0
<9.0
<4.8
0
<21.9
<82.4
<343
C-M23-51404-03
Concentration
(xlO3 ng/dscm)
0
<0.52
<0.84
0
<3.0
<8.9
<26.6
Emission Rate
(xWg/hr)
0
<1.8
<2.9
0
<10.2
<30.2
<90.1
(x10<2|b/hr)
0
<3.9
<6.3
0
<22.4
<66.5
<199
Average
Concentration
(x1(H ng/dscm)
0
ND
ND
0
ND
ND
ND
Emission Rate
(xWg/hr)
0
ND
ND
0
ND
ND
ND
(x10-'2|b/hr)
0
ND
ND
0
ND
ND
ND
In computing averages, when all measurements are ND, the average is reported as ND. When one or more measurement is above detection, the ND
measurement is treated as 50 percent of the stated MDL. If MDL is not reported, a ND measurement is treated as zero.
"<" denotes the measurement was non-detect. The value following the "<" sign is the detection limit.
4-16
-------
Source Test Report
for Landfill C
Table 4-13. Engine Stack Dioxins and Furans Toxicity Equivalent Emissions
Pollutant
Dioxins
2,3,7,8-TCDD
Other TCDD
1,2,3,7,8-PeCDD
Other PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
Other HxCDD
1,2,3,4,6,7,8-HpCDD
Other HpCDD
1,2,3,4,6,7,8,9-OCDD
Total ODD
Three-Run Average
Concentration
(xlO*3 ng/dscm)
Emission Rate
(xlO^g/hr)
(x10'12 Ib/hr)
1989 Toxicity
Equivalency
Factor
Toxicity Equivalent Emissions
Concentration
(x10~3 ng/dscm)
Emission Rate
(x10'9g/hr)
(x10'12 Ib/hr)
<0.56
8.2
<0.63
3.4
<1.2
<1.3
<1.4
1.2
<1.6
0
3.7
24.3
<1.9
27.3
<2.1
11.1
<4.1
<4.2
<4.8
3.9
<5.5
0
10.1
81.0
<4.2
60.2
<4.7
24.5
<9.0
<9.3
<10.6
8.6
<12.1
0
22.3
178.6
1
—
0.5
—
0.1
0.1
0.1
—
0.01
—
0.001
—
<0.56
NA
<0.32
NA
<0.12
<0.13
<0.14
NA
<0.016
NA
0.0037
NA
<1.9
NA
<1.1
NA
<0.41
<0.42
<0.48
NA
<0.055
NA
0.0101
NA
<4.2
NA
<2.3
NA
<0.90
<0.93
<1.1
NA
<0.121
0.0223
NA
Furans
2,3,7,8-TCDF
Other TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
<0.82
0.75
<0.84
<0.77
<2.7
2.5
<2.8
<2.6
<6.0
5.4
<6.2
<5.7
0.1
—
0.05
0.5
<0.082
NA
<0.042
<0.39
<0.27
NA
<0.14
<1.3
<0.60
<0.31
<2.9
4-17
-------
Source Test Report
for Landfill C
Pollutant
Other PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
Other HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
Other HpCDF
1,2,3,4,6,7,8,9-OCDF
Total CDF
Total CDD/CDF
Three-Run Average
Concentration
(xlO"3 ng/dscm)
0
<0.37
<0.35
<0.39
<0.61
0
<0.71
<0.72
0
<2.9
<8.5
<32.8
Emission Rate
(x10-°g/hr)
0
<1.2
<1.2
<1.3
<2.0
0
<2.4
<2.4
0
<9.7
<30.8
<112
(x10'12 Ib/hr)
0
<2.7
<2.6
<2.9
<4.5
0
<5.2
<5.3
0
<21.4
<68.0
<247
1989Toxicity
Equivalency
Factor
—
0.1
0.1
0.1
0.1
—
0.01
0.01
—
0.001
—
—
Toxicity Equivalent Emissions
Concentration
(x10~3 ng/dscm)
NA
<0.037
<0.035
<0.039
<0.061
NA
<0.0071
<0.0072
NA
<0.0029
NA
NA
Emission Rate
(x10-9g/hr)
NA
<0.12
<0.12
<0.13
<0.20
NA
<0.024
<0.024
NA
<0.0097
NA
NA
(x10'12 Ib/hr)
NA
<0.27
<0.26
<0.29
<0.45
NA
<0.052
<0.053
<0.0214
NA
NA
NA- not applicable because no Toxicity Equivalency Factor is available.
"<" denotes the measurement was non-detect. The value following the "<" sign is the detection limit.
4-18
-------
Source Test Report for
Landfill C
4.2.2.4 Engine Stack Polycyclic Aromatic Hydrocarbons (PAHs) Concentrations
The concentrations of PAHs were obtained by CARB Method 429 analysis
(comparable to EPA Method 23). The results are presented in Table 4-14.
4.2.2.5 Hydrogen Chloride (HCI) Concentrations
Engine stack HCI emissions results are presented in Table 4-15. Since EPA Method 26
(non-isokinetic procedure) was used, stack gas flows from the EPA Method 23 run
performed on the same day as the M26 runs (May 14) were used in the mass emissions
calculations.
4.2.2.6 Metals Concentrations
Engine stack metals emissions results are presented in Table 4-16. The metal
concentrations were determined by Method 29, and included those for As, Cd, Cr, Pb,
Mn, Hg (total), and Ni. Mercury (Hg) concentration (elemental) was separately
measured by the LUMEX instrument and those results are also included in Table 4-16.
The "<" symbol denotes that the notated metal was not detected in that sample. The
values following the "<" symbol represent the concentrations and emission rates that
would have been the case had the metal been found at the method detection limit.
Hence the values represent the upper limits of what might be present.
4.2.2.7 Gaseous Concentrations: Carbon Monoxide (CO), Sulfur Dioxide (SCy, and Nitrogen
Oxides (NOX)
Gaseous emissions measured with CEMs include CO, SO2 and NOX. These results are
summarized in Table 4-17. The detailed CEM measurement plots are shown in Figures
4-3 through 4-5. Carbon monoxide concentrations averaged 568 ppmdv. Sulfur dioxide
was not detected. Nitrogen oxides ranged from 2280 to 3150 ppmdv, averaging at 2730
ppmdv.
4.3 Comparison with AP-42 Values
One of the major objectives of the test program is to expand on the database of LFG
constituent compounds and their concentrations. If warranted, these data may
contribute towards updating the AP-42 default values.
4-19
-------
Source Test Report
for Landfill C
Table 4-14. Engine Stack Polycyclic Aromatic Hydrocarbons Emissions
Analyte
Acenaphthene3
Acenaphthylene 3
Anthracene 3
Benzo(a)anthracene 3
Benzo(a)pyrenea
Benzo(b)fluoranthene 3
Benzo(g,h,i)perylenea
Benzo(k)fluoranthenea
Chrysene3
Dibenzo(a,h)anthracene
a
Fluoranthene3
Fluorene3
lndeno(1,2,3-cd)pyrene
a
Naphthalene3
Phenanthrene3
Pyrene3
2-Methyl naphthalene3
Benzo(e)Pyrene3
Peryleneb
Formula
Weight
154.21
152.20
178.23
228.30
252.32
252.32
276.34
252.32
228.29
278.35
202.26
166.22
288.35
128.17
178.23
202.26
142.20
252.32
253.31
M23-I-C
Concentration
(xlO^ppmv)
101
270
56.8
7.7
0.292
5.6
0.503
1.4
21.4
0.314
51.5
127
0.924
7800
446
41.3
1400
4.0
<0.0907
(ng/dscm)
649
1700
421
73.2
3.1
59
5.8
15
203
3.6
433
878
11.1
41400
3300
347
8200
42.3
951000
Emission Rate
(x10«g/hr)
2500
6500
1600
278
11.6
224
21.9
56.5
770
13.8
1600
3300
42.0
157000
12500
1300
31000
160
3.6
(x10«lb/hr)
5.4
14.2
3.5
0.612
0.0256
0.495
0.0483
0.125
1.7
0.0304
3.6
7.3
0.0926
346
27.6
2.9
68.3
0.354
0.0079
M23-II-C
Concentration
(x10«ppmv)
84.5
252
51.2
6.5
0.343
3.8
0.680
0.952
16.6
0.233
45.1
97.1
0.627
8700
337
32.9
1100
2.5
<0.0952
(ng/dscm)
542
1600
380
61.4
3.6
40
7.8
10.0
158
2.7
380
671
7.5
46200
2500
277.0
6300
26.2
998000
Emission Rate
(x10«
g/hr)
2000
5800
1400
224
13.1
146
28.5
36.5
577
9.9
1400
2500
27.5
169000
9100
1000
23200
95.8
3.6
(x10«lb/hr)
4.4
12.8
3.1
0.495
0.0290
0.322
0.0629
0.0804
1.3
0.0217
3.1
5.4
0.0605
372
20.1
2.2
51.1
0.211
0.0080
M23-III-C
Concentration
(xlO^ppmv)
74.1
195
42.8
5.5
0.248
3.5
0.416
0.703
14.2
0.202
32.1
82.8
0.538
7800
300
28.7
948
2.3
<0.0902
(ng/dscm)
475
1230
317
52.0
2.6
36.9
4.8
7.4
135
2.3
270
572
6.5
41400
2220
241
5600
23.9
0.9
Emission Rate
(x10«
g/hr)
1800
4700
1200
199
9.9
141
18.2
28.2
513
8.9
1000
2200
24.6
158000
8500
920
21400
91.1
3.6
(x10«lb/hr)
4.0
10.4
2.7
0.438
0.0219
0.310
0.0402
0.0621
1.1
0.0197
2.3
4.8
0.0543
348
18.7
2.0
47.1
0.200
0.0080
Average
Concentration
(xlO^ppmv)
86.6
239
50.3
6.6
0.294
4.3
0.533
1.0
17.4
0.250
42.9
102
0.697
8100
361
34.3
1100
2.9
<0.0920
(ng/dscm)
555
1510
372
62.2
3.1
45.3
6.1
10.8
165
2.9
361
707
8.3
43000
2670
290
6700
30.8
1.0
Emission Rate
(x10«g/hr)
2100
5700
1400
233.5
11.6
170.3
22.9
40.4
620.1
10.9
1400
2700
31.4
161100
10000
1100
25200
115.8
3.6
(x10«lb/hr)
4.6
12.5
3.1
0.515
0.0255
0.376
0.0505
0.0890
1.4
0.0239
3.0
5.9
0.0691
355
22.1
2.4
55.5
0.255
0.0080
These analytes were detected in field blank sample. See Table 5-2 for detected concentrations
Recovery of d-\2 perylene was below acceptable range
4-20
-------
Source Test Report
for Landfill C
Table 4-15. Engine Stack Hydrogen Chloride (HCI) Emissions
Run 1
Run 2
Run 3
Average
HCI Concentration
(ppmdv)
9.1
12.5
14.3
12.0
(mg/m3)
13.8
19.7
20.6
18.0
HCI Emission Rate
(Ib/hr)
0.103
0.142
0.163
0.136
(g/hr)
46.6
64.4
73.7
61.6
Table 4-16. Engine Stack Metals Emissions
Analyte
Arsenic
Cadmium
Chromium
Lead
Manganese
Nickel a
Mercury (Total
by Method 29)
Mercury
(Elemental by
LUMEX)
C-POST-M29-051404-01
Concentration
(jjg/dscm)
2.7
0.75
5.2
0.73
3.7
30.6
<2.9
Emission Rate
(x10^
g/hr)
8.9
2.5
17
2.4
12
100
<10
(x10-«lb/hr)
19.6
5.4
37.6
5.3
26.5
220.3
<21.2
RUN1
0.147
0.457
1.0078
C-POST-M29-051404-02
Concentration
(jjg/dscm)
4.1
0.556
4.3
0.40
3.6
12.9
<2.9
Emission Rate
(x10^
g/hr)
14
1.8
14
1.3
12
43
<10
(x10-«lb/hr)
30.1
4.1
31.6
2.9
26.4
94.4
<21.1
RUN 2
0.230
0.722
1.59
C-POST-M29-051404-03
Concentration
(pg/dscm)
2.6
0.416
3.6
<0.83
8.9
8.9
<3.1
Emission Rate
(x10^
g/hr)
8.2
1.3
12
<2.7
28
29
<10
(x10-«lb/hr)
18.2
2.9
25.6
<5.9
62.5
63.0
<22
RUN 3
0.124
0.379
0.836
Average
Concentration
(pg/dscm)
3.1
0.574
4.4
0.52
5.4
18
ND
Emission Rate
(x10^
g/hr)
10
1.9
14
1.7
17
57
ND
(x10%/hr)
22.6
4.1
31.6
3.7
38.5
126
ND
Average
0.167
0.519
1.15
Two of four calibration verification samples were at 10.6 and 14.0 percent and were above the acceptable range of ±10 percent
4-21
-------
Source Test Report
for Landfill C
Table 4-17. Engine Stack CO, SO2, NOX Concentrations
Run 1
Run 2
Run 3
Average
Concentration (ppmdv)
CO
562
556
585
568
SO2
0
0
0
0
NOx (as NO)
2770
3150
2280
2730
onn
vnn
finn
°- ^nn
0
^ Ann
-------
Source Test Report
for Landfill C
pnn
ynn
finn
?
°- ^nn
c
o
•B 4DD
i
V
° ^nn
o
o
9DD
mn
n
Engine Stack Carbon Monoxide 5/13/04
Samplin
Carbon
g Period
Monoxide
12:00
^w^^^^tla^
ippww^^i
lE^f^j.^^
||WrW
13:12 14:24 15:36 16:48 18:00 19:12
Time
Engine Stack Carbon Monoxide 5/14//04
°nn
vnn
Rnn
o. ^nn
^ ouu
c
o
•^ 4nn
i
V
(J
= ^nn
o
o
?nn
mn
n -
u^j
~
•*K
f
Sampling Period
Carbon Monoxide
10:04 11:16 12:28 13:40 14:52 16:04 17:16 18:28
Time
Figure 4-4. Engine Stack Sulfur Dioxide Concentrations
4-23
-------
Source Test Report
for Landfill C
Engine Stack
ocnn
^nnn
?
9c;nn
Q.
a.
c onnn
13
S i^nn
o
o
mnn
^nn
n
Nitrogen Dioxide (NO2) 5/14//04
t II &N
tm
HIT Irll
r
10:04 11:16 12:28
Sampling Period
1
1
13:40 14:52 16:04 17:16 18:28
Time
Figure 4-5. Engine Stack Nitric Oxide Concentrations
Table 4-18 presents the concentrations of LFG constituents to provide direct comparisons with AP-42
default values. Table 4-19 presents the concentration of other constituents targeted by the various analyses
but are not listed in AP-42. An expanded discussion and comparison is included in the overall project
report.
4-24
-------
Source Test Report
for Landfill C
Table 4-18. Comparison of Raw Landfill Gas Constituent Concentrations with AP-42 Values
Method
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
No Test
M-40
No Test
M-40
M-40
M-40
M-40
M-40
M-40
M-40
Compound
1,1,1-Trichloroethane
1 ,1 ,2,2-Tetrachloroethane
1,1-Dichloroethane
(Ethylidene Dichloride)
1,1-Dichloroethene
1 ,2-Dichloroethane
1 ,2-Dichloropropane
Isopropyl alcohol
(2-Propanol)
Acetone
Acrylontrile
Bromodichloromethane
Butane
Carbon Disulfide
Carbon Monoxide
Carbon Tetrachloride
Carbonyl Sulfide
(Carbon oxysulfide)
Chlorobenzene
Chlorodiflouromethane
(Freon 22)
Chloroethane
(Ethyl Chloride)
Chloroform
Chloromethane
1 ,4-Dichlorobenzene
1 ,3-Dichlorobenzene
CAS
Number
71-55-6
79-34-5
75-34-3
75-35-4
107-06-2
78-87-5
67-63-0
67-64-1
107-13-1
75-27-4
106-97-8
75-15-0
630-08-0
56-23-5
463-58-1
108-90-7
75-45-6
75-00-3
67-66-3
74-87-3
106-46-7
541-73-1
Formula
Wt.
133.42
167.85
98.96
96.94
98.96
112.98
60.11
58.08
53.06
163.83
58.12
76.13
28.01
153.84
60.07
112.56
86.47
64.52
119.39
50.49
147.00
147.00
Default
Value
(ppmv)
0.48
1.11
2.35
0.20
0.41
0.18
50.10
7.01
6.33
3.13
5.03
0.58
141
0.004
0.49
0.25
1.30
1.25
0.03
1.21
0.21
0.21
Detection
Limit
(ppmv)
0.0003
0.0002
0.0004
0.0002
0.0003
0.0003
0.0002
0.0003
0.02
0.0002
0.0003
0.0005
0.0002
0.02
0.0002
0.0003
0.0001
0.0003
0.0002
Measured
Average
(ppmv)
ND
ND
0.423
0.055
0.037
ND
1.28
11.7
ND
ND
37.9
0.157
NM
ND
NM
0.833
ND
30.4
0.744
1.26
0.328
0.394
Concentration
in Inlet LFG
(xWib/fts)
ND
ND
108
13.9
9.5
ND
199
1800
ND
ND
5700
30.8
NM
ND
NM
242
ND
5100
230
165
125
150
(|jg/m3)
ND
ND
1730
222
152
ND
3190
28200
ND
ND
91200
494
NM
ND
NM
3880
ND
81200
3680
2640
2000
2400
Mass Flow Rate in Inlet
LFG Stream
(mg/hr)
ND
ND
2060
264
181
ND
3790
33500
ND
ND
108000
587
NM
ND
NM
4620
ND
966000
4370
3140
2380
2850
(xKHIb/hr)
ND
ND
4.5
0.582
0.399
ND
8.4
73.8
ND
ND
239
1.3
NM
ND
NM
10.2
ND
213
9.6
6.9
5.2
6.3
4-25
-------
Source Test Report
for Landfill C
Method
M-40
M-40
M-40
M-40
No Test
M-40
M-40
No Test
M-40
M-40
M-40
M-40
M-11
Organic
mercury
LUMEX
Organic
mercury
Organic
mercury
M-40
Compound
1 ,2-Dichlorobenzene
Dichlorodifluoromethane
(Freon21)
Dichlorofluoromethane
(Freon 12)
Methylene Chloride
(Dichloromethane)
Dimethyl Sulfide
(Methyl sulfide)
Ethane
Ethanol
Ethyl Mercaptan
(Ethanediol)
Ethylbenzene
1 ,2-Dibromoethane
(Ethylenedibromide)
Trichloromonofluoromethane
(Fluorotrichloromethane) (F11)
Hexane
Hydrogen Sulfide
Mercury (Dimethyl)
Mercury (Elemental)
Mercury (Monomethyl)
Mercury (Total)
2-Butanone
(Methyl Ethyl Ketone)
CAS
Number
95-50-1
75-71-8
75-43-4
75-09-2
75-18-3
74-84-0
64-17-5
75-08-1
100-41-4
106-93-4
75-69-4
110-54-3
7783-06-4
7439-97-6
78-93-3
Formula
Wt.
147.01
120.91
102.92
84.94
62.13
30.07
46.08
62.13
106.16
187.88
137.38
86.18
34.08
230.66
200.61
215.62
215.63
72.10
Default
Value
(ppmv)
0.21
15.70
2.62
14.30
7.82
889
27.20
2.28
4.61
0.001
0.76
6.57
35.50
Not Listed
Not Listed
Not Listed
253.0E-6
7.09
Detection
Limit
(ppmv)
0.0003
0.0003
0.0003
0.0001
1
0.0002
0.0003
0.0002
0.0002
0.0003
0.05E-06
0.014E-06
6E-06
0.0003
Measured
Average
(ppmv)
ND
1.61
ND
5.35
NM
14.3
0.172
NM
5.89
0.021
0.504
28.4
55.5
1.6E-06
11.8E-06
0.44E-06
51.2E-06
4.57
Concentration
in Inlet LFG
(xWib/fts)
ND
501
ND
1200
NM
1100
20.4
NM
1600
10.1
179
6300
4900
0.000934
0.0061
0.000245
0.0285
851
(|jg/m3)
ND
8020
ND
18800
NM
17800
328
NM
25900
161
2870
101000
78300
0.015
0.098
0.00393
0.46
13600
Mass Flow Rate in Inlet
LFG Stream
(mg/hr)
ND
9540
ND
22400
NM
21200
390
NM
30800
192
3410
120000
93100
0.01780
0.117
0.00467
0.54
16200
(xKHIb/hr)
ND
21.0
ND
49.3
NM
46.8
0.859
NM
67.9
0.422
7.5
265
205
0.0000392
0.000257
0.0000103
0.00120
35.7
4-26
-------
Source Test Report
for Landfill C
Method
M-40
No Test
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-41
M-25C
M-25C
M-40
M-40
Compound
2-Hexanone
(Methyl Butyl Ketone)
Methyl Mercaptan
(Methanethiol)
Pentane
Tetrachloroethylene
(Perch loroethylene)
Propane
t-1 ,2-Dichloroethene
Trich loroethylene
(Trichloroethene)
Vinyl Chloride
m/p-Xylene
(Dimethyl Benzene)
o-Xylene
(Dimethyl Benzene)
Benzene
(Co-disposal)
Benzene
(No-disposal or Unknown)
NMOC as Hexane
(Co-disposal)
NMOC as Hexane
(No-codispoal or Unknown)
Toluene (Methyl Benzen)
(Co-disposal)
Toluene (Methyl Benzene)
(No or Unknown)
CAS
Number
591-78-6
74-93-1
109-66-0
127-18-4
74-98-6
156-60-5
79-01-6
75-01-4
1330-20-7
95-47-6
71-43-2
71-43-2
108-88-3
108-88-3
Formula
Wt.
100.16
48.11
72.15
165.83
44.09
96.94
131.38
62.50
106.16
106.16
78.11
78.11
86.17
92.13
92.13
Default
Value
(ppmv)
1.87
2.49
3.29
3.73
11.10
2.84
2.82
7.34
12.10
12.10
11.10
1.91
2420.00
595.00
165.00
39.30
Detection
Limit
(ppmv)
0.0002
1
0.0003
0.0003
0.0002
0.0002
0.00065
0.0003
0.0002
0.0002
0.0003
0.0003
Measured
Average
(ppmv)
ND
NM
26.6
1.69
40.0
0.042
0.515
0.768
9.21
3.66
1.63
1.63
587
587
23.3
23.3
Concentration
in Inlet LFG
(xWib/fts)
ND
NM
5000
726
4600
10.4
175
124
2500
1000
328
328
1300000
1300000
5600
5600
(|jg/m3)
ND
NM
79400
11600
73000
167
2800
1990
40500
16100
5260
5260
20900000
20900000
89000
89000
Mass Flow Rate in Inlet
LFG Stream
(mg/hr)
ND
NM
94400
13800
86800
199
3330
2360
48100
19200
6260
6260
24900000
24900000
106000
106000
(xKHIb/hr)
ND
NM
208
30.5
191
0.439
7.4
5.2
106
42.2
13.8
13.8
54900
54900
233
233
4-27
-------
Source Test Report
for Landfill C
Table 4-19. Raw Landfill Gas Constituent Concentrations for Compounds without AP-42 Values
Method
M-0100
M-0100
M-23
M-23
M-25C
M-25C
M-25C
M40
M40
M40
M40
M40
M40
M-40
M-40
M-40
M-40
M-40
Compound
Acetaldehyde
Formaldehyde
Dioxins/Furans
PAHs
Carbon Dioxide
Methane
Oxygen
1 ,1 ,2,3,4,4-Hexachloro-1 ,3-butadiene
1 ,1 ,2-Trichloro-1 ,2,2-trifluoroethane
(CFC113)
1,1,2-Trichloroethane
1 ,2,4-Trichlorobenzene
1 ,2,4-Trimethylbenzene
1 ,2-Chloro-,1 ,2,2-Tetrafluoroethane
(CFC114)
1 ,3,5-Trimethylbenzene
1 ,3-Butadiene (Vinylethylene)
1 ,4-Dioxane
(1 ,4-Diethylene Dioxide)
1 -Ethyl-4-methylbenzene
(4-Ethyl Toluene)
4-Methyl-2-pentenone (MIBK)
CAS
Number
75-07-0
50-00-0
124-38-9
74-82-8
778244-7
87-68-3
76-13-1
79-00-5
120-82-1
95-63-6
76-14-2
108-67-8
106-99-0
123-91-1
622-96-8
108-10-1
Formula
Wt.
44.05
30.03
44.01
16.04
32.00
260.76
187.38
133.42
181.46
120.19
170.92
120.19
54.09
88.10
120.20
100.16
Detection
Limit
(ppmv)
0.0045
0.0064
0.0002
0.0002
0.0002
0.0003
0.0003
0.0002
0.0002
0.0003
0.0002
0.0002
0.0002
Measured
Average
(ppmv)
0.133
0.027
NM
NM
462000
560000
16000
ND
0.039
0.445
ND
1.51
0.127
0.894
0.642
0.007
0.894
2.17
Concentration in Inlet LFG
(xlO-oib/ft3)
15.1
2.1
NM
NM
52600000
23200000
1300000
ND
19.1
154
ND
469
56.1
278
89.7
1.5
278
562
OjgAn3)
242
34
NM
NM
842000000
372000000
21200000
ND
305
2460
ND
7510
899
4450
1440
24.3
4450
9000
Mass Flow Rate in Inlet LFG
Stream
(mg/hr)
288
40.4
NM
NM
1000000000
442000000
25200000
ND
363
2920
ND
8930
1070
5290
1710
28.9
5290
10700
(xKHIbAir)
0.635
0.0891
NM
NM
2200
975000
55600
ND
0.800
6.4
ND
19.7
2.4
11.7
3.8
0.0638
11.7
23.6
4-28
-------
Source Test Report
for Landfill C
Method
M-40
M40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
Compound
Benzyl Chloride
(Chloromethyl Benzene)
Bromomethane
(Methyl bromide)
cis-1 ,2-Dichloroethene
cis-1 ,3-Dichloropropene
Cyclohexane
Dibromochloromethane
Ethyl Acetate
Heptane
Methyl-t-butyl Ether (MTBE)
Styrene (Vinylbenzene)
t-1 ,3-Dichloropropene
Tetrahydrofuran
(Diethylene Oxide)
Tribromomethane
(Bromoform)
Vinyl Acetate
CAS
Number
100-44-7
74-83-9
156-59-2
10061-01-5
110-82-7
12448-1
141-78-6
142-82-5
1634-044
10042-5
1006-02-6
109-99-9
75-25-2
108-054
Formula
Wt.
126.58
94.95
96.94
110.98
84.16
208.29
88.10
100.20
88.15
104.14
110.98
72.10
252.77
86.09
Detection
Limit
(ppmv)
0.0002
0.0002
0.0003
0.0002
0.0003
0.0002
0.0003
0.0002
0.0003
0.0001
0.0002
0.0004
0.0003
0.0005
Measured
Average
(ppmv)
ND
0.023
1.64
ND
3.30
0.009
1.42
2.86
0.257
1.27
0.033
1.17
0.016
0.024
Concentration in Inlet LFG
(xlO-sib/ft3)
ND
5.7
411
ND
718
4.7
323
740
58.5
340
9.4
218
10.3
5.3
OjgAn3)
ND
92
6580
ND
11500
74.8
5180
11800
937
5450
150
3500
164
84
Mass Flow Rate in Inlet LFG
Stream
(mg/hr)
ND
109
7820
ND
13700
88.9
6160
14100
1110
6490
179
4160
195
100
(xKHIbAir)
ND
0.241
17.2
ND
30.2
0.196
13.6
31.1
2.5
14.3
0.394
9.2
0.431
0.221
4-29
-------
Source Test Report
for Landfill C
This page intentionally left blank
4-30
-------
Source Test Report
for Landfill C
5. Quality Assurance/Quality Control (QA/QC)
This project produced data that qualified to receive the "A" rating with respect to the rating
system described in section 4.4.2 of the Procedures for preparing Emission Factor
Documents (EPA-454/R-95-015). The cited EPA document provides a clear description of
the requirements for an "A" data quality rating. Tests were performed by using an EPA
reference test method, or when not applicable, a sound methodology. Tests were reported in
enough detail for adequate validation and raw data were provided that could be used to
duplicate the emission results presented in this report.
Throughout the results sections of this report, notations and footnotes were included to flag
data that, for various reasons, did not meet their associated measurement quality objectives.
5.1 Assessment of Measurement Quality Objectives
Measurement quality objectives (MQOs) were established for each critical measurement
and documented in the Site-Specific QAPP for the Field Evaluation of Landfill Gas Control
Technologies-Landfill C. The following subsections assess MQOs for each measurement to
determine if goals were achieved. When applicable, data validation elements performed on
laboratory analytical reports are also included.
5.1.1 Continuous Emissions Monitors (CEMs)
Oxygen (O2), CO/CO2, SO2 NOX and THC were measured in the field using CEMs. The
following MQOs were established for CEM measurements for Landfill C:
• Direct calibration bias: ±2 percent
• System bias checks: ±5 percent
• Zero and drift: ±3 percent
• Completeness: >90 percent
Direct calibrations were performed daily, prior to testing, at zero and a minimum of two
other concentrations (typically a mid-level concentration and one point towards the end of
the instrument range). System bias checks were performed pre-test and post-test. Drift
checks were performed daily, post-test. Table 5-1 summarizes these QC checks for all
instruments. All MQOs were met for Landfill C and were therefore, 100 percent complete.
5-1
-------
Source Testing
Final Report
Landfill C, Revision 3
Table 5-1. Continuous Emissions Monitor (CEM) Measurement Quality Objectives (MQO) Summary for Landfill C
Instrument and Range
Servomex O2 Analyzer
(0-21%)
Cal Analytical CO2 Analyzer
(0-20%)
Cal Analytical CO Analyzer
(0-650 ppm)
Cal Analytical SO2 Analyzer
(0-500 ppm)
TECO THC Analyzer
(0-1000 ppm)
TECO NOX Analyzer
(0-4000 ppm)
Direct Calibration (±2% criteria)
Total #
18
18
24
12
NA a
9
Bias
Range
(%)
0.1-1.5
0-1.9
0-1.2
0.1-7.4
NA a
0-1.4
Percent
Complete
100
100
100
92
NA a
100
System Bias Checks (±5% criteria)
Total #
24
24
24
12
18
6
Bias
Range
(%)
0-3.1
0.1-2.7
0-2.6
2.1-4.4
0.1-2.2
0.1-4
Percent
Complete
100
100
100
100
100
100
Drift Checks (±3% criteria)
Total #
12
12
12
8
6
6
Bias
Range
(%)
0-0.8
0-1.1
0-1.3
0-2.5
0-1.9
0-2.5
Percent
Complete
100
100
100
100
100
100
3 The method called for calibration gases to be
sample line. Calibration gases were not injected
introduced at a point of the sampling system close to the sampling probe for them to flow through the heated
directly to the analyzer
5-2
-------
Source Test Report
for Landfill C
5.1.2 Carbonyls (SW-846 Method 8315A)
The following MQOs were established in the QAPP for this method:
• Recovery (formaldehyde): 50-150 percent
• Completeness: >90 percent
Four samples (including one field blank) were submitted from Landfill C for
formaldehyde and acetaldehyde determination to Resolution Analytics. Results were
reported in RFA#RN990230. The report included information on instrument
calibration and internal QC checks. Samples were collected on May 14, 2004 received
by the laboratory on May 19, 2004 and analyzed on June 7, 2004, which met the 30
day hold-time limitation. Analytical detection limits were reported as 50 ppb for
formaldehyde and 51.7 ppb for acetaldehyde.
The field blank (LDFLC-M0100-051404-FB) did not have detectable levels of either
compound. To assess accuracy, an external performance evaluation audit (PEA)
sample containing 1.25 ppm formaldehyde and acetaldehyde was analyzed with the
sample set. Recovery was 101 percent for both compounds, which met the 50-150
percent MQO established in the QAPP. This spike was analyzed in duplicate with a
percent difference (%D) between injections of 4.8 percent. All project samples were
injected in duplicate and the %D range for formaldehyde was 0 to 4.5 percent and for
acetaldehyde was 0 to 3.6 percent. All MQOs were met for this method for a
completeness of 100 percent.
5.1.3 Hydrogen Sulfide (H2S) (EPA Method 11)
The following MQOs were established in the Landfill C QAPP for this method:
• Accuracy: ±5 percent bias
• Completeness: >90 percent
Four samples plus reagent blanks were submitted from Landfill C for H2S analysis by
EPA Method 11 to Oxford Laboratories. The samples were collected on May 14, 2004
submitted on May 27, 2004 and analyzed on June 17, 2004, which exceeded the 30-day
hold time established in the QAPP by three days.
5-3
-------
Source Test Report
for Landfill C
One spike and one set of duplicates were also performed by the laboratory as addition
QC checks. Spike recoveries were reported as 109 percent, which met the MQO. The
duplication of sample LDFLC-PRE-MOO11-51304-02 yielded a titration difference of
only 0.3 ml. Although the final values were greater than 10 percent difference, this is
an acceptable duplicate. The final difference is because of the small titration difference
between the sample and the blank.
5.1.4 Dioxinsand Furans (PCDD/PCDFs) (EPA Method 23/0011)
The following MQOs were established in the Landfill C QAPP for this method:
• Accuracy: 5 0-15 0 percent recovery
• Completeness: >90 percent
Five samples (including field blank and reagent blanks) from Landfill C were
submitted for PCDD/PCDF analysis to ALTA Analytical Perspectives. Results were
reported in Report #P4173. Detailed information on instrument calibration and
laboratory quality assurance (QA)/QC was received with the analytical report. Samples
were collected on May 14-15, 2004 received on May 26, 2004, extracted on June 1,
2004 and analyzed on June 11, 2004, which met the 14 day extraction and 30 day
analysis hold-time requirements.
The field blank (LDFLC-POST-M23-051304-FB) did not have detectable levels of any
dioxin or furan congeners or totals. The laboratory method blank was also clean. Mean
recoveries of extraction standards ranged from 78 to 91 percent. Mean recoveries of
sampling standards ranged from 95 to 101 percent. All MQOs were met and the
achieved completeness for this measurement was 100 percent.
5.1.5 Polycyclic Aromatic Hydrocarbons (PAHs) (CARB 429)
The following MQOs were established in the Landfill C QAPP for this method:
• Accuracy: 50-150 percent recovery
• Completeness: >90 percent
Five samples (including field blank and reagent blanks) from Landfill C were
submitted for PAH analysis to ALTA Analytical Perspectives. Results were reported in
5-4
-------
Source Test Report
for Landfill C
Report #P4173. Detailed information on instrument calibration and laboratory QA/QC
was received with the analytical report. Samples were collected on May 14-15, 2004,
received on May 26, 2004, extracted on June 1, 2004, and analyzed on June 11, 2004,
which met the 14 day extraction and 40 day analysis hold-time requirements.
There were reportable concentrations of PAHs detected in the field blank (LDFLC-
POST-M23-051304-FB). Table 5-2 presents the amounts of the target analytes found
in the blank samples and in the test samples. The amounts of PAHs in the test samples
were significantly larger than those in the field blank sample and the method blank
sample. Therefore, the presence of detectable quantities of PAHs in the blank samples
did not affect the conclusions drawn from PAH analysis.
Recoveries for all extraction standards (ES) ranged from 53 percent to 115 percent
with the exception of di2-perylene, which was consistently below the acceptable limits.
Sampling standards were all within acceptable limits ranging from 85.6 to 107 percent
recovery. Because of the low recoveries of di2-perylene, the reported concentrations of
perylene were noted in the results in Table 4-14.
5.1.6 Non-Methane Organic Compounds (NMOCs) (Method 25C)
The following MQOs were established in the QAPP for Landfill C:
• Accuracy: ±5 percent bias
• Completeness: >90 percent
Four canister samples (including a field blank) were submitted from Landfill C for
NMOC analysis by Method 25-C to Triangle Environmental Services. The samples
were collected on May 12-14, 2004, submitted on June 3, 2004, and analyzed June 7-
22, 2004, which met the 30 day hold time requirements. The laboratory report included
information on instrument calibration and internal QC checks.
5-5
-------
Source Test Report
for Landfill C
Table 5-2. Amounts of Polycyclic Aromatic Hydrocarbons in Blank Samples and
Samples
Test
Analyte
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(g,h,i)perylene
Benzo(k)fluoranthene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
lndeno(1 ,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
2-Methylnaphthalene
Benzo(e)Pyrene
Perylene
Method Blank
First Analysis
Amount (ng)
1.14
ND
1.84
ND
ND
1.08
ND
ND
0.434
ND
3.58
17.5
ND
968
13.3
3.61
14.6
ND
ND
Method Blank
Second Analysis
Amount (ng)
1.2
ND
ND
ND
ND
1.18
ND
ND
ND
ND
3.34
16
ND
768
11.7
3.53
11.9
ND
ND
Amount found in
Field Blank (ng)
3.74
0.885
3.85
4.55
3.89
22.5
6.77
6.08
29.2
ND
201
18.1
7.56
10900
113
84.4
60.5
ND
ND
Average Amount
Found in Test
Samples (ng)
2303
6260
1543
258
13
188
25
45
685
12
1493
2933
35
178000
11100
1200
27800
128
4
The only NMOC detected in the field blank (LDFLC-PRE-M40-051204-FB) was
reported at 8 ppm as carbon. Sample concentrations were well above this value.
Accuracy for the method was assessed by evaluating results of RF check samples that
were run prior to and following sample analysis. Acceptance criteria established by the
method is that the RF must be within 20 percent of the RF from initial calibration. All
RF checks were within 10 percent of the initial calibration, well within the acceptance
criteria. The %D between the pre and post-test checks were less than 1 percent.
Samples were run in triplicate and all percent relative standard deviations (RSDs) for
samples were <5 percent. The data set was determined valid. The MQOs for accuracy
were met and the completeness achieved for this measurement was 100 percent.
5-6
-------
Source Test Report
for Landfill C
5.1.7 Hydrogen Chloride (HCI) (EPA Method 26A)
The following MQOs were established in the QAPP for Landfill C:
• Accuracy: ± 10 percent bias
• Completeness: >90 percent
Four samples (including one field blank) were submitted from Landfill C for HCI and
chlorine (C12) determination to Resolution Analytics. Results were reported in
RFA#RN990230. The report included information on instrument calibration and
internal QC checks. Samples were collected on May 14, 2004, received on May 19,
2004, and analyzed on June 7, 2004, which met the 4 week hold-time requirement.
Analytical detection limits were reported as 2.6 ppm for HCI and 2.5 ppm for CL2.
The field blank (LDFLC-M26-051404-FB) submitted with samples did not have
detectable levels of HCL of C12. In-house audit samples were analyzed with each
respective group of field samples and fell within method criteria of 10 percent of their
expected values. A matrix spike was performed on sample LDFLC-051404-3. An
0.8 mis sample was spiked with 0.8 mis of standard (50 ppm for HC1/25 ppm for C12)
and analyzed in triplicate. The laboratory reported 99 percent recovery of the HCI
spike with a 0.4 percent RSD in triplicate injections and 102 percent recovery of the
C12 spike with a 0.3 percent RSD. This met the MQO of ±10 percent with very good
precision. In addition to the matrix spike, an internal QC check was performed after
every 10 samples. All samples were measured in triplicate. Calculated bias for internal
QC check was <1 percent for all measurements as was the %D between triplicates. All
MQOs were met for 100 percent completeness.
5.1.8 Metals (EPA Method 29)
The following MQOs were established in the Landfill C QAPP for this method:
• Accuracy: ±25 percent bias
• Completeness: >90 percent
Four sets of Method 29 Multi-Metals trains (including one field blank) were submitted
from Landfill C for As, Cd, Cr, Pb, Mn, Hg, and Ni determination to First Analytical
Laboratories. Results were reported in Project #40513. The report included information
5-7
-------
Source Test Report
for Landfill C
on instrument calibration and internal QC checks. Samples were collected on May 14,
2004, received on May 19, 2004, and analyzed on May 24-26, 2004, which met the 14
day hold-time requirement. Method detection limits for each of the target metals were
reported as follows:
• As = 5.0(ig/L
• Cd = 0.2(ig/L
• Cr = 5.0(ig/L
• Pb = 5.0(ig/L
• Mn = 5.0(ig/L
• Ni = lOjig/L
• Hg = 0.2^g/L
Traces of Cd, Cr, Mn, and Ni were found in the blanks, which is not unusual. Some of
the back half Mn samples are abnormally high. This is a common problem that can
occur in Method 29 if a tiny amount of the potassium permanganate reagent gets into
the hydrogen peroxide impingers.
All samples were spiked prior to analysis. The Cd back half spike recovery was poor
(56 percent), so the Cd back half analysis was conducted by the method of standard
additions to overcome the problem. All of the other spike recoveries were within the
acceptable range of 75-125 percent. In addition to spiking the samples, for each metal,
internal calibration verification samples (ICVs) and continuing calibration verification
samples (CCVs) were performed. ICVs were run at the beginning of each run set and
CCVs were run at a frequency of 1 for every 10 samples. The ICVs and CCVs
measured values were all <±10 percent for all metals with the exception of Ni. Two of
the four CCV measurements for Ni were slightly above the 10 percent acceptance
criteria at 10.6 percent and 14.0 percent. This was not considered a major failure and
data limitations were not applied. To evaluate precision, all samples were analyzed in
duplicate. Whenever the %RSD for duplicate measurements exceeded 20 percent, the
sample was re-analyzed. Though CCVs fell slightly outside of range for one metal
(Ni), all other metals were within acceptance criteria and data use was not limited,
5-8
-------
Source Test Report
for Landfill C
these analyses are considered 100 percent complete. The Ni results were notated in
Table 4-16 to reflect the out-of-range CCV check.
5.1.9 Total Mercury (Hg) and Organo-mercury (Hg) (Frontier)
The following MQOs were established in the Landfill C QAPP for this method:
• Recovery: 50-150 percent
• Completeness: >90 percent
For Hg samples, replicates and spikes were incorporated into the sampling scheme. In
addition, performance evaluation audit samples were also submitted to Frontier for
analysis. Results from the PEA are summarized in Section 5.2.2.2.
Four total Hg samples (including a field blank) were taken at Landfill C. Samples were
collected on May 13, 2004, extracted on May 28, 2004, and analyzed on June 3, 2004,
which did not meet the 14 day hold-time established in the QAPP. All other QA
measures indicated that the analysis of the traps were under good control. All field
blanks were consistent with historical values and indicated the detection limit was
likely to be at or below the previous estimated value of 50 ng/m3. Spike recoveries
were >95 percent and standard deviation between replicates was 1.9 percent, which
met MQOs and are 100 percent complete.
Six monomethyl mercury (MMHg) samples (including a field blank) were collected at
Landfill C on May 13, 2004. These samples were extracted on May 27, 2004 but
analyzed on May 28, 2004 which is one day past the 14 day hold-time. Analysis of
these samples was under good control with acceptable distillation spike recoveries and
distillation duplicates. All CCV standards had acceptable recoveries. One or the six gas
sample was lost because of accidental back flush of the sampling pump by the
operator. Spike recoveries were 80-117 percent, which met MQOs. The RSD between
replicates was <10 percent. Because of the loss of one sample, MMHg sampling and
analysis was 83 percent, which is slightly below the MQO.
Four dimethyl mercury (DMHg) samples (including a field blank) were collected at
Landfill C on May 13, 2004. These samples were extracted and analyzed on May 27,
2004, which met the 14 day hold-time. The analysis of samples was well within
control, with acceptable recoveries and good linear control standards and second
source standard recoveries. One of the triplicate samples taken at Landfill C displayed
5-9
-------
Source Test Report
for Landfill C
significantly lower concentrations compared to the other samples, potentially because
inadequate purging of the sampling line dead volume. The low value could not
statistically be excluded from the site average therefore the RSD for replicates at this
site is elevated to 50.4 percent.
The field blank was low indicating that the trap media, handling procedures, and
analytical techniques did not contribute to the reported values. Field matrix spike
recoveries ranged from 50-93 percent. The DMHg analysis was 100 percent complete.
5.1.10 Volatile Organic Compounds (VOCs) and Methane (CH4) (Method 0040/Method TO-15)
The following MQOs were established in the Landfill C QAPP for this method:
• Accuracy: 50-150 percent recovery
• Completeness: >90 percent
Four SUMMA canisters (including one field blank) were submitted from Landfill C to
RTF Laboratories for VOC and CFL, determination by EPA Method TO-15. Results
were reported in Project #04-107. Samples were collected on May 13, 2004, received
on May 20, 2004, and analyzed on May 25, 2004, which met the 30 day hold-time
requirement.
Analysis of the field blank (LDFLC-PRE-M40-51304-FB) resulted in significant levels
of several VOC compounds. Table 5-3 list the compounds identified in the field blank
that were >1 ppbv. This should be considered when evaluating sample data.
To assess accuracy of the analytical method, a field spike was performed by injecting
2130 ppbv of chlorobenzene into the third canister (LDFLC-PRE-M40-051304-3).
Recovery of the field spike was reported at 117 percent. Precision was demonstrated
through multiple injection of standards at five concentrations. The RSD between the
calculated relative RFs must be <30 percent with allowances that 2 may be >40
percent. The average RSD was 11.3 percent and method criteria were met for all
compounds. This met the established MQOs. Valid data was received for all SUMMA
canisters submitted; these analyses are considered to be 100 percent complete. The
results in Table 4-1 were notated accordingly. Moreover, the measured average sample
concentrations of these analytes were many folds the deleted blank concentrations.
Therefore, conclusions that may have been drawn from these results are not affected
materially.
5-10
-------
Source Test Report
for Landfill C
Table 5-3. VOCs Identified in Field Blank
Compound
Isopropyl alcohol
Methylene chloride
Acetone
Tetrahydrofuran
2-butanone
Heptane
Toluene
MIBK
Tetrachloroethylene
1,1,2-trichloroethane
Ethylbenzene
m/p-Xylene
o-Xylene
1 ,2,4-trimethylbenzene
Blank Sample
Concentration
(ppbv)
2.8
9.4
13.5
35.6
5.4
1.3
378
21.3
37
11.4
1.5
5.8
1.5
1.8
Test Sample Average
Concentration
(ppbv)
1280
5350
11700
1170
4570
2860
23300
2170
1690
445
5890
9200
3660
1510
5.2 Audits
5.2.1 EPA Technical Systems Audit
EPA/APPCD QA Representative, Robert Wright, conducted an on-site technical
systems audit (TSA) of the field evaluations at Landfill C on May 12-13, 2003. The
ARCADIS approved QAPP and the associated field sampling manual provided the
technical basis for the audit. The ARCADIS QA Officer, Laura Nessley, accompanied
the EPA auditor during the TSA. A report of preliminary findings was received on
May 19, 2004 and it is included below.
5-11
-------
Source Test Report
for Landfill C
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
NATIONAL RISK MANAGEMENT RESEARCH LABORATORY
Air Pollution Prevention and Control Division
Research Triangle Part, NC 27711
May 19.2004
MEMORANDUM
SUBJECT: Preliminary findings from technical systems audit conducted on May 12-13. 20-04
of ARCADIS' field evaluation of landfill gas control technologies at landfill C
FROM: Robert S. Wright, Technical Services Branch
TO: Susan A. Thonieloe, Atmospheric Protection Branch
I conducted a technical systems audit (TSA) on May 12-13, 2004 of ARCADIS" field evaluation
of landfill gas control technologies at Landfill C. Tins assessment was conducted according to
auditing procedures described in Guidance on Technical Audits and Related Assessments for
Enrimnmemal Data Operations (EPA QA.tQ-7). ARCADIS" approved quality assurance project
plan (QAPP) and its associated field sampling manual provided the technical basis for the TSA.
The checklist for the TSA was sent to ARCADIS on May 9. 2004 and was distributed to the
project staff prior to the audit. The following are preliminary findings of the audit.
1. In general. I observed that ARCADIS is doing a good job of evaluating landfill gas
control technologies at Landfill C. ARCADIS' project staff are well qualified to perform
the evaluation and they conducted themselves in a professional manner- They cooperated
with me during the TSA and took time out from then busy duties to explain what was
happening. They helped to ensure the successful completion of the TSA.
2. In general the evaluation is being implemented as stated in the QAPP for the project.
3. There were significant disruptions of the testing schedule for reasons beyond ARCADIS"
control: the long power loss at Landfill C' on May 12; the malfunction of the internal
combustion engine on May 12: the higher-fhan-expected pressure in the engine's exhaust
stack on May 13; and inclement weather on May 13. ARCADIS" project staff responded
well to these disruptions and modified the planned test matrix and schedule to allow
completion of the most important measurements within the available time and funding.
Some of these measurements were conducted on May 14.
4. Because some of the measurements were conducted after I had left OD May 13 to return to
North C arolina. the TSA did not cover all the items on the checklist. Given the general
level of expertise and competence displayed by ARCADIS" project staff, I believe that
the quality of the measurements that I did not observe is as high as the quality of the
measurements that I was able to observe.
5-12
-------
Source Test Report
for Landfill C
5. Sampling for the total mercury aid orgaoo-mercwy measurements was conducted by
Lucas Hawking of Frontier Geosciences. Inc. He approached the sampling in a careful,
competent, .and professional manner. He followed the standard operating procedures
(SOP?) for this sampling.
6. ARCADIS' project staff used both laboratory notebooks and data sheets to record data
and obsen-ations during the evaluation. In several instances, this information was written
ui the laboratory notebooks without including the date and the name of the person
recording this information. If there is not enough time during sampling activities to
follow ARCADIS" procedures for laboratory notebooks, the project staff should add the
date and name at the end of the day before they leave the site.
7. The field team leader had copies of equipment calibration certificates in a folder in his
possession. However, the certificates of analysts for the gaseous calibration standards
were attached to the cylinders uoder some plastic mesh and the cylinders were attached to
the wall behind a table. It was difficult to read the certificates without disrupting the
equipment. For future TSAs. ARCADIS may wish to include copies of the certificates of
analysis for gaseous calibration standards in the folder to minimize testing disruptions.
8. No check weights were brought into the field to verity that the balance was operating
correctly as was described in the QAPP. A crude quality control (QC) check was
performed using the weights of known volumes of water and suggested that the balance
was operating properly. Upon returning to North Carolina, the APPCD Metrology
Laboratory will use KTSI-traceable check weights to verify that the balance is operating
properly. For future field evaluations, ARCADIS should ensure that check weights are
taken with the balance.
9. A gas dilution system was used to calibrate the continuous emissioo monitors (CEMs)
according to EPA Method 205. The ARCADIS CEMs operator had a copy of the
September IT. 2003 calibration of this instrument in the APPCD Metrology Laboratory.
However, a label containing information about this calibration was not affixed to the gas
dilution system as is required by the method. ARCADIS should contact the APPCD
Metrology Laboratory to obtain such a label.
A draft findings report for this TSA will be completed in the corning month. It is possible that it
may contain additional findings that arise from closer consideration of the audit results, but I do
not expect any new findings will address significant problems relating to the project.
Please contact me if you have any questions about the TSA or about this memorandum.
5-13
-------
Source Test Report
for Landfill C
5.2.2 Laboratory Audits
Because of the developmental nature of the organo-Hg methods, an internal TSA and
PEA were performed by ARCADIS at Frontier Geosciences (Frontier), located in
Seattle, Washington.
5.2.2.1 Internal Technical Systems Audit (TSA)
In an effort to save project funds, a Senior Scientist at the ARCADIS Seattle office was
asked to perform the laboratory audit, which would include observation of spiking
procedures for MMHg and DMHg media prior to shipment to the field and subsequent
analysis of project samples for MMHg, DMHg and total Hg. Ms. Laura Nessley
provided Mr. Hicks with checklists to use during the audit. The audits of Frontier's
spiking procedures were carried out on April 29, 2003, for MMHg and May 4, 2004,
for DMHg and total Hg. Calibration, media spiking techniques, record keeping, and
good laboratory practices were the focus of the audit, with special attention paid to the
MMHg and DMHg spike preparation for the upcoming field effort. The following
Frontier personnel and their associated positions were present for some or all of the
audits conducted by ARCADIS.
Some of the primary observations resulting from the first audit included:
• A single source for calibration and spiking was used for MMHg and DMHg. The
laboratory had not been able to locate other stable standards for use as an
independent source. There were not National Institute of Standards and
Technology (NIST)-traceable standards for organo-Hg.
• There were not expiration dates for primary MMHg and MDHg standard materials.
The source of the MMHg standard had a 1998 date on the bottle.
• There are not written procedures for spiking of impinger solutions or carbon tubes.
• While work plans state that samples should be kept cold and the organometallic
analytes are light sensitive, the analytical standard for MMHg was stored in a clear
Teflon bottle on an un-refrigerated shelf across from a large picture window.
5-14
-------
Source Test Report
for Landfill C
• Frontier did not routinely retain an aliquot of spike solution nor spiked traps when
sending media to a field project.
The continuation of the earlier audit that focused on matrix spiking and media
preparation was performed in late May 2004. This audit concentrated on the analysis of
the sampling media sent to Landfill sites C and D, including extraction, analysis, and
calibration procedures for MMHg, DMHg, and total Hg. These audits were conducted
on three separate days to accommodate Frontier's analysis schedule. On May 27, 2004,
the audit focused on MMHg extraction and distillation and DMHg analysis. On May
28, 2004 MMHg analysis and total Hg extraction procedures were audited. On June 3,
2004, the procedures for total Hg analysis were audited.
Significant findings and recommendations resulting from the extraction and analysis
portion of the laboratory audit included:
• Efficiency factor (EF). An efficiency factor (EF) based on average results from
the analyses of distillation blanks was applied to all MMHg sample results. This
practice was not discussed in the narrative portion of the Frontier reports and not
mentioned by name in the standard operating procedures (SOPs) provided to
ARCADIS. This technique essentially boosts analyte recoveries through a
multiplied efficiency factor applied to all MMHg results. The current EF is 89.5
percent, therefore all results were normalized to 100 percent recovery levels. For
example, a measured value of 100.0 ng detected in an environmental sample was
corrected to 110.5ng after applying the EF. Without a data report disclaimer, this
practice misrepresents the results and biases all MMHg results high.
• Method blank subtraction. Frontier subtracts the average of the method blanks
from each extraction/preparation batch. While scientifically valid, this technique is
not acceptable for most EPA-referenced protocols. The laboratory has a
responsibility only to report blank concentrations, and it should be the
responsibility of the client to adjust environmental sample concentrations through a
data evaluation/validation process.
• MMHg Instrument stability. The MMHg analysis was performed over a 2-day
period because of poor instrument stability and issues associated with efficiency of
the ethylating reagent. Initially, two instruments were set up for calibration on May
27th. Only one of the instruments showed sufficient sensitivity and stability to
continue analysis. Unfortunately, the initial calibration curve did not meet method
specifications, so the instrument was recalibrated and environmental samples
5-15
-------
Source Test Report
for Landfill C
analyzed while the ARCADIS auditor was present. The following day, the auditor
was informed that the sample set did not meet the QAPP requirements because of
unexpected lower concentrations in the samples. The samples were successfully
reanalyzed the following day after maintenance was performed on the MMHg
analysis instrument. Reanalyzing samples is apparently common and sometimes
entire sample sets are analyzed more than once. Frontier stated that it is "the
nature" of this analysis to have to frequently recalibrate and reanalyze samples.
Calibrations should be closely reviewed during data validation.
Calibration Curve Forcing: ARCADIS learned that, in accordance with Frontier
policy, all calibration curve origin points were forced through zero. This procedure
is not consistent with most EPA-promulgated methods. ARCADIS recommends
reprocessing one calibration curve to determine the impact, if any, to the data.
Retention Time Marking: While observing the MMHg analysis, the analyst did
not mark the beginning of the analysis charts with a "tick" time marker, which is
particularly critical given that identification of MMHg is primarily by retention
times or relative retention times. Some of the samples being analyzed had
numerous chromatographic peaks including MMHg and other forms of Hg. Based
on observation of other laboratory "pods" within Frontier, the marking of the
actual start time on the strip chart recorder was not standardized as a procedural
practice. Some analysts mark the desorption time on the strip chart recorder and
others do not. However, marking of analysis start times should be a requirement of
each method in the place of automatic chromatographic data collection (integrators
or computer data acquisition) to avoid misidentification of analyte targets.
ARCADIS recommends the standardization of marking the start of analysis on
strip chart recorders.
Digestate Dilution Technique: The method of bringing the digested total Hg to
quantitative volume in a 20 milliliter glass vial was unusual as the technique does
not rely on marked, calibrated Class A or B glassware when bringing digested
samples to a known quantitative volume. The analyst did not know if the volume
of the unmarked vials was recently compared against calibrated glassware, but
assumed it was 20 mL. The analyst consistently brought the digested samples to a
consistent level that corresponded to the neck of the glass vial. At a minimum, the
vials should be calibrated to assure the final volumes are accurate.
Sample/Standard Storage: One refrigerator ("A") and one freezer ("A") used to
store samples, analytical standards, and frozen ethylating cocktails were not
5-16
-------
Source Test Report
for Landfill C
monitored for 3 days prior to the audit (5/25/04). This did not appear to be a
systematic problem, but the analyst did not have an explanation. Verification of
temperatures in standard and sample storage areas should be checked daily.
• Calibration Verification: While discussed in the previous ARCADIS Audit
report dated May 17, 2004, this observation is again included because it is critical
to the evaluation of the laboratory and the application of these methods to raw LFG
monitoring. Frontier uses a single source for calibration and spiking for MMHg
and DMHg methods. The laboratory has not been able to locate other acceptable,
stable standards, such as NIST-traceable standards. Frontier utilizes Standard
Reference Materials and certified standards however, accuracy is only measured
for MMHg by comparison to a digested tissue standard and for DMHg by
comparison to JSI-1, a material from the JSI Institute in Slovenia. ARCADIS
recommends that Frontier make an effort to locate alternate acceptable accuracy
standards to verify true concentrations of the main calibration standards.
• Holding Times: Holding times are generally not an issue with most analyses
Frontier performs, but based on the QAPP, specific holding times to analysis apply
to this analysis. This was not documented in the summary report; however the
total, MMHg and DMHg analyses were extracted, but not all analyzed within the
14 day holding time assuming May 27th was the 14th day after sampling. Some data
qualification might be necessary, depending on the professional judgment of the
data validator.
5.2.2.2 Internal Performance Evaluation Audit (PEA)
Because there is currently not a promulgated method for organo-Hg sampling and
analysis, PEA samples were integrated in to the sampling matrix to evaluate accuracy
and precision of the methods used by Frontier. ARCADIS subcontracted an
independent laboratory to assist in preparation of the PEA samples. The laboratory was
Cebam Analytical located in Seattle, Washington. All standards and stock solutions
were prepared and verified by a Cebam Analysical analyst.
Two PEA samples were prepared for total Hg. Trap A was spiked with 9.99 ng total
Hg by a Cebam analyst. This concentration was verified by Cebam by performing six
replicate analyses. Samples were analyzed by Frontier Geosciences as described in the
report titled: Determination of Total, Dimethyl, and Monomethyl Hg in raw LFG at
Pinconning and Montrose Michigan. Recovery results are presented in Table 5-3.
Relative percent difference (RPD) between the duplicate samples was 1.0 percent.
5-17
-------
Source Test Report
for Landfill C
Table 5-3. Total Mercury PEA Results
Sample ID
C-0521 04-01
C-0521 04-02
Total Hg Measured
(ng)
13.60
13.47
Total Hg Spiked
(ng)
9.99
9.99
Recovery
(%)
136
135
One PEA sample was prepared and analyzed for MMHg. A 2.0 ng/1 spiking solution
was prepared by transferring a 0.2 ml aliquot of 10 ng/ml standard into a 1-1 pre-
cleaned glass volumetric flask. The sample was analyzed by Frontier as described in
the report titled: Determination of Total, Dimethyl, and Monomethyl Mercury in raw
LFG at Pinconning and Montros, Michigan. Recovery results are presented in
Table 5-4. Because only one sample was prepared, precision for this analysis could not
be evaluated.
Table 5-4. MMHg PEA Results
Sample ID
04051 3-BR-
MHg7
Total MMHg
Measured
(ng/L)
2.327
Total MMHg Spiked
(ng/L)
2.00
Recovery
(%)
117
Two PEA samples were prepare and analyzed for DMHg. Trap A and Trap B were
spiked with 0.215 ng DMHg for a total concentration of 0.430 ng per train. This
concentration was verified by Cebam by analyzing five replicates samples of the
standard.
The samples were analyzed by Frontier as described in the report titled: Determination
of Total, Dimethyl, and Monomethyl Mercury in raw LFG at Pinconning and Montros,
Michigan. Recovery results are presented in Table 5-5. RPD between the duplicate
samples was 23 percent.
5-18
-------
Source Test Report
for Landfill C
Table 5-5. DMHg PEA Results
Sample ID
Arcadis DMM
Spike #1
Arcadis DMM
Spike #2
Total MMHg
Measured
(ngf
0.234
0.295
Total MMHg Spiked
(ngf
0.430
0.430
Recovery
(%)
54.4
68.6
Trap A and Trap B together
In conclusion, the MQO for recovery for total Hg and organo-Hg samples (as defined
in the QAPP) was established at 50 to 150 percent. All PEA samples met this
objective. The RPD between duplicate samples was also acceptable. The full text of the
TSA and PEA audit reports and completed checklists are included in Appendix S.
5-19
-------
Source Test Report
for Landfill C
This page intentionally left blank
5-20
-------
Field Test Measurements at Five Municipal Solid
Waste Landfills with Landfill Gas Control Technology
Final Report
Appendix D
SOURCE TEST REPORT
FOR LANDFILL D
-------
Table of Contents
Acronym List vii
1. Introduction 1-1
2. Landfill Facility Descriptions 2-1
2.1 Flare Process Description and Operation 2-1
2.2 Sampling Locations 2-1
2.2.1 Raw Landfill Gas (LFG) Header Pipe 2-1
2.2.2 Flare Stack 2-3
3. Test Operations 3-1
3.1 Test Team 3-1
3.2 Test Log 3-1
3.2.1 Planned Test Sample Matrices 3-1
3.2.2 Raw Landfill Gas (LFG) Pipe (Inlet) 3-3
3.2.3 Flare Stack 3-3
3.3 Field Test Changes and Deviations from Quality Assurance Project Plan
(QAPP) Specifications 3-9
3.3.1 Variation from Test Methods or Planned Activities 3-9
3.3.2 Application of Test Methods 3-10
3.3.3 Test Method Exceptions 3-10
4. Presentation of Test Results 4-1
4.1 Raw Landfill Gas (LFG) Results 4-1
4.1.1 Raw Landfill Gas (LFG) Flow Rate and Temperature 4-1
4.1.2 Raw Landfill Gas (LFG) Constituents 4-1
4.2 Enclosed Flare Stack Results 4-9
4.2.1 Flare Stack Gas Flow Rate and Temperature 4-10
4.2.2 Flare Stack Gas Constituents 4-10
4.3 Comparison with AP-42 Values 4-16
-------
Table of Contents
5. Quality Assurance/Quality Control (QA/QC) 5-1
5.1 Assessment of Measurement Quality Objectives 5-1
5.1.1 Continuous Emissions Monitors (CEMs) 5-1
5.1.2 Carbonyls (SW-846 Method 8315A) 5-2
5.1.3 Hydrogen Sulfide (H2S) (EPA Method 11) 5-3
5.1.4 Dioxins and Furans (PCDD/PCDFs) (EPA Method 23/0011) 5-4
5.1.5 Polycyclic Aromatic Hydrocarbons (PAH) (EPA Method 23/0011) 5-4
5.1.6 Non-Methane Organic Compounds (NMOC) (Method 25C) 5-4
5.1.7 Hydrogen Chloride (HCI) (EPA Method 26A) 5-5
5.1.8 Metals (EPA Method 29) 5-6
5.1.9 Organo-Mercury (Hg) and Total Mercury (Hg) (Frontier) 5-7
5.1.10 Volatile Organic Compound (VOCs) and Methane (CH4) (Method
TO-15) 5-8
5.2 Audits 5-10
5.2.1 EPA Technical Systems Audit 5-10
5.2.2 Laboratory Audits 5-11
5.2.3 Internal Performance Evaluation Audits (PEA) 5-15
-------
Table of Contents
Tables
Table 3-1. Test Team Members and Responsibilities 3-1
Table 3-2. Target Analytes for the Raw Landfill Gas 3-2
Table 3-3. Target Analytes for the Flare Stack Outlet Gas Stream 3-3
Table 3-4. Raw Landfill Gas Sample Log and Collection Times 3-4
Table 3-5. Flare Stack Test Sample Log and Collection Times 3-8
Table 3-6. Sampling Methods 3-11
Table 4-1. Raw Landfill Gas VOC Concentrations 4-2
Table 4-2. Raw Landfill Gas Non-Methane Organic Compound (NMOC)
Concentrations 4-6
Table 4-3. Raw Landfill Gas Hydrogen Sulfide Concentrations 4-6
Table 4-4. Raw Landfill Gas Carbonyls Concentrations 4-7
Table 4-5. Raw Landfill Gas Total Mercury Concentrations 4-7
Table 4-6. Raw Landfill Gas Dimethyl Mercury Concentrations 4-8
Table 4-7. Raw Landfill Gas Monomethyl Mercury Concentrations 4-9
Table 4-8. Raw Landfill Gas Elemental Mercury Concentrations 4-9
Table 4-9. Flare Stack Gas Operating Conditions Measured During Sampling 4-10
Table4-10. Flare Stack Combustion Products Concentrations 4-11
Table 4-11. Flare Stack THC Concentrations 4-13
Table 4-12. Flare Stack Hydrogen Chloride Emissions 4-15
Table 4-13. Flare Stack Metals Emissions 4-17
Table 4-14. Flare Stack CO, SO2, NOX Concentrations 4-17
Table 4-15. Comparison of Raw Landfill Gas Constituent Concentrations with AP-42
Values 4-18
Table 4-16. Raw Landfill Gas Constituent Concentrations for Compounds without AP-42
Default Values 4-22
Table 5-1. CEM MQO Summary for Landfill D 5-2
Table 5-2. VOCs Identified in Field Blank 5-9
Table 5-3. Total Mercury PEA Results 5-15
Table 5-4. MMHg PEA Results 5-15
Table 5-5. DMHg PEA Results 5-16
-------
Table of Contents
Figures
Figure 2-1. Simplified Flare Process Flow Diagram and Sampling Points
Figure 2-2. Raw Landfill Gas Collection Pipe
Figure 2-3. Enclosed Flare Unit Showing Stack Sampling Ports
Figure 2-4. Flare Stack Dimension and Sampling Traverse Locations
Figure 3-1. Sampling Operations at the Raw Landfill Gas Pipe Inlet
Figure 3-2. Sampling Operations at the Enclosed Flare
Figure 3-3. Sampling Train in Place on the Enclosed Flare Stack
Figure 4-1. Engine Stack Oxygen and Carbon Dioxide Concentrations
Figure 4-2. Flare Stack Total Hydrocarbon Concentrations
Figure 4-3. Flare Stack Carbon Monoxide Concentrations
Figure 4-4. Flare Stack Sulfur Dioxide Concentrations
Figure 4-5. Flare Stack Nitrogen Oxides Concentrations
2-2
2-2
2-3
2-4
3-6
3-6
3-7
4-11
4-12
4-13
4-14
4-15
IV
-------
Table of Contents
Appendices
A. Method TO-15 (VOCs, TICs, C2, C3, C4, C5, C6)
B. Method 25C (CH4, CO2, NMOC)
C. Method 3C (O2, N2, CH4, CO2)
D. Method TO-11 (Formaldehyde, Acetaldehyde)
E. Organic mercury Method (Mercury, Total, Monomethyl, Dimethyl)
F. LUMEX (Elemental Mercury)
G. Hydrogen Sulfide
H. Continuous Emission Monitor (Data and Charts)
L Method 29 (Metals)
M. Method 26A (HCI)
N. Analyte Concentration and Mass Flow Rate Computation Worksheets
P. Raw Field Data Records
Q. CEM Calibration Records and Span Gas Certification
R. Sampling Control Meter Boxes Calibration Record
-------
Acronym List
This page intentionally left blank
VI
-------
Acronym List
Acronym List
%D
AP-42
APPCD
ARCADIS
As
CCVs
Cd
CEMS
CH4
C12
CO
CO2
Cr
DMHg
EF
EPA
FID
Frontier
GC/FID
HC1
Hg
H2S
ICVs
LFG
MMHg
Mn
MQOs
MSW
Percent difference
Compilation of Air Pollutant Emission Factors
Air Pollution Prevention Control Division
ARCADIS G&M, Inc.
Arsenic
Continuing calibration verification samples
Cadmium
Continuous emission monitoring system
Methane
Chlorine
Carbon monoxide
Carbon dioxide
Chromium
Dimethyl mercury
Efficiency factor
US Environmental Protection Agency
Flame ionization detector
Frontier Geosciences
Gas chromatograph/flame ionization detector
Hydrogen chloride
Mercury
Hydrogen sulfide
Internal calibration verification samples
Landfill gas
Monomethyl mercury
Manganese
Measurement quality objectives
Municipal solid waste
VII
-------
Acronym List
N2 Nitrogen
Ni Nickel
NMOCs Non-methane organic compounds
NOX Nitrogen oxides
O2 Oxygen
PAHs Polynuclear aromatic hydrocarbons
Pb Lead
PEA Performance evaluation audit
QA Quality Assurance
QAPP Quality Assurance Project Plan
QC Quality control
RF Response factor
RPD Relative percent difference
RRF Relative response factors
RSD Relative standard deviation
RTP Research Triangle Park
SO2 Sulfur dioxide
SOPs Sstandard operating procedures
SVOC Semi-volatile organic compounds
TCDD/TCDFs Dioxins/furans
THCs Total hydrocarbons
TSA Technical systems audit
VOCs Volatile organic compounds
VIM
-------
Source Test Report
for Landfill D
1. Introduction
Large municipal solid waste (MSW) landfills are subject to Clean Air Act regulations
because of concerns related to their emissions and their potential adverse effects to
human health and the environment. Landfills are listed as a source of air toxics in the
Urban Air Toxics Strategy for future evaluation of residual risk. Existing emission
factors for landfill gas (LFG) were largely developed using data from the 1980s and
early 1990s. A database was developed summarizing data from approximately 1,200
landfills, along with emissions information from literature, test reports prepared by
state and local government agencies, and industry. These data were summarized in
Compilation of Air Pollutant Emission Factors (AP-42), Chapter 2.4. The final rule
and guidelines are contained in 40 CFR Parts 51, 52, and 60, Standards of
Performance for New Stationary Sources and Guidelines for Control of Existing
Sources: Municipal Solid Waste Landfills.
The overall purpose of this testing program was to generate data that could be used to
update AP-42 and to include data that reflect current waste management practices.
This report presents the results of a field test conducted at Landfill D, located in a
Midwest industrial state. Testing took place on May 15 and 16, 2004. Data from the
raw gas volatile organic compounds (VOCs) samples showed that an error had
occurred. Collection of samples to replace the defective samples was conducted on
September 14, 2004.
The site uses an enclosed flare for destruction of the LFG. A more detailed description
of the flare system is presented in Section 2. The specific purpose of the testing
program was to determine emissions from the raw pipe and from the flare stack. The
pollutants of interest for the raw untreated LFG were VOCs, non-methane organic
compounds (NMOCs), hydrogen sulfide (H2S), carbonyls (acetaldehyde,
formaldehyde), and mercury (Hg) compounds. The pollutants of interest for the treated
LFG, in this case at the enclosed flare stack, were carbon monoxide (CO), nitrogen
oxides (NOX), sulfur dioxide (SO2), NMOCs as total hydrocarbons (THCs), hydrogen
chloride (HC1), total Hg and metals.
ARCADIS Geraghty & Miller, Inc. (ARCADIS) as contractor to the US
Environmental Protection Agency (EPA) Air Pollution Prevention and Control
Division (APPCD), performed this work under Work Assignment 0-27 of Onsite
Laboratory Support Contract (EP-C-04-023). The testing activities followed the
specifications of the approved Site-Specific Quality Assurance Project Plan for the
Field Evaluations of Landfill Gas Control Technologies Landfill dated October 2003.
1-1
-------
Source Test Report
for Landfill D
This page intentionally left blank
1-2
-------
Source Test Report
for Landfill D
2. Landfill Facility Descriptions
Available information indicated that the site began operation in 1991.Based on
information provided by the site operator, Landfill D has approximately 2,350,000 tons
of waste in place as of August 2004.The waste covered an area of 31 acres. The LFG
generated at the landfill were extracted with 21 vertical wells producing a total of 400
cubic feet per minute. The collected LFG was piped to the enclosed flare system for
combustion.
2.1 Flare Process Description and Operation
A John Zink Model 72 Enclosed Ground Flare Station, rated at maximum LFG input
rate of 695 scfrn, received and destroyed the collected LFG. Figure 2-1 shows a
simplified process schematic of the flare system. A condensate removal system
prevented liquids from entering into the flare burners. A flame arrester prevented flame
from propagating from the burner array back into the LFG collection and flow control
system. A burner array and an automatic louver system controlled gas and air
distribution to achieve proper combustion. The unit could be operated satisfactorily
within a 5-to-l turndown ratio (from 20.9 to 4.0 MMBtu/hr). The system did not have
provisions for heat recovery.
According to manufacturer information, the John Zink Enclosed Ground Flare Station
was designed for a minimum residence time of 0.7 seconds at 1800 °F to insure
thermal destruction of CO and hydrocarbons, with minimal production of NOX.
Specific information related to the system's ability to destroy or reduce other potential
pollutants was not available.
2.2 Sampling Locations
Raw LFG sampling was conducted at the pipe feeding the John Zink enclosed ground
flare station and the flare stack as depicted in Figure 2-1.
2.2.1 Raw Landfill Gas (LFG) Header Pipe
J^aw untreated LFG samples were collected from the header pipe, upstream of any
processing units. The pipe was buried underground. Access to the pipe for sampling
was achieved by excavating the soil above and around the pipe. Figure 2-2 is a
photograph of the LFG inlet pipe. The pipe was 11 inches in inner diameter before it
connects to the gas control-and-process system. At the sampling point, four % inch gas
2-1
-------
Source Test Report
for Landfill D
STACK SAMPLING
PORTS
TYP. OF 4
Figure 2-1. Simplified Flare Process Flow Diagram and Sampling Points
Figure 2-2. Raw Landfill Gas Collection Pipe
2-2
-------
Source Test Report
for Landfill D
taps were installed and gases were withdrawn through these ports to obtain the test
samples.
Comparing the physical arrangement of the header pipe with the requirements of
standard sampling methodologies indicated that the header configuration rendered
isokinetic sampling at the gas collection pipe impossible. Therefore, isokinetic
sampling was not attempted at this location. Collected data showed that the particulate
loading in the sample was very low, confirming that the effect of not strictly adhering
to isokinetic sampling rates was insignificant.
2.2.2 Flare Stack
A picture of the flare stack and the arrangement of the sampling ports are shown in
Figure 2-3. The flare stack was 72 inches in diameter and had two 4-inch sampling
ports installed 90 degrees apart. Figure 2-4 is a schematic of the flare stack and it
includes the locations of the sample traverse points. Isokinetic sampling was possible at
this location and was followed.
Figure 2-3. Enclosed Flare Unit Showing Stack Sampling Ports
2-3
-------
Source Test Report
for Landfill D
Sampling
Ports
o
Stack Cross Section
Traverse Points
Points Distance
1
2
3
4
5
6
7
8
9
10
11
12
1.5"
4.75"
8.5"
1£.T5"
18"
!5.5"
«.5"
54"
59. !5"
63.5"
6V"
70.5"
\
Figure 2-4. Flare Stack Dimension and Sampling Traverse Locations
2-4
-------
Source Test Report
for Landfill D
3. Test Operations
As stated previously, the purpose of the sampling program was to determine the
concentrations of the target analytes in the raw LFG at the header pipe and emissions
from the flare stack.
3.1 Test Team
The tests were conducted by a team of seven individuals. The team members and their
primary duties are listed in Table 3-1.
Table 3-1. Test Team Members and Responsibilities
Role
Test Engineer
Test Engineer
Test Engineer
Test Engineer
Sampling Technician
Senior Chemist
Senior Chemist
(Frontier Geosciences)
Primary Duty
Field Supervisor
CEM operator
Sample train preparation and recovery
Sample train operator at LFG inlet pipe
Sample train operator at stack
Mercury measurements
Mercury measurements
3.2 Test Log
3.2.1 Planned Test Sample Matrices
The list of target samples to be collected and measurements to be conducted were
specified in the Quality Assurance Project Plan (QAPP) Revision 1 dated May 2004.
These are reiterated here for completeness. Tables 3-2 lists the target compounds of
interest for the raw untreated LFG. Table 3-3 lists the target compounds of interest for
the treated gas, collected at the flare stack.
3-1
-------
Source Test Report
for Landfill D
Table 3-2. Target Analytes for the Raw Landfill Gas
Volatile compounds
Methane
Ethane
Propane
Butane
Pentane
Hexane
Carbonyl sulfide
Chlorodifluoromethane
Chloromethane
Dichlorodifluoromethane
Dichlorofluoromethane
Ethyl chloride
Fluorotrichloromethane
1,3-Butadiene
Acetone
Acrylonitrile
Benzene
Bromodichloromethane
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chloroform
Dimethyl sulfide
Ethyl mercaptan
Volatile compounds
(continued)
Ethylene dibromide
Ethylene dichloride
Methyl chloroform
Methyl isobutyl ketone
Methylene chloride
Propylene dichloride
t-1,2-Dichloroethene
Tetrachloroethene
Toluene
Trichlorethylene
Vinyl chloride
Vinylidene chloride
Ethanol
Methyl ethyl ketone
2-Propanol
1,4-Dichlorobenzene
Ethylbenzene
Xylenes
Non-methane organic
compounds
Reduced sulfur compounds
Hydrogen sulfide
Carbonyls
Acetaldehyde
Formaldehyde
Mercury
Organo-mercury compounds
Total
Elemental
Gases
Carbon Dioxide
Oxygen
3-2
-------
Source Test Report
for Landfill D
Table 3-3. Target Analytes for the Flare Stack Outlet Gas Stream
Gases
Oxygen
Carbon dioxide
Carbon Monoxide
Nitrous Oxides
Sulfur Dioxide
Total Hydrocarbons
Non-methane organic
compounds (as Total
Hydrocarbons)
Hydrogen chloride
Dioxins/Furans
Polycyclic aromatic hydrocarbons
Mercury
Total
Metals
Lead, Arsenic, Cadmium, Chromium,
Manganese, Nickel
3.2.2 Raw Landfill Gas (LFG) Pipe (Inlet)
Sample collection took two days to complete. Table 3-4 lists the samples that were
collected from the LFG pipe. Figure 3-1 is a photograph of the sampling team in action
at this sample location.
3.2.3 Flare Stack
Sampling at the flare stack was conducted by accessing the sampling ports with the aid
of a scaffold. Figure 3-2 shows the flare and the sampling scaffold platform. Figure 3-3
shows a sampling in place during sample collection on the enclosed flare stack.
3-3
-------
Source Test Report
for Landfill D
Table 3-4. Raw Landfill Gas Sample Log and Collection Times
Sampling
Method
Run Number
EPA Method 40 (TO-15/25C, 3C) a
D-Pre-M40-051 504-01
D-Pre-M40-051 604-02
D-Pre-M40-051 604-03
D-Pre-M40-051604-OFB
D-Pre-M40-091 404-01
D-Pre-M40-091 404-02
D-Pre-M40-091 404-03
D-Pre-M40-091404-FB
D-Pre-M40-091 404-04
EPA Method 01 00
D-Pre-M01 00-051 604-01
D-Pre-M01 00-051 604-02
D-Pre-M01 00-051 604-03
D-Pre-M01 00-051 604-OFB
EPA Method 1 1
D-Pre-M001 1-051 504-01 b
D-Pre-M001 1-051604-02
D-Pre-M001 1-051604-03
D-Pre-M001 1-051604-04
D-Pre-M0011-051604-FB
Lumex Instrument
D-Pre-EM-051 604-01
D-Pre-EM-051 604-02
D-Pre-EM-051 604-03
Analyte(s)
VOCs/NMOCs/O2/CO2,N2
VOCs/NMOCs/O2/CO2,N2
VOCs/NMOCs/O2/CO2,N2
VOCs/NMOCs/O2/CO2,N2
VOCs/NMOCs
VOCs/NMOCs
VOCs/NMOCs
VOCs/NMOCs
VOCs/NMOCs
Carbonyls
Carbonyls
Carbonyls
Carbonyls
H2S
H2S
H2S
H2S
H2S
Elemental Hg °
Elemental Hg °
Elemental Hg c
Sample Class
Test
Test
Test
Field Blank
Test
Test
Test
Field Blank
Field Blank
Test
Test
Test
Field Blank
Test
Test
Test
Test
Field Blank
Test
Test
Test
Date
05/15/04
05/16/04
05/16/04
05/16/04
09/14/04
09/14/04
09/14/04
09/14/04
09/14/04
05/16/04
05/16/04
05/16/04
05/16/04
05/15/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
Run Period
12:43-13:44
09:56-10:55
11:43-12:43
14:27
10:32-11:32
12:08-13:08
13:43-14:43
15:11 -15:53
16:05-17:05
15:25-15:57
15:52-16:04
16:05-16:36
14:58
13:47-13:57
10:42-10:53
11:56-12:07
12:51 -13:02
13:40
09:15-09:17
13:10-13:12
15:10-15:12
3-4
-------
Source Test Report
for Landfill D
Sampling
Method
Run Number
Frontier
040515-WF-STM1
040515-WF-STM2
040515-WF-STM4
04051 5-WF-STM3BLK
Frontier
04051 5-WF-MHg5Spike
04051 5-WF-MHg3BLK
040515-WF-MHg1
04051 5-WF-MHg2
04051 5-WF-MHg4
Frontier
04051 5-WF-DMHg5Spike
04051 5-WF-DMHg6TripSpk
04051 5-WF-DMHg7
04051 5-WF-DMHg8
04051 5-WF-DMHg3BLK
04051 5-WF-DMHg1
04051 5-WF-DMHg2
04051 5-WF-DMHg4
Analyte(s)
Total gaseous Hg
Total gaseous Hg
Total gaseous Hg
Total gaseous Hg
Monomethyl Hg
Monomethyl Hg
Monomethyl Hg
Monomethyl Hg
Monomethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Sample Class
Test
Test
Test
Field Blank
Spike
Field Blank
Test
Test
Test
Spike
Trip Spike
Volume Experiment
Volume Experiment
Field Blank
Test
Test
Test
Date
05/15/04
05/15/04
05/15/04
05/15/04
05/15/04
05/15/04
05/15/04
05/15/04
05/15/04
05/15/04
05/15/04
05/15/04
05/15/04
05/15/04
05/15/04
05/15/04
05/15/04
Run Period
11:51 -12:37
13:10-13:50
14:32-15:22
14:15
16:10-17:04
14:15
11:53-12:40
13:12-13:59
14:33-15:22
17:42-17:45
17:55
18:00-18:03
18:15-18:26
17:15
16:41 -16:43
16:58-17:00
17:29-17:31
a The Method 40 SUMMA canister contents were first analyzed for speciated VOCs, then
analyzed for NMOCs by Method 25C
b Sampling train back flushed at end of run; run repeated
c Represents average of 3 readings, each 30-second in duration
3-5
-------
Source Test Report
for Landfill D
Figure 3-1. Sampling Operations at the Raw Landfill Gas Pipe Inlet
Figure 3-2. Sampling Operations at the Enclosed Flare
3-6
-------
Source Test Report
for Landfill D
Figure 3-3. Sampling Train in Place on the Enclosed Flare Stack
The flare stack was sampled for NMOCs (as THCs), HC1, lead (Pb), arsenic (As),
cadmium (Cd), chromium (Cr), manganese (Mn), nickel (Ni), total Hg, SO2, NOX,
CO, carbon dioxide (CO2), and oxygen (O2). Table 3-5 lists the test samples that were
collected from the flare stack.
The flare stack cross-section was divided into 24 equal areas according to EPA Method
1. Sampling at the flare stack was conducted at isokinetic conditions. Sample collection
times for the Method 26A HC1 train and the Method 29 metals train were 60-minutes.
Run time for continuous emission monitoring system (CEMS) parameters (SO2, NOX,
CO, O2, CO2, and THCs) was 60 minutes.
3-7
-------
Source Test Report
for Landfill D
Table 3-5. Flare Stack Test Sample Log and Collection Times
Sampling
Method
Run Number
EPA Method 3A (CEM)
D-Post-M3A-051 604-01
D-Post-M3A-051 604-02
D-Post-M3A-051 604-03
EPA Method 3A (CEM)
D-Post-M3A-051 604-01
D-Post-M3A-051 604-02
D-Post-M3A-051 604-03
EPA Method 10 (CEM)
D-Post-M 10-05 1604-01
D-Post-M 10-05 1604-02
D-Post-M 10-05 1604-03
EPA Method 7E (CEM)
D-Post-M7E-051 604-01
D-Post-M7E-051 604-02
D-Post-M7E-051 604-03
EPA Method 6C (CEM)
D-Post-M6C-051604-01
D-Post-M6C-051 604-02
D-Post-M6C-051 604-03
EPA Method 25A (CEM)
D-Post-M25A-051 604-01
D-Post-M25A-051 604-02
D-Post-M25A-051 604-03
Lumex Instrument
D-Post-EM-051604-01
D-Post-EM-051 604-02
D-Post-EM-051 604-03
Analyte(s)
02
02
02
CO2
CO2
CO2
CO
CO
CO
NOx
NOX
NOX
SO2
SO2
SO2
NMOCs (THC)
NMOCs (THC)
NMOCs (THC)
Elemental Hg a
Elemental Hg a
Elemental Hg a
Sample
Class
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Date
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
Run Period
10:40-11:39
12:20-13:19
14:40-15:39
10:40-11:39
12:20-13:19
14:40-15:39
10:40-11:39
12:20-13:19
14:40-15:39
10:40-11:39
12:20-13:19
14:40-15:39
10:40-11:39
12:20-13:19
14:40-15:39
10:40-11:39
12:20-13:19
14:40-15:39
09:15-09:17
13:10-13:12
15:10-15:12
3-8
-------
Source Test Report
for Landfill D
Sampling
Method
Run Number
EPA Method 26A
D-Post-M26A-051 604-01
D-Post-M26A-051 604-02
D-Post-M26A-051 604-03
EPA Method 29
D-Post-M29-05 1604-01
D-Post-M29-05 1604-02
D-Post-M29-05 1604-03
Analyte(s)
HCI
HCI
HCI
Metals
Metals
Metals
Sample
Class
Test
Test
Test
Test
Test
Test
Date
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
05/16/04
Run Period
10:35-11:38
13:03-14:05
15:00-16:02
10:34-11:38
13:02-14:05
14:59-16:04
a Represents 3 readings, each 30-seconds in duration
3.3 Field Test Changes and Deviations from Quality Assurance Project Plan (QAPP)
Specifications
3.3.1 Variation from Test Methods or Planned Activities
3.3.1.1 Sampling at the Raw Landfill Gas (LFG) Pipe
There were not variations from test methods or planned activities at the LFG pipe.
3.3.1.2 Raw Landfill Gas (LFG) Condensate Sample
A LFG pipe condensate sample was not specified in the QAPP and was not collected.
3.3.1.3 Raw Landfill Gas (LFG) Flow Rate Measurement
Gas flow as indicated by the John Zink enclosed ground flare station control panel was
recorded. The accuracy of the indicated measurement cannot be independently verified
because of the inability to measure gas velocity accurately, as discussed in the previous
section. The test team was only able to make crude velocity measurements by
traversing the pipe using a standard pitot probe. The accuracies of these measurements
are uncertain and do not agree closely with the control panel indicted flows which were
more stable and likely to be more accurate.
3-9
-------
Source Test Report
for Landfill D
3.3.1.4 Enclosed Flare Stack
There were not variations from test methods or planned activities at the enclosed flare
stack.
3.3.2 Application of Test Methods
The sampling and, where applicable, analytical methods used in this test program
follow those specified in the QAPP. Sampling methods are shown in Table 3-6
3.3.3 Test Method Exceptions
Laboratory analytical procedures followed those prescribed by the specified methods,
with the following exceptions for the stack flare:
• Non-Methane Organic Compounds (NMOCs) - Method 25A was used instead of
the specifically applicable Method 25C. This was necessitated by the low overall
VOC concentrations in the flare stack gas (<50 ppm as hexane). Moreover,
Method 25 C is specifically designed for and applicable to raw LFG. As such, the
test method is not applicable to the combustion effluents from the flare stack.
• Polycyclic aromatic hydrocarbons (PAH) were analyzed by CARB Method 429 as
opposed to Method 8270. However, these methods are comparable because CARB
Method 429 contains procedures for sampling, sample recovery, clean-up, and
analysis. Method 8270 is strictly an analytical method. CARB Method 429 is
specific to 19 PAHs, the target analytes of this portion of the specified tests. The
19 PAHs are a subset of the more than 200 target analytes listed for Method 8270
for semi-volatile organic compounds (SVOC). Though specific compounds called
out for use in instrument performance verifications, internal standard preparation,
surrogate standards, and continuing calibration verifications/ calibration checks are
slightly different, both methods require them. CARB Method 429 adds another
level of quality control (QC) with a required recovery standard. Method
performance and acceptance criteria for recoveries are better defined in CARB
Method 429 and meet or exceed those stated in Method 8270C. As long as any
additional compounds reported by the laboratory using CARB Method 429 are
included in the calibration standards and acceptable response factors are
demonstrated, using CARB Method 429 is essentially equivalent to using SW-846
Method 8270.
3-10
-------
Source Test Report
for Landfill D
Table 3-6. Sampling Methods
Procedure
EPA Method 1
EPA Method 2
EPA Method 3A
EPA Method 3C
EPA Method 4
EPA Method 6C
EPA Method 7E
EPA Method 10
EPA Method 1 1
EPA Method 25A
EPA Method 25C
EPA Method 26A
EPA Method 29
EPA Method 40
SW-846 Method
0100/TO-11
LUMEX
Instrument
Frontier Geo.
Methods
Description
Selection of enclosed flare stack
traverse points
Determination enclosed flare stack of
stack gas velocity and volumetric flow
rate
Determination of oxygen (O2) and
carbon dioxide (CO2) for enclosed flare
stack gas molecular weight calculations
Determination of carbon dioxide (CO2),
methane (ChU), nitrogen (N2), and
oxygen (O2) in raw LFG
Determination of enclosed flare stack
gas moisture
Determination of enclosed flare stack
sulfur dioxide (SO2)
Determination of enclosed flare stack
nitrogen oxides (NOx)
Determination of enclosed flare stack
carbon monoxide (CO)
Determination of raw LFG hydrogen
sulfide (H2S)
Determination of enclosed flare stack
gas non-methane organic compounds
(NMOCs)(as total hydrocarbons [THCs])
Determination of raw LFG NMOCs
(performed on Method 40 SUMMA
canister sample)
Determination of raw LFG hydrogen
chloride (HCI)
Determination of enclosed flare stack
metals
Determination of raw LFG volatile
organic compounds (VOCs)
Determination of raw LFG carbonyls
(formaldehyde, acetaldehyde)
Determination of raw LFG and enclosed
flare stack elemental mercury (Hg°)
Determination of raw LFG:
Monomethyl mercury
Dimethyl mercury
Total mercury
Organization Performing Analysis
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
Triangle Environmental Services
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
Oxford Laboratories
ARCADIS G&M
Triangle Environmental Services
Resolution Analytics
First Analytical Laboratories
Research Triangle Park Laboratories
Resolution Analytics
ARCADIS G&M
Frontier Geosciences
3-11
-------
Source Test Report
for Landfill D
This page intentionally left blank
3-12
-------
Source Test Report
for Landfill D
4. Presentation of Test Results
Testing took place at the Landfill D on May 15 and 16, 2004. Results of the testing are
presented in this section. Detailed test results are included in the Appendices. The
following subsections provide concise summaries of the test results.
4.1 Raw Landfill Gas (LFG) Results
As shown in Figure 2-2, sampling was conducted by extracting samples via the four %-
inch ports installed in the LFG pipe.
4.1.1 Raw Landfill Gas (LFG) Flow Rate and Temperature
4.1.1.1 Direct Measurements
The facility process system had a flow measurement system, which displays the flow
rate on an instrument panel meter. The panel meter read 400 scfm with fluctuations of
±3.5 percent during the testing period.
The small size of the sampling ports precluded the proper measurement of the velocity
profile within this pipe. Nonetheless, measurements with a velocity probe returned
readings ranging from 376 scfm to 845 scfm. These readings were considered to be
less reliable than those indicated by the facility panel meter. Therefore, mass emissions
calculations in this report are based on the facility's flow meter readings.
Direct measurement with thermocouples showed the LFG temperature to be 54 °F.
4.1.2 Raw Landfill Gas (LFG) Constituents
The concentrations of the constituents of interest in the LFG are presented in
Subsections 4.1.2.1 through 4.1.2.5. Following the presentation of the constituent
concentrations, Section 4.3 summarizes the data and presents a comparison with the
AP-42 values. Section 4.3 also presents the estimated mass flow rates of the
constituents at the LFG pipe.
4.1.2.1 Volatile Organic Compounds (VOCs)
Concentrations of VOCs were obtained collecting summa canister samples using
Method 40 procedures. Analysis was performed by Method TO-15, with gas
4-1
-------
Source Test Report
for Landfill D
chromatography and mass spectrometry (GC/MS). The alkanes (C2 through C6), being
present in much higher concentrations, were analyzed by GC flame ionization
detection (FID) on the same summa canister samples.
The data from the testing on May 15 and 16, 2004 were not useable because the results
suggested that the samples were not collected properly. The analyte concentrations
were extremely low and could not possibly be representative of the raw LFG.
Collection of samples to replace the defective samples was repeated on September 14,
2004. Analytical results of the September 14 samples are reported below in Table 4-1.
Table 4-1. Raw Landfill Gas VOC Concentrations
Compound
Unit
MDL
Concentration (ppmv)
Run1
Run 2
Run 3
Average a
Bv GC/FID
Ethane
Propane
Butane
Pentane
Hexane
ppmv
ppmv
ppmv
ppmv
ppmv
1
1
1
1
1
5.9
31.5
ND
ND
3.9
5.5
29.5
ND
6.1
3.0
5.4
30.5
ND
ND
ND
5.6
30.5
ND
2.4
2.5
BvTO-15GC/MS
Dichlorodifluoromethane (Freon 12)°
1,2-Chloro-,1,2,2-Tetrafluoroethane
(CFC114)
Chloromethane
Vinyl chloride0
1,3-Butadiene ((Vinylethylene)0
Bromomethane (Methyl Bromide)
Chloroethane (Ethyl Chloride)0
Trichloromonofluoromethane (CFC1 1 )
1,1-Dichloroethene
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
0.3
0.2
0.1
0.2
0.3
0.2
0.2
0.2
0.2
1310
115
695
1240
340
8
608
127
20
1200
116
ND
1280
347
ND
608
118
23
1190
99
ND
1080
292
ND
687
104
21
1240
110
232
1200
326
2.8
634
116
21
4-2
-------
Source Test Report
for Landfill D
Compound
1 ,1 ,2-Trichloro-1 ,2,2-trifluoroethane
(CFC113)
Carbon Disulfide
Ethanol0
Isopropyl Alcohol (2-Propanol)c
Methylene chloride (Dichloromethane)0
Acetone0
t-1,2-dichloroethene
Hexane0
Methyl-t-butyl ether (MTBE)
1,1-Dichloroethane
Vinyl Acetate0
cis-1 ,2-Dichloroethene °
Cyclohexane0
Chloroform0
Ethyl Acetate0
Carbon Tetrachloride
Tetrahydrofuran (Diethylene Oxide)0
1,1,1-Trichloroethane
2-Butanone (Methyl Ethyl Ketone)0
Heptane0
Benzene0
1,2-Dichloroethane
Unit
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
MDL
0.2
0.3
0.2
0.2
0.1
0.3
0.3
0.3
0.3
0.4
0.5
0.3
0.3
0.3
0.3
0.5
0.4
0.3
0.3
0.2
0.2
0.3
Concentration (ppmv)
Run 1
18
80
384
6920
1140
11900
60
4060
45
620
45
1830
2400
430
4880
ND
2140
ND
8320
3730
1220
23
Run 2
19
110
438
6260
1200
14600
53
4310
46
575
50
1850
2320
470
4760
114
2250
ND
8860
3730
1270
24
Run 3
19
88
359
6710
990
12000
47
3570
26
579
37
1650
2090
555
4170
ND
1800
ND
7040
3280
1120
20
Average a
19
93
394
6630
1110
12800
53
3980
39
591
44
1780
2270
485
4600
38
2060
ND
8070
3580
1200
22
4-3
-------
Source Test Report
for Landfill D
Compound
Trichloroethylene (Trichloroethene)
1,2-Dichloropropane
Bromodichloromethane
1,4-Dioxane (1,4-Diethylene Dioxide)
cis-1,3-Dichloropropene
Toluene (Methyl Benzene)
4-Methyl-2-pentanone (MIBK)
t-1 ,3-Dichloropropene
Tetrachloroethylene
(Perchloroethylene) c
1,1,2-Trichloroethane0
Dibromochloromethane
1,2-Dibromoethane (Ethylene
dibromide)
2-Hexanone (Methyl Butyl Ketone)
Ethylbenzene0
Chlorobenzene0
m/p-Xylene (Dimethyl Benzene)0
o-Xylene (Dimethyl Benzene)0
Styrene (Vinylbenzene)0
Tribromomethane (Bromoform)
1 , 1 ,2,2-Tetrachloroethane
1-Ethyl-4-methylbenzene (4-Ethyl
Toluene) b'°
1,3,5-Trimethylbenzene b'c
Unit
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
MDL
0.2
0.3
0.2
0.2
0.2
0.3
0.2
0.2
0.3
0.2
0.2
0.2
0.2
0.3
0.2
0.65
0.3
0.1
0.3
0.2
0.2
0.2
Concentration (ppmv)
Run 1
422
ND
ND
0.3
7
34000
ND
25
1030
ND
11
ND
ND
8290
ND
13800
5490
1120
ND
ND
1000 J
1000 J
Run 2
436
ND
ND
23
4
37300
ND
ND
1070
ND
21
ND
ND
8620
62
14700
5670
1320
3
ND
1010 J
1010 J
Run 3
397
ND
ND
14
ND
19500
ND
ND
963
ND
15
ND
ND
7460
ND
12400
5060
1090
25
ND
913 J
913 J
Average a
418
ND
ND
12
4
30300
ND
8
1020
ND
16
ND
ND
8120
21
13600
5410
1180
9
ND
976 J
976 J
4-4
-------
Source Test Report
for Landfill D
Compound
1 ,2,4-Trimethylbenzene c
1,4-Dichlorobenzenec
1 ,3-Dichlorobenzene c
Benzyl Chloride0
1,2-Dichlorobenzenec
1 , 1 ,2,3,4,4-Hexachloro-1 ,3-butadiene
1 ,2,4-Trichlorobenzene
Acrylonitirile
Unit
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
MDL
0.3
0.3
0.2
0.2
0.3
0.2
0.3
20
Concentration (ppmv)
Run 1
2230
707
671
ND
33
ND
ND
ND
Run 2
2290
683
647
ND
31
ND
ND
ND
Run 3
2040
669
631
ND
29
ND
ND
ND
Average a
2190
686
650
ND
31
ND
ND
ND
ND - Constituent not detected at the stated detection limits
a - In computing averages, when all measurements are ND, the average is reported as ND. When
one or more measurement is above detection, the ND measurement is treated as 50% of the
stated MDL. If MDL is not reported, a ND measurement is treated as zero.
b- 1-Ethyl-4-methylbenzene (4-Ethyl Toluene) and 1,3,5-Trimethylbenzene co-eluted from the GC
and also have the same quantitation ions, thus making them indistinguishable. Therefore, the
reported values represent the combined concentrations of these two compounds.
c Analyte detected in blank sample. See table 5-2 for analyte-specific detected levels.
4.1.2.2 Non-methane Organic Compounds (NMOCs)
Non-methane organic compounds (NMOCs) in the raw LFG were analyzed by Method
25C on the samples collected by Method 40. Table 4-2 shows the concentrations of
NMOC, methane (CFL), CO2 and O2 in the LFG. These results were obtained from the
samples that were collected during the retest that took place on September 14, 2004.
The analytes, oxygen (O2), carbon dioxide (CO2), and moisture, are not pollutants but
are of interest as they are useful indicators of the "quality" of the raw LFG. The
concentrations of nitrogen (N2) and O2 are also indicators of the extent of ambient air
infiltration into the LFG collection. Method 25C for NMOC determination specifically
recommends that these measurements be made to determine potential air infiltration.
Therefore, while measurements for methane (CFL,), CO2, O2, and N2 by Method 3C
were not included in the original QAPP, these measurements were included and
performed.
4-5
-------
Source Test Report
for Landfill D
Table 4-2. Raw Landfill Gas Non-Methane Organic Compound (NMOC) Concentrations
Run 1
Run 2
Run 3
Average
NMOC
(as ppmv
hexane)
Method
25C
971
1024
1024
1006
CH4
(% v/v)
Method
25C
58.9
57.4
59.5
58.6
Method
3C
55.6
54.3
55.5
55.1
CO2
(% v/v)
Method
25C
41.1
40.2
41.7
41.0
Method
3C
38.5
37.6
38.3
38.1
02
(% v/v)
Method
3C
0.02
0.02
0.01
0.02
N2
(% v/v)
Method
3C
11.4
12.8
9.5
11.2
Moisture
(% v/v)
Method
23
NM
NM
NM
NM
NM - not measured because Method 23 sampling train was not run. Data column is included to
retain format consistency with reports for Landfills A, B, and C
Concentrations are reported without correction for nitrogen
4.1.2.3 Hydrogen Sulfide (H2S)
Raw landfill gas H2S concentrations were obtained by collecting and analyzing the
samples in accordance with EPA Method 11. These results are presented in Table 4-3.
Table 4-3. Raw Landfill Gas Hydrogen Sulfide Concentrations
Run 1
Run 2
Run 3
Average
h^S Concentration
(mg/m3)
32.1
90.2
186
103
(ppmv)
22.7
63.9
132
72.7
Sample hold times exceeded the 30-day criteria by 2 days
4.1.2.4 Carbonyls
The target carbonyl compounds, formaldehyde and acetaldehyde, were analyzed by
SW-846 Method 8315 on samples collected by EPA Method 0100. The analysis results
are presented in Table 4-4.
4-6
-------
Source Test Report
for Landfill D
Table 4-4. Raw Landfill Gas Carbonyls Concentrations
MDL
Run 1
Run 2
Run 3
Average
Formaldehyde
(ug/m3)
8.0
39.0
19.9
16.0
25.0
(x10~3 ppmv)
6.4
31.5
16.0
12.9
20.1
Acetaldehyde
(ug/m3)
8.3
439
534
72
348
(x10~3 ppmv)
4.5
241
293
39
191
4.12.5 Mercury (Hg)
Mercury (Hg) can exist in several forms. This test program focused on the elemental,
monomethyl, and dimethyl forms of Hg, and total Hg. Elemental Hg was measured
with the LUMEX instrument. Organic monomethyl Hg, dimethyl Hg and total Hg were
sampled and analyzed using the organic mercury method.
4.1.2.5.1 Total Mercury (Hg) Samples
To collect the total Hg samples, an iodated charcoal trap was used as a sorbent. A
backup tube was also present to assess any breakthrough. The sorbent tube was heated
to above the dew point of the gas stream to prevent condensation on the sorbent. A
silica gel impinger was used to collect and quantify the water vapor from the stream. A
diaphragm air pump was used to pull the sample through the train and collect the
sample. A dry gas meter capable of measuring the volume in 10 ml increments was
used to monitor and quantify the volume of gas sampled.
Table 4-5 presents the total Hg concentrations in the LFG. They ranged from 723 to
751 ng/m3 with an average of 740 ng/m3.
Table 4-5. Raw Landfill Gas Total Mercury Concentrations
MDL
Run 1
Run 2
Run 3
Average
Total Mercury Concentration
(ng/m3)
50
747
723
751
740
(x10's ppm)
6.0
89.9
87.0
90.4
89.1
4-7
-------
Source Test Report
for Landfill D
4.1.2.5.2 Dimethyl Mercury (Hg) Samples
To collect the dimethyl Hg sample, a Carbotrap was used as a sorbent. A backup tube
was also present to assess any breakthrough. A third iodated carbon trap was also
present to collect any elemental Hg present. The sorbent tube was heated to above the
dew point of the gas stream to prevent condensation on the sorbent. A silica gel
impinger was used to collect and quantify the water vapor from the stream. A
diaphragm air pump was used to pull sample through the train and collect the sample.
A dry gas meter capable of measuring the volume in 10 ml increments was used to
monitor and quantify the volume of gas sampled.
Table 4-6 presents the dimethyl Hg concentrations in the LFG. These ranged from 49.7
to 53.1 ng/m3 with an average of 51.0 ng/m3.
Table 4-6. Raw Landfill Gas Dimethyl Mercury Concentrations
MDL
Run 1
Run 2
Run 3
Average
Dimethyl Mercury Concentration
(ng/m3)
0.5
50.3
49.7
53.1
51.0
(xlO"6 ppmv)
0.05
5.3
5.2
5.6
5.3
4.1.2.5.3 Monomethyl Mercury (Hg) Samples
To collect the sample, a set of three impingers filled with 0.001 M HC1 was used to
collect the monomethyl Hg. An empty forth impinger was used to knockout any
impinger solution carryover to the pump and meter system. A diaphragm air pump was
used to pull sample through the train and collect the sample. A dry gas meter capable
of measuring the volume in 10 ml increments was used to monitor and quantify the
volume of gas sampled.
As shown in Table 4-7, monomethyl Hg concentrations in the LFG ranged from 2.36
to 2.64 ng/m3 with an average amount of 2.47 ng/m3.
4-8
-------
Source Test Report
for Landfill D
Table 4-7. Raw Landfill Gas Monomethyl Mercury Concentrations
MDL
Run 1
Run 2
Run 3
Average
Monomethyl Mercury Concentration
(ng/m3)
0.13
2.40
2.64
2.36
2.47
(xlO"6 ppmv)
0.014
0.27
0.296
0.264
0.278
4.1.2.5.4 Elemental Mercury (Hg)
Elemental Hg was determined by the LUMEX instrument and the results are presented
in Table 4-8. The analyzed concentrations ranged from 265 to 290 ng/m3 with an
average of 278 ng/m3. each reported run consisted of an instrument reading over a
30-second period.
Table 4-8. Raw Landfill Gas Elemental Mercury Concentrations
Run 1
Run 2
Run 3
Average
Concentration a
Background
(ng/m3)
0
0
0
0
(x10's
ppmv)
0
0
0
0
Gas Pipe
(ng/m3)
265
280
290
278
(x10's
ppmv)
31.9
33.7
34.9
33.5
Average of three readings, each 30-second in duration
4.2 Enclosed Flare Stack Results
The enclosed flare stack was sampled for NMOCs (as THCs), HC1, metals (Pb, As, Cd,
Cr, Mn, Ni, total Hg), SO2, NOX, CO, CO2, and O2. The stack cross section was
divided into 24 equal areas according to EPA Method 1. Sampling run time for HC1
and metals was 60 minutes. Run time for CEMS parameters (SO2, NOX, CO, O2, CO2,
and THCs) was 60 minutes.
4-9
-------
Source Test Report
for Landfill D
4.2.1 Flare Stack Gas Flow Rate and Temperature
Sampling at the flare stack was conducted at isokinetic conditions. The procedures
provided stack gas velocity distribution across the flare stack and reliable
measurements of stack gas flow rates. Table 4-9 lists the volumetric flow rates and
temperatures at the flare stack measured during the various sampling runs.
Table 4-9. Flare Stack Gas Operating Conditions Measured During Sampling
Run Number
D-Post-M26A-051 604-01
D-Post-M26A-051 604-02
D-Post-M26A-051 604-03
D-Post-M29-05 1604-01
D-Post-M29-05 1604-02
D-Post-M29-05 1604-03
Average
Duration
10:35-11:38
13:03-14:05
15:00-16:02
10:34-11:38
13:02-14:05
14:59-16:04
Average
Stack Temp
(°F)
1412
1446
1446
1430
1444
1445
1437
Carbon
Dioxide
(%)
6.4
6.3
6.4
6.4
6.3
6.4
6.4
Oxygen
(%)
13.5
13.5
13.5
13.5
13.5
13.5
13.5
Moisture
(%)
10.3
7.9
7.9
8.3
8.0
8.1
8.4
Velocity
(actual
ft/sec)
18.1
19.0
19.0
17.9
19.0
18.2
18.5
Vol. Flow
Rate
(acfm)
30700
32200
32200
30400
32200
30900
31400
Vol. Flow
Rate
(dscfm)
7830
8290
8290
7850
8290
7930
8080
Flare stack cross-section flow area is 28.27 sq. ft.
4.2.2 Flare Stack Gas Constituents
The concentrations of the constituents of interest in the flare stack are presented in
Subsections 4.2.2.1 through 4.2.2.7.
4.2.2. 1 Flare Stack Oxygen (O2) and Carbon Dioxide (CO2)
Oxygen (O2) and CO2 concentrations provide an overall indication of the combustion
process. Figure 4-1 shows the O2 and CO2 concentrations measured by the CEMs
during the tests. The plotted data do not include the CEM responses to the instrument
zeroing and calibration periods. Table 4-10 presents the daily averages of O2 and CO2
concentrations.
4-10
-------
Source Test Report
for Landfill D
Flare Stack Oxygen & Carbon Dioxide 5/16/04
14
1 9
1 n
2
•2 A
1
0)
u
C C
8 °
0,
llLininli i LJyUk HJIillMd
Wfl ^fp
M
-
^p^
^Od
Sa
10:04 11:16 12:28 13:40
Time
ta
-bon Dioxide
/gen
npling Period
14:52 16:04
Figure 4-1. Engine Stack Oxygen and Carbon Dioxide Concentrations
Table 4-10. Flare Stack Combustion Products Concentrations
Run 1
Run 2
Run 3
Average
02
(%v)
13.5
13.5
13.5
13.5
CO2
(% v)
6.4
6.3
6.4
6.4
4-11
-------
4.2.2.2 Flare Stack Total Hydrocarbon (THC) Concentrations
Flare stack THC emissions were measured by EPA Method 25A, which used a CEM.
At the flare stack, hydrocarbon (including NMOCs) concentrations were found to be
below 50 ppmv. The low concentrations rendered Method 25 C, the method designed
specifically for NMOC measurement, unsuitable to be applied at this location.
EPA Method 25 A was used instead and produced concentrations of all hydrocarbons
that respond to flame ionization detector (FID) analysis. The responding hydrocarbons
were assumed to be NMOCs. Real-time continuous instrument responses are shown in
Figure 4-2. The time-averaged concentrations are presented in Table 4-11. As can be
seen, the instantaneous concentrations of total hydrocarbons ranged from 10 to over
175 ppmv, with time-averaged concentration of 17 ppmv as hexane.
Source Test Report
for Landfill D
400
350
300
?
|250
Q.
|200
ro
i:
c
o150
o
O
100
50
Flare Stack Total Hydrocarbon 5/16/04
Sampling Period
-Total Hydrocarbon
10:04 11:16 12:28 13:40 14:52 16:04
Time
Figure 4-2. Flare Stack Total Hydrocarbon Concentrations
4-12
-------
Source Test Report
for Landfill D
Table 4-11. Flare Stack THC Concentrations
Run 1
Run 2
Run 3
Average
THC
(ppmdv as propane)
35.6
35.5
31.3
34.1
THC
(ppmdv as hexane)
17.8
17.8
15.7
17.1
Flare Stack Carbon Monoxide 5/16/04
600
Sampling Period
Carbon Monoxide
16:04
Figure 4-3. Flare Stack Carbon Monoxide Concentrations
4-13
-------
Source Test Report
for Landfill D
10
9
8
I 6
S 4
o
o
o
3
2
1
0
10:04
Flare Stack Sulfur Dioxide 5/16/04
Sampling Period
-SO2
11:16
12:28 13:40
Time
14:52
16:04
Figure 4-4. Flare Stack Sulfur Dioxide Concentrations
4-14
-------
Source Test Report
for Landfill D
Flare Stack Nitrogen Oxides (NOx) 5/16/04
Figure 4-5. Flare Stack Nitrogen Oxides Concentrations
4.2.2.3 Flare Stack Hydrochloride (HCI) Emissions
Enclosed flare stack HCI emissions results are presented in Table 4-12.
Table 4-12. Flare Stack Hydrogen Chloride Emissions
Run 1
Run 2
Run 3
Average
HCI Concentration
(ppmdv)
1.3
1.3
1.3
1.3
(mg/m3)
2.0
2.2
2.2
2.2
HCL Emission Rate
(Ib/hr)
0.06
0.06
0.06
0.06
(g/hr)
27
27
27
27
4-15
-------
Source Test Report
for Landfill D
4.2.2.4 Flare Stack Metals Emissions
Flare stack metals emissions results are presented in Table 4-13. The metal
concentrations were determined by Method 29, and included those for As, Cd, Cr, Pb,
Mn, Hg (total) and Ni. Mercury (Hg) concentration (elemental) was separately
measured by the LUMEX instrument and those results are also included in Table 4-16.
The "<" symbol denotes that the notated metal was not detected in that sample. The
values following the "<" symbol represent the concentrations and emission rates that
would have been the case had the metal been found at the method detection limit.
Hence the values represent the upper limits of what might be present.
4.2.2.5 Flare Stack Gaseous Emissions: Carbon Monoxide (CO), Sulfur Dioxide (SCy, and
Nitrogen Oxides (NOX)
Gaseous emissions measured with CEMS include CO2, SO2, O2, and NOX. These results
are in Table 4-14. The detailed CEM measurement plots are shown in Figures 4-3
through 4-5.
4.3 Comparison with AP-42 Values
One of the major objectives of the test program was to expand on the database of LFG
constituent compounds and their concentrations. If warranted, these data may
contribute towards updating the AP-42 default values.
Table 4-15 presents the concentrations of LFG constituents to provide direct
comparisons with AP-42 default values. Table 4-16 presents the concentration of other
constituents targeted by the various analyses but are not listed in AP-42. An expanded
discussion and comparison is included in the overall project report.
4-16
-------
Source Test
Report for Landfill D
Table 4-13. Flare Stack Metals Emissions
Analyte
Arsenic
Cadmium
Chromium
Lead
Manganese
Nickel
Mercury
(Total by Method
29)
Mercury
(Elemental by
LUMEX)
C-POST-M29-051404-01
Concentration
(jjg/dscm)
5.0
0.174
5.1
<0.833
2.2
7.0
<2.1
Emission Rate
(9*0
0.067
0.002
0.068
<0.011
0.030
0.094
<0.028
(x10%/hr)
150
5.1
150
<25
65
210
<61
RUN1
0.603
0.00821
18.1
C-POST-M29-051404-02
Concentration
(pg/dscm)
4.4
0.262
3.4
<0.785
1.2
3.1
<2.5
Emission Rate
(g/hr)
0.063
0.004
0.048
<0.011
0.017
0.044
<0.035
(x10%/hr)
138
8.1
106
<24.4
39
98
<77
RUN 2
0.886
0.0121
26.6
C-POST-M29-05140403
Concentration
(jjg/dscm)
4.7
0.191
3.7
<0.817
20
4.4
<2.6
Emission Rate
(g/hr)
0.064
0.003
0.050
<0.011
0.273
0.059
<0.035
(x10-%yhr)
141
5.7
111
<24.3
603
129
<77
RUN 3
1.10
0.0152
33.5
Average
Concentration
(pg/dscm)
4.7
0.209
4.1
ND
7.9
4.8
ND
Emission Rate
(g/hr)
0.065
0.003
0.055
ND
0.107
0.065
ND
(x10-«IWhr)
142
6.3
122
ND
236
144
ND
Average
0.867
0.0118
26.1
Table 4-14. Flare Stack CO, SO2, NOX Concentrations
Run 1
Run 2
Run 3
Average
Concentration (ppmdv)
CO
69
79
92
80
SO2
0
0
0.7
0.2
NOx(asNO)a
8.2
9.7
7.7
8.5
One of six drift checks was 3.3 percent and exceeded the ±3 percent criteria
4-17
-------
Source Test
Report for Landfill D
Table 4-15. Comparison of Raw Landfill Gas Constituent Concentrations with AP-42 Values
Method
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
No Test
M-40
No Test
M-40
M-40
M-40
Compound
1,1,1-Trichloroethane
1 ,1 ,2,2-Tetrachloroethane
1,1-Dichloroethane
(Ethylidene Dichloride)
1,1-Dichloroethene
1 ,2-Dichloroethane
1 ,2-Dichloropropane
Isopropyl alcohol
(2-Propanol)
Acetone
Acrylontrile
Bromodichloromethane
Butane
Carbon Disulfide
Carbon Monoxide
Carbon Tetrachloride
Carbonyl Sulfide
(Carbon oxysulfide)
Chlorobenzene
Chlorodiflouromethane
(Freon 22)
Chloroethane
(Ethyl Chloride)
CAS
Number
71-55-6
79-34-5
75-34-3
75-354
107-06-2
78-87-5
67-63-0
67-64-1
107-13-1
75-27-4
106-97-8
75-15-0
630-08-0
56-23-5
463-58-1
108-90-7
75-45-6
75-00-3
Formula
Wt.
133.42
167.85
98.96
96.94
98.96
112.98
60.11
58.08
53.06
163.83
58.12
76.13
28.01
153.84
60.07
112.56
86.47
64.52
Default
Value
(ppmv)
0.48
1.11
2.35
0.20
0.41
0.18
50.10
7.01
6.33
3.13
5.03
0.58
141
0.004
0.49
0.25
1.30
1.25
Detection
Limit
(ppmv)
0.0003
0.0002
0.0004
0.0002
0.0003
0.0003
0.0002
0.0003
0.00002
0.0002
1
0.0003
0.0005
0.0002
0.0002
Measured
Average
(ppmv)
ND
ND
0.591
0.021
0.022
ND
6.63
12.8
ND
ND
ND
0.093
NM
0.038
NM
0.021
NM
0.63
Concentration
in Inlet LFG
(X10-9
Ib/ft3)
ND
ND
151
5.3
5.7
ND
1000
1900
ND
ND
ND
18.2
NM
15.1
NM
6.0
NM
106
QjgAn3)
ND
ND
2420
85.6
91.5
ND
16500
30800
ND
ND
ND
292
NM
242
NM
96
NM
1700
Mass Flow Rate in Inlet
LFG Stream
(mgAir)
ND
ND
1650
58.2
62.2
ND
11200
21000
ND
ND
ND
199
NM
165
NM
66
NM
1150
(X10-3
Ib/hr)
ND
ND
3.6
0.128
0.137
ND
24.7
46.2
ND
ND
ND
0.438
NM
0.363
NM
0.15
NM
2.5
4-18
-------
Source Test
Report for Landfill D
Method
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
No Test
M40
M40
No Test
M-40
M-40
M-40
M-40
M-11
Compound
Chloroform
Chloromethane
1 ,4-Dichlorobenzene
1 ,3-Dichlorobenzene
1 ,2-Dichlorobenzene
Dichlorodifluoromethane
(Freon 21)
Dichlorofluoromethane
(Freon 12)
Methylene Chloride
(Dichloromethane)
Dimethyl Sulfide
(Methyl sulfide)
Ethane
Ethanol
Ethyl Mercaptan
(Ethanediol)
Ethylbenzene
1 ,2-Dibromoethane
(Ethylene dibromide)
Trichloromonofluoromethane
(Fluorotrichloromethane) (F1 1)
Hexane
Hydrogen Sulfide
CAS
Number
67-66-3
74-87-3
106-46-7
541-73-1
95-50-1
75-71-8
75-434
75-09-2
75-18-3
74-84-0
64-17-5
75-08-1
100-414
106-934
75-694
110-54-3
7783-06-4
Formula
Wt.
119.39
50.49
147.00
147.00
147.01
120.91
102.92
84.94
62.13
30.07
46.08
62.13
106.16
187.88
137.38
86.18
34.08
Default
Value
(ppmv)
0.03
1.21
0.21
0.21
0.21
15.70
2.62
14.30
7.82
889
27.20
2.28
4.61
0.001
0.76
6.57
35.50
Detection
Limit
(ppmv)
0.0003
0.0001
0.0003
0.0002
0.0003
0.0003
0.0001
1
0.0002
0.0003
0.0002
0.0002
0.0003
Measured
Average
(ppmv)
0.485
0.232
0.686
0.650
0.031
1.24
NM
1.11
NM
5.6
0.394
NM
8.12
ND
0.116
2.47
72.7
Concentration
in Inlet LFG
(X10-9
Ib/ft3)
150
30.3
261
247
11.8
386
NM
243
NM
435
46.9
NM
2200
ND
41.3
550
6400
QjgAn3)
2400
485
4180
3950
189
6180
NM
3900
NM
6970
751
NM
35700
ND
662
8810
103000
Mass Flow Rate in Inlet
LFG Stream
(mgAir)
1630
330
2840
2690
128
4200
NM
2650
NM
4740
511
NM
24300
ND
450
5990
69700
(X10-3
Ib/hr)
3.6
0.727
6.3
5.9
0.283
9.3
NM
5.8
NM
10.4
1.1
NM
53.5
ND
0.992
13.2
154
4-19
-------
Source Test
Report for Landfill D
Method
Linberg
LUMEX
Linberg
Linberg
M-40
M-40
No Test
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
Compound
Mercury
(Dimethyl)
Mercury
(Elemental)
Mercury
(Monomethyl)
Mercury
(Total)
2-Butanone
(Methyl Ethyl Ketone)
2-Hexanone
(Methyl Butyl Ketone)
Methyl Mercaptan
(Methanethiol)
Pentane
Tetrachloroethylene
(Perchloroethylene)
Propane
t-1 ,2-Dichloroethene
Trichloroethylene
(Trichloroethene)
Vinyl Chloride
m/p-Xylene
(Dimethyl Benzene)
o-Xylene
(Dimethyl Benzene)
CAS
Number
7439-97-6
78-93-3
591-78-6
74-93-1
109-66-0
127-184
74-98-6
156-60-5
79-01-6
75-014
1330-20-7
95-47-6
Formula
Wt.
230.66
200.61
215.62
215.63
72.10
100.16
48.11
72.15
165.83
44.09
96.94
131.38
62.50
106.16
106.16
Default
Value
(ppmv)
Not Listed
Not Listed
Not Listed
253.0E-6
7.09
1.87
2.49
3.29
3.73
11.10
2.84
2.82
7.34
12.10
12.10
Detection
Limit
(ppmv)
0.05E-06
0.014E-06
6E-06
0.0003
0.0002
1
0.0003
1
0.0003
0.0002
0.0002
0.00065
0.0003
Measured
Average
(ppmv)
5.3E-06
33.5E-06
278E-06
89.1 E-06
8.07
ND
NM
2.37
1.02
30.5
0.053
0.418
1.20
13.7
5.41
Concentration
in Inlet LFG
(X10-9
Ib/ft3)
0.0032
0.0174
0.154
49.7
1500
ND
NM
442
438
3500
13.4
142
194
3800
1500
QjgAn3)
0.052
0.278
2.47
796
24100
ND
NM
7080
7004
55700
214
2280
3100
60100
23800
Mass Flow Rate in Inlet
LFG Stream
(mgAir)
0.035
0.189
1.68
541
16400
ND
NM
4820
4760
37800
146
1550
2110
40800
16100
(X10-3
Ib/hr)
0.0000768
0.000417
0.0037
1.19
36.1
ND
NM
10.6
10.5
83.4
0.321
3.4
4.6
90.0
35.6
4-20
-------
Method
M-40
M-40
M-25C
M-25C
M-40
M-40
Compound
Benzene
(Co-disposal)
Benzene
(No-disposal or Unknown)
NMOC as Hexane
(Co-disposal)
NMOC as Hexane
(No-codispoal or Unknown)
Toluene
(Methyl Benzen)
(Co-disposal)
Toluene
(Methyl Benzene)
(No or Unknown)
CAS
Number
71-43-2
71-43-2
108-88-3
Formula
Wt.
78.11
78.11
86.17
92.13
Default
Value
(ppmv)
11.10
1.91
2420.00
595.00
165.00
39.30
Detection
Limit
(ppmv)
0.0002
0.0002
0.0003
0.0003
Measured
Average
(ppmv)
1.20
1.20
668
668
30.3
30.3
Concentration
in Inlet LFG
(X10-9
Ib/ft3)
243
243
149000
149000
7200
7200
QjgAn3)
3890
3890
2380000
2380000
116000
116000
Mass Flow Rate in Inlet
LFG Stream
(mgAir)
2600
2600
1620000
1620000
78500
78500
(X10-3
Ib/hr)
5.8
5.8
3600
3600
173
173
Source Test
Report for Landfill D
4-21
-------
Source Test
Report for Landfill D
Table 4-16. Raw Landfill Gas Constituent Concentrations for Compounds without AP-42 Default Values
Method
M-0100
M-0100
M-23
M-23
M-25C
M-25C
M-25C
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
Compound
Acetaldehyde
Formaldehyde
Dioxins/Furans
PAHs
Carbon Dioxide
Methane
Oxygen
1 ,1 ,2,3,4 ,4-Hexachloro-1 ,3-butadiene
1 ,1 ,2-Trichloro-1 ,2,2-trifluoroethane (CFC1 13)
1,1,2-Trichloroethane
1,2,4-Trichlorobenzene
1 ,2,4-Trimethylbenzene
1 ,2-Chloro-,1 ,2,2-Tetrafluoroethane (CFC1 14)
1 ,3,5-Trimethylbenzene
1 ,3-Butadiene (Vinylethylene)
1 ,4-Dioxane (1 ,4-Diethylene Dioxide)
1-Ethyl-4-methylbenzene (4-Ethyl Toluene)
4-Methyl-2-pentanone (MIBK)
Benzyl Chloride (Chloromethyl Benzene)
Bromomethane (Methyl bromide)
cis-1 ,2-Dichloroethene
CAS
Number
75-07-0
50-00-0
124-38-9
74-82-8
7782-44-7
87-68-3
76-13-1
79-00-5
120-82-1
95-63-6
76-14-2
108-67-8
106-99-0
123-91-1
622-96-8
108-10-1
100-44-7
74-83-9
156-59-2
Formula
Wt.
44.05
30.03
44.01
16.04
32.00
260.76
187.38
133.42
181.46
120.19
170.92
120.19
54.09
88.10
120.20
100.16
126.58
94.95
96.94
Detection
Limit
(ppmv)
0.0045
0.0064
0.0002
0.0002
0.0002
0.0003
0.0003
0.0002
0.0002
0.0003
0.0002
0.0002
0.0002
0.0002
0.0002
0.0003
Measured
Average
(ppmv)
0.191
0.020
NM
NM
381333
551333
16667
ND
0.019
ND
ND
2.187
0.110
0.976
0.326
0.013
0.976
ND
ND
0.0027
1.78
Concentration in Inlet LFG
(xlO^lb/ft3)
21.7
1.6
NM
NM
43400000
22900000
1400000
ND
9.0
ND
ND
680
48.6
303
45.6
3.0
303
ND
ND
0.67
446
(MgAn3)
348
25
NM
NM
695000000
366000000
22100000
ND
145
ND
ND
10900
778
4860
731
48.2
4860
ND
ND
11
7140
Mass Flow Rate in
Inlet LFG Stream
(mg/hr)
237
17
NM
NM
472000000
249000000
15000000
ND
98.4
ND
ND
7400
529
3300
497
32.7
3300
ND
ND
7.3
4850
(xlO^IWhr)
0.522
0.0375
NM
NM
1.0
549000
33100
ND
0.217
ND
ND
16.3
1.2
7.3
1.1
0.0721
7.3
ND
ND
0.0161
10.7
4-22
-------
Source Test
Report for Landfill D
Method
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
M-40
Compound
cis-1 ,3-Dichloropropene
Cyclohexane
Dibromochloromethane
Ethyl Acetate
Heptane
Methyl-t-butyl Ether (MTBE)
Styrene (Vinylbenzene)
t-1 ,3-Dichloropropene
Tetrahydrofuran (Diethylene Oxide)
Tribromomethane (Bromoform)
Vinyl Acetate
CAS
Number
10061-01-5
110-82-7
124-48-1
141-78-6
142-82-5
1634-04-4
100-42-5
1006-02-6
109-99-9
75-25-2
108-05-4
Formula
Wt.
110.98
84.16
208.29
88.10
100.20
88.15
104.14
110.98
72.10
252.77
86.09
Detection
Limit
(ppmv)
0.0002
0.0003
0.0002
0.0003
0.0002
0.0003
0.0001
0.0002
0.0004
0.0003
0.0005
Measured
Average
(ppmv)
0.0037
2.268
0.0155
4.60
3.58
0.039
1.177
0.0084
2.06
0.0094
0.044
Concentration in Inlet LFG
(xlO^lb/ft3)
1.1
494
8.3
1000
927
8.9
317
2.4
385
6.1
9.8
(MgAn3)
17
7910
134
16800
14900
142
5070
39
6160
98
157
Mass Flow Rate in
Inlet LFG Stream
(mg/hr)
12
5370
91
11400
10100
97
3450
26.2
4190
67
107
(xlO^IWhr)
0.026
11.8
0.20
25.2
22.3
0.213
7.6
0.058
9.2
0.147
0.235
4-23
-------
Source Test Report
for Landfill D
This page intentionally left blank
4-24
-------
Source Test Report
for Landfill D
5. Quality Assurance/Quality Control (QA/QC)
This project produced data that qualified to receive the "A" rating with respect to the
rating system described in section 4.4.2 of the Procedures for preparing Emission
Factor Documents (EPA-454/R-95-015). The cited EPA document provides a clear
description of the requirements for an "A" data quality rating. Tests were performed by
using an EPA reference test method, or when not applicable, a sound methodology.
Tests were reported in enough detail for adequate validation and raw data were
provided that could be used to duplicate the emission results presented in this report.
Throughout the results sections of this report, notations and footnotes were included to
flag data that, for various reasons, did not meet their associated measurement quality
objectives.
5.1 Assessment of Measurement Quality Objectives
Measurement quality objectives (MQOs) were established for each critical
measurement and documented in the Site-Specific QAPP for the Field Evaluation of
Landfill Gas Control Technologies-Landfill D. The following subsections assess
MQOs for each measurement to determine if goals were achieved. When applicable,
data validation elements performed on laboratory analytical reports are also included.
5.1.1 Continuous Emissions Monitors (CEMs)
Oxygen (O2), CO/CO2, SO2 NOX and THC were measured in the field using CEMs.
The following MQOs were established for CEM measurements for Landfill D:
• Direct calibration bias: ±2 percent
• System bias checks: ±5 percent
• Zero and drift: ±3 percent
• Completeness: >90 percent
Direct calibrations were performed daily, prior to testing, at zero, and a minimum of
two other concentrations (typically a mid-level concentration and one point towards the
end of the instrument range). System bias checks were performed pre-test and post-test.
Drift checks were performed daily, post-test. Table 5-1 summarizes these QC checks
5-1
-------
Source Test Report
for Landfill D
for all instruments. All MQOs were met for all CEM measurements except the TECO
THC monitor drift checks. One of the six measurements fell slightly outside of the ±3.0
percent acceptance criteria at 3.3 percent, which dropped completeness to 83 percent,
below the 90 percent MQO. This was not considered a major failure. Limitation on
data use was not necessary. Nonetheless, the results in Table 4-14 were notated to
reflect this deviation.
Table 5-1. CEM MQO Summary for Landfill D
Instrument and
Range
Servomex O2
Analyzer (0-21%)
Cal Analytical CO2
Analyzer (0-20%)
Cal Analytical CO
Analyzer (0-650
ppm)
Cal Analytical SO2
Analyzer (0-500
ppm)
TECO THC
Analyzer (0-1 000
ppm)
TECO NOX
Analyzer (0-4000
ppm)
Direct Calibration
(±2% criteria)
Total
#
9
9
12
9
NA a
9
Bias
Range
0.1-0.5%
0-2.0%
0.2-0.6%
0-0.7%
NA a
0.3-1.3%
Complete
%
100
100
100
100
NA a
100
System Bias Checks
(±5% criteria)
Total
#
12
12
12
12
18
12
Bias
Range
0-1.1.2%
0.2-1.3%
0-1.4%
0.1-4.3%
0.2-1.5%
0.2-3.2%
Complete
%
100
100
100
100
100
100
Drift Checks
(±3% criteria)
Total
#
6
6
6
6
6
6
Bias
Range
0.3-0.7%
0.1-0.6%
0-1.8%
0-2.1%
0-1.8%
0-3.3
Complete
%
100
100
100
100
100
83 b
The method called for calibration gases to be introduced at a point of the sampling system close to the sampling
probe for them to flow through the heated sample line. Calibration gases were not injected directly to the analyzer
One of the six measurements was above acceptance criteria.
5.1.2 Carbonyls (SW-846 Method 8315A)
The following MQOs were established in the QAPP for this method:
• Recovery (formaldehyde): 50-150 percent
• Completeness: >90 percent
5-2
-------
Source Test Report
for Landfill D
Four samples (including one field blank) were submitted from Landfill D for
formaldehyde and acetaldehyde determination to Resolution Analytics. Results were
reported in RFA#RN990230. The report included information on instrument
calibration and internal QC checks. Samples collected on May 16, 2004 were received
by the laboratory on May 19, 2004 and analyzed on June 7, 2004. That met the 30-day
hold-time limitation. Analytical detection limits were reported as 50 ppb for
formaldehyde and 51.7 ppb for acetaldehyde in the extract. The extract volume was 5
ml. Therefore, the detectable quantities for formaldehyde and acetaldehyde were 250
ng and 258 ng, respectively. Based on a sample gas volume of about 31 liters (at
standard condition), the corresponding MDLS for formaldehyde and acetaldehyde
were 6.4 ppbv and 4.5 ppbv, respectively.
The field blank (LDFLD-MO100-051604-FB) did not have detectable levels of either
compound. To assess accuracy, an external performance evaluation audit sample
containing 1.25 ppm formaldehyde and acetaldehyde was analyzed with the sample set.
Recovery was 101 percent for both compounds, which meets the 50-150 percent MQO
established in the QAPP. This spike was analyzed in duplicate with a percent
difference (%D) between injections of 4.8 percent. All project samples were injected in
duplicate and the %D range for formaldehyde was 0 to 4.5 percent and for
acetaldehyde was 0 to 3.6 percent. All MQOs were met for this method for a
completeness of 100 percent.
5.1.3 Hydrogen Sulfide (H2S) (EPA Method 11)
The following MQOs were established in the Landfill D QAPP for this method:
• Accuracy: ±5 percent bias
• Completeness: >90 percent
Five samples (including a field blank) plus reagent blanks were submitted to Oxford
Laboratories for H2S analysis by EPA Method 11, as part of the Landfill D field test
effort. The samples were collected on May 15, 2004, submitted on May 27, 2004, and
were analyzed on June 17, 2004, which exceeded the 30-day hold time criteria
established in the QAPP by 2 days. The potential adverse effect of hold-time having
been exceeded on the results is unkown. The test results in Table 4-3 were notated
accordingly.
5-3
-------
Source Test Report
for Landfill D
The field blank submitted did not have quantifiable concentrations of H2S. One spike
and one set of duplicates were also performed by the laboratory as additional QC
checks. Spike recoveries were reported as 109 percent, which meets MQO. The
duplication of sample LDFLC-PRE-MOO11-513 04-02 yielded a titration difference of
only 0.3 ml. Although the computed sample concentration values showed greater than
10 percent difference, this was an acceptable duplicate. The final difference was
because of the small titration difference between the sample and the blank.
5.1.4 Dioxinsand Furans (PCDD/PCDFs) (EPA Method 23/0011)
The specification to conducting testing for these compounds was incorrectly retained in
the Site-Specific QAPP for Landfill D. The high gas temperatures (>1400 °F) at the
sampling location near the flare stack exit rendered the presence of dioxins and furans
(PCDD/PCDFs) improbable. Extensive research data showed that formation of
PCDD/PCDFs is favored within the temperature window between 500 and 700 °F. The
flare system did not provide for the gases to be cooled to these temperatures before the
gases were emitted into the atmosphere.
Furthermore, PCDD/PCDF test results showed that these targets were mostly non-
detectable. The cost of this measurement, which would most likely return non-detect
results, was not justified. Hence, consistent with the intent of this test program,
PCDD/PCDF samples were not collected from Landfill D.
5.1.5 Polycyclic Aromatic Hydrocarbons (PAH) (EPA Method 23/0011)
Polycyclic aromatic hydrocarbon (PAH) samples were not collected for the same
reason stated in Section 5.1.4.
5.1.6 Non-Methane Organic Compounds (NMOC) (Method 25C)
The following MQOs were established in the QAPP for Landfill D:
• Accuracy: ±5 percent bias
• Completeness: >90 percent
Four canister samples (including a field blank) were submitted from to Triangle
Environmental Services for NMOC analysis by Method 25-C. The samples were
collected on May 16, 2004, submitted on June 3, 2004, and analyzed June 7-22, 2004,
5-4
-------
Source Test Report
for Landfill D
which met the 30 day hold time requirements. The laboratory report included
information on instrument calibration and internal QC checks.
Non-methane organic compounds (NMOCs) in the field blank (LDFLD-PRE-M40-
051604-FB) were below detection limit. Accuracy for the method was assessed by
evaluating results of response factor (RF) check samples that were run prior to and
following sample analysis. Acceptance criteria established by the method is that the RF
must be within 20 percent of the RF from initial calibration. All RF checks were within
10 percent of the initial calibration, well within the acceptance criteria. The %D
between the pre and post-test checks were less than 1 percent. Samples were run in
triplicate and all percent relative standard deviation (RSD) for samples were <5
percent.
The data set was determined valid but there was a problem with the samples from the
Landfill D site. All three of the gas pipe samples had nitrogen (N2) and O2
concentrations that exceeded the Method 25C criteria of 20 percent for N2 and 5
percent for O2. The NMOC data for these samples could not be used. Since three of the
four samples could not be used, the completeness MQO for this measurement was 25
percent and did not meet the objective set in the QAPP.
5.1.7 Hydrogen Chloride (HCI) (EPA Method 26A)
The following MQOs were established in the QAPP for Landfill D:
• Accuracy: ± 10 percent bias
• Completeness: >90 percent
Four samples (including one field blank) were submitted from Landfill D for HCI and
chlorine (C12) determination to Resolution Analytics. Results were reported in
RFA#RN990230. The report included information on instrument calibration and
internal QC checks. Samples were collected on May 16, 2004, received by the
laboratory on May 19, 2004, and analyzed on June 7, 2004, which met the 4 week
hold-time requirement. Analytical detection limits were reported as 2.6 ppm for HCI
and 2.5 ppm for C12.
The field blank (LDFLD-M26-051604-FB), submitted with samples, did not contain
detectable levels of HCI or C12. In-house audit samples were analyzed with each
respective group of field samples and fell within method criteria of 10 percent of their
5-5
-------
Source Test Report
for Landfill D
expected values. A matrix spike was performed on sample LDFLC-051404-3. An 0.8
ml sample was spiked with 0.8 ml of standard (50 ppm for HC1/25 ppm for C12) and
analyzed in triplicate. The laboratory reported 99 percent recovery of the HC1 spike
with a 0.4 percent RSD in triplicate injections, and 102 percent recovery of the C12
spike with a 0.3 percent RSD. This met the MQO of ±10 percent with very good
precision. In addition to the matrix spike, an internal QC check was performed after
every 10 samples. All samples were measured in triplicate. Calculated bias for internal
QC check was <1 percent for all measurements as was the %D between triplicates. All
MQOs were met for 100 percent completeness.
5.1.8 Metals (EPA Method 29)
The following MQOs were established in the Landfill D QAPP for this method:
• Accuracy: ±25 percent bias
• Completeness: >90 percent
Four sets of Method 29 Multi-Metals trains (including one field blank) were submitted
from Landfill D for As, Cd, Cr, Pb, Mn, Hg, and Ni determination to First Analytical
Laboratories. Results were reported in Project #40513. The report included information
on instrument calibration and internal QC checks. Samples were collected on May 16,
2004, received by the laboratory on May 19, 2004, and analyzed on May 24-26, 2004,
which met the 14 day hold-time requirement. Method detection limits for each of the
target metals were reported as follows:
• As = 5.0 (ig/L
• Cd = 0.2(ig/L
• Cr = 5.0(ig/L
• Pb = 5.0(ig/L
• Mn = 5.0(ig/L
• Ni = 10ng/L
• Hg = 0.2^g/L
5-6
-------
Source Test Report
for Landfill D
Traces of Cd, Cr, Mn, and Ni were found in the blanks, which is not unusual. Some of
the back half Mn samples are abnormally high. This is a common problem which can
occur in Method 29 if a tiny amount of the potassium permanganate reagent gets in to
the hydrogen peroxide impingers.
All samples were spiked prior to analysis. The Cd back half spike recovery was poor
(56 percent), so the Cd back half analysis was conducted by the method of standard
additions to overcome the problem. All of the other spike recoveries were within the
acceptable range of 75-125 percent. In addition to spiking the samples, for each metal,
internal calibration verification samples (ICVs) and continuing calibration verification
samples (CCVs) were performed. ICVs were run at the beginning of each run set and
CCVs were run at a frequency of one for every 10 samples. The ICV and CCV
measured values were all 90 percent
For Hg samples, replicates and spikes were incorporated into the sampling scheme. In
addition, performance evaluation audit samples were also submitted to Frontier for
analysis. Results from the performance evaluation audit (PEA) are summarized in
Section 5.2.2.2.
Four total Hg samples (including a field blank) were taken at Landfill D. Samples were
collected on May 15, 2004, extracted on May 28, 2004, and analyzed on June 3, 2004.
That analysis schedule exceeded the 14-day hold-time specified in the QAPP. All other
quality assurance measures indicated that the analysis of the traps were under good
control. All field blanks were consistent with historical values and indicated the
detection limit was likely to be at or below the previous estimated value of 50ng/m3.
5-7
-------
Source Test Report
for Landfill D
Spike recoveries were >95 percent and standard deviation between replicates was 169
percent, which met MQOs and were 100 percent complete.
Five monomethyl mercury (MMHg) samples (including a field blank) were collected at
Landfill D on May 15, 2004. These samples were extracted on May 27, 2004 and
analyzed on May 28, 2004 which meets the 14-day hold-time. Analysis of these
samples was under good control with acceptable distillation spike recoveries and
distillation duplicates. All CCV standards had acceptable recoveries. Spike recoveries
were 80-117 percent, which meets MQOs. The RSD between replicates was <10
percent. For Landfill D, this analysis was 100 percent complete.
Six dimethyl mercury (DMHg) samples (including a field blank) were collected at
Landfill D on May 15, 2004. These samples were extracted and analyzed on May 27,
2004, which met the 14-day hold-time. The analysis of samples was well within
control, with acceptable recoveries as well as good linear control standards and second-
source standard recoveries. Spike recovery for Landfill D samples was 78-80 percent
and RSD between replicate samples was 3.6 percent. This meets MQOs established in
the QAPP and DMHg analysis was therefore 100 percent complete.
The field blank was low indicating that the trap media, handling procedures, and
analytical techniques did not contribute to the reported values. Field matrix spike
recoveries ranged from 50-93 percent. The DMHg analysis was 100 percent complete.
5.1.10 Volatile Organic Compound (VOCs) and Methane (CH4) (Method TO-15)
The following MQOs were established in the Landfill D QAPP for this method:
• Accuracy: 50-150 percent recovery
• Completeness: >90 percent
Five SUMMA canisters (including field blanks) were submitted from Landfill D to
Research Triangle Park (RTP) Laboratories for VOC and CFL, determination by EPA
Method TO-15. Results were reported in Project #04-162. Samples were collected on
September 14, 2004 and analyzed on October 4, 2004, which met the 30 day hold-time
requirement.
Analysis of the field blank (LDFLD-091404-M40-FB) resulted in significant levels of
several VOC compounds. Table 5-2 lists the compounds identified in the field blank
5-8
-------
Source Test Report
for Landfill D
that were >1 ppbv. This should be considered when evaluating sample data. Accuracy
was assessed using results of a 10 ppbv laboratory control sample containing all target
compounds. For all but one compound, recoveries ranged from 75-135 percent, which
met the established acceptance criteria of 50-150 percent. The recovery reported for
m/p-xylene was 250 percent. Results for this compound should be flagged as
estimated, "J". Precision was demonstrated through multiple injections of standards at
five concentration levels. The RSD between the calculated relative response factors
(RRF) must be <30 percent with allowances that two may be >40 percent. The average
RSD was 11.8 percent and method criteria were met for all compounds except
cyclohexane with an RSD of 41.2 percent and heptane with an RSD of 57.4 percent.
Results for these compounds should be flagged as estimated, "J". Valid data was
received for all SUMMA canisters submitted; these analyses are considered to be 100
percent complete.
Table 5-2.
VOCs Identified in Field Blank
Compound
Dichlordifluoromethane
Vinyl Chloride
1,3-butadiene
Chloroethane
Ethanol
Isopropyl alcohol
Methylene chloride
Acetone
Hexane
Vinyl acetate
Cis-1 ,2-dichloroethene
Cyclohexane
Chloroform
Ethyl acetate
Tetrahydrafuran
2-butanone
Heptane
Benzene
Trichloroethylene
Toluene
Concentration in Field
Blank Sample
(ppbv)
11.95
10.67
2.15
4.36
18.71
96.84
16.02
108.43
25.47
25.3
10.8
11.03 J
4.45
23.81
47.64
114.14
36.44 J
8.97
4.76
696.78
Average
Concentration in
Samples
(ppbv)
1240
1200
326
634
394
6630
1110
12800
3980
44
1780
2270
485
4600
2060
8070
3580
1200
418
30300
5-9
-------
Source Test Report
for Landfill D
Compound
Tetrachloroethylene
1 , 1 ,2-trichloroethane
Ethylbenzene
Chlorobenzene
m/p-xylene
o-xylene
Styrene
1-ethyl-4-methylbenzene
1 ,3,5-trimethylbenzene
1,2,4-trimethylbenzene
1,4-dichlorobenzene
1,3-dichlorobenzene
Benzyl chloride
1,2-dichlorobenzene
Concentration in Field
Blank Sample
(ppbv)
17.55
3.36
121.54
2.49
289.79 J
87.66
18.21
22.38
22.38
66.83
40.03
38.27
7.05
1.46
Average
Concentration in
Samples
(ppbv)
1020
ND
8120
21
13600
5410
1180
976
976
2190
686
650
ND
31
J -Value is categorized as an estimate per EPA QA/G-8 guidance
5.2 Audits
This project was designated as QA Category II effort. Hence, audits were required. The
internal and external audits performed for this project are described in the following
subsections.
5.2.1 EPA Technical Systems Audit
EPA audits were not performed at the Landfill D site. EPA/APPCD Quality Assurance
(QA) Representative, Robert Wright, conducted an on-site technical systems audit
(TSA) of the field evaluations at Landfill C on May 12-13, 2003. The approved Site-
Specific QAPP and the associated field sampling manual provided the technical basis
for the audit. The ARCADIS QA Officer, Laura Nessley, accompanied the EPA
auditor during the TSA. A report of preliminary findings was received on May 19,
2004 and it was included in the Landfill C report.
5-10
-------
Source Test Report
for Landfill D
5.2.2 Laboratory Audits
Because of the developmental nature of the organo-Hg methods, an internal TSA and
PEA were performed by ARCADIS at Frontier Geosciences (Frontier) facilities in
Seattle, Washington.
5.2.2.1 Internal Technical Systems Audit (TSA)
In an effort to save project funds by minimizing expenses associated with staff travel,
Mr. John Hicks, a Senior Scientist at the ARCADIS Seattle Office, was assigned to
perform the laboratory audit. The laboratory audit included observation of spiking
procedures for MMHg and DMHg media prior to shipment to the field, and subsequent
analysis of project samples for MMHg, DMHg and total Hg. Ms. Laura Nessley
provided Mr. Hicks with checklists to use during the audits.
The audits of Frontier's spiking procedures took place on April 29, 2003 for MMHg
and May 4, 2004 for DMHg and total Hg. Calibration, media spiking techniques,
record keeping and good laboratory practices were the focus of the audit, with special
attention paid to the MMHg and DMHg spike preparation for the upcoming field
effort. The following Frontier personnel were present for some or all of the audits
conducted by ARCADIS:
• Lucas Hawkins Research Associate/Field Sampling/Analyst
• Amber Stewart Total Mercury Laboratory Supervisor
• Melissa Oheara MMHg preparation and distillation
• Cindy Moulder MMHg analysis
• Matt Gomes Total Hg extractions
• Melinda Cowen Senior Laboratory Analyst for total Hg
Some of the primary observations resulting from the first audit included:
• A single source for calibration and spiking was used for MMHg and DMHg. The
laboratory had not been able to locate other stable standards for use as an
independent source. There were not NIST-traceable standards for organo-Hg.
5-11
-------
Source Test Report
for Landfill D
• Expiration dates for primary MMHg and DMHg standard materials were not
available. The MMHg standard bottle had a label dated 1998.
• Written procedures for spiking of impinger solutions or carbon tubes were not
evident.
• While work plans state that samples should be kept cold and the organometallic
analytes are light sensitive, the analytical standard for MMHg was stored in a clear
Teflon bottle on an un-refrigerated shelf across from a large picture window.
• Frontier did not routinely retain an aliquot of spike solution or spiked traps when
sending media to a field project.
The continuation of the earlier audit that focused on matrix spiking and media
preparation was performed in late May 2004. This audit concentrated on the analysis of
the sampling media sent to Landfill site D, including extraction, analysis and
calibration procedures for MMHg, DMHg, and total Hg. These audits were conducted
on three separate days to accommodate Frontier's analysis schedule. On May 27, 2004,
the audit focused on MMHg extraction and distillation as well as DMHg analysis. On
May 28, 2004 MMHg analysis and total Hg extraction procedures were audited. On
June 3, 2004, the procedures for total Hg analysis were audited.
Significant findings and recommendations resulting from the extraction and analysis
portion of the laboratory audit included:
• Efficiency factor (EF): An efficiency factor (EF) based on average results from
the analyses of distillation blanks was applied to all MMHg sample results. This
practice was not discussed in the narrative portion of the Frontier reports and not
mentioned by name in the standard operating procedures (SOPs) provided to
ARCADIS. This technique essentially boosted analyte recoveries through a
multiplied efficiency factor applied to all MMHg results. The current EF is 89.5
percent, therefore all results were normalized to 100 percent recovery levels. For
example, a measured value of 100.0 ng detected in an environmental sample was
corrected to 110.5 ng after applying the EF. Without a data report disclaimer, this
practice misrepresents the results and biases all MMHg results high.
• Method blank subtraction: Frontier subtracts the average of the method blanks
from each extraction/preparation batch. While scientifically valid, this technique is
not acceptable for most EPA-referenced protocols. The laboratory has a
5-12
-------
Source Test Report
for Landfill D
responsibility only to report blank concentrations; adjusting environmental sample
concentrations through a data evaluation/validation process is the client's
responsibility.
MMHg Instrument stability: Monomethyl Hg (MMHg) analysis was performed
over a 2-day period because of poor instrument stability and issues associated with
efficiency of the ethylating reagent. Initially, two instruments were set up for
calibration on May 27. Only one of the instruments showed sufficient sensitivity
and stability to continue analysis. Unfortunately, the initial calibration curve did
not meet method specifications, so the instrument was recalibrated and
environmental samples analyzed while the ARCADIS auditor was present. The
following day, the auditor was informed that the sample set did not meet the QAPP
requirements because of unexpected lower concentrations in the samples. The
samples were successfully reanalyzed the following day after maintenance was
performed on the MMHg analysis instrument. Reanalyzing samples is apparently
common and sometimes entire sample sets are reanalyzed more than once. Ms.
Moulder stated that it is "the nature" of this analysis to have to frequently
recalibrate and reanalyze samples. Calibrations should be closely reviewed during
data validation.
Calibration Curve Forcing. ARCADIS learned that, in accordance with Frontier
policy, all calibration curve origin points are forced through zero. ARCADIS notes
that this procedure is not consistent with most EPA-promulgated methods.
ARCADIS recommends reprocessing one calibration curve to determine the
impact, if any, to the data.
Retention Time Marking: While observing the MMHg analysis, the analyst did
not mark the beginning of the analysis charts with a "tick" time marker, which was
particularly critical given that identification of MMHg is primarily determined by
retention times or relative retention times. Some of the samples being analyzed had
numerous chromatographic peaks including MMHg and other forms of Hg. Based
on observation of other laboratory "pods" within Frontier, the marking of the
actual start time on the strip chart recorder was not standardized as a procedural
practice. Some analysts mark the desorption time on the strip chart recorder and
others do not. However, marking of analysis start times should be a requirement of
each method in the place of automatic chromatographic data collection (integrators
or computer data acquisition) to avoid misidentification of analyte targets.
ARCADIS recommends the standardization of marking the start of analysis on
strip chart recorders.
5-13
-------
Source Test Report
for Landfill D
Digestate Dilution Technique: The method of bringing the digested total Hg to
quantitative volume in a 20 milliliter glass vial was unusual as the technique does
not rely on marked, calibrated Class A or B glassware when bringing digested
samples to a known quantitative volume. The analyst did not know if the volume
of the unmarked vials was recently compared against calibrated glassware, but
assumed it was 20 mL. The analyst consistently brought the digested samples to a
consistent level that corresponded to the neck of the glass vial. At a minimum, the
vials should be calibrated to assure the final volumes are accurate.
Sample/Standard Storage: The temperatures of one refrigerator ("A") and one
freezer ("A") used to store samples, analytical standards, and frozen ethylating
cocktails were not monitored for three days prior to the audit (5/25/04). This did
not appear to be a systematic problem, but the analyst did not have an explanation.
Verification of temperatures in standard and sample storage areas should be
checked daily.
Calibration Verification: While discussed in the previous ARCADIS Audit
report dated May 17, 2004, this observation was again included because it is
critical to the evaluation of the laboratory and the application of these methods to
LFG monitoring. Frontier uses a single source for calibration and spiking for
MMHg and DMHg methods. The laboratory has not been able to locate other
acceptable, stable standards, such as NIST-traceable standards. Frontier utilizes
Standard Reference Materials and certified standards. However, accuracy was only
measured for MMHg by comparison to a digested tissue standard and for DMHg
by comparison to JSI-1, a material from the JSI Institute in Slovenia. ARCADIS
recommends that Frontier make an effort to locate alternate acceptable accuracy
standards to verify true concentrations of the main calibration standards.
Holding Times: Holding times were generally not an issue with most analyses
Frontier performs, but based on the QAPP, specific holding times to analysis apply
to this analysis. This was not documented in the summary report. However the
Total, MMHg and DMHg analyses were extracted, but not all analyzed within the
14 day holding time assuming May 27 was the 14th day after sampling. Some data
qualification might be necessary, depending on the professional judgment of the
data validator.
5-14
-------
Source Test Report
for Landfill D
5.2.3 Internal Performance Evaluation Audits (PEA)
Because there is not a currently promulgated method for organo-Hg sampling and
analysis, PEA samples were integrated in to the sampling matrix to evaluate accuracy
and precision of the methods used by Frontier. ARCADIS subcontracted an
independent laboratory to assist in preparation of the PEA samples. The laboratory was
Cebam Analytical located in Seattle, Washington. All standards and stock solutions
were prepared and verified by a Cebam Analytical analyst.
Two PEA samples were prepared for total Hg. Trap A was spiked with 9.99 ng THg by
a Cebam analyst. This concentration was verified by Cebam by performing six
replicate analyses. Samples were analyzed by Frontier Geosciences as described in the
report titled Determination of Total, Dimethyl, and Monomethyl Mercury in Raw
Landfill Gas atPinconning andMontrose Michigan. Recovery results are presented in
Table 5-3. Relative percent difference (RPD) between the duplicate samples was 1.0
percent.
Table 5-3. Total Mercury PEA Results
Sample ID
C-0521 04-01
C-0521 04-02
Total Hg Measured
(ng)
13.60
13.47
Total Hg Spiked
(ng)
9.99
9.99
Recovery
(%)
136
135
One PEA sample was prepared and analyzed for MMHg. A 2.0 ng/L spiking solution
was prepared by transferring a 0.2 mL aliquot of 10 ng/mL standard into a 1L pre-
cleaned glass volumetric flask. The sample was analyzed by Frontier Geosciences as
described in the report titled Determination of Total, Dimethyl, and Monomethyl
Mercury in Raw Landfill Gas atPinconning andMontros, Michigan. Recovery results
are presented in Table 5-4. Because only one sample was prepared, precision for this
analysis could not be evaluated.
Table 5-4. MMHg PEA Results
Sample ID
04051 3-BR-MHg7
Total MMHg Measured
(ng/L)
2.327
Total MMHg Spiked
(ng/L)
2.00
Recovery
(%)
117
5-15
-------
Source Test Report
for Landfill D
Two PEA samples were prepare and analyzed for DMHg. Trap A and Trap B were
spiked with 0.215 ng DMHg for a total concentration of 0.430 ng per train. This
concentration was verified by Cebam by analyzing five replicates samples of the
standard.
The samples were analyzed by Frontier Geosciences as described in the report titled
Determination of Total, Dimethyl, and Monomethyl Mercury in Raw Landfill Gas at
Pinconning andMontros, Michigan. Recovery results are presented in Table 5-5. The
RPD between the duplicate samples was 23 percent.
Table 5-5. DMHg PEA Results
Sample ID
ARCADIS DMM Spike #1
ARCADIS DMM Spike #2
Total MMHg Measured
(ngf
0.234
0.295
Total MMHg Spiked
(ngf
0.430
0.430
Recovery
(%)
54.4
68.6
Trap A and Trap B together
In conclusion, the MQO for recovery for total Hg and organo-Hg samples (as defined
in the QAPP) was established at 50-150 percent. All PEA samples met this objective.
The RPD between duplicate samples was also acceptable. The full text of the TSA and
PEA audit reports and completed checklists are included in Appendix S.
5-16
-------
EPA/600/R-07/043
Field Test Measurements at Five Municipal Solid
Waste Landfills with Landfill Gas Control Technology
Final Report
Appendix E
SOURCE TEST REPORT
FOR LANDFILL E
-------
Table of Contents
1. Introduction 1-1
2. Landfill E Facility Descriptions 2-1
2.1 Boiler Process Description and Operation 2-1
2.2 Source Sampling Locations 2-2
2.2.1 Landfill Gas (LFG) Header Pipe 2-2
2.2.2 Boiler Stack 2-3
3. Test Operations 3-1
3.1 Test Team 3-1
3.2 Test Log 3-1
3.2.1 Planned Test Sample Matrices 3-1
3.2.2 Landfill Gas (LFG) Pipe (Inlet) 3-3
3.2.3 Boiler Stack 3-6
3.3 Field Test Changes and Deviations from Quality Assurance Project Plan
(QAPP) Specifications 3-9
3.3.1 Variation from Test Methods or Planned Activities 3-9
3.3.2 Application of Test Methods 3-10
3.3.3 Test Method Exceptions 3-10
4. Presentation of Test Results 4-1
4.1 Raw Landfill Gas (LFG) Measurements 4-1
4.1.1 Raw Landfill Gas (LFG) Flow Rate and Temperature 4-1
4.1.2 Raw Landfill Gas (LFG) Constituent Analytes 4-2
4.2 Boiler Stack Results 4-11
4.2.1 Boiler Stack Gas Flow Rate and Temperature 4-13
4.2.2 Boiler Stack Oxygen and Carbon Dioxide 4-14
4.2.3 Boiler Stack Total Hydrocarbon (THC) 4-14
-------
Table of Contents
4.2.4 Boiler Stack Dioxin/Furan (PCDD/PCDFs) 4-17
4.2.5 Boiler Stack Polycyclic Aromatic Hydrocarbon (PAH) Emissions 4-17
4.2.6 Hydrogen Chloride (HCI) Emissions 4-24
4.2.7 Metals Emissions 4-24
4.2.8 Gaseous Emissions: Carbon Monoxide (CO), Sulfur Dioxide (SC>2),
and Nitrogen Oxides (NOX) 4-24
4.3 Comparison with AP-42 Default Values 4-29
5. Quality Assurance/Quality Control 5-1
5.1 Assessment of Measurement Quality Objectives 5-1
5.1.1 Continuous Emissions Monitors (CEMs) 5-1
5.1.2 Carbonyls (Method TO-11) 5-2
5.1.3 Hydrogen Sulfide (H2S) (EPA Method 11) 5-3
5.1.4 Dioxins and Furans (PCDD/PCDFs) (EPA Method 23/0011) 5-4
5.1.5 Polycyclic Aromatic Hydrocarbons (PAHs) (EPA Method 23/0011) 5-4
5.1.6 Non-Methane Organic Compounds (NMOCs) (Method 25C) 5-6
5.1.7 Hydrogen Chloride (HCI) (EPA Method 26A) 5-7
5.1.8 Metals (EPA Method 29) 5-7
5.1.9 Organo-Mercury (Hg) and Total Mercury (Hg) (Frontier and
Geochimica) 5-8
5.1.10 Volatile Organic Compounds (VOCs) and Methane (CH4) (Method
TO-15) 5-10
5.2 Audits 5-11
-------
Table of Contents
Tables
Table 2-1. Devices Utilizing Landfill E LFG 2-1
Table 3-1. Test Team Members and Responsibilities 3-1
Table 3-2. Target Analytes for the Raw Landfill Gas Stream 3-2
Table 3-3. Target Analytes for the Boiler Stack Outlet Gas Stream 3-3
Table 3-4. Landfill E Raw LFG Sample Log and Collection Times 3-4
Table 3-5. Boiler Stack Test Sample Log and Collection Times 3-8
Table 3-6. Test Methods and Performing Organizations 3-11
Table 4-1. Raw Landfill Gas VOC Concentrations 4-2
Table 4-2. Raw LFG Non-Methane Organic Compound (NMOC) 4-6
Table 4-3. Raw LFG Hydrogen Sulfide Concentrations 4-6
Table 4-4. Raw LFG Carbonyls Concentrations 4-7
Table 4-5. Raw LFG Total Mercury Concentrations 4-8
Table 4-6. Raw LFG Dimethyl Mercury Concentrations 4-9
Table 4-7. Raw LFG Monomethyl Mercury Concentrations 4-10
Table 4-8. Raw LFG Elemental Mercury Concentrations 4-10
Table 4-9a. Boiler Operating Condition on June 22, 2005 as indicated by Boiler Control
System 4-11
Table 4-9b. Boiler Operating Condition on June 23, 2005 as indicated by Boiler Control
System 4-12
Table 4-10. Boiler Stack Gas Conditions Measured during Sampling 4-13
Table 4-11. Boiler Stack Oxygen and Carbon Dioxide Concentrations 4-14
Table 4-12. Boiler Stack Total Hydrocarbon Concentration 4-17
Table 4-13. Boiler Stack Dioxins and Furans 4-18
Table 4-14. Boiler Stack Dioxins and Furans Toxicity Equivalent Emissions 4-20
Table 4-15. Boiler Stack Polycyclic Aromatic Hydrocarbons (PAHs) Emissions 4-22
Table 4-16. Boiler Stack Hydrogen Chloride Measurement Results 4-24
Table 4-17. Boiler Stack Metals Emissions 4-28
Table 4-18. Boiler Stack CO, SO2, NOX Concentrations 4-29
Table 4-19. Comparison of Raw Landfill Gas Constituent Concentrations with AP-42
Default Values 4-30
Table 4-20. Raw Landfill Gas Constituent Concentrations for Compounds without AP-42
Default Values 4-33
Table 5-1. CEM MQO Summary for Landfill E 5-2
-------
Table of Contents
Table 5-2. Polycyclic Aromatic Hydrocarbon Reagent Blank Target Analyte
Concentrations 5-5
IV
-------
Table of Contents
Figures
Figure 2-1. Simplified Landfill E LFG Boiler Process Flow Diagram
Figure 2-2. Raw Landfill Gas Collection Pipe
Figure 2-3. Boiler Stack
Figure 2-4. Boiler Stack Dimension and Sampling Traverse Locations
Figure 3-1. Sampling Operations at the Raw Landfill Gas Header Pipe
Figure 3-2. Sampling Operations at the Boiler Stack
Figure 3-3. Sampling Train at the Boiler Stack
Figure 4-1. Boiler Stack Oxygen and Carbon Dioxide Concentrations
Figure 4-2. Boiler Stack Total Hydrocarbon Concentration
Figure 4-3. Boiler Stack Carbon Monoxide Concentration
Figure 4-4. Boiler Stack Sulfur Dioxide Concentration
Figure 4-5. Boiler Stack Nitrogen Oxides Concentration
2-2
2-3
2-4
2-4
3-3
3-6
3-7
4-15
4-16
4-25
4-26
4-27
-------
Table of Contents
Appendices
A. Method TO-15 (VOCs, TICs, C2, C3, C4, C5, C6)
B. Method 25C (CH4, CO2, NMOC)
C. Method 3C (O2, N2, CH4, CO2)
D. Method TO-11 (Formaldehyde, Acetaldehyde)
E. Organic mercury Method (Mercury, Total, Monomethyl, Dimethyl)
F. LUMEX (Elemental Mercury)
G. Hydrogen Sulfide
H. Continuous Emission Monitor (Data and Charts)
I. Method 23 (PAH)
J. Method 23 (PCDD/PCDF)
K. Method 23 (PAH, PCDD/PCDF)
L Method 29 (Metals)
M. Method 26A (HCI)
N. Analyte Concentration and Mass Flow Rate Computation Worksheets
P. Raw Field Data Records
Q. CEM Calibration Records and Span Gas Certification
R. Sampling Control Meter Boxes Calibration Record
VI
-------
Acronym List
This page intentionally left blank
VII
-------
Acronym List
Acronym List
%D
AP-42
APPCD
ARCADIS
As
AS
CCVs
Cd
CEMS
CH4
C12
CO
CO2
Cr
DMHg
EPA
ES
FID
GC/FID
GC/MS
HC1
Hg
H2S
ICVs
LFG
MDLs
MMHg
Mn
Percent drift
Compilation of Air Pollutant Emission Factors
Air Pollution Prevention Control Division
ARCADIS G&M, Inc.
Arsenic
Alternative standard
Continuing calibration verification samples
Cadmium
Continuous emission monitoring system
Methane
Chlorine
Carbon monoxide
Carbon dioxide
Chromium
Dimethyl mercury
US Environmental Protection Agency
Extraction standard
Flame ionization detector
Gas chromatograph/flame ionization detector
Gas chromatograph/mass spectrometer
Hydrogen chloride
Mercury
Hydrogen sulfide
Internal calibration verification samples
Landfill gas
Method detection levels
Monomethyl mercury
Manganese
VIM
-------
Acronym List
MQOs Measurement quality objectives
MSW Municipal solid waste
N2 Nitrogen
Ni Nickel
NMOCs Non-methane organic compounds
NOX Nitrogen oxides
O2 Oxygen
PAHs Polynuclear aromatic hydrocarbons
Pb Lead
QA Quality Assurance
QAPP Quality Assurance Project Plan
QC Quality control
RF Response factor
RPD Relative percent difference
RRF Relative response factors
RSD Relative standard deviation
RTP Research Triangle Park
SO2 Sulfur dioxide
SS Sampling standards
TCDD/TCDFs Dioxins/furans
THCs Total hydrocarbons
TICs Tentatively identified compounds
VOCs Volatile organic compounds
IX
-------
Source Test Report
for Landfill E
1. Introduction
Large municipal solid waste (MSW) landfills are subject to Clean Air Act regulations
because of emissions that can contribute to environmental and health concerns.
Landfills are listed as a source of air toxics in the Urban Air Toxics Strategy for future
evaluation of residual risk. Existing emission factors for landfill gas (LFG) were
largely developed using data from the 1980s and early 1990s. A database was
developed summarizing data from approximately 1,200 landfills, along with emissions
information from literature, and from test reports prepared by state and local
government agencies and industry. These data were summarized in Compilation of Air
Pollutant Emission Factors (AP-42), Chapter 2.4. Requirements for landfill gas control
for new and existing MSW landfills are in 40 CFR Parts 51, 52, and 60, Standards of
Performance for New Stationary Sources and Guidelines for Control of Existing
Sources: Municipal Solid Waste Landfills.
The overall purpose of this testing program was to generate data that could be used to
update AP-42 and to include data that reflect current waste management operating
practices. Emission factors are used in determining applicability to Clean Air Act
regulations, developing emission inventories, and for evaluating potential health
concerns associated with LFG emissions.
This report presents the results of a field test conducted at Landfill E, located in a
Midwest state. Testing took place on June 22 and 23, 2005.
The site uses a boiler for destruction of the LFG. A more detailed description of the
boiler is presented in Section 2. The specific purpose of the testing program was to
determine the gas quality of raw LFG (sampling the header pipe prior to gas cleaning)
and the emissions of the boiler stack. The pollutants of interest for the raw untreated
landfill gas were volatile organic compounds (VOCs), non-methane organic
compounds (NMOCs), hydrogen sulfide (H2S), carbonyls (acetaldehyde and
formaldehyde), and mercury (Hg) compounds. The pollutants of interest for the treated
LFG, in this case at the boiler stack, were carbon monoxide (CO), nitrogen oxides
(NOX), sulfur dioxide (SO2), NMOCs as total hydrocarbons (THCs), hydrogen chloride
(HC1), total Hg, dioxins/furans (PCDD/PCDFs), polycyclic aromatics hydrocarbons
(PAHs), and metals.
ARCADIS G&M, Inc. (ARCADIS), as contractor to the US Environmental Protection
Agency's (EPA) Air Pollution Prevention and Control Division (APPCD), performed
this work under Work Assignment 1-27 of Onsite Laboratory Support Contract (EP-C-
1-1
-------
Source Test Report
for Landfill E
04-023). The testing activities followed the specifications of the approved "Site-
Specific Quality Assurance Project Plan for the Field Evaluations of Landfill Gas
Control Technologies Landfill E" dated May 2005.
1-2
-------
Source Test Report
for Landfill E
2. Landfill E Facility Descriptions
Available information indicates that Landfill E began operation in 1971. As of June
2005, the landfill had 14,500,000 metric tons of waste in place over an area of 240
acres. The LFG extraction rate was 4,800 standard cubic feet per minute. The landfill
had 320 vertical wells that feed into a main header pipe. The raw LFG was filtered, de-
watered, and compressed prior to being piped for use either off-site or on-site. The
different uses of LFG at this site are identified in Table 2-1. Demand and seasonal
factors largely determine the use pattern; maximum and minimum rates. The base-load
steam boiler at Customer A's facility was tested in this program.
Table 2-1. Devices Utilizing Landfill E LFG
LFG End User
Customer A
Customer A
Customer B
Customer C
On-site
On-site
On-site
Devices
Base-load Steam Boiler
Gas Turbine Generator
Greenhouse Hot Water Boiler
Asphalt Plant Kiln Burner
1C Engine/Micro Turbine Generators
Four Candlestick Flares
Candlestick Flare
LFG Utilization Rate
(scfm)
500 - 3400
1300-1700
100-500
500-1400
200
600 per flare
2825
2.1 Boiler Process Description and Operation
The tested boiler was a Combustion Engineering Model 33-7KT-10, A-Type Package
Boiler, rated at 80,000 pounds-per-hour of 250 psi steam. The boiler was fueled by the
collected LFG and produced base-load steam for Customer A's industrial facility. The
boiler was located on Customer A's property, approximately 3 miles from Landfill E.
Figure 2-1 shows a simplified process schematic of the LFG-boiler system.
Information related to the boiler's ability to destroy potential pollutants was not
available.
2-1
-------
Source Test Report
for Landfill E
(A)
r- %," SAMPLING PORTS
FROM (|)(|)(f){|) -r- x
LANDFILL GAS T Y T T ^ f ,
STACK SAMPLING
PORTS
TYP. OF 2
WELLS
Figure 2-1. Simplified Landfill E LFG Boiler Process Flow Diagram
2.2 Source Sampling Locations
Raw LFG samples were collected at the landfill gas pipe (location labeled "A").
Samples of treated gas were collected at the boiler stack (location labeled "B"), as
depicted in Figure 2-1.
2.2.1 Landfill Gas (LFG) Header Pipe
Raw untreated LFG samples were collected from the header pipe, as it emerged from
the ground, upstream of processing units. Figure 2-2 is a photograph of the raw LFG
header pipe before it passes into the gas control-and-process system. The pipe is 16
inches in inner diameter. At the sampling point, four %-inch gas taps were installed.
Through these ports, gases were withdrawn to obtain the test samples.
Isokinetic sampling and accurate velocity measurement requires the measurement point
to have at least eight pipe diameter of straight pipe upstream and two pipe diameter of
disturbance-free pipe downstream. The header pipe at Landfill E did not meet this
requirement. Therefore, isokinetic sampling was not attempted at this location.
Furthermore, the short pipes between the upstream and downstream bends precluded
accurate measurement of the volumetric flow rate of the raw LFG.
2-2
-------
Source Test Report
for Landfill E
Figure 2-2. Raw Landfill Gas Collection Pipe
2.2.2 Boiler Stack
A picture of the boiler stack is shown in Figure 2-3. The picture shows the arrangement
of the sampling ports. The boiler stack was 76.5 inches in diameter and had two 6-inch
sampling ports installed 90 degrees apart. Figure 2-4 illustrates the cross-sectional
dimensions of the boiler stack and includes the locations of the sample traverse points.
Isokinetic sampling was possible at this location and was followed.
2-3
-------
Source Test Report
for Landfill E
Figure 2-3. Boiler Stack
Sampling
Ports
O
Row
f
K'J"
Stack Cross Section
76.5"
ItS"
I
Traverse Points
Point* Distance
1
2
3
4
5
6
7
8
9
10
11
12
1.50"
Si!"
9.00"
13.50"
19.25"
17.15"
*.!5"
57.15"
63.00"
67.50"
JUS"
75.00"
Figure 2-4. Boiler Stack Dimension and Sampling Traverse Locations
2-4
-------
Source Test Report
for Landfill E
3. Test Operations
As stated previously, the purpose of the sampling program was to determine the quality
of raw LFG and emissions from the boiler stack.
3.1 Test Team
The tests were conducted by a team of seven individuals. The team members and their
primary duties are listed in Table 3-1.
Table 3-1. Test Team Members and Responsibilities
Role
Test Engineer
Chemical Technician
Test Engineer
Sampling Technician
Sampling Technician
CEMS Technician
Senior Chemist
(Frontier Geosciences)
Primary Duty
Field Supervisor
Sample train preparation and recovery
Sample train operator at raw LFG inlet pipe
Sample train operator at stack
Sample train operator at stack
CEMS operations
Mercury measurements
3.2 Test Log
3.2.1 Planned Test Sample Matrices
The list of target samples to be collected and measurements to be taken are specified in
the Quality Assurance Project Plan (QAPP) dated June 2005. These are reiterated here
for completeness. Table 3-2 lists the target compounds of interest for the raw untreated
LFG, collected at the raw LFG pipe. Table 3-3 lists the target compounds of interest for
the treated gas, at the boiler stack.
3-1
-------
Source Test Report
for Landfill E
Table 3-2. Target Analytes for the Raw Landfill Gas Stream
Volatile compounds
Methane
Ethane
Propane
Butane
Pentane
Hexane
Carbonyl sulfide
Chlorodifluoromethane
Chloromethane
Dichlorodifluoromethane
Dichlorofluoromethane
Ethyl chloride
Fluorotrichloromethane
1,3-Butadiene
Acetone
Acrylonitrile
Benzene
Bromodichloromethane
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chloroform
Dimethyl sulfide
Ethyl mercaptan
Volatile compounds
(continued)
Ethylene dibromide
Ethylene dichloride
Methyl chloroform
Methyl isobutyl ketone
Methylene chloride
Propylene dichloride
t-1 ,2-Dichloroethene
Tetrachloroethene
Toluene
Trichlorethylene
Vinyl chloride
Vinylidene chloride
Ethanol
Methyl ethyl ketone
2-Propanol
1 ,4-Dichlorobenzene
Ethylbenzene
Xylenes
Non -methane organic
compounds
Reduced sulfur compounds
Hydrogen sulfide
Carbonyls
Acetaldehyde
Formaldehyde
Mercury
Organo-mercury compounds
Total
Elemental
Gases
Carbon dioxide
Oxygen
3-2
-------
Source Test Report
for Landfill E
Table 3-3. Target Analytes for the Boiler Stack Outlet Gas Stream
Gases
Oxygen
Carbon dioxide
Carbon monoxide
Nitrogen oxide
Sulfur dioxide
Total hydrocarbons
Non-methane organic compounds
(as THCs)
Hydrogen chloride
Mercury
Total
Metals
Lead, arsenic, cadmium, chromium,
manganese, nickel
Dioxins/Furans
Polycyclic aromatic hydrocarbons
3.2.2 Landfill Gas (LFG) Pipe (Inlet)
Figure 3 -1 is a photograph of sampling operations taking place at the raw LFG header
pipe. Collection of raw LFG samples took two days to complete. Table 3-4 lists the
samples that were collected from the raw LFG pipe.
Figure 3-1. Sampling Operations at the Raw Landfill Gas Header Pipe
3-3
-------
Source Test Report
for Landfill E
Table 3-4. Landfill E Raw LFG Sample Log and Collection Times
Sampling
Method
Run Number
EPA Method 40 (TO-15, 25C 3C)
E-Pre-M40-062205-01
E-Pre-M40-062205-02
E-Pre-M40-062205-03
E-Pre-M40-062205-04
E-Pre-M40-062305-B
EPA Method 01 00
E-Pre-M01 00-062205-01
E-Pre-M01 00-062205-02
E-Pre-M01 00-062205-03
E-Pre-M0100-062205-B
EPA Method 1 1
E-Pre-M001 1-062205-01
E-Pre-M001 1-062205-02
E-Pre-M001 1-062205-03
E-Pre-M0011-062205-B
Lumex Instrument
E-Pre-EM-062305-01
E-Pre-EM-062305-02
E-Pre-EM-062305-03
Frontier
062205-Site E-STM1
062205-Site E-STM2
062205-Site E-STM3
062205-Site E-STMBLK
Frontier
062305-Site E-MMHg1
062305-Site E-MMHg2
062305-Site E-MMHg3
Analyte(s)
VOCs/NMOCs/O2/CO2,N2
VOCs/NMOCs/O2/CO2,N2
VOCs/NMOCs/O2/CO2,N2
VOCs/NMOCs/O2/CO2,N2
VOCs/NMOCs/O2/CO2,N2
Carbonyls
Carbonyls
Carbonyls
Carbonyls
H2S
H2S
H2S
H2S
Elemental Hg a
Elemental Hg a
Elemental Hg a
Total gaseous Hg
Total gaseous Hg
Total gaseous Hg
Total gaseous Hg
Monomethyl Hg
Monomethyl Hg
Monomethyl Hg
Sample Class
Test
Test
Test
Test
Field Blank
Test
Test
Test
Field Blank
Test
Test
Test
Reagent Blank
Test
Test
Test
Test
Test
Test
Field Blank
Test
Test
Test
Date
06/22/05
06/22/05
06/22/05
06/22/05
06/23/05
06/22/05
06/22/05
06/22/05
06/22/05
06/22/05
06/22/05
06/22/05
06/22/05
06/23/05
06/23/05
06/23/05
06/22/05
06/22/05
06/22/05
06/22/05
06/23/05
06/23/05
06/23/05
Run Period
08:03 - 09:03
10:25-11:25
12:24-13:24
14:20-15:20
08:28-09:28
09:11-09:41
11:39-12:09
13:28-13:58
14:01
15:32-15:42
16:31 -16:41
17:21 -17:31
-
-09:50
-09:55
-10:00
13:39-14:39
14:53-15:54
17:00-18:01
18:09
08:34 - 09:34
10:29-11:29
11:59-12:59
3-4
-------
Source Test Report
for Landfill E
Sampling
Method
Run Number
062305-Site E-MMHgBLK
062305-Site E-MMHgSPK
Frontier
062205-Site E-DMHg1
062205-Site E-DMHg2
062205-Site E-DMHg3
062205-Site E-DMHgBLK
062205-Site E-DMSPK
Geochimica
062205-Site-E-DMHg-blk
062205-Site-E-DMHg-1
062205-Site-E-DMHg-2
062205-Site-E-DMHg-3
062205-Site-E-DM Hg-spk
Geochimica
062205-Site-E-STM-1
062205-Site-E-STM-blk
062205-Site-E-STM-4
062205-Site-E-STM-2
Geochimica
062305-Site-E-M M Hg-spk
062305-Site-E-MMHg-1
062305-Site-E-MMHg-2
062305-Site-E-MMHg-3
062305-Site-E-MMHg-blk
Analyte(s)
Monomethyl Hg
Monomethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Dimethyl Hg
Total gaseous Hg
Total gaseous Hg
Total gaseous Hg
Total gaseous Hg
Monomethyl Hg
Monomethyl Hg
Monomethyl Hg
Monomethyl Hg
Monomethyl Hg
Sample Class
Field Blank
Spike
Test
Test
Test
Field Blank
Spike
Field Blank
Test
Test
Test
Spike
Test
Field Blank
Test
Test
Spike
Test
Test
Test
Field Blank
Date
06/23/05
06/23/05
06/22/05
06/22/05
06/22/05
06/22/05
06/22/05
06/22/05
06/22/05
06/22/05
06/22/05
06/22/05
06/22/05
06/22/05
06/22/05
06/22/05
06/23/05
06/23/05
06/23/05
06/23/05
06/23/05
Run Period
13:28
13:53-14:53
13:10-13:15
13:55-14:01
15:00-15:08
18:00
15:28-15:34
-
13:10-13:15
13:55-14:01
15:00-15:07
15:28-15:34
13:39-14:39
18:09
17:00-18:01
14:53-15:54
13:53-14:53
08:34 - 09:34
10:29-11:29
11:59-12:59
13:28
Represents 3 readings, each ~60-seconds in duration
3-5
-------
Source Test Report
for Landfill E
3.2.3 Boiler Stack
The boiler stack gases were sampled for measurement of NMOCs (as THCs), HC1,
metals (lead [Pb], arsenic [As], cadmium [Cd], chromium [Cr], manganese [Mn],
nickel [Ni]), PCDD/PCDFs, PAHs, total Hg, SO2, NOX, CO, carbon dioxide (CO2),
and oxygen (O2). Sampling of the boiler stack gases was conducted by inserting
sampling probes into the stack pipe and withdrawing the gases with the various
sampling trains. The boiler stack cross-section was divided into 24 equal areas
according to EPA Method 1. The sample probe was placed in each of these 24 areas to
extract equal amounts of gas sample from each area. Sampling at the boiler stack was
conducted at isokinetic conditions.
Accessing the sampling ports required the aid of scaffold platforms. Figure 3-2 shows
the stack and the sampling scaffold platforms. Figure 3-3 shows a sampling train in
place during sample collection at the boiler stack.
Figure 3-2. Sampling Operations at the Boiler Stack
3-6
-------
Source Test Report
for Landfill E
Figure 3-3. Sampling Train at the Boiler Stack
Sample run times for the Method 26A HC1 trains and the Method 29 metals trains were
120-minutes. Runs times for the Method 23 PCDD/PCDF and PAH trains were 240
minutes. Run times for continuous emission monitoring system (CEMS) parameters
(SO2, NOX, CO, O2, CO2, and THCs) varied and were timed to coincide with the
collection periods of the other samples. Table 3-5 lists the sample collections times and
samples collected from the boiler stack
3-7
-------
Source Test Report
for Landfill E
Table 3-5. Boiler Stack Test Sample Log and Collection Times
Sampling
Method
Run Number
EPA Method 3A (CEM)
E-Post-M3A-062205-01
E-Post-M3A-062205-02
E-Post-M3A-062305-03
E-Post-M3A-062305-04
EPA Method 3A (CEM)
E-Post-M3A-062205-01
E-Post-M3A-062205-02
E-Post-M3A-062305-03
E-Post-M3A-062305-04
EPA Method 10 (CEM)
E-Post-M 10-062205-01
E-Post-M 10-062205-02
E-Post-M 10-062305-03
E-Post-M 10-062305-04
EPA Method 7E (CEM)
E-Post-M7E-062205-01
E-Post-M7E-062205-02
E-Post-M7E-062305-03
E-Post-M7E-062305-04
EPA Method 6C (CEM)
E-Post-M6C-062205-01
E-Post-M6C-062205-02
E-Post-M6C-062305-03
E-Post-M6C-062305-04
EPA Method 25A (CEM)
E-Post-M25A-062205-01
E-Post-M25A-062205-02
E-Post-M25A-062305-03
E-Post-M25A-062305-04
_umex Instrument
E-Post-EM-062205-01
E-Post-EM-062205-02
Analyte(s)
02
02
02
02
CO2
C02
C02
C02
CO
CO
CO
CO
NOx
NOX
NOX
NOX
SO2
SO2
S02
S02
NMOCs (THC)
NMOCs (THC)
NMOCs (THC)
NMOCs (THC)
Elemental Hg a
Elemental Hg a
Sample
Class
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Date
06/22/05
06/22/05
06/23/05
06/23/05
06/22/05
06/22/05
06/23/05
06/23/05
06/22/05
06/22/05
06/23/05
06/23/05
06/22/05
06/22/05
06/23/05
06/23/05
06/22/05
06/22/05
06/23/05
06/23/05
06/22/05
06/22/05
06/23/05
06/23/05
06/23/05
06/23/05
Run Period
10:42-15:53
16:50-19:43
08:33-13:26
14:38-16:12
10:42-15:53
16:50-19:43
08:33-13:26
14:38-16:12
10:42-15:53
16:50-19:43
08:33-13:26
14:38-16:12
10:42-15:53
16:50-19:43
08:33-13:26
14:38-16:12
10:42-15:53
16:50-19:43
08:33-13:26
14:38-16:12
10:42-15:53
16:50-19:43
08:33-13:26
14:38-16:12
-16:30
-16:35
3-8
-------
Source Test Report
for Landfill E
Sampling
Method
Run Number
E-Post-EM-062305-03
E-Post-EM-062305-04
E-Post-EM-062305-05
EPA Method 26A
E-Post-M26A-062205-01
E-Post-M26A-062305-02
E-Post-M26A-062305-03
EPA Method 23
E-Post-M23-062205-01
E-Post-M23-062205-02
E-Post-M23-062305-03
EPA Method 29
E-Post-M29-062205-01
E-Post-M29-062305-02
E-Post-M29-062305-03
Analyte(s)
Elemental Hg a
Elemental Hg a
Elemental Hg a
HCI
HCI
HCI
PCDD/PCDFs, PAHs
PCDD/PCDFs, PAHs
PCDD/PCDFs, PAHs
Metals
Metals
Metals
Sample
Class
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Test
Date
06/23/05
06/23/05
06/23/05
06/22/05
06/23/05
06/23/05
06/22/05
06/22/05
06/23/05
06/22/05
06/23/05
06/23/05
Run Period
-16:40
-16:45
-16:50
17:18-19:42
08:47-10:50
14:09-16:12
11:41-16:02
11:43-15:58
08:52-12:56
17:21-19:45
11:27-13:31
14:06-16:19
a Represents three readings, each ~60-seconds in duration
3.3 Field Test Changes and Deviations from Quality Assurance Project Plan (QAPP)
Specifications
3.3.1 Variation from Test Methods or Planned Activities
3.3.1.1 Sampling at the Landfill Gas (LFG) Inlet Pipe
There were not variations from test methods or planned activities at the raw LFG pipe.
3.3.1.2 Raw Landfill Gas (LFG) Inlet Pipe Condensate Sample
Raw LFG pipe condensate sample was not planned and was not collected.
3.3.1.3 Raw Landfill Gas (LFG) Flow Rate Measurement
A control panel at the landfill displays real-time raw LFG flow rates. The accuracy of
the indicated measurement will need to be verified by the facility operator based on
instrument calibration and certification records. Moreover, the accuracy of the flow
3-9
-------
Source Test Report
for Landfill E
rate measurement cannot be verified as part of this program because of the tightly
configured geometry of the raw LFG pipe which precluded accurate gas velocity
measurements. Within these physical limitations, the test team nonetheless made
approximate velocity measurements by traversing the pipe using a standard pitot probe.
The accuracies of these measurements are unknown and the measurements should be
viewed with caution.
3.3.1.4 Boiler Stack
There were not variations from test methods or planned activities at the boiler stack.
3.3.2 Application of Test Methods
The sampling and, where applicable, analytical methods used in this test program
follow those specified in the QAPP.
3.3.3 Test Method Exceptions
Laboratory analytical procedures followed those prescribed by the specified methods,
with the following exceptions:
Raw LFG at Inlet
• Carbonyls were analyzed by Method TO-11 SW-846 Method 8315. Method TO-
11 and 8315 close resemble each other.
• Landfill gas NMOCs were analyzed by the gas chromatograph/mass spectrometer
(GC/MS) Method as described in EPA Publication EPA/600-R-98/16.
• For LFG inlet samples, VOCs and methane (CFL,) were analyzed by EPA Method
TO-15.
Boiler Stack
• Non-Methane Organic Compounds (NMOCs) - Method 25A was used instead of
the specifically applicable Method 25C. This was necessitated by the low analyte
concentration which rendered Method 25 C inappropriate for the intended
measurement.
3-10
-------
Source Test Report
for Landfill E
Table 3-6. Test Methods and Performing Organizations
Procedure
EPA Method 1
EPA Method 2
EPA Method 3A
EPA Method 3C
EPA Method 4
EPA Method 6C
EPA Method 7E
EPA Method 10
EPA Method 1 1
EPA Method 23
EPA Method 25A
EPA Method 25C
EPA Method 26A
EPA Method 29
EPA Method 40
SW-846 Method
0100/TO-11
LUMEX instrument
Organic mercury
methods
Description
Selection of boiler stack traverse points
Determination boiler stack gas velocity and
volumetric flow rate
Determination of oxygen (O2) and carbon
dioxide (CO2) for boiler stack gas molecular
weight calculations
Determination of carbon dioxide (CO2),
methane (CH4), nitrogen (N2), and oxygen (O2)
in raw LFG
Determination of boiler stack gas moisture
Determination of boiler stack sulfur dioxide
(S02)
Determination of boiler stack nitrogen oxides
(NOX)
Determination of boiler stack carbon monoxide
(CO)
Determination of raw LFG hydrogen sulfide
(H2S)
Determination of boiler stack:
Dioxins/furans by Method 8290
Polycyclic aromatic hydrocarbons (PAHs)
by Method 8270
Determination of boiler stack gas non-methane
organic compounds (NMOCs) (as total
hydrocarbons [THCs]) when total organic
concentration is less than the 50 ppm Method
25C applicability threshold
Determination of raw LFG NMOCs
Determination of boiler stack hydrogen chloride
(HCI)
Determination of boiler stack metals
Determination of raw LFG volatile organic
compounds (VOCs)
Determination of raw LFG carbonyls
(formaldehyde and acetaldehyde)
Determination of raw LFG and boiler stack
elemental mercury (Hg°)
Determination of raw LFG:
Monomethyl mercury
Dimethyl mercury
Total mercury.
Performing Organization
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
Triangle Environmental Services
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
ARCADIS G&M
Enthalpy Analytical
ALTA Analytical Perspectives
ARCADIS G&M
Triangle Environmental Services
Resolution Analytics
First Analytical Laboratories
Research Triangle Park Laboratories
Resolution Analytics
ARCADIS G&M
Frontier Geosciences
3-11
-------
Source Test Report
for Landfill E
This page intentionally left blank
3-12
-------
Source Test Report
for Landfill E
4. Presentation of Test Results
Results of the testing are presented in this section. Detailed test results are included in
the Appendices. The following subsections provide concise summaries of the test
results.
Section 4.1 and its subsections present the test results obtained from the raw LFG
measurements (at location "A", see Figure 2-1). The concentrations of the constituents
of interest in the raw LFG are presented in Sections 4.1.2.1 through 4.1.2.5.
Section 4.2 and its subsections present the test results related to the boiler and the
boiler stack (at location "B", see Figure 2-1).
Section 4.3 summarizes the data and presents a comparison with the AP-42 default
values.
4.1 Raw Landfill Gas (LFG) Measurements
As shown in Figure 2-2, sampling was conducted by extracting samples via the four %-
inch ports installed in the raw LFG pipe.
4.1.1 Raw Landfill Gas (LFG) Flow Rate and Temperature
4.1.1.1 Direct Measurements
The estimated mass flow rates of the constituents in the raw LFG pipe were calculated
based on the flow rate indicated by the facility's flowmeter display. This approach was
selected because:
• The pitot probe readings were subject to large errors because of the not fully
developed velocity profile inside the tightly configured LFG pipe.
• The facility flowmeter readings were likely accurate because the indicated readings
were probably the basis on which financial arrangements between the landfill
owner and its customers were made and settled.
During these tests, the panel meter displayed flow rates ranging from 4335 to 4340
scfm. This was the total LFG flow going to all users, not just to the tested boiler.
4-1
-------
Source Test Report
for Landfill E
Measurement of the velocity profile within the raw LFG pipe using a velocity probe
returned readings of approximately 3856 scfm.
A direct measurement with a thermocouple showed the raw LFG temperature to be
71°F.
4.1.2 Raw Landfill Gas (LFG) Constituent Analytes
4.1.2.1 Volatile Organic Compounds (VOCs)
Concentrations of VOCs were obtained by collecting summa canister samples using
Method 40 procedures. Analysis was performed by Method TO-15, with gas
chromatography and mass spectrometry (GC/MS). The alkanes (C2 through C6), being
present in much higher concentrations, were analyzed by GC flame ionization
detection (FID) on the same summa canister samples.
Table 4-1 lists the results of these analyses. Tentatively identified compounds (TICs)
can be seen in the Research Triangle Park (RTF) Laboratory reports in Appendix A.
Table 4-1.
Raw Landfill Gas VOC Concentrations
Compound
Unit
MDL
Concentration
Run 1
Run 2
Run 3
Average a
Analyzed bv GC/FID
Ethane
Propane
Butane
Pentane
Hexane
ppmv
ppmv
ppmv
ppmv
ppmv
1
1
1
1
1
13.0
13.6
3.7
2.9
ND
13.6
12.6
3.4
ND
ND
14.0
12.8
ND
ND
ND
14.0
13.0
3.6
1.0
ND
Analyzed by TO-15 GC/MS
Dichlorodifluoromethane
(Freon 12)
1,2-Chloro-1, 1,2,2-
tetrafluoroethane
Chloromethane
Vinyl chloride
1,3-Butadiene ((Vinylethylene)
ppbv
ppbv
ppbv
ppbv
ppbv
0.3
0.2
0.1
0.2
0.3
248
ND
ND
ND
ND
206
23.7
ND
190
ND
242
22.2
ND
ND
ND
232
15.3
ND
63
ND
4-2
-------
Source Test Report
for Landfill E
Compound
Bromomethane (Methyl
Bromide)
Chloroethane (Ethyl Chloride)
Trichloromonofluoromethane
(CFC11)
1,1-Dichloroethene
1,1,2-Trichloro-1,2,2-
trifluoroethane (CFC1 1 3)
Ethanol d
Carbon Disulfide
Isopropyl Alcohol
(2-Propanol) e
Methylene chloride
(Dichloromethane)
Acetone
t-1,2-dichloroethene
Hexane f
Methyl-t-butyl ether (MTBE)
1,1-Dichloroethane
Vinyl Acetate
cis-1 ,2-Dichloroethene
Cyclohexane
Chloroform
Ethyl Acetate
Tetrahydrofuran (Diethylene
Oxide)
1,1,1 -Trichloroethane
Carbon Tetrachloride
2-Butanone (Methyl Ethyl
Ketone)
Heptane b
Benzene
1,2-Dichloroethane
Unit
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
MDL
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.1
0.3
0.3
0.3
0.3
0.3
0.5
0.3
0.3
0.3
0.3
0.4
0.3
0.5
0.3
0.2
0.2
0.3
Concentration
Run 1
ND
ND
24.4
ND
ND
ND J
1020
5030 J
3720
21800
ND
655 J
ND
ND
110
180
ND
ND
ND
1090
ND
ND
3270
380
998
ND
Run 2
ND
ND
ND
ND
ND
ND J
ND
1110 J
3020
12900
ND
534 J
ND
ND
120
134
ND
ND
ND
692
ND
ND
1920
282
764
ND
Run 3
ND
ND
ND
ND
ND
ND J
ND
944 J
2400
11900
ND
601 J
ND
ND
102
175
ND
ND
ND
832
ND
ND
2290
332
900
ND
Average a
ND
ND
8.1
ND
ND
ND J
339
2360 J
3050
15500
ND
597 J
ND
ND
111
163
ND
ND
ND
870
ND
ND
2490
331
887
ND
4-3
-------
Source Test Report
for Landfill E
Compound
Trichloroethylene
(Trichloroethene)
1,2-Dichloropropane
Bromodichloro methane
1,4-Dioxane (1,4-Diethylene
Dioxide)
cis-1 ,3-Dichloropropene
Toluene (Methyl Benzene)
4-Methyl-2-pentanone (MIBK)
t-1 ,3-Dichloropropene
Tetrachloroethylene
(Perch loroethylene)
1,1,2-Trichloroethane
Dibromochloromethane
1,2-Dibromoethane (Ethylene
dibromide)
2-Hexanone (Methyl Butyl
Ketone)
Ethylbenzene
Chlorobenzene
m/p-Xylene (Dimethyl
Benzene) g
o-Xylene (Dimethyl Benzene)
Styrene (Vinylbenzene)
Tribromomethane (Bromoform)
1 , 1 ,2,2-Tetrachloroethane
1-Ethyl-4-methylbenzene (4-
Ethyl Toluene) °
1 ,3,5-Trimethylbenzene
1 ,2,4-Trimethylbenzene
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene
Unit
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
MDL
0.2
0.3
0.2
0.2
0.2
0.3
0.2
0.2
0.3
0.2
0.2
0.2
0.2
0.3
0.2
0.65
0.3
0.1
0.3
0.2
0.2
0.2
0.3
0.2
0.3
Concentration
Run 1
110
ND
ND
ND
ND
8780
ND
ND
128
ND
ND
ND
ND
ND
132
9670 J
3460
491
ND
ND
2540
1040
2740
ND
ND
Run 2
73.7
ND
ND
ND
ND
6860
ND
ND
125
ND
ND
ND
ND
ND
139
7830 J
2670
314
ND
ND
2250
919
2390
ND
ND
Run 3
98.3
ND
ND
ND
ND
8220
ND
ND
122
ND
ND
ND
ND
ND
134
9500 J
3180
455
ND
ND
2750
1150
2800
ND
ND
Average a
93.9
ND
ND
ND
ND
7950
ND
ND
125
ND
ND
ND
ND
ND
135
9000 J
3100
420
ND
ND
2510
1040
2640
ND
ND
4-4
-------
Source Test Report
for Landfill E
Compound
Benzyl Chloride
1 ,2-Dichlorobenzene
1,1,2,3,4,4-Hexachloro-1,3-
butadiene
1 ,2,4-Trichlorobenzene
Chlorodiflouromethane (Freon
22)
Acrylonitrile
Unit
ppbv
ppbv
ppbv
ppbv
ppbv
ppbv
MDL
0.2
0.3
0.2
0.3
20
20
Concentration
Run 1
ND
ND
ND
ND
ND
ND
Run 2
ND
ND
ND
ND
ND
ND
Run 3
ND
ND
ND
ND
ND
ND
Average a
ND
ND
ND
ND
ND
ND
ND - Constituent not found at detection stated method detection limit
3 Average - equals ND if all three measurements are ND. Otherwise, ND contribution to the
average is equal to 50 percent of the analyte MDL
b Field blank reported heptane at 32.1 ppbv
c Field blank reported 1-ethyl-4-methylbenzene at 161 ppbv
d Ethanol spike recovery was 2-4 percent
e Isopropyl alcohol relative standard deviation (RSD) was 56.3 percent
f Hexane RSD was 40.7 percent
g m/p-Xylene spike recovery was 230 percent
4.1.2.2 Non-methane Organic Compounds (NMOCs)
Non-methane organic compounds (NMOCs) in the raw LFG were analyzed by
Triangle Environmental Services in accordance with Method 25 C, performed on the
samples collected with Method 40. Table 4-2 presents the NMOC concentrations in the
LFG.
This table also includes concentrations of CFL,, CO2, and O2, which were obtained by
Method SC.The analytes, oxygen (O2), carbon dioxide (CO2), and moisture, are not
pollutants but are of interest as they are useful indicators of the "quality" of the raw
LFG. The concentrations of nitrogen (N2) and O2 are also indicators of the extent of
ambient air infiltration into the LFG collection. Method 25C for NMOC determination
specifically recommends that these measurements be made to determine potential air
infiltration. Therefore, while measurements for methane (CFL,), CO2, O2, and N2 by
Method 3C were not included in the original QAPP, these measurements were included
and performed.
4-5
-------
Source Test Report
for Landfill E
Table 4-2. Raw LFG Non-Methane Organic Compound (NMOC)
Run 1
Run 2
Run 3
Average
NMOC
(ppmv as
Hexane)
Method
25Ca
288
218
194
233
CH4
(% v/v)
Method
25Ca
50.9
46.7
50.8
49.5
Method
3C
51.7
46.8
49.9
49.5
CO2
(% v/v)
Method
25Ca
36.3
33.3
36.3
35.3
Method
3C
31.9
30.2
31.9
31.3
02 (%v/v)
Method
3C
2.1
3.4
2.2
2.6
N2
(% v/v)
Method
3C
11.9
16.4
12.4
13.6
Moisture
(% v/v)
Method
23
NM
NM
NM
NM
NM - not measured because Method 23 sampling train was not run. Data column is included to
retain format consistency with other reports.
Concentrations are reported without correction for nitrogen.
a Method 25C samples hold time were up to 42 days. Method specifies 30 days hold time.
Non-methane organic compounds ranged from 194 to 288 ppmv as hexane. The major
components in the LFG consisted of methane at an average concentration of 49.5
percent. Carbon dioxide ranged from approximately 30 to 36 percent. Oxygen was
present at about 2 to 6 percent. Nitrogen concentrations averaged at 13.6 percent.
4.1.2.3 Hydrogen Sulfide (H2S)
Raw LFG H2S concentrations were obtained by collecting and analyzing the samples in
accordance with EPA Method 11. The laboratory analysis reports and the
concentration calculation worksheet are included in Appendix G. Table 4-3 presents
the concentrations of H2S in the raw LFG.
Table 4-3. Raw LFG Hydrogen Sulfide Concentrations
Run 1
Run 2
Run 3
Average
H2S Concentration
(mg/m3)
519 J
438 J
413 J
458 J
(ppmv)
366 J
309 J
291 J
322 J
J - Estimated per EPA QA/G-8 guidance. Spike sample was not prepared.
Spike recovery data were not available.
4-6
-------
Source Test Report
for Landfill E
4.12.4 Carbonyls
The target carbonyl compounds, formaldehyde and acetaldehyde, were analyzed by
SW-846 Method 8315 on samples collected by EPA Method 0100. The analysis
reports, prepared by Resolution Analytics, are included as Appendix D. Calculation
worksheets to convert the laboratory results to carbonyl concentrations in the raw LFG
are presented as well. Table 4-4 below presents the concentrations of formaldehyde
and acetaldehyde in the raw LFG.
Table 4-4. Raw LFG Carbonyls Concentrations
MDL
Run 1
Run 2
Run 3
Average
Formaldehyde
(Mg/m3)
2.9
11.8
8.9
8.1
9.6
(xlO"3 ppmv)
2.3
9.6
7.2
6.5
7.8
Acetaldehyde
(Mg/m3)
3.8
27.9
151
98.1
92.4
(x10~3 ppmv)
2.1
15.3
82.8
53.8
50.6
4.12.5 Mercury (Hg)
Mercury (Hg) can exist in several forms. This test program focused on measuring the
concentrations of the elemental, monomethyl, and dimethyl forms of Hg and the total
Hg concentrations in the raw LFG. Total Hg, monomethyl Hg and dimethyl Hg were
sampled and analyzed using the organic mercury method. Elemental Hg was measured
with the LUMEX instrument.
Result tables that have data from both Frontier and Geochimica laboratories for the
same run signifies that the samples were collected simultaneously by these two groups.
4.1.2.5.1 Total Mercury (Hg)
To collect the total Hg samples, an iodated charcoal trap was used as a sorbent. A
backup tube was also present to assess any breakthrough. The sorbent tube was heated
to above the dew point of the gas stream to prevent condensation on the sorbent. A
silica gel impinger was used to collect and quantify the water vapor from the stream. A
diaphragm air pump was used to pull sample through the train and collect the sample.
A dry gas meter with 10 ml resolution was used to quantify the volume of gas sampled.
4-7
-------
Source Test Report
for Landfill E
Duplicate samples were collected simultaneously. One set was sent to Frontier
Geosciences and the second set was sent to Studio Geochimica. The two laboratories
performed the analysis independently. Their results provide a means of assessing the
precision of the analytical method. Frontier Geosciences' results are included as
Appendix E-l and Studio Geochimica's results are included as Appendix E-2.
Table 4-5 presents the total Hg concentrations in the raw LFG. Total Hg concentrations
ranged from 1330 to 1650 ng/m3. The average of all six measurements is 1460 ng/m3.
The deviation from the overall mean of the six measurements ranged from 0.05 percent
to 12.5 percent of the mean value.
Table 4-5. Raw LFG Total Mercury Concentrations
MDL
Run 1
Run 2
Run 3
Run 4
Average
Total Mercury Concentration
(ng/m3)
Frontier a
50
1460
1330
1520
NR
1430
Geochimica
9
1400
1410
NR
1650
1490
(x10~6 ppmv)
Frontier a
6
164
149
170
NR
161
Geochimica
1
156
158
NR
184
166
NR - No sampling while the other laboratory group was collecting sample.
a Sample hold times were 30 days. Specified hold time was 14 days.
4.1.2.5.2 Dimethyl Mercury (Hg) Samples:
A Carbotrap was used as sorbent to collect samples for dimethyl Hg analysis. A
backup trap was present to detect and assess breakthrough, if any. A third iodated
carbon trap was present to collect elemental Hg if any is present. The sorbent tube was
heated and maintained at temperatures above the dew point of the gas stream to prevent
condensation on the sorbent. A silica gel impinger was used to collect and quantify the
water vapor in the sampled gas. A diaphragm air pump was used to pull sample
through the sampling train. A dry gas meter with 10 ml resolution was used to quantify
the volume of gas sampled.
As in the measurement for total Hg, duplicate samples were collected simultaneously.
One set was sent to Frontier Geosciences and the second set was sent to Studio
4-8
-------
Source Test Report
for Landfill E
Geochimica. The two laboratories performed the analysis independently. Their results
provide a means of assessing the precision of the analytical method. Frontier
Geosciences' report of their results is included as Appendix E-l and Studio
Geochimica's report of their results is included as Appendix E-2.
Table 4-6 presents the dimethyl Hg concentrations in the raw LFG. Dimethyl Hg
concentrations ranged from 17.4 to 99.8 ng/m3. The average of the six measurements
was 52.5 ng/m3. Spike recoveries for the dimethyl Hg traps averaged at 98.3 percent.
Table 4-6. Raw LFG Dimethyl Mercury Concentrations
MDL
Run 1
Run 2
Run 3
Run 4
Average
Dimethyl Mercury Concentration
(ng/m3)
Frontier
0.5
NR
73.6
27.1
63.8
54.8
Geochimica
0.4
17.4
NR
33.4
99.8
50.2
(x10~6 ppmv)
Frontier
0.05
NR
7.71
2.84
6.68
5.74
Geochimica
0.04
1.82
NR
3.50
10.5
5.26
NR - No sampling while the other laboratory group was collecting sample.
4.1.2.5.3 Monomethyl Mercury (Hg) Samples
A sampling train, consisting of three impingers each filled with 0.001 M HC1, was used
to collect samples for monomethyl Hg analysis. An empty forth impinger was used to
knockout any impinger solution and prevent carryover to the pump and metering
system. A diaphragm air pump was used to pull sample through the train and collect
the sample. A dry gas meter with 10 ml resolution was used to the volume of gas
sampled.
As in the measurement for total Hg and dimethyl Hg, duplicate samples were collected
simultaneously. One set was sent to Frontier Geosciences and the second set was sent
to Studio Geochemica. The two laboratories performed the analysis independently.
Their results provide a means of assessing the precision of the analytical method.
Frontier Geosciences' results are included as Appendix E-l and Studio Geochimica's
results are included as Appendix E-2.
4-9
-------
Source Test Report
for Landfill E
As shown in Table 4-7, monomethyl Hg concentrations in the raw LFG ranged from
3.4 to 8.2 ng/m3 with an mean of the six measurements of 5.4 ng/m3. Spike recovery
for the monomethyl Hg sample was 89.7 percent.
Table 4-7. Raw LFG Monomethyl Mercury Concentrations
MDL
Run 1
Run 2
Run 3
Average
Monomethyl Mercury Concentration
(ng/m3)
Frontier
0.13
3.4
4.6
5.6
4.5
Geochimica
1.4
6.2
4.6
8.2
6.3
(x10~6 ppmv)
Frontier
0.014
0.38
0.52
0.63
0.50
Geochimica
0.15
0.69
0.52
0.92
0.71
4.1.2.5.4 Elemental Mercury (Hg)
Elemental Hg was determined by the LUMEX instrument. The measurement records
are included as Appendix F and the results are presented in Table 4-8.
The LFG sample was collected from a pressurized port downstream of the compressor,
as the LUMEX instrument was unable to draw a sample from the vacuum portion of
the LFG header pipe.
Table 4-8. Raw LFG Elemental Mercury Concentrations
Run 1
Run 2
Run 3
Average
Elemental Mercury Concentration a
Background
(ng/m3)
13
9
33
18
(xlO"6 ppmv)
1.6
1.1
4.0
2.2
Raw LFG
(ng/m3)
437
445
438
440
(x10~6 ppmv)
52.6
53.6
52.7
53.0
Reported value is the average of three readings, each about 60-second in duration
4-10
-------
Source Test Report
for Landfill E
4.2 Boiler Stack Results
During the tests, the boiler ran under nominally unchanged conditions. The boiler
operating conditions are shown in Tables 4-9a and 4-9b for a 2-day test period. The
reported data were recorded from the boiler process control system monitor.
Table 4-9a. Boiler Operating Condition on June 22, 2005 as indicated by Boiler Control
System
Time
06/22/05
12:14
12:52
13:25
13:58
14:38
15:12
15:45
17:20
17:52
18:42
19:23
19:46
Steam
Production
Rate (Ib/hr)
76,800
75,609
75,375
75,554
75,211
74,881
76,510
80,313
79,516
79,557
80,512
81,034
LFG Flow
Rate (scfm)
2,433
2,348
2,344
2,331
2,340
2,342
2,384
2,514
2,494
2,498
2,500
2,500
Stack O2
(% v/v)
6.88
7.27
7.29
7.26
7.28
7.30
7.11
6.59
6.61
6.70
6.75
6.76
Stack
Temperature
(°F)
492
489
489
489
489
489
490
494
494
494
494
494
% Load
41.0
41.0
41.0
41.0
41.0
41.0
41.0
41.0
41.0
41.0
41.0
41.0
Total
Cumulative
Heat Content
(MMBtu)
Not recorded a
Not recorded a
34,096
34,133
34,182
34,225
34,267
34,393
34,435
34,502
34,556
34,587
Event Notes:
11:41
11:43
15:55
17:18
19:45
Start M23 Run 1
Start M23 Run 2
Finished M23 Runs 1 and 2
Start M29 Run 1 and M26A Run 1
Finished M29 Run 1 and M26A Run 1
Reading was missed and not recorded during startup
4-11
-------
Source Test Report
for Landfill E
Table 4-9b. Boiler Operating Condition on June 23, 2005 as indicated by Boiler Control
System
Time
6/23/05
8:48
9:20
9:52
10:23
11:10
11:42
12:29
13:06
13:33
14:08
14:34
15:07
15:37
16:12
Steam
Production
Rate
(Ib/hr)
87,303
88,470
87,104
88,100
69,470
88,759
71,159
71,448
72,612
71,516
71,372
71,180
74,071
74,043
LFG Flow
Rate
(scfm)
2,745
2,741
2,731
2,742
2,134
2,779
2,277
2,273
2,281
2,269
2,285
2,271
2,362
2,365
Stack O2
(% v/v)
5.58
5.60
5.52
5.53
5.40
5.29
7.30
7.33
7.27
7.25
7.25
7.27
6.78
6.73
Stack
Temperature
(°F)
498
498
499
498
466
497
484
484
484
485
484
484
486
486
%
Load
41.0
41.0
41.0
41.0
41.0
41.0
40.0
40.0
40.0
40.0
40.0
40.0
40.0
40.0
Total
Cumulative
Heat Content
(MMBtu)
34,885
34,932
34,979
35,025
35,085
35,126
35,187
35,231
35,264
35,306
35,337
35,377
35,415
35,458
Event Notes:
8:47 Start M23 Run 3 and M26A Run 2
10:50 Finished M26A Run 2
11:00 Load dropped due to gas pressure problem. Will be back up to condition in 45 minutes.
11:27 Start M29 Run 2
12:05 Same pressure problem as at 11:00 will recover slowly.
12:56 Finished M23 Run 3
13:30 Finished M29 Run 2
14:06 Start M29 Run 3 and M26A Run 3
16:11 Finished M29 Run 3 and M26A Run 3
4-12
-------
Source Test Report
for Landfill E
The boiler stack was sampled for NMOCs (as THCs), HC1, Pb, As, Cd, Cr, Mn, Ni,
total Hg, PCDD/PCDFs, PAHs, SO2, NOX, CO, CO2, and O2. The stack cross section
was divided into 24 equal areas according to EPA Method 1. Sampling run time for
HC1 and metals was 120 minutes. Run time for PCDD/PCDFs and PAHs was 240
minute. Run time for CEMS parameters (SO2, NOX, CO, O2, CO2, and THCs) varied.
4.2.1 Boiler Stack Gas Flow Rate and Temperature
Samples from the boiler stack were collected under isokinetic conditions. As an
integral part of the procedure, the sampling operation measured stack gas velocity
distribution across the boiler stack and hence provided reliable measurements of stack
gas flow rates. Table 4-10 lists the volumetric flow rates and temperatures at the boiler
stack measured during the various sampling runs.
Table 4-10. Boiler Stack Gas Conditions Measured during Sampling
Run Number
E-Post-M26A-062205-01
E-Post-M26A-062305-02
E-Post-M26A-062305-03
E-Post-M29-062205-01
E-Post-M29-062305-02
E-Post-M29-062305-03
E-Post-M23-062205-01
E-Post-M23-062205-02
E-Post-M23-062305-03
Duration
06/22/05, 17:18-19:42
06/23/05,08:47-10:50
06/23/05, 14:09-16:12
06/22/05, 17:21 -19:45
06/23/05, 11:27-13:31
06/23/05, 14:06-16:19
06/22/05, 11:41 -16:02
06/22/05, 11:43-15:58
06/23/05,08:52-12:56
Average
Average
Stack
Temp (°F)
484
488
470
475
479
476
479
481
476
479
Carbon
Dioxide
(%)
12.2
12.2
12.5
12.1
12.5
12.5
12.1
12.1
12.5
12.3
Oxygen
(%)
7.9
7.2
7.2
7.9
7.2
7.2
7.9
7.9
7.2
7.5
Moisture
(%)
12.4
14.1
11.6
13.1
13.1
13.1
11.8
11.9
12.7
12.6
Velocity
(actual
ft/sec)
30.0
31.3
31.7
30.0
31.3
32.2
30.3
29.6
28.5
30.5
Vol. Flow
Rate
(acfm)
57,494
59,925
60,633
57,447
59,912
61,660
58,017
56,725
54,488
58,478
Vol. Flow
Rate
(dscfm)
28,116
28,629
30,397
28,134
29,244
30,192
28,710
27,986
26,819
28,692
Boiler stack cross-section flow area is 31.92 sq. ft.
4-13
-------
Source Test Report
for Landfill E
4.2.2 Boiler Stack Oxygen and Carbon Dioxide
Oxygen (O2) and CO2 concentrations provide an overall indication of the combustion
process. Figure 4-1 shows the O2and CO2 concentrations measured by the CEMs
during the two days of testing. Table 4-11 presents the run averages of O2 and CO2
concentrations.
Table 4-11. Boiler Stack Oxygen and Carbon Dioxide Concentrations
Run 1
Run 2
Run 3
Run 4
Average
02
(%v)
8.2
7.4
7.2
7.4
7.5
CO2
(% v)
11.8
12.1
12.9
12.8
12.3
4.2.3 Boiler Stack Total Hydrocarbon (THC)
With consideration focused on data relevant to AP-42, NMOC is the analyte of interest
at the boiler stack. Measurement of hydrocarbon concentrations EPA Method 25A,
which included NMOCs, showed that THC concentrations to be below 50 ppmv. These
low concentrations rendered Method 25 C, the method designed specifically for NMOC
measurement, unsuitable to be applied at this sample location. Hence, Method 25A
became the practical method of choice.
Method 25 A used a CEM and produced measurements of concentration of all
hydrocarbons that respond to flame ionization detector (FID) analysis. Real-time
continuous instrument responses are shown in Figure 4-2. The time-averaged
concentrations are presented in Table 4-12.
A conservative approach can be taken to assume all hydrocarbons to be NMOCs.
However, this interpretation will bias the NMOC concentration results high. As shown
by the measurements, the concentrations of THC were low throughout the tests. Hence,
concentrations of NMOC were also low at the boiler stack.
4-14
-------
Source Test Report
for Landfill E
Boiler Stack Oxygen & Carbon Dioxide 6/22/05
14
12
o>
" c
c 6
o
O
4
2
•Carbon Dioxide Run 1
Oxygen Run 1
•Carbon Dioxide Run 2
Oxygen Run 2
09:36 10:48 12:00 13:12 14:24 15:36 16:48 18:00 19:12 20:24
Time
14
12
•m
Boiler Stack Oxygen & Carbon Dioxide 6/23/05
i ^ — i
\i\
E
1 •
o
o
Oxygen
•Carbon Dioxide
07:55
09:07
10:19
Timd
1 31
12:43
13:55
Figure 4-1. Boiler Stack Oxygen and Carbon Dioxide Concentrations
4-15
-------
Source Test Report
for Landfill E
Concentration (ppm Dry)
*• -". ro ro co to Js.
0
09
Boiler Stack Total Hydrocarbon 6/22/05
1
1
36 10:48 12:00 13:12 14:24 15:36 16:48 18:00 19:12 20:24
Time
Boiler Stack Total Hydrocarbon 6/23/05
•:55
09.07
10.19
TimeU 31
12.43
13.55
Figure 4-2. Boiler Stack Total Hydrocarbon Concentration
4-16
-------
Source Test Report
for Landfill E
Table 4-12. Boiler Stack Total Hydrocarbon Concentration
Run 1
Run 2
Run 3
Run 4
Average
Total Hydrocarbon
(ppmdv as propane)
ND
1
1
1
1
(ppmdv as hexane)
ND
0.5
0.5
0.5
0.4
4.2.4 Boiler Stack Dioxin/Furan (PCDD/PCDFs)
Three EPA Method 23 sampling runs were performed. Table 4-13 presents the boiler
stack PCDD/PCDF emissions data. Table 4-14 presents the same data, but expressed in
terms of Toxicity Equivalent emissions.
The data showed that detectable levels of PCDD/PCDFs were found in concentrations
ranging from the single digit to several tens of picogram per standard cubic meter of
the exhaust gas.
4.2.5 Boiler Stack Polycyclic Aromatic Hydrocarbon (PAH) Emissions
The concentrations of PAH were also obtained by Method 23. The results are
presented in Table 4-15. The concentrations of PAHs in the boiler stack ranged from
10 ng/dscm of acenaphthylene to 1400 ng/dscm of fluoranthene.
4-17
-------
Source Test Report
for Landfill E
Table 4-13. Boiler Stack Dioxins and Furans
Analyte
E-062205-M23-1
Concentration
(x103ng/dscm)
Emission Rate
(x10*g/hr)
(x10-'2|b/hr)
E-062205-M23-2
Concentration
(x10-3ng/dscm)
Emission Rate
(x10*g/hr)
(x1&'2|b/hr)
E-062305-M233
Concentration
(x10*ng/dscm)
Emission Rate
(x10*g/hr)
(x1&'2|b/hr)
Average
Concentration
(x10*ng/dscm)
Emission Rate
(xWg/hr)
(x1&'2|b/hr)
Dioxins
2,3,7,8-TCDD
Other TCDD
1,2,3,7,8-PeCDD
Other PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
Other HxCDD
1,2,3,4,6,7,8-HpCDD
Other HpCDD
1,2,3,4,6,7,8,9-OCDD
Total CDD
1.1
78.1
<3.1
82.1
3.3
6.0
4.2
71.8
27.7
27.6
39.5
345
54.4
3800
<152
4000
162
291
207
3500
1400
1300
1900
16800
120
8400
<335
8800
356
642
456
7700
3000
3000
4200
37100
1.3
71.1
5.2
89.5
4.2
7.6
5.7
82.5
31.9
34.0
55.8
389
62.9
3400
249
4300
200
360
271
3900
1500
1600
2700
18500
139
7500
550
9400
441
794
598
8700
3300
3600
5900
40800
<0.685
77.4
<2.3
58.2
2.5
5.1
3.5
59.0
24.3
23.7
35.5
292
<31.2
3500
<103
2700
114
230
159
2700
1100
1100
1600
13300
<68.8
7800
<228
5800
252
508
351
5900
2400
2400
3600
29400
0.926
75.5
2.6
76.6
3.3
6.2
4.5
71.1
28.0
28.5
43.6
341
44.3
3600
126
3600
159
294
212
3400
1300
1300
2100
16200
97.6
7900
277
8000
350
648
468
7400
2900
3000
4600
35600
Furans
2,3,7,8-TCDF
Other TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
Other PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
6.2
198
9.4
13.0
127
11.1
11.7
12.0
2.8
302
9600
457
635
6200
541
569
585
139
666
21200
1000
1400
13600
1200
1300
1300
307
7.6
215
12.1
17.6
160
16.7
15.3
15.8
4.5
360
10200
578
837
7600
796
729
750
216
794
22600
1300
1800
16800
1800
1600
1700
476
3.7
114
6.0
7.9
69.4
7.4
7.8
7.6
1.9
171
5200
271
359
3200
338
356
347
89
376
11500
598
791
7000
746
785
765
196
5.8
176
9.2
12.8
119
11.8
11.6
11.8
3.1
278
8400
435
610
5700
559
551
560
148
612
18400
960
1300
12500
1200
1200
1200
326
4-18
-------
Source Test Report
for Landfill E
Analyte
Other HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
Other HpCDF
1,2,3,4,6,7,8,9-OCDF
Total CDF
Total CDD£DF
E-062205-M23-1
Concentration
(x1(>3ng/dscm)
57.8
28.3
3.8
10.2
11.0
304
648
Emission Rate
(x10*g/hr)
2800
1400
187
498
538
24500
41300
(x10-'2|b/hr)
6200
3000
412
1100
1200
53900
91000
E-062205-M23-2
Concentration
(x10-3ng/dscm)
84.4
38.9
5.0
15.5
12.9
407
796
Emission Rate
(x10*g/hr)
4000
1900
239
738
615
29600
48100
(x1&'2|b/hr)
8800
4100
527
1600
1400
65200
106000
E-062305-M233
Concentration
(x10*ng/dscm)
36.0
21.7
2.4
6.8
9.3
188
480
Emission Rate
(x10*g/hr)
1600
987
111
309
423
13800
27100
(x1&'2|b/hr)
3600
2200
244
682
932
30400
59800
Average
Concentration
(x10*ng/dscm)
59.4
29.6
3.8
10.8
11.1
300
640
Emission Rate
(xWg/hr)
2800
1400
179
515
526
22600
38800
(x1&'2|b/hr)
6200
3100
395
1100
1200
49900
85500
"<" denotes the measurement was non-detect. The value following the "<" sign is the detection limit.
4-19
-------
Source Test Report
for Landfill E
Table 4-14. Boiler Stack Dioxins and Furans Toxicity Equivalent Emissions
Pollutant
Dioxins
2,3,7,8-TCDD
Other TCDD
1,2,3,7,8-PeCDD
Other PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
Other HxCDD
1,2,3,4,6,7,8-HpCDD
Other HpCDD
1,2,3,4,6,7,8,9-OCDD
Total ODD
Concentration
(xlO"3 ng/dscm)
0.926
75.5
2.6
76.6
3.3
6.2
4.5
71.1
28.0
28.5
43.6
341
Emission Rate
(xlO^g/hr)
(x10'12 Ib/hr)
1989 Toxicity
Equivalency
Factor
Concentration
(x10^ ng/dscm)
Emission Rate
(xlO^g/hr)
(x10'12 Ib/hr)
44.3
3600
126
3600
159
294
212
3400
1300
1300
2100
16200
97.6
7900
277
8000
350
648
468
7400
2900
3000
4600
35600
1
—
0.5
—
0.1
0.1
0.1
—
0.01
—
0.001
—
0.926
NA
1.3
NA
0.33
0.62
0.45
NA
0.28
NA
0.0436
4.0
44.3
NA
63
NA
15.9
29.4
21.2
NA
13.2
NA
2.1
189
97.6
NA
139
NA
35
64.8
46.8
NA
29
NA
4.6
417
Furans
2,3,7,8-TCDF
Other TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
Other PeCDF
5.8
0.0084
9.2
12.8
119
278
8400
435
610
5700
612
18400
960
1300
12500
0.1
—
0.05
0.5
—
0.58
NA
0.46
6.4
NA
27.8
NA
21.8
305
NA
61.2
NA
48.0
673
NA
4-20
-------
Source Test Report
for Landfill E
Pollutant
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
Other HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
Other HpCDF
1,2,3,4,6,7,8,9-OCDF
Total CDF
Total CDD/CDF
Concentration
(xlO"3 ng/dscm)
11.8
11.6
11.8
3.1
59.4
29.6
3.8
10.8
11.1
300
640
Emission Rate
(x10"g/hr)
559
551
560
148
2800
1400
179
515
526
22600
38800
(x10'12 Ib/hr)
1230
1220
1240
326
6200
3100
395
1100
1200
49900
85500
1989 Toxicity
Equivalency
Factor
0.1
0.1
0.1
0.1
—
0.01
0.01
—
0.001
—
—
Concentration
(xlO"3 ng/dscm)
1.2
1.2
1.2
0.31
NA
0.296
0.038
NA
0.0111
11.6
15.6
Emission Rate
(xlQ-Vhr)
55.9
55.1
56.0
14.8
NA
14.1
1.8
NA
0.526
553
742
(x10'12 Ib/hr)
123
122
124
32.6
NA
31.0
3.9
NA
1.2
1200
1600
NA - Not applicable because no Toxicity Equivalent Factor is available
"<" denotes the measurement was non-detect. The value following the "<" sign is the detection limit.
4-21
-------
Source Test Report
for Landfill E
Table 4-15. Boiler Stack Polycyclic Aromatic Hydrocarbons (PAHs) Emissions
Analyte
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(g,h,i)perylene
Benzo(k)fluoranthene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
lndeno(1 ,2,3-cd)pyrene
Formula
Weight
154.21
152.20
178.23
228.30
252.32
252.32
276.34
252.32
228.29
278.35
202.26
166.22
288.35
E-062205-M23-1
Concentration
(x10«ppmv)
10.3
1.8
5.5
41.9
29.1
81.0
34.9
30.5
69.2
7.3
213
11.4
33.4
(ng/dscm)
66.3
11.1
40.6
398
305
850
401
320
657
84.4
1800
78.7
401
Emission Rate
(x10«g/hr)
3200
543
2000
19400
14900
41500
19500
15600
32000
41000
87300
3800
19500
(x10«IWhr)
7.1
1.2
4.4
42.8
32.8
91.4
43.1
34.4
70.7
9.1
192
8.5
43.1
E-062205-M23-2
Concentration
(xlO^ppmv)
10.2
2.5
6.7
37.2
36.3
70.5
28.3
25.7
59.5
6.1
190
12.1
27.9
(ng/dscm)
65.6
15.8
50.0
353
380
739
325
270
564
70.5
1600
83.4
334
Emission Rate
(x10«g/hr)
3100
750
2400
16800
18100
35100
15500
12800
26800
3400
76100
4000
15900
(x10«IWhr)
6.9
1.7
5.2
37.0
39.9
77.5
34.1
28.3
59.2
7.4
168
8.7
35.0
E-062305-M23-3
Concentration
(xlO^ppmv)
2.5
0.587
1.4
16.3
1.1
36.9
1.5
12.5
33.0
3.0
84.1
8.9
8.0
(ng/dscm)
16.0
3.7
10.0
154.
11.9
387
17.4
132
313
34.9
707
61.4
95.7
Emission Rate
(x10«g/hr)
728
169
458
7000
541
17600
795
6000
14300
1600
32200
2800
4400
(x10«lb/hr)
1.6
0.373
1.0
15.5
1.2
38.9
1.8
13.2
31.5
3.5
71.0
6.2
9.6
Average
Concentration
(xlO^ppmv)
7.7
1.6
4.5
31.8
22.2
62.8
21.6
22.9
53.9
5.5
162
10.8
23.1
(ng/dscm)
49.3
10.2
33.6
302
233
659
248
240
512
63.3
1400
74.5
277
Emission Rate
(x10«g/hr)
2400
487
1600
14400
11200
31400
11900
11500
24400
3000
65200
3500
13300
(x10«lb/hr)
5.2
1.1
3.5
31.7
24.6
69.3
26.3
25.3
53.8
6.7
144
7.8
29.2
4-22
-------
Source Test Report
for Landfill E
Analyte
Naphthalene
Phenanthrene
Pyrene
2-Methylnaphthalene
Benzo(e)Pyrene
Perylene
Formula
Weight
128.17
178.23
202.26
142.20
252.32
253.31
E-062205-M23-1
Concentration
(x10«ppmv)
183
174
131
136
45.3
3.6
(ng/dscm)
974
1300
1100
804
475
37.7
Emission Rate
(xKHg/hr)
47500
62800
53700
39200
23200
1800
(x10«IWhr)
105
139
118
86.5
51.1
4.1
E-062205-M23-2
Concentration
(xlO^ppmv)
175
242
128
170
39.5
7.7
(ng/dscm)
932
1800
1100
1000
414
81.3
Emission Rate
(xKHg/hr)
44300
85300
51300
47800
19700
3900
(x10«IWhr)
97.7
188
113
106
43.4
8.5
E-062305-M23-3
Concentration
(xlO^ppmv)
84.1
74.3
37.6
23.5
16.6
0.176
(ng/dscm)
448
550
316
139
174
1.8
Emission Rate
(x10«g/hr)
20400
25100
14400
6300
7900
84.1
(x10«lb/hr)
45.0
55.3
31.7
14.0
17.5
0.186
Average
Concentration
(xlO^ppmv)
147
163
99.0
110
33.8
3.8
(ng/dscm)
785
1200
832
650
355
40.3
Emission Rate
(x10«g/hr)
37400
57700
39800
31100
16900
1900
(x10«lb/hr)
82.5
127
87.8
68.6
37.3
4.3
4-23
-------
Source Test Report
for Landfill E
4.2.6 Hydrogen Chloride (HCI) Emissions
Boiler stack HCI emissions results are presented in Table 4-16. The concentrations
were low, averaging at 1.4 ppmdv.
Table 4-16. Boiler Stack Hydrogen Chloride Measurement Results
Run 1
Run 2
Run 3
Average
Concentration
(ppmdv)
1.6
1.3
1.3
1.4
(x103 ug/m3)
2.4
2.0
2.0
2.1
Emission
(Ib/hr)
0.26
0.21
0.22
0.23
(g/hr)
120
95
99
100
4.2.7 Metals Emissions
Concentrations Toxic heavy metals in the engine stack gases were measured by
Method 29. Manganese was determined by inductively coupled plasma - mass
spectroscopy (ICP-MS). Arsenic (As), Cd, Cr, Pb, and Ni were determined by graphite
furnace atomic absorption spectroscopy (GFAAS). Mercury was determined by cold
vapor (CV) AA and was not detected in any of the samples. Boiler stack metals
emissions results are presented in Table 4-17.
Mercury (Hg) concentration (elemental) was separately measured by the LUMEX
instrument and those results are also included in Table 4-17.
4.2.8 Gaseous Emissions: Carbon Monoxide (CO), Sulfur Dioxide (802), and Nitrogen Oxides
(NOX)
Gaseous emissions measured with CEMs include CO, SO2 and NOX. These results are
in Table 4-18. Figures 4-3 through 4-5 show the real-time concentrations of CO, SO2,
and NOX, respectively.
4-24
-------
Source Test Report
for Landfill E
Boiler Stack Carbon Monoxide 6/22/05
09:36 10:48 12:00 13:12 14:24 15:36 16:48 18:00 19:12 20:24
Time
60
50
I40
Q.
o
1 30
o 20
10
0
Boiler Stack Carbon Monoxide 6/23/05
07:55
09:07
10:19 11:31
Time
12:43
13:55
Figure 4-3. Boiler Stack Carbon Monoxide Concentration
4-25
-------
Source Test Report
for Landfill E
60
50
040
030
Boiler Stack Sulfur Dioxide 6/22/05
10
09:36 10:48 12:00 13:12 14:24 15:36 16:48 18:00 19:12 20:24
Time
80
70
60
Boiler Stack Sulfur Dioxide 6/23/05
50
•30
o
o
20
10
07:55
09:07
10:19 Timd1:31
12:43
13:55
Figure 4-4. Boiler Stack Sulfur Dioxide Concentration
4-26
-------
Source Test Report
for Landfill E
Concentration (ppm)
-*• ro co -t». 01 o -vj
n
Boiler Stack Nitrogen Oxides (NOx) 6/22/05
Hill
1
09:36 10:48 12:00 13:12 14:24 10:36 16:48 18:00 19:12 20:24
Time
Boiler Stack Nitrogen Oxides (NOx) 6/23/05
07:55 0907 1019 TimJ1'31 1243 13 55
Figure 4-5. Boiler Stack Nitrogen Oxides Concentration
4-27
-------
Source Test Report
for Landfill E
Table 4-17. Boiler Stack Metals Emissions
Analyte
Arsenic
Cadmium
Chromium
Lead
Manganese
Nickel
Mercury
(Total by
Method 29)
Mercury
(Elemental
by LUMEX)
E-062205-M29-1
Concentration
(|jg/dscm)
1.8
1.1
3.0
7.2
4.4
5.3
0.46
Emission Rate
(x1(Hg/hr)
87
52
140
340
210
250
22
(x10-«lb/hr)
190
120
320
760
460
560
49
RUN1
.057
2.7
6.0
E-062305-M29-2
Concentration
(|jg/dscm)
2.6
1.5
4.3
4.2
3.6
10.9
0.46
Emission Rate
(x1(Hg/hr)
130
74
210
210
180
540
23
(x10-«lb/hr)
260
160
470
460
390
1200
51
RUN 2
0.033
1.6
3.6
E-062305-M29-3
Concentration
(|jg/dscm)
2.4
1.1
24
6.4
4.1
120
ND
Emission Rate
(x10^»
g/hr)
120
57
1200
330
210
6400
ND
(x10%/hr)
240
130
2700
730
460
14100
ND
RUN 3
0.042
2.1
4.7
Average
Concentration
(|jg/dscm)
2.3
1.2
10
6.0
4.0
47
0.46
Emission Rate
(x10^»
g/hr)
110
61
530
300
200
2400
23
(x10-«lb/hr)
221
135
1200
649
439
5300
50
Average
0.044
2.2
4.8
4-28
-------
Source Test
Report for Landfill E
Table 4-18. Boiler Stack CO, SO2, NOX Concentrations
Run 1
Run 2
Run 3
Run 4
Average
Concentration (ppmdv)
CO
0
2
18
14
9
SO2
45
41
66
68
55
NOX (as NO)
3
5
21
21
13
4.3 Comparison with AP-42 Default Values
One of the major objectives of the test program is to expand on the database of LFG
constituent compounds and their concentrations. If warranted, these data may
contribute towards updating the AP-42 default values. Table 4-19 presents the
concentrations of LFG constituents to provide direct comparisons with AP-42 default
values. Table 4-20 presents the concentration of other constituents targeted by the
various analyses but not listed in AP-42. An expanded discussion and comparison is
included in the overall project summary report.
4-29
-------
Source Test Report
for Landfill E
Table 4-19. Comparison of Raw Landfill Gas Constituent Concentrations with AP-42 Default Values
Method
M-40
M40
M40
M40
M40
M40
M40
M40
M-40
M40
M40
M-40
No Test
M40
No Test
M-40
M-40
M40
M40
M40
M40
Compound
1,1,1-Trichloroethane
1,1,2,2-Tetrachloroethane
1 ,1-Dichloroethane (Ethylidene
Dichloride)
1,1-Dichloroethene
1 ,2-Dichloroethane
1 ,2-Dichloropropane
Isopropyl alcohol (2-Propanol)
Acetone
Acrylontrile
Bromodichloromethane
Butane
Carbon Disulfide
Carbon Monoxide
Carbon Tetrachloride
Carbonyl Sulfide (Carbon
oxysulfide)
Chlorobenzene
Chlorodiflouromethane (Freon
22)
Chloroethane (Ethyl Chloride)
Chloroform
Chloromethane
1 ,4-Dichlorobenzene
CAS
Number
71-55-6
79-34-5
75-34-3
75-35-4
107-06-2
78-87-5
67-63-0
67-64-1
107-13-1
75-27-4
106-97-8
75-15-0
630-08-0
56-23-5
463-58-1
108-90-7
75-45-6
75-00-3
67-66-3
74-87-3
10646-7
Formula
Wt.
133.42
167.85
98.96
96.94
98.96
112.98
60.11
58.08
53.06
163.83
58.12
76.13
28.01
153.84
60.07
112.56
86.47
64.52
119.39
50.49
147.00
Default
Value
(ppmv)
0.48
1.11
2.35
0.20
0.41
0.18
50.10
7.01
6.33
3.13
5.03
0.58
141
0.004
0.49
0.25
1.30
1.25
0.03
1.21
0.21
Detection
Limit
(ppmv)
0.0003
0.0002
0.0003
0.0002
0.0003
0.0003
0.0002
0.0003
0.02
0.0002
1
0.0002
NM
0.0005
NM
0.0002
0.02
0.0002
0.0003
0.0001
0.0003
Measured
Average
(ppmv)
ND
ND
ND
ND
ND
ND
2.36
15.5
ND
ND
2.53
0.34
NM
ND
NM
0.135
ND
ND
ND
ND
ND
Concentration
in Inlet LFG
(xK>9|b/ft3)
ND
ND
ND
ND
ND
ND
367
2300
ND
ND
380
66.9
NM
ND
NM
39.3
ND
ND
ND
ND
ND
(|jg/m3)
ND
ND
ND
ND
ND
ND
5870
37300
ND
ND
6090
1070
NM
ND
NM
629
ND
ND
ND
ND
ND
Mass Flow Rate in Inlet
LFG Stream
(mg/hr)
ND
ND
ND
ND
ND
ND
43300
275000
ND
ND
44900
7900
NM
ND
NM
4640
ND
ND
ND
ND
ND
(xWib/hr)
ND
ND
ND
ND
ND
ND
95.5
606
ND
ND
99.0
17.4
NM
ND
NM
10.2
ND
ND
ND
ND
ND
4-30
-------
Source Test Report
for Landfill E
Method
M40
M-40
M40
M40
M40
No Test
M40
M-40
No Test
M40
M40
M40
M40
M-11
Organic
mercury
LUMEX
Organic
mercury
Organic
mercury
Compound
1 ,3-Dichlorobenzene
1 ,2-Dichlorobenzene
Dichlorodifluoromethane (Freon
12)
Dichlorofluoromethane (Freon
12)
Methylene Chloride
(Dichloromethane)
Dimethyl Sulfide (Methyl
sulfide)
Ethane
Ethanol
Ethyl Mercaptan (Ethanediol)
Ethylbenzene
1 ,2-Dibromoethane (Ethylene
dibromide)
Trichloromonofluoromethane
(Fluorotrichloromethane) (F11)
Hexane
Hydrogen Sulfide
Mercury (Dimethyl)
Mercury (Elemental)
Mercury (Monomethyl)
Mercury (Total)
CAS
Number
541-73-1
95-50-1
75-71-8
75-434
75-09-2
75-18-3
74-84-0
64-17-5
75-08-1
100-414
106-934
75-69-4
110-54-3
7783-064
7439-97-6
Formula
Wt.
147.00
147.01
120.91
102.92
84.94
62.13
30.07
46.08
62.13
106.16
187.88
137.38
86.18
34.08
230.66
200.61
215.62
215.63
Default
Value
(ppmv)
0.21
0.21
15.70
2.62
14.30
7.82
889
27.20
2.28
4.61
0.001
0.76
6.57
35.50
Not Listed
Not Listed
Not Listed
253.0E-6
Detection
Limit
(ppmv)
0.0002
0.0003
NM
0.0003
0.0001
NM
1
0.0002
NM
0.0003
0.0002
0.0002
0.0003
NR
0.05E-06
NR
0.014E-06
6E-06
Measured
Average
(ppmv)
ND
ND
NM
0.232
3.05
NM
13.5
ND
NM
15.5
ND
0.00820
0.597
322
5.5E-06
53.E-06
0.61 E-06
163.E-06
Concentration
in Inlet LFG
(xK>9|b/ft3)
ND
ND
NM
61.7
670
NM
1000
ND
NM
4300
ND
2.9
133
28400
0.0033
0.0275
0.0003400
0.0909
(|jg/m3)
ND
ND
NM
989
10700
NM
16800
ND
NM
68100
ND
47
2130
454000
0.0526
0.440
0.00545
1.46
Mass Flow Rate in Inlet
LFG Stream
(mg/hr)
ND
ND
NM
7290
79100
NM
124000
ND
NM
502000
ND
344
15700
3350000
0.388
3.25
0.0402
10.7
(x1&3|b/hr)
ND
ND
NM
16.1
174
NM
273
ND
NM
1100
ND
0.758
34.6
7400
0.000856
0.0072
0.0000885
0.0000237
4-31
-------
Source Test Report
for Landfill E
Method
M40
M-40
No Test
M-40
M-40
M-40
M-40
M40
M-40
M40
M40
M40
M-40
M-25C
M-25C
M-40
M-40
Compound
2-Butanone (Methyl Ethyl
Ketone)
2-Hexanone (Methyl Butyl
Ketone)
Methyl Mercaptan
(Methanethiol)
Pentane
Tetrachloroethylene
(Perchloroethylene)
Propane
t-1 ,2-Dichloroethene
Trichloroethylene
(Trichloroethene)
Vinyl Chloride
m/p-Xylene (Dimethyl Benzene)
o-Xylene (Dimethyl Benzene)
Benzene (Co-disposal)
Benzene (No-disposal or
Unknown)
NMOC as Hexane (Co-
disposal)
NMOC as Hexane (No-
codispoal or Unknown)
Toluene (Methyl Benzen) (Co-
disposal)
Toluene (Methyl Benzene) (No
or Unknown)
CAS
Number
78-93-3
591-78-6
74-93-1
109-66-0
127-184
74-98-6
156-60-5
79-01-6
75-014
1330-20-7
95-47-6
71-43-2
71-43-2
108-88-3
Formula
Wt.
72.10
100.16
48.11
72.15
165.83
44.09
96.94
131.38
62.50
106.16
106.16
78.11
78.11
86.17
92.13
Default
Value
(ppmv)
7.09
1.87
2.49
3.29
3.73
11.10
2.84
2.82
7.34
12.10
12.10
11.10
1.91
2420.00
595.00
165.00
39.30
Detection
Limit
(ppmv)
0.0003
0.0002
NM
1
0.0003
1
0.0003
0.0002
0.0002
0.00065
0.0003
0.0002
0.0002
NR
NR
0.0003
0.0003
Measured
Average
(ppmv)
2.49
ND
NM
1.30
0.125
13.0
ND
0.0940
0.0634
9.00
3.10
0.887
0.887
233
233
7.95
7.95
Concentration
in Inlet LFG
(xK>"|b/ft3)
464
ND
NM
242
53.6
1500
ND
31.9
10.2
2500
851
179
179
51900
51900
1900
1900
(|jg/m3)
7430
ND
NM
3880
858
23700
ND
511
164
39600
13600
2870
2870
831000
831000
30300
30300
Mass Flow Rate in Inlet
LFG Stream
(mg/hr)
54800
ND
NM
28600
6330
175000
ND
3770
1210
292000
100000
21100
21100
6130000
6130000
224000
224000
(xWib/hr)
121
ND
NM
63.1
14.0
386
ND
8.3
2.7
643
222
46.6
46.6
13500
13500
493
493
4-32
-------
Source Test Report
for Landfill E
Table 4-20. Raw Landfill Gas Constituent Concentrations for Compounds without AP-42 Default Values
Method
M-0100
M-0100
M-25C
M-25C
M-25C
M-40
M-40
M-40
M-40
M40
M40
M40
M40
M40
M-40
M40
M40
M-40
M-40
M-40
M-40
Compound
Acetoldehyde
Formaldehyde
Carbon Dioxide
Methane
Oxygen
1 ,1 ,2,3,4,4-Hexachloro-1 ,3-butadiene
1 ,1 ,2-Trichloro-1 ,2,2-trifluoroethane
(CFC113)
1,1,2-Trichloroethane
1 ,2,4-Trichlorobenzene
1 ,2,4-Trimethylbenzene
1 ,2-Chloro-,1 ,2,2-Tetrafluoroethane
(CFC114)
1 ,3,5-Trimethylbenzene
1 ,3-Butadiene (Vinylethylene)
1 ,4-Dioxane (1 ,4-Diethylene Dioxide)
1 -Ethyl-4-methylbenzene (4-Ethyl Toluene)
4-Methyl-2-pentenone (MIBK)
Benzyl Chloride (Chloromethyl Benzene)
Bromomethane (Methyl bromide)
cis-1 ,2-Dichloroethene
cis-1 ,3-Dichloropropene
Cyclohexane
CAS
Number
75-07-0
50-00-0
124-38-9
74-82-8
778244-7
87-68-3
76-13-1
79-00-5
120-82-1
95-63-6
76-14-2
108-67-8
106-99-0
123-91-1
622-96-8
108-10-1
10044-7
74-83-9
156-59-2
10061-01-5
110-82-7
Formula
Wt.
44.05
30.03
44.01
16.04
32.00
260.76
187.38
133.42
181.46
120.19
170.92
120.19
54.09
88.10
120.20
100.16
126.58
94.95
96.94
110.98
84.16
Detection
Limit
(ppmv)
0.021
0.016
NR
NR
NR
0.0002
0.0002
0.0002
0.0003
0.0003
0.0002
0.0002
0.0003
0.0002
0.0002
0.0002
0.0002
0.0002
0.0003
0.0002
0.0003
Measured
Average
(ppmv)
0.0503
0.00767
353000
495000
25700
ND
ND
ND
ND
2.64
0.0153
1.04
ND
ND
2.51
ND
ND
ND
0.163
ND
ND
Concentration
in Inlet LFG
(xlO^lb/ft3)
5.7
0.595
40200000
20500000
2100000
ND
ND
ND
ND
820
6.8
323
ND
ND
780
ND
ND
ND
40.8
ND
ND
(MgAn3)
91.7
9.54
643000000
329000000
34100000
ND
ND
ND
ND
13100
108
5180
ND
ND
12500
ND
ND
ND
654
ND
ND
Mass Flow Rate
in Inlet LFG Stream
(mg/hr)
677
70.3
4740000000
2420000000
251000000
ND
ND
ND
ND
96900
799
38200
ND
ND
92100
ND
ND
ND
4820
ND
ND
(xlO^lbAir)
1.5
0.155
10500000
5300000
554000
ND
ND
ND
ND
214
1.8
84.1
ND
ND
203
ND
ND
ND
10.6
ND
ND
4-33
-------
Source Test Report
for Landfill E
Method
M-40
M40
M40
M40
M40
M-40
M-40
M-40
M-40
Compound
Dibromochloromethane
Ethyl Acetate
Heptane
Methyl-t-butyl Ether (MTBE)
Styrene (Vinylbenzene)
t-1 ,3-Dichloropropene
Tetrahydrofuran (Diethylene Oxide)
Tribromomethane (Bromoform)
Vinyl Acetate
CAS
Number
12448-1
141-78-6
142-82-5
1634-04-4
100-42-5
1006-02-6
109-99-9
75-25-2
108-05-4
Formula
Wt.
208.29
88.10
100.20
88.15
104.14
110.98
72.10
252.77
86.09
Detection
Limit
(ppmv)
0.0002
0.0003
0.0002
0.0003
0.0001
0.0002
0.0004
0.0003
0.0005
Measured
Average
(ppmv)
ND
ND
0.331
ND
0.420
ND
0.871
ND
0.111
Concentration
in Inlet LFG
(xlO^lb/ft3)
ND
ND
85.7
ND
113
ND
162
ND
24.7
(MgAn3)
ND
ND
1370
ND
1810
ND
2600
ND
396
Mass Flow Rate
in Inlet LFG Stream
(mg/hr)
ND
ND
10100
ND
13400
ND
19200
ND
2920
(xlO^lbAir)
ND
ND
22.3
ND
29.4
ND
42.3
ND
6.4
4-34
-------
Source Test Report
for Landfill E
This page intentionally left blank
4-35
-------
Source Test Report
for Landfill E
5. Quality Assurance/Quality Control
This project produced data that qualified to receive the "A" rating with respect to the
rating system described in section 4.4.2 of the Procedures for preparing Emission
Factor Documents (EPA-454/R-95-015). The cited EPA document provides a clear
description of the requirements for an "A" data quality rating. Tests were performed by
using an EPA reference test method, or when not applicable, a sound methodology.
Tests were reported in enough detail for adequate validation and raw data were
provided that could be used to duplicate the emission results presented in this report.
Throughout the results sections of this report, notations and footnotes were included to
flag data that, for various reasons, did not meet their associated measurement quality
objectives.
5.1 Assessment of Measurement Quality Objectives
Measurement quality objectives (MQOs) were established for each critical
measurement and documented in the Site-Specific QAPP for the Field Evaluation of
Landfill Gas Control Technologies-Landfill E. The following subsections assess
MQOs for each measurement to determine if goals were achieved. When applicable,
data validation elements performed on laboratory analytical reports are also included.
5.1.1 Continuous Emissions Monitors (CEMs)
Combustion produce gases O2, CO/CO2, SO2, NOX and THC were measured in the
field using CEMs. The following MQOs were established for CEM measurements for
Landfill E:
• Direct calibration bias: ±2 percent
• System bias checks: ±5 percent
• Zero and drift: ±3 percent
• Completeness: >90 percent
Direct calibrations were performed daily, prior to testing, with certified calibration
gases at zero and a minimum of two other concentrations (typically a mid-level
concentration and one point towards the full-scale end of the instrument range). System
5-1
-------
Source Test Report
for Landfill E
bias checks were performed pre-test and post-test. Drift checks were performed daily,
post-test. Table 5-1 summarizes these quality control (QC) checks for all instruments.
All MQOs were met for all CEM measurements
Table 5-1. CEM MQO Summary for Landfill E
Instrument
and Range
Servomex O2
Analyzer
(0-21%)
Cal Analytical
CO2 Analyzer
(0-20%)
Cal Analytical
CO Analyzer
(0-650 ppm)
Cal Analytical
SO2 Analyzer
(0-500 ppm)
TECO THC
Analyzer
(0-1000 ppm)
TECO NOX
Analyzer
(0^000 ppm)
Direct Calibration
(±2% criteria)
Total
(#)
8
8
12
8
NA a
8
Bias Range
(%)
0.1-0.3
0.0-0.6
0.0-1.2
0.0-1.4
NA a
0.0-0.2
Complete
(%)
100
100
100
100
NA a
100
System Bias Checks
(±5% criteria)
Total
(#)
8
8
8
8
12
8
Bias Range
(%)
0.3-1.0
0.1 -1.1
0.0-2.0
0.0-2.2
0.0-0.4
0.0-0.8
Complete
(%)
100
100
100
100
100
100
Drift Checks
(±3% criteria)
Total
(#)
8
8
8
8
8
8
Bias Range
(%)
0.05-1.0
0.0-1.2
0.0-1.4
0.0-2.2
0.0-1.0
0.0-0.5
Complete
(%)
100
100
100
100
100
100
The method called for calibration gases to
probe for them to flow through the heated
be introduced at a point of the sampling system close to the sampling
sample line. Calibration gases were not injected directly to the analyzer
5.1.2 Carbonyls (Method TO-11)
The following MQOs were established in the QAPP for this method:
• Recovery (formaldehyde): 50-150 percent
• Completeness: >90 percent
Four samples (including three raw LFG samples and one field blank) were submitted to
Resolution Analytics for formaldehyde and acetaldehyde determination. Results were
5-2
-------
Source Test Report
for Landfill E
reported in RFA# 90231. The report included information on instrument calibration
and internal QC checks. Samples collected on June 22, 2005 were received by the
laboratory on July 5, 2005 and analyzed on July 12, 2005. That met the 30-day hold-
time limitation. Analytical detection limits were reported as 15.9 ppb for formaldehyde
and 20.9 ppb for acetaldehyde in the liquid extract.
The extract value was 5 ml. Hence, the detection limit amounts were 79.5 ng and 104.5
ng, respectively. The sample gas volume was about 27 standard liters. Therefore, the
gas phase MDL for formaldehyde and acetaldehyde were 2.3 ppbv and 2.1 ppbv,
respectively.
The field blank did not have detectable levels of either compound. To assess accuracy,
an external performance evaluation audit sample containing 2.0 ppm formaldehyde and
acetaldehyde was analyzed with the sample set. Recovery was 95.2 percent for
formaldehyde and 99.8 percent for acetaldehyde, which met the 50-150 percent MQO.
All project samples were injected in duplicate and the percent drift (%D) range for
formaldehyde was 3.1 to 22.8 percent and for acetaldehyde was 0.2 to 4.4 percent. All
MQOs were met for this method for a completeness of 100 percent.
5.1.3 Hydrogen Sulfide (H2S) (EPA Method 11)
The following MQOs were established in the Landfill E QAPP for this method:
• Accuracy: ±5 percent bias
• Completeness: >90 percent
Four samples (including a reagent blank) plus two laboratory in-house reagent blanks
were submitted to Enthalpy Analytical Inc. for H2S analysis by EPA Method 11. The
samples were collected on June 22, 2005, submitted to the laboratory on June 30, 2005,
and the results report was dated July 15, 2005. Therefore the analysis met the 30-day
hold time criteria.
The field blank submitted did not have quantifiable concentrations of H2S. No field
spike or laboratory spike was performed. While Method 11 does not require sample
spike recovery in its procedure, the QAPP specified one spike sample to be analyzed.
The three test samples produced results of similar concentrations. The analysis was 75
percent complete. The lack of demonstrated satisfactory spike recovery data warrants
the data to be flagged as estimated and notated with a "J".
5-3
-------
Source Test Report
for Landfill E
5.1.4 Dioxinsand Furans (PCDD/PCDFs) (EPA Method 23/0011)
The following MQOs were established in the QAPP for this method:
• Recovery: 50-150 percent
• Completeness: >90 percent
Four sample sets (including one set of reagent blank and sample train rinsates) were
submitted to ALTA Analytical Perspectives for PCDD/PCDFs analysis. The samples
were collected on June 23, 2005, delivered to the laboratory on July 1, 2005, and
analyzed on July 14, 2005. That met the 14-day hold-time for extraction and 40-day
hold time for analysis.
The field blank did not have detectable levels of either compound. Detection limits for
the various congeners were in the single-digit pictogram level. To assess accuracy,
each sample train was spiked with standard Method 23 spiking compounds and
analysis of the samples yielded extraction standard (ES) recovery from 77 to 90
percent,. Recovery of sampling standards ranged from 96 to 103 percent. These
recoveries are well within the 50-150 percent MQO. All MQOs were met for this
method for a completeness of 100 percent.
5.1.5 Polycyclic Aromatic Hydrocarbons (PAHs) (EPA Method 23/0011)
The following MQOs were established in the QAPP for this method:
• Recovery: 50-150 percent
• Completeness: >90 percent
Four samples (including one reagent blank) were submitted to ALTA Analytical
Perspectives for PAH analysis. The report included information on instrument
calibration and internal QC checks. Samples collected on June 23, 2005 were received
by the laboratory on July 1, 2005 and analyzed on July 15, 2005. That met the 14-day
hold-time for extraction and 40-day hold time for analysis.
Table 5-2 shows the amounts of detectable target analytes in the reagent blank and the
average amounts of the respective target analytes that were found in the test samples.
The analysis yielded detectable but low levels of the target compounds, in the range of
5-4
-------
Source Test Report
for Landfill E
less than 1 ng for acenaphthylene to 385 ng for naphthalene. In contrast, the test
samples showed PAH levels that were significantly higher than those found in the
reagent blank. Therefore, the presence of detectable analytes in the reagent blank did
not change the conclusions that can be drawn from the test sample concentration
measurements,
Recovery of ES ranged from 90 to 105 percent. Recovery of sampling standards (SS),
dio-fluorene was 109 percent, and 111 percent for di4-terphenyl. Recovery of the
alternative standard (AS) dio-anthracene was 100 percent. These recoveries were well
within the 50 to 150 percent MQO. Hence, all MQOs were met for this method for a
completeness of 100 percent.
Table 5-2. Polycyclic Aromatic Hydrocarbon Reagent Blank Target Analyte Concentrations
Analyte
Naphthalene
2-Methylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)Anthracene
Chrysene
Benzo(b)Fluoranthene
Benzo(k)Fluoranthene
Benzo(e)Pyrene
Benzo(a)Pyrene
Perylene
lndeno(1 ,2,3-cd)Pyrene
Dibenzo(a,h)Anthracene
Benzo(ghi)Perylene
Amount found in
RR062305 - Reagent
Blank
(ng)
385
12.0
0.423
1.54
94.4
16.3
2.06
15.1
14.5
3.20
4.54
6.80
2.37
3.73
3.22
0.396
3.27
<4
3.43
Average Amount
found in Test
Samples
(ng)
2610
2170
33.9
165
246
4010
112
4550
2780
1000
1700
2190
800
1180
780
134
926
211
835
5-5
-------
Source Test Report
for Landfill E
5.1.6 Non-Methane Organic Compounds (NMOCs) (Method 25C)
The following MQOs were established in the QAPP for Landfill E:
• Recovery: 50 to 150 percent
• Completeness: >90 percent
Five canister samples (including a field blank) were submitted from Landfill E for
NMOC analysis by Method 25-C to Triangle Environmental Services. The samples
were collected on June 22, 2005, submitted on July 22, 2005, and analyzed July 27 -
August 4, 2005. Therefore the analysis did not meet the 30 day hold time requirements.
The apparent delay in sample delivery was partly attributed to the fact that the same
canisters had to be analyzed by RTF Laboratory for volatile organics first. The impact
of exceeding the prescribed 30-day hold time by up to 12 days is unknown.
The laboratory report included information on instrument calibration and internal QC
checks.
The only NMOC detected in the field blank was at 3 ppmv as hexane. Accuracy for the
method was assessed by evaluating results of response factor (RF) check samples that
were run prior to and following sample analysis. Acceptance criteria established by the
method is that the RF must be within 20 percent of the RF from initial calibration. All
RF checks were within 10 percent of the initial calibration, well within the acceptance
criteria. The %D between the pre and post-test checks were less than 2 percent.
Samples were run in triplicate and all percent relative standard deviations (RSDs) for
samples were less than 1.5 percent.
There was a problem with Sample #4 in that this sample contained nitrogen (N2) and
O2 concentrations that exceeded the Method 25 C criteria of 20 percent for N2 and 5
percent for O2. Therefore, the NMOC concentration value for Sample #4 could not be
used. With data from three of the four samples being usable, and the QAPP specified
that three test samples were to be analyzed, the completeness MQO for this
measurement was 100 percent and met the objective set in the QAPP. The problem
with Sample #4 notwithstanding, the data set was valid.
5-6
-------
Source Test Report
for Landfill E
5.1.7 Hydrogen Chloride (HCI) (EPA Method 26A)
The following MQOs were established in the QAPP for Landfill E:
• Accuracy: ± 10 percent bias
• Completeness: >90 percent
Four samples (including one field blank) were submitted to Resolution Analytics for
HCI and chlorine (C12) determination. The results were reported in RFA# 990231. The
report included information on instrument calibration and internal QC checks. Samples
were collected on June 22, 2005, received by the laboratory on July 5, 2005, and
analyzed on July 4, 2005, which met the 4 week hold-time requirement. Analytical
detection limits were reported as 0.188 ppm for both HCI and C12.
The field blank did not contain detectable levels of HCI or C12. In-house audit samples
were analyzed with each respective group of field samples and the measured
concentrations fell within method criteria of 10 percent of their expected values.
A matrix spike was performed on Sample #3 (T90 percent
Four sets of Method 29 Multi-Metals trains (including one field blank) were submitted
to First Analytical Laboratories for As, Cd, Cr, Pb, Mn, Hg, and Ni determination.
5-7
-------
Source Test Report
for Landfill E
Results were reported in Project #50627. The report included information on
instrument calibration and internal QC checks. Samples were collected on June 22,
2005, received by the laboratory on June 28, 2005, and analyzed on July 5, 2005,
which met the 14 day hold-time requirement. Method detection limits for each of the
target metals were reported as follows:
• As = 7.0(ig/L
• Cd = 0.2(ig/L
• Cr = 5.0(ig/L
• Pb = 5.0(ig/L
• Mn = 10(ig/L
• Ni = 10(ig/L
• Hg = 0.2^g/L
Traces of Cd, Cr, Mn and Ni were found in the blanks, which is not unusual. Some of
the back half Mn samples were abnormally high. This is a common problem which can
occur in Method 29 if a tiny amount of the potassium permanganate reagent gets in to
the hydrogen peroxide impingers.
All samples were spiked prior to analysis. Spike recoveries ranged from 75 to 108
percent and were within the acceptable range of 75-125 percent. In addition to spiking
the samples, for each metal, internal calibration verification samples (ICVs) and
continuing calibration verification samples (CCVs) were performed. ICVs were run at
the beginning of each run set and CCVs were run at a frequency of one for every ten
samples. ICV and CCV measured values were all less than ±10 percent for all metals
with the exception of Ni which had a CCV of+12.2 percent. This was not considered a
major failure and data limitations were not applied. Therefore, the MQO for this
measurement was 100 percent and met the objective set in the QAPP.
5.1.9 Organo-Mercury (Hg) and Total Mercury (Hg) (Frontier and Geochimica)
The following MQOs were established in the Landfill E QAPP for this method:
5-8
-------
Source Test Report
for Landfill E
• Recovery: 50-150 percent
• Completeness: >90 percent
Mercury (Hg) analysis was performed separately by Frontier Geosciences and Studio
Geochimica.
5.1.9.1 Frontier Geosciences
Four total Hg samples (including a field blank) were taken at Landfill E. Samples were
collected on June 22, 2005 and analyzed on July 22, 2005. That analysis schedule
exceeded the 14-day hold-time specified in the QAPP. All other quality assurance
measures indicated that the analysis of the traps were under good control. All field
blanks were consistent with historical values and indicated the detection limit was
likely to be at or below the previous estimated value of 50 ng/m3. Spike recoveries
were 106.5 to 108.1 percent and relative percent difference (RPD) between replicates
was 4 percent, which meets MQOs and are 100 percent complete.
Five monomethyl mercury (MMHg) samples (including a field blank and a field spike)
were collected on June 23, 2005. These samples were analyzed on July 14, 2005 which
exceeded the 14-day hold-time. Analysis of these samples was under good control with
acceptable distillation spike recoveries and distillation duplicates. All CCV standards
had acceptable recoveries. Spike recovery was 101 percent, which meets MQOs. RSD
between replicates was less than 10 percent. Monomethyl mercury (MMHg) analysis
was 100 percent complete.
Seven dimethyl mercury (DMHg) samples (including a field blank and two trip spikes)
were collected on June 22, 2005. These samples were analyzed on July 7 to 14, 2005
and did not meet the 14-day hold-time. The analysis of samples was well within
control, with acceptable recoveries as well as good linear control standards and second-
source standard recoveries. Spike recovery for these samples was 78 to 80 percent and
RSD between replicate samples was 2.5 percent. This meets MQOs established in the
QAPP and DMHg analysis was therefore 100 percent complete.
The field blank was low indicating that the trap media, handling procedures, and
analytical techniques do not contribute to the reported values. Field matrix spike
recoveries ranged from 67 to 93 percent. The DMHg analysis was 100 percent
complete.
5-9
-------
Source Test Report
for Landfill E
5.1.9.2 Studio Geochimica
Four total Hg samples (including a field blank) were taken at Landfill E. Samples were
collected on June 22, 2005, received at the laboratory on July 1, 2005 and analyzed on
July 2, 2005. This analysis schedule met the 14-day hold-time specified in the QAPP.
All other quality assurance (QA) measures indicated that the analysis of the traps were
under good control. All field blank concentrations were low and the detection limit is
estimated at 10 ng/m3. Spike recovery was 100.2 and RPD between replicates was 0.7
percent. These analyses meet the MQOs and are 100 percent complete.
Five MMHg samples (including a field blank and a field spike) were collected on June
23, 2005. These samples were analyzed on July 2, 2005. The analysis met the 14-day
hold-time requirement. Spike recovery was 98.7 percent, which met MQOs. The RSD
between replicates was 2.2 percent. The MMHg analysis was 100 percent complete.
Five DMHg samples (including a field blank and a field spike) were collected on June
22, 2005. These samples were extracted and analyzed on July 2, 2005, which meets the
14-day hold-time requirement. Spike recovery was 89.6 percent and RSD. This meets
MQOs the established in the QAPP and DMHg analysis is therefore 100 percent
complete.
5.1.10 Volatile Organic Compounds (VOCs) and Methane (CH4) (Method TO-15)
The following MQOs were established in the Landfill E QAPP for this method:
• Accuracy: 50-150 percent recovery
• Completeness: >90 percent
Five SUMMA canisters (including one field blank) were submitted from Landfill E to
RTP Laboratories for VOC and CFL, determination by EPA Method TO-15. Results
were reported in Project #05-072. Samples were collected on June 22 and 23, 2005 and
analysis was completed by July 13, 2005, which met the 30 day hold-time requirement.
Analysis of the field blank found 32.1 ppbv of heptane and 161 ppbv of l-ethyl-4-
methylbenzene. Other target analytes were not found at method detection levels
(MDLs) in the range of 0.1 to 0.65 ppbv.
5-10
-------
Source Test Report
for Landfill E
Accuracy was assessed using results of a 10 ppbv laboratory control sample containing
all target compounds. For all but two compounds, recoveries ranged from 60-150
percent, which met the established acceptance criteria of 50-150 percent. The recovery
reported for ethanol was 2.4 percent, and 230 percent for m/p-xylene. Results for these
two compounds should be flagged as estimated, "J".
Sample 062205-04 was spiked with 200 ppbv of chlorobenzene prior to dilution with
helium and analysis. The recovery of chlorobenzene was 89.5 percent.
Precision was demonstrated through multiple injections of standards at five
concentration levels. The RSD between the calculated relative response factors (RRF)
must be less than 30 percent with allowances that two may be greater than 40 percent.
The average RSD was 13.8 percent and method criteria were met for all compounds
except isopropyl alcohol with an RSD of 56.3 percent and hexane with an RSD of 40.7
percent. Results for these compounds should be flagged as estimated, "J". Valid data
was received for all SUMMA canisters submitted; these analyses are considered to be
100 percent complete.
5.2 Audits
This project was designated as QA Category II effort. Hence, audits were required. The
internal and external audits performed for this project were completed earlier and their
findings were included in the Landfill D report of this project.
5-11
-------
Source Test Report
for Landfill E
This page intentionally left blank
5-12
------- |