September 2003
Environmental Technology
Verification Report
Nippon Instruments Corporation
DM-6/DM-6P Mercury
Continuous Emission Monitor
Prepared by
Battelle
Battelle
. . . Putting Technology To Work
Under a cooperative agreement with
£EPA U.S. Environmental Protection Agency
ETV EtV ElV
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September 2003
Environmental Technology Verification
Report
ETV Advanced Monitoring Systems Center
Nippon Instruments Corporation
DM-6/DM-6P Mercury
Continuous Emission Monitor
by
Thomas Kelly
Zachary Willenberg
Karen Riggs
Battelle
Columbus, Ohio 43201
and
(under the support of the U.S. Department of Energy)
James Dunn
Shaw Environmental, Inc.
Oak Ridge, Tennessee
Kristopher Kinder
Shaw Environmental, Inc.
Knoxville, Tennessee
James Calcagno
University of Tennessee
Knoxville, Tennessee
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Notice
The U.S. Environmental Protection Agency (EPA), through its Office of Research and
Development, has financially supported and collaborated in the extramural program described
here. This document has been peer reviewed by the Agency and recommended for public release.
Mention of trade names or commercial products does not constitute endorsement or
recommendation by the EPA for use.
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Foreword
The U.S. Environmental Protection Agency (EPA) is charged by Congress with protecting the
nation's air, water, and land 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, the EPA's Office of Research and Development provides data and science support that
can be used to solve environmental problems and to build the scientific knowledge base needed
to manage our ecological resources wisely, to understand how pollutants affect our health, and to
prevent or reduce environmental risks.
The Environmental Technology Verification (ETV) Program has been established by the EPA to
verify the performance characteristics of innovative environmental technology across all media
and to report this objective information to permitters, buyers, and users of the technology, thus
substantially accelerating the entrance of new environmental technologies into the marketplace.
Verification organizations oversee and report verification activities based on testing and quality
assurance protocols developed with input from major stakeholders and customer groups
associated with the technology area. ETV consists of seven environmental technology centers.
Information about each of these centers can be found on the Internet at http://www.epa.gov/etv/.
Effective verifications of monitoring technologies are needed to assess environmental quality
and to supply cost and performance data to select the most appropriate technology for that
assessment. In 1997, through a competitive cooperative agreement, Battelle was awarded EPA
funding and support to plan, coordinate, and conduct such verification tests for "Advanced
Monitoring Systems for Air, Water, and Soil" and report the results to the community at large.
Information concerning this specific environmental technology area can be found on the Internet
at http://www.epa.gov/etv/centers/centerl .html.
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Acknowledgments
The authors wish to acknowledge the support of all those who helped plan and conduct the
verification test, analyze the data, and prepare this report. In particular we would like to thank
Wayne Davis of the University of Tennessee; Marshall Allen and Thomas Geisler of the
Hemispheric Center for Environmental Technology at Florida International University; and
Stephen Priebe of the Idaho National Engineering and Environmental Laboratory, U.S.
Department of Energy. We also acknowledge the assistance of ETV AMS Center stakeholders
Philip Galvin, New York State Department of Environmental Conservation; Will Ollison,
American Petroleum Institute; and Roy Owens, Owens Corning; and of Jeff Ryan of EPA's
National Risk Management Research Laboratory, as reviewers of the verification reports from
this test.
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Contents
Page
Notice ii
Foreword iii
Acknowledgments iv
List of Abbreviations viii
1 Background 1
2 Technology Description 2
3 Test Design and Procedures 3
3.1 Introduction 3
3.2 Facility Description 4
3.3 Test Design 8
3.3.1 Equipment Setup 8
3.3.2 Test Schedule 8
3.3.3 Reference Method Sampling 10
3.3.4 Verification Procedures 12
3.4 Materials and Equipment 15
3.4.1 High Purity Gases 15
3.4.2 Mercury Standard Gases 15
3.4.3 Mercury Spiking Standard 18
3.4.4 Sampling Trains 18
3.4.5 Analysis Equipment 18
4 Quality Assurance/Quality Control 19
4.1 Facility Calibrations 19
4.2 Ontario Hydro Sampling and Analysis 19
4.2.1 Ontario Hydro Reproducibility 20
4.2.2 Ontario Hydro Blank and Spike Results 23
4.3 Audits 24
4.3.1 Technical Systems Audit 24
4.3.2 Performance Evaluation Audits 25
4.3.3 Data Quality Audit 27
5 Statistical Methods 28
5.1 Relative Accuracy 28
5.2 Correlation with Reference Method 28
5.3 Precision 29
5.4 Sampling System Bias 29
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5.5 Relative Calibration and Zero Drift 30
5.6 Response Time 30
5.7 Data Completeness 31
5.8 Operational Factors 31
6 Test Results 32
6.1 Relative Accuracy 32
6.2 Correlation with Reference Method 33
6.3 Precision 34
6.4 Sampling System Bias 34
6.5 Relative Calibration and Zero Drift 35
6.6 Response Time 37
6.7 Data Completeness and Operational Factors 38
7 Performance Summary 42
8 References 43
Figures
Figure 2-1. Nippon Instruments DM-6/DM-6P CEM 2
Figure 3-1. Schematic of the TSCAI and Off-Gas Cleaning System 5
Figure 3-2. Overview of TSCAI Test Location 6
Figure 3-3. Side View of the TSCAI Stack 6
Figure 4-1. Plot of Ontario Hydro Train B Results vs. Train A Results 23
Figure 6-1. Linear Regression Plot of DM-6/DM-6P Hgx Results Against OH Results 33
Tables
Table 3-1. TSCAI Stack Gas Characteristics 7
Table 3-2. Mercury CEM Verification Test Schedule 9
Table 3-3. Schedule of OH Method Sampling Runs in Initial Sampling Period
(August 8 - 11, 2002) 11
Table 3-4. Schedule of OH Method Sampling Runs in Final Sampling Period
(September 16- 19, 2002) 12
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Table 3-5. Data Used for DM-6/DM-6P Performance Evaluation 13
Table 3-6. Results of Elemental Mercury Standard Analyses 16
Table 3-7. Precision of Elemental Mercury Standard Measurements 17
Table 4-1. Ontario Hydro Results from Initial Sampling Period (August 8- 11, 2002)
(|ig/dscm) 21
Table 4-2. Ontario Hydro Results from Final Sampling Period (September 16 - 19, 2002)
(|ig/dscm) 22
Table 4-3. Results of Linear Regression, Correlation, and Percent Relative Standard
Deviation of Paired Ontario Hydro Train Results (n = 18) 23
Table 4-4. Summary of PE Audits in Mercury CEM Verification
at the TSCAI 25
Table 4-5. Results of PE Audit of OH Train Recovery and Analysis 26
Table 6-1. Summary of Results from OH Reference Method and
DM-6/DM-6P 32
Table 6-2. Relative Accuracy Results for the DM-6/DM-6P 33
Table 6-3. Coefficients of Determination (r2) for DM-6/DM-6P Hgx with OH Results .... 34
Table 6-4. Precision of the DM-6/DM-6P During OH Runs 9 and 12 34
Table 6-5. Sampling System Bias Results 35
Table 6-6. Calibration and Zero Drift Results 36
Table 6-7. Summary of Data Used to Estimate Response Time 37
Table 6-8. Extent of Down Time and Service Time 39
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List of Abbreviations
AMS Advanced Monitoring Systems
CO carbon monoxide
C02 carbon dioxide
CEM continuous emission monitor
CVAA cold vapor atomic absorption
DOE U.S. Department of Energy
dscf dry standard cubic foot
dscm dry standard cubic meter
EPA U.S. Environmental Protection Agency
ETTP East Tennessee Technology Park
ETV Environmental Technology Verification
FIU-HCET Florida International University, Hemispheric Center for Environmental
Technology
Hg° elemental mercury
Hgox oxidized mercury
Hgx total vapor-phase mercury
hr hour
|ig microgram
mL milliliter
m3 cubic meter
mg milligram
min minute
NIST National Institute of Standards and Technology
02 oxygen
OH Ontario Hydro
ORD Office of Research and Development
PE performance evaluation
QA quality assurance
QA/QC quality assurance/quality control
QMP Quality Management Plan
RA relative accuracy
RCRA Resource Conservation and Recovery Act
RPD relative percent difference
RSD relative standard deviation
SEI Shaw Environmental, Inc.
STL Severn Trent Laboratories
TSA technical systems audit
TSCAI Toxic Substances Control Act Incinerator
viii
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Chapter 1
Background
The U.S. Environmental Protection Agency (EPA) supports the Environmental Technology
Verification (ETV) Program to facilitate the deployment of innovative environmental tech-
nologies through performance verification and dissemination of information. The goal of the
ETV Program is to further environmental protection by accelerating the acceptance and use of
improved and cost-effective technologies. ETV seeks to achieve this goal by providing high-
quality, peer-reviewed data on technology performance to those involved in the design,
distribution, financing, permitting, purchase, and use of environmental technologies.
ETV works in partnership with recognized testing organizations; with stakeholder groups
consisting of buyers, vendor organizations, and permitters; and with the full participation of
individual technology developers. The program evaluates the performance of innovative tech-
nologies by developing test plans that are responsive to the needs of stakeholders, conducting
field or laboratory tests (as appropriate), collecting and analyzing data, and preparing peer-
reviewed reports. All evaluations are conducted in accordance with rigorous quality assurance
(QA) protocols to ensure that data of known and adequate quality are generated and that the
results are defensible.
The EPA's National Exposure Research Laboratory and its verification organization partner,
Battelle, operate the Advanced Monitoring Systems (AMS) Center under ETV. The AMS Center
recently evaluated the performance of continuous emission monitors (CEMs) for mercury,
including the Nippon Instruments Corporation DM-6/DM-6P mercury CEM.
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Chapter 2
Technology Description
The objective of the ETV AMS Center is to verify the performance characteristics of
environmental monitoring technologies for air, water, and soil. This verification report provides
results for the verification testing of the DM-6/DM-6P mercury CEM. Following is a description
of the DM-6/DM-6P mercury CEM, based on information provided by the vendor. The
information provided below was not subjected to verification in this test.
The DM-6/DM-6P mercury CEM is designed to provide continuous measurement of total vapor-
phase mercury (Hgx) in stack gases. Stack gas is pulled from the stack through a glass-lined
probe maintained at 180°C (356°F) and a glass fiber particulate filter maintained at 200°C
(392°F). The sample then passes through a catalyst bed that is heated to 160°C (320°F) to
reduce oxidized mercury to elemental (Hg°) mercury. The catalytic process is housed in a heater
box that may be located either adjacent to the stack or remotely. If the catalyst is located
remotely from the stack, a heated Teflon sample line is used to connect the catalyst heater box to
the inlet probe and filter. After exiting the catalyst, the sample passes through a liquid/gas
separator and is cooled to 2°C by a solid-state Peltier chip. The cooled sample gas is then filtered
once again by a membrane filter before being transported to the detector. The detector is a cold
vapor atomic absorption (CVAA) analyzer that reports total mercury.
The detector is factory calibrated, although an
on-board permeation tube calibration source is
available as an option for field calibration. The
detector signal is zeroed automatically by passing
sample gas over a gold trap to collect and remove
mercury. The resulting zero gas is then introduced
directly into the DM-6/DM-6P The DM-6/DM-6P
response to the zero gas is automatically adjusted
to zero by the system. Figure 2-1 shows the
DM-6/DM-6P installed in the CEM trailer at the
base of the incinerator stack during this
verification test. The DM-6/DM-6P does not
require argon, compressed air, or other gas
supplies for operation.
Figure 2-1. Nippon Instruments
DM-6/DM-6P CEM
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Chapter 3
Test Design and Procedures
3.1 Introduction
This verification test was conducted according to procedures specified in the Test/QA Plan for
Field Demonstration of Mercury Continuous Emission Monitors at the TSCA Incinerator {l) The
purpose of the verification test was to evaluate the performance of mercury CEMs at a full-scale
field location, over a substantial period of continuous operation. The mercury CEMs were
challenged by stack gases generated from the thermal treatment of a variety of actual wastes in
the Toxic Substances Control Act Incinerator (TSCAI) at the East Tennessee Technology Park
(ETTP) in Oak Ridge, Tennessee. CEM responses were compared with reference mercury
measurements of total (Hgx), oxidized (Hgox), and elemental (Hg°) mercury. Mercury standard
gases were used to challenge the CEMs to assess stability in long-term operation, and the
instruments were operated for several weeks by TSCAI staff to assess operational aspects of their
use.
The performance of the DM-6/DM-6P was verified while monitoring emissions from the TSCAI
that were generated from treating actual waste. The reference method for establishing the
quantitative performance of the tested technologies was the Ontario Hydro (OH) method.(2)
The DM-6/DM-6P performance parameters addressed included
¦ Relative accuracy (RA) with respect to reference method results
¦ Correlation with reference method results
¦ Precision
¦ Sampling system bias
¦ Relative calibration and zero drift
¦ Response time
¦ Data completeness
¦ Operational factors.
Relative accuracy, correlation with the reference method, and precision (i.e., repeatability at
stable test conditions) were assessed for total mercury in the stack gas emissions. Sampling
system bias, calibration and zero drift, and response time were assessed for Hg° only, using
commercial compressed gas standards of Hg°. The data completeness, reliability, and maintain-
ability of the CEMs over the course of the verification test were assessed during several weeks of
continuous operation.
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This verification test was conducted jointly by the ETV AMS Center and the DOE. Under DOE
funding, Shaw Environmental, Inc. (SEI) under subcontract to Bechtel Jacobs Company LLC,
and the Hemispheric Center for Environmental Technology at Florida International University
(FIU-HCET) directed the field test. Reference method analyses were conducted by Severn Trent
Laboratories (STL), and data analysis was conducted by the University of Tennessee. Funding
for these activities was provided by DOE's Transuranic and Mixed Waste Focus Area; the
Characterization, Monitoring and Sensor Technology Crosscutting Program; and FIU-HCET.
3.2 Facility Description
The TSCAI is designed and permitted for receiving, sorting, storing, preparing, and thermally
destroying low-level radioactive and Resource Conservation and Recovery Act (RCRA) mixed
waste contaminated with polychlorinated biphenyls. This waste is treated in a rotary kiln
incinerator with a secondary combustion chamber and off-gas treatment system for cleaning
combustion effluent gases. The TSCAI includes various support buildings, an unloading and
storage area, a tank farm, an incinerator area, concrete collection sumps, and carbon adsorbers.
A schematic of the TSCAI is shown in Figure 3-1, and photographs of the facility are shown in
Figures 3-2 and 3-3.
The TSCAI treats a wide range of waste categories, including oils, solvents and chemicals,
aqueous liquids, solids, and sludges. Solid and non-pumpable sludge material is typically
received and stored in metal containers and repackaged into combustible containers prior to
feeding. A hydraulic ram feeds containerized solids and sludges to the rotary kiln. Aqueous
waste is injected into the kiln through a lance. High heat-of-combustion liquids are burned in
either the rotary kiln or a secondary combustion chamber with gas burners. Both solids and
waste liquids are permitted for treatment in the primary combustion chamber, but only organic
liquids may be treated in the secondary combustion chamber. The typical temperature in the
primary combustion chamber is approximately 870°C (1,600°F), and in the secondary
combustion chamber is greater than 1,200°C (2,200°F).
Ash residue from the wet ash removal system is collected and handled through hazardous and
radioactive waste storage facilities. Selected residues are sent to a commercial landfill. Kiln
off-gas flows to the secondary combustion chamber. The off-gas from the secondary combustion
chamber then passes through a four-stage treatment system that includes a quench chamber and
scrubber treatment system for cooling, removing particulate matter, and neutralizing acidic
by-products. An induced-draft fan forces flue gases through the stack. Liquid waste generated by
the scrubber systems is treated by the Central Neutralization Facility, an adjacent on-site waste
water treatment plant. Solid waste, such as scrubber sludge, is collected in drums for off-site
disposal.
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TREATED COMBUSTION OFF GAS
THERMAL RELIEF
VENT
EMERGENCY
VENT
LIQUID FEED TANK
SECONDARY
COMBUSTION
CHAMBER
STACK.
fP
CROSSOVER
SECONDARY
COMBUSTION
BURNER
IONIZING
WET SCRUBBERS
ROTARY KILN
VENTURI
SCRUBBER/DEMIST ER
PRIMARY WASTE-
BURNER
HYDRAULIC RAM
PACKED
BED SCRUBBER
INDUCED
DRAFT FAN
QUENCH
CHAMBER
ASH REMOVAL
BLOWDOWN
BLOWDOWN
SOLIDS
STORAGE & FEED
MIX CHAMBER
PURGE WATER
SUMPS
Figure 3-1. Schematic of the TSCAI and Off-Gas Cleaning System
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Figure 3-2. Overview of TSCAI Test Location. The incinerator stack is at left,
with waste feed area behind the stack. The trailers housing the mercury CEMs for
this test were located in the foreground at the base of the stack.
Figure 3-3. Side View of TSCAI Stack. Sampling platforms are at the left and
GEM trailers are at the lower right.
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The off-gas treatment system of the TSCAI produces a scrubbed, wet gas flow. The TSCAI stack
receives this water-saturated flue gas and vents it to the atmosphere. The stack is 100 feet high
and its inside diameter is 54 inches, with a gas velocity of approximately 20 feet per second. The
stack is equipped with several sample ports for flue gas sampling; a continuous emission
monitoring system for measuring carbon monoxide (CO), carbon dioxide (C02), and oxygen
(02); continuous sampling systems for radionuclides and metals; and two access platforms that
surround the full circumference of the stack at about 30 feet and 50 feet above ground level. The
combustion gas velocity is also monitored by means of the induced-draft fan current and
pressure drop across the fan.
The combustion process and off-gas cleaning systems are monitored by instrumentation for
process control and data collection. Operational parameters are automatically monitored and
logged by the incinerator Supervisory Control and Data Acquisition system.
Stack gas characteristics at the CEM sampling locations used in this test are summarized in
Table 3-1. Additional detail on the TSCAI configuration and operations are available in the
test/QA plan,(1) and in recent publications describing this test.(3"5)
Table 3-1. TSCAI Stack Gas Characteristics^
Parameter
Range
Units
Temperature
Static Pressure
Flow Rate
Velocity
02
C02
CO
Moisture
Particulate Matter Loading
83.7-86.0 (182.6
186.8)
-0.25
6,065 -9,100
14,920-23,450
15.78-19.73
8.4-11.6
4.3-7.0
0-10.3
47.1 -52.2
0.0012-0.0079
2.68-18.2
°C (°F)
inches H20
dry standard cubic feet (dscf)
per minute (min)
actual cubic feet per minute
feet per second
parts per million by volume
grain/dscf @ 7% 02
mg/dry standard cubic meters
(dscm) @ 7% 02
Values shown are actual conditions during OH reference method periods.
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3.3 Test Design
3.3.1 Equipment Setup
The DM-6/DM-6P was housed in the TSCAI Test Bed Mobile Laboratory Trailer located near the
base of the TSCAI stack. A dedicated data acquisition system was placed inside the trailer for
logging signals from the DM-6/DM-6P and other CEMs undergoing verification. The data logger
was also connected to the facility Supervisory Control and Data Acquisition system through an
Ethernet link to collect and log process parameters on the DM-6/DM-6P data logger.
At the lower of the two platforms on the TSCAI stack (i.e., about 30 feet above ground level), one
sampling port was dedicated to a probe that extracts stack gas to be analyzed for CO, C02, and 02
by the facility CEMs. Other ports at this level were used for the DM-6/DM-6P and other CEMs
being tested.
For the DM-6/DM-6P, the vendor-supplied extractive sampling probe was connected to the CEM by
means of a 1/4-inch outside diameter (0.156-inch inside diameter), heated PFA Teflon sample line.
A vendor representative oversaw installation of the DM-6/DM-6P, which shared the heated Teflon
sample line and extractive probe with another Nippon Instruments mercury CEM that was also
undergoing verification. The source sample was withdrawn from the TSCAI stack through a glass-
lined probe that was heated to 180°C (356°F). The sample then passed through a heated fiberglass
filter located outside the stack in a heater box maintained at 200°C (392°F). For this verification, the
heated mercury conversion catalyst was located in the trailer of the base of the TSCAI stack rather
than mounted on the stack. A pump located near the instrument drew the sample gas through the
130-foot PFA Teflon sample line maintained at 180°C (356°) and into the thermal catalyst unit that
converts oxidized mercury in the sample gas to Hg° for detection (see Chapter 2). The total sample
flow through the probe, filter, and Teflon line was approximately two liters per minute. Like all
CEMs in this verification test, the Nippon DM-6/DM-6P sampled at a single (fixed) point in the
stack. This CEM provides a continuous measurement of total vapor-phase mercury (Hgx) (i.e., the
sum of Hg° and oxidized [Hgox] mercury vapor), but does not determine particle-phase mercury.
Verification of the performance of the DM-6/DM-6P was based on comparison with the
corresponding Hgx results from the OH reference method.
3.3.2 Test Schedule
In this verification test, the CEMs undergoing testing sampled the TSCAI stack gas continuously for
nearly two months in the fall of 2002, while the TSCAI operated normally in destroying a variety of
waste materials. Stack sampling with the OH reference method was conducted in the first week and
the last week of the test, and between those two periods the CEMs operated continuously for
approximately five weeks. Table 3-2 summarizes the schedule of verification testing at the TSCAI
facility. Shown in this table are the activities conducted during various periods, and the performance
parameters addressed by those activities.
The TSCAI was operated continuously during the first and last weeks of the test and was not shut
down overnight. Such continuous round-the-clock operation is the standard mode of operation for
the TSCAI. During the OH reference method sampling runs, the TSCAI burned aqueous,
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Table 3-2. Mercury CEM Verification Test Schedule
Time Period (2002)
Activity
Performance Parameters
August 5-7
Installation and shakedown
—
August 8-11
OH method sampling; daily
challenge with mercury
standard gases
RA, correlation, precision;
sampling system bias,
calibration drift, zero drift,
response time
August 12 - September 15
Routine monitoring, with
scheduled challenges with
mercury standard gases
Calibration drift, zero drift
September 16-19
OH method sampling; daily
challenge with mercury
standard gases
RA, correlation, precision;
sampling system bias,
calibration drift, zero drift,
response time
solid, or a combination of aqueous and solid waste. The waste was characterized by chemical
analysis before the test began, and some measure of control of the stack mercury concentration
was achieved by varying the feed rate of aqueous waste and/or mixing solid and aqueous waste
materials.
After installation at the TSCAI in early August 2002, the CEMs went through a shakedown
period in which all CEMs sampled the facility stack gas. Sampling of the stack gas then
continued for the duration of the verification test, including during the performance of 10 OH
reference method sampling runs with dual OH trains on August 8 through 11. During this period,
the CEMs also were challenged with zero gas and with commercially prepared compressed gas
standards of Hg°. Vendor representatives oversaw installation and shakedown of the CEMs
through the first week of testing. Following this first OH sampling period, vendor representatives
trained site personnel on routine operation, maintenance, and calibration checks of each of the
mercury CEMs. The CEMs then operated for five weeks with only routine attention and main-
tenance from TSCAI staff. During this period, the staff recorded the maintenance and repair
needs of each CEM and made observations on the ease of use of each CEM. Finally, a second
four-day period of OH method sampling with dual trains was conducted on September 16
through 19, in which eight OH sampling runs were conducted. The zero gas and mercury
standard challenges were carried out by vendor representatives through this period as well.
The OH reference method results are presented in Section 4.2, along with evaluations of the
quality of these reference results. The commercial mercury gas standards are described in
Section 3.4.2, and the CEM results on those standards are reported in Section 6.
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3.3.3 Reference Method Sampling
OH method sampling at the TSCAI was conducted at the upper platform on the stack (50 feet
above ground) by staff of SEI, who prepared the trains, conducted sampling at the TSCAI stack
using dual OH trains, and then recovered the resulting samples in a laboratory facility near the
TSCAI site. The dual OH sampling trains sampled isokinetically at separate ports located 90° apart
on the stack circumference and traversed the stack at points determined by EPA Method 1. The two
trains were interchanged from port to port at the halfway point in the OH sampling period, so that
the trains completed full and identical traverses of the stack during each OH run. STL supplied the
chemical reagents used in the OH sampling train impingers and performed the mercury analyses on
the OH method samples. Containers for collecting and storing samples were labeled for tracking by
STL and subsequently supplied to the SEI field sampling team. Request for Analysis/Chain of C
ustody forms accompanied the samples from the time of collection by the field sampling team
through analysis by the laboratory. Modified QA procedures for the OH method were followed, as
described in Section 4.3.1. In addition, two blank OH trains (one in each week of OH method
sampling) were spiked with known quantities of mercury to assess recovery in sample analysis. The
results of those mercury spikes are reported in Section 4.3.2.
Tables 3-3 and 3-4 summarize the schedule of OH sampling in the initial and final weeks of the
verification test, respectively, indicating the run number, date, and start and stop times of each OH
run. These tables also show the type of waste burned in each OH run In most runs, the total
sampling period was made up of two separate periods of time, as necessitated by the port change
procedure noted above. In a few OH runs, other factors such as disturbances in the waste feed
required a stoppage in OH sampling; for those runs the total OH sampling period consists of three
or more segments, rather than two. A few OH runs of one hour duration were conducted in the
initial week of OH sampling (Table 3-3). However, it was recognized that this sample duration
allowed only a few measurements to be made within the OH sample period, by those CEMs that
provided sequential batch analyses, as opposed to continuous analysis. Consequently, all OH
periods in the final week (Table 3-4) were of two hours duration.
Note that the first 10 OH sampling runs (Table 3-3) were numbered 7 through 16, and the last eight
(Table 3-4) were numbered 18 through 25. The numbers 1 through 6 were assigned to OH trains
used in pre-test trial runs, and other numbers were assigned to trains used as field blanks or as field
spike trains. Each OH run number applies to two trains, designated A and B, which were used in
parallel sampling, as described above, or used for separate QA purposes. For example, OH train
17A was spiked with known amounts of mercury, as described in Section 4.3.2, and train 17B was
used as a blank. Similarly, train 28A was spiked and train 28B was a blank.
To ensure that the OH reference method and CEM data sets were indeed parallel and comparable
for each sampling period, the CEM vendors were notified of the start and stop times of each OH
period so that average analyte concentrations corresponding directly to the reference method
sampling period could be reported. The CEM vendors were given at least 15 minutes notice prior to
initiation of each OH method sampling run.
All OH trains were prepared, recovered, and analyzed in the same manner, with one exception. The
particulate filters from trains designated "A" and used for sampling at the TSCAI stack were
weighed before and after sampling to determine particulate matter loading in the flue gas,
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Table 3-3. Schedule of OH Method Sampling Runs in Initial Sampling Period
(August 8 - 11, 2002)
Run Number Date
Start Time
Stop Time
Waste Feed Type
09:10
09:28
7
8/8/02
09:43
10:55
10:25
11:55
Solids
8
8/8/02
14:40
16:10
15:40
17:10
Solids
9
8/9/02
10:50
12:15
11:50
13:15
Aqueous
10
8/9/02
14:35
16:10
15:35
17:10
Aqueous
11
8/10/0
2
9:35
10:25
10:05
10:55
Aqueous
12
8/10/0
2
12:15
13:10
12:45
13:40
Aqueous
13
8/10/0
2
15:00
15:50
15:30
16:20
Aqueous
14
8/11/0
2
08:20
09:10
08:50
09:40
Aqueous and Solids
8/11/0
2
10:40
10:52
15
11:05
11:45
11:23
12:15
Aqueous and Solids
16
8/11/0
2
13:45
15:00
14:15
15:30
Solids
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Table 3-4. Schedule of OH Method Sampling Runs in Final Sampling Period
(September 16 - 19, 2002)
Run Number Date
Start Time
Stop Time
Waste Feed Type
11:10
12:10
13:05
14:05
Aqueous
15:20
16:20
16:50
17:50
Aqueous
9:25
10:25
11:10
12:10
Aqueous and Solids
13:15
14:15
14:35
15:35
Aqueous and Solids
8:35
9:35
9:55
10:37
Aqueous
12:35
12:53
14:36
15:36
16:36
17:36
Aqueous
8:25
9:20
10:56
11:01
11:22
11:44
Aqueous and Solids
11:59
12:37
13:34
14:34
15:46
16:46
Aqueous and Solids
18
21
22
23
24
25
9/16/02
19 9/16/02
20 9/17/02
9/17/02
9/18/02
9/18/02
9/19/02
9/19/02
whereas those from the trains designated "B" were not. The particulate loadings determined
from the A trains ranged from 0.0012 to 0.0079 grain/dscf (2.68 to 18.2 mg/dscm). Particulate
mercury was determined from the filter catch and probe rinse of both the A and B trains in all
samples, but was never found at significant levels (i.e., maximum values of particulate Hg were
less than 0.003 |ig/dscm). Given this negligible amount of particulate mercury, the total
vapor-phase mercury (Hgx) determined by the OH method can be considered as the total
mercury content of the stack gas.
3.3.4 Verification Procedures
This section describes the test procedures that were used to verify mercury CEM performance on
each of the performance parameters listed in Section 3.1. Table 3-5 lists the quantitative per-
formance parameters and summarizes the types of data that were used to verify each of those
parameters.
12
-------
Table 3-5. Data Used for DM-6/DM-6P Performance Evaluation
Performance Parameter
Objective
Comparison Based On
Relative Accuracy
Correlation with Reference
Method
Precision
Sampling System Bias
Relative Calibration/Zero
Drift
Response Time
Determine degree of
quantitative agreement with
reference method
Determine degree of correlation
with reference method
Determine repeatability of
successive measurements at
relatively stable mercury levels
Determine effect of the CEM's
sample interface on response to
zero gas and Hg° standard
Determine relative response to
zero gas and span gas over
successive days
Estimate rise and fall times of
the CEMs
Reference method results
Reference method results
Repetitive measurements
under stable facility
conditions
Response to zero gas and
Hg° standards at analyzer vs.
through sample interface
Zero gas and Hg° standards
CEM results at start/stop of
Hg addition
3.3.4.1 Relative Accuracy
The RA of the DM-6/DM-6P was verified using the OH reference method data for total mercury.
The Hgx readings of the DM-6/DM-6P during each OH sampling interval were averaged and
compared with the average of the Hgx results from the paired OH trains (see Section 4.2.1). The
RA equation stated in Section 5.1 was applied to the averaged CEM data, using the OH data as
the reference values. To optimize the comparability of the CEM and OH data, the OH sampling
was coordinated with the CEM operations as noted in Section 3.3.3.
3.3.4.2 Correlation with Reference Method
The correlation of DM-6/DM-6P total mercury results with the OH results was based on the
same data used to assess RA. No additional test procedures were needed to verify the
correlation.
3.3.4.3 Precision
Precision is the degree of variability of successive CEM readings under conditions of stable
mercury concentration. In this test, the TSCAI stack gas mercury concentrations resulted entirely
from the waste feed material being burned (i.e., no mercury was spiked into the flue gas).
Consequently, mercury concentrations in the TSCAI stack would be most stable when a waste
material of uniform mercury content was being fed into the incinerator at a uniform rate. For this
verification test, an aqueous waste was stockpiled in quantities sufficient for all the testing and
13
-------
was characterized to document its mercury content. The aqueous feed rate data from the TSCAI
were then reviewed for the periods of each OH run in which only aqueous waste was burned (see
Tables 3-3 and 3-4). On the basis of the feed rate data, two OH runs (Runs 9 and 12, Table 3-3)
were selected as having relatively uniform feed rates. The variability of the responses of each
CEM during these two OH runs was then calculated to assess the variability of the CEM
response.
As described in Section 5.3, the assessment of precision is based on comparing the variability of
CEM readings to that of the aqueous feed rate, with variability expressed as a percent relative
standard deviation (RSD). This approach does not assume that the waste feed rate is the sole
factor affecting the variability of stack mercury concentrations, nor that the waste feed is
perfectly uniform in mercury content. This approach does provide a consistent basis for
reporting CEM variability in measuring mercury in the TSCAI stack gas.
3.3.4.4 Sampling System Bias
Sampling system bias was assessed using the commercial Hg°gas standards described in Section
3.4.2. To assess sampling system bias, a mercury gas standard was supplied at the analyzer
portion of the CEM, and separately at the stack gas sampling point of the CEM. Any difference
in the CEM responses in the two cases was attributed to the effect on the mercury level of the
sampling system components, i.e., the probe, filter, mercury conversion system, and transport
lines.
3.3.4.5 Relative Calibration and Zero Drift
Zero drift and calibration drift also were assessed using zero gas and the commercial Hg° gas
standards described in Section 3.4.2, respectively. Although the mercury standards were not
suitable for use as absolute standards, they did exhibit stable concentrations and so were useful
for assessing CEM relative calibration drift (see Section 3.4.2). These gases were supplied to the
CEMs on numerous occasions throughout the study; and the range, mean, and standard
deviation of the CEM readings were calculated as indicators of the drift of the instruments over
the course of the test. Both low (approximately 8 |ig/m3) and high (40 to 60 |ig/m3) mercury
standards were used for this evaluation. Zero gas (nitrogen) was used for a similar assessment of
the drift in CEM zero readings. The Hg° standards and zero gas were supplied to the analyzer
portion of each CEM for this assessment, with the exception of one, which was designed to
accept standard and zero gases only at its stack gas inlet.
3.3.4.6 Response Time
Mercury CEM response time was also verified using zero gas and the commercial Hg° standards.
Response time was determined as the time required for the CEM to reach 95% of its final value,
after switching from zero gas to the mercury gas standard, or vice versa. The former procedure
was used to assess rise time, and the latter to assess fall time.
14
-------
3.3.4.7 Data Completeness
Data completeness was determined as the percentage of data that each CEM produced, relative
to the total possible data return. This parameter was evaluated both in terms of the percentage of
OH sampling runs for which each CEM produced data and in terms of the overall fraction of the
two-month test period in which the CEM was operating and producing data.
3.3.4.8 Operational Factors
Throughout the field period of testing the mercury CEMs at the TSCAI (August 8 -
September 19, 2002), the CEM vendors and TSCAI staff operating the CEMs recorded the
repair, routine maintenance, and expendable needs of each CEM and noted operational issues
such as the ease of use and calibration of the instruments. These observations are summarized
for the DM-6/DM-6P in Section 6.7.
3.4 Materials and Equipment
3.4.1. High Purity Gases
The high purity gas used for zeroing the CEMs during testing was commercial, ultra-high purity
(i.e., minimum 99.999% purity) nitrogen. Argon of ultra-high or industrial-grade purity also was
obtained for those CEMs requiring it.
3.4.2 Mercury Standard Gases
Ten compressed gas standards of Hg° in nitrogen were obtained from Spectra Gases (Alpha,
New Jersey) for use in assessing drift and sampling system bias of the CEMs. These cylinders
were received in March 2002 and stored outdoors at the TSCAI site until the start of the verifica-
tion test. When used during the verification test, each mercury standard was placed inside the
instrument trailer near the CEMs for ease of access and to maintain the cylinders at room
temperature.
To assess their stability, the mercury gas standards were analyzed using various methods at
intervals before, during, and after the verification test. The 10 mercury standards were analyzed
by Spectra Gases in March, before shipment to the TSCAI site. In addition, a cold vapor atomic
absorption mercury analyzer (Seefelder Messtechnik) on loan from the EPA Office of Research
and Development (EPA-ORD) was used to analyze the mercury gas standards at the TSCAI field
site. Analysis of all 10 cylinders was conducted with the Seefelder analyzer on August 8 and on
nine of the cylinders on October 17, after the field test had been completed. The contents of one
cylinder (CC133537) were unintentionally depleted during the verification test, and post-test
analysis was not possible. Eight cylinders, including the depleted one, were returned to Spectra
Gases, where the seven cylinders with remaining gas were analyzed on November 13.
SEI staff also analyzed the remaining two cylinders (CC133359 and CC133367) using a
modified version of EPA Method 101 A(6), with sampling performed on November 5 and 6,
15
-------
respectively, for the two cylinders. Finally, the contents of these two cylinders were determined
on November 6 using the EPA-ORD Seefelder analyzer. Upon return to Spectra Gases, the gas
in these two cylinders was analyzed on November 21 by the vendor. The results of these diverse
measurements on each of the cylinders are summarized in Table 3-6. This table lists the cylinder
numbers, the various analytical results obtained on each cylinder (Hg° results in |ig/m3), and the
percent difference between the initial and final concentrations determined by the gas vendor.
Table 3-6. Results of Elemental Mercury Standard Analyses (a)
Post-Test
March 1
August 8
October 7
November
5 & 6
November 6
November
13 & 21
Difference
Cylinder
Number
Initial Gas
Vendor
Certified
Analysis
(Hg/m3)
EPA-ORD
Seefelder
Analysis
(Hg/m3)
EPA-ORD
Seefelder
Analysis
(Hg/m3)
Method
101A Mini-
Train
Analysis
(Hg/m3)
EPA-ORD
Seefelder
Analysis
(jig/m3)
Final Gas
Vendor
Certified
Analysis
(Hg/m3)
Initial and
Final Gas
Vendor
Certified
Analyses (%)
CC133146
14.0
11.3
11.4
NA
NA
12.1
-13.3
CC133172
64.3
44.7
42.4
NA
NA
44.7
-30.4
CC133174
59.6
46.0
45.2
NA
NA
47.5
-20.3
CC133345
11.2
7.9
6.8
NA
NA
5.6
-50.0
CC133357
53.1
37.6
37.1
NA
NA
40.1
-24.6
CC133359
60.6
37.2
34.5
30.6
35.4
44.7
-26.2
CC133367
10.2
6.3
5.4
4.6
5.6
5.6
-45.4
CC133537
15.8
14.9
NA
NA
NA
NA
NA
CC133612
57.8
36.9
34.4
NA
NA
35.4
-38.7
CC133619
59.6
39.9
37.8
NA
NA
40.1
-32.8
(a) All measurements corrected to 1 atmosphere and 20°C.
NA: Not available, analysis not performed.
It is apparent from the last column of Table 3-6 that there was a substantial decrease in all the
concentrations determined after the test by Spectra Gases, relative to those determined before the
test by Spectra Gases. This finding suggests a decay in the mercury content of all the standards
between these March and November analyses by the gas vendor. However, Table 3-6 also shows
that all analyses subsequent to the initial analysis by Spectra Gases show better agreement. This
observation suggests that any such decay in concentration must have occurred primarily before
the August 8 analyses. Unfortunately, no measurements were made between the original March
1, 2002, Spectra Gases analyses and the August 8 analyses made during the first week of CEM
testing. Thus, there is no way to determine whether the decrease occurred as a sudden, step-wise
drop or a gradual decay over time. However, the important point regarding Table 3-6 is that the
16
-------
data indicate stable mercury concentrations in all cylinders throughout the period of the
verification test.
This point is supported by Table 3-7, which shows the mean, standard deviation, and percent
RSD of all analyses of each mercury standard from August 8 on. Table 3-7 indicates that the
RSD values for six of the standard cylinders were about 4% or less, and the RSD values for the
other three cylinders having multiple analyses were less than 17%. These results indicate that the
contents of the mercury standard cylinders were stable over the course of the verification test
and, consequently, were suitable for assessing the stability of the CEMs themselves.
Table 3-7. Precision of Elemental Mercury Standard Measurements
Cylinder
Number
August 8 and Later Analyses
Mean
(lig/m3)
Standard Deviation
(Hg/m3)
RSD
(%)
CC133146
11.6
0.5
4.0
CC133172
43.9
1.3
3.0
CC133174
46.2
1.2
2.6
CC133345
6.8
1.1
16.8
CC133357
38.3
1.6
4.1
CC133359
36.5
5.2
14.2
CC133367
5.5
0.6
11.4
CC133537
14.9
NA(a)
NA
CC133612
35.6
1.3
3.5
CC133619
39.3
1.2
3.2
(a) Not applicable for one data point.
Spectra Gases conducted a quality review of its production and analytical records to determine
the cause of the concentration decay observed.(7) The preliminary conclusion from the review
was that an important step had been omitted from the manufacturing process. Spectra Gases
tested this hypothesis by manufacturing two separate cylinder batches of three cylinders each.
The first batch was made according to procedure, and the second batch was made with the
suspect step omitted from the manufacturing process. After the cylinders were prepared, each
cylinder was analyzed every seven days over a 49-day period. After 49 days, the concentration of
the first batch was stable, but the second batch (with the manufacturing step omitted) exhibited
a sharp decay in concentration. This test seemed to validate the theory that an important step had
been omitted from the manufacturing process, which led to a decrease in concentration from the
initial certified analysis of the gases used in the TSCAICEM test.
17
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3.4.3 Mercury Spiking Standard
A National Institute of Standards and Technology (NIST)-traceable aqueous mercury standard,
with a concentration of 1,000 mg/L of Hg as HgO in dilute nitric acid, was obtained from VWR
Scientific (Catalog No. VW4217-1). This solution was Lot No. B2015064 and had an expiration
date of August 2003. Dilution of this standard in American Society for Testing and Materials
Type II water with added nitric acid was used to prepare the 10 |ig/mL and 30 |ig/ml spiking
solutions for the performance evaluation (PE) audit of the reference method (Section 4.3.2).
3.4.4 Sampling Trains
The SEI field sampling team supplied the glassware, probes, heater boxes, meter boxes, and
other associated equipment for the OH method sampling. STL supplied the chemical reagents
and materials used in the OH sampling train impingers. Multiple trains were prepared each day
so that as many as six trains (i.e., three sampling runs with two trains each) could be sampled in
a single day, in addition to at least one blank train. The SEI field sampling team recovered
samples from OH method trains in a laboratory facility near the TSCAI site. Containers for
collecting and storing samples were purchased and labeled for tracking by STL. Samples were
packaged and delivered by the field sampling team to STL.
3.4.5 Analysis Equipment
Laboratory equipment for sample recovery and analysis was provided by STL. This included all
chemicals and solutions for rinsing train components and recovering impinger samples, as well
as cold vapor CVAA spectroscopy equipment for mercury determination.
18
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Chapter 4
Quality Assurance/Quality Control
Quality assurance/quality control (QA/QC) procedures were performed in accordance with the
quality management plan (QMP) for the AMS Center(7) and the test/QA plan for this verification
test.(1)
4.1 Facility Calibrations
During this verification test, the TSCAI facility was operated normally to carry out its function
of destroying hazardous waste. Consequently, calibration procedures and schedules for the
TSCAI monitoring equipment were followed throughout the verification test, as required to
maintain RCRA certification of the TSCAI. These procedures, which included both weekly and
monthly calibrations, took precedence over the conduct of the verification test. Included in these
activities were calibrations of the 02 and C02 CEMs on the incinerator stack. Records of all
such calibrations are maintained in the operation files of the TSCAI.
Measurements that factored into the verification test results were also the subject of PE audits,
as described in Section 4.3.2. Those audits included checks of the facility 02 and C02 CEMs.
4.2 Ontario Hydro Sampling and Analysis
The preparation, sampling, and recovery of samples from the OH trains adhered to all aspects of
the OH method,(2) with minor modifications as described in Section 4.3.1. The preparation and
recovery of trains was carried out by SEI staff in a laboratory on the ETTP site; trains were
sealed for transport between the preparation/recovery laboratory and the TSCAI. Blank trains
were prepared in both the initial and final weeks of OH sampling, taken to the sampling location
on the TSCAI stack, and recovered along with the sampled trains. Reagent blanks were collected
as specified in the OH method. OH trains and resulting samples were numbered uniquely, and
samples were transferred to the analysis laboratory (STL) within about 24 hours of collection,
using chain-of-custody forms prepared before the field period. As described in Section 4.3.1,
trial OH sampling by SEI and OH sample analysis by STL were both subjected to a pre-test
evaluation before the field verification took place.
Because of the importance of the OH data in this verification, the following sections present key
data quality results from the OH data.
19
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4.2.1 Ontario Hydro Reproducibility
The results of the OH flue gas sampling are shown in Tables 4-1 and 4-2, for the initial
(August 8-11) and final (September 16 - 19) weeks of OH method sampling, respectively.
Each table indicates the OH run number, and lists the Hg°, Hgox, and Hgx results from the paired
OH trains (designated A and B) in each run. Also shown are the mean values of the paired train
results, and the relative percent difference (RPD) of each pair of results (RPD = difference
between A and B results divided by sum of A and B results expressed as a percentage). All
mercury results are in |ig/dscm, adjusted to 20°C (68°F) at 7% flue gas 02 content. Particulate
mercury is not shown in Tables 4-1 and 4-2. Particulate mercury was determined from the
particulate filters in both OH trains for each run, but was always less than 0.003 |ig/dscm. Thus,
particulate mercury was a negligible fraction of the total mercury in the TSCAI stack.
Inspection of Tables 4-1 and 4-2 shows that Hg° composed most of the total mercury value,
consistent with the extent of scrubbing of the TSCAI flue gas. The total mercury level was
controlled to some extent by the choice of waste feed material and the waste feed rate entering
the TSCAI. Total mercury was less than 1.7 |ig/dscm in the first two OH runs and then was
progressively increased throughout the rest of the first 10 OH runs (Table 4-1), peaking at about
200 |ig/dscm in OH Run 16. In the eight OH runs conducted during the final week of the test
(Table 4-2), total mercury ranged from about 23 to 85 |ig/dscm. All the CEMs tested produced
readings of Hgx that generally paralleled this progression of mercury levels during the two weeks
of OH method sampling. Hgox was typically about 1% of the total mercury, and in 17 of the 18
OH runs, the Hgox results from both OH trains were less than 2 |ig/dscm. The one exception was
the Hgox level °f about 15 |ig/dscm observed with the peak mercury levels in OH Run 16, when
Hgox was about 7% of Hgx.
Tables 4-1 and 4-2 show generally close agreement between the A and B train results for all
three mercury fractions. The reproducibility of OH results is an important indicator of the
quality of the OH reference data for this verification test. Consequently, that reproducibility was
quantified by the RPD values for each A and B pair, by linear regression of the A and B train
results, including the correlation of the A and B results, and by calculation of the mean RSD of
the paired OH results for Hg°, Hgox, and Hgx. Considering the RPD values in Tables 4-1 and 4-
2, only one of the 18 RPD values for Hg° exceeds 7%, and the same is true for Hgx. The RPD
values for Hgox range from 0.5 to 39.4%, with a median of 9.7%. These results indicate close
agreement at the low Hgox concentrations found. Figure 4-1 shows the linear regression of B
train results versus A train results, for all three mercury fractions. The data for all three mercury
fractions lie closely along the 1-to-l line shown in this figure. Table 4-3 summarizes the results
of the linear regression, correlation, and %RSD analyses for the duplicate OH trains for Hg°,
Hgox, and Hgx. The correlation between paired trains is shown in terms of the coefficient of
determination (r2). Table 4-3 shows that the slopes of the paired OH regressions are all close to
1.0, the intercepts are near zero, and the r2 values are all approximately 0.99. Mean RSD values
of about 5.5%) were found for the paired results for Hg° and total mercury. The mean %>RSD for
Hgox was higher, due undoubtedly to the low Hgox levels in the TSCAI flue gas.
Based on the close agreement of the duplicate OH results for all mercury fractions in all sample
runs, the OH results in each run were used for comparison to the CEM results.
20
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Table 4-1. Ontario Hydro Results from Initial Sampling Period (August 8- 11, 2002)(jig/dscm)
OH Run
Number
Hg°
Hgox
HgT
A(a)
B(a)
Mean
RPD
A
B
Mean
RPD
A
B
Mean
RPD
7
1.46
1.53
1.49
2.4
0.17
0.15
0.16
7.2
1.63
1.68
1.65
1.5
8
0.17
0.19
0.18
6.7
0.17
0.19
0.18
5.1
0.34
0.38
0.36
5.9
9
17.9
18.3
18.1
1.1
0.34
0.42
0.38
10.4
18.2
18.7
18.4
1.3
10
34.7
39.0
36.8
5.9
0.32
0.48
0.40
19.8
35.0
39.5
37.2
6.0
11
48.5
36.0
42.3
14.8
0.34
0.40
0.37
8.1
48.9
36.4
42.6
14.6
12
47.8
47.4
47.6
0.5
0.64
0.45
0.54
17.2
48.5
47.8
48.1
0.7
13
36.9
37.9
37.4
1.3
0.26
0.58
0.42
37.5
37.1
38.4
37.8
1.7
14
38.1
43.3
40.7
6.5
0.44
0.44
0.44
0.5
38.5
43.8
41.1
6.4
15
68.6
66.3
67.5
1.7
0.84
1.93
1.39
39.4
69.4
68.3
68.8
0.8
16
187.5
181.4
184.4
1.7
13.7
15.1
14.4
5.1
201.2
196.5
198.8
1.2
(a) A and B are the paired OH trains used in sampling.
-------
Table 4-2. Ontario Hydro Results from Final Sampling Period (September 16 - 19, 2002) (jig/dscm)
OH Run
Number
Hg°
Hgox
HgT
A(a)
B(a)
Mean
RPD
A
B
Mean
RPD
A
B
Mean
RPD
18
74.1
67.7
70.9
4.5
0.45
0.95
0.70
35.9
74.6
68.7
71.6
4.1
19
77.5
76.6
77.0
0.6
0.47
0.49
0.48
2.0
77.9
77.1
77.5
0.6
20
82.3
84.7
83.5
1.4
0.59
0.63
0.61
3.7
82.9
85.4
84.1
1.4
21
50.3
54.1
52.2
3.7
0.30
0.36
0.33
9.0
50.6
54.4
52.5
3.7
22
21.7
23.9
22.8
4.7
0.22
0.32
0.27
18.5
22.0
24.2
23.1
4.9
23
30.5
35.1
32.8
7.0
0.45
0.32
0.39
16.6
30.9
35.4
33.1
6.7
24
23.4
23.0
23.2
0.9
0.26
0.27
0.27
1.6
23.6
23.2
23.4
0.9
25
55.3
63.1
59.2
6.6
1.04
0.59
0.82
28.2
56.3
63.6
60.0
6.1
(a:i A and B are the paired OH trains used in sampling.
-------
0 50 100 150 200
OH Train A Hg, ug/dscm
Figure 4-1. Plot of Ontario Hydro Train B Results vs. Train A Results
Table 4-3. Results of Linear Regression, Correlation, and Percent Relative Standard
Deviation of Paired Ontario Hydro Train Results (n = 18)
Analyte Slope (CI)(a) Intercept (CI) |i.g/m3 r2 %RSD
Hg° 0.959 (0.027) 2.19 (1.73) 0.988 5.55
Hgox 1.104 (0.025) 0.053 (0.082) 0.992 20.9
Hgj 0.969 (0.025) 1.93 (1.65) 0.990 5.36
(a) (CI) = 98% confidence interval shown in parentheses.
4.2.2 Ontario Hydro Blank and Spike Results
None of the OH reagent blanks showed any detectable mercury. Also, OH sampling trains were
prepared and taken to the sampling location at the TSCAI stack on two occasions, and then
returned for sample recovery without exposure to stack gas. These blank OH trains provide
additional assurance of the quality of the train preparation and recovery steps. Four sample
fractions were analyzed from these blank trains: the particulate filter and probe rinse; impingers
1-3 (KC1); impinger 4 (H202); and impingers 5-7 (KMn04). Mercury was not detected in any of
the blank train samples. The detection limits for analysis of these fractions (in terms of mass of
mercury detectable) were 0.019 |ig, 0.005 |ig, 0.021 |ig, and 0.031 |ig, respectively, which
correspond to stack gas concentrations of less than 0.001 |ig/dscm under all sampling conditions
in this verification. Thus, the blank OH train results confirm the cleanliness of the OH train
23
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preparation and analysis procedures. The recovery of mercury spiked into blank train samples as
part of the PE audit also met the prescribed criteria, as described in Section 4.3.2.
Mercury spike recovery was also evaluated using sample fractions from selected trains used for
the 18 OH method runs in the TSCA stack. Those spike recoveries ranged from 85 to 101%, and
the results for duplicate spikes never differed by more than 4%, well within the 10% duplicate
tolerance required by the OH method.
4.3 Audits
4.3.1 Technical Systems Audit
Battelle's Quality Manager performed a pre-test evaluation and an internal TSA of the verifica-
tion test at the TSCAI. The TSA ensures that the verification test is conducted according to the
test/QA plan(1) and that all activities in the test are in compliance with the AMS Center QMP.(8)
The pre-test evaluation consisted of a visit on May 14, 2002, by a representative of the Battelle
Quality Manager to observe trial OH method sampling and to audit the laboratory conducting
the OH method analyses. Trial sampling was observed at the facilities of SEI, and analytical
procedures were observed at STL, both in Knoxville, Tennessee. The Battelle representative was
a staff member highly familiar with the sampling and analysis requirements of the OH method.
He used detailed checklists to document the performance of OH method train preparation,
sampling, sample recovery, chain of custody, and sample analysis. All observations were
documented in an evaluation report, which indicated no adverse findings that could affect data
quality. An amendment to the test/QA plan(1) was prepared as a result of this evaluation,
documenting several minor procedural changes implemented in the OH sample recovery by
STL. These procedural changes were based on the experience of STL personnel in conducting
OH mercury analyses, and other metals analyses, as well as on the numbers and types of
analyses needed for this verification. The most significant such changes were
¦ The analysis of one matrix spike duplicate for each type of sample received (i.e., filter catch
and probe rinse, KC1 impingers, H202 impingers, etc.), rather than the duplicate and
triplicate analyses stated in section 13.4.2.3 of the OH method.
¦ The analysis of one spiked sample for each type of sample received, rather than a spike after
every 10 samples as stated in section 13.4.2.4 of the OH method.
¦ The use of a 25% tolerance on spike recovery values based on the requirements of EPA
Method 7460 for metals analysis, rather than the 10% tolerance stated in section 13.4.2.4 of
the OH method.
The Battelle Quality Manager conducted the TSA in a visit to the TSCAI test location on August
8, 2002, which was the first day of OH sampling in the first intensive period. In that visit he
toured the incinerator and CEM locations; observed the OH method sampling; observed OH
sample recovery and documentation in the on-site laboratory at the ETTP; reviewed Battelle
24
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notebooks, gas standard certifications, and the CEM data acquisition procedures; and conferred
with the CEM vendors and facility personnel. The TSA report from this audit found no issues
that could adversely affect data quality. All records from both the pre-test evaluation and the
TSA are permanently in the custody of the Battelle Quality Manager.
4.3.2 Performance Evaluation Audits
A series of PE audits was conducted on several measurement devices at the TSCAI facility to
assess the quality of the measurements made in the verification test. These audits were
performed by Battelle staff and were carried out with the cooperation of SEI staff. These audits
addressed only measurements that factored directly into the data used for verification, i.e., the
CEMs undergoing testing were not the subject of the PE audit. Each PE audit was performed by
analyzing a standard or comparing to a reference that was independent of standards used during
the testing. Each PE audit procedure was performed once during the verification test, with the
exception that blank OH sampling trains were spiked with a mercury standard during both the
first and last intensive OH sampling periods, approximately six weeks apart. Table 4-4
summarizes the PE audit results on several measurement devices at the TSCAI facility.
Table 4-4. Summary of PE Audits
Measurement
Audited
Date
Audit Method
Observed
Difference
Acceptable
Difference
Flue gas 02
8/9/02
Comparison to independent
02 measurement
0.16% 02(a)
0.24% 02
1% 02
Flue gas C02
8/9/02
Comparison to independent
C02 measurement
0.0%) of reading(b)
3.3%o of reading
10% of
reading
OH gas flow rate
8/7/02
Comparison to independent
flow measurement
1.3%(c)
3.2%
5%
Flue gas
temperature
8/7/02
Comparison to independent
temperature measurement
0.33%(c)
0.07%
2% absolute
temperature
Barometric
pressure
8/7/02
Comparison to independent
barometric pressure
measurement
0.5" H20
0.5" H20
Impinger weights
(electronic
balance)
8/7/02
Weighing certified weights
0.37%
(1.7 gat 454 g)
greater of 1%>
or 0.5 g
The two results shown are for the two Siemens Oxymate 5E units (Serial Nos. D1-447 and D3-491, respectively)
used at the TSCAI facility.
(b) The two results shown are for the two Siemens Ultramat 22P units (Serial Nos. U01-483 and A03-277,
respectively) used at the TSCAI facility.
(c:i The two results shown are for the two NuTech meter boxes designated Unit A (Serial No. 80563) and Unit B
(Serial No. 008068), respectively.
25
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Table 4-4 shows the type of measurement audited, the date the PE audit was conducted, the
basis for the audit comparison, the difference between the measurement and the PE audit value,
and the acceptable difference stated in the test/QA plan. As Table 4-4 shows, all the PE audits
met the required tolerances stated in the test/QA plan.(1) The PE audits for 02 and C02 were
conducted by sampling the same cooled and dried flue gas analyzed by the facility's CEMs for
these gases. The 02 and C02 content of the flue gas were about 9.5% 02 and 6% C02. The
independent audit monitor and the facility CEMs sampled this gas simultaneously for the PE
audit. As noted in the footnotes to Table 4-4, both of the dual 02 monitors and dual C02
monitors installed at the TSCAI facility were audited. The gas flow rate measurements of the
two OH trains were audited using a certified mass flow meter. The temperature measurements
were audited at ambient temperature (approximately 27°C), rather than in the flue gas, because
of the limited access to the TSCAI stack. The PE audit of the electronic balance used certified
weights of approximately 200 and 500 grams; the observed agreement shown in Table 4-4 is for
the 500-gram weight, which showed the greater percentage deviation. A planned audit of the
flue gas static pressure(1) was not conducted, because the minimal differential relative to
atmospheric pressure (approximately -0.25 inches of H20) makes this measurement both
difficult to audit and relatively unimportant in calculating the reference mercury results. An
amendment to the test/QA plan was prepared and approved to document this change.
The PE audit of the OH train mercury recovery and analysis was performed by spiking blank
OH trains with NIST-traceable mercury solutions. In each case, impingers 1 (KC1), 4
(H202/HN03), and 5 (KMn04/H2S04) of a blank OH train were spiked. In the first week of OH
sampling, each impinger was spiked with 1 mL of a 10-|ig/mL mercury solution, and in the final
week of OH sampling each impinger was spiked with 1 mL of a 30-|ig/mL mercury solution.
Table 4-5 identifies the OH trains that were spiked, the date of the spike, the amount of the
spike, and the analytical results for each spiked impinger in the train (i.e., impingers 1, 4, and 5
of each OH train).
Table 4-5. Results of PE Audit of OH Train Recovery and Analysis
Train
Date
Impinger
Number
Hg Spiked
(M-g)
Hg Found
(M-g)
Observed
Agreement
Target
Agreement
17A
8/8/02
1
10
9.7
3%
25%
4
10
7.8
22%
25%
5
10
8.3
17%
25%
28A
9/16/02
1
30
32.5
8.3%
25%
4
30
26.7
11.0%
25%
5
30
30.6
2.0%
25%
26
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Table 4-5 shows that all of the six spike recoveries were well within the target of 25% agreement
with the spiked values that was stated in the amended test/QA plan (see Section 4.3.1). Further-
more, four of the six results were near or within the 10% tolerance stated in the OH method.(2)
These results support the validity of the OH reference method results used in this verification.
4.3.3 Data Quality Audit
An audit was conducted to trace the test data from initial acquisition, through reduction and
statistical comparisons, to final reporting. All calculations performed on data leading to
verification results were checked. The Battelle Quality Manager reviewed the procedures and
results of this audit, and conducted his own independent review of a small portion of the data.
27
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Chapter 5
Statistical Methods
This chapter presents the statistical procedures that were used in calculations for verifying the
performance factors listed in Section 3.1.
5.1 Relative Accuracy
RA was verified by comparing the DM-6/DM-6P results against the reference results for total
mercury. The average of the paired OH train results was used as the reference value for each OH
run. The CEM readings in each OH run were averaged for comparison to the reference data.
The RA of the DM-6/DM-6P with respect to the reference method was calculated using
PI
+ -^-SD
RA--
yfn
X
KM
(1)
Where
M = the absolute value of the arithmetic mean of the differences, d, of the paired
DM-6/DM-6P reference method results
Xrm = arithmetic mean of the reference method result
n = number of data points
t0975 = the lvalue at the 97.5% confidence with n-1 degrees of freedom
SD = standard deviation of the differences between the paired DM-6/DM-6P and
reference method results.
RA was calculated separately for the first and last weeks of OH sampling (n = 10 and n = 8,
respectively), and for all reference data combined (n = 18).
5.2 Correlation with Reference Method
Correlation of the DM-6/DM-6P with the OH method was calculated using the same data used
to assess RA. The coefficient of determination (r2) was calculated to determine the degree of
correlation of the DM-6/DM-6P Hgx results with the reference method results. This calculation
28
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was conducted using data from the first week, the last week, and both weeks of OH reference
method sampling.
5.3 Precision
As described in Section 3.3.4.3, precision was assessed based on the individual readings provided
by the DM-6/DM-6P over the duration of OH method sampling Runs 9 and 12. Precision of the
DM-6/DM-6P was determined by calculating the percent relative standard deviation (RSD) of a
series of DM-6/DM-6P measurements made during stable operation of the TSCAI in these OH
runs. The %RSD is the ratio of the standard deviation of those readings to the mean of the
readings, expressed as a percentage:
SD = standard deviation of the DM-6/DM-6P readings
X = mean of the DM-6/DM-6P readings.
The calculated precision values from Equation 2 include the variability of the TSCAI stack gas
mercury concentration, as well as the variability of the DM-6/DM-6P itself. To estimate the
precision of the DM-6/DM-6P, it was assumed that the two sources of variability combine in
root-mean-square fashion, with the variability of the TSCAI mercury concentration represented
by the variability of the aqueous waste feed rate. Consequently, the CEM precision was estimated
in terms of a %RSD by means of Equation 3:
where %RSDr is the relative standard deviation of the CEM readings, %RSDWF is the relative
standard deviation of the aqueous waste feed readings, and %RSDCEM is the resulting relative
standard deviation attributable to the CEM variability. It must be noted that the total variability
of the TSCAI may not be fully represented by the variability of the waste feed rate. Consequently,
the CEM variability (%RSDCEM) calculated from Equation 3 must be considered as the maximum
variability that could be attributable to the CEM.
5.4 Sampling System Bias
Sampling system bias (B) reflects the difference in DM-6/DM-6P response when sampling Hg°
standard gas through the DM-6/DM-6P's entire sample interface, compared with that when
sampling the same gas directly at the DM-6/DM-6P's mercury analyzer, i.e.:
%RSD = ^xlOO
(2)
where
%RSDr = [(%RSDW)2 + (%RSDcem)2]1/2
(3)
B =
xlOO
(4)
29
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where
R, =DM-6/DM-6P reading when the standard gas is supplied at the sampling inlet
Ra = DM-6/DM-6P reading when the standard is supplied directly to the analyzer.
Since the effect of the inlet is expected to be a negative bias on measured Hg levels, R, is
expected to be less than Ra. Equation 4 thus gives a positive percent bias value for what is
understood to be an inherently negative bias. In rare instances R, was found to exceed Ra slightly
due to normal instrument variation. In such instances, B was reported as 0.0%.
The purpose of this part of the verification was to assess the bias introduced by the sampling
probe, filter, gas drier, and long (> 100-foot) sampling lines in sampling Hg°. It must be pointed
out that delivery of the standard gas to the sample inlet also required a Teflon line over 100 feet
in length. Thus, the observed bias may include a contribution from the standard gas delivery
system, as well as from the sampling system.
5.5 Relative Calibration and Zero Drift
Calibration and zero drift were reported in terms of the mean, relative standard deviation, and
range (maximum and minimum) of the readings obtained from the DM-6/DM-6P in the repeated
sampling of the same Hg° standard gas and of zero gas. The relative standard deviation of
standard gas or zero gas readings was calculated as according to Equation 2 above. This
calculation, along with the range of the data, indicates the variation in zero and standard gas
readings.
The DM-6/DM-6P was challenged with three Hg° gas standards in this test, cylinders CC133359,
CC133367, and CC133172, which had nominal average Hg° concentrations of 36.5, 5.5, and
43.9 |ig/m3, respectively. These nominal averages are based on all analyses of the gas standards
from August 8, 2002, through November 21, 2002 (Table 3-7), i.e., excluding the vendor's initial
pre-test analysis of the standards in March 2002.
5.6 Response Time
The response time refers to the time interval between the start of a step change in mercury input
and the time when the CEM reading reached 95% of the final value. Both rise time and fall time
were determined. CEM response times were obtained in conjunction with a calibration/zero drift
check or sampling system bias check by starting or stopping delivery of the mercury standard gas
to the CEM or sampling interface. The procedure of this test was to record all readings until
stable readings were obtained, and estimate the 95% response time.
30
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5.7 Data Completeness
Data completeness was assessed by comparing the data recovered from the DM-6/DM-P with the
amount of data that would be recovered upon completion of all portions of these test procedures.
5.8 Operational Factors
Maintenance and operational needs were documented qualitatively, both through observation and
through communication with the vendor during the test. Factors noted included the frequency of
scheduled maintenance activities, the down time of the DM-6/DM-6P, and the staff time needed
for maintaining it during the verification test.
31
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Chapter 6
Test Results
The results of the verification test of the DM-6/DM-6P are presented below for each of the
performance parameters.
6.1 Relative Accuracy
Tale 6-1 lists the OH reference method results and the corresponding DM-6/DM-6P results, for
Hgx in all 18 OH sampling runs. The OH results are the averages of the Hgx results from the
paired A and B trains in each run; the DM-6/DM-6P results are the averages of the DM-6/DM-6P
readings over the period of each OH run.
Table 6-1. Summary of Results from OH Reference Method and DM-6/DM-6P (|i,g/dscm)
Date
Hgx, ng/dscm
OH Run
OH
DM-6/DM-6P
8/8/2002
7
1.65
1.64
8
0.36
0.66
8/9/2002
9
18.4
13.1
10
37.2
28.9
8/10/2002
11
42.6
42.8
12
48.1
37.3
13
37.8
30.6
8/11/2002
14
41.1
28.6
15
68.9
52.0
16
198.8
158.0
9/16/2002
18
71.6
74.3
19
77.5
86.2
9/17/2002
20
84.1
85.5
21
52.5
50.2
9/18/2002
22
23.1
22.7
23
33.1
33.8
9/19/2002
24
23.4
22.7
25
60.0
62.3
32
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Table 6-1 shows that, during the first week of the verification test (OH Runs 7-16), the
DM-6/DM-6P readings were often somewhat lower than the corresponding OH results. In the last
week of the test (OH Runs 18-25), the DM-6/DM-6P readings agreed more closely with the OH
results. This observation is reflected in the RA results for the DM-6/DM-6P, shown in Table 6-2.
The RA for the second week of OH sampling was substantially improved relative to that for the
first week, and an overall RA of 20.3% was found for the entire data set.
Table 6-2. Relative Accuracy Results for the DM-6/DM-6P
Test Period
Relative Accuracy (%)
First Week (n = 10)
38.2
Last Week (n = 8)
8.1
Overall (n = 18)
20.3
6.2 Correlation with Reference Method
The correlation of the DM-6/DM-6P readings with the OH results for Hgx was calculated using
the data shown in Table 6-1. To illustrate the correlation, Figure 6-1 shows a linear regression
plot of the DM-6/DM-6P Hgx results against the corresponding OH results. The linear regression
equation and r are shown on the graph. Table 6-3 shows the coefficients of determination (r2) for
the first and last weeks of OH sampling and for the two periods combined. All the r values in
Table 6-3 exceed 0.95, with an overall r2 of 0.953.
180
160
140
y= 0.8347x +3.5033
r2 = 0.953
33 120
O)
100
O)
to
0
40
80
120
160
200
240
Ontario Hydro HgT, ug/dscm
Figure 6-1. Linear Regression Plot of DM-6/DM-6P HgT Results Against OH
Results
33
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Table 6-3. Coefficients of Determination (r2) for DM-6/DM-6P Hgx with OH Results
Test Period
r2
First Week (n = 10)
0.994
Last Week (n = 8)
0.990
Overall (n = 18)
0.953
6.3 Precision
Table 6-4 summarizes the observed precision of the DM-6/DM-6P in terms of the stability of its
readings during two periods of relatively stable introduction of mercury in aqueous waste into the
TSCAI. For OH Runs 9 and 12, Table 6-4 shows the %RSD of the aqueous waste feed rate into
the TSCAI, the corresponding %RSD of the DM-6/DM-6P Hgx readings, and the resulting
estimate of the variability attributable to the DM-6/DM-6P, calculated according to Equation 3 in
Section 5.3. (The integrated OH and average DM-6/DM-6P results in these two runs are shown in
Table 6-1.)
Table 6-4. Precision of the DM-6/DM-6P During OH Runs 9 and 12
Aqueous Feed Rate
DM-6/DM-6P
Maximum CEM
OH Run
Variability
Readings
Variability
Number
(%RSDwr)
(%RSDr)
(%RSDcem)
9
2.4
11.2
10.9
12
13.9
16.6
9.1
The results in Table 6-4 show that the DM-6/DM-6P readings exhibited variability of about 11 to
17%RSD under conditions of relatively stable mercury feed into the TSCAI. The maximum
variability attributable to the DM-6/DM-6P was 10.9%RSD in OH Run 9 and 9.1%RSD in OH
Run 12.
6.4 Sampling System Bias
On eight occasions during the verification test, an Hg° gas standard was supplied directly to the
analyzer of the DM-6/DM-6P and then to the inlet of the sampling system on the TSCAI stack. In
five of these tests, a relatively low concentration mercury standard was used, and in three a
relatively high concentration standard was used. Table 6-5 shows the date, the mercury standard,
and the DM-6/DM-6P readings obtained for each of these sampling system bias checks. The last
column in Table 6-5 also shows the sampling system bias, calculated according to Equation 4 in
Section 5.4.
34
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Table 6-5. Sampling System Bias Test Results
Date
Hg° Standard'3'
Response at Inlet
(Ri) (|ig/m3)
Response at Analyzer
(Ra) ((ig/m3)
Bias(b)
%
8/8/02
CC133367
7.5
8.1
7.4
8/9/02
CC133367
7.0
8.1
13.6
8/10/02
CC133367
8.6
8.6
0.0
9/18/02
CC133367
7.0
7.3
4.1
9/19/02
CC133367
7.2
7.5
4.0
9/17/02
CC133359
44.4
45.4
2.2
9/18/02
CC133359
43.9
45.6
3.7
9/19/02
CC133359
44.7
46.5
3.9
(a:i See Section 3.4.2 for information on mercury standard gases.
^ Calculated according to Equation 4, Section 5.4.
Table 6-5 shows that the sampling system bias was 7.4 to 13.6% in the first two bias checks, and
0.0 to 4.1% in the last six checks. After August 10, a sampling system bias of about 4% or less
was characteristic of the Nippon inlet system, with both the low and high mercury gas standards.
6.5 Relative Calibration and Zero Drift
Mercury gas standards and zero gas (high-purity nitrogen) were analyzed by the DM-6/DM-6P
periodically throughout the verification test to assess the drift in calibration and zero response of
the DM-6/DM-6P. The results of these analyses are shown in Table 6-6, which lists the date of
each analysis and the DM-6/DM-6P readings on zero gas and on the mercury standards. Also
shown in Table 6-6 are the mean, standard deviation, %RSD, and range of the DM-6/DM-6P
readings.
Table 6-6 shows that the zero gas readings of the DM-6/DM-6P averaged -0.01 |ig/m3 over the
duration of the verification test, with a standard deviation of 0.35 |ig/m3. These results indicate
minimal drift of the zero readings of the CEM. The results for the three mercury standard gases
also show consistent responses. The 25 analyses of the lowest concentration standard
(CC133367) took place over a period of about six weeks and exhibit an RSD of 7.1%. The seven
analyses of the middle concentration standard (CC133359), over a four-day period, show an RSD
of 2.7%). Finally, the 12 analyses of the highest concentration standard (CC133172) over a one-
month period resulted in an RSD of 1.7%.
35
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Table 6-6. Calibration and Zero Drift Results
DM-6/DM-6P Readings (|ig/m3)
Mercury Standard
Mercury Standard
Mercury Standard
Date
Zero Gas(a)
CC133367(b)
CC133359(b)
CC133172(b)
8/8/02
0.1
8.1
8/9/02
0.0
8.1
8/10/02
0.4
8.6
8/11/02
0.1
7.7
8/12/02
0.2
8.4
8/14/02
0.2
7.9
8/14/02
0.3
8.4
60.6
8/15/02
0.6
60.7
8/24/02
-1.5
6.0
8/28/02
0.1
7.5
59.9
8/29/02
-0.4
7.7
62.0
9/4/02
-0.2
7.3
60.7
9/5/02
0.0
8.1
62.1
9/11/02
0.2
7.7
61.7
9/12/02
0.1
8.0
61.9
9/13/02
-0.2
7.1
61.6
9/14/02
-0.1
7.3
62.2
9/15/02
-0.2
7.1
60.0
9/15/02
-0.1
59.0
9/16/02
-0.1
7.1
60.4
9/16/02
0.0
43.0
9/16/02
0.0
7.5
45.0
9/17/02
0.0
7.2
44.5
9/17/02
0.1
7.5
45.4
9/18/02
-0.1
7.3
45.6
9/18/02
0.1
7.6
46.5
9/19/02
0.0
7.5
46.5
9/19/02
0.1
7.7
Mean
-0.01
7.62
45.2
61.0
Std. Dev.
0.35
0.54
1.22
1.01
%RSD
--
7.1%
2.7%
1.7%
Range
-1.5-0.6
vq
OO
1
o
vd
43.0-46.5
59.0-62.2
(lL) High purity nitrogen used for zero checks.
^ See Section 3.4.2 for information on mercury standard gases.
36
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6.6 Response Time
Response time of the DM-6/DM-6P was determined using zero gas and two mercury standard
gases in a test conducted on September 18, 2002. These gases were supplied sequentially to the
inlet of the sampling system shared by the DM-6/DM-6P and another Nippon Instruments CEM,
and the response of the DM-6/DM-6P was recorded. Table 6-7 lists the data from this test,
showing the date and time of each reading, the indicated concentration from the DM-6/DM-6P,
and the resulting percent rise or fall in successive readings.
Table 6-7. Summary of Data Used to Estimate Response Time
Zero/Span
DM-6/DM-6P
Date
Time
Gas
Response (ug/m3)
Result
9/18/02
11:11:56
Z
0.0
11:12:56
Z
-0.1
11:13:56
CC133367
2.5
11:14:56
CC133367
6.9
98.6%) rise in two minutes
11:15:56
CC133367
7.0
11:16:56
CC133367
7.0
11:17:56
CC133367
7.0
11:18:56
Z
4.5
11:19:56
Z
0.2
97.1% fall in two minutes(a)
11:23:42
z
0.6
11:24:42
CC133359
24.7
11:25:42
CC133359
42.5
96.8%o rise in two minutes
11:26:42
CC133359
43.3
11:27:42
CC133359
43.7
11:27:59
CC133359
43.9
11:31:00
CC133359
43.4
11:32:00
CC133359
5.8
11:33:00
Z
0.6
98.6% fall in two minutes(a)
(a) Fall time calculations assume that final response would be 0.0 if data recording was continued.
Table 6-7 shows that the DM-6/DM-6P readings rose to more than 95% of their final readings in
two minutes in both test cases, with the test gases supplied to the inlet of the DM-6/DM-6P's
sampling system. Thus the DM-6/DM-6P rise time was two minutes. The fall in DM-6/DM-6P
readings was over 95% within two minutes in the two cases, indicating a fall time of two
37
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minutes. The DM-6/DM-6P data were not recorded for long after the mercury standard was
removed from the inlet. These fall time results are based on assuming that the CEM response
would have returned to a reading of 0.0 ug/m3 if data recording had continued.
6.7 Data Completeness and Operational Factors
The operational factors associated with using the DM-6/DM-6P were evaluated by SEI staff, who
operated the DM-6/DM-6P during the five-week period of routine monitoring. These operators
recorded observations on daily maintenance, repair, expendables use, waste generation and
disposal, etc., in a separate logbook for each CEM. The vendor also recorded activities in the first
and last weeks of the field period. Particular attention was paid to the cause and extent of any
down time of the DM-6/DM-6P during the field period. Table 6-8 lists the dates of significant
down time of the DM-6/DM-6P during the entire verification period, along with the duration of
the down time, the duration of the service time, and a description of the cause and resolution of
each problem.
The operation and maintenance activities listed in Table 6-8 include only those that were not
required by the test/QA plan(1) (e.g., time required to conduct zero and standard gas checks was
not considered down time) and that were responsible for either CEM down time or for operator
intervention. As Table 6-8 shows, maintenance on the DM-6/DM-6P included replacing the
sampling pump, repairing the inlet line, installing a new transformer, and reconnecting the
condensate drain line. The longest period of down time (12 hours) was experienced on August
29, 2002, when the laptop data logger was found to be not working properly and had to be
restarted. The second longest period of down time (3.5 hours) occurred on September 13, 2002,
when the vendor replaced the read-only-memory in the analyzer to facilitate easier time keeping.
The total down time experienced during the six-week test period was 1,500 minutes (25 hours);
the down time includes a total required service time of 1,020 minutes (17 hours). The total down
time amounted to about 2.5% of the duration of the field period (August 8 through
September 19), so that data completeness was 97.5%.
The cost of the DM-6/DM-6P also was considered as an operational factor. The approximate
purchase cost of the DM-6/DM-6P as tested was $44,000.
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Table 6-8. Extent of Down Time and Service Time
Date Down Time(a) Service Time(b)
8/10/02 lhour(hr) 1 hr
8/11/02 45 min 20 min
8/12/02 45 min 15 min
8/13/02 3 hr 3 hr
8/13/02 1 hr 1 hr
8/14/02 1 1/2 hr 1 1/2 hr
8/25/02 NA(C) 1 hr
8/26/02 NA 30 min
Activity
The DM-6 sample pump was weaker than the DM-5
pump. Since both analyzers were connected to the
same sample line, the vendor suspected that the DM-5
pump affected the absorption cell pressure in the DM-
6 analyzer.
Analyzer stopped responding. Had to stop and restart
analyzer.
Adjusted the range for reporting mercury
measurements.
Removed moisture filter from analyzer to reduce
pressure loss.
Discovered that the heated sample line was not
working due to failed fuse in the heater controller.(d)
Disconnected the analyzer from the sample line. The
analyzer remained on while sampling ambient air
from the room while the problem with the sample line
was investigated.
Local vendor representative reset the date and time to
correct the date stamp on the laptop computer. (The
date was apparently incorrectly entered on 8/22/02 at
the analyzer touch pad as 8/17/02. The mercury
measurements made between 8/22/02 and 8/26/02
Installed PC communications software for data
transfer.
Installed a new transformer and supplied power
through the new transformer.
Tested a higher capacity sample pump, but returned to
original pump.
Higher capacity sample pump installed.
were recovered from the data files.)
Vendor representative also completed instrument
checks.
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Table 6-8. Extent of Down Time and Service Time (continued)
Date Down Time(a) Service Time(b) Activity
8/27/02
NA
2 hr
Fuse failure in heater controller was traced to the fuse
holder. It is believed that there may have been a loose
connection at the fuse holder, which allowed heat to
buildup overtime, causing the fuse holder to deform
and the fuse to fail. A new fuse holder was installed
and tested overnight.
8/28/02
NA
1 hr
Sample line was at temperature and working properly
since installing and testing the new fuse holder on
8/27/02. Disconnected sample line at the probe and
purged line with nitrogen for five minutes.
Reconnected sample line at probe and at analyzer and
began sampling flue gas.
Probe filter was inspected and was clean.
8/29/02
12 hr
NA
Found the laptop data logger was not working. The
windows that had been tracking the mercury
measurements were closed, and a system error was
displayed. The error occurred at 20:47 on 8/28/02. The
analyzer was in good working order.
8/29/02
1 hr
1 hr
Consulted with the vendor and followed instructions to
turn off the laptop computer and restart it. The trend
windows were restored, and the data logging was
reinitiated.
8/29/02
NA
20 min
Drain pipe for draining condensate from flue gas had
become disconnected from tygon tubing drain line, and
a puddle of water had collected on the countertop
surface. Wiped up water and reconnected the line.
8/30/02
NA
5 min
Found drain line disconnected from drain pipe. Wiped
up water and reconnected the line with tie-wrap.
9/13/02
3 1/2 hr
3 1/2 hr
Vendor representative came to site to check instrument
before starting OH reference method testing. Routine
maintenance and operation of DM-6/DM-6P returned
to vendor.
Replaced ROM in the analyzer. With the new ROM,
there is no need to adjust the clock when performing
measurements of standard gases.
Replaced the probe filter.
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Table 6-8. Extent of Down Time and Service Time (continued)
Date Down Time (a) Service Time(b)
9/15/02 30 min 30 min
Activity
Replaced calibration inlet Teflon tubing with a
short section of heated Teflon tubing to prevent
condensate from being aspirated into the analyzer.
Reinstalled moisture filter in analyzer (that was
removed on 8/14/02).
TOTAL 1,500 min 1,020 min 97.5% availability and 17 service man-hours (e)
1 Down Time = time that the CEM was taken off line for zero or standard gas
measurements, was not operating, or was operating but not reporting reliable
measurements. The period over which down time was evaluated begins at the start of OH
method testing on 8/8/02 and ends at the conclusion of testing on 9/19/02. The amount of
time was rounded to the nearest 5 minutes.
' Service Time = time spent performing daily checks, conducting routine operation and
maintenance activities, and troubleshooting problems. The period over which service time
was evaluated begins at the start of OH method testing on 8/8/02 and ends at the
conclusion of testing on 9/19/02. The amount of time was rounded to the nearest 5
minutes.
' NA = not applicable.
* Failure of the heated sample line did not affect operation of the analyzer. Therefore, the
time that the analyzer was not sampling the flue gas was not included in the calculation of
availability.
' Availability = the ratio of time that the CEM was not experiencing down time to the total
time available for monitoring mercury emissions from the start of OH reference method
testing on 8/8/02 to the end of testing on 9/19/02. The total time that was available for
monitoring was 60,936 minutes or 1,015.6 hours.
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Chapter 7
Performance Summary
The RA of the DM-6/DM-6P for measuring Hgx was verified by comparison to the results of
18 sampling runs using dual trains of the OH reference method at Hgx levels from <1 to
200 |ig/dscm. When all 18 OH runs were included in the comparison, an overall RA of 20.3%
was found.
Correlation of the DM-6/DM-6P Hgx results with the OH results showed an r2 value of 0.953.
Precision of the DM-6/DM-6P was estimated using two OH sampling periods having relatively
stable introduction of mercury in aqueous waste into the TSCAI. The maximum variability
attributable to the DM-6/DM-6P itself was 9.1% and 10.9% RSD for these two periods.
The bias introduced by the DM-6/DM-6P sampling system was evaluated by introducing Hg°
standard gas both at the CEM analyzer and at the inlet to the sampling system. In the first two
days of the verification test, sampling system bias results of 7.4% and 13.6% were found, at an
Hg° level of about 8 |ig/m3. In six subsequent evaluations through the end of the verification,
sampling system bias results of 0.0 to 4.1% were found, at Hg° levels of about 7 to 45 |ig/m3.
Repeated analysis of zero gas and Hg° standards was used to assess the zero and calibration drift
of the DM-6/DM-6P over the six-week field period. Twenty-five analyses of an approximately
5.5 |ig/m3 Hg° standard over six weeks resulted in an RSD of 7.1%>. Seven analyses of an approx-
imately 36.5 |ig/m3 Hg° standard over four days resulted in an RSD of 2.7%. Thirteen readings of
an approximately 43.9 |ig/m3 Hg° standard over four weeks resulted in an RSD of 1.7%.
Rise and fall times of the DM-6/DM-6P were determined at times of switching between zero and
mercury standard gases. The 95% rise time and fall time of the DM-6/DM-6P were both two
minutes.
The DM-6/DM-6P operated reliably throughout the verification period, with the result that data
completeness was 97.5%. The longest period of down time was when the laptop data logger was
not working properly, and the second longest period of down time was when the vendor replaced
the read-only-memory in the analyzer to facilitate easier time keeping.
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Chapter 8
References
1. Test/QA Plan for Field Demonstration of Mercury Continuous Emission Monitors at the
TSCA Incinerator, Revision 3, Battelle, Columbus, Ohio, June 2002.
2. Standard Test Methodfor Elemental, Oxidized, Particle-Bound, and Total Mercury in Flue
Gas Generated From Coal-Fired Stationary Sources (Ontario Hydro Method), American
Society for Testing and Materials, Draft Method, September 3, 2001.
3. Dunn, J. E., Jr., Kelly, T. J., and Allen, M. W., "Field Demonstration of Mercury Continuous
Emission Monitors at the TSCA Incinerator," in Proceedings of the International Conference
on Air Quality III: Mercury, Trace Elements, and Particulate Matter, Arlington, Virginia,
September 1-12, 2002.
4. Kelly, T. J., Dunn, J. E., Jr., and Allen, M. W., "Evaluation of Mercury Continuous Emission
Monitors at the Oak Ridge TSCA Incinerator: ETV Phase II Verification Test," presented at
the EPRICEM User's Group Meeting, San Diego, California, May 13-16, 2003.
5. Dunn, J. E., Jr., Kinder, K. K., Calcagno, J. A. m, Davis, W. T., Geisler, T. J., Allen, M. W.,
Kelly, T. J., and Priebe, S. J., "Evaluation of Mercury Continuous Emission Monitors at the
U.S. DOE TSCA Incinerator," paper #70249, presented at the Air and Waste Management
Association 96th National Conference and Exposition, San Diego, California, June 22-26,
2003.
6. Method 101A - Determination of Particulate and Gaseous Mercury Emissions from Sewage
Sludge Incinerators, 40 Code of Federal Regulations 61, Appendix B, pp. 1,731-1,754.
7. Dunn, J., Klamm, S., and Mandel, S., "Status of Mercury Calibration Gas for Mercury
CEMs," presented at the EPRI CEM User's Group Meeting, San Diego, California,
May 13-16, 2003.
8. Quality Management Plan (QMP) for the ETV Advanced Monitoring Systems Pilot,
Version 3.0, U.S. EPA Environmental Technology Verification Program, Battelle, Columbus,
Ohio, December 2001.
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