September 2003
Environmental Technology
Verification Report
Nippon Instruments Corporation
MS-1/DM-5 Mercury
Continuous Emission Monitor
Prepared by
Battelle
Battelle
. . . Putting Technology To Work
Under a cooperative agreement with
£EPA U.S. Environmental Protection Agency
ETV EI VetV
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September 2003
Environmental Technology Verification
Report
ETV Advanced Monitoring Systems Center
Nippon Instruments Corporation
MS-1/DM-5 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 13
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 29
5.3 Precision 29
5.4 Sampling System Bias 30
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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 the Reference Method 33
6.3 Precision 35
6.4 Sampling System Bias 36
6.5 Relative Calibration and Zero Drift 37
6.6 Response Time 37
6.7 Data Completeness and Operational Factors 39
7 Performance Summary 43
8 References 44
Figures
Figure 2-1. Nippon Instruments MS-l/DM-5 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 TSCAI Stack 6
Figure 4-1. Plot of Ontario Hydro Train B Results vs. Train A Results 23
Figure 6-la. Linear Regression Plot of MS-l/DM-5 Hg° Results Against OH Results 34
Figure 6-lb. Linear Regression Plot of MS-l/DM-5 Hgox Results Against OH Results 34
Figure 6-lc. Linear Regression Plot of MS-l/DM-5 Hgx Results Against OH Results 35
Tables
Table 3-1. TSCAI Stack Gas Characteristics 7
Table 3-2. Mercury CEM Verification Test Schedule 9
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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
Table 3-5. Data Used for MS-l/DM-5 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 25
Table 4-5. Results of PE Audit of OH Train Recovery and Analysis 26
Table 6-1. Summary of Total Mercury Results from OH Reference Method
and MS-l/DM-5 CEM (fig/dscm) 32
Table 6-2. Relative Accuracy Results for the MS-l/DM-5 33
Table 6-3. Coefficients of Determination (r2) for Correlation of MS-l/DM-5
Results with OH Results 35
Table 6-4. Precision of the MS-l/DM-5 During OH Runs 9 and 12 36
Table 6-5. Sampling System Bias Results 36
Table 6-6. Calibration and Zero Drift Results 38
Table 6-7. Summary of Data Used to Estimate Response Time 39
Table 6-8. Extent of Down Time and Service Time 40
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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
mm millimeter
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
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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 MS-l/DM-5 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 MS-l/DM-5 mercury CEM. Following is a description
of the MS-l/DM-5 mercury CEM, based on information provided by the vendor. The
information provided below was not subjected to verification in this test.
The MS-l/DM-5 monitors elemental (Hg°) and oxidized (Hgox) mercury in stack gas. This
continuous mercury speciation analyzer consists of the MS-1 speciation unit and two DM-5
detectors, one for Hg°, the other for Hgox. The DM-5 detectors are connected to the MS-1 by a
linking cable and a 6-millimeter (mm) (0.24-inch) Teflon tube. To measure Hg°, sample gas and
potassium chloride solution are mixed in a reaction tube to remove water-soluble Hgox and
water-soluble organic mercury. Then, the gas and solution are separated in a gas/liquid-
separating tube. After the gas is washed with a potassium hydroxide solution and dehumidified,
the mercury is guided to the detector where gaseous Hg° is measured. To measure Hgox, the
solution containing Hgox and water-soluble organic mercury is guided to the lower part of the
reaction tube to be mixed with a reducing solution of tin chloride. There, Hgox and the water-
soluble organic mercury in the solution are
reduced to gaseous Hg°. The gas is washed by
potassium hydroxide solution and dehumidified in
an electronic cooler. The mercury then is guided to
the detector for measurement.
The MS-l/DM-5 reports mass concentration in
micrograms per cubic meter. It requires manual
calibration and chemical reagents. Control keys
are used to change sequence times, and a liquid
crystal display shows the times. The MS-l/DM-5
operates on 100-volt AC power. The MS-1 is
480 mm (19 inches) wide, 230 mm (9 inches)
deep, and 620 mm (24 inches) high and weighs 16
kilograms (35 pounds). Each DM-5 is 430 mm
(17 inches) wide, 220 mm (nine inches) deep, and
550 mm (22 inches) high and weighs 16
kilograms (25 pounds).
Figure 2-1. Nippon Instruments
MS-l/DM-5 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 MS-l/DM-5 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 MS-l/DM-5 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 and correlation with the reference method were assessed for total, elemental,
and oxidized mercury in the stack gas. Precision (i.e., repeatability at stable test conditions) was
assessed for total mercury in the stack gas. 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 maintainability 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° (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.
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
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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
CEM trailers are at the lower right.
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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
Condition
Units
Temperature
83.7-86.0 (182.6 - 186.8)
°C (°F)
Static Pressure
-0.25
inches H20
Flow Rate
6,065 -9,100
dry standard cubic feet (dscf) pi
minute (min)
14,920-23,450
actual cubic feet per minute
Velocity
15.78-19.73
feet per second
o2
8.4-11.6
%
o
o
N)
4.3-7.0
%
CO
0- 10.3
parts per million by volume
Moisture
47.1 -52.2
%
Particulate Matter
Loading
0.0012-0.079
2.68-18.2
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 MS-l/DM-5 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 MS-l/DM-5 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 MS-l/DM-5 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 MS-l/DM-5 and other
CEMs being tested.
For the MS-l/DM-5, 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 MS-l/DM-5, which shared a
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 (390°F). A
pump located near the instrument drew the sample gas through the 130-foot PFA Teflon sample
line maintained at 180°C (356°F) and into the MS-1 wet chemical conversion unit that separates
oxidized and elemental mercury in the sample gas for detection (see Chapter 2). The total
sample flow through the probe, filter, and Teflon line was approximately two liters per
minute (L/min). Like all CEMs in this verification test, the Nippon MS-l/DM-5 sampled at a
single (fixed) point in the stack. This CEM provides parallel and continuous measurements of
elemental mercury (Hg°) and oxidized mercury (Hgox) from which are derived total vapor-phase
mercury (Hgx) (i.e., the sum of Hg° and Hgox). The MS-l/DM-5 does not determine particle-
phase mercury. Verification of the performance of the MS-l/DM-5 was based on comparison
with the corresponding 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.
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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 - Sept. 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
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, 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 and operated 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 maintenance 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 Custody 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.
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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
10:25
Solids
10:55
11:55
14:40
15:40
8
8/8/02
Solids
16:10
17:10
10:50
11:50
9
8/9/02
12:15
13:15
Aqueous
14:35
15:35
10
8/9/02
16:10
17:10
Aqueous
9:35
10:05
11
8/10/02
10:25
10:55
Aqueous
12:15
12:45
12
8/10/02
13:10
13:40
Aqueous
15:00
15:30
13
8/10/02
15:50
16:20
Aqueous
08:20
08:50
14
8/11/02
09:10
09:40
Aqueous and Solids
10:40
10:52
15
8/11/02
11:05
11:23
Aqueous and Solids
11:45
12:15
13:45
14:15
16
8/11/02
Solids
15:00
15:30
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,
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.
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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
12
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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
performance parameters and summarizes the types of data that were used to verify each of those
parameters.
Table 3-5. Data Used for MS-l/DM-5 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 MS-l/DM-5 was verified using the OH reference method data for total mercury.
The Hgx readings of the MS-l/DM-5 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 MS-l/DM-5 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.
13
-------
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
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 test; 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.
14
-------
3.3.4.6 Response Time
Mercury CEM response time also was 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.
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 of 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 expendables 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 MS-l/DM-5 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
15
-------
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,
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 17
November
5 & 6
November
6
November
13 & 21
Difference
Between
Cylinder
Number
Initial Gas
Vendor
Certified
Analysis
(Hg/m3)
EPA-
ORD
Seefelder
Analysis
(jig/m3)
EPA-ORD
Seefelder
Analysis
(Hg/m3)
Method
101A Mini-
Train
Analysis
(jig/m3)
EPA-ORD
Seefelder
Analysis
(Hg/m3)
Final Gas
Vendor
Certified
Analysis
(jig/m3)
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 mbar and 20°C.
NA: Not available, analysis not performed.
16
-------
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
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
{!i> Not applicable for one data point.
17
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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.
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 atomic absorption (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 mean OH results in each run were used.
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 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
Hg°
Hgox
HgT
Number
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 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
verification 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 TSA 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. 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
o
L/i
X
bJ
o
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
{!i> 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® 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 MS-l/DM-5 results against the reference results for each
parameter that the MS-l/DM-5 measured. 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 MS-l/DM-5 with respect to the reference method was calculated using
®+'-jfSD (.)
RA = v 1
X
RM
Where
M = the absolute value of the arithmetic mean of the differences, d, of the paired
MS-l/DM-5 and reference method results
Xrm = arithmetic mean of the reference method results
n = number of data points
tog75 = the lvalue at the 97.5% confidence with n-1 degrees of freedom
SD = standard deviation of the differences between the paired MS-l/DM-5 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).
28
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5.2 Correlation with Reference Method
Correlation of the MS-l/DM-5 with the OH method was calculated using the same data used to
assess RA. Correlation was calculated for each parameter measured by the MS-l/DM-5. The
coefficient of determination (r2) was calculated to determine the degree of correlation of the
MS-l/DM-5 Hgx results with the reference method results. This calculation was conducted using
data from the first week, the last week, and both weeks of OH reference method samplings.
5.3 Precision
As described in Section 3.3.4.3, precision was assessed based on the individual readings
provided by the MS-l/DM-5 over the duration of OH method sampling Runs 9 and 12.
Precision of the MS-l/DM-5 was determined by calculating the percent relative standard
deviation (%RSD) of a series of MS-l/DM-5 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
o/0RSD = ^XlOO (2)
X
where
SD = standard deviation of the MS-l/DM-5 readings
X = mean of the MS-l/DM-5 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 MS-l/DM-5 itself. To estimate the
precision of the MS-l/DM-5, 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:
%RSDr = [(%RSDwf)2 + (%RSDcem)2]1/2 (3)
where %RSDr is the relative standard deviation of the CEM readings, %RSDW 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. Conse-
quently, the CEM variability (%RSDCEM) calculated from Equation 3 must be considered as the
maximum variability that could be attributable to the CEM.
29
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5.4 Sampling System Bias
Sampling system bias (B) reflects the difference in MS-l/DM-5 response when sampling Hg°
standard gas through the MS-l/DM-5's entire sample interface, compared with that when
sampling the same gas directly at the MS-l/DM-5's mercury analyzer, i.e.:
Ra~R,
B = — Lxl00 (4)
Ra K)
where
R, =MS-l/DM-5 reading when the standard gas is supplied at the sampling inlet
Ra = MS-l/DM-5 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, Rt 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 MS-l/DM-5 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 according to Equation 2 above. This
calculation, along with the range of the data, indicates the variation in zero and standard
readings.
The MS-l/DM-5 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
30
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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.
5.7 Data Completeness
Data completeness was assessed by comparing the data recovered from the MS-l/DM-5 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 MS-l/DM-5, 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 of the MS-l/DM-5 are presented below for each of the
performance parameters.
6.1 Relative Accuracy
Table 6-1 lists the OH reference method results and the corresponding MS-l/DM-5 results, for
Hg°, Hgox, and Hgx in all 18 OH sampling runs. The OH results are the averages of the results
from the paired A and B trains in each run; the MS-l/DM-5 results are the averages of the
MS-l/DM-5 readings over the period of each OH run. The Hgx results for the MS-l/DM-5 are
the sum of the simultaneous Hg° and Hgox results in each OH period.
Table 6-1. Summary of Results from OH Reference Method and MS-l/DM-5 (|i,g/dscm)
Hg°
Hgox
HgT
OH Run
((ig/dscm)
((ig/dscm)
((ig/dscm)
Date
Number
OH
MS-l/DM-5
OH
MS-l/DM-5
OH
MS-l/DM-5
8/8/2002
7
1.49
1.74
0.16
0.60
1.65
2.35
8
0.18
0.51
0.18
0.59
0.36
1.10
8/9/2002
9
18.1
15.5
0.38
0.89
18.4
16.4
10
36.8
34.8
0.40
0.79
37.2
35.6
8/10/2002
11
42.3
38.2
0.37
0.85
42.6
39.0
12
47.6
42.9
0.54
1.11
48.1
44.0
13
37.4
36.3
0.42
1.02
37.8
37.3
8/11/2002
14
40.7
33.5
0.44
1.04
41.1
34.6
15
67.5
60.1
1.39
1.63
68.9
63.0
16
184.4
167.7
14.4
6.71
198.8
174.4
9/16/2002
18
70.9
74.9
0.70
1.12
71.6
76.0
19
77.0
82.5
0.48
1.02
77.5
83.5
9/17/2002
20
83.5
82.6
0.61
0.99
84.1
83.6
21
52.2
46.6
0.33
0.82
52.5
47.4
9/18/2002
22
22.8
21.9
0.27
0.75
23.1
22.6
23
32.8
31.6
0.39
0.69
33.1
32.3
9/19/2002
24
23.2
21.4
0.27
0.64
23.4
22.0
25
59.2
57.8
0.82
0.71
60.0
58.5
32
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Table 6-1 shows that the MS-l/DM-5 readings were close to the corresponding OH results for
Hg° and Hgx, throughout both weeks of OH sampling. Also the Hgox results from the
MS-l/DM-5 were predominantly less than 1 |ig/dscm, consistent with the OH results. However,
the differences between the CEM and OH Hgox results at these low levels were often a factor of
two or more. Only in OH Run 16 did the OH Hgox results exceed 2 |ig/dscm; and, in that run,
the MS-l/DM-5 Hgox value was about half of the OH result.
Table 6-2 shows the resulting RA values for the MS-l/DM-5, for Hg°, Hgox, and Hgx, based on
the first week, the last week, and both weeks of OH sampling. All the RA results for Hg° and
Hgx are within about 20% or less, and the overall RA for Hgx is 11.2%. The RA results for Hgox
all exceed 75%. The RA values for Hg° and Hgx suggest that the relatively high RA values for
Hgox may be due primarily to the low concentrations of Hgox in the TSCAI stack gas.
Table 6-2. Relative Accuracy Results for the MS-l/DM-5
Test Period
Relative Acciiracv ("/«)
Hg°
Hgox
HgT
First Week (n = 10)
17.1
117
20.2
Last Week (n = 8)
6.1
110
5.7
Overall (n = 18)
10.1
78.6
11.2
6.2 Correlation with the Reference Method
The correlations of the MS-l/DM-5 readings with the OH results for Hg°, Hgox, and Hgx were
calculated using the data shown in Table 6-1. To illustrate the correlations, Figures 6-1 a to 6-1 c
show linear regression plots of the MS-l/DM-5 results against the corresponding OH results for
Hg°, Hgox, and Hgx, respectively. The linear regression equations and coefficients of deter-
mination (r2) are shown on the graphs. Table 6-3 shows the r2 values for the first and last weeks
of OH sampling and for the two periods combined for Hg°, Hgox, and Hgx.
Table 6-3 shows that the MS-l/DM-5 results were highly correlated with the OH results for Hg°
and Hgx; the overall r2 value for Hgx was 0.987. Correlation with the Hgox results was strong in
the first week and overall, primarily due to the dominance of the large Hgox value in OH Run
16. For example, exclusion of that one run from the calculations results in an overall r2 value for
the Hgox data of 0.673.
33
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Ontario Hydro Hg°, ug/dscm
Figure 6-la. Linear Regression Plot of MS-l/DM-5 Hg° Results Against OH
Results
Ontario Hydro Hgox, ug/dscm
Figure 6-lb. Linear Regression Plot of MS-l/DM-5 Hgox Results Against
OH Results
34
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Ontario Hydro Hg-r, ug/dscm
Figure 6-lc. Linear Regression Plot of MS-l/DM-5 HgT Results Against OH
Results
Table 6-3. Coefficients of Determination (r2) for Correlation of MS-l/DM-5 Results with
OH Results
r2
Test Period
Hg°
Hgox
HgT
First Week (n = 10)
0.999
0.992
0.999
Last Week (n = 8)
0.986
0.212
0.986
Overall (n = 18)
0.989
0.985
0.987
6.3 Precision
Table 6-4 summarizes the observed precision of the MS-l/DM-5, in terms of the stability of its
Hgx 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 MS-l/DM-5 Hgxreadings, and the resulting
estimate of the variability attributable to the MS-l/DM-5, calculated according to Equation 3 in
Section 5.3. (The integrated OH and average MS-l/DM-5 results in these two runs are shown in
Table 6-1 above.)
35
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Table 6-4. Precision of the MS-l/DM-5 During OH Runs 9 and 12
Aqueous Feed Rate
MS-l/DM-5
Maximum CEM
OH Run
Variability
Readings
Variability
Number
(%RSDwr)
(%RSDr)
(%RSDcem)
9
2.4
9.5
9.2
12
13.9
22.2
17.3
The results in Table 6-4 show that the MS-l/DM-5 readings exhibited variability of approxi-
mately 9 to 22%RSD under conditions of relatively stable mercury feed into the TSCAI.
maximum variability attributable to the MS-l/DM-5 was 9.2%RSD in OH Run 9 and
17.3%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 MS-l/DM-5 and then to the inlet of the MS-l/DM-5's sampling system on the
TSCAI stack. Table 6-5 shows the date, the mercury standard, and the MS-l/DM-5 Hg° 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.
Table 6-5. Sampling System Bias Results
Date
Hg° Standard'3'
Response at Inlet (Rj)
(ng/m3)
Response at Analyzer
(Ra) ((ig/m3)
Bias(b)
%
8/8/02
CC133367
7.4
7.3
0.0
8/9/02
CC133367
7.2
7.3
1.4
8/10/02
CC133367
7.0
7.3
4.1
9/18/02
CC133367
7.0
7.4
5.4
9/19/02
CC133367
7.1
7.6
6.6
9/17/02
CC133359
43.6
44.9
2.9
9/18/02
CC133359
42.2
44.7
5.6
9/19/02
CC133359
43.9
45.2
2.9
{!i> See Section 3.4.2 for information on mercury standard gases.
(b:i Calculated according to Equation 4, Section 5.4.
Table 6-5 shows that, in the first bias test on August 8, the MS-l/DM-5 response to standard gas
at the inlet actually slightly exceeded the response at the analyzer, indicating no negative
sampling system bias. The other sampling system bias results ranged from 1.4 to 6.6%.
36
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6.5 Relative Calibration and Zero Drift
Mercury gas standards and zero gas (high purity nitrogen) were analyzed by the MS-l/DM-5
periodically throughout the verification test to assess the drift in calibration and zero response of
the MS-l/DM-5. The results of these analyses are shown in Table 6-6, which lists the date of
each analysis and the MS-l/DM-5 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 MS-l/DM-5
readings on zero gas and on the mercury standard gases.
Table 6-6 shows that the zero gas readings of the MS-l/DM-5 averaged 0.0 |ig/m3 over the
duration of the verification test, with a standard deviation of 0.1 |ig/m3. These results indicate
minimal drift of the zero readings of the MS-l/DM-5. The results for the three mercury standard
gases also show consistent responses through the testing period. Twenty-one analyses of the
lowest concentration standard (CC133367) took place over a period of about six weeks and
exhibited a %RSD value of 10.4%. The six analyses of the middle concentration standard
(CC133359) over a three-day period showed an RSD of 2.4%. Finally, the 11 analyses of the
highest concentration standard (CC133172) over a one-month period resulted in an RSD of
8.1%.
6.6 Response Time
Response time of the MS-l/DM-5 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 MS-l/DM-5 and another Nippon Instruments CEM,
and the Hg° response of the MS-l/DM-5 was recorded. Table 6-7 lists the data from this test,
showing the date and time of each reading, the indicated Hg° concentration from the
MS-l/DM-5, and the resulting percent rise or fall in successive readings.
Table 6-7 shows that the 95% rise time of the MS-l/DM-5 was about two minutes in both cases,
with the test gases supplied to the inlet of the CEM's sampling system. Determination of the fall
time was hampered by interruption of the data collection as the CEM response fell. However, the
two results obtained (77.3% fall in one minute and 85.1%> fall in two minutes) suggest that the
95% fall time of the MS-l/DM-5 was probably somewhat longer than the rise time, i.e.,
approximately three minutes.
37
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Table 6-6. Calibration and Zero Drift Results
MS-l/DM-5 Readings (|ig/m3)
Date
Zero
Gas
Mercury Standard
CC133367
Mercury Standard
CC133359
Mercury Standard
CC133172
8/8/02
0.1
7.3
8/9/02
0.0
7.3
8/10/02
0.0
7.3
8/11/02
0.1
7.3
8/12/02
0.0
8.8
8/14/02
0.1
8.6
8/14/02
-0.2
8.6
60.7
8/15/02
0.1
60.4
8/24/02
-0.1
6.0
8/28/02
0.0
6.6
51.6
8/29/02
0.0
6.5
51.5
9/4/02
-0.1
6.1
50.4
9/5/02
0.0
6.5
51.0
9/11/02
0.0
6.0
50.5
9/12/02
0.0
6.3
50.5
9/14/02
0.0
7.1
58.3
9/15/02
0.0
7.1
58.7
9/16/02
0.1
7.1
58.0
9/16/02
0.0
42.3
9/16/02
0.1
7.4
44.0
9/17/02
0.0
7.2
43.5
9/17/02
0.0
7.5
44.9
9/18/02
0.0
7.4
44.7
9/18/02
0.1
7.4
45.1
9/19/02
0.0
7.6
45.2
9/19/02
0.0
7.6
Mean
0.0
7.2
44.2
54.7
Std. Dev.
0.1
0.8
1.1
4.4
%RSD
—
10.6%
2.4%
8.1%
Range
-0.2-0.1
6.0-8.8
42.3-45.1
50.4-60.7
38
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Table 6-7. Summary of Data Used to Estimate Response Time
Date
Time
Zero/Span
Gas
MS-l/DM-5
Response (ug/m3)
Result
11
:12
Z
0.1
11
:13
Z
0.2
11
:14
CC133367
2.2
11
:15
CC133367
6.6
94.1% rise in two minutes
11
:16
CC133367
6.9
98.5% rise in three minutes
11
:17
CC133367
7.0
11
:18
CC133367
7.0
11
:19
Z
5.2
11
:20
Z
1.3
85.1% fall in two minutes
11
:23
z
0.3
11
:24
z
0.6
11
:25
CC133359
28.5
11
:26
CC133359
40.1
95.6% rise in two minutes(a)
11
21
CC133359
41.1
98.1% rise in two minutes(a)
11
:28
CC133359
41.5
11
:29
CC133359
41.8
11
:30
CC133359
42.1
11
:31
CC133359
41.8
11
:32
Z
9.5
77.3% fall in one minute(a)
9/18/02
(^ Final reading of 41.9 ug/m3 (average of readings 11:29 to 11:31) used for this calculation.
6.7 Data Completeness and Operational Factors
The operational factors associated with using the MS-l/DM-5 were evaluated by SEI staff, who
operated the MS-l/DM-5 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 MS-l/DM-5 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 MS-l/DM-5 during the field period. Table 6-8 lists the dates
of significant down time of the MS-l/DM-5 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.
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Table 6-8. Extent of Down Time and Service Time
Date Down Time(a) Service Time(b) Activity
8/12/02
45 min
15 min
Adjusted the range for reporting mercury
measurements.
8/13/02
1 hour (hr)
1 hr
Prepared KC1 and SnCl2 reagents. Changed
out reagent containers.
8/19/02
10 min
10 min
Per vendor's instructions, performed
troubleshooting to investigate cause of low
flow to DM-5 Hg° unit. No blockage of the
lines or malfunction of equipment was
discovered. Adjusted the flow through the
DM-5 Hg° rotameter up to the nominal
desired flow.
8/20/02
NA(c)
1 hr
Prepared SnCl2 reagent. Changed out SnCl2
and KC1 reagent containers.
8/25/02
NA
1 hr
Discovered that the heated sample line was
not working due to failed fuse in the heater
controller. Disconnected the analyzer from
the sample line. The MS-1/DM-5 remained
on while sampling ambient air from the
room while the problem with the sample line
was investigated.
8/26/02
NA
1 hr
Local vendor representative prepared SnCl2
and KC1 reagents. Changed out SnCl2
reagent container.
Vendor representative also completed
instrument checks.
8/27/02
NA
15 min
Changed out KC1 reagent container.
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 over
time, causing the fuse holder to deform and
the fuse to fail. A new fuse holder was
installed and tested overnight.
40
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Table 6-8. Extent of Down Time and Service Time (continued)
Date Down Time(a) Service Time(b) Activity
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.
9/02/02
NA
1 hr
Prepared SnCl2 reagent and changed out
SnCl2 container.
9/8/02
NA
1 hr
Prepared SnCl2 reagent and changed out
SnCl2 container. Replenished KC1 reagent
container.
9/10/02
NA
20 min
Prepared KC1 reagent and changed out KC1
reagent container.
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 MS-l/DM-5 returned to vendor.
Investigated why MS-l/DM-5 response to
standard gases was lower than DM-6.
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)
9/14/02 3 1/2 hr 3 1/2 hr
9/15/02 1 hr 1 1/2 hr
Totals 1,375 min 1,170 min
Activity
Adjusted the span to the MS-l/DM-5 Hg°
unit based on response to mercury standard
gases earlier in the test.
Replaced calibration inlet Teflon tubing with
a short section of heated Teflon tubing to
prevent condensate from being aspirated into
the analyzer.
Prepared SnCl2 and KC1 reagents and
changed out reagent containers.
97.7% availability and 19.5 service man-
hours (d)
(^ 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.
(b:i 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.
(c) NA = not applicable.
(d:i 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 1015.6 hours.
The operation and maintenance activities listed in Table 6-8 include only those that were not
required by the test/QA plan (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, the most common maintenance on the MS-l/DM-5 was
preparing the needed chemical reagent solutions. This activity is counted in service time in
Table 6-8, but not in down time, since operation of the CEM need not be interrupted to make or
replace reagents. The longest period of down time (12 hrs) was experienced on August 29, 2002,
when the laptop data logger was not working properly and had to be restarted. Other items
needing service included the sample inlet line and flow rate. The total down time experienced
during the six-week test period was 1,375 minutes (approximately 23 hrs), and the required
service time during the same period was 1,170 minutes (19.5 hrs). The total down time
amounted to about 2.3% of the duration of the field period (August 8 through September 19), so
that data completeness was 97.7%.
The cost of the MS-l/DM-5 was also considered as an operational factor. The approximate
purchase cost of the MS-l/DM-5 as tested was $47,000.
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Chapter 7
Performance Summary
The RA of the MS-l/DM-5 for measuring Hgx, Hg°, and Hgox 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, the overall RA
values were 11.2% for Hgx and 10.1% for Hg°. The overall RA for Hgox was 78.6%, at Hgox
levels that were below 1.4 |ig/dscm in all but one OH run.
Correlation of the MS-l/DM-5 results with the OH results showed an r2 values of 0.987, 0.985,
and 0.989 for Hgx, Hgox, and Hg°, respectively, when all 18 OH results were included.
Precision of the MS-l/DM-5 was estimated using two OH sampling periods having relatively
stable introduction of mercury on aqueous waste into the TSCAI. The maximum variability
attributable to the MS-l/DM-5 itself was 9.2% and 17.3% RSD for these two periods.
The bias introduced by the MS-l/DM-5 sampling system was evaluated by introducing Hg°
standard gas both at the CEM analyzer and at the inlet to the sampling system. In eight such
evaluations, sampling system bias results of 0.0% to 6.6% 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 MS-l/DM-5 over the six-week field period. Twenty-four analyses of an approximately
5.5 |ig/m3 Hg° standard over six weeks resulted in an RSD of 10.6%. Seven analyses of an
approximately 36.5 |ig/m3 Hg° standard over three days resulted in an RSD of 2.4%. Eleven
readings of an approximately 43.9 |ig/m3 Hg° standard over four weeks resulted in an RSD of
8.1% .
Rise and fall times of the MS-l/DM-5 were determined at times of switching between zero and
mercury standard gases. The MS-l/DM-5 achieved 95% rise in two minutes and 95% fall in
approximately three minutes.
The MS-l/DM-5 operated reliably throughout the verification period, with the result that data
completeness was 97.7%. The most common maintenance needed was to prepare the chemical
reagent solutions. The longest period of down time occurred due to a malfunction of the laptop
data logger.
43
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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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