United States
Environmental Protection
Agency
EPA/600/R-07/077
July 2007
Measurement of Total Site
Mercury Emissions for a
Chlor-alkali Plant Using
Open-Path UV-DOAS
26 54
Flux: 22.0
108 162
Leakage: 1.2 [fi/hr] Wind Dir/Soeed: 11.0 [
Example Plume Map
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EPA/R-07/077
July 2007
Measurement of Total Site Mercury Emissions from a Chlor-alkali Plant Using
Open-Path UV-DOAS
Final Report to OAQPS
Category Il/Support for Development of Environmental Regulations and Standards
by
ARCADIS U.S., Inc.
Contract No. EP-C-04-023
Work Assignment No. 2-52 (3-13)
Project No. RN990232.0052 (RN990233.0013)
Project Officer
Eben Thoma
Air Pollution Prevention and Control Division
National Risk Management Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
RTP, NC 27711
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Foreword
The U.S. Environmental Protection Agency (EPA) is charged by Congress with protecting the
Nation's land, air, and water resources. Under a mandate of national environmental laws, the
Agency strives to formulate and implement actions leading to a compatible balance between
human activities and the ability of natural systems to support and nurture life. To meet this
mandate, EPA's research program is providing data and technical support for solving
environmental problems today and building a science knowledge base necessary to manage
our ecological resources wisely, understand how pollutants affect our health, and prevent or
reduce environmental risks in the future.
The National Risk Management Research Laboratory (NRMRL) is the Agency's center for
investigation of technological and management approaches for preventing and reducing risks
from pollution that threaten human health and the environment. The focus of the Laboratory's
research program is on methods and their cost-effectiveness for prevention and control of
pollution to air, land, water, and subsurface resources; protection of water quality in public water
systems; remediation of contaminated sites, sediments and ground water; prevention and
control of indoor air pollution; and restoration of ecosystems. NRMRL collaborates with both
public and private sector partners to foster technologies that reduce the cost of compliance and
to anticipate emerging problems. NRMRL's research provides solutions to environmental
problems by: developing and promoting technologies that protect and improve the environment;
advancing scientific and engineering information to support regulatory and policy decisions; and
providing the technical support and information transfer to ensure implementation of
environmental regulations and strategies at the national, state, and community levels.
This publication has been produced as part of the Laboratory's strategic long-term research
plan. It is published and made available by EPA's Office of Research and Development to
assist the user community and to link researchers with their clients.
Sally Gutierrez, Director
National Risk Management Research Laboratory
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Notice
The U.S. Environmental Protection Agency through its Office of
Research and Development funded and managed the research described here under
contract number EP-C-04-023 to Arcadis U.S., Inc. It has been subjected to the Agency's
review and has been approved for publication as an EPA document.
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Table of Contents
Lists v
Executive Summary x
1. Introduction 1
1.1 Background 1
1.2 Project Description 3
2. Description of Measurement Methods and Site Deployment 5
2.1 Vertical Radial Plume Mapping Method 5
2.2 Ground-level Point Sampling 10
2.3 Site Deployment Description 10
3. Results and Discussion 15
3.1 Data Averaging and Calculation Description 15
3.1.1 Acceptable Data Criteria and Emission Flux Correction Factors 16
3.2 Data Graphs and Tables 19
3.2.1 Climatronics Meteorological Data 19
3.2.2 R.M. Young Meteorological Data 34
3.3 Summary 86
4. QA/QC 89
4.1 Instrument Calibration 89
4.2 Assessment of DQI Goals 89
4.2.1 DQI Check for UV-DOAS PAC Measurements 91
4.2.1.1 Problems Encountered 94
4.2.2 DQI Checks for Lumex Measurements 94
4.2.3 DQI Checks for Ambient Wind Speed and Wind Direction
Measurements 95
4.2.4 DQI Checks for the Topcon Theodolite 102
4.2.5 Daily Telemetry Check Assessment 103
4.2.6 Problems Encountered 103
4.3 EPA and ARCADIS Audits and Corrective Actions 104
5. References 105
IV
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Lists
List of Tables
Table 3-1. Data Deemed Unacceptable Based on Wind Rose Data
Table 3-2. Wind Rose Data for Climatronics Monitor
Table 3-3. Correction Factors Applied to Four Days of Climatronics Data
Table 3-4. Summary of Results for September 21, 2006
Table 3-5. Summary of Results for September 22, 2006
Table 3-6. Summary of Results for October 11, 2006
Table 3-7. Summary of Results for October 14, 2006
Table 3-8. Summary of Results for October 17, 2006
Table 3-9. Summary of Results for October 18, 2006
Table 3-10. Wind Rose Data for R.M. Young Monitor
Table 3-11. Summary of Results for October 20, 2006
Table 3-12. Summary of Results for October 21, 2006
Table 3-13. Summary of Results for October 24, 2006
Table 3-14. Summary of Results for October 25, 2006
Table 3-15. Summary of Results for October 26, 2006
Table 3-16. Summary of Results for October 27, 2006
Table 3-17. Summary of Results for October 30, 2006
Table 3-18. Summary of Results for October 31, 2006
Table 3-19. Summary of Results for November 1, 2006
Table 3-20. Summary of Results for November 3, 2006
Table 3-21. Summary of Results for November 4, 2006
Table 3-22. Summary of Results for November 5, 2006
Table 3-23. Summary of Results for November 6, 2006
Table 3-24. Summary of Results for November 7, 2006
Table 3-25. Summary of Results for November 10, 2006
Table 3-26. Summary of Results for November 11, 2006
Table 3-27. Summary of Results for November 12, 2006
Table 4-1. Instrumentation Calibration Frequency and Description
Table 4-2. DQI Goals for the Project
Table 4-3. Low Path (Analyzer Ser. No. E-202)
Table 4-4. Middle Path (Analyzer Ser. No. E-700 )
Table 4-5. High Path (Analyzer Ser. No. E-466)
16
20
21
22
26
29
31
32
33
34
35
37
41
43
45
49
54
56
60
62
64
69
75
79
81
83
85
90
91
93
93
94
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Lists
List of Figures
Figure E-1. Summary of 24-hour extrapolated mercury emission values. viii
Figure 2-1. Example of a Vertical Radial Plume Mapping configuration setup. 7
Figure 2-2. Site plot of Occidental Chemical showing cell room, water tower, instrument
trailer, meteorological station and Vertical Radial Plume Mapping plane
locations. 11
Figure 2-3. Average wind rose data from 1961 -1990 for September and October from
HuntsvilleAL 12
Figure 2-4. Image of site showing Vertical Radial Plume Mapping configuration, Lumex
mercury analyzer sampling locations, cell room and cell room roof vents. 13
Figure 2-5. Side view of the Vertical Radial Plume Mapping configuration and locations
of the Lumex mercury analyzer and its sampling points. 14
Figure 3-1. Plot of calculated mercury flux values (grams/day) versus prevailing wind
direction, with respect to the plane of the Vertical Radial Plume Mapping
configuration, during the time of the measurements. 17
Figure 3-2. Time series of emission rate for September 21, 2006. 21
Figure 3-3. Example plume map for September 21, 2006. 25
Figure 3-4. Time series of emission rate for September 22, 2006. 25
Figure 3-5. Example plume map for September 22, 2006. 28
Figure 3-6. Time series of emission rate for October 11, 2006. 29
Figure 3-7. Example plume map for October 11, 2006. 30
Figure 3-8. Time series of emission rate for October 14, 2006. 30
Figure 3-9. Example plume map for October 14, 2006. 31
Figure3-10. Time series of emission rate for October 17, 2006. 32
Figure3-11. Time series of emission rate for October 18, 2006. 33
Figure 3-12. Example plume map for October 18, 2006. 34
Figure 3-13. Time series of emission rate for October, 20 2006. 35
Figure 3-14. Example plume map for October 20, 2006. 36
Figure3-15. Time series of emission rate for October 21, 2006. 36
Figure 3-16. Example plume map for October 21, 2006. 40
Figure3-17. Time series of emission rate for October 24, 2006. 41
Figure 3-18. Example plume map for October 24, 2006. 42
Figure3-19. Time series of emission rate for October 25, 2006. 42
Figure 3-20. Example plume map for October 25, 2006. 44
Figure 3-21. Time series of emission rate for October 26, 2006. 44
Figure 3-22. Example plume map for October 26, 2006. 48
VI
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Lists
Figure 3-23. Time series of emission rate for October 27, 2006. 49
Figure 3-24. Example plume map for October 27, 2006. 53
Figure 3-25. Time series of emission rate for October 30, 2006. 53
Figure 3-26. Example plume map for October 30, 2006. 55
Figure 3-27. Time series of emission rate for October 31, 2006. 56
Figure 3-28. Example plume map for October 31, 2006. 58
Figure 3-29. Time series of emission rate for November 1, 2006. 59
Figure 3-30. Example plume map for November 1, 2006. 61
Figure 3-31. Time series of emission rate for November 3, 2006. 61
Figure 3-32. Example plume map for November 3, 2006. 63
Figure 3-33. Time series of emission rate for November 4, 2006. 63
Figure 3-34. Example plume map for November 4, 2006. 68
Figure 3-35. Time series of emission rate for November 5, 2006. 68
Figure 3-36. Example plume map for November 5, 2006. 73
Figure 3-37. Time series of emission rate for November 6, 2006. 74
Figure 3-38. Example plume map for November 6, 2006. 78
Figure 3-39. Time series of emission rate for November 7, 2006. 78
Figure 3-40. Example plume map for November 7, 2006. 79
Figure 3-41. Time series of emission rate for November 10, 2006. 80
Figure 3-42. Example plume map for November 10, 2006. 82
Figure 3-43. Time series of emission rate for November 11, 2006. 83
Figure 3-44. Example plume map for November 11, 2006. 84
Figure 3-45. Time series of emission rate for November 12, 2006. 84
Figure 3-46. Example plume map for November 12, 2006. 85
Figure 3-47. Summary of 24-hour extrapolated mercury emission values. 87
Figure 4-1. Comparison of prevailing wind directions from September 21, 2006
measured with the Climatronics meteorological head and the National
Weather Service Automated Surface Observation System located at
Northwest Alabama Regional Airport. 97
Figure 4-2. Comparison of prevailing wind directions from September 22, 2006
measured with the Climatronics meteorological head and the National
Weather Service Automated Surface Observation System located at
Northwest Alabama Regional Airport. 97
Figure 4-3. Comparison of prevailing wind directions from September 30, 2006
measured with the Climatronics meteorological head and the National
Weather Service Automated Surface Observation System located at
Northwest Alabama Regional Airport. 98
VII
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Lists
Figure 4-4. Comparison of prevailing wind directions from October 8, 2006 measured
with the Climatronics meteorological head and the National Weather
Service Automated Surface Observation System located at Northwest
Alabama Regional Airport. 98
Figure 4-5. Comparison of prevailing wind directions from October 11, 2006 measured
with the Climatronics meteorological head and the National Weather
Service Automated Surface Observation System located at Northwest
Alabama Regional Airport. 100
Figure 4-6. Comparison of prevailing wind directions from October 14, 2006 measured
with the Climatronics meteorological head and the National Weather
Service Automated Surface Observation System located at Northwest
Alabama Regional Airport. 101
Figure 4-7. Comparison of prevailing wind directions from October 17, 2006 measured
with the Climatronics meteorological head and the National Weather
Service Automated Surface Observation System located at Northwest
Alabama Regional Airport. 101
Figure 4-8. Comparison of prevailing wind directions from October 18, 2006 measured
with the Climatronics meteorological head and the National Weather
Service Automated Surface Observation System located at Northwest
Alabama Regional Airport. 102
List of Appendices
A. OAQPS Project Plan:
Study of Gaseous Mercury Fugitive Emissions from Cell Rooms and Other Sources at
Mercury Cell Chlor-Alkali Plants (dated September 8, 2005)
B. EPA Memorandum and Response:
Findings from the Technical Systems Audit of Measurements of Total Site Mercury
Emissions from a Chlor-Alkali Plant using Ultraviolet Differential Optical Absorption
Spectroscopy
VIM
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Lists
List of Acronyms
APPCD
ASOS
CCF
DQI
ECPB
EPA
MACT
MCCAP
NESHAP
NIST
NRDC
NRMRL
OAQPS
ORD
ORS
OTM-10
PAC
PDC
PIC
PI-ORS
QA
QAPP
QC
RPM
RSD
ISA
UV-DOAS
VC
VRPM
Air Pollution Prevention and Control Division
Automated Surface Observation System
Concordance Correlation Factor
Data Quality Indicators
Emissions Characterization and Prevention Branch
Environmental Protection Agency
Maximum Achievable Control Technology
Mercury Cell Chlor-Alkali Plants
National Emission Standard for Hazardous Air Pollutants
National Institute of Standards and Technology
National Resources Defense Council
National Risk Management Research Laboratory
Office of Air Quality Planning and Standards
Office of Research and Development
Optical Remote Sensing
EPA Other Test Method-10
Path-Averaged Concentration
Path-Defining Component
Path Integrated Concentration
Path-Integrated Optical Remote Sensing
Quality Assurance
Quality Assurance Project Plan
Quality Control
Radial Plume Mapping
Relative Standard Deviation
Sum of Squared Errors
Technical Systems Audit
Ultraviolet Differential Absorption Spectroscopy
Vertical Capture Criteria
Vertical Radial Plume Mapping
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Executive Summary
Executive Summary
This test report addresses the ARCADIS portion of the overall OAQPS Project Plan
entitled, Study of Mercury Fugitive Emissions from Cell Rooms and Other Sources at
Mercury Cell Chlor-Alkali Plants, dated September 8, 2005 (Appendix A). The OAQPS
project reflects EPA's efforts to obtain additional information regarding fugitive mercury
emissions from mercury cell chlor-alkali plants in response to issues raised by the
Natural Resources Defense Council (NRDC) on 02/07/04 in its petition for
reconsideration of the MACT rule for mercury cell chlor-alkali facilities promulgated on
12/19/03 (68FR70904). Presented in this report are total site mercury emissions data
acquired at Occidental Chemical's Muscle Shoals, Alabama chlor-alkali plant from
September 21, 2006 through November 12, 2006. The mercury emission data
presented here will be used by OAQPS to determine if the fugitive cell room elemental
mercury emissions are on the order of historical assumptions (1,300 g/day) or on the
order of 2002 levels of unaccounted for mercury (approximately 10,000 g/day). This
work was performed by ARCADIS U.S., Inc. (ARCADIS), under contract to the National
Risk Management Research Laboratory (NRMRL) of EPA's Office of Research and
Development (ORD). The report is limited to presentation of data associated with the
measurements conducted by ARCADIS/NRMRL during this campaign. Synthesis of
data from other sources separately acquired, analysis of maintenance activities, and
comparisons of emissions to historical results will be conducted by OAQPS as part of
the overall project summary.
To accomplish the goal of total site elemental mercury emission measurement, the
monitoring systems were set up outside and downwind of the cell room building, as
well as downwind of all ancillary processes both inside and outside the cell room
building. Potential sources of emissions include: cell room sources (stacks, roof
ventilation systems, and building leaks); leaks of mercury-contaminated brine in the
brine treatment area; the wastewater system; the handling and storage of mercury
contaminated wastes; and process vent stacks. OAQPS will also use the results here
along with separate cell room and point source mercury emissions data for the same
time period to estimate whether there are significant fugitive mercury sources outside
the cell room.
The measurement approach used a Vertical Radial Plume Mapping (VRPM)
measurement configuration employing three open-path ultraviolet differential optical
absorption spectroscopy (UV-DOAS) instruments for elemental mercury concentration
measurements, in conjunction with multipoint ground level mercury measurements with
a Lumex mercury analyzer. The measurement systems operated on a 24-hour, 7-day
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Executive Summary
per week basis for the 53 day campaign. Full details on the measurement campaign
are contained in the EPA quality assurance project plan entitled, Measurement of Total
Site Mercury Emissions from a Chlor-alkali Plant Using Open-Path UV-DOAS (rev. 0.3
September, 2006).
The 3-beam VRPM configuration used to estimate elemental mercury emissions from
the facility was located at a fixed position and fixed orientation on site for the duration
of the project. Calculations of mercury flux through the VRPM plane were conducted
only when specific data quality indicators involving wind speed, wind direction, path
averaged concentration ratios and instrument operation were met. Out of the 53 day
deployment, VRPM mercury flux values were calculated for 23 days of the
measurement campaign. Data is presented as 20 minute moving averages consisting
of a sequential collection of 4 minute measurement cycles. A total of 1170 mercury
emission flux estimates were produced for 20 minute time periods. The 24 hour
extrapolated mercury emission rate values ranged from 18 to 1210 grams per day, with
an average of 410 grams per day. The extrapolated emission rate is summarized in
the figure below. Overall measurement uncertainty is estimated to be within +/-20%
which is sufficient to meet the order of magnitude data quality objective for this project.
70
1200
'WOO
Extrapolated Hg Emissions (g/ttay)
Figure E-1. Summary of 24-hour extrapolated fugitive mercury site emission values
(by VRPM).
XI
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1. Introduction
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
1.1 Background
In December 2003, the EPA promulgated the National Emission Standard for
Hazardous Air Pollutants (NESHAP) for mercury cell chlor-alkali plants (40 CFR 63
Subpart Mill) (Federal Register Summary: 68 FR 70903, Federal Register Vol. 68 No.
244, Friday, December 19, 2003; Pp. 70903-70946 Regulation: 40 CFR Part 63).
In February 2004, the Natural Resources Defense Council (NRDC) filed petitions on
the final rule in U.S. district court citing among other issues, uncertainty associated with
EPA fugitive mercury emission estimates and the inability of mercury cell industry to
fully account for mercury added to their processes to make up for losses via wastes,
product and emissions.
For example, according to the EPA's 2002 Toxic Release Inventory, approximately 7
Mg of mercury was released by the nine operating mercury cell chlor-alkali plants
(MCCAPs) in the U.S. Approximately 4.5 Mg was estimated to be air emissions with
89% (4 Mg) assumed to be fugitive emissions (non-stack emissions). Industry
estimates indicate that approximately 33 Mg of Hg was "used" by the operating plants
indicating that 25.5 Mg was unaccounted for. NRDC and other interested parties
maintain that the majority of unaccounted for Hg must be lost through fugitive
emissions and that recognition of this fact would have affected decisions made in
developing and promulgating the Mercury Cell MACT rule.
In April 2004, EPA agreed to reconsider aspects of the rulemaking which led to
planning and execution of emission measurement projects designed to reduce
uncertainty in fugitive emissions of Hg from MCCAPs. An OAQPS project plan
describing these measurement efforts along, with additional history of this topic and
physical descriptions of the mercury cell chlor-alkali process, is contained in Appendix
A: Study of Mercury Fugitive Emissions from Cell Rooms and Other Sources at
Mercury Cell Chlor-Alkali Plants, dated September 8, 2005, prepared for OAQPS,
Sector Policies and Programs Division by EC/R (ECR) Incorporated.
As an overall project goal, OAQPS will use the total site mercury emission data
presented in this report, in conjunction with cell room vent monitoring, stack emission,
and maintenance activity data from this and other facilities acquired by OAQPS under
other parts of the Project Plan, to determine if the elemental mercury cell room fugitive
emissions from the observed facilities are on the order of historical assumptions (1,300
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
g/day) or on the order of 2002 levels of unaccounted for mercury (approximately
10,000 g/day). This test report only addresses the ARCADIS/NRMRL subproject area
of the OAQPS plan presenting site elemental mercury emission data from the
Occidental Chemical's Muscle Shoals facility acquired during a continuous monitoring
campaign from September 21, 2006 to November 12, 2006 using an ORS/VRPM
measurement configuration.
As part of the overall OAQPS project, Occidental Chemical was responsible for
documenting plant process and maintenance activities that occurred during the
sampling period. This information included production levels, waste-handling activities,
thermal mercury recovery activity, maintenance activities, and housekeeping activities.
Records of any major malfunctions or other circumstances that resulted in large
mercury emission episodes were also maintained by Occidental Chemical and
provided to OAQPS. The purpose of the ARCADIS/NRMRL total site mercury
emissions monitoring and the Occidental Chemical recordkeeping is to allow OAQPS
to draw correlations between these activities and short-term mercury emission rates.
OAQPS will use this information, in concert with the stack monitoring and point source
data (from the cell room monitored roof ventilation systems) provided by others, to
determine the order of magnitude of the unaccounted mercury air emissions.
In addition to the cell room, there is the possibility that fugitive mercury emissions could
occur from sources outside the cell rooms. The ARCADIS/NRMRL test in Muscle
Shoals, Alabama, was a short-term measurement study designed to estimate the total
elemental mercury emission from the site. These data will be used by OAQPS in
combination with cell room roof vent monitoring data to determine if sources outside
the cell room could be significant sources of fugitive mercury emissions for this plant.
To accomplish the goal of total site elemental mercury emission measurement, the
monitoring systems were set up outside and downwind of the of the cell room building,
as well as downwind of all ancillary processes both inside and outside the cell room
building. OAQPS will use these results along with the cell room and point source
mercury emissions data for the same time period to estimate whether there are
significant fugitive mercury sources outside the cell room.
After all the test programs and monitoring data collection activities are complete,
OAQPS will analyze the information obtained to determine if an improvement can be
made to the previous estimation of fugitive mercury emissions for the industry. EPA will
then consider this estimation in the reconsideration of the MACT rule, as requested by
NRDC's petition. As relevant, EPA will publish a notice in the Federal Register
summarizing any plans for changes to the current MACT rule.
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Additional information on the subproject area addressed in this test report can be found
in the EPA ORD Quality Assurance Project Plan, Measurement of Total Site Mercury
Emissions from a Chlor-alkali Plant Using Open-Path UV-DOAS, Rev. 0.3, September
2006.
1.2 Project Description
To estimate the total site elemental mercury emissions from the Occidental Chemical
Muscle Shoals, Alabama plant, two measurement systems were deployed on site
downwind from the cell room and other potential mercury sources. The primary
measurement system, described in Section 2.1, consists of an Optical Remote
Sensing/Vertical Radial Plume Mapping (ORS/VRPM) flux measurement configuration
utilizing Ultraviolet Differential Optical Absorption spectroscopy (UV-DOAS)
instruments for path-integrated elemental mercury concentration measurements. The
ORS/VRPM data were augmented by a multi-point ground level elemental mercury
point monitor measurement system described in Section 2.2. Together these data
provide an estimate of total site mercury emission from the facility of sufficient certainty
to meet the data quality objective for the project.
The field study was seven weeks (53 days) in duration, conducted from September 21,
2006 through November 12, 2006. Although the original schedule was for a six-week
study, instrumentation problems encountered with the Climatronics meteorological
head (discussed in detail in Section 3.2.3) and unfavorable wind conditions during the
initial weeks of the campaign resulted in the 11 day extension. Forthis project,
ARCADIS was responsible for collecting and analyzing all data. Gary Secrest of EPA's
Office of Enforcement and Compliance Assurance supported the measurement
campaign by operating the UV-DOAS instrumentation.
The sampling configuration for this study was placed so as to maximize the capture of
mercury emissions from the site. Potential sources of these total emissions could
include: cell room sources (stacks, roof ventilation systems, and building leaks); leaks
of mercury-contaminated brine in the brine treatment area; the wastewater system; the
handling and storage of mercury contaminated wastes; and process vent stacks.
The following data was collected on a 24-hour, 7-day per week basis as part of the
measurement campaign:
• Path-averaged concentration (PAC) of elemental mercury using the three
independent UV-DOAS instruments arranged in vertical VRPM flux plane.
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
• Ground level elemental mercury point monitoring using the Lumex Mercury
Analyzer.
• Meteorological data
These data were combined as detailed in Section 3 to yield average elemental mercury
emission flux estimates for 20 minute time periods throughout the study. Flux emission
estimates were calculated only for those time periods which met specific data
acceptance criteria discussed in Section 3 and the quality assurance project plan.
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2. Description of Measurement Methods and Site Deployment
The following section describes the measurement methods, site deployment, and
calculations used to obtain elemental mercury flux information from the acquired data.
Section 2.1 describes the ORS/VRPM method used to assess mass emission flux of
elemental mercury from the site. Section 2.2 describes the multipoint Lumex
measurement providing ground level mercury data in the area under the VRPM flux
plane. Section 2.3 describes the site deployment, the emission flux measurement
calculation and averaging periods are described in Section 3.
2.1 Vertical Radial Plume Mapping Method
The ORS/VRPM method was the primary means used to estimate mercury emission
from the site. The Radial Plume Mapping method (RPM) was developed at the
University of Washington in the mid-1990s. The method uses positional scanning or
multiple single-beam ORS instruments to collect path-integrated concentration data
along multiple beam paths in the configuration deployed in the survey area. The beam
paths can be configured in a horizontal plane (Horizontal Radial Plume Mapping) to
produce surface concentration contour maps, or, as used in this project, in a vertical
plane deployed downwind of the survey area (Vertical Radial Plume Mapping) to map
the downwind plume from the site. By including meteorological data collected
concurrently with the ORS measurements, the Vertical Radial Plume Mapping (VRPM)
method can be used to calculate the downwind emission flux from the site. This leads
to a direct, measurement-based estimate of the emission rate from the survey area. A
more detailed discussion of the RPM methodology and of the VRPM configuration can
be found in EPA's Other Test Method 10 (OTM-10) entitled, "Optical Remote Sensing
for Emission Characterization from Non-point Sources" and can be found on EPA's
website at www.epa.gov/ttn/emc/tmethods.html.
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Two different beam configurations of the VRPM methodology are recommended: the
five-beam (or more) and the three-beam VRPM configuration. The three-beam
configuration is used to provide flux calculations downwind of an area source, but does
not provide crosswind spatial information on the plume. This configuration is typically
used downwind of area sources that are suspected to be homogenous in nature and
the collection of spatial information is not necessary or desired. For this project, the
three-beam configuration provided adequate spatial coverage for measuring the total
site mercury emissions.
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Figure 2-1 illustrates the setup for the three-beam VRPM configuration. In the three-
beam configuration, the PI-ORS instrument would typically scan over the three PDCs
(pathlength-defining components) sequentially. However, for this project which utilized
three independent UV-DOAS instruments, the data were collected simultaneously
along each optical path. The UV-DOAS systems used for this study were bistatic in
configuration having separate transmitters (UV light sources) and receivers. The
transmitters were mounted on a water tower present on site (shown as PDCs in Figure
2-1), and the UV-DOAS receivers were placed together, indicated as the PI-ORS
Instrument in Figure 2-1. The lowest beam of the VRPM configuration is usually at
ground level. Due to site constraints, an elevated VRPM plane was utilized for this
project. The UV-DOAS receivers were mounted to specially constructed concrete piers
at a height of approximately 3 m above ground level. The lowest transmitter on the
water tower was mounted at 18 m above ground level making the average height of
the lowest beam at approximately 10 m above the ground. This will be discussed
further in subsequent sections.
The VRPM computer algorithm uses a smooth basis function minimization routine of a
bivarate Gaussian function to generate mass emission flux information from species
concentration and wind data. To derive the bivariate Gaussian function, it is
convenient to express the generic bivariate function G in polar coordinates r and 9:
G(r,0)=-
A
(r-cos0-my)2 2ft2(r-cosd-my^r-smd-
(1)
The bivariate Gaussian has six unknown independent parameters:
A = normalizing coefficient which adjusts for the peak value of the
bivariate surface;
Pi2 = correlation coefficient which defines the direction of the distribution-
independent variations in relation to the Cartesian directions y and z
(Pf2=0 means that the distribution variations overlap the Cartesian
coordinates);
my and mz = peak locations in Cartesian coordinates; and
a, and a, = standard deviations in Cartesian coordinates.
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
PI-ORS
Instrument
Figure 2-1. Example of a Vertical Radial Plume Mapping configuration setup.
Six independent beam paths are sufficient to determine one bivariate Gaussian that
has six independent unknown parameters. Some reasonable assumptions are made
when applying the VRPM methodology to this problem, to reduce the number of
unknown parameters. The first is setting the correlation parameter p12 equal to zero.
This assumes that the reconstructed bivariate Gaussian is limited only to changes in
the vertical and crosswind directions. In this case, Equation 1 reduces into Equation 2:
G(r,0) =
(r-cos0-my)2 (r-sind-mz)2
(2)
-------
When the VRPM configuration consists only of three beam paths, the width of the
plume can be arbitrarily assigned to be very wide, compared to the longest beam path.
Therefore, the three-beam VRPM configuration is most suitable for area sources or for
sources with a series of point and fugitive sources that are known to be distributed
across the upwind area. The standard deviation in the crosswind direction is typically
assumed to be about four times that of the ground level beam path (length of vertical
plane). If r-, represents the length of the vertical plane, the bivariate Gaussian would be
as follows:
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
G(A,crz,mz) =
(r •
(3)
A, mz, and crzare the unknown parameters to be retrieved in this case of the fitting
procedure. An error function (SSE) for minimization is defined for this phase in a similar
manner. The SSE function for the second phase is defined as:
(4)
Where PAC, is the measured PAC value for the / beam. The SSE function is
minimized using the Simplex method to solve for the three unknown parameters.
This process is for determining the vertical gradient in concentration. It allows an
accurate integration of concentrations across the vertical plane as the long-beam
ground-level PAC provides a direct integration of concentration at the lowest level.
Once the parameters of the function are found for a specific run, the VRPM procedure
calculates the concentration values for every square elementary unit in a vertical plane.
Then, the VRPM procedure integrates the values, incorporating wind speed data at
each height level to compute the flux. This enables the direct calculation of the flux in
grams per day (g/day), using wind speed data in meters per second (m/s).
As described in earlier studies (Hashmonay et al., 2001), the concordance correlation
factor (CCF) was used to represent the level of fit for the reconstruction in the path-
integrated domain (predicted versus measured PAC). CCF is defined as the product of
two components:
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
CCF = rA (5)
Where:
r = the Pearson correlation coefficient;
A = a correction factor for the shift in population and location.
This shift is a function of the relationship between the averages and standard
deviations of the measured and predicted PAC vectors:
~"
°
PAC*
PAC-pAC
Where:
0.90). However, when both rand A are low one can
assume that the flux calculation is inaccurate.
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
2.2 Ground-level Point Sampling
To augment data acquired with the ORS/VRPM technique, elemental mercury
concentration measurements were made in areas underneath of the VRPM flux plane.
The purpose of these measurements was to establish approximate ground level
concentrations coincident with the VRPM flux measurements to understand if
significant amounts of mercury emissions were present underneath the VRPM flux
plane that may not be accounted for by the VRPM measurement. This was necessary
since the VRPM flux plane was elevated for this study and because of the complex
ground level air flow caused by the numerous obstructions below the VRPM plane. To
estimate the ground level mercury concentration under the VRPM plane, a Lumex
mercury analyzer (model RA-915+) was deployed downwind from the cell room, with
three sampling tubes deployed outward from the analyzer. The sampling tubes which,
were approximately 15 m apart and 4 m above ground level (detailed in Section 2.3),
delivered a combined sample to the Lumex analyzer establishing an estimate of
average elemental mercury concentration for a 7 m high by 45 m long area underneath
the VRPM plane. These data were used in conjunction with free flowing wind speed
projections to establish an estimate of uncertainty in the elevated VRPM measurement.
Additional information on the ground-level point sampling configuration can be found in
the EPA ORD Quality Assurance Project Plan, Measurement of Total Site Mercury
Emissions from a Chlor-alkali Plant Using Open-Path UV-DOAS, Rev. 0.3, September
2006.
2.3 Site Deployment Description
Figure 2-2 is a site plot showing the locations of the cell room, the water tower
supporting UV-DOAS transmitters, the instrument trailer containing the OPSIS
analyzers and communication equipment, and the approximate location of the
meteorological (met.) station in an open field. The optical beam paths of the VRPM
plane are indicated by the gold-colored arrow from the instrument trailer to the water
tower. The position of the VRPM plane was chosen to maximize the total capture of
fugitive mercury from the site taking into account potential source locations, prevailing
wind directions and site constraints.
10
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Met Statin
Figure 2-2. Site plot of Occidental Chemical showing cell room, water tower,
instrument trailer, meteorological station and Vertical Radial Plume
Mapping plane locations.
As part of communications with OAQPS, Occidental Chemical identified four known
mercury-emitting sources/discharge points. These included the cell room roof vents
and several sources outside the cell room building adjoining its West wall and in the
areas in close proximity to the cell room just to West and South West of the building.
These sources included: an emergency low-pressure vent stack for the hydrogen
compression process, the high pressure hydrogen system vent stack, and the retort
vent stack. Additionally the caustic filter operation is attached to the West wall of the
cell room building and the brine operations are located just to the south of the cell room
building. All of these potential sources were located to the southeast of the VRPM
Plane. Since the regional prevailing wind directions were predominately from the
southeast during September and October (Figure 2-3), the VRPM configuration was
positioned downwind of the potential source with an orientation approximately normal
to the expected prevailing wind directions for the study.
11
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
West
I
September
North
South
East
West
October
North
South
Figure 2-3. Average wind rose data from 1961-1990 for September and October from
Huntsville, AL.
Figure 2-4 shows an overhead image of the facility showing the location of the VRPM
plane and the Lumex mercury analyzer sampling points. Also shown are the
approximate locations of the cell room roof vents which consisted of two rows of
induced draft fans (65 fans total). The Lumex analyzer was located in a temperature
controlled enclosure that was placed inside of an air-conditioned mechanical room
located close to the central sampling location shown in Figure 2-4. The Lumex
analyzer sampled from a combined air stream of the three sampling points which were
separated by approximately 15 m. The tubing used for the sampling was 25 m lengths
of % inch i.d. Teflon and was attached to an overhead pipe rack to allow suspension of
the sampling inlets at 4 m above ground level. A three-way Teflon splitter was used to
combine the sampling tubes. A heated head Teflon coated pre-sampling pump
supplied the combined sample to the Lumex analyzer.
12
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Figure 2-4. Image of site showing Vertical Radial Plume Mapping configuration,
Lumex mercury analyzer sampling locations, cell room and cell room roof
vents.
For the VRPM configuration, the three UV-DOAS sources (transmitters) were mounted
at heights of 18, 28, and 37 meters on the water tower. This resulted in optical
pathlengths of 217, 218, and 219 meters from source to receiver. The UV-DOAS
receivers were mounted at a height of 3 meters. Accounting for that offset, the source
heights in relationship to the receivers were therefore 15, 25, and 34 meters. The
Climatronics/R.M. Young meteorological heads were deployed at a height of
approximately 12 meters. Figure 2-5 shows an illustrative side view of the VRPM
configuration, showing the locations of the three UV-DOAS bistatic sources and the
approximate positions of the Lumex analyzer sampling locations.
13
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Water Tower
T 53 m
Bistatic UV-DOAS
Sources (3)
Lumex analyzer (center)
and sampling points
Figure 2-5. Side view of the Vertical Radial Plume Mapping configuration and
locations of the Lumex mercury analyzer and its sampling points.
14
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
3. Results and Discussion
3.1 Data Averaging and Calculation Description
The individual instruments used in this study had measurement averaging times of
either 30 seconds (meteorological instruments and Lumex) or 1-minute (UV-DOAS).
Since the instrument measurement times were not fully synchronized, a 4-minute base
averaging period forthe data from each instrument was established. The 4-minute
base averaging period parameters were then used in a 20-minute moving average.
Each flux calculation presented consists of a group average of five consecutive 4-
minute base periods resulting in an emission flux estimate for a 20-minute time interval,
reported at its temporal midpoint. The fundamental units of emission flux produced by
the VRPM method are grams per second. For presentation in this test report, each
average mercury emission flux value was extrapolated to represent a 24 hour time
period by converting from units of grams per second to grams per day. This was
accomplished by multiplying each flux result by a factor of 86,400.
For this project, the VRPM flux plane extended from 5 m above ground level to the top
boundary of the integration plane, defined as the point where the extrapolated
concentration values (in the vertical direction) go to zero. This height was determined
when the data was processed in the VRPM algorithm. As discussed previously, the
VRPM data was augmented with data acquired by the Lumex analyzer sampling below
the VRPM plane. Using the same averaging sequence described above, an
approximate maximum flux through the Lumex plane was calculated by multiplying the
area represented by the plane (7m height by 45 m length) by the average
concentration measured by the Lumex and by the free-flowing wind vector projections
on to the Lumex plane which was defined to be parallel to the VRPM plane. The free-
flowing wind vector was used since characterization of wind movement in the area of
the Lumex plane was known to be complex due to nearby structures, but would be
spanned by the magnitude of the free flowing wind projection (positive and negative)
when considering flux through the Lumex plane. The Lumex data are represented by
the error bars in the presented data with the high value indicating flux through the plane
in the same direction as the calculated VRPM flux and low values indicating a potential
negative flow through the Lumex plane.
Total mercury flux was calculated when (1) the horizontal plume capture criteria and
UV-DOAS and Lumex Mercury Analyzer Data Quality Indicators (DQIs) were met; and
(2) the vertical capture criteria were met. When these criteria were met, all total flux
calculations are reported, including the emissions leakage through the bottom 5-meters
15
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
of the vertical plane based on flux values calculated using data collected with the
Lumex Mercury Analyzer.
3.1.1 Acceptable Data Criteria and Emission Flux Correction Factors
Only data which met all of the following criteria were deemed acceptable and included
in the data presented in Sections 3.2.1 (the Climatronics data) and 3.2.2 (the R.M.
Young data):
1. Prevailing wind speed >1 m/s. Table 3-1 shows a summary of the wind rose data
where the wind speed was less than 1 m/s. Mercury concentration data collected
during periods that the prevailing wind speed was < 1 m/s were excluded from the
presented data.
Table 3-1. Data Deemed Unacceptable Based on Wind Rose Data
Total Measurement Campaign
(21 September through 12 November 2006)
Wind
Direction
N
NE
E
SE
S
sw
w
NW
Percent of Winds
from each Direction
16.20%
7.40%
2.50%
10.40%
3.20%
5.90%
32.00%
22.60%
Wind Speed
(m/s)
0.2
0.5
0.5
0.6
0.4
0.5
0.4
0.5
BOLD values indicate wind data that meet the ±60% horizontal wind criteria.
2. Horizontal plume capture: ±60°.
Mercury flux values were calculated only during periods when the prevailing wind
direction was within ± 60° to perpendicular to the plane of the VRPM configuration.
The mercury flux values calculated during these periods are presented as
"Unadjusted Flux Values" in the summary tables presented later in the document. In
orderto provide an assessment of the horizontal plume capture by the VRPM
configuration, the project team analyzed the calculated mercury flux values and
16
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
prevailing wind direction, with respect to the orientation of the VRPM configuration
plane, at the time of the measurements. The assessment was done by plotting the
calculated mercury flux values as a function of prevailing wind direction (see Figure
3-1).
A linear fit of the data was performed for prevailing winds from 0° to -60°, and 0° to
60°. The resulting linear regression equations (shown in Figure 3-1) were then
used to calculate a mercury flux value adjusted for the prevailing wind direction
during the time of the measurements. The adjusted values are presented as
"Adjusted Emission Rates" in the summary tables presented later in the document
y =-6.4112x+408.25
R2 = 0.7568
X
3
y = 4.2833X + 406.65
R2 = 0.6235
-60 -40 -20 0 20 40 60
Prevailing Wind Direction From Perpendicular to VRPM Configuration
80
Figure 3-1. Plot of calculated mercury flux values (grams/day) versus prevailing wind
direction, with respect to the plane of the Vertical Radial Plume Mapping
configuration, during the time of the measurements.
17
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
3. Vertical capture criteria (refer to Figure 2-1).
beam 2 cone. - beam 3 cone. ^ ,
70% plume capture by VRPM configuration = > 0.1
beam 2 cone.
This was the optimum beam capture, and this data is color coded blue in the time
series of emission rate graphs and in the summary data tables.
.. beam 2 cone.-beam 3 cone. n.
60% plume capture by VRPM configuration: 0 > > 0.1
beam 2 cone.
Although this data does not meet the original 70% capture goal, the majority of the
plume is still being captured by the configuration. Therefore, this data is included below
and is color coded orange in the time series of emission rate graphs and in the
summary data tables.
The assessment of the vertical plume capture is done by comparing the path-averaged
mercury concentration (PAC) data measured along the upper two beam paths of the
VRPM configuration, averaged over a 20-minute interval. If the 20-minute average PAC
measured along the uppermost beam path is not at least 10 percent lower than the
PAC measured along the next lowest beam path, this indicates that the VRPM
configuration did not provide an adequate vertical capture of the plume, and data from
this particular 20-minute time period was not used for the flux calculation.
4. The CCF must be > 0.80.
As mentioned earlier in the document, the concordance correlation factor (CCF) is
used in the VRPM method to represent the level of fit for the reconstruction in the path-
integrated domain (predicted versus measured PAC).
Although a poor CCF value (CCF < 0.80) at the end of the fitting procedure does not
necessarily indicate an inaccurate flux calculation, for the purposes of this project,
mercury flux values are reported only when the corresponding CCF value of the
reconstruction is greater than 0.80.
18
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
3.2 Data Graphs and Tables
This section presents results form the test campaign. Section 3.2.1 presents data
acquired from the first 3 weeks of the project. During this time, a Climatronics
meteorological station was employed to collect wind data. Section 3.2.2 presents data
from the last 4 weeks of the project which utilized an R.M. Young meteorological
station. For each day of sampling, a times series graph of extrapolated emission rates,
a summary of results table, and an example plume map are presented. Each data
point represents a moving 20-minute average to a 24-hour time basis with the error
bars representing the Lumex plane value previously described. The graphically
represented data are the "adjusted" values. For each reported average, the following
information will be provided: Lumex data, wind speed, wind direction, concordance
correlation factors (used to represent the level of fit for the reconstruction in the path-
integrated domain, i.e., predicted versus measured path-averaged concentration), the
calculated mercury flux values, and the mercury emission rates.
For each of the 53 days of sampling, when all quality control criteria were met, the
following data will be presented:
• A graph showing a time series of mercury emission rates,
• An example mercury plume map, and
• A summary table of results including the following for data for the reported
average: ground-level flux value based on data from the Lumex mercury analyzer,
wind speed, wind direction, CCF (used to represent the level of fit for the
reconstruction in the path-integrated domain, i.e., predicted versus measured
PAC), the flux values (actual flux values calculated during periods that the
prevailing wind direction was from -60° to +60° from perpendicular to the VRPM
configuration, but not adjusted for the angle of the prevailing wind direction), and
the emission rates (flux values adjusted forthe angle of the prevailing wind
direction).
3.2.1 Climatronics Meteorological Data
Although the Climatronics monitor had been calibrated prior to field deployment, and
had passed the QC checks in the field, some questionable readings were noted during
the initial weeks of the measurement campaign. Because of concerns forthe reliability
of the data being produced by this instrument, it was replaced with the R.M. Young
19
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
monitor on 19 October 2006. Table 3-2 shows that the amount of data acquired with
the Climatronics was relatively small in comparison to data acquired with the R.M.
Young, since wind directions were not favorable during the early part of the study.
Since OAQPS requested data reporting to be as complete as possible for this project,
the emission flux data taken using corrected values of Climatronics data are included in
this report. Assessment descriptions for the Climatronics operation and offset
determinations are described subsequently and in Section 4.
Table 3-2. Wind Rose Data for Climatronics Monitor
Total Measurement Campaign
(September 21 through November 12, 2006)
Wind
Direction
N
NE
E
SE
S
sw
w
NW
Percent of Winds
from each
Direction
19.10%
12.80%
3.60%
16.60%
4.20%
5.00%
17.40%
21 .30%
Wind
Speed
(mis)
1.9
2
1.7
1.6
1.6
1.3
1.1
1.5
Climatronics Data
(September 21 through October 18, 2006)
Wind
Direction
N
NE
E
SE
S
SW
w
NW
Percent of Winds
from each
Direction
24.30%
19.90%
1.50%
3.50%
1.00%
1 .00%
24.70%
24.00%
Wind
Speed
(mis)
1.9
2
1.7
1.6
1.6
1.3
1.1
1.5
BOLD values indicate wind data that meet the ±60% wind criteria.
In order to assess the reliability of the Climatronics wind speed and wind direction data,
the data were compared with National Weather Service data obtained from the
Automated Surface Observation System (ASOS) at the Northwest Alabama Regional
Airport, located approximately two miles from the project site. Based on two minute
wind averages, there were four days in which the directional trends matched, but
where the wind direction data were offset by a consistent factor. Those days and the
correction factors applied are shown in Table 3-3. All other wind direction data and all
wind speed data produced by the Climatronics monitor were found to be acceptable.
More information on the procedure used to determine the wind direction correction
factors presented in Table 3-3 can be found in Section 4.2.3 of this document.
20
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Table 3-3. Correction Factors Applied to Four Days of Climatronics Data
Date
September 21, 2006
September 22, 2006
September 30, 2006
October 8, 2006
Directional Correction Factor
Applied
110°
110°
100°
60°
Figures 3-2 through 3-46 and Tables 3-4 through 3-27 present time series graphs of
extrapolated emission rates, a summary of results table, and an example plume map
for each day of sampling.
09/21/06
1200
1000 -
800 -
•8
a
600 -
400 -
200
3:36 PM 4:48 PM
6:00 PM 7:12 PM 8:24 PM
Time
9:36 PM
10:48 PM
12:00 AM
Figure 3-2. Time series of emission rate for September 21, 2006.
21
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Table 3-4. Summary of Results for September 21, 2006
Time
4:02 PM
4:06 PM
4:10 PM
4:14 PM
4:18 PM
4:22 PM
4:26 PM
4:30 PM
4:34 PM
4:38 PM
4:42 PM
4:46 PM
4:50 PM
4:54 PM
4:58 PM
5:02 PM
5:06 PM
5:10 PM
5:14 PM
5:18 PM
5:22 PM
5:26 PM
5:50 PM
5:54 PM
5:58 PM
6:02 PM
6:06 PM
6:10 PM
6:14 PM
6:18 PM
6:22 PM
6:26 PM
6:30 PM
Lumex
Flux
Value
[g/day]
0
0
0
0
0
0
0
0
0
0
-1
5
11
18
24
31
30
28
29
32
35
38
54
53
55
55
54
54
55
50
49
42
42
Wind
Speed
[m/s]
2.9
2.8
2.8
2.8
2.7
2.6
2.7
2.8
2.9
3
3.2
3.1
3.2
3.2
3.2
3.1
3
2.8
2.7
2.8
2.8
3.1
2.8
2.7
2.6
2.5
2.3
2.2
2.1
1.9
1.9
1.8
1.9
Wind
Direction
[deg from
normal to
VRPM
config.]
34
28
29
25
24
28
32
30
32
32
28
24
25
25
26
29
30
28
25
21
16
14
10
7
7
6
7
4
5
7
6
8
10
Concordance
Correlation
Factor
0.964
0.984
0.997
0.995
1
1
1
1
1
0.999
1
0.954
0.982
0.988
0.994
0.991
0.988
0.982
0.99
0.998
0.995
0.996
1
1
1
1
1
1
1
1
1
1
1
Unadjusted
Flux Values
[g/day]
384
326
339
245
147
126
329
299
360
402
451
254
275
235
208
200
230
234
268
281
273
261
386
466
481
425
420
469
482
460
475
452
454
Adjusted
Emission
Rate
[g/day]
824
586
624
408
238
224
667
568
719
795
798
407
455
386
347
370
439
413
444
420
364
337
460
523
537
466
472
503
525
520
528
515
541
22
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
6:34 PM
6:38 PM
6:42 PM
6:46 PM
6:50 PM
6:54 PM
6:58 PM
7:02 PM
7:30 PM
7:34 PM
7:58 PM
8:02 PM
8:06 PM
8:10 PM
8:14 PM
8:18 PM
8:22 PM
8:26 PM
8:30 PM
8:54 PM
8:58 PM
9:02 PM
9:06 PM
9:10 PM
9:14 PM
9:18 PM
9:22 PM
9:26 PM
9:30 PM
9:34 PM
9:38 PM
9:42 PM
9:46 PM
9:50 PM
9:54 PM
Lumex
Flux
Value
[g/day]
42
43
42
41
39
32
29
25
36
30
36
32
35
43
46
47
49
49
47
52
52
50
49
48
49
48
44
40
38
36
36
41
41
39
36
Wind
Speed
[m/s]
1.9
2
2
1.9
1.9
1.7
1.6
1.4
1.5
1.3
1.6
1.5
1.6
1.9
2
2
2.1
2.1
2
2.2
2.3
2.4
2.5
2.4
2.4
2.4
2.4
2.3
2.2
2.2
2.2
2.2
2.1
2
1.9
Wind
Direction
[deg from
normal to
VRPM
config.]
13
11
12
12
13
11
11
11
0
3
-5
3
11
11
11
11
12
12
12
8
10
13
11
9
11
10
9
10
10
8
9
8
7
8
7
Concordance
Correlation
Factor
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0.997
1
1
1
1
1
1
1
1
1
1
1
1
Unadjusted
Flux Values
[g/day]
441
477
512
490
547
561
547
502
510
435
502
403
363
384
384
368
387
376
353
335
309
318
323
317
287
296
305
307
292
285
308
324
333
325
333
Adjusted
Emission
Rate
[g/day]
549
576
631
601
687
676
662
610
515
454
537
423
435
462
461
444
472
466
435
381
366
396
393
370
343
350
354
361
343
329
359
369
373
371
377
23
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
9:58 PM
10:02PM
10:06PM
10:10 PM
10:14 PM
10:18 PM
10:22PM
10:26PM
10:30 PM
10:34PM
10:38 PM
10:42PM
10:46PM
10:50 PM
10:54PM
10:58 PM
11:02PM
11:06PM
11:10PM
11:14PM
11:18PM
11:22PM
11:26PM
11:30PM
11:34PM
11:38PM
11:42PM
11:46PM
11:50PM
Lumex
Flux
Value
[g/day]
34
33
32
31
34
36
39
42
40
41
41
43
40
42
46
49
51
51
51
47
42
45
53
58
62
65
54
49
44
Wind
Speed
[m/s]
1.8
1.9
1.9
1.9
2
2.1
2.2
2.3
2.2
2.3
2.3
2.3
2.1
2.2
2.2
2.2
2.3
2.4
2.5
2.5
2.6
2.8
3.1
3.2
3.2
3.2
2.9
2.7
2.4
Wind
Direction
[deg from
normal to
VRPM
config.]
5
7
8
7
7
7
7
6
5
5
6
4
4
3
1
0
0
1
3
4
5
3
1
2
2
0
3
5
4
Concordance
Correlation
Factor
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0.999
0.999
1
1
1
Unadjusted
Flux Values
[g/day]
329
325
280
282
286
288
291
302
286
303
316
333
314
352
356
360
377
374
354
335
319
332
336
377
367
384
358
331
321
Adjusted
Emission
Rate
[g/day]
357
364
320
314
323
323
327
332
311
330
347
355
333
367
362
363
381
381
372
357
347
347
340
388
378
384
377
357
342
24
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
26 54
Flux: 22.0
881.0
ng
5T3
660.7
440.5
220.2
108 162 216
Leakage: 1.2 [g/hr] Wind Dir/Speed: 11.0 [degrees] / 1.6 [m/s]
Figure 3-3. Example plume map for September 21, 2006.
1200
1000
800
09/22/06
•5
OL
600
400
200
12:00 AM 1:12 AM 2:24 AM 3:36 AM 4:48 AM 6:00 AM 7:12 AM 8:24 AM 9:36 AM
Time
0< VC< .1
VC>= . 1
Figure 3-4. Time series of emission rate for September 22, 2006.
25
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Table 3-5. Summary of Results for September 22, 2006
Time
12:10AM
12:14AM
12:18AM
2:18 AM
2:22 AM
2:26 AM
2:30 AM
2:34 AM
2:58 AM
3:02 AM
3:06 AM
3:14 AM
3:18 AM
3:22 AM
3:26 AM
3:30 AM
3:34 AM
3:38 AM
3:42 AM
3:46 AM
3:50 AM
3:54 AM
3:58 AM
4:02 AM
4:06 AM
4:10 AM
4:14 AM
4:18 AM
4:22 AM
4:26 AM
4:30 AM
4:34 AM
4:38 AM
4:42 AM
Lumex
Flux
Value
[g/day]
48
48
47
46
53
56
53
47
35
34
34
36
34
33
35
37
36
39
42
39
38
37
35
34
36
36
36
36
31
30
31
32
34
40
Wind
Speed
[m/s]
2.1
2.1
2.1
2
2.1
2.2
2.3
2.4
3.1
3
3.1
3.2
3.2
3.2
3.5
3.8
3.8
3.9
4
3.6
3.4
3.3
3.2
3.1
3.2
3.1
3.1
3.2
3.1
3.1
3.1
3.3
3.4
3.8
Wind
Direction
[deg from
normal to
VRPM
config.]
-4
-6
-6
-8
-4
1
7
10
21
23
23
20
19
17
20
23
23
24
23
21
17
16
14
14
13
12
11
13
16
17
17
21
22
23
Concordance
Correlation
Factor
1
1
1
1
1
1
1
1
0.991
0.987
0.99
0.992
0.989
0.987
0.978
0.977
0.972
0.987
0.994
1
1
0.999
0.999
0.999
1
1
0.996
0.995
0.991
0.994
0.996
0.994
0.989
0.989
Unadjusted
Flux Values
[g/day]
465
509
492
508
488
430
375
328
149
133
158
185
172
187
188
164
158
172
175
192
220
265
271
264
206
196
189
196
201
188
190
190
175
181
Adjusted
Emission
Rate
[g/day]
491
547
529
559
513
439
418
391
224
206
246
267
243
258
271
256
248
272
275
284
302
356
350
336
257
239
230
248
266
255
256
283
267
281
26
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
4:50 AM
4:54 AM
5:02 AM
5:06 AM
5:10 AM
5:14 AM
5:18 AM
5:22 AM
5:26 AM
5:30 AM
5:34 AM
5:38 AM
6:02 AM
6:06 AM
6:10 AM
6:14 AM
6:18 AM
6:22 AM
6:26 AM
6:30 AM
6:34 AM
6:38 AM
6:58 AM
7:02 AM
7:06 AM
7:10 AM
7:34 AM
7:42 AM
7:46 AM
7:50 AM
7:54 AM
7:58 AM
8:02 AM
8:06 AM
8:10 AM
Lumex
Flux
Value
[g/day]
42
41
34
30
28
26
27
28
30
30
33
35
32
30
30
30
31
33
34
34
32
31
8
4
0
0
0
0
0
0
0
0
0
0
0
Wind
Speed
[m/s]
4.7
4.7
4.4
3.8
3.4
3.1
3
3
3.2
3.2
3.3
3.4
3.3
3.2
3.2
3.4
3.7
3.8
3.9
4
3.7
3.7
4.2
3.9
3.7
3.6
3.2
3.1
3.1
3.2
3.3
3.4
3.3
3.4
3.5
Wind
Direction
[deg from
normal to
VRPM
config.]
29
30
29
28
25
21
20
18
18
17
16
16
18
18
19
20
21
21
23
23
25
26
30
30
29
29
21
20
21
21
20
23
23
24
26
Concordance
Correlation
Factor
0.964
0.944
0.924
0.931
0.953
0.994
1
1
1
1
1
1
0.998
1
0.998
0.996
0.994
0.991
0.976
0.973
0.953
0.935
0.926
0.946
0.942
0.955
0.991
0.995
0.994
0.995
0.988
0.977
0.971
0.959
0.903
Unadjusted
Flux Values
[g/day]
158
158
245
253
291
282
266
235
239
222
208
186
205
198
197
211
218
218
226
227
220
228
173
140
146
146
157
209
213
231
251
241
234
286
310
Adjusted
Emission
Rate
[g/day]
292
299
448
447
484
420
385
331
332
300
280
250
285
273
281
304
323
328
351
351
363
390
329
264
269
265
237
306
321
343
364
377
365
454
525
27
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
8:14 AM
8:18 AM
8:22 AM
8:26 AM
8:30 AM
8:34 AM
8:38 AM
8:42 AM
8:46 AM
8:50 AM
8:54 AM
8:58 AM
9:02 AM
9:06 AM
9:10 AM
9:14 AM
9:18 AM
9:22 AM
9:26 AM
Lumex
Flux
Value
[g/day]
0
-15
-9
-1
6
17
41
44
42
39
35
36
34
34
36
36
36
35
33
Wind
Speed
[m/s]
3.5
3.6
3.7
3.7
3.8
3.7
3.6
3.5
3.4
3.2
3.2
3.3
3.3
3.3
3.4
3.3
3.4
3.4
3.4
Wind
Direction
[deg from
normal to
VRPM
config.]
27
26
28
25
23
22
21
20
20
21
22
23
23
24
25
29
30
29
31
Concordance
Correlation
Factor
1
1
1
1
1
1
1
1
1
0.998
0.979
0.992
0.984
0.988
0.98
0.987
0.957
0.957
0.912
Unadjusted
Flux Values
[g/day]
350
407
423
467
519
399
397
355
330
315
367
361
382
353
288
261
291
307
313
Adjusted
Emission
Rate
[g/day]
615
695
753
772
810
608
589
513
485
465
561
564
596
560
473
472
544
568
603
(689.4
ng
m"3
517.1
344.7
172.4
26 54 108 162 216
Flux: £6.7 Leakage: 0.3 [g/hr] Wind Dir/Speed: 22.9 [degrees] / 3.8 [m/s]
Figure 3-5. Example plume map for September 22, 2006.
28
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
10/11/06
1200
1000 -
800 -
600 -
400 -
200 -
4:41 PM
4:42 PM
4:42 PM
4:43 PM 4:44 PM
Time
4:45 PM
4:45 PM
4:46 PM
Figure 3-6. Time series of emission rate for October 11, 2006.
Table 3-6. Summary of Results for October 11, 2006
Time
4:42 PM
4:46 PM
Lumex
Flux
Value
[g/day]
2
1
Wind
Speed
[m/s]
4
1.5
Wind
Direction
[deg from
normal to
VRPM
config.]
-13
-12
Concordance
Correlation
Factor
1
1
Unadjusted
Flux Values
[g/day]
47
16
Adjusted
Emission
Rate
[g/day]
55
18
29
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
26 54
Flux: 0.7
m"3
Leakage: 0.0 [g/hr] Wind Dir/Speed: -12.8 [degrees] / 1.5 [m/s]
Figure 3-7. Example plume map for October 11, 2006.
10/14/06
1200
1000
800
600
400
200
0=.1
10:04AM 10:19AM 10:33AM 10:48AM 11:02 AM 11:16AM 11:31 AM 11:45AM
Time
Figure 3-8. Time series of emission rate for October 14, 2006.
30
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Table 3-7. Summary of Results for October 14, 2006
Time
10:10AM
10:14AM
10:18AM
1 1 :26 AM
11:30 AM
11:34 AM
Lumex
Flux
Value
[g/day]
16
18
25
36
34
30
Wind
Speed
[m/s]
2.5
2.4
2.4
1.8
1.9
1.8
Wind
Direction
[deg from
normal to
VRPM
config.]
-54
-48
-46
-49
-58
-59
Concordance
Correlation
Factor
1
1
1
0.995
1
1
Unadjusted
Flux Values
[g/day]
58
84
101
92
67
47
Adjusted
Emission
Rate
[g/day]
136
173
201
193
174
127
26 54
Flux: 3.9
108 162 216
Leakage: 1.5 [g/hr] Wind Din/Speed: -49.6 [degrees] / 1.8 [m/s]
Figure 3-9. Example plume map for October 14, 2006.
31
-------
10/17/06
1200
1000
800
600
400
200
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
12:00 AM 1:12 AM 2:24 AM 3:36 AM 4:48 AM 6:00 AM 7:12 AM 8:24 AM 9:36 AM 10:48 AM 12:OOPM
Time
Figure 3-10. Time series of emission rate for October 17, 2006.
Table 3-8. Summary of Results for October 17, 2006
Time
10:38 AM
Lumex
Flux
Value
[g/day]
21
Wind
Speed
[m/s]
5
Wind
Direction
[deg from
normal to
VRPM
config.]
-39
Concordance
Correlation
Factor
0.99
Unadjusted
Flux Values
[g/day]
52
Adjusted
Emission
Rate
[g/day]
91
32
-------
10/18/06
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
1000
600
400
12:00 AM 2:24 AM
4:48 AM 7:12 AM 9:36 AM
Time
12:00 PM 2:24 PM
Figure 3-11. Time series of emission rate for October 18, 2006.
Table 3-9. Summary of Results for October 18, 2006
Time
2:46 PM
Lumex
Flux
Value
[g/day]
64
Wind
Speed
[m/s]
1.6
Wind
Direction
[deg from
normal to
VRPM
config.]
-20
Concordance
Correlation
Factor
1
Unadjusted
Flux Values
[g/day]
727
Adjusted
Emission
Rate
[g/day]
929
33
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
ng
S"3
372.2
26 5
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
10/20/06
1200
1000
800
600
400
200
5:13 PM 5:13 PM 5:14 PM
5:15 PM 5:16 PM 5:16 PM
Time
5:17 PM
5:18 PM
Figure 3-13. Time series of emission rate for October, 20 2006.
Table 3-11. Summary of Results for October 20, 2006
Time
5:14 PM
5:18 PM
Lumex
Flux
Value
[g/day]
20
23
Wind
Speed
[m/s]
1.4
1.5
Wind
Direction
[deg from
normal to
VRPM
config.]
-15
-16
Concordance
Correlation
Factor
1
1
Unadjusted
Flux Values
[g/day]
235
312
Adjusted
Emission
Rate
[g/day]
282
381
35
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
351.1
26 54
Flux: 13.3
108 162 216
Leakage: 0.9 [g/hr] Wind Din/Speed: -17.4 [degrees] / 1.5 [m/s]
Figure 3-14. Example plume map for October 20, 2006.
10/21/06
8-
1
-696-
1:12AM 3:36AM 6:OOAM 8:24 AM 10:48AM 1:12PM 3:36 PM 6:00 PM 8:24 PM
Time
Figure 3-15. Time series of emission rate for October 21, 2006.
36
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Table 3-12. Summary of Results for October 21, 2006
Time
9:02 AM
9:06 AM
10:26 AM
10:30 AM
10:34 AM
10:38 AM
10:42 AM
10:46 AM
10:50 AM
1 1 :26 AM
11:30 AM
11:34 AM
11:38 AM
1 1 :42 AM
1 1 :46 AM
11:50 AM
11:54 AM
11:58 AM
12:10AM
12:14AM
12:18AM
12:22 AM
12:26 AM
12:54 AM
12:58 AM
1:02 PM
1:06 PM
1:1 0PM
1:14 PM
1:1 8PM
1:22 PM
1:26 PM
1:30 PM
1:34 PM
Lumex
Flux
Value
[g/day]
10
11
30
30
26
24
24
23
24
29
34
33
30
31
35
32
31
42
30
35
31
26
30
30
35
31
30
39
42
39
37
36
38
33
Wind
Speed
[m/s]
1.4
1.6
2.1
2.1
2
2
1.9
1.8
1.7
2
1.8
1.7
1.7
1.8
1.8
1.9
1.9
2.1
1.8
1.8
1.6
1.4
1.5
1.4
1.5
1.4
1.5
1.8
1.9
1.8
1.8
1.8
1.7
1.6
Wind
Direction
[deg from
normal to
VRPM
config.]
6
15
-6
-2
1
3
3
4
-2
-1
0
0
0
0
0
-1
-9
-17
-17
-13
-8
-6
-3
6
5
7
5
12
13
12
9
10
2
-1
Concordance
Correlation
Factor
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0.988
1
1
1
1
1
0.999
0.994
0.982
0.987
0.973
Unadjusted
Flux Values
[g/day]
162
159
339
330
294
276
255
255
262
395
338
321
310
327
328
327
454
545
410
399
338
315
389
337
315
247
280
359
343
247
250
224
215
239
Adjusted
Emission
Rate
[g/day]
179
206
364
339
297
288
267
271
269
401
341
324
314
328
330
334
506
676
504
466
372
340
408
372
344
278
302
446
429
305
293
266
221
243
37
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
1:38 PM
1:46 PM
1:50 PM
1:54 PM
1:58 PM
2:02 PM
2:06 PM
2:10 PM
2:26 PM
2:30 PM
2:34 PM
2:38 PM
2:50 PM
2:54 PM
2:58 PM
3:02 PM
3:06 PM
3:14 PM
3:18 PM
3:22 PM
3:26 PM
3:30 PM
3:34 PM
3:38 PM
3:42 PM
3:46 PM
3:50 PM
4:02 PM
4:06 PM
4:10 PM
4:14 PM
4:18 PM
4:22 PM
4:26 PM
4:30 PM
Lumex
Flux
Value
[g/day]
25
35
23
32
47
44
38
46
49
46
43
48
52
59
54
46
51
42
37
33
21
15
15
14
13
16
14
16
22
24
33
36
34
34
35
Wind
Speed
[m/s]
1.4
1.5
1.3
1.4
1.6
1.5
1.5
1.6
1.7
1.6
1.7
1.8
1.9
1.9
1.8
1.6
1.7
1.7
1.8
1.8
1.7
1.6
1.7
1.7
1.7
1.8
1.7
2
2.2
2.2
2.1
2
1.9
1.9
1.9
Wind
Direction
[deg from
normal to
VRPM
config.]
-4
-3
-4
-12
-12
-15
-15
-9
-11
-11
-16
-6
7
9
12
7
0
17
18
27
44
44
39
45
38
30
26
22
19
22
19
21
24
24
25
Concordance
Correlation
Factor
1
1
0.963
0.994
0.978
0.982
0.915
0.976
0.952
0.92
0.934
0.913
0.931
0.95
0.992
0.995
0.997
0.964
0.985
0.992
0.996
0.994
0.996
0.983
0.967
0.952
0.937
0.988
0.992
0.985
0.991
0.99
0.967
0.976
0.982
Unadjusted
Flux Values
[g/day]
322
342
293
301
359
326
322
486
427
364
360
395
357
449
452
517
512
430
319
201
123
113
126
104
121
141
165
146
180
207
217
206
223
216
188
Adjusted
Emission
Rate
[g/day]
338
355
311
350
416
393
388
544
487
415
437
426
401
522
557
585
519
583
447
348
389
355
320
358
302
266
281
221
254
319
310
308
357
350
306
38
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
4:34 PM
4:38 PM
4:42 PM
4:46 PM
4:50 PM
4:54 PM
4:58 PM
5:02 PM
5:06 PM
5:10 PM
5:14 PM
5:18 PM
5:22 PM
5:26 PM
5:30 PM
5:34 PM
5:38 PM
5:42 PM
5:46 PM
5:50 PM
5:54 PM
5:58 PM
6:02 PM
6:06 PM
6:10 PM
6:14 PM
6:18 PM
6:22 PM
6:26 PM
6:30 PM
6:34 PM
6:38 PM
6:42 PM
6:46 PM
6:50 PM
Lumex
Flux
Value
[g/day]
25
28
33
29
31
32
31
31
32
28
29
26
24
20
22
19
15
11
10
7
6
7
9
11
11
12
12
10
9
9
10
12
14
15
17
Wind
Speed
[m/s]
1.8
1.8
1.9
1.9
2
2.1
2.1
2.2
2.1
2
2.1
2
1.9
1.8
1.7
1.5
1.4
1.2
1.2
1.2
1.2
1.3
1.4
1.5
1.6
1.7
1.7
1.6
1.6
1.6
1.5
1.6
1.7
1.7
1.8
Wind
Direction
[deg from
normal to
VRPM
config.]
24
19
15
16
14
14
16
13
12
12
14
15
17
17
16
14
15
16
17
19
22
20
18
18
18
17
19
21
20
19
17
15
13
13
13
Concordance
Correlation
Factor
0.974
0.974
0.988
0.996
1
1
1
1
0.999
0.999
0.999
0.993
0.995
0.994
0.991
0.965
0.968
0.941
0.95
0.956
0.994
0.998
1
1
1
1
1
0.996
0.987
0.991
0.989
0.996
1
1
1
Unadjusted
Flux Values
[g/day]
209
253
266
258
289
255
301
244
233
183
207
219
227
225
267
281
281
236
223
172
118
100
98
112
110
119
115
107
100
100
93
106
115
112
121
Adjusted
Emission
Rate
[g/day]
333
361
344
344
367
329
401
306
289
225
266
286
307
306
360
362
368
313
304
245
178
145
137
157
153
162
164
158
147
142
127
138
145
140
151
39
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
6:54 PM
6:58 PM
7:02 PM
7:06 PM
7:10 PM
7:14 PM
7:18 PM
7:22 PM
7:30 PM
7:34 PM
7:38 PM
7:42 PM
7:46 PM
Lumex
Flux
Value
[g/day]
17
18
17
15
12
10
9
9
11
11
9
7
5
Wind
Speed
[m/s]
1.9
1.9
1.9
1.8
1.6
1.5
1.5
1.5
1.6
1.5
1.4
1.2
1.1
Wind
Direction
[deg from
normal to
VRPM
config.]
13
14
16
19
22
23
24
22
17
17
17
17
18
Concordance
Correlation
Factor
1
1
0.999
0.996
0.996
0.992
0.986
0.979
0.992
0.984
0.977
0.965
0.93
Unadjusted
Flux Values
[g/day]
144
216
160
160
149
139
114
98
108
109
115
107
118
Adjusted
Emission
Rate
[g/day]
181
277
215
227
226
219
184
151
147
149
159
146
163
26 54
Flux: 16.4
103 162 216
Leakage: 1.3 [g/hr] Uind Dir/Speed: -2.1 [degrees] / 1.9 [m/s]
Figure 3-16. Example plume map for October 21, 2006.
40
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
10/24/06
1200
1:33 PM 1:40 PM 1:48 PM 1:55 PM 2:02 PM 2:09 PM 2:16 PM 2:24 PM 2:31 PM
Time
Figure 3-17. Time series of emission rate for October 24, 2006.
Table 3-13. Summary of Results for October 24, 2006
Time
1:38 PM
1:42 PM
2:22 PM
2:26 PM
Lumex
Flux
Value
[g/day]
14
18
24
30
Wind
Speed
[m/s]
1.1
1.2
1.1
1.4
Wind
Direction
[deg from
normal to
VRPM
config.]
-49
-58
-48
-32
Concordance
Correlation
Factor
0.908
0.996
1
1
Unadjusted
Flux Values
[g/day]
100
69
91
208
Adjusted
Emission
Rate
[g/day]
212
184
189
317
41
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
26 5=.1
12:00 AM 2:24 AM 4:48 AM 7:12 AM 9:36 AM 12:00 PM 2:24 PM
Time
Figure 3-19. Time series of emission rate for October 25, 2006.
42
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Table 3-14. Summary of Results for October 25, 2006
Time
8:34 AM
8:38 AM
8:42 AM
8:46 AM
8:50 AM
8:54 AM
9:18 AM
9:22 AM
10:10AM
10:14AM
10:18AM
10:22 AM
10:26 AM
10:30 AM
10:34 AM
10:38 AM
12:46 AM
12:50 AM
12:54 AM
12:58 AM
1:02 PM
1:06 PM
Lumex
Flux
Value
[g/day]
3
7
11
18
19
19
12
15
27
26
26
27
24
16
12
7
7
7
3
1
1
0
Wind
Speed
[m/s]
1.8
1.7
1.7
1.8
1.8
2
1.9
1.8
2
2
2.1
2.2
2.2
2
2
1.8
2
2
1.8
1.5
1.4
1.5
Wind
Direction
[deg from
normal to
VRPM
config.]
4
3
4
6
10
11
9
8
1
1
4
6
9
16
25
29
11
11
10
13
7
1
Concordance
Correlation
Factor
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Unadjusted
Flux Values
[g/day]
278
254
243
244
235
252
211
235
423
417
436
409
352
348
305
257
207
241
244
212
225
259
Adjusted
Emission
Rate
[g/day]
297
268
261
270
276
304
248
268
427
425
465
453
411
463
501
473
251
294
291
265
253
262
43
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
26 54
Flux: 9.3
13S.2
108 162 216
Leakage: 0.1 [g/hr] Wind Dir/Speed: 3.9 [degrees] / 1.8 [m/s]
Figure 3-20. Example plume map for October 25, 2006.
10/26/06
§
(0
(0
1
1200
1000
800
600
400
200
*fr
0=.1
12:00 AM 2:24 AM 4:48 AM 7:12 AM 9:36 AM 12:00 PM 2:24 PM 4:48 PM 7:12 PM 9:36 PM 12:00 AM
Time
Figure 3-21. Time series of emission rate for October 26, 2006.
44
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Table 3-15. Summary of Results for October 26, 2006
Time
2:10 AM
2:14 AM
3:34 AM
4:46 AM
4:50 AM
5:14 AM
5:18 AM
5:22 AM
5:26 AM
5:30 AM
5:34 AM
6:14 AM
6:18 AM
6:22 AM
6:26 AM
6:30 AM
6:34 AM
6:58 AM
7:02 AM
7:06 AM
7:10 AM
7:14 AM
7:18 AM
7:22 AM
7:26 AM
7:50 AM
7:54 AM
7:58 AM
8:02 AM
8:06 AM
8:10 AM
8:14 AM
8:18 AM
8:42 AM
Lumex
Flux
Value
[g/day]
13
14
13
11
13
16
15
15
14
13
13
18
18
18
18
17
18
26
26
23
24
23
25
24
26
16
17
16
19
15
11
13
18
36
Wind
Speed
[m/s]
1.7
1.8
1.5
1.6
1.7
1.7
1.7
1.8
1.8
1.8
1.8
1.7
1.8
1.9
2.1
2.2
2.2
1.8
1.8
1.7
1.9
1.9
1.9
1.8
1.9
1.6
1.6
1.6
1.7
1.7
1.7
1.8
1.8
1.8
Wind
Direction
[deg from
normal to
VRPM
config.]
14
15
7
21
19
13
16
17
19
18
16
9
15
18
18
16
16
7
8
8
9
11
14
15
16
17
13
9
9
8
9
8
9
25
Concordance
Correlation
Factor
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Unadjusted
Flux Values
[g/day]
194
183
276
211
205
239
215
204
189
204
255
285
259
239
231
239
248
280
268
257
277
274
273
252
253
223
253
288
337
355
384
419
444
250
Adjusted
Emission
Rate
[g/day]
249
240
309
313
295
302
286
279
267
285
344
333
336
330
320
322
328
316
308
293
325
333
350
332
340
304
320
336
390
404
446
483
514
413
45
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
8:46 AM
8:50 AM
8:54 AM
8:58 AM
9:02 AM
9:06 AM
9:10 AM
9:34 AM
9:38 AM
9:42 AM
9:46 AM
9:50 AM
9:54 AM
9:58 AM
10:02 AM
10:26 AM
10:30 AM
10:34 AM
10:38 AM
10:42 AM
11:18 AM
1 1 :22 AM
1 1 :26 AM
11:30 AM
11:34 AM
12:26 AM
1:58 PM
2:02 PM
2:06 PM
2:10 PM
2:14 PM
2:18 PM
2:22 PM
2:46 PM
2:50 PM
Lumex
Flux
Value
[g/day]
38
39
31
27
27
30
32
22
19
16
21
29
39
46
48
42
57
63
71
68
37
31
28
22
20
22
23
22
30
27
27
28
31
52
59
Wind
Speed
[m/s]
1.8
1.7
1.5
1.4
1.5
1.6
1.7
2
2
2.1
2.2
2.3
2.3
2.3
2.2
1.9
1.9
1.9
1.9
1.7
1.7
1.6
1.5
1.4
1.4
1.4
1.8
1.8
2
2
2.1
2
2
2.1
2.2
Wind
Direction
[deg from
normal to
VRPM
config.]
27
27
28
25
19
13
12
19
20
23
24
25
25
28
28
12
10
7
6
8
14
14
14
14
13
19
18
19
19
19
19
18
15
13
12
Concordance
Correlation
Factor
1
1
1
1
1
1
1
1
1
1
1
0.998
0.993
0.976
0.977
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0.995
0.994
0.997
Unadjusted
Flux Values
[g/day]
219
204
192
181
217
249
282
263
224
219
209
213
208
246
225
308
323
357
418
405
274
264
272
235
246
206
326
288
300
307
332
374
439
251
259
Adjusted
Emission
Rate
[g/day]
376
354
344
295
309
313
344
372
324
340
337
347
345
435
400
375
381
404
460
460
354
338
346
299
311
291
458
410
430
436
475
517
576
318
320
46
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
2:54 PM
2:58 PM
3:02 PM
3:06 PM
3:10 PM
3:14 PM
3:38 PM
5:42 PM
6:14 PM
6:18 PM
6:22 PM
6:26 PM
6:30 PM
6:34 PM
6:38 PM
6:42 PM
7:06 PM
7:10 PM
7:14 PM
7:18 PM
7:22 PM
7:26 PM
7:30 PM
7:34 PM
7:58 PM
8:02 PM
8:06 PM
8:10 PM
8:14 PM
8:18 PM
9:10 PM
9:14 PM
9:18 PM
9:42 PM
9:46 PM
Lumex
Flux
Value
[g/day]
65
70
69
67
62
59
34
30
24
25
25
28
33
31
31
30
36
35
31
27
24
24
26
27
35
33
32
27
25
22
31
31
29
35
35
Wind
Speed
[m/s]
2.2
2.3
2.2
2.2
2.1
2.1
1.5
1.4
2.1
2.1
2.1
2.1
2.2
2.1
2.1
2.2
2.4
2.3
2.1
2
1.9
1.9
2
2
2.3
2.3
2.2
2.2
2.2
2
1.9
2
2
2.4
2.5
Wind
Direction
[deg from
normal to
VRPM
config.]
9
8
9
10
10
13
11
10
23
22
20
19
19
20
19
20
19
18
16
17
17
18
17
17
19
20
20
21
22
20
13
16
18
18
18
Concordance
Correlation
Factor
0.996
0.995
1
1
1
1
1
0.905
1
1
1
1
1
1
0.997
0.992
1
1
1
1
1
1
0.987
1
1
0.998
0.999
0.996
0.99
0.926
0.97
0.977
0.997
0.994
0.992
Unadjusted
Flux Values
[g/day]
237
258
234
244
230
245
313
379
240
254
218
205
234
226
224
176
217
226
256
273
288
255
286
237
249
240
203
220
246
305
325
275
254
205
219
Adjusted
Emission
Rate
[g/day]
276
293
271
290
271
307
377
451
373
388
321
293
331
325
322
258
308
313
345
369
391
353
388
322
358
351
295
332
372
446
406
364
356
283
307
47
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
9:50 PM
9:54 PM
9:58 PM
10:34PM
10:38 PM
10:42PM
10:46PM
10:50 PM
10:54PM
10:58 PM
11:02PM
11:26PM
11:30PM
11:34PM
11:38PM
11:42PM
11:46PM
11:50PM
Lumex
Flux
Value
[g/day]
34
30
25
35
35
32
32
32
32
32
34
32
27
27
25
23
22
21
Wind
Speed
[m/s]
2.4
2.3
2.1
2.4
2.5
2.4
2.4
2.5
2.6
2.6
2.8
2.6
2.4
2.4
2.3
2.3
2.3
2.2
Wind
Direction
[deg from
normal to
VRPM
config.]
19
19
20
23
22
22
22
20
20
23
22
23
23
24
26
25
26
26
Concordance
Correlation
Factor
0.996
0.99
0.971
0.983
0.997
0.998
0.992
0.994
0.997
0.992
0.989
0.975
0.965
0.981
0.985
0.976
0.976
0.993
Unadjusted
Flux Values
[g/day]
220
264
302
218
209
205
195
202
203
192
184
196
190
193
182
213
172
156
Adjusted
Emission
Rate
[g/day]
314
379
438
340
317
316
294
296
299
298
281
305
296
309
306
350
288
262
26 54
Flux: 13.9
103 162 216
Leakage: 0.6 [g/hr] Wind Dir/Speed: 7.8 [degrees] / 1.7 [m/s]
Figure 3-22. Example plume map for October 26, 2006.
48
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
10/27/06
1200
1000
800
600
400
200
12:00 AM 1:12 AM 2:24 AM 3:36 AM 4:48 AM 6:00 AM 7:12 AM 8:24 AM 9:36 AM 10:48 AM 12:OOPM
Time
Figure 3-23. Time series of emission rate for October 27, 2006.
Table 3-16. Summary of Results for October 27, 2006
Time
12:22 AM
12:26 AM
12:30 AM
12:34 AM
12:38 AM
12:42 AM
12:46 AM
1:1 0AM
Lumex
Flux
Value
[g/day]
17
17
21
23
24
25
27
32
Wind
Speed
[m/s]
2
1.9
1.9
1.9
1.9
1.9
1.9
2.1
Wind
Direction
[deg from
normal to
VRPM
config.]
17
16
16
17
17
17
16
10
Concordance
Correlation
Factor
0.953
0.957
0.915
0.947
0.97
0.998
0.999
1
Unadjusted
Flux Values
[g/day]
292
279
274
259
271
265
243
323
Adjusted
Emission
Rate
[g/day]
394
372
367
353
366
364
321
383
49
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
1:14 AM
1:1 8 AM
1 :22 AM
1 :26 AM
1:30 AM
1:34 AM
1:38 AM
2:02 AM
2:06 AM
2:10 AM
2:14 AM
2:18 AM
2:22 AM
2:26 AM
2:30 AM
2:54 AM
2:58 AM
3:02 AM
3:06 AM
3:10 AM
3:14 AM
3:22 AM
3:46 AM
3:50 AM
3:54 AM
3:58 AM
4:02 AM
4:06 AM
4:10 AM
4:14 AM
4:38 AM
4:42 AM
4:46 AM
4:50 AM
4:54 AM
Lumex
Flux
Value
[g/day]
32
32
32
30
30
31
29
32
33
31
31
30
28
27
34
42
44
40
36
34
31
25
35
32
32
34
36
37
34
35
18
18
17
18
19
Wind
Speed
[m/s]
2.1
2
2
2
2
2
2
2
2
2.1
2
2.1
2.1
2.1
2.2
2.5
2.6
2.5
2.4
2.3
2.2
1.9
2.4
2.4
2.4
2.4
2.4
2.5
2.6
2.8
2.7
2.8
2.8
2.9
3
Wind
Direction
[deg from
normal to
VRPM
config.]
9
10
11
13
15
16
13
8
9
10
11
14
17
17
16
15
14
15
16
14
15
12
21
19
17
17
16
16
15
19
26
25
22
21
21
Concordance
Correlation
Factor
0.996
0.983
0.973
0.998
1
1
1
0.994
1
1
1
1
1
1
1
1
1
1
0.999
0.984
0.968
0.931
0.993
0.953
0.956
0.971
0.986
0.996
0.999
0.994
0.968
0.969
0.96
0.967
0.973
Unadjusted
Flux Values
[g/day]
345
329
304
282
263
301
384
339
255
242
210
200
185
204
225
200
202
184
208
219
245
269
289
298
269
244
210
191
163
175
152
164
174
166
178
Adjusted
Emission
Rate
[g/day]
403
388
368
355
346
398
485
387
296
286
255
257
254
279
299
260
261
242
276
282
320
333
430
429
367
334
280
253
214
250
256
272
263
248
264
50
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
4:58 AM
5:02 AM
5:06 AM
5:30 AM
5:34 AM
5:38 AM
5:42 AM
5:46 AM
5:50 AM
5:54 AM
5:58 AM
6:22 AM
6:26 AM
6:30 AM
6:34 AM
6:38 AM
6:42 AM
6:46 AM
6:50 AM
7:14 AM
7:18 AM
7:22 AM
7:26 AM
7:30 AM
7:34 AM
7:38 AM
7:42 AM
8:06 AM
8:10 AM
8:14 AM
8:18 AM
8:22 AM
8:26 AM
8:30 AM
8:34 AM
Lumex
Flux
Value
[g/day]
21
22
23
18
17
16
15
14
15
12
10
3
6
7
9
9
9
10
12
29
33
36
38
43
44
44
46
2
0
8
11
24
38
53
53
Wind
Speed
[m/s]
2.9
2.7
2.6
2.2
2.2
2.4
2.5
2.4
2.4
2.3
2.3
2.2
2.1
2.1
2.1
2
2
1.9
1.8
2.3
2.5
2.6
2.5
2.6
2.6
2.5
2.5
2.5
2.5
2.6
2.5
2.5
2.7
2.8
2.6
Wind
Direction
[deg from
normal to
VRPM
config.]
18
17
16
13
12
12
14
15
15
17
19
13
10
10
9
11
12
10
9
1
0
1
2
3
6
8
8
5
3
0
1
2
3
3
6
Concordance
Correlation
Factor
0.985
0.992
0.998
1
1
0.999
0.999
1
1
1
1
1
1
1
1
1
1
1
0.998
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Unadjusted
Flux Values
[g/day]
156
151
157
305
269
248
237
190
192
186
189
255
266
307
368
385
391
458
488
511
503
474
431
402
379
355
365
389
441
453
386
360
342
330
280
Adjusted
Emission
Rate
[g/day]
218
204
210
379
331
306
307
249
252
255
272
323
317
364
428
463
479
543
570
515
503
483
444
421
416
403
417
423
462
453
389
373
358
348
310
51
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
8:58 AM
9:02 AM
9:06 AM
9:10 AM
9:14 AM
9:18 AM
9:22 AM
9:26 AM
9:50 AM
9:54 AM
9:58 AM
10:02 AM
10:06 AM
10:10AM
10:14AM
10:18AM
10:42 AM
10:46 AM
10:50 AM
10:54 AM
10:58 AM
11:02 AM
11:06 AM
11:10 AM
11:34 AM
11:38 AM
1 1 :42 AM
1 1 :46 AM
11:50 AM
11:54 AM
11:58 AM
Lumex
Flux
Value
[g/day]
53
51
55
51
49
44
48
45
31
28
27
29
31
39
48
41
37
37
32
31
30
30
31
31
23
22
21
20
20
21
22
Wind
Speed
[m/s]
2.7
2.6
2.9
2.9
2.9
2.8
2.9
2.6
1.8
1.8
1.8
2
2.3
2.7
3
3.1
3.1
3.1
2.8
2.7
2.6
2.5
2.4
2.5
2.1
2.1
2
1.9
1.9
2
2.1
Wind
Direction
[deg from
normal to
VRPM
config.]
17
16
18
19
19
17
17
15
23
23
19
22
21
17
19
24
28
28
29
27
27
25
24
26
29
31
29
32
33
36
39
Concordance
Correlation
Factor
1
1
1
1
1
1
1
1
1
1
0.948
0.986
0.91
0.98
0.994
0.994
0.981
0.945
0.946
0.911
0.976
0.969
0.976
0.96
0.993
1
1
1
1
1
0.909
Unadjusted
Flux Values
[g/day]
310
295
277
259
255
253
288
282
250
289
290
294
289
318
252
185
192
254
254
306
247
223
187
228
227
224
193
175
191
194
215
Adjusted
Emission
Rate
[g/day]
426
396
386
371
365
346
393
367
390
453
416
453
428
434
362
295
344
457
460
524
423
366
302
388
420
437
354
353
401
452
557
52
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
26 54
Flux: 14.2
108 162 216
Leakage: 2.2 [g/hr] Wind Dir/Speed: 17.3 [degrees] / 2.7 [m/s]
Figure 3-24. Example plume map for October 27, 2006.
10/30/06
1200
1000
800
600
400
200
12:00 AM 2:24 AM 4:48 AM 7:12 AM 9:36 AM 12:00 PM 2:24 PM 4:48 PM 7:12 PM 9:36 PM 12:00 AM
Time
Figure 3-25. Time series of emission rate for October 30, 2006.
53
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Table 3-17. Summary of Results for October 30, 2006
Time
8:34 AM
8:58 AM
9:22 AM
9:26 AM
10:14AM
10:42 AM
10:46 AM
10:50 AM
10:54 AM
11:38 AM
1 1 :42 AM
1 1 :46 AM
11:50 AM
11:54 AM
12:26 AM
12:30 AM
3:58 PM
4:02 PM
4:06 PM
4:10 PM
4:14 PM
4:18 PM
4:22 PM
4:58 PM
5:02 PM
5:06 PM
5:10 PM
5:14 PM
5:38 PM
6:46 PM
6:50 PM
6:54 PM
6:58 PM
7:22 PM
Lumex
Flux
Value
[g/day]
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Wind
Speed
[m/s]
1.9
1.7
2.2
2.2
2.4
2.2
2.2
2
1.9
2.2
2.1
2.2
2.2
1.8
1.9
1.9
1.8
1.9
1.8
1.8
1.8
1.8
1.9
1.3
1.4
1.3
1.4
1.4
1.3
1.2
1.2
1.3
1.3
1.5
Wind
Direction
[deg from
normal to
VRPM
config.]
28
21
32
34
56
55
59
57
57
55
50
54
55
59
56
56
48
43
45
44
46
49
51
34
26
19
16
15
7
-3
-5
-2
2
3
Concordance
Correlation
Factor
1
1
0.905
0.967
0.97
0.982
0.964
0.949
0.964
0.998
1
0.997
0.985
0.985
0.951
0.971
0.958
0.968
0.97
0.982
0.975
0.951
0.951
0.969
0.998
1
1
1
0.994
1
1
1
1
1
Unadjusted
Flux Values
[g/day]
244
250
273
243
77
62
65
73
64
94
121
98
57
51
108
79
88
115
101
87
63
57
59
177
225
220
216
218
370
441
450
438
411
465
Adjusted
Emission
Rate
[g/day]
440
369
540
529
617
461
850
743
625
700
549
675
418
649
929
691
357
352
335
285
230
253
291
377
378
316
288
284
412
460
478
453
423
488
54
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
7:26 PM
7:30 PM
8:22 PM
8:26 PM
8:30 PM
8:34 PM
8:38 PM
8:42 PM
Lumex
Flux
Value
[g/day]
0
0
0
0
0
0
0
0
Wind
Speed
[m/s]
1.5
1.5
1.3
1.4
1.5
1.7
1.8
1.7
Wind
Direction
[deg from
normal to
VRPM
config.]
6
4
0
-1
0
-1
0
-2
Concordance
Correlation
Factor
1
1
1
1
1
1
1
1
Unadjusted
Flux Values
[g/day]
524
546
476
415
380
391
384
338
Adjusted
Emission
Rate
[g/day]
578
581
483
423
380
399
390
349
26 54
Flux: 17.3
108 162 216
Leakage: 0.0 [g/hr] Wind Dir/Speed: 1.7 [degrees] / 1.3 [m/s]
Figure 3-26. Example plume map for October 30, 2006.
55
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
10/31/06
1200
1000
800
600
400
200
12:00 AM 2:24 AM 4:48 AM 7:12 AM 9:36 AM 12:00 PM 2:24 PM 4:48 PM 7:12 PM 9:36 PM 12:00 AM
Time
Figure 3-27. Time series of emission rate for October 31, 2006.
Table 3-18. Summary of Results for October 31, 2006
Time
12:10AM
12:34 AM
12:38 AM
12:42 AM
12:46 AM
12:50 AM
12:54 AM
12:58 AM
Lumex Flux
Value
[g/day]
0
0
0
0
0
0
0
0
Wind
Speed
[m/s]
1.2
1.3
1.3
1.5
1.6
1.7
1.8
1.8
Wind
Direction
[deg from
normal to
VRPM
config.]
-11
-10
-9
-7
-3
1
6
12
Concordance
Correlation
Factor
1
1
1
1
1
1
1
0.994
Unadjusted
Flux Values
[g/day]
271
332
319
336
319
295
284
255
Adjusted
Emission
Rate
[g/day]
311
375
357
365
332
299
315
314
56
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
1 :02 AM
1 :26 AM
1:30 AM
1 :34 AM
4:10 AM
4:14 AM
4:18 AM
4:22 AM
4:26 AM
5:22 AM
5:58 AM
6:02 AM
6:06 AM
6:10 AM
6:46 AM
6:50 AM
6:54 AM
6:58 AM
7:02 AM
7:06 AM
7:30 AM
7:34 AM
7:38 AM
7:42 AM
7:46 AM
7:50 AM
7:54 AM
7:58 AM
4:10 PM
4:14 PM
4:22 PM
4:26 PM
4:30 PM
4:38 PM
4:46 PM
Lumex Flux
Value
[g/day]
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
27
27
24
19
12
9
8
Wind
Speed
[m/s]
1.8
1.2
1.1
1.1
1.2
1.2
1.2
1.2
1.2
1.3
1.3
1.3
1.2
1.2
1.2
1.4
1.4
1.4
1.3
1.2
1.7
1.6
1.6
1.6
1.4
1.3
1.3
1.1
2.3
2.3
2.3
2.4
2.2
2.3
1.7
Wind
Direction
[deg from
normal to
VRPM
config.]
17
19
14
13
16
13
11
11
8
7
-1
1
6
10
7
3
0
0
0
1
13
14
15
15
16
23
33
46
15
15
21
23
29
27
28
Concordance
Correlation
Factor
0.991
0.953
0.951
0.997
0.939
0.941
0.957
0.957
0.944
0.98
0.965
0.986
0.989
0.984
0.991
0.992
0.992
0.99
0.982
0.974
1
0.996
0.985
0.979
0.965
0.948
0.993
0.989
1
1
0.995
0.969
0.974
0.965
0.952
Unadjusted
Flux Values
[g/day]
224
168
176
180
115
125
133
122
142
68
162
106
410
100
222
88
235
292
335
303
195
192
237
290
276
236
254
124
277
246
185
163
133
144
230
Adjusted
Emission
Rate
[g/day]
305
240
226
226
153
159
160
146
163
76
166
108
449
118
250
92
236
294
339
308
246
245
312
377
371
366
534
440
359
324
277
255
243
252
414
57
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
4:50 PM
4:54 PM
4:58 PM
5:02 PM
5:06 PM
5:10 PM
5:14 PM
5:18 PM
8:42 PM
8:46 PM
8:50 PM
8:54 PM
8:58 PM
9:02 PM
9:42 PM
9:46 PM
9:50 PM
9:54 PM
Lumex Flux
Value
[g/day]
8
7
7
8
8
8
7
5
14
15
18
19
19
19
12
14
16
16
Wind
Speed
[m/s]
1.7
1.4
1.4
1.5
1.6
1.5
1.4
1.1
1.1
1.1
1.2
1.4
1.4
1.4
1.2
1.3
1.3
1.3
Wind
Direction
[deg from
normal to
VRPM
config.]
26
24
25
26
26
27
38
48
1
8
16
18
20
20
7
9
14
17
Concordance
Correlation
Factor
0.97
0.995
0.994
1
1
1
1
0.947
1
1
1
1
1
1
1
1
1
1
Unadjusted
Flux Values
[g/day]
235
268
279
238
243
263
188
115
318
322
395
530
563
601
373
435
465
472
Adjusted
Emission
Rate
[g/day]
400
427
463
406
415
459
458
460
321
371
532
743
814
866
416
510
597
643
26 54
Flux: 14.7
I 2195'i
103 162 216
Leakage: 0.0 [g/hr] Wind Dir/Speed: 1.3 [degrees] / 1.3 [m/s]
Figure 3-28. Example plume map for October 31, 2006.
58
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
11/01/06
1200
1000 -
800 -
•8
a
»
E
600 -
400
200 -
*
12:OOAM 1:12AM 2:24AM 3:36AM 4:48 AM 6:OOAM 7:12AM 8:24 AM 9:36AM 10:48AM
Time
Figure 3-29. Time series of emission rate for November 1, 2006.
59
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Table 3-19. Summary of Results for November 1,2006
Time
12:22 AM
12:26 AM
1 :46 AM
2:14 AM
3:38 AM
3:42 AM
3:54 AM
4:22 AM
4:26 AM
4:30 AM
4:34 AM
4:38 AM
5:14 AM
5:22 AM
5:26 AM
5:30 AM
5:34 AM
5:38 AM
5:42 AM
6:06 AM
6:10 AM
6:14 AM
9:10 AM
Lumex
Flux
Value
[g/day]
30
33
16
15
19
24
26
45
72
70
89
91
83
120
150
160
130
110
87
66
53
39
27
Wind
Speed
[m/s]
1.3
1.4
1.1
1.3
1.5
1.5
1.6
1.1
1.3
1.2
1.3
1.3
1.6
1.7
1.7
1.6
1.5
1.4
1.4
1.4
1.5
1.5
1.6
Wind
Direction
[deg from
normal to
VRPM
config.]
-10
-7
-15
-15
-15
-15
-15
-29
-24
-23
-17
-15
-15
-15
-15
-17
-17
-16
-16
-19
-18
-17
12
Concordance
Correlation
Factor
0.911
1
0.925
0.932
0.961
0.95
0.963
0.98
0.99
0.995
0.985
0.975
0.956
0.944
0.932
0.942
0.97
0.974
0.975
0.965
0.919
0.915
1
Unadjusted
Flux Values
[g/day]
362
700
221
229
113
114
124
121
73
74
289
99
162
575
614
526
445
438
417
286
371
452
886
Adjusted
Emission
Rate
[g/day]
411
765
264
275
136
136
149
176
99
98
357
119
195
692
742
650
550
532
510
363
465
558
1100
60
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
26 54
Flux: 38.1
3407.3
2555.5
108 162 216
Leakage: 1.1 [g/hr] Wind Dir/Speed: 12.3 [degrees] / 1.6 [m/s]
Figure 3-30. Example plume map for November 1, 2006.
11/03/06
1200
1000
800
•D
a
£
S. 600
400
200
0=.1
12:00 AM 2:24 AM 4:48 AM 7:12 AM 9:36 AM 12:00 PM 2:24 PM 4:48 PM 7:12 PM 9:36 PM 12:00 AM
Time
Figure 3-31. Time series of emission rate for November 3, 2006.
61
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Table 3-20. Summary of Results for November 3,2006
Time
8:10 AM
8:14 AM
8:18 AM
8:22 AM
8:26 AM
8:30 AM
8:34 AM
8:46 AM
8:50 AM
8:54 AM
8:58 AM
9:30 AM
9:34 AM
9:38 AM
9:42 AM
8:26 PM
8:30 PM
8:34 PM
8:38 PM
8:42 PM
8:46 PM
8:50 PM
8:58 PM
Lumex
Flux
Value
[g/day]
20
16
12
8
4
2
6
23
31
33
35
48
50
47
47
27
24
22
20
19
18
21
18
Wind
Speed
[m/s]
1.4
1.3
1.3
1.5
1.8
2
2.2
2
2
2.1
2.1
2.5
2.4
2.4
2.4
1.8
1.8
1.7
1.6
1.6
1.6
1.6
1.5
Wind
Direction
[deg from
normal to
VRPM
config.]
-58
-49
-54
-53
-46
-36
-37
-43
-46
-44
-53
-53
-48
-50
-54
-30
-29
-29
-30
-30
-30
-31
-32
Concordance
Correlation
Factor
1
1
1
1
0.995
0.986
0.888
0.909
1
1
1
1
1
1
1
0.97
0.997
0.989
0.983
0.964
0.941
0.969
0.983
Unadjusted
Flux Values
[g/day]
94
105
86
110
178
265
334
354
311
312
225
378
393
392
327
319
254
214
199
220
244
289
274
Adjusted
Emission
Rate
[g/day]
246
223
204
257
350
437
557
654
616
593
520
876
807
852
778
470
373
310
296
327
363
434
417
62
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
26 54
Flux: 14.9
108 162 216
Leakage: 1.9 [g/hr] Wind Dir/Speed: -51.3 [degrees] / 2.4 [m/s]
Figure 3-32. Example plume map for November 3, 2006.
11/04/06
1000
0< VC<.1
IVC>= .1
12:00 AM 2:24 AM 4:48 AM 7:12 AM 9:36 AM 12:00 PM 2:24 PM 4:48 PM 7:12 PM 9:36 PM 12:00 AM
Time
Figure 3-33. Time series of emission rate for November 4, 2006.
63
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Table 3-21. Summary of Results for November 4,2006
Time
8:02 AM
8:06 AM
8:10 AM
8:14 AM
8:18 AM
8:22 AM
8:26 AM
8:30 AM
8:34 AM
8:38 AM
8:42 AM
8:46 AM
8:50 AM
8:54 AM
8:58 AM
9:02 AM
9:06 AM
9:10 AM
9:14 AM
9:18 AM
9:22 AM
9:26 AM
9:30 AM
9:34 AM
9:38 AM
9:42 AM
9:46 AM
9:50 AM
9:54 AM
9:58 AM
10:02 AM
10:06 AM
10:30 AM
10:34 AM
Lumex
Flux
Value
[g/day]
22
30
37
39
39
37
31
25
23
16
10
12
19
25
31
37
39
37
32
35
40
36
35
37
33
31
29
32
33
37
39
37
50
44
Wind
Speed
[m/s]
2.3
2.6
2.7
2.6
2.5
2.4
2.1
2
2.1
2.1
2.3
2.4
2.6
2.6
2.6
2.6
2.6
2.6
2.6
2.5
2.4
2.5
2.6
2.7
2.7
2.8
2.7
2.7
2.6
2.4
2.4
2.4
2.4
2.3
Wind
Direction
[deg from
normal to
VRPM
config.]
1
1
0
-2
-6
-6
-5
-5
-5
-3
4
6
11
16
22
19
16
13
11
11
13
20
25
28
30
28
24
25
25
23
29
32
10
11
Concordance
Correlation
Factor
1
1
1
1
1
1
1
1
1
1
1
0.998
0.995
1
1
0.997
1
1
1
1
1
1
0.997
0.999
1
1
1
1
0.998
0.974
0.986
0.984
0.971
0.983
Unadjusted
Flux Values
[g/day]
300
328
324
308
296
317
299
277
269
271
281
298
326
325
293
296
291
286
285
286
281
276
272
268
248
248
250
254
265
264
267
267
294
263
Adjusted
Emission
Rate
[g/day]
304
333
327
317
318
343
319
296
287
283
301
330
392
435
450
417
389
361
343
344
351
399
453
479
475
442
398
421
432
411
484
544
350
315
64
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
10:38 AM
10:42 AM
10:46 AM
10:50 AM
10:54 AM
10:58 AM
11:02 AM
11:06 AM
11:10AM
11:14 AM
11:18 AM
1 1 :22 AM
1 1 :26 AM
11:30 AM
11:34 AM
11:38 AM
1 1 :42 AM
1 1 :46 AM
11:50 AM
11:54 AM
11:58 AM
12:02 PM
12:06 PM
12:10 PM
12:14 PM
12:18 PM
12:22 PM
12:26 PM
12:30 PM
12:34 PM
12:38 PM
12:42 PM
12:46 PM
12:50 PM
12:54 PM
Lumex
Flux
Value
[g/day]
40
26
29
27
24
27
30
26
27
29
31
40
47
41
31
24
22
16
18
22
21
17
12
13
12
14
12
14
10
13
20
25
24
19
16
Wind
Speed
[m/s]
2.3
2.1
2
1.9
1.8
1.8
1.8
1.9
2.1
2.3
2.4
2.6
2.6
2.3
1.9
1.9
1.9
1.5
1.5
1.8
1.7
1.6
1.7
1.9
1.6
1.6
1.6
1.7
1.3
1.3
1.3
1.5
1.4
1.4
1.5
Wind
Direction
[deg from
normal to
VRPM
config.]
19
15
13
11
9
1
6
12
21
25
27
24
25
28
39
44
51
45
35
29
36
37
51
50
45
35
36
42
41
38
33
28
28
41
35
Concordance
Correlation
Factor
0.985
0.996
1
1
1
1
1
1
1
0.986
0.973
0.988
0.989
1
0.997
0.968
0.995
0.984
1
1
0.999
1
0.99
0.987
0.999
0.997
0.999
1
1
1
1
1
1
1
0.997
Unadjusted
Flux Values
[g/day]
234
247
242
258
277
314
274
272
254
254
255
326
326
257
163
155
121
149
218
204
206
135
124
137
147
206
209
173
151
194
253
313
292
217
282
Adjusted
Emission
Rate
[g/day]
334
322
302
308
321
319
301
333
377
413
448
521
537
464
413
488
584
507
481
374
478
317
615
630
507
455
487
511
429
486
522
559
526
608
626
65
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
12:58 PM
1:02 PM
1:06 PM
1:1 0PM
1:14 PM
1:18PM
1:22 PM
1:42 PM
1:46 PM
1:50 PM
1:54 PM
1:58 PM
2:02 PM
2:06 PM
2:10 PM
2:14 PM
2:18 PM
2:22 PM
2:26 PM
2:30 PM
2:34 PM
2:38 PM
2:46 PM
2:50 PM
2:54 PM
2:58 PM
3:02 PM
3:06 PM
3:10 PM
3:14 PM
3:18 PM
3:22 PM
3:26 PM
3:30 PM
3:34 PM
Lumex
Flux
Value
[g/day]
12
14
27
34
32
22
14
10
8
6
5
8
8
21
33
37
36
42
27
30
27
29
30
27
25
31
38
40
36
37
31
24
24
30
33
Wind
Speed
[m/s]
1.4
1.2
1.6
1.7
1.5
1.2
1.1
1.4
1.4
1.3
1.1
1.2
1.1
1.5
1.9
1.7
1.6
1.8
1.5
1.6
1.7
1.7
1.8
1.7
1.7
1.8
1.9
2
2
2
1.9
1.9
1.8
1.8
1.9
Wind
Direction
[deg from
normal to
VRPM
config.]
27
23
2
-8
4
20
28
40
47
55
55
50
33
14
8
12
12
11
7
0
-2
-2
12
22
21
18
16
13
10
11
14
12
10
8
7
Concordance
Correlation
Factor
1
0.982
0.998
1
1
1
0.998
0.91
0.991
0.986
0.971
1
0.971
0.981
1
1
1
1
0.995
0.965
0.912
0.937
0.977
1
0.995
1
1
0.998
1
0.997
0.999
0.998
1
0.996
1
Unadjusted
Flux Values
[g/day]
270
269
468
608
399
249
259
181
152
100
91
140
237
354
466
377
383
405
386
499
658
676
828
519
459
364
356
392
412
426
354
317
344
353
211
Adjusted
Emission
Rate
[g/day]
464
417
479
673
422
359
467
480
570
707
670
667
493
451
530
467
471
493
437
499
678
698
1010
799
679
502
470
495
491
511
456
388
410
403
236
66
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
3:38 PM
3:42 PM
3:46 PM
3:50 PM
3:54 PM
3:58 PM
4:02 PM
4:06 PM
4:10 PM
4:14 PM
4:18 PM
4:22 PM
4:26 PM
8:10 PM
8:18 PM
8:22 PM
8:46 PM
8:50 PM
8:54 PM
10:02PM
10:54PM
10:58 PM
11:02PM
11:06PM
Lumex
Flux
Value
[g/day]
37
41
48
46
44
39
35
30
27
24
20
19
17
48
55
57
18
27
25
34
10
13
15
13
Wind
Speed
[m/s]
1.9
1.7
1.9
2
2
2
2
1.9
1.7
1.5
1.4
1.3
1.2
1.2
1.5
1.5
1.4
1.5
1.4
1.3
1.2
1.3
1.2
1.1
Wind
Direction
[deg from
normal to
VRPM
config.]
7
10
11
10
12
10
10
10
10
9
9
9
9
-17
-19
-19
-18
-19
-17
-14
18
18
15
13
Concordance
Correlation
Factor
0.998
0.999
0.993
0.994
0.989
0.993
1
1
1
1
1
1
1
0.937
0.962
0.959
0.937
0.948
0.93
0.946
1
1
1
1
Unadjusted
Flux Values
[g/day]
386
378
404
433
439
454
457
444
437
462
538
522
532
495
507
476
273
274
257
233
462
493
434
363
Adjusted
Emission
Rate
[g/day]
437
450
490
515
539
542
539
523
514
533
628
611
621
609
641
604
341
345
318
275
637
686
570
456
67
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
2853.9
2140.4
26 54
Flux: 27.5
108 162 216
Leakage: 2.3 [g/hr] Wind Dir/Speed: -19.8 [degrees] / 1.5 [m/s]
Figure 3-34. Example plume map for November 4, 2006.
1200
1000
11/05/06
•D
a
800
0=.1
12:00 AM 2:24 AM 4:48 AM 7:12 AM 9:36 AM 12:00 PM 2:24 PM 4:48 PM 7:12 PM 9:36 PM 12:00 AM
Time
Figure 3-35. Time series of emission rate for November 5, 2006.
68
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Table 3-22. Summary of Results for November 5,2006
Time
12:10AM
12:14AM
12:18AM
2:06 AM
2:10 AM
2:14 AM
2:18 AM
2:22 AM
2:26 AM
2:34 AM
2:38 AM
2:42 AM
2:46 AM
2:54 AM
2:58 AM
4:26 AM
4:30 AM
4:34 AM
5:22 AM
5:26 AM
5:30 AM
5:34 AM
5:38 AM
5:42 AM
5:46 AM
6:30 AM
6:34 AM
6:38 AM
6:42 AM
6:54 AM
6:58 AM
7:02 AM
7:06 AM
7:10 AM
7:14 AM
7:18 AM
Lumex Flux
Value
[g/day]
18
17
13
15
20
23
26
27
32
32
34
31
29
32
26
16
11
6
30
32
38
41
36
34
30
24
23
21
18
25
29
33
36
36
40
43
Wind Speed
[m/s]
1.2
1.2
1.2
1.4
1.3
1.2
1.2
1.1
1.1
1.3
1.3
1.3
1.2
1.2
1.1
1.5
1.4
1.2
1.3
1.3
1.5
1.5
1.4
1.5
1.5
2
1.9
1.8
1.7
1.7
1.8
1.8
1.8
1.9
2.1
2.2
Wind
Direction [deg
from normal
to VRPM
config.]
9
5
1
-18
-18
-17
-17
-16
-17
-17
-17
-18
-20
-17
-15
-18
-17
-17
-23
-20
-17
-16
-15
-15
-14
1
0
-2
-7
-18
-18
-17
-16
-15
-13
-13
Concordance
Correlation
Factor
1
1
1
0.993
1
0.997
0.987
0.981
0.989
0.974
0.967
0.983
0.974
0.982
0.992
1
1
1
0.957
0.994
0.998
0.993
0.992
1
1
1
1
1
1
1
1
1
1
1
1
1
Unadjusted
Flux Values
[g/day]
452
490
522
262
170
123
74
76
64
122
120
25
195
56
78
275
273
228
151
137
142
134
161
222
252
380
365
348
327
287
286
281
289
304
341
328
Adjusted
Emission Rate
[g/day]
530
535
533
327
212
152
91
93
78
150
149
32
249
69
94
343
338
279
200
175
175
164
195
266
301
385
366
359
355
359
355
345
351
366
402
385
69
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
7:22 AM
7:26 AM
7:30 AM
7:34 AM
7:38 AM
8:26 AM
8:30 AM
8:34 AM
8:38 AM
8:42 AM
8:46 AM
8:50 AM
8:54 AM
8:58 AM
9:02 AM
9:06 AM
9:10 AM
9:14 AM
9:18 AM
9:22 AM
9:26 AM
9:30 AM
9:34 AM
9:38 AM
9:42 AM
9:46 AM
9:50 AM
9:54 AM
9:58 AM
10:02 AM
10:06 AM
10:10AM
10:14AM
10:18AM
10:22 AM
10:26 AM
10:30 AM
Lumex Flux
Value
[g/day]
49
48
44
42
38
14
14
16
16
14
13
12
11
13
17
18
20
26
25
25
28
26
19
18
17
15
24
30
35
34
38
34
31
28
42
43
45
Wind Speed
[m/s]
2.4
2.4
2.4
2.3
2.3
1.9
1.9
2
2.1
2.3
2.4
2.2
2.1
2.1
2.1
2
2.2
2.2
2.2
2.3
2.3
2.3
2.3
2.3
2.2
2
2.2
2.3
2.3
2.3
2.4
2.3
2.2
2
2.3
2.4
2.6
Wind
Direction [deg
from normal
to VRPM
config.]
-12
-9
-5
-5
-2
10
4
1
3
1
1
5
5
5
4
5
10
14
15
20
24
26
24
26
21
19
13
12
16
27
27
29
29
19
6
7
2
Concordance
Correlation
Factor
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0.993
0.98
0.984
0.967
0.973
0.98
0.996
0.994
1
1
1
Unadjusted
Flux Values
[g/day]
319
317
325
316
364
298
210
212
231
241
273
268
273
267
259
256
281
248
251
244
212
199
189
171
191
210
253
280
281
256
244
215
210
167
226
303
338
Adjusted
Emission Rate
[g/day]
368
354
346
337
375
350
223
215
240
246
279
291
297
289
275
278
332
320
325
356
338
333
307
292
283
297
320
343
378
444
420
390
390
237
250
342
349
70
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
10:34 AM
10:38 AM
10:42 AM
10:46 AM
10:50 AM
10:54 AM
10:58 AM
11:02 AM
11:06 AM
11:10 AM
11:14 AM
1 1 :46 AM
11:50 AM
11:54 AM
12:02 AM
12:22 AM
12:26 AM
12:30 AM
12:34 AM
12:38 AM
12:42 AM
12:54 AM
12:58 AM
1:02 PM
1:06 PM
1:10 PM
1:14 PM
1:18 PM
1 :26 PM
1:30 PM
1:34 PM
1:38 PM
1 :42 PM
2:26 PM
2:30 PM
2:34 PM
2:38 PM
Lumex Flux
Value
[g/day]
44
42
27
18
25
27
27
41
40
30
26
13
11
11
15
40
48
62
46
33
32
7
5
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Wind Speed
[m/s]
2.7
2.7
2.4
2.3
2.3
2.1
2.1
2.3
2.2
2
1.9
1.4
1.3
1.3
1.2
1.7
1.9
1.9
1.6
1.3
1.4
1.4
1.7
1.7
1.6
1.6
1.8
1.8
1.5
1.5
1.3
1.3
1.2
2
2.2
2.4
2.4
Wind
Direction [deg
from normal
to VRPM
config.]
0
2
10
9
13
9
12
7
4
9
20
2
-3
-8
-39
-12
-17
-15
-10
-10
0
-16
-15
-14
-8
-4
-3
0
-8
-11
-18
-31
-44
-10
-6
-8
-10
Concordance
Correlation
Factor
1
0.999
0.988
0.986
0.98
0.967
0.976
0.993
0.997
1
0.916
1
1
1
1
0.904
0.992
0.982
0.988
1
1
0.999
0.963
0.965
0.966
0.978
0.973
0.942
0.998
1
0.948
0.973
0.958
0.892
1
1
1
Unadjusted
Flux Values
[g/day]
342
350
275
284
298
316
316
362
320
297
380
225
179
205
180
508
550
577
503
485
464
582
508
431
371
319
385
390
300
316
259
210
136
837
718
613
595
Adjusted
Emission Rate
[g/day]
344
362
323
332
372
370
386
404
343
344
551
234
186
227
310
585
676
695
567
547
468
713
608
512
408
336
400
392
330
363
324
317
258
952
771
681
670
71
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
2:42 PM
2:46 PM
2:50 PM
2:54 PM
2:58 PM
3:02 PM
3:22 PM
3:26 PM
3:30 PM
3:34 PM
3:38 PM
3:42 PM
3:46 PM
3:50 PM
3:54 PM
3:58 PM
5:30 PM
5:34 PM
5:38 PM
5:42 PM
5:50 PM
5:54 PM
6:06 PM
6:10 PM
8:14 PM
8:18 PM
8:22 PM
8:26 PM
8:30 PM
8:34 PM
8:38 PM
8:42 PM
9:06 PM
9:10 PM
9:58 PM
10:02PM
10:06PM
Lumex Flux
Value
[g/day]
0
9
21
35
47
59
78
84
90
89
83
78
80
75
78
70
30
27
28
34
28
33
30
32
34
38
38
39
42
41
43
38
49
43
25
27
27
Wind Speed
[m/s]
2.5
2.4
2.5
2.4
2.4
2.4
2.9
2.9
2.9
2.7
2.4
2.4
2.5
2.6
2.7
2.6
1.2
1.1
1.2
1.3
1.2
1.3
1.1
1.2
2.2
2.2
2.2
2.2
2.3
2.3
2.4
2.4
2.5
2.4
1.9
1.9
1.9
Wind
Direction [deg
from normal
to VRPM
config.]
-18
-28
-36
-41
-46
-57
-51
-44
-44
-45
-47
-47
-46
-44
-42
-41
-20
-14
-12
-14
-16
-16
-7
-7
0
0
-1
-1
0
0
0
0
-2
-1
1
2
1
Concordance
Correlation
Factor
0.991
0.977
0.962
0.961
0.97
0.968
0.931
0.961
0.945
0.935
0.94
0.954
0.942
0.951
0.959
0.947
0.947
0.94
0.958
0.956
0.941
0.984
0.982
0.949
1
1
1
1
1
1
1
1
1
1
1
1
1
Unadjusted
Flux Values
[g/day]
518
445
389
333
303
226
370
396
368
321
313
308
302
282
334
365
152
145
155
177
129
79
99
147
611
580
575
565
583
557
578
569
722
790
511
491
500
Adjusted
Emission Rate
[g/day]
643
643
632
597
601
580
817
759
700
620
626
622
598
540
614
659
196
172
178
208
157
96
108
160
611
585
584
574
590
558
578
569
746
805
521
503
507
72
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
10:10 PM
10:14 PM
11:06PM
11:10PM
11:18PM
Lumex Flux
Value
[g/day]
26
25
15
17
18
Wind Speed
1.8
1.7
1.3
1.4
1.4
Wind
Direction [deg
from normal
to VRPM
config.]
1
0
-9
-8
-4
Concordance
Correlation
Factor
1
1
1
1
1
Unadjusted
Flux Values
[g/day]
471
460
424
449
462
Adjusted
Emission Rate
[g/day]
476
464
474
498
487
ng
26 54
Flux: 17.3
910.6
455.3
108 162 216
Leakage: 0.8 [g/hr] Wind Dir/Speed: 9.4 [degrees] / 1.2 [m/s]
Figure 3-36. Example plume map for November 5, 2006.
73
-------
Figure 3-37. Time series of emission rate for November 6, 2006.
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
11/06/06
1200
1000
800
600
400
200
12:OOAM 2:24AM
0=.1
4:48 AM 7:12 AM 9:36 AM
Time
12:OOPM 2:24 PM 4:48 PM
74
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Table 3-23. Summary of Results for November 6,2006
Time
4:18 AM
4:22 AM
4:26 AM
4:30 AM
5:50 AM
5:54 AM
5:58 AM
6:02 AM
6:06 AM
6:10 AM
6:14 AM
6:58 AM
7:02 AM
7:06 AM
7:30 AM
7:34 AM
7:38 AM
7:42 AM
7:46 AM
7:50 AM
7:54 AM
7:58 AM
8:22 AM
8:26 AM
8:30 AM
8:34 AM
8:38 AM
8:42 AM
8:46 AM
8:50 AM
9:14 AM
9:18 AM
9:22 AM
Lumex
Flux
Value
[g/day]
21
25
27
29
21
22
24
23
23
22
21
24
27
31
35
33
33
28
22
13
9
3
24
42
54
67
73
86
99
110
93
98
96
Wind
Speed
[m/s]
1.8
1.9
1.9
2
2
2
2.1
2.1
2
1.9
1.9
2.2
2.2
2.3
2
2
2.1
2.1
2.3
2.3
2.4
2.4
2.3
2.3
2.2
2.3
2.3
2.6
2.7
2.7
2.9
3
3.1
Wind
Direction
[deg from
normal to
VRPM
config.]
-4
-3
-3
-2
0
0
0
0
0
1
1
0
0
0
4
5
4
6
7
6
6
6
8
8
6
6
2
-1
0
0
1
3
4
Concordance
Correlation
Factor
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0.995
0.99
0.996
0.997
1
1
1
0.999
0.977
0.959
0.974
0.97
Unadjusted
Flux Values
[g/day]
409
395
386
403
485
479
487
469
450
434
443
531
484
463
366
384
410
396
426
432
448
452
675
751
764
833
803
836
766
715
589
595
587
Adjusted
Emission
Rate
[g/day]
431
412
401
415
488
482
490
472
452
438
448
531
489
463
389
416
437
434
479
478
491
498
778
851
850
922
832
856
773
717
596
619
627
75
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
9:26 AM
9:30 AM
9:34 AM
9:38 AM
9:42 AM
10:06 AM
10:10AM
10:14AM
10:18AM
10:22 AM
10:26 AM
10:30 AM
10:34 AM
10:58 AM
11:02 AM
11:06 AM
11:10AM
11:14 AM
11:18 AM
1 1 :22 AM
1 1 :26 AM
11:50 AM
11:54 AM
11:58 AM
12:02 AM
12:06 AM
12:10AM
12:14AM
12:18AM
12:42 AM
12:46 AM
12:50 AM
12:54 AM
12:58 AM
1:02 PM
Lumex
Flux
Value
[g/day]
89
88
88
84
92
84
74
70
68
72
68
78
90
90
110
120
120
110
110
94
80
57
70
73
81
69
48
49
58
130
130
140
130
100
120
Wind
Speed
[m/s]
3
2.9
2.9
2.9
2.9
2.7
3
2.9
3
3
2.9
2.6
2.8
2.7
2.9
3.1
3.1
3.3
3.5
3.6
3.9
3
3.2
3.3
3.6
3.5
3.1
3
2.9
3.5
3.5
3.6
3.5
3.5
3.5
Wind
Direction
[deg from
normal to
VRPM
config.]
6
6
6
4
3
9
8
10
10
10
11
12
11
11
10
11
12
12
13
13
15
14
14
13
12
12
13
13
14
6
6
6
9
10
9
Concordance
Correlation
Factor
0.976
0.989
0.991
0.979
0.974
0.96
0.969
0.974
0.974
0.99
0.986
0.98
0.967
0.985
0.98
0.983
0.981
0.972
0.979
0.967
0.943
0.978
0.96
0.947
0.939
0.978
0.981
0.992
0.994
0.977
0.986
0.988
0.98
0.979
0.965
Unadjusted
Flux Values
[g/day]
536
522
543
534
518
561
671
613
607
599
523
459
564
622
628
636
544
562
553
513
498
221
525
529
614
189
572
572
616
813
744
251
189
217
634
Adjusted
Emission
Rate
[g/day]
589
572
597
566
546
647
767
730
714
711
630
565
681
746
738
767
669
692
696
648
648
285
666
659
759
234
713
724
789
904
822
277
221
256
737
76
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
1:06 PM
1:1 0PM
1:34 PM
1:38 PM
1:42 PM
1:46 PM
1:50 PM
1:54 PM
2:02 PM
2:26 PM
2:30 PM
2:34 PM
2:38 PM
2:42 PM
2:46 PM
2:50 PM
2:54 PM
3:18 PM
3:22 PM
3:26 PM
3:30 PM
3:34 PM
3:38 PM
3:42 PM
3:46 PM
Lumex
Flux
Value
[g/day]
110
110
79
85
88
77
76
66
47
44
51
70
79
88
92
100
100
110
100
110
110
110
100
91
69
Wind
Speed
[m/s]
3.4
3.4
2.9
3.3
3.7
3.8
4
4.3
4
3.7
3.4
3.1
3
2.7
2.6
2.7
2.7
2.8
2.6
2.6
2.5
2.5
2.3
2.2
1.9
Wind
Direction
[deg from
normal to
VRPM
config.]
11
11
15
18
20
21
24
25
24
22
16
14
13
10
12
12
12
9
6
4
4
5
5
6
7
Concordance
Correlation
Factor
0.971
0.959
0.958
0.956
0.965
0.951
0.937
0.963
0.951
0.958
0.959
0.967
0.977
0.975
0.983
0.985
0.984
0.984
0.983
0.977
0.976
0.973
0.975
0.994
1
Unadjusted
Flux Values
[g/day]
617
624
540
560
588
527
501
510
474
548
556
558
281
352
519
593
621
710
710
752
735
747
712
722
623
Adjusted
Emission
Rate
[g/day]
748
754
706
111
855
785
799
840
759
832
746
718
353
417
637
728
761
819
786
804
782
808
111
794
705
77
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Flux: 32,9
ice isj 216
Leakage: 2.8 tg/hr] Ulna Olr/Speed: 6,1 tdegrees] / 2,3 [«/sJ
Figure 3-38. Example plume map for November 6, 2006.
1200
11/07/06
0=.1
12:00 AM 12:14 AM 12:28 AM 12:43 AM 12:57 AM 1:12 AM 1:26 AM 1:40 AM 1:55 AM 2:09 AM
Time
Figure 3-39. Time series of emission rate for November 7, 2006.
78
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Table 3-24. Summary of Results for November 7,2006
Time
12:10AM
12:14AM
12:18AM
12:22 AM
12:26 AM
12:30 AM
1:1 8 AM
1 :22 AM
1 :46 AM
1:50 AM
1 :54 AM
Lumex
Flux
Value
[g/day]
65
63
52
54
57
66
39
48
73
57
50
Wind
Speed
[m/s]
3.5
3.5
3.1
3.2
3.2
3.1
2.5
2.8
3.6
3
2.7
Wind
Direction
[deg from
normal to
VRPM
config.]
-4
-2
-1
2
1
0
-1
0
1
2
3
Concordance
Correlation
Factor
1
1
1
1
1
1
0.94
0.998
0.996
0.979
0.886
Unadjusted
Flux Values
[g/day]
468
453
389
360
368
381
342
377
429
486
538
Adjusted
Emission
Rate
[g/day]
493
468
396
371
372
383
350
381
432
504
564
26 54
Flux: 16.7
108 162 216
Leakage: 2.1 [g/hr] Uind Dir/Speed: 0.4 [degrees] / 3.1 [m/s]
Figure 3-40. Example plume map for November 7, 2006.
79
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
11/10/06
1200
1000
800
600
400
200
*
7:12AM 9:36AM
0=.1
12:00 PM 2:24 PM 4:48 PM
Time
7:12PM 9:36 PM 12:00 AM
Figure 3-41. Time series of emission rate for November 10, 2006.
80
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Table 3-25. Summary of Results for November 10,2006
Time
8:42 AM
8:46 AM
8:50 AM
8:54 AM
8:58 AM
9:02 AM
9:06 AM
9:30 AM
9:34 AM
9:38 AM
9:42 AM
9:46 AM
9:50 AM
9:54 AM
9:58 AM
4:30 PM
4:34 PM
4:38 PM
4:50 PM
4:54 PM
5:18 PM
5:22 PM
5:26 PM
5:30 PM
5:34 PM
5:38 PM
5:42 PM
5:46 PM
6:10 PM
6:14 PM
6:18 PM
6:22 PM
6:30 PM
Lumex
Flux
Value
[g/day]
20
24
24
27
25
23
21
8
9
9
9
10
11
9
7
9
9
12
12
12
8
9
11
14
16
20
25
26
13
11
11
10
10
Wind
Speed
[m/s]
1.4
1.7
1.9
1.8
1.8
1.7
1.8
1.2
1.3
1.3
1.3
1.3
1.2
1.2
1.2
1.5
1.6
1.6
1.6
1.5
1.7
1.7
1.7
1.8
1.9
2.1
2.3
2.3
2.2
2.1
1.9
1.9
1.8
Wind
Direction
[deg from
normal to
VRPM
config.]
18
21
24
24
24
23
24
49
39
32
39
35
45
56
56
48
47
47
49
49
45
44
39
33
30
27
28
28
37
38
41
39
44
Concordance
Correlation
Factor
1
1
1
0.999
0.991
0.994
0.996
1
0.998
1
1
1
0.999
1
0.999
0.992
0.995
0.992
0.987
0.984
0.994
0.994
0.999
0.998
1
0.993
0.985
0.99
0.999
0.998
0.998
0.998
0.997
Unadjusted
Flux Values
[g/day]
692
684
593
481
424
367
355
112
184
204
211
182
125
73
69
90
150
65
59
49
69
114
129
167
145
140
430
413
117
85
147
126
87
Adjusted
Emission
Rate
[g/day]
961
1020
950
766
679
573
568
476
467
413
538
399
435
594
569
369
556
248
257
211
235
376
332
350
274
244
762
734
282
211
404
331
285
81
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Time
6:34 PM
6:38 PM
7:10 PM
8:02 PM
8:06 PM
8:14 PM
8:46 PM
8:50 PM
8:54 PM
8:58 PM
9:06 PM
9:10 PM
9:58 PM
10:50 PM
11:22PM
Lumex
Flux
Value
[g/day]
10
9
6
3
5
6
9
12
13
11
13
12
8
6
6
Wind
Speed
[mis]
1.8
1.9
1.3
1.1
1.2
1.2
1.8
1.8
1.8
1.7
1.8
1.9
1.9
2
1.5
Wind
Direction
[deg from
normal to
VRPM
config.]
45
48
58
56
53
49
45
46
47
48
51
53
59
60
59
Concordance
Correlation
Factor
0.994
0.995
0.982
0.993
0.997
0.989
0.992
0.998
0.998
0.998
0.996
0.989
0.913
0.954
0.983
Unadjusted
Flux Values
[g/day]
110
141
100
54
36
90
119
118
92
70
75
61
70
63
20
Adjusted
Emission
Rate
[g/day]
370
557
1210
445
221
381
403
428
352
280
386
348
875
987
278
26 54
Flux: 32.0
1969.2
1476.9
103 162 216
Leakage: 1.0 [g/hr] Wind Dir/Speed: 21.1 [degrees] / 1.7 [m/s]
Figure 3-42. Example plume map for November 10, 2006.
82
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
11/11/06
1200
1000 -
800 -
•8
a
»
E
600 -
400 -
200 -
12:00 AM 12:28 AM 12:57 AM
1:26 AM 1:55 AM
Time
2:24 AM 2:52 AM 3:21 AM
Figure 3-43. Time series of emission rate for November 11, 2006.
Table 3-26. Summary of Results for November 11,2006
Time
12:26 AM
12:34 AM
1:10AM
1:1 4 AM
2:50 AM
2:54 AM
Lumex
Flux
Value
[g/day]
3
4
10
11
9
8
Wind
Speed
[m/s]
1.6
1.6
2
2
1.5
1.2
Wind
Direction
[deg from
normal to
VRPM
config.]
59
58
54
55
42
35
Concordance
Correlation
Factor
0.944
0.93
0.94
0.938
0.938
0.946
Unadjusted
Flux Values
[g/day]
20
22
28
38
144
130
Adjusted
Emission
Rate
[g/day]
248
247
178
278
418
288
83
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
561.0
42u.fi
26 54 108 162 216
Flux: 8.3 Leakage: 0.4 [g/hr] Wind Dir/Speed: 41.8 [degrees] / 1.5 [m/s]
Figure 3-44. Example plume map for November 11, 2006.
11/12/06
a
600 -
i
5
1
0=.1
12:00 AM 2:24 AM 4:48 AM 7:12 AM 9:36 AM 12:00 PM 2:24 PM
Time
Figure 3-45. Time series of emission rate for November 12, 2006.
84
-------
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
Table 3-27. Summary of Results for November 12,2006
Time
9:42 AM
9:46 AM
9:50 AM
9:54 AM
9:58 AM
12:02 AM
12:06 AM
12:14AM
1:34 PM
1:38 PM
1 :42 PM
1:50 PM
Lumex
Flux
Value
[g/day]
24
22
28
29
29
24
27
26
28
23
20
21
Wind
Speed
[m/s]
2.4
2.5
2.7
2.6
2.5
1.5
1.6
1.8
1.8
1.6
1.4
1.7
Wind
Direction
[deg from
normal to
VRPM
config.]
-55
-50
-41
-48
-50
-19
-12
0
-55
-59
-58
-53
Concordance
Correlation
Factor
0.99
0.976
0.986
1
1
0.998
1
1
0.959
0.91
0.943
0.925
Unadjusted
Flux Values
[g/day]
145
200
250
182
171
423
496
465
191
131
95
124
Adjusted
Emission
Rate
[g/day]
356
429
449
372
370
538
573
466
469
356
251
285
523.1
26 54
Flux: 19.9
'ft
392.3
261.5
130.8
108 162 216
Leakage: 1.1 [g/hr] Wind Dir/Speed: -0.3 [degrees] / 1.6 [m/s]
Figure 3-46. Example plume map for November 12, 2006.
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3.3 Summary
ARCADIS and EPA ORD conducted one continuous, seven-week (53 day) monitoring
study for total site mercury emissions at Occidental Chemical's Muscle Shoals,
Alabama plant. The measurement campaign was conducted using a Vertical Radial
Plume Mapping (VRPM) measurement configuration, using three bistatic, open-path,
Ultra-Violet Differential Optical Absorption Spectroscopy (UV-DOAS) instruments,
operated on a 24-hour, 7-day per week basis. Site constraints necessitated the use of
an elevated VRPM configuration setup. Additionally, a Lumex Mercury Analyzer was
deployed along the ground, downwind from the cell room. The purpose of this
instrument was to provide an assessment of any emissions leakage, or emissions not
captured by the VRPM calculation due to the complex air flow caused by the numerous
obstructions in the vicinity of the lowest five meters of the VRPM configuration.
Mercury flux values were calculated for 23 days of the measurement campaign during
instances when the prevailing wind direction was ± 60° from perpendicular to the
VRPM configuration and the vertical plume capture criterion was met. Additionally, the
mercury emission rate for each period was calculated by applying an adjustment factor
to the calculated flux value, considering the plume capture in the horizontal direction.
Mercury Flux and emission rate values were also calculated for periods when the
vertical plume capture criterion was not met.
A total of 1170 mercury emission flux estimates were produced for 20 minute time
periods. The 24 hour extrapolated mercury emission rate values ranged from 18 to
1210 grams per day, with an average of 410 grams per day. The extrapolated
emission rate is summarized in figure 3-47. Overall measurement uncertainty is
estimated to be within +/-20% which is sufficient to meet the order of magnitude data
quality objective for this project.
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
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Measurement of Total Site
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Open-Path UV-DOAS
24 hr Extrapolated Fugitive Hg Emissions (by VRPM)
70
60
50
= 40
£ 30
JQ!
-5
20
10
200 400 600 600 1000
Extrapolated Hg Emissions (g/day)
1200 14-00
Figure 3-47. Summary of 24-hour extrapolated mercury emission values.
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Open-Path UV-DOAS
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4. QA/QC
The data collected during this project was intended to provide support for the
development of environmental regulations and standards. It is of sufficient scope and
substance that these results could be combined with those from other projects of
similar scope and substance to provide necessary information for decisions. They are
not intended for direct use in enforcement activities, litigation, or human studies. They
are not sufficient to make the needed decisions without input from other projects. This
project data was collected in conformance with the quality requirements of NRMRL QA
Category II.
4.1 Instrument Calibration
All equipment is calibrated annually and/or cal-checked as part of standard operating
procedures. Certificates of calibration are kept on file. Maintenance records are kept for
any equipment adjustments or repairs in bound project logbooks that include the data
and description of maintenance performed. Instrument calibration and QC procedures
and frequency are listed in Table 4-1 and are further described in the text.
As part of the preparation forthis project, a Category II Quality Assurance Project Plan
(QAPP) was prepared and approved for the field campaign.
4.2 Assessment of DQI Goals
The critical measurements associated with this project and the established data quality
indicator (DQI) goals in terms of accuracy, precision, and completeness are listed in
Table 4-2. More information on the procedures used to assess DQI goals can be found
in Section 10 of the ECPD Optical Remote Sensing Facility Manual (USEPA, 2004).
Measurement of Total Site
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Measurement of Total Site
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Open-Path UV-DOAS
Table 4-1. Instrumentation Calibration Frequency and Description
Instrument
OPSIS UV-DOAS
Lumex Mercury Analyzer
Climatronics Model 101990-G1
Meteorological Head
Climatronics Model 101990-G1
Meteorological Head
R.M. Young Meteorological
Head
R.M. Young Meteorological
Head
Topcon Model GTS-21 1D
Theodolite
Topcon Model GTS-21 1D
Theodolite
Measurement
Analyte PAC
Mercury concentration
Wind Speed in
miles/hour
Wind direction in
degrees from North
Wnd Speed in
miles/hour
Wnd direction in
degrees from North
Distance Measurement
Angle Measurement
Calibration Date
Pre-deployment and in-field
QC Checks
Pre-deployment and in-field
checks
June 7, 2006
June 7, 2006
June 7, 2006
July 14, 2006
April 19, 2006
April 19, 2006
Calibration Detail
Appendix E and H of this
document of project QAPP
Appendix F of project QAPP
APPCD Metrology Lab Cal.
Records on file
APPCD Metrology Lab Cal.
Records on file
APPCD Metrology Lab Cal.
Records on file
APPCD Metrology Lab Cal.
Records on file
Calibration of distance
measurement.
Actual distance=19.6 m
Measured distance= 19.56 m
Calibration of angle
measurement.
Actual angle= 360°
Measured angle=
360°28'47"
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Measurement of Total Site
Mercury Emissions from a
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Open-Path UV-DOAS
Table 4-2. DQI Goals for the Project
Measurement
Parameter
Mercury PAC
Mercury
concentrations
Ambient Wind
Speed
Ambient Wind
Direction
Distance
Measurement
Beam angle
Analysis Method
UV-DOAS, bistatic
Lumex Mercury Analyzer
Climatronics
meteorological head post-
field calibration by EPA
Metrology Lab
Climatronics
meteorological head with
clip to North
Theodolite- Topcon
Theodolite- Topcon
Accuracy
±15%1
±25%3
±10% of actual
wind speed
±10°
±1m
±0.1°
Precision
±15%1
±25%3
±10% of
actual wind
speed
±10°
±1m
±0.1°
Detection Limit
-0.003 ppbv2
-0.0002 ppbv
Not applicable
Not applicable
Not applicable
Not applicable
Completeness
75%
90%
90%
90%
100%
100%
1. The QC check procedures for determining the accuracy and precision of the UV-DOAS
instruments can be found in Appendix H of the project QAPP.
2. The procedures used for determining the minimum detection limit of the UV-DOAS
instruments can be found in Section 5.3 of Appendix E of the project QAPP.
3. The QC check procedures for determining the accuracy and precision of the Lumex Mercury
Analyzer can be found in Section 4.4.2, and Appendix F of the project QAPP.
4.2.1 DQI Check for UV-DOAS PAC Measurements
Three ultraviolet differential absorption spectroscopy measurement (UV DOAS)
instruments, manufactured by OPSIS AB, Furulund, Sweden, were employed to
capture elemental Hg° vapor concentrations in the VRPM plane. Before arriving at the
site, EPA inspected and tested the instruments at the ORD laboratory in Research
Triangle Park, North Carolina. The components included three UV DOAS opto-
analyzers (model AR500), three emitter telescopes utilizing xenon arc lamps, three
receiver telescopes, and an optical calibration bench. Each receiver telescope was
connected to an AR500 opto-analyzer, located in the mobile lab, by a uv-transparent
fiber optic cable.
An OPSIS calibration bench, located in the mobile lab, was used to calibrate the
analyzers and to conduct periodic calibration checks. The optical bench consisted of a
xenon arc lamp and paired emitter and receiver parabolic mirrors of similar optical
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design as the telescopes. During calibration, the fiber optic cables were disconnected
from the receiver telescopes and then reconnected to the receiver end of the optical
bench. Using the same fiber optic cable ensured that measurement bias that may be
caused by damaged fibers would be apparent during calibration checks.
Before challenging the analyzers with known concentrations of Hg° as described
below, detector and signal processing functions were tested by conducting a System
Check and Wave Precision Check, and by observing the spectral evaluation in Scan
Signals to ensure the hardware was operating normally and that adequate signal was
being transmitted to the analyzer from the receiver telescope. During calibration,
closed UV-transparent cells containing liquid Hg° and vapor were placed in the optical
bench light path to challenge the analyzers. The Hg° vapor concentrations were
determined by measuring the cell temperature using a laboratory-grade digital
thermometer and a headspace temperature-concentration curve provided by the
manufacturer. Cells of differing lengths were used for multi-point span calibrations and
periodic calibration checks. The linear range of calibration was approximately 0 to
14,000 ng/m3 during the first month of measurements, and was reduced during the
second month after it was concluded that 14,000 ng/m3 was much higher than the
recorded ambient concentrations. The linear calibration range was greater than the
ambient concentrations measured during the project, and the accuracy and precision
was within the acceptable range of ±15%.
The schedule of calibration checks is summarized in Tables 4-3, 4-4, and 4-5.
Measurement of Total Site
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Table 4-3. Low Path (Analyzer Ser. No. E-202)
Date
(2006)
9-14
9-21
9-22
10-17
11-13
Calibration Type
Reference, span,
offset
Span, offset check
Reference, span,
offset
Span, offset check
Span, offset check
Range
(ng/m3)
0-13,528
0-8,373
0-11,094
0-7,434
0-9419
Analyzer
Response
(%)
1 to 2
-9 to 7
-6 to 14
-8 toO
-12 to 5
Notes
Pre-measurement
calibration.
New calibration after
replacing receiver fiber.
Post-measurement
calibration check.
Table 4-4. Middle Path (Analyzer Ser. No. E-700 )
Date
(2006)
9-15
9-19
9-23
10-17
11-13
Calibration Type
Reference, span,
offset
Span offset check
Reference, span,
offset
Span, offset check
Span, offset check
Range
(ng/m3)
0-12,581
0-12,446
0-5,291
0-8,411
0-6,665
Analyzer
Response
(%)
-1 to 8
-8 to 10
-15 to 5
-9 to 13
-9 to -1 1
Notes
Pre-measurement
calibration.
Recalibration following
hardware adjustments.
Post-measurement
calibration check.
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Open-Path UV-DOAS
Table 4-5. High Path (Analyzer Ser. No. E-466)
Date
(2006)
9-07
9-21
10-18
11-14
Calibration Type
Span, offset
Span, offset check
Span, offset check
Span, offset check
Range
(ng/m3)
0 - 8772
0-14,053
0-6,268
0-7,092
Analyzer
Response
(%)
3 to 8
-7 to 10
-6 toO
-3 to -5
Notes
Pre-measurement calibration.
Post-measurement calibration check.
The primary DQI is the standard deviation of the Hg concentration measurement. A
concentration measurement is valid when the ratio of the concentration to deviation
(C:D) is greater than or equal to 10:1. The lowest C:D observed during calibration was
15:1 and the majority of the measurement points were in excess of 50:1, therefore the
calibration data indicated that the analyzers performed normally during the project.
A secondary DQI is the signal strength, represented by the analyzer software as
percent light, with 100% light being the saturation point of the detector. The minimum
light level for valid measurements is determined by observing the point at which the
measurement standard deviation increases sharply as a function of declining signal
strength. Light levels below the minimum, or 10% to 15% light, occurred during
periods of fog and heavy rain. However, there was adequate signal during all times
when the wind direction and wind speed were within the VRPM acceptance
parameters. Data capture during such periods was 100%.
The estimated minimum detection limit of the OPSIS analyzers is 49.6 ng/m3.
4.2.1.1 Problems Encountered
There were no problems encountered that affected the data.
4.2.2 DQI Checks for Lumex Measurements
A quality control check was performed on the Lumex Mercury Analyzer at the EPA
facility prior to deployment to the field. The check was done using a Tekran 3310
instrument to generate a known concentration of mercury. The effluent from the
Tekran 3310 was attached to the sample port of the Lumex Mercury Analyzer. A
Thermo 80i monitor was used to measure the mercury concentration from the Tekran
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Open-Path UV-DOAS
3310 effluent line. The Lumex Mercury Analyzer collected ten consecutive mercury
concentration measurements. The results were then compared to the mercury
concentration measured with the Thermo 80i monitor (10.43 ug/m3). The average
mercury concentration measured by the Lumex Mercury Analyzer was 12.20 ug/m3, or
a 17% difference from the ThermoSOi mercury concentration. The %RSD of the
Lumex Mercury Analyzer measurements was 0.09. Based on the DQI criterion set
forth for precision and accuracy (25%), the results of this QC check indicated that the
Lumex Mercury Analyzer was operating within acceptable limits at the time of
deployment.
Additional DQI checks were conducted in the field by performing a Serviceability Test
described in the Lumex Mercury Analyzer User's Manual (Appendix F of the project
QAPP). The test is done by performing measurements using a test cell, containing
gas from the calibration standard. The cell is built into the instrument, and is accessed
by setting the instrument to the "test" mode, and collecting measurements. According
to the instrument User's Manual, if all measured relative deviation values (R%) are less
than 25%, the instrument is operating adequately, and measurements may be
collected. This check was conducted during the first week of deployment and during
the calibration and maintenance visit by ARCADIS personnel.
During the Serviceability Test performed on 26 September 2006, all R% values were
less than 25% (4, 6, 4, 5, 5, 6, 5, 5, 6. 6. 4, 5, 7, 5, 7, 7, 7, 6,8,6,11, 7, 7, 7, and 7).
During the Serviceability Test performed on 18 October 2006, all R% values were also
less than 25% (5, 5, 5, 5, 5, 6, 5, 6, 5, 5, 5, 4, 6, 6, 6, 6, 6, 7, 7, 7, 7, 7, 6, 8, 6, 7, 6, 7,
6,8,8,8,8,8,8,6,6,7,9,6,6,6).
The results of the two tests indicated that the instrument was operating in an
acceptable manner.
4.2.3 DQI Checks for Ambient Wind Speed and Wind Direction Measurements
The meteorological head DQIs are checked annually as part of the routine calibration
procedure. The Climatronics Model 101990-G1 Meteorological Head used during the
first four weeks of this field campaign (September 21, 2006 through October 18, 2006)
was calibrated by the EPA's APPCD Metrology Laboratory on June 7, 2006. Validation
of wind data collected were performed initially at the time of deployment. Upon
deployment, the Field Team Leader performed a visual inspection of the wind vane,
and compared the compass heading of the vane to the data displayed from the
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instrumentation. The data was also validated as part of the weekday telemetry and
data check procedures to ensure that data was being collected, and there were no
communication problems with the instrumentation. While data collection was occurring
(and ARCADIS and EPA staff were present at the site), the measured wind direction
was compared to the forecasted and observed wind direction for that particular day.
Although the Climatronics monitor had been calibrated prior to field deployment, and
had passed the QC checks in the field, some questionable wind direction readings
were noted during the initial weeks of the measurement campaign. At times, the
recorded wind direction did not agree with the actual wind direction observed by project
personnel. Because of concerns for the reliability of the data being produced by this
instrument, it was replaced with the R.M. Young monitor on 19 October 2006. The wind
speed measurement collected with the R.M. Young head was calibrated by the EPA's
APPCD Metrology Laboratory on June 7, 2006. The wind direction measurement was
calibrated by the EPA's APPCD Metrology Laboratory on July 14, 2006.
In order to assess the reliability of the wind direction data collected with the
Climatronics instrument during the first four weeks of the project, the wind direction
data collected with the instrument were compared with National Weather Service data
obtained from the Automated Surface Observation System (ASOS) located at the -
Northwest Alabama Regional Airport, located approximately two miles from the project
site. Based on two minutes wind averages, there were four days in which the
directional trends matched, but where the wind direction data was offset by a
consistent factor. Figures 4-1, 4-2, 4-3, and 4-4 present a time series comparison of
wind direction data collected with the Climatronics head, and wind direction data from
the National Weather Service ASOS for 21 September, 22 September, 30 September,
and 8 October, respectively. The wind direction correction factors obtained from these
comparisons are presented in Table 3-3 of this document.
Measurement of Total Site
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Chlor-alkali Plant Using
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Measurement of Total Site
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Open-Path UV-DOAS
360
22 43 64 85 106 127 148 169 190 211 232 253 274 295 316 337 3
-ASOS Data
- Climatronics Data
Time Period
Figure 4-1. Comparison of prevailing wind directions from September 21, 2006 measured with the
Climatronics meteorological head and the National Weather Service Automated Surface
Observation System located at Northwest Alabama Regional Airport.
20 39 58 77 96 115 134 153 172 191 210 229 248 267 286 305 324 343
-ASOS Data
-Climatronics Data
Time Period
Figure 4-2. Comparison of prevailing wind directions from September 22, 2006 measured with the
Climatronics meteorological head and the National Weather Service Automated Surface
Observation System located at Northwest Alabama Regional Airport.
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Open-Path UV-DOAS
360
-ASOS Data
• Climatronics Data
20 39 58 77 96115134153172191210229248267286305324343
Time Period
Figure 4-3. Comparison of prevailing wind directions from September 30, 2006
measured with the Climatronics meteorological head and the National
Weather Service Automated Surface Observation System located at
Northwest Alabama Regional Airport.
-ASOS Data
- Climatronics Data
20 39 58 77 96 115134153172191210229248267286305324343
Time Period
Figure 4-4. Comparison of prevailing wind directions from October 8, 2006 measured
with the Climatronics meteorological head and the National Weather
Service Automated Surface Observation System located at Northwest
Alabama Regional Airport.
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Open-Path UV-DOAS
Figure 4-1 shows that wind direction data was collected with the Climatronics
instrument from approximately time period 180 to 345. During this period, the
Climatronics instrument was generally recording wind directions ranging from
approximately 260° to 360°. However, the instrument recorded a baseline reading of
approximately 260° for a long period of time. During this same period, the ASOS
instrument recorded a baseline wind direction of approximately 10°. Based on this, a
wind direction correction factor of 110° was applied to all wind direction data collected
with the Climatronics instrument on September 21, 2006. It is additionally noted that
the wind direction was visually verified by onsite personal during this day and found to
be similar to the ASOS data. The Climatronics met head was aligned properly with the
onsite wind sock but the collected data was displaying improper values. A malfunction
with the auto north feature of the instrument was suspected.
Figure 4-2 shows that wind direction data was collected with the Climatronics
instrument from approximately time period 20 to 150. During this period, the
Climatronics instrument recorded a baseline wind direction of approximately 280°.
During this same period, the ASOS instrument recorded a baseline wind direction of
approximately 30°. Based on this, a wind direction correction factor of 110° was
applied to all wind direction data collected with the Climatronics instrument on
September 22, 2006. It is additionally noted that the wind direction was visually verified
by onsite personal for during this day agreeing with ASOS data. Malfunctions in the
Climatronics auto north alignment feature was suspected and were addressed at this
point but intermittent operation of the unit continued
Figure 4-3 shows that wind direction data was collected with the Climatronics
instrument from approximately time period 1 to 130. During this period, the
Climatronics instrument recorded a baseline wind direction of approximately 140°.
During this same period, the ASOS instrument recorded wind direction values ranging
from 0° to 60°. Since the 0° values represent times when the wind conditions were
calm, the actual baseline wind direction recorded with the ASOS instrument was
approximately 40°. Based on this, a wind direction correction factor of 100° was applied
to all wind direction data collected with the Climatronics instrument on September 30,
2006.
Figure 4-4 shows that wind direction data was collected with the Climatronics
instrument for the entire day. Although there are instances of variable wind directions,
the baseline wind direction recorded with the Climatronics instrument was
approximately 270°. During this same period, the ASOS instrument recorded a
baseline wind direction of approximately 330°. Based on this, a wind direction
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correction factor of 60° was applied to all wind direction data collected with the
Climatronics instrument on Octobers, 2006.
The same analysis was performed on all other wind direction data produced by the
Climatronics monitor during the project. The results of this analysis found that wind
direction data collected with the Climatronics monitor on all other days were
acceptable. Figures 4-5, 4-6, 4-7, and 4-8 present a time series comparison of wind
direction data collected with the Climatronics head, and wind direction data from the
National Weather Service ASOS for October 11, October 14, October 17, and October
18, respectively.
Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
360
19 37 55 73 91 109127145163181199217235253271289307325343
ASOS Data
Climatronics Data
Time Period
Figure 4-5. Comparison of prevailing wind directions from October 11, 2006
measured with the Climatronics meteorological head and the National
Weather Service Automated Surface Observation System located at
Northwest Alabama Regional Airport.
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Measurement of Total Site
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Open-Path UV-DOAS
360
23 45 67 89 111 133 155 177 199 221 243 265 287 309 331 353
-ASOS Data
-Climatronics Data
Time Period
Figure 4-6. Comparison of prevailing wind directions from October 14, 2006 measured with the
Climatronics meteorological head and the National Weather Service Automated
Surface Observation System located at Northwest Alabama Regional Airport.
360
•ASOS Data
•Climatronics Data
Time Period
Figure 4-7. Comparison of prevailing wind directions from October 17, 2006 measured with
the Climatronics meteorological head and the National Weather Service Automated
Surface Observation System located at Northwest Alabama Regional Airport.
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Open-Path UV-DOAS
-ASOS Data
-Climatronics Data
24 47 70 93 116 139 162 185 208 231 254 277 300 323 346
Time Period
Figure 4-8. Comparison of prevailing wind directions from October 18, 2006 measured with
the Climatronics meteorological head and the National Weather Service Automated
Surface Observation System located at Northwest Alabama Regional Airport.
4.2.4 DQI Checks for the Topcon Theodolite
QC checks are not performed before each field campaign; however, the calibration
date of the instrument was verified by referencing the calibration sticker. Before field
deployment, the battery packs were charged. The following additional QC checks were
made on April 19, 2006. The QC check of distance measurement was done at the EPA
facility using a tape measure. The actual distance was 30.58 meters, and the
measured distances were 30.61 and 30.59 meters. The results indicate accuracy and
precision fall well within the DQI goals of ±1 m. The QC check of angle measurement
was also performed. The actual angle was 360°, and the measured angled were
359°37'53" and 360°27'27". The results indicate accuracy and precision fall well within
the DQI goals of ±0.1°.
Additionally, there are several internal checks in the theodolite software that prevent
data collection from occurring if the instrument is not properly aligned on the object
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being measured, or if the instrument has not been balanced correctly. When this
occurs, it is necessary to re-initialize the instrument to collect data.
4.2.5 Daily Telemetry Check Assessment
Each weekday of the six-week measurement campaign, the ARCADIS field team
leader performed a telemetry check, downloaded and archived all data since the last
check, and verified that continuous, acceptable data (according to UV-DOAS and
Lumex Mercury Analyzer QC criteria) were collected. The data was downloaded
following the procedures described in Appendix J of the project QAPP: Project-Specific
Operating Procedures for Data Downloading and Validation Via Telemetry. Section 6.1
of this document details the data naming scheme that was used for the project. Data
included path-averaged concentration (PAC) data from the three UV-DOAS
instruments, mercury concentrations from the Lumex Mercury Analyzer, and wind data
from both meteorological heads. All of this data were considered critical, as it was
needed to meet project objectives.
4.2.6 Problems Encountered
During the six-week measurement campaign, the project encountered some problems
with instrumentation and data telemetry. The issues encountered with the Climatronics
meteorological head are discussed at length in Section 4.2.3 of this document.
The project team encountered some problems with the remote telemetry system used
to download the data remotely. These problems primarily occurred during the first
couple of weeks, and were expected. The problems included issues with the phone
line which was installed to the field trailer, and problems with the interface between the
data collection computer and the remote telemetry software. These issues were
resolved by contacting Occidental Chemical personnel on site, who were able to assist
in correcting the problems. During a subsequent site visit by ARCADIS and EPA ORD
personnel, the settings on the data collection computer and remote communication
software were adjusted, which resolved many of the problems, and improved the
performance of the remote telemetry system for the duration of the project.
The project team encountered another minor problem in obtaining the distances and
angles of the OPSIS sources mounted on the water tower, with respect to the location
of the OPSIS receivers. Since it was not possible to deploy a retro reflecting mirror at
the location of the sources mounted on the tower, it was necessary to use a Bushnell
Field Rangefinderand Suunto Climometerto obtain the distances and angles of the
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location of the OPSIS sources, respectively. The manufacturer states that the Bushnell
Field Rangefinder has an accuracy of ±1 meter at a range of 100 meters.
4.3 EPA and ARCADIS Audits and Corrective Actions
Because this project has been designated QA Category II, an EPA internal technical
systems audit (TSA) was performed at the site on October 19, 2006 by the EPA QA
officer. In general, the auditors found that the EPA and ARCADIS project staff were
doing a good job of measuring the mercury path-integrated concentrations at the plant,
and the measurements were being implemented as stated in the project QAPP. The
auditors did not find any issues that required corrective actions. A copy of the TSA
report and responses to findings can be found in Appendix B of this document.
In addition to the EPA audit, the ARCADIS QA officer performed internal assessments.
An internal on-site technical systems audit performed by the ARCADIS QA officer
could not be scheduled for this project due to funding and time conflicts. To ensure
field operations were conducted according to this QAPP, the ARCADIS QA officer
prepared an internal technical systems audit checklist. Completion of the checklist was
not considered an internal technical systems audit, but served as documentation that
implementation of QAPP elements were reviewed at the site.
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5. References
EPA quality assurance project plan entitled, Measurement of Total Site Mercury
Emissions from a Chlor-alkali Plant Using Open-Path UV-DOAS (rev. 0.3 September,
2006).
Hashmonay, R.A., D.F. Natschke, K.Wagoner, D.B. Harris, E.L.Thompson, and M.G.
Yost, Field evaluation of a method for estimating gaseous fluxes from area sources
using open-path Fourier transform infrared, Environ. Sci. Technol., 35, 2309-2313,
2001.
U.S. Environmental Protection Agency, ECPB Optical Remote Sensing Facility
Manual, U.S. EPA National Risk Management Research Laboratory, Air Pollution
Prevention and Control Division, Emissions Characterization and Prevention Branch,
Contract No. EP-C-04-023, Work Assignment 0-33, April 2004.
105
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Measurement of Total Site
Mercury Emissions from a
Chlor-alkali Plant Using
Open-Path UV-DOAS
This page intentionally left blank.
106
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Appendix A
APPENDIX A
OAQPS Project Plan:
Study of Gaseous Mercury Fugitive Emissions from Cell Rooms and Other
Sources at Mercury Cell Chlor-Alkali Plants
(dated September 8, 2005)
A-1
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Appendix A
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A-2
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Appendix A
PROJECT PLAN
STUPY OF CASEOUS MERCURY FUOTIVFJ EMISSIONS FROM CELL ROOMS
AM> OTHER SOURCES AT MERCURY CELL CHLOR-ALKALI PLANTS
Prepare*! for:
Hi am Rftsarlo, Work Assignment Manager (C439-02)
U.8* En* iron menial Protocliun Agency
Research Triangle Park, North Carolina 27711
September 8,20O5
Revision Ku* 2
EC/R Inenrpnrated
6330 Quadrangle Drive, Suite 325
Chapel Hill, N'C 27517
<919)4$4-0222
A-3
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Appendix A
TABLE OF CONTENTS
1,0 INTRODUCTION AND BACKGROUND Page 1 of 14
I.I Description of Mercury Cell Chi or- Alkali Process Page I of 14
1.2 Mercury Releases From Mercury Cell Chlor-Alkali Plants Page 3 of 14
1.3 Overall Fate of Mercury Page 6 of 14
1.4 FPA's Reams (derail on of the Mercury Cell MACT Page 6 of 14
2.0 PROBLEM DEFINITION , Page 7 of 14
3.0 PROJECT ORGANIZATION Page 7 of 14
4.0 SOURCES INSIOR THE CELL ROOM Page 9 of 14
4.1 Cell Room Continuous Monitoring System* Page 10 of 14
4,2 Validation of Systems Page 11 of 14
4.3 Monitoring of Process and .Maintenance Activities Page I i of 14
5.0 SOURCES OUTSIDE THE CELL ROOM Page i I of 14
5.1 Emissions Data Collection Page 12 of 14
5.2 Monitoring of Process and Maintenance Activities Page 12 of 14
6.0 RECEIPT AND ANALYSIS OF DATA Page 12 of 14
6.1 Data to Be Received Page 12 of 14
6.2 Analyses to IK Performed Page 13 of 14
6.3 How tliis Project Will Information the MACT Reconsideration . . . Page 13 of 14
LIST OF TABLES
Table 1. Summary of 2002 Mercury Releases from Mercury Cell Chlor-Alkali Plants
in the Toxics Release Inventory Page 3 of 14
Table 2. Summary of Previous Studies to Measure Mercury Fugitive Emissions From Mercury
Cell Chlor-Alkali Plant Cell Rooms Page 5 of 14
Table 3. Summary of Project Elements and Specific Data-Information Expected . . Page K of 14
A-4
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Appendix A
DISTRIBUTION LIST
Ruth Carter. Mew Jersey Attorney General's Office
Jon Be vine. Natural Resources Defense Council
Paul Dre&sel, EPA/Region III
Arthur Dungai), Chlorine Iii&lilute
Sieve Fruh^F.P A/O AQPS/F.S D
Walter Gray, MACTEC
Ray Givonctlu Oxychcm Corporate Office
Bill Grimley, liPA-OAQPS/LMAD
Eric I tall EPA'ORD/NRMRL
Ram ila^timaimy, ARCADIS
Bruce Harris, FPA/ORD/NRMRI.
John Jenks, New Jersey DEP
Donna Lee Jones. EPA/OAQPS/ESD
Frank Meadows, MACTEC
Mark Modrak, ARCADIS
Sam Mortis.. Oxychem Delaware City Plant
Phil Norwood, RC/R Incorporated
Conn i cSuc OWham. E PA/OAQPS/F.M A D
Stephen Ours, Del a ware DNREC
James Pew. Earlhjuslice
Iliani Rosario, EPA/OAQPS/ESO
Dave Rysoski, Oxyehem Muscle Slioals, Plaul
Rex Stow-ers.. Oxycliem Muscle Shoals Plant
F.ben Tliwnia, FPA/ORD/NRMRI.
Richard Timnions, Oxychem Delaware Cily Plant
John Wcslcndorf, Oxychem Corporate OtT5cc
A-5
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Appendix A
Prisjt>tl Plan
^stiftn* Siedl^
Kfs iykwi %i>> 2
i-mhM 8, 2IMIS
,0 INTRODLCT1O1N AND BACKGHOUND
Mercury cell cMor-alkali plants produce chlorine and caustic soda (sodium hydroxide) or
caustic potash (potassium hydroxide) in an electrolytic reaction. This process results in releases
of mercury K.i the air from pisinl ami fugitive sources. Quantifying the level of emissions from
fugitive KiHirces has proven to be di ITicult. Since mercury cell chkir-ulkali plants are unable to
totally account for all the mercury entering and leaving their plants, this uncertainly in the
amount of mercury that is emitted from fugitive emission sources has caused considerable
debate. Currently, this discrepancy is at the center of litigation on the recently promulgated
maximum achievable control technology (MACT) regulation tor mercury emissions from
mercury cell chlor-alkali plants. As pan of the reconsideration oflhis regulation in response to
this litigation, EPA is conducting a project to determine if the fugitive emissions from mercury
cell chlor-aikali are better characterized by the historical assumptions or by the amount of
mercury that is unaccounted for each year. This document describes this project,
The remainder of this section provides background on the industry, the air emissions and
other lei eases, the fate of mercury, and the regulatory history. Section 2 provides, the definition
of ihe problem lo be addressed in this, project- Section 3 introduces the elements of the project,
and Sections 4 and 5 provide more detail on the two elements Section ft discusses how ihc
information received will be analysed and potentially used in the reconsideration of the MACT
regulation.
1.1 Description of Mercury Cell Chlor-Alkali Process
At a chlor-alkuli plant, two chemicals (chlorine and an alkaline base (NaQH or KQHJ I
arc simultaneously produced as a result of the electrolysis of saltwater. Most commonly the
alkali is sodium hydroxide (caustic soda), winch is produced from sodium chloride and water.
Potassium hydroxide can also be produced from potassium chloride. This process also produces
hydrogen as a by-product. The basic chlor-alkali reaction is shown in Equation i:
If/zO -» INaOfI + Ci'i + H2 Equation (1)
'['here are three types of electrolytic chlor-alkali processes: the diaphragm cell process.
the mercury cell process, and the membrane cell process. Membrane cells are the state-of-the-art
technology, and all new chlor-alkali plants thai are built today use membrane cells. While
mercury cells once made up the majority of the clilor-alkali industry, no new mercury cell plants
have been constructed since the 1960s. In I*)K4, there were 24 mercury cell plants operating in
the United Stales, When the NESHAP for Mercury Emissions from Mercury Cell Chlor-Alkali
Plants (40 CFR 63, subpart Hill) was proposed in 2002 <6« FR 44672> July 3. 2D02K the number
of operating mercury cell plants had decreased to 12. Currently, there are 9 mercury cell plants
operating in the United Slates. Mercury cell plants are the only type of chlor-alkali plants that
use and emit mercury.
1 Of 14
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Appendix A
Prisj**! Plan
MfreHiy FiijjHive Fm^stiftn* Sind^-
Kfs iiit'HI %i>> 2
Septemhrr ft, 2IMIS
A mercury cell plant typically has scores of individual cells ( around 60 feel long and Q
feel wide) housed in one or more cell buildings. Mercury cells are electrically connected together
in series in circuits, of 30 or more ceils. In the mercury cell process, each cell involves (wo
distinct operations. The electrolytic cell producer chlorine gas. and a separate decomposer
produces hydrogen gas and caustic soda/potash .solution. There is one decomposer associated
with each cell. The cell and the decomposer are linked at the two ends by an inlet cndbox and an
outlet endbox,
A stream of liquid mercury flows in a continuous loop between the electrolytic cell and
the decomposer. The mercury enters, the cell at the inlet endbox and Hows down a .slight grade to
the outlet endbox. At the outlet endbox, the mercury Hows out of the cell and Mh down to lite
decomposer. After being processed in the decomposer, the mercury is pumped back up to the
inlet endbox of the electrolytic cell.
Saturated salt brine (using either sodium chloride or potassium chloride) is fed to the
electrolytic cell at the inlet endbox and Hows toward the outlet endbox on top of the mercury
stream. The brine and mercury How under a dimensional ly stable metal anode made of a
titanium substrate with a metal catalyst. The mercury forms the cathode of the cell. An electric
current is applied between the anode and the mercury cathode, The electric current causes a
reaction producing chlorine gas at ihc anode and a rnercury:sodium < HgNa) or
inercury:potassium (HgK) amalgam at the cathode. Chlorine is collected at the tap of the cell.
The amalgam ultimately exits at the outlet endbox, falling into the decomposer. Depleted brine
also exits the cell at the outlet endbox. This brine is generally piped to a tank for ^saturation and
reuse.
The decomposer is a packed bed reactor where (he mercury amalgam is contacted with
deioni/ed water in the presence of a catalyst.. The amalgam reacts with the water, regenerating
elemental mercury and producing caustic soda/potash (NaOH or K.OH) and hydrogen. The
caustic soda>'poiash and mercury are separated in a trap at the end of the decomposer. The
caustic soda/potash and hydrogen arc transferred to auxiliary processes for purification, and ihe
mercury is recycled back to Ihe cell.
Chlorine is collected from the tops of the mercury- cells by a common header system
which runs through the cell building. Hydrogen is collected from the amalgam decomposers in a
common header .system. 71 le hydrogen stream contains a small amount of mercury vapor from
the liquid mercury processed in the decomposer. To remove Ihe mercury vapor, the hydrogen
stream is typically cooled, passed through a mist eliminator, and usually sent to a finishing device
such as a carbon adsorber, The hydrogen may ihen be discharged to I he atmosphere, used on-
site, or sold for use ofT-site.
In a mercury cell process, a 50 percent caustic solution is obtained directly from the
amalgam decomposers. Thus, the mercury cell caustic requires little further processing to yield a
commercial product.
of 14
A-7
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Appendix A
Projitl nan
wry Fnjjisib* I'ifflH&irtns Siiadv
Hf* iiioti No. 1
September 8, JlMlS
1.2 Mercury Releases From Mercury Cell t'hlor-Aikali Plants
At a mercury cell ehlor-alkali plant, mercury is emitted from point sources (i.e.. stacks)
arid fugitive sources. Mercury also leaves the plant in \vastewaler and solid wastes. Table 1
summari/es the 2002 mercury releases from the nine mercury eel! chlor-alkali planis currenlly
operating in the United Stales.
'['here are three primary point sources at mercury cell plants: the end-box ventilation
system vent, the by-product hydrogen system vent, and mercury thermal recovery unit vents.
While every mercury cell plant has a hydrogen by-product stream ami an end-box, ventilation
system, only live of the nine plants have thermal mercury recovery units. As shown in Table 1,
the tola I mercury emissions reported in 2002 from point sources are I ,(577 pounds, which
averages around 1 20 pounds per plant
Table I. Summary of 2002 Mercury Releases tram Mercury Cell Chlor-Alkall Plants
in the Toxics RvliMUfe Inventory1'
Plant
ASISTA-Ohio
Occidental Chemical - Alabama
Occidental Chemical - Delaware
Olin - Georgia
Olin - Tennessee
Pioneer - Louisiana
PPG - Louisuiid
PH"( i - \Vi-si Virginia
Vukail Wiscimsin
Total
Total Overall
21102 Mercury Releases (IbsAr) In TRI
Fugitive
Air
1,046
1 ,!)fi7
1 ,046
5S5
1 ,045
«62
1 .045
1,045
1,054
S.7<)5
Point
Source Air
349
20
28
154
N5
4W
i 77
»KS
28
1.077
Total Air
1 ,395
1 ,087
1 ,074
739
1 , 1 30
910
1.222
I.J.ii
1 ,(«2
9,X72
Surfafi1
Water
0
10
21
7
14
13
34
2
I OS
Other Oil-
Site and
OfT-Site
* "7 "I
ft64
: J44
2K2
?.V»N
261
23!
VI Ht
5.4(Ht
11380
1 Toxics Release Inventory Program. United States Environmental Protection Agency.
P*J«€- > Of
A-8
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Appendix A
Pri»j**l Plan
Mercury Fii^Hh* r.Rnhsions Sledy
Ht* iiiiwi \ft. 2
September 8, JlMlS
Subpart Hill or "The Mercury Cell MACT," contains numerical emission limits for each
of these point sources. It also requires that the plants either install continuous mercury emission
monitors or that they test each vent at least once per week. While the compliance date for the
Mercury Cell NESHAP Ls not until December 6. 2006. most mercury cell plant!* have relatively
recent test or monitoring data for these point sources. This is because these plants have been
(and still arc, until the new NESHAP takes effect on December o, 2006) subject Us 40 CFR 61,
subpart E (the "Old Part ft I Mercury NESHAP"), which contains a numerical emission limit for
point sources,
In addition, there are mercury fugitive emissions. The majority of fugitive mercury
emissions occur from sources in the eel I room such as leaks, from cells, decomposers, hydrogen
piping, and other equipment. Fugitive mercury emissions also occur during maintenance
activities such as cell or decomposer openings, mercury pump change-outs, end-box seal
replacements., etc. All of (his equipment and activities occur in the cell room, so these fugitive
mercury emissions would be emitted via the cell room ventilation system.
There are fugitive emission sources outside of the cell room, but ilie.se luive generally
been assumed to be insignificant in comparison to those from the eel! room. Potential outside
sources include leaks of mercury-contaminated brine in the bnne treatment area, the wastcwaicr
system, and (he handling and storage of mercury contaminated wastes,
The Old Part 61 Mercury NESHAP effectively contains a mercury emission limit of
! .300 grams per day for fugitive emissions from the cell room. However, mercury ceil plants are
allowed to demonstrate compliance by following a series of design, maintenance, and
housekeeping procedures. All mercury cell plants have complied via these procedures rather
than testing and complying directly with !he 1,300 .grams per day limit. The Mercury fell
MACT does not include a numerical emission limit for fugitive emissions from the cell room.
Rather, it contains a set of work practice standards determined to represent the best practices
from the industry, which are considerably more stringent lisa]) the Old Part 61 Mercury NESHAP
procedures. It also contains an alternative program lhat involves continuous mercury
concentration monitoring and problem correction when an action level is exceeded.
The difficulty in measuring fugitive mercury emissions from mercury cell chlor-alkali
plants, and the fact lhat no regulation has. required the quantification of these emissions, has
resulted in a very limited data set on fugitive mercury emissions at mercury cell chlor-alkali
plants. Specifically, we are aware of only five published studies in the last 30 - years that have
measured fugitive emissions from mercury cell chlor-alkali plant cell rooms. These studies arc
summarised in Table 2, Because of this lack of data, mercury ceil chlor-alkali plants have
historically just used the 1,30<1 grams per day assumption (which is 1,045 'pounds per year
assuming continuous operation) from the Old Part 61 Mercury NESHAP in reporting fugitive
emission*.. This i.s reflected in the fugitive emission estimates shown in Table I. The
1.300 grams per day level was based on the 1971 and 1972 studies shown in Table 2, and the
estimate for Qlin in Georgia is based on the 2000 .study at their plant. Pioneer in Louisiana also
f»g(--l Si' 14
A-9
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Projtfl Plan
^larewry Fiigirtir*- F:mN$dn'emissions into the atmosphere from a chlor-aSkali complex measured with the lidar
technique. Atmospheric Environment 26A, 1253-125X.
0 Kmsey, J.S., 2002. Characterisation of mercury emissions at a chlor-alkali plant, vols. I
and II. U.S. Envimnnietitiil Protection Agency, National Risk Management Research Laboratory,
Research Triangle Park. NC, FPA-600/R-02-007a ant! I-PA-nO(VR-02-007b.
P*g€- 5 Of 14
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Appendix A
Prisjt>tl Plan
b* EnfiNKinms Siedv
Kev iiiitffl \(t, 2
September H, IMS
.3 Overall Fate of Mercury
As the mercury in the cells diminishes, additional mercury is added to the cells to
maintain the desired level for optimum process efficiency. Many assume that the amount of
mercury added to Ihe pnxrcss Us replace "losl" mercury leaves Ihe plant in wastes or wasiewaler,
in products, or via air emissions. However, mercury cell plants have nol been able Us account for
all the lost mercury The issue of unaccounted for mercury has been the subject of intense
scrutiny from groups within EPA and the industry. As pan of the Great Lakes Binational Toxics
Strategy, mercury cell chlorine producers annually report the total mercury consumption for the
industry.' For the years 1990-1995, the industry reported an average of 160 tons-_yr of mercury
used. They have achieved significant reductions in tisis amount since that time, down to
79 tons,'yr in 2000, 30 tons/yr in 2001, 36 lorus.-'yT in 2002, and 38 lom.'yr in 200,1. Even with this
decrease in usage, significant mercury remains unaccounted for by the industry1, In 2(100, the 12
operating mercury cell plants reported total mercury releases of around 14 tons, meaning (hat
there were approximately 65 tons of mercury unaccounted for in that year. As shown in Table I,
the 2002 releases reported total just under 8 tans, meaning that there were around 28 tons of
mercury unaccounted lor in 2002. These amounts equate to an average of between 3 and 5Vj tons
of unaccounted for mercury per mercury cell chlor-alkali plant.
There are two basic theories regarding the fate of this unaccounted for mercury. The first
is it is emitted to the air. This would substantially increase the emissions from the levels reported
and the levels, measured in the previous studies. Since the point source emissions are relatively
well studied, the assumption is that these emissions are fugitive in nature and originate from the
cell room ami/or other areas, of the plan!. The second is that mercury- condenses and accumulates
in pipes, tanks, ant! other plant equipment. Since this equipment is not routinely opened and Ihe
mercury removed and recovered, a substantial amount could build up that would nol be
accounted for in a shorter time period.
1.4 EP.Vs Reconsideration of the Mercury Cell M ACT
On December 19, 2003 <6K FR 70">04), the EPA promulgated the Mercury Cell MACT.
On February 17, 2004, the National Resource Defense Council (KRDO filed petitions on lire
final rule in DC District Court. The foundation behind many of Ihe issues raised in the petitions
was the uncertainty associated with the fugitive emission estimates used by the EPA in the
ruleniakiiig- In particular, the NRDC has concerns over the inability of mercury cell plants to
account for all the mercury added to their processes to replace mercury that leaves in products or
wastes or leaves via air emissions- The KRDC (along with a number of other concerned jiarliies)
maintains that ihc majority of this missing mercury must be lost through fugitive emissions.
They also contend that recognition of this fact would cause EPA would change many of the
decisions that were made in developing and promulgating the Mercury Cell MACT.
Binational Toxics Strategy Mercury Workgroup - Reducing Mercury in the Great Lakes
Region, Chlor-Alkali Industry, http: • '':' www ,cpa.j{pv •region? ••' air •'merctify'reducins;. htm I
14
A-11
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Appendix A
Pr«jt*1 Plan
M**nc«rj FiijsBtiv** Firamsmn* Sisdv
Mts ivifrai Nr>. 1
Srjjlfnnher «, ilMlS
On April 8, 2(KM, Jeffrey Hohnslcad, EPA Assistant Administrator for Air and Radiation,
notified the NRDC that the EPA granted iheir petition and would reconsider aspects of the
rulemakmg, .4s part of this reconsideration, the EPA has agreed lo conduct a project to address
the uncertainty of the-mercury fugitive emissions from this industry. Currently. NRDC has
agreed to a slay of litigation while the Agency is conducting this study.
2.0 PROBLEM DEFINITION
The problem that this project will address is whether she fugitive emissions Prom a
mercurv cell chJor-alkali plant are on the order of magnitude of the historical assumption of
1.300 grams per day (0.5 toi&'yr) or on the order of magnitude of One unaccounted for mercury
(3-5 lons/yr).
3.0 PROJ ECT OKI; A M ZAT I ON
Sources of fugitive mercury emissions at a mercury cell chlor-alkali plant can be
classified in two major categories: (1) sources inside the cell room and (2) sources outside the
cell room. This project contains two primary elements corresponding lo these two categories.
Table 3 shows thc.sc elements, along with an explanation of the daui to be received related to
each and the responsibilities for collecting these data, Table 3 also provides the dale when data
are expected from each element. Section 4 discusses sources inside die cell room and Section 5
discusser sources outside the cell room.
Data collected will be received and analyzed by F.CVR Incorporated (EC'Rk under contract
to EPA's Office of Air Quality Planning and StandardsnOAQPS), Emissions Standards Division,
(BSD), Data will be collected by three basic organisations: ARCADIS, under contract to ihe
National Risk Management Research Laboratory (NKMKL) oTHPA's Office of Research and
Development (ORD): MAC'fEC, under contract lo the Emissions and Measurement Analysis
Division (EMAD) of OAQPS, and mercury cell chlor-alkali companies.
)4
A-12
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Appendix A
Prtjt*! Plan
M*rewr> FiigirtKe ErnHdnms Stedv
Ittviiittffl \ft. J
September 8, 2IMIS
Table 3. Summary of Project Elements and Specific DataVlnformation Expected
Prnjtct Elemeal
l:U^>ilivc l:ITlHS|t>H*
From Inside ihe Tell
RmMI!
l"iii! ilivi.' Slrni^^sDns
l-'iuiu Oulsidi: UK- fell
RiHMYi
Daia/10r«'riiifltkin to Be Received'4
VAlitUiiitn o;" oominu^un mercury TtiniiiKiri'n^
^yjirerif'i inKUlleti in ihe csll mctni ar O^iridf-nlal
C'htmical in De law-are ("sly, DL'1;iwj,rc
, t ..
Occidental <.. h^nnicHl's Ri'lau-aK t ii\.
r)X.iu.ir^ ?I.4PI
PruttM , and n. L'll iuom tnjiTiU'tiJin.c .uusis;-.
• hi ^ ii-r iii.K.tK-ri«H i hr'iui .<) - i)cL\« IK- 1 iv
U.^a^iirf DLinl
?ysu*rn nisi^Ilcii in ihec<-1l roun^ &i Oals,
Aliih-^nii pbiu
Process and cell-rcKiin rrfiiifityfia-ncc iicnvity
data cu>rrL*spiind3iR,!J, ID \\n\i" period PS" ynnis.-ssoas
diilss fViii OL*cidt'iU,si] <"hcniK-;jir> Murflc Shuals,
•^lah'^mi phnii
MciTuiy llo;^ dila irscm ncin cell TDIMH t-"TUL^sicin
suurcca ul Ore ideals! Chi'micnl'^ Mu^C'lc
.^lijHiis, Aldbaoia piyri't
K«n cell-ronni p?4i«ce^ nnd niiiinlenancc
aL-li-i'ily data cairL'^paadiay, In limt' pt'Tiad D!"
IliiK nicssuicmcnl eiius-s-iuns d^ls I'y-i
Uccidc-nul < hvrnic«l's Muscle -Shoals,
A In Harris plant
Or-^iin^tipM'i
RespejsisiUIt' Fu-r
t'ulit'tliij'ia * f
thf Dilii
MAt'TKl1-1
l:MAf>
I'hcmicAl
Occidcnlal
I:MAO
Occsdt'ntal
tlicisucaj
Occidcmiil
Cliemica]
ARCADIS.'
NKMRL
t'Krci-slunoil
C'Jicmica]
AlipiinimaU
D»1c When
Data,'
Inf^rmatkin
Art" Kxpeclert
>J.!H5
I ^ -l^
i:.'«s
12- '115
i;.'us
2/06
2'tif,
r. The si- arc ihc dali itL'tris or olltm siifbrmaisoii idcnlificd :is of llic dale «fthc L-iurtrnl VLM-^H:>II oi'lkis pr«jci.-i
ll rii cxpcitcd Ural a'ddihunul sifuifcs *,*! dala will be Eilt-nCHjfd and iiicnnpur^lfd is'ilu llic prfi-jt-C'L
A-13
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Appendix A
Prwjt>tl Plan
b* F.mhsiin'ns Siedv
Htviiiiwi \ft. 2
Scptcmlwr S, IMS
4.0 SOURCES INSIDE THE CELL ROOM
The objective of this element is to obtain emission estimates of ihe fugitive mercury
emissions thai occur inside the celi room of a mercury cell chipr-alkaii plant. Thtse estimates
will represent emissions thai occur during a wide range of maintenance and other activities in the
cell room.
In mid-2004, L'PA began scoping out a basic testing plan concept with the intention of
conducting EPA-sponsored tests at two or more mercury cell chlor-alkali plants. Alter initial
information gathering efforts to identily candidate mercury cell chlor-alkali plants lor testing,
F.PA visiles! five planl siies a_s the first step in developing site-specific test plans. These efforts
confirmed thai there arc significant technical, logistical, andw safety issues associated with the
measurement of fugitive emissions from mercury cell rooms, 'fliese issues are particularly
monumental when contemplating a short-term (four to six week) testing effort, til1 A has
consulted industry representatives and testing experts inside and outside of the EPA, and is
currently attempting to design a comprehensive .short-terra testing program.
In the meantime, the mercury cell chlor-alkali industry has been working toward long-
term mercury measurement efforts. Two Occidental Chemical mercury cell plants (Delaware
City. Delaware and Muscle Shoals, Alabama) have already installed continuous mercury
monitoring .systems in their cell rooms, which they are using to identify and correct mercury
emission episodes in accordance wills the alternative cell room monitoring program in the
Mercury Cell MAC T standard. In addition, they are also monitoring parameters lo allow the
continuous estimation of the mass of mercury emissions from Ihcccll room, The more
permanent nature of these systems has allowed these plants 10 overcome some of lite obstacles
that have been encountered for the short-term effort testing effort. As a result of the success of
this program, other mercury cell plants are investigating similar systems.
Given the difficulties encountered in designing is shorl-temi testing program to measure
mercury fugitive emissions from celi rooms, and the fact that plants have already installed
continuous mercury monitoring equipment, the focus has shifted from EPA conducting or
sponsoring a short-term test to til1 A receiving data collected by these systems.* Therefore, the
primary source of data for this element (fugitive emissions from inside cell rooms) will be data
collected by the industry from continuous, mercury monitoring systems. However, since these
data will he collected by the industry rather than EP,\ or their contractors, F.PA requires that a
t|ualily control regime is in place to determine ihe quality oflhe data. Specifically, EPA will
conduct .studies to validate each cell-room mercury monitoring system prior to receiving data thai
will be used in this project. The following section includes brief descriptions of she cell room
monitoring systems that will be included in the study and section 4.2 discusses the validation of
these systems.
*Note: F.PA has not abandoned the concept of conducting or sponsoring a short-term lest at one
or more mercury cell chlor-alkali plants, Rather. EPA is focusing current efforts on obtaining
data already being collected by the industry.
f»fi-1 »f 14
A-14
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Appendix A
Prtjt*! Plan
iv*- KmNsiftns Sledv
Ktviiittffl \ft. 2
September JJ, 2MS
4.1 Cell RiKtm Continuous Monitoring Systems
At this time, data will be collected from the cell room mercury monitoring systems at two
mercury cell chlor-alkali plants for approximately a six-week period (luring the lime periods
.shown:
• Occidental Chemical in Delaware City. Delaware (August 2006 •
November 2006)
• Occidental Chemical in Muscle Shoals. Alabama (August 2006 - November 2006)
F.mis?>kin.s data from these systems will be collected by the companies and provided to F.CR/FSD
as described in Attachment 1, Following arc brief descriptions of the systems at these plants;
Occidental Chemical, Delaware City, Delaware
The ceil mom at the Delaware City Plant is. a rectangular building measuring 352 Seel by
140 |eei_ Ti-ie (•£[] room eonsisK of two [independent circuits, and each circuit Ls broken into two
sections, resulting in four quadrants. The air flow in the cell room is via natural convection;
there are no lans to provided either induced or forced draft air flow. During the summer months,
approximately 40 percent of «he sides on the lengthwise span are removed lo improve ventilation.
There are two rows of roof ventilators, liach ventilator is in two discrete sections for a total of
four sections (corresponding to the four quadrants of the cell room).
The mercury-concentration monitoring system is a Mercury Monitoring System Mode!
MMS-HS analyzer manufacturin)! by Mercury Instruments GmbH Analytical Instruments in
Germany, li collects samples from 16 points and analyzes them for elemental mercury using a
Model VM-3000 ultraviolet absorption analyzer. The system takes one sample per minute,
meaning that a sample is taken from each point once every 16 minutes. 'The sampling sequence
is established so that a sample is taken from each quadrant otiee every lour minutes. The How
rate for the building is estimated using a convective air flow model. The inputs to this model are
atmospheric and ritlgc vent temperatures (which arc continuously monitored), intake and
discharge areas, and stack height.
Occidental Chemical, Muscle Shoals, Alabama
The cell room at the Muscle Shoals planl is a rectangular building measuring 260 feet by
357 feet. The cell room consists of two rows, of cells, broken into four-quarter sections. The cell
room takes up hall ol a larger building, with a wall separating the cell room from the large open
half that is used for equipment storage. The peak of the roofis over the center of the larger
building {meaning that il is over the wall separating (he cell room from the other side of the
building). The ventilation for the cell room consists of both induced and forced draft. There are
43 forced draft fans positioned on the sklewali of the building pushing air towards the cent of the
building. There are two rows of induced draft lans on the roof of the cell building. One row.
Page II* of 14
A-15
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Appendix A
Prisjt>tl Plan
Merewry FiigHb* EnfiNKinms Siedv
Kev iiiitffl \ft. 2
September H, IMS
containing 33 fans, is directly over the center of the two rows of ceils. 'Hie other row, which
contains 32 fans, is over the wall separating the cell room from the other side of the build i tig.
The mercury concentration monilonng system is a Mercury Monitoring System Model
MMS-16 isnalwer manufacturing by Mercury Instruments GmbH Analytical Instruments in
Germany. It collects samples from 65 points {at the inlci to each induced draft fan) ami combines
them in groups, of three or four to provide a representative profile of the cell room in a 20 point
sample array. The elemental mercury concentration will be measured using a Model VM-3000
ultraviolet absorption analyzer. The system lakes, one sample per minute, meaning chat a sample
is taken from each point once every 20 minute*. Occidental tested each fan to determine the flow
rate at standard conditions and is correcting to actual flow rate based on continuous monitoring
of icmpcralure, pressure, and humidity,
4.2 Validation of Systems
Each system described above will be validate J to assess the quality of the data that will be
received from the continuous cell room mercury monitoring system. This validation will consist
of a review of the data collection, calculation, and archiving system; an assessment of the data
quality provided by the mercury analy/cr; and an assessment of the data quality provided by the
air flow estimation technique. Attachment 2 contains the Validation Plan for the Occidental
Chemical plant in Delaware Ciiy, Delaware and Attachment 3 contains the draft Validation Plan
for the Occidental Chemical plant in Muscle Shoals. Alabama. Data will be collected for these
validation studies in accordance with the plan.s in Attachment 2 and 3 by MACTF.C'.''nMAD, and
reports will be prepared, These reports and data will be provided to ECR./ESD,
4,3 Monitoring of Process and Maintenance Activities
For the period represented by die emissions data dial will be provided by the plants.,
operational information will also be provided regarding production, process, anil cell-room
maintenance activity. Specifically, this information will include chlorine production (or a
.surrogate parameter such as electrical load); (he number of cells online/offline; maintenance
activities such as cell openings, decomposer openings, etc.: and housekeeping activities. Records
of any major malfunctions or other circumstances that resulted in large mercury emission
episodes will also be maintained. These activity data will be collected by the companies and
provided to FCR/EI.SD.
5.0 SOURCES OUTSIDE THE CELL ROOM
The objective of this element is to determine if the fugitive emissions from outside the
cell room are .significant with respect to the emissions from inside the cell room. If it is
determined that these "outside" fugitive emissions are significant, emission estimates from this
activity will used in the addressing the overall problem. The.se estimates will represent emissions
thai occur during a wide range of maintenance and other activities outside the cell room,
Page II of 14
A-16
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Appendix A
Prtjt*! Plan
September 8, 2IMIS
5.1 Emissions Data Collection
The emission rale of fugitive mercury emissions, from outside the cell room will be
measured using Optical Remote Sensing''Vertical Radial Plume Mapping {ORS-'VRP\1). At this
lime, data will he collected at Ihe following mercury cell chlor-alkali plants for approximately a
six-week period during the lime periods shown:
* Occidental Chemical in Muscle Shoals, Alabama (October 2005 -
December 2005)
These data will be collected by ARCADIS/NRMRI. in accordance with Ihe site-specific Quality
Assurance Projccl Plan (GAPP) provided in Attachment 4 and provided to ECWESD,
5,2 Monitoring of Process and Maintenance Activities
For the period represented by die outside fugitive emissions data that will be collected
(.see section 5,1), information will also be provided regarding process and maintenance activity
that occurs outside the cell room, Specifically, this information will include waste-handling
activities, thermal mercury recovery activity, maintenance activities, and housekeeping activities.
Records of any major malfunctions or other circumstances that resulted, in large mercury
emission episodes will also be maintained. These activity data will be collected by the company
and provided to ECR.'ESD.
6,0 RECEIPT AND ANALYSIS OF DATA
6,1 Data to Be Received
EClt'ESD will receive the following data and information:
• From M.4CTEC/EM.4D - Validation reports and associated data for the cell room
continuous mercury emissions system at Occidental Chemical in Delaware City,
Delaware.
* From Oci-iJental Cfti'mit-ui • Mercury emissions data from sources inside the cell room at
Occidental Chemical in Delaware City, Delaware.
* From Ot'dds'itta! Chemical - Operational information al Occidental Chemical in
Delaware City, Delaware.
• From MACTEC/EMAD - Validation reports and associated data for the cell room
continuous mercury- emissions system at Occidental Chemical in Muscle Shoals,
Alabama, Delaware.
* From Otfiili'iitai Chamtttd - Mercury emissions data from sources inside the cell room al
Occidental Chemical iti Muscle Shoals, Alabama.
* From Oi't'.iduiital Chemical - Operational information al Occidental Chemical in Muscle
Shoals, Alabama,
Page 12 of 14
A-17
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Appendix A
Prtjt*! Plan
Merewry Fiigirtiv*- KmNsiftns Sledv
Ktviiittffl \ft. 2
September JJ, 2MS
Fi-ftm AKCADIS/NKMKL • Mercury emissions data from fugitive emission sources
cmbiicie the cell room at Occidental Chemical in Muscle Shoals,. Alabama if such sources
are found to be significant with respect to the emissions from inside the cell room.
• from ('k'ciilcntiil Chemical - Process and maintenance activity for activities outside of the
cell room at al Occidental Chemical in Muscle Shoals, Alabama.
6,2 Analysts to be Performed
Following receipt of this data and information. ECR/ESD will, at a minimum, conduct
the fallowing analyses:
• Determine whether the fugitive mercury emissions from the cell room al Occidental
Chemical in Delaware City, Delaware are on the order of magnitude of the historical
assumption of 1,300 grains per day (0.5 tons/yr) or on the order of magnitude of the
unaccounted for mercury (3-5 totis.''yr).
* Determine whether the Fugitive mercury emissions from the ceil room a! Occidental
Chemical in Muscle Shoals, Alabama are on the order of magnitude of the historical
assumption of 1,30(1 grams per day tO.5 toti.v'yr) or on the order of magnitude of the
unaccounted for mercury (3-5 tons/yr").
* Detenuine whether the combined fugitive mercury emissions from inside and outside the
cell room al Occidental Chemical in Muscle Shoals, Alabama are on ihe order of
magnitude of the historical assumption of 1,300 grams per day (0.5 tons/yr) or on the
order of magnitude of the unaccounted for mercury (3-5 tons''yr).
• Detenu ine the process,, maintenance, and other operational activities that most
significantly impact fugitive mercury emissions,.
• Evaluate whether a relationship exists between the fugitive mercury emissions and any
activity factor (e.g., chlorine production, numbcrof mercury cells, amount of mercury in
cells, etc) that could be used to develop an emissions factor that could be applied
industry-wide.
6J How this Project Will Impact the MACT Reconsideration
During the rulemaking for the Mercury Cell MACT, the baseline fugitive mercury
emission levels were assumed to be 1,300 grams/day per plant,. Based on this assumption, the
current level of fugitive mercury emissions from mercury cell chlor-atkali plants in the United
States would be around 4.7 tons/yr. I iowever. if this project concludes that the fugitive mercury
emissions are on the order of magnitude of the unaccounted for mercury (3-5 tons.'yr/plant), the
total fugitive mercury emission from mercury cell eh tor-alkali plants in the United Stales could
be as high as 45 Sons'yr This level would approximately be equivalent to (lie current mercury
emissions from utilities, and would he (hroc times higher than the mercury emissions expected
Page l.t of 14
A-18
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Appendix A
Praj«t Plan
M**esiiy Fugitive EraiBSKifiniK Slaily
Ki's IMI'JSI %i>, 2'
Scptcmhcr ft, 200S
from utilities after implementation of the Clean Air Mercury Rule/ This obviously could impact
all aspects ofEPA's reconsideration of the Mercury Cell MACT.
In its February I 7, 20
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Appendix A
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A-20
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Appendix B
APPENDIX B
EPA Memorandum and Response:
Findings from the Technical Systems Audit of Measurements of Total Site
Mercury Emissions from a Chlor-Alkali Plant using Ultraviolet Differential
Optical Absorption Spectroscopy
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Appendix B
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Appendix B
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
NATIONAL RISK MANAGEMENT RESEARCH LABORATORY
fc\r Pollution Prevention and Control Division
Research Triangle Park, NC 27711
October 27, 2006
MEMORANDUM
SUBJECT: Preliminary Findings from Technical Systems Audit of
Measurements of Total Site Mercury Emissions from a Chlor-alkali
Plant using Ultraviolet Differential Optical Absorption Spectroscopy
FROM: Robert S. Wright, Technical Services Branch
TO: Eben Thoma, Emissions Characterization and Prevention Branch
EPA conducted an internal technical systems audit (TSA) on October 19, 2006 of
measurements of total site mercury emissions from a chlor-alkali plant in Muscle
Shoals, Alabama using ultraviolet differential optical absorption spectroscopy (UV-
DOAS). I was accompanied by Mark Bahner, a technical expert auditor from RTI
International. This TSA was conducted according to auditing procedures described
in Guidance on Technical Audits and Related Assessments for Environmental Data
Operations (EPA QA/G-7). ARCADIS' approved quality assurance project plan
(QAPP), its appendices, and EPA's quality requirements provided the technical
bases for the TSA. The checklist for the TSA was sent to EPA and ARCADIS
project staff on October 16, 2006 and was distributed to the project staff prior to the
audit. The following are preliminary findings of the audit.
1. The TSA addresses only the field measurements campaign during which
path-integrated concentrations (PICs) for mercury were measured. It does
not address the subsequent vertical radial plume mapping (VRPM)
B-3
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Appendix B
calculations by ARCADIS which will convert the measured PICs and
meteorological data into mercury emission flux estimates.
2. In general, the auditors observed that the EPA and ARCADIS project staff
are doing a good job of measuring mercury PICs at the plant. The project
staff are well qualified to perform the work and they conduct themselves in
a professional manner. They cooperated with the auditors and took time
out from their busy duties to explain what was happening. They helped to
ensure the successful completion of the TSA.
3. In general, the measurements are being implemented as stated in the
QAPP for the project. There are no findings that require corrective actions.
4. There were significant disruptions of the 10-meter meteorological
measurements due to the failure of multiple Climatronics meteorological
heads since the beginning of the project. This problem was solved on
October 19 with the installation of an R.M. Young meteorological head and
it appeared that valid measurements would be collected for the remainder
of the project. For the earlier periods during which no valid meteorological
data were collected at the chlor-alkali plant, the project staff will attempt to
use hourly 10-meter meteorological data from the Automated Surface
Observing System (ASOS) at the Northwest Alabama Regional Airport in
the calculation of the mercury emission flux estimates. The airport is
located approximately 1-3/4 miles south-southeast from that plant and
meteorological data collected there should be representative of winds at
the plant. EPA may be able to obtain 5-minute data for the airport. For
those periods in which valid data are collected at both the plant and the
airport, the auditors recommend that statistical analysis of these data be
performed to assess representativeness of the airport data on a
quantitative basis. If they are found to be representative, the airport data
can be used for calculating mercury emission flux estimates.
5. Mercury PICs are calculated using a multipoint calibration whose values
are based on a graph of the mercury saturation vapor pressure versus
temperature. This graph was provided by OPSIS, the manufacturer of the
UV-DOAS instrument. There is no information available about how the
pressure values on the graph were obtained, the uncertainty of these
values or the traceability of these values to national standards. Recently,
Friend etal. of the National Institute of Standards and Technology (NIST)
reviewed the available measurements of the vapor pressure of mercury
and developed an equation predicting the vapor pressure over a wide
B-4
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Appendix B
range of temperatures. The auditors recommend that the values from the
OPSIS graph be compared to the NIST equation to determine whether
these values reflect the current state of knowledge regarding mercury
vapor pressure. If significant differences are detected, EPA should
consider using the NIST equation, rather than the OPSIS values, in the
multipoint calibration.
6. Near-ground mercury concentration measurements were obtained using
three 25-meter-long, 1/4-inch ID sampling lines that were joined at the inlet
of a Lumex mercury analyzer. The auditors recommend that the sample
flow rates through these lines be measured at the conclusion of the project
to allow calculation of the sample residence time and to demonstrate that
the flow rates are equal in the three sampling lines.
A draft findings report for this TSA will be completed in the coming month. It is
possible that it may contain additional findings that arise from closer consideration
of the audit results, but I do not expect any new findings will address significant
problems relating to the project.
Please contact me if you have any questions about the TSA or about this
memorandum.
B-5
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Appendix B
Response to "Preliminary Findings from Technical Systems Audit of
Measurements of Total Site Mercury Emissions from a Chlor-alkali Plant
using Ultraviolet Differential Optical Absorption Spectroscopy"
The following is a response to the internal technical systems audit (TSA) performed
on October 19, 2006 of measurements of total site mercury emissions from a chlor-
alkali plant in Muscle Shoals, Alabama using ultraviolet differential optical
absorption spectroscopy (UV-DOAS).
Finding 1. The TSA addresses only the field measurements campaign during
which path-integrated concentrations (PICs) for mercury were measured. It
does not address the subsequent vertical radial plume mapping (VRPM)
calculations by ARCADIS which will convert the measured PICs and
meteorological data into mercury emission flux estimates.
Response 1. The final report outlines the VRPM calculations in section 1.3.1.
Finding 2. In general, the auditors observed that the EPA and ARCADIS
project staff are doing a good job of measuring mercury PICs at the plant. The
project staff are well qualified to perform the work and they conduct themselves
in a professional manner. They cooperated with the auditors and took time out
from their busy duties to explain what was happening. They helped to ensure
the successful completion of the TSA.
Response 2. No response required.
Finding 3. In general, the measurements are being implemented as stated in
the QAPP for the project. There are no findings that require corrective actions.
Response 3. No response required.
Finding 4. There were significant disruptions of the 10-meter meteorological
measurements due to the failure of multiple Climatronics meteorological heads
since the beginning of the project. This problem was solved on October 19
with the installation of an R.M. Young meteorological head and it appeared that
valid measurements would be collected for the remainder of the project. For
the earlier periods during which no valid meteorological data were collected at
the chlor-alkali plant, the project staff will attempt to use hourly 10-meter
meteorological data from the Automated Surface Observing System (ASOS) at
the Northwest Alabama Regional Airport in the calculation of the mercury
emission flux estimates. The airport is located approximately 1-3/4 miles south-
B-6
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Appendix B
southeast from that plant and meteorological data collected there should be
representative of winds at the plant. EPA may be able to obtain 5-minute data
for the airport. For those periods in which valid data are collected at both the
plant and the airport, the auditors recommend that statistical analysis of these
data be performed to assess representativeness of the airport data on a
quantitative basis. If they are found to be representative, the airport data can
be used for calculating mercury emission flux estimates.
Response 4. In order to assess the reliability of the Climatronics wind speed
and wind direction data, the data were compared with National Weather
Service data obtained from the Automated Surface Observation System
(ASOS) at the Northwest Alabama Regional Airport, located approximately two
miles from the project site. Based on two minutes wind averages, there were
four days in which the directional trends matched, but where the wind direction
data was offset by a consistent factor. Those days and the correction factors
applied are shown in Table 2-3 and described in Section 3.2.3 of the final
report.
Finding 5. Mercury PICs are calculated using a multipoint calibration whose
values are based on a graph of the mercury saturation vapor pressure versus
temperature. This graph was provided by OPSIS, the manufacturer of the UV-
DOAS instrument. There is no information available about how the pressure
values on the graph were obtained, the uncertainty of these values or the
traceability of these values to national standards. Recently, Friend et al. of the
National Institute of Standards and Technology (NIST) reviewed the available
measurements of the vapor pressure of mercury and developed an equation
predicting the vapor pressure over a wide range of temperatures. The auditors
recommend that the values from the OPSIS graph be compared to the NIST
equation to determine whether these values reflect the current state of
knowledge regarding mercury vapor pressure. If significant differences are
detected, EPA should consider using the NIST equation, rather than the OPSIS
values, in the multipoint calibration.
Response 5. This comparison was performed and a graph is attached. The
NIST data was generated from "The Vapor Pressure of Mercury", D.G. Friend,
M.L. Huber, and A. Laesecke, Physical and Chemical Properties Division,
National Institute of Standards and Technology, Boulder, CO 80305 USA,
prepared for Western Research Institute under Purchase Order No. 053003,
July 2005. The OPSIS data was taken from the hard-print readouts used in
this study. The differences in NIST and OPISIS saturated mercury values were
deemed to be not significant in the context of this work.
B-7
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Appendix B
Finding 6. Near-ground mercury concentration measurements were obtained
using three 25-meter-long, 1/4-inch ID sampling lines that were joined at the
inlet of a Lumex mercury analyzer. The auditors recommend that the sample
flow rates through these lines be measured at the conclusion of the project to
allow calculation of the sample residence time and to demonstrate that the flow
rates are equal in the three sampling lines.
Response 6. The sample floe rates were measured as recommended,
reference the attached calibration report (Met Lab ID 03140,11/16/2006). The
flow rates in the three lines were shown to be approximately equal (9.0 + 0.25
SLPM). The volume of the 25 m , 0.635 cm dia. tube was 0.792 L indicating an
approximate sample residence time of approximately 5 seconds. This
residence time was deemed to be not significant in context of this work.
Comparison of NIST and OPSIS Hg Data (ver.1)
oc
oo ^
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1 5 ^
n
i
• NIST Calculation n 8
0 OPSIS Chart Q 8
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Temperature (deg. C)
B-8
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