EPA-650/2-74-039
June 1974
Environmental Protection Technology Series
I
55
UJ
O
;:^;:^
-------
EPA-650/2-74-039
EVALUATION OF INSTRUMENTATION
FOR MONITORING TOTAL MERCURY
EMISSIONS FROM STATIONARY SOURCES
by
L. Katzman, R. Lisk, and 0. Ehrenfeld
Wai den Research Division of Abcor, Inc.
201 Vassar Street
Cambridge, Massachusetts 02139
Contract No. 68-02-0590
Project No. 26AAN
Program Element No. 1AA010
EPA Project Officer: Roy L. Bennett
Chemistry and Physics Laboratory
National Environmental Research Center
Research Triangle Park, North Carolina 27711
Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
June 1974
-------
This report has been reviewed by the Environmental Protection
Agency and approved for publication. Approval does not signify
that the contents necessarily reflect the views apd policies
of the agency, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.
-------
TABLE OF CONTENTS
Section Title Page
I INTRODUCTION 1-1
A. BACKGROUND 1-1
B. SUMMARY 1-2
II MERCURY EMISSIONS AND INSTRUMENTATION 2-1
A. BRIEF DESCRIPTION OF MERCURY EMISSIONS 2-1
B. INSTRUMENT SUMMARY 2-2
111 RESULTS OBTAINED IN THE WALDEN LABORATORY 3-1
A. DESCRIPTION OF MERCURY GENERATING SYSTEM 3-1
B. INTERFERENCES 3-5
C. ZERO AND SPAN STABILITY 3-21
D. RESPONSE TIME 3-23
E. SENSITIVITY 3-24
F. RELIABILITY 3-24
G. RELATIVE ACCURACY AND PRECISION 3-25
IV RESULTS OBTAINED IN THE FIELD 4-1
A. FIELD SAMPLING SYSTEM 4-1
B. MERCURY PROCESSING PLANT 4-1
C. CHLOR-ALKALI PLANT 4-8
D. ZINC SMELTER 4-13
V CONCLUSIONS 5-1
IV RECOMMENDATIONS 6-1
VII REFERENCES 7-1
APPENDIX A A-l
APPENDIX B B-l
111
llUaUem
-------
LIST OF TABLES
Table No.
3-1
3-2
3-3
3-4
3-5
3-6
3-7
3-8
3-9
3-10
3-11
4-1
4-2
4-3
4-4
4-5
4-6
4-7
Title
Mercury Concentration (Vapor Pressure) As a Function
of Temperature
Comparison of Mercury Generating System and AA
Analysi s
Sulfur Dioxide Interference
Zero Dri ft Measurements
Laboratory Data for Beckman
Laboratory Data for 01 i n
Laboratory Data for Sunshine
Laboratory Data for Dupont Twenty Inch Cel 1
Laboratory Data for Dupont Two Inch Cel 1
Relative Accuracy of Instruments
Precision of Instruments
Red Oxide of Mercury Test Results
Comparison of Reference Tests and Instruments
Measurements
Chi or-Al kali End-Box Stack Test Results
End-Box Sample Tests
Hydrogen Stream Test Resul ts
Hydrogen Stream Samples
Test Results at Zinc Smelter
Page
3-3
3-5
3-21
3-22
*
*
*
*
*
3-32
3-33
*
4-6
*
*
*
*
4-18
* See Appendix A for these Tables.
IttlaUem
-------
Figure No.
2-1
2-2
2-3
2-4
2-5
2-6
2-7
2-8
2-9
2-10
3-1
3-2
3-3
3-4
3-5
3-6
3-7
3-8
3-9
LIST OF FIGURES
Caption
Beckman Mercury Vapor Meter, Model K-23A
Operating Principle of Single Beam Instrument
Dupont 400 Photometric Analyzer
Operating Principle of Dual Beam Instrument
Geomet Mercury Air Monitor
Geomet Air Dilution Kit
01 in Mercury Monitor, Gas
Schematic, Olin Mercury Monitor, Gas
Sunshine Instantaneous Vapor Detector
RAC AISI Tape Stain Sampler
Mercury Generati ng System
Conversion of Methane with a Quartz Tube Pyrolyzer..
Conversion of Ethyl ene with a Quartz Tube Pyrolyzer.
Conversion of Methane with the Geomet Catalytic
Converter (with Catalyst)
Conversion of Ethyl ene with the Geomet Catalytic
Converter (with Catalyst)
Conversion of Ethyl ene with the Geomet Catalytic
Converter (without Catalyst)
Conversion of Benzene with the Geomet Catalytic
Converter (without Catalyst)
Conversion of Methane with the Olin Pyrolyzer
Laboratory System for Generation and Decomposition
of Mercuric Chloride Aerosol
Page
2-6
2-7
2-8
2-10
2-11
2-13
2-14
2-15
2-17
2-19
3-2
3-7
3-8
3-10
3-11
3-12
3-13
3-14
3-15
lUlakkn,
-------
LIST OF FIGURES (Cont.)
Figure No. Caption
3-1Oa Effect of Pyrolyzer Temperature in the Decomposition
of Mercuric Chloride Aerosol - Test 1 3-16
3-10b Effect of Pyrolyzer Temperature in the Decomposition
of Mercuric Chloride Aerosol - Test 2 3-17
i
3-11 Sulfur Dioxide Removal System 3-19
3-12 Mercury Generating System with Sulfur Dioxide
Removal 3-20
3-13 Regression Line for Beckman Monitor 3-27
3-14 Regression Line for 01 in Monitor 3-28
3-15 Regression Line for Sunshine Monitor 3-29
3-16 Regression Line for Dupont Monitor (Twenty Inch
Cell) 3-30
3-17 Regression Line for Dupont Monitor (Two Inch Cell).. 3-31
4-1 Field Sampling System 4-2
4-2 Red Oxide of Mercury Facility 4-4
4-3 Schematic of the Chlor-Alkali Process 4-9
4-4 Zinc Smelter Schematic Diagram 4-15
4-5 Schematic of Test Site at Zinc Smelter 4-16
UlaUeni
-------
I. INTRODUCTION
A. BACKGROUND
This program was Initiated in July 1972. The principal objective
was to identify and evaluate monitoring instrumentation which represents
the current state-of-the-art in the measurement of total mercury emissions
from stationary sources. The requirements for continuous mercury monitors
are set principally by the characteristics of the emission sources to
which they are applied. Since emissions from these sources are of dif-
ferent chemical and physical compositions, the choice of and operations
of the several monitors and sampling system had to be varied.
The program was initially scheduled for nine months, including
a three month field program conducted at the following three mercury
sources: (1) chlor-alkali production; (2) primary processing of mercury;
and (3) secondary recovery of mercury. The field test program was to be
preceded by a two-month laboratory test program. During this phase,
the uniformity of response of each instrument acquired for the program
to all expected forms of mercury emissions from stationary sources includ-
ing particulate and organomercury compounds as well as elemental mercury
vapor would be established.
The following data was to be obtained on each instrument during
the lab and field tests:
a. accuracy
b. precision
c. sensitivity
d. stability
e. response time
f. interferences
g. reliability
h. response to different mercury species
i. sample treatment required
UHaii
-------
Finally, all data obtained in the laboratory and field tests
was to be evaluated and recommendations made in the following areas:
(1) standard procedure for use of recommended instruments; (2) perform-
ance specifications for a total mercury monitor in given application;
and (3) recommendations for future research and development programs to
correct deficiencies in existing instruments.
A four-month extension was granted due to delays in receipt of
certain equipment and delays attendant upon the change- in Program Director,
extending the completion date to July 28, 1973. Also, the "Scope of Work"
was modified by altering the three mercury sources for the field test
program to be as follows: (1) secondary processing of mercury; (2) chlor-
alkali production; and (3) nonferrous (zinc) smelting. This change
reflected the relative importance of nonferrous smelting since primary
processing of mercury has virtually disappeared as a source of mercury
in the United States.
B. SUMMARY
It was found that available mercury measuring instrumentation can
be adapted for the measurement of total mercury emissions from certain
stationary sources, in particular, chlor-alkali plants. The transporting
and conditioning of the sample poses considerable difficulties requiring
additional research. The necessity of a dynamic dilution system to condi-
tion high level mercury emissions sets the requirement for a fairly
sophisticated automatic interfacing subsystem. Manual control was accomp-
lished during the field and laboratory portions of the program. Manual
control in the field was sufficient for our studies, however, continuous
monitoring could not be accomplished by this means.
The two-wavelength instruments evaluated in this program, i.e.,
Dupont and 01 in units appeared to be amenable to applications as continuous
monitors. The single-beam instruments evaluated in this program were not
designed for continuous monitoring although the Beckman unit performed
1-2
llUaUeni
-------
adequately to be employed as a portable analyzer. Again, the problem
of system Interfacing would limit the Instruments applicability. The
inherent very high sensitivity of the Geomet unit would require either
analyzer modifications or an extremely delicate interface system in
order to use it or similar instruments in a continuous monitoring system.
The Sunshine monitor and the tape stain sampler did not perform satis-
factorily to be considered as adaptable for monitoring use.
1-3
lUhUeni
-------
II. MERCURY EMISSIONS AND INSTRUMENTATION
A. BRIEF DESCRIPTION OF MERCURY EMISSIONS
The principal sources of mercury In the atmosphere include:
a. chlor-alkali production
b. primary mercury production
c. secondary mercury production
d. non-ferrous smelting
e. coal burning power plants
f. incinerators
g. organic mercurial products decomposition
h. laboratories and hospitals
The latter two sources are not stationary sources in the conven-
tional sense; however, the others represent potential stationary sources.
Although the EPA emission standards for mercury (40 CFR 61:38 FR8820,
April 6, 1973) were applicable only to those stationary sources which
process mercury ore to recover mercury and mercury chlor-alkali production,
other sources listed above emit mercury at significant levels.
Data from the background document on mercury standards (EPA, 1971)
indicates that total mercury emissions from 31 chlor-alkali plants in the
U.S. in 1969 (uncontrolled) was about 300 tons per year. Uncontrolled
emissions from primary mercury producers are estimated to amount to 2 to 3%
of the mercury recovered or about 20 to 25 tons per year. However, no
primary mercury facilities are presently in operation. Emissions figures
from secondary processing of mercury are not available, but it seems reason-
able that unit losses will be in the same range as those for primary sources,
Thus, secondary losses should be of the order of 20 to 25 tons per year.
Ulaldeni
-------
Coal contains mercury in amounts ranging from less than 0.05 ppm
to around 0.5 ppm. The utility coal consumption (306,000,000 tons) from
1969 data (NCA, 1970) and a representative Illinois coal (0.18 ppm), yield
a calculated value of mercury emitted from coal-fired boilers nationally
of about 50 to 60 tons per year.
Estimates of emissions from the other two large sources, incinera-
tors and non-ferrous smelters are more difficult to determine.
The first three of the sources listed above not only are important
from a total emission basis, but also may release emissions at high con-
centrations (100 milligram per cubic meter and higher). Non-ferrous
smelters also may release emissions of high concentrations. This data
indicates that instruments with high ranges of mercury concentrations
would be preferable; however, no monitoring instruments were found avail--
able that responded at this high a level. The alternative method developed
in this program was a dilution system capable of reducing high mercury con-
centrations to those levels of the instruments.
B. INSTRUMENT SUMMARY
1. General Summary
Mercury has very strong absorption at 253.7 nm, the mercury
resonance line, with an extinction coefficient of approximately 5 x 10 .
This absorption is one hundred to one hundred thousand times higher than
that of other species. Thus, if $ mercury lamp is used as a light source,
the detection of mercury is quite sensitive and selective. All but one
of the mercury monitors employed in this contract was based on this tech-
nique of ultraviolet absorption.
The remaining monitor was a tape-stain sampler operating on
the principle that free mercury reacts with selenium sulfide-coated paper
to produce black HgS. The decrease in the percent transmittance of the
paper is directly proportional to the mercury concentration. Radiochemical
2-2
I Maiden,
-------
detection, neutron activation analysis, and flame!ess atomic absorption
spectroscopy, which are used routinely in the laboratory are not con-
sidered monitoring equipment and are not included.
The monitors relying on the technique of ultraviolet detec-
tion (absorption) of elemental mercury at 253.7 nm must be treated so
that the mercury vapor is free of interferences and all particulate
mercury converted to elemental mercury. The major interferences would
be from organic (aromatic) compounds which have high extinction coefficients
(e ~ 10-20,000 A/mole-cm) and sulfur dioxide which has a low extinction
coefficient but occurs in high concentrations at smelters. A pyrolyzer
operating at a temperature of 600°C was employed to convert all organic
compounds to carbon dioxide and water vapor, and a sodium carbonate scrub-
bing solution was used to selectively absorb sulfur dioxide. The pyrolyzer
also converted all organic and inorganic mercury compounds to elemental
mercury.
The 01 in and Dupont are dual-wavelength instruments capable of
minimizing or eliminating the effects of interfering materials in the
sample stream. The Beckman and Sunshine are single-beam instruments,
electronically less sophisticated than the 01 in and Dupont, and are unable
to minimize or eliminate any effects of interfering materials in the sample
stream. The Geomet is also a single-beam instrument, yet removes inter-
ferences through the consecutive heating of two silver grids.
The majority of mercury monitors available are based on the
technique of UV absorption. It is for this reason that most of the instru-
ments studied in this program were based on this principle of operation.
However, there are other methods of measurement that warrant a description
of their principles of operation.
Correlation spectroscopy is a special technique which can be
applied to UV absorption spectroscopy. A high resolution mask of the absorption
spectrum of mercury is vibrated in and out of the beam and the signal is detected
llUaUeni
-------
with an AC amplifier (phase-sensitive detector). The advantage of this
technique Is that Interferences from hydrocarbons and sulfur dioxide are
eliminated. The major drawback Is that the cost of the Instrument Is
prohibitive (approximately twenty thousand dollars). An example of an
Instrument that employs this technique Is manufactured by Barringer
Research Corporation.
A commercially available analyzer for measuring elemental
mercury vapor by means of condensation nuclei formation has been Introduced
by Environment/One Corporation. A .1-100 liter sample Is drawn through
a silver wool cartridge and heated. The mercury Is then passed over a
mercury ultraviolet lamp to cause formation of mercuric oxide partlculates.
This air stream Is humidified and drawn Into a vacuum chamber where constant
volume expansion produces a cloud. The transmission of the cloud Is related
to the concentration of mercury. This Instrument was not Included In this
program due to Us high cost and applicability to only extremely low level
concentrations of mercury. The Scintrex 1 analyzer employs a pulsed
magnetic field applied to a mercury lamp source to obtain pulsed Zeeman
components used as reference wavelengths. The elemental vapor concentration
Is measured as the difference between the absorptions at the 253.7 nm line
and at the Zeeman components.
The choice of Instruments for use In the program was made to
provide a typical array of commercially available and moderate cost instru-
ments. The Beckman was chosen as a single-beam instrument reportedly tp
be of high quality. The Sunshine was chosen as a second single beam instru-
ment with no knowledge of its past performance. The 01 in and Dupont were
included as dual-wavelength instruments, based on their present use throughout
industry. The Geomet was included as a single-beam instrument capable of
removing interferences through the application of silver grids. Finally,
the RAC Tape Stain Sampler was included to determine whether it had possible
applications in the continuous monitoring field.
2-4
-------
2. Beckman K-23A Mercury Vapor Meter
The Beckman Model K-23A Mercury Vapor Meter (Figure 2-1) is
a small, portable, ultraviolet photometer. It is set for a wavelength
of 253.7 nanometers, and with its two meter scales, reads a full range
of 0-1.0 milligram of mercury per cubic meter of air. The meter is used
to determine the vapor concentration of mercury in air. However, the
instrument used in this study was adapted for monitoring gas samples by
inserting an 8 3/4" aluminum cell with fused quartz windows to transport
the sample through the analytical beam. Also, the Beckman K-23A was
designed for intermittent checking of mercury vapor levels and was not
specifically designed for continuous monitoring.
A mercury vapor lamp emits ultraviolet energy with a wave-
length of 253.7 nanometers. A mercury vapor sample absorbs energy of
the same wavelength while passing through the cell. The mercury vapor
lamp is used as a source for both the analytical and reference beams.
The analytical beam runs through the cell and passes through a single
ultraviolet filter before it falls on the analytical phototube. The
reference beam is enclosed and is shorter than the analytical beam extend-
ing across the width of the instrument. It passes through a screen atten-
uator, an adjusting aperture, a fixed aperture and an ultraviolet filter
before falling on the reference phototube. The operating principle is
diagrammed in Figure 2-2.
3. Dupont 400 Photometric Analyzer
The Dupont 400 Photometric Analyzer (Figure 2-3) provides a
means to continuously analyze, on stream, a variety of liquids and gases.
Various configurations of optical filters and light sources provide
selectivity for liquids or gases which absorb ultraviolet or visible
light in the 210 to 1,000 nanometers range. In the analyzer, the light
beam is split into a measuring beam and a reference beam after passing
through the sample. The analyzer used in this program was provided with
optical filters selective for the measurement of mercury.
/UtUmi
-------
TOP VIEW
Upscale
Adjust
Control
Range
Selector
Control
Handle
Fuse
Calibrator Control
Meter Face
Fuse
Power Cord
Start Switch
Zero Adjust
Zero Adjust
END VIEW
Figure I. Controls of Model K-23A Mercury Vapor Meter
CONTROL
FUNCTION
START SWITCH
UPSCALE ADJUST
RANGE SELECTOR
CALIBRATOR
Double-action pushbutton switch. Activates power to instrument.
Sensitivity control. Used to set span sensitivity when calibrating instrument.
Used to select 0 to 0.1 or 0 to 1.0 range on the meter.
Three-position switch. SET A is used in calibration of 0 to 0.1 range, SET B
for calibration of 0 to 1.0 range, and OPERATE for taking test readings.
METER FACE The meter has two scales. The top scale is used to read the 0 to 0.1 mg/cubic
meter range of mercury contamination. The bottom scale is used to reod the 0 to
1.0 mg/cubic meter range of mercury contamination.
ZERO ADJUST Used to balance the optical zero. Clockwise rotation of the ZERO ADJUST must
cause the meter needle to move upscale.
Figure 2-1. Beckman Mercury Vapor Meter, Model K-23A
2-6
-------
ANALYTICAL
BEAM
VAPOR
Is,
1
ZERC
ADJUST «=
o-CD
LAMP SAMPLE SA^M,PTLE UV ANALYTICAL
-v IN -, UJ' FILTER PHOTOTUBE
.'} T I n s — -v
'\ »1 1 *(
J n ... . 1
x L 1 |_ V
r
REFERENCE bEAM
= SCREEN ATTENUATOR
CD ADJUSTABLE APERTURE
szzf FIXED APERTURE
0)
AC RECTIFIER
AMPLIFIER /
rJ . / ^
\ & + (^
UP METER
SCALE
JV FILTER
REFERENCE
PHOTOTUBE
Figure 2-2. Operating Principle of Single Beam Instrument.
2-7
-------
Typical Du Pont 400 Photometric Analyzer
PHOTOMETER HOUSING
\-j/c Ana'.yzsr
Figure 2-3. Dupont 400 Photometric Analyzer
2-8
-------
Analyzer operation is based on the absorption of light by
the sample material. Radiation from a Pen-Ray lamp passes through the
sample and light at a wavelength of 253.7 nm is absorbed by the sample.
Light transmitted through the sample is divided by a semi-transparent
mirror into two beams and each beam then passes through its own optical
filter bundle. Each filter bundle permits only a particular wavelength
to reach its associated phototube. Optical filters in one beam permit
only radiation at the measuring wavelength to pass through, whereas the
optical filters in the second beam permits only light at the reference
wavelength to pass through. Measuring and reference wavelengths were
chosen so that sample constituents not to be measured would absorb light
to the same degree. Thus, effects of variations in concentration of these
interfering materials in the sample are minimized or eliminated. The
operating principle is shown in Figure 2-4. The analyzer was provided
with a twenty-inch Teflon cell and two quartz windows contained in a cell
housing maintained at a temperature of 140°F. The instrument was adjusted
for the measurement of mercury levels in the range of 0-1.0 milligrams per
cubic meter.
During the field tests at the zinc smelter, the original cell
was replaced with a two-inch Teflon cell.
4. Geomet Air Mercury Monitor
The Geomet Air Mercury Monitor (Figure 2-5) is a highly sensi-
tive instrument designed to measure elemental and total mercury in air.
The system can only determine elemental mercury in the vapor state, as do
the other photometric analyzers, however; conversion to a particulate and
gas analyzer for total mercury requires combination with a pyrolyzer.
The Geomet Air Mercury Monitor draws air into the grid section
at a nominal flow rate of 175 liters per minute. Selected sampling rates
are available by the use of limiting orifices. Mercury vapor is extracted
from the air by two silver wire grids wound around a grid tube. At the
-------
MEASURING
WAVELENGTH
ro
o
SAMPLE
SEMI-TRANSPARENT OUT
MIRROR
OPTICAL
FILTER
RECORDER
CONTROL
STATION
REFERENCE
WAVELENGTH
PHOTOTUBE
LIGHT
SOURCF
Figure 2-4. Operating Principle of Dual-Wavelength Instrument.
-------
PHOTO- tMHAL
METER RESET COOECT HOLD
emoi PEAK i omot
MERCURY
AIR MONITOR
Digital
Voltmeber
Sequence
Indicator
Lamps
Air Sampling
Inlet
Instrument Zero
Adjustment
Figure 2-5. Geomet Mercury Air Monitor
-------
end of the sampling period, these grids are consecutively heated to
desorb collected mercury. The stored signal from grid one is equivalent
to any collected interferences and is cancelled out upon final readout.
During this process, the air flow valve is closed to divert air, at
approximately 2.0 liters per minute, from the grid chamber through an
ultraviolet photometer. The peak signal difference obtained when the
two grids are heated is displayed in arbitrary units on a digital volt-
meter.
For use in other than ambient levels of mercury, the air
diluter (Figure 2-6) must be utilized. The diluter consists of a small
manifold connected to a clean air inlet and a rotameter through which
the sample stream (100-500 cc per minute) with a relatively large amount
of clean air (16-20 liters per minute) pass. The clean air is created
by passage through a bed of silver on alumina pellets (approximately 12%
silver on 1/8" pellets). By closing the flow control valve (to avoid
sampling the air except through the absorbent), the instrument should
indicate zero. The air diluter was required throughout the program due
to the sensitivity of the unit.
5. 01 in Mercury Monitor, Gas
The 01 in Mercury Monitor, Gas (Figure 2-7) detects elemental
mercury vapor by ultraviolet light absorption with a Dupont 400 photometric
analyzer (refer to section 3). The measurement is based on the utiliza-
tion of stannous chloride as a reducing agent as this instrument was pri-
marily designed for application in a chlor-alkali plant. The stannous
chloride serves to remove excess halogen, such as chlorine, from the air
sample, thereby preventing its recombination with mercury. Stannous
chloride reacts with chlorine to form stannic chloride. A pyrolyzer was
also incorporated in the 01 in Monitor prior to the reducing agent for
those applications that involve organic mercury compounds. Up to ten gas
samples can be continuously drawn to the instrument by vacuum and chosen
by a stream selector for analysis (Figure 2-8).
-12 HiU
ulaldeni
-------
Retaining
nuts and
washers.
Clean Air
Filter
Canister
Pellet
Retaining Screen
0.06-0.50 1pm
Rotameter
Flow
Control
Valve
Figure 2-6. Geomet Air Dilution Kit
2-13
Input
Sampling-
Line -
(from M109
tubing or
ambient air)
-------
RECORDER
DETECTOR SECTION
(Rear)
CHART STORAGE
CABINET
CONTROL SECTION
ANALYZER
SECTION (Front)
REAGENT RESERVOIR
(Ciblnit on right)
MERCURY MONITOR-GAS
Figure 2-7. Olin Mercury Monitor, Gas
2-14
-------
SAMPLE
FLOWMETER
0-5 LPM
Figure 2-8. Schematic, Olin Mercury Monitor, Gas.
-------
The reagent section of this instrument consists of a reagent
reservoir, a reagent circulating pump, a reagent loop and a reagent
solenoid. The reagent pump is energized by a timer-programmer to fill
the reagent loop with overflow to the reagent reservoir. Activation of
the reagent solenoid by a timer micro-switch drains the fixed reagent
volume into the scrubber. The scrubber-reactor of this monitor is a
glass chamber in which the reagent comes in contact with the gas sample
to convert ionizable mercury salts, particulates or vapors to metallic
mercury.
The pyrolyzer is a portable, temperature controlled furnace
placed in the sample system prior to the scrubber. It houses a fifteen-
foot quartz coil, through which the sample flows, and in which any inter-
fering gaseous material such as aromatics are broken down. It also assures
total mercury analysis for those applications where organic mercury is
involved.
The 01 in monitor was tested in the laboratory phase of the
program and was only available for testing at the chlor-alkali facility
in the field portion of the program. The stannous chloride scrubbing system
was bypassed during the laboratory studies performed on the 01 in.
6. Sunshine Instantaneous Vapor Detector
The Sunshine Instantaneous Vapor Detector (Figure 2-9) is a
small, portable, ultraviolet photometer. It is set for a wavelength of
253.7 nanometers and is used to determine the vapor concentration of
mercury in air. However, the instrument used in this study was adapted
for monitoring gas samples by inserting a 10 x 25 mm stainless steel
cell with quartz windows to transport the sample through the analytical
beam. Inlet and outlet Tygon tubing lines were replaced with Teflon
tubing and the calibration system supplied was modified for application
with the cell.
The instrument employs basically the same principle of opera-
tions as that of the Beckman (Refer to section 2).
2-16
-------
Figure 2-9. Sunshine Instantaneous Vapor Detector.
2-17
-------
7. RAG Tape Stain Sampler
The RAC Tape Stain Sampler, AISI type (Figure 2-10) uses
impregnated tapes to trap mercury vapor. The method is based on the
reaction between active selenium sulfide and mercury vapor. The selenium
sulfide is applied as a coating to paper and the coated paper is blackened
on exposure to air containing mercury vapor, the degree of blackening
being a function of time of exposure, concentration of mercury vapor, and
other factors which can definitely be controlled.
The air or gas to be analyzed is blown into the apparatus by
means of a small blower, the velocity of the sample stream being measured
and controlled through a flowmeter. The air then passes over an electric
heater to attain the proper temperature and into another tube, which ends
in a nozzle. The selenium sulfide sensitized paper is exposed to the air
containing the mercury vapor opposite the nozzle. The tape stain sampler
suffers from interferences due to light, incomplete conversion of mercury
compounds, and participate matter.
The tape-stain sampler was modified by replacing the Tygon
tubing with teflon tubing, adding a heating unit for the inlet line, and
suppling charcoal traps on the outlet.
Initial attempts to prepare the selenium sulfide coated paper
resulted in blotchy, uneven films having no uniformity. Some of the
selenium sulfide powder was then suspended in ammonium sulfide solution
(22%) and coated on strips of the paper drawn through a nip device. This
coated paper when dried in a hood had an even consistency and the amount
of coating applied could be varied by the speed with which it was drawn
through the nip. The calibration technique of the tape-stain sampler
involves calibration of the blackening of the paper against known mercury
concentrations. This technique demands a relatively constant coating on
the paper, a condition that could not be maintained at length.
2-18
llUaldenl
-------
Figure 2-10. RAC AISI Tape Stain Sampler
2-19
-------
The basic principle of operation was applied In the labora-
tory. Nevertheless, the accuracy of this method was severely hampered
by the variations In coating thickness. We also felt that the applica-
tion of this instrument in the field would not adequately determine short-
term variations in the concentration of mercury and, at best, the instru-
ment would indicate relative variations.
Therefore, it was decided that the tape stain sampler would
not be used in the remainder of the laboratory program or adapted for use
in the field.
2-20
llUaldenl
-------
III. RESULTS OBTAINED IN THE MAIDEN LABORATORY
A. DESCRIPTION OF MERCURY GENERATING SYSTEM
A schematic of the mercury generating system is shown in Figure 3-1.
The intake air is drawn through a charcoal filter to remove any mercury or
hydrocarbons from the air. The air is pumped through a Metal Bellows (M21)
pump, a Moore low pressure flow controller, and then a calibrated orifice.
This measured air stream bubbles through a flask containing mercury and water
maintained at its boiling point. The vapors of water and mercury are refluxed
and condensed and passed through an ice-cooled spiral-tube condenser that
maintains the exit temperature at very nearly 0°C. The exit temperature is
read from a thermometer placed in the gas stream. The purpose of the spiral
condenser is to reduce the temperature sufficiently to ensure that the mercury
vapor is saturated at that temperature. In that way, knowing the vapor pres-
sure of mercury as a function of temperature (Table 3-1), the concentration of
mercury can be calculated.
A dilution air stream is employed as a means for varying the mercury
concentration in the working range of the monitoring instruments. Intake air
is pumped through a charcoal filter and then a calibrated orifice. The mea-
sured dilution air is added to the mercury flow downstream of the spiral con-
denser and then passes through the mercury monitor. Finally, an evacuation
pump serves to control the pressure at the inlet to the monitor and also vent
the-mercury vapor. An inclined manometer is connected to the inlet line to
the monitor to determine the pressure. All lines and fittings contacting the
mercury stream were either Teflon or glass.
The accuracy of the laboratory mercury-generating system was
checked by comparison with samples of mercury collected in iodine mono-
chloride. A Heath Model 700 atomic absorption analyzer operating in the
fTameless mode was used for the analysis of the mercury samples. The pro-
cedure for collection and analysis of mercury was a modified version of the
EPA Regulations, Federal Register, April 6, 1973. The results of the
-------
CO
I
ro
VAPOR
MOORE
LOW PRESSURE
FLOW CONT ROLLE R
AIR
AIR
THERMOMETER
SPIRAL TUBE
CONDENSER
METAL
BELLOWS
PUMP
HEATING
MANTLE->
O
O
O
THERMOMETER ICE
.x BATH
U TUBE
MANOMETER
MI-6-^
ORIFICE
DILUTION STREAM
VENTED
CHARCOAL
FILTER
AUXILIARY .PUMP
TO BALANCE PRESSUP£
Hg MONITOR
U TUBE
MANOMETER
MERCURY STREAM
INCLINED
MANOMETER
I
Figure'3-1. Mercury Generating System.
-------
TABLE 3-1
MERCURY CONCENTRATION (VAPOR PRESSURE) AS A
FUNCTION OF TEMPERATURE
Temperature °C
0
2
4
6
8
10
12
14
16
18
20
22
24
26
28
30
32
34
36
38
40
42
44
46
48
50
52
54
56
58
Temperature °F
32.0
35.6
39.2
42.8
46.4
50.0
53.6
57.2
60. r
64.4
68.0
71.6
75.2
78.8
82.4
86.0
89.6
93.2
96.8
100.4
104.0
107.6
111.2
114.8
118.4
122.0
125.6
129.2
132.8
136.4
mm Hgll)
0.000185
0.000228
0.000276
0.000335
0.000406
0.000490
0.000588
0.000706
0.000846
0.001009
0.001201
0.001426
0.001691
0.002000
0.002359
0.002777
0.003261
0.003823
0.004471
0.005219
0.006079
0.007067
0.008200
0.009497
0.01098
0.01267
0.01459
0.01677
0.01925
0.02206
ppm Hg
0.24
0.30
0.36
0.44
0.53
0.64
0.77
0.93
1.11
1.33
1.58
1.88
2.22
2.63
3.10
3.65
4.29
5.03
5.88
6.87
8.00
9.30
10.79
12.50
14.45
16.67
19.20
22.07
25.33
29.03
mg Hg/m ' '
2.17
2.66
3.20
3.85
4.64
5.56
6.63
7.90
9.41
11.14
13.17
15.54
18.30
21.50
25.19
29.46
34.33
40.03
46.51
53.95
62.43
72.12
83.16
95.71
109.97
126.11
144.32
164.88
188.11
214.27
3-3 Ulaldeni
-------
TABLE 3-1 (continued)
Temperature
60
62
64
66
68
70
72
74
76
78
80
82
84
86
88
90
92
94
96
98
100
(1) From "
(2) ppm Hg
M\ mg Hg
°C Temperature °F
140.0
143.6
147.2
150.8
154.4
158.0
161.6
165.2
168.8
172.4
176.0
179.6
183.2
186.8
190.4
194.0
• 197.6
201.2
204.8
208.4
212.0
Handbook of Chemistry" by
_ mm Hg ,Q6
760 mm x 10
_ mm Hg 200.59 g Hg/mole
mm Hgll)
0.02524
0.02883
0.03287
0.08740
0.04251
0.04825
0.05469
0.06189
0.06993
0.07889
0.08880
0.1000
0.1124
0.1261
0.1413
0.1582
0.1769
0.1976
0.2202
0.2453
0.2729
Lange, N.
273.2°
ppm Hg(Z)
33.21
37.93
43.25
49.21
55.93
63.49
71.96
81.43
92.01
103.80
116.84
131.58
147.89
165.92
185.92
208.16
232.76
260.00
289.74
322.76
359.08
A., 1952, pp.
IP3 mg IP3 1
mg Hg/m3 (3}
243.68
276.68
313.59
354.70
400.80
452.27
509.66
573.44
644.22
722.63
808.80
905.68
1012.29
1129.35
1258.47
1401.23
1558.28
1731.15
1918.69
2125.88
2352.40
1499-1500.
I/mole
3-4
llUaldenl
-------
AA analysis compared to the calculated concentrations of the generating sys-
tem are shown in Table 3-2. Two of the three preliminary analyses taken in
February 1973 averaged within fifteen percent of the calculated value. Ad-
ditional work was performed to improve the reliability of the AA analysis
prior to the tests run in May 1973. The revised AA procedure gave close
agreement with the calculated results as tests 4 through 8 were within ten
percent of the calculated values.
TABLE 3-2
COMPARISON OF MERCURY GENERATING SYSTEM
AND AA ANALYSIS
Mercury Generated Mercury Collected
Run No. Date by Calculation by AA Analysis
(ygm) (ygm)
1
2
3
4
5
6
7
8
2/20
2/20
2/21
5/3
5/3
5/4
5/8
5/8
28.9
35.0
21.8
39.2
20.4
20.3
29.0
' 25.9
16.6
31.0
18.5
43.0
21.2
21.4
30.9
23.7
B. INTERFERENCES
1. Pyrolyzers for Removal of Hydrocarbons and Particulate Mer-
cury Compounds
Three pyrolyzer units, the Geomet catalytic converter, a
quartz tube pyrolyzer, and the 01 in quartz tube pyrolyzer, were evaluated
for the removal of hydrocarbons and particulate mercury compounds. The
Geomet catalytic converter was employed in the field sampling system due
to its ability to convert hydrocarbons at a lower temperature than the
other pyrolyzers and its durable construction.
3-5
lUUbii
-------
The quartz tube pyrolyzer consisted of a straight quartz tube
60 cm x 2.5 cm (with a volume of 423 cc) Inside a tube furnace. The tem-
perature of the furnace was controlled by a variable auto-transformer with
an iron-constantan thermocouple wire Inserted along the quartz tube wall.
About 50 percent of the length of the quartz tube was in the furnace.
The 01 in quartz tube pyrolyzer consisted of a fifteen foot
colled quartz tube within a Hotpack Corp. muffle furnace. This pyrolyzer
was incorporated into the 01 in monitor in front of the scrubber.
The Geomet catalytic converter normally contains alumina
catalyst in a stainless steel reactor with stainless steel tubing. The
air sampling rate of the Geomet ranges up to thirty liters per minute
and operates at temperatures up to 800°C. The alumina pellets were re-
moved from the furnace upon notification from Geomet, Inc. that this bed
packing tended to adsorb mercury during high level tests.
2. Hydrocarbon Conversion
Laboratory tests were performed to evaluate the hydrocarbon
conversion efficiency of the three pyrolyzer units. Since hydrocarbons, in
particular aromatics, act as interferents for the ultraviolet analyzers, it
is necessary to convert the organic species to non-absorbing species (COg)
in our field sampling system. Samples of known quantities of hydrocarbons
were made up by injecting measured amounts of hydrocarbons into mylar bags
and diluting with charcoal-filtered air. The gas samples were then pumped
through the converter being tested and the effluent stream captured In
another mylar bag. The converted samples were introduced into a Beckman
400 hydrocarbon analyzer to determine the ppm of unconverted hydrocarbons.
Methane and ethylene were pumped through the quartz tube
pyrolyzer at a flow rate of 6.4 liters per minute. Figures 3-2 and 3-3
show that this unit, at its maximum temperature of 1205°C was capable of
only a 77 and 98 percent conversion of methane and ethylene, respectively.
The Geomet catalytic converter (containing the alumina
catalyst) was initially tested and at a later time with the catalyst removed.
3-6 Ulaldeni
-------
80-
bO—
co
-sj
I
I-
LJ
LL
O
z
O 40"-
> _
Z
O
°° 20-
r —
400
I.
5CO
1...
_L L_ . 1
6 DO 700 800 9OO 1000 1100 1200 1300 I4OO
TEMP(°C)
Figure 3-2. Conversion of Methane with a Quartz Tube Pyrolyzer
..I . .
1500 1600
-------
100
60
00
UJ
5 60
u.
O
O 4°
LO
UJ
O
u
60 20
400
L
500
. JL...
600
. J.
7OO
_J_ I .
900 1000
I _ _ I _
nob 1200
800 900 1000 1100 I20O 1300 1400
TEMP(°C)
Figure 3-3. Conversion of Ethylene with a Quartz Tube Pyrolyzer
1500
I6OO
-------
The tests with the catalyst were at a flow rate of 34 liters per minute
while the tests without catalyst were performed at a flow rate of 28.3
liters per minute. It should be noted that the field system would require
a pyrolyzer flow rate of only approximately one liter per minute. Figures
3-4 and 3-5 Indicate that the Geomet converter with catalyst provides 100
percent conversion of methane and ethylene at temperatures of 690°C and
670°C, respectively. Figures 3-6 and 3-7 show that the Geomet unit with-
out catalyst provides 100 percent conversion of ethylene and benzene at
temperatures of 760°C and 860°C, respectively.
Methane was pumped through the 01 in pyrolyzer at a flow rate
of 4.5 liters per minute. Figure 3-8 indicates that methane was 100 per-
cent converted at a temperature of 850°C.
It was concluded that the Geomet catalytic converter without
the catalyst would convert all hydrocarbons at a flow rate of one liter per
minute within its working temperature range. Therefore, the Geomet unit
was employed as the pyrolyzer in the field sampling system.
3. Decomposition of Mercuric Chloride Aerosol
Since mercuric chloride aerosol might occur in chlor-alkali
plant effluents, the thermal decomposition of mercuric chloride aerosol
was investigated. A block diagram of the generating and decomposing sys-
tem for mercuric chloride aerosol is shown in Figure 3-9.
The quartz tube pyrolyzer served to decompose the mercuric
chloride to elemental mercury and chlorine. The Beckman monitor was em-
ployed to measure the mercury concentration as a function of pyrolyzer
temperature. A flow rate of one liter per minute was maintained. The ef-
fect of pyrolyzer temperature on the decomposition of mercuric chloride
aerosol is shown in Figure 3-10a and 3-10b. The data indicates that at
least a temperature of 900°C is required to convert mercuric chloride to
mercury in the quartz tube pyrolyzer.
Geomet, Inc. performed tests with mercury compounds conclud-
ing that the alumina catalyst in the catalytic converter is not absolutely
3-9
llUaUen,
-------
100
80
i
UJ
u_
O
| 40
v/)
L
O
,20—
J
100
I
200
I
3CO
40O 500 600
TEMP (°C)
700
8OO
900
Figure 3-4. Conversion of Methane with the Geomet Catalytic Converter (with Catalyst)
-------
IOO
r
Ld
2
UJ
60-
X
UJ
Li_
c
z 40 —
z
o
0
100
1 __ _
200
I
300
400
T E M P
50O
._ 1.
600
700
800
9OO
Figure 3-5. Conversion of Ethylene with the Geomet Catalytic Converter (with Catalyst)
-------
IOO
60
LJ
60
X
t-
LJ
U.
O
Z 40-
u O
-^ */»
ro ££
UJ
>
2
O
I
IOO
Figure 3-6.
2OO
300
600
700
800
400 500
TEMP (°C )
Conversion of Ethylene with the Geomet Catalytic Converter (without Catalyst),
900
-------
ICOp-
?0r
rr 60;-
LJ
LL)
m
w O
Ul
O
O
fiP
20i
r
o
IOO
Figure 3-7.
200
„ ..I
300
600
..A .
700
_ 1...
800
400 500
TEMP (°C )
Conversion of Benzene with the Geomet Catalytic Converter (without Catalyst).
•300
-------
100
60
LU
60 —
X
UJ
£|
ce
UJ
O
40
L
.J.
100
200
300
400 500
TEMP (°C )
600
7OO
800
Figure 3-8. Conversion of Methane with the Olin Pyrolyzer.
-------
ROTA METER
'SURGE
TANK
•
QUARTZ TUBE
-
Hg INSTUKENT
o
—
G
CHARCOAL
FILTER
NEBULIZER
HaCl
I AIR
METAL BELLOWS
MB2I PUMP
*
VAR1AC
TUBE FURNACE
PUMP
NOTE: ALL LINES ARE TEFLON WITH GLASS CONNECTORS
Figure 3-9. Laboratory System for Generation and Decomposition of Mercuric Chloride Aerosol
-------
\
o
X
o
Ul
o:
O
Q.
.1
o
o
o
o
o
8
o
o
o
^ TEST 1
cP
I
200 400 600 800 1000
PYROLYZER TEMP (*C )
Figure 3-10a. Effect of Pyrolyzer Temperature 1n the Decomposition of
Mercuric Chloride Aerosol.
3-16
-------
o
o
o
o
o
z
UJ
0
2
O
oe
O
Q.
TEST 2.
I I I I I
0 200 400 600 800 1000
PYROL.YZER TEMP (°c)
Figure 3-10b. Effect of Pyrolyzer Temperature in the Decomposition of
Mercuric Chloride Aerosol.
3-17
-------
necessary. At operating temperatures of nearly 500°C, they found many
mercury compounds, including mercuric chloride, decomposed without
catalyst. The Geomet converter will be employed in the field at an
operating temperature of 600°C.
4. Sulfur Dioxide Removal
Laboratory tests were performed to determine the efficiency
of various systems for removing SOg. The test apparatus is shown in Figure
3-11. A mixture of five percent sulfur dioxide was passed through a series
of Impingers containing a scrubbing solution at the volumetric flow rate of
one liter per minute. The scrubbed gas was then analyzed by a Dynasciences
sulfur dioxide monitor (SS-330) to determine the efficiency of various
scrubbing solutions. Also, a packed tube was used to test the absorption
of sulfur dioxide by various solids. It was found that both sodium car-
bonate and hydrogen peroxide completely removed sulfur dioxide; however,
sodium carbonate removed sulfur dioxide to its theoretical limit whereas
hydrogen peroxide did not. None of the solid absorbents were found effec-
tive in the removal of sulfur dioxide.
Three midget impingers were added to the mercury generating
system in the mercury stream as shown in Figure 3-12. Several tests were
run with varying solutions of sodium carbonate added to the impingers.
The Beckman was used as the monitoring instrument. The mercury stream was
alternated at three minute intervals for a thirty minute period through
the impingers and bypass. No significant change in instrument readings
occurred during these shifts, although minor fluctuations were observed
due to variations in flow. Calculations of the mercury flow consistently
agreed with the instrument readout. Five percent sulfur dioxide was added
to the mercury stream while bubbling through the sodium carbonate and
again no change in the mercury concentration occurred. Varying concentra-
tions of sodium carbonate were used in the impn'nger solutions with all sam-
ples indicating complete removal. Sulfur dioxide and mercury were bubbled
through one sample until all the sodium carbonate was completely reacted.
Upon depletion of the sodium carbonate, the instrument readout immediately
rose above scale and remained there. Each test run indicated sodium
carbonate would totally scrub out sulfur dioxide with no removal of mercury.
HUm
-------
. E'iT
e-
Pi OTA METER
(TOTAL FLOW)
IMPINGE RS
ROTA METER
(S02 FLOVrf)
CYLINDER
I SC2
lirJSTRUMENT
VENT
Figure 3-11. Sulfur Dioxide Removal System.
-------
Hg VAPGR
PO
o
THCr?Mf MCTCS
MOORE
LOW PKESSU^E
FLOW CONT ROLLE R
AIR-
CHARCOAL
Fl LTEIx
\
SPIRAL TUBE
CONDENSER
METAL
BELLOWS
I-' U M P
-^
(\ I
THERMOMETER
BATh
r
AIR
CHARCOAL
F IL1C l»
_|_| |_^
ORIFICE
HEATING
[-,^IITLE-
U TUBE
MANOMETER
V E N T E D -4-
CHAK'COAL
FILTCN
AUXILIARY PUMP
TO BALANCE
DILU Tl'. II STREAM
ME hCUHY ST..CA/
U TUBE
MANOMETER
INCLINED
MANOME!ER
4 '
Figure 3-12. Mercury Generating System with Sulfur Dioxide Removal.
-------
Similar tests were performed with hydrogen peroxide as the
scrubbing agent. Hydrogen peroxide solutions Indicated not only complete
removal of sulfur dioxide but also substantial removal of mercury. As the
peroxide reacted with the sulfur dioxide, the Instrument concentration
would drop until the level approached zero. It was concluded that sodium
carbonate would serve as an adequate scrubbing solution for use in the
field system.
The effective Interference of sulfur dioxide on the instru-
ments was observed by introducing known quantities of the gas into each
monitor. The equivalent mercury levels were recorded and the results are
shown in Table 3-3. The Dupont and 01 in indicated the largest interfer-
ence and the Beckman and Sunshine showed less response to the sample gas.
The Dupont and 01 in were operated lacking the optical filters capable of
cancelling sulfur dioxide interference. During the field study at the
zinc smelter, the Dupont was equipped with this filter as the sulfur di-
oxide levels were quite high.
TABLE 3-3
SULFUR DIOXIDE INTERFERENCE
mg/m S02
1,290
1,600
5,710
1,430
5,710
Volumetric Flow
(cc/min)
2,030
2,030
2,030
550
550
Beckman
(mg/m3)
0.027
0.036
0.068
0.032
0.070
Dupont
(mg/m3)
0.13
0.27
0.44
0.19
0.41
Sunshine
(mg/m3)
0.04
0.08
0.18
0.04
0.15
Olin
(mg/m3)
0.10
0.25
0.39
0.12
0.34
C. ZERO AND SPAN STABILITY
Determination of span and zero drift was made during both the
laboratory tests and also in the field. Zero gas was passed into the Beck-
man, Sunshine, Dupont, and Olin with the outputs of the instruments recorded
3-21
Maiden l
-------
at various Intervals of time. Throughout these periods of time, mercury was
Intermittently passed through the Instruments with a return to zero air
prior to any zero measurement. Table 3-4 shows the Indicated Instrument
readings versus the hours of operation.
TABLE 3-4
ZERO DRIFT MEASUREMENTS
Time (hr)
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
8.0
12.0
24.0
68.0
Beckman
(mg/m3)
0
0
0
0
0
0
0.01
0.01
0.005
0.012
0.015
0.02
Sunshine
(mg/m3)
0.03
0.04
0.06
0.07
0.07
0.06
0.07
0.08
0.09
0.09
0.08
Needle pinned
below zero
Dupont
(mg/m3)
0
0
0
0
0
0
0
0
0
0.05
0.03
0.02
01 In
(mg/m3)
0
0
0.01
0.01
0.02
0.01
0.01
0.01
0.01
0.01
0
0.02
88.0 0.015 Needle pinned 0.02 0.02
below zero
96.0 0.03 0.04
120.0 0.05 0.03
o
The maximum deviation from zero for the Beckman was 0.02 mg/m (0-
0.1 mg/m range) after sixty-eight hours of operation. The Beckman, not be-
ing a continuous monitor, maintained an excellent zero through short Inter-
vals of time (eight hours or less). The maximum deviation from zero for the
3 3
Sunshine was 0.09 mg/m (0-1 mg/m range) after only eight hours. The Sun-
shine never maintained a steady zero and continually drifted up and down
3-22
-------
scale after short periods of time (one hour or less). The maximum devia-
3 3
tion from zero for the Dupont was 0.05 mg/m (0-1 mg/m range) after twelve
hours. The Dupont showed no detectable zero drift for up to twelve hours
and maintained extremely good stability throughout the program. The maxi-
3 3
mum deviation from zero for the 01 in was 0.04 mg/m (0-1 mg/m range) after
ninety-six hours. The 01 in drifted only slightly through eighty hours, and
as did the Dupont, also indicated unusually good stability.
The span drift was observed with the use of the calibration fil-
ters contained in each instrument. The span drift was not quantitatively
noted; however, qualitative assessments were based on laboratory and field
experience. The span stability for the Olin, Dupont, and Beckman was quite
precise as corrections in span adjustment were seldom required. The Sun-
shine required span adjustments at frequent intervals which might be ac-
countable to the special calibration system installed at the Maiden labora-
tory. The Geomet was tested for zero from time to time, generally each of
many times we encountered difficulties with the applicability of the instru-
ment. However, throughout our use of the instrument, approximately one
hundred and forty hours, no zero drift was observed. We were unable to
test the span drift of the Geomet. No stability tests were run with the
tape stain sampler.
D. RESPONSE TIME
The response time of the instruments was observed in the labora-
tory. The time interval from a change in mercury concentration to the time
the final value 1s displayed on the measuring device of the instruments was
interpreted as response time. The dead time of the sample lines and flow
metering components of the laboratory setup was negligible with respect to
instrument lag. The Olin, Sunshine, and Beckman responded quite similarly
in the laboratory with the Sunshine responding the most quickly. The re-
sponse time of these three instruments varied from fifteen seconds to ap-
proximately forty-five seconds depending on the flow rate of the mercury
stream. The response time of the Dupont was somewhat slower due to the
twenty inch cell used in the laboratory. It ranged from about twenty-five
3-23
-------
seconds to one minute. The Dupont's response time was not observed with
the two inch cell installed.
The response time of the instruments in the field increased due
to sampling system dead-time as they were located some distance from the
mercury source, particularly at the red oxide of mercury facility and the
zinc smelter. The response time exceeded three minutes at the end box test-
ing with only the 01 in monitor. This was due to the need for locating the
01 in monitor, considering its size, out of the cell room. In this instance,
the response time of the 01 in ran as much as four minutes. The response
time of the Geomet was dependent on the timing cycle desired for storing
the mercury sample on the silver grids. For all applications in this pro-
gram, the timer was adjusted to the minimum cycle of two minutes.
E. SENSITIVITY
The sensitivity of the monitoring instruments was interpreted as
the minimum detectable instrument response. The Beckman, Dupont, and 01 in
provide range selection for a measuring scale of 0-0.1 milligram per cubic
meter, whereas the Sunshine is designed with only a 0-1.0 milligram per
cubic meter scale. The minimum detectable level of the Beckman was 0.005
milligrams per cubic meter, the 01 in and Dupont was 0.01 milligrams per
cubic meter, and the Sunshine was 0.02 milligrams per cubic meter. The
Geomet was by far the most highly sensitive instrument evaluated, with a
minimum detectable response in the range of nanograms per cubic meter.
The high sensitivity of the Geomet represents a distinct disadvantage for
continuously measuring high level emissions from mercury sources. None of
the instruments tested are capable of measuring mercury for source emissions
without the use of a dilution system. The intrinsic high sensitivity of
each instrument is not necessary for the applications required by this
program.
F. RELIABILITY
The reliability of each instrument was observed throughout the
laboratory and field studies. The 01 in was operated in the laboratory for
limited periods of time and was not the same instrument tested in the field.
3-24 UhUeni
-------
Neither of these Instruments had any electronic failures during the program.
The recorder on the field monitor required replacement of the slldewlre, but
remained operational throughout the testing. The Dupont was kept on almost
constantly while in the laboratory and remained turned on five days a week
In the field. During the field testing of the hydrogen stream, the Dupont
was not operational due to a loose connection In the control station. The
connection apparently loosened during the shipment and movement of the In-
strument. Also, the zero potentiometer on the control station needed re-
placement as It tended to slip upon zero adjustments. Both the 01 In and
Dupont had been used frequently prior to this program and had numerous
operating hours.
The Beckman, Sunshine, and Geomet were relatively new Instruments.
The Beckman, not designed as a continuous monitor, frequently required new
mercury vapor lamps. Adjustments were also necessary on the coarse sensi-
tivity and range ratio as the front panel controls were not adequate. Dur-
ing the field trip to the red oxide of mercury facility, the phototubes and
mercury lamp were replaced by a Beckman technical representative. The Sun-
shine also required replacement of the light source but not as frequently
as the Beckman. While testing at the end box vent of the chlor-alkali
plant, the Sunshine stopped responding to mercury. Replacement of the mer-
cury light source did not alter this situation and only after considerable
efforts was the instrument made operational. The exact cause was never re-
solved although from that point on, the Sunshine could not be left on con-
tinuously without the meter readings dropping to zero. The Geomet remained
in good working order throughout its use in the field while in the labora-
tory the grid had to be replaced. While attempting to zero the Geomet with
air scrubbed in iodine monochloride, moisture entered the grid and shorted
the grid wires. A replacement grid was sent immediately and remained in
operation through the remainder of the program.
G. RELATIVE ACCURACY AND PRECISION
The relative accuracy and precision of the Beckman, Olin, Sun-
shine, and Dupont with both the twenty inch and two inch cell was deter-
mined by testing the monitors separately in conjunction with the mercury
UUeni
-------
generating system. Each Instrument was operated for a conditioning period
of at least four hours prior to the performance tests. Instrument calibra-
tions were carried out before each series of tests while as many as twelve
test series were performed on each instrument. No more than fifteen sepa-
rate sample points were taken in each series so that the operation of the
monitors would somewhat simulate the day to day monitoring anticipated in
the field. The calculated concentrations of the generating system were re-
corded and compared to those of the Instruments. This data is shown for
each instrument in Table 3-5 through Table 3-9, see Appendix A.
The relative accuracy was determined by linear regression analy-
sis of the paired data for the generating system and instrument readings.
The linear regression line for each instrument was obtained and employed
in the accuracy calculations. These equations and the regression lines
are indicated in Figure 3-13 through Figure 3-17. The relative accuracy
was defined as the correctness of the instrument relative to the value
given by the reference method (mercury generating system). The relative
accuracy was expressed as the instrument readings relative to concentra-
tions of 0.30, 0.60, and 0.90 milligrams per cubic meter of mercury (30,
60, and 90 percent of full scale) as calculated from the generating sys-
tem. The relative accuracy of the instruments is shown in Table 3-10.
The information in Table 3-10, in itself, does not provide a completely
clear picture of the accuracy. The correlation coefficient, a statistic
that measures the strength of the linear relationship between the two
variables, further assists in developing a total statement on the accu-
racy of the instruments.
The Beckman was very accurate for a portable monitor with an ex-
tremely high correlation coefficient of 0.980. The Dupont, tested with the
twenty inch cell, was quite inaccurate, however, it should be noted that
the correlation coefficient was quite high at 0.986. The Dupont, tested
with the two inch cell, also was relatively inaccurate but showed a high
correlation coefficient of 0.988. The major causes of the inaccuracy were
directly related to the cell length and manufacturer's calibration data.
In using a twenty inch cell, the Dupont was incapable of maintaining
3-26
lUMkn/
-------
10
ro
rv
ui
•v
i.oi—
0.9
^ 0.8
- CORRELATION COEFFICIENT =.980
0.7
/
/
C.I
C.2 0.3 0.4 0.5 0.6 / 0.7 0.8
BECKMAN READINGS ( M I LL I G RA M5/C U. MET ER )
Figure 3-13. Regression Line for Beckrnan Monitor.
1.0
-------
CO
I
ro
00
Hi
z
rj
u
Q:
z
o
1.0
0.9
0.8
0.6
I 0.5
ce.
\-
UJ
0.4
o
^ 0-3
t—
<
_i
u
< 0.2
O.I
CORRELATION COEFFICIENT = .996
Y=.98X+.005
I
I
I
0 0.1 0.2 0.3 0.4 0.5 0.6 , 0.7 0.8
OCIN READINGS ( Ml LLI GRAMS/C U METER)
Figure 3-14. Regression Line for 01 in Monitor.
0.9
1.0
-------
CO
I
ro
vo
ce.
LU
2
1/1
o
ce
»-
z
a
LU
'.O
O.9
08
0.7
- 0.6
0.5
z 0.4
O
0.3
< 0.2
0-1
CORRELATION COE FRClENT = 8 78
Y= X-.045
I
I
0.1 0.2 0-3 0.4 0.5 0.6 O.7 C.8
SUNSHINE READINGS ( MILLIGRAMS/CU. METER)
Figure 3-15. Regression Line for Sunshine Monitor.
0.9
1.0
-------
co
i
OJ
o
cc
LJ
t-
U
10
0.9
0.8
13
tf*> 0-7
o:
-i 0.6
O
O:
h-
-z.
LJ
O
o
U.I
\
05 —
0.1
Y=|.54X-08
(LARGE CELL)
I
I
CORRELATION COEFFICIENT =.986
I
I
o r.i 0.2 0.3 C.A o.: 0.6 0.7 o.e
CUPONT READINGS ( MILL I G R A v-S/ C'j. METER)
Figure 3-16. Regression Line for Dupont Monitor (Twenty Inch Cell)
C.9
i.O
-------
I
to
a:
Ui
in
tr
o
z
o
1.01-
0.9
0.8
0.7
0.6
0.5
z
UJ
z 0.4
o
o
£ 0.3
-------
TABLE 3-10
RELATIVE ACCURACY OF INSTRUMENTS
Generating System Concentration
333
0.30 mg/m 0.60 mg/m 0.90 mg/m
Instrument Variation
(% of full scale)
Beckman
01 in
Sunshine
Dupont (20"
Dupont (2"
cell)
cell)
97%
100%
115%
83%
123%
103%
102%
108%
73%
127%
106%
101%
105%
71%
128%
linearity. Applying Beer's Law, at high concentrations with a twenty inch
cell, the log amplifier is extended beyond its linear range.
The 01 in was the most accurate instrument with almost no devia-
tion from the reference method. The correlation coefficient was 0.996.
The Sunshine appeared to be quite accurate applying the regression analy-
sis, however, the correlation coefficient was extremely low, 0.878, com-
pared to the other instruments.
The precision was defined as the standard error of the mean, in
terms of the quantity being measured, as plus or minus so many milligrams
per cubic meter of mercury. It is derived from the following equations:
-2 _ , c~2
Sy
and
2 i _^. 2
sy = FE(y-y)
where the quantity r is the correlation coefficient, Se is the standard
2
error of the mean, Sy is the error variance, n is the number of sample
3-32
iHUbii
-------
points, y Is the value of the standard concentration, and y Is the mean of
those values. From these two equations, the standard error is found to
equal the following:
Se =
The correlation coefficients and error variances were determined by linear
regression analysis of the data for the generating system and each instru-
ment. The precision of each instrument is given in Table 3-11.
TABLE 3-11
PRECISION OF INSTRUMENTS
Instrument Precision
Beckman +_ 0.052 mg/m3
Olin +0.027 mg/m3
Sunshine +_ 0.109 mg/m3
Dupont (20" cell) +0.028 mg/m3
Dupont (2" cell) +0.040 mg/m3
As might be expected, the precision of the 01 in and Dupont are in
good agreement as they both employ the same analyzer. Their level of pre-
cision appears adequate for use as a continuous monitor. The precision of
the Beckman is exceptionally high for a portable monitor, indicative of the
overall performance of the Beckman. The precision of the Sunshine was con-
siderably less than the other instruments.
Summarizing, the Olin performed well within any accuracy require-
ments for a continuous monitor. The Beckman also performed with high ac-
curacy, but cannot be employed in its present configuration as a continuous
monitor. The Dupont, with a twenty inch cell, is not an accurate instru-
ment for source monitoring even though the electronic accuracy of the in-
strument is confirmed by the results of the Olin tests. Tested with a two
inch cell, the Dupont again did not perform well due to calibration errors.
HaUm
-------
Nevertheless, these problems are associated with Instrument application and
not the direct electronic performance of the Instrument. As shown by the
011n, the proper application and standardization of the Dupont will result
In a highly accurate Instrument.
3-34 UlaHeni
-------
IV. RESULTS OBTAINED IN THE FIELD
A. FIELD SAMPLING SYSTEM
The original field sampling system is shown in Figure 4-1. The
system consisted of an EPA sampling train for mercury emissions (40 CFR
61:38 FR8820, April 6, 1973) and a sampling leg that contained the mercury
monitors. Isokinetic flow was maintained in this stream at all times, and
iodine monochloride impingers were only included when referee tests were
run. About one liter of gas sample was drawn from the isokinetic stream
prior to the impingers. This sample stream was passed through the pyrolyzer
unit (catalytic converter) to convert any gaseous and particulate mercury
compounds to elemental mercury and break down all hydrocarbons. Following
the pyrolyzer, the stream was split passing approximately six to ten milli-
liters of gas to the Geomet instrument. The main stream was pumped through
a rotameter by a teflon lined pump and then diluted with clean, regulated
air. Depending on the flow requirements for dilution, the instrument flow
rates were maintained at approximately one liter per minute by evacuating
the excess gas through a pressure-regulated flow meter. The instruments
were located in parallel, each followed by a flowmeter. The evacuation
stream also contained a flow meter. A sodium carbonate scrubber was added
upstream of the instruments when sulfur dioxide was present in the gas
stream.
B. MERCURY PROCESSING PLANT
1. Description of Red Oxide of Mercury Process
Prime virgin mercury is pumped from flasks to a holding tank
and then added to a reactor. Nitric acid pumped from storage to a holdup
tank, combines with the mercury in the reactor. The reactor serves to
heat about two thousand pounds of mercury plus the required nitric acid
to approximately 120°F for eix to eight hours. The reaction occuring is
exothermic and yields mercurous nitrate which is passed into any of three
vats positioned above the three furnaces. The mercurous nitrate is added
to the furnaces which have been preheated to 80°F and three additional
UhUen,
-------
i
ro
HEATED
AREA
TEMP
VACUUM
GAUGE
BY-PASS
VALVE
HE AT ED GLASS
NOZZLE LINED PROBE
'S* TYPE
PITOT TUBE
CARBON
SCRUBBERF
n
GEOMET
MONI TOR
DRY TEST MANOMETER
METER
/
-TEFLON PUMP
CAPBON
T
X
I
•
n
i
-M
£=^
DILUTION AIR STREAM
\
\
ROTOMETERS
3
I
ROTOMETER
\
•
11
PR
RE(
/<- n
\j(J2
ESSURE
JULATOR
SCRUBBER, WHEN REQUII
?ED
2
>
1
1
ROTOMETER
-
•
IT
i i
ROTOMETER
MERCURY MONITORS
Figure 4-1. Field Sampling System
-------
flasks of mercury are poured into each furnace operating. Increasing
the furnace temperature to 120-150°F for two hours, mercuric nitrate
is formed. The furnace temperature is increased to 280°F for two hours
to initiate the conversion of mecuric nitrate to mecuric oxide and
gradually increasing the temperature to 590-600°F for six to eight
hours, the reaction is run to completion.
Furnace fumes are vented with the spillover of liquid into a
mother liquor storage tank. From this tank, the fumes are passed into a
common six-inch duct and then into two low efficiency wetted towers. The
gases are vented to the atmosphere.
Sampling for total mercury emissions was accomplished by
introducing the sample probe into the six inch vent line through a three
inch test port at the location shown in Figure 4-2. The test point was
located at the midpoint of the vent. The test site was chosen so that
the equipment could be operated within the building.
2. Test Results
The tests at the red oxide facility were conducted from
April 10, 1973 to April 25, 1973. Data were taken every five minutes while
the sampling system was in operation. This data is shown in Table 4-1,
(see Appendix A). The pyrolyzer temperature was set at 600°C and the heated
teflon tubing temperature was adjusted for 200°C. The instruments tested
at this site were the Beckman, Sunshine, and Dupont. The Dupont was left
running continuously whereas the Beckman and Sunshine were operated only
ten hours per day. Instrument calibrations were performed twice a day
except during zero drift tests.
No data was obtained on April 10 and April 11 as both days
were required for system set-up.
Initially, the Beckman and Sunshine could not be zeroed. The
zero air was produced by pumping ambient air through carbon scrubbers and,
later in the tests, through three impingers of iodine monochloride with
4-3
lUlaUen,
-------
WASH TANKS
VENT
TEST PORT
PROBE
NITRIC ACID
HOLDUP
HG
MONITOR
FIELD
SYSTEM
NO 3
FURNACE
NO I
FURNACE
M OT H E R
LIQUOR
TANK
VATS
REACTOR
Figure 4-2. Red Oxide of Mercury Facility.
4-4
-------
silica gel. It was deduced that nitrogen oxides from the process emissions
were present and not being scrubbed out. The single wave-length Instruments
were apparently affected by the Interference of nitrogen oxides. The
Dupont dual wavelength scheme appeared to show no effects due to the
interferences.
Finally, a cylinder of zero test air was purchased for use as
a zero standard and dilution air source replacing the on-site generated
source. Preliminary tests were carried out, but no useful data were ob-
tained. All three furnaces shut down in mid-afternoon at which time labora-
tory work was initiated for iodine monochloride testing.
On April 17, data was obtained while one furnace was in opera-
tion, until the Beckman instrument failed, at which point the test was ter-
minated. The Beckman unit could not be repaired at the test site and arrange-
ments were made to transport the instrument to the local service representa-
tive.
Four reference tests were taken during the field testing at
the mercury processing plant. A quarter-inch stainless-steel nozzle was
employed at the probe inlet for all four tests. During each reference test
the instrument meter readings and flow rates were taken every five minutes
and then averaged over the total test time. The necessary flow rates, tem-
peratures, pressures and other data, and laboratory measured and analyzed
parameters were recorded and used to calculate the mercury concentrations
in the reference samples. Comparison of the reference tests and the instru-
ment measurements are shown in Table 4-2. The analyses were performed in
the Maiden laboratory on a Heath Model 703 Spectrophotometer by Wai den person-
nel. The method of analysis was the procedure described in the Federal Register,
April 6, 1973.
During tests 1 and 2, a dark purplish precipitate formed in the
second impinger. Also the silica gel was tinted to the color of iodine indi-
cating possible carryover of some iodine monochloride. The sample recovery
procedure was modified so as to dissolve the precipitate into solution for
lutUait
-------
TABLE 4-2
COMPARISON OF REFERENCE TESTS AND INSTRUMENTS MEASUREMENTS
Test No.
1
2
3*
4*
Date
4/18
4/20
4/23
4/24
Time
10:00-11:30 am
3:00-4:00 pm
11:00-12:00 am
11:25-11:25 am
Reference Test (ICL)
mg/m3 Hg
11.4
295.45
3.97
1.05
No. of
Furnaces
Operating
2
3
2
1
Dupont*
mg/m3 Hg
0.04
0.15
0.97
0.54
*
Beckman
mg/m3 Hg
0.18
2.42
0.93
Sunshine
mg/m3 Hg
0.37
0.06
0.69
The instrument concentrations were determined by multiplying the instrument meter readings by the dilution
ratio when the dilution system was operating.
-------
analysis. All AA analyses were run upon completion of testing at this
field site. The unusually low levels of mercury recorded by the instru-
ments during test 1 and 2 appeared suspicious. As the results later in-
dicated, the sampling system was not transporting a representative sample
to the instruments.
The sampling system was modified prior to obtaining the third
iodine monochloride test. The instrument sampling line was disconnected
from the EPA train and a separate quarter-inch teflon nozzle was placed on
the inlet of the effluent stream. The Teflon nozzle was attached in the
stack adjacent to the EPA probe. As can be noted from the data in Table
4-2, the mercury levels in the instrument stream increased significantly
in tests 3 and 4. During these tests, the agreement between the refer-
ence tests and the instrument stream concentrations was much better than
that of the first two tests. No precipitate was found in the impingers
following the completion of the third and fourth tests. Although this
sampling scheme produced closer agreement between instrument readings and
reference test results, this method precluded sampling isokinetically
through the instrument stream.
On April 25, preparations for a fifth iodine monochloride
test were interrupted by a nitric acid spill. A flange, located above the
test area, burst, spraying nitric acid over the equipment and surrounding
area. The remainder of the day was spent on cleaning the equipment and
determining the extent of damage. It was decided to return to the Wai den
laboratory to fully evaluate the extent of damage and effect appropriate
repairs. The result of this accident was a two-week delay. Fortunately,
no internal damage was incurred in any instrumentation although the ex-
ternal features of much of the equipment was harmed.
The field program was developed with the intention that the
testing at the first site would serve mainly to establish the integrity
of the sampling system and testing methods as well as gathering perfor-
mance data. Our aim was to modify any aspects of the system as opposed
to generating extensive data as the main source of data was planned to
be a chlor-alkali plant. In this respect, the field testing at the red
UhUeni
-------
oxide of mercury facility did serve the intended ends. The third and
fourth tests indicated a major improvement in the sampling system as the
instrument readings compared fairly well with the reference test results.
The Beckman monitor showed close agreement with the fourth reference test
and the sampling system appeared to be operating more effectively than at
first.
It was also found that the heated Teflon tubing appeared to
evolve mercury for extensive periods of T;ime before instrument zeroing
could be achieved. The heating unit was shut off and consequently the
instruments zeroed quite rapidly.
C. CHLOR-ALKALI PLANT
1. Description of Chior-Alkali Process
The following process description is substantially extracted
from Reference [5]. In this process, schematically shown in Figure 4-3,
purified and nearly saturated brine is fed continuously through the inlet
end-box to the electrolyzer where it flows between a stationary graphite
anode and a flowing mercury cathode. The inlet end-box provides a connec-
tion for the feed brine and the stripped mercury as it returns from the
decomposer and also serves to keep the incoming mercury covered with
brine. The chlorine gas formed at the anode is discharged from the elec-
trolyzer for further treatment. The sodium amalgam flows from the elec-
trolyzer through the outlet end-box to the decomposer where it acts as the
anode to a short-circuited graphite cathode in an electrolyte of sodium
hydroxide solution. The outlet end-box is placed on the outlet of the
electrolyzer to keep the sodium amalgam covered with spent brine and
physically separate these two streams. Purified water is fed continu-
ously to the decomposer and reacts with the sodium amalgam. The products
of this reaction are sodium hydroxide solution and hydrogen gas. The
caustic soda is of high purity and leaves the decomposer at a concentra-
tion of about 50 percent by weight. At the test site, the by-product
hydrogen gas, which saturated with mercury corresponding to the tempera-
ture, is burned in a waste-heat boiler.
4-8
-------
BASIC TREATMENT CHEMICALS
(SODA ASH, CAUSTIC LIME,
ACID, CaCL2, ETC.)
CHLORINE
PRODUCT
CHLORINE
SOLID
NaCL FEED
1 OTHER
I
MAIN
STREAM
RECYCLE
I
BRINE
DECHLORINATOR
SPENT BRINE
TREATED
MAIN BRINE
SATURATION,
PURIFICATION, AND
FILTRATION
BRINE
INLET
END-BOX-
END-BOX
VENTILATION SYSTEM*
AQUEOUS
LAYER
COOLING,
DRYING,
COMPRESSION, AND
LIQUEFACTION
ELECTROLYZER
STRIPPED
AMALGAM
END-BOX
VENTILATION SYSTEM
i
—OUTLET END-BOX
^ END-BOX
VENTILATION SYSTEM
•* AQUEOUS LAYER
WATER COLLECTION
SYSTEM
END-BOX
' VENTILATION SYSTEM
HYDROGEN GAS
BYPRODUCT
AMALGAM
Kg PUMP
AQUEOUS LAYER
* PROPRIETARY TREATMENT CHEMICALS INCLUDE PRECIPITATORS,
FLOCCULANTS, POLYELECTROLYTES, AND SIMILAR MATERIALS
DECOMPOSER
(DENUDER)
CAUSTIC SODA
SOLUTION
^TION.AND » -CAUSTIC
PRODUCT
Figure 4-3. Schematic of the Chlor-Alkali Process
4-9
-------
Sampling for total mercury emissions was performed at two lo-
cations 1n the chlor-alkall process. Testing at the end-box vent was ac-
complished by Introducing the sample probe and Teflon line into the eight-
inch vent line through a three-inch hole. The stack was located adjacent
to the cell room, therefore, the instrumentation was situated in the build-
ing while the EPA mercury train was located outside of the cell room.
Testing of the hydrogen stream was accomplished by attaching quarter-inch
Teflon tubing to a valve outlet of the hydrogen stream to the boiler
burners. Although this stream does not emit directly to the atmosphere,
as required by EPA testing regulations, the importance of testing in a
hydrogen stream warranted this exception. Verbal approval was granted
by the Program Manager.
2. Test Results at the End-Box Vent
The end-box vent stack was tested from May 15, 1973 through
May 25, 1973. The Beckman, Dupont, 01 in, Geomet, and Sunshine monitors
were tested at this site. The 01 in unit was provided by the plant as
they employed the instrument for monitoring air quality in the cell room.
The 01 in instrument was modified to provide a range of 0 to 2.0 milligrams
per cubic meters by inserting the same cell that was calibrated in the
laboratory program. The stannous chloride scrubber was also operated
throughout the test period. Instrument readings were recorded every five
minutes except for the Geomet unit whose readings were recorded every two
and one-half minutes and then averaged for five-minute intervals. The
data obtained from this site is shown in Table 4-3, see Appendix A.
Due to the strong magnetic field within the cell room, the
meters for the Beckman and Sunshine unit had to be shielded with Mu metal.
Representatives from Geomet arrived on May 16 to assist in the preparation
of their instrument for monitoring. A newly-calibrated grid was inserted
in the instrument and additional silver-coated pellets were added to the
dilution kit. The plant was shut down on May 16 for repairs which pro-
vided ample time for system checks and laboratory preparations. The AA
analyses were performed on a Perkin-Elmer spectrophotometer provided by
the plant. Plant personnel, experienced in mercury analysis, completed
each analysis within one day of testing.
4-10
lUUaii
-------
Initially, the Geomet unit was unable to achieve a true Instru-
ment zero. Therefore, It was decided to determine the background level of
mercury due to ambient air alone and then subtract that value from subse-
quent mercury readings. The mercury lamp In the Beckman monitor had to be
replaced to achieve acceptable Instrument response.
On May 18, tests were begun to determine whether the sampling
system or the Instruments were the source of error In comparison to the
reference tests (Iodine monochlorlde stack samples). Midget impingers con-
taining either Iodine monochlorlde or potassium permanganate were placed In
the exit streams of at least one of the Instruments. A comparison of these
samples with those tests taken directly from the stack would Indicate any
variation between the stack concentrations and the sample stream concentra-
tions, assuming that no mercury Is lost In the Instruments. Each stream
sample was run for thirty minutes. In addition, several Impingers contain-
ing potassium permanganate were placed downstream of the 01 In Instrument
(by plant personnel) to determine the stream concentration. A summary of
all samples taken as this site 1s shown In Table 4-4, see Appendix A. It
should be noted that the average instrument concentrations recorded during
reference tests have been multiplied by the dilution factor for comparison
with the reference test results.
The exit stream samples indicate that at least the Olin unit
was adequately detecting the mercury in the sample stream. The fact that
the Olin monitor was in closer agreement with the stream samples than the
other instruments could be due to its stannous chloride scrubber. It was
believed that the only mercury species in the end-box vent would be ele-
mental mercury and some mercuric chloride. The pyrolyzer serves to con-
vert the mercuric chloride to elemental mercury, however, with chlorine
present, there was the likelihood of mercury recombining with chlorine to
reform mercuric chloride. The stannous chloride scrubber serves to con-
vert mercury salts, particulates, or vapors to metallic mercury and remove
chlorine, thus removing any possibility of reformation of mercuric chloride.
For the six stream samples analyzed, the Olin instrument averaged 88.8 per-
cent of the AA values. The Beckman and Dupont units operated during five
of the six samples and averaged 67 and 39.3 percent of the AA values,
4-11
IllbUenl
-------
respectively. The Geomet monitor operated during three of the six samples
and showed close agreement (averaged within 12 percent) with the stream
samples during two of the tests while indicating poor agreement on the
third test. The Sunshine unit did not operate properly during a majority
of the tests due to a damaged light source and phototube.
The large differences between the reference tests and instru-
ment readings were apparently related to sample interfacing. If particulate
mercury were present in the end-box vent, the sampling system, not operating
isokinetically, would not accurately represent the total mercury concentra-
tion. Yet the expected particulate mercury levels were so low that this
error alone could not account for the large differences.
3. Test Results at the Hydrogen Stream
The hydrogen stream was tested from May 30 through June 6,
1973. The pyrolyzer was taken out of the system and the Geomet analyzer
was not operated so as to avoid dangers associated with sparking in the
presence of hydrogen. Correction charts for the flow meters were provided
to convert flow rates in air to flow rates in a hydrogen atmosphere. Only
the Beckman, Sunshine, and 01 in units were tested as the Dupont instrument
could not be made operable. Data obtained at this test site is shown in
Table 4-5, (see Appendix A).
No adequate sampling probe entry ports were available on the
hydrogen lines, necessitating certain modifications in the standard sampl-
ing equipment. The only available test port was a quarter-inch valve out-
let prior to the boiler burners, therefore, no isokinetic reference
samples were obtained. Instead, the instrument exit streams were mea-
sured for mercury by bubbling the streams through impingers containing
either iodine monochloride or potassium permanganate. A total of twenty
instrument stream samples were taken and a comparison of the stream con-
centrations with average instrument readings is presented in Table 4-6
(see Appendix A).
The 01 in and Beckman instrument readings remained close
throughout all hydrogen stream tests. A regression analysis on the paired
4-12
lUtiden,
-------
average mercury concentrations for the Beckman and OUn units were derived
to illustrate their relationship. The regression equation is the follow-
ing:
Y = 0.887X + 0.078
with a correlation coefficient of 0.88. Y represents the average Beckman
instrument readings and X the average 01 in instrument readings for each
test.
The information in Table 4-6 also indicates that the two
absorbing solutions used in the instrument stream samples yielded sig-
nificantly different results. On four occasions, iodine monochloride
and potassium permanganate stream samples were taken simultaneously.
Three of the four simultaneous samples indicated the mercury concentra-
tions determined by the iodine monochloride samples to be greater than
the mercury concentrations determined by the potassium permanganate
samples. Also, based on the other stream samples taken, the instrument
mercury concentrations were considerably lower than the iodine mono-
chloride results, yet in close agreement with the potassium permanganate
results. Apparently, iodine monochloride was absorbing non-elemental
mercury species that were neither absorbed with potassium permanganate
nor detected with the monitoring instruments. Lacking a pyrolyzer for
conversion of mercury compounds to elemental mercury, this is quite un-
derstandable.
D. ZINC SMELTER
1. Process Description
Raw zinc ore containing approximately 30 percent sulfur by
weight is roasted in two roasters, each handling approximately 300 tons
of ore per day. The effluent from each roaster passes through Its own
collecting system and acid plant. Electrostatic precipitators remove
dust and other impurities, and counter-current gas scrubbers located
downstream of the precipitators also help to clean the gas. A mist
precipitator removes carry-over water and some dust before the gas
enters the converter.
4-13 Hi U
Ulalaeni
-------
Converted gas, after cooling, enters a packed absorbing
tower. Circulating oleum is fortified by the absorption of sulfur
trioxide as it passes through the tower, but it is reduced in concen-
tration again by the addition of 98 percent acid. Product oleum is
bled off continuously from the system in proportion to the amount of
98 percent acid added to the oleum system.
The gas leaving the oleum tower contains unabsorbed sulfur
trioxide, and is passed to the 98 percent acid absorbing tower where
absorption is completed. The effluent from this absorber and from the
98 percent absorber in the other acid plant are ducted to one common
breaching and are discharged to the atmosphere through a 300 foot stack.
This same stack also services the acid sintering operations. A schematic
of this process is shown in Figure 4-4.
Mercury, originally present in the zinc ore, is volatilized
during the roasting process and is carried through the subsequent process
steps in the off-gases. Other non-ferrous smelting processes also will,
similarly, generate mercury-laden effluents. In cases where no sulfur
recovery process is employed, so that the effluent is vented directly
to the atmosphere through tall stacks, the mercury content in the stream
can be substantial. The incorporation of a suIfuric acid plant will
reduce the concentration of mercury as a result of condensation and scrub-
bing out mercury in the last steps of the acid-making process.
In order to simulate testing at an uncontrolled smelter
where an acid plant is not incorporated to remove sulfur dioxide, it
was decided to test downstream of the primary precipitators where prior
tests had indicated mercury concentrations in the presence of high levels
of sulfur dioxide. The duct diameter at that point (see Figure 4-5) was
four feet and was located approximately two pipe diameters upstream of
a bend in the pipe. The nearest upstream disturbance was approximately
twenty pipe diameters.
4-14 UbHeni
-------
CYCLONE
ROASTER
FINE ORE
STORAGE
BIN-x
RETURNED
TO ROASTED
DFU TOWER CONVERTER
Figure 4-4. Zinc Smelter Schematic Diagram
-------
TO
ACID PLANT
PROBE
INSTRUMENT
TEST SITE
UUL^
CTt
ELECTROSTATIC PRECIPITATORS
Figure 4-5. Schematic of Test Site at Zinc Smelter
-------
2. Test Results
Due to excessively high ambient levels of sulfur dioxide in
the test area, continuous instrument readings were usually not obtainable
as the test personnel were forced to evacuate the test area. Gas leakage
in the duct upstream of the primary precipitator and through the precipi-
tator doors due to problems associated with the acid plant fan bearings
was the source of the unusually high ambient levels of sulfur dioxide.
A schematic of the test area is shown in Figure 4-5. Throughout the
test period, the plant was shut down to repair the fan, but attempts were
unsuccessful.
The Dupont unit had been fitted with a two-inch cell and
associated filters used to correct for the interference of sulfur dioxide.
The Dupont unit, with the short cell, had been preliminarily calibrated
by a Dupont representative at the Maiden laboratory. The Geomet unit
could not be zeroed or achieve a steady background level of mercury,
therefore, no data was obtained on the Geomet monitor, at this site.
A sodium carbonate scrubber was placed upstream of the Beckman and Sunshine
units. The pyrolyzer temperature was adjusted to 600°C, while the duct
temperature averaged 500°F. The data obtained at this site is shown in
Table 4-7.
On June 22, intermittent readings were taken that indicated
the Dupont instrument to be recording substantially higher levels of
mercury than the Beckman and Sunshine. However, further tests were cut
short as the plant shut down. It was discovered that the Teflon nozzle
and that part of the sampling line exposed to the high gas temperatures
decomposed. Consequently, the original sampling system containing the
sampling tee off of the glass lined probe was employed.
The following day, the system was operable for a short
period at which time the sodium carbonate scrubber was relocated so that
the gas stream entering the Dupont instrument was also scrubbed. Prior
to this change, instrument readings were taken. Following the relocation
of the scrubber, the Beckman and Sunshine units continued to indicate
almost no change in concentration, while the Dupont unit dropped from 1.90
to 0.75 milligrams per cubic meter. Apparently, the Dupont unit had not
been completely cancelling sulfur dioxide as an interferrent.
-------
TABLE 4-7
TEST RESULTS AT ZINC SMELTER
Date-
Time
Dilution
Ratio
Milligrams per Cubic Meter
Beckman Dupont Sunshine
6/22/73
10:05
10:20
10:55
11:00
11:40
6/23/73
9:15
9:45
10:00
10:35
10:40
10:45
2.49
2.78
2.78
2.82
2.24
2.24
2.24
2.73
2.45
0.58
0.47
0.95
0.48
0.40
0.37
0.46
0.56
3.60
2.45
1.20
2.30
>4.0
2.2
1.85
1.90
0.75
0.72
0.78
0.50
0.35
0.59
0.58
0.56
0.58
0.62
4-18
/Ulaldeni
-------
No useful data could be obtained the following three days
due to the excessive sulfur dioxide levels and plant shut downs. It
was decided to cancel the remaining test schedule due to the dangerous
testing conditions.
It was qualitatively determined that the Dupont filtering
system did not completely remove the Interference of sulfur dioxide.
Also, It was shown that sodium carbonate did scrub out sulfur dioxide,
yet It was not proven whether 100 percent removal was achieved. How-
ever, the laboratory study successfully demonstrated this point.
4-19
lUUeni
-------
V. CONCLUSIONS
The Olin instrument, when applied with a proper sample interface
system, can perform adequately for use as a continuous stationary source
monitor. It was particularly adaptable to applications at chlor-alkali
plants because' of the stannous chloride scrubber incorporated in its
sampling system. The precision and accuracy of the unit in the labora-
tory program was exceptionally good with a range of 0-2.0 milligrams
per cubic meter. However, the Olin monitor must be used, as would the
other instruments, in conjunction with a highly accurate dynamic dilution
system. The Dupont unit did not perform well in the laboratory or field,
yet the instrument should be adequate as a continuous monitor if properly
adjusted. The problems associated with this instrument were strictly
due to calibration errors and improper cell path length. The potential
ability of the instrument was verified by the test results of the Olin
unit, which contains the complete Dupont analyzer. The Olin unit was
independently calibrated and contained a shorter cell than the Dupont
unit.
The Beckman monitor performed extremely well in the laboratory and
field, although the unit is not designed for continuous use. As a light-
weight, sturdy instrument, the Beckman could be employed as a portable
continuous monitor if a portable sample interface subsystem could be
designed. The Sunshine unit did not perform well in the laboratory or
field and was not found acceptable for determining mercury emissions from
stationary sources.
The data obtained from the Geomet instrument was limited and incon-
clusive. The high sensitivity of the unit posed considerable problems,
yet there were some indications that the instrument might have applica-
tion as a continuous monitor. It was found that the RAC Tape Stain
Sampler would require major modifications beyond the scope of this study
to adapt the instrument to a continuous monitoring mode. Therefore, it
was decided early in the laboratory phase that a tape stain sampler
would not be evaluated any further.
5-1
lUtidaii
-------
The precision and accuracy of the monitoring instruments is greatly
affected by the sampling interface system and its ability to transport
a representative sample. The mercury concentrations sampled in the
field ranged as high as forty milligrams per cubic meter setting the
requirement for a dilution system capable of controlling the mercury
concentration in the range of the instruments (normally 0-1.0 milligram
per cubic meter). The system employed in the field performed less than
adequately in terms of these requirements; however, sample treatment for
interfering species and conversion of particulate and organomercury
compounds to elemental mercury was accomplished successfully. The
laboratory results indicated that sodium carbonate absorbed sulfur
dioxide without removal of mercury and all species of mercury tested
were converted to elemental mercury by pyrolysis in the Geomet catalytic
converter.
The hydrogen stream test results indicated that mercury species other
than elemental mercury were present. Therefore, total mercury monitoring
of chlor-alkali hydrogen lines would require some means of gas stream
pyrolysis to convert particulate mercury or organomercury species to
elemental form.
5-2
-------
VI. RECOMMENDATIONS
There are presently no instruments available that can easily be
employed as continuous stationary source monitors. Certain instru-
ments, such as the Olin and Dupont units, can be adapted to continuous
monitoring with the addition of sampling interface equipment that
dilute the mercury source concentrations to those levels provided in
the instruments. There are definite areas where further study and
development are recommended, such as:
(1) Development studies should be performed on the dual beam in-
struments to determine if they can be modified to monitor
mercury concentrations encountered at stationary sources with-
out the use of a dynamic dilution system.
(2) Further study of sample interface subsystems should be made
to develop possible schemes for automatic dynamic dilution
systems.
(3) Although the field and laboratory results provided data to
characterize the applicability and accuracy of the several
types of instruments, additional data would be very useful
and further work is recommended.
(4) Additional development of the Geomet dilution kit should be
made to obtain an operating scheme applicable to stationary
source monitoring. Additional study of this instrument
should be made to obtain more complete data and to evaluate
the operating parameters in a laboratory program.
(5) Further field studies should be made to determine the re-
liability of the Beckman unit as a portable monitor.
(6) Other dual-beam instruments should be studied to determine
their performance as continuous monitors in comparison to
6-1
llUakkm
-------
the 01 in and Dupont Instrument results. The study should
provide sufficient data to determine the applicability of
dual-beam Instruments, as a class, for use as continuous
monitors.
(7) Investigation of a pyrolyzer that can safely be used in the
presence of hydrogen should be made so that future instrument
studies on chlor-alkall hydrogen streams can be evaluated in
terms of total mercury monitoring.
6-2
IllhUem
-------
VII. REFERENCES
1. Anonymous, "Cell Systems Keep Mercury from Atmospheres," Chemical
and Engineering News, p. 14, February 14, 1972.
2. Anonymous, "Mercury in the Air," Environment. 13, 24, May 1971.
3. Dannelson, 0., Ed., "Air Pollution Engineering Manual," U.S. Dept.
of H.E.W., Pub. No. 999-AP-40, 1967.
4, EPA, Background Information - Proposed National Emission Standards
for Hazardous Air Pollutants, Asbestos, Beryllium, Mercury, APTD-
0753, December 1971.
5. EPA, "Control Techniques for Mercury Emissions from Extraction and
Chior-Alkali Plants," February 1973.
6. EPA, "Environmental Protection Agency Regulations on National
Emission Standards for Hazardous Air Pollutants," 40 CFR 61, 38 FR
8820, April 6, 1973.
7. EPA, "Mercury and Air Pollution: A Bibliography with Abstracts,"
October 1972.
8. Jacobs, M., Toxicology of Industrial Inorganic Poisons. Inter-
science Publishers.
9. Kensall, M.G., and Stuart, A., The Advanced Theory of Statistics,
Hafner Publishing Company, New York, 1963.
10. Lange, N.A., Handbook of Chemistry. Handbook Publishers, Inc.,
Sandusky, Ohio, 1952.
11. National Coal Association (NCA), Steam Electric Plant Factors,
1970 Edition.
12. Shreve, R.N., "Chemical Process Industries," McGraw-Hill, 1967.
13. Stahl, Q.R., "Air Pollution Aspects of Mercury and Its Compounds,"
Litton Systems, Inc., NTIS PB-188074, September 1969.
14. Stantnick, R.M., Oestreich, D.K., and Steiber, R., "Sampling and
Analysis of Mercury Vapor in Industrial Streams Containing Sulfur
Dioxide," Research Branch, Control Systems Laboratory, EPA.
15. Mineral Year Book, U.S. Bureau of Mines, 1967.
16. Wadsworth, G.P., and Bryan, J.G., Introduction to Probability and
Random Variables. McGraw-Hill, 1960.
17. "Zinc, a Mine to Market Outline," Zinc Institute, Inc., New York.
7-1
lUlaldeni
-------
APPENDIX A
IlllaUeni
-------
TABLE 3-5
LABORATORY DATA FOR BECKMAN
Date
12/18/72
4
1/9/73
1/12/73
1/19/73
2/12/73
2/27/73
3/5/73
Hg Flow
cc/mln
142
350
452
470
288
327
485
470
440
270
300
407
507
355
568
358
525
540
550
200
405
540
573
615
485
200
350
125
Dilution
Flow
cc/ml n
3693
2536
2444
2444
2462
3997
1756
3694
1827
2654
3299
2319
2321
2526
2455
3467
2575
1825
1825
3355
3730
3430
3280
3000
2360
1950
1850
2200
Hg Cone, at
Exit of Condenser
4.9
5.25
3.5
3.5
4.3
4.2
3.6
4.0
4.4
4.3
4.4
4.1
3.9
3.9
3.5
4.4
3.8
3.8
3.8
4.8
4.4
4.15
4.0
3.9
2.6
2.2
2.2
2.2
Dilution
Ratio*
27.0
8.25
6.41
6.20
9.55
13.22
4.62
8.86
5.15
10.83
12.00
6.70
5.58
8.12
5.32
10.68
5.90
4.38
4.32
17.78
10.21
7.35
6.72
5.88
5.87
10.75
6.29
18.60
Calculated
Hg Cone.
0.18
0.64
0.55
0.56
0.45
0.32
0.78
0.45
0.85
0.40
0.37
0.61
0.70
0.48
0.66
0.41
0.64
0.87
0.88
0.27
0.43
0.56
0.59
0.66
0.44
0.20
0.35
0.12
Beckman
Reading
mg/m3
0.20
0.72
0.68
0.64
0.30
0.28
0.77
0.45
0.85
0.40
0.34
0.64
0.82
0.35
0.75
0.33
0.64
0.95
0.89
0.28
0.35
0.60
0.65
0.70
0.40
0.13
0.24
0.11
-------
TABLE 3-5 (continued)
ro
Date
3/5/73
3/7/73
3/19/73
3/20/73
Hg Flow
cc/mi n
65
125
165
205
310
380
460
450
630
710
105
235
315
497
637
672
190
272
457
446
533
672
680
135
225
300
396
456
540
655
700
720
Dilution
Flow
cc/min
2200
2200
2200
2200
2200
2200
1350
1350
1350
1350
3175
2135
1900
1580
1380
1350
2830
2150
2150
1650
1475
1380
1090
3350
2870
2550
2280
1950
1620
1380
1200
1000
Hg Cone, at
Exit of Condenser
mg/m3
2.2
2.2
2.2
2.2
2.2
2.2
2.3
2.3
2.3
2.35
2.4
2.5
2.45
2.4
2.4
2.4
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.3
2.25
2.25
2.25
2.25
2.25
2.2
Dilution
Ratio*
34.85
18.60
14.33
11.73
8.10
6.79
3.93
4.00
3.14
2.90
31.24
10.09
7.03
4.18
3.17
3.01
15.89
8.90
5.70
4.70
3.77
3.05
2.60
25.81
13.76
9.50
6.76
5.28
4.00
3.11
2.71
2.39
Calculated
Hg Cone.
mg/m3
0.063
0.12
0.15
0.19
0.27
0.32
0.58
0.57
0.73
0.81
0.077
0.25
0.35
0.57
0.76
0.80
0.14
0.25
0.39
0.47
0.58
0.72
0.85
0.085
0.16
0.24
0.33
0.43
0.56
0.72
0.83
0.92
Beckman
Reading
mg/m3
0.06
0.12
0.13
0.18
0.30
0.38
0.60
0.51
0.78
0.85
0.076
0.18
0.29
0.54
0.75
0.81
0.13
0.19
0.36
0.42
0.55
0.67
0.79
0.075
0.16
0.21
0.30
0.45
0.60
0.83
0.91
1.00
-------
TABLE 3-5 (continued)
GO
Date
3/21/73
3/22/73
Oil nt inn i
Hg Flow
cc/min
180
265
135
207
328
397
488
533
653
722
125
167
363
446
525
688
727
605
605
488
415
300
197
222
180
.a^n = Dilution
Dilution
Flow
cc/min
2250
1970
2140
2140
2075
1650
1650
1420
1420
1280
2600
2225
2200
1970
1550
1545
1280
1150
1600
1625
1730
1750
1970
3017
3300
flow + Hg
Hg Cone, at
Exit of Condenser
mg/m3
2.2
2.2
2.2
2.25
2.25
2.25
2.25
2.25
2.25
2.25
2.2
2.25
2.25
2.25
2.25
2.25
2.25
2.3
2.35
2.35
2.45
2.5
2.6
2.6
2.7
flow
Dilution
Ratio*
13.50
8.43
16.85
11.34
7.33
5.16
4.38
3.66
3.17
2.77
21.80
14.32
7.06
5.42
3.95
3.25
2.76
2.90
3.64
4.33
5.17
6.83
11.00
14.59
19.33
Calculated
Hg Cone.
mg/n>3
0.16
0.26
0.13
0.20
0.31
0.44
0.51
0.61
0.71
0.81
0.10
0.16
0.32
0.42
0.57
0.69
0.82
0.79
0.64
0.54
0.47
0.37
0.24
0.18
0.14
Beckman
Readi ng
mg/m3
0.18
0.32
0.13
0.22
0.30
0.45
0.53
0.62
0.75
0.83
0.11
0.18
0.35
0.46
0.62
0.83
0.92
0.87
0.78
0.61
0.50
0.36
0.22
0.16
0.13
Hg flow
-------
TABLE 3-6
LABORATORY DATA FOR OLIN
Date
3/8/73
3/9/73
3/12/73
Hg Flow
cc/min
195
320
415
410
178
365
361
361
458
460
537
652
167
228
300
388
420
430
472
563
83
213
292
368
430
427
515
575
638
693
Dilution
Flow
cc/min
1750
1720
1720
1600
3080
3030
2330
1925
1850
1580
1430
1280
3070
2720
2450
2200
1850
1500
1470
1550
3035
3025
2810
2310
1925
1400
1350
1350
1270
1050
Hg Cone, at
Exit of Condenser
mg/m3
2.3
2.3
2.3
2.35
2.35
2.35
2.3
2.4
2.4
2.4
2.4
2.4
2.25
2.25
2.3
2.3
2.35
2.2
2.25
2.25
2.2
2.25
2.25
2.25
2.25
2.25
2.25
2.25
2.25
2.25
Dilution
Ratio*
9.97
6.38
5.14
4.90
18.30
9.30
7.45
6.33
5.04
4.43
3.66
2.96
19.38
12.93
9.17
6.67
5.40
4.49
4.11
3.76
37.57
15.20
10.62
7.28
5.48
4.28
3.62
3.35
2.99
2.52
Calculated
Hg Cone.
mg/m3
0.23
0.35
0.45
0.48
0.13
0.25
0.31
0.38
0.48s
0.54
0.66
0.81
0.12
0.17
0.25
0.34
0.43
0.49
0.55
0.60
0.059
0.15
0.21
0.31
0.41
0.53
0.62
0.67
0.75
0.89
01 in
Reading
mg/m3
0.22
0.36
0.45
0.51
0.14
0.22
0.30
0.38
0.48
0.56
0.68
0.87
0.08
0.19
0.26
0.38
0.48
0.52
0.61
0.64
0.05
0.13
0.19
0.29
0.40
0.49
0.58
0.65
0.74
0.91
-------
TABLE 3-6 (continued)
Date
Hg Flow
cc/mi n
Dilution
Flow
cc/mi n
Hg Cone, at
Exit of Condenser
mg/m3
Dilution
Ratio*
Calculated
Hg Cone.
01 in
Reading
mg/m3
3/12/73
3/13/73
667
670
555
605
653
705
705
670
670
870
1150
1100
1100
1100
1030
920
1050
920
2.25
2.25
2.2
2.2
2.2
2.2
2.2
2.35
2.4
2.
2.
2.
2.
2.
2.
2.
.30
.72
.98
.82
.68
.46
.31
2.57
2.37
0,
0,
0,
0,
0,
98
83
74
78
82
0.89
0.95
0.92
1.01
0.97
0.85
0.71
0.78
0.82
0.92
.97
.92
0.
0.
0.99
i
in
Dilution ratio =
"9 fl°W
-------
TABLE 3-7
LABORATORY DATA FOR SUNSHINE
Date
1/19/73
2/27/73
3/5/73
3/7/73
3/8/73
Kg Flow
cc/min
200
405
540
573
615
200
350
125
65
125
165
205
310
380
460
450
630
710
105
235
315
497
637
672
195
320
415
410
178
365
Dilution
Flow
cc/min
3355
3730
3430
3280
3000
1950
1850
2200
2200
2200
2200
2200
2200
2200
1350
1350
1350
1350
3175
2135
1900
1580
1380
1350
1750
1720
1720
1600
3080
3030
Hg Cone, at
Exit of Condenser
mg/m3
4.8
4.4
4.15
4.0
3.9
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.3
2.3
2.3
2.35
2.4
2.5
2.45
2.4
2.4
2.4
2.3
2.3
2.3
2.35
2.35
2.35
Dilution
Ratio*
17.78
10.21
7.35
6.72
5.88
10.75
6.29
18.60
34.85
18.60
14.33
11.73
8.10
6.79
3.93
4.00
3.14
2.90
31.24
10.09
7.03
4.18
3.17
3.01
9.97
6.38
5.14
4.90
18.30
9.30
Calculated
Hg Cone.
mg/m3
0.27
0.43
0.56
0.59
0.66
0.20
0.35
0.12
0.063
0.12
0.15
0.19
0.27
0.32
0.58
0.57
0.73
0.81
0.077
0.25
0.35
0.57
0.76
0.80
0.23
0.35
0.45
0.48
0.13
0.25
Sunshine
Reading
mg/m3
0.25
0.47
0.80
0.85
0.86
0.18
0.25
0.12
0.05
0.11
0.13
0.19
0.28
0.35
0.65
0.47
0.71
0.67
0.14
0.27
0.36
0.59
0.72
0.74
0.22
0.28
0.49
0.53
0.18
0.33
-------
TABLE 3-7 (continued)
Date
3/8/73
3/9/73
3/14/73
3/15/73
3/16/73
Hg Flow
cc/min
361
361
458
460
537
652
167
228
300
388
420
430
472
563
225
460
590
150
682
210
390
333
455
600
660
333
258
298
250
375
573
520
Dilution
Flow
cc/tni n
2330
1925
1850
1580
1430
1280
3070
2720
2450
2200
1850
1500
1470
1500
1675
1430
1100
880
1080
1530
1560
1260
1525
2010
2010
3500
2115
2035
2900
1540
1900
2200
Hg Cone, at
Exit of Condenser
mg/m3
2.3
2.4
2.4
2.4
2.4
2.4
2.25
2.25
2.3
2.3
2.35
2.2
2.25
2.25
2.3
2.3
2.25
2.2
2.4
2.4
2.4
2.35
2.35
2.35
2.35
2.3
2.3
2.35
2.4
2.4
2.2
2.2
Dilution
Ratio*
7.45
6.33
5.04
4.43
3.66
2.96
19.38
12.93
9.17
6.67
5.40
4.49
4.11
3.76
8.44
4.11
2.86
6.87
2.58
8.29
5.00
4.78
4.35
4.35
4.05
11.51
9.20
7.83
12.60
5.11
4.32
5.23
Calculated
Hg Cone.
mg/m3
0.31
0.38
0.48
0.54
0.66
0.81
0.12
0.17
0.25
0.34
0.43
0.49
0.55
0.60
0.27
0.56
0.78
0.32
0.93
0.29
0.48
0.49
0.54
0.54
0.58
0.20
0.25
0.30
0.19
0.47
0.51
0.42
Sunshine
Reading
mg/m3
0.28
0.34
0.42
0.48
0.57
0.70
0.18
0.26
0.34
0.44
0.43
0.57
0.48
0.62
0.38
0.92
1.00
0.40
0.85
0.32
0.65
0.41
0.65
0.63
0.74
0.30
0.35
0.39
0.19
0.63
0.64
0.74
-------
TABLE 3-7 (continued)
Date
3/16/73
3/23/73
Hg Flow
cc/min
497
625
640
583
710
485
352
230
295
420
490
Dilution
Flow
cc/mi n
1605
1745
2240
1680
1825
1940
1670
1305
1180
1315
2260
Hg Cone, at
Exit of Condenser
mg/m3
2.2
2.2
2.25
2.25
2.25
2.3
2.3
2.4
2.4
2.4
2.3
Dilution
Ratio*
4.23
3.79
4.50
3.88
3.57
5.00
5.74
6.67
5.00
4.13
5.61
Calculated
Hg Cone.
mg/m3
0.52
0.58
0.50
0.58
0.63
0.46
0.40
0.36
0.48
0.58
0.41
Sunshine
Reading
mg/m3
0.58
0.58
0.64
0.59
0.74
0.58
0.65
0.22
0.75
0.77
0.31
00
Dilution ratio
Dilution flow + Hg flow
Hg flow
-------
TABLE 3-8
LABORATORY DATA FOR DUPONT TWENTY INCH CELL
3>
10
Date
3/1/73
3/19/73
3/20/73
Hg Flow
cc/mi n
693
693
675
648
540
540
543
458
412
250
215
230
275
190
272
457
446
533
672
680
712
135
225
300
396
456
540
655
700
720
750
Dilution
Flow
cc/mi n
1200
1600
1650
1730
1620
1950
2810
2810
2820
2820
2840
2840
3370
2830
2150
2150
1650
1475
1380
1090
1000
3350
2870
2550
2280
1950
1620
1380
1200
1000
900
Hg Cone, at
Exit of Condenser
mg/m3
2.2
2.22
2.24
2.27
2.32
2.32
2.35
2.37
2.5
2.5
2.32
2.3
2.42
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.3
2.25
2.25
2.25
2.25
2.25
2.2
2.25
Dilution
. Ratio*
2.73
3.31
3.44
3.67
4.00
4.61
6.18
7.14
7.84
12.28
14.21
13.35
13.25
15.89
8.90
5.70
4.70
3.77
3.05
2.60
2.40
25.81
13.76
9.50
6.76
5.28
4.00
3.11
2.71
2.39
2.20
Calculated
Hg Cone.
mg/m3
0.81
0.67
0.65
0.62
0.58
0.50
0.38
0.33
0.32
0.20
0.16
0.17
0.18
0.14
0.25
0.39
0.47
0.58
0.72
0.85
0.91
0.085
0.16
0.24
0.33
0.43
0.56
0.72
0.83
0.92
1.02
Dupont
Reading
mg/m3
0.53
0.47
0.46
0.44
0.41
0.385
0.30
0.27
0.25
0.18
0.15
0.16
0.16
0.10
0.19
0.30
0.36
0.42
0.50
0.56
0.59
0.06
0.14
0.20
0.28
0.36
0.45
0.54
0.585
0.62
0.65
-------
TABLE 3-8 (continued)
I
o
Date "9 Flow
Date cc/min
3/21/73 180
265
135
207
328
397
488
533
653
722
3/22/73 125
167
363
446
525
688
727
727
605
605
488
415
300
197
222
180
Dilution
Flow
cc/min
2250
1970
2140
2140
2075
1650
1650
1420
1420
1280
2600
2225
2200
1970
1550
1545
1280
1000
1150
1600
1625
1730
1750
1970
3017
3300
Hg Cone, at
Exit of Condenser
mg/m3
2.2
2.2
2.2
2.25
2.25
2.25
2.25
2.25
2.25
2.25
2.2
2.25
2.25
2.25
2.25
2.25
2.25
2.3
2.3
2.35
2.35
2.45
2.5
2.6
2.6
2.7
Dilution
Ratio*
13.50
8.43
16.85
11.34
7.33
5.16
4.38
3.66
3.17
2.77
21.80
14.32
7.06
5.42
3.95
3.25
2.76
2.38
2.90
3.64
4.33
5.17
6.83
11.00
14.59
19.33
Calculated
Hg Cone.
mg/m3
0.16
0.26
0.13
0.20
0.31
0.44
0.51
0.61
0.71
0.81
0.10
0.16
0.32
0.42
0.57
0.69
0.82
0.97
0.79
0.64
0.54
0.47
0.37
0.24
0.18
0.14
Dupont
Reading
mg/m3
0.15
0.24
0.09
0.17
0.27
0.38
0.435
0.485
0.55
0.59
0.08
0.16
0.27
0.36
0.445
0.545
0.59
0.62
0.56
0.51
0.435
0.37
0.28
0.19
0.14
0.11
Dilution ratio
Dilution flow + Hg flow
Hg flow
-------
TABLE 3-9
LABORATORY DATA FOR DUPONT TWO INCH CELL
:>
i
Date
7/4/73
7/5/73
7/6/73
7/7/73
Hg Flow
cc/min
370
445
450
480
463
420
447
107
130
230
290
400
407
415
478
458
458
110
152
173
238
238
253
257
250
300
340
370
415
422
Dilution
Flow
cc/min
2020
2020
2275
1850
1450
1125
1125
2310
2250
2140
1900
1900
1350
1025
1035
1035
950
2280
2250
2200
2200
1925
1670
1472
1150
1150
1150
1075
1055
875
Hg Cone, at
Exit of Condenser
mg/m3
2.25
2.25
2.3
2.2
2.2
2.3
2.3
2.55
2.2
2.2
2.2
2.2
2.2
2.25
2.25
2.25
2.30
2.2
2.25
2.25
2.2
2.25
225
2.3
2.3
2.2
2.2
2.2
2.25
2.25
Dilution
Ratio*
6.46
5.54
6.06
4.85
4.13
3.68
3.52
22.59
18.31
10.30
7.55
5.75
4.32
3.47
3.17
3.26
3.07
21.73
15.80
13.72
10.24
9.09
7.60
6.73
5.60
4.83
4.38
3.91
3.54
3.07
Calculated
Hg Cone.
mg/m3
0.35
0.41
0.38
0.45
0.53
0.62
0.65
0.11
0.13
0.21
0.29
0.38
0.51
0.65
0.71
0.69
0.75
0.10
0.14
0.16
0.21
0.25
0.30
0.34
0.41
0.46
0.50
0.56
0.64
0.73
Dupont
Readi ng
mg/m3
0.48
0.60
0.56
0.61
0.73
0.74
0.84
0.16
0.21
0.27
0.35
0.49
0.65
0.78
0.94
0.90
0.96
0.09
0.14
0.16
0.24
0.28
0.32
0.37
0.46
0.53
0.62
0.71
0.83
0.97
-------
TABLE 3-9 (continued)
Date
7/7/73
Hg Flow
cc/mi n
80
293
372
400
397
412
400
Dilution
Flow
cc/mi n
2312
1950
2050
1950
1700
1020
1040
Hg Cone, at
Exit of Condenser
mg/m3
2.35
2.35
2.3
2.3
2.38
2.43
2.5
Dilution
Ratio*
29.90
7.66
6.51
5.88
5.28
3.48
3.60
Calculated
Hg Cone.
mg/m3
0.08
0.31
0.35
0.39
0.45
0.70
0.69
Dupont
Reading
mg/m3
0.11
0.32
0.43
0.51
0.57
0.865
0.82
"Dilution ratio = D11ut1onu
Hg f1°W
ro
-------
TABLE 4-1
RED OXIDE OF MERCURY TEST RESULTS
Date-Time
4/17/73
10:30
10:45
10:50
10:55
11:15
11:30
11:45
12:00
1:15
1:25
1:40
1:55
4/18/73
9:45
9:55
10:00
10:05
10:10
10:15
Instrument Readings
Beckman Sunshine Dupont
mg/m3 mg/m3 mg/m3
.17
.25
.33
.60
.45
.52
.63
.44
.71
.53
.42
.48
.16
.24
.31
.66
.40
.58
.71
.41
.83
.49
.37
.45
.30
.36
.42
.37
.33
.34
.15
.18
.21
.16
.13
.15
.17
.14
.19
.10
.08
.09
.05
.05
.05
.04
.02
.02
Stream Concentration*
Dilution Beckman Sunshine Dupont
Ratio mg/m3 mg/m3 mg/m3
No dilution
•
air
No dilution
•
air
No dilution
air
No dilution
air
No dilution
air
No dilution
air
No dilution
_ • „
air
No dilution
A • U
air
No dilution
_ 4 .-
air
No dilution
air
No dilution
~ 4 «
air
No dilution
. • „
air
No dilution
air
No dilution
_ • u
air
No dilution
«. J u.
air
No dilution
•K m u
air
No dilution
air
No dilution
air
A-13
llWdeni
-------
TABLE 4-1 (Continued)
Instrument Readings
Beckman Sunshine Dupont
Date-Time mg/m3 mg/m3 mg/m3
10:20
10:25
10:30
10:40
10:50
10:55
11:00
11:05
11:10
11:20
11:25
11:35
4/19/73
11:00 .15
11:05 .15
11:10 .15
11:15 .17
11:20 .19
11:25 .17
11:30 .14
11:35 .'16
11:40 .16
.32
.38
.36
.40
.42
.40
.34
.38
.44
.30
.32
.38
.14
.14
.12
.13
.14
.13
.10
.13
.13
.02
.04
.03
.04
.04
.04
.04
.03
.03
.05
.05
.04
.04
.04
.045
.048
.053
.05
.044
.043
.043
Stream Concentration*
Dilution Beckman Sunshine Dupont
Ratio mg/m3 mg/m3 mg/m3
No dilution
•k • U
air
No dilution
«. • _
air
No dilution
_ • „
air
No dilution
_ • M
air
No dilution
•
air
No dilution
•k • U
air
No dilution
. £ u.
air
No dilution
_ • „
air
No dilution
air
No dilution
_ • „
air
No dilution
_ • „
air
No dilution
air
No dilution
_ • ._
air
No dilution
air
No dilution
air
No dilution
•k • U
air
No dilution
air
No dilution
_ •
air
No dilution
air
No dilution
air
No dilution
air
A-14
IllhSdeni
-------
TABLE 4-1 (Continued)
Instrument Readings
Beckman Sunshine Dupont
Date-Time mg/m3 mg/m3 mg/m3
11:45
11:50
11:55
12:00
4/20/73
2:00
2:05
2:10
2:15
2:20
2:25
2:30
2:35
2:40
2:45
2:50
2:55
3:00
3:05
3:10
3:15
3:20
.15
.16
.15
.11
.12
.13
.15
.13
.11
.13
.13
.13
.14
.14
.15
.16
.16
.14
.15
.16
.17
.14
.15
.14
.08
.09
.08
.10
.09
.08
.09
.09
.10
.12
.12
.13
.14
.14
.13
.14
.14
.15
.044
.046
.047
.035
.04
.04
.05
.04
.04
.042
.043
.044
.048
.046
.047
.05
.049
.050
.053
.053
.057
Stream Concentration*
Dilution Beckman Sunshine Dupont
Ratio mg/m3 mg/m3 mg/m3
No dilution
air
No dilution
-k • U.
air
No dilution
air
No dilution
* m _
air
No dilution
air
No dilution
K m U
air
No dilution
. • „
air
No dilution
air
No dilution
air
No dilution
•. m u
air
No dilution
_ J ut
air
No dilution
air
No dilution
air
No dilution
_ •
air
No dilution
air
No dilution
~ 4 -_
air
No dilution
air
No dilution
•
air
No dilution
air
No dilution
•k
-------
TABLE 4-1 (Continued)
Date-Time
3:25
3:30
3:35
3:40
3:45
3:50
3:55
4:00
4:05
4:10
4:15
4:20
4:25
4:30
4:35
4:40
4:45
4/23/73
8:40
8:45
8:50
8:55
Instrument Readings
Beckman Sunshine Dupont
mg/m3 mg/m3 mg/m3
.20
.18
.19
.19
.21
.18
.18
.19
.18
.20
.20
.16
.17
.19
.22
.25
.26
.12
.12
.13
.12
.17
.16
.17
.16
.17
.15
.15
.16
.16
.17
.18
.16
.18
.19
.21
.26
.27
.14
.13
.14
.13
.065
.060
.060
.058
.063
.055
.057
.058
.055
.060
.058
.053
.054
.057
.062
.068
.066
.043
.044
.047
.043
Stream Concentration*
Dilution Beckman Sunshine Dupont
Ratio mg/m3 mg/m3 mg/m3
No dilution
A • u
air
No dilution
M. • U
air
No dilution
_ • ._
air
No dilution
air
No dilution
air
No dilution
air
No dilution
air
No dilution
. • __
air
No dilution
air
No dilution
._ • __
air
No dilution
air
No dilution
» £ u
air
No dilution
air
No dilution
._ • __
air
No dilution
air
No dilution
air
No dilution
. • „
air
No dilution
_ j
air
No dilution
•» m u
air
No dilution
air
No dilution
air
A-16 I
UMkni
-------
TABLE 4-1 (Continued)
Date-Time
9:00
9:05
9:10
9:15
9:20
9:25
9:30
9:35
10:55
11:00
11:05
11:10
11:15
11:20
11:25
11:30
11:35
11:40
11:45
11:50
11:55
12:00
12:05
12:10
12:15
12:20
Instrument Readings
Beckman Sunshine Dupont
mg/m3 mg/nr mg/m3
.12
.11
.18
.20
.22
.25
.17
.21
.72
.85
.40
.40
.36
.40
.37
.48
.74
.95
.90
.80
.70
.77
.83
.80
.79
.68
.13
.13
.21
.22
.20
.23
.14
.18
.63
.71
.10
.05
0
—
___
—
.04
.13
.16
.10
.10
.12
.20
.22
.21
.16
.062
.06
.08
.10
.09
.11
.09
.10
.19
.23
.16
.20
.19
.21
.20
.30
.31
.33
.31
.29
.30
.30
.30
.29
.28
.26
Dilution
Ratio
No dilution
air
No dilution
air
No dilution
air
No dilution
air
No dilution
air
No dilution
air
No dilution
air
No dilution
air
6.0
7.2
6.5
5.75
7.0
4.33
3.25
3.33
2.75
2.75
2.75
2.75
2.75
2.75
2.75
2.82
2.82
2.82
Stream
Beckman
mg/m3
4.23
6.12
2.60
2.30
2.52
1.73
1.20
1.60
2.04
2.61
2.48
2.20
1.93
2.12
2.28
2.26
2.23
1.92
Concentration*
Sunshine Dupont
mg/m3 mg/m3
3.78
5.11
.65
.29
0
0
0
0
.11
.36
.44
.28
.28
.33
.55
.62
.59
.45
1.14
1.66
1.04
.92
1.33
.91
.65
1.00
.85
.91
.85
.80
.83
.83
.83
.82
.79
.73
A-17
llUalden,
-------
TABLE 4-1 (Continued)
Date-Time
12:25
12:30
12:35
12:40
4/24/73
9:20
9:30
9:35
9:40
9:45
9:50
10:00
10:05
10:10
10:15
10:20
10:25
10:30
10:35
10:40
10:45
10:50
10:55
11:00
11:05
11:10
11:15
Instrument Readings
Beckman Sunshine Dupont Dilution
mg/m3 mg/m3 mg/m3 Ratio
.42
.15
.10
.02
>1.0
.90
.90
.85
.78
.72
.65
.70
.72
.68
.68
.74
.86
.92
.84
.83
.87
.89
.90
.90
.96
.88
.16
.04
.04
.07
.55
.72
.60
.51
.43
.35
.30
.38
.45
.43
.46
.57
.57
.59
.62
.60
.63
.64
.70
.68
.74
.72
.26
.21
.21
.16
.45
.32
.30
.17
.19
.16
.22
.22
.27
.32
.25
.39
.40
.48
.49
.52
.55
.58
.57
.54
.58
.56
2.86
2.98
3.12
3.28
6.00
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.20
1.20
No dilution
air
No dilution
air
No dilution
air
No dilution
_ j ._
air
No dilution
air
No dilution
air
No dilution
air
No dilution
air
Stream
Beckman
mg/m3
1.20
.45 ,
.31
.07
>6.00
.35
.35
.28
.17
.08
.98
1.05
1.08
1.02
1.02
1.11
1.03
1.10
Concentration*
Sunshine Dupont
mg/m3 mg/nH
.46
.12
.12
.23
3.3
1.08
.9
.77
.65
.53
.45
.57
.68
.65
.69
.86
.68
.71
.74
.63
.66
.52
2.7
.48
.45
.26
.29
.24
.33
.33
.41
.48
.38
.59
.48
.58
A-18
llUabJenl
-------
TABLE 4-1 (Continued)
Instrument Readings Stream Concentration*
Beckman Sunshine Dupont Dilution Beckman Sunshine Dupont
Date-Time mg/m3 mg/m3 mg/m3 Ratio mg/m3 mg/m3 mg/m3
11:20
11:25
11:30
11:35
11:40
11:45
11:50
12:00
1:20
1:30
1:35
1:45
1:55
2:00
2:10
* Instrument
.87
.88
.85
.89
.90
.90
.90
.88
.86
.83
.81
.78
.77
.77
.75
readings
.71
.71
.68
.68
.70
.72
.73
.70
.71
.70
.68
.65
.61
.60
.60
multipl
.52
.51
.49
.49
.52
.53
.52
.48
.45
.42
.40
.38
.35
.37
.36
ied by
No dilution
•. m w
air
No dilution
air
No dilution
_ j i*
air
No dilution-
air
No dilution
fc • „
air
No dilution
air
No dilution
air
No dilution
_ • „
air
No dilution
air
No dilution
•.« u»
air
No dilution
air
No dilution
_ £ i«
air
No dilution
_ j ._
air
No dilution
_ • ._
air
No dilution
_ 4 ...
air
dilution ratio.
A-19 I
lltiden,
-------
ro
o
TABLE 4-3
CHLOR-ALKALI END-BOX STACK TEST RESULTS
Date
Time
5/17/73
11:05
11:25
11:30
11:35
11:40
11:45
11:50
12:55
1:00
1:05
1:10
1:15
1:20
1:25
1:30
1:35
4:30
4:35
4:40
5/18/73
10:20
10:25
10:30
10:35
10:45
10:50
10:55
11:00
11:10
11:15
Instrument Readings (mg/m )
Beckman Sunshine Dupont 01 in
1.0
0.67
0.69'
0.66
0.67
0.66
0.70
0.87
1.0
1.0
1.0
>1.0
1.0
1.0
1.05
0.99
0.82
0.83
0.85
0.91
0.90
0.95
1.0
0.80
0.83
0.84
0.88
0.96
0.95
0.78
0.52
0.54
0.51
0.49
0.49
0.51
0.77
0.89
0.85
0.79
0.79
0.79
0.80
0.71
0.61
0.40
0.39
0.36
0.24
0.24
0.23
0.16
0.03
0.09
0.05
0.14
0.24
0.19
0.28
0.24
0.24
0.22
0.21
0.21
0.22
0.34
0.38
0.39
0.38
0.35
0.34
0.38
0.33
0.29
0.11
0.10
0.09
0.055
0.05
0.053
0.045
0.040
0.037
0.035
0.045
0.05
0.037
0.88
0.90
0.88
0.88
0.88
0.91
0.92
0.72
0.74
0.72
0.96
1.04
1.06
Dilution
Ratio
4.88
4.74
4.74
4.74
4.74
4.74
4.74
4.85
4.51
5.18
6.38
6.54
9.25
7.14
7.95
9.75
8.57
10.07
9.13
6.88
6.61
6.61
7.36
8.19
9.49
8.34
7.03
7.69
7.32
Beckman
4.88
3.18
3.27
3.13
3.18
3.13
3.32
4.22
4.51
5.18
6.38
>6.54
9.25
7.14
8.35
9.65
7.03
8.36
7.76
6.26
5.95
6.28
7.36
6.55
7.88
7.01
6.19
7.38
6.95
Stream Concentration41
Sunshine Dupont 01 in
3.81
2.46
2.56
2.42
2.32
2.32
2.42
3.73
4.01
4.40
5.04
5.17
7.31
5.71
5.64
5.95
3.43
3.93
3.29
1.65
1.59
1.52
1.18
0.25
0.85
0.42
0.98
1.85
1.39
.37
.14
.14
.04
.00
.00
.04
.65
.71
2.02
2.42
2.92
3.15
2.71
2.62
2.83
0.94
1.01
0.82
0.38
0.33
0.35
0.33
0.33
0.35
0.29
0.32
0.38
0.27
7.54
9.06
8.03
6.05
5.82
6.02
6.77
5.90
7.02
6.00
6.74
8.00
7.76
Geomet
4.8
5.0
6.6
9.15
9.49
9.68
9.68
9.68
13.8
11.7
-------
TABLE 4-3 (continued)
ro
Date
Time
5/18/73
11:20
11:25
11:35
11:45
12:00
5/21/73
10:30
10:40
11:15
11:20
11:30
11:35
11:40
2:00
2:10
2:15
2:20
2:25
2:30
2:40
2:50
2:55
3:00
3:05
3:10
3:15
3:20
3:35
3:45
3:50
3:55
4:00
o
Instrument Readings (mg/m
Beckman Sunshine Dupont i
1.0
1.0
1.05
0.95
0.90
>1 .0
>1 .0
1.0
0.95
>1 .0
>1 .0
>1 .0
0.67
0.84
0.92
0.96
0.99
0.95
0.95
0.79
0.86
0.80
0.85
0.88
0.89
0.83
0.92
0.98
0.99
1.0
0.95
0.19
0.22
0.26
0.18
0.16
0.31
0.09
0.27
0.20
0.29
0.24
0.22
0.14
0.18
0.08
0.06
0
0.01
<0
<0
<0
<0
<0
<0
<0
<0
31in
0.04 1.06
0.041 1.04
0.075 1.16
0.067 1.06
0.062 1.12
0.09 1.5
0.04 0.72
0.13 1.04
0.12 0.96
0.19 1.02
0.18 1.00
0.19 0.98
0.14 0.60
0.185 0.78
0.19 0.82
0.20 0.88
0.18 0.96
0.21
0.21
0.20
0.19
0.16
0.17
0.19
0.19
0.17
0.18
0.17
0.19
0.20
0.14
.00
.08
3.96
.11
.06
.10
.15
.23
.20
.24
.69
.74
.76
.40
Dilution
Ratio
8.44
8.44
8.69
15.53
18.22
6.92
5.97
13.30
13.64
57.88
42.36
22.67
6.43
6.40
6.52
6.37
6.37
7.91
8.31
10.32
10.32
10.32
10.32
10.06
10.06
10.32
10.13
10.13
10.13
10.13
10.13
Beckman
8.44
8.44
9.12
14.75
16.40
>6.92
>5.97
13.30
12.96
>57.88
>42.36
>22.67
4.31
5.38
6.00
6.12
6.31
7.51
7.89
8.15
8.88
8.26
8.77
8.85
8.95
8.57
9.31
9.93
10.03
10.13
9.62
Stream Concentration
Sunshine Dupont 01 in
1.60
1.86
2.26
2.80
2.92
2.15
0.54
3.59
2.73
16.79
10.17
4.99
0.90
1.15
0.52
0.38
0
0.08
<0
<0
<0
<0
<0
<0
<0
0.34
0.35
0.65
1.04
1.13
0.62
0.24
1.73
1.64
11.00
7.62
4.31
0.90
1.18
1.24
1.27
1.15
1.66
1.75
2.06
1.96
1.65
1.75
1.91
1.91
1.75
1.82
1.72
1.92
2.03
1.42
8.95
8.78
10.08
16.46
20.41
10.38
4.30
13.83
13.09
59.04
42.36
22.22
3.86
4.99
5.35
5.61
6.12
7.91
8.97
9.91
11.45
10.94
11.35
11.57
12.37
12.38
12.56
17.12
17.63
17.83
14.18
Geomet
11.4
11.45
>
>
16.5
2.63
4.94
5.40
5.40
4.36
3.85
3.96
3.55
3.70
3.01
3.25
4.88
5.16
5.23
3.08
-------
TABLE 4-3 (continued)
ro
ro
Date
Time
5/21/73
4:10
4:15
4:25
4:35
4:40
5/22/73
9:45
9:50
9:55
10:00
10:05
10:10
10:15
10:20
10:25
10:30
10:45
10:50
11:35
11:40
11:45
11:50
11:55
12:00
1:35
1:40
1:45
1:50
1:55
2:00
2:05
2:10
2:15
Instrument Readings (mg/ra )
Beckman Sunshine Dupont 01 in
0.98
0.97
0.95
0.94
0.93
0.35
0.35
0.40
0.44
0.56
0.70
0.62
0.55
0.55
0.48
0.85
0.88
0.16
0.15
0.14
0.21
0.19
0.435
0.425
0.48
0.50
0.54
0.55
0.525
0.51
0.50
0.475
0.17
0.16
0.49
0.56
0.60
0.57
0.55
0.545
0.56
0.555
0.615
0.61
0.60
0.615
0.63
0.50
0.44
1.56
1.46
1.44
1.46
1.48
0.96
0.98
1.14
1.24
1.30
1.36
1.36
1.26
1.12
1.20
1.08
1.30
0.96
1.16
1.34
1.18
1.22
1.08
1.24
1.30
1.38
1.42
1.48
0.94
0.82
Dilution
Ratio
10.26
10.13
10.20
10.13
10.13
10.08
10.84
9.40
9.15
9.24
9.30
9.62
9.15
9.62
9.90
9.98
9.90
6.43
6.74
7.04
6.94
6.87
6.87
5.55
5.61
5.59
5.69
5.69
5.69
5.76
8.65
8.65
Stream Concentration
Beckman Sunshine Dupont 01 in
9.93
9.83
9.62
9.52
9.42
3.53
3.81
3.76
4.03
5.17
6.51
5.96
5.03
5.29
4.75
8.48
8.71
1.62
1.52
1.42
2.13
1.92
.38
.63
.51
.58
.99
5.12
5.05
4.67
4.81
4.70
1.70
1.58
3.15
3.77
4.22
3.96
3.78
3.74
3.11
3.11
3.44
3.47
3.41
3.50
3.63
4.33
3.81
15.80
14.79
14.59
14.79
14.99
9.68
10.67
10.71
11.35
12.01
12.65
13.08
11.53
10.77
11.88
10.78
12.87
6.43
9.44
11.40
9.99
10.17
9.21
6.93
7.40
7.85
8.08
8.52
8.13
7.09
Geomet
4.21
4.08
4.49
3.58
3.27
_
14.37
16.38
12.96
11.47
10.12
7.35
7.07
9.12
8.72
8.33
7.28
9.67
4.15
9.24
10.66
13.16
11.47
12.48
15.31
-------
TABLE 4-3 (continued)
Date
Time
5/22/73
2:20
2:55
3:05
3:10
3:20
3:25
3:35
5/23/73
11:05
11:10
11:15
11:20
11:25
11:30
11:35
11:40
1:00
1:05
1:10
1:15
1:25
1:30
1:35
1:40
1:45
1:50
1:55
2:00
2:05
2:10
3:35
3:40
Instrument Readings (mg/m )
Beckman Sunshine Dupont 01 in
0.97
0.98
1.00
0.93
0.85
0.92
0.80
0.76
0.60
0.75
0.58
0.60
0.67
0.56
0.75
0.76
0.78
0.66
0.54
0.55
0.77
0.58
0.58
0.67
0.475
0.135
0.28
0.41
0.33
0.35
0.37
0.63
0.62
0.64
0.59
0.555
0.60
0.55
0.54
0.45
0.53
0.45
0.46
0.49
0.44
0.51
0.54
0.52
0.45
0.425
0.41
0.51
0.44
0.40
0.45
0.94
0.36
0.60
0.76
0.60
0.60
0.65
1.24
1.43
1.52
1.28
1.22
1.32
1.04
1.12
0.68
1.10
0.78
0.80
1.00
0.88
1.22
1.14
1.14
1.04
0.86
0.80
1.12
0.90
0.65
0.76
Dilution
Ratio
8.65
7.94
8.02
8.52
8.32
8.36
8.32
7.62
7.62
9.53
10.38
11.95
12.28
16.32
17.55
6.11
9.51
15.55
15.12
17.00
17.55
17.96
17.96
18.96
18.32
17.72
17.72
17.72
18.96
19.70
17.03
Stream Concentration*
Beckman Sunshine Dupont 01 in
7.39
7.46
9.53
9.65
10.15
11.30
13.06
13.34
3.67
7.13
9.02
9.07
11.39
9.83
13.47
13.65
14.79
12.09
9.57
9.75
13.64
11.00
11.43
11.41
4.11
1.07
2.25
3.49
2.75
2.93
3.08
4.80
4.72
6.10
6.12
6.63
7.37
8.98
9.48
2.75
5.04
7.00
6.96
8.33
7.72
9.16
9.70
9.86
8.24
7.53
7.26
9.04
8.34
7.88
7.66
8.13
2.86
4.81
6.48
4.99
5.02
5.41
9.45
10.90
14.49
13.29
14.58
16.21
16.97
19.66
4.15
10.46
12.13
12.10
17.00
15.44
21.91
20.47
21.61
19.05
15.24
14.18
19.85
17.06
12.81
12.94
Geomet
10.40
7.18
8.10
7.34
9.01
8.42
9.01
-------
TABLE 4-3 (continued)
*>
ro
Date
Time
5/23/73
3:45
3:50
3:55
4:00
4:05
4:10
4:15
4:20
5/24/73
10:25
10:35
10:50
10:55
11:00
11:05
11:10
11:15
11:20
11:25
11:30
11:35
11:40
11:45
11:50
11:55
12:00
12:05
12:10
2:35
2:40
2:45
2:50
2:55
Instrument Readings (mg/m )
Beckman Sunshine Dupont 01 in
0.55
0.60
0.63
0.64
0.60
0.60
0.59
0.58
0.67
0.53
0.35
0.40
0.46
0.50
0.54
0.54
0.37
0.40
0.58
0.75
0.55
0.53
0.53
0.56
0.76
0.64
0.58
0.80
0.86
0.80
0.93
0.95
0.39
0.42
0.44
0.43
0.42
0.415
0.40
0.41
0.51
0.45
0.34
0.37
0.415
0.43
0.44
0.45
0.36
0.36
0.46
0.54
0.45
0.44
0.43
0.45
0.53
0.48
0.47
0.57
0.60
0.585
0.60
0.62
0.60
0.66
0.64
0.72
0.72
0.74
0.76
0.54
0.66
0.74
0.76
0.80
0.56
0.68
0.85
1.08
0.84
0.84
0.83
1.11
0.90
0.92
1.20
1.40
1.24
1.40
1.44
Dilution
Ratio
23.50
21.83
21.83
21.83
19.52
21.83
21.83
21.83
12.05
11.64
6.54
6.54
6.54
6.54
6.54
6.54
6.73
6.73
6.83
6.83
6.73
6.83
6.83
6.83
6.83
6.83
6.83
3.50
3.88
3.88
3.88
3.88
Stream Concentration*
Beckman Sunshine Dupont 01 in Geomet
12.93
13.10
13.75
13.97
11.71
13.10
12.88
12.66
8.07
6.17
2.29
2.62
3.01
3.27
3.53
3.53
2.49
2.69
3.96
5.12
3.70
3.62
3.62
3.82
5.19
4.37
3.96
4.30
3.33
3.10
3.61
3.69
9.17
9.17
9.61
9.39
8.20
9.06
8.73
8.95
6.15
5.24
2.22
2.42
2.71
2.81
2.88
2.94
2.42
2.42
3.14
3.69
3.03
3.01
2.94
3.07
3.62
3.28
3.21
4.87
2.33
2.27
2.33
2.41
14.10
14.41
13.97
14.05
15.72
16.15
16.59
3.53
4.32
4.84
4.97
5.23
3.77
4.58
5.81
7.38
5.74
5.74
5.67
7.58
6.15
6.28
6.07
5.43
4.81
5.43
5.59
-------
TABLE 4-3 (continued)
ro
on
Date
Time
5/24/73
3:00
3:05
3:10
3:20
3:25
3:30
3:35
3:40
3:45
3:50
3:55
4:00
4:05
4:10
4:15
4:20
4:25
5/25/73
11:00
11:05
11:10
11:15
11:20
11:25
11:30
11:35
11:40
11:45
11:50
11:55
12:00
Instrument Readings (mg/m )
Beckman Sunshine Dupont 01 in
0.79
0.68
0.72
0.80
0.68
0.75
0.79
0.80
0.87
0.80
0.77
0.74
0.60
0.68
0.75
0.65
0.70
0.65
0.60
0.60
0.83
0.86
0.85
0.82
0.64
0.69
0.79
0.76
0.67
0.74
0.565
0.51
0.52
0.55
0.50
0.52
0.545
0.55
0.57
0.51
0.54
0.52
0.465
0.49
0.52
0.48
0.49
0.56
0.52
0.52
0.59
0.595
0.605
0.595
0.53
0.54
0.585
0.58
0.54
0.555
1.20
1.02
1.10
1.08
.06
.04
.10
.12
.16
.00
.10
.04
0.88
0.96
1.00
0.89
0.91
0.98
0.92
0.90
1.16
1.19
1.20
1.20
0.94
1.00
1.13
1.10
1.00
1.06
Dilution
Ratio
4.81
4.88
4.88
4.88
4.96
4.88
4.88
4.88
4.88
4.96
5.02
5.09
5.02
5.02
5.09
5.02
5.08
3.11
3.17
3.11
3.13
3.19
3.23
3.23
3.29
3.23
3.17
3.23
3.23
3.10
Stream Concentration*
Beckman Sunshine Dupont 01 in
3.80
3.32
3.51
3.90
3.37
3.66
3.86
3.90
4.25
3.97
3.87
3.77
3.01
3.41
3.82
3.26
3.56
2.02
1.90
1.87
2.60
2.74
2.75
2.65
2.11
2.23
2.50
2.45
2.16
2.29
2.72
2.49
2.54
2.68
2.48
2.54
2.66
2.68
2.78
2.53
2.71
2.65
2.33
2.46
2.65
2.41
2.49
1.74
1.65
1.62
1.85
1.90
1.95
1.92
1.74
1.74
1.85
1.87
1.74
1.72
5.77
4.98
5.37
5.27
5.26
5.08
5.37
5.47
5.66
4.96
5.52
5.29
4.42
4.82
5.09
4.47
4.62
3.05
2.92
2.80
3.63
3.80
3.88
3.88
3.09
3.23
3.58
3.55
3.23
3.29
Geomet
1.21
1.10
1.10
1.05
0.87
1.28
1.14
1.34
Instrument readings multiplied by dilution ratio
-------
TABLE 4-4
END-BOX SAMPLE TESTS
ro
Date
5/18
5/21
5/22
5/23
5/23
5/24
5/21
5/24
5/24
5/25
Reference Tests
(Stack Samples)
Method
IC1
IC1
IC1
IC1
Instrument Stream
Samples , Method
KMn04
KMn04
IC1
IC1
KMn04
KMn04
Hg Concentration by
AA Analysis (mg/m3)
1.28
1.35
1.18
1.08
0.82
1.33
35.01
35.30
10.74
7.90
Olin
mg/m3
1.05
1.10
1.16
1.01
0.71
1.21
15.15
5.44
5.08
3.38
Beckman
mg/m3
0.97
0.85
0.66
0.61
0.81
9.63
3.58
3.67
2.33
Dupont
mg/m3
0.048
0.18
0.55
0.47
0.42
0.56
1.75
2.93
2.57
1.79
Geomet
mg/m3
1.50
0.38
1.25
4.02
1.13
-------
TABLE 4-5
HYDROGEN STREAM TEST RESULTS
ro
Date-
Time
5/30/73
2:50
2:55
3:05
3:10
3:15
3:25
3:35
3:45
3:55
4:00
4:05
4:10
4:15
4:25
4:35
4:40
4:45
4:50
5:00
5:10
5:15
5:20
5:30
5/31/73
10:00
10:05
10:10
10:15
10:20
10:25
•»
Instrument Readings (mg/m )
Beckman Sunshine Dupont 01 in
0.64
0.61
0.57
0.56
0.55
0.54
0.53
0.50
0.50
0.49
0.51
0.54
0.55
0.57
0.55
0.52
0.53
0.51
0.52
0.54
0.56
0.56
0.53
0.65
0.74
0.69
0.65
0.90
0.77
0.74
0.68
0.59
0.56
0.54
0.49
0.45
0.40
0.36
0.33
0.30
0.28
0.26
0.24
0.23
0.25
0.22
0.20
0.17
0.19
0.16
0.18
0.18
0.66
0.67
0.60
0.50
0.80
0.60
0.66
0.64
0.63
0.62
0.62
0.62
0.62
0.61
0.62
0.62
0.64
0.65
0.66
0.68
0.66
0.64
0.63
0.63
0.62
0.63
0.67
0.65
0.63
0.64
0.74
0.69
0.65
0.89
0.77
Dilution
Ratio
23.94
23.94
23.94
23.94
23.94
23.94
23.94
23.94
23.94
23.94
23.94
23.66
23.94
23.94
23.94
23.94
23.66
23.66
23.66
23.66
23.94
23.94
23.94
22.69
21.51
21.00
20.74
20.50
20.25
Stream
Beckman
15.32
14.60
13.65
13.41
13.17
12.93
12.69
11.97
11.97
11.73
12.21
12.78
13.17
13.65
13.17
12.45
12.54
12.07
12.30
12.78
13.41
13.41
12.69
14.75
15.92
14.49
13.48
18.45
15.59
Concentration* (mg/m )
Sunshine Dupont 01 in
17.72
16.28
14.12
13.41
12.93
11.73
10.77
9.58
8.62
7.90
7.18
6.62
6.22
5.75
5.51
5.99
5.21
4.73
4.02
4.50
3.83
4.31
4.31
14.98
14.41
,12.60
10.37
16.40
12.15
15.80
15.32
15.08
14.84
14.84
14.84
14.84
14.60
14.84
14.84
15.32
15.38
15.80
16.28
15.80
15.32
14.91
14.91
14.67
14.91
16.04
15.56
15.08
14.52
15.92
14.49
13.48
18.25
15.59
-------
TABLE 4-5 (CONTINUED)
ro
oo
Date-
Time
10:30
10:35
10:40
10:45
10:50
10:55
11:00
11:10
11:20
11:25
11:30
11:35
11:40
11:45
11:50
2:10
2:40
2:50
2:55
3:00
3:03
3:06
3:09
3:12
3:15
3:18
3:21
3:25
3:30
Instrument Readings (mg/m3)
Beckman Sunshine Dupont 01 in
0.77
0.83
0.53
0.81
0.74
0.75
0.80
0.67
0.78
0.90
0.75
0.82
0.73
0.78
0.72
0.69
0.70
0.50
0.85
0.65
0.55
0.49
0.62
0.65
0.62
0.74
0.65
0.62
0.62
0.51
0.54
0.36
0.52
0.44
0.44
0.49
0.46
0.49
0.52
0.46
0.48
0.44
0.46
0.40
0.50
0.43
0.34
0.52
0.43
0.35
0.33
0.45
0.45
0.44
0.53
0.46
0.45
0.43
0.79
0.86
0.56
0.81
0.76
0.80
0.79
0.72
0.81
0.92
0.78
0.84
0.77
0.80
0.75
0.81
0.67
0.90
0.73
0.60
0.58
0.72
0.75
0.67
0.76
0.68
0.63
0.63
Dilution
Ratio
19.57
18.22
23.14
17.85
19.45
15.81
15.81
17.00
18.39
17.00
19.18
19.18
21.00
18.39
19.18
21.00
22.88
26.74
20.02
23.00
27.52
29.23
23.00
21.00
23.00
24.16
21.95
21.95
24.16
Stream
Beckman
15.07
15.12
12.26
14.46
14.39
11.86
12.65
11.39
14.34
15.30
14.39
15.73
15.33
14.34
13.81
14.49
16.02
13.37
17.02
14.95
15.14
14.32
14.26
13.65
14.26
17.88
14.27
13.61
14.98
Concentration* (mg/m3)
Sunshine Dupont 01 in
9.98
9.84
8.33
9.28
8.56
6.96
7.75
7.82
9.01
8.84
8.82
9.21
9.24
8.46
7.67
10.50
9.84
9.09
10.41
9.89
9.63
9.65
10.35
9.45
10.12
12.80
10.10
9.88
10.39
15.46
15.67
12.96
14.46
14.78
12.65
12.49
12.24
14.90
15.64
14.96
16.11
16.17
14.71
14.39
17.01
17.92
18.02
16.79
16.51
16.95
16.56
15.75
15.41
18.36
14.93
13.83
15.22
-------
TABLE 4-5 (CONTINUED)
i
ro
10
Date-
Time
3:35
3:40
3:45
3:50
3:55
4:00
4:05
4:08
4:11
4:14
4:17
4:20
4:23
4:26
4:29
4:32
6/1/73
10:35
10:40
10:45
10:48
10:51
10:54
10:57
11:00
11:03
11:06
11:09
11:12
11:15
11:16
11:19
11:22
11:25
Instrument Readings (mg/m3)
Beckman Sunshine Dupont 01 in
0.80
0.82
0.75
0.72
0.76
0.75
0.85
0.80
0.62
0.67
0.79
0.80
0.82
0.90
0.85
0.86
0.97
0.76
0.80
0.77
0.76
0.74
0.80
0.64
0.77
0.90
0.87
0.76
0.83
0.70
0.73
0.80
0.75
0.53
0.55
0.52
0.48
0.49
0.45
0.50
0.45
0.36
0.39
0.46
0.49
0.47
0.51
0.48
0.47
0.67
0.56
0.54
0.56
0.58
0.57
0.61
0.52
0.59
0.66
0.63
0.58
0.64
0.55
0.56
0.60
0.57
0.81
0.79
0.73
0.71
0.76
0.74
0.82
0.76
0.60
0.63
0.77
0.78
0.80
0.88
0.85
0.85
0.94
0 75
0.73
0.75
0.73
0.67
0.73
0.60
0.72
0.84
0.80
0.71
0.79
0.72
0.76
0.83
0.78
Dilution
Ratio
16.80
19.44
18.02
18.02
21.11
20.24
18.01
19.44
23.13
21.00
20.13
18.60
17.92
17.30
17.30
17.30
17.39
23.13
22.07
22.07
22.07
24.29
21.11
24.92
21.95
20.13
20.13
20.13
20.13
21.00
21.92
21.00
21.92
Stream
Beckman
13.44
15.94
13.52
12.97
16.04
15.18
15.31
15.55
14.34
14.07
15.90
14.88
14.69
15.57
14.71
14.88
16.87
17.58
17.66
16.99
16.77
17.97
16.89
15.95
16.90
18.12
17.51
15.30
16.71
14.70
16.00
16.80
16.44
Concentration* (mg/m3)
Sunshine Dupont Olin
8.90
10.69
9.37
8.65
10.34
9.11
9.01
8.75
8.33
8.19
9.26
9.11
8.42
8.82
8.30
8.13
11.65
12.95
11.92
12.36
12.80
13.85
12.88
12.96
12.95
13.29
12.68
11.68
12.88
11.55
12.28
12.60
12.49
13.61
15.36
13.15
12.79
16.04
14.98
14.77
14.77
13.88
13.23
15.50
14.51
14.34
15.22
14.71
14.71
16.35
17.35
16.11
16.55
16.11
16.27
15.41
14.95
15.80
16.91
16.10
14.29
15.90
15.12
16.66
17.43
17.10
-------
TABLE 4-5 (CONTINUED)
•f
Date-
Time
11:28
11:31
11:34
11:37
11:40
11:43
11:46
6/4/73
11:15
11:18
11:21
11:24
11:27
11:30
11:33
11:36
3:04
3:07
3:10
3:13
3:16
3:19
3:22
3:25
3:28
3:31
3:35
3:40
3:45
3:50
3:55
4:00
Instrument Readings (mg/m3)
Beckman Sunshine Dupont 01 in
0.87
0.90
0.90
0.91
0.90
0.95
0.95
0.52
0.52
0.53
0.54
0.54
0.66
0.66
0.66
0.95
0.90
0.90
0.94
0.94
0.90
0.93
0.92
0.98
0.97
0.67
0.55
0.40
0.31
0.30
0.25
0.66
0.67
0.64
0.65
0.66
0.68
0.70
0.25
0.22
0.18
0.18
0.17
0.22
0.19
0.15
0.46
0.43
0.43
0.43
0.43
0.41
0.41
0.42
0.44
0.43
0.30
0.24
0.17
0.13
0.12
0.10
0.90
0.94
0.93
0.93
0.92
0.98
0.93
0.51
0.52
0.53
0.53
0.53
0.66
0.66
0.66
0.90
0.88
0.88
0.92
0.91
0.91
0.92
0.92
0.96
0.95
0.62
0.51
0.39
0.31
0.30
0.25
Dilution
Ratio
19.33
18.70
18.70
18.70
18.70
18.70
18.70
21.78
21.78
21.78
21.78
21.78
17.67
17.67
17.67
14.89
15.81
15.81
15.29
15.46
16.00
16.00
15.56
14.50
14.97
17.00
20.05
24.48
31.65
31.31
35.64
Stream
Beckman
16.82
16.83
16.83
17.02
16.83
17.77
17.77
11.33
11.33
11.54
11.76
11.76
11.66
11.66
11.66
14.15
14.23
14.23
14.37
14.53
14.40
14.88
14.22
14.21
14.52
11.39
11.03
9.79
9.81
9.39
8.91
Concentration* (mg/m^)
Sunshine Dupont 01 in
12.76
12.53
11.97
12.16
12.34
12.72
13.09
5.45
4.79
3.92
3.92
3.70
3.89
3.36
2.65
6.85
6.80
6.80
6.57
6.65
6.56
6.56
6.49
6.38
6.44
5.10
4.81
4.16
4.11
3.75
3.56
17.40
17.58
17.39
17.39
17.20
18.33
18.33
11.11
11.33
11.54
11.54
11.54
11.66
11.66
11.66
13.40
13.91
13.91
14.07
14.07
14.56
14.72
14.22
13.92
14.22
10.54
10.23
9.55
9.81
9.39
8.91
-------
TABLE 4-5 (CONTINUED)
CO
I
5=
Date-
Time
4:05
6/5/73
2:56
3:00
3:03
3:06
3:09
3:12
3:15
3:18
3:21
3:24
3:27
3:30
4:08
4:11
4:14
4:17
4:20
4:23
4:26
4:29
4:32
4:35
4:38
6/6/73
9:05
9:10
9:13
9:16
9:19
9:22
9:25
Instrument Readings (mg/m^)
Beckman Sunshine Dupont 01 in
0.75
0.52
0.60
0.60
0.58
0.55
0.63
0.61
0.60
0.60
0.69
0.69
0.68
0.90
0.95
0.98
1.00
0.89
0.87
0.90
0.90
0.90
0.85
0.87
0.60
0.95
0.80
0.80
0.85
0.76
0.73
0.35
0.24
0.25
0.24
0.22
0.21
0.23
0.20
0.20
0.18
0.21
0.20
0.20
0.37
0.38
0.39
0.40
0.36
0.36
0.38
0.38
0.38
0.36
0.36
0.37
0.49
0.41
0.39
0.39
0.32
0.28
0.66
0.49
0.54
0.51
0.50
0.48
0.55
0.53
0.54
0.52
0.59
0.58
0.58
0.74
0.80
0.80
0.82
0.71
0.73
0.74
0.72
0.72
0.70
0.71
0.66
0.92
0.89
0.88
0.85
0.85
0.82
Dilution
Ratio
13.08
16.45
15.17
16.45
17.19
18.66
16.45
16.45
17.19
17.59
15.78
17.19
17.19
13.50
13.50
13.27
13.05
13.88
13.88
13.88
14.40
14.40
14.96
14.96
18.37
17.25
18.57
18.57
20.51
19.18
20.51
Stream Concentration* (mg/m3)
Beckman Sunshine Dupont 01 in
9.81
8.55
9.10
9.87
9.97
10.26
10.36
10.03
10.31
10.55
10.98
11.86
11.69
12.15
12.83
13.00
13.05
12.35
12.08
12.49
12.96
12.96
12.72
13.02
11.02
16.39
14.86
14.86
17.43
14.58
14.97
4.58
3.95
3.79
3.95
3.78
3.92
3.78
3.29
3.44
3.17
3.31
3.44
3.44
5.00
5.13
5.18
5.22
5.00
5.00
5.27
5.47
5.47
5.39
5.39
6.80
8.45
7.61
7.24
8.00
6.14
5.74
8.63
8.06
8.19
8.40
8.60
8.96
9.05
8.72
9.28
9.15
9.31
9.97
9.97
9.99
10.80
10.62
10.70
9.85
10.13
10.27
10.37
10.37
10.47
10.62
12.12
17.25
18.01
17.83
19.07
17.84
18.46
-------
TABLE 4-5 (CONTINUED)
CA)
ro
Date-
Time
9:28
9:31
9:34
9:37
9:40
10:10
10:15
10:20
10:23
10:26
10:29
10:32
10:35
10:38
10:41
10:44
10:47
10:50
10:55
11:00
11:05
11:10
11:15
11:20
11:23
11:26
11:29
11:32
11:35
11:38
11:41
11:44
11:47
11:50
Instrument Readings (mg/m3)
Beckman Sunshine Dupont 01 in
0.73
0.71
0.71
0.70
0.70
0.85
0.84
0.85
0.85
0.82
0.83
0.83
0.81
0.82
0.84
0.84
0.82
0.81
0.81
0.85
0.85
0.85
0.84
0.85
0.85
0.80
0.85
0.85
0.85
0.85
0.85
0.85
0.86
0.87
0.26
0.22
0.19
0.17
0.17
0.52
0.49
0.49
0.48
0.47
0.48
0.48
0.47
0.48
0.48
0.49
0.47
0.47
0.46
0.47
0.46
0.46
0.46
0.46
0.46
0.45
0.47
0.45
0.45
0.44
0.44
0.43
0.44
0.44
0.81
0.81
0.81
0.81
0.81
0.90
0.87
0.85
0.90
0.85
0.88
0.86
0.85
0.86
0.87
0.88
0.84
0.85
0.83
0.83
0.82
0.84
0.82
0.82
0.91
0.85
0.92
0.93
0.93
0.93
0.94
0.95
0.96
0.97
Dilution
Ratio
20.05
20.51
20.51
21.00
21.00
16.09
16.38
17.00
17.33
18.39
17.00
17.67
17.67
20.05
18.39
17.00
17.67
19.18
17.00
16.38
16.38
16.38
16.38
16.38
16.38
14.79
15.81
16.09
15.81
15.81
15.81
15.55
15.81
14.79
Stream
Beckman
14.64
14.56
14.56
14.70
14.70
14.45
13.76
14.45
14.73
15.08
14.11
14.67
14.31
16.44
15.45
14.28
14.49
15.54
13.77
13.92
13.92
13.92
13.76
13.92
13.92
11.83
13.44
14.37
13.44
13.44
13.44
13.22
13.60
12.87
Concentration* (mg/m3)
Sunshine Dupont Olin
5.21
4.51
3.90
3.57
3.57
8.84
8.03
8.33
8.32
8.64
8.16
8.48
8.30
9.62
8.83
8.33
8.30
9.01
7.82
7.70
7.53
7.53
7.53
7.53
7.53
6.66
7.43
7.61
7.11
6.96
6.96
6.69
6.96
6.51
17.84
18.25
18.25
18.69
18.69
15.30
14.25
14.45
15.60
15.63
14.96
15.20
15.02
17.24
16.00
14.96
14.84
16.30
14.11
13.60
13.43
13.76
13.43
13.43
14.91
12.57
14.55
15.72
14.70
14.70
14.86
14.77
15.18
14.35
-------
TABLE 4-5 (CONTINUED)
co
CO
Date-
Time
1:30
1:33
1:36
1:39
1:42
1:45
1:48
1:51
1:54
1:57
2:00
2:05
2:08
2:11
2:14
2:17
2:20
2:23
2:26
2:30
2:55
2:58
3:01
3:04
3:07
3:10
3:13
3:16
3:19
3:22
3:25
3:35
3:38
3:41
Instrument Readings (mg/m3)
Beckman Sunshine Dupont 01 in
0.60
0.72
0.70
0.68
0.65
0.80
0.90
0.89
0.89
0.87
0.85
0.83
0.83
0.82
0.84
0.80
0.81
1.00
0.92
0.80
0.81
0.67
0.83
0.93
0.87
0.78
0.82
0.78
0.77
0.75
0.77
0.65
0.63
0.57
0.33
0.41
0.40
0.39
0.36
0.44
0.50
0.49
0.48
0.48
0.47
0.46
0.45
0.45
0.46
0.44
0.45
0.52
0.51
0.43
0.46
0.35
0.45
0.50
0.48
0.42
0.47
0.46
0.44
0.44
0.44
0.42
0.39
0.36
0.59
0.69
0.67
0.65
0.63
0.77
0.90
0.88
0.88
0.88
0.87
0.87
0.89
0.88
0.90
0.87
0.88
1.00
0.98
0.84
0.79
0.68
0.83
0.92
0.84
0.74
0.79
0.73
0.73
0.70
0.73
0.68
0.66
0.61
Dilution
Ratio
18.86
17.20
17.20
18.74
19.63
16.20
13.93
13.93
14.16
13.93
13.93
14.89
14.89
14.89
14.39
15.15
15.15
13.50
10.80
13.14
17.67
19.18
18.78
17.00
17.67
19.18
17.00
18.39
18.39
18.39
18.39
22.62
22.62
25.24
Stream
Beckman
11.31
12.38
12.04
12.74
12.76
12.96
12.54
12.40
12.60
12.12
11.85
12.36
12.36
12.21
12.09
12.12
12.27
13.50
9.94
10.51
14.31
12.85
15.59
15.81
15.37
14.96
13.94
14.34
14.16
13.79
14.16
14.70
14.25
14.39
Concentration* (mg/m^)
Sunshine Dupont 01 in
6.22
7.05
6.88
7.31
7.07
7.13
6.97
6.83
6.80
6.69
6.55
6.85
6.70
6.70
6.62
6.67
6.82
7.88
5.51
5.65
8.13
6.71
8.45
8.50
8.48
8.06
7.99
8.46
8.09
8.09
8.09
9.50
8.82
9.09
11.13
11.87
11.52
12.18
12.37
12.47
12.54
12.26
12.46
12.26
12.12
12.95
13.25
13.10
12.95
13.18
13.33
13.50
10.58
11.04
13.96
13.04
15.59
15.64
14.84
14.19
13.43
13.42
13.42
12.87
13.42
15.38
14.92
15.40
-------
TABLE 4-5 (CONTINUED)
Date-
Time
3:44
3:47
3:50
3:53
3:56
3:59
4:02
4:05
Instrument Readings (mg/m^)
Beckman Sunshine Dupont 01 in
0.58
0.61
0.60
0.52
0.45
0.44
0.45
0.42
0.37
0.39
0.38
0.34
0.28
0.28
0.27
0.26
0.62
0.66
0.62
0.57
0.48
0.49
0.48
0.46
Dilution
Ratio
24.19
23.22
24.19
25.24
28.59
29.27
28.59
30.63
Stream
Beckman
14.03
14.16
14.51
13.12
12.73
12.88
12.87
12.86
Concentration* (mg/m^)
Sunshine Dupont 01 in
8.95
9.06
9.19
8.58
7.92
8.20
7.72
7.96
15.00
15.33
15.00
14.36
13.58
14.34
13.72
14.09
Instrument readings multiplied by dilution ratio.
CO
-p.
-------
TABLE 4-6
HYDROGEN STREAM SAMPLES
LO
U1
1.)
2.)
3.)
4.)
5.)
6.)
7.)
8.)
9.)
10.)
11.)
12.)
13.)
14.)
15.)
16.)
Date
5/31
5/31
5/31*
5/31*
5/31
6/1
6/1
6/4*
6/4*
6/5
6/5
6/6*
6/6*
6/6*
6/6*
6/6
Type
ICL
ICL
ICL
KMN04
ICL
ICL
KMN04
ICL
KMN04
ICL
ICL
ICL
KMN04
ICL
KMN04
KMN04
Hg Cone by
AA Analysis (mg/m3)
0.94
0.95
1.08
1.25
1.28
1.06
0.85
1.33
1.22
0.94
1.28
1.07
0.75
1.23
0.86
0.84
Beckman
mg/m3
0.74
0.78
0.65
0.65
0.80
0.79
0.85
0.93
0.93
0.62
0.91
0.77
0.77
0.83
0.83
0.85
01 in
mg/m3
0.74
0.81
0.71
0.71
0.77
0.73
0.88
0.92
0.92
0.54
0.81
0.84
0.84
0.86
0.86
0.92
Sunshine
imj/tn*'
0.62
0.46
0.44
0.44
0.46
0.59
0.63
0.43
0.43
0.21
0.37
0.30
0.30
0.48
0.48
0.42
Simultaneous Tests
-------
I
CO
ot
TABLE 4-6
HYDROGEN STREAM SAMPLES
17.)
18.)
19.)
20.)
Date
6/6
6/6
6/6
6/6
Type
KMN04
KMN04
KMN04
KMN04
Hg Cone by
AA Analysis (mg/m3)
0.70
0.68
0.60
0.53
Beckman
mg/m3
0.77
0.70
0.80
0.53
01 1n
mg/nr
0.76
0.74
0.77
0.58
Sunshine
mg/nr
0.43
0.42
0.45
0.34
-------
APPENDIX B
STATE-OF-THE-ART REPORT ON
EVALUATION OF INSTRUMENTATION FOR MONITORING
TOTAL MERCURY EMISSIONS FROM
STATIONARY SOURCES
B-i Ulaldeni
-------
I. INTRODUCTION
This report reviews the physical and chemical principles for the
continuous monitoring of mercury. Although UV absorption has been the most
popular technique for monitoring mercury, many different configurations have
been employed, e.g., single beam, dual beam, dual wavelength. The advantages
and disadvantages of each technique are discussed in Section 2.
Mercury can be present in several different forms, namely elemental
mercury, inorganic compounds (HgC^. HgO, etc.) and organic compounds
[Hg(CH3)2]. Since all the commercially available mercury detectors sense
only elemental mercury, inorganic and organic mercury compounds must be
decomposed in order to have a system which is capable of monitoring total
mercury emissions. In Section 3, the requirements for sampling mercury in
different stationary sources are covered.
Section 4 describes the characteristics of a number of commercially
available mercury monitors and evaluates their use as either continuous-
inplace monitors or portable monitors for compliance testing.
B-2
llUaldenl
-------
II. PRINCIPLES OF DETECTION
A. ULTRAVIOLET ABSORBANCE
Optical Instrumentation has been the most universal approach for
mercury analysis and monitoring. These optical techniques utilize the
strong ultraviolet absorbance of mercury vapor at 253.7 nm. Since mercury
Is an atomic species, It absorbes and emits energy of the same frequency.
This phenomenon Is termed resonance radiation. Thus, a high voltage
or high frequency discharge containing mercury In the presence of an Inert
gas will emit radiation which will be absorbed by mercury vapor. If the
pressure of the discharge 1s low, the mercury will emit 85-95% of its energy
at the 253.7 nm resonance line.
The extinction coefficients for mercury and a number of other
species [1,2] are given in Table 2-1. The list contains only a few of
many compounds which absorb at 253.7 nm. The technique is clearly not
specific for mercury, but its strong absorption allows mercury to be
determined in the presence of 100-1000 times the concentration of weakly
absorbing species. This is not enough, however, for sources which emit
mercury in low concentrations in the presence of high levels of sulfur
dioxide.
UV analyzers are commercially available in a variety of con-
figurations Including single beam, dual wavelength and dual beam.
Several approaches have been used to Increase the rejection ratio for
interferences and make the instruments more specific for mercury. One
approach uses Zeeman splitting of the mercury resonance line while an-
other makes use of the pressure broadening of the 253.7 nm mercury line.
A third approach to imporve the specificity involves the isolation of
mercury by absorption on a noble metal (silver or gold) collector and
subsequent thermal desorption and analysis.
B-3
llUakknl
-------
TABLE 2-1
COMPARISON OF SOME ULTRAVIOLET ABSORBING
SPECIES AT 253.7 NM
Approximate
Extinction Coefficient
Species (I/mole-cm) at 253.7 nm Rejection Ratio*
mercury
sulfur dioxide
hydrogen sulfide
ozone
di nitrogen tetroxide
(N204)
benzene
chlorine
nitrogen dioxide
4 x 106
40
2
3000
200
200
1
10
104
2 x 105
133
2 x 103
2 x 103
4 x 105
4 x 104
* defined as the concentration ratio which will produce less than a 10%
error in the mercury concentration
B-4
ItUnl
-------
The various techniques are described in the following sections.
1. Single Beam UV
A single beam UV monitor consists of a low pressure mercury
light source, a sample cell* phototube and amplifier. A typical block dia-
gram is shown in Figure 2-1(a). Most of these instruments have a dual photo-
tube arrangement. One phototube (a) is placed adjacent to the light source
and measures the intensity of the source (IQ). The other phototube (b)
measures the attenuation of the light source (I) by mercury in the sample
cell. These instruments measure the ratio of I/IQ which is related to
the concentration. In some instruments, a nonlinear (logarithmic) scale
is provided, while others utilize logarithmic amplifiers to perform a
subtraction of I -IQ and have a linear output.
2. Dual Wavelength
This is similar to the single beam system except that two
different wavelengths are used. In dual wavelength-single cell systems,
the unfiltered radiation from a low pressure mercury discharge passes through
the sample cell and then is split into two beams by a half-silvered mirror.
The radiation in each beam is then isolated into two discrete wavelengths
by a 253.7 nm or a 313 nm interference filter respectively. The later
wavelength where mercury does not absorb is used as a reference signal for
comparison to 253.7 nm where mercury absorbes strongly.
The intensities of the absorbing and reference wavelengths are
measured with phototubes coupled to logarithmic amplifiers. Subtraction
of the 253.7 nm signal from the 313 nm value provides an output which
increases linearly with mercury concentration. A schematic of this
system is given in Figure 2-1(b).
Another version of this instrument employs two interference
filters mounted on a rotating plate and a single phototube detector.
B-5
IWakkni
-------
MERCURY
LIGHT SOURCE SAMPLE CELL
CALIB.
FILTERS
-K » PHOTOTUBE
PHOTOTUBE
AMPLIFIER
METERl
(a) SINGLE BEAM SYSTEM
LOGRITHMIC
MERCURY
AMP
^m^m
\
LIFIERS
-*«-
_/l
SPL^EP. SAMPLE CELL USHT,
tF\i n
\U* LJ *
FILTER
253.7
nm
rpu n ^
-« U fie
r ^
»
^»
CONTROLLER
FILTER MIRROR
313.0
nm
(b) DUAL WAVELENGTH SYSTEM
Figure 2-1. Single beam and Dual Wavelength UV Analyzers
B-6
Ittlddenl
-------
The advantages of the single cell-dual wavelength approach in-
clude compensation for: a) the aging of the lamp; b) the buildup of dust
or deposits on the cell windows; and c) the presence of particulate matter
in the sample stream. This system will also compensate for UV absorbing
gases which have the same absorbances at the two wavelengths. Corte and
Dubois [3] have demonstrated, however, that organics, sulfur dioxide, and
many other interfering species may not be adequately compensated for with
this approach.
Another version of the dual wavelength approach involves splitting
the beam before it is passed through the sample. A separate cell is used
for the reference wavelength. This approach does not offer any advantage
for mercury monitoring over the two techniques described above. In fact,
it is less favorable in that buildup of particulate on the cell windows
and particulate matter in the gas stream is not compensated for.
Although some of the differences between the instruments appear
slight, these simple modifications may influence the results obtained.
Many of these dual wavelength instruments are very expensive and
not very portable.
3. Dual Beam
A dual beam system, in the usual sense, refers to comparison
of intensity measurements in a sample cell and reference cell where light
of the same frequency is passed through both cells. Two schematics of
possible dual beam systems are shown in Figure 2-2 (a and b).
The dual beam system, as normally used, does not offer any
advantage over the single beam system. Corte and Dubois [3] have inves-
tigated methods for improving the specificity'of mercury analyzers. Their
approach involves the use of a modified dual-beam system where a mercury
B-7
lUMkni
-------
MIRRORS
(OPTIONAL)
SAMPLE CELL FILTER PHOTOTUBE AMPLIFIERS
REFERENCE CELL
PHOTOTUBE
LIGHT SOURCE
FILTER
DUAL BEAM SYSTEM (a)
BEAM
SPLITTER
1
L
FILTER
O-r-i-U
SAMPLE CELL
PHOTOTUBE AMPLIFIERS
£—i
LIGHT SOURCE
V-E
REFERENCE CELL
PHOTOTUBE
MIRROR
DUAL BEAM SYSTEM (b)
SAMPLE
IN
n SAMPLE CELL
SELECTIVE
. SCRUBBER
FOR H
PREFERENCE CELL
SAMPLEOUT I
fi
MODIFIED DUAL BEAM SYSTEM (c)
Figure 2-2. Dual Beam UV Mercury Analyzers
B-8
llUAknl
-------
scrubber Is placed in series with the sample cell. The sample then flows
through the sample cell, the mercury scrubber, and into the reference cell.
A schematic of the system is given in Figure 2-2(c). The advantage of
this system is that if only mercury is removed in the scrubber the dif-
ference between the sample cell and reference cell represents the absorp-
tion due to mercury and a truly mercury specific analyzer is available.
Corte and Dubois [3] found that either palladium chloride or silver wool
filters effectively removed mercury while quantitatively passing organics
and fine particulate matter. Although granulated zinc and charcoal absorb
mercury, the former absorbent melts when heated to release the mercury,
and the latter compound also absorbs organics, sulfur dioxide, etc..
Corte and Dubois [3] conclude that only a "true double beam"
UV instrument with a mercury scrubber is satisfacotry for obtaining a
signal which is specified for mercury in air.
4. Zeeman Effect
In a strong magnetic field, the resonance line of mercury
(253.7 nm) is split into three components o , a" and IT. The frequencies of
these three Zeeman components can be defined by [4].
v (a+) = Vo + 6v
v (TT) = Vo
v (a") = Vo - 6v
where Vo is the frequency of mercury and 6v is the frequency shift due to
the Zeeman effect. As the strength of the magnetic field increases, 6v
increases linearly and only the IT component lies within the absorption pro-
file [4] in a strong magnetic field [see Figure 2 in Reference 4]. Several
different schemes utilizing this concept have been demonstrated.
B-9
-------
One Is described In detail by HadelsM and Mclaughlin [4].
The radiation from an electreeless mercury discharge lamp* placed 1n a
magnetic field passes first through the absorption cell, then through 253.7
nm filter, and to a beam splitter. The beam perpendicular to the optical
path passes directly to a phototube and amplifier. The other beam passes
through a cell filled with mercury vapor then to a phototube and associated
amplifier. A schematic of the system is shown in Figure 2-3. Since the
magnetic field is on continuously, phototube (a) perpendicular to the
optical path measures the a and o~, and ir components. The other phototube
(b) measures only the a* and a" components since the IT component (but not
the a components) would be absorbed by the mercury vapor. The difference
between these two signals provide a response which is specific for mercury.
Another system which is similar in principle to that of Hadeishi
and Mclaughlin yet different in design is commercially available from
201
Scintrex. This instrument is bulky, and employs a Hg discharge lamp
with a large magnet (high magnetic fields). Since the instrument was de-
signed to measure mercury in the ambient air (ng/m region), an optical
path length of about 30 ft is employed. The dual beam system uses a
pulsed magnetic field and measures the difference in absorption with the
magnetic field pulsed on and off with a phase sensitive amplifier. The
reference signal (zero) is obtained by passing the sample through a
palladium chloride coated filter to remove mercury. The selectivity ratio
for Hg/S02 is 500,000:1. When this is compared with the rejection ratio
for UV absorbance (Table 2-1), the advantages of this instrument become
quite apparent.
5. Pressure Broadening
Other approaches for increasing the specificity of UV absorption
for mercury utilize the pressure broadening of atomic emission lines (0253.7
nm) from mercury discharges.
199
The HG isotope lamp was used to reduce the strength of the magnetic
field required, and hence the weight of the magnet.
B-10
lUlaldenl
-------
pg
199
Ha LAMP . «t» ^\
/-x
r JL
1 j
ri_i i i tn
CELL FILLED /-PHOTOTUBE
WITH /
\ MERCURY VAPOR i AMPLIRER
7 fc-/'*^ r^s
VV \s^
READOUT
*r?i IN
PHOTOTUBE AMPLIFIER
Figure 2-3. Zeeman Effect Mercury Meter
B-ll
-------
A schematic of Barringer's [5] mercury monitor is shown in
Figure 2-4. The output from the low pressure mercury lamp passes sequen-
tially through the sample, a 253.7 nm interference filter, then is split
into two components. One beam is deflected onto a phototube (a) while the
other passes through a cell filled with mercury vapor prior to measurement
by another phototube (b). The output of the lamp is slightly broadened and
passage of the beam through the mercury vapor cell causes complete absorption
of only the center of the broadened 253.7 nm line. This phototube then
does not respond to mercury addition to the sample cell but will respond
to species which absorb at the edges of broadened 253.7 nm line. The
other phototube (a) is very sensitive to mercury. The output of these two
photobubes is coupled to a differential amplifier. If a boradened UV
absorber, e.g., an organic species, is placed in the sample cell, this will
result in a reduction in intensity in both phototubes and record a net
change of zero. The rejection of interferences for this instrument is
demonstrated in Table 2-2 below:
TABLE 2-2
Rejection of Interferences for Barringer Spectrometer
Compound Rejection Ratio
Benzene 1:2 x 10
Toluene 1:2 x 10
Cyclohexene 1:2 x 10
Dioxane 1:1 x 10
Carbon Dioxide 1:2 x 10
These data can be compared with benzene rejection for a simple UV absorption
system in Table 2-1. The improvement in specificity is quite impressive.
Ling [6,7] described an instrument of different configuration
which used essentially the same principle. His instrument is shown in
Figure 2-4. Ling [6] irradiated the sample alternately with a pressure
B-12
llUaldenl
-------
MERCURY
LISHT
SOURCE
SAMPLE CELL
253.7nm
• INTERFERENCE
FILTER
i-BEAM SPLITTER
L
PHOTOTUBE
±
MERCURY VAPOR
CELL
DIFFERENTIAL
AMPLIFIER
PHOTOTUBE
(a) AFTER BAR RINGER
(BROADENED SOURCE)
MERCURY PLUS
NITROGEN
MERCURY
RESONANCE
SOURCE
ATTENUATOR
i
LIGHT
SOURCE
i
SAMPLE CELL PHOTOTUBE .AMPLIFIER
•£=J '<»-H>
SHUTTERS
MiRRO RS
(b) AFTER LIN6
Figure 2-4. Mercury Analyzers Depending on Pressure Broadening Effects
B-13
-------
broadened mercury source (mercury plus nitrogen) and a high vacuum mercury
resonance lamp. The difference in absorbance obtained between these two
lamps provides a signal which is specific for mercury. When mercury vapor
is added to the sample cell, 99% of the radiation from the mercury resonance
line is absorbed whereas only 2% of the intensity from the pressure broadened
source is absorbed.
Neither of these instruments is commercially available on a
regular basis although several prototypes of the Barringer instrument have
been used in prospecting.
6. Amalgamation
Mercury forms amalgams with a number of noble metals including
gold and silver. Willisten [8] and Long et.al. [9] have utilized silver
wool for collection of mercury in ambient air. Tradet [10] developed a
procedure for collection of mercury in the presence of high concentrations
of SOp by amalgamation on gold or silver to concentrate the mercury in the
sample and pass interferences such as sulfur dioxide and hydrocarbons. These
instruments are batchtype analyzers in that mercury is collected by amalgam-
ation for a known period of time at a constant flow, then the mercury is
desorbed by heating. Two of the commercial analyzers employing this
principle are of the single beam UV type while one employes condensation
nuclei formation for mercury detection. The difficulties are the dependence
on flow rate, the low collection efficiency for mercury on the commercial
type amalgamators, and the effect which corrosive materials (H2S04, CU. etc.)
have on the surface characteristics of the amalgamators. This latter feature
also leads to low recoveries of mercury.
B-14
IWaldenl
-------
B. SELENIUM SULFIOE
Elemental mercury reacts with selenium sulfide to produce the
black precipitate mercuric sulfide. Paper coated with selenium sulfide
has been used to detect mercury [11]. The instrument normally used for
this application is the tape stain sampler where a decrease in the % of the
paper due to the formation of HgS is directly proportional to the mercury
concentration. No continuous monitors utilizing this principle are com-
mercially available. Considerable modifications to commercial tape stain
samplers would be required to obtain a continuous monitor. In addition,
this technique requires the temperature to be maintained constant, and
the paper to be shielded from strong light. The useful life of the paper
is of the order of six months to one year as a result of aging.
C. CONDENSATION NUCLEI
When elemental mercury, in the presence of oxygen is irradiated
with ultraviolet light, fine particles of mercuric oxide are formed.
These nuclei are drawn into a chamber where an expansion at constant
volume produces an opaque cloud. A light scattering photometer is then
used for determining the transmission which is related to the concentration.
Participate matter must be very efficiently removed to prevent an
interference. This could result in losses of mercury vapor by absorption
on the filter. Some problems may be observed as a result of the require-
ment to produce particles of uniform size.
B'15 iiiU
ulaldeni
-------
III. SAMPLING REQUIREMENTS FOR STATIONARY SOURCES
The principal industrial sources of mercury emitted to the atmosphere
include:
—chlor-alkali
—primary mercury production
—secondary mercury processing
—non-ferrous smelting
—coal burning power plants
—incinerators
Each of these sources will have its own characteristic problems with sampling.
For example, the chlor-alkali and mercury smelting processes have high
mercury levels which may require the use of a short path cell and/or possibly
sample dilution. Participate mercury compounds such as HgCl2 or HgO are also
present which require a catalytic converter to decompose them to elemental
mercury. The latter source has high concentrations of S02 which may require
a scrubber for most types of analyzers. The non-ferrous smelters and coal-
fired power plants are typified by high levels of S02 and relatively low
levels of mercury. Most commercial mercury monitors will require a scrubber
to remove SO-. A summary of mercury concentrations for some stationary
sources is given in Table 3-1.
The sampling conditioning requirements for the different types of
mercury analyzers is given in Table 3-2. Note that all the mercury analyzers,
regardless of the principle of detection, require a pyrolyzer or catalytic
converter to reduce particulate mercury compounds to mercury vapor. An
additional feature of the pyrolyzer is that all hydrocarbons are combusted
to COgi thereby eliminating the hydrocarbon interference noted for the UV
absorption analyzers in Table 3-2. Commercially available pyrolyzers
usually operate, at about 600°C to decompose organic and inorganic (particulate)
mercury compounds [12, 13, 14] but they are capable of operation at
temperatures as high as 800°C.
B-16
/OtUsm
-------
TABLE 3-1
SUMMARY OF EPA MERCURY EMISSIONS DATA
SUMMARY OF EPA MERCURY EMISSIONS DATA
Type of
Plant
Chi or-al kali (Wynd.)
Chlor-alkali (B.F.G.)
Chlor-alkali (D.S.)
Chlor-alkali (G.P.)
Coal -Fired P.P.
Mercury Smelter
(El Paso Gas)
Hg Smelter (N.I.)
Hg Smelter
(Sonoma)
Site
H2 Stack
H2 Stack
Fume System
Cell Room
H2 Stack
End Box Vent
Vent System
(end room)
H2 Stack
Stack
Stack
Stack
Range of Total
Hg Cone.
40-1.6 x 103 mg/m3
2.5-10 mg/m3
4-12 mg/m3
3 x 10"3-5 x .O"3 mg/m3
1-3 mg/m
1 x 103-2.5 x 103 mg/m3
2.7 x 103 mg/m3
2 x 102-4 x 102 mg/m3
0.1 mg/m3
1 x 102-6 x 102 mg/m3
9 x 102-11 x 102 mg/m3
-1.3 mg/m3
B-17
-------
TABLE 3-2
SAMPLE CONDITIONING REQUIREMENTS FOR DIFFERENT TYPES
OF MERCURY ANALYZERS
CO
GO
Principle
UV Absorption
Pressure Broadening
Zeeman Effect
Condensation Nuclei
Tape Stain*
Parti cul ate matter
transmission.
Manufacturer
Sunshine
Beckman
01 1n
Dupont
Geomet
Barrlnger
Slntrex
Environment
One
Isok1net1c
Sampling
Yes
Yes
Yes
Yes
Hydrocarbon
Removal
Yes
No
No
?
RAC Yes No
Sunshine
Scien.
must be very efficiently removed, otherwise
S02 Pyrolyzer to Convert Parti cul ate
Removal to Elemental Mercury
Yes
No
No
?
No
it will also result 1n a
Yes
Yes
Yes
Yes
Yes
decrease in
-------
For those sources which contain high levels of SO. an aqueous sodium
carbonate scrubber has shown to remove SCL but quantitatively pass elemental
mercury [15].
A compilation of the sample conditioning requirements for the different
Industrial processes Is given In Table 3-3. An additional sampling require-
ment which may be necessary Is the use of isokinetic sampling for sources
which contain participate mercury.
B-19
lUlalden,
-------
TABLE 3-3
SAMPLE CONDITIONING REQUIREMENTS FOR DIFFERENT PROCESSES
O3
o
Source
Chloral kali
Hg Smelter
Non-ferrous
Smelter
Secondary Hg
Elemental
Mercury
Yes
Yes
Yes
Yes
Participate
Mercury
Yes
(HgClp.HgO)
£.
Yes
(uar\\
^nyu;
NO
No
Organic
Mercury
No
No
No
Yes
so2
No
Yes
Yes
No
Hydrocarbons
No
Yes
Yes
Yes
Requirements
(a) Isokinetic sampling
(b) Pyrolyzer to decompose inorganic
mercury compounds
(a) S00 removal necessary only for
c.
low Hg emissions
jb) HC removal (?)
(c) Isokinetic sampling (?)
(a) S02 removal
(a) Conversion of organic Hg to
Processing
Incinerator
Coal -Fired
Power Plant
Yes Possibly (b)
Yes No
No
Yes
Yes
Yes
ffl
ft
elemental Hg
Hydrocarbon removal
Possibly particulate Hg where
large quantities of PVC are
Incinerated
SOp removal
HC removal in the case of poor
combustion
-------
IV COMMERCIALLY AVAILABLE MERCURY MONITORS
Commercially available mercury monitors can be divided into portable
instruments and contlnuous-in-place monitors. The former instruments are
most useful for compliance testing because of their light weight, e.g.
about 50 Ibs. or less. Many of the instruments, however, can be used for
both categories. The portable monitors are not expected to be exceptionally
stable with regard to zero and span while the continuous-in-pi ace monitors
are expected to have better stability characteristics. None of the instru-
ments, as sold, have sampling systems which are adequate for monitoring
total mercury emissions from the sources listed in Section III. The Olin
monitor has both a catalytic converter and an acidic SnCl2 scrubber. Both
of these are located in the instrument and could lead tp serious loss of
particulate mercury compounds, especially if long sampling lines are utilized.
The characteristics of some commercially available, portable and contlnuous-
in-place monitors are given in Tables 4-1 and 4-2 respectively. The approxi-
mate prices in the tables are for the analyzer alone unless otherwise noted.
B-21
ItUaii
-------
TABLE 4-1
PORTABLE MERCURY MONITORS
CO
ro
ro
Manufacturer
Beckman (K23)
Sunshine
Scientific
(38E)
Principle
Single boain
UV-dual de-
tector
Single beam
UV-dual de-
tector
Concentration
Range
0-1 mg/m3
0-0.3 mg/m
Approximate
Price
$890
$240
$1500
Weight
(Ibs) Remarks
7 has built In calibrator;
optional cell required
for use as an extractive
sampl er
8 must be modified before
use
Geomet (103-4)
Bacharach
Environment/
One
L.D.C.
Mercometer
Amalgamation
Amalgamation -
single beam UV
Amalgamation -
Condensation
Nuclei
Dual beam UV
Dual beam-UV
ng/m - mg/m
0-1 mg/m
0.01-1 yg/m
0-0.25 yg/m
10 yg/m •* up
$7600
35
$1900
$5800
$1800
$1200
20
54
25
27
mercury preconcentrated in
gold or silver gridbatch
type operation
Gold collection matrix and
internal combustion furnace
Silver wool collector
30 cm absorption cell used
mainly for ambient air
-------
ro
CO
Environment/
One
TABLE 4-2
CONTINUOUS-IN-PLACE MERCURY MONITORS
Manufacturer,
DuPont (400)
01 In
Geomet
(103-4)
Scintrex
Tel edyne
Principle
Dual wavo-
length UV
Dual wave-
length UV
Amalgamation-
single beam UV
UV absorption-
Zeeman effect
Dual wavelength-
UV; single beam
Concentration
Range
0.1-2000 yg/m3
0-2 ng/m or
higher
10 ng/m •*• up
0-2.5 yg/m
0-8000 yg/m3
Approximate
Price
$5000
$19,000
$7600
$17,300
$5800
$4400
Weight
Hbs)
130
800
35
100
100
Remarks
Has SnCl2 scrubber, pyrolyzei
and multipoint sampling cap-
ability
(see previous table)
Designed mainly for ambient
air but would be useful for
stacks with a shorter cell
UV
Amalgamation-
condensation
nuclei
0.01-1 yg/nf
$5800
Silver wool collection
-------
REFERENCES
1. Calvert, J.G. and J.N. Pitts, Photochemistry, Interscience, New
York (1969).
2. Sullivan, J.O., and A.C. Holland, "A Congeries of Absorption Cross
Sections ", 6CA Technical Report on Contract No. AFAL-TR-650
228 (1964).
3. Corte, G., and L. Dubois, "Application of Selective Absorbers in the
Analysis of Mercury in Air", Paper No. 73-297 presented at the 66th
Annual APCA Meeting (1973).
4. Hadeishi, T. and R.D. Mclaughlin, Science, 174, 404 (1971).
5. Barringer, A.R., Trans. Inst. Mln. Met., 75_, B120 (1966).
6. Ling, C., Anal. Chem. 39, 798 (1967).
7. Ling, C., Anal. Chem. 40, 1876 (1968).
8. Williston, S.H., J. Geophys. Res. 73. 7051 (1968).
9. Long, S.J., Scott, D.R., and R. J. Thompson, Anal. Chem. 45, 2227 (1973).
10. Tradet Corp., "Development of the Gold Amalgamation Technique for
Mercury in Stack Gases", APTD 1171, PB 210-817.
11. Jacobs, M.B., "The Analytical Toxicology of Industrial Inorganic Poisons",
Interscience, New York (1967).
12. Saltzmann, R.S. et.al., "A Multipoint Analyzer for Atmospheric
Monitoring for ppb Organic Mercury", Paper presented at the 17th
Annual ISA Conference (1962).
13. Geomet Corp., Rockville, Md.
14. Capuano, I.A., "Automatic Environmental Total Mercury Analyzers",
presented at the 17th Annual ISA meeting (1971).
15. Statnick, R.M.. Oestreich, O.K., and R. Steiber, "Sampling and
Analysis of Mercury Vapor in Industrial Streams Containing SO/,
presented at ACS National Meeting (August, 1973).
B-24
IttUbil
-------
TECHNICAL REPORT DATA
(Please read liiitnicnons on the reverse before comiileinif)
1 REPORT NO
EPA-650/2-74-039
2.
3 RECIPIENT'S ACCESSION-NO
4 TITLE AND SUBTITLE
Evaluation of Instrumentation for Monitoring Total
Mercury Emissions from Stationary Sources
5 REPORT DATE
Issue - 6/74
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8 PERFORMING ORGANIZATION REPORT NO
L. Katzman, R. Lisk and J. Ehrenfcld
9 PERFORMING ORGANIZATION NAME AND ADDRESS
Walden Research Division of Abcor, Inc.
201 Vassdr Street
Cambridge, Mass. 02139
10 PROGRAM ELEMENT NO
1A1010
11 CONTRACT/GRANT NO
68-02-0590
12 SPONSORING AGENCY NAME AND ADDRESS
EPA
Office of Research and Development
Washington, U. C. 20460
13 TYPE OF REPORT AND PERIOD COVERED
1-inal 7/72 - 6/74
14 SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16 ABSTRACT
The principal objective of this project wjs to identify ;md evaluate monitoring
instrumentation winch represents the current state-of-the-art in measurement of
total mercury emissions from stationary sources. During the laboratory test program
the uniformity of response of each instrument acquired for the program to expected
forms of mercury emissions from stationary sources including particulatc and organo-
mcrcury compounds as well as elemental mercury vapor was established. Field tests
were conducted at the following sources: (1J secondary processing of mercury;
(2) chloralkali production; and (3) nonferrous (zinc) smelting. I'rom the evaluation
of these data the investigators concluded that available mercury measuring instru-
mentation can be adapted for the measurement of total mercury emissions from certain
sources, in particular, chlor-alkali plants. Tin* transporting and conditioning of
the sample poses considerable difficulties requiring additional research. The
necessity of a dynamic dilution system to condition high level mercury emissions sets
the requirement for a fairly sophisticated automatic interfacing subsystem. Manual
control was accomplished during the field and laboratory portions of the program.
Manual control in the field was sufficient for these studies; however, continuous
monitoring could not be accomplished by this means.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
I) IDENTIFIERS/OPEN ENDED TERMS
c COSATi I ickl/Group
Mercury
Source Monitors
Mercury Source Emissions
Monitors for mercury
compounds.
13 DISTRIBUTION STATEMENT
Release Unlimited
19 SECURITY CLASS (Tins Keport)
Unclassified
21 NO OF PAGES
20 SECURITY CLASS (Thispage)
Unclassified
22 PRICE
EPA Form 2220-1 (9-73)
B-25
------- |