United States Office of Air Quality EMB Report 02-CEP-21
Environmental Protection Planning and Standards Volume I
Agency Research Triangle Park, NC 27711 June 1082
Air
Trivalent Chromium
Emission Test Report
True Temper Sports
Seneca, South Carolina
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TRIVALENT AND TOTAL CHROMIUM EMISSIONS EVALUATION
THE TRUE TEMPER COMPANY
Seneca, South Carolina
Prepared for:
United States Environmental Protection Agency
Emission Measurement Branch
Research Triangle Park, North Carolina
EPA Contract No. 68-D-90155
Prepared by:
ADVANCED SYSTEMS TECHNOLOGY, INC.
3490 Piedmont Road, NE • Suite 1410
Atlanta, GA 30305-4810
(404)240-2930
December 9, 1992
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TABLE OF CONTENTS
**********************************************
SECTION NO.
TITLE
EXECUTIVE SUMMARY
Section 1.0 INTRODUCTION
1.1
1.2
1.3
Objectives
Basis
Emission Evaluations
Section 2.0 PROCESS OPERATION
2.1
2.2
2.3
Process Description
Air Pollution Control
Process Conditions During Testing
Section 3.0 SUMMARY AND DISCUSSION OF RESULTS
3.1
3.2
3.3
3.4
Sampling
Summary of Stack Gas Conditions
Chromium Results
Results Discussion
Section 4.0 SAMPLING LOCATIONS AND TEST METHODS
4.1 Sampling Locations
4.1.1 Plating Tank
4.1.2 Stack Samples
4.1.2.1 Test Methods
4.1.2.1.1 Traverse Points
4.1.2.1.2 Stack Gas Velocity
4.1.2.1.3 Stack Gas Moisture
4.1.2.1.4 Method 13-B Sampling Train
4.2 Sample Collections
4.3 Sample Analysis Methods
4.3.1 Inductively Coupled Plasma (ICP)
4.3.2 lon-Chromatography with Post Column Reactor (ICPCR)
Section 5.0 QUALITY ASSURANCE PROCEDURES AND
SUMMARY OF FIELD ACTIVITIES
5.1 Quality Assurance
5.2 Summary of Field Activities
PAGE NO.
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1-1
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2-2
2-2
3-1
3-1
3-1
3-1
3-2
4-1
4-1
4-1
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4-4
4-4
4-6
4-6
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4-7
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TABLES AND FIGURES
TABLE NO
Table S-l
Table 2.1
Table 2.2
Table 2.3
Table 3.1
Table 3.2
Table 3.3
Table 3.4
Table 3.5
Figure 4. 1
Figure 4.2
Figure 4.3
TITLE PAGE NO
Average Emission Concentrations and Mass Emission Rates
Average Operating Parameters Monitored During Emission Tests
Total Current Supplied During Each Emission Test Run
Surface Tension Measurements During Each Emission Test Run
Summary of Stack Conditions During Sample Collection
Analytical Results of Chromium Mass Emission Testing
Average Emission Concentrations and Mass Emission Rates
Sample Train and Reagent Blanks
Total Chromium Concentration of Plating Bath Solutions
Schematic of Outlet Duct and Stack Dimensions
Outlet Traverse Point Locations
Schematic of the Modified U.S. EPA Method 13-B
ii
2-2
2-3
2-4
3-2
3-3
3-4
3-4
3-5
4-2
4-3
Sampling Train
4-5
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APPENDICES
APPENDIX TITLE PAGE NO
Appendix A Computer Print Out of Field Data A-0 - A-12
Appendix B Field Data Sheets B-0 - B-ll
Appendix C Sampling Summary Sheets C-0 - C-3
Appendix D Laboratory Analysis Reports and Chain of Custody D-0 - D-6
Appendix E Amp Hour Calculations E-0 - E-6
Appendix F Sample Calculations F-0 - F-6
Appendix G Determination of Total Chromium and Hexavalent
Chromium Emissions from Stationary Sources
(CARS 425) G-0 - G-21
Appendix H Equipment Calibration Data H-0 - H-7
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EXECUTIVE SUMMARY
The objective of this project was to measure the emission rate of trivalent chromium (Cr-III)
from plating solutions at the True Temper Company located in Seneca, South Carolina. The
True Temper Company operates five (5) plating tanks in the production of metal shafts used in
golf clubs. A relatively new Cr-III plating process is being used at the plant and the use of a
wetting agent to suppress Cr-III emissions was evaluated.
To meet the project objective, three (3) mass emission tests were performed, using a
modification of US EPA Method 13-B. A wetting agent was added to the plating tank solution.
All testing was performed during the week of June 8, 1992. Test samples were collected from
a straight section of plating tank hood exhaust ducting. The duration of each test was
approximately three hours and isokinetic sampling conditions prevailed throughout the tests.
After each test run, samples were recovered in the field, logged and stored in coolers. During
each test run, a sample of plating solution was also collected for analysis.
All samples were stored in a cooler and upon completion of field activities, were transported to
the Research Triangle Institute Laboratory (RTIL), Research Triangle Park, North Carolina for
analysis of:
• Total chromium (Cr-T) determinations using Inductively Coupled Plasma (ICP)
• Chromium-VI (Cr-VI) determinations using lon-Chromatography with Post Column
Reactor (ICPCR)
Plating tank solution samples were analyzed for Cr-T. Samples collected using Method 13-B
were analyzed for both Cr-T and Cr-VI. The concentrations of Cr-III were obtained by
subtracting the values of Cr-VI from Cr-T. The average emission concentrations (mg/dscm) and
mass emission rates (lb/hr) for Cr-T, Cr-III and Cr-VI are tabulated in Table S-l.
REPORT ORGANIZATION
This report is organized into five (5) sections and seven (7) supporting appendices. Section 1
provides the objective of testing, some details of True Temper Company, sampling and analysis
briefs. The plating bath process details are outlined in Section 2. The information in Section
2 was provided by Midwest Research Institute (MRI). Section 3 gives a summary and discussion
of results. The details of sampling locations, field test methods used, sample collection and
analysis methods are given in Section 4. The quality assurance protocol details associated with
the project work are outlined in Section 5. This report also includes Appendices A through H,
each with related raw test data.
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Table S-l
AVERAGE* EMISSION CONCENTRATIONS AND
MASS EMISSION RATES
Analyte
Total Chromium*
Chromium - III"
Chromium - Vf
Emission Concentrations
(mg/dscm)
0.0266
0.0230
0.0036
Mass Emission Rates
(Ib/hr)
1.008 x lO'3
8.776 x 10"
1.306x 10"
* Represents average of three (3) test runs when plating bath contained a wetting agent
+ Analysis method, Inductively Coupled Plasma (ICP)
1 Cr-HI = Cr-T - Cr-VI
b Analysis method, lon-Chromatography with Post Column Reactor (ICPCR)
ii
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Section 1.0 INTRODUCTION
1.1 OBJECTIVE
The objective of testing at the True Temper Company in Seneca, South Carolina was to quantify
mass emissions of chromium-Ill (Cr-HI) from a chromium plating operation. The plating
solution contained a wetting agent to suppress airborne emissions from the plating tank.
1.2 BASIS
The U.S. Environmental Protection Agency's Office of Air Quality Planning and Standards
(OAQPS), Emission Measurement Branch (EMB), Technical Support Division (TSD) was
requested by the Industrial Studies Branch (ISB) to perform an air emission evaluation at the
True Temper Company in Seneca, South Carolina.
The True Temper Company operates five (5) plating tanks that are used in the production of
metal shafts for golf clubs. The plating line was originally designed and built to use a
hexavalent chromium (Cr-VI) plating process, however, after the plant was built, a new Cr-III
plating process was introduced and was adopted for use at this plant. As a result of the change
to the Cr-IH plating process, the installed scrubber is not being used.
This plant was chosen for testing because the trivalent chromium (Cr-III) plating process was
used. Also, the exhaust ducting from the hood is well-suited for measuring the emissions.
1.3 EMISSION EVALUATIONS
To evaluate Cr-III emissions, testing was performed during the week of June 8, 1992. A
modification of U.S. EPA Method 13-B was used to collect the samples. The emission samples
were collected from a straight section of the duct located between the non-functional scrubber
and the exhaust duct roof penetration. Three (3) test runs, each lasting approximately three (3)
hours, were performed under isokinetic sampling conditions.
Upon completion of the test run, samples were recovered in the field. During each test run, one
sample of plating bath solution was also collected for Cr-T analysis. All samples were
transported in a cooler to Research Triangle Institute Laboratory (RTIL), Research Triangle
Park, North Carolina for analysis. Three (3) plating bath solution samples were analyzed for
Cr-T using Inductively Coupled Plasma (ICP). Samples collected using Method 13-B were
analyzed for Cr-T using ICP and Cr-VI using lon-Chromatography with Post Column Reactor
(ICPCR).
The organizations involved in the field testing program were Advanced Systems Technology,
Inc., True Temper Company, Midwest Research Institute and U.S. EPA - Emission
Measurement Branch.
1-1
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Section 2.0 PROCESS OPERATION
2.1 PROCESS DESCRIPTION
True Temper Sports in Seneca, South Carolina, is a captive shop that performs trivalent
chromium electroplating of golf shafts. The plating facility consists of one decorative chromium
plating line. The plating line operates two shifts per day, five days per week. The purpose of
this source test was to characterize uncontrolled chromium emissions levels from the trivalent
chromium plating tank used in the decorative chromium plating process.
The plating line consists of a series of tanks that are used to clean and plate the golf shafts. The
line is serviced by an automatically controlled overhead hoist system that transfers racks of parts
to each tank in a programmed sequence.
The first portion of the plating line is used to clean and prepare the parts for plating. The parts
are first placed in a alkaline soak tank to clean the parts. The alkaline soak tank is followed by
two countercurrent rinse tanks. The parts are then transferred to a second alkaline soak tank for
further cleaning. The second alkaline soak tank is also followed by two countercurrent rinse
tanks. The third step in the cleaning process is an anodic electroclean followed by two
countercurrent rinses. The final cleaning step consists of two acid pickles that are used to
remove any rust and any alkaline film that might have built up in the prior cleaning stages. The
parts are then ready to be plated. The plating sequence used in this process is nickel followed
by chromium.
The parts are first plated in a semi-bright nickel tank followed by a second layer of bright
nickel. The nickel plating tanks are followed by a nickel dragout tank and two countercurrent
rinse tanks. The last stage of the plating sequence is the chromium plating sequence. The
chromium plating sequence consists of a trivalent chromium plating tank and a series of rinse
tanks. The chromium plating tank is 8.1 meters (m) (26.5 feet [ft]) long, 1.4 m (4.7 ft) wide,
and 2.0 m (6.5 ft) deep and is divided into four work stations. The tank holds approximately
20,400 liters (L) (5,400 gallons [gal]) of plating solution, which contains trivalent chromium in
a concentration ranging from 21 to 24 grams/liter (g/L) (2.8 to 3.2 ounces per gallon [oz/gal])
of water.
Three of the four work stations in the chromium plating tank are used for plating. One rack of
parts is plated per work station. Each rack contains between 36 to 44 shafts. Each rack is
transferred through the tank by pushers on the hoist system. The plating time per work station
is 50 seconds for a total plating time of 2.5 minutes. The plating thickness on each golf shaft
is slightly less than 2.5 /xm (0.10 mils). The plating tank is equipped with one rectifier with a
maximum rectification capacity of 12 volts and 14,000 amperes. The rectifier is set to operate
at 5,500 amperes and 8 volts at the maximum plating capacity of 168 shafts. This rectifier
setting relates to a current density of 1,300 amperes per square foot of surface area plated.
2-1
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The chromium plating tank is followed by a chromium dragout tank and three countercurrent
rinse tanks. Following the rinse tanks, the parts are placed in an anti-rust dip tank to enhance
the corrosion resistance of the part. The anti-rust tank is followed by an anti-friction spray,
which is used to coat the shafts and protect them against scratches. The final stage in the
process line is an air dryer used to dry the parts.
2.2 AIR POLLUTION CONTROL
The chromium plating tank is equipped with a push-pull ventilation system. The ventilation rate
for the tank is approximately 320 cubic meters per minute (11,300 cubic feet per minute). The
tank is vented to a scrubber system that was originally designed and installed to control
emissions from a hexavalent chromium plating tank. However, prior to the initial start-up of
the plating line, the plant elected to use the trivalent chromium process; therefore, the scrubber
system was no longer required.
2.3 PROCESS CONDITIONS DURING TESTING
Three test runs were conducted at the inlet of the scrubber system to characterize the
uncontrolled emissions from the trivalent chromium plating tank. Process operating parameters
such as voltage, current, and plating solution temperature were monitored and recorded during
each test run. Data sheets documenting the process operating conditions during each test run
are presented in Appendix E. Average values for the operating conditions recorded during each
emission test run are presented in Table 2.1.
TABLE 2.1
AVERAGE OPERATING PARAMETERS
MONITORED DURING EMISSION TESTS
Run No.
1
2
3
Average
Current amperes
5,600
5,600
5,300
5,500
Voltage, volts
10.8
10.7
10.6
10.7
Temperature, °F
97
97
98
97
In addition, composite samples of the plating solution were taken during the course of each test
run to determine the chromium concentration of the plating solution. The total chromium
concentration of the plating solution during each test run is presented in Section 3 of this report.
The total power supplied to the tank during each test run is calculated as ampere-hours and
included in Appendix E. A summary of the total current supplied during each emission test run
is presented in Table 2.2.
2-2
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Table 2.2
TOTAL CURRENT SUPPLIED DURING
EACH EMISSION TEST RUN
Run No.
1
2
3
Average
Total current,
ampere-hours
17,640
17,750
16,850
17,410
Trivalent chromium plating solutions contain wetting agents. The presence of the wetting agent
in the bath results in a lower bath surface tension. The surface tension of a bath in the absence
of a wetting agent is approximately 72 dynes per centimeter. Based on data on hexavalent
chromium baths, the addition of a wetting agent to the plating bath will reduce the surface
tension of the bath below 40 dynes/cm. The lower bath surface tension enhances the ability of
the bath to provide a more uniform plate thickness over the entire surface area of the part. In
addition, the lower surface tension also minimizes the potential of emissions from the bath by
reducing the tendency of the gas bubbles generated at the electrodes to burst at the surface of
the solution to form a fine mist. During the emission tests, no visible emissions from the tank
were observed.
Prior to testing, a total of 7.6 L (2.0 gals) of Regulator™ was manually added to the plating
tank. Regulator™ is the component of the plating solution that contains a wetting agent. The
surface tension of the plating solution was monitored over the course of each test run. Plating
solution samples were taken from the plating bath at the beginning, midpoint, and end of each
test run. The surface tension of each of these samples was measured with a stalagmometer and
recorded. The measured surface tensions of each plating solution sample are included in
Appendix E. The average surface tension measurements during each test run are shown in Table
2.3. As shown in Table 2.3, the addition of a wetting agent to the trivalent chromium bath did
not reduce the surface tension below 40 dynes per centimeter.
The vendor of the trivalent chromium solution, who was on site during the emission test, was
consulted to determine if these surface tension levels were representative of the levels typically
maintained in trivalent chromium baths. Mr. Dennis Masarik, M&T/Harshaw, responded that
the surface tension of the bath is not one of the recommended monitoring parameters for the
bath, therefore, he could not judge the representativeness of the surface tension measurements.
However, Mr. Masarik did state that the amount of Regulator ™ in the bath was representative
of the amounts used in all their trivalent chromium plating baths.
2-3
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Table 2.3
SURFACE TENSION MEASUREMENTS
DURING EACH EMISSION TEST RUN
Run No.
1
2
3
Average
Surface tension,
dynes/cm1 b
43
47
53
48
"Based on an average of three samples. For each test run, sample
was collected prior to the run, at the midpoint of the run, and at the
end of the run.
'Surface tension of the plating solution was determined from a
stalagmometer.
In addition to the manual addition of Regulator™ to the bath, maintenance additions of
Regulator™ were supplied to the bath by an automatic controller connected to the tank. The
controller supplied additions of Regulator™ based on the amount of current or ampere-hours
supplied to the tank. A second manual addition of 3.8 L (1.0 gal) was made at the beginning
of the second test run when the surface tension of the solution was starting to increase.
Because of the higher than expected surface tension readings, a laboratory test was designed to
determine the effect of wetting agents to the solution. A sample of the plating solution was
taken from the tank and spiked with varying amounts of Regulator™ and then the surface
tension of the sample was measured. Based on these lab tests, it was concluded that further
additions of Regulator™ would not significantly reduce the surface tension of the bath.
Therefore, following the manual addition at the beginning of the second run, no further manual
additions of Regulator™ were made and the maintenance additions of the wetting agent were
controlled by the automatic controller on the tank.
All of the emission test runs were interrupted briefly to change test ports. No process
interruptions occurred during sampling. Based on the information supplied by the vendor and
the results of the laboratory tests, it is believed that the emission test results are representative
of emissions from a trivalent chromium plating operation.
2-4
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Section 3.0 SUMMARY AND DISCUSSION OF RESULTS
3.1 SAMPLING
Samples were collected from a straight section of duct work between the non-functional scrubber
and the location where the exhaust duct penetrates the roof. The test runs were performed when
the plating tank solution was homogeneously mixed with a wetting agent and other plating
process conditions were normal. Each test run lasted approximately three (3) hours and
isokinetic sampling conditioned were maintained throughout each testing period. In addition to
the mass emission samples, a grab sample of the operating plating bath solution was collected
during each of the three (3) test runs.
3.2 SUMMARY OF STACK GAS CONDITIONS
Stack gas conditions during each of the Method 13-B runs are summarized in Table 3-1. The
stack gas velocity during the runs averaged 32.34 feet per second (fps), with an average gas
temperature of 84°F and an average moisture content of 2.59 percent. Volumetric flow rates
averaged 10,583 cubic feet per minute (acfm) and 9,830 dry standard cubic feet per minute
(dscfm).
Since the stack gas was essentially ambient air, a dry molecular weight of 28.95 Ib/lb mole was
used for all calculations. Variations in isokinetic sampling rates were within acceptable limits
for all sampling runs.
3.3 CHROMIUM RESULTS
Chromium samples were recovered on-site, after completion of each sampling run. The samples
were labeled and a chain-of-custody was prepared. The samples were delivered in a cooler to
Research Triangle Institute Laboratory (RTIL), Research Triangle Park, North Carolina for
chemical analysis.
Results of all sample analyses are included in Table 3-2. Inductively Coupled Plasma (ICP) was
used to analyze samples for total chromium (Cr-T). Chromium -VI (Cr-VI) concentrations in
the samples were quantified using lon-Chromatography with Post Column Reactor (ICPCR).
Plating tank solution samples were analyzed for Cr-T. Samples collected using Method 13-B
were analyzed for both Cr-T and Cr-VI. The total mass values for trivalent chromium (Cr-HI)
was determined by subtracting the total mass values of Cr-VI from Cr-T. The total micrograms
3-1
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Table 3.1
SUMMARY OF STACK CONDITIONS DURING
SAMPLE COLLECTION
Stack Conditions
Sampling time (min)
Velocity (fps)
Stack Temperature (°F)
Flow Rate (acfm)
Flow Rate (dscfm)
Moisture (96)
Isokinetic Variation (%)
Run#l
192
28.7999
77
9,426.08
8,788.28
2.5541
95.2410
Run #2
192
34.1182
84
11,166.74
10,410.62
2.6134
91.6384
Run #3
192
34.0884
90
11,156.98
10,290.72
2.6047
90.6154
Averages
192
32.34
84
10,583
9,830
2.59
92.50
fps = Feet per second
•cfm = Actual cubic feet per minute
dscfm = Dry standard cubic feet per minutes at 68°F and 29.92" Hg
of chromium collected and the dry standard cubic feet of volume sampled using Method 13-B were utilized to
determine emission concentrations (mg/dscm). Emission concentrations and the volumetric flow rates (dscfm)
were computed and used to calculate mass emission rates.
The average of emission concentrations and mass emission rates for Cr-T, Cr-III and Cr-VI are tabulated in
Table 3.3. Table 3.4 indicates the sample train and reagent blanks were less than the detectable concentration.
Table 3.5 provides Cr-T concentrations found in the plating bath solution samples. This plating bath solution
contained a wetting agent used to reduce air emissions.
3.4 RESULTS DISCUSSION
The data included in Table 3.2 indicates some variation in chromium mass emissions during test runs when the
plating bath solution contained wetting agent. Since no emission samples were collected without the wetting
agent in the bath, its effect on emission reductions cannot be evaluated.
The data also indicated that nearly 87% of mass emissions from the plating tank are Cr-III and 13% of mass
emissions are Cr-VI. The total chromium concentration of the plating bath solution remained essentially
constant during all test runs.
3-2
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Table 3.2
ANALYTICAL RESULTS OF CHROMIUM MASS
EMISSION TESTING
TOTAL CHROMIUM
Total Mass Collected, (/ig)a
Emission Concentration
(grain/dscf)b
Emission Concentration (mg/dscm)c
Mass Emission Rate (lt>/hr)d
Mass Emission Rate (Kg/hr)°
Run#l
36.90
5.63 x 10*
0.0129
4.240 x 104
1.923 x 1O4
Run #2
156.00
2.09 x lO"5
0.0478
1.863 x 10*
8.450 x 1O4
Run #3
61.10
8.37 x 10*
0.0191
7.379 x 104
3.347 x lO"4
Average
84.67
1.16x ia5
0.0266
l.OOSx 10-3
4.573 x lO"4
HEXAVALENT CHROMIUM
Total Mass Collected, (^ig)a
Emission Concentration
(grain/dscf)k
Emission Concentration (mg/dscm)c
Mass Emission Rate (lt>/hr)d
Mass Emission rate (Kg/hr)e
Run#l
10.20
1.56x 10*
0.0036
1.172x 104
5.316 x lO"3
Run #2
14.90
1.99x 10*
0.0046
1.779 x 10-4
8.071 x ia5
Run #3
8.01
l.lOx 10*
0.0025
9.673 x 10-3
4.388 x lO"5
Average
11.04
1.55x lO'6
0.0036
1.306 x 10-4
5.925 x 10'3
TRTVALENT CHROMIUM*
Total Mass Collected, (/*g)a
Emission Concentration
(grain/dscf)b
Emission Concentration (mg/dscm)c
Mass Emission Rate (lb/hr)d
Mass Emission Rate (Kg/hr)'
Run#l
26.70
4.07 x 10*
0.0093
3.068 x 104
1.392x Ifr4
Run #2
141.10
1.89x 10"s
0.0432
1.685x lO"3
7.643 x 104
Run #3
53.09
7.27 x 10*
0.0166
6.411 x 104
2.908 x 104
Average
73.63
l.OOx 10s
0.0230
8.776 x 10"4
3.981 x 10-4
* Grains per Dry Standard Cubic feet per minute at 68°F and 29.92" Hg
* Milligrams per Dry Standard Cubic Meter
' Pounds per hour
* Kilograms per hour
* Cr-ID Concentration = Cr-T - Cr-VI
3-3
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Table 3.3
AVERAGE* EMISSION CONCENTRATIONS
AND MASS EMISSION RATES
Analyte
Total Chromium*
Chromium - in*
Chromium - V^
Emission Concentrations
(mg/dscm)
0.0266
0.0230
0.0036
Mass Emission Rates
(Ib/hr)
1.008 x lO'3
8.776 x 10"
1.306x 10-4
Table 3.4
SAMPLE TRAIN AND REAGENT BLANKS
Sample I.D.
Sample Train
Reagent Blank
Test Run No.
Blank
Blank
Total Chromium (fig)
NDC <0.62
NDC < 0.736
* Represents average of three (3) test runs when plating bath contained a wetting agent,
Regulator™
+ Analysis method, Inductively Coupled Plasma (ICP)
a Cr-m = Cr-T - Cr-VI
b Analysis method, lon-Chromatography with Post Column Reactor (ICPCR)
c Non-detectable - less than 0.006
3-4
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Table 3.5
TOTAL CHROMIUM CONCENTRATION* OF PLATING
BATH SOLUTIONS
SAMPLE I.D.
Runl
Run 2
Run 3
TEST RUN NO.
1
2
3
CONCENTRATION (jig/ml)
18,850
18,100
18,100
Average 18,350
* Inductively Coupled Plasma, analysis method
3-5
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Section 4.0 SAMPLING LOCATIONS AND TEST METHODS
4.1 SAMPLING LOCATIONS
Two types of samples were collected during field testing at the True Temper site. Samples of
both the plating tank liquid and gas samples of the plating tank exhaust were collected.
4.1.1 PLATING TANK
Plating tank solution containing the wetting agent, Regulator™, was sampled during the test run.
Grab samples were collected in pre-cleaned plastic jars and stored for later chromium analysis.
4.1.2 STACK SAMPLES
Gaseous samples were collected from the stack in accordance with EPA approved methods.
Sampling was conducted in a straight section of the duct work located between the non-functional
scrubber and the exhaust duct roof penetration. The duct work at this location measured 31.625
inches in diameter. Two (2) test ports were cut into the duct work at a 90° angle from each
other. Twelve (12) points were sampled at each of the two ports, for a total of 24 sample
points. Figure 4.1 shows a schematic of the Exhaust Duct and Stack Dimensions.
4.1.2.1 TEST METHODS
The test methods used during the sampling were in accordance with U.S. EPA Methods 1, 2,
4 and a modification of the Method 13-B. Method 13-B, designed for total fluoride emission
testing, was used for the chromium paniculate collection.
4.1.2.1.1 TRAVERSE POINTS
U.S. EPA Method 1 "Sample and Velocity Traverses for Stationary Sources" was used to
determine the location of traverse points. A basic cyclonic flow check was made which
indicated that cyclonic flow conditions did not exist at the sampling location. Figure 4.2 shows
Traverse Point Locations.
4.1.2.1.2 STACK GAS VELOCITY
U.S. EPA Method 2 "Determination of Stack Gas Velocity and Volumetric Flow Rate (Type
S Pilot Tube)" was used to measure the stack gas velocity and temperature at each test point.
Type "K" thermocouples were affixed to S-type pilot tubes having an assigned coefficient of
0.84. The velocity pressure was measured on an inclined manometer. The volumetric flow
rate was calculated from Ihe slack gas velocity and Ihe slack cross-sectional area. Since Ihis
source was an ambienl source, a dry molecular weighl of 28.95 Ib/lb mole was used.
4-1
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31.625" D.
NON - FUNCTIONING SCRUBBER
FIGURE 4-1
SCHEMATIC OF OUTLET DUCT AND STACK DIMENSIONS
4-2
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FIGURE 4-2
OUTLET TRAVERSE POINT LOCATIONS
4-3
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4.1.2.1.3 STACK GAS MOISTURE
U.S. EPA Method 4 "Determination of Moisture Content in Stack Gas" was used to determine
the stack gas moisture content. These moisture determinations were made during the modified
Method 13-B test runs.
4.1.2.1.4 METHOD 13-B SAMPLING TRAIN
A modification of U.S. EPA Method 13-B, Determination of Total Fluoride Emissions from
Stationary Sources, was used to determine total and hexavalent chromium concentrations in the
stack gases. The sampling train consisted of a "Pyrex" nozzle and probe connected to a series
of four impingers. A schematic of the Method 13-B train used at the test site is presented in
Figure 4.3.
Isokinetic samples were collected during each test run. During sampling, stack gases were
pulled through the nozzle, past the probe and then through four impingers, where the chromium
was collected and retained. The contents of the impingers are given below.
1. The first, impinger contained 100 ml of 0. IN NaOH.
2. The second impinger contained 100 ml of 0. IN NaOH.
3. The third impinger was empty.
4. The fourth impinger contained a weighted amount of silica gel (200 grams).
The remainder of the train consisted of vacuum pump, dry gas meter, calibrated orifice and
related temperature and pressure measuring equipment. Figure 4.3 shows a Schematic of the
Modified U.S. EPA Method 13-B Sampling Train.
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CONTAINER I.D.
Impinger #1
Impinger #2
Impinger #3
Impinger #4
CONTAINER CONTENT
Modified Greenburg-Smith - 100 ml
ofO.lNNaOH
Standard Greenburg-Smith - 100 ml
Modified Greenburg-Smith - Empty
Modified Greenburg - Smith 200
grams of Silica Gel
HECX VALVE
VACUUM GAUGE
TIGHT mur
Figure 4.3 SCHEMATIC OF THE MODIFIED U.S. EPA METHOD 13-B
SAMPLING TRAIN
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4.2 SAMPLE COLLECTIONS
Plastic jars were used to collect liquid samples from the plating tank solution. After collection,
each sample was labeled with date, run number and sample location.
Stack samples of Method 13-B were recovered immediately after each test run. The impingers
were weighed to determine the moisture (water) collected during the run. The contents of the
first three impingers were transferred to a Mason Jar, along with the rinseate of the connecting
glassware. The nozzle and probe liner were washed with 0. IN NaOH, and the washings were
added to the Mason Jar. Finally the bottle was labeled, and dated. Silica gel from the fourth
impinger was weighed to determine weight gain from stack gas moisture absorption, labeled and
stored in coolers. Field blank samples were also collected and analyzed for any chromium
cross-contamination.
All samples were placed in a cooler and transferred to the Research Triangle Institute Laboratory
(RTIL), Research Triangle Park, North Carolina for:
• Total chromium (Cr-T) determinations using Inductively Coupled Plasma (ICP)
• Chromium-VI (Cr-VI) determinations using lon-Chromatography with Post Column
Reactor (ICPCR)
Plating tank solution samples were analyzed for Cr-T. Samples collected using Method 13-B
were analyzed for both Cr-T and Cr-VI. The reported Cr-IU concentrations were calculated by
subtracting the values of Cr-VI from Cr-T.
4.3 SAMPLE ANALYSIS METHODS
The samples collected during the Modified 13-B testing were analyzed using one of two
analytical techniques. The techniques were: 1) Inductively Coupled Plasma (ICP); and 2) Ion
Chromatography with a Post Column Reactor (ICPRC). Each analytical technique is briefly
described below.
4.3.1 INDUCTIVELY COUPLED PLASMA (ICP)
ICP is a simple and fast technique used for analysis of major and minor trace elements in
samples of all kinds and matrices. It has a detection limit of 1 part per billion (ppb) or less.
Samples are aspirated into a high temperature argon plasma. The argon plasma causes molecular
breakdown, atomization and/or ionization and excitation of metals in solution. The excited
atoms release characteristic radiation which is detected by a photomultiplier tube (PMT). The
PMT produces an electrical current which is transformed into concentration values by reference
to a standard.
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4.3.2. ION-CHROMATOGRAPHY WITH POST COLUMN REACTOR (ICPCR)
ICPCR can be used to determine hexavalent chromium (Cr-VI). Hexavalent chromium is
chromatographed as CrO4~2 on an ion column. After separation, the Cr-VI diphenylcarbazide
complex is quantified by visible spectrometry at 520 nm. ICPCR has a sub-part per billion
detection limit. Typically, ICPCR instrumentation consists of: 1) an ion column; 2) a visible
spectrophotometer detector; and 3) an integrator.
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Section 5.0
QUALITY ASSURANCE PROCEDURES AND
SUMMARY OF FIELD ACTIVITIES
5.1 QUALITY ASSURANCE
The equipment used in this test program was calibrated as specified in each respective method.
Pre- and post- test equipment calibration data are presented in Appendix H. All field data were
recorded on standard data sheets which are included in Appendix B. All analytical data are
maintained in a secure file at AST.
Quality Assurance (QA) of the sample analyses included the preparation of a standard curve and
reagent solutions on a daily basis. Sample QA also included analyzing reagent blanks and one
standard or duplicate sample with each set of samples being analyzed.
5.2 SUMMARY OF FIELD ACTIVITIES
6/07/92 Traveled to Seneca, South Carolina
6/08/92 Inventoried equipment and prepared site
Completed site set-up, performed preliminary velocity traverses,
Modified process operation to meet test condition
requirements
Performed velocity traverse and initial calculations
6/09/92 Completed one, three-hour measurement run, Run #1 and recovered
emission samples
6/10/92 Completed two, three-hour measurement runs, Run #2 and Run #3 and
recovered Run #2 and Run #3 emission samples
6/11/92 Packed and delivered samples for analyses to Research Triangle
Institute, restored site, packed and shipped equipment
RETURNED TO ATLANTA
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