Page iPage ii ACKNOWLEDGEMENTS

The project leader was Shobna Sahni with ARB Stationary Source Division. The sampling team was led by David Todd and included Don Ridgley and Ron Barros with the ARB Monitoring and Laboratory Division (MLD). Betsy Ronsee and Roxana W alker with MLD Northern Laboratory Branch conducted the laboratory analysis. Dominick Nole and Paramo Hernandez of Alta Plating and Anodizing provided plating bath surface tension and chromium content analysis.

This report pr esents results based on samples collected and analyzed by the Air Resources Board (ARB) staff using ARB test methods. The results have been reviewed by the staff and are believed to be accurate within the limits of the methods. However, data may have been affected by variables that were not known to staff during sampling

and review.Page iii California Environmental Protection Agency

AIR RESOURCES BOARD Monitoring and Laboratory Division

TABLE OF CONTENTS

I. INTRODUCTION

.................................................................................................. 1

II. PROCESS DESC RIPTION................................................................................... 1

III. SHERM'S PLATING SOURCE TEST

................................................................... 2

IV. TEST METHODS

................................................................................................ . 4

V. QUALITY ASSURANCE / QUALITY CONTROL

.................................................. 6

VI. TEST RESULTS

................................................................................................... 8

TABLES AND FIGURES

FIGURE II -1 Front View of Decorative Chromium Plating Tank

................................... 2

FIGURE III

- 1 Capture Hood A ssembly

.......................................................................... 3

TABLE VI

- 1. ARB Method 425 Test Results

................................................................ 9

TABLE VI

- 2. Indoor Ambient Cr(VI) Data

................................................................... 10

APPENDICES

A. Individual Test Run Summaries and Results

B. Field Data Sheets

C. ARB Laboratory Results

D. Capture Hood Drawing

E. Sample of Chain of Custody Sheet and Chain of Custody Log

F. Test Run Data Provided by ARB/SSD

G. Recovery Moisture Content Data SheetPage 1 California Environmental Protection Agency

AIR RESOURCES BOARD Monitoring and Laboratory Division



### Total and Hexavalent Chromium Emissions from

She rm's Custom Plating Decorative Chromium Plating Tank

I. INTRODUCTION

At the request of the Air Resources Board (ARB) Stationary Source Division (SSD), staff of the Monitoring and Laboratory Division (MLD) performed emissions testing of a decorative chrome electroplating tank operated by Sherm's Custom Plating located at 2140 Acoma Street in Sacramento, California. Emissions tests for total and hexavalent chromium were conducted from March 8 through March 11, 2004.

II. PROCESS DESCRIPTION

Sherm's Custom Plating performs decorative chromium plating on a variety of small parts. Sherm’s decorative chrome plating tank has a capacity of 607 gallons and is 95 inches long, 41 inches wide, and 36 inches deep (See Figure II

- 1). Freeboard depth averaged 4.1 inches throughout the emissions testing. The plating tank is equipped with its own adjustable current and voltage rectifier. Plating bath temperature was
maintained at approximately 110 **°** F during plating operations. SSD staff periodically collected amperage, bath temperature, and amp

- hour readings for the plating tank during the source test (see Appendix F).

Plating tank emissions are controlled with a chemical fume suppressant (Protab 1000 manufactured by MacDermid) that decreases the bath surface tension reducing the escape energy of the chromic acid mist generated during plating operations. No additional emissions controls are used (i.e., tank ventilating system). Emissions from the plating tank vent to the work area. A large ventilation fan on a distant wall pulls the air outside the facility.Page 2 Figure II -1 Front View of Decorative Chromium Plating Tank

III. SHERM'S CUSTOM PLATING CHROMIUM SOURCE TEST

The source test consisted of three sample runs collected from Sherm's Custom Plating’s

decorat ive chrome plating tank between March 9

- 11, 2004. Set up and preliminary equipment checks took place the day before. The average plating solution surface tension during the test runs was 36.7 dynes/cm which is normal for this facility.

ARB Method 425 was used to determine hexavalent and total chromium emissions collected during the source tests. Sample runs one and two were continuously sampled for 360 minutes, whereas, sample run three was reduced to 312 minutes. During sampling, production or “dummy” parts were plated in the tank. The mix of production and dummy parts was necessary to obtain a target of about 400 ampere

- hours per run. Sherms prepared each dummy part for plating in the same manner as production parts, and repeated the preparation each time the part reentered the plating tank.

ARB staff fabricated a ventilation system to direct plating tank emissions to the source sampling area (see Figure III

- 1). The system consisted of a capture hood with an open bottom, plastic

- sheeted top and sides, and an opened front with minor additions of plastic strips to contain the emissions. A 12

- inch diameter flexible exhaust duct, ported on top of the hood, directed emissions from the tank to a sample collection area and then vented the exhaust inside the facility fifteen feet beyond the sampling area. The fabricated ventilation system was designed to allow droplets to return to the tank but yet collect fumes floating above it. (Note: As per South Coast AQMD procedures for plating tanks and fume suppre ssant certification, the average "lift" velocity between the tank and the ventilation system should be less than 50 feet/minute.). PQ

- 100 Ambient Air Sampler

Location

Chromium Plating TankPage 3 The capture hood was suspended from the ceiling rafters which allowed relatively uninhibited access for the workers. Its top dimensions were slightly smaller than the tank top opening. The backside of the tank was totally enclosed by either the hood's plastic sheeting or the tank's plastic splash panel. The right side was enclosed the same way except for a 10

- inch high (appr oximately 2 square feet) opening at the bottom in the tank's plastic splash panel. One third of the left side splash panel (approximately 3.6 square feet) was opened to allow easy access to the adjacent rinse tank. The front of the hood was totally opened for access except for some draped plastic sheeting in the upper right corner needed to contain air currents detected during smoke tests (see Appendix D, Hood Drawing).

The 12

- inch diameter PVC flexible ducting had a 27

- inch inside radius arc (180o) from the top of the hood to the top of the vertical 67

- inch PVC sampling duct. The sampling duct rested on top of a fan box with a variable motor controller. Method 425 samples

were collected from two 3

- inch diameter holes cut 90 degrees apart into the samp ling duct, 18 inches (11⁄2 diameter) above the fan box and 49 inches (4 diameter) below the flexible/rigid duct connection. The emissions are directed out of the fan into the inside of the building. Inside air is removed by the facility's ventilation syste m.

Figure III -1 Rear View of Fabricated ARB Capture Hood Assembly (Shown before installation at Sherm's Custom Plating)

Hood (Rear View) Sample Ports

F an &

Controller ExhaustPage 4 The capture hood was designed to capture plating tank emissions having less than 50 feet per minute of vertical lift above the plating tank. Fifty feet per minute under the hood equals 1,367 cubic feet per minute (cfm) at the sample collection point. The actual average three

- day source test flow at the collection point was 957cfm. Smoke tests were conducted during each test run to ensure no emissions leaked from the hood. The smoke did not contain any chromium or other compounds that would interfere with chromium sampling and analysis.

Indoor ambient samples were collected concurrently with the three source test runs. Samples were collected on sodium bicarbonate

- impregnated filters. The BGI, Inc. PQ

100 ambient sampler was set on top of the rectifier next to the decorative chrome tank. Indoor ambient samples were analyzed for hexavalent chromium only. One indoor ambient sample was collected with each source test stack sample. Another three indoor ambient samples were collected March 17

- 19, 2004, after the source sampling was completed and the capture hood removed.

IV. TEST METHODS

A. Source Sam pling Procedure

Samples were collected and recovered by the ARB Stationary Source Testing Branch. Stack and duct flows were determined by ARB Stationary Source Test Method 1 (velocity traverse), Method 2 (stack velocity and flow rate), Method 3 (stack ga s dry molecular weight), and Method 4 (moisture content). For Method 3, atmospheric concentrations of carbon dioxide, nitrogen, and oxygen were used to determine dry molecular weight.

Hexavalent and total chromium samples were collected isokineticaly in accordance with ARB draft Method 425, “Determination of Total Chromium and Hexavalent Chromium Emissions from Stationary Sources. ARB Method 425 was originally adopted January 22, 1987, and amended August 27, 2002. ARB draft Method 425 incorporates sev eral approved modifications from the current amended version. These include the use of unheated sample lines and probes, the use of 0.1 N sodium bicarbonate impinger solution in place of 0.1 N sodium hydroxide solution, and deletion of the sample train filter and filter heater.

The chromium sampling train configuration consisted of the following:

**•** a glass 3/8

- inch nozzle; a Teflon **** union, a 48 inch glass

- lined stainless steel probe (with attached pitot tube and thermocouple);

**•** a ten

- foot Teflon **** line fro m the probe to the first of two Greenburg

- Smith impingers, each containing 100 milliliters of 0.1 normal (N) sodium
bicarbonate solution;Page 5 **•** an empty impinger;

**•** a silica gel holder;

**•** a 50 foot umbilical line; and

**•** a sampling console consisting of a vacuum pump, dry gas meter, calibrated orifice connected to an inclined oil manometer, and additional monitors and controls for collecting a sample isokinetically.

Each of the three days consisted of either 360 minute test runs (test runs 1 and 2) or

a 312 minute test run (test run 3) using a single sample train. An additional blank impinger train was assembled adjacent to test run 2's impinger train (QA control).

In accordance with Method 1, the sampling location required 24 traverse points, 12 sampling points on each diagonal ninety degrees apart.

In accordance with Method 2, thermocouples and Type S pitot tubes bundled with the sampling probes were used to determine stack velocity. The weight of the impinger solutions and silica gel were recorded before and after each test to obtain the gas stack moisture content as required by Method 4. In addition, stack temperature, ambient temperature, and barometric pressure were measured and recorded during each test. Leak checks were performed on each sample train an d pitot tube assembly before and after each sample collection.

After sampling, rinses of the sampling train nozzle, probe and transfer line, as well as the catch from the impingers, were recovered into three 500

- ml glass sample jars as follows (all sample jars were pre

- cleaned and tested to ensure the absence of chromium prior to the source test):

**•** Container 1
– rinses from the nozzle, sample probe, and transfer line;

**•** Container 2
– first impinger catch; and

**•** Container 3
– second and third impinger catch.

The pH of the sodium bicarbonate solution used for the probe rinse and impingers

was maintained at **≥** 8.0. Additionally, the impinger solution was chilled with ice to

4 **°** C (39 **°** F) or less during sample collection. All samples were also chilled with ice

and refrigerated to 4 **°** C (39 **°** F) or less during transport and storage prior to analysis to minimize the conversion of hexavalent chromium to trivalent chromium. During sample recovery prior to analysis, disposable vinyl gloves were worn to help prevent

contami nation. At the conclusion of each sampling day, staff transported the collected samples to the laboratory for analyses.

The current supplied by the rectifier was monitored and recorded by SSD staff during the source test runs. SSD also recorded tank temperature and totalizer amp

-Page 6 hours. Additionally, plating bath samples were collected and analyzed by Alta Plating to determine plating bath surface tension and chromic acid content.

B. Indoor Ambient Sampling

Indoor ambient samples were collected on 47 m m filters using a PQ

- 100 ambient sampler. The filters were specially treated with sodium bicarbonate to preserve the sample for hexavalent chromium analysis. Indoor ambient samples were collected in parallel with the plating source test. Because the capture hood interfered with normal plating tank emissions, three additional samples were collected after the hood was removed. After sampling, the filters were placed back into their storage cassettes using sterile gloves and returned to the laboratory for analysis.

C. Analytical Procedures

The plating tank stack emissions were analyzed for both hexavalent and total chromium. The indoor filters were extracted into a solution and analyzed for hexavalent chromium only using the same procedure as the stack sample. Laboratory analyses for hexavalent and total chromium of the collected samples was performed by ARB’s Northern Laboratory Branch. Hexavalent chromium (also known as hex chrome, Cr (VI), or Cr +6 ) was measured using ion chromatography (IC) in accord ance with ARB standard operating procedure (SOP), MLD039. The limit of detection (LOD) of the analytical procedure for hexavalent chromium is 0.2 nanograms per milliliter (ng/ml). Total chromium was determined using an atomic absorption/ graphite furnace (GFAA) technique. To deal with the high carbonate fixative concentrations, staff used a variation of ARB SOP MLD005. The LOD of the analytical procedure for total chromium is 1.0 ng/ml.

V. QUALITY ASSURANCE / QUALITY CONTROL

To ensure that data collected are consistent, relevant, and defensible, appropriate field and laboratory Quality Assurance (QA) procedures were followed throughout the source test. A detailed explanation of the ARB’s standard field and laboratory QA procedures

are contained in ARB Quality Assurance manuals, Stationary Source Test Methods, and laboratory SOPs.

As required by ARB Method 425, all surfaces that came into contact with a sample were either glass or Teflon **** and were pre

- cleaned using the following procedure:

**•** the glassware was first washed with detergent;

**•** soaked with a 10% solution of nitric acid for several hours;

**•** flushed with liberal amounts of tap water;

**•** rinsed with de

- ionized water; and

**•** rinsed with 0.1 N sodium bicarbonate solution.Page 7 To ensure that the sampling equipment was clean and free of chromium contamination, a sample of the final sodium bicarbonate rinse was analyzed for total hexavalent

chromium (Cr). If any Cr was detected in the final rinse, all sampling equipment were

re

- cleaned until a sample of the final rinse contained no detectable Cr. In addition, extra

pre

- cleaned equipment was deployed to ensure that no equipment needed to be re

cleaned or re

- used during field sampling.

Baseline and post source tests were performed on the ARB capture hood and ducting in

the 1900 14 th Street warehouse before and after sampling at Sherm's. The purpose for these tests was to ensure no chrome contamination from the hood and ducting. The baseline test was conducted February 6, 2004. Results indicated less th an the LOD for both total and hexavelent chromium. The post

- test was conducted March 17, 2004. Small amounts (right at the LOD) of hexavalent chromium were detected in the first impinger rinse with the probe rinse slightly higher (see Appendix C, ARB Lab oratory Results).

The sampling console used during the source test was calibrated December 23, 2003. A post

- test calibration was performed March 23, 2004. The Type S pitot tubes used for stack velocity determinations met the required specifications for a baseline coefficient of 0.84 as specified in ARB Method 2. The console assembly, including pitot tubes, passed leak checks before and after each velocity determination. In addition, all sampling train assemblies passed leak checks before and after each test.

Prior to deploying to the field, MLD laboratory analysis verified chromium content in the sodium bicarbonate solution (used for recovery and impinger catches) was below the LOD. Although planned, staff did not collect and submit to the laboratory a blank sample of the sodium bicarbonate solution used for sample recovery during the week of testing. However, an analysis of the blank collected in parallel with test run 2 and the laboratory analysis of the second and third impinger catch for all tests was below the LOD which establishes the purity of the sodium bicarbonate solution.

All test samples were collected using an iced impinger set. After recovery, samples
were stored on ice to maintain their temperature at or below 4 **°** C (39 **°** F) as require d by ARB Method 425. Collected and recovered samples remained on ice while on site and during transport to the laboratory for analyses. Staff of the Northern Laboratory Branch
ensured that the samples were maintained at or below 4 **°** C (39 **°** F) while awaiti ng analysis.

During sample collection and transport, the pH of the sodium bicarbonate solution used for the probe rinse and impinger charging was maintained at **≥** 8.0 as required by Method 425. This is necessary to ensure that any collected hexavalent chr omium is not reduced to trivalent chromium. The pH of the impinger solutions was checked before sampling, after sample recovery, and during transfer to the laboratory.Page 8 Chain of custody was maintained for all collected samples. A chain of custody sheet was prepared for each sample train and a copy of the sheet for run number one is included in Appendix E as an example.

VI. TEST RESULTS

Results of the ARB Method 425 source tests for the Sherm's Custom Plating decorative chromium plating tank are present ed in Table VI

- I. The measured emission rates ranged from 0.046 to 0.053 milligrams per amp

- hour (mg/amp

- hr) for total chromium and 0.046 to 0.056 mg/amp

- hr for hexavalent chromium.

Indoor ambient results are presented in Tables VI

- 2a and VI

- 2b. Copies of run sheets are in Appendix A. Field data sheets are in Appendix B. Laboratory results are presented in Appendix C. Additional plating tank information is in Appendix F.Page 9 Table VI

- 1 Sherm's Custom Plating Decorative Chromium Plating Tank Results Sa mpling

Dates

-- March 9, 10, & 11, 2004 Sampling Location Chromium Plating tank Chromium Plating tank Chromium Plating tank Sample Date March 9, 2004 March 10, 2004 March 11, 2004 Sample Number S

- 1 S

- 2 S

- 3 Plating Tank Data

Totalizer (amp

- hours ) 415 459 425 Production Rate (amp

- hrs/hr) 69.2 76.5 81.7 Freeboard (inches to overflow)* 5.0

- 4.9 3.0

- 3.5 4.0

- 4.0 Chromic Acid Conc. (oz/gal) 34.2 32.6 Not Done Temperature (oF) 109.5 109.8 109.8 Surface Tension (dynes/cm)* 35.6

- 35.9 37.5

- 35 .9 37.8

- 37.9

Stack Data

Stack Temp. (oF) 75 75 72 Velocity (ft/sec) 19.49 22.19 20.33 Static Pressure ("H 2 O)

- 0.23

- 0.29

- 0.19 Stack Area (sq. ft.) 0.785 0.785 0.785 Flow Rate (DSCFM) 904 1030 943 Moisture (% of v/v) 1.1 0.6 1.0 Samp ling Data

Sampling Time (minutes) 360 360 312 Sampling Volume (DSCF) 330.08 360.50 295.40 Chromium Data (ng/sample)

Total Chromium 19,440 22,600 22,730

Hexavalent Chromium 19,413 21,490 23,693 Isokinetic Ratio(%) 103.9 99.6 102.9

EMISSIONS

Concentration (ng/DSCF)

Total Chromium 58.89 62.69 76.95

Hexavalent Chromium 58.81 59.61 80.21 Emission Rate (mg/hr)

Total Chromium 3.19 3.87 4.35

Hexavalent Chromium 3.19 3.68 4.54

Emission Factors (mg/amp

- hr) **

Total Chromium 0.046 0.051 0.053

Hexavalent Chromium 0.046 0.048 0.056

DSCF means dry standard cubic feet at 68oF and 29.92" Hg. DSCFM means dry standard cubic feet per

minute. *Paired values separated by a hyphen are "start

- end" of day measurements.

**Emission Factor = Emission rate/Production rate.Page 10 Table VI

- 2a Sherm's Custom Plating Indoor (PQ

- 100) Ambient Hexavalent Chromium Sampling Results

Ambient sampling during source testing with the hood in place

Sample Number: S1

- A S2

- A S3

- A

Sample Date: 03/09/2004 03/10/2004 03/11/2004

Sampling Time (minutes) 300 335 300*

Volume Collected (liters) 3000 3350 3000

Cr (VI) Collected (nanograms) 200 130 190

Indoor Ambient Concentration (ng/m 3 ) 67 39 65

* Note: Difference between the annotated start and stop time does not equal 300 minutes. It is assumed the start time was written incorrectly since the sampling interval is read directly from the PQ

- 100.

Table VI

- 2b Sherm's Custom Plating Indoor (PQ

- 100) Ambient Hexavalent Chromium Samp ling Results

Ambient sampling after source testing with the hood removed

Sample Number: S11

- A S12

- A S13

- A

Sample Date: 03/19/2004 03/20/2004 03/21/2004

Sampling Time (minutes) 393 417 340

Volume Collected (liters) 3930 4170 3400

Cr (VI) C ollected (nanograms) 390 870 410

Indoor Ambient Concentration (ng/m 3 ) 100 210 120