TECHNICAL MEMORANDUM

TO: Jodi Howard, US EPA/OAQPS/SPPD/RCG

FROM: Eastern Research Group, Inc.

DATE: February 8, 2012
SUBJECT: Updated Information Collection and Additional Data R eceived for the

Polyvinyl Chloride and Copolymers (PVC) Production Source Cat egory

1.0 Introduction The U.S. Environmental Protection Agency (EPA), under sect ion 112 of the Clean Air Act (CAA), is required to establish National Emissions Standa rds for Hazardous Air Pollutants (NESHAP) emitted from polyvinyl chloride and copolymer (PV C) production facilities. The complete set of air pollutants (HAP) is listed under CAA section 112(b). This memorandum describes the data collection and data preparation complet ed by EPA and ERG in an effort to develop NESHAP standards for the PVC production source cat egory. This memorandum also describes additional data received by EPA during and after the public comment period for the May 20, 2011 proposed PVC production rule. Section 2.0 describes the data collection steps and Section 3.0 describes the data preparation and standardizati on completed in order to perform subsequent analyses.

2.0 Data Collection To collect data on PVC production, EPA reviewed previously collected information, current literature, and data from the National Emissions Inventory (NEI). EPA also held several meetings with the PVC Industry and the primary industry tr ade group, the Vinyl Institute (VI). On August 21, 2009, EPA issued a section 114 survey and testing reque st to 9 companies operating an estimated 19 PVC production facilities in the U.S. A list of companies and corresponding facilities is presented in Table 2-1.
Table 2-1: Companies/Facilities Issued a Section 114 Information Collection Request

Company Facility
The Dow Chemical Company Texas City, TX Plaquemine, LA Midland, MI
Formosa Plastics Corporation Delaware City, DE Baton Rouge, LA Point Comfort, TX Georgia Gulf Corporation Aberdeen, MS

1Company Facility Plaquemine, LA

Occidental Chemical Corporation (OxyVinyls, LP Deer Park, TX Pasadena, TX Pedricktown, NJ PolyOne Specialty Resins Group Pedricktown, NJ Henry, IL Saint

- Gobain Corporation North America CertainTeed Corporation Lake Charles, LA

Shintech Incorporated Addis, LA Plaquemine, LA

Westlake Chemical Company Calvert City, KY

Geismar, LA

Following the issue of the August 21 section 114 survey and tes ting request, the EPA learned that the Dow Plaquemine facility did not produce P VC, but instead supplied the Shintech Addis facility with raw materials. Dow also informed t he EPA of the impending closure of the Texas City facility, operated by Union Carbide, a wholly owned subsidiary of Dow. Due to the impending closure, emissions testing and resin sampling, as de scribed in this memo, were not performed at the Texas City facility. Discounting the D ow Plaquemine and Texas City facility, the EPA determined there are 17 PVC production facilities o perating in the U.S. The August 21 section 114 survey and testing request required compani es to complete an electronic based survey and conduct emissions testing and re sin sampling. The survey was formatted as a series of Microsoft (MS) Excel workshee ts and collected basic data on each facility such as location, contact information, and per mitting information. The survey also collected process and control equipment information such as equipment type, flow rates, emission concentrations, and fuel types. The survey include d specific sections such as wastewater, startup and shutdown, heat exchange systems , and feedstock unloading. The testing requirement included 2 parts: emissions testing and resin s ampling. The EPA required facilities to perform testing on the inlet and outlet to at least o ne of the systems used to control emissions from PVC production. Facilities were required to dedicat e the control system to the PVC production unit during testing since several of the facilitie s are co-located with processes that produce products and intermediates other than PVC. Each te st consisted of 3, 4-hour runs, in accordance with the EPA test memorandum on testing requi rements. Each facility tested only for those HAP which were known or suspected to be emitted fr om their process based on a review of the different resin types and grades manufactured by each f acility. The following HAP were commonly tested: acetaldehyde (75-07-0), acetophenone (98-86-2), 1,3 -butadiene (106-99-0), chlorine (7782-50-5), cumene (98-82-8), ethyl chloride (75-00-3), ethylene dichloride (107-06- 2), formaldehyde (50-00-0), hydrogen chloride (7647-01-0), methanol (67-56 -1), methyl chloride (74-87-3), phenol (108-95-2), polychlorinated biphenyls (1336-36-3), poly-ar omatic

2hydrocarbons (both volatile and semi-volatile), vinyl ace tate (108-05-4), vinyl bromide (593-60-

2), vinyl chloride (VC) (75-01-4), dioxins and furans (CDD/CDF), any other HAP contained in initiators or inhibitors used in the process, and total hydro carbons (THC). In addition to the testing, the EPA requested process data concurrent with th e duration of the emissions testing including continuous emissions monitoring system records, con trol equipment operating parameters, and fuel usage. The second testing requirement consisted of 30 days of res in sampling during which the emissions testing took place. The EPA required sampling of the PVC resin immediately following the resin slurry stripper(s) and the resin drye r(s). The EPA also requested 30 days of process data concurrent with the resin sampling such as resin stripper slurry flow rates and dryer throughput rates. Responses to the survey were due to the EPA by November 30, 2009. The testing section of the response was due by February 28 th , 2010. On March 16, 2011, the EPA issued a section 114 survey and testi ng request to vinyl chloride monomer (VCM) and ethylene dichloride (EDC) manuf acturing facilities, some of which are co-located with PVC production facilities. The March 16 section 114 testing request required VCM/EDC facilities to conduct process vent testi ng for VC, CDD/CDF and THC. The EPA requested that facilities conduct testing under normal operating conditions (i.e., including any normally controlled process vent streams). Process vent emissions data were collected from 3 facilities co-located with PVC production facilities ( Formosa Point Comfort, OxyVinyls Deer Park and Shintech Plaquemine). In a letter dated July 12, 2011, the VI submitted additional in formation on how each facility’s control system was configured for testing in response to the August 21 section 114 by indicating whether they were typically co-controlled n on-PVC streams such as EDC/VCM. The VI also provided clarification of the conditions (e.g., percentage contribution of the PVC process to the total process vent stream) during stack testing conduct ed in response to the August 21, 2009 section 114 testing request. On August 2, 2011, the VI also submitted approximately one year of VC concentration data at the outlet of the wastewater strippers for 9 PV C production facilities. All concentrations were obtained using EPA Method 107. The data were provided on a varying basis across facilities (e.g., daily, weekly, monthly). On that sa me date, the VI submitted four years worth of residual VC stripped resin measurements for 13 suspension, 3 dispersion, 1 suspension blending and 1 copolymer resin producing facilities. The August 2 str ipped resin data set represents daily VC concentration data from year 2007 to 2010, determined by EPA M ethod 107 as part of compliance with 40 CFR Part 61, subpart F. On September 16, 2011, PolyOne Henry submitted new VC and tot al non-vinyl chloride organic HAP (total non-VC organic HAP) data for suspension blending resin as a result of additional sampling and testing performed by the facility i ndependently of the original August 12, 2009 section 114 testing request.On September 21, 2011, the EPA received supplemental informati on from Shintech Inc.,

regarding gasholders in use at their PVC production facilit ies. This information included estimated emissions, emission reductions and costs of th e applicable work practices. The VI also provided similar data regarding the number of gasholders in ope rations, estimated emissions, and costs and emissions reductions of applicable work practice s for the entire PVC industry in their September 22, 2011 submission.

3.0 Data Processing and Standardization The survey responses, emissions testing results, and resin sampling results were standardized before performing technical analyses. Sectio ns 3.1 and Section 3.2 contain descriptions of the data preparation and standardization s teps.

3.1 Survey Data The ICR survey was originally formatted as a series of MS Excel spreadsheets designed to be imported into a MS Access database. Two sets of s urvey files were combined before analysis. The first set of surveys consisted of the or iginal November 30 th , 2009 facility submissions. The second set of survey files contained dec lassified confidential business information (CBI) provided by the EPA. Data originally cl aimed as CBI were declassified by the EPA for the following facilities:

o Formosa – Baton Rouge

o Formosa – Delaware City

o Formosa – Point Comfort

o Georgia Gulf – Aberdeen

o Georgia Gulf – Plaquemine

o Shintech – Addis

o Shintech – Freeport

o Shintech – Plaquemine Five facilities completed their survey response using a pr evious version of the survey template. The survey submissions were copied, archived, a nd reformatted to properly import into the MS Access database. The following facilities used a previous version of the survey template:

o Georgia Gulf – Aberdeen

o Georgia Gulf – Plaquemine

o OxyVinyls – Deer Park

o OxyVinyls – Pasadena

o PolyOne – Pedricktown

The structures of certain forms were also corrected due to modification by facilities. Data contained in the forms requiring correction were n ot altered. The following forms, listed by facility, required correction:

o OxyVinyls – Pasadena: C-1-a, K-3-a, K-3-b

o Shintech – Freeport: K-1-b

4o Georgia Gulf Chemicals – Plaquemine: C-1-a, C-2-a, C-2-c, D, K-1-a

o Georgia Gulf Chemicals – Aberdeen: C-1-a The corrected forms were imported into a MS Access data base. 1 Quality assurance and quality control (QA/QC) checks were performed to ensure t he data in each MS Excel form were correctly imported into the Access database. Errors ide ntified as a result of the QA/QC effort were addressed in subsequent iterations of the database. Limited amounts of data were modified to improve present ation and analysis. Data were only modified if the intention of the facility was di rectly obvious. Company and facility names, along with corresponding information were standardized in Forms A-1 and A-2. Units of latitude and longitude were also standardized. The standar dized information was propagated throughout the database. Records contained in table Form_C 2A were also modified. The extent of the modifications included, for example, separation of records containing multiple pieces of equipment and/or emission points in one field. Records from the following facilities were separated in table Form_C2A:

o Formosa – Baton Rouge

o Formosa – Point Comfort Five administrative tables were created in conjunction with the Section 114 survey form tables in the Access database. Two tables provide standa rdized process and control equipment descriptions while the 3 remaining tables provide a cross-walk b etween the MS Excel survey to MS Access field names, descriptions of the survey form tables, and a list of HAP and corresponding Chemical Abstract Service (CAS) number.

3.2 Emissions Test Data The emissions testing data were originally formatted as a series of MS Excel workbooks. Each facility submission was compiled into a single w orkbook 2 and quality assured by comparing the compilation with the original facility su bmission.

Several corrections and clarifications were made to the compiled MS Excel work book in preparation of data analysis. Blank and duplicate records were removed. Process unit identifiers, resin grades, equipment identifiers, and dat es were standardized to the format requested by the EPA. Control equipment gas flow rates we re standardized to units of dry standard cubic meters per minute and gas temperatures reported a s Fahrenheit (°F) were converted to Celsius (°C). Facilities that reported f low rate data with incorrect units were identified since such data resulted in unnecessary and er roneous unit conversion. Gas flow rate units were corrected by comparing the facility submitted e missions testing template to the stack test report, if the report was available. The compound na mes that were reported were compared with reported CAS numbers. Multiple incorrect CAS num ber and compound name combinations were identified. The combinations were corrected based o n facility input when available. If no facility guidance was provided, the CAS number was standard ized based on the facility submitted compound name and CAS numbers from the year 2005 Natio nal Emissions Inventory and the National Institute of Standards and Technology Che mistry WebBook. 3

5Facilities reported several HAP concentrations as non -detect (ND) values by using the

“less than” (<) symbol. The notation was removed a nd an indicator column was added to the data set to note which values were reported as ND. Several facilities also reported multiple emissions concentrations for a single HAP. Facilities reported multiple concentrations due to overla p of applicable HAP for each emission test. Therefore; a single concentration result was selected based on the criteria presented in Table 3-1. Table 3-1: Criteria for Selecting Emissions Testing Result

Methods Used to Report Compound Result Selection Cri teria

Method 0031 & Method 0010 Method resulting in higher concentration Method 320 and Method 0031 Method 0031 Method 23/23A & Method 0031 Method 0031 Method 320 & Method 0010 Method 0010
Method 26A & Method 320 > 1 ppm; Method 26A < 1ppm; Method 320 ppm – parts per million

Mass concentration data were converted to volumetric concentration (parts per million, dry volume (ppmvd)) corrected to 3 percent oxygen using Equati on 1.

6 3

6 2 

### 10 L 1000 m 1 mol 1 dsL 22.4 g MW mol
μ g 10 g 1 dscm μ g O 3% @ ppmvd × × × × × = (Eq. 1)

Equation 2 was used to convert nanograms per dry standard cubic m eter (ng/dscm) at 3 percent oxygen to ppmvd corrected to 3 percent oxygen.

6 3

6 2 

### 10 L 1000 m 1 mol 1 dsL 22.4 g MW mol
μ g 10 g 1 ng 1000 μ g 1 dscm ng O 3% @ ppmvd × × × × × × = (Eq. 2)

Chlorinated dibenzodioxin and chlorinated dibenzofuran (CDD/CD F) concentrations were standardized to ng/dscm corrected to 3 percent oxygen . CDD/CDF concentrations were converted to a toxic equivalency basis (TEQ) using year 2005 World Health Organization ReEvaluation of Human and Mammalian Toxic Equivalency Fac tors for Dioxins and Dioxin like Compounds. 4 Concentrations for all HAP were also converted to ma ss flow rates using Equation 3.



### hr min 60 V MW 385.3ft mol lb1

m 0.028 ft1 3 20.9 O 20.9 10 1 C hr lb

i 3 3 3 2 6 i 

### × × × × ×

− − × × = & (Eq. 3)

where:

6lb/hr = mass flow rate in pounds per hour,

C i = pollutant concentration in ppmvd at 3 percent oxygen, O 2 = average oxygen concentration of all pollutant three run tests, 385.3 ft 3 = volume, in cubic feet, of 1 pound mole of ideal gas at 20 ° C (68 ° F) and 1 atmosphere of pressure, MW i = molecular weight of the pollutant in pounds per pound mol e, and 

### V & = volumetric flow rate of the exhaust gas in dry standa rd cubic meters per

minute. The above corrections and standardizations represent th e extent to which the emissions testing data set was modified.

3.3 Resin Sampling Data The resin sampling results were reported by each facili ty in a MS Excel spreadsheet template provided by the EPA. A total of 15 facilities repor ted results from resin sampling and reported those results in the requested spreadsheet template . Data were submitted to the EPA beginning in late February 2010 and continuing through early Augus t 2010. The resin sampling results were reported as pollutant mass values for eac h day of sampling that was conducted at the outlet of the resin stripper(s). Three facilities repo rted their resin sampling results in terms of concentrations. CertainTeed – Lake Charles did not provide resin sampling results, and Dow – Midland provided resin sampling data in lieu of completing t he requested templates. Each facility submission was compiled into a single master file. QA/QC was performed by comparing the master compilation with the original facility subm issions.

Data in the master MS Excel workbook were standardized a nd corrected in preparation of data analysis. Blank and duplicate records were identifie d and removed. Process unit identifiers, resin grades, equipment identifiers, production rates, moi sture contents, and dates were standardized to the format requested by the EPA. The compo und names reported by the facilities were compared with reported CAS numbers and several incor rect CAS number and compound name combinations were identified. Combinations were corre cted based on facility input when available. If no facility guidance was provided, CAS numb ers were corrected based on the facility submitted compound name using standard CAS numbers from the 2005 National Emissions Inventory and the National Institute of Standar ds and Technology Chemistry WebBook. 3
Several tasks were completed to prepare the emissions testing data set for analysis. Facilities reported several HAP mass values as below detection limit or non-detect values by using the “less than” (<) symbol or brackets (“[ ]”) as requeste d. The symbol was removed and an indicator column was added to note which values were reporte d as below detection limit or as ND. Pollutant results that were already reported as con centrations (micrograms per liter (ug/L) or micrograms per kilogram (ug/kg),) were converted to parts per million (ppm) assuming a density of 1 gram per milliliter (g/ml) for the resin. On September 9, 2010, the VI submitted a spreadsheet of the r esin sampling results for all facilities as a supplemental data submission to the EPA. The results in the VI-supplied data were

7reported as concentration values for each pollutant, and n ot as the calculated or corrected mass

values requested by the Agency. No standardization or corr ections were made to this data set. A revised data set was submitted to the EPA by the VI on Sept ember 28, 2010. Additionally, on August 2, 2011, the VI submitted an updated 30-day resin sampling concentration database for total non-VC organic HAP providing additional specific on r esin types and corrections to previously submitted data. Specifically, vinyl acetate copol ymer (VACO) and suspension blending data were separated from dispersion and suspension dat a, respectively. Results that were previously reported as composites of two or more res in types were identified by resin type, and previous results from OxyVinyls suspension plants indic ated as a reporting limit were changed to ND. Vinylidene/vinyl chloride copolymer concentr ation data from Dow Chemical were also added to the database.

84.0 References

1. Facility Information Collection Request Survey Database for the Polyvinyl Chloride Production Source Category. Docket ID EPA-HQ-OAR-2002-0037.

2. Emissions Testing and Resin Sampling Workbook for the Poly vinyl Chloride Production Source Category. Docket ID EPA-HQ-OAR-2002-0037.

3. National Institute of Standards and Technology Chemistry WebBook, Standard Reference Database Number 69. http://webbook.nist.gov/chemistry/

4. 2005 World Health Organization Re-Evaluation of Human and Mam malian Toxic Equivalency Factors for Dioxins and Dioxin Like Compounds http://www.who.int/ipcs/assessment/tef_update/en/

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