1

TECHNICAL MEMORANDUM
TO: Jodi Howard , U.S. EPA, Sector Policies and Programs Division/ Coatings and

Chemicals Group
FROM: Eastern Research Group, Inc.

DATE: April 11 , 201 1
SUBJECT: Information Collection for the Polyvinyl Chloride and Copolymers (PVC)

Production Source Category

1.0 Introduction The U.S. Environmental Protection Agency (EPA), under section 112 of the Clean Air Act (CAA), is required to establish National Emissions Standards for Hazardous Air Pollutants (NESHAP) emitted from polyvinyl chloride and copolymer (PVC) production facilit ies

. The complete set of regulated HAP is listed in CAA section 112(b). This memorandum describes the data collection and data preparation completed by EPA and ERG in an effort to develop NESHAP standards for the PVC production source category. Section 2.0 describes the data collection steps and Section 3.0 describes the data preparation and standardization 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 Industry and the primary industry trade group, the Vinyl Institute (VI)

. O n August 12, 2009, EPA issued a Section 114 Inform ation Collection Req uest (ICR) to 9 companies operating an estimated 19 PVC and copolymer 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 Collectio n 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, MS2 Company 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 Char l es, LA

Shintech Incorporated Addis, LA Plaquemine, LA

Westlake Chemical Company Calvert City, KY

Geismar, LA

Following the issue of the ICR, EPA learned that the Dow Plaquemine facility did not produce PVC, but instead supplied the Shintech Addis facility with raw materials. Dow also informed EPA of the impending closure of the Texa s City facility, operated by Union Carbide, a wholly owned subsidiary of Dow. Due to the impending closure, emissions testing and resin sampling, as described in this memo, were not performed at the Texas C ity facility. Discounting the Dow Plaquemine and Texas City facility, EPA determined there are 17 PVC and copolymer production facilities operating in the U.S.
The ICR survey required companies to complete an electronic based survey and conduct emissions testing and resin sampling

. T he survey was formatted as a series of Microsoft (MS) Excel worksheets and collected basic data on each facility such as location, contact information, and permitting information. The survey also collected process and contro l equipment information such as equipment type, flow rates, emission concentrations, and fuel types

. The survey included specific sections such as wastewater, startup and shutdown, heat exchange systems, and feedstock unloading. The testing requirement i ncluded 2 parts ; emissions testing and resin sampling. EPA required facilities to perform testing on the inlet and outlet to at least one of the systems used to control emissions from PVC and copolymer production

. Facilities were required to dedicate the control system to the PVC and copolymer production unit during testing since several of the facilities are co

- located with processes that produce products and intermediates other than PVC

. Each test was required to consist of 3 , 4

- hour runs, in accordance with the EPA test memorandum on testing requirements. Each facility tested only for those HAPs which were known or suspected to be emitted from their process. The following HAPs were commonly tested: acetaldehyde (75

- 07

- 0), acetophenone (98

- 86

- 2), 1,3

- b utadiene (106

- 99

- 0), chlorine (7782

- 50

- 5), cumene (98

- 82

- 8), e thyl c hloride (75

- 00

- 3) , e thylene d ichloride (107

- 06

- 2) , f ormaldehyde (50

- 00

- 0) , h ydrogen c hloride (7647

- 01

- 0) , methanol (67

- 56

- 1), m ethyl
c hloride (74

- 87

- 3) , p henol (108

- 95

- 2) , p olychlorinated b iphenyls (1336

- 36

- 3) , p oly

- aromatic h ydrocarbons (both volatile and semi

- volatile) , v inyl a cetate (108

- 05

- 4) , v inyl b romide (593

- 60

-3

2) , v inyl c hloride (75

- 01

- 4 ), dioxins and furans, any other HAP contained in initiators or inhibitors used in the process, and total hydrocarbons (THC). In addition to the testing, EPA requested process data concurrent with the duration of the emissions testing including continuous emissions monitoring system records, control equipment operating parameters, and fuel usage

. The second testing requirement cons isted of 30 days of resin sampling during which the emissions testing took place

. EPA required sampling of the PVC and copolymer resin immediately following the resin slurry stripper (s) and the resin dryer (s)

. EPA also requested 30 days of process data concurrent with the resin sampling such as resin stripper slurry flow rates and dryer throughput rates. The survey response was due to EPA by November 30, 2009. The testing section of the response was due by February 28 th , 2010.
3.0 Data Processing and Standardization The survey responses, emissions testing results, and resin sampling results were standardize d before performing technical analyses. Section s 3.1 and Section 3.2 contain descriptions of the data preparation a nd standardization steps

. 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 set s of survey files were combined before analysis

. The first set of surveys consisted of original November 30 th , 2009 facility submission s

. The second set of survey files contained declassified confidential business information (CBI) provided by EPA. Data originally claimed as CBI were declassified by EPA for the following faci lities :

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 previous v ersion of the survey template. The survey submissions were copied, archived, and 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

– P laquemine
o OxyVinyls

– Deer Park
o OxyVinyls

– Pasadena
o PolyOne

– Pedricktown4

T he structure s of certain forms were also corrected due to modification by facilities

. Data contained in the forms requiring correction were not 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
o 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 database. 1 Q uality assurance and quality control checks (QA/QC) were performed to ensure the data in each MS Excel form were correctly imported into the Access database. Errors identified as a result of the QA/QC effort were ad dressed in subsequent iterations of the database.

L imited amounts of data were modified to improve presentation and analysis. Data were modified if, and only if, the intention of the facility was directly obvious

. C ompany and facility names, along with corresponding information were standardized in Forms A

- 1 and A

- 2. U nits of latitude and longitude were also standardized

. The standardized information was propagated through the database

. R ecords contained in table Form_C2A were also modified

. The exte nt 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

F ive administrative tables were created in conjunction with the ICR survey form tables in the Access database

. Two tables provide standardized process and control equipment descriptions while the 3 remaining tables provide a cross

- walk between t he 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

. E ach facility submission was compiled into a single workbook 2 and quality assured by comparing the compilation with the original facility submission.
S everal corrections and clarification s were made to the compiled MS Excel work book in preparation of data analysis

. B lank and duplicate records were removed

. P rocess unit identifiers , resin grades, equipment identifiers, and dates were standardized to the format requested by EPA

. C ontrol equipment gas flow rates were standardized to unit s of dry st andard cubic meters per minute and gas temperatures reported as Fahrenheit (°F) were converted to Celsius (°C)

. F acilities that reported flow rate data with incorrect units were identified

. The incorrect units resulted in unnecessary and erron eous unit conversion

. G as flow rate units were corrected by comparing the facility submitted emissions testing template to the stack test report, if the report was available

. F acility reported compound names were compared with reported CAS numbers

. M ult iple incorrect CAS number and compound name combinations were5

identified

. The combinations were corrected based o n facility input when available

. If no facility guidance was provided, the CAS number was standardized based on the f acility submitted compou nd name and CAS numbers from the year 2005 National Emissions Inventory and the National Institute of Standards and Technology Chemistry WebBook. 3 Facilities reported several HAP concentrations as non

- detect (ND) values by using the “less than” (<) symbol

. T he notation was removed and 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 t o overlap 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 Sele ction Criteria

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

M ass concentration data were converted to volumetric concentration (parts per million, dry volume ( ppmvd ) ) correct ed to 3 percent oxygen using Equation 1.

(Eq. 1)

Equation 2 was used to convert nanogra ms per dry standard cubic meter (ng/dscm) at 3 perc ent oxygen to ppmvd correct ed to 3 percent oxygen.
(Eq. 2)

C hlorinated dibenzodiox in and chlorinated dibenzofuran (CDD/CDF) concentrations were standardized to ng/dscm correct ed to 3 percent oxygen

. CDD/CDF concentrations were converted to a toxic equivalency basis (TEQ) using year 2005 World Health Organization Re

Evaluation of Human and Mammalian Toxic Equivalency Factors for Dioxins and Dioxin like Compounds. 4 Conce ntrations for all HAP were also converted to m ass flow rates using Equation 3.6 (Eq. 3)

where:
lb/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 mole, and

= volumetric flow rate of the exhaust gas in dry standard cubic meters per minute.
The above correct ions and standardizations represent the extent to which the emissions testing data set was modified

.

3.3 Resin Sampling Data The resin sampling results were r eported by each facility in a MS Excel spreadsheet template provided by EPA. A total of 15 facilities reported results from resin sampling and reported those results in the requested spreadsheet template. Data was submitted to EPA beginning in late Febru ary 2010 and continuing through early August 2010. The resin sampling results were reported as pollutant mass values for each day of sampling that was conducted at the outlet of the resin stripper(s). Three facilities reported their resin sampling result s in terms of concentrations. CertainTeed

– Lake Charles did not provide resin sampling results, and Dow

– Midland provide d resin sampling data in lieu of compl eting the requested templates

. E ach facility submission was compiled into a single master file

. QA/QC was performed by comparing the master compilation with the original facility submissions.

Data in the master MS Excel work book were standardized and corrected in preparation of data analysis. B lank and duplicate records were identified and removed

. P rocess unit identifiers, resin grades, equipment identifiers, production rates, moisture contents, and dates were standardized to the format requested by EPA. F acility reported compound names were compared with reported CAS numbers and several incorrect CAS number and compound name combinations were identified. C ombinations were corrected based of facility input when available. If no facility guidance was provided, CAS number s were corrected based on the fa cility submitted compound name using standard CAS numbers from the 2005 National Emissions Inventory and the National Institute of Standards and Technology Chemistry WebBook. 3

S everal 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 requested

. T he symbol was removed and an indicator column was added to note which values were reported as below dete ction limit or as ND

. P ollutant results that were already reported as concentrations ( micrograms per liter ( ug/L )7

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 res in. On September 9, 2010, the VI also submitted a spreadsheet of the resin sampling results for all facilities as a supplemental data submission to EPA. The results in the VI

- supplied data were reported as concentration values for each pollutant, and not as the calculated or corrected mass
v alues requested by the Agency. No standardization or corrections were made to this data set. A revised data set was submitted to EPA by the VI on September 28, 2010.

4.0 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 Polyvinyl Chloride Production Source Category. Docket ID EPA

- HQ

- OAR

- 2002

- 0037

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

4. 2005 World Health Organization Re

- Evaluation of Human and Mammalian Toxic Equivalency Factors for Dioxins and Dioxin Li ke Compounds http://www.who.int/ipcs/assessment/tef_update/en/