Page 1 of 5 1737 King Street, Suite 390 ● Alexandria, VA 22314 ● (571) 970

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www.vinylinfo.org ● www.vinylindesign.com Novem ber 2 , 2009

Ms. Jodi Howard U.S. EPA

- Office of Air Quality Planning and Standards Sector Policies and Program Divisions Coatings and Chemicals Group Mail Code: E143

- 01 Researc h Triangle Park, NC 27711

RE: PVC MACT Resin Testing Program Pursuant to Section 114 Letter s , Vinyl Institute (VI) Working Group

Dear Ms. Howard,

The Vinyl Institute’s Working Group on PVC MACT Testing Requirements recently met via teleconfere nce to discuss HAP testing methods specific to PVC resin , and timing requirements of the U.S. Environmental Protection Agency ’s (EPA ’s ) 42 U.S.C. § 7414 information collection request (hereinafter, “114 Request”)

. PVC r esin testing using EPA SW

- 846 method s presents some unique analytical challenge s . Therefore, we are presenting this analytical response plan to inform EPA of the issues and how we will
address them.

Specifically, PVC resin testing using EPA SW

- 846 methods presents challenges
because:

(1) ce rtain hazardous air pollutants ( HAPs ) are not amenable to analysis in PVC resin,

(2) the slurry stripper discharge samples need to be separated for analysis into two separate phases (water and resin), and

(3) PVC resin particles tend to clump together duri ng certain standard sample extraction procedures

.Page 2 of 5 1737 King Street, Suite 390 ● Alexandria, VA 22314 ● (571) 970

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www.vinylinfo.org ● www.vinylindesign.com We believe these unique challenges can be addressed via allowable modifications to sample preparation steps , but full validation of these modifi ed methods can not be performed ahead of time, du e to time constraints prescribed by the February 28, 2010 reporting deadline in the 114 Request

.

The known analytical challenges and p lanned modifications are more fully described
below. Although there is not enough time to fully validate all of these mod ifications, we
believe the solutions presented represent the best efforts of the memb er compan ies to properly balance analytical quality assurance requirements with the 114 Request time
constraints

. If the EPA has comments, suggestions or specific guidanc e regarding
the s e challenges and the path forward, we would be happy to receive and d iscuss them. Since at least two member companies plan to begin PVC resin testing in early November, we would appreciate receiving EPA’s comments , on an expedited basis

. 1) SW

- 846 test methods are not appropriate for analyzing PVC resin for certain specific HAPs

Certain HAP s targeted for testing by the 114 Request , specifically hydrochloric acid ( HCl ) and Chlorine gas (Cl 2 )

, do not appear on the analyte list s for the SW

- 846 test methods

. These t wo HAPs can not readily be separated or extracted from solid PVC resin as molecular HCl or CL2 for analysis

, due to their reactivity.

HCl extracted into water would immediately ionize to H+ and Cl

-

. A pH test of a water

extra ct could be done, but would only measure hydrogen ion concentration (from all
extracted acidic components), not molecular HCl. Molecular HCl is a minor impurity in vinyl chloride monomer (VCM), and would partition almost exclusively to the aqueous phase ( as ionized H+ and Cl

- ) in the PVC reactor. Therefore, this minor component
would exit the PVC dewatering and drying process as either ionized H+ and Cl

- with the separated water , or be present on the resin particles as small quantities of chloride salts ( e.g. NaCl or common table salt), not as molecular HCl.

Similarly, molecular Cl 2 cannot be analytically determined in solid PVC resin either . The
chlorine molecule would react ( disassociate ) in a water extract

, and establish an equilibrium between hypochlo rous acid, hypochlorite ion and the chlorine molecule . APage 3 of 5 1737 King Street, Suite 390 ● Alexandria, VA 22314 ● (571) 970

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www.vinylinfo.org ● www.vinylindesign.com total residual chlorine test could be performed , but would measure many more species
than molecular chlorine

. In any case, w e do not expec t molecular chlorine (C l 2 ) to be present in PVC resins , and so it could not be emitted as a HAP

.

B ased o n the above discussion, neither hydrochloric acid, nor chlorine

, are expected to be present in the resin as it leaves the slurry stripper. There i s , therefore, no need to attempt develop ment of special techniques to analyze for them at trace levels in the
resin slurry or the final resin product. They will not be included in the testing program, since they are not expected to be present in the PVC r esin.

Other potential HAPs, such as butadiene and vinyl bromide, are also not listed as analytes in SW

- 846 methods, but may be amenable to quantitative analysis via the development of a calibration curve, once standards are purchased (if available) . If an unknown peak is identified as a significant HAP by mass spectra (Methods 8260 and 8270)

, most companies and their laboratories will make best efforts to obtain standards and prepare calibration curves for use in subsequent analyses.

2) Dual phase slurry str ipper discharge

The slurry strippe r discharge (SSD) is normally composed of 2 0 % or more PVC resin in an aqueous matrix, which requires that the solid phase (resin) be separated from the liquid phase

, to ensure sample integrity is maintained for application of subsequent SW

846 methods

. This separation results in the need to perform two analyses ( on the liquid
and the solid) for each HAP method

, the results of which w ill then be mathematically
combin ed and expressed on a dry weight PVC resin basis.

There are se veral ways to accomplish the separation and analysis of the two phases of the SSD samples

. Due to time constraints resulting from the reporting schedule in the 114 Request, a single industry

- wide , VI sponsored validation program can not be completed befor e resin sampling begins

. E ach company will be responsible for independently choosing sample handling, extraction and analytical methods for use in their resin sampling program. Obviously, some v ariability may be introduced in the final results, given t he various methodological approaches available to each company

. Given the large data sets to be provided by VI members, howe ver, a s well as otherPage 4 of 5 1737 King Street, Suite 390 ● Alexandria, VA 22314 ● (571) 970

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www.vinylinfo.org ● www.vinylindesign.com inherent variations in the calculation of HAP emission rate s, we would not expect the sampling and analytical variations to adversely impact the resin testing program as a
whole.

3) Modifications to extraction of HAPs from PVC resin

PVC resin tend s to swell in the presence of organic solvents used for extraction under SW

- 846 methods . This is a particular concern when using solvent extraction procedures prior to semi

- volatile analyses via EPA Method 8270. Another concern is
that PVC resin

, near its glass transition temperature

, will clump together in sample preparation proce dures , especially those which heat the sample at or near the PVC
soften ing point. Thus, f or solvent extraction procedures, it may be necessary to disperse the PVC resin particles in a granular matrix, for example

, clean sand or glass
beads

, before extract ion.

To the extent that HAP chemicals are dispersed in side the PVC matrix

, extraction times may need to be extended to ensure acceptable recovery from the PVC matrix. Due to
time constraints for the PVC MACT resin testing program

, selecting and validating PVC resin extraction procedures ahead of time is not feasible. Instead, the VI Work Group members propose that laborator ies retained by VI member facilities will perform
additional preliminary and ongoing quality assurance ( QA ) checks to ensure the chose n sample preparation technique ( s ) maintain the high surface area of the PVC resin particles (no clumping or melting together) and provide adequate solvent extraction
duration. The Vinyl Institute members have used such method modifications before, during method development and validation studies on PVC resins. Whichever

m odifications to extraction techniques and associated QA are adopted for use by individual companies , they will be described in the final PVC resin reports to be submitted to EPA by Februa ry 28, 2010.

T he industry looks forward to receiving any Agency comments , suggestions

, or spe c ific guidance on our planned path forward

. Since two companies are planning to begin PVC resin testing in early November, we would appreciate an expedited respon se. Please do not hesitate to contact me with any questions or comments.Page 5 of 5 1737 King Street, Suite 390 ● Alexandria, VA 22314 ● (571) 970

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www.vinylinfo.org ● www.vinylindesign.com Sincerely,

Richard P. Krock Technical Director

e

- mail: rkrock@vinylinfo.org phone: 571

- 970

- 3392 cell: 571

- 216

- 4474