1

September 22 , 2010

Mr. Richard Krock The Vinyl Institute 1737 King Street, Suite 390
Alexandria, VA, 22314

RE: Status of Method Development for Analysis of Hazardous Air Pollutants (HAPs)

Dear Mr. Krock:

The purpose of this letter is to advise you o f the current status of the Method Development Project that Environmental Chemistry, Inc. (ECI) is conducting for The Vinyl Institute (VI). As you know, our focused method development/validation work was triggered by the observation of several VI members that EPA Method 8260 for solids (like PVC resin) did not appear to recover nearly as much vinyl chloride (VC) as Method 107. Method 107 was developed specifically for VC in PVC resin to ensure quantitative recovery. The difference between standard Metho d 8260 and

concurrent Method 107 data was substantial

– 8260 appears to recover only about 10

- 20% of the amount measured by Method 107. At the same time, several other HAPs were being detected as present in PVC resin via Method 8260, and there are signifi cant questions about the recovery of these other HAPs from a PVC resin matrix.

Goals of the first phase of the method development project included:

1. Based on initial work done at Accutest, OxyVinyls and Westlake laboratories, as well as a limited instrume nt manufacturer literature search, there appeared to be an opportunity to modify Method 107 and/or Method 8260 to analyze for most (all?) of the VI HAPs list using Method 8260. Thus, experimentation with sample pretreatments and Method 8260 analysis param eters was deemed a high priority.

2. Since it is believed that the group of water soluble HAPs could be analyzed via a single method, namely EPA Method 8015, experimentation using mixtures of the aldehydes and methanol are to be analyzed by direct aqueous inj ection Method 8015. It is also believed that these highly water soluble HAPs are partitioned mainly to the water phase of the slurry stripper PVC discharge , so recovery from PVC resin may not be important. Work will be conducted to determine if these wat er soluble HAPs are partitioned such that the amount of these HAPs in the water phase of the slurry stripper discharge can be used to represent the amount in the whole slurry stripper discharge.

3. Alternative methods may be appropriate for selected HAPs on t he VI list. Initial work done by the OxyVinyls lab indicates that a colorimetric method may be selective and sensitive for formaldehyde, a water soluble HAP. The colorimetric method, in conjunction with a few EPA approved NCASI methods, will be evaluated as
alternative method s to the more complex EPA Method 8315 ( derivatization followed by liquid chromatography ).

4. Review the data on hydroquinone (HQ), recognizing that it is in equilibrium with another HAP, benzoquinone (BQ) and prepare standards of both HQ and BQ to evaluate their analytical method response.

5. Other methods may be evaluated if the above investigations do not prove to be fruitful.

ECI began evaluation of different sample introduction technique s for Method 8260 on August 5, 2010. The

purpose of this study wa s to gather additional information to determine if other sample introduction techniques such as Static Headspace or Dynamic Purge Method s are likely to yield better recovery than is currently obtained when analyzing resin samples by Method 8260 following methanol extraction.

Initial evaluation o f three different sample introduction techniques by Method 8260 was performed and from this data, a fourth technique was derived and subjected to further evaluation as described below.2

HAPS40 Method : Pre

- treat for one hour at 90 degrees C in a hot block prior to loading in Autosampler and purging at 40 degrees C using Method 8260 purge conditions . This technique is similar to the protocol presente d by Georgia Gulf, ETC

Lab. Note: Although the sample is heated to 90 for one hour, it cools down after being removed from the hot block.

HAPS90 Method : This method is the same as HAPS 40, except a 90 degree C purge temp erature is used after

pre treatment instead of 40 degrees . Note: Although t he sample is heated to 90 for one hour, it cools down after being removed from the hot block prior to being purged at 90.

HAPD Method : This method uses a one hour continuous purge time at 90 degrees C.

A review of the calibration data from the HAPS40 a nd HAPS90 methods presented some initial concerns. These

include:

Hydroquinone or Benzoquinone were not detected. Formaldehyde was removed from the compound list because Method 8260 does not scan to a low enough mass

range to detect formaldehyde

. 1,1,2, 2 Tetrachloroethane was not present and appears to have converted to Trichloroethene. The pre

- treatment step is most likely responsible for this occurrence since it did not occur when the instrument was calibrated using

standard 8260 conditions with 40 de gree p urge temperature. Vinyl acetate exhibited inconsistent re sponse. This is possibly a result of the pre

- treatment step as well, based on the calibration results obtained using regular 8260 conditions. Vinyl chloride and Acetaldehyde do not yield compl ete chromatographic peak separation but the quantitation ions are different, so co

- elution should not be an issue when identifying and reporting compounds in samples. Internal standard (IS) recovery was comparable to regular 8260 so the pre

- treatment step does not appear to

affect IS results.
All other compounds were detected with no apparent issues. Inconsistent response for 1,1,2,2

- Tetrachloroethane was observed (converted to Trichloroethene)

. Acetaldehyde, Vinyl acetate, 1,3

- Butadiene,and Acetophenone all exhibited poor average response factors when compared to other compounds and to average response factors obtained under routine 8260 analysis. There was a noticeable decrease in the response factor for standard concentra tions at and above 100 ppb for

V inyl chloride and other compounds. This would suggest that it may be necessary to calibrate over a lower concentration range when using the pre

- treatment step.

ECI was unable to establish an acc eptable calibration for the HAP D one hour continuous purge method. Several

issues were encountered:

Results of triplicate (analysis of 3 different standards of same concentration, not consecutive runs of the same standard) analyses are not consistent.

Internal standard response is inconsistent

. Poor chromatogra phy on early eluting peaks that will cause identification and quantitation problems with 1,3

Butadiene. No recovery of Vinyl acetate, Vinyl bromide, Vinyl chloride, Methyl chloride and Ethyl chloride. All retention times for internal standards, surrogate standards, and compounds of interest were approximately one minute later than in regular 8260 method.

It was suspected that the early eluting compounds were being pushed off the trap before the GC run starts due to the extended purge time and volume. A study was performed to determine the effect of purge time on the response for the compounds of interest. It was believed that the 60 minute continuous purge method at 90 degrees (HAPSD) was not working due to a loss of analytes, including vinyl chloride, as the purge time increased. Purge times between 15 and 60 minutes were tested to determine the affect of purge time on analyte response.3

The data clearly show ed a reduction in response as the purge time is increased. In general, the response for lig hter, early eluting compounds such as Vinyl Chloride, Acetaldehyde, and Chloromethane decreased significantly as purge time increased. From Method 8260, we know that total purge volume (purge flow rate times purge time) is a critical factor in the ability to obtain consistent acceptable response to the wide range of volatile compounds

. The lab r educed the purge flow rate during a 60 minute purge time at 90 degrees to achieve a total purge volume similar to that normally used during Method 8260 analysis. Although some analytes show ed higher response at the 60 minute purge time at 10

mL/minut e, lower response for compounds such as Chloromethane, Vinyl chloride, Chloroethane, Bromoethene, 1,1

- Dichloroethene, and Chloroform indicates that the response was no t sufficient to support calibration for these six compounds.

8260 HM : Hybridization of Techniques D escribed in EPA Methods 5021, 5030, 5035

Upon evaluation of the information obtained from the various techniques and the purge times and purge flow data

, the lab established a five point calibration using the following pretreatment and purging conditions:

Sample Pre

- Heat Temperature: @90 degrees Sample Pre

- Heat Time: 60 minutes Purge Temperature: @90 degrees Purge Time: 9 minutes Purge Flow: 40 mL/ minute GC/MS Settings: Same as used during routine Method 8260 analysis

Note: No cooling occurred between the Sample Pre

- Heat and Purge Start Time. The sample was preheated by

the Autosampler directly in the purge tube and purging was initiated and co ntinued at 90 degrees.

A Stripper Wet Cake (wet PVC resin from filtration of slurry stripper discharge) sample was analyzed three

consecutive times (same sample aliquot analyzed over again) to evaluate recovery efficiency. The sample was placed in

a 40 mL vial, pre

- heated, and purged directly in the vial. After the first and second analysis runs, the sample was cooled to room temperature. Additional internal and surrogate standards were added through the septa with a small gauge needle as specified in EPA Method 5035. The results of the three consecutive runs using 0.5 gra m of sample are shown

in the attached table . Runs were made using 0.5 gram of sample and 1 gram of sample. The runs using 1 gram of sample exhibited erratic internal standard r esponse, inconsistent results, and poor chromatography and were not

evaluated.

Acetaldehyde and Chloroethane exhibited poor chromatographic behavior in the second and third runs using 0.5 gram of sample. Slight retention time shifts were observed for Vi nyl Chloride and Chloroethane in the first run. These shifts may have been due to the concentrations present. Results for Vinyl Chloride and Chloroethane in Run 1 are reported as estimated concentrations above the calibration range. The 200 ppb standard in the calibration curve was dropped from the calibration curve for Vinyl Chloride because the response factor was inconsistent with the response factor obtained at lower concentrations. It is possible that this reflects an error in the standard preparat ion or is an issue that can be solved with increased familiarity and experience with the new operating conditions.

I t will be necessary to determine how results above the calibration range will be handled. While it is possible to accurately weigh sample weights less than 0.5 gram, consideration will need to be given to the impact on representative

sub

- sampling. Further work to investigate the acetaldehyde results is also recommended. Due to the poor chromatography associated with the second and third runs, it is unclear at this point if acetaldehyde was truly not recovered in the first run or if its presence in the second and third runs is an "artifact" or potential degradation by

- product caused by the sequential heating and cooling (between runs) proc ess. 1,1

- Dichloroethane also shows higher concentrations in the second and third run than were expected. Acetophenone and 1,2

- Dichloroethane show incomplete recovery in the first run, but are absent in the third run.

The result obtained for vinyl chlor ide was compared to the result provided for Method 107. The lab also analyzed the sample using traditional Method 8260 via methanol extraction. All methods were run on the same sample on the same day. Results were corrected to dry weight basis using the moisture results obtained by the lab that submitted the sample.4

The results obtained by the Traditional Method 8260 (methanol extraction) were almost 10 times lower than the results obtained by Method 107. The results obtained by the Modified Method 8 260 were 56

- 69% of the value obtained by Method 107, depending on whether the first run or total of all runs are used for calculating the results from the Modified

Method 8260.

Dispersion resin and suspension resin from two other facilities were also an alyzed. Evaluation of surrogate standard and internal standard response indicate that the method developed should work on various resin types. It also appears that the method developed can be used to analyze slurry samples without separation of the two p hases if a homogenous subsample can be obtained.

Conclusion

The following modifications to the Sample Introduction Technique for Method 8260 appeared to yield the best

success across t he entire list of HAPs for the four techniques evaluated:

Pre

- Heat T emperature: @90 degrees

Pre

- Heat Time: 60 minutes Purge Temperature: @90 degrees Purge Time: 9 minutes Purge Flow: 40 mL/minute

Initial data indicate recovery may be 5

- 10 times higher for Vinyl chloride than is obtained when analyzed using

methan ol extraction and Method 8260. The result of the split sample for Vinyl chloride was closer to what was obtained by the Benchmark Method 107 than has been seen in the past when results obtained from methanol extractions are compared to results from Method 107. However, multiple data points will be needed to determine if this is indeed the

case.

Recommendations for Further Study Method 8260

Because of the multiple variations of modification to Method 8260 that were attempted, it was not possible to full y evaluate the performance of the final method modifications during this first phase of the method development study. Additional work should be conducted to further evaluate method performance using these conditions.

Further evaluation of chromatography and integration parameters to optimize calibration results. Determine significance of surrogate recovery results for Toluene d8 and 4

- Bromofluorobenzene. These are lower than would normally be expected in 8260, but might be associated with absorption int o the resin. Determine if the concentrations in the second and third extractions of the same sample are significant or if recovery in the first extraction is sufficient. This would prevent interference from potential degradation/decomposition reactions th at are thought to be occurring due to sequential heating and cooling cycles. It is unlikely that recovery for compounds such as Acetaldehyde and Isopropylbenzene would be zero in the initial analysis based on prior performance data from Method 8260. The recovery data for 1,1

- Dichlorethane
and 1,2

- Dichloroethane from the first analysis in the sequence was also unexpected and needs further research to determine if this is an anomaly. The poor chromatography for compounds in the second and third runs

indica tes that something unusual is occurring upon sequential analysis of the same sample aliquot

. It is suspected that the retention time shifts that were observed for V inyl ch loride and C hloroethane during the first analysis sequence was due to the concentra tions present in the sample relative to the calibration standard. Further evaluation of the chromatogram s will confirm this idea. Determine precision of analysis from replicate analysis of the same sample for suspension resin, dispersion resin, and slurry resin.

Perform a M ethod D etection L imit (MDL) study. Determine minimum amount of sample that can be used (which will establish upper working range of method). It has already been determined that there is also an upper limit to the sample amount that can b e used.5

Acetophenone appeared to demonstrate good performance using an extended purge time. A decision should be made whether or not to pursue this option as an alternative to Method 8270. The recovery of Acetophenone in

the first of three consecutive extractions using the 60 minute Pre

- treat method was 39% of the total from three consecutive extractions. Acetophenone was not detected in the third consecutive extraction. The QC targets that were adopted from Method 8270 were 35

- 119% recovery. Additi onal work to determine potential for carryover and reproducibility using Modified Method 8260 may be warranted. Hydroquinone and Benzoquinone were not detected during Method 8260 analysis. However, because of the number of different pre

- treatment options being evaluated, ECI did not determine if pH adjustment would affect the ability to analyze these compounds by purge and trap. Since method performance of Method 8270 is known to yield poor recoveries for these analytes , it would be worthwhile to run at l east one sta ndard at a basic pH using

the 60/9 0 Pre

- Heat option. Collect additional samples to be analyzed by EPA Method 8260 (methanol extract) and the 60/90 Pre

- Heat Sample Introduction Technique to determine if the initial finding of improved recovery i s statistically significant. A minimum of 20 samples would be needed to perform statistical evaluation of the data.

Water Soluble HAPs (Methanol, Acetaldehyde, Formaldehyde, Acetophenone )

ECI also performed evaluations of Method 8015 and the colorimetr ic procedure for Formaldehyde. The

evaluation for these methods/compounds was conducted in an attempt to determine if the HAPs are so preferentially partitioned to the water phase (including that washed off the resin particles with a water rinse/extractio n), that the amount of them in the solid resin phase is negligible. This would allow future analysis of the water phase of the slurry without

need ing to perform a separate solvent extract of the solid resin phase

. No conclusions have been reached due to analytical problems encountered upon method development for these compounds using Method 8015.

Thank you very much for the opportunity to work with the Vinyl Institute on this project. ECI will prepare a final report of this first phase of the method de velopment and submit to the VI on or before October 2, 2010

. If you have any questions, please contact me at 713

- 666

- 0020 or via e

- mail at nthomey@envchem.com.

Sincerely,

Nan Thomey

President6 Results of Method 8260 HM Hybridization of Techniques De scribed in EPA Methods 5021, 5030, 5035

Modified Method 8260, Consecutive Purge,

60 minute Pre

- Heat at 90 o , 9 Minute Purge @ 90 o
With Comparison to Methods 107 and 8260 Methanol Extracts

Stripper Stripper Stripper Total %

Rec % Rec % Rec Total

of 3

Runs Method

107 Method

8260

Methanol

Extract

Wet Cake

Run 1 Wet

Cake

Run 2 Wet Cake

Run 3 Runs 1

- 3 Run

1 Run

2 Run

3 ppm, Dry

Wt ppm,

Dry Wt ppm, Dry

Wt.

Chloromethane ND ND ND ND

Acetaldehyde ND 1090 RP 725 RP 1815 0 60 39.9

Vinyl chloride 1300 ER 300 ND 1600 81.2 18.8 0 2.9 4.2 0.481

1,3

- Butadiene ND ND ND ND

Chloroethane 2070 ER 624 P 210 RP 2904 71.2 21.5 7.2

Bromoethene ND ND ND ND

1,1

- Dichloroethene ND ND ND ND

1,1

- Dichloroethane 194 155 101 450 43.1 34.4 22.4

Vinyl Acetate ND ND ND ND

2

- Chloro

- 1,3

- butadiene ND ND ND ND

Chloroform ND ND ND ND

1,2

- Dichloroethane 133 87 ND 220 60.4 39.5 0

Benzene ND ND ND ND

Toluene ND ND ND ND

m

- Xylene, p

- Xylene ND ND ND ND

o

- X ylene ND ND ND ND

1,1,2,2

- Tetrachloroethane ND ND ND ND

Isopropylbenzene ND 91 52 143 0 63.6 36.4

Acetophenone 2090 3260 ND 5350 39.1 60.9 0

Dibromofluoromethane, SR 94 71 63

Toluene, d8 SR 62 67 79

4

- Bromo fluorobenzene, SR 32 78 88

E

- Reading above highest Calibration Standard (Have not determined Upper Linear Range or best way to handle dilutions.

R

- Retention Time Shift

P

- Poor Chromatography Formatted: Font: 10 pt, Not Bold, No

underline