From: Richard Krock <rkrock@vinylinfo.org>

To: Jodi Howard/RTP/USEPA/US@EPA

Date: 11/01/2010 03:39 PM

Subject: Report to Vinyl Institute by ECI of Phase I Resin Test Method Development

Dear Ms. Howard, In an effort to keep EPA apprised of our progress on Vinyl Institute’s PVC resin test method development program as it pertains to the PVC MACT, ECI’s report regarding phase I conclusion is attached for the Agency’s information. As the report indicates, there are a number of issues that came up during the study that should be resolved. ECI is preparing a proposal for phase II to continue the development work that may include among other things 1.) Continuing evaluation and optimization of the Hybrid 8260 method; 2.) Further evaluation of aqueous phase test methods; 3.)Additional study of partitioning of water soluble HAPs; 4.) Other work to be outlined. The Vinyl Institute has received approval from its members to proceed with phase II work, which we expect to be completed over the next 8 weeks. We will again keep the Agency informed of our findings. Please do not hesitate to contact me with any questions regarding the attached ECI report. Thank you for the opportunity to submit this important work. Regards,

Richard Krock Technical Director The Vinyl Institute 1737 King Street Suite 390 Alexandria, VA 22314 Direct: 571.970.3392 Mobile: 571.216.4474 Fax: 571.970.3271 Email: rkrock@vinylinfo.org http://www.vinylinfo.org http://www.vinylindesign.com(See attached file: ECI Final Report for Phase I VI PVC MACT Resin Test Method Development Study 10-05-10FINAL REPORT METHOD DEVELOPMENT STUDY CONDUCTED FOR THE VINYL INSTITUTE OCTOBER 1, 2010 I. Introduction This report presents the results of the method development study conducted by Environmental Chemistry, Inc. (ECI). The focused method development/validation work was triggered by the observation of several Vinyl Institute (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 Method 8260 and concurrent Me thod 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. The VI contracted with EC I and work began in the laboratory on August 5, 2010.

II. Goals 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 instrument manufacturer literature search, there appeared to be an opportunity to modify Method 107 and/or Method 8260 to analyze for most, or all, of the VI HAPs list using Method 8260. Thus, experimentation with sample pretreatments and Method 8260 analysis parameters 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 injection Method 8015. It is also believed t hat 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 th ese water soluble HAPs are partitioned such that the amount of these HAPs in the water phase of the slur ry 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 the VI list. Initial work done by the OxyVinyls lab indicates that a colorimetric method may be sele ctive 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 methods 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 in vestigations do not prove to be fruitful.

Page 1 of 18III. Methods Method 8260 Conditions HAPS40 HAPS90 HAPD Hybrid Method 8260
Pretreatment 60 minutes at 90 o C in Hot Block, transferred to Autosampler 60 minutes at
90 o C in Hot Block, transferred to Autosampler None None

Purge Preheat Temp/Time 40 o C/2 min 40 o C/2 min 40 o C/2 min 90 o /60 min

Purge Temperature 40 o C 90 o C 90 o C 90 o C Purge Time 9 min 9 min 60 min 9 min Purge Flow Rate 40 mL min 40 mL min 40 mL min 40 mL min Dry Purge Time 0.5 min 0.5 min 2.0 min 0.5 min
Desorb Preheat 255 o C 255 o C 245oC 255 o C
Desorb Time 0.7 min 0.7 min 0.5 min 0.7 min Desorb Temp 260 o C 260 o C 250 o C 260 o C
Helium Flow 1.0 mL/min 1.0 mL/min 1.6 mL/min 1.0 mL/min Initial Temp 50oC 50oC 40oC 50oC
Hold Time 5 min 5 min 2 min 5 min Ramp 1 12 o /min to 180 o C 12 o /min to 180 o C 8 o /min to 220oC 12 o /min to 180 o C
Hold Time 2 min 2 min 5 min 2 min Ramp 2 35 o C/min to 225 o C 35 o C/min to
225 o C NA 35 o C/min to 225 o C

Hold Time 3.88 min 3.88 min NA 3.88 min Injector Temp 180 o C 180 o C 220oC 180 o C Detector Temp 250 o C 250 o C 220oC 250 o C Column Supelco SPB-5, 60m, 0.25 mm, 1.0um film thickness Supelco SPB-5, 60m, 0.25 mm, 1.0um film thickness Supelco SPB-5, 60m, 0.25 mm, 1.0um film thickness; J&W DBVRX, 60m, 0.25mm, 1.4um film thickness J&W DBVRX, 60m, 0.25mm, 1.4um film thickness

Trap VOCARB 3000 VOCARB 3000 VOCARB 3000 VOCARB 3000

Page 2 of 18Method 8015, GC/FID Analytical Conditions

Injection Direct Aqueous Injection Direct Injection Direct Injection Direct Injection Direct Injection

Column Supelco Nukol , 15m, 0.53mm, 0.5um Restek DB-5, 30m, 0.25mm, 0.5um Supelco Nukol , 15m, 0.53mm, 0.5um Agilent DB624, 30m x 0.53mm x 3.0um Agilent DB624, 30m x 0.53mm x 3.0um Solvent Water Methylene Chloride: Acetone Methylene Chloride: Acetone Hexane Water

Initial Temp 40oC 35oC 40oC 35oC 35oC
Hold Time 2 min 3 min 2 min 3 min 3 min Ramp 30 o C/min 15 o C/min 30 o C/min 15 o C/min 15 o C/min Final Temp 190 o C 300oC 200oC 260oC 260oC
Hold Time 1.00 min 9.33 min 1.00 min 0 min 0 min Injector Temp 190oC 285oC 190oC 170oC 170oC Detector Temp 190oC 325oC 200oC 275oC 275oC

The colorimetric method used for Formaldehyde may be found in NCASI METHOD IM/CAN/WP-99.02 that reportedly has been app roved by EPA for paper in dustry HAP analysis. Solid samples were prepared in accordance with the procedure described in EPA Method 8315.

IV. Results

A. Modifications to EPA Method 8260 The first steps undertaken were to gather additional inform ation to determine if the Static Headspace Method or Dynamic Purge Method is likely to yield better recovery than is currently obtained for thes e compounds when analyzing by Method 8260 following methanol extraction. There are advantage s and concerns associated with initial development work that had to be resolved in order to select which method should be used as the basis for further method development.

Page 3 of 18Method Advantage Concern No modification to Method 8260 instrument conditions. Adds a "pretreatment" step to analysis that is based on headspace analysis EPA Method 5021. Data to support acceptable internal and surrogate standard recovery and other QC requirements of Method 8260 is available Insufficient data to determine if adequate extraction from resin is obtained

Would be more available commercially and shorter run time Static headspace is not thought to be as efficient as dynamic purge technique Static Headspace - Based on initial development by ETC using a 90 degree pretreatment step for one hour and then purging at 40 and 90 (Referred to as HAPs40 and HAPs90) The same technique could be used for dry resin, wet cake, and slurry samples reducing the amount of time required for validation of different matrices 40 degree purge temperature may not be as effective as 90 degrees. One hour sample preparation at 90C while on the autosampler will be conceptually evaluated and adopted if proven advantageous. Dynamic purge would be more effective than static headspace for measuring constituents within the resin No data obtained to indicate if QC requirements of Method 8260 could be met for calibration criteria, surrogate, and internal standards, among others Data from consecutive runs indicates acceptable recovery from within the resin Moisture from continuous heated purge could be an issue Dynamic Purge - Initial development by Oxy Wichita - (90 degree continuous purge for 60 minutes to the trap - (Referred to as HAPSD) Lengthy run time/conditions would inhibit availability or increase cost of analysis significantly compared to a standard 8260 analysis

ECI began evaluation of different sample introduction techniques for Method 8260 on August 5, 2010. Initial evaluation of 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. The raw data fr om the initial evaluation of the three different sample introduction techniques in included in Appendix A.

1. HAPS40 Method : (Pre-treat for one hour at 90 o C in a hot block prior to loading in Autosampler and purging at 40 degrees C using Method 8260 purge conditions similar to protoc ol presented by Georgia Gulf, ETC Lab. ETC reportedly did not subject calibration standards to the pre-treatment step. The method was evaluated using two variations. In one, 5 mL of deionized water (DI) was added to the sample prior to pre-treatment. In the second variation, no water was added

Page 4 of 18prior to pre-treatment. In both variations, 5ml of deionized water containing internal standards were added by the Archon Autosampler prior to purging. Note: Although the sample is heated to 90 for one hour, it cools down after being removed from the hot block. The following observations were noted when the initial standard was evaluated:

 Hydroquinone and Benzoquinone were not detected.

 Formaldehyde was removed from the compound list because Method 8260 does not scan low enough to detect ions.

 1,1,2,2 Tetrachloroethane was not present and appears to ha ve 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 0 Purge temperature.

 Vinyl acetate shows very poor recovery. May not be able to get a successful calibration. This is likely a result of the pre-treatment step as well, based on the calibra tion results obtained using regular 8260 conditions.

 Vinyl chloride and Acetaldehyde do not yield complete ch romatographic separation but the quantitation ions are different, so co-elution should not be an issue w hen identifying and reporting compounds in samples.

 Internal standard (IS) recovery was comparable to re gular 8260 so the pre-treatment step does not appear to affect IS results.

 Surrogate standard recovery for Dibromofluoromethane was lower than observed in regular 8260 and is probably due to the pre-treatment. However, this should not be an issue when the calibration is performed using standards that have been subjected to pre-treatment pr ovided the lower recovery is consistent.

 All other compounds were detected with no apparent issues.

Two sets of 6-point calibrations were performed and re viewed from the HAPS40 Met hod. One set was pretreated for one hour at 90 degrees C with 5mL of DI water added bef ore pretreatment, pretreated wet, (PW) and the other was pretreated without deionized wate r added, pretreated dry, (PD).

 1,1,2,2-Tetrachloroethane is present in PD but not PW (converted to Trichloroethene) and trace amounts start to be seen at the 100ug/L level, but response is poor.

 Vinyl acetate has a poor response in PW at about 0.100 AR F (average response factor) but much better in PD at 0.884 ARF

 The surrogate, Dibromofluoromethane, had a lower response of 0.209 in PW than in PD at 0.579.

 Acetaldehyde, Vinyl acetate 1,3-Bu tadiene,and Acetophenone all exhibited poor average response factors when compared to other compounds and to average response factors obtained under routine 8260 analysis in both PW and PD. There was a noticeable decrease in the respon se factor for standard concentrations at and above 100 ppb for Vinyl chloride and other compounds. This would su ggest that it may be necessary to calibrate over a lower concentration range when using the pre-treatment step.

Page 5 of 182. HAPS90 Method : (Same as HAPS 40, except using a 90 o C purge temp after pretreatment instead of 40 o ). Note: Although the sample is heated to 90 o C for one hour, it cools down after being removed from the hot block prior to being purged at 90 o

.

 All of the items noted for the HAPS 40 Met hod were evident in the HAPS 90 method.

 Co-elution of Vinyl chloride and Acet aldehyde was even more pronounced, but as in HAPS40, they can be separated and quantified based on their mass spectra.

 Vinyl chloride response is approximately half the response as observed in HAPS40.

 Acetophenone showed a response approximately three times higher than HAPS40.

Two sets of 6-point calibrations were performed and reviewed using the HAPS90 Method. One set was pretreated for one hour at 90 o C with 5mL of DI water added, pretreated wet, (PW) and the other was pretreated without DI water added, pretreated dry, (PD).

 All of the items noted for the HAPS 40 Method were ob served in the HAPS 90 Method, with response factors generally the same or lower than HAPS40 in bot h PW and PD conditions.

In general, upon review of the calibration curve data for the HAPS40 and HAPS90 methods, the RSD of the response factors for Acetaldehyde, Vi nyl chloride, 1,3-Butadiene and Acetoph enone were higher than desired when putting the standards through the pre-treatment process. It was also observed that the response factor decreases with increasing concentrations for some compounds. Additional evaluation would be needed to determine if a different calibration range should be used when employing the pre-treatme nt step for some compounds. Some of these issues may have been due to a variation in the amount of time betwe en when a standard was removed from the hot block and when it was purged on the autosampler. This would create different cooling periods. There does not seem to be a substantial difference between the HAPS 40 and HAPS 90 in both PW and PD curves.

3. HAPD Method: (One hour continuous purge time at 90 o C).

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

 Internal standard result s were not consistent.

 Poor chromatography on early eluting peaks were noted that will cause identificat ion and quantitation problems with 1,3 Butadiene.

 No recovery of Vinyl acetate, Vinyl bromide, Vinyl chloride, Chloromethane, and Chloroethane.

 1,1,2,2 Tetrachloroethane br eak down to Trichloroeth ene is only about 10% as opposed to 100% in HAPS40 and
90.

Page 6 of 18 All retention times for internal standards, surrogate st andards, and compounds of interest were approximately one minute later than in regular 8260 method.

 It was suspected that the early eluti ng compounds were being pushed off the trap before the GC run starts due to the extended purge time and volume.

Based on teleconference August 12, 2010 with the VI technical workgroup, the development on Method 8260 next focused on trying to reproduce the work done by Oxy Wichita. An analytical column identical to the one used in Wichita's preliminary work was ordered and installed. Since the instrument had to be taken down to install the new column, a new trap was installed in the purge and trap conc entrator to make sure deterioration of the trap was not a factor in the inability to capture vinyl chloride and other lighter compounds using the 60 minute continuous purge. ECI was still unable to capture the early eluting compounds of interest such as Vinyl chloride, Chloromethane, and 1,3-Butadiene

. The inability to capture early eluting compounds could be due to loss of anal ytes from the trap or from excessive water caused by the purge temperature. To determine if analytes were being pushed off the en d of the trap during the 60 minute continuous purge method
at 90 o C (HAPSD), purge times between 15 and 60 minutes were test ed to determine the affect of purge time on analyte response. Table 1 shows the relative concentration of analytes detected at various purge times using a standard prepared in Ottawa Sand. All results are quantified usi ng the same five point calibration based on the 9 minute purge time from the HAPS pre-treatment method. The data clearly show a reduction in response as the purge time is increased. In general, the response for lighter, early eluting compounds such as Vinyl Chloride, Acetaldehyde, and Chloromethane decreased significantly as purge time increased. From Met hod 8260, we know that total purge volume (purge flow rate X purge time) is a critical factor in the ability to obtain consistent acceptable resp onse to the wide range of volatile compounds. It was determined that the next action taken would be to try runs that matched the total purge flow obtained in the 15 minute purge time. The lab ran the Ottawa Sand Standard using a 60 minute purge time at 90 o , but reduced the purge flow rate to 10 mL/minute to match the total purge volume of the 15 minute purge time at 40 mL/min. Although some analytes show significantly higher response at the 60 minut e purge time at 10 mL/minute, the lower response for compounds such as Chloromethane, Vinyl chloride, Chlo roethane, Bromoethene, 1,1-Dichloroethene, and Chloroform indicates that the ability to obtain sufficient and consistent response necessary for five-point calibration could be compromised for these six compounds.

Page 7 of 18Table 1 Effect of Different Purge Times and Volumes Results in ppb

Ottawa Sand Ottawa Sand Ottawa Sand Ottawa Sand Ottawa Sand Ottawa Sand
15 min Purge 30 min Purge 45 min Purge 60 min Purge 60 minPurgeWater 60 min Purge-Dry

Chloromethane 83 17 17 ND 26 5 Acetaldehyde 3050 2699 1376 1175 4187 1260 Vinyl chloride 46 38 38 ND 28 ND 1,3- Butadiene 35 26 17 10 46 ND Chloroethane 87 19 ND ND ND 1
Bromoethene 118 90 20 1 57 2 1,1- Dichloroethene 97 95 57 60 49 18 1,1- Dichloroethane 93 57 43 59 91 3 Vinyl Acetate 691 659 706 404 1250 154 2-Chloro- 1,3-butadiene 86 89 99 82 185 36 Chloroform 121 116 123 98 62 25 1,2- Dichloroethane 134 133 139 108 243 26
Benzene 105 99 114 92 198 46
Toluene 96 95 96 98 98 65 m-Xylene, p-Xylene 106 99 92 95 89 69 o-Xylene 108 98 93 95 90 71 1,1,2,2-Tetrachloroethane 3651 3343 3415 3576 3088 2686 Isopropylbenzene 101 95 91 95 91 40 Acetophenone 1828 14109 28491 37198 28633 24189

Purge Flow 40 mL/min 40 mL/min 40 mL/min 40 mL/min 10 mL/min 10 mL/min Purge Volume, ml 600 1200 1800 2400 600 600 All results were quantified using the five point calibration with a 9 minute purge time

Page 8 of 184. Hybrid Method - Final Modifications to Sample Introduction Procedure for Method 8260 Upon evaluation of the information obtained from t he various purge times and purge flow rates, the lab established a five point calibration using the following pretreatment and purging conditions:

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

Note: There was no cooling that occurred between the Pre- Heat and Purge Start Time. The sample was preheated by the autosampler directly in the purge tube and purging was initiated and continued at 90 degrees.

The sample introduction technique used is a hybridization of techniques described in EPA Me thods 5021, 5030, 5035. Gas Chromatograph and Mass Spectrometer settings were the same settings used by the lab during Method 8260 analysis using sample introduction techniques 5030/5035. Al ternate method approval should not be required for these modifications. The calibration results are included in Appendix B.

5. Results of Sample Analyses Using Hybrid Method 8260

A Stripper Wet Cake sample was analyzed three cons ecutive times to determine recovery efficiency. The sample was placed in a 40 mL vial, pre-heated, and purged directly in the vial. After the first and second runs, the sample was cooled to room temperature. Additional internal and su rrogate standards were added through the septa with a small gauge needle as specified in EPA Method 5035. The results of the three consec utive runs using 0.5 gram of sample are shown in Table 2. 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 response, inconsistent results, and poor chromatogr aphy and were not evaluated.

Acetaldehyde and Chloroethane exhibited poor chromatogra phic behavior in the second and third runs using 0.5 gram of sample. Slight retention time shifts were observed for Vinyl Chloride and Chloroethane in the first run. These shifts may have been due to the concentrations present. The poor chromatography and retention time shifts could also be an indication that moisture management from the elevated purge temperature is an issue in the method. Results for Vinyl Chloride and Chloroethane in Run 1 are reported as estimat ed concentrations above the calibration range. The 200 ppb standard in the calibration curve was dropped from the calibrat ion curve for Vinyl Chloride because the response factor was inconsistent with the response factor obtained at lower conc entrations. It is possible that this reflects an error in the

Page 9 of 18Page 10 of 18 standard preparation or is an issue that can be solved with increased familiarity and experience with the new operating conditions.

It will be necessary to determine how results above the ca libration range will be handled. While it is possible to accurately weigh sample weights less than 0.5 gram, consid eration will need to be given to the impact on representative sub-sampling. Further work to investigate the acet aldehyde 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 ru ns) process. 1,1-Dichloroethane also shows higher concentrations in the second and third run than were expecte d. Acetophenone and 1,2-Dichloroethane show incomplete recovery in the first run, but are absent in the third run.

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

The results obtained by the Traditional Method 8260 (Met hanol Extraction) were almost 10 times lower than the results obtained by Method 107. The results obtained by t he Hybrid Method 8260 were 56 -6 9% 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. No other HAPs were measured above the detecti on limit in the Methanol Extract. The detection limits for the Methanol Extraction procedure ar e approximately five times higher than by the Hybrid Method 8260.

Dispersion resin and suspension resin from two other facilities were also analyzed. Ev aluation 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 phases if a homogenous subsample can be obtained. The data should be compared to prior data gathered using traditional 8260. Process knowledge should be used to as sess whether the Hybrid Method 8260 is "creating" HAP compounds through thermal decomposition and/or other reactions.

The raw data from all sample analyses are included in Appendix C.Table 2 Results of Hybrid 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 Stripp

er Stripper Total % Rec % Rec % Rec Total of 3 Runs Method 107 Method 8260 Methanol Extract Wet Cake Run 1, ug/KG Wet Cake Run 2, ug/KG Wet Cake Run 3, ug/KG Runs 1-3, ug/KG Run 1 Run 2 Run 3 ppm, Dry Wt ppm, Dry Wt ppm, Dry Wt.

Chloromethane ND ND ND ND ND Acetaldehyde ND 1090 RP 725 RP 1815 0 60 39.9 NA

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 NA Chloroethane 2070 ER 624 P 210 RP 2904 71.2 21.5 7.2 ND
Bromoethene ND ND ND ND ND 1,1- Dichloroethene ND ND ND ND ND 1,1- Dichloroethane 194 155 101 450 43.1 34.4 22.4 ND Vinyl Acetate ND ND ND ND ND 2-Chloro- 1,3-butadiene ND ND ND ND ND Chloroform ND ND ND ND ND 1,2- Dichloroethane 133 87 ND 220 60.4 39.5 0 ND
Benzene ND ND ND ND ND
Toluene ND ND ND ND ND m-Xylene, p-Xylene ND ND ND ND ND o-Xylene ND ND ND ND ND 1,1,2,2-Tetrachloroethane ND ND ND ND ND Isopropylbenzene ND 91 52 143 0 63.6 36.4 ND Acetophenone 2090 3260 ND 5350 39.1 60.9 0 NA Dibromofluoromethane, SR 94 71 63 101 Toluene, d8 SR 62 67 79 95 4-Bromofluorobenzene, SR 32 78 88 93 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 ND - Not Detected NA- Not Analyzed

Page 11 of 18Table 3 Results of Resin Samples from Three Facilities

Using Hybrid Method 8260, Single Extraction

OxyVinyls Wet Cake,

ug/KG Detection Limit Shintech Dryer Wet

Cake, ug/KG Detection Limit Formosa Dispersion

Resin, ug/KG Detection Limit

Chloromethane ND 50 ND 50 ND 25 Acetaldehyde ND 500 ND 500 5980 250 Vinyl chloride 1300 E 50 5120 E 50 ND 25 1,3- Butadiene ND 50 ND 50 ND 25 Chloroethane 2070 E 50 421 50 175 25
Bromoethene ND 50 ND 50 ND 25 1,1- Dichloroethene ND 50 ND 50 ND 25 1,1- Dichloroethane 194 50 ND 50 30 25 Vinyl Acetate ND 50 ND 50 368000 E 25 2-Chloro- 1,3-butadiene ND 50 ND 50 ND 25 Chloroform ND 50 ND 50 ND 25 1,2- Dichloroethane 133 50 58 50 205 25
Benzene ND 50 ND 50 ND 25
Toluene ND 50 ND 50 69 25 m-Xylene, p-Xylene ND 100 ND 100 ND 50 o-Xylene ND 50 ND 50 ND 25 1,1,2,2-Tetrachloroethane ND 50 ND 50 ND 25 Isopropylbenzene ND 50 117 50 ND 25

Acetophenone 2090 2000 ND 2000 2070 1000 Dibromofluoromethane, SR 94 113 294 Toluene, d8 SR 62 105 163 4-Bromofluorobenzene, SR 32 71 88

Note: The Formosa Dispersion Resin sample analysis was pe rformed using 1 gram of samp le instead of the 0.5g that was determined to work more effectively. This and the hi gh concentration of Vinyl Acetat e may have contributed to the high surrogate recovery.

Page 12 of 18B. Water Soluble HAPs (Methanol, Acetaldehyde, Formaldehyde, Acetophenone) The second major objective was to try to determine if the water soluble HAPs - methanol, acetaldehyde, formaldehyde, and acetophenone are so preferentially partitioned to the water phase (including that washed off the resin particles with a water rinse/extraction), that the amount of t hem in the solid resin phase is negligible. This would allow future analysis of the water phase of the slurry without need to perform separate solvent extractions of the solid resin phase and the aqueous phase. For this portion of the study , an evaluation was performed to determine if Method 8015 could be used for the water soluble HAPs instead of Method 8270. A colorimetric method for Formaldehyde was also used to determine its suitability for measurement of water soluble HAPs. To support this objective, an a ttempt was made to develop a method based on EPA Method 8015 that could be used to perform a single analysis and obtain results for the water soluble HAPs. Various columns and solvent combinations were tested to see if it was feasible to obta in results from a single analysis. Standards containing methanol, acetaldehyde formaldehyde, acetophenone, benzoquinone, and hydroquinone were analyzed using various solvent and column configurations. Standards were analyzed individually or as part of a combined standard (as deemed appropriate) and analyzed by GC/FID. The results of the variations performed are described in the following sections.

1. Direct Aqueous Injection (DAI) on Nukol Column The chromatograms are included in Appendix D1-D3.

 Methanol had to be analyzed separately from other com pounds due to issues with separation and finding compatible solvent for all compounds.

 Were able to see 1 ppm standard of me thanol, acetaldehyde, and formaldehyde.

 Formaldehyde co-elutes with methanol (especially at higher concentrations). ECI attempted to resolve this issue by adjusting chromatographic conditions and using a longer column, but was not successful during the course of the study.

 Some standard solubility issues were initially encountered trying to prepare Benzoquinone and Acetophenone in water. The concentration needed for stock solution proba bly exceeded their solubility in water. This was resolved by preparing an intermediate standard in methanol but will preclude using a single calibration for all compounds since Methanol is one of the analytes of interest.

 Acetophenone and Hydroquinone were not detected using the Nu kol column via direct aqueous injection. This is most likely because these compounds have boiling points higher than the upper temperature limit of the column.

2. Standards in Methylene Chloride: Acetone Solvent on DB-5 The raw data are included in Appendix D4-D8.

 Were able to see 10 ppm Acetophenone, Benzoquinone, and Hydroquinone.

Page 13 of 18 Were able to separate Benzoquinone and Hydroquinone when both compounds are in standard.

 "Ghost" peaks were observed when 1000 ppm individual standards of Benzoquinone and Hydroquinone are run separately indicating some potential breakdown between the two at this high concentration.

 Could not do methanol in this solvent because acetone co-elutes.

 Determined that some form of concentration w ill be required to achieve 1 ppm detection limit.

3. Standards in Methylene Chloride: Acetone Solvent on Nukol Column The raw data are included in pages D9-D11.

 Were able to see 10 ppm of Acetophenone.

 Benzoquinone and Hydroquinone did not come out at 100 ppm; however there were carryover peaks in subsequent 10 ppm and 1 ppm runs. This may indicate that the maximum temperature that can be used for this column is too low relative to the boiling point of these compounds.

 Determined that some form of concentration will be requi red to achieve 1 ppm detection limit for Acetophenone in solid samples. 4. Standards in Hexane if Micro-extracti on of Water Extract is Performed on DB-624 :

 Issues with Acetophenone, Benzoqui none, and Hydroquinone were init ially encountered when trying to prepare/run directly in hexane. These were reso lved by preparing an intermediate standard in methanol.

 Were unable to separate Acetaldehyde, Methanol or Formaldehyde from Hexane.

 Based on prior experience with DB-5 column, it was determined that it would not be possible to separate these compounds from the Hexane solvent using a DB-5 Column.

5. Standard s in Water on DB-624, Direct Aqueous Injection Chromatograms are shown in pages D12-D13

.

 Cannot see Benzoquinone on DB624 column.

 ECI was not able to separate Acetaldehyde and Methanol on DB624 during the course of this study although there is evidence in the literature (NCASI METHOD DI/MEOH-94.03) su ggests this should be possible through adjustment of chromatographic conditions. The NCASI method uses a longer column and different temperature program than was used by ECI.

 Some standard solubility issues were initially enco untered trying to prepare Acetophenone, Benzoquinone, and Hydroquinone in water. The concentration needed for the stock solution probably exceeded their solubility in water. This was resolved by preparing an intermediate standard in methanol, but will preclude using a single calibration for all compounds since Methanol is one of the analytes of interest.

Page 14 of 18The DB-5 column appears to be the most appropriate ch oice for separation of Acetophenone, Benzoquinone, and Hydroquinone. The Nukol column will work best for Metha nol and Acetaldehyde, but additional work will be needed to adequately separate Methanol and Fo rmaldehyde. Co-elution of other water soluble HAPS with methanol may have been an unrecognized problem during methanol analysis for prior samples, depending on what column was used by the laboratory. It has been determined that the lowest possible detection limit achievable for the water soluble compounds by direct aqueous injection is approximately 1 mg/L for Me thanol, Acetaldehyde, and Formaldehyde. An extraction/ concentration step will be necessary to achieve detection limits lower than 10 mg/L for aqueous and 50 mg/KG for solid samples for acetophenone, benzoquinone, and hydroquinone. The hexane micro-extraction can possibly be used for these compounds, but ECI is not sure that this would yield significantly better results than are obtained by the methylene chloride: acetone extraction/concentration of Method 8270. It is possible that the recovery for benzoquinone and hydroquinone could be improved.

C. Colorimetric Method for Formaldehyde

 Set up colorimetric method and established calibration curve in water.

 MDL study showed 0.10 mg/L in water detection limit.

 Successful recovery and calibration when using the extr action fluid specified in Method 8315 (HPLC) indicating that this would be an acceptable extraction flui d for solids using the colorimetric method.

 Extraction fluid blank had some residual formaldehyde background when compared to water calibration.

 Calibrating using standards prepared in the extraction fluid w ill probably resolve background issue.

 Calibration using the TCLP extraction fluid of Method 8315 was successful with an MDL of 0.10 mg/L. The raw data for the Formaldehyde analyses are included in Appendix E.

D. Results of Partitioning Study for Water Soluble HAPS

A Stripper Wet Cake (wet PVC resin from filtration of slurry stripper discharge) sample was extracted three consecutive times (same sample aliquot extracted over again) to evaluate recovery efficiency. Two extraction media were used, Deionized Water and TCLP Extr action Fluid #1 (as per EPA Method 8315). The samp le was extracted as described in Method 8315. Extraction fluid (100 mL) and 20 grams of sample were added to a jar and tumbled at 30 rpm for 18 + 2 hours. The liquid was separated from the solid using a luer lock 60 mL syringe equipped with a 0.7 micron syringe filter. The volume removed after each extraction was measured so that the volume of water absorbed by the resin could be determined. The water and TCLP fluid extracts were analyzed for Formaldehyde and Methanol. Formaldehyde was not detected in any of the extracts from the stripper Wet Cake. The raw data are included in Appendix E.

Page 15 of 18The residues remaining after the third extraction were sent to the Oxy-Wichita research laboratory for dissolution in Tetrahydrofuran (THF) and subsequent analysis by GC/FID. The OxyWichita lab reported some difficulty with the resin analysis. The peaks did not resolve completely and the THF solution of the samples got very viscous and hard to work with. The chromatograms, included in Appendix D, seem to i ndicate the presence of some residual water soluble HAPs in the resin. Since the results were not quantified, it was not possible to determine if their pr esence was associated with the residual water or the actual resin. The compounds were not detected in the aqueous extracts, so it would be assumed they were not separated from the resin itself. However, since the data were not quantified, it is not possible to determine where the concentration was in relation to the detection limit so no definitive conclusion should be drawn from this data.

E. Results of Examination of Benzoquinone and Hydroquinone Resolution Additional work was performed by Gas Chromatography /Mass Spectrometry to determine if Benzoquinone and Hydroquinone could be distinguished from each other during an alysis by Method 8270. The lab ran a standard containing equal amounts of each of the two compounds. Separate peaks were observed for Benzoquinone and Hydroquinone. However, a standard containing just Benzoquinone was analyzed; there was some apparent breakdown to Hydroquinone. This would indicate that under the analytical conditi ons used by ECI for hydroquinone analysis, some benzoquinone would be included in the quantitation of hydroquinone. It is important to note that these standards did not go through the extraction process so the stability of these compounds through t he extraction process is unknown at this time. It is not possible to say if this is true for other laboratories, unless t hey are using the exact same conditions as ECI. The data are included in Appendix F.

V. Conclusions

A. Modifications to Method 8260

The Hybrid Method 8260 appeared to yield the best success across the entire list of HAPs included. Initial data indicate recovery may be 5-10 times higher for Vinyl chloride than is obtained when analyzed using methanol extraction and Method 8260 which seems to support the observations of the VI . The result of the split sample for Vinyl chloride was closer to what was obtained by Method 107 than has been seen in the past when results obtained from methanol extractions are compared to results from Method 107. HAPs were detected using the Hybrid Method that were not present in the methanol extraction/analysis of the resin. The data from Hybrid Method 8260 demonstrates the potential for use for the following compounds: Chloromethane, Vinyl chloride, 1,3-Butadiene, Bromoethene, 1, 1-Dichloroethene, Vinyl Acetate, 2-Chloro-1,3-butadiene, Chloroform, Benzene, Toluene, Xylenes, and 1,1,2,2-Tetrachloroethane. While there were indications during the consecutive extraction study that the method might not be suitable as performed for Acetaldehyde, Chloroethane, 1,1-

Page 16 of 18Dichloroethane, 1,2-Dichloroethane, and Is opropylbenzene, it is possible that the in itial results were affected by carryover or moisture management issues that could be resolved. The data indicate that the method would not be app ropriate for Acetophenone, Methanol, Formaldehyde, Benzoquinone and Hydroquinone. Acetophenone required two cycles for complete "recovery". Methanol and Formaldehyde were dropped from the method because the io n masses for these two compounds are lower than the specified scanning range for Method 8260. Benzoquinone and Hydroquinone were not detected in the analytical standard. Because of the multiple variations of modification to Method 8260 that were attempted, it was not possible to fully evaluate the performance of the final method modifications during this phase of the method development study. Additional work would be necessary to validate method perfo rmance of the Hybrid Method 8260 using these conditions and to determine if the method is sufficiently robust to demonstrate acceptable performance on an on-going basis. Issues which were not resolved include, but are not limited to:

 Further evaluation of chromatography and integration parameters to optimize calibration results.

 Determine significance of surrogate recovery results fo r Toluene d8 and 4-Bromofluorobenzene. These are lower than would normally be expected in 8260, but might be associated with absorption into 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 su fficient. This would include identifying if the problems are from moisture or from potential degradation/decomposition reactions that are thought to be occurring due to sequential heating and cooling cycles. It is unlikely that recovery for compou nds 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 anal ysis 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 indicates that something unusual is occurring upon sequential analysis.

 The data should be compared to prior data gathered using traditional 8260. Process knowledge should be used to asses whether the Hybrid Method 8260 is "creating" HAP compounds through thermal decomposition and/or other reactions.

 Determine precision of analysis from replicate analysis of the same sample for suspension resin, dispersion resin, and slurry resin.

 Perform MDL study.

 Determine minimum amount of sample that can be used (w hich will establish upper working range of method). It has already been determined that there is also an uppe r limit to the sample amount that can be used.

 Hydroquinone and Benzoquinone were not detected durin g 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

Page 17 of 18Page 18 of 18 to yield poor recoveries, it may be worthwhile to run at least one standard at a basic pH using the Hybrid Method 8260.

B. Water Soluble HAPS

ECI was unsuccessful in the attempts to develop a single method for the water soluble HAPs. Due to the analytical difficulties encountered with Method 8015 for the wa ter soluble HAPs and the THF dissolution procedure for the extracted resin, it could not be determine d analytically whether the analytes were preferentially partitioned into the water phase. Analysis of existing data may yield the best available empirical determination of the partitioning properties of these compounds in the resin slurry.

C. Formaldehyde by Colorimetric Procedure

The colorimetric procedure for formaldehyde seemed to be an effective technique. The lab was able to determine that acetaldehyde does not react as formaldehyde during t he test. The colorimetric method used for Formaldehyde (NCASI METHOD IM/CAN/WP- 99.02) reportedly has been approved by EPA fo r paper industry HAP analysis. Solid samples were prepared in accordance with the procedure de scribed in EPA Method 8315. The colorimetric procedure should be considered for use as a cost -effective alternative to Method 8315.