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 10-05-10
FINAL 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 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 significant questions about the recovery of these other HAPs 

from a PVC resin matrix. The VI contracted with ECI 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 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 water 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 the 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 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 investigations do not prove to be fruitful. 

Page 1 of 18 
III. Methods 

Method 8260 Conditions 

HAPS40 HAPS90 HAPD Hybrid Method 8260 

Pretreatment 60 minutes at 90o

C 

in Hot Block, 

transferred to 

Autosampler 

60 minutes at 

90o

C in Hot 

Block, 

transferred to 

Autosampler 

None None 

Purge Preheat 

Temp/Time 

40o

C/2 min 40oC/2 min 40oC/2 min 90o/60 min 

Purge Temperature 40o

 C 90o C 90o C 90o 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 255o

C 255oC 245oC 255oC 

Desorb Time 0.7 min 0.7 min 0.5 min 0.7 min 

Desorb Temp 260o

C 260oC 250 oC 260oC 

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 12o

/min to 180oC 12o/min to 180oC 8o/min to 220oC 12o/min to 180oC 

Hold Time 2 min 2 min 5 min 2 min 

Ramp 2 35o

C/min to 225oC 35oC/min to 

225o

C 

NA 35o

C/min to 225oC 

Hold Time 3.88 min 3.88 min NA 3.88 min 

Injector Temp 180o

 C 180o C 220oC 180o C 

Detector Temp 250o

 C 250o C 220oC 250o 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 18 
Method 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 30o

 C/min 15oC/min 30oC/min 15oC/min 15oC/min 

Final Temp 190o 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 approved by EPA for paper industry 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 information to determine if the Static Headspace Method or 

Dynamic Purge Method is likely to yield better recovery than is currently obtained for these compounds when analyzing by 

Method 8260 following methanol extraction. There are advantages 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 18 
Method 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 from the initial evaluation of 

the three different sample introduction techniques in included in Appendix A. 

1. HAPS40 Method: (Pre-treat for one hour at 90o C in a hot block prior to loading in Autosampler and purging at 40 

degrees C using Method 8260 purge conditions similar to protocol 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 18 
prior 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 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 400

 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 calibration results obtained using regular 8260 conditions. 

 Vinyl chloride and Acetaldehyde do not yield complete chromatographic 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. 

 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 provided the lower recovery is consistent. 

 All other compounds were detected with no apparent issues. 

 Two sets of 6-point calibrations were performed and reviewed from the HAPS40 Method. One set was pretreated 

for one hour at 90 degrees C with 5mL of DI water added before pretreatment, pretreated wet, (PW) and the other was 

pretreated without deionized water 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 ARF (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-Butadiene,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 response factor for standard concentrations at and above 100 

ppb for Vinyl 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. 

Page 5 of 18 
2. HAPS90 Method: (Same as HAPS 40, except using a 90o

 C purge temp after pretreatment instead of 40o). Note: 

Although the sample is heated to 90o

C for one hour, it cools down after being removed from the hot block prior to being 

purged at 90o

. 

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

 Co-elution of Vinyl chloride and Acetaldehyde 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 90o

 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 observed in the HAPS 90 Method, with response factors 

generally the same or lower than HAPS40 in both 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, Vinyl chloride, 1,3-Butadiene and Acetophenone 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-treatment step for some compounds. Some of these issues 

may have been due to a variation in the amount of time between 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 90o

C). 

 Results of triplicate (analysis of 3 different standards of same concentration, not consecutive runs of the same 

standard) analyses are not consistent. 

 Internal standard results were not consistent. 

 Poor chromatography on early eluting peaks were noted that will cause identification and quantitation problems 

with 1,3 Butadiene. 

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

 1,1,2,2 Tetrachloroethane break down to Trichloroethene is only about 10% as opposed to 100% in HAPS40 and 

90. 

Page 6 of 18 
 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. 

 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 concentrator 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 analytes from the trap or from excessive water caused by the 

purge temperature. 

 To determine if analytes were being pushed off the end of the trap during the 60 minute continuous purge method 

at 90o

C (HAPSD), purge times between 15 and 60 minutes were tested 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 using 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 Method 8260, we know that total purge volume (purge flow rate X 

purge time) is a critical factor in the ability to obtain consistent acceptable response 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 90o

, 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 minute purge time at 10 mL/minute, the lower response for 

compounds such as Chloromethane, Vinyl chloride, Chloroethane, 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 18 
Table 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 min 

PurgeWater 

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 18 
4. Hybrid Method - Final Modifications to Sample Introduction Procedure for Method 8260

 Upon evaluation of the information obtained from the 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 Methods 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. Alternate 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 consecutive 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 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 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 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 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 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 

Page 9 of 18 
Page 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 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) process. 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 chloride 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. 

 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 Hybrid Method 8260 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. No other HAPs were measured above the detection limit in the Methanol Extract. The detection limits for 

the Methanol Extraction procedure are approximately five times higher than by the Hybrid Method 8260. 

 Dispersion resin and suspension resin from two other facilities were also analyzed. 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 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 assess 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 90o

, 9 Minute Purge @ 90o

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 18 
Table 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 performed using 1 gram of sample instead of the 0.5g that 

was determined to work more effectively. This and the high concentration of Vinyl Acetate may have contributed to the 

high surrogate recovery.

Page 12 of 18 
B. 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 them 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 attempt 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 obtain 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 compounds due to issues with separation and finding 

compatible solvent for all compounds. 

 Were able to see 1 ppm standard of methanol, 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 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. 

 Acetophenone and Hydroquinone were not detected using the Nukol 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.

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 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 will 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 required to achieve 1 ppm detection limit for Acetophenone in 

solid samples. 

4. Standards in Hexane if Micro-extraction of Water Extract is Performed on DB-624: 

 Issues with Acetophenone, Benzoquinone, and Hydroquinone were initially encountered when trying to 

prepare/run directly in hexane. These were resolved 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. Standards 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) suggests 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 encountered 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. 

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The DB-5 column appears to be the most appropriate choice for separation of Acetophenone, Benzoquinone, and 

Hydroquinone. The Nukol column will work best for Methanol and Acetaldehyde, but additional work will be needed to 

adequately separate Methanol and Formaldehyde. 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 Methanol, 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 extraction fluid specified in Method 8315 (HPLC) indicating 

that this would be an acceptable extraction fluid 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 will 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 Extraction Fluid #1 (as per EPA Method 8315). The sample 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. 

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 The 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 indicate 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 presence 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 analysis 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 conditions 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 the extraction process is unknown at this time. It is not 

possible to say if this is true for other laboratories, unless they 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-

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Dichloroethane, 1,2-Dichloroethane, and Isopropylbenzene, it is possible that the initial results were affected by carryover 

or moisture management issues that could be resolved. 

 The data indicate that the method would not be appropriate for Acetophenone, Methanol, Formaldehyde, 

Benzoquinone and Hydroquinone. Acetophenone required two cycles for complete "recovery". Methanol and 

Formaldehyde were dropped from the method because the ion 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 performance 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 for 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 sufficient. 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 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 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 (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 be used. 

 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 

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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 water soluble HAPs and the THF dissolution procedure for the 

extracted resin, it could not be determined 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 the test. The colorimetric method used for Formaldehyde 

(NCASI METHOD IM/CAN/WP-99.02) reportedly has been approved by EPA for paper industry HAP analysis. Solid 

samples were prepared in accordance with the procedure described in EPA Method 8315. The colorimetric procedure 

should be considered for use as a cost-effective alternative to Method 8315.