Acrolein, Acrylonitrile, Styrene, and Vinyl Chloride; Acid Reactive Compounds or Not?

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Stephen T. Zeiner, CEAC Environmental Standards, Inc. Co-authors: David R.

1 Acrolein, Acrylonitrile, Styrene, and Vinyl Chloride; Acid Reactive Compounds or Not? National Environmental Monitoring Conference San Antonio, TX August 2013 Stephen T. Zeiner, CEAC Environmental Standards, Inc. Co-authors: David R. Blye, CEAC Environmental Standards, Inc. Lance Holman URS Corporation Kelly Rinehimer URS Corporation

2 Discussion Topics EPA Preservation Requirements Logistical Issues Study Objectives Study Design Study Results Study Summary Conclusions 2

3 Current Aqueous Sample EPA Preservation Requirements Vinyl Chloride and Styrene: No chemical preservation; temperature < 6⁰C Analyze within 7 days Acrolein and Acrylonitrile: Chemical preservation to ph 4 to 5; temperature < 6⁰C Analyze within 14 days Analyze within 3 days if not chemical preserved 2-Chloroethyl Vinyl Ether No chemical preservation; temperature < 6⁰C Analyze within 7 days Preservation for Majority of Volatile Organic Compounds (VOCs) Chemical preservation to ph< 2 w/hcl; temperature < 6⁰C Analyze within 14 days 3

4 Logistical Issues These five compounds are generally included in a longer list of VOC target analytes resulting in: Potentially up to 3 analyses for volatile lists Additional costs for shipping Higher costs for expedited analysis Difficulty in field preservation of samples to ph 4 to 5 4

5 Study Objectives Does preservation to ph< 2 degrade compounds? Is unpreserved holding time of 7 days for 2-Chloroethyl Vinyl Ether, Styrene, and Vinyl Chloride valid? Is unpreserved holding time of 3 days for Acrolein and Acrylonitrile valid? Study conducted on behalf of DuPont; study design by URS, analyses conducted by Lancaster Laboratories, Inc. (now Eurofins Lancaster Laboratories Environmental, LLC) 5

6 Study Design Matrices: Deionized (DI) water and authentic site groundwater (GW) Sample Types: Unpreserved - temperature < 6⁰C; no chemical preservation Preserved - temperature < 6⁰C and ph< 2 using HCl Each aliquot spiked with 100 µg/l of analyte. Analyzed 3 aliquots of each sample type every other day for 16 days. 6

7 Study Design Samples were stored in a monitored refrigerator at < 6⁰C, but not frozen SW-846 Method 5030B was used for the purge and trap step SW-846 Method 8260B was used for the analytical determination Instrument calibrated over a range of concentrations Periodic instrument tune and calibration verifications Surrogate recoveries monitored Internal standard areas monitored 7

8 Study Evaluation Sample results between 70 and 130 µg/l. Relative standard deviation < 20%. Any trends in results over study time. 8

9 Concentration, µg/l Acrolein Results 140 Acrolein, Deionized Water Unpreserved Preserved Day 16, #3 Day 16, #2 Day 16, #1 Day 14, #3 Day 14, #2 Day 14, #1 Day 12, #3 Day 12, #2 Day 12, #1 Day 10, #3 Day 10, #2 Day 10, #1 Day 8, #3 Day 8, #2 Day 8, #1 Day 6, #3 Day 6, #2 Day 6, #1 Day 4, #3 Day 4, #2 Day 4, #1 Day 2, #3 Day 2, #2 Day 2, #1 Day 0, #3 Day 0, #2 Day 0, #1 9

10 Concentration, µg/l Acrolein Results (Cont.) 140 Acrolein, Groundwater Unpreserved Preserved Day 16, #3 Day 16, #2 Day 16, #1 Day 14, #3 Day 14, #2 Day 14, #1 Day 12, #3 Day 12, #2 Day 12, #1 Day 10, #3 Day 10, #2 Day 10, #1 Day 8, #3 Day 8, #2 Day 8, #1 Day 6, #3 Day 6, #2 Day 6, #1 Day 4, #3 Day 4, #2 Day 4, #1 Day 2, #3 Day 2, #2 Day 2, #1 Day 0, #3 Day 0, #2 Day 0, #1 10

11 Acrolein Results (Cont.) Average Result (µg/l) Minimum Result (µg/l) Maximum Result (µg/l) %RSD DI, Unpreserved DI, Preserved GW, Unpreserved GW, Preserved

12 Concentration, µg/l Acrylonitrile Results 140 Acrylonitrile, Deionized Water Unpreserved Preserved Day 16, #3 Day 16, #2 Day 16, #1 Day 14, #3 Day 14, #2 Day 14, #1 Day 12, #3 Day 12, #2 Day 12, #1 Day 10, #3 Day 10, #2 Day 10, #1 Day 8, #3 Day 8, #2 Day 8, #1 Day 6, #3 Day 6, #2 Day 6, #1 Day 4, #3 Day 4, #2 Day 4, #1 Day 2, #3 Day 2, #2 Day 2, #1 Day 0, #3 Day 0, #2 Day 0, #1 12

13 Concentration, µg/l Acrylonitrile Results (Cont.) 140 Acrylonitrile, Groundwater Unpreserved Preserved Day 16, #3 Day 16, #2 Day 16, #1 Day 14, #3 Day 14, #2 Day 14, #1 Day 12, #3 Day 12, #2 Day 12, #1 Day 10, #3 Day 10, #2 Day 10, #1 Day 8, #3 Day 8, #2 Day 8, #1 Day 6, #3 Day 6, #2 Day 6, #1 Day 4, #3 Day 4, #2 Day 4, #1 Day 2, #3 Day 2, #2 Day 2, #1 Day 0, #3 Day 0, #2 Day 0, #1 13

14 Acrylonitrile Results (Cont.) Average Result (µg/l) Minimum Result (µg/l) Maximum Result (µg/l) %RSD DI, Unpreserved DI, Preserved GW, Unpreserved GW, Preserved

15 Concentration, µg/l 2-Chloroethyl Vinyl Ether Results Chloroethyl Vinyl Ether, Deionized Water Unpreserved Preserved 20 0 Day 16, #3 Day 16, #2 Day 16, #1 Day 14, #3 Day 14, #2 Day 14, #1 Day 12, #3 Day 12, #2 Day 12, #1 Day 10, #3 Day 10, #2 Day 10, #1 Day 8, #3 Day 8, #2 Day 8, #1 Day 6, #3 Day 6, #2 Day 6, #1 Day 4, #3 Day 4, #2 Day 4, #1 Day 2, #3 Day 2, #2 Day 2, #1 Day 0, #3 Day 0, #2 Day 0, #1 15

16 Concentration, µg/l 2-Chloroethyl Vinyl Ether Results (Cont.) Chloroethyl Vinyl Ether, Groundwater Unpreserved Preserved 20 0 Day 16, #3 Day 16, #2 Day 16, #1 Day 14, #3 Day 14, #2 Day 14, #1 Day 12, #3 Day 12, #2 Day 12, #1 Day 10, #3 Day 10, #2 Day 10, #1 Day 8, #3 Day 8, #2 Day 8, #1 Day 6, #3 Day 6, #2 Day 6, #1 Day 4, #3 Day 4, #2 Day 4, #1 Day 2, #3 Day 2, #2 Day 2, #1 Day 0, #3 Day 0, #2 Day 0, #1 16

17 2-Chloroethyl Vinyl Ether Results (Cont.) Average Result (µg/l) Minimum Result (µg/l) Maximum Result (µg/l) %RSD DI, Unpreserved DI, Preserved GW, Unpreserved GW, Preserved

18 Concentration, µg/l Styrene Results 140 Styrene, Deionized Water Unpreserved Preserved Day 16, #3 Day 16, #2 Day 16, #1 Day 14, #3 Day 14, #2 Day 14, #1 Day 12, #3 Day 12, #2 Day 12, #1 Day 10, #3 Day 10, #2 Day 10, #1 Day 8, #3 Day 8, #2 Day 8, #1 Day 6, #3 Day 6, #2 Day 6, #1 Day 4, #3 Day 4, #2 Day 4, #1 Day 2, #3 Day 2, #2 Day 2, #1 Day 0, #3 Day 0, #2 Day 0, #1 18

19 Concentration, µg/l Styrene Results (Cont.) 140 Styrene, Groundwater Unpreserved Preserved Day 16, #3 Day 16, #2 Day 16, #1 Day 14, #3 Day 14, #2 Day 14, #1 Day 12, #3 Day 12, #2 Day 12, #1 Day 10, #3 Day 10, #2 Day 10, #1 Day 8, #3 Day 8, #2 Day 8, #1 Day 6, #3 Day 6, #2 Day 6, #1 Day 4, #3 Day 4, #2 Day 4, #1 Day 2, #3 Day 2, #2 Day 2, #1 Day 0, #3 Day 0, #2 Day 0, #1 19

20 Styrene Results (Cont.) Average Result (µg/l) Minimum Result (µg/l) Maximum Result (µg/l) %RSD DI, Unpreserved DI, Preserved GW, Unpreserved GW, Preserved

21 Concentration, µg/l Vinyl Chloride Results 140 Vinyl Chloride, Deionized Water Unpreserved Preserved Day 16, #3 Day 16, #2 Day 16, #1 Day 14, #3 Day 14, #2 Day 14, #1 Day 12, #3 Day 12, #2 Day 12, #1 Day 10, #3 Day 10, #2 Day 10, #1 Day 8, #3 Day 8, #2 Day 8, #1 Day 6, #3 Day 6, #2 Day 6, #1 Day 4, #3 Day 4, #2 Day 4, #1 Day 2, #3 Day 2, #2 Day 2, #1 Day 0, #3 Day 0, #2 Day 0, #1 21

22 Concentration, µg/l Vinyl Chloride Results (Cont.) 140 Vinyl Chloride, Groundwater Unpreserved Preserved Day 16, #3 Day 16, #2 Day 16, #1 Day 14, #3 Day 14, #2 Day 14, #1 Day 12, #3 Day 12, #2 Day 12, #1 Day 10, #3 Day 10, #2 Day 10, #1 Day 8, #3 Day 8, #2 Day 8, #1 Day 6, #3 Day 6, #2 Day 6, #1 Day 4, #3 Day 4, #2 Day 4, #1 Day 2, #3 Day 2, #2 Day 2, #1 Day 0, #3 Day 0, #2 Day 0, #1 22

23 Vinyl Chloride Results (Cont.) Average Result (µg/l) Minimum Result (µg/l) Maximum Result (µg/l) %RSD DI, Unpreserved DI, Preserved GW, Unpreserved GW, Preserved

24 Study Summary 2-Chloroethyl Vinyl Ether recoveries for the chemical preserved samples were 0%. Recoveries for deionized water were within µg/l for all except 2-Chloroethyl Vinyl Ether. %RSDs were below 20%. No trends in recovery were observed. 24

25 Study Summary Current Aqueous Sample EPA Preservation Requirements Parameter Preservation Hold Time Vinyl Chloride Styrene 2-Chloroethyl Vinyl Ether Acrolein Acrylonitrile Remainder of VOCs <6 C 7 Days ph between 4-5 <6 C <6 C ph <2 <6 C 14 Days 3 Days 14 Days 25

26 Study Summary Proposed Aqueous Sample EPA Preservation Requirements Parameter Preservation Hold Time 2-Chloroethyl Vinyl Ether* <6 C 7 Days Vinyl Chloride Styrene ph <2 Acrolein <6 C Acrylonitrile 14 Days Remainder of VOCs *Evaluate site for 2-Chloroethyl Vinyl Ether as Contaminate of Potential Concern during initial investigation phase. 26

27 Conclusions Acrolein, Acrylonitrile, 2-Chloroethyl Vinyl Ether, Styrene, and Vinyl Chloride without chemical preservative were stable for 16 days. Appears that chemical preservation may not be necessary. Shortened holding time may not be necessary. Acrolein, Acrylonitrile, Styrene, and Vinyl Chloride with chemical preservative were stable for 16 days Appears that these parameters are not acid reactive. 27

28 Conclusions Additional study is indicated to support the proposed holding times and preservation. Potential items worthy of additional evaluation include: Variation of results in larger study sample populations Regional groundwater quality influence on VOC stability in aqueous samples 28

29 Thank You David R. Blye Environmental Standards, Inc. Lance Holman URS Corporation Kelly Rinehimer URS Corporation Eurofins Lancaster Laboratories Environmental, LLC 29

30 References Test Methods for Evaluating Solid Wastes Physical/Chemical Methods Update IVB. US EPA. February /online/index.htm Federal Register, Volume 77, Number 97. May 18,

31 Contact Environmental Standards, Inc. Setting the Standards for Innovative Environmental Solutions Headquarters 1140 Valley Forge Road PO Box 810 Valley Forge, PA Virginia 1208 East Market Street Charlottesville, VA Tennessee 8331 East Walker Springs Lane, Suite 402 Knoxville, TN Texas Richmond Avenue, Suite 350 Houston, TX Web 31

APPENDIX H CHEMICAL TESTING

APPENDIX H CHEMICAL TESTING APPENDIX H CHEMICAL TESTING TABLE OF CONTENTS ATTACHMENTS AETL Report B-10 and B-11for Disposal (16 pages) Disposal Manifest Form (3 pages) R1-AH/wp/ADY H-i Ordered By Shannon