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
Acrolein, Acrylonitrile, Styrene,
and Vinyl Chloride;
Acid Reactive Compounds or Not?
Discussion Topics
EPA Preservation Requirements
Logistical Issues
Study Objectives
Study Design
Study Results
Study Summary
Conclusions
2
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
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
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
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
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
Study Evaluation
Sample results
between 70 and
130 µg/L.
Relative standard
deviation < 20%.
Any trends in results
over study time.
8
Acrolein Results
9
60
70
80
90
100
110
120
130
140
Day 0
, #1
Day 0
, #2
Day 0
, #3
Day 2
, #1
Day 2
, #2
Day 2
, #3
Day 4
, #1
Day 4
, #2
Day 4
, #3
Day 6
, #1
Day 6
, #2
Day 6
, #3
Day 8
, #1
Day 8
, #2
Day 8
, #3
Day 1
0, #
1
Day 1
0, #
2
Day 1
0, #
3
Day 1
2, #
1
Day 1
2, #
2
Day 1
2, #
3
Day 1
4, #
1
Day 1
4, #
2
Day 1
4, #
3
Day 1
6, #
1
Day 1
6, #
2
Day 1
6, #
3
Acrolein, Deionized Water
Unpreserved
Preserved Con
ce
ntr
atio
n, µ
g/L
Acrolein Results (Cont.)
10
60
70
80
90
100
110
120
130
140
Day 0
, #1
Day 0
, #2
Day 0
, #3
Day 2
, #1
Day 2
, #2
Day 2
, #3
Day 4
, #1
Day 4
, #2
Day 4
, #3
Day 6
, #1
Day 6
, #2
Day 6
, #3
Day 8
, #1
Day 8
, #2
Day 8
, #3
Day 1
0, #
1
Day 1
0, #
2
Day 1
0, #
3
Day 1
2, #
1
Day 1
2, #
2
Day 1
2, #
3
Day 1
4, #
1
Day 1
4, #
2
Day 1
4, #
3
Day 1
6, #
1
Day 1
6, #
2
Day 1
6, #
3
Acrolein, Groundwater
Unpreserved
Preserved Con
ce
ntr
atio
n, µ
g/L
Acrolein Results (Cont.)
11
Average
Result
(µg/L)
Minimum
Result
(µg/L)
Maximum
Result
(µg/L)
%RSD
DI, Unpreserved 111 100 120 5
DI, Preserved 101 86 120 9
GW, Unpreserved 99 80 120 10
GW, Preserved 98 88 120 9
Acrylonitrile Results
12
60
70
80
90
100
110
120
130
140
Day 0
, #1
Day 0
, #2
Day 0
, #3
Day 2
, #1
Day 2
, #2
Day 2
, #3
Day 4
, #1
Day 4
, #2
Day 4
, #3
Day 6
, #1
Day 6
, #2
Day 6
, #3
Day 8
, #1
Day 8
, #2
Day 8
, #3
Day 1
0, #
1
Day 1
0, #
2
Day 1
0, #
3
Day 1
2, #
1
Day 1
2, #
2
Day 1
2, #
3
Day 1
4, #
1
Day 1
4, #
2
Day 1
4, #
3
Day 1
6, #
1
Day 1
6, #
2
Day 1
6, #
3
Acrylonitrile, Deionized Water
Unpreserved
Preserved Con
ce
ntr
atio
n, µ
g/L
Acrylonitrile Results (Cont.)
13
60
70
80
90
100
110
120
130
140
Day 0
, #1
Day 0
, #2
Day 0
, #3
Day 2
, #1
Day 2
, #2
Day 2
, #3
Day 4
, #1
Day 4
, #2
Day 4
, #3
Day 6
, #1
Day 6
, #2
Day 6
, #3
Day 8
, #1
Day 8
, #2
Day 8
, #3
Day 1
0, #
1
Day 1
0, #
2
Day 1
0, #
3
Day 1
2, #
1
Day 1
2, #
2
Day 1
2, #
3
Day 1
4, #
1
Day 1
4, #
2
Day 1
4, #
3
Day 1
6, #
1
Day 1
6, #
2
Day 1
6, #
3
Acrylonitrile, Groundwater
Unpreserved
Preserved Con
ce
ntr
atio
n, µ
g/L
Acrylonitrile Results (Cont.)
14
Average
Result
(µg/L)
Minimum
Result
(µg/L)
Maximum
Result
(µg/L)
%RSD
DI, Unpreserved 110 100 120 4
DI, Preserved 110 110 110 0
GW, Unpreserved 110 100 120 4
GW, Preserved 109 100 120 4
2-Chloroethyl Vinyl Ether Results
15
0
20
40
60
80
100
120
140
Day 0
, #1
Day 0
, #2
Day 0
, #3
Day 2
, #1
Day 2
, #2
Day 2
, #3
Day 4
, #1
Day 4
, #2
Day 4
, #3
Day 6
, #1
Day 6
, #2
Day 6
, #3
Day 8
, #1
Day 8
, #2
Day 8
, #3
Day 1
0, #
1
Day 1
0, #
2
Day 1
0, #
3
Day 1
2, #
1
Day 1
2, #
2
Day 1
2, #
3
Day 1
4, #
1
Day 1
4, #
2
Day 1
4, #
3
Day 1
6, #
1
Day 1
6, #
2
Day 1
6, #
3
2-Chloroethyl Vinyl Ether, Deionized Water
Unpreserved
Preserved Con
ce
ntr
atio
n, µ
g/L
2-Chloroethyl Vinyl Ether Results (Cont.)
16
0
20
40
60
80
100
120
140
Day 0
, #1
Day 0
, #2
Day 0
, #3
Day 2
, #1
Day 2
, #2
Day 2
, #3
Day 4
, #1
Day 4
, #2
Day 4
, #3
Day 6
, #1
Day 6
, #2
Day 6
, #3
Day 8
, #1
Day 8
, #2
Day 8
, #3
Day 1
0, #
1
Day 1
0, #
2
Day 1
0, #
3
Day 1
2, #
1
Day 1
2, #
2
Day 1
2, #
3
Day 1
4, #
1
Day 1
4, #
2
Day 1
4, #
3
Day 1
6, #
1
Day 1
6, #
2
Day 1
6, #
3
2-Chloroethyl Vinyl Ether, Groundwater
Unpreserved
Preserved Con
ce
ntr
atio
n, µ
g/L
2-Chloroethyl Vinyl Ether Results (Cont.)
17
Average
Result
(µg/L)
Minimum
Result
(µg/L)
Maximum
Result
(µg/L)
%RSD
DI, Unpreserved 92 86 99 3
DI, Preserved 0 0 0 0
GW, Unpreserved 98 93 100 2
GW, Preserved 0 0 0 0
Styrene Results
18
60
70
80
90
100
110
120
130
140
Day 0
, #1
Day 0
, #2
Day 0
, #3
Day 2
, #1
Day 2
, #2
Day 2
, #3
Day 4
, #1
Day 4
, #2
Day 4
, #3
Day 6
, #1
Day 6
, #2
Day 6
, #3
Day 8
, #1
Day 8
, #2
Day 8
, #3
Day 1
0, #
1
Day 1
0, #
2
Day 1
0, #
3
Day 1
2, #
1
Day 1
2, #
2
Day 1
2, #
3
Day 1
4, #
1
Day 1
4, #
2
Day 1
4, #
3
Day 1
6, #
1
Day 1
6, #
2
Day 1
6, #
3
Styrene, Deionized Water
Unpreserved
Preserved Con
ce
ntr
atio
n, µ
g/L
Styrene Results (Cont.)
19
60
70
80
90
100
110
120
130
140
Day 0
, #1
Day 0
, #2
Day 0
, #3
Day 2
, #1
Day 2
, #2
Day 2
, #3
Day 4
, #1
Day 4
, #2
Day 4
, #3
Day 6
, #1
Day 6
, #2
Day 6
, #3
Day 8
, #1
Day 8
, #2
Day 8
, #3
Day 1
0, #
1
Day 1
0, #
2
Day 1
0, #
3
Day 1
2, #
1
Day 1
2, #
2
Day 1
2, #
3
Day 1
4, #
1
Day 1
4, #
2
Day 1
4, #
3
Day 1
6, #
1
Day 1
6, #
2
Day 1
6, #
3
Styrene, Groundwater
Unpreserved
Preserved Con
ce
ntr
atio
n, µ
g/L
Styrene Results (Cont.)
20
Average
Result
(µg/L)
Minimum
Result
(µg/L)
Maximum
Result
(µg/L)
%RSD
DI, Unpreserved 88 78 98 6
DI, Preserved 91 80 100 7
GW, Unpreserved 94 89 99 3
GW, Preserved 90 86 95 3
Vinyl Chloride Results
21
60
70
80
90
100
110
120
130
140
Day 0
, #1
Day 0
, #2
Day 0
, #3
Day 2
, #1
Day 2
, #2
Day 2
, #3
Day 4
, #1
Day 4
, #2
Day 4
, #3
Day 6
, #1
Day 6
, #2
Day 6
, #3
Day 8
, #1
Day 8
, #2
Day 8
, #3
Day 1
0, #
1
Day 1
0, #
2
Day 1
0, #
3
Day 1
2, #
1
Day 1
2, #
2
Day 1
2, #
3
Day 1
4, #
1
Day 1
4, #
2
Day 1
4, #
3
Day 1
6, #
1
Day 1
6, #
2
Day 1
6, #
3
Vinyl Chloride, Deionized Water
Unpreserved
Preserved Con
ce
ntr
atio
n, µ
g/L
Vinyl Chloride Results (Cont.)
22
60
70
80
90
100
110
120
130
140
Day 0
, #1
Day 0
, #2
Day 0
, #3
Day 2
, #1
Day 2
, #2
Day 2
, #3
Day 4
, #1
Day 4
, #2
Day 4
, #3
Day 6
, #1
Day 6
, #2
Day 6
, #3
Day 8
, #1
Day 8
, #2
Day 8
, #3
Day 1
0, #
1
Day 1
0, #
2
Day 1
0, #
3
Day 1
2, #
1
Day 1
2, #
2
Day 1
2, #
3
Day 1
4, #
1
Day 1
4, #
2
Day 1
4, #
3
Day 1
6, #
1
Day 1
6, #
2
Day 1
6, #
3
Vinyl Chloride, Groundwater
Unpreserved
Preserved Con
ce
ntr
atio
n, µ
g/L
Vinyl Chloride Results (Cont.)
23
Average
Result
(µg/L)
Minimum
Result
(µg/L)
Maximum
Result
(µg/L)
%RSD
DI, Unpreserved 105 72 130 14
DI, Preserved 106 85 120 8
GW, Unpreserved 105 85 120 10
GW, Preserved 109 92 120 7
Study Summary
2-Chloroethyl Vinyl Ether recoveries for the
chemical preserved samples were 0%.
Recoveries for deionized water were within
70-130 µg/L for all except 2-Chloroethyl Vinyl
Ether.
%RSDs were below 20%.
No trends in recovery were observed.
24
Study Summary
Current Aqueous Sample EPA Preservation
Requirements
Parameter Preservation Hold Time
Vinyl Chloride <6° C 7 Days
Styrene
2-Chloroethyl Vinyl Ether
Acrolein
pH between 4 - 5
<6°C 14 Days
Acrylonitrile <6°C 3 Days
Remainder of VOCs
pH <2
<6° C 14 Days
25
Study Summary
Proposed Aqueous Sample EPA
Preservation Requirements
Parameter Preservation Hold Time
2-Chloroethyl Vinyl Ether* <6° C 7 Days
Vinyl Chloride
pH <2
<6° C 14 Days
Styrene
Acrolein
Acrylonitrile
Remainder of VOCs
*Evaluate site for 2-Chloroethyl Vinyl Ether as Contaminate of Potential Concern
during initial investigation phase.
26
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
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
Thank You
David R. Blye – Environmental Standards, Inc.
Lance Holman – URS Corporation
Kelly Rinehimer – URS Corporation
Eurofins Lancaster Laboratories Environmental, LLC
29
References
Test Methods for Evaluating Solid Wastes
Physical/Chemical Methods Update IVB.
US EPA. February 2007.
www.epa.gov/epawaste/hazard/testmethods/sw8
46/online/index.htm
Federal Register, Volume 77, Number 97.
May 18, 2012. www.gpo.gov/fdsys/pkg/FR-2012-
05-18/html/2012-10210.htm
30
Contact
31
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