1. Overview of the Technology and Best Practices
for
Sample Collection and Preservation
Judy Morgan
VP, CCO
8260
524.2
SOM02.4
624.1
SM6200

2. Six Methods…..Four Programs
RCRA
8260B, C, D
SDWA
524.2
SOM02.4
VOA
Trace & Low/Med
CWA
624.1
SM6200

3. Just Imagine…..if there were only ONE Method
Weighted? Not Weighted?
2nd Source? Primary Source?
LFB? LCS?
LOQ? CRDL? RL? MRL?
RSD? 15%, 20%, 30%
RF? Linear? Options???
Tune? There’s more than 1 way?
MDL? LOD?
In-house limits? Method limits?
Suggested? Recommended? Required?
Qualify? Okay? Not Allowed?
Recalc curve pts back to ICAL?
% D, Recovery? Etc.
Verify ICV, CCV, LCS, MS/MSD
12 hour? 24 Hour?
QUESTIONS
Standardized terms
One set of criteria
Performance Appropriate
Holding time..3,7,14
Cal Points - 5
Cal Conc – Range established for use
Internal Stds
Surrogates (not DMCs)
Batch Criteria – set
Time (12 or 24 hr) - set
QC Frequency – set
Sensitivity Ck - Set
ANSWERS
VOA by GCMS

4. WAKE UP! …..You’re Dreaming
CLP
524.2
SM6200
ONE NEW METHOD
8260
624.1

5. Finding the Foundation
Goal of VOA Analysis and GCMS Technology
Common PURPOSE
To identify purgeable organic pollutants in all types of water, including but not limited to the following: ground water, surface water, industrial (permitted) discharge, waste water, storm water, drinking water, estuaries, rivers, streams, lakes, etc.
Many contamination issues are traceable to any of the following: leaking underground fuel or solvent storage vessels, landfills, agriculture practices, and wastewater disposal.
The most probable cause for the contamination of some aquifers and surface waters has never been firmly established.

6. Finding the Foundation
Goal of VOA Analysis and GCMS Technology
Summary of Methods
Inert gas is bubbled through a known volume of water via a purging chamber.
Target analytes are efficiently transferred from aqueous to vapor phase
Vapor enters a sorbent trap where the purgeables are trapped
The trap is heated & backflushed with the gas to desorb the purgeables onto a gas chromatographic column.
The column is temperature programmed to separate the purgeables which are then detected with a mass spectrometer.
Common technique…

7. Water Related Programs & Methods
Environmental Protection Agency
Est by Exec Order
Clean Water Act
1948, 1972
Specific Methods: EPA and SM
VOA – 624.1, 6200
Safe Drinking
Water Act
1974
VOA 524.2
Resource Conservation and Recovery Act
1976
Guidance Methods: EPA SW846
VOA 8260D
Comprehensive Environmental Response, Compensation, and Liability Act 1980
Specific Methods: EPA
SOM 02.4
Trace VOA & Low/Med VOA

8. Sample Collection - Field
Method
Blank Required
Container #
524.2
(2) Field Reagent Blanks
40mL vial* w/TFE septum 2
624.1 NA
25–40mL vial* w/TFE septum NS
6200
8260 D
Trip Blank Recommended
CLP Trace
Storage Blank Required
40mL vial 3
CLP Low Med
* Wash vials, caps, and septa with detergent, rinse, and dry at 105°C for 1 h, before use in an area free of organic vapors.

9. Sample Preservation Method Unpres Pres <2 HCl Chlorinated 524.2
24 hour
14 d
Dechlorinate * prior to adding acid
624.1
7 d (Acrolein – 3 d) “
6200 NA
8260C, D
7 d (2-CEVE ASAP)
CLP Trace
10 d from rcpt.
CLP Low/med
24 hr
* Ascorbic Acid, Sodium thiosulfate

10. Blank Criteria Method Detection Levels Purge Volume 524.2 <MDL 25mL
624.1
<MDL, 1/3 Reg Limit, <1/10 conc of spl
5-25mL
6200
<MQL
8260 D
<1/2 LLOQ or <10% of conc of spls
5mL
CLP Trace
<CRQL
CLP Low Med

11. Sample Processing Method Batch Processing Calibration Levels 524.2 3
QC is per 12 hour Shift 3
624.1 5
6200
8260C, D
CLP Trace
CLP Low Med

12. Total Analytes Represented =139
Method
Analytes
524.2 84
624.1 93
6200 61
8260D
128
CLP Trace 51
CLP Low Med

13. 38 Analytes appear in ALL Methods
1,1,1-Trichloroethane
1,1,2,2-Tetrachloroethane
1,1,2-Trichloroethane
1,1-Dichloroethane
1,1-Dichloroethene (Vinylidene chloride)
1,2,3-Trichlorobenzene
1,2-Dibromo-3-chloropropane (DBCP)
1,2-Dibromoethane (EDB, Ethylene dibromide)
1,2-Dichlorobenzene
1,2-Dichloroethane
1,2-Dichloropropane
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Benzene
Bromochloromethane
Bromodichloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chlorodibromomethane (Dibromochloromethane)
Chloroethane
Chloroform
Chloromethane
cis-1,2-Dichloroethene
cis-1,3-Dichloropropene
Dichlorodifluoromethane
Ethylbenzene
Methylene chloride (DCM)
o-Xylene
Styrene
Tetrachloroethene
Toluene
trans-1,2-Dichloroethene
trans-1,3-Dichloropropene
Trichloroethene (Trichloroethylene)
Trichlorofluoromethane
Vinyl chloride

14. 6 More Analytes are Common to at least 5 Methods
CAS
624.1
6200
8260D
CLP Low Med
CLP Trace
1,2,4-Trichlorobenzene 1
2-Butanone (MEK)
Acetone
Carbon disulfide
Isopropylbenzene
Methyl tert-butyl ether (MTBE)

15. 17 More Analytes are Common to at least 4 Methods
CAS
624.1
6200
8260D
CLP Low Med
CLP Trace
1,1,1,2-Tetrachloroethane 1
1,2,3-Trichloropropane
1,2,4-Trimethylbenzene
1,3,5-Trimethylbenzene
1,3-Dichloropropane
2-Chlorotoluene
4-Chlorotoluene
Bromobenzene
Dibromomethane
m-Xylene
n-Butylbenzene
n-Propylbenzene
p-Xylene
sec-Butylbenzene
tert-Butylbenzene
2-Hexanone
4-Methyl-2-pentanone (MIBK)

16. 15 More Analytes are Common to at least 3 Methods
CAS
624.1
6200
8260D
CLP Low Med
CLP Trace
1,1-Dichloropropene 1
2,2-Dichloropropane
4-Isopropyltoluene
Hexachlorobutadiene
Naphthalene
1-Chlorobutane
Acrylonitrile
Allyl chloride
Propionitrile (ethyl cyanide)
trans-1,4-Dichloro-2-butene
m+p- Xylene
Cyclohexane
Methyl acetate
Methylcyclohexane
1,1,2-Trichloro-1,2,2-trifluoroethane

17. Analytes
Analyte
CAS
624.1
6200
8260D
CLP Low Med
CLP Trace
1,2,3-Trimethylbenzene 1
2-Chloroethanol
2-Chloroethyl vinyl ether
2-Nitropropane
Acetonitrile
Acrolein (Propenal)
Allyl alcohol
Benzyl chloride
Bromoacetone
Chloral hydrate
Chloroprene (2-chloro-1,3-butadiene)
cis-1,4-Dichloro-2-butene
Crotonaldehyde
Diethyl ether
Ethyl methacrylate
Ethyl t-butyl ether (ETBE)
Hexachloroethane
Iodomethane (Methyl iodide)
Methacrylonitrile
Methyl acrylate
Methylmethacrylate
n-Butanol (1-Butanol, n-Butyl alcohol)
Nitrobenzene (NB)
n-Propylamine
o-Toluidine
Pentachloroethane
Pyridine
t-Amyl ethyl ether (TAEE, 4,4-Dimethyl-3-oxahexane)
t-Amyl methyl ether (TAME)
t-Butyl alcohol (TBA)
Vinyl acetate
Chloroacetonitrile
Tetrahydrofuran
33 More Analytes are Common to at Least 2 of the 3 Most Common Methods (624.1, 524.2, 8260D)

18. The FINAL 30 are unique to only 1 Method
Analytes
Analyte
CAS
624.1
6200
8260D
CLP Low Med
CLP Trace
1,2,3,4-Diepoxybutane 1
1,3-Dichloro-2-propanol
1,4-Dioxane
1-Chlorohexane
1-Propanol (n-Propyl alcohol)
2-Pentanone
2-Picoline (2-Methylpyridine)
2-Propanol (Isopropyl alcohol)
Diisopropyl ether (DIPE)
Epichlorohydrin
Ethanol
Ethyl acetate
Ethylene oxide
Isobutyl alcohol
Malononitrile
Methanol
N-Nitroso-di-n-butylamine (N- Nitrosodibutylamine)
Paraldehyde
Pentafluorobenzene
Propargyl alcohol
β-Propiolactone
1,1-Dichloropropanone (1,1-Dichloro-2-propanone)
1,3-Butadiene
1-Chlorohexanone
3-Chloropropionitrile
bis (2-Chloroethyl) sulfide
Chlorodifluoromethane
Cyclohexanone
m+o- Xylene
o+p- Xylene
The FINAL 30 are unique to only 1 Method

19. Similarities & Coverage
More similarities than differences……..
Summary of Comparison
Methods were developed by the individual programs to meet the needs of that program……but there are numerous targets that are common to all programs
Enough similarities exist to form a good basis for a single method
The comparison of collection and handling requirements show that the methods have enough similarity that a best practice could easily be determined
The differences could easily be addressed by sample type:
Common sense would disallow using the method for the analysis of a trace or DW sample and known contaminated samples in the same analytical run

20. There is enough interest to support further exploration……..
Conclusion
There is enough interest to support further exploration……..
FUTURE FOCUS
Fit for Use
Flexibility to meet compliance needs
Sensitivity
Technology
Quality

21. Questions?
Thank you!