Volatile Organic Compounds in Water by Purge and Trap/Capillary Column Gas Chromatography with Photoionization (PID) and Electrolytic

Conductivity Detectors (ELCD) in Series

Elizabeth Almasi and Norman A. Kirshen Varian Chromatography Systems

Varian Application Note

Number 9

The 1986 amendments to the Safe Drinking Water Act require the determination of eight newly regulated Volatile Organic Compounds (VOCs) in addition to the trihalomethanes, and the monitoring of fifty-one other VOCs in finished drinking water, raw source water, or drinking water in any treatment stage. This analysis is performed using EPA Method 502.2. The VOCs are purged and subsequently trapped on a Tenax-silica gel-charcoal trap, as in the Method 601*, but after desorption the analysis is carried out on a capillary column and the VOCs are detected on a Photoionization Detector (aromatics) connected to an Electrolytic Conductivity Detector (halocarbons) in series. The DB-624 (30m x 0.53 mm 3 film), VOCOL (30m x 0.53 mm 3 film) or equivalent column provides improved resolution of the many VOCs and also ensures lower detection limits than was attainable with the packed column. Figure 1 shows a dual channel chromatogram of selected VOCs.
Column: Oven: Carrier: Trap: Concentration:
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19.

DB-624 30m x 0.53 mm 3 film 10/10 min, 5/min to 160/0 min Helium, 6.0 mL/min Tenax/Silica Gel/Charcoal, 11 min purge 20 ppb each component
20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. Toluene Toluene T-1,3-Dichloropropene 1,1,2-Trichloroethane Tetrachloroethene Dibromochloromethane Chlorobenzene Ethylbenzene m/p-Xylene O-Xylene Bromoform 1,1,2,2-Tetrachloroethane Bromobenzene p-Chlorotoluene 1,3-Dichlorobenzene 1,4-Dichlorobenzene 1,2-Dichlorobenzene 1,2,4-Trichlorobenzene Hexachlorobutadien

Dichlorodifluoromethane Chloromethane Vinyl Chloride Bromomethane Chloroethane Trichlorofluoromethane 1,1-Dichloroethene Methylene Chloride T-1,2-Dichloroethene 1,1-Dichloroethane Chloroform 1,1,1-Trichloroethane Tetrachloromethane Benzene 1,2-Dichloroethane Trichloroethene 1,2-Dichloropropane Bromodichloromethane C-1,3-Dichloropropene

Figure 1. The Analysis of Volatile Organic Compounds Employing a DB-624 Column and PID/ELCD Detectors

Someative identificatifurther these compounds are accsecond columnompaaing GC retention phase.with tthis e of Tent states require ons of confirmation employing a omplished by c with r dissimilar liquid times For hos purpose a column selector (Figure 2) was designed to allow confirmatory analysis by simply turning a valve (manually or standards obtained under the same chromatographic conditions. automatically) and thereby eliminating the column exchange and conditioning normally necessary. *Varian GC at W ork No. 46

Figure 2. Column Selector for VOC Analysis

The chromatograms shown in Figures 1 and 3 were obtained using the column selector. Different retention times on the DB-624 and VOCOL columns, and in a few cases reversed elution orders help provide positive identification by two column confirmation. Additional confirmatory information can be acquired for some compounds by result ratioing of VOCs which respond to both detectors, e.g., halogenated aromatic and unsaturated compounds. The result ratio of 1 indicates the presence of these dual detected contaminants. The column selector system is fully automatic in the sequence mode allowing unattended operation. Blank, calibration, and analysis runs may be executed first with the primary column and then with the confirmatory column.
Column: Oven: Carrier: Trap: Concentration: VOCOL 30m x 0.53 mm 3 film 10/10 min, 5/min to 160/0 min Helium, 6.0 mL/min Tenax/Silica Gel/Charcoal, 11 min purge 20 ppb each component

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19.

Dichlorodifluoromethane Chloromethane Vinyl Chloride Bromomethane Chloroethane Trichlorofluoromethane 1,1-Dichloroethene Methylene Chloride T-1,2-Dichloroethene 1,1-Dichloroethane Chloroform 1,1,1-Trichloroethane Tetrachloromethane Benzene 1,2-Dichloroethane Trichloroethene 1,2-Dichloropropane Bromodichloromethane C-1,3-Dichloropropene

20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37.

Toluene T-1,3-Dichloropropene 1,1,2-Trichloroethane Tetrachloroethene Dibromochloromethane Chlorobenzene Ethylbenzene m/p-Xylene O-Xylene Bromoform 1,1,2,2-Tetrachloroethane Bromobenzene p-Chlorotoluene 1,3-Dichlorobenzene 1,4-Dichlorobenzene 1,2-Dichlorobenzene 1,2,4-Trichlorobenzene Hexachlorobutadien

Figure 3. The Analysis of Volatile Organic Compounds Employing a VOCOL Column and PID/ELCD Detectors

These data represent typical results. For further information, contact your local Varian Sales Office.

GC9:1290