Evaluating CLP and EPA Methods for Pesticides in Water Using Agilent J&W DB-CLP1/DB-CLP2 GC Columns

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1 Evaluating CLP and EPA Methods for Pesticides in Water Using Agilent J&W DB-CLP/DB-CLP GC Columns Application Note Environmental Authors Doris Smith and Ken Lynam Agilent Technologies, Inc. Abstract The Agilent J&W DB-CLP and DB-CLP column pair has the selectivity to separate many different halogenated compounds by GC/ECD. Chlorinated pesticides, herbicides, organohalides, and PCBs in drinking and ground water are well resolved by these columns with multiple Contract Laboratory Program (CLP) and United States Environmental Protection Agency (US EPA) methods. Some manufacturers offer different column sets for the different methods. However, the Agilent CLP single column set avoids the downtime of switching between different columns and analyzes multiple methods. This productivity increase can lead to more billable instrument-hours. Compared to other vendors columns, the J&W DB-CLP/DB- CLP provides better combinations of faster analysis times and fewer coelutions, for analysis of a wider range of pesticides and pollutants covered by US EPA methods, all in a single operation.

2 Introduction GC column manufacturers design columns specifically for pesticide residue analysis, with differing capability and efficacy. This type of measurement is typically done on columns for simultaneous primary and confirmation analysis, using a retention gap and y-splitter to connect the columns. In this application note, we analyzed pesticides and other potential water contaants according to United States Environmental Protection Agency (US EPA) and Contract Laboratory Program (CLP) methods. We used Agilent J&W DB-CLP and DB-CLP columns, a pair of arylene phases that handle high oven temperatures for rapid analysis of CLP chlorinated pesticides in drinking and ground water. We demonstrated the columns suitability for phenoxy acids, haloacetic acids, polychlorinated biphenyls, and other pollutants, according to EPA methods for the analysis of water samples. Nine CLP and EPA methods were investigated. CLP Pesticides - targeted organohalides EPA 0 -,-dibromoethane (EDB),,-dibromo--chloropropane (DBCP), and,,-trichloropropane (TCP) EPA 0 - organohalides EPA 0. - chlorinated pesticides, herbicides, and organohalides EPA - chlorinated solvents, trihalomethanes (THMs), and disinfection byproducts (DBPs) EPA. - haloacetic acids and dalapon EPA 0B (extended analyte list) - organochlorine pesticides EPA 0A - polychlorinated biphenyls (PCBs) and aroclors EPA A - chlorophenoxyacid herbicides Materials and Methods The same column pair was used for every analysis. Other conditions varied and are shown with their respective results. Traditionally, replacement of the retention gap or analytical column involved replacing the quartz y-splitter and re-establishing all column connections. To avoid the downtime and extra maintenance associated with y-splitters, we also used an Agilent Capillary Flow Technology (CFT) reusable splitter. The CFT splitter uses column connections that are individually connected to the splitter, allowing inlet and column maintenance independent of the other analytical column connection. Column : Agilent J&W DB-CLP, 0 m x 0. mm, 0. µm (p/n -) Column : Agilent J&W DB-CLP, 0 m x 0. mm, 0. µm (p/n -) Guard column: m x 0. mm, deactivated CFT device: Inert tee (p/n G-00), split ratio : Inlet liner: Inlet liner (EPA Method 0): Instrument: Sampler: Sampler (EPA Method 0 and 0.): Results and Discussion Agilent Ultra Inert, single taper splitless (p/n 0-) Agilent Ultra Inert, double taper splitless (p/n 0-) Agilent 0 GC with dual µecd Agilent Automatic Liquid Sampler Agilent B Automatic Liquid Sampler Figures to 0 show the analytical results obtained on the DB-CLP and DB-CLP columns.

3 Fast CLP pesticides - chlorinated pesticides Helium, constant flow,. ml/ Injection temperature: 0 C µl, splitless 0 C, hold 0., C/ to 0 C, C/ to 00 C, 0 C/ to 0 C, hold. Detector: µecd, 0 C 0 ng/ml CLP Pesticides Agilent J&W DB-CLP 0 0 Agilent J&W DB-CLP 0, 0. Tetrachloro-m-xylene. a-bhc. g-bhc. b-bhc. Heptachlor. d-bhc. Aldrin. Heptachlor epoxide. g-chlordane 0. a-chlordane. Endosulfan I., -DDE. Dieldrin. Endrin., -DDD. Endosulfan II., -DDT. Endrin aldehyde. Endosulfan sulphate 0. Methoxychlor. Endrin ketone. Decachlorobiphenyl Figure. Agilent J&W CLP/CLP columns analyze chlorinated pesticides according to the CLP Pesticides method in. utes.

4 EPA Method 0. -,-dibromoethane (EDB),,-dibromo--chloropropane (DBCP), and,,-trichloropropane (TCP) Helium, constant flow,. ml/ Injection temperature: 00 C µl, splitless 0 C, hold., 0 C/ to C, 0 C/ to C, hold. Detector: µecd, 00 C 00 ng/ml EPA 0. analytes, 00 ng/ml chlorinated solvents + trihalomethanes Agilent J&W DB-CLP 0 00 ng/ml chlorinated solvents + THMs 00 ng/ml EPA 0. analytes Agilent J&W DB-CLP 0 00 ng/ml chlorinated solvents + THMs 00 ng/ml EPA 0. analytes. Chloroform.,,-Trichloroethane. Carbon tetrachloride. Trichloroethene. Bromodichloromethane. Tetrachloroethene.,,-Trichloroethane. Dibromochloromethane.,-Dibromoethane (EDB) 0. Bromoform.,,-Trichloropropane (TCP).,-Dibromo--chloropropane (DBCP Figure. Agilent J&W CLP/CLP columns analyze,-dibromoethane (EDB),,-dibromo--chloropropane (DBCP), and,,-trichloropropane (TCP) according to EPA Method 0., with cooler analysis temperatures allowing a faster GC cycle time.

5 EPA Method 0 - organohalide pesticides Helium, constant flow,. ml/ Injection temperature: 0 C µl, splitless 0 C, hold 0., C/ to C, C/ to 00 C, hold. Detector: µecd, C 00 ng/ml EPA 0 analytes Agilent J&W DB-CLP 0 0, Agilent J&W DB-CLP 0 0. Hexachlorocyclopentadiene. Hexachlorobenzene. Atrazine ( µg/ml). Simazine ( µg/ml). g-bhc. Heptachlor. Alachlor ( µg/ml). Aldrin. Heptachlor epoxide 0. g-chlordane. trans-nonachlor. a-chlordane. Dieldrin. Endrin. cis-nonachlor. Methoxychlor (0. µg/ml) Figure. Agilent J&W CLP/CLP columns analyze organohalide pesticides in under utes according to EPA Method 0.

6 EPA Method 0. chlorinated pesticides and herbicides Helium, constant flow, cm/s Injection temperature: 0 C µl, splitless 0 C, hold 0., C/ to C,. C/ to C, C/ to 00 C, hold Detector: µecd, 0 C 00 ng/ml EPA 0. analytes, 00 ng/ml pesticide surrogate mix Agilent J&W DB-CLP Agilent J&W DB-CLP 0-0, Hexachlorocyclopentadiene. Etradiazole. Chloroneb. Trifluralin. Tetrachloro-m-xylene. Propachlor. Hexachlorobenzene. a-bhc. Atrazine 0. Simazine. g-bhc. b-bhc. Heptachlor. Alachlor. d-bhc. Chlorothalonil. Aldrin. Metribuzin. Metolachlor 0. DCPA. Heptachlor epoxide. Cyanazine. Butachlor. g-chlordane. a-chlordane. Endosulfan I., -DDE. Dieldrin. Chlorobenzilate 0. Endrin., -DDD. Endosulfan II., -DDT. Endrin aldehyde. Endosulfan sulfate. Methoxychlor. cis-permethrin. trans-permethrin. Decachlorobiphenyl Figure. The Agilent J&W CLP column separates all chlorinated pesticide and herbicide analytes according to EPA Method 0.

7 EPA Method - chlorinated solvents, trihalomethanes (THMs), and disinfection byproducts (DBPs) Helium, constant flow, cm/s Injection temperature: 00 C µl, splitless C, hold., 0 C/ to C, 0 C/ to 00 C, hold. Detector: µecd, 00 C 00 ng/ml chlorinated solvents, THMs and DPBs Agilent J&W DB-CLP Agilent J&W DB-CLP, Chloroform.,,-Trichloroethane. Carbon tetrachloride. Trichloroacetonitrile. Trichloroethene. Chloral hydrate. Bromodichloromethane.,-Dichloro--propanone. Dichloroacetonitrile 0. Chloropicrin. Tetrachloroethene.,,-Trichloroethane. Dibromochloromethane.,-Dibromoethane.,,-Trichloro--propanone. Bromochloroacetonitrile. Bromoform.,,-Trichloropropane. Dibromoacetonitrile 0.,-Dibromo--chloropropane Figure. The Agilent J&W CLP column separates all 0 analytes in utes according to EPA Method.

8 EPA Method. - haloacetic acids and dalapon Helium, constant flow,. cm/s Injection temperature: 0 C µl, splitless 0 C, hold 0., 0 C/ to C, 0 C/ to 00 C, hold Detector: µecd, 0 C 0 to 00 ng/ml haloacetic acids and dalapon (methyl esters) Agilent J&W DB-CLP 0, 0 Agilent J&W DB-CLP. Methyl chloroacetate (0 ng/ml). Methyl bromoacetate (0 ng/ml). Methyl dichloroacetate (0 ng/ml). Dalapon methyl ester (0 ng/ml). Methyl trichloroacetate (0 ng/ml).,,-trichloropropane (IS) (0 ng/ml. Methyl bromochloroacetate (0 ng/ml). Methyl bromodichloroacetate (0 ng/ml). Methyl dibromoacetate (0 ng/ml) 0. Methyl dibromochloroacetate (0 ng/ml). Methyl tribromoacetate (00 ng/ml) Figure. The Agilent J&W CLP/CLP column pair separates haloacetic acids and dalapon in utes according to EPA Method..

9 EPA Method 0B (extended) - organochlorine pesticides Helium, constant flow,. cm/s Injection temperature: 0 C µl, splitless 0 C, hold 0., 0 C/ to 0 C, C/ to C, C/ to 00 C, hold Detector: µecd, C 0 ng/ml EPA 0B analytes Agilent J&W DB-CLP , 0 0 Agilent J&W DB-CLP, 0 0 0, 0, 0 0.,-Dibromo--chloropropane. Hexachlorocyclopentadiene. -Bromo--nitrobenzene. Etradiazole. Chloroneb. Trifluralin. Terachloro-m-xylene. Propachlor. Diallate isomers (0 ng/ml) 0. Hexachlorobenzene. a-bhc. Pentachloronitrobenzene. g-bhc. b-bhc. Heptachlor. Dichlone. Alachlor. d-bhc. Chlorothalonil 0. Aldrin. DCPA. Isodrin. Kelthane. Heptachlor epoxide. g-chlordane. trans-nonachlor. a-chlordane. Endosulfan I., -DDE 0. Dieldrin. Chlorobenzilate (0 ng/ml). Perthane (0 ng/ml). Chloropropylate (0 ng/ml). Endrin. Nitrofen., -DDD. Endosulfan II., -DDT. Endrin aldehyde 0. Endosulfan sulphate. Captafol. Methoxychlor. Endrin ketone. Mirex. cis-permethrin. trans-permethrin. Decachlorobiphenyl Figure. The Agilent J&W CLP and CLP column separate organochlorine pesticides in less than 0 utes according to EPA Method 0B (extended).

10 EPA Method 0A- PCBs and aroclors - PCBs Helium, constant flow, ml/ Injection temperature: 0 C µl, splitless C, hold 0., 0 C/ to 0 C, hold 0., C/ to C, hold 0., C/ to C, hold Detector: µecd, 0 C 00 ng/ml PCB congeners, 00 ng/ml pesticides surrogate mix Agilent J&W DB-CLP, Agilent J&W DB-CLP BZ #. Tetrachloro-m-xylene. BZ #. BZ #. BZ #. BZ #. BZ #. BZ #. BZ #0 0. BZ #. BZ #0. BZ #. BZ #. BZ #. BZ #. BZ #. BZ #. BZ #0. BZ #0 0. BZ #0. Decachlorobiphenyl Figure. The Agilent J&W CLP/CLP column pair resolves PCB congeners and surrogates in less than utes according to EPA Method 0A. 0

11 - aroclors Inlet liner: Agilent Ultra Inert, single taper splitless (p/n 0-) Helium, constant flow,. ml/ Injection temperature: 0 C µl, splitless 0 C, hold 0., C/ to 0 C, hold Detector: µecd, 0 C 00 ng/ml individual aloclor, 00 ng/ml decachlorobiphenyl Agilent J&W DB-CLP Agilent J&W DB-CLP Aroclor 0 Aroclor Aroclor Aroclor Aroclor Aroclor Aroclor Aroclor (Continued)

12 Aroclor Aroclor Aroclor Aroclor Aroclor 0 Aroclor Decachlorobiphenyl Figure. The Agilent J&W CLP/CLP column pair resolves aroclors in under utes according to EPA Method 0A.

13 EPA Method A - chlorophenoxyacid herbicides Helium, constant flow, ml/ Injection temperature: 0 C µl, splitless C, hold 0., C/ to C, C/ to 00 C, 0 C/ to 00 C, hold. Detector: µecd, C 0 ng/ml chlorophenoxyacid herbicides (methyl esters), 0 ng/ml DCAA methyl ester, 0 ng/ml, -dibromooctafluorobiphenyl Agilent J&W DB-CLP Agilent J&W DB-CLP Dalapon methyl ester.,-dichlorobenzoic acid methyl ester. -Nitroanisole. DCAA methyl ester (surrogate satndard). Dicamba methyl ester. MCPP methyl ester. MCPA methyl ester., -DBOB (IS). Dichlorprop methyl ester 0.,-D methyl ester. Pentachloroanisole.,,-TP methyl ester.,,-t methyl ester. Chloramben methyl ester Figure 0. The Agilent J&W CLP/CLP column pair resolves chlorophenoxyacid herbicides in utes according to EPA Method A.. Dinoseb methyl ester.,-db methyl ester. Bentazon methyl ester. DCPA methyl ester. Picloram methyl ester 0. Acifluorfen methyl ester

14 Conclusions Agilent J&W DB-CLP and DB-CLP columns successfully analyze EPA methods along with CLP pesticides, without changing column sets. This capability increases sample throughput with faster analysis times for greater lab productivity. In addition, this column pair delivers fewer coelutions, allowing more accurate deteration. This column pair is the pair of choice for your dual ECD methods. For More Information These data represent typical results. For more information on our products and services, visit our Web site at To learn more about the Agilent J&W CLP & CLP GC column pair please visit Agilent shall not be liable for errors contained herein or for incidental or consequential damages in connection with the furnishing, performance, or use of this material. Information, descriptions, and specifications in this publication are subject to change without notice. Agilent Technologies, Inc., 0 Printed in the USA August, 0-0EN