2. ENVIRONMENTAL ANALYSIS I. Solid Phase Extraction SPE sorbents

3. SORBENT SELECTION

4. Which Sorbent? EPA 525.1 analytes ä OC / OP / ON-pesticides ä PCBs ä PAHs ä Phthalates

5. Analyte Properties OCH 2 COOH Cl 2,4 D Benzo [b] fluoranthene Heptachlor 2 CCl Cl

6. InstrumentationInstrumentation v Tekmar AutoTrace SPE workstation v HP 5890 GC w. 5971 MSD v IST Isolute SPE columns

7. The Method: EPA 525.1 1. Sample pre-treatment 2. Column solvation 3. Column equilibration 4. Sample application 5. Interference elution 6. Analyte elution Na 2 SO 3, HCl to pH=2, IPA wetting agent 10 mL IPA 10 mL water One liter in 1/2 hour 10 mL water, one min N 2 Two x 2 mL Ace/EtAc 75:25 60 minutes for ten samples

8. A Data Snapshot | COMPOUNDREP 1REP 2REP 3AVGRSD 1hexachlorocyclopentadiene817084787 2dimethylphthalate958598937 3acenaphthalene978996945 4acenaphthene-d10IS 52-chlorobiphenyl908392895 6diethylphthalate107991061044 7fluorene938592904 82,3-dichlorobiphenyl817481794 9hexachlorobenzene756873723 10simazine868088844 11atrazine10293102995 12pentachlorophenolND 13lindane10090108999 14phenanthrene-d10IS 15phenanthrene878086844 16anthracene847681 4 172,4,5-trichlorobiphenyl807376 4 18alachlor120115 1173 19heptachlor958890914 20di-n-butylphthalate1181091121135 212,2',4,4'-tetrachlorobiphenyl897980836 22aldrin888185 3 23heptachlor epoxide1039596985 242,2',3',4,6-pentachlorobiphenyl958385886 25gamma-chlordane10694 987 26pyrene948284866 27alpha-chlordane1049293977 28trans nonachlor10593 977 292,2',4,4',5,6'-hexachlorobiphenyl917586848 30endrin105100981014 31butylbenzylphthalate1211221131195 32di(2-ethylhexyl)adipate1341281221286 33benz[a]anthracene937985867 34chrysene d-12IS 35chrysene928084856 362,2'3,3',4,4',6-heptachlorobiphenyl1008495939 37methoxychlor12611310711510 382,2',3,3',4,5',6,6'-octachlorobenzene977989889 39di(2-ethylhexyl)phthalate1361301231296 40benzo[b]fluoranthene958886905 41benzo[k]fluoranthene978688906 42benzo[a]pyrene918583864 43perylene-d121001111011046 44indeno[1,2,3,c,d]pyrene110109951058 45dibenz[a,h]anthracene1201171031139 46benzo[g,h,i]perylene1019792964

9. Reducing the Data 39di(2-ethylhexyl)phthalate1361301231296 40benzo[b]fluoranthene958886905 41benzo[k]fluoranthene978688906 42benzo[a]pyrene918583864 43perylene-d121001111011046 44indeno[1,2,3,c,d]pyrene110109951058 45dibenz[a,h]anthracene1201171031139 46benzo[g,h,i]perylene1019792964 OVERALL: 88 EARLY: 91 MID: 85 LATE: 89

10. Bonded Silica Surface Si O Si O Si O Si O Si O Si Si O Si O Si OH Si OH OH OH C18C8C2PhenylC18C8C2Phenyl

11. Sorbent Screening C2C8C18PH

12. Which Sorbent? ELUTION VOLUME: 2 + 2 mL CONDITIONING: IPA SOLVENT: Acetone / EtAc 75:25 ABSOLUTE RECOVERIES ABSOLUTE RECOVERIES ± 4% C18 (EC) C18 (EC) C2 Phenyl 1g 1/2 g 1 g 1 g 1g 1/2 g 1 g 1 g SORBENT TYPE 89 75 14 39 89 75 14 39 75 75 70 60 75 75 70 60 68 67 85 82 68 67 85 82 76 73 56 66 76 73 56 66 Small, polar High MW, non-polar AVERAGE

13. What is the Compromise? ABSOLUTE RECOVERIES ABSOLUTE RECOVERIES ± 4% C18 (EC) C8 (EC) 89 91 89 91 75 85 75 85 68 89 68 89 76 88 Small, polar High MW, non-polar AVERAGE

14. So far... v Previous work compared C2, C8, C18, and Phenyl where C8 found to offer a compromise v New phases synthesized

15. New Phases Selectivity?Selectivity? Si O Si O OH Si(CH 2 ) 3 CH 3 Si O Si O Si(CH 2 ) 5 CH 3 C4 C6

16. OC Pesticides Extraction 1. Sample pre-treatment 2. Column solvation 3. Column equilibration 4. Sample application 5. Interference elution 6. Analyte elution HCl to pH=2, MeOH, 0.5% 5 mL MeOH 10 mL water One liter in 1/2 hour 10 mL water, ten min N 2 Two x 2 mL Ace/EtAc 75:25 ISOLUTE C2... C18

17. Recovery of OC Pesticides C2 C4 C6 C8 C18 alpha-BHC 0.0 33.3 84.8 89.8 90.8 beta-BHC 0.0 54.6100.2 95.0 96.9 gama-BHC 0.0 52.9102.0 96.0 98.9 delta-BHC 0.0 36.9 95.9105.8105.2 Heptachlor 88.2 91.9105.8101.0100.6 Aldrin 86.2 75.9 88.1 83.9 86.5 Heptachlor epoxide 65.4106.9103.7104.7107.1 Endosulfan I 59.3107.0107.5107.5106.5 4,4' DDE 72.4 61.9 71.3 70.0 72.8 Dieldrin 88.7103.0106.3105.0107.2 4,4' DDD 82.3 84.1 91.8 87.0 93.5 4,4' DDT 79.1 69.1 83.6 82.4 85.2 Methoxychlor105.2110.2115.0114.7121.3 Avg: 56 76 97 96 98

18. In Conclusion... v C6 and C8 have a unique balance of polar and non-polar interactions available. v Each may represent a potential compromise or optimal sorbent for addressing environmental problems.

19. ISOLUTE SPE SORBENTS

20. Non-Polar Interactions SorbentsInteractions C8 PH C2 van der Waals Si

21. ISOLUTE Non-Polar Sorbents C18 * Octadecyl MFC18 Octadecyl C8 * Octyl C2 * Ethyl C4Butyl C6Hexyl PH * Phenyl CN (EC) Cyanopropyl CH (EC) Cyclohexyl 101Polystyrene ENV+Polystyrene* EC

22. Non-Polar Sorbents (CH 2 ) 7 CH 3 CH 2 CH 3 (CH 2 ) 3 CN (CH 2 ) 17 CH 3 OctadecylOctylEthyl PhenylCyclohexylCyanopropyl

23. Polar Interactions Sorbents Interactions CN NH 2 2OH Dipole / Dipole Hydrogen-Bonding Hydrogen-Bonding O H Si N H H N O H C O O H OO H H

24. ISOLUTE Polar Sorbents SiSilica FlFlorisil NH 2 Aminopropyl PSAPrimary Secondary Amine Diol2,3-Dihydroxypropyl CN *Cyanopropyl * Also available in endcapped chemistry Used to extract polar compounds from non-aqueous matrices (e.g. Hexane, ethyl acetate, dichloromethane, etc.)

25. Polar Sorbents (CH 2 ) 3 OCH 2 CHCH 2 HOOH SiOH Cyanopropyl (CH 2 ) 3 CN(CH 2 ) 3 NH 2 Aminopropyl SilicaDiol

26. NH 2 vs. Silica Columns The use of NH 2 columns in place of silica columns is strongly recommended. This is because the activity of silica columns can be affected by moisture content. IST columns are manufactured to a constant standard moisture level, so their activity will always be reliable, but adaption of literature methods using other types of silica can be problematic. Different moisture levels will affect the amount and polarity of solvents necessary for elution of the analytes. NH 2 columns are recommended as they are much less susceptible to this variation.

27. Ionic Interactions SorbentsInteractions PRS CBA SAX Electrostatic Electrostatic Electrostatic H 3 + N SO 3 - Si H 3 + N O - O N + (CH 3 ) 3 Si - O 3 S

28. ISOLUTE Ion-Exchange Sorbents Anion Exchange: Weak: NH 2 Aminopropyl PSA Primary Secondary Amine Strong: SAX Quaternary amine PE-AX Pre-Equilibrated SAX Cation exchange: Weak: CBA Carboxypropyl Strong: SCX Benzenesulphonic acid SCX-2 Propylsulphonic acid SCX-3 Ethylbenzenesulphonic acid PRS Propylsulphonic acid

29. Ion-Exchange Sorbents (CH 2 ) 3 NH 2 Aminopropyl (CH 2 ) 3 N + (CH 3 ) 3 (CH 2 ) 3 SO 3 H SAX (quaternary amine) (CH 2 ) 3 COH O CBA (carboxylic acid) SCX (benzenesulfonic acid)PRS (propylsulfonic acid) SO 3 H

30. ISOLUTE SCX Sorbents v Extending the range of strong cation exchange sorbents in the ISOLUTE range. v The range now consists of: ä ISOLUTE SCX – medium secondary hydrophobic interactions ä ISOLUTE SCX-2 – low secondary hydrophobic interactions ä ISOLUTE SCX-3 – high secondary hydrophobic interactions

31. Strong Cation Exchangers ISOLUTE SCX Benzenesulphonic acid ISOLUTE SCX-2 Propylsulphonic acid ISOLUTE SCX-3 Ethyl benzenesulphonic acid