The Road to Recovery. Mapping Advanced Sample Preparation Techniques for GC, GC-MS and HPLC Analysis

Transcription

1 The Road to Recovery Mapping Advanced Sample Preparation Techniques for GC, GC-MS and HPLC Analysis Stephen MacDonald WCTOW April 2007

2 Outline Automated Sample Preparation Solid Phase Extraction Drying Concentration Applications Explosives SPE/HPLC List 1 Pesticides SPE/GC-MS Part per trillion PCBs SPE/GC-ECD ECD Summary

3 Sample Extraction Liquid-Liquid Solid Phase Cartridges Disks

4 Disk SPE Advantages of SPE Less Solvent No emulsions Faster Lower cost Advantages of Automation Increases productivity/sample throughput Improves accuracy and precision Reduces laboratory costs Reduces worker exposure to solvents Consistent control over critical air dry steps

5 Current Methods for Disk SPE Drinking Water (500 Series) Waste Water (600 Series) Oil and Grease (1664A) SW-846 (3535A Series) Endocrine Disruptors / Hormones Food and Beverages Crops / Soils All of these methods specify SPE disks

6 EPA Drinking Water Methods 506 Phthalates Semivolatiles Chlorinated Herbicides Semivolatiles (MS) 548 Paraquat / Diquat 549 Endothall PAH s Haloacetic Acids

7 Waste Water Methods Chlorinated Pesticides and PCB s Dioxin 1664A - Oil and Grease / Non-Polar Materials 1668A - Congener PCB s

8 Solid Waste Methods 8061 Phthalate esters 8081 Organochlorine pesticides 8082 PCB s 8095 Explosives 8141 Organophosphorus pesticides 8270 TCLP semivolatiles 8321 TCLP phenoxyacid herbicides 8330 Nitroaromatics / nitramines

9 Other SPE Methods Endocrine Disruptors TPH Total Petroleum Hydrocarbons GRO s and DRO s (Gas and Diesel Range Organics) Dioxin SPE IR for Off-Shore Shore Oil Platforms

10 SPE-DEX 4790 Extractor System Fully Automated, Modular Design Run up to 8 Extractors Run independently Run individual methods Use 47, 50, and 90-mm SPE disks Designed for all SPE Chemistries Preprogrammed EPA methods Bench top operation High Sample Throughput

11 SPE-DEX 4790 Extractor System Gas to deliver solvents Vacuum to remove liquids All solvents are contained in separate bottles Separates waste solvent and waste water All sample and solvent pathways are PTFE, PEEK, and Kalrez Automatically rinses sample bottle Utilizes liquid sensors; keeps disk wet

12 SPE-DEX 4790 Extractor System Analysis of PCB s in Hudson River; 8 liter sample size

13 The Drying Step Remove residual water Na 2 SO 4 Membrane Drying

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15 DryDisk Technology Unlimited water capacity The DryDisk technology is a PTFE membrane that allows organic solvent to pass through but retains residual water. The DryDisk has been optimally designed to use vacuum to increase the drying process. Typical flow rates are 100 ml / min Retained residual water can be re-extracted extracted DryDisk is available in 2 sizes: 65 mm diameter disk 20cc syringe barrel

16 The Concentration Step Purpose Methods Enrich Analytes Exchange Solvents Rotary evaporation Kuderna-Danish Water Bath with Nitrogen DryVap

17 DryVap Automated Drying and Concentrating Automatic In-Line Solvent Drying Selectable Solvent Dry Times Internal Heating Elements Automatic Heater Shutoff Utilizes Vac, Gas, and Heat Innovative Gas Sparging System Individually Sealed Vessels Reliable End Point Detection Bench Top Operation Combines KD and Nitrogen blow down into a single system

18 Samples can be poured into Disk or Tube When sample drying is required, the extract is poured into the DryDisk Assembly. The Drying time is set to the appropriate volume on the control panel. If drying is not required, the extracted sample is poured directly into the concentrator tube. The Drying time is set to zero.

19 Solvent Rinse Tube Vacuum is used to pull the solvent into the concentration tube. Pressure can also be used to assist with the solvent rinsing. During the rinse action, the solvent washes the Lid and the glass walls. Very beneficial for high boiling compounds.

20 Results PCB Congeners - GC-ECD Northeast Analytical Labs List 1Pesticides - GC-MS MN Dept of Agriculture Explosives HPLC Alpha Analytical Labs

21 Trace Level PCBs in Water (1 ppt) Northeast Analytical, Inc Technology Dr., Schenectady, NY 12308, Tel: , 4592, Fax: Rugged, Fast and Cost effective Achieves MDLs (1 PPT (ng( ng/l) for 8-liter 8 samples and 9 PPT (ng( ng/l) for 1-liter 1 samples) Reproducible results Capable of extracting 1 to 8 liter sample volume Minimal solvent usage (30ml/sample) No glassware to replace or clean Unattended operation Limited technician time Easy to use

22 SPE MDL 1-Liter Analysis ng/l per Congener Spiked mv Minutes Northeast Analytical Lab

23 SPE MDL for PCB Congeners 1-Liter Analysis ng/l per Congener Spiked Congener Conc Rcvry SD RSD MDL (2) IUPAC# ng/l (%) (ng/l) (%) (ng/l) Northeast Analytical Lab

24 SPE MDL for PCB Congeners 1-Liter Analysis ng/l per Congener Spiked Congener Conc Rcvry SD RSD MDL (2) IUPAC# ng/l (%) (ng/l) (%) (ng/l) Northeast Analytical Lab

25 Recovery of List 1 Pesticides MN Dept. Agriculture Laboratory 601 Robert Street North St. Paul, MN

26 Recovery of List 1 Pesticides Compound % Rec. RSD MDL Rep 1 Rep 2 Rep 3 Rep 4 Rep 5 Rep 6 Rep 7 Rep 8 Spike level EPTC Propachlor Ethafluralin Trifluralin Phorate Dimethoate Simazine Propazine Terbufos Fonofos Diazinon Triallate Methyl Parathion Malathion Chlorpyrifos Pendimethalin MN Dept Agriculture

27 List 1 Pesticides Continued Compound % Rec. RSD MDL Rep 1 Rep 2 Rep 3 Rep 4 Rep 5 Rep 6 Rep 7 Rep 8 Spike level Deisopropylatrazine Deethylatrazine Prometon Atrazine Chlorothalonil Metribuzin Acetochlor Alachlor Metolachlor Cyanazine Dimethenamid Tebupirimphos Tetraconazole Myclobutanil Propiconazole Tebuconazole Boscalid MN Dept Agriculture

28 Explosives Set 1 Set 2 Set 3 Ave Ext 1-5 Ext 1-5 Ext 1-5 All Runs Analyte (ng) (ng) (ng) (ng) Ave %Rec SD %RSD 26DANT DANT HMX RDX PICRIC ,3,5-TNB ,2-DNB (Surrogate) ,3-DNB NB Tetryl Alpha Labs, Weston MA

29 Explosives Set 1 Set 2 Set 3 Ave Ext 1-5 Ext 1-5 Ext 1-5 All Runs Analyte (ng) (ng) (ng) (ng) Ave %Rec SD %RSD 2,4,6-TNT Am-2,6-DNT Am-4,6-DNT ,6-DNT #### 2,4-DNT NT NT NT NG PETN Alpha Labs, Weston MA

30 Explosives Analyte Blank 1A Blank 2A Blank 3A Blank 4A Blank 5A 26DANT n.a. n.a. n.a. n.a. n.a. 24DANT n.a. n.a. n.a. n.a. n.a. HMX n.a. n.a. n.a. n.a. n.a. RDX n.a. n.a. n.a. n.a. n.a. NB n.a. n.a. n.a. n.a. n.a. 1,2-DNB (Surrogate) ,3-DNB n.a. n.a. n.a. n.a. n.a. 2-NT n.a. n.a. n.a. n.a. n.a. 4-NT n.a. n.a. n.a. n.a. n.a. 1,3,5-TNB n.a. n.a. n.a. n.a. n.a. Alpha Labs, Weston MA

31 Explosives Analyte Blank 1A Blank 2A Blank 3A Blank 4A Blank 5A 4-Am-2,6-DNT n.a. n.a. n.a. n.a. n.a. 3-NT n.a. n.a. n.a. n.a. n.a. 2-Am-4,6-DNT n.a. n.a. n.a. n.a. n.a. 2,6-DNT n.a. n.a. n.a. n.a. n.a. 2,4-DNT n.a. n.a. n.a. n.a. n.a. 2,4,6-TNT n.a. n.a. n.a. n.a. n.a. Tetryl n.a. n.a. n.a. n.a. n.a. Picric Acid n.a. n.a. n.a. n.a. n.a. NG n.a. n.a. n.a. n.a. n.a. PETN n.a. n.a. n.a. n.a. n.a. Alpha Labs, Weston MA

32 Summary Automated Sample Preparation Techniques for GC, GC-MS, and HPLC Analysis SPE - Drying - Concentrating Wide Range of Applications EPA Approved Field Proven Better precision Reduced solvent use Reduced manpower Cost effective