The Road to Recovery Mapping Advanced Sample Preparation Techniques for GC, GC-MS and HPLC Analysis Stephen MacDonald WCTOW April 2007
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
Sample Extraction Liquid-Liquid Solid Phase Cartridges Disks
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
Current Methods for Disk SPE Drinking Water (500 Series) Waste Water (600 Series) Oil and Grease (1664A) SW-846 (3535A - 8000 Series) Endocrine Disruptors / Hormones Food and Beverages Crops / Soils All of these methods specify SPE disks
EPA Drinking Water Methods 506 Phthalates 508.1 Semivolatiles 515.1 Chlorinated Herbicides 525.2 Semivolatiles (MS) 548 Paraquat / Diquat 549 Endothall 550.1 PAH s 552.1 Haloacetic Acids
Waste Water Methods 608 - Chlorinated Pesticides and PCB s 1613 - Dioxin 1664A - Oil and Grease / Non-Polar Materials 1668A - Congener PCB s
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
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
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
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
SPE-DEX 4790 Extractor System Analysis of PCB s in Hudson River; 8 liter sample size
The Drying Step Remove residual water Na 2 SO 4 Membrane Drying
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
The Concentration Step Purpose Methods Enrich Analytes Exchange Solvents Rotary evaporation Kuderna-Danish Water Bath with Nitrogen DryVap
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
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.
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.
Results PCB Congeners - GC-ECD Northeast Analytical Labs List 1Pesticides - GC-MS MN Dept of Agriculture Explosives HPLC Alpha Analytical Labs
Trace Level PCBs in Water (1 ppt) Northeast Analytical, Inc. 2190 Technology Dr., Schenectady, NY 12308, Tel: 518-346 346-4592, 4592, Fax: 518-381 381-6055 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
SPE MDL 1-Liter Analysis - 1.25 ng/l per Congener Spiked -1.40-1.60-1.80-2.00-2.20 mv -2.40-2.60 22-32.006 23-32.298 24-33.020 25-33.314 26-33.517 27-34.267 29-35.153 30-35.291 31-35.596 32-36.210 33-39.043 34-39.220 35-39.427 36-39.868 37-40.098 38-40.583 39-40.724 28-34.904 40-41.256 41-41.906 42-42.077 43-42.371 44-43.322 46-44.234-2.80 47-44.670 45-43.645-3.00-3.20 32.00 33.00 34.00 35.00 36.00 37.00 38.00 39.00 40.00 41.00 42.00 43.00 44.00 45.00 Minutes Northeast Analytical Lab
SPE MDL for PCB Congeners 1-Liter Analysis - 1.25 ng/l per Congener Spiked Congener Conc Rcvry SD RSD MDL (2) IUPAC# ng/l (%) (ng/l) (%) (ng/l) 22 1.24 98.92 0.06 5.11 0.20 23 1.25 100.01 0.04 3.46 0.14 24 1.24 98.86 0.04 3.00 0.12 25 1.20 96.21 0.02 1.26 0.05 26 1.32 105.38 0.04 2.93 0.12 27 1.24 98.86 0.04 3.00 0.12 28 1.14 91.46 0.06 4.86 0.17 29 1.29 103.00 0.06 4.55 0.18 30 1.16 92.69 0.04 3.51 0.13 31 1.20 96.40 0.05 4.00 0.15 32 1.21 96.91 0.06 5.21 0.20 33 1.32 105.62 0.04 2.73 0.11 34 1.25 100.20 0.04 3.06 0.12 Northeast Analytical Lab
SPE MDL for PCB Congeners 1-Liter Analysis - 1.25 ng/l per Congener Spiked Congener Conc Rcvry SD RSD MDL (2) IUPAC# ng/l (%) (ng/l) (%) (ng/l) 35 1.27 101.25 0.04 3.40 0.14 36 1.23 98.54 0.05 3.75 0.15 37 1.31 105.02 0.04 2.88 0.12 38 1.32 105.62 0.04 2.73 0.11 39 1.17 93.71 0.06 4.89 0.18 40 1.23 98.54 0.05 3.75 0.15 41 1.23 98.32 0.05 3.80 0.15 42 1.31 105.02 0.04 2.88 0.12 43 1.32 105.38 0.04 2.93 0.12 44 1.23 98.64 0.06 4.76 0.18 45 1.32 105.38 0.04 2.93 0.12 46 1.23 98.64 0.06 4.76 0.18 47 1.31 105.02 0.04 2.88 0.12 Northeast Analytical Lab
Recovery of List 1 Pesticides MN Dept. Agriculture Laboratory 601 Robert Street North St. Paul, MN 55155-2531
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 70 13.65 0.14 0.41 0.36 0.29 0.37 0.31 0.39 0.29 0.39 0.50 Propachlor 96 7.39 0.11 0.53 0.49 0.44 0.49 0.44 0.51 0.44 0.50 0.50 Ethafluralin 85 6.97 0.09 0.45 0.45 0.41 0.44 0.40 0.44 0.37 0.45 0.50 Trifluralin 85 4.70 0.06 0.43 0.43 0.41 0.44 0.41 0.45 0.39 0.44 0.50 Phorate 87 8.48 0.11 0.48 0.45 0.39 0.45 0.39 0.47 0.40 0.46 0.50 Dimethoate 108 4.26 0.07 0.51 0.52 0.57 0.54 0.56 0.55 0.55 0.51 0.50 Simazine 94 2.19 0.03 0.46 0.47 0.49 0.48 0.46 0.48 0.47 0.47 0.50 Propazine 95 1.59 0.02 0.46 0.48 0.48 0.48 0.47 0.48 0.47 0.48 0.50 Terbufos 91 6.34 0.09 0.47 0.47 0.43 0.47 0.42 0.48 0.41 0.48 0.50 Fonofos 88 5.30 0.07 0.47 0.45 0.42 0.45 0.41 0.46 0.41 0.45 0.50 Diazinon 98 3.45 0.05 0.50 0.50 0.49 0.51 0.46 0.49 0.47 0.50 0.50 Triallate 86 4.65 0.06 0.44 0.44 0.41 0.45 0.41 0.44 0.40 0.45 0.50 Methyl Parathion 108 3.50 0.06 0.55 0.55 0.56 0.55 0.52 0.55 0.52 0.51 0.50 Malathion 111 1.34 0.02 0.55 0.56 0.56 0.56 0.55 0.57 0.55 0.55 0.50 Chlorpyrifos 99 2.60 0.04 0.47 0.50 0.49 0.50 0.49 0.50 0.48 0.51 0.50 Pendimethalin 96 2.60 0.04 0.46 0.48 0.48 0.50 0.47 0.49 0.47 0.48 0.50 MN Dept Agriculture
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 75 5.52 0.06 0.33 0.37 0.39 0.38 0.40 0.38 0.38 0.37 0.50 Deethylatrazine 100 1.85 0.03 0.48 0.50 0.51 0.50 0.51 0.50 0.50 0.50 0.50 Prometon 94 1.36 0.02 0.46 0.47 0.48 0.47 0.48 0.47 0.47 0.47 0.50 Atrazine 100 1.85 0.03 0.50 0.49 0.51 0.51 0.49 0.50 0.49 0.51 0.50 Chlorothalonil 57 4.19 0.04 0.29 0.29 0.29 0.28 0.28 0.30 0.26 0.28 0.50 Metribuzin 96 1.57 0.02 0.48 0.48 0.49 0.48 0.48 0.49 0.47 0.47 0.50 Acetochlor 101 2.10 0.03 0.51 0.51 0.51 0.51 0.49 0.52 0.49 0.51 0.50 Alachlor 98 1.54 0.02 0.49 0.49 0.49 0.50 0.48 0.50 0.48 0.49 0.50 Metolachlor 104 3.47 0.05 0.51 0.52 0.56 0.52 0.50 0.53 0.51 0.52 0.50 Cyanazine 126 3.17 0.06 0.66 0.63 0.64 0.63 0.59 0.63 0.62 0.64 0.50 Dimethenamid 99 1.80 0.03 0.50 0.49 0.49 0.50 0.48 0.50 0.48 0.50 0.50 Tebupirimphos 83 6.58 0.08 0.44 0.41 0.38 0.40 0.41 0.38 0.44 0.45 0.50 Tetraconazole 108 3.45 0.11 1.09 1.05 1.03 1.06 1.11 1.05 1.10 1.14 1.00 Myclobutanil 99 5.96 0.18 1.07 1.07 0.90 0.99 1.03 0.96 0.96 0.97 1.00 Propiconazole 122 3.86 0.07 0.66 0.60 0.60 0.62 0.61 0.58 0.62 0.60 0.50 Tebuconazole 115 1.86 0.06 1.14 1.16 1.12 1.14 1.19 1.13 1.15 1.14 1.00 Boscalid 124 7.05 0.26 1.16 1.27 1.31 1.11 1.18 1.19 1.34 1.33 1.00 MN Dept Agriculture
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 22.99 23.08 23.12 23.06 92 0.832 3.607 24DANT 22.94 23.28 23.62 23.28 93 0.864 3.711 HMX 23.21 23.43 22.00 22.88 92 1.146 5.010 RDX 24.49 24.39 23.42 24.10 96 1.129 4.686 PICRIC 24.57 24.92 25.40 24.96 100 1.034 4.143 1,3,5-TNB 18.64 18.83 18.16 18.54 74 0.920 4.963 1,2-DNB (Surrogate) 23.42 23.54 23.59 23.52 94 0.853 3.626 1,3-DNB 24.46 24.56 23.37 24.13 97 1.289 5.342 NB 22.91 23.04 22.16 22.70 91 1.383 6.092 Tetryl 36.28 35.38 35.13 35.59 142 1.476 4.147 Alpha Labs, Weston MA
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 19.81 19.79 18.67 19.42 78 0.963 4.956 4-Am-2,6-DNT 25.61 25.76 25.54 25.64 103 1.149 4.481 2-Am-4,6-DNT 22.47 22.46 22.21 22.38 90 0.841 3.759 2,6-DNT 19.54 21.29 18.17 19.67 79 1.982 #### 2,4-DNT 26.53 26.39 26.60 26.51 106 1.455 5.488 2-NT 22.78 22.88 22.77 22.81 91 1.268 5.557 4-NT 24.76 25.00 24.78 24.85 99 0.980 3.946 3-NT 23.65 23.79 23.62 23.69 95 1.319 5.569 NG 246.10 241.15 250.61 245.95 98 8.605 3.499 PETN 241.44 237.70 234.46 237.87 95 10.449 4.393 Alpha Labs, Weston MA
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) 18.80 21.60 21.50 21.73 21.84 1,3-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
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
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