1 The world leader in serving science
Innovations in Automated Sample Preparation
Pranathi Perati, Jing Hong, Carl Fisher, and Richard Jack
PITTCON™ Conference & Expo March 4, 2014
OT70969_E 03/14S
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The Challenge for Analysis
1.5 mL GC/LC Vial
How do we get analytes out of these samples?
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Thermo Scientific Sample Prep Product Line
Thermo Scientific™ Dionex™ ASE™ 150 and 350
Accelerated Solvent Extractors
Novel and Innovative Solutions
Thermo Scientific™ Dionex™ SolEx™ SPE Cartridges
Thermo Scientific™ Dionex™ AutoTrace™ 280 Solid-Phase Extraction (SPE) Instrument
Thermo Scientific™ Rocket™ Evaporator
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Dionex AutoTrace 280 for Liquid Samples
• Automated SPE instrument for large-volume samples (20 mL to 4 L) • Drinking water and groundwater • Wastewater with total dissolved solids (TDS) > 5%
• Dionex AutoTrace 280 Values • Reduced sample extraction cost
• Solvent consumption • Labor cost
• Reduced exposure to hazardous solvents
• Improved productivity • Six samples in 15 minutes
• Improved analytical precision • Automated sample loading and elution
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Dionex SolEx Solid-Phase Extraction Cartridges
• Cartridges designed for fast, and easy preconcentration of contaminants prior to analysis
• Offered in a variety of chemistries and sizes to fit your sample extraction needs • Silica-Based SPE Cartridges SolEx C8 SolEx C18 SolEx C8-Clean (Phthalate-Free) SolEx C18-Clean (Phthalate-Free) SolEx C18-525 SolEx Unbonded Silica
• Carbon Based SPE Cartridges SolEx Activated Carbon SolEx Graphatized Carbon
• Polymeric New SolEx Phases SolEx HRPHS SolEx SAX SolEx SCX SolEx WAX SolEx WCX
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Dionex SolEx SPE Cartridge Product Line with Associated Chemistries and Recommended Applications
Cartridge Sorbent Media Example Applications
C8 Irregular Bonded Silica Particles EPA-Approved Methods: Concentration of Pesticides, Herbicides, Hydrocarbons, Organics
C18 Irregular Bonded Silica Particles EPA-Approved Methods: Concentration of Pesticides, Herbicides, Hydrocarbons, Organics
C18-Clean Phthalate-Free Irregular Bonded Silica Particles
Contaminants: Pesticides from Water Excellent for Trace Analysis
C8-Clean Phthalate-Free Irregular Bonded Silica Particles
Contaminants: Pesticides from Water Excellent for Trace Analysis
C18-525 Irregular Bonded Silica Particles Specific for EPA Method 525.2
Concentration of Semivolatiles from Drinking Water (EPA Method 525.2)
Silica Irregular Unbonded Silica Particles (Acid Washed) Removal of Polar Impurities; Purify Polar Compounds
Silica-Based SPE Cartridges
Carbon-Based SPE Cartridges Cartridge Sorbent Media Example Applications
Carbon Activated Carbon Particles Concentration of Nitrosamines in Drinking Water (EPA Method 521) and 1.4 Dioxane in Drinking Water (EPA Method 522)
GCB No Porous Graphatized Carbon Particles
EPA-Approved Methods: Concentration of Pesticides, Herbicides, Hydrocarbons, Organics
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Dionex SolEx SPE Cartridge Product Line with Associated Chemistries and Recommended Applications
Cartridge Sorbent Media Example Applications
HRPHS Divinylbenzene (DVB) /Polyvinylpyrrolidone
Concentration: hydrophobic targets such as triclosan polyphenols, azo compounds
SAX DVB-Quaternary Ammonium Concentration: weak anions such as carboxylates
SCX DVB-Sulfonate Concentration: weak cations such as amines
WAX DVB-Amine Concentration: strong inorganic and organic anions, sulfonates, and sulfates
WCX DVB-Carboxylate Concentration: strong inorganic and organic cations, quaternary ammonium ions
Polymer-Based SPE Cartridges
Uniquely Grafted Phases to Isolate and Concentrate
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EPA Method Analytes Extraction/Analytical
Methods Chemistry Used Part Numbers
506 Pthalate and Adipate Esters SPE and GC/PID C18 074410, 074417, 074412, 074623
507 N and P-Containing Pesticides SPE and GC C18 074410, 074417, 074412, 074623
508.1 Chlorinated Pesticides, Herbicides & Organohallides SPE and GC-ECD C18 074410, 074417, 074412, 074623
521 Nitrosamines SPE and GC/MS/MS Carbon 074590
522 Dioxane SPE and GC/MS Carbon 074590
525.2 Semivolatile Organic Compounds (SVOC) SPE and GC/MS C18 074410, 074417, 074412, 074623
525.3 Semivolatile Organic Compounds (SVOC) SPE and GC/MS C18 074410, 074417, 074412, 074623
526 Semivolatile Organic in Drinking Water SPE and GC/MS HRPHS 088124, 088125, 088126, 088127, 088128
527 Flame Retardants SPE and GC/MS HRPHS 088124, 088125, 088126, 088127, 088128
528 Phenols SPE and GC/MS HRPHS 088124, 088125, 088126, 088127, 088128
529 Explosives SPE and GC/MS HRPHS 088124, 088125, 088126, 088127, 088128
532 Phenylurea SPE and HPLC C18 074410, 074417, 074412, 074623
535 Acetic Herbicides SPE and LC/MS/MS Graphitized Carbon 075898
548 Endothal SPE and GC/ECD C18 074410, 074417, 074412, 074623
539 Hormones SPE and LC/MS/MS HRPHS 088124, 088125, 088126, 088127, 088128
553 Benzidines and N-Containing Pesticides SPE and LC/MS C18 074410, 074417, 074412, 074623
554 Carbonyl Compounds SPE and LC C18 074410, 074417, 074412, 074623
U.S. EPA SPE 500 Series Methods
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EPA Method Analytes Extraction and Analytical Methods Chemistry Used Part Numbers
606, 608, 609, 611, 612
Organochlorine Pesticides and PCB’s SPE and GC/ECD C18 074410, 074417, 074412,
074623
1613 Dioxins and Furans SPE and GC/MS C18 074410, 074417, 074412, 074623
1614 Brominated Diphenyl Esters SPE and HRGCMS C18 074410, 074417, 074412,
074623
1657 OrganoPhosphorous Pesticides GPC/SPE and GC C18 074410, 074417, 074412,
074623
1664 Oil & Grease LLE and Gravimetry if less than 10% solids; 3M disks
1668a PCB and congeners SPE and HRGC/HRMS C18 074410, 074417, 074412,
074623
1694 Pharmaceuticals & Personal Care Products SPE and LC/MS/MS HRPHS 088124, 088125, 088126,
088127, 088128
U.S. EPA SPE 600/1600 Series Methods
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EPA Method Analytes Extraction and
Analytical Methods Chemistry
Used Part Numbers
8015 Non-Halogenated Organics SPE and GC (SDVB)
8061 Phthalate Esters SPE and GC C18/(SDVB) 074410, 074417, 074412, 074623
8081 Organochlorine Pesticides SPE and GC C18/(SDVB) 074410, 074417, 074412,
074623
8082 PCBs SPE and GC C18/(SDVB) 074410, 074417, 074412, 074623
8141 Organophosphorous Pesticides SPE and GC (SDVB)
8151 Chlorinated Herbicides SPE and GC (SDVB)
8270 Semivolatile Organics SPE and GC/MS C18 074410, 074417, 074412, 074623
8315 Carbonyl Compounds SPE and LC C18/(SDVB) 074410, 074417, 074412, 074623
8318 N-Methyl Carbamates SPE and LC HRPHS 088124, 088125, 088126, 088127, 088128
8330 Nitroaromatics and Nitramines SPE and LC HRPHS 088124, 088125, 088126,
088127, 088128
U.S. EPA SPE 8000 Series Methods
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EPA Method Analytes Extraction and
Analytical Methods Chemistry Used Part Numbers
1613 Dioxins and Furans SPE and HPLC C18/(SDVB) 074410, 074417, 074412, 074623
1614 Brominated Diphenyl Ethers SPE and GC/MS C18/(SDVB) 074410, 074417, 074412,
074623
1657 OrganoPhosphorous Pesticides GPC/SPE and GC C18 074410, 074417, 074412,
074623
1664 Oil and Grease LLE and Gravimetry if less than 10% solids; 3M disks
Recommend Ordering from 3M
1668 PCB and Congeners SPE and HRGC/HRMS C18 074410, 074417, 074412,
074623
1694 Pharmaceuticals and Personal Care Products SPE and LC/MS/MS HRPHS 088124, 088125, 088126,
088127, 088128
U.S. EPA SPE Emerging Contaminants Series Methods
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Triclosan
• An antibacterial used in hand soaps
• Triclosan and triclocarban linked to endocrine disruption effects
• Contaminates water and has negative impact on aquatic ecosystems
• Recoveries ranged from 96–103% when elution was performed using methanol and acetonitrile, respectively
Sample Prep Instrument: Dionex AutoTrace 280 for 6 mL Cartridge Cartridge: 6 mL, 200 mg Resin HRPHS Sample: 100mL 0.033% liquid antibacterial hand soap in Sunnyvale, CA tap water Flow Rate: 10 mL/min Elution: Acetonitrile or methanol Analytical Column: Thermo Scientific™ Acclaim™ 120, 2 × 50 mm Eluent: 65/35 Acetonitrile/water Flow Rate: 0.21mL/min Detection: UV 254nm Peak: 1. Triclosan 10mg/L Final Concn
Recovery: 103% for Acetonitrile 96% for Methanol
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Explosives (EPA Method 8330)
• Munitions disposed through combustion
• Soil and groundwater contaminated
• Target compounds are carcinogens, mutagens
Analytical Column: Acclaim Explosives E2, 3 µm, 3.0 × 250 mm Mobile Phase: 48/52 v/v MeOH/H2O Temperature: 25º C Flow Rate: 0.3 mL/min Inj. Volume: 5 µL Detection: UV at 254 nm Samples: EPA 8330 Mix, 2 ppm each)
Peaks: 1. HMX 2. RDX 3. 1,3,5-trinitrobenzene 4. 1,3-Dinitrobenzene 5. Nitrobenenze 6. 2,4,6-trinitrobenzene 7. Tetryl 8. 2,6-Dinitrotoluene 9. 2,4-Dinitrotoluene 10. 2-Nitrotoluene 11. 4-Nitrotoluene 12. 3-Nitrotoluene 13. 4-Amino-2,6-Dinitrotoluene 14. 2-Amino-4,6-Dinitrotoluene
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Sample Prep Instrument: Dionex AutoTrace 280 for 6 mL Cartridge Cartridge: 6 mL, 500 mg Resin HRPHS Eluent: Acetonitrile Flow Rate: 10 mL/min Sample: 100mL, 2ppb14 explosive Standard
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Explosives (EPA Method 8330) Recovery Data
Peaks % Recovery RSD
HMX 109% 5.6%
RDX 95% 4.0%
1,3,5-Trinitrobenzene 100% 4.0%
1,3-Dinitrobenzene 106% 5.2%
Nitrobenzene 108% 5.0%
2,4,6-Trinitrotoluene 102% 5.2%
Tetryl 112% 1.8%
2,6-Dinitrotoluene 103% 6.0%
2,4-Dinitrotoluene 105% 3.9%
2-Nitrotoluene 120% 4.3%
4-Nitrotoluene 120% 2.7%
3-Nitrotoluene 118% 4.0%
4-Amino-2,6-Dinitrotoluene 108% 3.1%
2-Amino-2,4-Dinitrotoluene 103% 5.2%
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Recovery of Hormones from Drinking Water
Hormone Cartridge 1 Cartridge 2 Cartridge 3
% Recovery RSD % Recovery RSD % Recovery RSD
Estriol 93 2.1 95 2.7 109 2.0
β-Estradiol 102 2.7 102 2.5 118 2.0
Testosterone 95 1.4 95 2.1 108 1.5
17α-Ethynylestradiol 104 1.6 107 2.7 124 2.2
Equilin 103 1.5 103 2.3 116 2.2
Estrone 101 2.3 101 2.6 115 2.1
4-Androstene-3,17-Dione 90 1.9 90 2.0 102 1.5
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Dionex ASE Systems for Solid and Semisolid Samples
Dionex ASE 350 • High-end system • Ideal for
high-throughput labs requiring automation
• Unattended extraction of up to 24 samples
• Mixing or selection of three different solvents for complex extractions
Dionex ASE 150 • Low-end system • Ideal for
low-throughput labs
• Smaller footprint that is economically priced
• Fast and efficient extraction of a single sample
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Dionex ASE Sorbents and Dispersants
• Dionex ASE Prep DE Dispersant • Pelletized diatomaceous earth dispersant and drying agent • Mixed with sample prior to adding to the extraction cell
• Dionex ASE Prep CR, Na Form • Cation-exchange resin in the sodium form • Nuetralizes strong mineral acids
• Dionex ASE Prep CR H+ • Cation-exchange resin in the hydrogen • Nuetralizes strong bases
• Dionex ASE Prep MAP • A proprietary copolymer designed to remove moisture
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Dionex ASE Prep MAP Moisture-Absorbing Polymer
• Proprietary copolymer designed to remove moisture from wet samples including soils, tissues, and food products
• Increases extraction efficiencies compared to conventional drying methods
• Polymer, when mixed with ASE Prep DE, can be used for moisture removal applications under the ASE operation conditions for extraction
• Mode of use • In-cell, in-line • In-vial, off-line • Combination
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Organochlorine Pesticide (OCP) Extraction
• A class of chemicals used to control insects since the 1940s • Pesticides are regulated by the EPA
• Federal Insecticides, Fungicide, and Rodenticide Act (FIFRA) • Maximum EPA contaminant level for OCPs
• 0.2 µg/L for lindane • 2 µg/L for endrin
Compound
% Recovery Oyster Dried with
Dionex ASE Prep MAP and DE* (n = 3)
% Recovery Oyster Dried with Sodium Sulfate**
(n = 3) Lindane 91 81
Heptachlor 93 64 Aldrin 94 66
Dieldrin 105 75 Endrin 106 70 DDT 114 69 Total 101 71
In-Cell Moisture Removal of Oyster Samples A Comparative Study of Sodium Sulfate
* Data courtesy of Department of Toxicology, Texas Tech University, Lubbock ** In-cell drying with sodium sulfate is not recommended using the Dionex ASE system
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Total Fat Extraction from Animal Tissues
• Industrial food processors are concerned with the reduction of total fat, saturated fat, and cholesterol
• The FDA Nutrition Labeling and Education Act of 1990 (NLEA) requires that all nutrient content claims (i.e., 'low fat')
• In-cell moisture removal and fat extraction
• A time-savings of three days when compared to the currently used freeze drying method
Animal No.
% Fat Extracted by Current Freeze Drying Method
% Fat Extracted Using Dionex ASE
Prep MAP Difference
111 8.5 9.0 0.55
83 4.1 4.4 0.25
26 9.5 9.6 0.02
112 8.4 8.9 0.50
* Data courtesy of Processed Foods Research Unit USDA
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Integrated Workflow Solutions for Automated Sample Preparation
Sample Prep Analysis
Total Workflow with Fast, Simplified Sample Prep
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Importance of Sample Preparation
“Eighty percent of the variance in an assay usually arises from the sample prep.” Stevenson, R. The World of Separation Science - Pittcon® 98 - Part 3 - Sample Prep - The Place to Make a Difference. Am. Lab. 1998 30 (14).
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Thank You