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