Accelerated Solvent Extraction (ASE) and Productivity ... - Dionex

Accelerated Solvent Extraction (ASE) and
Productivity Gains in Environmental Analyses
Bruce Richter1 , Sheldon Henderson1 , Eric Francis1 , Richard Carlson1 , Brett Murphy1 ,
Brian Dorich1 , Jennifer Peterson1 , Kannan Srinivasan2 , and Rahmat Ullah2 Bruce Richter
1Dionex Corporation, Salt Lake City Technical Center, Salt Lake City, Utah
2Dionex Corporation, Sunnyvale, CA USA
1 , Sheldon Henderson1 , Eric Francis1 , Richard Carlson1 , Brett Murphy1 ,
Brian Dorich1 , Jennifer Peterson1 , Kannan Srinivasan2 , and Rahmat Ullah2 1Dionex Corporation, Salt Lake City Technical Center, Salt Lake City, Utah
2Dionex Corporation, Sunnyvale, CA USA
Current ASe ® ProduCt Line
• ASE 200 introduced as an accelerated solvent extractor in 1995
– Accommodates up to 24 cells ranging from 1 to 33 mL
– Most popular ASE product
• ASE 300 introduced in 2000
– Accommodates up 12 cells ranging from 10 to 100 mL
• ASE 100 introduced in 2002
– Accommodates single sample ranging from 10 to 100 mL
Figure 1. ASE 100, ASE 200, and ASE 300.
Load Cell
Fill with 0.5–1 min
solvent
Heat and 5 min
pressurize
Static 5 min
Extraction
Flush with 0.5 min
fresh solvent
Purge with 1–2 min
nitrogen
Figure 2. ASE schematic
Pittcon 2008 Presentation
Cycle
Extract Total
ready 12–18 min
Solvent
N2
Nitrogen
Pump
Purge Valve
Oven
Extraction
Cell
Static
Valve
Collection
Vial
17567-01
Pittcon 2008 Presentation 1

ASe teChnoLogy
• Patented flow-thru design that allows solvent control separately for
each sample
– In-line filtration
– In-cell cleanup
– Fractionation or selectivity
• Control of temperature and pressure for each individual sample:
– Requires small quantities of solvent and short periods of time
– 50 mL vs. hundreds of mL
– 15 min vs. several hours
• Multiple cell sizes that support a wide range of sample sizes
(1–100 g)
• Platform for automation
• Used by government agencies and laboratories worldwide
ASe StAndArd MethodS uPdAte
• US EPA Method 3545A
– OCP, OPP, BNA, TPH, PCDD, herbicides and semivolatiles
– No other vendor has submitted data demonstrating validity
• Accepted under CLP SOW OLM04.2 (Contract Laboratory Program
Statement of Work)
• Chinese Method GB/T 19649–2005 for 405 pesticides in grains and
grain products
• German Method L00.00–34 for pesticides in foodstuffs
• ASTM Standard Practice D 7210 for additives in polymers
• Other methods in various stages of approval globally
– 16 environmental methods in China
APPLiCAtionS
Environmental Applications
• US EPA method 3545A
– Pesticides and herbicides
– PAHs and semi-volatiles
– PCBs
– Dioxins and furans
– TPH (Total Petroleum
Hydrocarbons)
– Explosives
• Air samples
– PUF (polyurethane foam) cartridges
– Quartz filters
– XAD and charcoal
• PBDEs in flora, fauna, sediments and soils
• Method 6860
– Perchlorate in soils, plants and animal tissues
• Organo-mercury, arsenic, tin and selenium
Figure 3. Schematic of selective extraction using ASE.
2 Accelerated Solvent Extraction (ASE) and Productivity Gains in Environmental Analyses
Extraction
Sample plus
dispersant
In cell absorbents to
reduce interferences
(alumina, silica, etc.)
22854

PCBs in Animal Tissues
One-Step Selective Extraction
• Egg, oyster, clam, fish, and mussel samples collected, freeze-dried,
and ground
• 2 g samples mixed with Florisil, placed on 6 g of Florisil in extraction
cell (use of in-cell absorbents)
• DCM/pentane (15:85, v/v) at 40 °C
• 1500 psi (10.34 MPa)
• 25-min extraction, 40 mL of solvent
• GC with ECD for analysis
Gomez-Ariza, J. L., et al., J. Chromatogr. A, 2002, 946, 209–219.
PCBs in Animal Tissues: Selective Extraction
• Lipid content of samples ranged from 2.9 to 10.2% by weight
• 85–120% recovery as compared to Soxhlet
• Less than 0.1% of the lipids in
sample were collected in vials
because of selective extraction
• MDLs of 0.001 to 0.004 ng/g
• Less than 11% RSD
Integrated Clean-Up: Salmon Extracts
Figure 4. Extracts with and without in-cell clean-up
of fish tissue using alumina, silica gel, and acidic
silica gel (40% H 2 SO 4 ).
Clx Clx
• Analyzed by Agilent Tech., (GC) 6890N, with a GCMate II (MS), ionization
mode, electron-capture negative ionization (ECNI), monitoring
bromines (79 and 81 m/z).
• DB5-HT column (30m)
• Top chromatogram is calibration check
• Second chromatogram is the salmon sample extract with in cell
clean-up
Data courtesy of Mark LaGuardia of VIMS
Figure 5. ASE PBDE results.
Pittcon 2008 Presentation 3

introduCing the new ASe 150 And 350
ASE 150
• Improved and repackaged ASE 100
• Faster pump (70 mL/min vs. 35 mL/min)
• Accepts both sizes of collection bottles (60- and 250-mL)
• New pneumatics use less compressed gas
• New oven block design for improved heating
• pH hardened pathway with Dionium components
– Optional Dionium cells
– Adsorbent or resin mixed with samples to
neutralize acid
• Accommodates all cell sizes (1, 5, 10, 22, 34, 66, and 100 mL)
• New industrial design: new colors and outside design; safety shields
Figure 6. ASE 150.
4 Accelerated Solvent Extraction (ASE) and Productivity Gains in Environmental Analyses
ASE 350: the New Standard
• New pump, oven block, pneumatics, safety shield, etc.
• Combination of ASE 200 and 300 capabilities
– 24 smaller cells (1, 5, 10, 22, or 34 mL)
– 19 larger cells (66 or 100 mL)
– 19 smaller cells and 5 larger cells
– 60- or 250-mL collection bottles (up to 28 small and 5 large)
• New colors and industrial design
• pH hardened pathway with Dionium components
– Optional Dionium cells
– Adsorbent or resin mixed with samples to neutralize acid
• Integrated Solvent Controller
• New mode of operation—Solvent Saver Mode
• USB port for firmware update and computer connection
– Chromeleon ® control not available at introduction
Figure 7. ASE 350.

Figure 8. ASE 350 (blue) and ASE 300 with solvent controller (orange). Smaller
overall footprint; less total bench space required
innovAtion in teChnoLogy
pH-Hardened pathway
• Resistant to acids and bases
– 0.1 M HCl, H SO , NaOH, KOH
2 4
– Cannot pump strong acids or bases
– Can perform acidic or alkaline
pretreatments
• Inert cells with Dionium
– Stainless steel standard
• Acidic adsorbents can be better utilized for
selective extractions
Solvent
Pretreated
Matrix
In-cell
Clean-up
Relief Valve
Solvent Solvent
Mixing Valve
Figure 9. 66-mL
Dionium cell body.
Figure 10. New ASE Schematic. Inherently the same ASE, accepted under standard
methods, but you can do more!
Pump
N 2
Chemistry
Solvent extraction
Static Valve
Collection Bottle
new APPLiCAtionS with new
ASe ProduCtS
• Environmental
– Acid pretreatment for improved recoveries of phenols,
herbicides, etc.
– Improved in cell clean-up for dioxins, PCBs, etc.
– Oil and grease after acidification
– High pH extraction of Cr (VI)
• Bio/Pharma
– Drugs and metabolites from animal tissue after pH adjustment
– Pretreatment of capsules or tablets for potency testing
– Natural products after pH adjustment
• Food and Beverage
– Lipid content after acid hydrolysis or base saponification
• Chem/Petrochem
– Biomass after acidic treatments—ethanol production
– Lipid content in bio-diesel processes
SuMMAry
New ASE 150 and 350
Same Advantages as with Current ASE
• Save Time
– Fast extraction and walk-away automation provides greater
throughput than other techniques
• Save Solvents
– Reduced solvent consumption using standard ASE operation or
Solvent Saver Mode
• Save Labor
– Integrated steps save chemists and technicians sample
handling time
Additional Advantages of New ASE 150 and 350
• Increased Capability
– pH hardened flow path allows for extraction of acidic or
basic matrices for new applications
• Increased Productivity
– Combining pretreatment, extraction and cleanup all in one step
• Increased Flexibility
– New modes of operation
– New absorbent
• Increased Value
– Built-in Solvent Controller
– Different sample sizes on same instrument
Pittcon 2008 Presentation 5

Passion. Power. Productivity.
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LPN 2018-01 3/08
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