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Content
• Metal SPME Fibers• New PEG Fiber• DIN Method for Pesticides in Water with SPME
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SPME Fiber Assembly Detail (Manual)
713-1344
94-0034
Color-Coded Screw Hub
Tensioning Spring
Sealing Septum
Ferrule
Septum-Piercing Needle
Fiber-Attachment Needle
Coated SPME Fused Silica Fiber
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CTC Analytics Combi Pal
License bearer:CTC, Varian, Gerstel, Thermo, Alfatech, HTA, PAS, Leap
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Types of SPME Fiber Assemblies
• Assemblies for holders- manual - autosampler style (no spring)
• Gauge size of piercing needle- Standard size - 24 GA- Larger bore size - 23 GA (for septum free inj. ports)
• Types of fiber core- Fused silica- Stableflex- Metal NEW!
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Why Develop New SPME Metal Fiber Assemblies?
• Extend assembly lifetime
• Improve the durability and reproducibility of the extraction fiber
• Enhance compatibility with a autosampler (e.g. CTC)
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Super Elastic vs. Standard SPME Fiber Assemblies
Needle
Plunger
Metal SPME Fiber
Standard SPME Fiber
Super Elastic SPME Fibers
Standard SPME Fibers
Needle 23 gauge metal alloyBeveled tip
24 or 23 gauge. SS
Blunt tip
Fused silicaor Stableflex
SS tubing
Fiber Core Metal alloy
Plunger Solid metal alloy
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Advantages Of The New Assembly Design
• Increased durability results in up to 10 times the fiber life • Inert fiber core, does not contain iron• Coating bonds better to the metal core compared to the
Stableflex core• Crimped in assembly without adhesives.
- Does not produce extraneous peaks
• Stronger, more flexible plunger• Beveled needle tip for easier septa penetration
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Comparison of Fiber Cores (PDMS-DVB)
0 2 4 6 8Time (min)
1
2
3
4 5
Fused SilicaStableflex
Metal
1. Methylamine2. Dimethylamine3. n-Propanol (IS)4. Diethylamine5. Triethylamine
Sample: 1ppm each in waterwith 25%NaCl, 0.05M phospateBuffer pH 11
Extraction: 10min immersionFiber: PDMS-DVB various coreDesorb: 3min @ 250°CColumn: 30m x 0.32mm x 4.0µm
SPB-1 Sulfur (amine deactivate)
Oven: 45°C(1.5min) to 80°C@ 8°C/min to 200°C@
20°C/minInjector: 250°C, splitless closed
initial 0.75min. Detector: FID
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Improvements for Metal Fibers
• Advanced Metal Working Techniques - Precision EDM cutting and drilling- Specially designed crimp tool with torque measurement- Additional cleaning of alloy parts during processing
• Quality Assurance Improvements- QA data sheet for individual assemblies- 100% Inspection of critical parameters- Individual lot number assignments for assembly tracking- Raw material tracking
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Improvement of Fiber Coating
• Up to now - Manual process- Fiber strands of approx. 80-90
cm
• New coating technique- Coating tower- in-line curing- Fiber strands of 20m possible
→ More reproducible coatings→ More reproducible results
Coating &
Curing
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Variation Between Batch-Coated Lots
Analytes Average % RSD Analytes Average % RSDMethanol 217 24,3% 1-Butanol 2155 22,8%DMA 7223 43,4% TEA 4529 8,0%Ethanol 535 16,8% Dioxane 1694 23,3%Acetonitrile 1149 21,5% Pyridine 1772 20,4%Acetone 2052 23,2% 2-Hexanone 3227 16,9%Isopropano 1475 20,8% Hexanal 215 12,6%n-Propanol 1412 21,2% Aniline 4234 22,2%MTBE 1531 23,7% 21,1%
16,0%Overall Average
Coating Average, 59µm
(PDMS-DVB n = 36, 6 fibers per lot, 6 lots)
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Variation Between Automated-Coated Lots
Analytes Average %RSD Analytes Average %RSDMethanol 291 7.1% 1-Butanol 3119 9.6%DMA 5069 19.1% TEA 4747 8.5%Ethanol 715 9.1% Dioxane 2405 8.6%Acetonitrile 1571 7.8% Pyridine 2599 8.5%Acetone 2873 6.9% 2-Hexanone 3939 3.3%Isopropanol 2118 9.9% Hexanal 242 7.8%n-Propanol 2011 9.8% Aniline 4745 5.5%MTBE 2126 7.4% Overall 8.6%
Coating µm 71.7 4.1%
(PDMS-DVB n = 36, 6 fibers per lot, 6 lots)
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Important Notes About Metal Assemblies
• Superelastic assemblies will core septa, they should be used with Merlin Microseal or other septum-less injection port heads
• Adjust CombiPal home position to insure fiber does not extend beyond the needle during microseal penetration.- Merlin Microseal can be cut if not adjusted
• The assembly can be damaged by excessive heat or conditioning time.
• Use the appropriate sample vial and tops
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Available Metal Fibers
• Particle Phases- 57902-U 65 µm PDMS/DVB, Metall Alloy, 1 cm length, - 57906-U 85 µm Carboxen/PDMS, Metall Alloy, 1 cm length- 57912-U 50/30 µm DVB/Carboxen-PDMS, Metall Alloy, 1 cm length- 57914-U 50/30 µm DVB/Carboxen-PDMS, Metall Alloy, 2 cm length
• Film Phases- 57919-U 7 μm PDMS, Metall Alloy, 1 cm length- 57922-U 30 μm PDMS, Metall Alloy, 1 cm length- 57928-U 100 μm PDMS, Metall Alloy, 1 cm length
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PEG SPME FiberGoals for Development of New Polar Fiber
• Find a replacement for discontinued Carbowax/DVB fiber
• Develop a polar fiber with a durable coating that will withstand multiple extractions from water
• Develop a polar fiber that does not contain an adsorbent• Put the coating on an unbreakable metal fiber core• Compare new coating with other fiber coatings• Develop a fiber that enhances selectivity for polar
analytes
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Extraction of Solvents in Water with 60µm PEG Fiber
min0 2 4 6 8 10 12
uV
600
800
1000
1200
1400
1600
1
2
3
4
5
6
7
89
10
1112
Component ppm 1. Methanol 202. Ethanol 20 3. Acetonitrile 204. Acetone 205. Isopropanol 20 6. n-Propanol 20
Component ppm 7. MTBE 38. Ethyl acetate 59. n-Butanol 10
10. 1,4-Dioxane 2011. Butyric acid 512. Phenol 0.2
Sample Polar solvents in water with 25%NaCl Fiber: 60µm PEGExtraction: 10min, Direct Immersion with agitation (Varian 8200)Desorption: 5min at 240°CInjector: Splitless/split, closed initial 0.75min than opened 50:1
with 0.75mm ID linerColumn: SPB-1 Sulfur, 30m x 0.32mm, 4.0µmColumn oven: 45°C(1.5min) to 80°C at 8°C/min to 230°C at 20°C/min
(10min)Carrier gas: He @t 13psi const. pressure, 40cm/sec at 40°CDetector: FID at 300°C
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Comparison of Fibers for Extraction of Solvents
22375
0
3000
6000
9000
12000
15000
Methanol Ethanol Acetonitrile Acetone IPA n-PrOH MTBE Et Acetate n-BuOH 1,4,Dioxane ButryicAcid
Phenol
Are
a co
utns
85µm PA60µm PEGCW/DVB 100um PDMS
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Durability of PEG Fibers with Repeated Extractions
0
100
200
300
400
500
600
700
0 15 30 45 60 75 90 105
Extraction number
Are
a co
unts
Ethanol 20ppmAcetonitrile 20ppmAcetone 10ppmIsopropanol 10ppmn-Propanol 10ppm1,4,Dioxane 20ppm
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Comparison of Fibers, Phenols 25ppb
1987222
0
50000
00000
50000
00000
50000
00000
Pheno
l2-C
l-Ph
3-MeP
hUnd
ecane
2-Nitro
P2,4
-DMP
2,4-D
ClPNap
hthalen
e4-C
l-3-m
eP2,4
,5-TClP
2,4-di
nitroP
4-nitro
P2,3
,4,6-t
eClP
2-me-4
,6-diN
P
PClPDino
seb
PAPEGCWDVB
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Comparison of SPME Fibers Base-Neutrals (Basic Fraction)
3777
8
2088
5
1556
58
3249
48
2088
06
8987
2
6461
1
5741
0
3316
9
1860
25
5341
94
3906
94
2517
79 3104
21
1859
3
3558
8725
2
2449
29
1438
93
6442
6
7261
2
4217
405
5745
3
1982
16
1856
806
1202
0
100000
200000
300000
400000
500000
600000
Aniline Benzyl alcohol o-Toluidine p-Chloroaniline o-Nitroaniline m-Nitroaniline p-Nitroaniline
85µm Polyacrylate60µm PEG65µm CW-DVB100µm PDMS
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Comparison of SPME Fibers Base-Neutrals (Neutral Fraction)
0,0E+00
2,0E+06
4,0E+06
6,0E+06
8,0E+06
1,0E+07
1,2E+07
1,4E+07
1,6E+07
1,8E+07
Undecane Benzoanthracene Naphthalene Acenaphthene
Are
a co
unts
85um PA60µm PEGCW/DVB100um PDMS
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Applications with SPME PEG FiberOrganophosphorus Pesticides at 10ppb by SPME
Extraction:
Sample: OPPs at 10ppb in 0.1M Phosphate buffer, pH 7, 25% NaCl30min, direct immersion with agitation (CombiPal)
Fiber: 60µm PEGDesorption: 2min at 250°C, splitless for 0.75min than opened Column: SLB-5 MS 30m x 0.25mm ID, 0.5µm film Oven: 60°C(1min) to 215°C @20°C/min to 290°C
@ 6°C/min (1min)Carrier: Helium, 1mL/min constant flow, Injector: Splitless/split w/ 0.75mmID linerDetector ITMS m/z = 50-326 @ 0.6µsec per scan,
transfer line 310°C
1. Triethylthiophosphodiate2. Thionazine3. Sufulfotep4. Phorate5. Dimetholate6. Diazinon7. Terbuphos8. Disulfoton9. Methyl parathion10. Malithion11.Parathion12. Merphos13.Fenamiphos14.Carboxin15.Famophos
7.5 10.0 12.5 15.00 17.5 minutes
0.0
0.5
1.0
1.5
2.0
2.5
MCounts
1
2
3
4
67
8
5
910
11
12
13
14 15
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Applications with SPME PEG FiberTriazine Herbicides at 2ppb by SPME
1 Desisopropyl atrazine
7 Simetryn
2 Desethyl atrazine
8 Ametryn
3 Prometon
9 Prometryn
4 Simazine
10 Terbutryn
5 Atrazine
11 Cyanazine
6 Propazine
Triazine pesticides at 2ppb in 0.1M Phosphate buffer, pH 7, with25% NaCl, 9mL in 10mL vial
Sample:
Extraction: 30min, direct immersion with agitation using CombiPal, Fibers: 60µm PEGDesorption: 2min at 250°C, splitless for 0.75min than opened
Column: SLB-5 MS 30m x 0.25mm ID, 0.5µm film Oven Program: 60°C(1min) to 150°C @25°C/min to 230°C @ 5°C/min (5min hold)Carrier gas: Helium, 1mL/min constant flow, Injector: Splitless/split with 0.75mmID liner and
Merlin MicrosealDetector ITMS m/z = 150-250 @ 0.5µsec per scan,
transfer line 310°C
1 2
3
4
5
6
7
8
9 10
11
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Comparison of Oxygenates in Gasoline Direct Injection vs. SPME (Chromatograms normalized)
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
min0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
uV
0
5000
10000
15000
20000
25000
Ethanol
Butane
IPA
Pentane
n-Propanol
min
uV
0
50000
100000
150000
200000
Ethanol
Butane
IPA
Pentane
n-Propanol
SPME
Direct injection
15min direct immersion,5min desorption (240°C)
Split 50:1
Oxygenates in gasoline at 400ppm (0.4%)
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Enhancement of Oxygenates in Gasoline using SPME
Relative to Butane SPMESPME Injection SPME Injection Enhancement
Ethanol 21.214 2.055 0,493 0,003 155Isopropanol 12.403 2.191 0,288 0,003 85n-Propanol 16.212 2.636 0,376 0,004 92Butane IS 43.071 644.669
Area Counts
Oxygenates in gasoline at 400ppm (0.4%)
Direct injection of gasoline, 0.2µl, split 50:1
SPME Extraction 15min, direct immersion with PEG Fiber, Split 50:1
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Findings Concerning 60µm PEG Fiber
• Methanol may be produced by the fiber under acidic conditions for the first several extractions. (trace amount of inhibitor)
• The fiber can swell when exposed to water samples with total soluble organic content exceeding 200ppm. ->Best suited for trace level analyses.
• The fiber does not swell in hydrocarbon solvents - suitable for extraction of polar analytes out of hydrocarbon
solvents.
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Conclusions
• New more durable and flexible metal alloy assembly has been designed
• Super-elastic properties make it more compatible with autosamplers• Coatings on a new metal fiber core made with the same super-elastic
properties have been developed• The fiber core is inert, durable and the coating bonds well to it• New PEG fiber coating has been developed without an adsorbent
- The coat is durable and long lasting- PEG fiber is available in standard stainless steel assemblies- PEG fiber is suitable for extraction of polar analytes out of hydrocarbon
solutions
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Official Methods / Applications applying SPME
DIN 38407-F 34 (NEW)- Determination of selected plant treatment agents, biocides
and break-down products; Method using gas chromatography (GC-MS) after solid-phase micro extraction (SPME)
Other norms• ASTM D 6438, 2005 • ASTM D 6520, 2000 • ASTM D 6889, 2003 • ASTM E 2154, 2001 • OENORM A 1117, 2004-05-01
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DIN 38407-34 – Compounds Analyzed
1. Aldrin 12. Lindan 2. Atrazin 13. Mefenpyr-diethyl 3. Carfentrazon-ethyl 14. Metolachlor 4. Desethylatrazin 15. Metribuzin 5. Desethylterbutylazin 16. Parathion-ethyl 6. Dichlobenil 17. Parathion-methyl 7. Dieldrin 18. Pendimethalin 8. Diflufenican 19. Simazin 9. endo-Heptachlorepoxid 20. Terbutryn
10. exo-Heptachlorepoxid 21. Terbutylazin 11. Heptachlor 22. Triclosan
Method might be suitabel for others – need to be evaluated individially
Operational range of method the above 0.05µg/Ldepending on matrix
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DIN 38407-34 conditions
SPME Conditions- Fiber: Polyacrylate- Conditioning: Fiber 20 min @300°C- Extraction: pH 6-8, NaCl close to saturation (e.g. 2.4g/8mL sample)
60 min @ 30°C, stirring 250 rpm- Desorption: 10 min @ 280°,splitless (6 min)
GC conditions (example)- Injection KAS/CIS 60°C; 10°C/s to 280°C;10min;Splitless- Column 5% Phenyl, 30m x 0.25mm, 0.25µm- Carrier gas Helium (5.0), 0,9mL/min- Oven 60°C, 2 min; 4°C/min to 220°C; 10°C/min to 300°C- Detector MS, EI 70eV, SIM
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Other official methods for SPME
• ASTM D 6438, 2005- Standard Test Method for Acetone, Methyl Acetate, and
Parachlorobenzotrifluoride Content of Paints, and Coatings by Solid Phase Microextraction-Gas Chromatography
• ASTM D 6520, 2000- Standard Practice for the Solid Phase Micro Extraction (SPME) of Water
and its Headspace for the Analysis of Volatile and Semi-Volatile OrganicCompounds
• ASTM D 6889, 2003 - Standard Practice for Fast Screening for Volatile Organic Compounds in
Water Using Solid Phase Microextraction (SPME)• ASTM E 2154, 2001
- Standard Practice for Separation and Concentration of Ignitable Liquid Residues from Fire Debris Samples by Passive Headspace Concentration with Solid Phase Microextraction (SPME)
• OENORM A 1117, 2004-05-01 - Determination of volatile compounds in cellulose-based materials by Solid
Phase Micro Extraction (SPME)
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New SPME CD
• NEW! Video demo
• 600 new application references
• SPME Applications by Area - Environmental 720 - Food, Flavors and Fragrances 550 - Forensics/ Toxicology 243 - Pharmaceutical/Biologicals 150