Optimizing EPA Method 8270: PerkinElmer Clarus SQ8 Gas...
Transcript of Optimizing EPA Method 8270: PerkinElmer Clarus SQ8 Gas...
© 2013 Perkin Elmer
Optimizing EPA Method 8270:
PerkinElmer Clarus SQ8 Gas Chromatograph/Mass Spectrometer
(GC/MS) … Meeting the Challenges and Optimizing Results and
Profitability
Lee Marotta, Sr Field Application Scientist
The NEW
Clarus SQ 8™ GC/MS
© 2013 Perkin Elmer
Hydrogen vs Helium
DFTPP in Hydrogen Passes
3
Passes tuning criteria!
Passing Criteria
• All targets quant and qualifying ions were compared in hydrogen versus helium
• All other criteria were met
4
© 2013 Perkin Elmer
Why should we reduce sample amount for analysis?
Reducing Sample Amount
Using 1mL instead of 1L sample delivers you more profits…
By enhancing productivity
Elimination of concentration step increases throughput
Able to use faster methods, such as SPE
By reducing costs
Save on expensive extraction solvent required for liquid/liquid extractions
Save on precious refrigerator space and glassware
Save on disposal costs of recovered solvents
Save on shipping costs
By increasing instrument uptime
Injecting less sample matrix = cleaner system = more time running samples
By delivering better performance
Meeting required detection limits
Enhancing recoveries
Optimizing dynamic range
… use less solvent … evaporate less solvent into environment … a “greener” analysis
© 2013 Perkin Elmer 7
1 mL sample size (or 40mL)
1 liter liquid/liquid extraction: Disadvantages
1.0 liter of sample
Extract with 300 mL dichloromethane
Concentrate to 1mL
Separate Phases
Inject
Disadvantages
High costs (solvent, glassware, shipping)
Requires more space
Large containers
Laborious sample prep
Expensive
Environmentally unfriendly
Enhance sample prep time and save on laboratory costs!
1mL sample volume (or 40mL)
Easily meet DL requirement
Extract with 1mL of DCM
Separate phases
Inject organic phase or use SPE
Inject!
Advantages:
Reduced operating costs
Requires less space (smaller containers)
Significantly less solvent used
Enhanced instrument uptime!
Faster sample prep improves lab efficiency
GREENER analysis!!!
© 2013 Perkin Elmer
Data and Injector Functions
10
PAH detection limits using 1mL extraction volume
11
Injection Calibration Lowest Conc
Volume Range Analyzed (DL)
1uL Full Scan 0.4 to 200 ppb 0.4 ppb
1uL SIM 0.2 to 200 ppb 0.2 ppb
5uL Full Scan 0.2 to 50 ppb 0.2 ppb
5uL Sim 0.06 to 50 ppb 0.06 ppb
10 uL Full Scan 0.08 to 50 ppb 0.08 ppb
50 uL Full Scan 0.02 to 50 ppb 0.02 ppb
© 2013 Perkin Elmer
Why use controlled volatilization (solvent
purge) injections instead of hot splitless injections?
Disadvantages to hot (flash-vaporizing) injections
Potential for backflash
and condensation of
High boiling components
Flash
evaporation
(expansion)
Split Vent
Column
Hot zone
Syringe fractionation
Potential thermal
and catalytic
breakdown
Keeping your analytes in the liner: Potential backflash
Backflash of analytes due to vapor expansion volume of solvent in hot injector exceeding the available volume of liner … full injection will not make its way to column.
Vapor (with sample) can enter pneumatics causing contamination requiring maintenance
Affect
Poor precision and recovery
Condensation of high boiling components causing discrimination
Carryover into later injections causing “ghost peaks” and poor performance
Why does this happen … avoid Backflash
Liner Volume … Equation of a cylinder (Liner length)(π) r2
Example for a 4cm x 2mm liner:
(4cm)(0.2cm/2)2π
Parameters to consider (V = nRT/P) Injector temperature
Injection volume
Injector pressure
Solvents (have different expansion volumes)
In this example, a 1µL injection of DCM at 10 psig and 250oC expands to a 400µL vapor volume which exceeds the volume of the liner being used
Vapor Expansion: ex. Dichloromethane – 1 uL injection volumes
Pressure Pulse during injection
V=nRT/P.
Increase pressure reduces vapor expansion
Advantages to Pressure Pulse
reduce vapor expansion
Effect of Pressure
© 2013 Perkin Elmer
Temperature programmed injections is superior than
splitless pressure-pulsed (PP)
… better results!
Benefits of Controlled Volatilization
Sample
introduced as
a liquid onto
glass wool
(not flashed)
Syringe
Split Vent
Column
Cold zone
Advantages of a Cold Injection
Controlled
Volatilization
Split Vent
Column
Eliminate problems
associated with
backflash
Enhance accuracy
by preventing
discrimination caused
By syringe fractionation
Programmed Evaporation Takes Place after the Syringe is Removed
Enhance recoveries by
significantly minimizing
high boiler condensation
which is caused by
backflash
Enhance recoveries
by reducing or preventing
thermal and catalytic
breakdown of thermally
labile and active targets
© 2013 Perkin Elmer
The Technique of Solvent Purge with
Enhanced Large Volume Injection for semi-volatile analysis
Amount of matrix injected
1 liter sample extract concentrated to 1mL with a 1uL injection 1000x matrix injected
1mL sample with a 50uL injection 50x matrix injected (enhance instrument uptime)
Reduce matrix into analytical system using 1 mL sample volume
Do you want even better detection limits ?
Purge Pneumatics with Swafer – Solvent Purge Step
Temperature programmable (PSS) inlet
• Purge solvent while maintaining semi-volatiles in inlet
• Enables enhanced detection limits
• Prevents thermal breakdown and flashback (controlled volatilization)
SwaferTM (micro channel switcher)
• Allows for the easy, automated control of effluent stream
for many applications
• Inert
• For this application, it is used to isolate injector from
column and detector
S-Swafer
Elite-5 … 30m x 0.25mm x 0.25um
Inlet @ 45°C
Inlet pressure lower
than Mid-point
pressure during purge
Split vent opened
Mid-point pressure is
greater than inlet pressure
during purge
Mass Spectrometer
deactivated fused silica (fs)
Injection Step
Temperature programmable (PSS) inlet
• Purge solvent while maintaining semi-volatiles in inlet
• Enables enhanced detection limits
• Prevents thermal breakdown and flashback (controlled volatilization)
S-Swafer
Elite-5 … 30m x 0.25mm x 0.25um
Inlet @ 320°C
Inlet pressure higher
than Mid-point
pressure for injection
Split vent closed
Mid-point pressure is lower than
inlet pressure during injection
Mass Spectrometer
Deactivated fused silica (fs)
Bake Step
Temperature programmable (PSS) inlet
• Purge solvent while maintaining semi-volatiles in inlet
• Enables enhanced detection limits
• Prevents thermal breakdown and flashback (controlled volatilization)
S-Swafer
Elite-5 … 30m x 0.25mm x 0.25um
Inlet @ 450°C
Inlet pressure lower
than Mid-point
pressure during purge
Split vent opened with
faster flows
Mid-point pressure is
greater than inlet pressure
during purge
Mass Spectrometer
deactivated fused silica (fs)
Full Scan/Single Ion Monitoring: Both Acquisitions in One Injection!
Pyrene (0.06 ppb)
SIM mass 202
S/N: 1903 to 1
Pyrene (0.06 ppb)
Full Scan mass 202
S/N: 67 to 1
0.06 05-Apr-2012 + 04:45:45
10.77 10.82 10.87 10.92 10.97 11.02 11.07 11.12 11.17 11.22 11.27 11.32 11.37 11.42 11.47Time0
100
%
0
100
%
PAH_040412_42 NR 6: SIR of 1 Channel EI+ 202.002.52e3
S/N:RMS=1903.47
PAH_040412_42 NR 1: Scan EI+ 202
4.99e4S/N:RMS=67.02
10.8911.07
PAH detection limit results varying injection volume
25
0.4 ppb 0.2 ppb 0.2 ppb 0.06 ppb 0.08 ppb 0.02 ppb
1uL FS 1uL SIM 5uL FS 5uL SIM 10uL FS 50 uL FS
Name r2 S/N r2 S/N r2 S/N r2 S/N r2 S/N r2 S/N
2-fluorobiphenyl (Sur) 0.9952 51 : 1 0.9990 232 : 1 0.9958 306 : 1 0.9964 268 : 1 0.9984 111 : 1 0.9990 238 : 1
p-Terphenyl-d14 (Sur) 0.9989 355 : 1 0.9980 56 : 1 0.9959 460 : 1 0.9956 561 : 1 0.9994 313 : 1 0.9997 1118 : 1
Napthalene 0.9957 75 : 1 0.9969 103 : 1 0.9998 410 : 1 0.9985 357 : 1 0.9998 142 : 1 0.9987 446 : 1
Acenapthalene 0.9998 311 : 1 0.9962 109 : 1 0.9983 118 : 1 0.9973 330 : 1** 0.9952 30 : 1 0.9988 20 : 1
Acenapthene 0.9972 30 : 1 0.9994 81 : 1 0.9982 410 : 1 0.9965 50 : 1 0.9987 47 : 1 0.9981 557 : 1
Fluorene 0.9990 343 : 1 n/a n/a 0.9987 386 : 1 0.9983 455 : 1 0.9997 100 : 1 0.9983 232 : 1
Phenanthrene 0.9980 375 : 1 0.9962 420 : 1 0.9983 773 : 1 0.9970 324 : 1 0.9988 327 : 1 0.9994 335 : 1
Anthracene 0.9989 130 : 1 0.9993 62 : 1 0.9981 280 : 1 0.9989 261 : 1 0.9967 70 : 1 0.9986 83 : 1
Fluoranthene 0.9997 1232 : 1 0.9998 485 : 1 0.9987 865 : 1 0.9955 407 : 1 0.9976 250 : 1 0.9950 201 : 1
Pyrene 0.9983 322 : 1 0.9989 457 : 1 0.9993 771 : 1 0.9991 671 : 1 0.9996 230 : 1 0.9992 368 : 1
Benzo (a) anthracene 0.9991 1100 : 1 0.9981 224 : 1 0.9990 550 : 1 0.9999 463 : 1 0.9996 206 : 1 0.9983 476: 1
Chrysene 0.9991 1949 : 1 0.9994 252 : 1 0.9996 175 : 1 0.9994 405 : 1 0.9997 380 : 1 0.9999 241 : 1
Benzo (b) fluoranthene 0.9950 25 : 1 0.9992 220 : 1 0.9981 60 : 1 0.9993 28 : 1 0.9983 117 : 1 0.9979 16 : 1
Benzo (k) fluoranthene 0.9960 101 : 1 0.9945 474 : 1 0.9998 35 : 1 0.9996* 27 : 1 0.9962 155 : 1 0.9987 15 : 1
Benzo (a) pyrene 0.9985 n/a 0.9992 56 : 1 0.9994 10 : 1 0.9993 33 : 1 0.9951 10 : 1 0.9950 17 : 1
Indeno (1,2,3-cd) pyrene 0.9974 35 : 1 0.9985 247 : 1 0.9976 71 : 1 0.9959* 67 : 1 0.9971 15 : 1 0.9966 101 : 1
Dibenzo (a,h) anthracene 0.9988 258 : 1 0.9990 301 : 1 0.9990 40 : 1 0.9950* 62 : 1 0.9995 41 : 1 0.9973 90 : 1
Benzo (g,h.i) perylene 0.9968 85 : 1 0.9959 220 : 1 0.9950 150 : 1 0.9993 147 : 1 0.9974 27 : 1 0.9989 203 : 1
* removed lower level point from curve
**0.2 point not 0.06 point
Pyrene Calibration from 0.06 to 50 ppb (10uL injection) SIM
26
, 05-Apr-2012 + 04:45:45
0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0Conc-0.00241
12.5
Response
Compound 14 name: PyreneCoefficient of Determination: 0.999242Calibration curve: 0.249596 * x + -0.00241141Response type: Internal Std ( Ref 3 ), Area * ( IS Conc. / IS Area )Curve type: Linear, Origin: Exclude, Weighting: 1/x, Axis trans: None
Concentration: 0.06 ppb
Fluoranthene and Pyrene
r2: 0.9992
Extraction Volume: 1mL
Compound 8 name: ChlordaneCoefficient of Determination: 0.999640Calibration curve: 34983.8 * x + -297.362Response type: External Std, AreaCurve type: Linear, Origin: Exclude, Weighting: 1/x, Axis trans: None
0.0 20.0 40.0 60.0 80.0 100.0 120.0 140.0 160.0 180.0 200.0Conc-297
7.00e6
Response
File Name Std Conc Calc. % dev
Result
Pest_01603_06 0.2 ppb std 0.23 15
Pest_01603_07 2 ppb std 1.89 -6
Pest_01603_08 10 ppb std 10.04 0
Pest_01603_09 20 ppb std 17.61 -12
Pest_01603_10 100 ppb std 102.45 2
Pest_01603_11 200 ppb std 199.98 0
7 level Calibration – Full Scan processing from FS/SIM Acquisition
Chlordane – 0.2 ppb to 200 ppb Extraction Volume: 1mL
7 level Calibration – SIM processing from FS/SIM Acquistion
Compound 6 name: AldrinCoefficient of Determination: 0.999984Calibration curve: 1119.20 * x + 41.5440Response type: External Std, AreaCurve type: Linear, Origin: Exclude, Weighting: 1/x, Axis trans: None
0.0 20.0 40.0 60.0 80.0 100.0 120.0 140.0 160.0 180.0 200.0Conc0
2.24e5
Response
File Standard Area Result % dev
Conc (PPB)
Pest_01603_05 0.1 ppb std 153 0.1 0
Pest_01603_06 0.2 ppb std 233 0.17 -14
Pest_01603_07 2 ppb std 2673 2.35 18
Pest_01603_08 10 ppb std 10955 9.75 -2
Pest_01603_09 20 ppb std 22186 19.79 -1
Pest_01603_10 100 ppb std 112484 100.47 0
Pest_01603_11 200 ppb std 223516 199.67 0
Aldrin – 0.1 ppb to 200 ppb Extraction Volume: 1mL
Increasing Productivity, Efficiency and Performance
Meet required reporting limits while using less sample
New detector technology
SIFI
Larger injection volumes
Inject less matrix – cleaner system means enhanced instrument uptime increasing productivity
Extract less sample – reduce operating costs (less solvent, less glassware and less storage space required)
Adds up to faster return on investment and a more productive laboratory with improved recoveries
© 2013 Perkin Elmer
100mL injection volume
Collected at an Environmental Testing lab in Shelton, CT
Enhancing Instrument uptime …
Injecting less matrix
Extending maintenance
interval!
Experiments performed
at environmental testing lab
Results Comparing 1L to 100mL
Detection limit achieved 10x improved over regulated detection limits for all targets
More Clocks achieved than 1L extract because less matrix being injecting
1.0uL splitless injection 13.78 13.98 14.18
Time0
100
%
0
100
%
022504_02 8: SIR of 6 Channels EI+ 202.002.91e4
13.73S/N:RMS=1102.04
022504_02 1: Scan EI+ 202
5.74e5S/N:RMS=57.47
13.72
13.79 13.92 14.2614.11
From Matrix spike
Pyrene – 0.025 ppb
100mL extract conc to 5mL
SIM
FS
© 2013 Perkin Elmer
Getting more from your GC/MS! Enable lower detection limits!
Easy to Use and Maintain … SMARTSource
Change source components in under 5 minutes with no tools
Now it is “Plug and Play” with a twist no wires to remove
Clarifi Detector
Enhance Sensitivity
Increase Operating Range
More Flexibility
Longer Life – Less Downtime
Enhance Library Matches
Enhance Performance … Enhance Uptime!
… most sensitive (improve detection limits) and robust (increase throughput)!