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


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


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!!!


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


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


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


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





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





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


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


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)!

Contact Information

[email protected]

The Clarus SQ8 GC/MS

optimizing epa method 8270: perkinelmer clarus sq8 gas...

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