agilent 9000 intuvo gc applications...most of the analytes can be differentiated from the baseline...

Agilent 9000 IntuvoGC Applications

Matthew Giardina, Ph.D.

James McCurry, Ph.D.

Rebecca Veeneman, Ph. D.

Summary of Intuvo Applications by Industry

Environmental• EPA Method 8270 – Semivolatile Organic Compounds (SVOC)

• Ultra-Fast Total Petroleum Hydrocarbons (TPH)

Energy and Chemical• Ultra-Fast SimDis using ASTM D7798

• Monocyclic Aromatic Purity using ASTM D7504

• Sulfur in Light Petroleum Liquids

Food• Multiresidue Pesticide Analysis in Food

Pharma• Extractables and Leachables

Consumer Products• Longevity of Phthalates

• Fragrance Impurities using Intuvo with OpenLab Match/Compare

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Results

Equivalency

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Resilience to

Matrix and

Difficult

Compounds

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Low Level

Detection

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Ease of

Use

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Speed and

High Boilers

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Agilent 9000 Intuvo GC Equivalency to 7890

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Semivolatiles GC Methods

Injection volume 1 µL

Inlet Split/Splitless 300 C

Pulsed splitless 60 psi until 0.5 min

Purge 50 mL/min at 0.5 min

Septum purge switched flow mode 3mL/min

Liner UI Splitless liner with a single taper and glass wool at the bottom

Guard chip (Intuvo only) 60 C for 2 min, 20 C/min to 260 C, 6 C/min to 330 C hold 1.333 min

(standards) or 10.333 min (soil extract)

Column Agilent DB-5ms UI 30 m x 0.25 mm x 0.5 µm

Flow 2 mL/min constant flow

Column temperature 40 C for 2 min, 20 C/min to 260 C, 6 C/min to 330 C hold 1.333 min

(standards) or 10.333 min (soil extract)

Transferline temperature 330 C

Drawout plate 6 mm

Ion source temperature 330 C

Quadrupole temperature 200 C

Scan 35 to 550 m/z

Gain factor 1

Threshold 50

A/D samples 2

GC (7890 & Intuvo)

MSD (5977)

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Chromatographic Comparison – Which Is Intuvo?

8270 Calibration Standard – 77 Acids/Bases/Neutrals (PAHs), 6 ISTDs

Intuvo

7890

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Retention Time Comparison

Relative Retention Time = RTtarget / RTISTD

0.5

0.6

0.7

0.8

0.9

1

1.1

1.2

0 10 20 30 40 50 60 70 80

Rela

tive R

ete

ntion T

ime

Compound Number

7890

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0.5

0.6

0.7

0.8

0.9

1

1.1

1.2

0 10 20 30 40 50 60 70 80

Rela

tive R

ete

ntion T

ime

Compound Number

7890

Retention Time Comparison

Relative Retention Time = RTtarget / RTISTD

0.5

0.6

0.7

0.8

0.9

1

1.1

1.2

0 10 20 30 40 50 60 70 80

Rela

tive R

ete

ntion T

ime

Compound Number

7890 Intuvo

Average relative retention time difference = 0.0006

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Response Comparison

Response Factor = (Areatarget * ConcentrationISTD)/(AreaISTD * Concentrationtarget)

Average response factor difference = 4.6%

0.00

0.50

1.00

1.50

2.00

2.50

0 10 20 30 40 50 60 70 80

Response F

acto

r

Compound Number

7890 Intuvo

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Sulfur in Gasoline GC Methods

Injection volume 1 µL

Inlet Split/Splitless 300 C

Split 10:1

Septum purge flow 3mL/min

Liner UI Splitless liner with a single taper and glass wool at the

bottom

Guard chip (Intuvo only) 300 C

Column Agilent DB-1 30 m x 0.32 mm x 1 µm

Flow 2 mL/min constant flow

Column temperature 40 C for 0.71 min, 14.1 C/min to 250 C hold 1 min

Burner 800 C

Base 280 C (7890: 250 C)

Oxidizer 50 mL/min (7890: 60 mL/min)

Upper H2 38 mL/min (7890: 40 mL/min)

Lower H2 8 mL/min

Ozone 36 mL/min

Range (stand alone) 6

GC (7890 & Intuvo)

SCD (8355)

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Light Petroleum Sulfur AnalysisA 20ppb standard containing 23 compounds was evaluated with a 10:1 split.

Most of the analytes can be differentiated from the baseline at 20ppb making

the practical limit of detection 2ppb.

# Analyte SNR

(20ppb)

1 ethanethiol 1.76

2 dimethyl sulfide 2.43

3 carbon disulfide 3.35

4 2-propanethiol 2.04

5 2-methyl-2-propanethiol 3.35

6 1-propanethiol 1.48

7 ethylmethyl sulfide 2.47

8 2-butanethiol 4.02

9 thiophene coleution

10 2-methyl-1-propanethiol 2.00

11 diethyl sulfide 1.34

12 1-butanethiol 6.45

13 dimethyl disulfide 4.79

14 2-methylthiophene 4.83

15 3-methylthiophene 5.04

16 3-chlorothiophene 4.44

17 2-bromothiophene 4.83

18 diethyl disulfide 3.81

19 di-tert-butyl disulfide 4.44

20 thianaphthene 2.40

21 2-methylbenzothiophene 3.31

22 3-methylbenzothiophene 4.79

23 diphenyl sulfide ISTD

min0 2 4 6 8 10 12 14 16

pA

0

5

10

15

20

25

FID1 B, Back Signal (AQM-SCD\SCD_160503\20ppb_23S_iso_160506-2.D)

23

21

22

20

1917

185

12

3

4

6

78,9

10

11

12

13

1415

16

Intuvo

min2 4 6 8 10 12 14

pA

5

10

15

20

25

SCD1 A, Front Signal (Chromatogr...2_DB1-1um_10192015\DB1_1um_O2 2015-10-19 16-35-05\20ppb-july_19oct2.D)

2321

22

20

191718

5

12

3

4

67

8,9

1011

1213

1415 16

7890

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Active Compounds Resilience to MatrixLow Level Detection

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Semivolatiles Suitability Standard

Test system acid/base activity, inertness and MSD tuning ratios (25 µg/mL)

Pentachlorophenol

Criteria: TF < 2 @ 10%

height

DFTPP

Criteria: IE fragments within

specified ion ratios

Benzidine

Criteria: TF < 2 @ 10% height

DDT

Criteria: Breakdown to DDD and DDE < 20%

0

10

20

30

40

50

60

70

80

90

100

11.50 12.00 12.50 13.00 13.50 14.00 14.50 15.00 15.50

Norm

ailz

ed R

esponse

Time (min)

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Semivolatiles Suitability Standard

Test system acid/base activity, inertness and MSD tuning ratios (25 µg/mL)

Pentachlorophenol

PassTF = 1.0

DFTPP

PassIon ratios in spec

Benzidine

PassTF = 0.8

DDT

PassBreakdown = 1.4%

0

10

20

30

40

50

60

70

80

90

100

11.50 12.00 12.50 13.00 13.50 14.00 14.50 15.00 15.50

Norm

ailz

ed R

esponse

Time (min)

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Decision Flow Diagram

Matrix Study for Semivolatiles

Initial QC and

Calibration

Inject Matrix

Set (N=20)

Check

QC / CCV /

ISTD

Pass Check?

Change

septum, liner

Corrective

Maintenance

Attempt 1?

Corrective

Maintenance

Attempt 2

Replace Guard

Chip

Yes

No No

Yes YesNo

New Column

Check

QC / CCV /

ISTD

Pass Check?

MSD

Maintenance

Check

QC / CCV /

ISTD

Yes

No

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Semivolatiles Matrix Extracts

Composite soil extracts in methylene chloride from ESC Lab Sciences

(Mt. Juliet, TN)

20 sequential injections on a wool packed liner

Typical of their “Worst

Matrix”

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Semivolatiles Suitability Standard - Matrix Study

Pentachlorophenol and Benzidine Tailing Factor – After Liner Change

Guard Chip Replacement

0

0.5

1

1.5

2

2.5

3

0

20

40

60

80

10

0

12

0

14

0

16

0

18

0

20

0

22

0

24

0

26

0

28

0

30

0

32

0

34

0

36

0

38

0

40

0

Taili

ng F

acto

r at

10%

Peak H

eig

ht

Number of Matrix Injections

Pentachlorophenol Benzidine

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Semivolatiles Calibration Verification – Matrix Study

Continuing Calibration Verification

-40

-30

-20

-10

0

10

20

30

40

0 10 20 30 40 50 60 70 80

Calib

ration C

heck %

E

rror

Compound Number

After Calibration

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Hexachlorocyclopentadiene

4-Nitrophenol

Pentachlorophenol

-40

-30

-20

-10

0

10

20

30

40

0 10 20 30 40 50 60 70 80

Calib

ration C

heck %

E

rror

Compound Number

After Calibration

After 680 Matrix Injections

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Benzidine

4-Nitrophenol

Pentachlorophenol

Hexachlorocyclopentadiene-40

-30

-20

-10

0

10

20

30

40

0 10 20 30 40 50 60 70 80

Calib

ration C

heck %

E

rror

Compound Number

After Calibration

After 680 Matrix Injections

After Column Replacement

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Semivolatiles ISTDs – Matrix Study

Internal Standard Response

0.00

0.20

0.40

0.60

0.80

1.00

1.20

1.40

1.60

0 100 200 300 400 500 600 700

Norm

aliz

ed I

nte

rnal S

tandard

Are

a

Number of Matrix Injections

1,4-Dichlorobenzene-d4 Naphthalene-d8

Acenaphthene-d10 Phenanthrene-d10

Chrysene-d12 Perylene-d12

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Semivolatiles Comparison to 7890 – Matrix Study

• Parallel studies carried out on 7890 using three separate columns

• Mechanisms of failure:

• Column 1 and 3

- ISTD response below 50% and greater than 10% CCV failure

- ISTD response recovered with source cleaning

• Column 2 – greater than 10% CCV failure

- CCV failure recovered after column replacement

Column

Number

Number of Liners and

Septa Replaced

Number of Inlet

Seals Replaced

Number of Column

Trims (30.5 cm each)

Total Number of Matrix

Injections

1 12 2 6 240

2 4 2 5 80

3 6 3 4 120

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Multiresidue Pesticides in Food - Experimental

• Seven different matrices were prepared with a QuEChERS method including

dSPE (honey, rice, olive oil, onion, cucumber, black tea, and orange)

• 21 pesticides and 6 deuterated PAHs (ISTDs) were used for calibration and

recovery assessment

• Intuvo GC was configured with a SSL inlet, simple MS flow path, and 7000C

• 8 level calibration curve (1ppb to 1000ppb) was performed followed by a cal check

with the 50ppb standard then ~60 additional injections with the 50ppb standard

• 3-layer sandwich injections used standard, analyte protectants, and matrix

• After calibration, cal check, and matrix analysis maintenance was performed:

• Septum replacement

• Liner replacement

• Guard chip replacement

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Average recoveries for 60 matrix injections

• Average recoveries for 60 injections with the seven extracts are shown.

• Average recovery was 82%

• RSD was 6.3%

• 70% and 120% recovery thresholds are noted

0

20

40

60

80

100

120

140

160

Rec

ove

ry

Honey

Rice

Orange

Black Tea

Olive Oil

Onion

Cucumber

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• Using a spinach matrix, longevity of the Intuvo GC was compared to a 7890

• Splitless injection, 15m HP5-MSUI column, simple flow path configuration (no backflush)

• The 7890 lasted 192 matrix injections before being unrecoverable

• The 15m column prevented significant column trimming in order to maintain a retention time locked system

• 3 liner changes and 2 column trims were performed

• The Intuvo lasted 302 matrix injections before being stopped

• 4 liner changes and 1 guard chip change was performed

• Liner replacements often bring the system back into spec

Iprodione-7890

Pre-

spinac

h

Pre-spinach

After 30

matrix inj

After 30

matrix inj

After liner

replacement

After liner

replacemen

t

Intuvo vs. 7890: A longevity comparisonIprodione-Intuvo

Pre-spinach After 30

matrix inj

After liner

replacement

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Intuvo Guard Chip and No-trim ColumnsNo retention time shifts after maintenance

0.5 min

Shifts beyond

retention time

window

Pesticide mix injected before and

after 300 mm column trim

0.5 min

Maintaining

retention times

Pesticide mix injected before and

after guard chip change

Conventional Column Intuvo Column

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Speed of Analysis and

Recovery of High Boiling Point Compounds

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Total Petroleum Hydrocarbon Analysis Using Ultra-Fast GC

Total Petroleum Hydrocarbon Analysis (TPH)

• C10 to C40 hydrocarbon contamination in the environment (water soil, sediment)

• GC analysis of extracts with FID

• Measure TOTAL hydrocarbons, speciation not needed

Ultra-Fast Gas Chromatography (UFGC)

• Run times are typically 3-5 minutes

- Rapid column heating (> 100 oC/min over entire oven temp range)

- Short columns ( 3 - 5 m)

- High carrier flow rates (> 5 mL/min)

• Challenges

- Retention Time Precision

• precise column temperature control

• precise flow control during fast column heating

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Intuvo GC Conditions for UFGC TPH AnalysisIntuvo GC Conditions:

• ALS with 10 mL syringe, 1 mL injection

• SSL Inlet, splitless mode, 5190-2293 UI liner, 400 oC, Merlin Microseal

• Guard Chip, 350 oC

• D1 Flow Path, 350 oC

• DB-1ht column, 5 m x 0.32 mm ID x 0.1 mm

- helium carrier gas @ 10 mL/min constant flow

- oven program, 40 oC for 0.5 min, 250 oC/min to 350 oC, hold 0.5 min

• FID, 350 oC

TPH Samples - Certified Reference Materials from Bundesanstalt für

Materialforschung und –prüfung (BAM)

• Soil and river sediment sample matrices

• Real samples with certified consensus TPH values

• Samples prepared in LFS using ISO 16703 protocol

- Ultrasonic liquid/solid extraction, centrifuge fines, liquid/liquid cleanup, SPE final cleanup

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C40 recovery must be > 0.80

UFGC TPH Discrimination Performance Test

min.0.6 0.8 1.0 1.2 1.4 1.6 1.8

pA

0

500

1000

1500

2000

2500

3000

C10

C12

C14

C16 C18 C20C22C24

C26C28

C30C32

C34C36

C38C40

Peak Area Recovery

C10 861 0.98

C12 867 0.98

C14 877 0.99

C16 890 1.01

C18 875 0.99

C20* 882 1.00

C22 882 1.00

C24 882 1.00

C26 873 0.99

C28 846 0.96

C30 867 0.98

C32 859 0.97

C34 853 0.97

C36 853 0.97

C38 829 0.94

C40 817 0.93

33

min0.8 1 1.2 1.4 1.6 1.8

pA

0

200

400

600

800

1000

FID1 A, Front Signal (C:\CHEM32\...TPH_APP_160225\AP73_TPH_APP_160225 2016-02-25 18-47-07\Check Std 03.D)


TPH Standard 3


C10 C44

UFGC TPH Repeatability Test – 3 Runs of Mid-Level Calibration Standard

Std 3

Run Peak Area

1 17644

2 18044

3 18236

Mean 17975

Std Dev 301.9

RSD 1.7%

ISO 16703 RSD <= 5%

34

min0.8 1.0 1.2 1.4 1.6 1.8

pA

0

250

500

750

1000

1250

1500

1750

2000

2250

C10 C40

Avg 0.752 1.804

StdDev 0.0008 0.0003

RSD 0.109% 0.018%

Retention Time (min.)

C10

min0.740 0.750 0.760

pA

0

400

800

1200 0.7540.751

C40

min1.795 1.800 1.805 1.810

pA

600

1000

1400

1.8051.804

UFGC TPH Analysis in Soil – Sample Analysis Precision

35

min0 0.5 1 1.5 2 2.5

pA

0

1000

2000

3000

4000

5000

6000

C10

TPH

min0 0.5 1 1.5 2 2.5

pA

0

1000

2000

3000

4000

5000

6000

TPH

C44

C10

C44

BAM-U021

Certified Reference Sample

Mineral Oil Contaminated Soil

BAM-U022

Certified Reference Sample

Mineral Oil Contaminated Sediment

UFGC TPH Analysis for Soil and Sediment Samples

36

TPH Sample Performance Using the Intuvo UFGC

U021 A U021 B U022 A U022 B

Run mg/kg mg/kg mg/kg mg/kg

1 3462 3480 8701 8630

2 3487 3485 8724 8658

3 3502 3482 8656 8610

4 3513 3479 8736 8732

5 3538 3492 8728 8606

Mean 3500 3484 8709 8647

Cert. Value

Std Dev 28.547 5.234 32.319 51.704

RSD 0.82% 0.15% 0.37% 0.60%

r (exp)

r* (ref)

3560 +/- 260 8270 +/- 550

59 126

136 337

Method Accuracy

Instrument Precision

Method Precision

Intuvo Delivers:

*r = ISO 16703 single lab precision requirement

37

Ease of Use

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Why Intuvo for D7504 Analysis of Aromatic Solvent Purity

• D7504 is designed as an easy-to-use method

- no sample prep or calibration standards

Why not have an easy-to use GC for an easy-to-use method?

• Intuvo’s FID is ideally suited to using Effective Carbon Number response

- uses the Agilent’s FID with autoranging electronics

• detector response is linear for peaks from ppm to 99+ % in a single run

• Intuvo is an easy to use

- Intuvo click and run connections for easy column install

- Intuvo Smart ID Key

- Intuvo Health Report and Early Maintenance Feedback (EMF)

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D7504 Analysis of Purified ToluenePrecisely measures very large components (99.97%) and very small components (18 ppm) in a single run

min5 10 15 20 25 30

pA

8

10

12

14

16

18

20

min10.8 10.9 11 11.1 11.2 11.3

pA

0

2000

4000

6000

8000

10000

12000

14000toluene

C9+ aromatics

ethylbenzene

non-aromatics

0.16 pA

13500 pA

40











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Notes and Briefs!

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agilent 9000 intuvo gc applications...most of the analytes can be differentiated from the baseline...

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