agilent 9000 intuvo gc applications...most of the analytes can be differentiated from the baseline...
TRANSCRIPT
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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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
Results
Equivalency
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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
Resilience to
Matrix and
Difficult
Compounds
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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
Low Level
Detection
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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
Ease of
Use
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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
Speed and
High Boilers
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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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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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Semivolatiles Calibration Verification – Matrix Study
Continuing Calibration Verification
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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Semivolatiles Calibration Verification – Matrix Study
Continuing Calibration Verification
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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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)
FID1 A, Front Signal (C:\CHEM32\...TPH_APP_160225\AP73_TPH_APP_160225 2016-02-25 18-47-07\Check Std 04.D)
TPH Standard 3
FID1 A, Front Signal (C:\CHEM32\...TPH_APP_160225\AP73_TPH_APP_160225 2016-02-25 18-47-07\Check Std 05.D)
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
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
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
Visit Agilent’s Website to
Download the Application
Notes and Briefs!
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