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Group/Presentation TitleAgilent Restricted
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Is there still a need for selective GC detectors?
M Ramesh
Application Engg
Agilent Technologies India Pvt Ltd.
Group/Presentation TitleAgilent Restricted
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Outline
GC Detectors Available from Agilent
Electron Capture Detector (ECD)
Nitrogen Phosphorus Detector (NPD)
Flame Photometric Detector (FPD)
Sulfur and Nitrogen Chemiluminescence Detectors (SCD/NCD)
Inductively Coupled Plasma/Mass Spec as a GC Detect or (ICP-MS)
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GC Detectors Available Through Agilent
Thermal Conductivity Detector (TCD)
Flame Ionization Detector (FID)
Micro Electron Capture Detector (µECD)
Nitrogen Phosphorus Detector (NPD)
Flame Photometric Detector (FPD)
Sulfur Chemiluminescence Detector (SCD)
Nitrogen Chemiluminescence Detector (NCD)
Inductively Coupled Plasma-Mass Spec (ICP-MS)
Mass Selective Detector (MSD)
Triple Quadrupole MS (QQQ-MS)
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Typical Detector Operating Ranges
fg pg ng µg mg
10 -15 10 -1210 -9 10 -6 10 -3
ppt ppb ppm 0.1%
TCD
FID
AED
NPD (N)
FPD (S)
SCD (S)
PFPD (S)
NPD (P)
MSD (SIM) (SCAN)
µECD
FPD (P)
HID
ICP-MS
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Analysis of PCBs in Fish Oil Using GC with Dual ECD Detectors - Background
Fish are an excellent source of omega-3 fatty acids (DHA & EPA)
American Heart Association recommends eating fatty fish at least two times per week or taking a daily fish oil supplement
0.5-1.8 g of DHA + EPA /day “significantly reduces deaths from heart disease and all causes”
But fish and fish oil may contain pollutants:
PCBs, PBDEs, PCDDs, PCDFs, & heavy metals
American Heart Association (http://www.americanheart.org/presenter.jhtml?identifier=4632)
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ECD 1
S/S Inlet
ECD 2
PCM
solenoid valve (off)
restrictor
DB-XLB
DB-200
41.040 psig 20.160 psig
No Cut
PCB Analysis: Agilent 7890A with Deans Switch for Heart Cutting and Backflushing
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Heart Cutting with the Deans Switch to Isolate Target PCBs from Fish Oil Spiked with Aroclor 1260
min6 8 10 1 2 14 1 6 18
Hz
15 0
20 0
25 0
30 0
35 0
E C D 1 A , E C D 1A , F ron t S ign al (C H U A N H O N G F IS H O IL D A T A J AN 20 07\20 07 01 22- PC B \P C B0 2-C A L IBR A T IO N IN IS O - O C T AN E 200 7- 01 - 22
min4 6 8 10 12 14 16 18
Hz
500
1000
1500
2000
2500
3000
3500
4000
28 52 101 118 153 138 180Heart Cuts
Column 2: DB-200 P/N 122-2033
Column 1: DB-XLB P/N 121-1232
52 101118
153
138
180
28
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GC-FID Chromatogram of Fish Oil with No Backflushing
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
500000
1000000
1500000
2000000
2500000
3000000
3500000
4000000
4500000
5000000
5500000
Signal: FISHOIL H2.D\FID1A.CH
1-µL splitless injection of 10% fish oil without backflushing.GC oven was held at 290 oC for 30 min at the end of the run.
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
1st Blank run
2nd Blank run
Highlighted areas are backflushed
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Deans Switch in Backflush Mode
Backflushing Column (3 min @ 295 oC)
ECD 1
S/S Inlet
ECD 2
PCM
solenoid valve (off)
restrictor
DB-XLB
DB-200
1.000 psig 80.000 psig
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Retention Time Precision Column 1 with and without Backflushing
m in5 .3 5 .4 5 .5 5 .6 5 .7 5 .8 5 .9 6 6 . 1
N or m .
0
2 0 0 0
4 0 0 0
6 0 0 0
8 0 0 0
1 0 0 0 0
1 2 0 0 0
1 4 0 0 0
1 6 0 0 0
m in5 .3 5 .4 5 .5 5 . 6 5 .7 5 .8 5 .9 6 6 .1 6 .2
N or m .
2 0 0 0
4 0 0 0
6 0 0 0
8 0 0 0
1 0 0 0 0
1 2 0 0 0
1 4 0 0 0
10 Runs with Backflushing
10 Runs without BackflushingRetention times shift ~4-5 secduring 10 runs
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Comparing Area Count Stability on Secondary Column for 2 PCBs – With and Without Backflushing
Comparing PCB Area Counts on Column 2 With and Without Backflushing in a 10-Injection Series
0
200
400
600
800
1000
1200
2 4 6 8 10 12 14 16 18 20
Injection number
Raw
Are
a C
ount
s
PCB 118
PCB 153
118 No BF
153 No BF
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NPD: Blos Bead � Better Results, Longer Lifetime
The Blos bead is available as an aftermarket consumable (part number G3434-60806) to retrofit into existing 6890 and 7890 NPDs.
•Longer bead lifetime (2–3X)
•More stable operation throughout the bead’s lifetime
•For nitrogen containing compounds –similar sensitivity and selectivity specifications
•For phosphorous containing compounds – superior sensitivity and selectivity specifications
•Superior resistance to ambient humidity and moisture
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What’s better about the Blos bead NPD (vs today’s white ceramic bead NPD)
Agilent’s Blos NPD bead perfomance Blos vs. Ceramic
� Nitrogen containing compounds specs: - Similar* sensitivity (pg/s) 0.4* 0.4 - Similar selectivity (gN/gC) 25,000 25,000
* some users got 2-3X improvement in N signal/noise
� Phosphorous compounds specs: - Superior sensitivity (pg/s) 0.06 0.2 - Superior selectivity (gP/gC) 200,000 75,000
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NPD Jets, Standard vs Extended Tip
G1531-80560 Standard Capillary Jet
G1534-80580 Optional Capillary Jet with extended tip
NPD Jet Tip extends ~ 9mm beyond old one Analytes are positioned closer to the bead, minimizing tailing.
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Drug Standard by NPD using Different Jets
min7.05 7.1 7.15 7.2 7.25 7.3 7.35 7.4 7.45
pA
0
200
400
600
800
1000
*NPD1 B, (NPD\0202003.D)*NPD1 B, (NPD\0201001.D)
Blue is Extended Tip, less tailing
Red is Standard Tip, more tailing
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Extended NPD Jet For Improved Nitrogen
Extended Jet Part Numbers are the same for 6890 and 7890:
• G1534-80580 NPD Jet Capillary Detector
• G1534-80590 NPD Jet Universal Detector
The extended jet comes installed in all 7890 NPDs ( with a the standard jet in the ship kit for legacy SOP requirements)
The standard jet came installed in all 6890 NPDs (w ith a the extended jet in the ship kit for last ~year of 6890s shipped)
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Tox Screen of Whole Blood, GC/NPD/MSD
1 2 3 4 5 6 7
Scan TIC3
21
54
8
7
610
9 11
3
21
5
4
6
7
8
10
9
11
NPD
1 Nicotine2 Nicotinamide3 Carisoprodol artifact4 Cotinine5 Meprobamate6 Caffeine
7 Carisoprodol8 Methadone9 Cyheptamide (ISTD)
10 Oxycodone11 Cholesterol
Column effluentsplit between NPD and MSD
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Improvements to Agilent’s Flame Photometric Detector (FPD) for P and S
Sulfur Sensitivity (pg/sec)
Phosphorus Sensitivity (fg/sec)
Sulfur Selectivity (gS/gC)
Phosphorus Selectivity (gP/gC)
Maximum Temp-
erature (oC)
Previous Agilent FPD
20 900 1.00X105 1.00X106 250
Enhanced Agilent FPD
3.6 60 1.00X106 1.00X106 250
New optics include both a lens and wide-band optical filter setNew transfer line design eliminates leaks
Upgrade kits available for 6890 & 6850 FPDs
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Pesticides: Three Way Splitter with Makeup
1X method with 1:1:1/10 split FPD:MSD:ECD
3-Way Splitter with Makeup
Auto-sampler
7890GC
Column
Phosphorus FPD
30 m X 0.25 mm id X 0.25 um HP-5MS
5975C MSD
µECDAUX EPC3.8 psig
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Full scan TIC
SIM
µECD
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
FPD(P)
Milk Extract (1 injection)
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Nitrogen and Sulfur Chemiluminescence Detectors• Acquired by Agilent in December 2006 from General E lectric
• Primarily applied in the energy and petrochemical i ndustries.
• Sulfur chemiluminescence detection growing use corr esponds to increasing regulation of sulfur monitoring in fuels worldwide.
• Nitrogen chemiluminescence detection is complementa ry to the sulfur detector in both technology and application.
Chemistry Behind Detector Operation
R-N + O2 � NONO + O3 � NO2* � NO2 + hν (800-3200 nm)
R-S + O2 � SOSO + O3 � SO2* � SO2 + hν (300-400 nm)
Nitrogen (NCD)
Sulfur (SCD)
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Highest selectivity for Nitrogen and Sulfur over Carbon
High Selectivity
Detector response not inhibited by hydrocarbons
Simplifies quantification of unknowns
Simplifies calibration
Options for fast GC or comprehensive 2D GC
No Quenching
Equimolar
Linear
Fast
Key Attributes of NCD and SCD
Complimentary NCD and SCD complement other Agilent detectors, such as NPD, FPD, FID and MS (e.g. for nitrosamines)
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Sulfur Selective Detector Comparison
Detector Sensitivity (pg S/sec)
Selectivity (g S/g C)
Other Properties
FPD 3.6 106 Nonlinear, quenching PFPD <1 ≥106 Nonlinear; quenching
not as bad, less repeatable
AED ~1 105-106 Linear, equimolar, true multielement
ICP-MS ~1 ~ 109 Linear, equimolar, expensive
SCD* <0.5 > 107 Linear, equimolar
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Example of Sensitivity and Selectivity - SCD
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Key Points
SCD
NCD• Highest nitrogen selectivity over carbon
• Very little or no quenching
• Linear and equimolar response
• Most stable nitrogen detector
• Designed with selective nitrosamines mode
• Highest sulfur selectivity over carbon
• Very little or no quenching
• Linear and equimolar response
• Simultaneous FID SCD Signals are possible
S16
32.07
N7
14.01
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Sulfur Determination in Fresh and Roasted Garlic by Static Headspace GC Sulfur Chemiluminescence
FreshGarlic
RoastedGarlic
S16
32.07
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Selected Nitrosamines by GC/NCD1 µL injection of a 2.0 µg/mL standard, 10:1 split
Peak Compound1 N-Nitrosodimethylamine2 N-Nitrosomethylethylamine3 N-Nitrosodiethylamine4 N-Nitrosopyrrolidine5 N-Nitrosomorpholine6 N-Nitrosodi-n-propylamine7 N-Nitrosopiperidine8 N-Nitrosodi-n-butylamine9 N-Nitrosodiphenylamine
1
2
3 456
7
8
9
200 pg each on column
N7
14.01
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The Inductively-Coupled Plasma
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The Domain of ICP-MS
Traditional ElementsNon-Traditional Elements
ImpossibleElements
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6890 GC coupled to 7500 ICP-MS
Silcosteel lined heated transfer line and heated ICP torch injector both under 6890 control (Aux heated zones)
Bidirectional communication between GC and ICP-MS via APG remote
GC control via GC LUI or co-resident GC chemstation
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Where would you use it instead of other “element specific” detectors?
Need to measure multiple elements simultaneously ( universal and specific at the same time)
Need better selectivity than ECD or ELCD (comparable sensitivity for Cl, better for heavier halogens)
Need better sensitivity than FPD or PFPD
Need isotopic information (IDMS)
Need larger dynamic range (larger than any other GC detector)
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Sulfur in CARB Low Sulfur Reformulated Gasoline
1.502.002.503.003.504.004.505.005.506.006.507.007.508.008.509.00
-450000
-400000
-350000
-300000
-250000
-200000
-150000
-100000
-50000
0
50000
100000
150000
200000
250000
Time-->
Abundance
Ion 32.00 (31.70 to 32.70): GAS02.DIon 13.00 (12.70 to 13.70): GAS02.D (*)
Sulfur 32 elemental chromatogram on top, Carbon 13 chromatogram inverted below
S16
32.07
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Why ICP-MS as a GC detector for PBDEs?
Sensitive (low fg sensitivity, reduced need for pre-concentration or large volume injections)
Specific (no interference from other halogenated compounds)
Wide linear range
Compound independent response (can quantify without standards)
Tolerant of wide range of GC gases and flows
MS confirmation of Bromine isotope ratios
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Low fg Sensitivity for PBDEs with Nointerference from other halogens
2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00 8.50
-120000
-100000
-80000
-60000
-40000
-20000
0
20000
Time-->
Abundance
Ion 35.00 (34.70 to 35.70): STD100W.D (*)Ion 79.00 (78.70 to 79.70): STD100W.D
Extracted ion chromatogram, m/z 79 (Br) and 35 (Cl, inverted) of mixture of 50 ppb PBDE mix spiked into 500 ppm tota l PCB as Aroclors 1016 and 1260 (hydrogen carrier)
PBDEs
PCBs
Br35
79.90
Cl17
35.45
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Organotins in marine sediment CRM
400 500 6000
100000
200000
300000
400000
500000
Time / s
Sign
al in
tens
ity
/ CP
S
118 Sn
120 Sn
TBT
DBT
TPrT
MBT
Sn
GC-ICP-MS chromatograms of 118Sn and 120Sn obtained for spiked PACS-2 extract
Data kindly provided by Dr. Kazumi Inagaki, National Metrology Institute of Japan
DL ~ 0.03pg as Sn
Sn50
118.710
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Iodophenols in river water by SPME/GC/ICP-MS
DL ~ 0.1 ppbData kindly provided by Rodolfo Wuilloud et. al. University of Cincinnati
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P, S, Cl, Br and I containing pesticides GC-ICP-MS
DL ~ 0.02 - 2 ppb
Dichlobenil, 2,4,6-TBA, DBOB, Phorate, PCNB, Terbufos, Diazinon, Malathion, Dursban, Ioxynil
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The End
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References – Element Selective GC DetectorsECD
Philip L. Wylie, “Direct Injection of Fish Oil for the GC-ECD Analysis of PCBs: Results Using a Deans Switch With Backflushing,” Agilent Application Note 5989-6095EN, January 2007.
NPD
Sindy Zhou and Han-wen Wang, “Improving your NPD System Efficiency, “ Agilent Application Note 5989-1511EN, October 2004
Bruce Quimby, “Improved Forensic Toxicology Screening Using A GC/MS/NPD System with a 725-Compound DRS Database,” Agilent Application Note 5989-8582EN, May 2008
“Blos technology enhances NPD lifetime and stability,” http://www.chem.agilent.com/en-US/Products/Instruments/gc/Pages/gp66770.aspx
FPD
Chin-Kai Meng, “Improving Productivity and Extending Column Life with Backflush,” Agilent Application Note 5989-6018EN, December 2006
Chin-Kai Meng and Mike Szelewski, “Replacing Multiple 50-Minute FPD/ELCD/SIM Analyses with One 15-Minute Full-Scan Analysis for 10x Productivity Gain,” Agilent Application Note 5989-7670EN, November 2007
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References – Element Selective GC Detectors (Continued)
SCD/NCD
ChunXiao Wang, “Dual Channel Simulated Distillation of Carbon and Sulfur with the Agilent 7890A GC and 355 SulfurChemiluminescence Detector,” Agilent Application Note 5990-3237EN, Dec. 2008
“Sulfur Compounds in Air – Agilent Model 355 SCD,” Agilent Technical Overview 5989-6778EN, May 2007
“Agilent Model 355 Sulfur Chemiluminescence Detector (SCD): Wine Samples,” Agilent Technical Overview 5989-6789EN, June 2007
“Agilent Model 355 Sulfur Chemiluminescence Detector (SCD): Sulfur Simulated Distillation,” Agilent Technical Overview 5989-6787EN, June 2007
“Agilent Model 255 Nitrogen Chemiluminescence Detector (NCD) Simultaneous Hydrocarbon Analysis with the NCD and an FID,” Agilent Technical Overview 5989-6772EN, May 2007.
“Nitrosamine Analysis by Gas Chromatography and Agilent 255 Nitrogen Chemiluminescence Detector (NCD),” Agilent Technical Overview 5989-6773EN, August 2007
ICP-MS
Steven Wilbur, “GC-ICP-MS – a Powerful Alternative for Detection of Brominated Flame-Retardants,” eSeparation Times, Vol 18:2, http://www.chem.agilent.com/en-US/Newsletters/septimes/vol18/issue2/Pages/g31616.aspx
Raimund Wahlen, “A Comparison of GC-ICP-MS and HPLC-ICP-MS for the Analysis of Organotin Compounds,” Agilent Application Note 5988-6697EN, August 2002
Steven M. Wilbur and Emmett Soffey, “Quantification and Characterization of Sulfur in Low Sulfur Reformulated Gasolines by GC-ICP-MS,” Agilent Application Note 5988-9880EN, August 2003