is there still a need for selective gc detectors? 4_gc... · group/presentation title agilent...

Group/Presentation TitleAgilent Restricted

Month ##, 200X

Is there still a need for selective GC detectors?

M Ramesh

Application Engg

Agilent Technologies India Pvt Ltd.


Month ##, 200X

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

��

A��

��

��

��

��

��

�� A� ��

�� A� ��

��

��

��

��

��

Q��

��


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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


Month ##, 200X

The End


Month ##, 200X

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


Month ##, 200X

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

is there still a need for selective gc detectors? 4_gc... · group/presentation title agilent...

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