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PFPD Training Course – Part 5Applications

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Sulfur in PetrochemicalMatrices by PFPD

Hydrocarbons: C1 – C100+

H2 C1 C5 C12 C16 // C30 C100+

Light Gases

Natural Gas

Refinery Gas

C4 Liquids Aromatics

Natural Gas Liquids

MTBE Industrial Solvents

Naphthas

Gasoline

Oxygenates Middle Distillates Asphalt

Lube Oils - Waxes

Crude

Sulfur

Sulfur in Petrochem Matrices

• Sulfur is present in most petrochemical matrices

• Wide range of concentrations, from sub-ppb up to % of total weight

• Total sulfur content regulated• Sulfur speciation important for process

adjustments• Unknowns quantified using equimolar

response of PFPD

Sulfur Standards in Propylene

1 COS2 H2S3 CS2

4 Methylmercaptan5 Ethylmercaptan6 Thiophene7 DMS8 2-Propanethiol9 1-Propanethiol10 2-Methyl-2-propanethiol11 2-Methyl-1-propanethiol12 1-Methyl-1-propanethiol13 1-Butanethiol

min2.5 5 7.5 10 12.5 15 17.5 20

unknown

0

500

1000

1500

2000

2500

3000

AIB1 A, (SPRO\SIG10004.D)

2

4

5

6

8

9

7

3

11

12

pro

pyle

ne

Sulfur Channel

1

2

3

4

5

6

8

7

11

9 13

12

10

0.2 mL gas sampling loop; split 5:1.Each compound present in this propylene standard

at approximately 1 ppm.

Sulfur in Propane-Propylene Mix

• Acquired on the OI Analytical S-PRO 3200 System• [COS] & [S] determined with COS permeation wafer device and

equimolar response of the PFPD• 0.2 mL gas loop, 5:1 split, GasPro column, ramped oven

SulfurChannel

HydrocarbonChannel

0.2 ppmvCOS

C1 & C2

Propane Propylene

C4s +

0.3 ppmvSulfur

0.05 ppmvSulfur

Sulfur in 97% Propane

0.5 mL gas sampling loop; split 10:1.Analyzed on the OI Analytical S-PRO 3200.

~400-500 ppbvCOS

~80-100 ppbvH2S

Propane

Sulfur Channel

Hydrocarbon Channel

Ethane

COS and H2S in Propane by PFPD

min5.4 5.6 5.8 6 6.2 6.4 6.6

counts

200000

300000

400000

500000

600000

700000

800000

min5.4 5.6 5.8 6 6.2 6.4 6.6

counts

2000000

4000000

6000000

8000000

10000000

12000000

14000000

50 m x 0.32 mm Silica-Plot - Chrompack

40 C (0) to 225 C @ 20 C/min1:100 split

2 mL gas loopPFPD - OI Analytical

min5.4 5.6 5.8 6 6.2 6.4 6.6

counts

200000

300000

400000

500000

600000

700000

800000

5.9

24

6.2

58

min5.4 5.6 5.8 6 6.2 6.4 6.6

counts

2000000

4000000

6000000

8000000

10000000

12000000

14000000

5 ppm hydrogen sulfide5 ppm carbonyl sulfide

in propane

COS

H2S

Propane

Chromatogram courtesy of DCG Partnership 1, Ltd.

Sulfur Compounds in CO2

0.5 mL gas sampling loop; slit 20:1.10 replicate analyses on the S-PRO 3200.

7

Sulfur Channel

112 ppbSas SO2

12.4 ppbSas MeSH

Sulfur in Beverage Grade CO2

SO2 Peak Area Variability Over ~4 Days

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

Run Number

PFP

D R

es

po

ns

e

11.7 ppm injected25 uL loopSplit 20:1699 runs

3.5% RSD

MeSH Peak Area Variability Over ~4 Days

0

500

1000

1500

2000

2500

3000

3500

4000

Run Number

PFP

D R

es

po

ns

e

1.5 ppm injected15.4% RSD

580 ppbS (19 pg S)on column as SO2 in CO2

75 ppbS (3 pg S)on column as MeSH in CO2

Sulfur in Pipeline Natural Gas

• Acquired on the OI Analytical S-PRO 3200 System• [H2S] determined with H2S permeation wafer device• [S] determined with COS permeation device & equimolar

resp.• 0.5 mL gas loop, 9:1 split, GasPro column, isothermal oven

SulfurChannel

HydrocarbonChannel

3.4 ppmv H2S

~10 ppbvSulfur

~20 ppbvSulfur

C1 C2 C3C4s

C5s +

S-PRO Sensitivity

COS45 ppbv

H2S125 ppbv

• 1 mL gas sampling loop; 9:1 split ratio

• 60 m GASPRO column (30°C for 1 minute then ramped)

• H2S is absorptive on the GASPRO column; higher DLs

• H2S DLs similar to COS on other columns (e.g. DB1 or DB5)

Repeatability of COS at 50 ppbv

Run Number Peak Area Counts

1 173.6

2 180.3

3 188.7

4 175.0

5 193.2

6 170.9

7 186.7

8 186.4

9 177.4

10 195.9

Average Count

182.8

%RSD 4.7

Repeatability of H2S at 125 ppbv

125 ppb H2S12.8 pg S on column

4.5% RSD (n=10)

• 125 ppb H2S from S-PRO permeation oven

• 1 mL gas sampling loop; split 9:1• 60 m GASPRO column; 30°C for 1 minute then ramped

ASTM Round Robin Gasoline #10

A Methyl mercaptanB ThiopheneC C1-ThiophenesD TetrahydrothiopheneE C2-ThiophenesF C3-ThiophenesG BenzothiopheneH C1-BenzothiophenesI C2-BenzothiophenesJ C3-BenzothiophenesK DibenzothiopheneL C1-DibenzothiophenesM C2-DibenzothiophenesN C3-DibenzothiophenesO Alkyl sulfides & substituted thiophenes

1 L injection; split 100:1.Used as an external calibration standard

for quantitation of unknowns.

min10 20 30 40 50

15 uV

100

200

300

400

500

600

700

800

900

AIB1 A, (ATOFIN~1\SPLIT1~1\ATOFN002.D)

min10 20 30 40 50

15 uV

0

10000

20000

30000

40000

50000

AIB2 B, (ATOFIN~1\SPLIT1~1\ATOFN002.D)

Sulfur Channel

Hydrocarbon Channel

55.76 ppm total sulfur(consensus value)

A

B C

D

E

F G

Gasoline Before Sulfur Treatment


min5 10 15 20 25 30 35 40

15 uV

0

250

500

750

1000

1250

1500

1750

AIB1 A, (MONT\SPLIT1~1\SF3700~1.D)

min5 10 15 20 25 30 35 40

15 uV

0

10000

20000

30000

40000

50000

AIB2 B, (MONT\SPLIT1~1\SF3700~1.D)

Sulfur Channel

Hydrocarbon Channel

492 ppm total sulfur

A

B C

D

E

F

G

LK

H MN

I J

1 L injection; split 100:1.Quantified using ASTM RR gasoline #10

as an external calibration standard.

Gasoline After Sulfur Treatment


min5 10 15 20 25 30 35

15 uV

200

400

600

800

1000

AIB1 A, (MONT\SPLIT1~1\SF3701~1.D)

min5 10 15 20 25 30 35

15 uV

0

10000

20000

30000

40000

50000

AIB2 B, (MONT\SPLIT1~1\SF3701~1.D)

Sulfur Channel

Hydrocarbon Channel

26.4 ppm total sulfur

A

B

C

D

Note loss of somehydrocarbon species

E



Low Level Gasoline: 5 ppm Total Sulfur


min5 10 15 20 25 30 35

unknown

0

1000

2000

3000

4000

5000

6000

AIB1 A, (PHILLI~1\5PPMGA~1\5PPM0004.D)

min5 10 15 20 25 30 35

15 uV

0

10000

20000

30000

40000

50000

60000

AIB2 B, (PHILLI~1\5PPMGA~1\5PPM0004.D)

Sulfur Channel

Hydrocarbon Channel

5 ppm total sulfur

B

C

D E G

H

I

Little interference from highhydrocarbon background

1 L injection; split 10:1.Concentration reported by client as 5 ppm.

“DHA-Type” Analysis of Unknown Gas


1 L injection; split 50:1.Quantified using thiophene as an external standard.

B


CE F

G H

I

Total Sulfur in LCO


min5 10 15 20 25 30 35

unknown

0

10000

20000

30000

40000

50000

60000

AIB1 A, (PHILLI~1\LIGHTC~1\LTOIL004.D)

min5 10 15 20 25 30 35

15 uV

0

10000

20000

30000

40000

50000

AIB2 B, (PHILLI~1\LIGHTC~1\LTOIL004.D)

Sulfur Channel

Hydrocarbon Channel

245 ppm total sulfur G H

IFED

o.2 L injection; split 250:1.Quantified using ASTM RR gasoline #10


High Level Total Sulfur in Diesel


min10 20 30 40 50 60

15 uV

100

200

300

400

500

600

700

AIB1 A, (GRACED~1\DILUTI~1\GDAVI106.D)

min10 20 30 40 50 60

15 uV

0

10000

20000

30000

40000

AIB2 B, (GRACED~1\DILUTI~1\GDAVI106.D)

Sulfur Channel

Hydrocarbon Channel

3.54% total sulfur

G

H

I

JLK

M N

Dilution solvent

Diluted 1:100 with hexane; 1 L injection; split 100:1.Quantified using ASTM RR gasoline #10


Mid-Range Total Sulfur in Diesel


min10 20 30 40 50 60

15 uV

0

250

500

750

1000

1250

1500

1750

AIB1 A, (VALERO\SPLIT1~1\VALR0002.D)

min10 20 30 40 50 60

15 uV

0

5000

10000

15000

20000

25000

30000

35000

40000

AIB2 B, (VALERO\SPLIT1~1\VALR0002.D)

Sulfur Channel

Hydrocarbon Channel


LK

M

N



Total Sulfur in Diesel Quantified by IS


min10 20 30 40 50

15 uV

0

250

500

750

1000

1250

1500

1750

AIB1 A, (ATOFIN~2\REPEAT~1\ATFNX021.D)

min10 20 30 40 50

15 uV

0

10000

20000

30000

40000

50000

AIB2 B, (ATOFIN~2\REPEAT~1\ATFNX021.D)

32 ppm total sulfur

Sulfur Channel

Hydrocarbon Channel

K

LThiophene (IS)

M

N

1 L injection; split 100:1.Quantified using thiophene as an internal standard.

Naptha Stabilizer Bottoms


min10 20 30 40 50

15 uV

0

250

500

750

1000

1250

1500

1750

2000


min10 20 30 40 50

15 uV

0

10000

20000

30000

40000

50000


Sulfur Channel

Hydrocarbon Channel


ED

C

B

A*

*Includes additional light sulfur compounds, e.g.

H2S



Heavy Catalytic Naptha Before Merox


min10 20 30 40 50

15 uV

0

250

500

750

1000

1250

1500

1750


min10 20 30 40 50

15 uV

0

10000

20000

30000

40000

50000


Sulfur Channel

Hydrocarbon Channel

0.21% total sulfur

K

L

E

N

M

D

C

BA

FG-J



Low Level Sulfur in Jet Fuel by PFPD


1 L injection; split 10:1.No reference was available for identification of

sulfur peak groupings in jet fuel.

min10 20 30 40 50 60

15 uV

100

120

140

160

180

AIB1 A, (PATTER~1\LOWERS~1\RERUN004.D)

min10 20 30 40 50 60

15 uV

0

10000

20000

30000

40000

50000

AIB2 B, (PATTER~1\LOWERS~1\RERUN004.D)

Sulfur Channel

Hydrocarbon Channel

4 ppm total sulfur

High Sulfur Content in Jet Fuel


1 L injection; split 100:1.No reference was available for identification of

sulfur peak groupings in jet fuel.

min10 20 30 40 50 60

15 uV

250

500

750

1000

1250

1500

1750

AIB1 A, (PATTER~1\100TO1~1\PAFB0006.D)

min10 20 30 40 50 60

15 uV

0

5000

10000

15000

20000

25000

30000

35000

40000

AIB2 B, (PATTER~1\100TO1~1\PAFB0006.D)

Sulfur Channel

Hydrocarbon Channel

0.14% total sulfur

Sulfur by Simulated Distillation

min0 2 4 6 8 10 12 14

Norm.

0

2000

4000

6000

8000

FID1 A, (F:\APPLIC~2\GCAPPL~1\DATAFR~1\ACCONT~1\SIMDIS~1\104F0401.D) AIB2 B, (F:\APPLIC~2\GCAPPL~1\DATAFR~1\ACCONT~1\SIMDIS~1\104F0401.D)

HC SeriesBy FID

SimultaneousSulfur Analysis

By PFPD

Reference standard for ASTM Method D2887-02used as a calibration standard for simulated distillation.

Total Sulfur in Crude Oil by PFPD


min10 20 30 40 50

unknown

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

ELC1 A, (C:\HPCHEM\3\DATA\CITGO\CRUDE002.D)

Sulfur Channel


K

L

M

N

O

I

J



Synthetic Crude


min10 20 30 40 50 60

15 uV

200

400

600

800

1000

1200

AIB1 A, (GRACED~1\DILUTI~1\GDAVI202.D)

min10 20 30 40 50 60

15 uV

0

10000

20000

30000

40000

AIB2 B, (GRACED~1\DILUTI~1\GDAVI202.D)

Sulfur Channel

Hydrocarbon Channel

0.6% total sulfur

G H

I

J

L

KM

N

Dilution solvent

O



High Sulfur Content Furnace Oil


min10 20 30 40 50

15 uV

250

500

750

1000

1250

1500

1750


min10 20 30 40 50

15 uV

0

10000

20000

30000

40000

50000


Sulfur Channel

Hydrocarbon Channel

0.11% total sulfur

H

M

LKJ

I

N



Coker Light Gas Oil by PFPD


min10 20 30 40 50 60

15 uV

100

200

300

400

500

600

700

800

900

AIB1 A, (VALERO\DILUTI~1\VALR0108.D)

min10 20 30 40 50 60

15 uV

0

10000

20000

30000

40000

AIB2 B, (VALERO\DILUTI~1\VALR0108.D)

Sulfur Channel

Hydrocarbon Channel

2.4% total sulfur

LKM

N

Dilution solvent

H

I

JG

Diluted 1:50 with isooctane; 1 L injection; split 100:1.Quantified using ASTM RR gasoline #10


Sulfur in an Acidic Product

SulfurChannel

HydrocarbonChannel

20 ppm S asThiophenol (IS)

35 ppm S asBenzothiophene

56.7 ppm S asDPDS

• 20 ppm S as thiophenol added as Internal Standard

• Two speciated sulfur peaks identified and quantified

• Total sulfur measured at 270 ppm sulfur

• 0.2 L injection; split 50:1; DB-5MS column; 3 mm combustor; tuned for sulfur

Analysis of Thiophene in Benzene by ASTM Standard Method D4735-09

ASTM Standard D4735 - 96

“Standard Test Method for Determination of Trace Thiophene in Refined Benzene by

Gas Chromatography”

First re-approved in 2000

Re-approved again in 2002With modifications to include PFPD

Re-approved in 2009 with addition of Interlaboratory Study and new precision

statement for PFPD

ASTM Standard D4735 - 96

• Section 5.3 Detector – “Any flame photometric detector (FPD) can be used, provided it has sufficient sensitivity to produce a minimum peak height twice that of the base noise . . .”

0.5 ppm Thiophene by PFPD

• 0.5 ppm thiophene in benzene• 1 L injection split 50:1• 3.8 pg S on-column• linear acquisition mode• S/N >5:1

Benzene

Thiophene Calibration Repeatability

Calibration Level % RSD (n = 3)

0.5 ppm 3.7

1.0 ppm 6.1

2.0 ppm 1.9

3.0 ppm 0.6

4.0 ppm 0.2

5.0 ppm 0.6

Thiophene Linear Calibration Plot

Linear Calibration of Thiophene in Benzene 5/ 18/ 010.5 ppm to 5.0 ppm

R2 = 0.9992

0.E+00

5.E+02

1.E+03

2.E+03

2.E+03

3.E+03

0 1 2 3 4 5 6

Concentration (ppm)

PFP

D R

esponse

(A

rea)

Thiophene Calibration Results

• Log/log plot (cited by original method)– R2 = 0.9995

• Quadratic plot (PFPD in quadratic mode)– R2 = 0.9997

• Linear plot (PFPD in linear mode)– R2 = 0.9992

All three plot techniques result in excellent and equivalent calibration

curves

Precision Measured as %RSD

Thiophene Calculated Concentrations (ppm)

Run #1 0.51 0.97 2.98 4.91

Run #2 0.49 0.96 2.92 4.96

Run #3 0.50 0.96 2.97 4.97

Run #4 0.49 0.98 2.98 5.01

Run #5 0.49 0.97 2.97 4.98

Run #6 0.49 0.97 2.96 4.99

Run #7 0.50 0.99 2.99 4.96

Average 0.50 0.97 2.97 4.97

%RSD 1.4% 1.3% 0.8% 0.6%

Thiophene Accuracy as % Recy

Expected Concentration

(ppm)

Avg. Measured Concentration

(n = 7)% Recovery

0.50 0.50 99.1

1.0 0.97 97.2

3.0 2.97 98.9

5.0 4.97 99.3

Comparison of Thiophene QC Data

Intermediate Precision Data From D4735 - 96

Thiophene Conc. (mg/kg)

Intermediate Precision (mg/kg)

0.80 0.040

1.80 0.078

Intermediate Precision Data From D4735 – 02

Thiophene Conc. (mg/kg)

Intermediate Precision (mg/kg)

0.50 0.010

1.00 0.010

3.00 0.023

5.00 0.031

The new PFPD precision is ~3-4 times better than the original

FPD precision

Thiophene Precision on the PFPD

• Overlaid chromatograms• 4 concentrations• 7 replicate analyses over ~ 1 week

0.5 ppmRSD = 1.4%

1.0 ppmRSD = 1.3%

3.0 ppmRSD = 0.8%

5.0 ppmRSD = 0.6%

Improved Sensitivity on the PFPD

• 0.05 ppm thiophene in benzene• 1 L injection split 10:1• 1.9 pg S on-column• linear acquisition mode• S/N ~ 3:1

Thiophene

Benzene

Organophosphorus Pesticidesby PFPD

OP Pesticides by PFPD - Sulfur Mode

11 12 13 14 152.0e5

4.0e5

6.0e5

8.0e5

1.0e6

1.2e6

1.4e6

1.6e6

1.8e6

2.0e6

2.2e6

Sig. 1 in C:\H

PCH

EM

\...\PFPDS016.D

Time (min.)

1. Disulfoton2. Demeton3. Diazinon4. Methyl Parathion5. Malathion6. Parathion7. Ethion8. Guthion

1

2

3

4

5

6

7

8

80 pg each compound

OP Pesticides by PFPD – Phosphorus Mode

min8 10 12 14 16 18 20

15 uV

2000

4000

6000

8000

10000

12000

14000

9.2

33

9.7

75

10

.14

1

10

.73

2

11

.81

3 11

.99

4

13

.38

5

14

.68

9

15

.11

0

20

.01

7

20

.74

8

21

.71

9

1. Dematon-o2. Diazinon3. Dematon-s4. Disulfoton5. Parathion-methyl6. Malathion7. Parathion-Ethyl8. Ethion9.Azinphosmethyl

1

2 3

4

56

7

8

9

1

1-3 pg P in each compound

Pesticide Mix on PFPD & XSD

Compound Low Concentration (ppb)

1. Methamidophos – 1002. Acephate - 603. Dimethoate - 60 4. Diazinon – 605. me. Chlorpyrifos – 506. Chlorpyrifos – 507. Disulfoton sulfone – 508. Ethion – 609. Phosmet – 100 10.Azinphos-me – 150

min5 7.5 10 12.5 15 17.5 20 22.5

Norm.

100

200

300

400

500

600

700

800

AIB1 A, (FLADOAP\002F0201.D)

min5 7.5 10 12.5 15 17.5 20 22.5

Norm.

0

5000

10000

15000

20000

25000

AIB1 A, (FLADOAS\003F0301.D)

min5 7.5 10 12.5 15 17.5 20 22.5

Norm.

100

125

150

175

200

225

250

275

AIB2 B, (FLADOAX\002F0201.D)

1

4

2

536

8

7

9 10

XSDLow Level

4

53

6

8

7

9 10

5 6

Imazali(Cl only)l

Thiabendazole(S only)

min5 7.5 10 12.5 15 17.5 20 22.5

15 uV

200

400

600

800

1000

1200

1400

AIB1 A, (FLADOAN\003F0301.D)

PFPD S-ModeBG-12 FilterHigh Level

PFPD P-ModeWG-345 FilterLow level

PFPD N-ModeHigh Standard

Garlic Extract on PFPD

min0 2 4 6 8 10 12

unknown

0

500

1000

1500

2000

2500

AIB1 A, (990304H\003F0301.D)

min0 2 4 6 8 10 12

15 uV

0

200

400

600

800

1000

1200

1400

1600

1800

AIB2 B, (990304G\001F0101.D)

This chromatogram was reprocessed in PFPDView

and imported back into HP Chemstation for

reintegration and analysis

Single Gate

Dual Gate Subtraction

OP Pesticides

Interfering SulfurBackground

#3#1

1 ppb standardP mode

Lowest Concentration Phosphorus

10 ppb standardS mode#1 #6#4

#3

•Two compounds detected at 1 ppb•#1 with unknown number of P

atoms•#3 with 2 P atoms•Compare to 10 ppb in S mode

Elemental Confirmation

• Chromatogram of 100 ppb mix has all 9 stds• Labeled with # of P atoms on each compound• Areas closely match wt % of P in each

1P

1P

1P 1P

1P

1P

1P2P

2P (?)

Calibration Over Linear Range

Sulfotepp Calibration in Phosphorus Mode4 - 10 msec Phosphorus Gate

1 - 100 ppb

R2 = 0.9971

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

50000

0 20 40 60 80 100 120

Concentration (ppb)

PF

PD

Re

spo

nse

(A

rea

Cn

ts)

Identify The Linear Range For P

Fully Saturated

Not Saturated

P Emission Saturated at Top of Linear Range

Note contribution from SAt this concentration

(2000 ppb)

Calibration Over Linear Range

Sulfotepp Calibration in Phosphorus Mode6-10 msec Phosphorus Gate

1 - 2000 ppb

R2 = 0.9997

0

20000

40000

60000

80000

100000

120000

140000

160000

180000

0 500 1000 1500 2000 2500

Concentration (ppb)

PF

PD

Re

sp

on

se

(A

rea

Cn

ts)

R2 = 0.9936(Linear fit)

(Polynomial fit)

Summary of P-Mode Results

• 10x lower detection levels in P mode– 1 ppb in P mode– 10 ppb in S mode

• Choice of proper gate can extend calibration range– 4-10 msec gate: 1-100 ppb– 6-10 msec gate: 1-2000 ppb

• Watch for contributions from sulfur at high concentrations, even in “P only” mode– Especially important for matrices with lots of sulfur

background, such as onion or garlic

Garlic Matrix in P Mode

• PFPD configured for P• 6-25 msec S gate• All peaks due to strong S

background

• 4-10 msec P gate• No dual gate subtraction used• P chromatogram nearly identical

to S chromatogram• S “intrusion” into P gate

P-only peak in S due to

gate overlap

Garlic Matrix in P Mode

• 4-10 msec P gate• No dual gate subtraction used• P chromatogram nearly identical

to S chromatogram

• 4-10 msec P gate• Dual-gate subtraction used• P compound now easily identified• Improved interheteroatom selectivity

4 P peaks isolated from sulfur background

P-only peak stronger in P

channel

Dual-gate Subtraction

• Advanced selectivity technique that can be used to remove sulfur background (matrix) for phosphorus identification

• Semi-quantitative, depends on relative concentrations of S and P

• Can improve calibration curves• Conditions are optimized using PFPDView

software– Optional software package with PFPD

PFPDView Software

• Allows post-run optimization of dual gate parameters

• View emission profiles of individual peaks to confirm S or P

• Also used for troubleshooting

PFPDView For Unknowns

Background

tributyl phosphate - P only

Malathion - 2X S vs. P

Chlopyriphos - Equal S&P

• Get heteroatom composition information using PFPDView

• Elemental composition of the unknowns

• Blue = P• Green = S

Dual Gate Subtraction

min0 2 4 6 8 10 12 14 16 18

15 uV

0

1000

2000

3000

4000

AIB1 A, (F:\APPLIC~2\SIG10031.D)

3.201

3.317

7.008

7.159

8.824

9.157

9.263

9.672

10.52

1

16.50

7 16.62

8 16.89

1 17.01

2 17.19

7

min0 2 4 6 8 10 12 14 16 18

15 uV

0

1000

2000

3000

4000

AIB2 B, (F:\APPLIC~2\SIG10031.D)

3.193

3.291

8.824

17.19

7

Channel 1P-modeNo Dual Gate Used

Channel 2 P-ModeDual Gate Subtraction

• Onion extract; no clean-up

• Large interfering sulfur background

• Ch1 – No subtraction

• Ch2 – sulfur background subtracted using PFPDView & dual gating

OP Pesticides

Carbamate Pesticidesby PFPD

Calibration Curves 5 - 200 ppb

Calibration of Thiocarbamates5 to 200 ppb (2uL Injections)

R2 = 0.9995

R2 = 0.9993

0.0E+00

5.0E+02

1.0E+03

1.5E+03

2.0E+03

2.5E+03

0 50 100 150 200 250

Concentration (ppb)

PFP

D R

esponse (A

rea C

nts

)

Pebulate Thiobencarb

10 ppb Pebulate & Thiobencarb

• 2 L injection; pulsed splitless mode• Injector temperature 250C• HP-5 column, 30m x 0.32 mm ID x 0.25 m film• 60C for 1 minute, 20C /min to 300C, hold 1 minute

10 ppb Pebulate

10 ppb Thiobencarb

Repeatability at 10 ppb

• 10 ppb Pebulate RSD = 4.3% (n=10)• 10 ppb Thiobencarb RSD = 6.9% (n=10)

10 ppb PebulateRSD = 4.3%

Thiabendazole

Repeatability at 100 ppbRestek Siltek Uniliner

in the injection portRSD = 2.0%

(n = 10)

ThiabendazoleRSD = 2.0%

n = 10

Without the special liner significant breakdown

prevented reliable analyses of thiabendazole

PFPD: Carbamates in Beef Fat

• Direct injection – GC – PFPD– Pulsed Flame Photometric Detector– Sulfur selective & Equimolar– 2 L injection; splitless

• Pebulate & Thiobencarb at 10 ppb or less

Beef Liver ExtractUnspiked

10 ppb Spike

100 ppb Spike


PFPD: Carbamates in Beef Muscle




10 ppb Spike

100 ppb SpikePebulate

Thiobencarb

Two Simultaneous Signals

• 10 ppb spike in beef liver extract• S channel to quantify S compounds• HC channel to monitor potential

interferences

SulfurChannel

HydrocarbonChannel

10 ppbPebulate

10 ppbThiobencarb

Chlorinated Pesticides by XSD

• Direct injection – GC – XSD

– Halogen Specific Detector– 1 L injection; split 9;1

• 1 LOQ Standard• Solvent venting option for chlorinated solvents

Solvent completely vented

XSD Chromatogram of 1 LOQ Standard

PFPD: Carbamates in Beef Liver




10 ppb Spike

100 ppb Spike


Sulfur Compounds

Analysis of Aldicarb, Methomyl, and Methiocarb by GC/PFPD in Under 5 Minutes!

Chromatogram at 100 ppb

• 100 ppb each aldicarb, methomyl, and methiocarb

• Linear acquisition mode• S/N of 10 or better

AldicarbMethomyl

MethiocarbACN

Total analysis time less than

5 minutes.

Aldicarb Calibration Curve

Calibration of Aldicarb on the PFPD50 to 1000 ppb

R2 = 0.9993

0

500

1000

1500

2000

2500

3000

0 200 400 600 800 1000 1200

Concentration (ppb)

PF

PD

Re

sp

on

se

Calibration Summary

Compound Calibration Range

R2

Aldicarb 50 – 1000 ppb

0.9993

Methomyl 50 – 1000 ppb

0.9990

Methiocarb 50 – 2000 ppb

0.9987

Repeatability at 100 ppb

• Overlaid chromatograms; n = 10• 100 ppb• 1 L splitless injections; 4 m column

Aldicarb

Methomyl

Methiocarb

Repeatability Summary

Compound 100 ppb

500 ppb

1 ppm

Aldicarb 5.5 4.0 2.5

Methomyl 6.1 6.8 3.9

Methiocarb 9.4 6.2 3.2

%RSD for 10 Replicate AnalysesAt Different Concentrations

Carbamate Conclusions

• Thiocarbamates thermally labile• Usually analyzed by LC methods• GC with PFPD works well for selected

thiocarbamate pesticides• Faster, simpler, more sensitive• Monitor for hydrocarbon interferences• Use with XSD for simultaneous

measurement of Cl pesticides

Food & Flavor Analysisby PFPD

Introduction

• Sulfur compounds are an important component of flavor analysis

• Responsible for specific and distinctive flavors in many foods & beverages

• Difficult to analyze and identify because present at minimal concentrations

• MS or FID commonly used, but not sensitive enough to detect sulfur compounds at trace levels

GC Configuration MS/FID/PFPD

6890N GC with5973N MS

Agilent FID in Front for Sulfur Marking

OI Analytical PFPD in BackFor Quantitation

PFPD

FID

Column Configuration for 3 Detectors

Standard installationat injection port

Detector end split using low dead volumeconnector and a 3-hole ferrule

LDV connector

3-hole ferrule

3 transfer lines

Headspace Apparatus

~20 grams coffee

GC inlet liner packedWith 100 mg Tenax

Line carrying Hepurge gas

Coffee Headspace by MS/FID/PFPD

MS

FID

Sulfur by PFPD

3 Simultaneous Chromatograms From Coffee “A”

Over 200 sulfur peaks detected

PFPD Used To Identify Sulfur RTs

MS

PFPD

A

NIST search resultsfor peak “A”

Compound Retention Times

• MS and PFPD (and FID) chromatograms very slightly offset by 4-5 seconds– Reproducible

• Due to fact that MS is under vacuum and PFPD and FID are under slightly positive pressure

• Offset easily determined with a standard prior to analysis of unknowns

MS

PFPD

23.75 min

23.67 min

Competitive Analysis

• Can be used to identify differences between specific blends

• Determine which sulfur compounds contribute distinctive flavor and aroma

•The sulfur chromatogram, or “fingerprint” is unique for each coffee blend

Sulfur by PFPD

Competitive Analysis of 3 Coffees

Sulfur inCoffee “A”

Sulfur inCoffee “B”

Sulfur inCoffee “C”

Note differencesIn the 3 chros

Sulfur in Galbanum Oil by PFPD

• Essential oil distilled from the galbanum plant

• Green, fresh leafy odor, dry woody undertones, pine highlights

• Used in production of fragrances

• Using an FPD only 4 sulfur peaks were detected

MS

FID

Sulfur by PFPD

Expanded view of sulfur

Sulfur in Fishwort Oil

MS

Sulfur by PFPD

FIDMint Sulfide onlyDetectable with

The PFPD

• 0.1 L injection• Essential oil distilled

from the fishwort, or “Chinese Lizard Tail”, plant (2 varieties)

• Corriander aroma or lemon/orange odor

• Used in production of flavors

• Using an FPD no sulfur peaks were detected

Sulfur in Beverage Grade CO2

H2S

COS CS2

Each compound present at ~2.0 ppm in CO2

Chromatogram courtesy of JAS

Sulfur in Strawberry by PFPD

CamaorsaCamaorsaSweet CharlieSweet Charlie

Chromatogram courtesy of Russell Rouseff, PhD, at University of Florida

Sulfur in Grapefruit by PFPD

Chromatogram courtesy of Russell Rouseff, PhD, at University of Florida

Sulfur in Beer by Headspace

Eth

aneth

iol

Meth

yl su

lfide

2-M

eth

ylp

ropaneth

iol

1-M

eth

ylp

ropaneth

iol

Thio

phene

Dim

eth

yl dis

ulfi

de

Am

yl su

lfide

Hepta

neth

iol

tert

-Buty

l dis

ulfi

de

min2 4 6 8 10 12 14

Norm.

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

AIB1 A, (SULFUR1\SIG16006.D) AIB1 A, (SULFUR1\SIG16007.D) AIB1 A, (SULFUR1\SIG16008.D) AIB1 A, (SULFUR1\SIG16009.D) AIB1 A, (SULFUR1\SIG16010.D) AIB1 A, (SULFUR1\SIG16011.D) AIB1 A, (SULFUR1\SIG16012.D) AIB1 A, (SULFUR1\SIG16013.D) AIB1 A, (SULFUR1\SIG16014.D) AIB1 A, (SULFUR1\SIG16015.D)

PFPD repeatability

at 10 ppb better than

10%

Sulfur in Beer by PFPD

Miller Genuine Draft

Miller Lite

Budweiser

Sam Adams

Unk

ES

MS

MTHIOAC

MDS

Unk

Sulfur concentrations in beers tested ranged from 0.1 ppbS to ~4 ppbS

Sulfur in Wine and Rum by PFPD

Red Wine “B”Dark Rum

White Rum Red Wine “A”

0.15 ppbSAs ES

0.5 ppbSAs MS

~4.5 ppbSAs MDS

UnkUnk

Unk

MS

MDS

~0.1 ppbSIn Unknown

0.3 ppbSAs MTS

Sulfur in Liquor by PFPD

min0 2 4 6 8 10 12 14 16

15 uV

100

120

140

160

180

200

220

240

260

AIB1 A, (SULFUR1\SIG17017.D)

Jack Daniels

min0 2 4 6 8 10 12 14 16

15 uV

120

140

160

180


Kaluha

min0 2 4 6 8 10 12 14 16

15 uV

120

140

160

180

200

220

240


Crown Royal

min2 4 6 8 10 12 14 16

15 uV

100

200

300

400

500

600

700

800

900

1000


Finnish Cranberry Liquor

Methyl sulfide8.4 ppb

Dimethyl disulfide0.6ppb

Methyl sulfide<0.5 ppb

Unknown1.4 ppb

Sulfur in Coffee & Tea by P&T/PFPD

Iced Tea

Brewed Coffee

Unknown<0.05 ppb S

~4 ppbSAs MDS

1.0 ppbSAs MTS

0.65 ppbSAs MS

Sulfur in Juice by P&T/PFPD

Grapefruit Juice

Apple Juice

Orange Juice

MS reached“Self-Quenching”

MS saturatedThe detector

1.0 ppbS as MS

PFPD-MS Configuration

OI 5380PFPD

Split/SplitlessInjector

HP-5973AMS

HP-5MS30 meter, 0.25 mm ID, 0.25 m film1.0 mL/min He

DB-120 cm, 0.1 mm ID, 0.1 m film0.6 mL/min He

HP-5MS30 cm, 0.25 mm ID0.4 mL/min He

Twister by Gerstal, Inc.

Sulfur in Cola by PFPD/MS with Twister

MS

PFPD

MS

PFPD

Sulfur in Coffee by PFPD/MS with Twister

Other Applications by PFPD

Chemical Warfare Analyses

• A 2-headed PFPD for simultaneous, selective P and S detection

• One body/combustor, two filter/PMTs• One side filter and gates optimized for S• One side filter and gates optimized for P

Dual-Headed PFPD

This one configured for S on both “sides”

Identical, matching S

emissions

CW Agent Detection with PFPD

Phosphorus channel

Sulfur channel

GB

HD

VX

• Typical GB, VX and HD chromatogram– HP 6890 with PFPD configured to favor phosphorus response– HP-5 30-m x 0.32-mm-od x 25μm film m film

with He flow of 2.5 mL/min; ramped from 40° to 230°C– P gate: 4-15 msec; S Gate: 6-24.9

msec– 39 pg GB; 39 pg VX; 50 pg HD

• Excellent peak shapes and responses illustrate detector potential for multi-element-based multi-agent analysis

• Background peaks lower in S channel than P channel, although S gate opens only two msec after P gate

– Proper gate settings allow enhanced discrimination against background constituents.

P Detectivity and GB Limit of Detection

• Response from a 1.9 pg injection of GB, assuming S/N of three as the LOD– GB LOD 400 fg– Phosphorus detectivity 43 fg P/sec

• PFPD was configured for general use; LOD and detectivity can be improved by optimizing for P response

Phosphorus channel

Sulfur channel

GB

Reduced Sulfur in Pulp Mill Effluent

200 g S/L aqueous standard

Chromatogram courtesy of NCASI

End of Part 5

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