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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
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
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
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
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
1 L injection; split 100:1.Quantified using ASTM RR gasoline #10
as an external calibration standard.
Low Level Gasoline: 5 ppm Total Sulfur
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
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
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 50:1.Quantified using thiophene as an external standard.
B
325 ppm total sulfur
CE F
G H
I
Total Sulfur in LCO
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
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
as an external calibration standard.
High Level Total Sulfur in Diesel
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
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
as an external calibration standard.
Mid-Range Total Sulfur in Diesel
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
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
302 ppm total sulfur
LK
M
N
1 L injection; split 100:1.Quantified using ASTM RR gasoline #10
as an external calibration standard.
Total Sulfur in Diesel Quantified by IS
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
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
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
min10 20 30 40 50
15 uV
0
250
500
750
1000
1250
1500
1750
2000
AIB1 A, (ATOFIN~1\SPLIT2~1\ATOFN108.D)
min10 20 30 40 50
15 uV
0
10000
20000
30000
40000
50000
AIB2 B, (ATOFIN~1\SPLIT2~1\ATOFN108.D)
Sulfur Channel
Hydrocarbon Channel
113 ppm total sulfur
ED
C
B
A*
*Includes additional light sulfur compounds, e.g.
H2S
1 L injection; split 250:1.Quantified using ASTM RR gasoline #10
as an external calibration standard.
Heavy Catalytic Naptha Before Merox
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
min10 20 30 40 50
15 uV
0
250
500
750
1000
1250
1500
1750
AIB1 A, (ATOFIN~1\SPLIT2~1\ATOFN105.D)
min10 20 30 40 50
15 uV
0
10000
20000
30000
40000
50000
AIB2 B, (ATOFIN~1\SPLIT2~1\ATOFN105.D)
Sulfur Channel
Hydrocarbon Channel
0.21% total sulfur
K
L
E
N
M
D
C
BA
FG-J
1 L injection; split 250:1.Quantified using ASTM RR gasoline #10
as an external calibration standard.
Low Level Sulfur in Jet Fuel by PFPD
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 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
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.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
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
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
500 ppm total sulfur
K
L
M
N
O
I
J
Diluted 1:10 with hexane; 1 L injection; split 25:1.Quantified using ASTM RR gasoline #10
as an external calibration standard.
Synthetic Crude
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
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
Diluted 1:10 with hexane; 1 L injection; split 100:1.Quantified using ASTM RR gasoline #10
as an external calibration standard.
High Sulfur Content Furnace Oil
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
min10 20 30 40 50
15 uV
250
500
750
1000
1250
1500
1750
AIB1 A, (ATOFIN~1\SPLIT2~1\ATOFN102.D)
min10 20 30 40 50
15 uV
0
10000
20000
30000
40000
50000
AIB2 B, (ATOFIN~1\SPLIT2~1\ATOFN102.D)
Sulfur Channel
Hydrocarbon Channel
0.11% total sulfur
H
M
LKJ
I
N
1 L injection; split 250:1.Quantified using ASTM RR gasoline #10
as an external calibration standard.
Coker Light Gas Oil by PFPD
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
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
as an external calibration standard.
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
Pebulate Thiobencarb
PFPD: Carbamates in Beef Muscle
• 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 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
• 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
Pebulate Thiobencarb
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
AIB1 A, (SULFUR1\SIG17012.D)
Kaluha
min0 2 4 6 8 10 12 14 16
15 uV
120
140
160
180
200
220
240
AIB1 A, (SULFUR1\SIG17019.D)
Crown Royal
min2 4 6 8 10 12 14 16
15 uV
100
200
300
400
500
600
700
800
900
1000
AIB1 A, (SULFUR1\SIG17011.D)
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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