Page 1
GC Columns Specifically Optimized for Environmental Analysis
-DB-CLP1 and DB-CLP2-DB-8270D -DB-624UI
Daron DeckerChromatography Technical Specialist
Major Challenges for Pesticides and Semi-Volatiles AnalysesDirty Samples/Trace Active Analytes
-Peak shapes
-Breakdown
Instrument Down Time (Maintenance)
Long Analysis Times (Time is Money!)
Page 2
Trace Analyses of Active Analytes Enemy
ADSORPTION (reversible/irreversible)- results in poor detection limits
-decreases response (s/n), gives poorer precision
• Improving peak shapes improves resolution and peak integration
• Higher response per unit concentration results in more injections before required system maintenance
GC Surfaces that Samples Contact (possible adsorption)
Capillary Flow Technology Devices GC Column
Gold Seal
Inlet Liner
Ferrules
The Inlet
MS Source Components
Detector surfaces
Solution = Make EVERYTHING Inert!
Deactivated – FPD, TCD,NPD/FID Jets
Deactivated Capillary Flow Technology Devices Ultra Inert GC ColumnUltra Inert Gold Seal
Ultra Inert Inlet Liner
Flexible Metal Ferrules
Deactivated Inlet Weldments,Shell and Transfer Lines
The Column Part
1
2
3
4
56 7 8
9 10
11
min0 2 4 6 8 10
pA
6
8
10
12
14
16
18
1
2 34
5
67
8
9 1011
min0 2 4 6 8 10
pA
6
8
10
12
14
16
18
20
1
2 34
5
67
8
9 1011
min0 2 4 6 8 10
pA
6
8
10
12
14
16
18
20 1. 1-Propionic acid
2. 1-Octene
3. n-Octane
4 4-Picoline
5. n-Nonane
6. Trimethyl phosphate
7. 1,2-Pentanediol
8. n-Propylbenzene
9. 1-Heptanol
10. 3-Octanone
11. n-Decane
Brand X Column
Agilent J&W ColumnDB-5ms Ultra Inert
Symptom – Tailing of Active Compounds1. n-Nitrosodimethylamine2. Aniline3. 1,4-Dichlorobenzene-d44. Benzoic Acid5. Naphthalene-d86. Acenaphthene-d107. 2,4-Dinitrophenol8. 4-Nitrophenol9. 2-Me-4,6-dinitrophenol10. 4-Aminobiphenyl11. Pentachlorophenol12. Phenanthrene-d1013. Benzidine14. Chrysene-d1215. 3,3’-Dichlorobenzidine16. Benzo[b]fluoranthene17. Benzo[k]fluoranthene18. Perylene-d12
Sample: 0.5 ng on column loading with ISTDColumn: 20m 0.18mm 0.18µm Carrier: Helium 37cm/sec, Ramped flow; 0.7ml/min (0.1min) to 1.3ml/min (15ml/min2)Oven: 35oC (2.5 min) to 80oC (40oC/min), 15oC/min to 200oC, 8oC/min to 275oC (2 min)Injection: 0.5µl, Splitless, 280oC, purge flow 30ml/min at 0.75 min MSD: Transfer Line 290oC, Source 300oC, Quad 180oC
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.000
50000
100000
Time (min)
Abundance
1
2
3 56
78
10
11
9
12
13
14
15
16
17
18
4
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.000
50000
100000
Time (min)
Abundance
1
2
3 56
78
10
11
9
12
13
14
15
16
17
18
4
Page 7
Solution – Ultra Inert GC Column1. n-Nitrosodimethylamine2. Aniline3. 1,4-Dichlorobenzene-d44. Benzoic Acid5. Naphthalene-d86. Acenaphthene-d107. 2,4-Dinitrophenol8. 4-Nitrophenol9. 2-Me-4,6-dinitrophenol10. 4-Aminobiphenyl11. Pentachlorophenol12. Phenanthrene-d1013. Benzidine14. Chrysene-d1215. 3,3’-Dichlorobenzidine16. Benzo[b]fluoranthene17. Benzo[k]fluoranthene18. Perylene-d12
Sample: 0.5 ng on column loading with ISTDColumn: 20m 0.18mm 0.18µm Carrier: Helium 37cm/sec, Ramped flow; 0.7ml/min (0.1min) to 1.3ml/min (15ml/min2)Oven: 35oC (2.5 min) to 80oC (40oC/min), 15oC/min to 200oC, 8oC/min to 275oC (2 min)Injection: 0.5µl, Splitless, 280oC, purge flow 30ml/min at 0.75 min MSD: Transfer Line 290oC, Source 300oC, Quad 180oC
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00
0
50000
100000
Time (min)
Abundance
1
2
3
4
5
6
78
9
10
11
12
13
14
15
16
17
18
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00
0
50000
100000
Time (min)
Abundance
1
2
3
4
5
6
78
9
10
11
12
13
14
15
16
17
18
Page 8
500 ng/mL Pesticides Test – (GC/QQQ –MRM)4x10
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
1.1
1.2
1.3
1.4
1.5
1.6
+EI MRM CID@** (136.0 -> 42.0) 500ppb.D
Counts vs. Acquisition Time (min)4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10 10.5 11 11.5 12 12.5 13 13.5 14 14.5 15 15.5 16 16.5 17 17.5 18 18.5 19 19.5 20 20.5
1
2a
2b
3
4
5
6
7
8
9
1011
12
13
14
15 16 17 18
19 20
2122
23
2425
26
IS
1. Acephate; 2. Methacrifos3. Omethoate4. Ethalfluralin5. Sulfotep6. Demeton-S7. Simazine8. Lindane9. Chlorothalonil10. Chlorpyrifos-methyl11. Fenitrothion12. Aldrin13. Pendimethalin14. Tolyfluanid15. Folpet
16. Dielderin17. Bupirimate18. Triazophos19. Propargite20. Iprodioone21. EPN22. Phosalone23. Mirex24. Coumaphos25. Pyraclostrobin26. Deltamethrin
IS: Internal Standard (TPP)
Inlet: 250 ºC Pulsed Splitless: 30 psi for 0.75 min Purge flow: 30 mL/min at 0.75 minInlet liner: UI single tape with wool or standard single taper with wool,1 µL injection volume Column: HP-5ms UI 30m x 0.25mm x 0.25 umCarrier: He Constant flow = 1.1343 mL/min set at 60°C, RT lock: Chlorpyrifos methyl @ 9.145 minOven: 60°C, hold 1min; 40°C/min to 170°C at, then 10°C/min 310°C (3 min hold)Detector: 7000 QQQ, MRM mode Transfer line temp = 280°C MSD source temp 300°C, Q1,Q3 temp150°C
Agilent J&W DB-CLP1 and DB-CLP2 Columns
10
GC/ECD Analyses of Chlorinated Pesticides, Herbicides, Organohalides, and PCBs Multiple EPA Methods
Testing contaminants in drinking water and groundwater
Dual Column analysis: Primary and Confirmation Column Sets
Issues Many methods use different column sets to achieve desired separation
Downtime of switching between different column sets for different methods
Solution Agilent’s J&W DB-CLP1 and DB-CLP2 column set
Provides the selectivity to separate many different halogenated compounds
One column set is able to analyze via multiple methods
EPA Methods Covered by DB-CLP1 & DB-CLP2 columns
11
CLP Pesticides 19 Targeted Organohalide pesticides
EPA 504.1 1,2-Dibromoethane (EDB), 1,2-Dibromo-3-chloropropane (DBCP), and 1,2,3-Trichloropropane (123TCP)
EPA 505 Organohalide pesticides
EPA 508.1 Chlorinated pesticides, herbicides, and organohalides
EPA 551 Chlorinated solvents, Trihalomethanes (THMs), and Disinfection Byproducts (DBPs)
EPA 552.3 Haloacetic acids and Dalapon
EPA 8081B (extended analyte list) Organochlorine pesticides
EPA 8082A Polychlorinated biphenyls (PCBs) and Aroclors
EPA 8151A Chlorophenoxyacid herbicides
1. Tetrachloro-m-xylene*
2. α-BHC
3. γ-BHC
4. β-BHC
5. Heptachlor
6. δ-BHC
7. Aldrin
8. Heptachlor epoxide
16. Endosulfan II
17. 4,4’-DDT
18. Endrin aldehyde
19. Endosulfan sulfate
20. Methoxychlor
21. Endrin ketone
22. Decachlorobiphenyl*
*surrogate standard
9. γ-Chlordane
10. α-Chlordane
11. Endosulfan I
12. 4,4’-DDE
13. Dieldrin
14. Endrin
15. 4,4’-DDD
Agilent DB-CLP2
Agilent DB-CLP1
min2 3 4 5 6 7 8
1
2 3
4
5
7
8 910 12
14
11
15
161718
20
19
13
22
21
6
min2 3 4 5 6 7 8
1
23
4
5
7
89
10,11
12
14
151618
17
20
19
13
22
21
6
Fast CLP PesticidesChlorinated Pesticides
DB-CLP1 30m 0.32mm ID 0.25µm (cat.# 123-8232)
DB-CLP2 30m 0.32mm ID 0.5µm (cat.# 123-8336)
5m x 0.32mm ID deact. guard column
Inert Tee CFT device (cat.# G3184-60065) 1:1 Split
Instrument: Agilent 7890 GC with dual µECD
Sampler: Agilent 7693
Sample: 50 ng/mL CLP Pesticides
Inj. Vol.: 1 µL splitless
Liner: Ultra Inert liner, single taper splitless
(cat.#5190-2292)
Inj. Temp.: 250°C
Oven Temp: 150°C (hold 0.2 min),
45°C/min to 250°C, 18°C/min to 300°C,
30°C/min to 330°C, hold 2.5 min
Carrier Gas: Helium, constant flow 3.5 mL/min
Detector: µECD @ 340 °C
12
Agilent DB-CLP2
Agilent DB-CLP1
min2 3 4 5 6
min2 3 4 5 6
1
2
3
4
5
7
8
910
12
11
6
1
2
3
4
5
7
8
910
12
116
100 ng/mL Chlorinated solvents + THMs
100 ng/mL 504.1 analytes
100 ng/mL Chlorinated solvents + THMs
100 ng/mL 504.1 analytes
1. Chloroform
2. 1,1,1-Trichloroethane
3. Carbon tetrachloride
4. Trichloroethene
5. Bromodichlormethane
6. Tetrachloroethene
7. 1,1,2-Trichloroethane
8. Dibromochloromethane
9. 1,2-Dibromoethane (EDB)
10. Bromoform
11. 1,2,3-Trichloropropane (123TCP)
12. 1,2-Dibromo-3-chloropropane (DBCP)
EPA Method 504.1EDB, DBCP, and 123TCP
DB-CLP1 30m 0.32mm ID 0.25µm (cat.# 123-8232)
DB-CLP2 30m 0.32mm ID 0.5µm (cat.# 123-8336)
5m x 0.32mm ID deact. guard column
Inert Tee CFT device (cat.# G3184-60065) 1:1 Split
Instrument: Agilent 7890 GC with dual µECD
Sampler: Agilent 7693
Sample: 100 ng/mL 504.1 analytes
100 ng/mL Chlorinated Solvents + Trihalomethanes
Inj. Vol.: 2 µL splitless
Liner: Ultra Inert liner, single taper splitless
(cat.#5190-2292)
Inj. Temp.: 200°C
Oven Temp: 50°C (hold 1.5 min) to 95°C at 20°C/min,
40°C/min to 175°C, hold 1.25 min
Carrier Gas: Helium, constant flow 3.75 mL/min
Detector: µECD @ 300 °C
13
EPA Method 505Organohalide Pesticides
DB-CLP1 30m 0.32mm ID 0.25µm (cat.# 123-8232)
DB-CLP2 30m 0.32mm ID 0.5µm (cat.# 123-8336)
5m x 0.32mm ID deact. guard column
Inert Tee CFT device (cat.# G3184-60065) 1:1 Split
Instrument: Agilent 7890 GC with dual µECD
Sampler: Agilent 7873B
Sample: 100 ng/mL 505 analytes
Inj. Vol.: 2 µL splitless
Liner: Ultra Inert Liner double taper, splitless
(cat.# 5190-3983)
Inj. Temp.: 250°C
Oven Temp: 90°C (hold 0.5 min), 35°C/min to 175°C,
12°C/min to 300°C, hold 1.75 min
Carrier Gas: Helium, constant flow 2.5 mL/min
Detector: µECD @ 325 °C
min4 6 8 10 12
1
2
5
6
7 8
12
119
14
1513
16
10
3,4
min4 6 8 10 12
25 7
89
10 1214
11
15
16
136
3
4
1
Agilent DB-CLP2
Agilent DB-CLP1
1. Hexachlorocyclopentadiene
2. Hexachlorobenzene
3. Atrazine (25 µg/mL)
4. Simazine (25 µg/mL)
5. γ-BHC
6. Heptachlor
7. Alachlor (1 µg/mL)
8. Aldrin
9. Heptachlor epoxide
10. γ-Chlordane
11. trans-Nonachlor
12. α-Chlordane
13. Dieldrin
14. Endrin
15. cis-Nonachlor
16. Methoxychlor (0.5 µg/mL)
14
EPA Method 508.1Chlorinated Pesticides and Herbicides
11. γ-BHC
12. β-BHC
13. Heptachlor
14. Alachlor
15. δ-BHC
16. Chlorothalonil
17. Aldrin
18. Metribuzin
19. Metolachlor
20. DCPA
1. Hexachlorocyclopentadiene
2. Etradiazole
3. Chloroneb
4. Trifluralin
5. TCMX*
6. Propachlor
7. Hexachlorobenzene
8. α-BHC
9. Atrazine
10. Simazine
21. Heptachlor epoxide
22. Cyanazine
23. Butachlor
24. γ-Chlordane
25. α-Chlordane
26. Endosulfan I
27. 4,4’-DDE
28. Dieldrin
29. Chlorobenzilate
30. Endrin
31. 4,4’-DDD
32. Endosulfan II
33. 4,4’-DDT
34. Endrin aldehyde
35. Endosulfan sulfate
36. Methoxychlor
37. cis-Permethrin
38. trans-Permethrin
39. Decachlorobiphenyl*
*surrogate standard
DB-CLP1 30m 0.32mm ID 0.25µm (cat.# 123-8232)
DB-CLP2 30m 0.32mm ID 0.5µm (cat.# 123-8336)
5m x 0.32mm ID deact. guard column
Inert Tee CFT device (cat.# G3184-60065) 1:1 Split
min5 7.5 10 12.5 15 17.5 20 22.5
1
2
3 4
5 7
8
9 10
12
14
11
15
16
17
18
20
19
13
27
2223
24252621
28
29
3031
32
3334
35
36
37
39
386
min5 7.5 10 12.5 15 17.5 20 22.5
1
2
3 4
5
6
7
8
11
1218
15
13
16
19
17 21
22 23
24-26
20
2728
29
30
31 32
34 35
36
3837
33
39
9,10 14
Instrument: Agilent 7890 GC with dual µECD
Sampler: Agilent 7873B
Sample: 100 ng/mL 508.1 analytes
100 ng/mL Pesticide Surrogate Mix
Inj. Vol.: 2 µL splitless
Liner: Ultra Inert liner, single taper splitless
(cat.#5190-2292)
Inj. Temp.: 250°C
Oven Temp: 80°C (hold 0.5 min) to 175°C at 26°C/min,
6.5°C/min to 235°C, 15°C/min to 300°C,
hold 6 min
Carrier Gas: Helium at 35 cm/sec (constant flow)
Detector: µECD @ 340 °C
Agilent DB-CLP2
Agilent DB-CLP1
15
1
2
3
4
5
7
8
9
10
12 1411
15
16
1718
20
19
136
1
2
3
4
5
8
910
12
14
11
15
16
17
20
18,19
13
6
min2 4 6 8 10 12
min2 4 6 8 10 12
7
EPA Method 551Chlorinated Solvents, THMs, and DBPs
DB-CLP1 30m 0.32mm ID 0.25µm (cat.# 123-8232)
DB-CLP2 30m 0.32mm ID 0.5µm (cat.# 123-8336)
5m x 0.32mm ID deact. guard column
Inert Tee CFT device (cat.# G3184-60065) 1:1 Split
1. Chloroform
2. 1,1,1-Trichloroethane
3. Carbon tetrachloride
4. Trichloroacetonitrile
5. Trichloroethene
6. Chloral hydrate
7. Bromodichloromethane
8. 1,1-Dichloro-2-propanone
9. Dichloroacetonitrlie
10. Chloropicrin
11. Tetrachloroethene
12. 1,1,2-Trichloroethane
13. Dibromochloromethane
14. 1,2-Dibromoethane
15. 1,1,1-Trichloro-2-propanone
16. Bromochloroacetonitrile
17. Bromoform
18. 1,2,3-Trichloropropane
19. Dibromoacetonitrile
20. 1,2-Dibromo-3-chloropropane
Agilent DB-CLP2
Agilent DB-CLP1
Instrument: Agilent 7890 GC with dual µECD
Sampler: Agilent 7693
Sample: 100 ng/mL Chlorinated Solvents, THMs, and DPBs
Inj. Vol.: 2 µL splitless
Liner: Ultra Inert liner, single taper splitless
(cat.#5190-2292)
Inj. Temp.: 200°C
Oven Temp: 35°C (hold 5.75 min) to 95°C at 20°C/min,
40°C/min to 200°C, hold 1.25 min
Carrier Gas: Helium at 45 cm/sec (constant flow)
Detector: µECD @ 300 °C
16
1. Methyl chloroacetate (30ng/mL)
2. Methyl bromoacetate (20ng/mL)
3. Methyl dichloroacetate (30ng/mL)
4. Dalapon methyl ester (20ng/mL)
5. Methyl trichloroacetate (10ng/mL)
6. 1,2,3-Trichloropropane (IS) (50ng/mL)
7. Methyl bromochloroacetate (20ng/mL)
8. Methyl bromodichloroacetate (20ng/mL)
9. Methyl dibromoacetate (10ng/mL)
10. Methyl dibromochloroacetate (50ng/mL)
11. Methyl tribromoacetate (100ng/mL)
min3 4 5 6 7 8 9
3 4 5 6 7 8 9 min
1
2
4
5
78 9
10
11
6
1
2
3
4
5
7
8,9 10 11
6
3
DB-CLP1 30m 0.32mm ID 0.25µm (cat.# 123-8232)
DB-CLP2 30m 0.32mm ID 0.5µm (cat.# 123-8336)
5m x 0.32mm ID deact. guard column
Inert Tee CFT device (cat.# G3184-60065) 1:1 Split
EPA Method 552.3Haloacetic Acids and Dalapon
Agilent DB-CLP2
Agilent DB-CLP1
Instrument: Agilent 7890 GC with dual µECD
Sampler: Agilent 7693
Sample: 10-100 ng/mL Haloacetic acids and Dalapon
(methyl esters)
Inj. Vol.: 1 µL splitless
Liner: Ultra Inert liner, single taper splitless
(cat.#5190-2292)
Inj. Temp.: 180°C
Oven Temp: 40°C (hold 0.5 min) to 95°C at 10°C/min,
30°C/min to 200°C, hold 1 min
Carrier Gas: Helium at 54.79 cm/sec (constant flow)
Detector: µECD @ 340 °C
17
EPA Method 8081B (extended)Organochlorine Pesticides
1. 1,2-Dibromo-3-chloropropane
2. Hexachlorocyclopentadiene
3. 1-Bromo-2-nitrobenzene
4. Etradiazole
5. Chloroneb
6. Trifluralin
7. TCMX*
8. Propachlor
9. Diallate isomers (250ng/mL)
10. Hexachlorobenzene
21. DCPA
22. Isodrin
23. Kelthane
24. Heptachlor epoxide
25. γ-Chlordane
26. trans-Nonachlor
27. α-Chlordane
28. Endosulfan I
29. 4,4’-DDE
30. Dieldrin
11. α-BHC
12. Pentachloronitrobenzene
13. γ-BHC
14. β-BHC
15. Heptachlor
16. Dichlone
17. Alachlor
18. δ-BHC
19. Chlorothalonil
20. Aldrin
31. Chlorobenzilate (250ng/mL)
32. Perthane (250ng/mL)
33. Chloropropylate (250ng/mL)
34. Endrin
35. Nitrofen
36. 4,4’-DDD
37. Endosulfan II
38. 4,4’-DDT
39. Endrin aldehyde
40. Endosulfan sulfate
41. Captafol
42. Methoxychlor
43. Endrin ketone
44. Mirex
45. cis-Permethrin
46. trans-Permethrin
47. Decachlorobiphenyl*
*surrogate standard
DB-CLP1 30m 0.32mm ID 0.25µm (cat.# 123-8232)
DB-CLP2 30m 0.32mm ID 0.5µm (cat.# 123-8336)
5m x 0.32mm ID deact. guard column
Inert Tee CFT device (cat.# G3184-60065) 1:1 Split
1 2 3
4
5
7
8
9
1012
14
11
15
16
17
1820
19
13
27
22
23
2425
26
2128
2930
31-33
34
35
3637
39
38
642
40
41
47
45,46
44
43
min5 10 15 20 25
1
2
3
4
5
6
7
8
11
12
9
14
18
15
13
16
19
17
2122
23
2420 26
29
31,33
32
34
35
36 38
37
39
40
45,46
44
43
4241
47
10 25
27,2830
min5 10 15 20 25
Instrument: Agilent 7890 GC with dual µECD
Sampler: Agilent 7693
Sample: 50 ng/mL 8081B analytes
Inj. Vol.: 2 µL splitless
Liner: Ultra Inert liner, single taper splitless
(cat.#5190-2292)
Inj. Temp.: 250°C
Oven Temp: 80°C (hold 0.5 min) to 150°C at 20°C/min,
5°C/min to 235°C, 15°C/min to 300°C,
hold 5 min
Carrier Gas: Helium at 43.5 cm/sec (constant flow)
Detector: µECD @ 325 °C
Agilent DB-CLP2
Agilent DB-CLP1
18
DB-CLP1 30m 0.32mm ID 0.25µm (cat.# 123-8232)
DB-CLP2 30m 0.32mm ID 0.5µm (cat.# 123-8336)
5m x 0.32mm ID deact. guard column
Inert Tee CFT device (cat.# G3184-60065) 1:1 Split
min4 6 8 10 12 14
min4 6 8 10 12 14
1
2
3
4
5 7 89
10
14
11,1215
16
17
1820
19
13 21
6
1
2
3
4
5 7
89
1012
1411
15
16
17
18
20
19
13
21
6
EPA Method 8082APCB Congeners
Instrument: Agilent 7890 GC with dual µECD
Sampler: Agilent 7693
Sample: 100 ng/mL PCB congeners
100 ng/mL Pesticide Surrogate Mix
Inj. Vol.: 2 µL splitless
Liner: Ultra Inert liner, single taper splitless
(cat.#5190-2292)
Inj. Temp.: 250°C
Oven Temp: 125°C (hold 0.25 min),
20°C/min to 210°C, hold 0.5 min
7°C/min to 235°C, hold 0.75 min,
25°C/min to 325°C, hold 2 min,
Carrier Gas: Helium, constant flow 3 mL/min
Detector: µECD @ 340 °C
8. BZ #66
9. BZ #101
10. BZ #87
11. BZ #110
12. BZ #151
13. BZ #153
14. BZ #141
1. BZ #1
2. TCMX*
3. BZ #5
4. BZ #18
5. BZ #31
6. BZ #52
7. BZ #44
15. BZ #138
16. BZ #187
17. BZ #183
18. BZ #180
19. BZ #170
20. BZ #206
21. Decachlorobiphenyl*
*surrogate standard
Agilent DB-CLP2
Agilent DB-CLP1
19
EPA Method 8082AAroclors
DB-CLP1 30m 0.32mm ID 0.25µm (cat.# 123-8232)
DB-CLP2 30m 0.32mm ID 0.5µm (cat.# 123-8336)
5m x 0.32mm ID deact. guard column
Inert Tee CFT device (cat.# G3184-60065) 1:1 Split
Instrument: Agilent 7890 GC with dual µECD
Sampler: Agilent 7693
Sample: 100 ng/mL Individual Aroclor
100 ng/mL Decachlorobiphenyl
Inj. Vol.: 2 µL splitless
Liner: Ultra Inert liner, single taper splitless
(cat.#5190-2292)
Inj. Temp.: 250°C
Oven Temp: 160°C (hold 0.25 min),
35°C/min to 330°C, hold 3 min
Carrier Gas: Helium, constant flow 3.75 mL/min
Detector: µECD @ 340 °C
Agilent DB-CLP1
Aroclor 1242
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1254
Aroclor 1248
Aroclor 1260
min2.5 3 3.5 4 4.5 5 5.5 6 6.5
min2.5 3 3.5 4 4.5 5 5.5 6 6.5
min2.5 3 3.5 4 4.5 5 5.5 6 6.5
min2.5 3 3.5 4 4.5 5 5.5 6 6.5
min2.5 3 3.5 4 4.5 5 5.5 6 6.5
min2.5 3 3.5 4 4.5 5 5.5 6 6.5
min2.5 3 3.5 4 4.5 5 5.5 6 6.5
1
1
1
1
1
1
1
Agilent DB-CLP2
Aroclor 1242
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1254
Aroclor 1248
Aroclor 1260
min2.5 3 3.5 4 4.5 5 5.5 6 6.5
min2.5 3 3.5 4 4.5 5 5.5 6 6.5
min2.5 3 3.5 4 4.5 5 5.5 6 6.5
min2.5 3 3.5 4 4.5 5 5.5 6 6.5
min2.5 3 3.5 4 4.5 5 5.5 6 6.5
min2.5 3 3.5 4 4.5 5 5.5 6 6.5
min2.5 3 3.5 4 5 5.5 6 6.5
1
1
1
1
1
1
1
1. Decachlorobiphenyl
20
1. Dalapon methyl ester
2. 3,5-dichlorobenzoic acid methyl ester
3. 4-Nitroanisole
4. DCAA methyl ester (SS)
5. Dicamba methyl ester
6. MCPP methyl ester
7. MCPA methyl ester
8. 4,4’-DBOB (IS)
9. Dichlorprop methyl ester
10. 2,4-D methyl ester
11. Pentachloroanisole
12. 2,4,5-TP methyl ester
13. 2,4,5-T methyl ester
14. Chloramben methyl ester
15. Dinoseb methyl ester
16. 2,4-DB methyl ester
17. Bentazon methyl ester
18. DCPA methyl ester
19. Picloram methyl ester
20. Acifluorfen methyl ester
EPA Method 8151AChlorophenoxyacid Herbicides
12
34
5
7
8
9 10
12
14
11
15
16 17
18
20
1913
6
min2 4 6 8 10 12 14
1
2
34
5
7
8
9 10
12
13
11
15
16 17
18
20
19
14
6
min2 4 6 8 10 12 14
Agilent DB-CLP2
DB-CLP1 30m 0.32mm ID 0.25µm (cat.# 123-8232)
DB-CLP2 30m 0.32mm ID 0.5µm (cat.# 123-8336)
5m x 0.32mm ID deact. guard column
Inert Tee CFT device (cat.# G3184-60065) 1:1 Split
Agilent DB-CLP1
Instrument: Agilent 7890 GC with dual µECD
Sampler: Agilent 7693
Sample: 50 ng/mL Chlorophenoxyacid Herbicides
(methyl esters)
50 ng/mL DCAA methyl ester
50 ng/mL 4,4'-Dibromooctafluorobiphenyl
Inj. Vol.: 2 µL splitless
Liner: Ultra Inert liner, single taper splitless
(cat.#5190-2292)
Inj. Temp.: 250°C
Oven Temp: 85°C (hold 0.25 min) to 135°C at 25°C/min,
11°C/min to 200°C, 20°C/min to 300°C,
hold 1.5 min
Carrier Gas: Helium, constant flow 3 mL/min
Detector: µECD @ 325 °C
21
DB-UI 8270D
22
World wide recognized EPA method for Semi-volatiles analysis
Column is tested for optimal inertness, selectivity and low bleed
Most popular dimensions in the US for high volume labs
20 m x 0.18mm x 0.36um 30m x 0.25mm x 0.25um
DB-UI 8270D flyer
6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00
0
200000
1000000
2000000
2800000
Time-->
Abundance
78 Semi-Volatile Components on a DB-UI 8270D 30m x 0.25 x 0.25
25 minute Semi-Volatile AnalysisApplication note 5991-0250EN
23
Resolution of benzo-b & k fluoranthene isomers
24
19.00 19.500
100000
500000
1000000
1500000
Time-->
Abundance
Benzo-b-fluorantheneBenzo-k-fluoranthene
Resolution of 1.2
Column: Agilent DB-UI 8270D, 30 m x 0.25 mm, 0.25 µm (p/n 122-9732)Liner: Dual taper direct connect liner (p/n G1544-80700)Inlet: MMI in non-pulsed splitless mode 1 µL at 275 oCCarrier: He, 1.2 mL/min, constant flowSeptum purge flow: 3 mL/min, purge time on 0.7 min 50 mL/minOven program: 30 oC (1.0 min), 15 oC/min to 100 oC, 20 oC/min to 240 oC (0.5 min),
15 oC/min to 325 oC (6.7 min) Gas saver OffGC/MSD: Agilent 7890/5975C, 325 oC transfer line, 280 oC source,
150 oC quad, 35-500 AMU range
DB-8270D GC Column using UI Liner with Wool10 ng/ul Semivolatile Checkout Standard on 20m x 0.18mm x 0.36um
25
3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.000
400000
1000000
1800000
Abundance
1
3
2
4
6
57 8
9
12
13
14
15
16
17
18
1920
21
26
27
28
29
22
23
24
25
110
10
11
1 N-Nitrosodimethylamine 11 4-nitrophenol 21 Phenanthrene-d10
2 Aniline 12 2,4-dinitrotoluene 22 Aldrin
3 1,4-Dichlorobenzene-d4 13 Flourene 23 Heptachlor epoxide
4 Isophorone 14 4,6-dinitro-2-methyl phenol 24 Endrin
5 1,3-dimethyl-2-nitrobenzene 15 Trifluralin 25 4,4'-DDT
6 Naphthalene 16 Simazine 26 3,3'-dichlorobenzidine
7 hexachlorocyclopentadiene 17 Atrazine 27 Chrysene d-12
8 Mevinphos 18 pentachorophenol 28 benzo[b]flouranthene
9 Acenaphthene-d10 19 Terbufos 29 Perylene-d12
10 2,4-dinitrophenol 20 Chlorothanlonil
Checkout Standard mix Agilent part # 5190-047316 minute Semi-Volatile Analysis
Excellent Peak Shape and Response for 2,4 Dinitrophenol
26
10
9
11
12
9.30 9.35 9.40 9.45 9.50 9.55 9.60 9.65 9.70 9.75
0
100000
500000
950000
Time-->
Abundance
Peak # Compound9 Acenaphthalene D10
10 2,4 Dinitrophenol11 4 Nitro phenol12 2,4 Dinitro toluene
Column 1: Agilent J&W 8270-D 20 m x 0.18mm x 0.36 um
Column 2: 1 m 0.15 mm ID deactivated 2 psi with 5ml/min bleeder
Carrier: 1 ml/min constant flow at 40O/C, AUX EPC 2 PSI constant pressure
Backflush: postrun 75 psi AUX EPC 2 PSI inlet
Oven: 40oC (2.5min) to 320OC (25O/min) 4.8 min hold
Injection: 280oC Pulsed splitless 44 psi until 0.3 min,
purge flow 60ml/min on at 0.35 min
Liner: UI single taper
MSD: Transfer Line 290OC , Source 300OC, Quad 150OC 50 -550 AMU
Semi-Volatiles Column Choice Summary
27
• DB-CLP1 and DB-CLP2 columns for dual ECD methods• Specifically tested for optimal CLP method performance,
cover 9 EPA methods
• DB-UI8270D columns for semi-volatile analysis• Specifically tested for optimal semi-volatile selectivity
and inertness performance
• HP-5msUI best “standard” column choice for high resolution MS work
Major Challenges for Volatiles Analyses
Clean samples won’t hurt the Column so little GC instrument down time (Maintenance)
P&T/Headspace unit(concentrator) issues/maintenance
Lots of peaks to separate (some are somewhat active)
Long analysis times (time is money!)
Page 28
Example VOC Components 1. Dichlorodifluoromethane 21. 1,2-Dichloropropane 41. 1,1,2,2-Tetrachloroethane
2. Chloromethane 22. Dibromomethane 42. Brombenzene
3. Vinyl chloride 23. Bromodichloromethane 43. 1,2,3-Trichloropropane
4. Bromomethane 24. cis-1,3-Dichloropropene 44. n-Propylbenzene
5. Chloroethane 25. Toluene 45. 2-Chlorotoluene
6. Trichlorofluoromethane 26. trans-1,3-Dichloropropene 46. 1,3,5-Trimethylbenzene
7. 1,1-Dichloroethene 27. 1,1,2-Trichloroethane 47. 4-Chlorotoluene
8. Methylene chloride 28. Tetrachloroethene 48. tert-Butylbenzene
9. trans-1,2-Dichloroethene 29. 1,3-Dichloropropane 49. 1,2,4-Trimethylbenzene
10. 1,1-Dichloroethane 30. Dibromochloromethane 50. sec-Butylbenzene
11. cis-1,2-Dichloroethene 31. 1,2-Dibromomethane 51. 1,3-Dichlorobenzene
12. 2,2-Dichloropropane 32. Chlorobenzene 52. p-Isopropyltoluene
13. Bromochloromethane 33. 1,1,1,2-Tetrachloroethane 53. 1,4-Dichlorobenzene
14. Chloroform 34. Ethylebenzene 54. n-Butylbenzene
15. 1,1,1-Trichloroethane 35. m-Xylene 55. 1,2-Dichlorobenzene
16. Carbon tetrachloride 36. p-Xylene 56. 1,2-Dibromo-3-chloropropane
17. 1,1-Dichloropropene 37. o-Xylene 57. 1,2,4-Trichlorobenzene
18. Benzene 38. Styrene 58. Hexachlorobutadiene
19. 1,2-Dichloroethane 39. Bromoform 59. Naphthalene
20. Trichloroethene 40. Isopropylbenzene 60. 1,2,3-Trichlorobenzene
Agilent Columns for VOC Analysis
DB-VRX (proprietary phase composition)
-The ‘Original’, accept no substitute
-Computer designed phase specifically for VOC analysis
DB-624UI (6% Cyanopropylphenyl methylsiloxane)
-Improvement on the first VOC specific phase
VF-624ms (Optimized for low bleed MS work)
HP-VOC (proprietary phase composition)
DB-502.2 (Diphenyl methylsiloxane)-Available in 105m 0.53mm and 75m 0.45mm
Considerations For Optimum Performance Using MS For Volatiles
•Use the smallest I.D. column possible, within reason: - 20m x 0.18 mm I.D., 1.0 um film is ideal
•Use as high of a split as possible
•DO NOT use BFB Autotune procedure-See publication number 5988-4373EN for optimized MS tuning process
EPA 8260B Using DB-VRXExcellent Resolution Of 114 VOCs In Under 8 Minutes
7.6 Minutes!
Optimized System Conditions Column: DB-VRX, 20 m x 0.18 mm I.D., 1.0um film
Carrier: Helium at 55 cm/sec (1.5 mL/min)
Interface: Split injector at 150C, 60:1 split ratio
Agilent 5973 MSD
Scan range: 35-260 amu
Scan rate: 3.25 scans/sec
Quad temperature: 150C
Source temperature: 200°C
Transfer line temp: 200°C
Tekmar 3100 Purge and Trap
Trap: Vocarb 3000
Sample volume: 5 mL
Purge: 11 minutes
Desorb preheat: 245°C
Desorb: 1 minute at 250°C
Bake: 10 minutes at 260°C
Line and valve temp: 100°C
GC Oven Program
45°C for 3.0 minutes
45-190°C at 36°C/min
190-225°C at 20°C/min
225°C for 0.5 min
Agilent J&W DB-624UI vs. Competitor 624ms Organic Acid Performance at 200 ppm
Column: Agilent J&W DB-624UI 30 m x 0.32 mm x 1.8 um vs Rxi-624Sil MSOven: 35C 7.45 min hold, 6.72/min to100C (2.23min hold),10.08 /min to 220C(4.47 min hold),
16.79 /min (4.17 min hold)Carrier : Helium 39.6 cm/s (approx. 2.6 mL/min) set at 35C, EPC-Constant FlowInlet: Split, 20:1 at 250C (total flow approx 51 mL/min, and 11.2 psi)Inlet liner: Ultra Inert with wool Detector: FID at 280C, H2 @ 40 mL/min, Air @ 400 mL/min, N2 makeup @ 30 mL/min
min10 12 14 16 18 20 22 24 26
pA
2
4
6
8
10
12
14
16
18
Acetic acid
propionic acidbutanoic acid Octanoic acid
No detection on Competitor’s 624ms
Severe tailing on competitor’s 624ms
Oxygenated Compounds in Waste Water
1. Methanol 2. Acetaldehyde 3. Ethylene oxide 4. Ethanol
5. 2-Propanol 6. 1-Propanol 7. Tetrahydrofuran 8. 1,3-Dioxolane
9. Crotonaldehyde 10. 1-Butanol 11. 1,4-Dioxane
12. Trimethyl trioxane 13. 2-Chloromethyl-1,3-Dioxolane
Data courtesy of K. Gras1, R, Gras2 and J Luong2
1. University of Alberta, Edmonton, Alberta, Canada2. Dow Chemicals Canada, Fort Saskatchewan, Alberta, Canada
Conclusions
• DB-VRX – Computer designed phase specifically for VOC’s
• DB-624UI improves peak shape and sensitivity for low level active analytes like alcohols and organic acids vs traditional 624 columns
• VF-624ms – designed for low bleed use with MS