gc columns specifically optimized for environmental ... · gc columns specifically optimized for...

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!)

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

http://intranet.chem.agilent.com/Workspaces/Images1/Entitled Partner/082865/Shared Images/7890B_5977A_7693A_Tray_Front.tif

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

http://intranet.chem.agilent.com/Workspaces/Images1/Entitled Partner/082865/Shared Images/7890B_5977A_7693A_Tray_Front.tif

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

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

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)


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


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







Sample: 100 ng/mL 504.1 analytes

100 ng/mL Chlorinated Solvents + Trihalomethanes



(cat.#5190-2292)

Inj. Temp.: 200°C

Oven Temp: 50°C (hold 1.5 min) to 95°C at 20°C/min,




13

EPA Method 505Organohalide Pesticides






Sampler: Agilent 7873B

Sample: 100 ng/mL 505 analytes


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,




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


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


2. Etradiazole

3. Chloroneb

4. Trifluralin

5. TCMX*

6. Propachlor


8. α-BHC

9. Atrazine

10. Simazine


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


36. Methoxychlor

37. cis-Permethrin

38. trans-Permethrin


*surrogate standard





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


Sampler: Agilent 7873B

Sample: 100 ng/mL 508.1 analytes

100 ng/mL Pesticide Surrogate Mix



(cat.#5190-2292)

Inj. Temp.: 250°C


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)


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





1. Chloroform


3. Carbon tetrachloride

4. Trichloroacetonitrile

5. Trichloroethene

6. Chloral hydrate

7. Bromodichloromethane

8. 1,1-Dichloro-2-propanone

9. Dichloroacetonitrlie

10. Chloropicrin

11. Tetrachloroethene


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



Sample: 100 ng/mL Chlorinated Solvents, THMs, and DPBs



(cat.#5190-2292)

Inj. Temp.: 200°C



Carrier Gas: Helium at 45 cm/sec (constant flow)


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





EPA Method 552.3Haloacetic Acids and Dalapon

Agilent DB-CLP2

Agilent DB-CLP1



Sample: 10-100 ng/mL Haloacetic acids and Dalapon

(methyl esters)



(cat.#5190-2292)

Inj. Temp.: 180°C


30°C/min to 200°C, hold 1 min

Carrier Gas: Helium at 54.79 cm/sec (constant flow)


17

EPA Method 8081B (extended)Organochlorine Pesticides

1. 1,2-Dibromo-3-chloropropane


3. 1-Bromo-2-nitrobenzene

4. Etradiazole

5. Chloroneb

6. Trifluralin

7. TCMX*

8. Propachlor

9. Diallate isomers (250ng/mL)


21. DCPA

22. Isodrin

23. Kelthane


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


41. Captafol

42. Methoxychlor

43. Endrin ketone

44. Mirex

45. cis-Permethrin

46. trans-Permethrin


*surrogate standard





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



Sample: 50 ng/mL 8081B analytes



(cat.#5190-2292)

Inj. Temp.: 250°C


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)


Agilent DB-CLP2

Agilent DB-CLP1

18





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



Sample: 100 ng/mL PCB congeners

100 ng/mL Pesticide Surrogate Mix



(cat.#5190-2292)

Inj. Temp.: 250°C



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


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


*surrogate standard

Agilent DB-CLP2

Agilent DB-CLP1

19

EPA Method 8082AAroclors







Sample: 100 ng/mL Individual Aroclor

100 ng/mL Decachlorobiphenyl



(cat.#5190-2292)

Inj. Temp.: 250°C


35°C/min to 330°C, hold 3 min



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





Agilent DB-CLP1



Sample: 50 ng/mL Chlorophenoxyacid Herbicides

(methyl esters)

50 ng/mL DCAA methyl ester

50 ng/mL 4,4'-Dibromooctafluorobiphenyl



(cat.#5190-2292)

Inj. Temp.: 250°C


11°C/min to 200°C, 20°C/min to 300°C,

hold 1.5 min

Carrier Gas: Helium, constant flow 3 mL/min


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!)

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

TECHNICAL SUPPORT1-800-227-9770, #3, 3, 1

E-mail: [email protected]

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