BP Gulf Oil Spill: Modified EPA Method 8260 for the BP Gulf Oil - - PowerPoint PPT Presentation

BP Gulf Oil Spill: Modified EPA Method 8260 for the BP Gulf Oil Spill: Modified EPA Method 8260 for the Analysis of Crude Oils by Purge Analysis of Crude Oils by Purge-

• and

and-

• Trap GC

Trap GC-

• MS.

MS.

• C. English, J. Konschnik, J. Cochran, M. Misselwitz, R. Lautamo, and G. Stidsen

Restek Corporation 110 Benner Circle Bellefonte PA 16823

1

Restek Corporation, 110 Benner Circle, Bellefonte, PA 16823

Typical Crude Oil Analysis Typical Crude Oil Analysis

Inj………………..COC (oven track) Det……...............FID @ 330 C Oven……………50 > 300 @ 10/min > hold > 20 min Carrier gas……..H2 @ 40cm/sec MU………………30 mls/min N2 Sample…………. Light Crude Oil W / C10-40 overlay Conc……………. 500 PPM

C10 C40

Conc……………. 500 PPM Sample size…… 1ul

10 20 30 Time (min)

2

T t C d T t C d

1 1,4-Difluorobenzene 2 isobutane

17 n-octane 18 ethylbenzene

Target Compounds Target Compounds

2 isobutane 3 n-butane 4 2-methylbutane 5 pentane 6 2-methylpentane

18 ethylbenzene 19 m/p-xylene 20 n-nonane 21 o-xylene 22 isopropylbenzene 23 lb

7 3-methylpentane 8 hexane 9 methylcyclopentane 10 cyclohexane 11 benzene

23 n-propylbenzene 24 n-decane 25 sec-butylbenzene 26 n-butylcyclohexane 27 p-isopropyltoluene

11 benzene 12 2,2,4-trimethylhexane 13 heptane 14 methylcyclohexane 16 toluene

28 n-butylbenzene 29 n-dodecane 30 naphthalene 31 2-methylnaphthalene 32 1-methylnaphthalene 32 1 methylnaphthalene

TIC: D10081026.D\data.ms 9.75

14 16

fluorobenzene 10.37 12.57 13 53 14.47 12.76 ane ane

9.59 9.76

13.37 13.71 13.82 14.11 14.16 14.36 14.28 13.85 14.40 14.72

f 11.36 13.53 hlorobenzene‐d5 luorobenzene hlorobenzene‐d4 isoocta hepta

Isopropylbenzene n‐propylbenzene n‐decane t‐butylbenzene 1,2,4‐trimethylbenzene n‐butylcyclohexane sec‐butylbenzene 5‐trimethylbenzene p‐isoproyltoluene n‐butylbenzene

4.22 6.25 8.21 9.09

9.42 11.46

13.08 14.15 7.24 2 53 c 4‐bromofl

12.66

1,4‐dich

1,3,

nonane hexane pentane entane hexane entane butane 3.71 6.73 15.61 17.28 entane enzene

• butane

butane 2.79 2.53 hexane

• luene

ctane zene xylene halene alene 16.26 thalene

• decane

m/p‐xylene / n cycloh 2‐methylp 3‐methylp h p 2‐methylb methylcyclop be iso n‐b methylcycloh to

• ethylben
• ‐x

2‐methylnaphth 1‐methylnaphtha napht n‐do

Rxi‐624Sil MS 30m x 0.25mm x 1.4df, 1ml/min, 45C heated 5ml purge Oven: 35C(hold 5min) 11C/60C (0 hold) 20C/320C (hold 1)

Crude Oil Chromatogram at 10 ppm Crude Oil Chromatogram at 10 ppm

toluene m/p-xylene benzene

• -xylene

isobutane butane benzene

nzene e-ben

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00

Crude Oil Chromatogram at 10 ppm Crude Oil Chromatogram at 10 ppm

43 1 43.1

Isobutane Found in all samples BP -11C Isobutane

41.1 39.0 57.0 51.1 45.0 37.1

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00

Study: Study:

• Salt water vs. fresh water

Salt water vs. fresh water

• Dispersed oil vs. non

Dispersed oil vs. non-

• dipersed oil

dipersed oil

• Feasibility of detecting ppb levels of total crude

Feasibility of detecting ppb levels of total crude Require ppt levels of single analytes Require ppt levels of single analytes

• Comparison of WAFs of different crude oils

Comparison of WAFs of different crude oils Mississippi Canyon, Maya & California Mississippi Canyon, Maya & California

Salt Water vs. Fresh Water Purge Salt Water vs. Fresh Water Purge

Fresh Water vs. Salt Water Analysis Fresh Water vs. Salt Water Analysis

4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

Curve Points 1, 10, 50,

p p b B T E X h

• d

B l a n k m C

• m

p

• s

i t e

• l

i n e m C

• m

p

• s

i t e

• l

i n e m M C 2 5 2 d e m M C 2 5 2 d e

100, 200

1 p p M e t h

• 1

p p m G a s

• l

i 1 p p m G a s

• l

i 1 p p m C r u d e 1 p p m C r u d e

Target Compound Salt Salt Fresh Salt Fresh Salt

1,4-difluorobenzene %RSD %Rec. 2-methyl pentane 8% ND 44.2 43.9 66.8 63.2 2 methyl pentane 8% ND 44.2 43.9 66.8 63.2 benzene 9% 107% ND 12.6 13.0 22.2 22.1 2,2,4-trimethylpentane 10% ND 28.1 27.7 0.0 0.0 n-heptane 10% ND 12.8 11.1 132.6 121.2 toluene 10% 106% ND 98.0 101.9 63.2 61.3 ethylbenzene 11% 109% ND 21 2 22 2 13 5 13 8 ethylbenzene 11% 109% ND 21.2 22.2 13.5 13.8 m/p-xylene 12% 109% ND 77.7 81.5 70.1 68.0

• -xylene

12% 109% ND 31.5 32.8 25.4 25.6 1,2,4-trimethylbenzene 16% ND 35.9 36.7 33.5 33.1 naphthalene 21% ND 1.9 2.1 9.7 11.2 b fl b 12% 110% 106 8% 102 4% 100 3% 96 1% 89 1% bromofluorobenzene 12% 110% 106.8% 102.4% 100.3% 96.1% 89.1%

Curve: D100818

Dispersed Oil vs. Non Dispersed Oil vs. Non-

• Dispersed Oil

Dispersed Oil

Dispersed Oil vs. Non Dispersed Oil vs. Non-

• Dispersed Oil

Dispersed Oil

4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

Points: 0.5, 10, 50,

b B T E X d B l a n k

MC252 Crude MC252 Crude sant Added

100, 200

1 p p b M e t h

• d

B

10ppm MC 10ppm MC Dispersa

Target Compound Salt Salt Salt Salt

1,4-difluorobenzene (IS) %RSD %Rec. ppb ppb 2 h l ND 1 0 63 2 2-methyl pentane

10%

ND 51.0 63.2 benzene

5%

119% ND 19.9 22.1 2,2,4-trimethylpentane

5%

ND 0.0 0.0 n-heptane

11%

ND 99.3 118.3 toluene

3%

114% ND 58.2 69.5 th lb

13%

121% ND 13 0 15 3 ethylbenzene

13%

121% ND 13.0 15.3 m/p-xylene

11%

125% ND 67.7 87.1

• -xylene

10%

111% ND 24.7 30.5 1,2,4-trimethylbenzene

13%

ND 30.6 40.2 naphthalene

20%

ND 9.8 12.2 bromofluorobenzene

7%

110% 107 1% 92 1% 95 8%

D100819

bromofluorobenzene

7%

110% 107.1% 92.1% 95.8%

curve: D100819

P&T P&T-

• GC/MS

GC/MS-

• SIM

SIM

P&T P&T-

• GC/MS

GC/MS-

• SIM: toluene, ethylbenzene, m, p, o, xylene

SIM: toluene, ethylbenzene, m, p, o, xylene Detection of TEX crude volatiles to 100 ppb total crude

B t 10 t Benzene at 10 ppt

• calibration: 50, 100, 500, 1000, 2000 ppt
• benzene did not pass calibration
• toluene Low Point 100ppt (background

75 ppt)

• toluene Low Point 100ppt (background ~ 75 ppt)
• e-benzene low point 50ppt
• m/p xylene Low Point 100ppt
• -xylene Low Point 50ppt

SIM: toluene, ethylbenzene, m, p, o, xylene SIM: toluene, ethylbenzene, m, p, o, xylene Recoveries of volatiles in 100ppb total crude. Recoveries of volatiles in 100ppb total crude.

BFB m/z 95

Points: 50, 100 500

E X n k

5 2 C r u d e 5 2 C r u d e C r u d e

100, 500, 1000, 2000 ppt.

1 p p t B T E X M e t h

• d

B l a n

1 p p b M C 2 5 2 1 p p b M C 2 5 2 R e p 1 p p b M a y a C

Target Compound

1,4-difluorobenzene (IS) %RSD %Rec. ppt ppt ppt toluene**

12%

121% ND 574.2 544.8 355.1 ethylbenzene

8%

99% ND 119.9 121.2 116.7 m/p-xylene

10%

102% ND 322.3 324.7 170.0

• -xylene

8%

112% ND 238.2 238.2 138.2 bromofluorobenzene

10%

82% 106% 122.9% 124.2% 103.8%

** 50 ppt point dropped.

Comparison Between SIM & Full Scan Comparison Between SIM & Full Scan

4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

2 5 2 C r u d e e # 2 2 5 2 C r u d e e # 3 2 ) M C 2 5 2 r v e # 5 1 ) M C 2 5 2 r v e # 6 1 p p m M C 2 5 2 C u r v e # 1 p p m M C 2 5 2 C u r v e # 5 p p b ( x 2 ) S i m C u r v 1 p p b ( x 1 ) S i m C u r v

T t C d Target Compound 1,4-difluorobenzene (IS) ppb ppb ppb ppb benzene 2.56 2.40 toluene 7.45 6.98 5.50 5.47 ethylbenzene 1.51 1.38 1.06 1.19 m/p-xylene 8.40 7.66 6.00 6.44

• -xylene

3.00 2.68 2.20 2.38 bromofluorobenzene 104% 93.4% 142.5% 122.9%

Comparisons of MC252, Maya and California Crude Oil Comparisons of MC252, Maya and California Crude Oil

4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

Points: 0.5, 10, 50,

B l a n k

C 2 5 2 C r u d e a y a C r u d e a l i f

• r

n i a C r u d e

, , , 100, 200

M e t h

• d

B

1 p p m M C 2 1 p p m M a y 1 p p m C a l

Target Compound

1,4-difluorobenzene (IS) %RSD ppb ppb ppb 2-methyl pentane

10%

ND 51.0 22.6 12.0 benzene

5%

ND 19.9 5.5 3.2 2,2,4-trimethylpentane

5%

ND 0.0 0.0 5.6 n-heptane

11%

ND 99.3 35.6 3.7 toluene

3%

ND 58.2 16.6 20.6 ethylbenzene

13%

ND 13 0 5 3 4 6 ethylbenzene

13%

ND 13.0 5.3 4.6 m/p-xylene

11%

ND 67.7 16.2 16.1

• -xylene

10%

ND 24.7 6.9 6.4 1,2,4-trimethylbenzene

13%

ND 30.6 7.8 7.0 naphthalene

20%

ND 9.8 1.1 0.5 bromofluorobenzene

7%

107.1% 92.1% 110.4% 100.8% bromofluorobenzene

7%

107.1% 92.1% 110.4% 100.8%

Analytical Challenges Analytical Challenges

• Salt Clogging Autosamplers

Salt Clogging Autosamplers

• Making up standards

Making up standards Making up standards Making up standards

• Background BTEX limits this method

Background BTEX limits this method

• Proper choice of SS & IS is critical

Proper choice of SS & IS is critical

Observations Observations

• Salt water vs. fresh water

Salt water vs. fresh water

• Dispersed oil vs. non

Dispersed oil vs. non-

• dipersed oil

dipersed oil

• Total crude detected at 100 ppb

Total crude detected at 100 ppb

• Total crude detected at 100 ppb

Total crude detected at 100 ppb

• Crude showed measurable differences

Crude showed measurable differences

• Butanes present in all crudes

Butanes present in all crudes

Questions ? Questions ?