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 Restek Corporation, 110 Benner Circle, Bellefonte, PA 16823 1

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 Conc……………. 500 PPM C10 Sample size…… 1ul C40 0 10 20 30 Time (min) 2

T Target Compounds Target Compounds T t C t C d d 1 1,4-Difluorobenzene 17 n-octane 18 ethylbenzene 18 ethylbenzene 2 isobutane 2 isobutane 19 m/p-xylene 3 n-butane 20 n-nonane 4 2-methylbutane 21 o-xylene 5 pentane 22 isopropylbenzene 6 2-methylpentane 23 n-propylbenzene 23 lb 7 3-methylpentane 24 n-decane 8 hexane 25 sec-butylbenzene 9 methylcyclopentane 26 n-butylcyclohexane 10 cyclohexane 27 p-isopropyltoluene 11 benzene 11 benzene 28 n-butylbenzene 12 2,2,4-trimethylhexane 29 n-dodecane 13 heptane 30 naphthalene 14 methylcyclohexane 31 2-methylnaphthalene 16 toluene 32 1-methylnaphthalene 32 1 methylnaphthalene

2.53 2 53 iso obutane 2.79 n ‐ b butane Oven: 35C(hold 5min) 11C/60C (0 hold) 20C/320C (hold 1) Rxi ‐ 624Sil MS 30m x 0.25mm x 1.4df, 1ml/min, 45C heated 5ml purge 3.71 2 ‐ methylb butane 4.22 p entane 6.25 2 ‐ methylp pentane 9.59 isoocta ane 6.73 3 ‐ methylp entane 7.24 h hexane hepta ane 9.76 8.21 methylcyclop entane 9.09 cycloh hexane TIC: D10081026.D\data.ms 9.42 be enzene fluorobenzene f 9.75 10.37 methylcycloh hexane 11.36 to oluene 11.46 o ctane 12.66 12.57 ethylben zene c hlorobenzene ‐ d5 m/p ‐ xylene / n nonane 13.08 12.76 o ‐ x xylene 13 53 13.53 4 ‐ bromofl luorobenzene 14.15 14.47 1,4 ‐ dich hlorobenzene ‐ d4 15.61 n ‐ do odecane 16.26 napht thalene 2 ‐ methylnaphth halene 13.37 Isopropylbenzene 1 ‐ methylnaphtha alene 17.28 13.71 n ‐ propylbenzene 13.82 n ‐ decane 13.85 1,3, 5 ‐ trimethylbenzene 14.11 t ‐ butylbenzene 14 16 14.16 1,2,4 ‐ trimethylbenzene 14.28 sec ‐ butylbenzene 14.36 n ‐ butylcyclohexane p ‐ isoproyltoluene 14.40 14.72 n ‐ butylbenzene

Crude Oil Chromatogram at 10 ppm Crude Oil Chromatogram at 10 ppm toluene m/p-xylene isobutane o-xylene benzene benzene butane 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 e e Curve t t i i s s X 2 2 k o o 5 5 E Points n p p 2 2 T a m m C C l B B o o M M e e 1, 10, 50, b C n C n d p p m m m m i i i i o o e e e e l l l l m m m m p p o o o o h h p d d p d d 100, 200 s s p p 0 t p u p u e a a p p 0 0 r 0 r M G G C C 1 1 1 1 1 Target Compound Salt Salt Fresh Salt Fresh Salt 1,4-difluorobenzene %RSD %Rec. 2 methyl pentane 2-methyl pentane 8% 8% ND ND 44.2 44.2 43.9 43.9 66.8 66.8 63.2 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 ethylbenzene 11% 11% 109% 109% ND ND 21.2 21 2 22 2 22.2 13 5 13.5 13 8 13.8 m/p-xylene 12% 109% ND 77.7 81.5 70.1 68.0 o-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 bromofluorobenzene fl b 12% 12% 110% 110% 106.8% 102.4% 100.3% 106 8% 102 4% 100 3% 96.1% 96 1% 89 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 MC252 Crude MC252 Crude sant Added X Points: k E n T a 0.5, 10, 50, B l B B 10ppm MC 10ppm MC Dispersa b b d d p 100, 200 o p h 0 t e 0 M 1 Target Compound Salt Salt Salt Salt 1,4-difluorobenzene (IS) %RSD %Rec. ppb ppb 2-methyl pentane 2 h l 10% ND ND 51.0 1 0 63 2 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 ethylbenzene th lb 13% 13% 121% 121% ND ND 13 0 13.0 15 3 15.3 m/p-xylene 11% 125% ND 67.7 87.1 o-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 bromofluorobenzene 110% 110% 107 1% 107.1% 92 1% 92.1% 95 8% 95.8% 7% 7% curve: D100819 D100819

-SIM SIM GC/MS- -GC/MS P&T- P&T

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 Benzene at 10 ppt t 10 t calibration: 50, 100, 500, 1000, 2000 ppt • benzene did not pass calibration • • • toluene Low Point 100ppt (background toluene Low Point 100ppt (background ~ 75 ppt) 75 ppt) • e-benzene low point 50ppt • m/p xylene Low Point 100ppt • o-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 e e d d e u u d r r Points: 50, u C C k X X r C C n n 2 2 2 2 E E 100, 500, 100 500 a 5 5 5 5 a T 2 2 p l y B B C C e a 1000, 2000 R M M M t d p o b b b ppt. p h p p p p p p t 0 e 0 0 0 0 M 0 0 0 1 1 1 1 Target Compound 1,4-difluorobenzene (IS) %RSD %Rec. ppt ppt ppt toluene** 12% 121% ND 574.2 544.8 355.1 ethylbenzene 99% ND 119.9 121.2 116.7 8% m/p-xylene 102% ND 322.3 324.7 170.0 10% o-xylene 112% ND 238.2 238.2 138.2 8% 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 e e 2 5 d d 5 2 u u 2 C 6 r r 5 C # M C C # 2 3 M e e 2 2 2 2 # # # # ) ) v v v v 0 0 5 5 5 5 ) ) e e e e r r r r 2 2 1 1 2 2 2 2 u v v u x x C C C r r C ( ( u u M M b b m C C m p p m m i i p p S S p p 0 0 p p 0 0 1 1 5 1 Target Compound T t C d 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 o-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 e d u e r d e C u d r a u Points: k C i r n n C 2 r a o 5 a 0.5, 10, 50, , , , l 2 2 f B B y y i C C l l a a a a d M M C 100, 200 o m m m h p p p t e p p p M 0 0 0 1 1 1 Target Compound 1,4-difluorobenzene (IS) %RSD ppb ppb ppb 2-methyl pentane ND 51.0 22.6 12.0 10% benzene ND 19.9 5.5 3.2 5% 2,2,4-trimethylpentane ND 0.0 0.0 5.6 5% n-heptane ND 99.3 35.6 3.7 11% toluene ND 58.2 16.6 20.6 3% ethylbenzene ethylbenzene ND ND 13 0 13.0 5 3 5.3 4.6 4 6 13% 13% m/p-xylene ND 67.7 16.2 16.1 11% o-xylene ND 24.7 6.9 6.4 10% 1,2,4-trimethylbenzene ND 30.6 7.8 7.0 13% naphthalene 20% ND 9.8 1.1 0.5 bromofluorobenzene bromofluorobenzene 107.1% 107.1% 92.1% 92.1% 110.4% 110.4% 100.8% 100.8% 7% 7%

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