BP Gulf Oil Spill: Modified EPA Method 8260 for the Analysis of Crude Oils by PurgePurge--andand--TrapTrap GCGC--MS.MS.

C. English, J. Konschnik, J. Cochran, M. Misselwitz, R. Lautamo, and G. Stidsen Restek Corporation, 110 Benner Circle, Bellefonte, PA 16823

1 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 Sample size…… 1ul

C40

0 102030 Time (min)

2 TtCTarget Compoun ds

1 1,4-Difluorobenzene 17 n-octane 2 isobutane 18 ethylbenzene 3 n-butane 19 m/p-xylene 4 2-methylbutane 20 n-nonane 5 pentane 21 o-xylene 6 2-methylpentane 22 isopropylbenzene 7 3-methylpentane 23 n-propylbenzene 24 n-decane 8 hexane 25 sec-butylbenzene 9 methylcyclopentane 26 n-butylcyclohexane 10 cyclohexane 27 p-isopropyltoluene 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 TIC: D10081026.D\data.ms

9.75

14. 16 9.59 9.76 13.82 13.85

14.40 12.57 13.37 13.71 14.11 14.36

10.37 14.47 14.72 12.76 14.28 ne ne luorobenzene aa ff aa 13. 53 d5 d4 ‐ ‐ hept decane ‐ isooct 11.36 n butylbenzene ‐ propylbenzene butylcyclohexane butylbenzene ‐ ‐ ‐ trimethylbenzene butylbenzene n Isopropylbenzene n ‐ ‐ sec n t isoproyltoluene ‐ p 1,2,4 trimethylbenzene lorobenzene ‐ uorobenzene 5 hlorobenzene ll hh c 1,3, dic 11.46 ‐ 7.24 9.09 1,4 bromof

8.21 ‐ 4.22 4 12.66 13.08 6.25 14.15 9.42 2532.53 6.73 2.79 3.71 15.61 17.28 16.26 alene utane utane exane exane ylene luene exane halene lene nzene onane decane butane entane entane ctane entane zene entane bb tt hh bb xx hh hh oo aa hh ee ‐ oo oo nn ‐ pp t o p

b / o n d is ‐

n naph cyclo methyl ‐ methyl methylp ethylben 2 ‐ ‐ xylene 2 3 ‐ methylcyclo methylnapht methylcyclop ‐ m/p methylnaphth 2 ‐ 1

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

toluene

m/p-xylene

isobutane o-xylene

benzene butane zene nn e-be

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 Crude Oil Chromatogram at 10 ppm

43. 1 Isobutane Found in all samples BP -11C

41.1 Isobutane

39.0

57.0 37.1 45.0 51.1

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 Study:

• Salt water vs. fresh water

• Dispersed oil vs. nonnon--diperseddipersed oil

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

• Comparison of WAFs of different crude oils Mississippi Canyon, Maya & California Salt Water vs. Fresh Water Purge Fresh Water vs. Salt Water Analysis

4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

Curve e sit Points nk o mp mposite 1, 10, 50, e o b BTEX d Bla Co n C ne MC252 MC252 o li li e pp o o m m 100, 200 h m s m de d a pp as ru 100 Met 1pp G 1 G 10ppCru 10ppC Target Compound Salt Salt Fresh Salt Fresh Salt 1,4-difluorobenzene %RSD %Rec. 22methyl-methyl pentane 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 2 22.2 2 13.5 5 13.8 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 bflbbromofluorobenzene 12% 110% 106.8% 8% 102.4% 4% 100.3% 3% 96.1% 1% 89.1% 1% Curve: D100818

Dispersed Oil vs. NonNon--DispersedDispersed Oil Dispersed Oil vs. NonNon--DispersedDispersed Oil

4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

de u Points: X k rude r C 2 C TE lan 252 25 0.5, 10, 50, B BB nt Added b C C sa 100, 200 d M M r pp tho pm pm 00 e Dispe 1 M 10p 10p Target Compound Salt Salt Salt Salt 1,4-difluorobenzene (IS) %RSD %Rec. ppb ppb 2hl2-met hyl pentane 10% ND 5101.0 63. 22 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 ethy lblbenzene 13% 121% ND 13. 00 15. 33 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 7% 110% 107. 1%1% 92. 1%1% 95. 8%8% curve: D100819

P&TP&T--GC/MSGC/MS--SIMSIM P&TP&T--GC/MSGC/MS--SIM:SIM: toluene, ethylbenzene, m, p, o, xylene

Detection of TEX crude volatiles to 100 ppb total crude

Bt10tBenzene at 10 ppt

• calibration: 50, 100, 500, 1000, 2000 ppt • benzene did not pass calibration • toluene Low Point 100ppt (background ~ 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 Recoveries of volatiles in 100ppb total crude.

BFB m/z 95

de u Points: 50, rude r ude k C C r 2 2 C 100, 500500, EX n 5 5 1000, 2000 ya BT C2 C2 Rep a ppt. t d Bla pb M p 0ppb M 0 0ppb M etho 0 100 pp M 10 10 1 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 o-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

4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

e e d 52 u 2 r C Crud C MC252 2 3 M e#5 e #6 # 52 ) rv 252 e 2 e# 2 rv 10) rv u u (x (x C MC b C MC Curv p pb im m p p S 0 Sim Cu 1ppm 1pp 50 100 TtCdTarget 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 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

4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

e

rud e C Points: rude d a C ni 52 r ,,,, 10 , 50 , lank 2 a Cru ifo 0.5 B C ay al 100, 200 C ppm Method 10ppm M 10ppm M 10 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. 00 535.3 464.6 m/p-xylene 11% ND 67.7 16.2 16.1 o-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%

Analytical Challenges

• Salt Clogging Autosamplers

• Making up standards

• Background BTEX limits this method

• Proper choice of SS & IS is critical Observations

• Salt water vs. fresh water

• Dispersed oil vs. nonnon--diperseddipersed oil

• Total crude detected at 100 ppb

• Crude showed measurable differences

• Butanes present in all crudes Questions ?