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 PurgeAnalysis of Crude Oils by Purge--andand--Trap GCTrap 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 COven……………50 > 300 @ 10/min > hold > 20 minCarrier gas……..H2 @ 40cm/secMU………………30 mls/min N2Sample…………. Light Crude Oil W / C10-40 overlayConc……………. 500 PPM

C10

C40

Conc……………. 500 PPMSample size…… 1ul

0 10 20 30Time (min)

2

T t C dT t C d

1 1,4-Difluorobenzene2 isobutane

17 n-octane18 ethylbenzene

Target Compounds Target Compounds

2 isobutane 3 n-butane4 2-methylbutane5 pentane6 2-methylpentane

18 ethylbenzene19 m/p-xylene20 n-nonane21 o-xylene22 isopropylbenzene23 lb7 3-methylpentane

8 hexane9 methylcyclopentane

10 cyclohexane11 benzene

23 n-propylbenzene24 n-decane25 sec-butylbenzene26 n-butylcyclohexane27 p-isopropyltoluene

11 benzene12 2,2,4-trimethylhexane13 heptane14 methylcyclohexane16 toluene

28 n-butylbenzene29 n-dodecane30 naphthalene31 2-methylnaphthalene32 1-methylnaphthalene32 1 methylnaphthalene

TIC: D10081026.D\data.ms

9.75

14 16

fluorobenzene

10.37 12.57

13 53

14.4712.76

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

8.219.09

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

3.716.73 15.61 17.28

entane

enzene

obutane

butane

2.792.53

hexane

oluene

ctane

zene

xylene

halene

alene

16.26

thalene

odecane

m/p‐xylene  / n

cycloh

2‐methylp

3‐methylphp

2‐methyl b

methylcyclop beiso n‐b

methylcycloh to o

ethylben o‐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

o-xyleneisobutane

butane benzene

nzen

ee-

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

43 143.1Isobutane

Found in all samplesBP -11C

Isobutane41.1

39.0

57.051.145.037.1

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00

Study: Study:

•• Salt water vs. fresh waterSalt water vs. fresh water

•• Dispersed oil vs. nonDispersed oil vs. non--dipersed oildipersed oil

•• Feasibility of detecting ppb levels of total crudeFeasibility of detecting ppb levels of total crudeRequire ppt levels of single analytes Require ppt levels of single analytes

•• Comparison of WAFs of different crude oilsComparison of WAFs of different crude oilsMississippi 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,

ppb BTEX hod Blan

km

Composite

oline

mComposit

e

oline

m MC25

2

de m MC25

2

de100, 200

100 p

p

Metho

1ppm

Gasoli

1ppm

Gasoli

10ppm

Crude10

ppmCrude

Target Compound Salt Salt Fresh Salt Fresh Salt1,4-difluorobenzene %RSD %Rec. 2-methyl pentane 8% ND 44.2 43.9 66.8 63.22 methyl pentane 8% ND 44.2 43.9 66.8 63.2benzene 9% 107% ND 12.6 13.0 22.2 22.12,2,4-trimethylpentane 10% ND 28.1 27.7 0.0 0.0n-heptane 10% ND 12.8 11.1 132.6 121.2toluene 10% 106% ND 98.0 101.9 63.2 61.3ethylbenzene 11% 109% ND 21 2 22 2 13 5 13 8ethylbenzene 11% 109% ND 21.2 22.2 13.5 13.8m/p-xylene 12% 109% ND 77.7 81.5 70.1 68.0o-xylene 12% 109% ND 31.5 32.8 25.4 25.61,2,4-trimethylbenzene 16% ND 35.9 36.7 33.5 33.1naphthalene 21% ND 1.9 2.1 9.7 11.2b 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. NonDispersed Oil vs. Non--Dispersed Oil Dispersed Oil

Dispersed Oil vs. NonDispersed 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 BTEX

d Blank

MC252 C

rude

MC252 C

rude

sant

Add

ed

100, 200

100 p

pb

Method

B

10pp

m MC

10pp

m MC

Disper

sa

Target Compound Salt Salt Salt Salt 1,4-difluorobenzene (IS) %RSD %Rec. ppb ppb 2 h l ND 1 0 63 22-methyl pentane 10% ND 51.0 63.2benzene 5% 119% ND 19.9 22.12,2,4-trimethylpentane 5% ND 0.0 0.0n-heptane 11% ND 99.3 118.3toluene 3% 114% ND 58.2 69.5th lb 13% 121% ND 13 0 15 3ethylbenzene 13% 121% ND 13.0 15.3

m/p-xylene 11% 125% ND 67.7 87.1o-xylene 10% 111% ND 24.7 30.51,2,4-trimethylbenzene 13% ND 30.6 40.2naphthalene 20% ND 9.8 12.2bromofluorobenzene 7% 110% 107 1% 92 1% 95 8% D100819bromofluorobenzene 7% 110% 107.1% 92.1% 95.8% curve: D100819

P&TP&T--GC/MSGC/MS--SIMSIM

P&TP&T--GC/MSGC/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 tBenzene 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 • 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

Points: 50, 100 500 EX

nk

52 C

rude

52 C

rude

Crude

100, 500, 1000, 2000

ppt.

100 p

pt BTE

XMeth

od B

lan10

0ppb M

C252

100p

pb MC25

2Rep

100p

pb May

a C

Target Compound 1,4-difluorobenzene (IS) %RSD %Rec. ppt ppt ppttoluene** 12% 121% ND 574.2 544.8 355.1ethylbenzene 8% 99% ND 119.9 121.2 116.7m/p-xylene 10% 102% ND 322.3 324.7 170.0o-xylene 8% 112% ND 238.2 238.2 138.2bromofluorobenzene 10% 82% 106% 122.9% 124.2% 103.8% ** 50 ppt point dropped.

Comparison Between SIM & Full ScanComparison Between SIM & Full Scan

4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

252 C

rude

e#2

252 C

rude

e#3

2)MC25

2 rve

#510

) MC25

2 rve

#6

1ppm M

C252

Curve#

1ppm M

C252

Curve#

500p

pb (x2)

Sim C

urv10

0ppb (x

10)

Sim C

urv

T t C dTarget Compound 1,4-difluorobenzene (IS) ppb ppb ppb ppbbenzene 2.56 2.40 toluene 7.45 6.98 5.50 5.47ethylbenzene 1.51 1.38 1.06 1.19m/p-xylene 8.40 7.66 6.00 6.44o-xylene 3.00 2.68 2.20 2.38bromofluorobenzene 104% 93.4% 142.5% 122.9%

Comparisons of MC252, Maya and California Crude OilComparisons 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, Blan

k

C252 C

rude

aya C

rude

alifo

rnia

Crude

, , ,100, 200

Method

B

10pp

m MC2

10pp

m May

10pp

m Cal

Target Compound 1,4-difluorobenzene (IS) %RSD ppb ppb ppb 2-methyl pentane 10% ND 51.0 22.6 12.0benzene 5% ND 19.9 5.5 3.22,2,4-trimethylpentane 5% ND 0.0 0.0 5.6n-heptane 11% ND 99.3 35.6 3.7toluene 3% ND 58.2 16.6 20.6ethylbenzene 13% ND 13 0 5 3 4 6ethylbenzene 13% ND 13.0 5.3 4.6m/p-xylene 11% ND 67.7 16.2 16.1o-xylene 10% ND 24.7 6.9 6.41,2,4-trimethylbenzene 13% ND 30.6 7.8 7.0naphthalene 20% ND 9.8 1.1 0.5bromofluorobenzene 7% 107.1% 92.1% 110.4% 100.8%bromofluorobenzene 7% 107.1% 92.1% 110.4% 100.8%

Analytical ChallengesAnalytical Challenges

•• Salt Clogging Autosamplers Salt Clogging Autosamplers

•• Making up standardsMaking up standardsMaking 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. nonDispersed oil vs. non--dipersed oildipersed oil

•• Total crude detected at 100 ppbTotal crude detected at 100 ppb•• Total crude detected at 100 ppb Total crude detected at 100 ppb

•• Crude showed measurable differencesCrude showed measurable differences

•• Butanes present in all crudes Butanes present in all crudes

Questions ?  Questions ?