36. PRELIMINARY ORGANIC GEOCHEMICAL ANALYSES OF THE SITE 217 CORE SAMPLESIN THE BENGAL BASIN, DSDP LEG 221
Bernd R. Simoneit and A. L. Burlingame, Space Sciences Laboratory, University of California, Berkeley, California
ABSTRACTFour core samples from Site 217 were extracted, and the
solvent soluble organic matter was characterized by GC (gaschromatography) and GC/MS (gas chromatography /mass spec-trometry). The samples range in age from the Quaternary to theUpper Cretaceous and contain only traces of organic carbon. Thenormal alkanes are the major homologous series present in all thesamples. They do not exhibit a carbon number preference.Unresolved cyclic and aromatic compounds comprise the bulk ofthe extracts. The Quaternary sample may be contaminated bydrill pipe joint grease. The other samples appear to be maturedsediments.
INTRODUCTION
The samples discussed herein were taken from Site 217,situated on the northern end of Ninetyeast Ridge(8°55.6'N, 90°32.3'E) in 3020 meters of water. Thestratigraphy at this site is comprised predominantly ofcalcareous ooze and chalk as detailed by von der Borch,Sclater, et al. (1971). All the samples are low in organiccarbon content (average about 0.1%). The details of eachsample are given in Table 1.
EXPERIMENTAL
Analyses using GC/MS were carried out on a modifiedVarian MAT model 311 GC/MS linked on-line to an XDSSigma 2 computer (Smith et al., 1971). The columnconditions used in the GC and GC/MS analyses are cited inthe respective figure legends, and the mass spectrometricand computer operating parameters are analogous to thosereported by Smith et al. (1971). Certain mass spectra fromthe various GC/MS analyses were identified by using acompound classifier (Smith, 1972; Chang et al., inpreparation).
Gas chromatographic analyses were carried out using aPerkin-Elmer model 900 gas chromatograph fitted with aflame ionization detector and operating under the condi-tions stated in the respective figure legends.
All solvents used, e.g., toluene, benzene, methanol, and«-heptane were Mallinckrodt nanograde quality. Thetoluene, benzene, and methanol were redistilled in anall-glass apparatus prior to use.
The samples were dried under vacuum (60°C and 25 cmHg pressure) and then extracted in a sealed ball mill jar withbenzene or toluene and methanol solvent mixture (3:1)according to the method of Rittenberg et al. (1963). After
Research supported by the Oceanographic Section, NationalScience Foundation, NSF Grant GA-24214.
filtration through a fine-glass frit, the extracts wereconcentrated on a rotary evaporator (bath at 30-40°C) andthen repartitioned into a heptane-diethyl-ether-soluble frac-tion and a toluene or benzene-methanol-soluble fraction.The heptane-soluble fraction of Sample 217-1-3, 0-20 cm,was subjected for further separation using silica gel chrom-atography. A 15 mm × 15 cm glass column was packedwith 10-g conditioned SiC»2 (washed with methanol, driedat 100°C overnight, and conditioned with heptane) and thesample eluted into 13 fractions. Each cut was analyzed byGC and similar fractions were combined.
RESULTS
The extraction yields for the Site 217 preliminaryanalysis are given in Table 1. The gas chromatographictraces for the total extract fractions are shown in Figure 1.Each extract is a complex unresolved mixture. The totalfractions were then partitioned between heptane andbenzene and methanol (3:1). Most of each fraction wassoluble in heptane (cf. Table 1) which is unlike previousresults from other DSDP samples (Simoneit and Burlin-game, 1972; in press a). The GC traces of these fractions areshown in Figures 2 through 5. The total fractions were alsosubjected to GC/MS analysis, and the salient features ofthose data are shown in Figures 6, 7, and 8. The GC/MSresults for the total extracts are summarized in Table 2.
The predominant components in all four samples arenormal alkanes. The series CnH2«+2 ranges from n = 13 to29, with a maximum at n = 17 and essentially no carbonnumber preference for Sample 217-1-3, 0-20 cm. The«-alkanes amount to 6 ppm of the dry weight for thissample. It should be noted that total ion currentsuppression occurs in these capillary GC/MS analyses whena large unresolved hump is injected. For example, in thedata for Sample 217-1-3 (cf. Figure 6a) the scans 120-170are detuned, resulting in the minimum observed. Thenormal paraffins, CwH2«+2, in Sample 217-6-5, 10-30 cm,are also equivalent to about 6 ppm and range from n = 14to 34, with a maximum at n = 24 and essentially no carbon
681
B. R. SIMONEIT, A. L. BURLINGAME
TABLE 1Sample Descriptions and Extract Yields, Site 217
Samplea
217-1-3,0-20 cm217-6-5,10-30 cm217-14-4,20-40 cm217-30-3,0-20 cm
Depth BelowSea Floor (m)
3.1
188.6
397.3
547.1
Age
Quaternary
UpperOligocenePaleocene
UpperQetaceous
Description
Pale gray greenclay-rich nannofossil oozeYellowish graynannofossil oozeVery pale orangenannofossil chalkGreenish gray and light graybiomicrite and chert
OrganicCarbonb
(%)
0.3
0.1
0.0
0.1
TotalExtract(µg/g)
193
26
14
42
HeptaneExtract(Mg/g)
180
16
12
24
Benzene/MethanolExtract(µg/g)
13
10
2
18
H2O(%)
51
37
26
11
^Location 8°55.6 'N, 90°32.3 'E , water depth 3020 m.bData provided by G. Bode, DSDP staff.
number preference. Sample 217-14-4, 20-40 cm, has anormal alkane distribution rnaging from n = 17 to 33 forC«H2n+2> with a maximum at n = 22 and no carbonnumber preference. The alkanes account for approximately4 ppm of the dry sample. The series C«H2«+2 ranges fromn = 17 to 35, with a maximum at n = 22 and again nocarbon number preference in Sample 217-30-3, 0-20 cm.The w-alkanes amount to approximately 8 ppm of the dryweight of this sample.
Possible contaminants from core tube material, mainlythe compound dioctyl 2,3-dimethylsuccinate (Simoneit etal., 1973; Simoneit and Burlingame, in press (b), werefound in all of the samples. Phthalate esters were detectedin two samples (cf. Figures 6d and f). The Cretaceoussample (217-30-3) had a suite of unknown compounds ofshort GC retention times (cf. Figures 7d and 8a,b) and twopeaks probably due to dipentylbenzene (Structure I). Thescan 112 spectrum (Figure 7c) fits the fragmentationpattern of probably the ortho isomer of Structure I. Thecompound classifier matched the spectrum to an alkyl-benzene. The scan 88 spectrum (Figure 8b) is a mixture ofa dipentylbenzene and an unknown of molecular weight220.
The recombined extract fractions from Sample 217-1-3,0-20 cm, were subjected to liquid chromatography on silicagel. The fraction yields and descriptions are listed in Table3. Representative GC traces for this separation are found inFigure 9. Fraction 1 (cf. Figure 9a) closely resembles theinitial heptane extract. Fractions 2 through 4 consist of ahighly unresolved mixture of cyclic and aromatic hydro-carbons (cf. Figure 9b). Fractions 5 through 11 have thesame unresolved GC traces as is the case for fractions 2through 4. Fractions 12 and 13 consist of the more polarcompounds. A GC/MS analysis of this cut was carried out.The major peaks are phthalate esters and dioctyl2,3-dimethylsuccinate.
DISCUSSION AND CONCLUSION
The distribution histograms for the n-alkanes in thesesamples are shown in Figure 10. No carbon numberpreference is evident. The Quaternary sample has a maxi-mum at C17, the Oligocene sample at C24, the Paleocene atC22» and the Cretaceous is bimodal with maxima at C22and C27. These alkane distributions indicate maturedsediments (Bray and Evans, 1961). This distribution for the
Quaternary sediment seems peculiar, especially since theGC trace closely resembles that for drill pipe joint grease(Simoneit et al., 1972). In view of the low extract yields,contamination by drilling oils must be considered. Samples217-144, 2040 cm, and 217-30-3, 0-20 cm, exhibit apredominance of the C22 n-alkane.Schenck(l969) observedthis predominance in a large number of terrestrial sedimentsranging in age from Miocene to Permian. Such a predomin-ance has not been observed in crude oils (Schenck, 1969).
The contaminants such as phthalate esters and dioctyl2,3-dimethylsuccinate were minor in all samples, indicatingthat the bulk of the solvent-soluble organic matter isindigenous to the sediments. The anomaly in the case of theQuaternary sample may be due to drilling lubricants orpossibly petroliferous sediments of terrigenous origineroded and brought in by the Ganges River system.
ACKNOWLEDGMENTS
We thank Mrs. Esther Roitman for technical assistanceand Dr. Robert E. Cox for GC/MS analyses. The financialsupport from the Oceanography Section of the NationalScience Foundation (NSF Grant GA-24214) is gratefullyacknowledged.
REFERENCES
Bray, E. E. and Evans, E. D., 1961. Distribution ofrc-paraffins as a clue to recognition of source beds:Geochim. Cosmochim. Acta, v. 22, p. 1.
Chang, J. J., Walls, F. C, Smith, D. H., Simoneit, B. R., andBurlingame, A. L., in preparation. The LOGOS com-pound classifier for background corrected low resolutionmass spectral data: Anal. Chern.
Rittenberg, S. C, Emery, K. O., Hülsemann, J., Degens,E. T., Fay, R. C, Reuter, J. H., Grady, J. R., Richard-son, S.H., and Bray, E. E., 1963. Biogeochemistry ofsediments in experimental Mohole: J. Sediment. Petrol.,v. 33, p. 140.
Schenck, P. A., 1969. The predominance of the C22rc-alkane in rock extracts. In Advances in organicgeochemistry, 1968: Schenck, P. A. and Havenaar, I.(Eds.), Braunschweig (Pergamon-Vieweg), p. 261.
Simoneit, B. R. and Burlingame, A. L., 1972. Preliminaryorganic analyses of the Deep Sea Drilling Project(JOIDES) cores, legs V-IX. In Advances in organicgeochemistry 1971: von Gaertner, H. R. and Wehner, H.(Eds.), Braunschweig (Pergamon-Vieweg), p. 189.
682
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PRELIMINARY ORGANIC GEOCHEMICAL ANALYSES
b
TIME
LTIME TIME
Figure 1. Gas chromatograms of the total extract fractions from core samples: (a) 217-1-3, 0-20 cm; (b) 217-6-5,10-30 cm;(c) 217-14-4, 20-40 cm; (d) 217-30-3, 0-20 cm. (GC conditions: lOft× 1/8 in. stainless steel column, packed with 3%OV-1 on 100-120 mesh Gaschrom Q, programmed from 100-270°C at 6°/min, and using He carrier gas at 40 ml/min).
, 1973 in press (a). Comparative compositionalstudies of organic matter in the DSDP (JOIDES) cores,legs 5-15: Am. Assoc. Petrol. Geol. Bull.
., in press (b). Preliminary organic analyses ofDSDP cores, legs 12 and 13. In Winterer, E. L., Ewing, J.et al., Initial Reports of the Deep Sea Drilling Project,Volume XVII: Washington (U.S. Government PrintingOffice).
Simoneit, B. R., Scott, E. S., Howells, W. G., andBurlingame, A. L., 1972. Preliminary organic analyses ofthe Deep Sea Drilling Project cores from leg 11. InHollister, C. D., Ewing, J. I., et al. Initial Reports of the
Deep Sea Drilling Project, Volume XI: Washington (U. S.Government Printing Office), p. 1013.
Simoneit, B. R., Scott, E. S., and Burlingame, A. L., 1973.Preliminary organic analyses of DSDP cores, Leg 14,Atlantic Ocean. In van Andel, T. H., Heath, G. R., et al.,Initial Reports of the Deep Sea Drilling Project, VolumeXVI: Washington (U. S. Government Printing Office), p.575.
Smith, D. H., 1972. A compound classifier based oncomputer analysis of low resolution mass spectral data.Geochemical and environmental applications: Anal.Chern., v. 44, p. 536.
683
B. R. SIMONEIT, A. L. BURLINGAME
TIME
TIME—
Figure 2. GC traces of two solvent extract fractions fromSample 217-1-3, 0-20 cm: (a) heptane-soluble material;(b) benzene and methanol-soluble material (GC condi-tions as cited in Figure 1).
Smith, D. H., Olsen, R. W., Walls, F. C, and Burlingame,A. L., 1971. Realtime organic mass spectrometry:LOGOS—a generalized laboratory system for high andlow resolution, GC/MS and closed-loop applications:Anal. Chern., v. 43, p. 1796.
von der Borch, C. C, Sclater, J. G., Gartner, S., Jr.,Hekinian, R., Johnson, D.A., McGowran, B., Pimm,A. C, Thompson, R. W., Veevers, J. J. and Waterman,L. S., 1972. Deep Sea Drilling Project Leg 22: Geotimes,v. 17,p. 15.
TIME
Figure 3. GC traces of two solvent extract fractions fromSample 217-6-5, 10-30 cm: (a) heptane-soluble material;(b) benzene and methanol-soluble material. (GCconditions as cited in Figure 1).
684
PRELIMINARY ORGANIC GEOCHEMICAL ANALYSES
TIME -
Figure 4. GC traces of two solvent extract fractions fromSample 217-14-4, 20-40 cm: (a) heptane-solublematerial; (b) benzene and methanol-soluble material.(GC conditions as cited in Figure 1).
685
B. R. SIMONEIT, A. L. BURLINGAME
TIME
TIME-
Figure 5. GC traces of two solvent extract fractions fromSample 217-30-3, 0-20 cm: (a) heptane-soluble material;(b) benzene and methanol-soluble material. (GC condi-tions as cited in Figure 1).
686
DSDP222171
TI= 216497. DELETED HRSSES 17. IB. 2B. 32. 40. 44.PRELIMINARY ORGANIC GEOCHEMICAL ANALYSES
10 20 30 40 50 GO 70 BO 90 100 110 120 130 140 150 1G0 170 1B0 190 200 210 220 230 240 250 260 270 2B0
TI= 39904. SUM π/E= 57.0000
10 20 30 40 50 60 70 BO 90 100 110 120 130 140 150 160 170 ISO 190 200 210 220 230 240 250 260 270 2B0
DSDP222176
TI= 91B31. DELETED MflSSES 17. IB. 2B. 32. 40. 44.
10 20 30 40 50 60 70 BO 90 100 U0 120 130 140 150 160 170 1B0 190 200 210 220 230 240
M/E= 57.0000 HRX= 11415.π/E= 149.0000 MRX= 7632.
rp•iTππ •π ' • i •T""T""T""|i
10 20 30 40 50 60 70 BO 90 100 110 120 130 140 150 160 170 1B0 190 200 210 220 230 240
DSDP22217144
TI= 119067. DELETED HflSSES 17. IB. 2B. 32. 40. 44.
10 20 30 40 50 60 70 BO 90 100 110 120 130 140 150 160 170 1B0 190 200 210 220 230
π/E= 57.0000 MRX= 17545.π/E= 149.0000 MRX= 12561.
10 20 30 40 50 60 70 BO 90 100 110 120 130 140 150 1G0 170 1B0 190 200 210 220 230
Figure 6. (a) Sample 217A-17-1, 83 cm. Euhedral dolomite rhombs of Stage 3 (Figure 2) showing dolomite zone. Matrix. possibly cristobalite. Innermost calcite zone appears to be corroding dolomite core. Calcite zone retouched in black, (b)
Sample 217A-17-1, 65 cm. Euhedral dolomite rhombs of Stage 3 (Figure 2) showing corroded dolomite nuclei, followedby calcite-dolomite-calcite-dolomite zones. Slide stained, calcite zones retouched in black, (c) Sample 217A-17-1, 65 cm.Similar to (b).
687
B. R. SIMONEIT, A. L. BURLINGAME
DSDP22217303
TI= 11B564. DELETED MASSES 17. IB. 2B. 32. 40. 44.
' i < r r p r r r r i M M M M 1 ! 1 ! 111 I M M M M y r r P r i M M M T i M M M M y i M T r i T r π ^ r i M M y r r i M ' ! 1 ! ! 1 1 1 1 1 1 i | i 11
20 30 40 50 60 70 BO 90 100 110 120 130 140 150 160 170 1B0 190 200 210 220 230
M/E=
rVE=4i.oooo57.0000
πflx=MfiX=
4474.16429.
rrM•i i i i i i•i•i i•i 11111 j 1111 | 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
20 30 40 50 60 70 BO 90 100 110 120 130 140 150 160 170 1B0 190 200 210 220 230
SCPN 112 DSDP22217303
161= , 11B57
.i-l liJI. ij.i. ,.i .1.. •l 1, A , U l 1JU I50
SCPN 129 DSDP22217303
57= ,, 2417
250
, i IP ,H J ü l U i • l • l •'11'l I . " . l y • • • • l l , l •I • ' l ' T
50 100 150 200
Figure 7. Selected GC/MS data for the total extract of Sample 217-30-3, 0-20 cm: (a) totalionization sum plot; (b) m/e 41 and 57sum plot; (c) mass spectrum scan 112 (dipentylbenzene,MW 218); (d) mass spectrum scan 129 (unknown, MW 234). (GC conditions as cited in Figure6).
688
PRELIMINARY ORGANIC GEOCHEMICAL ANALYSES
SCHN 63 DSDP22217303165= . 10260
SCRN BB DSDP22217303
205= t 1461B
l • ÷ • • •' . •"• • l " • ' l •• I • • ' • • • • • • f •50 100 150
SCHN 174 DSDP2221730357= , 1637B
J ,L I iM ..in., n ,1 .200
/ X 5
50 100SCPN 1B0 0SDP22217303
57= , 15B59
350
/ X 5
-TU-
SCAN IBB
••l•l, ,4. ,i ) ,WM V I50 100
DSDP22217303
iT200
vu 1 I • I1 • I • I
250 350 400
57= , 155B5 / X 5
300 350 400
Figure 8. Selected GC/MS data for the total extract of Sample 217-30-3, 0-20 cm): (a) mass spectrum scan 69(unknown, MW 165); (b) mass spectrum scan 88 (dipentylbenzene, MW 218; unknown, MW 220); (c) massspectrum scan 174 (n-heptacosane, MW 380); (d) mass spectrum scan 180 (n-octacosane, MW 394); (e)massspectrum scan 188 (n-nonacosane, MW 408).
689
B. R. SIMONEIT, A. L. BURLINGAME
TABLE 2Major Components of the Total Benzene-Methanol-Soluble Extracts
from the Core Samples of Site 217, Determined by GC/MS
Compound
Tridecane
Tetradecane
Pentadecane
Diethyl phthalatea
«-Hexadecane
Dipentylbenzene
«-Heptadecane
«-Octadecane
n-Nonadecane
Dibutyl phthalatea
wo-Eicosane
«-Eicosane
iso-Heneicosane
«-Heneicosane
rc-Docosane
w-Tricosane
wo-Tetracosane
Dioctyl 2,3-di-methylsuc cinate c
«-Tetracosane
«-Pentacosane
Dioctyl phthalatea
w-Hexacosane
H-Heptacosane
n-Octacosane
rc-Nonacosane
H-Triacontane
«-Hentriacontane
π-Dotriacontane
n-Tritriacontane
«-Tetratriacontane
Composition andMolecular Weight
C13H28
C14H3O
C15H32
C12H14O4
CI6H34
Cl6H 26
Q7H36
Cl8H 38C19H40
CI6H22O4
C20H42
C20H42C21H44
C21H44
C22H46
C23H48
C24H50
C24H42O4
C24H5O
C25H52
C24H38O4
C26H54
C27H56
C28H58
C29H60
C30H62
C3lH 64
C32H66
C33H68
C34H7O
184
198
212
222
226
218
240
254
268
278
282
282
296
296
310
324
338
370
338
352
390
366
380
394
408
422
436
450
464
478
217-1-3,0-20 cm
Spectrum Scan No.(cf. Fig. 6a)
52
70
86
n.d.b
97n.d.
104
112
119
n.d.
n.d.
126
n.d.
134
141
148
n.d.
153
155
162
n.d.
170178187
199
n.d.
n.d.
n.d.
n.d.
n.d.
Sample
217-6-5,10-30 cm
217-14-4,2040 cm
Spectrum Scan No. Spectrum Scan No.(cf. Fig. 6c)
n.d.
95
101
104
109
n.d.
116
123
130
132,138
n.d.
136
140
142
148
153
158
159
160
164
169
168
173180
187
197
208
222
240
254
(cf. Fig. 6e)
n.d.
n.d.
n.d.
105
n.d.
n.d.
116
123
130
132,138
135
137
n.d.
142
147
153
n.d.
157
159
165
169170175181
189
198
210
225
n.d.
n.d.
217-30-3,0-20 cm
Spectrum Scan No.(cf. Fig. 7a)
n.d.
n.d.
n.d.
n.d.
108
112
117
124
130
n.d.
n.d.
136
n.d.
142
148
153
n.d.
156
159
164
n.d.
169
174179
188
197
209
223
238
255
^Probably plasticizer and bagging contamination."n.d. = not detected.cProbably core tube contamination.
690
PRELIMINARY ORGANIC GEOCHEMICAL ANALYSES
TIME TIME
TIME
Figure 9. Representative GC traces of various fractions separated by silica gel chromatography of theextract from Sample 217-1-3, 0-20 cm: (a) fraction 1; (b) combined fractions 2, 3, and 4; (c) combinedfractions 12 and 13. (GC conditions as cited in Figure 1).
691
B. R. SIMONEIT; A. L. BURLINGAME
TABLE 3Column Chromatographic Separation of the Total Solvent-
Soluble Fractions from Sample 217-1-3, 0-20 cm
Fraction
12,3,45,6,7
8,910,1112,13
Weight(mg)
54111.2
1.34.7
16.5
Eluent
15 ml heptane60 ml heptane90 ml heptane
60 ml heptane/5% benzene60 ml heptane/20% benzene60 ml benzene to benzene/50% methanol
Description
Yellow liquidYellow oilLight greenoily solidYellow residueGreenish solidDark greenresidue
U " i *i' i i j • i • i i i i * i • i i i
I0 20 30 40C
I0c—- c—
Figure 10. Normal alkane distribution histograms for the core samples from Site 217: (a) 217-1-3, 0-20 cm;(b) 217-6-5, 10-30 cm; (c) 217-14-4, 20-40 cm; (d) 217-30-3, 0-20 cm. (Concentrations are approximateas determined by GC).
692