17. PRELIMINARY ORGANIC ANALYSES OF DSDP ...(9 27.2'N, 54 20.5'W) was cored on the northern flank of...

17. PRELIMINARY ORGANIC ANALYSES OF DSDP CORES, LEG 14, ATLANTIC OCEAN1

Bernd R. Simoneit, E. Sloan Scott, and A. L. Burlingame, Space Sciences Laboratory, University of California, Berkeley

ABSTRACT

Organic carbon-rich samples from Sites 138 and 144 of DSDPLeg 14 were analyzed. A sample of Oligocene age yielded mainlyalkanes, CnH2w +2 for n = 19 to 36 with an odd over evenpredominance; carboxylic acid methyl esters (formed by claycatalysis with solvent methanol), CπH2Wθ2 for n = 14 to 25 withan even over odd predominance; and steranes (e.g. cholestane,ergostane, and stigmastane), sterones, and triterpanes. The othersamples, all of Cretaceous age, yielded mainly alkanes, CnU2n+2for n = 19 to 30+ with no significant predominance; carboxylicacid methyl esters, CwH2nθ2 for n = 14 to 24 with nopredominance; and sterones and steranes probably of marineorigin. These Cretaceous sediments contain large amounts ofkerogen and the extractable petroliferous material appears tohave gone through maturation processes.

INTRODUCTION

Organic carbon-rich samples from two drill sites of Leg14 were analyzed. Site 138 (25°55.4'N, 25°33.8'W) wascored in the abyssal hills (water depth 5288 m) at the footof the continental rise, about 870 km west of Cap Blanc,West Africa (Hayes et al., 1971). The upper sample is ofOligocene age (approximately 35 m.y.) and consists of darkolive gray clay. The lower sample is of close to middleCretaceous age (approximately 90-100 m.y.) and consists ofa mixture of clay, dolomite, silt, and carbonaceous blackclayey mud, all occurring just above an altered aphaniticbasalt layer (Pimm, personal communication). Site 144(9°27.2'N, 54°20.5'W) was cored on the northern flank ofthe Demerara Rise (water depth 2957 m) approximately400 km north of Surinam (Hayes et al., 1971). Fourorganic carbon-rich samples, all of upper Cretaceous age(range approximately 80-93 m.y.), were analyzed from thiscore. The samples from 181.0 and 190.1 meters below theseabed consist of black zeolitic, calcareous clays and finelaminated black shale. Large quantities of hydrogen sulfidewere encountered at this level and the sequence wasinterbedded with marly limestone (Pimm, personal com-munication). The samples from 214.7 and 216.1 metersbelow the seabed consist of laminated dark olive graycalcareous clay with significant amounts of organic parti-culate matter and fossil foraminifera and nannoplankton.Again large quantities of hydrogen sulfide wereencountered at this level. Similar organic-rich laminatedsediments from the Black Sea and the Mediterranean Seahave been analyzed (Simoneit, in press; Simoneit et al., inpress), and Site 105 in the western Atlantic Ocean alsoyielded some organic-rich clay sediments (Simoneit et al.,1972).

1 Manuscript received too late to be included in Volume 14.

EXPERIMENTAL PROCEDURES

High resolution mass spectrometric analyses of thebenzene/methanol- or tolune/methanol-soluble extractswere carried out on a GEC-AEI MS-902 mass spectrometeron-line to an XDS Sigma 7 computer (described byBurlingame, 1968 and 1970, and Burlingame et al., 1970).The samples were introduced via a ceramic direct inletprobe into the ion source, operated at the followingconditions: resolution 10,000; ionizing current 500µA;ionizing voltage 50 eV; and temperature 200 to 220°C. Thescan rate was 16 sec per decade with a clock rate of 24 kHz.Multiple scans were taken during each analysis and thensum averaged together during data reduction. Selected highresolution mass spectral data are presented as heteroatomicplots (Burlingame and Smith, 1968) in various figures in thetext.

Analyses using gas chromatography-mass spectrometrywere carried out on a modified Varian MAT Model 311GC/MS linked on-line to an XDS Sigma 2 computer (Smithet al., 1971). The GC conditions used in the GC/MSanalyses are the same as cited in the respective GCconditions used in the GC/MS analyses are the same as citedin the respective GC figure legends, and the mass spectro-metric and computer operating parameters are as reported(Smith et al., 1971). Certain mass spectra from the variousGC/MS analyses were identified by use of a compoundclassifier (Smith, 1972; Chang et al., in preparation).

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, andw-heptane were Mallinckrodt Nanograde quality. Thetoluene, benzene, and methanol were redistilled in an allglass apparatus prior to use.

575

B. R. SIMONEIT, E. S. SCOTT, A. L. BURLINGAME

All the samples were dried under vacuum (60°C and25 cm Hg pressure) and then powdered using a mortar andpestle. The dry weights averaged 3 g. The powders werethen extracted in a small, all glass Soxhlet apparatus for 3to 5 days. After filtration through a fine glass frit theextracts were concentrated on a rotary evaporator (bath at30-40°C) and then repartitioned into a heptane-diethylether-soluble fraction and a tolune/methanol- or benzene/methanol-soluble fraction. These fractions were not sepa-rated further and were subjected directly to GC and massspectrometric analyses.

RESULTS

The solvent extract yields from the core samples arelisted in Table 1 and the elemental analyses of thesesamples are found in Table 2.

Site 138

The two Site 138 samples were subjected to GC, HRMS,and GC/MS analyses. The GC traces for the 117.6 meterssample (14-138-2-6) are shown in Figure 1 and the highresolution mass spectrometric data for the toluene/methanol-soluble fraction is shown in Figure 2.2 The majorconstituents are hydrocarbons of the series C M H 2 M + 2 toCnH 2 r t_ 12, ranging from n = 3 to 20; however, not everyhomolog has been detected. The peaks of compositionsC 1 4 H 2 3 at m/e 191 (Structure I) and C 1 6 H 2 5 at m/e 217(Structure II) are significantly above the background.Contaminants from the core tube (dibutyl esters) orphthalate esters are minor. Carboxylic acids or their estersand other oxygenated higher molecular weight compoundshave not been detected.

C 14 H 23'

The GC/MS data for the heptane/ether-soluble fractionare summarized in Table 3 and the salient features of thesedata appear in Figure 3. The major constituents are alkanes,CnH2«+2> r a nB i ng f r o m n~ 18 to 34 with strong odd overeven predominance. Methyl esters of carboxylic acids weredetected for the series C n H 2 π O 2 ranging from n = 14 to 25,with an even over odd predominance. Minor amounts ofsteranes, sterones, and triterpenes were detected. The majorcomponents match well to the standard spectra and consistof cholestane (Structure III), ergostane (Structure IV), andsitostane or stigmastane (Structure V). The sterones belongto the series C π H 2 π . 8 O for n = 27 to 30. The massspectrum (scan 270) in Figure 3g fits the fragmentation

III , m/e 371 IV C 2 g H 5 0 , m/e 386

C 2 9 H 5 j , 400

pattern of cholestanone (Structure VI) as published byBudzikiewicz and Djerassi (1962), exhibiting the molecularion at m/e 386 and the base peak at m/e 231 (StructureVII). The scan 291 spectrum fits the fragmentation pattern

VI C 2 7 H 4 6 O , m/e 386 VII , m/e 231

In this report, all high resolution mass spectra are presented asheteroatomic plots (Burlingame and Smith, 1968) with the massesplotted in methylene units. On the abscissa, each principal divisionmarker corresponds to the saturated alkyl fragment (even-electronion), for example, C π H 2 n + i , with the number of carbon andhydrogen atoms given subsequently. Each principal division of theabscissa is further divided into seven units. The number of hydrogenatoms of an unsaturated or cyclic-fragment ion is obtained bysubtracting the number of units (two hydrogen atoms) or half-unitsfrom the 2n+l hydrogen atoms of the respective saturated principaldivision, Cnll2n+l Fragments with more than seven degrees ofunsaturation are plotted with each principal division marker on the

abscissa corresponding to the fragment ion CnU2n-13• Eachprincipal division is again further divided into seven units, and thenumber of hydrogen atoms of a fragment ion is derived as discussedabove. The origin of the abscissas is the same m/e ratio for eachplot, thus the nominal masses, indicated in 50 mass unit intervalsbelow the carbon/hydrogen ratio scale, lie directly above oneanother from plot to plot. All plots are normalized to a base peak(usually the base peak of the entire spectrum, unless otherwisespecified) on the relative intensity scale. In order to make high mass,low intensity features of the spectrum observable, the wholespectrum or any region thereof can be multiplied by a scale factor.This factor is indicated by /X00 at the point of scale expansion. Acomposite low resolution mass spectrum for each set of data appearsplotted separately at the bottom of the plot series.

576

PRELIMINARY ORGANIC ANALYSES

TABLE 1DSDP Small Core Sample Extracts, Leg 14

Sample

14-138-2-6(12-13 cm)

14-138-6-3(49-50 cm)

14-144A-5-1(114416 cm)

14444A-6-1(100-101 cm)

14-144-4-2(20-21 cm)

14-144-4-3(14-15 cm)

Depth BelowSeafloor

(m)

117.6

428.5

181.0

190.1

214.7

216.1

ApproximateAge

Oligocene

MiddleCretaceous

UpperCretaceous

UpperCretaceous

UpperCretaceous

UpperCretaceous

OrganicCarbon

% a

2.3

16.8

11.1

10.4

10.3

6.5

Heptane/EtherExtract

%

0.15

0.44

0.04

0.35

0.27

0.23

Benzene/MethanolExtract

%

0.42

1.22

0.14

0.92

0.70

1.03

aData supplied by G. Bode, DSDP staff.

TABLE 2Elemental Analyses of DSDP Core Samples From Leg 14

Sample

14-138-2-6(12-13 cm)

14-138-6-3(49-50 cm)

14-144A-5-1(114-116 cm)

14-144A-6-1(100-101 cm)

14.144-4-2(20-21 cm)

14-144-4-3

(14-15 cm)

driedextracted

driedextracted

driedextracted

driedextracted

dried

driedextracted

Total C(%)

2.592.47

11.9911.21

11.2612.72

16.4515.54

13.37

15.0413.52

H

(%)

1.561.42

1.911.79

0.310.34

1.591.50

1.85

1.211.14

Residue

(%)

84.986.9

76.677.9

62.559.4

62.063.3

74.0

61.562.1

Oxygen

(%)a

10.99.2

9.59.1

25.927.5

20.020,7

10.8

22.223.2

aDetermined by difference.

of ergostanone (Structure VIII) and the scan 322 spectrum(cf. Figure 3h) fits for stigmastanone (Structure IX). Thetriterpanes belong to the series CnU2n.g a n d C w H 2 π _ 1 0 forn = 30 to 31. The major peak in these data is due to dibutyl

VIII C 2 g H 4 8 O, m/e 400

O

IX C 2 9 H 5 Q O , m/e 414

azelate, probably from core tube contamination. Phthalateesters were detected as minor components and probablyderive from the sample vial caps.

The scan 191 mass spectrum (cf. Figure 3f) occurs at themaximum concentration of an unknown compound ofmolecular weight 382, which exhibits a base peak of m/e115 (cf. Figure 3e). The fragmentation pattern appears tofit a diester of glutaric acid, probably octyl (5-cyclo-pentylpentyl) glutarate, and this compound is a possiblecontaminant from the core tube material.

The GC traces for the 428.5 meter sample (14-138-6-3)are shown in Figure 4 and the GC/MS data are alsosummarized in Table 3. The salient features of the GC/MSdata are shown in Figure 5. The alkanes, C W H 2 M + 2 , areagain the major constituents of the heltane/ether fractionand range from n = 13 to 26 with no predominance andmaximizing at n = 17. Significant amounts of carboxylicacid methyl esters are also present; the series C w H 2 π O 2extends from n = 9 to 24 with no predominance apparentand maximum at n = 16. Sterones and minor amounts ofsteranes and triterpanes were detected. The steranes were inthe series CnH 2 M_ 6 for n = 27 to 28; the sterones,c « H 2 « - 8 0 ' r a n ë e d f r o m n= 21 to 29 (the spectrum ofcholestanone and stigmastanone appear in Figure 5g and hrespectively); and the triterpanes, CwH 2 π. (- 8 t o l2)

w e r e

found for n = 30 to 31. The scan 106 spectrum (Figure 5f)is an unknown compound of molecular weight 250.Pristane and to a much lesser extent phytane were detectedin this sample. Contaminants from the core tube materialwere also identified, as well as trace amounts of phthalatesfrom the sample vial caps.

Site 144

The four Site 144 samples were subjected to GC,GC/MS, and HRMS analyses. The GC traces for the 181.0meter sample (14-144A-5-1) are shown in Figure 6. TheGC/MS data of the heptane/ether-soluble fraction aresummarized in Table 4 and the salient features are shown inFigure 7. Methyl esters of carboxylic acids are present in

577


TIME

TIME

Figure la. Gas chromatogram of the heptane /ether-soluble extract fraction from Sample 14-138-2-6 (12-13 cm).(Conditions: 7.5 ft X 1/8 in. stainless steel column packed with 3% OV-1 on 100-200 mesh gas chrom Q, programmedfrom 100-275° C at 8°/min and using He carrier gas at 60 ml/min). The relative retention times of various normal al kanesand methyl esters of normal carboxylic acids are indicated on the GC traces (determined by coinjection).

Figure lb. Gas chromatogram of the toluene/methanol-soluble extract fraction from Sample 14-138-2-6 (12-13 cm).(Conditions as cited in Figure la).

578


I u I I I I I I I I 1 1 I I I I I I F H i l l 1 I I I F T I I 1 1 1 1 I I n i l m m H i l l I M M I I I I I I Π n u n I I M I I J I I I I I I I

3x7 4X9 Sxl l ft/13 7x15 9x17 9x19 HJx21 11x23 12x28 13x27 14x29 15x31 16x33 17x36 18x37 19x39 20x41 21x43

I I I I I I50 100 ISO 200 250 300

C/H

I " 1 1 1 1 ! 1

I150

'I | l l l T T . | l l l l l l | π T T T T | T l i m | m i U j Uixl9 17x21 18x23 19x25 20x27 21x29 22x31

IZOO

f i 1111 Ith111 l'1'l 11 π 111111111111111111 j 1111111111111111111 |iinii|iiiiii|i2x5 3x7 4xβ 6x11 6x13 7x15 Bxl7 9xl» 10x21 11x23 12x28 13x27 14x29 15x31 16x33 17x35 IB/37 19x39 20x41

I100

I150

I200

I250

I300

Oxl 1x3 2x5 V 7 4x9 6x11 6x13 7x15 B/17 «xl9 10x21 11x23 12x25 13x27 14x29 15x31 16x33 17x36

Figure 2. Partial high resolution mass spectrometric data for the toluene-and methanol-soluble fraction from the exhaustiveextract of Sample 14-138-2-6 (12-13 cm).

579


TABLE 3Major Components of the Heptane/Ether-Soluble Extracts from the Core Samples

of DSDP Site 138, Determined by GC/MS

Compound Name

Methyl w-nonanoate

Methyl caprate

Acenaphthene

«-Tetradecane

Methyl «-undecanoate

π-Pentadecane

Methyl laurate

Diethyl phthalateb

H-Hexadecane

Methyl «-tridecanoate

M-Heptadecane

Pristane

Methyl myristate

ft-Octadecane

Phytane

Methyl M-pentadecanoate

UnknownM-Nonadecane

Methyl palmitate

Dibutyl phthalateb

M-Eicosane

Methyl margarate

Dibutyl azelate

Methyl stearate

«-Heneicosane

Dibutyl sebacatea

n-Docosane

Methyl w-nonadecanoate

«-Tricosane

Methyl arachidate

Unknownn-Tetracosane

Methyl w-heneicosanoate

M-Pentacosane

Methyl behenate

Dioctyl phthalateb

o-Hexacosane

Methyl tricosanoate

tt-Heptacosane

Methyl lignocerate

Cholestane

w-Octacosane

Composition andMolecular Weight

C 10 H 20°2C 11 H 22°2C 12 H 10C 14 H 30C 12 H 24°2

C 15 H 32C 13 H 26°2C 12 H 14°4C 16 H 34C 14 H 28°2

C 17 H 36C 19 H 40C 15 H 30°2C 18 H 38C 20 H 42

C 16 H 32°2

C 19 H 40C 17 H 34°2C 16 H 22°4

C 20 H 42C 18 H 36°2C 17 H 32°4C 19 H 38°2C 21 H 44

C 18 H 34°4C22H46C 20 H 40°2C 23 H 48C 21 H 42°2

_

C24H50C 22 H 44°2C 25 H 52C 23 H 46°2

C 24 H 38°4C26H54C 24 H 48°2C 27 H 56C 25 H 50°2

C 27 H 48C 28 H 58

172

186

154

198

200

212

214

222

226

228

240

268

242

254

282

256

250268

270

278

282

284

300

298

296

314

310

312

324

326

382338

340

352

354

390

366

368

380

382

372

394

Sample

14-138-2-6(12-13 cm)

14-138-6-3(49-50 cm)

Spectrum Scan No. Spectrum Scan No.(cf. Fig. 3a)

n.d.

n.d.

n.d.

n.d.

n.d.

n.d.

n.d.

n.d.

n.d.

n.d.

n.d.

n.d.

94

114

n.d.

116

120137

140

142

156

158

163

170

171

173

178

180

186

187

191195

196

204

205

206

215

217

229

231

241

244

(cf. Fig. 5 a)

5

17

27

30

33

48

52

65

71

73

89

90

91

102

103

104

106113

115

n.d.

123

125

125

136

n.d.

138

n.d.

146

n.d.

155

n.d.n.d.

164

n.d.

175

n.d.

n.d.

185

n.d.

195

221

n.d.

580


TABLE 3 - Continued

Compound Name

Methyl pentacosanoate

Ergostane

M-Nonacosane

Methyl cerotate

Triterpane

Cholestanone

Sterane

Stigmastane (sitostane)

«-Triacontane

Sterone

Sterane

fl-Hentriacontane

Triterpane

Triterpane

Methyl octacosanoate

Stigmastanone

Dotriacontane

Sterone

n-Tritriacontane

Triterpane

Tetratriacontane


C26H52°2C28H50C29H60

C27H54°2C30H48C27H46°C29H50C29H52

C30H62C28H48°C30H54C31H64C30H50

C30H52C29H58°2C29H50°C32H66C30H52°

C33H68C31H54C34H70

396

386

408

410

408

386

398

400

422

400

414

436

410

412

438

414

450

428

464

426

478

14-138-2-6(12-13 cm)

Sample

14-138-6-3(49-50 cm)

Spectrum Scan No. Spectrum Scan No.(cf. Fig. 3a) (cf. Fig. 5a)

248

262

263

268

269

270

272

272

288

291

294

315

316

316

321

322

346

352

384

385

419

n.d.

236

n.d.

n.d.

284

291

n.d.

282

n.d.

332

n.d.

n.d.

332

332

n.d.

364

n.d.

n.d.

n.d.

386

n.d.

Probably core tube contamination.Probably bagging contamination,

n.d. — Not detected.

almost equal abundance; the series CwH2wO2 ranges fromn= 14 to 22, also with no specific predominance and abimodal maximum at n = 16 and 18 (cf. Figure 7c). Smallamounts of steranes and triterpanes were detected. Thesteranes found are in the series CwH2w_6 ranging from n =27'to 29 and two triterpanes, C3 0H4 8 and C 3 Q H 5 4 O , weredetected. The major sterane components match the frag-mentation patterns of cholestane (Structure III), ergostane(Structure IV), and sitostane (Structure V) respectively.Each of the spectra exhibiting the triterpane compositions(i.e., molecular ions, M - CH3, and large m/e 191 peaks) is amixture of several compounds. Minor amounts of phthalateester contaminants were detected. An unknown compoundof molecular weight 476, possible composition C34H68,and the less saturated homolog at m/e 474, were detected.These compounds have a base peak at m/e 213 (cf.Figure 7d).

The GC traces for the 190.1 meter sample (14-144A-6-1)are shown in Figure 8. The GC/MS data of the heptane/ether-soluble fraction are summarized in Table 4 and thesalient features are shown in Figure 9. There were twomajor component series present in this case. The carboxylic

acids (detected as the methyl esters) of the series CnH2 nO2ranged from n = 14 to 24, with no predominance and amaximum at n - 16 (cf. Figure 9c). An unknown group ofcompounds exhibiting molecular ions at m/e 490, 488, 476,474, 460, 446, and 444 were present, with the homolog atm/e 476 (cf. scan 300 in Figure 9h) being the mostabundant. These compounds exhibit a base peak at m/e 213(cf. Figure 9d) and were found in minor amounts at the181.0 meter level of this core. No known chemicalstructures could at this time be fit to the mass spectro-metric fragmentation pattern of these compounds; how-ever, from the ratio of the 13C isotope parent peak to theparent ion, the compositional series CwH2w (for n = 34 and35) and CnH2n.2 (for n = 32 to 35) appear to fit the databest. The compound of mass 476 (cf. Figure 9h) fragmentsby losing: CH3 to m/e 461, C6H1 3 to m/e 391, andC8H17to m/e 363, which indicates an isoprenoidal Cg sidechain.

The alkanes were found in lesser amounts. The seriesC77H2/J+2 ranged from n = 16 to 30, with a slight odd overeven predominance and maximizing at n = 17. There is alsoa large amount of zso-tetradecane in this mixture (cf. scan45 in Figure 9f). The mass spectrum (cf. scan 159 in Figure

581


1 XIU-l3β-J'6 112-13

10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 310 320 330 340 350 360 370 380 390 400 410 420 430 440 450 460 470 480 490 500 510 520

TI. 43275. SUP rve• 57.0000

TI. 15613. SUti O-E- 74.0000

10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 ISO 190 200 210 220 230 240 250 2βO 270 290 290 300 310 320 330 340 350 360 370 380 390 400 410 420 430 440 450 460 470 480 490 500 510 520

TI. 11275. SUπ n/F- 9B.OOO0

0 20 30 40 50 60 70 BO 90 100 110 120 130 140 150 160 170 1B0 190 200 210 220 230 240 250 260 270 280 290 300 310 320 330 340 350 360 370 380 390 400 410 420 430 440 450 460 470 480 490 500 510 520

0 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 310 320 330 340 350 360 370 380 390 400 410 420 430 440 450 460 470 480 490 500 510 520

Figure 3. GC/MS data for total heptane-soluble extract from Sample 14-138-2-6 (12-13 cm). (GC conditions as cited inFigure la).a) total ionization sum plot.b) m/e 57sum plot.c) m/e 74 sum plot.d) m/e 98 sum plot.e) m/e 115 sum plot.f) Mass spectrum scan 191 (unknown, M-382).g) mass spectrum scan 270 (cholestanone).h) mass spectrum scan 322 (stigmastanone).

582


8 XIV-138-8/β(18-13)

: > 300 εε= loess

Figure 3. (Continued).

9g) of the largest peak in the GC trace (cf. Figure 8a) fitsthe fragmentation pattern of dibutyl azelate. The homologsn = 17 to 19 of this series, CnH 2 λ 2_ 2O 4 were detected andare probably derived from core tube contamination.Phthalate ester contaminants were not found.

The GC traces for the 214.7 meter sample (14-144-4-2)are shown in Figure 10 and the high resolution massspectrometric data of the toluene- and methanol-solublefraction are shown in Figure 11. A low amount of dibutylphthalate is present, as indicated by the peaks of composi-tions C 8 H 5 O 3 , C 8 H 7 O 4 , C 1 2 H 1 5 O 4 , and C 1 6 H 2 2 O 4 .Significant amounts of hydrocarbons are present for theseries C n H 2 / 7 + 2 to C n H 2 / J . 1 4 for n = 3 to 30, however, notevery homolog was detected. Minor amounts of sterols orsterones of the series CwH 2 n_ 8O and C π H 2 n . 1 Q O for n = 27to 29 were also found in this sample. The peaks at m/e 217of composition C 1 6 H 2 5 (Structure II) and at m/e 215 ofcomposition C 1 6 H 2 3 (Structure X) are significantly abovethe background, corroborating the presence of steroidalcompounds. Carboxylic acids or their esters were notdetected in these data.

The GC traces of the 216.1 meter sample (14-144-4-3)are shown in Figure 12. The GC/MS data are summarized inTable 4 and the salient features are shown in Figure 13. The

X C 1 6 H 2 3 , m/e 215

GC trace of the heptane/ether-soluble fraction stronglyresembles the GC trace of the same fraction of the 214.7meter sample (14-144 4-2) (cf. Figure 10a). The majorcomponents are hydrocarbons of the series C M H 2 n + 2 ,ranging from n= 14 to 28, with no predominance and amaximum at n = 17. Lesser amounts of carboxylic acids (asthe methyl esters) and steranes were detected. The acidseries, C n H 2 w O 2 , ranged from n= 11 to 24, with nopredominance and a maximum at n = 18 (cf. Figure 13c).The major steroidal compounds found are of the seriesC w H 2 w _ 6 , ranging from n= 21 to 30 and the mass spectrafit the fragmentation patterns of cholestane (Structure III)

583


TIME

- n - C 2 4 Alkαnβ

TIME -

Figure 4a. Gas chromatogram of the heptane j ether-soluble extract fraction from Sample 14-138-6-3 (49-50 cm). Conditionsas cited in Figure la.

Figure 4b. Gas chromatogram of the benzene/methanol-soluble extract fraction from Sample 14-138-6-3 (49-50 cm).Conditions as cited in Figure la.

584


(cf. scan 320 in Figure 13g), ergostane (Structure IV), andsitostane (Structure V) (cf. scan 349 in Figure 13h)respectively. The scan 141 spectrum (cf. Figure 13f) fits thefragmentation pattern of /so-nonadecane, one of the fewzso-alkanes found in these samples. The unknown com-pound series (CnH2w and CnH2n_2,« = 32-35) found in theSamples 14-144A-5-1 and 14-144A-6-1 were not detectedand triterpenoidal compounds were also not present. Themajor GC peak (at lower retention time in Figure 12a) isagain dibutyl azelate, probably from core tube contamina-tion. Phthalate esters were detected in minor amounts only.

The benzene- and methanol-soluble extract fractions ofthe samples from the Leg 14 Sites 138-2-6 (12-13),138-6-3 (49-50), 144A-5-1 (114-116), 144-4-2 (20-21),and 144-4-3 (14-15) exhibited one dominant GC compo-nent (cf. Figures lb, 4b 6b, 10b and 12b). This peak isfound in small quantities in the Core Barrel Extract(Simoneit et al., 1972, Leg 11) and is a major componentof the Black Sea core sample 1474 (855 cm level)(Simoneit, in press). A representative GC/MS scan of thiscompound is shown in Figure 14. From high resolutionmass spectrometric data the base peak, m/e 129, has thecomposition C6H9O3 and m/e 147 is C 6 H n O 4 . Thecompound is dioctyl or di-zso-heptyl 2,3-dimethylsuccinate(Structure XI) and its mass spectrometric fragmentationpattern is shown by Structures XI to XV. Synthetic dioctyl

C8Hir° '8 17 C8H17°OH

OHXI C 2 2H 4 2O 4, m/e 370 XII C 1 4H 2 70 4, m/e 259

HOOH

OH

XIII C T - H ^ - O , , m/e 241 XIV C 6 H 1 1 0 4 , m/e 147

SJ

0-H-SrXV C6HgO3 , m/e 129

2,3-dimethylsuccinate exhibits an identical mass spectrumand the same GC retention time as this major compound inthe benzene and methanol extract fractions.

DISCUSSION AND CONCLUSION

These samples constitute some of the richest (withrespect to organic carbon) analyzed to date (Simoneit andBurlingame, 1971a and b, and 1972a and b; Simoneit et al.,1972, in press, and in preparation). The relatively lowamounts of solvent-extractable material indicate that thebulk of the organic carbon in these samples is present askerogen (cf. Table 1). All the extracts contained significantamounts of carboxylic acid esters, which probably formedduring the extraction by clay catalyzed esterification of theacids with solvent methanol.xArpino and Ourisson (1971)observed the same phenomenon during extractions ofterrestrial sediments. The amounts of acids in these samplesthus derivatized indicate that the clay content still has asignificant portion of the organic carbon bound as fattyacid salts (adipocere). It has been well established that clayis a good fatty acid scavenger (Simoneit et al., 1972, inpress, and in preparation; Meyers and Quinn, 1971).

The distribution histogram for Sample 14-138-2-6(12-13 cm) of Oligocene age is shown in Figure 15a. Thealkanes exhibit a strong odd to even predominance andmarine alkanes maximizing at C17 are absent. Thecarboxylic acid distribution maximizes at C1 8 with an evento odd predominance. The soluble organic matter in thissample appears to be derived mainly from terrigenoussources.

The distribution histogram for Sample 14-138-6-3(49-50 cm) of Cretaceous age is shown in Figure 15b. Thealkanes and acids exhibit no homolog predominance andmaximize in concentration at C1 7 and C1 6 respectively.Only steranes consisting mainly of cholestane, ergostane,and sitostane, and the corresponding sterones, are presentand are probably all of marine derivation. The narrowdistribution envelope of both alkanes and acids (cf. Figure15b) substantiates the pure marine source of this sampledsoluble organic matter. The geological history of Site 138indicates that symmetrical cycles of black cherty muds anddolomitic clayey silts were deposited during the Cretaceous.The origin of these 20 to 30 cm thick sedimentary cyclesmay possibly indicate a fluctuating chemical environment(Hayes, Pimm et al., 1972). Sample 14-138-6-3 (49-50 cm)was thus probably sedimented during a productive marineplankton bloom.

The distribution histograms of the Site 144 samples, allof Cretaceous age, are shown in Figure 16. Sample14-144A-5-1 (114-116 cm) exhibits no homolog pre-dominance for the alkanes and acids and they maximize atC17 and C1 6 respectively. Again, the narrow distributionenvelope of both the alkanes and acids (cf. Figure 16a)indicates essentially a marine source of the soluble organicmatter. Sample 14-144A-6-1 (100-101 cm) (cf. Figure 16b)contains a low amount of alkanes, maximizing at C1 7 , witha slight odd to even predominance and extending to C3Q.The acids exhibit a narrow envelope maximizing at Cjg andthe major components are a series of probably cyclichydrocarbons maximizing at C34 (cf. Figure 16b). Thesource of this soluble organic matter appears to be marine,and it may have had a major contribution from anunknown species analogous to the present day algaBotryococcus braunü, which contains various C3 4 hydro-carbons at one stage of its life cycle (Maxwell et al., 1968).

585


| | T η T Y T | T T l Φ l ^10 2G 30 40 50 60 70 BO 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 2B0 230 300 310 320 330 340 350 360 370 3BO 390 400 410 420 430 440 450 460 470

Tl= 1433B. SUM n--ε- 57.0000

10 20 30 40 50 60 70 BO 90 100 U0 120 130 140 150 160 170 1B0 190 200 210 220 230 240 250 260 270 2B0 290 300 310 320 330 340 350 360 370 3B0 390 400 410 420 430 440 450 460 470

TI 4776. SUπ rVE- 74.0000

{ ^^M^N^

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 290 300 310 320 330 340 350 360 370 3B0 390 400 410 420 430 440 450 460 470

Tl= 5013. sun π--E- 191.0000

10 20 30 40 50 60 70 BO 90 100 110 120 130 140 150 160 170 1BO 190 200 210 220 230 240 250 260 270 2B0 290 300 310 320 330 340 350 360 370 3B0 390 400 410 420 430 440 450 460 470

T U 6455. sun n^E- 231.0000

! ! ! ! l'l'l'l'|' 1'ri't'l'I'!1!

1!'!'!';

1!

1;

1!

1!

1!

1 l'1'l'l'l'l'l'l'l"'''''I'l'r''l'l''TI'l'l'r|'l•l I'!']

1!'!

1!'!

1!

1!

1!']'!

1!'!

1!

1!'! l'|'I'!

1!'!'!'!'!'!

1!'!'!

1!

1!'!'!

1)'!'!

1!

1!

1!'I''

1!'!'''!'!

1'

1! 1•|•|'I'H|'||| |'!••

10 20 30 40 50 60 70 BO 90 100 110 120 130 140 150 160 170 1B0 190 200 210 220 230 240 250 260 270 2B0 290 300 310 320 330 340 350 360 370 3B0 390 400 410 420 43C 440 4•>t) 460

Figure 5. GC/MS data for the total heptane-soluble extract from Sample 14-138-6-3 (49-50 cm). (GC conditions as cited inFigure la).a) total ionization sum plot.b) m/e 57 sum plot.c) m/e 74 sum plot.d) m/e 191 sum plot.e) m/e 231 sum plot.f) mass spectrum scan 106 (unknown, M-250).g) mass spectrum scan 291 (cholestanone).h) mass spectrum scan 364 (stigmastanone).

586


Figure 5. (Continued).

587


TIME

n-C24 Alkoπβn-C 2 β Alkαnβ

n-C 2 0 Alkαnβ

TIME

Figure 6a. Gas chromatogram of the heptane I ether-soluble extract fraction from Sample 14-144A-5-1 (114-116 cm).Conditions as cited in Figure la, except column length is 10 ft.

Figure 6b. Gas chromatogram of the benzene /me thanol-soluble extract fraction from Sample 14-144A-5-1 (114-116 cm).Conditions as cited in Figure 4a.

588


TABLE 4Major Components of the Heptane-Ether Soluble Extracts from the Core Samples of

DSDP Site 144, Determined by GC/MS

Compound Name

?so-Tetradecane

Methyl n-undecanoate

Methyl laurate

Pentadecane

Diethyl phthalateb

Methyl M-tridecanoate

Hexadecane

Pristane

Heptadecane

Methyl myristate

Unknownw-OctadecaneMethyl w-pentadecanoate

Unknownwo-Nonadecane

UnknownM-NonadecaneMethyl palmitate

Dibutyl phthalateb

fl-Eicosane

Methyl margarate

Dibutyl azelatea

Methyl stearate

Docosene

rc-Heneicosane

Dibutyl sebacatea

w-Docosane

Methyl nonadecanoate

Dibutyl hendecanedioatea

Methyl arachidate

n-Tetracosane

Methyl heneicosanoate

w-PentacosaneUnknownUnknown

Methyl behenate

Hexacosane

UnknownMethyl tricosanoateHeptacosane

Methyl lignocerate

Unknown


C14H30C12H24°2C13H26°2

^15^32C12H14°4

C14H28°2C16H34C19H40C17H36C15H30°2

_C18H38C16H32°2

C19H40_

C19H40C17H34°2C16H22°4C20H42

C18H36°2C17H32°4C19H38°2C22H44C21H44

C18H34°4C22H46C20H40°2C19H36°4C21H42°2

C24H50C22H44°2C25H52

-

C23H46°2C26H54

C24H48°2C27H56

C25H50°2

198

200

214

212

222

228

226

268

240

242

266254

256

250268

306268

270

278

282

284

300

298

308

296

314

310

312

328

326

338

340

352

378444

354

366

446368

380

382

460

14-144A-5-1(114-116 cm)

Spectrum Scan No.(cf. Fig. 7a)

n.d.

n.d.

n.d.

49

61

n.d.

67

n.d.

82

83

n.d.95

96

99n.d.

n.d.109

110

112

127

128

n.d.

143

n.d.

147

n.d.

n.d.

157

n.d.

171

n.d.

183

n.d.

n.d.191

197

n.d.

n.d.n.d.

n.d.

n.d.

n.d.

Sample

14-144A-6-1(100-101 cm)


45

n.d.

n.d.

n.d.

n.d.

n.d.

62

n.d.

87

88

n.d.102

115

120n.d.

128133

135

n.d.

153

154

159

172

172

171

177

186

188

192

201

213

214

227

228228

229

245

246247

264

268

277

14-144-4-3(14-15 cm)


n.d.

49

66

n.d.

75

84

78

98

100

102

108123

126

n.d.141

n.d.153

157

159

173

175

181

188

n.d.

187

192

200

201

n.d.

217

232

234

252

n.d.n.d.

255

277

n.d.282

297

308

n.d.

589


TABLE 4 - Continued

Sample

14-144A-5-1 14-144A-6-1 14-144-4-3(114-116 cm) (100-101 cm) (14-15 cm)

Composition and Spectrum Scan No. Spectrum Scan No. Spectrum Scan No.Compound Name Molecular Weight (cf. Fig. 7a) (cf. Fig. 9a) (cf. Fig. 13a)

Octacosane C28H58 3 9 4 n d 2 8 3 3 1 8

Unknown - 476 211 306 n.d.Unknown - 474 211 314 n.d.

Cholestane C27H48 3 7 2 n d 3 1 4 3 2 °

Ergostane C28H50 3 8 6 n d n d 3 3 3

Sterane C28H48 3 8 4 n ' d ' n ' d 3 3 3

Triterpane C30H48 4 0 8 2 2 5 n • d n d

Stigmastane C29H52 4 0 0 2 2 5 n d 3 4 9

Triterpane C3 QH5 4O 430 240 n.d. n.d.

Unknown 490 n.d. 321 n.d.Unknown 488 n.d. 336 n.d.

aProbably core tube contamination.

"Probably bagging contamination,

n.d. — Not detected.

590


O 10 20 30 40 » β> 70 BO 90 100 U 0 120 130 140 150 160 170 1B0 190 200 210 220 230 240 2S0 260 270 280 290 300 310

0 10 20 40 90 CO 70 BO 90 100 U0 120 130 140 150 ICO 170 180 190 200 210 220 230 240 250 260 270 280 290 300 310

Tl 11(79. sun ivε- 74.0000

UJISO 160 170 190 190 200 210 220 230 240 250 260 270 280 290 300 310

t u turn. tun ri•c 113.0000

0 10 20 JO 40 SO (0 70 (0 to 100 U0 120 130 140 150 1(0 170 1(0 190 200 210 220 230 240 290 260 270 290 290 300 310

200 210 220 230 240 250 2(0 270 2(0 290 300 310

Figure 7. GC/MS data for the total heptane-soluble extract fromSample 14-144A-5-1 (114-116 cm). (GC conditions as cited inFigure la).a) total ionization sum plot.b) m/e 57 sum plot.c) m/e 74 sum plot.d) m/e 213 sum plot.e) m/e 231 sum plot.

591


TIME

TIMEFigure 8a. Gas chromatogram of the heptane/ether-soluble extract fraction from Sample 14-144A-6-1 (100-101 cm).

Conditions as cited in Figure 4a.Figure 8b. Gas chromatogram of the benzene Imethanol-soluble extract fraction from Sample 14-144A-6-1 (100-101 cm).

Conditions as cited in Figure 4a.

592

>-β'i iioo-ion n-t

TI- 24007. Sun IVE 74.0000

230 300 310 320 330 340 350

I0 20 30 « SO 70 BO 90 100 110 120 130 140 IK Ito ITO 110 ISO 200 210 J20 230 MO 230 2 270 2B0 230 300 310 320 330 340 390

A 'Pv• 1 I '**l ' I ' I ' I ' I ' I

I I I I

j , . j , . ., .fill, , ,, ijlLl,. |.lll|l.,l| li|llL| I, jilllllll,!,, |Jll|l,l |,l.l|llll|ll,l|lll,tllll|hl,|,lil|ln.|.l.l|l.l.| l•l.l I,...,!., IXl^llLll ,...!«..! lill.!..., I;I I ' " ' 1 " 1 ! I ' • • r " ' 1 I '•' I • I • 1 • I r•i•'••i'•'1 i i I 1 ' - . i - ' I - 1 •••i • i• i 1 '

Figure 9. GC/MS data for the total heptane-soluble extract from Sample 14-144A-6-1 (100-101 cm). (GC conditions as cited in Figure la).a) total ionization sum plot. e) m/e 231 sum plot.b) m/e 57 sum plot. f) mass spectrum scan 45 (iso-tetradecane).c) m/e 74 sum plot. g) mass spectrum scan 159 (dibutyl azelate).d) m/e 213 sum plot. h) mass spectrum scan 300 (unknown, M-576).

t - 1

S

>JS

oO>2


TIME

Figure 10a. Gas chromatogram of the heptane /ether-soluble extract fraction from Sample 14-144-4-2(20-21 cm). Conditions as cited in Figure la.

Figure 10b. Gas chromatogram of the toluene/methanol-soluble extract fraction from Sample14-144-4-2 (20-21 cm). Conditions as cited in Figure la.

594


XlU-144-4-j(jO-Jl) «.*•/«

T p 11 rπ•| i T 1 tMT[ i rπ•f I•| 111! IMM | r•ll I H•f M ) l•l•l | r )i't n | r l I•I 11 i'i M l r T r l 1111 r 1111111; t r•t I•I•T i i•l•l•l•l•i | i•IM I T T I M • I 11 T i TM•I•I T I |•H I•I T i ) 11 I'I i T i I•I1. I I I I H I I H I T T I I T I J I I I H i | I T I I I I )•T i||•iiiii| i |uiui|

3/7 4/9 8/11 6/13 7/1S 8/17 9/1* 10/21 11/23 12/28 1J/27 14/2* 16/31 16/33 17/38 18/37 19/31 20/41 21/43 22/46 23/47 24/49 25/51 26/53 27/55 28/57 29/59 30/61 31/63 32/ β

L I I I I I I L J.

_3Q_

O H

III IM l|l | ',! I, r t J|,, 11

1,1!1,,, J.

1!1!1!! I Jl

1, l'| I

1,1!1!8! If, lUI 11

1! I iHΦPI

1! J Jl 11 ̂ ,'l J, I

1] I J, 11 M| 11,, 11•| 11

1,, iΦ]

1!1,11 l'l'| i

1! I

1!1! l| 11! 1, 111

1!!, M'l 11,1 I! I j I', l'l I, I 11I

JM 11 ,|l 11'!

1,, I ,'l Λ I!;! 111

1! 11

1

7/1 8/3 9/5 10/7 11/9 12/11 13/13 14/15 15/17 16/19 17/21 IB/23 19/25 20/27 21/29 22/31 23/33 24/38 25/37 26/39 27/41 2B/43 29/45 30/47 31/4* 32/51 33/83

I I I I I I I I j

OH D.

il,li, ],„>,, u . i In D.)11 rt'1'l'l ] I i•l l I i| i i I l•i i| I l•l•l 111 )'| l 11111'( | l l i i i i | i n '2/5 3/7 4/5 5/11 6/13 7/15 8/17 9/19 10/21 11/23 12/25 13/27 14/29 15/31 16/33 17/35 IB/37 19/38 20^41 21/43 22/45 23/47 24/49 25/51 26/53 27-;55 2B/S7 23/59 3O>6I I I I I I I I I

1111111111111111111111 11111 i'l 11111 I'I 111111111 11111111111 i n i |'i 111111 h 11 Pi 1111 iT! A11 n 111 l'i 111 I'I 111111 IVI 11111111111111 m 111111111 iVI 1111111111111 n 1111111111 I•H 1111111111111 n 11 I•I 111 1/3 2/5 3/7 4/9 5/11 6/13 7/15 B/17 8/19 10/21 11/23 12/25 13/27 14/29 15/31 16/33 17/35 18/37 19/39 20/41 21/43 22/48 23/47 24/49 25/51 26/53 27/55 2B/57

C/H π

1111 ii 1111111'| 1111 •'1'• 11111111 l'i 11111111111 ii 1*111111A 1111111 Pi I I I A Pi I A i A P| 111111 IVI 1111111 J l 111 ITi 1111111111111 m | Pi 11111 m 11111111111111111111111111111111111117 4/8 5/11 6/13 7/15 β/17 9/18 10/21 11/23 12/25 13/27 14/29 15/31 16/33 17/35 18/37 19/39 20/41 21/43 22/45 23/47 24/4* 25/51 26/53 2

11 π r27/55

Figure 11. Partial high resolution mass spectrometric data for the toluene- and methanol-soluble fraction from theexhaustive extract of Sample 14-144-4-2 (20-21 cm).

595


TIME

n - C 2 0 Alkonβ

n-C24 Alkαnβ

TIME

Figure 12a. Gas chromatogram of the heptane/ether-soluble extract fraction from Sample 14-144-4-3 (14-15 cm). Conditionsas cited in Figure la.

Figure 12b. Gas chromatogram of the benzene/methanol-soluble extract fraction from Sample 14-144-4-3 (14-15 cm).Conditions as cited in Figure la.

596

i w i ovu BBU ouu aou « w

Figure 13. GC/MS data for the total heptane-soluble extract from Sample 14-144-4-3 (14-15 cm). (GC conditions as cited in Figure la).a) total ionization sum plot. e) mass spectrum scan 108 (unknown, M-266).b) m/e 57 sum plot. f) mass spectrum scan 141 (iso-nonadecane).c) m/e 74 sum plot. g) mass spectrum scan 320 (cholestane).d) m/e 217 sum plot. h) mass spectrum scan 349 (stigmastane).


248 XI^-U4-4/2(2O-21)BE/ME

× 6 > SIO 139= 83481

Figure 14. GC/MS scan of the major peak in the benzenejmethanol-soluble fraction from Sample 14-144-4-2 (20-21 cm)scan 248 (probably dioctyl 2,3-dimethylsuccinate).

3?o-i

lo

Figure 15. Homologous series distribution histograms for the Site 138 samples.a) 14-138-2-6 (12-13 cm).b) 14-138-6-3 (49-50 cm).

4 ©

598


Figure 16. Homologous series distribution histograms for the Site 144 samples.a) 14-144A-5-1 (114-116 cm).b) 14-144A-6-1 (100-101 cm).c) 14-144-4-3 (14-15 cm).

599


Sample 14-144-4-3 (14-15 cm) contains mainly threehomologous series: alkanes with no predominance and amaximum at C 1 7 ; acids with no predominance and amaximum at C 1 8 ; and steranes, consisting of cholestaneergostane, and sitostane (cf. Figure 16c). The narrowdistribution envelope of the alkanes and acids and thesterane distribution indicate a marine source for the solubleorganic matter.

The bulk of the organic matter in these Cretaceoussamples consists of kerogen. The extractable petroliterousmaterial appears to have derived from marine sources andhas gone through diagenetic maturation.

ACKNOWLEDGMENTS

We thank Mr. Fred Walls for assistance with GC/MS andMiss Rosalynd Jackson and Dr. James Chang for assistancewith high resolution mass spectrometry. The financialsupport from the Oceanography Section of the NationalScience Foundation (NSF Grant GA-24214) and from theNational Aeronautics and Space Administration (NASAGrant NGL 05-003-003) is gratefully acknowledged.

REFERENCES

Arpino, P. and Ourisson, G. 1971. Interactions betweenrock and organic matter. Esterification and transesterifi-cation induced in sediments by methanol and ethanol.Anal. Cham. 43, 1656.

Budzikiewicz, H. and Djerassi, C, 1962. Mass spectrometryin structural and stereochemical problems. I. Steroidketones. J. Am. Chern. Soc. 84, 1430.

Burlingame, A. L., 1968. Data acquisition, processing andinterpretation via coupled high-speed real-time digitalcomputer and high resolution mass spectrometer sys-tems. In Advances in Mass Spectrometry, Vol. 4, E.Kendrick (Ed.). London (The Institute of Petroleum).15.

, 1970. Developments and applications of real-timehigh resolution mass spectrometry. In Recent Develop-ments in Mass Spectroscopy, K. Ogata and T. Hayakawa(Eds.). Tokyo (University of Tokyo Press). 104.

Burlingame, A. L. and Smith, D. H., 1968. Automatedheteroatomic plotting as an aid to the presentation andinterpretation of high resolution mass spectral data.Tetrahedron. 24, 5749.

Burlingame, A. L., Smith, D. H., Merren, T. O. and Olsen,R. W., 1970. Real-time high resolution mass spectrom-etry. In Computers in Analytical Chemistry (VoL 4,Progress in Analytical Chemistry Series), C H . Orr and J.Norris (Eds). New York (Plenum Press). 17

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.

Hayes, D. E., Pimm, A. C , Benson, W. E., Berger, W. H.,von Rad, IL, Supko P. R., Beckmann, J. P., Roth, P. H.and Musich, L. F., 1971. Deep Sea Drilling Project Leg14. Geotimes. 16(2), 14.

Hayes, D. E., Pimm, A. C. et al., 1972. Initial Reports ofthe Deep Sea Drilling Project, Volume 14. Washington(U.S. Government Printing Office).

Maxwell, J. R., Douglas, A. G., Eglinton, G. andMcCormick, A., 1968. The botryococcenes - hydro-carbons of novel structure from the alga Botryoccoccusbraunii, Kützing. Phytochemistry. 7, 2157.

Meyers, P. A. and Quinn, J. G., 1971. Fatty acid-claymineral association in artificial and natural sea watersolutions. Geochim. Cosmochim. Acta. 35, 628.

Simoneit, B. R., in press. Organic analyses of the Black Seacores. In the Black Sea: Geology, Chemistry andBiology, E. T. Degens and D. A. Ross (Eds.). Am. Assoc.Petrol. Geologists Mem.

Simoneit, B. R. and Burlingame, A. L., 1971a. Somepreliminary results on the higher weight hydrocarbonsand fatty acids in the Deep Sea Drilling Project cores,Legs 5-7. In Winterer, E. L., Riedel, W. R. et al., 1971.Initial Reports of the Deep Sea Drilling Project, Volume7. Washington (U.S. Government Printing Office). 889.

, 1971b. Further preliminary results on the higherweight hydrocarbons and fatty acids in the Deep SeaDrilling Project cores, Legs 5-8. In Tracey, J. I., Jr.,Sutton, G. H. et al, 1971. Initial Reports of the DeepSea Drilling Project, Volume 8. Washington (U. S.Government Printing Office). 8973.

, 1972a. Further preliminary results on the higherweight hydrocarbons and fatty acids in the Deep SeaDrilling Project cores, Leg 9. In Hays, J. et al.,1972. Initial Reports of the Deep Sea Drilling Project,Volume 9. Washington (U.S. Government PrintingOffice). 859.

, 1972b. Preliminary organic analyses of the DeepSea Drilling Project (JOIDES) cores, legs V-IX. InAdvances in Organic Geochemistry 1971, H. R.von Gaertner and H. Wehner (Eds.). Braunschwig(Pergamon-Vieweg). 189.

Simoneit, B. R., Scott, E. S., Howells, W. G. and Burlin-game, A. L., 1972. Preliminary organic analyses of theDeep Sea Drilling Project cores from Leg 11. InHollister, C. D., Ewing, J. I. et. al. 1972. Initial Reportsof the Deep Sea Drilling Project, Volume 11. Washington(U.S. Government Printing Office). 1013.

Simoneit, B. R., Scott, E. S. and Burlingame, A. L., inpress. Preliminary organic analyses of Deep Sea DrillingProject cores from Legs 12 and 13. In Ryan, W. B., Hsu,K. J. et al. Initial Reports of the Deep Sea DrillingProject, Volume 13. Washington (U.S. GovernmentPrinting Office).

, in preparation. Preliminary organic analyses ofthe Deep Sea Drilling Project Cores, Leg 10. In Worzel,J. L., Bryant, W. et al. Initial Reports of the Deep SeaDrilling Project. Volume 10. Washington (U.S. Govern-ment Printing Office).

Simoneit, B. R., Howells, W. G. and Burlingame, A. L., inpreparation. Preliminary organic geochemical analyses ofthe Cariaco Trench Site 147, Deep Sea Drilling Project,Leg 15. In Edgar, N. T., Saunders, J. B. et al. InitialReports of the Deep Sea Drilling Project, Volume 15.Washington (U.S. Government Printing Office).

Smith, D. H., 1972. A compound classifier based oncomputer analysis of low resolution mass spectral data.Geochemical and environmental applications. Anal.Chern. 44, 536.

Smith, D. H., Olsen, R. W., Walls, F. C. and Burlingame, A.L., 1971. Real-time organic mass spectrometry: LOGOS— a generalized laboratory system for high and lowresolution, GC/MS and closed-loop applications. Anal.Chern. 43, 1796.

600

17. PRELIMINARY ORGANIC ANALYSES OF DSDP ...(9 27.2'N, 54 20.5'W) was cored on the northern flank of...

Documents

Transcript of 17. PRELIMINARY ORGANIC ANALYSES OF DSDP ...(9 27.2'N, 54 20.5'W) was cored on the northern flank of...