14. some preliminary results on the higher … preliminary results on the higher weight hydrocarbons...

14. SOME PRELIMINARY RESULTS ON THE HIGHER WEIGHT HYDROCARBONSAND FATTY ACIDS IN THE DEEP SEA DRILLING PROJECT CORES. LEGS 5 - 7 1

Bernd R. Simoneit and A. L. BurlingameSpace Sciences Laboratory

University of California, Berkeley

The following report describes the preliminary organicanalyses performed on the DSDP cores (Legs 5 to 7) atthe Space Sciences Laboratory, University of Cali-fornia, Berkeley. In order to get a general idea of whatorganic compound families and their respective molec-ular weight distributions are present in these cores thefollowing approach was initiated. The small (approxi-mately 1 to 2 grams) samples remaining from theorganic carbon analyses of Legs 5 through 7 weresolvent extracted and the extract residues subjected tohigh resolution mass spectrometry. Based on thefindings from this initial survey the experimentalprocedures for the larger (approximately 100 grams)samples were modified and applied as discussed later inthis report.

The small samples, which were received as driedpowders, were extracted—usually for five days—with3:1 benzene/methanol (redistilled nanograde purity) ina Soxhlet extractor. The solvent was removed from theextract under water aspirator vacuum and the residuefurther fractionated to remove the large quantities ofinorganic salts. The bulk of the organics were removedfrom the residue by solution in heptane and weighedafter solvent removal (see Table 1). The residue wasthen treated with methanol to dissolve the more polarorganics and, of course, large amounts of inorganicsalts (see Table 1). It should be noted that in sampleswhere the methanol solubles are high, a large saltresidue remained insoluble. All the heptane extractsand some of the methanol extracts were subjected tohigh resolution mass spectrometry. These analyses werecarried out on a GEC-AEI MS-902 mass spectrometeronline to an XDS Sigma 7 Computer (described byBurlingame, 1968 and 1969, and Burlingame et al,1970). The samples were introduced via a direct inletprobe into the ion source, operated at the followingconditions: resolution 10,000 to 12,000; ionizing cur-rent 500 µÅ; ionizing voltage 50 eV; and temperature200 to 220°C. The scan rate was 16 seconds per decadewith a clock rate of 24 kHz. Multiple scans were takenduring each analysis and then sum averaged togetherduring data reduction. Selected high resolution massspectral data are presented as heteroatomic plots

Research supported by the Oceanography Section, NationalScience Foundation, NSF Grant GA-24214.

(Burlingame and Smith, 1968) in various figures in thetext. The low resolution mass spectra were alsodetermined on a GEC-AEI MS-902 mass spectrometer.Gas chromatography was carried out using a Perkin-Elmer Model 900 gas chromatograph with a flameionization detector and operating conditions as statedin the respective figure legends.

The methanol extracts consist mainly of inorganic salts(mostly chlorides), water, low molecular-weight hydro-carbons and fatty acids. The largest skeleton observedwas C|5 for the alkanes and Cj2 f° r t n e acids.

The heptane extracts are quite diverse, the mostpredominant compounds being hydrocarbons in allcases, with minor amounts of mono- and dioxygenatedspecies present and trace amounts of poly oxygenatedcompounds. No nitrogen or sulfur containing specieswere detected above background in these totalextracts.

The general formula for organics as hydrocarbons,alcohols and acids is CnH2n.zO , where n is thenumber of carbons in the molecule, z is a measure ofthe degree of unsaturation of the molecule, and m isthe number of oxygen heteroatoms. In all the samplesanalyzed the most commonly encountered degrees ofunsaturation (see Table 2) are zero (deduced from thefragment ions mainly), one and four, with less of two,three and five, and a trace of seven but no six. In otherwords, there is an abundance of more saturatedsystems with lesser amounts of polycyclic systems, butvirtual absence of higher weight condensed aromaticsystems (as found in some shale oils and petroleums).

The major compound series are listed with therespective source cores in Table 1. Some of the moreinteresting and promising findings follow in greaterdetail.

SMALLER SAMPLE ANALYSES

Leg 6, Hole 52.0-3-6

The saturated alkanes CnH2n+2 and CnH2n range fromn = 9 to 19, with minor amounts of the CnH2n.2 seriesranging from n = 10 to 20. The only more aromatizedspecies found is C j g t ^ (possible Structure II) which

889

Samplea

Leg 5

32-6-3

32-12-3

33-5-3

34-4-4

34-5-4

34-10-1

35-6-3

36-8-0

36-11-0

36-12-0

37-3-0

38-5-0

40-15-5

42-5-0

42-10-0

42-10-2

Leg 6

47.0-1-4

47.2-10-5

49.0-1-3

50.1-1-2

50.1-3-6

51.0-1-6

52.0-3-6

53.1-2-6

53.2-1-5

55.0-6-5

55.0-10-5

56.2-10-6

58.2-1-6

Leg 7

62.0-3-3

62.1-12-2

Per CentOrganicCarbon

0.28

0.05

0.43

0.59

0.65

0.27

0.39

0.35

0.32

0.25

0.20

0.22

0.02

0.11

0.15

-

0.30

0.10

0.08

0.13

0.08

0.12

0.04

0.08

0.08

0.09

0.05

0.13

0.05

0.9-1.2

0.41

TABLE 1DSDP Core Extracts

PPMHeptaneExtract

282

254

372

259

458

434

360

110

960(hi)

146

212

7

<IO

670

760

534

156

36

145

85

263

88

118

288

75

<l

26

150

142

502

86

PPMMethanolExtract

6900

2040

1890

4000

5640

3340

4660

770

7240

3700

12,300

5140

8900

-20,400

12,700

12,050

1600

1360

6370

1670

865

1920

1530

9160

3550

6900

3700

18,750

9700

1950

722

Legs 5-7

ApproximateAgeb

L. Pliocene

U. Oligocene

L. Pliocene

L. Pliocene

L. Pliocene

M. Miocene

Pleistocene

U. Pliocene

L. Pliocene

U. Miocene

L. Pliocene7

L. Eocene

L. Oligocene

L. Eocene

L. Eocene

Pleistocene

L. Paleocene

L. Pleistocene

Pleistocene?

Miocene

Paleocene

U. Miocene

U. Miocene

M. Miocene

L. Miocene

U. Oligocene

U. Oligocene

L. Miocene?

U. Pliocene

Compound TypesFoundc

A + C

A + C

A,C + T

A,C + T

A + C

A,C + T

A + C

A+C

A + C

A,C + T

A + C

A + C

A + C

A + C

A + C

A + C

A,C,S + T

A + C

A + C

A,C,S + T

A,C,S + T

A + C

A+C

A + C

A + C

A + C

A,C + T

A,C + T

890

TABLE 1 - Continued

Sample a

64.1-2-5

65.0-9-2

65.0-9-6

65.1-4-3

66.0-6-2

66.0-7-4

Per CentOrganicCarbon

0.24

0.12

0.06

0.08

0.05

0.07

PPMHeptaneExtract

164

210

118

177

259

18

PPMMethanolExtract

3060

-25,300

2900

7960

5200

2130

ApproximateAgeb

M. Miocene

U. Miocene

U. Miocene

M. Eocene

L. Oligocene

L. Oligocene

Compound TypesFoundc

A + C

A,C + T

A, C, S + T

A,C + S

A,C + T

Hole-Core-SectionPleistocene (106 years); Pliocene (107 years); Miocene (2.5 × 107 years); Oligocene (4 × 107 years); Eocene (6 × 107

years); Paleocene (7 X 10 years).

Compound Types: A- Alkanes; C-Carboxylic Acids (includes ketones, etc.); S—Steroidal Compounds; T-TriterpenoidalCompounds.

TABLE 2Various Carbon Skeletons i^ )^ Found

Degrees ofUnsaturation Skeletal Structures of Lowest Homolog

Found inthe CoreExtracts

+2 0 C - C fully saturated Major

-8

-10

-12

C = Cor

2 C = C or

3 C = C or

cocoMajor

Minor

Minor

Major

Minor

Absent

Trace

891

conceivably could be derived from the following typeof intramolecular oxidative crosslinking of an unsatu-rated Cjg alkane, for example, Structure I.

[0]

II

1968)2. The general appearance of the data indicates amuch more aromatized extract (compare the peakswith tics in the two heteroatomic plots). There were nofatty acids detected above background levels. Thesteroidal series, CnH2n_6, is further substantiated bythe peak at m/e 217 of composition C j ^ H ^ (Struc-ture III). The major components however are alkanesof the series: C n H 2 n +2 f° r n = 8 to 18, C n H2 n forn = 8 to 20, and CnH2 n_2 for n = 8 to 21.

Leg 5, Hole 34-4-4

This extract contains quite a variety of alkanes, but nosignificant amounts of oxygenated material. The majorseries found are C n H 2 n + 2 , C n H 2 n _ 2 and CnH2n-4>ranging from n = l O to 23. The minor series are

CnH2n-12 a n d cnH2n-14 forc n H 2n-6' C n H 2i . .various values of n from about 9 to a maximum of 23for some of the series, not every homolog being found.

Leg 5, Hole 32-12-3

This extract consists mainly of saturated alkanes toabout C j 3 and two compounds of compositionsC15H32O2 (probably palmitic acid) and CjgF^<>?(probably stearic acid).

Leg 5, Hole 37-3-0

The extract is essentially only three hydrocarbonseries: C n H 2 n , CnH2 n_2 and CnH2 n_6, ranging fromn = 10 to a maximum of 22. The peak at m/e 217 ofcomposition C25H25 (Structure HI) is present in thehigh resolution mass spectral data, lending support to asteroidal structure for the higher members of the

I I I m / e 2 1 7 , C 1 6 H 2 5

^n^2n-6 s e r i e s (n= 16-22). There is a significantamount of the series CnH2nO for n = 10-20, but onlythe even members are present. Since alcohols do notexhibit any appreciable molecular ions under 70 eVionization, this series is postulated to be a series ofethers or ketones.

Leg 5, Hole 34-5-4

The partial high resolution mass spectral data for thisextract is shown in Figure 1 (Burlingame and Smith,

Leg 5, Hole 34-10-1

The partial high resolution mass spectral data of thisheptane extract is shown in Figure 2 and exhibitsmainly molecular ions of four degrees of unsaturation.The fragment peaks of compositions C 16^25 (Struc-ture III) at m/e 217, C 1 4 H 2 3 (Structure IV) atm/e 191 and C 1 3 H 2 i (Structure V) at m/e 177 are allpresent above background, indicating possible steroidaland pentacyclic triterpenoidal structures for theCnH2n.6 and CnH2n_8 series (n found: 34, 36 and 40),as well as the CnH2n_6θ and CnH2n.gO series(n found: 22, 24, 25, 32 and 38) are present. The C 4 0

alkane (see to compare peak C40H74 in the C/H plot

IV m/e 191,C 1 4 H 2 3Vm/e 1 7 7 , C 1 3 H 2 1

of Figure 2) fits a carotenoidal structure, such as VI.The series C n H 2 n 4 and CnH2n_2 are found in minor

VI m/e 554.6, C 4 Q H 7 4

The high resolution mass spectra are presented as hetero-atomic plots. The masses are plotted in methylene units. Onthe abscissa, each principal division marker corresponds to thesaturated alkyl fragment, for example, CnH2n+j, with thenumber of carbon/hydrogen atoms given below. There arefourteen units between each principal division, and thenumber of hydrogen atoms of an unsaturated or cyclicfragment ion is obtained simply by subtracting the number ofunits (hydrogens) from the 2n+l hydrogens of the respectivesaturated principal division, C n H2 n + i . A peak with a singletic mark above it indicates more than seven degrees ofunsaturation. Fragments of this kind are plotted below thenext lower major saturated division, that is, Cn_^H2n-l Toconvert the apparent composition of these ions as they appearon the plot to their actual composition, add one carbon andsubtract 12 hydrogen atoms. A peak with a double tic markabove it indicates more than 14 degrees of unsaturation.Fragments of this kind are plotted below the next two lowermajor saturated divisions, that is, Cn-2H2n-3' an<* a r e c o n "verted to their actual composition by adding two carbons andsubtracting 24 hydrogen atoms.

892

Figure 1. Partial summed high resolution mass spectral data for the total extract from Leg 5, Core 34-5-4.

X10

LdJ i.i,hi, i.i.lilii..i.i.U,i.

U-34-10/1

Inliillll Mill 111 I h ii

C/H

l l'i'1'i'i'ri'i'i'i'i'iji 111111111111111111111111111 i>i i i i i•j tn i i i i•j i•i•i•i i•i•j1

2/5 3/7 «/9 5/11 6/13 7/15 β/17 S/19 10/:i""" i ' i" f r"""""i i i r'l•l'l l•l l'l'l'l 'l't•l't'1'1 1 !•| T1'1'1 1 1 1

xio

i l l i i imillii ii i\

C/H D

In i l l l i•iltt i l l l l l l l i i l i l l i l i l i l l i l i , HI IiIIII•IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII•IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII JJ I

|l|iµ|l|l|l|l|l|l|l|l|l|l|i|l|l|l|l|l|iµ|l|l|l|l|iµµ|l|l|l|l|l|l|l|p

/3 2/5 3/

C/H D2

XIO

iliiillllii iililin llh l l l l i —Jl . I L L _ J . , .W H W H w i w nwm•i>wΦiww η i i<w nywwn•i iΦiMMM ivwwiyHWWYi1!1!1^

0/1 1/3 2^5

C/H D3

ii|i|i|ii>ii|ii>ii|i|iif lWiyi WIHVpi HI fWIIWIWWIITIWW•l•WIH<HWWVWtHWWηV^

Figure 2. Partial summed high resolution mass spectral data for the total heptane extract from Leg 5, Core 34-10-1.

amounts, the high molecular weight members beingn = 18, 20, 21, 22 and 24, but ranging down to n = 10.The saturated series C nH2 n +2, C n H2 n and CnH2n_2are deduced present from the respective fragments forn = 10 to 20. The monooxygenated species consist ofCnH2nO for n = 1 to 20 and two peaks of compositionC3gH5gO and C29H52O. Small amounts of dioxygen-ated species are also present: C21H35O2 andC24H44O2 and the fragment ion series CnH2n_5θ2for n = 5 to 14, 16 to 25 and 27. The large peak ofcomposition C g ^ C ^ in the C/H O3 plot of Figure 2 isderived from phthalate ester contamination and isassigned Structure VII. The source of this type of

VII m/e 149, C 8H 5O 3

contamination is discussed later in this report. Thegroup of peaks at C1QH9O3 in the same plot are alsophthalate ester fragments; such as, possibly Struc-ture VIII.

The peaks of composition 033^1390, C36H49O andC33H55O are the only species found at high mass inthe C/H O plot.

Leg 7, Hole 62.1-12-2

The partial high resolution mass spectral data for thisextract is shown in Figure 4. Again, the major constitu-ents are the alkane series: CnH2n+2 (deduced mostlyfrom its fragments), C n H2 n , CnH2n-2 and CnH2n_4 forn = 8 to 22. The group of peaks at high mass in theC/H plot of Figure 4 are of the series CnH2n.6 forn = 34, 36, 38 and 40 (even carbon numbers only).This series could be of carotenoidal structure (forexample, Structure VI). The peaks at m/e 217,C 16^25 a n ^ m / e 191, C24H23 are slightly above thebackground and indicate minor amounts of steroidaland triterpenoidal compounds. The fatty acids areminor constituents, the peak of compositionC15H32O2 (probably palmitic acid) being the mostintense molecular ion found in the series. The largepeak in the C/H O3 plot of Figure 4 has the composi-tion CgH5U3 (Structure VII) and is sample contamina-tion as discussed later. It is derived in this case fromdioctyl phthalate (the most ubiquitous member of thephthalate esters), as substantiated by the two peaksfound of composition CgHyC^ at m/e 167 (StructureX) and C 1 6 H 2 3 θ 4 at m/e 279 (Structure XI). Dioc-tyl phthalate exhibits no molecular ion.

O — C 2 H 5

VII m/e 177,C 1 0 H 9 O 3

Leg 7, Hole 62.0-3-3

The partial high resolution mass spectral data is foundin Figure 3. The virtual absence of low weight frag-ments should be noted. The higher weight species areC40H54 and C 32H 5g in the C/H plot of Figure 3. Alsothe peak of composition CjgHj2 in the same plot canbe considered as chrysene (Structure IX) or tetracene.

OPIXm/e228,C l 8H1 2

O - C 8 H 1 7

OH

+OH

XIm/e279,C1 6H2 3O4

Leg 7, Hole 65.0-9-2

The partial high resolution mass spectra data for thisheptane extract is shown in Figure 5. The C4QH74peak (Structure VI) is present and the following seriesis found in major amounts at high mass in the C/H

895

Figure 3. Partial summed high resolution mass spectral data for the extract from Leg 7, Core 62.0-3-3.

3 x7» 17x79 Jtsrr J xT <Ox•l

- i • . • • i - - i • •

•xio

l•lil.l.l•:.i•l.i.i:i•lll•i 1-.•.iLii Hi i l i i , . i i • L • i i i n ü . i i • • - L . n • • . i • jPWPI pWPMpΦPIMMWMMU•PIHMMHΦM H•l PH••p Pm^^

i •

C/H D

•• ,'li•PIM•PIM•PII Pll•PI•l p>l•Plt•Pp<PWPII>PI•UPMI>p•MPI IM•p•P IMMWMMMMpMMTIΦp PWPI•pWPIipWMM•pMΦI•PPIΦIWm PWPIV•p PIW^^

Oxl 1/3 2x8 3x7 4x9 5/11 β/13 7/15 Bxl7 Sxl9 10/H 11x23 12x28 13x27 14x» 18x31 11x33 17x38 11x37 11/31 20x41 21x43 22x48 23x47 24x41 29X91 21X93 27X99 21x97 21x91 30x11 3|x 3 32x19 33x17

X20C/H 02

IllllllnllullyjliLullLlhllil J l.l•l ll••l• 1 .11.'IMMM>l p>IΦII•PpiPI•l•PII<PI MPII>p l>PI•MPpM•lfPII>PI l•Pll p l PPI>Pp>PI l<PII>PIM PII p i PII PI

1x3 2x8 3x7 4x3 β/u 1x13 7x18 B/17 3x13 10x21 11x23 12x29 13x27 14/2* 19x31 11x33 17x39 I x37 11x31 20x41 21x43 22x49 23x47 24x4* 28x91 21x93 27X99 21/37 2>x9 30x11 31x«3 32XC9 33/*7 34xU 3Sx71 3C/73 37x73 3BX7T

C/H D3 ×IO

i•i•i-iiiJj•LLi•J-i•l l• • . . •

W'OT'P|1'PH'PiyPI•l•PH•H•l•PIH•P|1•PI•l'PI•|•PIHipiiY'H'Pi^V|•i'PW•PI•|•piH•W•p•l•m

Oxl 1x3 2x9 3x7 4x1 9x11 1x13 7x18 1x17 1X11 10x21 11x23 12x28 13x27 14x21 18x31 11x33 17/M l•x3 31x13 32XC9 3Jx«7 Mxss 39x71 3«x73 37x79


plot: CnH2 n_6 for n = 29, 34, 36, 38 and 40. The seriesC n H2 n occurs in minor amounts for n = 18 and 20.The other hydrocarbon series are present in minoramounts, as substantiated by the respective fragmention peaks. There are also ions fitting poly cyclicstructures with 26 to 29 carbon atoms. The major fattyacid found is C j g ^ g C ^ (probably stearic acid) andless of C17H34O2. The series is indicated by thepresence of the fragment ions of compositionc n H 2 n - l ° 2 for n = 6 to 16.

Leg 7, Hole 65.1-4-3

The partial high resolution mass spectral data appearsin Figure 6. This extract contains mostly low molecularweight alkanes, such as the series fragments CnH2n+jfor n = 2 to 23 and CnH 2 n_i for n = 2 to 16 and 18.The series CnH2n_6 i s indicated present for n = 36, 38and 40. The C/H 0 plot consists mainly of ions ofcomposition CnH2n_i0 for n = 1 to 12, 14 to 20 andCnH2nO for n= 16 and 20. The molecular ions ofcomposition CJ5H32O2 (possibly palmitic acid) andC15H30O2 are found in the C/H O2 plot; the lowerhomologs are indicated present in minor amounts bytheir respective fragment ions C n ^ n - l ^ for n = 1 to14. At high mass there is a peak of compositionC37H74O2 which possibly could be a wax ester. Forcomparison purposes with the high resolution massspectral data, a scan at low resolution is shown inFigure 7. The overall appearance of the spectrum fitsfor alkanes but the peaks at higher mass should benoted. The peak at m/e 256 corresponds to thecomposition C16H32O2 a n d the molecular ions atm/e 498, 526 and 554 correspond to the compositionsc n H 2n-6 f o r n = 3 6> 3 8 a n d 40, the carotenoidal(Structure VI) type alkanes.

LARGER SAMPLE ANALYSES

The larger samples packed and frozen in Kapakpouches were defrosted and extracted under a nitrogenatmosphere with 3:1 benzene/methanol in a Soxhletextractor. The procedures used for extraction andfunctional group separations were the same asdescribed by Burlingame et al. (1969), except that alloperations were carried out under nitrogen whereverpossible and the isolated fractions were stored underrefrigeration.

Leg 5, Hole 35-6-3

The benzene/methanol (3:1) extract of 68.3 grams ofthis core was extracted with methylene chloride(CH2CI2) yielding 16.1 milligrams residue after solventremoval equivalent to 236 ppm. This fraction wasseparated by the wet chemical methods described byBurlingame et al. (1969) into acids, 15.6 per cent ofthe extract; alkanes (neutrals), 68.0 per cent of the

extract; and bases, less than 1 per cent of the extract.A gas chromatogram of the total CH2CI2 extract isshown in Figure 8, and a gas chromatogram of thealkane fraction in Figure 9. The acids were esterifiedwith BF3 in methanol, and the gas chromatogram isshown in Figure 10. A low resolution mass spectrum ofthe total extract was run and is shown in Figure 11.The major peaks at high mass are at m/e 858, then aseries at m/e 502, 516, 530, 542 and 544 and groupsaround m/e 430, 412, 396, 382 and 368. It should benoted that the peak at m/e 191 (probably Struc-ture IV) is significantly above the background. Thepartial high resolution mass spectral data for the sameextract is shown in Figure 12. The major constituentsindicated are the alkane series Cn^2n+2> ^n^2n> a n d

CnH2n.2 to CnH2n.]2 f°r most values of n = 2 to 20,with the more saturated series being the more abun-dant. The aromatic series plotted in the aromatic C/Hplot of Figure 12 are only trace constituents.3 Athigher mass the series CnH2n.g for n = 27 and 29,cnH2n-10 f o r n = 2 8 a n d 2 9 a n d cnH2n-12 f o r n = 2 7>28 and 29, as well as, several fragments appear quitestrongly. This series appears to be a group of penta-cyclic triterpenoidal molecules, as further substantiatedby the peak of composition C14H23 (Structure IV,m/e 191), which is diagnostic for such structures. TheC/H O plot of Figure 12 exhibits mainly low weightfragment peaks and the high weight series CnH2n_i()Ofor n = 27, 29 and 30, C n H 2 n . i 2 θ for n = 27 to 30and CnH2n_8θ for n = 28. The ions of interest in theC/H O2 plot of Figure 12 are the series C n H2 n θ2 forn = 2 to 7, 16 to 18, 21, 22, 25, 26, 28 and 30.

The alkanes (neutrals) were analyzed by high resolu-tion mass spectrometry and the data indicated mainlyhydrocarbons with minor amounts of oxygenatedspecies. The saturated series CnH2n+2> C n H2 n andCnH2n-2 for n = 1 to 18 are the major constituents. Athigh mass are significant peaks of compositionsC16H26> C27H46> C 29 H 48 a n d a s t r o n 8 C 31 H 56fitting molecular ions, and the fragments C29H27,C30H39 and C37H57. The major C/H O peaks at highmass are a group around m/e 502 of compositions sucha s C 3 6 H 5 6 O .

The methyl esters were also subjected to high resolu-tion mass spectrometry and the data are shown inFigure 13. The salient features of this data are asfollows. The saturated acid esters of the seriesC n H2 n θ2 for n= 1 to 21 (the lowest homologs beingmostly rearrangement ions), CnH2n.2θ2 for n = 1to 20 and C n H 2 n 4 θ 2 for n = l t o l 9 are present,

Aromatics usually exhibit only strong molecular ions orM-HC=CH type fragments, also of high relative intensity.Thus, abundance quantitation of these series is only anestimate and probably on the high side.

899

•XIOUII-651-4/-3

1 1 i n 111 m i l l l i l l . h i I I H I I l i iI I' I' l 1" I'( 1'1'j t f l l•l l i l•l lit j •I I•II•I•I 1't l l'JM1 t•l>j t |'l'l 1'| l'•i•iJj!1 i•'1" i•r••i i• i . i r i• i• i••j i i i " i.i:i!'yi•i•i' W•'i•'|M'g•"•""™|™•P'•"•'P'"iSiH'•FW•"•'•'J •'i"P•i•W•B^ i•i•ffj•iJ•Wgl iwj tfiη' Mj \vW\ i•i i••t•j.11 l•Vj f|iiM'| WJH•i•mη n | p i p |'t pi | | ••

J L, : i • µ i• . i i

,|l|l|l|l|,|,|i|,|,|i|,|,|i|l|,|l|l|,|l|,|,|l|l|,|,|i|,|,|,|l|l|l|l{,|,|l|iµ|.|l|•|l|l|l|l|l|^^

75 3B'77

C/H D2•×IO

I I 1


III, , , , l50

1

00 150 200 250 300 350 400 450

UI

— xlO

1 - 6 5 1 - 4 / 3

li, li

HEP

I"l""l"!'| |—Mt> " I

3.32 é

Figure 7. Low resolution mass spectrum of the extract from Leg 7, Core 65.1-4-3.

Figure 8. Gas chromatogram of the total methylene chloride extract from Leg 5, Core 35-6-3 (conditions: 10 ft. x 1/8" stainless steel column, packedwith 3 per cent SE-30 on 100-120 mesh Gaschrom Q, programmed from 100-250° Cat 8° /minute and using helium at 40 ml/minute).

Figure 9. Gas chromatogram of the alkane fraction from the methylene chloride extract of Leg 5, Core 35-6-3 (conditions as cited in Figure 8).

6

Figure 10. Gas chromatogram of the acid methyl esters from the methylene chloride extract of Leg 5, Core 35-6-3(conditions as cited in Figure 8).

903

Figure 11. Low resolution mass spectrum of the total methylene chloride extract from Leg 5, Core 35-6-3.

X 10U-35-6/3 TDT C/H

RRDΠRTIC O H D X 10

i i' " I ' ; i i i ' i

11I , : > I

I I I I I I I

C/H D2

X 10

I 1 ! 1 ! 1 ! 1 !'! 1 !'! 1 !'!'! 1 ! 1 !'! 1 ! 1 ! 1 ! 1 !'! 1 ! 1 !'! 1 ! 1 ! 1 ! 1 ! 1 ! 1 !'! 1 ! 1 ! 1 !'!'!'!'!'! 1 !'!'

Figure 12. Partial summed high resolution mass spectral data for the total methylene chloride extract from Leg 5, Core 35-6-3.

IIIIIIIIIIHIIIIIIIIIMMIl i • • • II•llll•ll•l•tlltl•l•l•l••l111 " I I I 11II111 III1111 (1111" II i l l I "11111 Ml 111111II1111

,1

1 ~X 5

1 1 11 ''•j 1

1111 I>I Π i | i I I

i, i!

ÉJLi i i j i

1

l l l l11

ll ll

11

11

1

C/H D

i

I

H I'!*!'!1!'!'l'1'f r 1*1' 1*1 ' I ' 1*1 r 1' |'l'l'l'iMM1'l1'r Pi•CrPrrrl 't VPHtMT"! W'l p WH* jH pHT'Hi'πH'iT'1'l'rrHI'i'H r W I W r j

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J_LI i i i , i

il n I I I m i I l l i

I l

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Figure 13. Partial summed high resolution mass spectral data for the methyl esters derived from Leg 5, Core 35-6-3.

although in low concentrations. At higher mass in theC/H O2 plot of Figure 13 are strong ions of composi-tions C19H25O2 and C20H27O2 and molecular ions of

the series C n H2 n . i2°2 f o r n = 2 0> 2 1> 2 2 a n d 2 6 a n d

various unsaturated or cyclic species with 23 to 29carbons. The peak at composition C39Hygθ2 fits intothe C n H2 n θ2 series and could be a wax ester. Thelarge peak on the C/H O3 plot of composition Cglr^C^(Structure VII) is derived from various phthalates andis not necessarily all contamination since the peak atm/e 279 of composition C15H23O4 (Structure XI) istoo low in intensity. There are minor amounts ofaromatic acid esters as for example, the seriesC-nH2n-8()2 for n = 8 to 12 and 14 to 16 (benzoicacids), CnH2n_i()θ2 f° r n = 12 to 14 and C n H2 n . j2θ2for n = 12 to 15. Small amounts of oxoacids of theseries CnH2n_2θ3 are found (n = 5 to 8 and 12). Thepeak at C9H7O3 in the C/H O3 plot is derived fromdimethyl phthalate and has the Structure XII.

XIIm/el63,C 9 H 7 O 3

It belongs to the series C n H2 n . io^4 which is presentfor n = 10 to 13. The normal dicarboxylic acids of theseries CnH2n_2θ4 are present for n = 5 to 10, asdeduced from the M - CH3O fragments (CnH2n-3θ3)The C/H plot of Figure 13 shows the ions of composi-tion CjgH23, CjgH27 and C29H3J rather intense.Otherwise the pattern indicates the alkane chainfragmentation and the peak of composition CJ4H23(Structure IV) is significantly above background.

The basic compounds separated from the methylenechloride extract were also analyzed by high resolutionmass spectrometry and the data is shown in Figure 14.The small amount of sample only allowed this totalmass spectral analysis. The compound series found arelisted in Table 3. The series CnH2n_5N (pyridines) forn = 6 to 9, CnH2n_9N (indoles) for n = 8, 9,13,14and 20, and C n H 2 n . u N (quinolines) for n = 9 to 14are the most abundant. The other series listed inTable 3 are found in minor amounts. The generaldistribution of these nitrogen compounds is analogousto that in the Green River Formation Oil Shale(Simoneit et al, 1970). Species of compositionsC/HN2, C/HN3, C/HN4 and C/H NO were notdetected.

A general flow sheet for the extraction and fractiona-tion of this core is given in Figure 15 (the fractionsanalyzed to date are so indicated). In order to isolateany organics entrapped or bound to the mineral matrix(for example, adipocere — insoluble fatty acid salts),the extracted core residue was treated with hydro-chloric acid and then reextracted. The methylenechloride/heptane extract amounted to 15 milligramsand a subsequent ether extract yielded an additional10.2 milligrams of more polar material. The breakdownof the methylene chloride/heptane extract is shown inFigure 15. Further work on these fractions is inprogress.

CONTAMINATION FROM SAMPLING BAGS

The samples received for preliminary examination werepackaged on board the Glomar Challenger in mylarfilm and new paint cans, and were sealed in smaller lotsin the Kapak pouches for the organic examinations. Asample bag (Kapak pouches are made of scotchpakpolyester film) was extracted with 3:1 benzene/methanol yielding an extract of 2.1 milligrams aftersolvent removal. The bag weighed 13.07 grams and thearea extracted was 280 cm , thus the soluble organicsamounted to 7.5 µg/cm2, rather significant. The highresolution mass spectral data is shown in Figure 16 andindicates that the extract consists mainly of fullysaturated hydrocarbons. The main two series presentare CnH2n+2 and C n H2 n for n = 2 to 25, the lowerhomologs most likely being rearrangement fragments.The series CnH2n_2> CnH2n_4 and CnH2n.6 for n = 3to 22 are found in minor amounts. More aromaticseries and fatty acids were not detected. Phthalateesters and mono-oxygenated compounds are foundonly in trace amounts. Contamination by phthalates isquite common and is usually from multiple sources.The organic contamination of the Apollo LunarSample program was monitored by these same tech-niques and the report by Simoneit and Flory (in press)covers the ubiquitous phthalates as well as othercommonly encountered contaminants and their respec-tive sources in detail.

In conclusion, this report has presented some prelimi-nary results on the higher weight hydrocarbons andoxygen and nitrogen containing molecules isolatedfrom the DSDP Cores. Further work is in progress toelucidate the structures of these interesting moleculesas well as continuing the preliminary analytical survey.

ACKNOWLEDGEMENTS

We thank Sadalla Nassar and Ellen Scott for technicalassistance and Martha Petrie for assistance with thehigh resolution mass spectral data.

907

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1/3 2/5 3/7 4/9 5/11 6/13 7/15 .B/17 9/19 10/2111/2312/2513/2714/2915/3116/3317/351B/3719/3920/41 21/4322/4523/4724/4925/5126/5327/552B/5729/5930/6131Z6332/65

Figure 14. Partial summed high resolution mass spectral data for the bases derived from Leg 5, Core 35-6-3.

TABLE 3General Nitrogen Compound Distribution Found in the Base Extract of Core 35-6-3, Leg 5

Skeletal Examples Series n Found

1)

2)

3)

4)

00 0 OQ

N

5)

6)

V)

8)

H

NN

CnH2n-5N

CnH2n-7N

CnH2n-9N

CnH2n-l lN

CnH2n-13N

6-9

9,11 +

8,9,13

9-14

12-15

12

,14 + 20

CnH2n-17N

1 2 " 1 6

909

Leg 5, Core 35-6-368.3 g (frozen)

Soxhlet Extraction(10h with 3:1 benzene/methanol)

extract

63.0 g residuerecovered

Demineralizationwith6/VHCI4h stir andsonicate

methylene chloride

16.1 mg(brown)

benzene

6.7 mg(brown)

Mass spec.GLC

residue(yellow-green)

acids1.0 mg

filtrate

sonicatewithsolvents

used 8.8 mg

ether

207.3 mgyellowviscousliquid

neutrals5.4 mg(brown)

BF3/MeOH

esters0.8 mg

sonicatewithsolvents

Mass spec.GLC

Methylene chloride/heptane

15.0 mg

ether

10.2 mg(colorless)

neutrals

heptane

6.7 mg(colorless)

methylene chloride

3.0 mg(colorless)

acids

heptane

1.3 mg(colorless)

methylene chloride

1.0 mg(colorless)

BF3/MeOH

esters0.2 mg

BF3/MeOH

esters0.3 mg

Figure 15. Flow Sheet for the Extractions of Leg 5, Core 35-6-3.

910

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i|.|i|Φ|.|i ΦI'1'I'IΦ ΦIΦI'1'I' ΦI'IΦI'1' .|i|i|i|i|i|i|i|i|i|i|i|.,i|i|i|i|

2/5 3/7 4/9 5/11 6/13 7/15 B/17 9/19 10/21 11/23 12/25 13/27 14/29 15/31 16/33 17/35 IB/37 19/39 20/41 21/43 22/45 23/47 24/49 25/51 26/53 27/55 2B/57

Figure 16. Partial summed high resolution mass spectral data for the extract from the Kapak sample pouches.

REFERENCESBurlingame, A. L., 1968. Data acquisition, processing

and interpretation via coupled high speed real-timedigital computer and high resolution mass spectrom-eter systems. Advances in Mass Spectrometry. E.Kendrick (Ed), London (The Institute of Petro-leum), 4, 15.

Burlingame, A. L., 1971. Developments and applica-tions of real-time high resolution mass spectrom-etry. Presented at the Intern. Conf. on MassSpectroscopy, Kyoto, Sept. 8-12, 1969. Advances inMass Spectrometry. 5, in press.

Burlingame, A. L., Haug, P. A., Schnoes, H. K., andSimoneit, B. R., 1969. Fatty acids derived from theGreen River Formation Oil Shale by extractions andoxidations — a review. Advances in Organic Geo-chemistry 1968. P. A. Schenck and I. Havenaar(Eds.) Braunschweig (Pergamon — Viewig), 85.

Burlingame, A. L., and Smith, D. H., 1968. Automatedheteroatomic plotting as an aid to the presentationand interpretation of high resolution mass spectraldata. Tetrahedron. 24, 5749.

Burlingame, A. L., Smith, D. H., Merren, T. O., andOlsen, R. W., 1970. Real-time high resolution massspectrometry. In Computers in Analytical Chem-istry. C. H. Orr and J. Norris (Eds.), (Vol. 4 inProgress in Analytical Chemistry series), New York(Plenum Press), 17.

Simoneit, B. R., and Flory, D. A. In press. Apollo 11,12 and 13 Organic Contamination Monitoring His-tory. Proposed NASA Scientific Publication.

Simoneit, B. R., Schnoes, H. K., Haug, P. andBurlingame, A. L., 1970. Nitrogenous compoundsof the Colorado Green River Formation OilShale: a preliminary analysis by mass spectrometry.Nature. 226,15.

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14. some preliminary results on the higher … preliminary results on the higher weight hydrocarbons...

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