Early diagenesis in a reducing fjord, Saanich Inlet, British Columbia—III. Changes in organic constituents of sediment

~cfbetCormoahimiorAcW,1972,

Vol. 86,~&1186 to1208. ParmmonPrt*s. &f&d InNorthernIreland

Early diagcn& iu a rducing fjord, &w&h I&t, Eritish Cohmbia-III. changes in orgauic constituenb of sediment* F.

s. IBROwN

Biosciencesand Ele&rochemistry Department, TRW Systems Redondo Beach, California 90278

Group,

One Spaoe Park,

and M. J. BAEDE~KER, A. NISSEXBAUH~ and I. IL -r&r Department of Geology and Institute of Geophysics and Plauetary Physics, Dnivemity of California, Los Angeles, California 90024 (Rscaiued9 Sqtembw

1971;

mwptedin revbdform 30 March 1972)

&&&-As part of a larger study of diagenesis in the sediment of Saanich Inlet, several groups of organio compounds were isolated from the sediment, identified, their concentration quantitatively determined and where possible, the C1afC” isotope ratio determined. Four 2.6 m aores and one 38 m core were studied. It was found that chlorius show the greatest decrease with depth followed by amino acids and then fatty acids. Aliphatio straight chain hydrocarbonsshow little chauge in conoentxation with depth of sediment, although the aromatic hydrocarbon perylene gave evidence for in situ formation. Fulvic acids, highly abundant at the surface of the sediment, decreasedsignikantly with depth, whereas humic acids did not appearto show any significantchange. The amount of insoluble residue increased with depth, constituting the don&ant organic carbon form at 17 m and below. There is no strong evidence for siguiflcant hydrocarbon formation under mild oonditions prevailing, although C,, fatty acids appear to be degrading preferentially and may partially convert to the C,, pan&n. There is no evidence for in s&w formation of isoprenoid hydrooarbons from the phytol side chain of chlorophyll. Pristane and phytane, present in small concentrationsat the sediment surface, deureaseor disappeer with burial. Carbon isotope (Cra/Cr2)ratios, were used to determine the relative amounts of orgauio matter derived from terrigenousand marine sources. Humic acids appear to form largely from planhton-derived material and not from terrigenousplant or soil sources.

TEE SUCH Inleten~onment has been described in Part 1 (~ISSE~B~UM etak., 1972a)and previously by GROSSet at. (1963)and by GUOLUERand GROSS (1964). Investigation on the distribution and nature of organic matter in Saanich Inlet sediments was undertaken for several reasons. First, the sediments contain large amounts of organic carbon (up to 5 per cent in the central basin), thus making it a possible recent analogue of ancient black shales, and a potential source for oil. Second, the reported rate of sedimentation is as high as 4 m per 1000 years (GROSSet cd,, 1963), thus, the whole sediment column (35 m deep) overlying the glacially eroded basement represents a time span of less than 8500 years B.P. This rate is four to five times as rapid as that in near shore marine basins such as Santa Barbara Basin on the CaWornia borderland which enables us, therefore, to follow more easily very early diagenetic changes in sedimentary organic material. Third, two possible sources exist for the organic material, the first is the humus rich soil from the highly forested * ContributionNo. 909: Institute of Geophysics and Plauetary Physias.

t Present address: Department of Isotopes, W&mann Israel. 1

1186

Institute of Science, Rehovot,

1186

F. S. Bnowrr, hi. J. RAEIIJKXER,A.

and I. R. W

NISSENBAUX

area snrrounding the Inlet and the other is the plaukton populrttion of the waterpredominantly dicltoms. Part of the study w&s therefore undertaken to establish criteria which would allow us to distinguish between those two sources. Since the studies of TRASE (1955) and STRUM(1956), it has become generally accepted that the reducing sediment of fjords, contain the highest concentration of organic matter in the marine environment. Strom reported an organic ombon content of 234o/o, for a sediment from an unmnned Norwegian fjord. Saanich Inlet sediments range from oxidizing detritus-rich deposits of the sill area, to highly reducing sediments in the central basin Thus, Sssnich Inlet provides an opportunity to investigate not only the time dependent diageuetic changes, but &so changes produced due to difference in the de~~t~~ environment. The study reported here is part of a lsrger investig&ion concterned with the chemistry and isotopic composition of Ssenich Inlet sediments and interstitial water described in Part I (NISSEXBAUM et d., 197%) and Psrt II (PBI~~LEYet aE., lQ72), hereafter ref4 to as Part I and Part II, and by KOLODNYand KAF.UX (1972).

The short cores were obtained in 4-m long, 6.in. &a plaatiobarrels, by piston oaring in December, 1967. ‘Fhe GIL dia, 36-m COW,in Station 3, were taken in June, 1968by Global MarineCompany. The sediments were kept refrigeratedat 4% from the time of co&&ion to the time of analysis. Core 1 wae taken at the oxidisiug sill, whereee the others are from the reducing areas of the central basin. The plankton sample, co&&d in July 1968, wee obtained from the Canadian Bureau of F’isheries,Nanaimo. The plankton was composed mainly of diatom frustulesof the generaSm and Melosircrand resting spores of severalChaetoceroo species (GUCLUERan& GBOSS, 1964). A sample of humus-rich forest soil was collected near XcPhail Point, British Columbiain September1968. Carbonate and organi carbon The sediments were rapidly washed with cold distihed water to remove interstitial water and dried under vacuum. The sediment wss rested with 199°/0 phosphoric acid (Ed[ofhiEA, 1950) and the evolved CO, volme was used to caluul&e the calcium carbonate content of the sediment (Table 1). The sample wes then washed repeatedly to remove all the acid, dried in vacuum, aad cornbustedin an oxygen atmosphere at 1190%. The volume of CO, evolved was messured and used to e&date the amount of orgsnia carbon in the aample. The me oombustion technique was used to convert the organiu aompounh extra&xl from the interstitial water to CO,.

The Crs/C1sratio wae measured on a Nuclide Co. 69’ &in. radius, du~-~o~~t~ mass spectrometer, against & calcite l&oratory substandard, which had been standardized against PDB and NBS &mdards. AU values are given relative to PDB by the followiog relationship:

&PO/ [

C1y.Y~ sample c*/crs sttuxd&rd

I

1

x 1000.

The solvents used in the extrractionprocedureswere distilled and the purity monitored by gas c~~to~aphy. The adsorbents for column c~ornoto~~phy~~cie void (minus 325

Early diagenosisin a reducingfjord, Saauioh Inlet, British Columbia-III

1187

Table 1. Carbon content and SC” of sediment and interstitial water Coreand

depth (om)

C&O %

b%

Orgmia C 8C”%

%

I.W.* m&j

Orgenio C Total I.W.* SC”O/MI m&c/l

No. 1 -21.7

33 163 286 367 436

-11.2 -37.1 - 11.3 +3*3 +9-a

-23.9 - 20.9 -31.1

488 690 616

+12*0 -j- 16.4

70 68 72 73 68

-21.3 -

362 490 -

-6.6 -0.1

- 20.6

436 470

fB.6 + 12.7

-20.6 -21.6 -21-7 -22.6

72 92 I46 I48

-21.6 -21.0 -21.7 -21.9

696 794 636 636

+ 10.3 f17.8 +1&l +13*3

4.76 4.66 1.33 3.77 6.06 4.72

-20.9 -20.2 -21-7 -20.8 -20.4 - 20.2

42 48 60 62 62 62

-21.6 -20.8 -23.0 -21.2 -20-Q - 20.6

390 416 440 477 610 482

-0.7 +1-a l-4.0 -f-4*7 +“a*3 +6*6

16.40 16.64

-26.6 - 19.2

O-16 4@-60 36-100 136-160 176-186

$0.3 -0.8 -0.4 -8.8 -8.2

1.23 1.06 0.96 1.07 1.13

-21.4 -21.3 -21.1 -21.1 -21.6

60 68 73 116 120

-21.4

0.47 0.66 1.10 1.76

O-16 76-86 160-160 226-236

O-89 0.98 0.89 0.90

+:.: +1*2 +O*Q

2-74 2.66 2.83 2.42

-20.1 -20.6 - 20.7 - 20.6

104 148 98 104

O-10 60-60 100-110 146-160 lQf&2OQ

1.60 1.37 1.42 1.16

+o*s +0*7 +O*S +0*7 -

3.87 3.68 3.62 3.49 -

-20.2 -20.1 -20.3 -20.3 -

790-820 1710-1740 262S-2660 3450-3480

0.67 1.42 6.66 3.67

+0*1 -0.6 -1.6 -6.6

3.67 2.82 2.96 2.63

O-16 60-66 100-110 160-160 200-210 240-260

1.96 1.66 1.19 1.68 1.82 X-62

+0.1 +0*1 -11.2 +0*1 +O*S +0*3

0456

CO, &Fag

No. 2

+;*7

No. 3

No. 3B

No. 4

8oil Plankton

mesh), florisil (minus 100 mesh) and the ion exchsnge resins (Dowex l-X3, 100-200 mesh, Dowex 6OW-X8, 60-100 mesh) were washed with the appropriate solvents prior to use. The samples were pnmessedunder identiotdconditionsto insurethat the resultswould be compamble. The analytical proaedureswere designedto isolate and identify consecutivelyin a single sample: hydrooerbons,fatty a&k, amino aoids, humio and fulvic a&&r. A flow chart is shown in Fig. 1. A sepsrate semple was used for extraction of chlorins. Interstitial waters were analysed for total dissolved orgsnic carbon, &ph&ic hytiarbons, fatty ircidsand a high molecular-weight dissolved polymer (see ~%S~EXBAUX et al., 197233). Prior to snalysis, the sediment was pressure-filteredto remove the interstitial water as desaribed by PBESIAUY et al. (1967). The sediment was extracted sequentially four times as shown in Fig. 1: (i) wet sediment wes extmcted three times with a&Go (0.1 N HCl) beneenemethanol (70:30) using a Virtis Co. Model 43 homogenixerfor a period of 10 min for each extraction (with a solvent to dry sediment ratio of 6). The extra& was then examined for aliphatio hydrocsrbons and fatty voids. Perylene WSBalso identified and the method is described in detail by AIZENSETAT (1972). (ii) The residue from step (if was extracted twice by sh&iug for 10 min with I-ON HCl and vacuum filtered. The extra& was used for studying free amiuo acids. (iii) The residue from (ii) was hydrolyzed with 0 N HCI for 22 hr at 110°C k uac~~, and vw)uum filtered. The hydrolymte was then aualyxedfor amino acids. (iv) Finally, the rem&ing residue was extra&d with O-3N NaOH mtil the extrect wes oolorless. This solution was then used for separation of humic and fulvio acids. The chlorins were extmuted from a rqamte sediment sample with 90% acetone in water using a Virtis homogenixerae previously deeoribed. The acetone wz~ removed from the extract

1188

F. S. BROWN, M. J. BAEDE-,

A.

and I. R. KAPLAN

NIBSENBADM

Sediment

0

Extract 3 times with acidic benzene: Methanol (70-303 Fitte’r

Total lipid extract Aqueous

Eva orate benzene: Met Ronol. Add H&J Extract 3 times with heuane

phase

Residue

Hexane

soluble

3

lipids

(2iHexane: Ether(,,,) (IlHexane r-

Total Urea adduction. hydrocarbons

I !

Fllt;ote

Branched and cyclic hydrocarbons

Filter.

fatty

-7 Aqueous

Adyuct

Total

Extract

twice with

acids 0.1 N NOOH.

j

phase

Hexane~ Ether

phase

“‘p&l; h drocar ‘b ons

Hydrolyzobje’ fatty Aqueous on

OCidS

L

Acidify. Extract w,th helane: Ether (I I).

Hexane:

phase

methyl esters of free

I

Ether

Add methanol to 5%. Esterify ,with CH2N2.

Fig. la. Flow chart of procedures.

IRemove

Salts

-Hydrolyze in 6 N HCI. Filter.

salts with EtOH Fitter

J-l 60%

Amino

Hydrolyzable

acids

8

_

Ninhydrin POS Remove HCI.

Ninh&$”

Discard

NH.,OH. Apply to Dowex I. Elute with HCI.

Humic and fulvic acids $a&t”~;l

Ninhydrin

Nirhydrin

~::,,e

Residue

Remove tkl. Apply to Dowex 50. Elute with NH,OH

Remove EtOH Add t-t20 A ply to Dowex 5 Elute with NH40H.

V Discard

amino acids

Ninhydrin

coIorless. Acidify.

Remove NH,Oi+ A ply to Oowex I. Ekk with HCI.

Solution

Nmhydrin

Hurnic acid

Fulvic acid

Ninhydfin neg.

DlaliZe Lyophylize.

Discard V

.

/Fulvic

and omino acid

Fig. lb. Flow chart of procedures.

Preccitote

acid for

Dissolve in NoOH. Acidify. Redissolve in NoOH. Acidify Diolize and tyophyhze.

Humic acid for If?, chemical onalysis and ~13102 . measurement

Early diageneaia in a reducingfjord, SaanichInlet, BritishColumbia--III

1189

evaporationand the pigm8nti extra&& from the aqueousphase with chloroform. The chloroformextractwasevaporatedto ne8rdrynessand appliedto a florisilo&mm. Elution withchloroformremovedmost of the carotenoidpigmentsand sube8qu8nt elutionwithmethanol mmovedthe chiorins. Quantitativedeterminationof hydrocarbonaand fatty acids was achieved by gas-liquid ohromatographyon a vsriety of stationaryphase.8(sea NISEIXONBAUM et oz., 1972~). Peaks wereassignedon a basicof comparisonof retentiontimeawith knownstandardsand by ooiujection. Individualaminoacids were identifiedon acid and base resim~ of a Beckman12QCautomati amino acid analyzer. Humic acid was purified and weighed in order to obtain its mneantrationin the sediment. ?%lvie acid concentrationwas determinedby oxidizingknown volumesof acid solutionand measuringthe axuountof evolvedCO,. A Gary 15 s~ropho~meter was u88d to measurethe absorbanceof the chlorineat 660nm (HODGSON et a;l.,IQSSe) end peryleneat 440nm (AIZENSETAT, 1972).

by rotary

RESULTS &n&,1 The data presented iu Table 1 show the concentration aud C1s/C1*distribution of the four reservoirs of carbon in the sediments and the interstitial water. Data presented in Part I show core 1 to represent the most oxidizing environment and core 4, the most reduciug. Those two oores and core 3B were studied in the greateet detail and will provide the basis for Bubsequent dissuasion. For comparison, the plankton and the fore& soil samples were put through the same analytical procedures as the sediment samples. The data show Saanich Inlet to be a relatively carbonate-poor environment, with the calculated CWO, concentration reaching a maximum of 6.66% in the lower part of core 3B. The isotopic com~sition rang8s from normal marine carbonate (NY = -2 to +2ym) to CWdepleted carbonate where &Ya = - 11~2%,. Total organic oarbon varies from 1% at the sill station to 5% in core 4 ; the more reduced areaa are rich& in organic carbon. The sill core, 1, aonsi&ently yielded the most negative 88s values for organic carbon (average value, --21*3&J. This may indicate that the sill sediment contains the greatest amount of terrigenous plant material which ia isotopically lighter than the iudigenous planktonic flora, as can be seen by comparing the 8Cla value of the plankton ( - 19*2yW)with that of the forest soil ( -266~&,). The 8Cis values of the basin cores (2,3 and 4) are very similar, and lie in the range of --20*1yW to -20*9y& Exceptions to these valuea are the data &om the lower part of core 3B and from core 4 at 100-l 10 cm depth, which are depleted iu Cls and have values of -21.6 to -22G%,. Sedimentological evidence (Part II) indioate that the samples which are CWdepleted contain a siguificantly higher content of detrital minerals. Introduction of plant and soil organic matter due to flooding in the early Holocene may explain the lighter values in core 3B. Active diagenesie is occurring in the sediment column. This can be seen by the gradual disappearance of sulfate with depth (Part I) and by the increase with depth in ooncentration of the dissolved organic matter (DOM) and dissolved CO, in the interstitial water. The isotopic composition of carbon in the DOM is quit8 constant with depth; with the exception of two values, it varies less than a part per mil from au average of -21*25(/,. This is assumed to be due to the fact that the DOM ia produced from similar source material throughout the sediment column, and is mainly a result of condensation reactions which do not cause isotopic fractionation (NISSE-NBAUM

1190

F. S. Boom,

M. J. BAEDECK~,

A. NISSEXBAUM and I. R. KAPW

et al., 197213). The increase in concentration of the total dissolved carbonate species in cores 1 and 3B is most logically explained by decomposition of organic metter in the sediment. The fact that it is isotopically heavier than the org8nic matter is assumed to be due to methane production by hydrogenation of CO, (TAILU and IcbMuRIL,1966). This process leads to preferential removal of CY*as meth8ne, le8ving the residual CO, enriched in C1s (see Part I). NWVWJhydmcarbolas and fatty a&% The distribution of individual saturated hydrocarbons and free 8hphatic fatty acids is plotted in Fig. 2, where8s other significant d8t8 are presented in Trtbles 2, 3 and 4.

; m B $ .^

I

--

Saturated

n-hydrocarbons

-

Saturated

free fatty

”

acids

30/3445-3475 @\

\

‘\A

\

IO

12

16

w

20

24

28

32

Number of carbon

Fig. 2. Saturated hydrocarbon

12

16 20

24

28

32

atoms per molecule

and free fatty acid abumlames.

Both fatty acids arndhydrocarbons h8ve bimodal distribution: high concentrations in the range of Cl&, 8nd C,, to C,, low concentration in the C&,-C&,region. This is in marked contrast to the distribution of these species in the soil or in the plankton. Whereas, in the former, long chain fatty acids (Xl,) are moat 8bund8nt, Cl, domin8tes in the plankton. No hydrocarbons smaller than C, could be extr8cted from the soil, whereas the plankton had a relatively uniform hydreaarbon distribution from C,, to C,.

Early diagenti Table 2. Analytkl sample

--

ooNdqpth @m)

-

soil Plonkton l/O-16 l/175-185 4/O-16 C/200-210 3B/796-620 3B/1710-1740 3B/2620-2660 3B13450-3480

1191

in a reducing fjord, Sam&h Inlet, British Columbis--fII data for hydrocarbon extra& in sediment, soil and plankton

Total n-psraf%a @pm)

@WJOg

Pri&me (ppmt

30.8 11.4 2.3 7-O 32.7 27.9 28.4 48.4 23.4 11.1

7.2 10.4 08 2.9 14.1 12.0 11.2 14.8 8.6 4.2

0.09 2‘06 0.14 O-61 2.14 1.61 0.63 0.29 0.38 0.09

Phytane

y?

F

(ppmt

- u

049 0.12 Tr. Tr. 0.01 0.00 Tr. 0.00 Tr. Tr.

10.2 0.6 0.7 0.8 0.7 0.3 0.3 0.4 0.0

“OZ? x

V?

ioa

CPIH Ratio

0.6 1.7 5.7 6.1

11.4 1.0 1.6 l-8 2.7

8”:; 14.3 6.7 3.7

3.1 1.3 1.4 1.7 2.3

l-7 1.4 1.1 2.3 2.8 3.2 4.0 4.6 4.8 6.0

CReaee 23-31 21-31 21-27 21-27 21-29 21-29 21-31 21-31 21-31 21-31

-29.

“-24% -26. - 2c -27. -26. -25. -25. -30. --es*

Table 3. Analytical data for free and hydrolyzable fatty acids Hydxolpable

Frw fatty soida Oore/depth @m) 1p15 l/175-186 4/O-15 4/206-210 3l3/790-020 SB/171O-1740 3B/262@-2650 3B/345@-3480 Soil

PhUktOn

Total ,um/lOOg

Total @pm)

&w wn/lOO 13

Total (ppm)

xc.

l-2 3.7 58.6 46.4 32-5 10.5 4.2 3.0

0.4 I-2 20.4 16.6 11.6 3.3 1.4 0.9

2.7 0.9 1.4 0.5 0.3 0.0

0.1 2.6 9.5 7.0 7-O 2.8 1.0 0.9

64.3 407.2

18.2 164.2

1.2 2.1

3.2 18.9

-

6.7 s-4 94.7 50.6 61.5 7.1 30.0 11.4

2.4 * 3E 16.7 18.4 2.8 11.x 3.6

8.3 6.1 6.8 o-4 3.0 0.6

4.2 5.7 l&3 7.7 11.1 2.1 7.8 3.4

-24. -26. -25. -23. -23. -ar. -24.

44.6 394.6

15.8 120.1

6.9 3.7

2.2 14.1

-29. -24.

-24.3 -24.1 -26.6 -24.0 -24.1 -22.9 -Se.9 - 30.2 --eO*l

Total ~m/lOO g

fatty aoida

UnTotal % of naturated orgc x 10’ crm/lOO2

Table 4. Total fatty acids data Sample core/depth (om)

fat:;:, (ppm)

2: Hydrolpable r: Free

4/o-M 4/200-210 3B/799-820 SB/l71~1740 3Bj2620-2660 SB~3450-3480

163.4 97.0 64.0 18.3 34.2 14.4

1.6 0.8 7.6 3.6

Soil. Pllmkton

109.1 711.8

0.8 0.7

CC,,

sat a,,

=G,

8at Cl8 -

1.1 1.2

sat Cl, uneet c,,

sat u,, U-t

(A,

CPI c,,-c,,

1.6 o-9 0.7

2.6 3-l 2-7 I.7 2.1 l-5

22.8 14.0 8.3 194 2.3 11.0

0.7 0.6 0.4 1.2 O-6 0.8

22.1 14.3 7.6 11.2 6.6 3.8

1.1 4.5

7.4 84.6

5.2 2.5

0.1 (0.1

6.1 117.7

0.9

Both the hydrocarbon and fatty scid abundances decrertae with depth, although the hydrocarbons show a much less mmked decrease. The decrease in the quantity of fatty acids with depth is certainly a ~st-devotion effect, as the percentage of fatty &ds reltative to tot& organic aarbon &o de-es. This is in contrast to the hydrocarbon data where the tot&l hydrocarbons decrease slightly with depth but the abundances related to the organio content do not decrease signilicantly.

1192

F. S. BROW, M. J. BAEDEOKER,A. N~sssmmuas aad I. R. Kumx

Biological systems preferentially produce even-numbered fatty aoids, and thus have a relatively high GPI. * Indeed, the plankton sample was measured to have a GPI,, of 117.7. !L’hesediment and soil show a much lower GPI,, which, in the case of the sediment, generally decreases with depth. The GPI data for the hydrocarbons shows similar trends. It is interesting to note that the plankton sample yielded a GPI, of around 1, whereas in the soil a much larger abundance of the odd-carbon hy~c~bo~ were found (GPI-1 l-4). The CPIn is greater than 1 in the sediment, which is probably due to long-chained hydrocarbons of odd-carbon numbers from plant waxes of continental origin. In both the soil and plaukton, free fatty acids are more abundant than the hydrolyzable fatty acids (Tables 3 and 41, whereas the reverse is true for the sediment (the exception being core 3B at 1710-1740 cm). This may indicate that the free fatty acids, which are more reactive, are removed from the sediment through biological and chemical processes, possibly incorporated into kerogen as suggested by HOEBINS and ABELNBN (1965). The free fatty acids may also have been biologic~ly converted by &oxidation to CO, (%m~D et al., 1971). Table 3 clearly shows the fatty acid fractions to be isotopically lighter than that of the total organic carbon. Incorporation of isotopically light material into kerogen may explain why kerogen in ancient rocks is isotopica~y lighter than modern marine organic carbon. Values for the 6GlS in the extracted hydrocarbons (Table 2) are similar to those of the fatty acids; in most cases the hydrocarbons are more depleted in C13. It is generally believed that hydrocarbons are produced in sediments from biological lipids, but how this process occurs is not completely understood. A direct relationship between the abundance of hydrocarbons and fatty acids is not evident. Only in the sediment of core 3B at 1710 cm do the fatty acids show a marked decrease and the hy~ocarbo~s a co~es~n~ increase in concentration. Possible evidence for the conversion of fatty acids to hydrocarbons by decarboxylation (KVENVOLDEN and WEISER, 1967) is provided by the comparison between the changes in abundance of the most abundant fatty acids, C,, and G1swith Cl6 and C,, hy~ocarbons. There is a slight decrease in the C~~~C~s saturated fatty acid values with depth (Table 4) and an increase in the corresponding Gx6/G1,hydrocarbon ratios (Table 2). Although the total fatty acids of recent sediments contain C&/Cx8ratios greater than 1.0 (PARKER1970), the sediment samples from Saanich Inlet have C,,/C,, ratios close to unity. The isotopic and abundance data for fatty acids in the sediment indioate that a, sizable fixction of the fatty acids are derived from plankton. However, Ct&8 ratios of total fatty acids in the plankton is 4.63, whereas in the soil it is l-1 1. * The oarbon preferenceiudex (CPI) is defined by COON and BUY (1963)aad expresses the relative abundance of normal hydrocarbons having odd carbon mu&era to those having even carbon numbers. The following equation is used: cm,

=

Zevenn

22oddta -C,,ton -Cc,, -Cmton -C, + Cevenm -C&,tora

Similarly, CPI’s are calculated for normal fatty acids

(~VENVOLDIICN,

-C,,’

1960)by the equation:

Early diagenesisin a reducing fjord, Saanich Inlet, British Columbia-III

1193

This ratio difference can be explained by (i) contribution of C,, from an additional source, (ii) preferential removal of C,, relative to C,,; or (iii) biological conversion of C,, to C,, acid (WAKIL, 1961). In the Saanich Inlet environment, there are few available sources of lipids that contain C,, as the dominant acid, especially C,, saturated aoid. SHAW(1966) reported that green algae contain large amounts of C,, acids, but probably do not comprise a signitloant portion of the sediment biota. A possible mechanism for removal of C,, from the sediment could be the aforementioned preferential decarboxylation of C,, fatty acid. However, this process cannot entirely explain loss of C,, acid, as the concentration of Cl6 acid lost relative to total carbon in the plankton (0.1 o/0 cell carbon) is far greater than C,, hydrocarbon gained by the sediment (16 x 1O-2% organic carbon). Saturated C,, fatty acids are more abundant than the unsaturated C,, acids in the sediment, soil and plankton. The reverse is true with the C,, acids. Monounsaturated C,, was the only unsaturated acid identified, whereas mono- and polyunsaturated C,, acids were found. A slight increase in saturation with depth is found in the ratios of saturated to unsaturated C,, acids (Table 4) ; the ratio approaching unity. This has also been described by PARKERand LEO (1965) in algal mats, where unsaturated acids found in living mats preferentially disappeared from the dead mats. ABELSON ( 1962) demonstrated the instability and reactivity of polyunsaturated acids by heating algal cells in the absence of oxygen and measuring the fatty acids remaining. Core 1 (the sill core) has a greater concentration of fatty acids at the bottom than at the top of the core (Table 3). The high molecular weight fatty acids are particularly enriched at the bottom, and are probably terrestrially-derived from plant waxes. This is also indicated by the KY5 of the carbonate in this sample which has fresh water values, presumably due to continental contribution (Table 1). Isoprenoid and aromatic hydrocarbons and pigments Quantitative data for isoprenoid hydrocarbons in recent sediments are scant. It is generally believed they are absent or present only in trace amounts in recent marine sediments (HOD~SON,et al., 1968b). The study of CLARKand BLUMER(1967) showed pristane to be present in benthonic and planktonic algae and in one sample of surface marine sediment, whereas phytane could not be detected in the organisms or the ‘sediments studied. The present results largely confirm the above findings. Phytane was detected in low abundance (0.12 ppm, Table 2) in the natural planktonic flora and in trace amounts (O-01 ppm) in the surface sediment of core No. 4, but it was absent or present in insignificant amounts elsewhere in the sediment. Pristane, however, appeared to be the single most abundant hydrocarbon extracted from the planhtonic algae, representing 17.9% of the total identifiable aliphatic hydrocarbons. In the surface sediment of core No. 4, it still represents 6-l y. of total aliphatic hydrocarbons, but its concentration declines with depth. It has been suggested that the isoprenoid hydrocarbons arise from the phytol side chain of chlorophyll. If so, we would expect that the decrease in chlorophyll degradation products with depth would be accompanied by increase in pristane and phytane. Table 5 shows that the chlorins decrease markedly with depth, no parallel increase in isoprenoid hydrocarbons is, however, observed. Therefore, phytane in ancient rocks may arise by a different, or yet unknown, mechanism. Alternatively, the phytol may berapidly complexed and

1194

F. S. BROW,

M. J. BAEDECIKB~~L, A. NISSENBAU~~~ and I. R. UM

inactivated, preventing its rapid conversion to the hydrocarbon during early diagenesis. BL~~;B and SNYDER (1966)suggest that phytol is dehydrated to phytadienes and later hydrogenated to phytaue. Aromatio hydrocarbons are also considered to be iu very low abundance in recent marine sediments (M~Ms~~~zcM,1970).O&R and GUY (1967), however, conclusively demonstrated the presence of the five ring condensed hydrooarbon, perylene, in sediments from the southern California borderland. Thereis some question whether natural submarine petroleum seepages may have contributed a portion of this wtmpound. Such a situation almost certainly does not exist in Saanich Inlet. It is significant to note (Table 6) that the perylene content increases with depth of burial, and in the lowermost sediment (core 3B, 3460-3480 om, Table 5) it reaches a concentration of 2.4 ppm, which is 214% asabundant as the total aliphatia hydrocarbon &&ion. The source material or reactions involved iu perylene production are Table 6. Perylene and ohlorins in Ssanioh sediments CkdOrins

Sample core/depth (cm)

Perylene (ppmf

3-2 2.8 71.1 64.7 63.0 63.2 41.1 14.9 6.4 4.6

1~0-16 l/176-186 0.3

3/o-16 s/60-so

3/m-110 3/190-200 3B~7~820 3B/1710-1740 3B/2620-2660 3B/3460-3480

% 0fOgC x 10%

ppm

0.7 1.7 2.4

2-o 1.9 14.0 11.6 11.4 8.7 4.0 1.4 1.4

The major source for amino aoids in sediments is d~om~tion of proteins either from dead plankters or terrigenous-derived material, or from the indigenous microbial flora of the sediment. In the plankton and soil from the Saaniah Inlet environment, the order of hydrolyxable amino aoid abundance is neutral, acidic, aromatio, Table 6. Distribution and scab of hydrolyzable amino acids sample corelartpth (ma) l/O-M l/176-186 4/O-16 4/100-110 4/200-210 3B[790-820 3E~l71~1740 331262~2060 3B/3460-3430 Soil Plankton

AU&O

B&k Pm 69.2 41.9 337.6 101-o 315.6 317-o 462.3 165.6 73.2 679.7 4114.3

%

PP=

Iveuti %

PPm

%

11.3 19.2 6.2 11.0 7.9 11.3 29.7 19-8 l&S

38.8 6.1 2039.7 181-2 727.0 447.4 354.0 02.6 26-4

7.6 a*3 31-2 19.8 18-l 16-O 23.2 7.5 6.1

367.9 146.1 3699.4 607*0 2376.3 l&%*2 623.1 600‘4 272-o

63.8 67.1 66.1 61.8 69.1 69.2 41-2 69.9 62.9

3-l 6-l

4361.3 19200.1

19-8 2bO

16283.2 43000*0

69-6 66.0

Early diegeneaisin a redwing fjord, Saenich Inlet, Britkh Columbia-III

1196

basic and sulfur containing (T8ble 6). The top of oore 4 hss the same order of abundance, however, the deep cores are different. The greatest relative change occurs in the acidic amino acids (Table 6). Their abundance decreases from 31 per cent of the total amino aoids at the mdace of core 4, to 6 per cent at the bottom of core 3B. On the other hand, basic amino acids increase in concentration from 6% at the surface to 17 per cent of the total amino acids at the bottom of core 3B. Neutral, sromatio and sulfur-containing acids change relatively little with depth During disgenesis (= depth) the overall #n~n~ation of amino a&ls decre8ses by more than one order of magnitude. Free amino aoids were separated during analysis, from those which could be relessed by hydrolysis only. The concentration of free amino acids ~8s found to be very low and usually below the limit of detection (~2.5 ,um/lOOg sediment). In the deeper sediments, conoentr8tion decre8sed rapidly with depth, only sample 17101740 yielded fkee amino acids cozening to 4 per cent of the hydrolyzable amino acids (Table 7). It is possible that the tit extraction with organic solvent removed a portion of the non-hydrolyzable amino acids, and the values should therefore be viewed as minimal only. Diagenetic change in the amino acids is reflected not only by their decrease in ~n~n~~on relative to that of the organ& carbon, but also in the relative abundance of the individual amino acids, shown in Fig. 3. It should be noted that in Fig. 3 sample 100-110 seems to be highly depleted in amino acids. Tbis stlmple, however, only contains about * the organic, carbon content of the surface sample and the apparent anomaly is not as large as it appears. Other anomalous results conneoted with this sample have been described in the text. Glumly and aspartic acids were the most ab~d&~t in the pkkton, soil and surface sediment of core 4; both, however, showed rapid decre8se with depth in the sediment. Isoleucine, aerine and the other neutral acids were very abund8nt in the plankton, but ,%alanine, could not be identified. In the soil, alanine, glycine and proline were the most abundant neutral acids, and /?-alauine wss slso present in the concentration of 39 ppm. The sediment showed ohsracteristics of both the soil and pkkton. Surface sediment had isoleucine and glycine in greatest abodes and no fl-ahnine was detected, whereas in the deep sediment, isoleucine, @sine, leucine, valine, phenylalanine, alanine, glycine and proline were most abundant, following the order given. @lanine was detected in small amounts, 6 ppm. The distribution of (results88 pp~ndry tight

mdimmt and % of totmlamino soids)

Aromatia mm 66.6 21.6 470~6 61-O 63%.6 337.2 61.9 94.6 63.6 1322.3 8114.3

% 10.9 0.9 I:; 1s*a 12.0 4.1 11.3 12.4

* 1X.8

sulfur mm

7.3

Total %

wm

TOW % of orgc

3.0 86.2 6-6 62.7 40.2 26.7 X2.6 7.6

I.4 I.6 1.3 0.7 1.6 I.4 1.8 1.6 I.7

619.8 217*8 6532.4 916.7 4020.1 2798.0 I623*6 836*6 432.6

I.91 0.87 8.24 3.12 3.61 3.66 2.46 I.28 0.76

302.7 1767.1

1.4 2.3

21040*2 76796.8

6.46 21.06

W’S %a -21.9 -22.1 - 10.6

S8Ulpb oore~depth (am)

-10.6 -19.2 -20.6 -21.9 -22.2

l/O-l6 l/176-186 4/O-16 4/100-110 4/200-210 3Bj?90-820 333~1710-1740 3B/2620-2660 3B/3460-SISO

-21.6 -16.8

&oil Phktom

1196

F. S. BBOWN, M. J. B-DECKER, A. NISSENB~TJM and I. R. KAPLAN Table 7. Free and hydrolyzable amino acids in the a&mplesof core 3B Sample (-1

Hydrolyzable amino*

Free amino amidst

Hydrolyzable A.A.

soids (E/M/100g)

(~M~IOQ8)

Free A.A.

790-820 1710-1740 2620-2660 3450-3480

2210 1203 660 342

37 44.6 <2*6
00 27 >264 >I37

Soil Pl&nkton

17337 60660

<2-5 867

>693Ei 70

* Data from amino aoid aualyzer. t Data from ninhyti method [CLAME,19641 (due to smrtllamounts, temples not run on amino aoid analyzer). NEUTRAL AMINO ACIDS

Lrutina

Iwircioe TlwSic4

Srina

Fig. 3. Distribution (ppm) of individual amino aci& in sediment hydrolyze&+.

the amino acidft ie different from that given by RITTE~~ERG et al. (1963) for decomposition in sediments of an oxidizing environment. Isotopioally, the amino acids in the sediment closely reflect the 6CP of the total carbon (within &l~&$ This, however, is not the case for the amino acid data in the plankton or soil. In these samples rXY is isotopically heavier than the total carbon, an effect previously described in algae and plankton (ABELSON and HOERINCI,1961; DEGENS et al., 1968a, 1968b). The close resemblance between isotopic data for the

Early diagenesisin a reducingfjord, Saanioh Inlet, British Columbia-III

1197

amino acids and total sediment carbon, may be added evidenoe that the former are derived from & &ZJ processes, which may cause isotopic exchange and the manufaoture of new compounds.

These oomplex molecules constitute the largest portion of extra&able organic compounds in sediment. Compared to studies undertaken on soil, there have been very few ~v~tigatio~ of these substances in the marine en~nment (RASHIDand KIX~, 1969). Table 8 gives a comparison of some analytical results of humic acid extracted from the forest soil surrounding Saanioh Inlet and humic acid from the sediment. The concentration of carbon and hydrogen in humic acids from both sources is similar, although the ratio C/H is somewhat higher in the sediment samples. The main differences are in the nitrogen, sulfur and oxygen content. Humic acids from soil and nearsurface sediment contain the highest conaentration of nitrogen. Nitrogen decreases with depth in core 4 and 3B, and henoe there is an increase in the C/N ratio. The nature of this loss is not clear, but it may be an important source for the dissolved ammonia found in large concentration in the interstitial water {see Part I). Table 8. Chemical and isotopic composition of hnmie acids [All results on ash-free basis; oxygen determined by differencseJ Core and depth @m)

%C

%H

%N

%S

%O

C/H

C/N

&Pa,&

o-15 176-185

67.0 63.8

&2 5.7

2.6 3.7

8.3

28.3

9.2 9.3

21.5 14.4

-22-l -23.0

6-16 240-250

66.7 56.1

Pi.9 8.7

2-l 3.4

5.9 4.7

29.3 28.7

9.6 8.3

26.1 16.1

-22.0 -21.9

790-820 1710-1740 2620-2660 3466-3480

56.7 64-5 68-3 57.7

6.5 4.7 5.3 5.3

2.5 1.6 1.6 1.4

5.7 6.0 4.0 3.0

29.3 34.1 30-l 32.3

10.2 11.6 9.s IO.7

22.2 33.7 34.6 39.3

-22.4 -23.1 -22.7 -23.4

Soil

55.1

6.2

3.5

0.4

36.4

8.8

15.5

-29.1

No. 1

No. 4

No. 3B

The greatest difference between the soil and the sedimentary humio acids is in their sulfur content. The sediment material contains up to ten times as much sulfur as the soil humic acids. Although it is possible that a portion of the sulfur is not bound to organic matter, but was produced by the action of acids or bases on unstable sulfides, we believe that most, if not all, the sulfur analyzed is part of the humic acid structure. This is based on the fact that some samples were benzene-extracted after precipitation of the humic acid by acid treatment, but no elemental sulfur could be detected in those extracts. The sulfur content decreases with depth of burial, suggesting that the CL-SH bond may be cleaved and sulfur released as SH-. It has generally been assumed that humic acids are derived from the lignins and cellulose derivatives of higher plants (BREWER,1951; KONONOVA,1966). However, the isotopic data shown in Table 8 argue strongly against this terrigenous source as a unique origin. The &F of the sediment humic acids ( - 22+%,,) is considerably heavier

1198

F. S.

BBOWN,M. J. B~DECKIC&, A. NISS~NBMJM and I. R. KAPW

than that of soil humic actid( --29.1%), and falls closer to the bCl* of the total organic carbon in planhton ( --19y&,) than to higher plants or soil humic acids. DEGEXS d d. (1968b) showed that the lignin fraotion of plankton is enriched in C’s by several parts per mil compared to the total organic carbon. Furthermore, algae living in cold water are oapable of preferentially enriobing C*a,and that the lignin &a&on of such algae appear to be depleted in CU by 2 or 3j&, (DEMUXSet al., 1963a). Lower water temperatures iu the early Holocene may, therefore, be responsible for au enrichment of @a in the humio a&l.s of the sediment. Data for humic ac&ls from other msrine environmeuts, also give isotopic results which show a olose correspondence between WP of the humio aoid and plankton, but not to terrestrial plants (NISBIRTBATJM md KAPLAN,1972).

IratemtitiaZwa&r A surprisingly large amount of orgaui~ matter waS found to be dissolved in the interstitial water (Table 1). Mueh of this meter&l is condensed iuto oomplexes of high-molecular weight, whmh would not pass through a dialysis bag. Analysis of this material (NISSENBAUBI et at., 1972b) shows the compounds to be highly enriched iu amino aoid and oerbohydrate groups. Hydrocarbons and fatty acids were extracted from the interstitial waters with beneena. ~~~titial water from near-surface sediment (from core No. 2 ; 215-226 cm) showed a hydrocarbon content iu about the same range as the overlying sea water (7 fig/l.) whereas the content increased three-fold in the deep oores (23 pg/l.). The high moleoular-weight hydrocarbons were most abundant. Frcxl fatty acids, on the other hand, were most ooncentrated iu the nesr-surface sediment (39 &l.) but diminished to 1 pgjl. in the deep sediment (Table 9). Table 9. Hydrooarbons and fatty acids from Saaniah Inlet water and inter&it&J waters Sample (core-depth) No. Zfshallow core 216 cm No. 3B/4 deep cores 800-3600am Sea water 200m

Hydrocarbons f/&u

Free fatty aoids (5%3/l.)

7.3

39-l

22-7

1-o

7.1

o-3

DISUUSSION It is evident fiom data in Table 10, that humic aoids ootitvte the most abundant form of extra&able oarbon in the reduoiug sediment. In the oxidiSing sill sediment, which contained less total carbon, fulvio a&d wss present in grea& abundance. However, whereas the humie a&d abundance showed only a small decrease with depth, the fuIvio aoid demeaned by three- to four-fold. As the eonoeutration of fulvic there is an increase in the oontent of insoluble acid and other components A, remainder, whiuh ohsugeS from 26% of the total oarbon at the surf&~ of oore No. 4

1199

Early disgenesis in a reducingfjord, Swnich Inlet, British Columbia-III

at the base of core 3B. Most of this material would ultimately be converted to kerogen after lithification of the sediment. It is evident from Fig. 4 that the greatest change occurs in decrease of the chlorins, followed by the amino acids and fatty acids. The saturated hydrocarbon concentration does not show a significant trend with depth. In oxidizing sediment, all these components are greatly depleted, even at the very surface (core No. 1). Of particular interest, is the fact that hydrocarbons are not continuously forming as one may expect from the depletion of fatty acids. Only in one core (3B, 17101740 cm) was there any evidence that fatty acids may be transforming into para5s. Further evidence that hydrocarbons do not appear to form under the mild diagenetic conditions of Saanich Inlet, as compared with high temperature and pressure conditions when sediments are buried to large depths, is the decrease in concentration of to 69%

Table 10. Separate components of organic substanceeaa percentage of total organic carbon in the sediment Coreand depth kW

Hydracarbona

Fetty aaids

ChlOrine

Amino soida

Humio acids

Fulvio mi&

Remeinder

l/O-l6 1/1761S6

o-02 0.06

O-06 0.03

0.02 0.02

1.91 o-37

14.3 26-S

23.9 32.9

64-3 40.6

4/O-16 4/20&210 3B/790-020 3B/1710-1740 3B/2620-2660 3B/3460-3490

0.06 O-06 0.07 o-14 o-07 0.01

0.26 O-16 o-13 0.05 o-09 o-04

o-14 o-11 O-OS o-04 0.01 0.01

8.24 3.01 3-65 t-46 l-2.9 0.78

39.9 31-o 3&S 21.3 32-O 31.3

28.3 30.7 26-O 18.7 8-S 3.7

25.1 34.4 33.3 67.3 67.6 69.1

Soil PhktoIl

o-02 o-01

O-06 0.33

6.46 21.06 Amino

~ot”““““““““““““l 0

5

4.

OCU%

15

IO Hydrocarbons,

I’ig.

acids

fotty

acids,

20 and

chlorlnr

OCU%

25

”

0

x IOF

Changes in concentration of hydrocarbons, fatty acids, chlorins and amino acids with depth in cores 4 and 3B.

1200

F. S. Baow~, M. J. BAEDECKEB, A. NISSENBA~M and I. R. W

extrs,cta;bleisoprenoid hydrocarbons. Pristane showed a marked decrease in depth from 2.14 ppm to 0.09 ppm, whereas phytcmne,present in traces at the surface, was undetectable at depth (see Table 2). As the chlorophyll derivatives show more than one hundred-fold decrease with depth of burial to 26 m, it may be assumed that the derivation of these isoprenoid hydrocarbons from the phytol side chain of ohlorophyll does not follow a simple path. It appears, therefore, that the conditions prevailing in a low temperature anaerobic environment alone are insticient to produce significant quantities of hydrocarbon within 10,000 years of accumulation. The conditions are adeqnate, however, for the generation of the aromtltio hydrocarbon, perylene, whioh may inorease in amount with age. Amino acids, among the most abundant recognizable constituents in the surface sediment, decompose readily with depth. This study indic&d that the ecidic amino acids were broken down most rapidly and the basic ones the least. Our data indicate that arginine is the most stable and aspartic acid and serine are the least stable. However, srginine may be synthesized in some sediment layers, possibly as a result of biological activity involving the urea cycle, and decarboxylation of aspartic soid may be responsible for formation of /L&nine whioh could not be isolated from the plankton. Further evidence for diagenetic slteration is the fact that with depth there is an increase in the degree of recemization of the amino acids (KVENVOLDEN et al., 1970). The high concentrstion of polymerized sugars and amino acids in interstitial water suggests that the psthwsy for the transfer of soluble oxygenated and aminorich groups is through complexing in solution. As the high molecular-weight components grow in complexity, a point is reached where they can no longer remain soluble and therefore precipitate out as fulvic and humic acids. Since the fulvic acids beoome depleted down the sediment column, it may be argued that these compounds represent the first stage in oomplexity, followed by conversion to humic acids and insoluble residues. As dehydmtion proceeds during lithificstion, most of the soluble polymer will transfer to humic acids and insoluble residue. Initial alteration in the organic constituents, down to 7 or 10 m, is catalyzed most effectively by microbial fermentation (or respiration in an oxidizing environment). This conclusion is supported by the lsrge concentration of dissolved CO,, NH.,+ and H,S (see Part I) found in the interstitial water. No evidence was found to support the claim that petroleum can form under these diagenetic conditions. Although the sediment is highly organic-rich, hydrocarbons constitute a minute fraction of the organic matter (10-O of the organic carbon). Assuming an average concentration of 30 ppm, one m3 of sediment would contain about 60 g hydrocarbon, the total column of 35 m would contain 2-l kg and Saanich Inlet sediment contains s, total of 30 x 1Oatons of aliphatic hydrocarbons. It is obvious, that for this sediment column to become a potential petroleum source, the rate of hydrocarbon production must increase, allowing, of course, a much longer period of accumulation. The relatively high hydrocarbon content of the deeper interstitial water and the high water content of the sediment add some support to the hypothesis of BAKER (1959) and MEMSCEEIN(1970) that petroleum accumulations may arise from redistribution of the hydrocarbons, possibly through the agency of pore water.

Early diageneaisin a reducingfjord, &a&h

Inlet, British Columbia-III

1201

, o & A Al x

Amino acids Hydrotyzable faffy acids Free fatty odds Hydrocarbons Ha& acids Carbon

Fig. 6. C1a/C1achange in extracted orgenio molecules.

A useful indicator for the source of organic matter is the Cl*/(P ratio. Although several authors have reported data for both living orgaaisxm and sediment orgtio matter (see DEQENS, 1970 for a recent review) documentation has not been as extensive as presented here. Figure 6 indicates that the r&tion&ip of 8C~*of the various groups of organic compounds to each other in the sediment is nearly the mrne aa in the plankton and in the soil extracts. The marine sediment samples, however, yield KP values which fall between the plankton and soil (although most often closest to the plankton). This constitutes ooncrete evidence for a dual origin of the organic matter in the sediment of S&an&h Inlet. At&twwMgemwWe wish to thank Mrs. C. -mow= and Mr. En Ru~fl for sample prepmtion and msss speotroscopicanalysis of carbon compounds; Mrs. N. SAHEL for the amino acid analysis of extra&d compounds, Miss H. KIN0 for elemental @nalysesof the humio wids, Dr. P. W~mum for carbon content of interstitial water polymer and fidvic acids and Dr. 2. Axzmsm~ for analysis of the perylene. The plankton sample wae presentedto us by Dr. T. R. PARSONS (FiiherieaResearch Board, Canada). The soil sample was collected by Mr. ED. Rm (UCLA) in 1988. This project was undertaken by support from an AEC contract No. AT(O43)-34, P.A. 134. ABBCLSON P. II. (1962). Thermal stability of algae. Ccumegie In&. Wash. YemE. 61,179-181. A.muoa P. H. and Homa T. C. (1961). Carbon isotope fractionation in formation of do acids by photosynthetic organisms. Proc. Nat. Acud. Sci. U.S, 47, 023-32. AIZENSETAT Z. (1972). Perylene and its geoohemicalsignifkanae. In preparation, Bm E. G. (1969). Origin and migration of oil. ScienceUQ, 871-874. BL~ M. and 8-m W. D. (1965). Isoprenoid hydrocarbonsin recent sediments: preaenoe of pristane and probable absence of phytane. Soierkw150, 1688-l&$9. 2

1202

F. S. BE~OWN,

M. J. BAEDEIJXER,

A. NISSEXBAUMmd I. R. KAPLAN

BREUNRI. A. (1951). Chemicel and structural relationship of liguin to humic substances. 5%&eE 0,204-203. Clwla~ J. M. (1904). Expevimentd Biochemtitry p. 96. W. F. Freeman C-K R. C. and BLUXNR M. (1967). Distribution of n-par&&s in marine organisms 8nd sediment. Li7nnol.Ooeanogr.I& (I), 79-87. COOPER 3. E. and BRAY E. E. (1963). A post&&d role of fatty 8cids in petrolenm formation. &oc?&n. ~o~~~. A&o fl, 11X5-1127. DEUIENS E. T., GUILLARD R. L., SACS W. M., HXXLEBUST J. A. (1968a). Metabolic fractionation of carbon isotopes in marine plankton Part I. Deep-Sea Rec. 16 L-Q. DE~ENS E. T., BEHRENDT M., GO~~H~~RDT B. 8nd RBSPIYLANN E. (1968b). Metabolic fractionation of carbon isotopes in marine plaslkton, Part II. Deep-Sea Rea. 16, 11-20. DECJENSE. T. (1970). Biogeochemistry of stable oarbon isotopes. In Organic Gochemiut8tpll (editors G. Eglinton and M. T. J. Murphy) pp. 304-329. Springer-Verlsg. GROSSM. G., Guo~Nun S. M., C&A~NB J. S. and DAWSON W. A. (1963). v8rVed IllWiIl8 esdiments in a stagnant fjord. ScienceI#& 913-919. Gua~Nun S. M. and GROSSM. G. (1964). Recent m8rine sediments in Saanich Inlet, 8 stagnant m8rine bssin. firnsol. Oceorwgr.Q, 359-376. HO~USONG. W., HITCHONB., TA~U~HIK., BAKN~B. L. end PEAKXZ E. (19088). Geochemistry of porphyrins, chlorins and polycyolic aromatics in soils, sediments and sedimentary rocks. &o&im. Cowwchim. A&a 88, 737-772. HODUSONG. W., Bm 13.L. and PEAKEE. (1968b). The role of porphyrinsin the geochemistry of petroleum. Proc. 7th Wodd Petrol. Crew. pp. 117-128. HOI+ZR.INU T. C. and A.nNLSON P. H. (1966). Fatty acids from the oxidation of kerogen. Carnegie Is&. Wash. YewB. No. i&218-223. KOLODNYY. and KAPLANI. R. (1972). Deposition of uranium in the sediment and interstitial w8ter of 8n anoxic fjord. PTOC.Int, Symp. on Hyd~ogeochem. and Biogeochem. Tokyo, Japan. In press. KONONOVAM. M. (1966). Soil Organic Matter. 2nd English Edition, pp. x31-142. Pergamon Press. K~PX~OLDENK. (1966). Moleculer distributions of norm81 fatty acids and paraffins in some lower cret8eeonssediments. Nature 80@, 673-637. K~NN~OLDENK. A. rendWrrrsNnD. (1967). A mathematical model of 8 geochemiealprocess: Cosmo&m. Acta 81, 1281-1309. norm81psraflln formation from norm81f8tty scids. urn. K~NNVOLD~NK. A., PNT~~~oNE. and Baowrr F. 5. (lQ?O). Raeemh&ion of 8mino acids in sediments from Saanio-hInlet, British Columbi8. SoienceIfi@, 107Q-1082. McCmr~ J. M. (1960). On the isotopic chemistry of carbonates and 8 paleotemper8turesc8le. J. Chem. Phys. 118,849-887. MEINSCHEIN W. G. (1970). Hydrocsrbon&setur8ted, uns8tur8ted end 8rom8tic. In orgaroic &ochsm&y (editors G. Eglinton and M. T. J. Murphy) pp. 330-366. Springer-Verlag. NISS~NXAUM A., PRESLZXB. J. and KAPLAN 1. R. (19728). Early disgenesis in a reducing fjord, Saanich Inlet, British CohunbitiI. Chemical and isotopic study of interstitial W8ter. #&whim. modern. Acta Se, 1007-1027. NXSSNNEAUX A., BAEDECNN~M. J. 8nd KAPLANI. R. (1972b). Dissolved organic metter from interstitial weter of e reducingfjord. To be published in A&awes in Oqa& C&w&em-, 1971. Paper preaentedat the Qrganic GeochemistryConference; Hanover, Germany, September, 1971. NIS~EN~AUMA., BAEDEOEER M. J. and K.uI,AN I. R. (1972~). Organic geochemistry of Dead See sediments. Ueochim. Coamochim. Acta 86, 709-729. ~ISSLW33AWM A. end KAPUN I. R. (1972). Humic acids, indicators of marine origin for organic compounds. fn prepamtion. ORE W. L. and G-Y J. R. (1967). Perylene in baain sediments off southern California. Ueoc&m. ~0~~~~~. Acta $1, 1201-1209. PARKEX~ P. L. and LEO R. F. (1966). Fetty scids in blue-green 8lg8e m8t community. S&nc.s 148, 373-376.

Early dhgeneaia in 8 reducing fjord, Seenioh Inlet, British Columbia--III

1203

Pm P. L. (1970). Petty acids and alcohols. In Orgo& Gmhetnistly (editors G. Eglinton and M. T. J. Murphy) pp. 367-373. Springer-Verleg. PJSEBIJZY B. J., Bsoous R. R. and KAPPELH. M. (1967). A simple squeezer for removing interstitial water from ocean sediments. J. Mar. &a. IIS,366-367. PsEsm~ B. J., KOLODNYY., NISSENBAUXA. and I. R. KAPLAN (1972). Early di8genesis iu a reducing fjord, Sssnich Inlet, British Cohunbis&lI. Trace elementdistributionin inter&it&l water end sediment. ffeochim. Coemochim.Acta 88, ~073-1090. Rasmn M. A. and KINO L. H. (1BtlB). Moleoular weight distribution meeeurementson humic and fulvia acid fractions from marine clays on the Scoticm shelf. Geochim. Coemoehim.Acta 88, 147-161. REED M. M., E~LINT~N G., D~AFFANG. H. and ENGLANDP. J. (1971). Conversion of oleic acid to s8tur8ted fatty rtcidsin Severn Estuary sediments. Nature 383, 327-330. Rrrzr~~~uno S. C., E=Y K. O., Hasur.r~~~ J., DEOENSE. T., FAY R. C., REUTEB J. H., SON 8. H. end BRAY E. E. (1963). Biogeochemistry of sediments in G-Y J. R., RIexperimental mohole. J. Sed. Pet. 88, 140-172. SEAW R. (1966). Polyuns8tumted fetty scids of micro-orgenisms. Advan. Lipid Res. 4, 107174. Srnm K. M. (1965). Lend-locked weters and the deposition of bleck muds. In Recent Marine Sedimente (editor P. D. Track) pp. 366-372. Am. Assoc. Petrol. Geol. TA.xrArY.8ndKAxun.A T. (1966). The mech8nism of reduction in waterloggedpaddy soil. Polka iKicro&ioZ.(Prague) 11,(4) 304-313. TMSK P. D. (1966). Orga4io content of recent marine sediments. In Recent Marine Sedimente (editor P. D. Tmsk) pp. 423453. Am. Assoo. Petrol. Geol. WAKIL S. J. (lB61). Meahmim of fetty acid synthesis. J. Lipid Rw. 8, l-24.