Calcium carbonate, organic carbon, sediment description and hydrogen and oxygen index at DSDP Sites 93-603, 93-605, 93-604 and 95-603

The organic matter contents of sediments and rocks sampled during DSDP Leg 93 have been characterized by CHN and Rock-Eval analyses. Most samples from Sites 604 and 605 on the New Jersey continental slope and from Site 603 on the Hatteras outer continental rise contained less than 0.5% organic carbon. Some Neogene samples from the slope contained 1 to 2% organic carbon, and Cretaceous samples from the outer rise were as rich as 13.6% organic carbon by weight. Thin layers of black claystones of Santonian, Cenomanian, and Albian age were found interbedded in organiccarbon- lean, bioturbated, turbiditic claystones. Similar layers of turbiditic black marlstones were interspersed among Neocomian limestones and sandstones. Although the organic matter in many of the samples appeared to be detrital continental material, according to Rock-Eval and C/N values, Cenomanian black shales, in particular, contained substantial proportions of marine-derived organic matter.

Calcium carbonate in sediments at DSDP Leg 92

The carbonate contents of sediments recovered at Leg 92 Sites 597, 598, and 601 were determined at 5-cm intervals. The long-term record of carbonate variation at Sites 597 and 598 shows the effect of decreasing dilution by hydrothermal phases as the sites moved away from the ridge crest at which they formed. Superimposed on this trend are high-amplitude variations in carbonate content. In the lower portions of Sites 597 and 598 the high-amplitude variations have a duration of a few hundred thousand years. The upper portion of the sediment column at both sites was deposited below the lysocline, and high-amplitude variations in this interval represent 1 to 2 m.y. The data suggest that only very intense carbonate dissolution events can be identified reliably at sites with low accumulation rates. At sites like Site 598, where the sedimentation rate is higher, the details of carbonate variation can be correlated with the carbonate lithostratigraphies developed for sites in the equatorial and North Pacific oceans.

(Table 1) Total organic carbon, calcium carbonate and nitrogen at DSDP Holes 80-559 and 80-550B

Concentrations of organic and inorganic nitrogen have been measured on Leg 80 sediments. The inorganic nitrogen content is relatively constant, 0.02-0.03 wt.%. Because most of the inorganic nitrogen occurs as NH3 or (NH4)+ fixed on clays, clay-poor sediments have lower inorganic nitrogen contents. Organic nitrogen content depends upon both the type and the quantity of organic matter present. In Leg 80 sediments, woody kerogens contain much less organic nitrogen than do kerogens of algal origin. Furthermore, pelagic samples of low organic carbon content have less organic nitrogen than predicted, because of loss during diagenesis. DSDP shipboard analytical procedures do not distinguish between organic and inorganic nitrogen. Great caution must therefore be exercised in interpreting C/N ratios.

Stable carbon isotope record and geochemistry of late Miocene-early Pliocene sediments from DSDP Site 90-590 in the Tasman Sea

Biogenic components of sediment accumulated at high rates beneath frontal zones of the Indian and Pacific oceans during the late Miocene and early Pliocene. The delta13C of bulk and foraminiferal carbonate also decreased during this time interval. Although the two observations may be causally linked, and signify a major perturbation in global biogeochemical cycling, no site beneath a frontal zone has independent records of export production and delta13C on multiple carbonate phases across the critical interval of interest. Deep Sea Drilling Project (DSDP) site 590 lies beneath the Tasman Front (TF), an eddy-generating jetstream in the southwest Pacific Ocean. To complement previous delta13C records of planktic and benthic foraminifera at this location, late Neogene records of CaCO3 mass accumulation rate (MAR), Ca/Ti, Ba/Ti, Al/Ti, and of bulk carbonate and foraminiferal delta13C were constructed at site 590. The delta13C records include bulk sediment, bulk sediment fractions (<63 µm and 5-25 µm), and the planktic foraminifera Globigerina bulloides, Globigerinoides sacculifer (with and without sac), and Orbulina universa. Using current time scales, CaCO3 MARs, Ca/Ti, Al/Ti and Ba/Ti ratios are two to three times higher in upper Miocene and lower Pliocene sediment relative to overlying and underlying units. A significant decrease also occurs in all delta13C records. All evidence indicates that enhanced export production - the 'biogenic bloom' - extended to the southwest Pacific Ocean between ca. 9 and 3.8 Ma, and this phenomenon is coupled with changes in delta13C - the 'Chron C3AR carbon shift'. However, CaCO3 MARs peak ca. 5 Ma whereas elemental ratios are highest ca. 6.5 Ma; foraminiferal delta13C starts to decrease ca. 8 Ma whereas bulk carbonate delta13C begins to drop ca. 5.6 Ma. Temporal discrepancies between the records can be explained by changes in the upwelling regime at the TF, perhaps signifying a link between changes in ocean-atmosphere circulation change and widespread primary productivity.

Organic geochemistry at DSDP Leg 80 Holes

The four sites drilled on the Irish continental margin (Goban Spur) yielded sediments ranging in age from Holocene to Barremian. Most of the sediments were deposited in well oxygenated waters, and the small amounts of organic matter they contain are highly oxidized. During a few time intervals from the Cenomanian to earliest Turonian, however, the oxygen content of the bottom waters reached very low levels, resulting in the deposition of homogeneous or laminated black sediments containing from 0.5 to 11% total organic carbon (TOC). The original organic matter was of mixed marine and terrestrial origin. The oxidizing-reducing cycles represented by interbedded black and light sediments are probably a result of changes in both circulation and productivity. The black sediments at Sites 550, 551, and 549 were probably deposited near the lower end, middle, and upper end, respectively, of an expanded oxygen-minimum layer. The oil and gas source potential of the laminated black sediments is very good to excellent. The organic-carbon-lean sediments deposited under oxidizing conditions have no oil or gas source potential. The thermal maturity of all sediments is low.

(Table 1) Bulk carbonate content of ODP Hole 194-1198A sediments, east of the Great Barrier Reef

Upper Quaternary sediment sequences east of the Great Barrier Reef are characterized by alternating siliciclastic- and carbonate-rich horizons caused by changes in the input of various sedimentary components and reflected in cores by variations in bulk carbonate content. A total of 153 measurements of bulk carbonate content were determined using the carbonate-bomb technique for late Pleistocene sediments between 0 and 23.69 meters below sea floor (mbsf) in Ocean Drilling Program Hole 1198A. Average sample resolution was 15 cm and multiple analyses were performed on each sample. Bulk carbonate content ranges from a maximum of 94 wt% at 13.63 mbsf to a minimum of 73 wt% at 14.54 mbsf. Five cyclic trends are observed that may relate to five major glacial events during the last 500 k.y. of the Quaternary.

(Appendix) Grain-size distribution, calcium carbonate content and proportion of cemented aggregates in ODP Site 133-820

The textural and compositional characteristics of the 400 m sequence of Pleistocene wackestones and packstones intersected at Ocean Drilling Program (ODP) Site 820 reflect deposition controlled by fluctuations in sea-level, and by variations in the rate of sediment supply. The development of an effective reefal barrier adjacent to Site 820, between 760 k.y. and 1.01 Ma, resulted in a marked reduction in sediment accumulation rates on the central Great Barrier Reef outermost shelf and upper slope. This marked change corresponds with the transition from sigmoidal prograding seismic geometry in the lower 254 m of the sequence, to aggradational geometry in the top 146 m. The reduction in the rate of sediment accumulation that followed development of the reefal barrier also caused a fundamental change in the way in which fluctuations in sea-level controlled sediment deposition. In the lower, progradational portion of the sequence, sea-level cyclicity is represented by superimposed coarsening-upward cycles. Although moderately calcareous throughout (mostly 35%-75% CaCO3), the depositional system acted in a similar manner to siliciclastic shelf depositional systems. Relative sea-level rises resulted in deposition of more condensed, less calcareous, fine, muddy wackestones at the base of each cycle. Sea-level highstands resulted in increased sedimentation rates and greater influx of coarse bioclastic material. Continued high rates of sedimentation of both coarse bioclastic material and mixed carbonate and terrigenous mud marked falling and low sea-levels. This lower part of the sequence therefore is dominated by coarse packstones, with only thin wackestone intervals representing transgressions. In contrast, sea-level fluctuations following formation of an effective reefal barrier produced a markedly different sedimentary record. The more slowly deposited aggradational sequence is characterized by discrete thin interbeds of relatively coarse packstone within a predominantly fine wackestone sequence. These thin packstone beds resulted from relatively low sedimentation rates during falling and low sea-levels, with much higher rates of muddy sediment accumulation during rising and high sea-levels. The transition from progradational to aggradational sequence geometry therefore corresponds to a transition from a "siliciclastic-type" to a "carbonate-type" depositional system.

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