Calcium carbonate concentrations of ODP Sites 113-689 and 113-690

An almost continuous Upper Cretaceous through Pleistocene biogenic sediment section was recovered from two sites on Maud Rise, a volcanic edifice in the Weddell Sea, off eastern Antarctica. Calcium carbonate values were determined for 1100 closely spaced samples using a Coulometrics CO2 Coulometer. Following a very brief decrease in the percentage of calcium carbonate immediately above the Cretaceous/Tertiary boundary, values remain high (~70%-80%), throughout most of the Paleocene, with variations primarily attributed to changes in the relative abundance of terrigenous and biogenic components. A small general decrease in calcium carbonate is observed from the upper Paleocene to lower middle Eocene. Eocene values continue to show small to moderate fluctuations. These fluctuations become more pronounced in the Oligocene as biosiliceous and carbonate sediments are mixed and interlayered. A distinct decrease in the calcium carbonate component is observed in the upper Oligocene through lower middle Miocene. Calcium carbonate becomes dominant again in the middle and lower upper Miocene, followed by almost exclusive biosiliceous sedimentation until the Pleistocene, where foraminifer-dominated calcareous ooze was recovered. Interpretation of this data will be carried out when a more finalized chronostratigraphy for the sequence has been produced.

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.

Granulometry, calcium carbonate content and radiocarbon ages of soil profiles obtained in Quinghai Province, northeast Tibet

Colluvial deposits consisting of silts and loams were detected in several climatologically different areas of NE Tibet (3200-3700 m a.s.l.). Layering, distinct organic content and low content of coarse matter as well as location in the relief revealed an origin from low-energy slope erosion (hillwash). Underlying and intercalated paleosols were classified as Chernozems, Phaeozems, Regosols and Fluvisols. Fifteen radiocarbon datings predominant on charcoal from both colluvial layers and paleosols yielded ages between 8988 ± 66 and 3512 ± 56 uncal BP. Natural or anthropogenic factors could have been the triggers of the erosional processes derived. It remains unclear which reason was mainly responsible, due to controversial paleoclimatic and geomorphic records as well as insufficient archaeological knowledge from this region. Determinations of charcoal and fossil wood revealed the Holocene occurrence of tree species (spruce, juniper) for areas which nowadays have no trees or only few forest islands. Thus large areas of NE Tibet which are at present steppes and alpine pastures were forested in the past.

(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.

Calcium carbonate global LGM Burial rate data

Global databases of calcium carbonate concentrations and mass accumulation rates in Holocene and last glacial maximum sediments were used to estimate the deep-sea sedimentary calcium carbonate burial rate during these two time intervals. Sparse calcite mass accumulation rate data were extrapolated across regions of varying calcium carbonate concentration using a gridded map of calcium carbonate concentrations and the assumption that accumulation of noncarbonate material is uncorrelated with calcite concentration within some geographical region. Mean noncarbonate accumulation rates were estimated within each of nine regions, determined by the distribution and nature of the accumulation rate data. For core-top sediments the regions of reasonable data coverage encompass 67% of the high-calcite (>75%) sediments globally, and within these regions we estimate an accumulation rate of 55.9 ± 3.6 x 10**11 mol/yr. The same regions cover 48% of glacial high-CaCO3 sediments (the smaller fraction is due to a shift of calcite deposition to the poorly sampled South Pacific) and total 44.1 ± 6.0 x 10**11 mol/yr. Projecting both estimates to 100 % coverage yields accumulation estimates of 8.3 x 10**12 mol/yr today and 9.2 x 10**12 mol/yr during glacial time. This is little better than a guess given the incomplete data coverage, but it suggests that glacial deep sea calcite burial rate was probably not considerably faster than today in spite of a presumed decrease in shallow water burial during glacial time.

Calcium carbonate preservation in the equatorial Pacific

The Pliocene-Pleistocene history of CaCO3 preservation in the central equatorial Pacific is reconstructed from a suite of deep-sea cores and is compared to fluctuations in global ice volume inferred from delta18O records. The results are highlighted by: (1) a strong covariation between CaCO3 preservation and ice volume over 104 to 106 year time scales; (2) a long-term increase in ice volume and CaCO3 preservation since 3.9 Ma demonstrated by a deepening of the lysocline and the carbonate critical depth; (3) a dramatic shift to greater CaCO3 preservation at 2.9 Ma; (4) distinctive ice-volume growth and CaCO3 preservation events at 2.4 Ma, which are associated with the significant intensification of northern hemisphere glaciation; (5) a mid-Pleistocene transition to 100-kyr cyclicity in both CaCO3 preservation and ice volume; and (6) a 600-kyr Brunhes dissolution cycle superimposed on the late Pleistocene glacial/interglacial 100-kyr cycles. CaCO3 preservation primarily reflects the carbonate chemistry of abyssal waters and is controlled by long-term (106 year) and short-term (104 to 105 year) biogeochemical cycling and by distinct paleoclimatic events. We attribute the long-term increase in CaCO3 preservation primarily to a fractionation of CaCO3 deposition from continental shelf to ocean basin, and secondarily to a gradual rise in the riverine and glaciofluvial flux of Ca++. On shorter time scales, the fluctuations in CaCO3 preservation slightly lag ice volume fluctuations and are attributed to climatically induced changes in the circulation and chemistry of Pacific deep water.

(Table T1) Geochemistry of calcium carbonate veins from ODP Holes 206-1256C and 206-1256D

Drilling a complete deep crustal section has been a primary yet elusive goal since the inception of scientific ocean drilling. In situ ocean crustal sections would contribute enormously to our understanding of the formation and subsequent evolution of the ocean crust, in particular the interplay between magmatic, hydrothermal, and tectonic processes. Ocean Drilling Program (ODP) Leg 206 was the first of a multileg project to drill an in situ crustal section that penetrated the gabbroic rocks of the Cocos plate (6°44.2'N, 91°56.1'W), which formed ~15 m.y. ago on the East Pacific Rise during a period of superfast spreading (>200 mm/yr) (Wilson, Teagle, Acton, et al., 2003, doi:10.2973/odp.proc.ir.206.2003). During Leg 206, the upper 500 m of basement was cored in Holes 1256C and 1256D with moderate to high recovery rates. The igneous rocks recovered are predominantly thin (10 cm to 3 m) basalt flows separated by chilled margins. There are also several massive flows (>3 m thick), although their abundance decreases with depth in Hole 1256D, as well as minor pillow basalts, hyaloclastites, and rare dikes. The lavas have been slightly (<10%) altered by low-temperature hydrothermal fluids, which resulted in pervasive dark gray background alteration and precipitation of saponite, pyrite, silica, celadonite, and calcium carbonate veins. Here we present a geochemical analysis of the CaCO3 recovered from cores. The compositions of ridge flank fluids within superfast spreading crust will be determined from these data, following the approach of Hart et al. (1994, doi:10.1029/93JB02035), Yatabe et al. (2000, doi:10.2973/odp.proc.sr.168.003.2000), and Coggon et al. (2004, doi:10.1016/S0012-821X(03)00697-6).

(Table 1) Calcium carbonate and trace elements at DSDP Leg 80 Holes

The evolution through time of trace element contents (Sr, Mg, Mn, and Fe) of sediments at Sites 549 and 550 is similar to that of previously studied oceanic sites. A comparison with some North Atlantic sites and with outcrops of the Gubbio section (Italy) allowed us to show that 1. A negative correlation between Sr and Mg contents, generally characteristic of pelagic carbonate having undergone diagenesis, is confirmed. 2. Magnesium diagenesis occurs over a relatively short time and is sensitive to the sedimentation rate of each individual time period, whereas Sr diagenesis is a long-term phenomenon and is sensitive to the overall average sedimentation rate at the site. Strontium loss by sediments is related to sediment age (i.e., residence time of sediments in a given diagenetic environment) and could be a rough method of dating individual sediment layers. 3. The nature of the seafloor (oceanic or continental) does not appear to play an important part in the content of Fe and Mn in sediments. Their distribution depends more on mid-oceanic ridge activity, paleodepth (through mediation of CaCO3 dissolution and environment), and distance of the site from the ridge.

(Table 1) Uranium and Thorium concentrations, activity ratios and calcium carbonate content of DSDP Site 54-424

The geochemical behaviour of uranium and thorium in metalliferous sediments and hydrothermal deposits has been widely studied and the main results have been summarised by Boström and Rydell. These isotopes may be used to clarify how the metal-rich solutions are introduced into sediment cover and seawater. Using radiochemistry followed by alpha spectrometry, we have measured uranium concentrations as high as several hundred p.p.m., which must clearly be associated with ocean ridge thermal activity, in sediments interbedded between the basaltic basement and the green hydrothermal mud at DSDP Site 424. These high uranium concentrations indicate the path followed by the hydrothermal fluid which, debouching at the sediment-water interface, formed the green mud.

Stable isotope (carbonates), organic carbon, calcium carbonate and occurrence of coccoliths at DSDP Hole 71-511

Thin but discrete pelagic limestone beds intercalated among the black mudstones near the top of the extensive Mesozoic black shale sequence of the Falkland Plateau are reminiscent of similar occurrences in the central and North Atlantic and may be cyclic in nature. They have been studied via carbonate, organic carbon, stable isotope, nannofloral, and ultrastructural analysis in an attempt to determine their mode of origin. Nannofossil diversity and preservation suggest that selective dissolution or diagenesis did not produce the interbedded coccolith-rich and coccolith-poor layers, nor did blooms of opportunistic species play a role. Stable isotope measurements of carbonate do not adequately constrain the origin of the cyclicity; however, the d13C data suggest that the more nannofossil-rich intervals may be due to higher nutrient supply and overturn of deeper waters at the site rather than influxes of well-oxygenated waters into an otherwise anoxic environment. Such an explanation is in accord with the nannofloral evidence

Stable-isotopes and calcium carbonate at DSDP Hole 73-524

This paper presents a compilation of stable-isotope and percentage-of-carbonate data for the Upper Cretaceous/ lower Tertiary hemipelagic sediments from DSDP Leg 73, Site 524.

Organic carbon and calcium carbonate concentrations of K/T boundary samples from southern Tethyan margin location (Table 1)

Regional consequences of the biotic extinctions and of the changes in biological productivity that occurred at the time of the Cretaceous/Tertiary (K/T) boundary were investigated by comparison of organic matter in sediments from three southern Tethyan margin locations. Organic matter characterization comprised Rock-Eval pyrolysis and organic carbon measurements. Low concentrations of organic matter precluded additional detailed determinations. At all three locations, the organic matter has been microbially reworked and evidently was deposited in oxygenated marine environments.