Calcium carbonate content in surface sediments and benthic fauna on Antarctic shelves

We analyzed 214 new core-top samples for their CaCO3 content from shelves all around Antarctica in order to understand their distribution and contribution to the marine carbon cycle. The distribution of sedimentary CaCO3 on the Antarctic shelves is connected to environmental parameters where we considered water depth, width of the shelf, sea-ice coverage and primary production. While CaCO3 contents of surface sediments are usually low, high(> 15%) CaCO3 contents occur at shallow water depths (150-200 m) on narrow shelves of the eastern Weddell Sea and at a depth range of 600-900 m on the broader and deeper shelves of the Amundsen, Bellingshausen and western Weddell Seas. Regions with high primary production, such as the Ross Sea and the western Antarctic Peninsula region, have generally low CaCO3 contents in the surface sediments. The predominant mineral phase of CaCO3 on the Antarctic shelves is low-magnesium calcite. With respect to ocean acidification, our findings suggest that dissolution of carbonates in Antarctic shelf sediments may be an important negative feedback only after the onset of calcite undersaturation on the Antarctic shelves. Macrozoobenthic CaCO3 standing stocks do not increase the CaCO3 budget significantly as they are two orders of magnitude lower than the budget of the sediments. This first circumpolar compilation of Antarctic shelf carbonate data does not claim to be complete. Future studies are encouraged and needed to fill data gaps especially in the under-sampled southwest Pacific and Indian Ocean sectors of the Southern Ocean.

Trace element concentrations and Li isotope composition in DSDP and ODP sediments from island arcs

We have studied the sedimentary and basaltic inputs of lithium to subduction zones. Various sediments from DSDP and ODP drill cores in front of the Mariana, South Sandwich, Banda, East Sunda and Lesser Antilles island arcs have been analysed and show highly variable Li contents and d7Li values. The sediment piles in front of the Mariana and South Sandwich arcs largely consist of pelagic sediments (clays and oozes). The pelagic clays have high Li contents (up to 57.3 ppm) and Li isotope compositions ranging from +1.3? to +4.1?. The oozes have lower Li contents (7.3-16 ppm) with d7Li values of the diatom oozes from the South Sandwich lower (+2.8? to +3.2?) than those of the radiolarian oozes from the Mariana arc (+8.1? to +14.5?). Mariana sediment also contains a significant portion of volcanogenic material, which is characterised by a moderate Li content (14 ppm) and a relatively heavy isotope composition (+6.4?). Sediments from the Banda and Lesser Antilles contain considerable amounts of continental detritus, and have high Li contents (up to 74.3 ppm) and low d7Li values (around 0?), caused by weathering of continental bedrock. East Sunda sediments largely consist of calcareous oozes. These carbonate sediments display intermediate to high Li contents (2.4-41.9 ppm) and highly variable d7Li values (-1.6? to +12.8?). Basaltic oceanic crust samples from worldwide DSDP and ODP drill cores are characterised by enrichment of Li compared to fresh MORB (6.6-33.1 vs. 3.6-7.5 ppm, respectively), and show a large range in Li isotope compositions (+1.7? to +11.8?). The elemental and isotopic enrichment of Li in altered basalts is due to the uptake of isotopically heavy seawater Li during weathering. However, old oceanic crust samples from Sites 417/418 exhibit lighter Li isotope compositions compared to young basaltic crust samples from Sites 332B and 504B. This lighter Li isotope signature in old crust is unexpected and further research is needed to explore this issue.

Calcareous nannofossil abundance in ODP Site 185-1149 sediments

Basal carbonate sediments recovered at Ocean Drilling Program (ODP) Site 1149 lie directly on magnetic Anomaly M12. They contain abundant and moderately well preserved calcareous nannofossils. Two nannofossil zones are recognized: the lower Calcicalathina oblongata Zone and the upper Lithraphidites bollii Zone, indicating a late Valanginian-late Hauterivian age. The close occurrence of two significant bioevents, the first occurrence (FO) of L. bollii and the FO of Rucinolithus terebrodentarius in Core 185-1149B-20R, together with dip data recorded during in situ geophysical logging, suggest the presence of an unconformity that corresponds to the lower Hauterivian sedimentary section. The continuous occurrence of L. bollii is reported for the first time in sediments from the Pacific Ocean. Other marker species regarded as cosmopolitan (e.g., C. oblongata) have a sporadic occurrence. Nannoconids, very useful zonal markers for Tethyan areas, are virtually absent. The presence of an unusually high abundance of Diazomatolithus lehmanii is also recorded and correlates with the Valanginian 13C positive excursion.

Chemical and Sr isotopic compositions of 3 step leachates and residues of bulk samples, zeolites, and smectites from Lower Miocene sediments at ODP Site 166-1007

Massive clinoptilolite authigenesis was observed at about 1105 meters below sea floor (mbsf) in lower Miocene wellcompacted carbonate periplatform sediments from the Great Bahama Bank [Ocean Drilling Program, ODP Leg 166, Site 1007]. The diagenetic assemblage comprises abundant zeolite crystallized within foraminifer tests and sedimentary matrix, as well as Mg smectites. In carbonate-rich deposits, the formation of the zeolite requires a supply of silica. Thus, the objective of the study is to determine the origin of the silica supply, its diagenetic evolution, and consequently the related implications on interpretation of the sedimentary record, in terms of local or global paleoceanographic change. For lack of evidence for any volcaniclastic input or traces of Si-enriched deep fluids circulation, an in situ biogenic source of silica is validated by isotopic data and chemical modeling for the formation of such secondary minerals in shallow-water carbonate sequences. Geochemical and strontium isotopic data clearly establish the marine signature of the diagenetic zeolite, as well as its contemporaneous formation with the carbonate deposition (Sr model ages of 19.6-23.2 Ma). The test of saturation for the pore fluids specifies the equilibrium state of the present mineralogical assemblage. Seawater-rock modeling specifies that clinoptilolite precipitates from the dissolution of biogenic silica, which reacts with clay minerals. The amount of silica (opal-A) involved in the reaction has to be significant enough, at least 10 wt.%, to account for the observed content of clinoptilolite occurring at the most zeolite-rich level. Modeling also shows that the observed amount of clinoptilolite (~19%) reflects an in situ and short-term reaction due to the high reactivity of primary biogenic silica (opal-A) until its complete depletion. The episodic occurrence of these well-lithified zeolite-rich levels is consistent with the occurrence of seismic reflectors, particularly the P2 seismic sequence boundary located at 1115 mbsf depth and dated as 23.2 Ma. The age range of most zeolitic sedimentary levels (biostratigraphic ages of 21.5-22 Ma) correlates well with that of the early Miocene glaciation Mi-1 and Mi-1a global events. Thus, the clinoptilolite occurrence in the shallow carbonate platform environment far from volcanogenic supply, or in other sensitive marine areas, is potentially a significant new proxy for paleoproductivity and oceanic global events, such as the Miocene events, which are usually recognized in deep-sea pelagic sediments and high latitude deposits.

Composition of sediment pore water and isotopes in carbonate and benthic foraminifera at DSDP Holes 68-501, 69-505 and Site 69-504

Two sites on the southern flank of the Costa Rica Rift were drilled on DSDP Legs 68 and 69, one on crust 3.9 m.y. old and the other on crust 5.9 m.y. old. The basement of the younger site is effectively cooled by the circulation of seawater. The basement of the older site has been sealed by sediment, and an interval in the uppermost 560 meters of basement recently reheated to temperatures of 60 to 120°C. Although the thickness of the sediments at the two sites is similar (150-240 m versus 270 m), the much rougher basement topography at the younger Site 505 produces occasional basement outcrops, through which 80 to 90% of the total heat loss apparently occurs by advection of warm seawater. This seawater has been heated only slightly, however; the temperature at the base of the sediments is only 9°C. Changes in its composition due to reaction with the basement basalts are negligible, as indicated by profiles of sediment pore water chemistry. Bacterial sulfate reduction in the sediments produces a decrease in SO4 (and Ca) and an increase in alkalinity (and Sr and NH3) as depth increases to an intermediate level, but at deeper levels these trends reverse, and all of these species plus Mg, K, Na, and chlorinity approach seawater values near basement. Si, however, is higher, and Li may be lower. At the older site, Site 501/504, where heat loss is entirely by conduction, the temperature at the sediment/basement contact is 59°C. Sediment pore water chemistry is heavily affected by reaction with the basaltic basement, as indicated by large decreases in d18O, Mg, alkalinity, Na, and K and an increase in Ca with increasing depth. The size of the changes in d18O, Mg, alkalinity, Ca, Sr, and SO4 varies laterally over 500 meters, indicating lateral gradients in pore water chemistry that are nearly as large as the vertical gradients. The lateral gradients are believed to result from similar lateral gradients in the composition of the basement formation water, which propagate upward through the sediments by diffusion. A model of the d18O profile suggests that the basement at Site 501/504 was sealed off from advection about 1 m.y. ago, so that reaction rates began to dominate the basement pore water chemistry. A limestone-chert diagenetic front began to move upward through the lower sediments less than 200,000 yr. ago.

Accumulation rates of sediments and main sedimentary components in ODP Leg 121 holes on Broken Ridge

Broken Ridge, in the eastern Indian Ocean,is overlain by about 1600 m of middle Cretaceous to Pleistocene tuffaceous and carbonate sediments that record the oceanographic history of southern hemisphere mid-to high-latitude regions. Prior to about 42 Ma, Broken Ridge formed the northern part of the broad Kerguelen-Broken Ridge Plateau. During the middle Eocene, this feature was split by the newly forming Southeast Indian Ocean Ridge; since then, Broken Ridge has drifted north from about 55° to 31°S. The lower part of the sedimentary section is characterized by Turonian to Santonian tuffs that contain abundant glauconite and some carbonate. The tuffs record a large but apparently local volcanic input that characterized the central part of Broken Ridge into the early Tertiary. Maestrichtian shallow-water(several hundred to 1000 m depth) limestones and cherts accumulated at some of the highest rates ever documented from the open ocean, 4 to 5 g/cm**2/kyr. A complete (with all biostratigraphic zones) Cretaceous-Tertiary boundary section was recovered from site 752. The first 1.5 m.y. of the Tertiary is characterized by an order-of-magnitude reduction in the flux of biogenic sediments, indicating a period of sharply reduced biological productivity at 55°S, following which the carbonate and silica sedimentation rates almost reach the previous high values of the latest Cretaceous. We recovered a complete section through the Paleocene that contains all major fossil groups and is more than 300 m thick, perhaps the best pelagic Paleocene section encountered in ocean drilling. About 42 Ma, Broken Ridge was uplifted 2500 m in response to the intra-plateau rifting event; subsequent erosion and deposition has resulted in a prominent Eocene angular unconformity atop the ridge. An Oligocene disconformity characterized by a widespread pebble layer probably represents the 30 Ma sea-level fall. The Neogene pelagic ooze on Broken Ridge has been winnowed, and thus its grain size provides a direct physical record of the energy of the southern hemisphere drift current in the Indian Ocean for the past 30 m.y.

Chemical composition of interstitial solutions from sediments of DSDP Legs 6-8, 11, 12, 14, 15, and 22

Through the Deep Sea Drilling Project samples of interstitial solutions of deeply buried marine sediments throughout the World Ocean have been obtained and analyzed. The studies have shown that in all but the most slowly deposited sediments pore fluids exhibit changes in composition upon burial. These changes can be grouped into a few consistent patterns that facilitate identification of the diagenetic reactions occurring in the sediments. Pelagic clays and slowly deposited (<1 cm/1000 yr) biogenic sediments are the only types that exhibit little evidence of reaction in the pore waters. In most biogenic sediments sea water undergoes considerable alteration. In sediments deposited at rates up to a few cm/1000 yr the changes chiefly involve gains of Ca(2+) and Sr(2+) and losses of Mg(2+) which balance the Ca(2+) enrichment. The Ca-Mg substitution may often reach 30 mM/kg while Sr(2+) may be enriched 15-fold over sea water. These changes reflect recrystallization of biogenic calcite and the substitution of Mg(2+) for Ca(2+) during this reaction. The Ca-Mg-carbonate formed is most likely a dolomitic phase. A related but more complex pattern is found in carbonate sediments deposited at somewhat greater rates. Ca(2+) and Sr(2+) enrichment is again characteristic, but Mg(2+) losses exceed Ca(2+) gains with the excess being balanced by SO4(post staggered 2-) losses. The data indicate that the reactions are similar to those noted above, except that the Ca(2+) released is not kept in solution but is precipitated by the HCO3(post staggered -) produced in SO4(post staggered 2-) reduction. In both these types of pore waters Na(+) is usually conservative, but K(+) depletions are frequent. In several partly consolidated sediment sections approaching igneous basement contact, very marked interstitial calcium enrichment has been found (to 5.5 g/kg). These phenomena are marked by pronounced depletion in Na(+), Si and CO2, and slight enhancement in Cl(-). The changes are attributed to exchange of Na(+) for Ca(2+) in silicate minerals forming from submarine weathering of igneous rocks such as basalts. Water is also consumed in these reactions, accounting for minor increases in total interstitial salinity. Terrigenous, organic-rich sediments deposited rapidly along continental margins also exhibit significant evidences of alteration. Microbial reactions involving organic matter lead to complete removal of SO4(post staggered 2-), strong HCO3(post staggered -) enrichment, formation of NH4(post staggered +), and methane synthesis from H2 and CO2 once SO4(post staggered 2-) is eliminated. K+ and often Na+ (slightly) are depleted in the interstitial waters. Ca(2+) depletion may occur owing to precipitation of CaCO3. In most cases interstitial Cl- remains relatively constant, but increases are noted over evaporitic strata, and decreases in interstitial Cl- are observed in some sediments adjacent to continents.

Calcium carbonate mineralogy and stable isotopic composition of Leg 182 sites, Great Australian Bight

An intensive stable isotopic investigation was conducted on sediments recovered from the Great Australian Bight during Ocean Drilling Program Leg 182 at Sites 1127, 1129, and 1131. The sites comprise a transect from the shelf edge to upper slope through a thick sequence of predominately Quaternary cool-water carbonate sediments. Detailed mineralogic and stable isotopic (d18O and d13C) analyses of sediments from a total of 306 samples are presented from all three sites.

Calcium carbonate and trace element composition of ODP Leg 182 sites

An intensive geochemical investigation was conducted on carbonate sediments recovered during Ocean Drilling Program Leg 182. Four trace elements in 635 sediment samples from Sites 1126-1132 on the Great Australian Bight were examined by atomic absorption spectrometry on the acid-soluble fraction. Downhole profiles of these elements exhibit complicated fluctuations throughout the late Eocene to Pleistocene, principally because of the variations in the acid-soluble fraction. The purpose of this study is to present initial results on the geochemical composition of Cenozoic cool-water carbonates as a basis for a future detailed investigation to determine the paleoenvironment of a carbonate-dominated continental margin during the evolution of the Southern Ocean.

Grain size investigations of sediments off the coast of Istria

Composition, grain-size distribution, and areal extent of Recent sediments from the Northern Adriatic Sea along the Istrian coast have been studied. Thirty one stations in four sections vertical to the coast were investigated; for comparison 58 samples from five small bays were also analyzed. Biogenic carbonate sediments are deposited on the shallow North Adriatic shelf off the Istrian coast. Only at a greater distance from the coast are these carbonate sediments being mixed with siliceous material brought in by the Alpine rivers Po, Adige, and Brenta. Graphical analysis of grain-size distribution curves shows a sediment composition of normally three, and only in the most seaward area, of four major constituents. Constituent 1 represents the washed-in terrestrial material of clay size (Terra Rossa) from the Istrian coastal area. Constituent 2 consists of fine to medium sand. Constituent 3 contains the heterogeneous biogenic material. Crushing by organisms and by sediment eaters reduces the coarse biogenic material into small pieces generating constituent 2. Between these two constituents there is a dynamic equilibrium. Depending upon where the equilibrium is, between the extremes of production and crushing, the resulting constituent 2 is finer or coarser. Constituent 4 is composed of the fine sandy material from the Alpine rivers. In the most seaward area constituents 2 and 4 are mixed. The total carbonate content of the samples depends on the distance from the coast. In the near coastal area in high energy environments, the carbonate content is about 80 %. At a distance of 2 to 3 km from the coast there is a carbonate minimum because of the higher rate of sedimentation of clay-sized terrestrial, noncarbonate material at extremely low energy environments. In an area between 5 and 20 km off the coast, the carbonate content is about 75 %. More than 20 km from the shore, the carbonate content diminishes rapidly to values of about 30 % through mixing with siliceous material from the Alpine rivers. The carbonate content of the individual fractions increases with increasing grain-size to a maximum of about 90 % within the coarse sand fractions. Beyond 20 km from the coast the samples show a carbonate minimum of about 13 % within the sand-size classes from 1.5 to 0.7 zeta¬? through mixing with siliceous material from the alpine rivers. By means of grain-size distribution and carbonate content, four sediment zones parallel to the coast were separated. Genetically they are closely connected with the zonation of the benthic fauna. Two cores show a characteristic vertical distribution of the sediment. The surface zone is inversely graded, that means the coarse fractions are at the top and the fine fractions are at the bottom. This is the effect of crushing of the biogenic material produced at the surface by predatory organisms and by sediment eaters. lt is proposed that at a depth of about 30 cm a chemical solution process begins which leads to diminution of the original sediment from a fine to medium sand to a silt. The carbonate content decreases from about 75 % at the surface to 65 % at a depth of 100 cm. The increase of the noncarbonate components by 10 % corresponds to a decrease in the initial amount of sediment (CaC03=75 %) by roughly 30 % through solution. With increasing depth the carbonate content of the individual fractions becomes more and more uniform. At the surface the variation is from 30 % to 90 %, at the bottom it varies only between 50 % and 75 %. Comparable investigations of small-bay sediments showed a c1ear dependence of sediment/faunal zonation from the energy of the environment. The investigations show that the composition and three-dimensional distribution of the Istrian coastal sediments can not be predicted only from one or a few measurable factors. Sedimentation and syngenetic changes must be considered as a complex interaction between external factors and the actions of producing and destroying organisms that are in dynamic equilibrium. The results obtained from investigations of these recent sediments may be of value for interpreting fossil sediments only with strong limitations.

Carbonate accumulation rates of the Ninetyeast Ridge, Indian Ocean

More than 95% of the carbon lost from the "blue-ocean" reservoir to the sedimentary sink appears to be transferred as skeletal CaCO3, produced in the surface waters. This skeletal CaCO3 carries a productivity signal which is much better preserved in the underlying pelagic carbonate sediments than that of the refractory organic carbon accompanying it. Here, we develop a new method to quantify this signal in terms of organic carbon paleoproductivity, using the sedimentary mass accumulation rates of pelagic carbonate. These are converted into carbonate transit-paleofluxes, which are then translated into the corresponding transit-fluxes of organic carbon, via the carbonate to organic carbon ratios reported from deep-moored sediment trap experiments in modern blue-ocean environments. Paleoproductivity can then be estimated quantitatively by using published algorithms describing the relationship between the export production of particulate organic carbon at depth and primary productivity in the euphotic zone. Although our approach seems rather straightforward, it contains several pitfalls, the effects of which are highlighted by an example comprising three Paleocene/Oligocene to Recent pelagic carbonate sequences drilled during ODP Leg 121 in the eastern Indian Ocean. Although some extreme values are likely due to errors, such as poorly constrained datum levels and dissolution peaks, the results for the Quaternary and Neogene correlate well from site to site and are within the productivity range of present-day low to medium latitude open oceans. Our method may provide an opportunity to actually quantify blue-ocean primary productivity in sedimentary carbonate environments, but requires validation by other, more established ones.