Influence of the type of phospholipid head and of the conformation of the polyelectrolyte on the growth of calcium carbonate thin films on LB/LbL matrices

Calcium carbonate is one of the most important biominerals, and it is the main constituent of pearls, seashells, and teeth. The in vitro crystallization of calcium carbonate using different organic matrices as templates has been reported. In this work, the growth of calcium carbonate thin films on special organic matrices consisting of layer-by-layer (LbL) polyelectrolyte films deposited on a pre-formed phospholipid Langmuir-Blodgett (LB) film has been studied. Two types of randomly coiled polyelectrolytes have been used: lambda-carrageenan and poly(acrylic acid). A precoating comprised of LB films has been prepared by employing a negatively charged phospholipid, the sodium salt of dimyristoilphosphatidyl acid (DMPA), or a zwitterionic phospholipid, namely dimyristoilphosphatidylethanolamine (DMPE). This approach resulted in the formation of particulate calcium carbonate continuous films with different morphologies, particle sizes, and roughness, as revealed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The crystalline structure of the calcium carbonate particles was analyzed by Raman spectroscopy. The randomly coiled conformation of the polyelectrolytes seems to be the main reason for the formation of continuous films rather than CaCO3 isolated crystals. (C) 2012 Elsevier B.V. All rights reserved.

Carbon isotope fractionation during calcium carbonate precipitation induced by urease-catalysed hydrolysis of urea

Stable carbon isotopic fractionation during calcium carbonate precipitation induced by urease-catalysed hydrolysis of urea was experimentally investigated in artificial water at a constant temperature of 30 degrees C. Carbon isotope fractionation during urea hydrolysis follows a Rayleigh distillation trend characterized by a C-13-enrichment factor of -20 to -22 parts per thousand. CaCO3 precipitate is up to 17.9 parts per thousand C-13-depleted relative to the urea substrate (-48.9 +/- 0.07 parts per thousand). Initial CaCO3 precipitate forms close to isotopic equilibrium with dissolved inorganic carbon. Subsequent precipitation occurs at -2 to -3 parts per thousand offset from isotopic equilibrium, suggesting that the initial delta C-13 value of CaCO3 is reset through dissolution followed by reprecipitation with urease molecules playing a role in offsetting the delta C-13 value of CaCO3 from isotopic equilibrium. Potentially, this isotopic systematics may provide a tool for the diagnosis of ureolytically-formed carbonate cements used as sealing agent. Moreover, it may serve as a basis to develop a carbon isotope tool for the quantification of ureolytically-induced CO2 sequestration. Finally, it suggests carbon isotope disequilibrium as a hallmark of past enzymatic activity in ancient microbial carbonate formation. (C) 2012 Elsevier B.V. All rights reserved.

Palaeoceanographic changes in the North Atlantic during the Mid-Pleistocene Transition (MIS 31-19) as inferred from planktonic foraminiferal and calcium carbonate records

Marine sediments from the Integrated Ocean Drilling Project (IODP) Site U1314 (56.36°N, 27.88°W), in the subpolar North Atlantic, were studied for their planktonic foraminifera, calcium carbonate content, and Neogloboqudrina pachyderma sinistral (sin.) δ13C records in order to reconstruct surface and intermediate conditions in this region during the Mid-Pleistocene Transition (MPT). Variations in the palaeoceanography and regional dynamics of the Arctic Front were estimated by comparing CaCO3 content, planktonic foraminiferal species abundances, carbon isotopes and ice-rafted debris (IRD) data from Site U1314 with published data from other North Atlantic sites. Site U1314 exhibited high abundances of the polar planktonic foraminifera N. pachyderma sin. and low CaCO3 content until Marine Isotope Stage (MIS) 26, indicating a relatively southeastward position of the Arctic Front (AF) and penetration of colder and low-salinity surface arctic water-masses. Changing conditions after MIS 25, with oscillations in the position of the AF, caused an increase in the northward export of the warmer North Atlantic Current (NAC), indicated by greater abundances of non-polar planktonic foraminifera and higher CaCO3. The N. pachyderma sin. δ13C data indicate good ventilation of the upper part of the intermediate water layer in the eastern North Atlantic during both glacial and interglacial stages, except during Terminations 24/23, 22/21 and 20/1. In addition, for N. pachyderma (sin.) we distinguished two morphotypes: non-encrusted and heavily encrusted test. Results indicate that increases in the encrusted morphotype and lower planktonic foraminiferal diversity are related to the intensification of glacial conditions (lower sea-surface temperatures, sea-ice formation) during MIS 22 and 20.

(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.

Calcium carbonate, isotopes and Rock-Eval pyrolysis at DSDP Holes 77-535 and 77-540

At DSDP Sites 534 (Central Atlantic) and 535 and 540 (Gulf of Mexico), and in the Vocontian Basin (France), Lower Cretaceous deposits show a very pronounced alternation of limestone and marl. This rhythm characterizes the pelagic background sedimentation and is independent of detritic intercalations related to contour and turbidity currents. Bed-scale cycles, estimated to be 6000-26,000 yr. long, comprise major and minor units. Their biological and mineralogic components, burrowing, heavy isotopes C and O, and some geochemical indicators, vary in close correlation with CaCO3 content. Vertical changes of frequency and asymmetry of the cycles are connected with fluctuations of the sedimentation rate. Plots of cycle thickness ("cyclograms") permit detailed correlations of the three areas and improve the stratigraphic subdivision of Neocomian deposits at the DSDP sites. Small-scale alternations, only observed in DSDP cores, comprise centimetric to millimetric banding and millimetric to micrometric lamination, here interpreted as varvelike alternations between laminae that are rich in calcareous plankton and others rich in clay. The laminations are estimated to correspond to cycles approximately 1,3, and 13 yr. in duration. The cyclic patterns appear to be governed by an interplay of continental and oceanic processes. Oceanic controls express themselves in variations of the biogenic carbonate flux, which depends on variations of such elements as temperature, oxygenation, salinity, and nutrient content. Continental controls modulate the influxes of terrigenous material, organic matter, and nutrients derived from cyclic erosion on land. Among the possible causes of cyclic sedimentation, episodic carbonate dissolution has been ruled out in favor of climatic fluctuations with a large range of periods. Such fluctuations are consistent with the great geographic extension shown by alternation controls and with the continuous spectrum of scales that characterizes limestone-marl cycles. The climatic variations induced by the Earth's orbital parameters (Milankovitch cycles) could be connected to bed-interbed alternations.

Stable isotopes and calcium carbonate at DSDP Holes 85-574 and 85-574A

Detailed stable isotopic and calcium carbonate records (with a sampling resolution of 3000 yr.) from the middle Miocene section of hydraulic piston corer (HPC) Hole 574A provide a sequence that records the major shift in the oxygen isotopic composition of the world's oceans that occurred at about 14 Ma. The data suggest that this transition was rapid and spans about 30,000 yr. of sediment deposition. In intervals before and after the shift, the mean d18O values are characterized by a constant mean with a high degree of variability. The degree of variability in both the d18O and d13C records is comparable to that observed for the Pliocene and earliest Pleistocene and does not show a significant change before or after the major shift in the d18O record. Whereas the oxygen isotopic record is characterized by relatively stable mean values before and after the middle Miocene event, the d13C record shows a number of significant offsets in the mean value separated by intervals of high-frequency variations. Time and frequency domain analysis of all records from Hole 574A indicate that the frequency components shown to be related to orbital changes in the Pleistocene record are also present in the middle Miocene. The high variability observed in the Site 574 isotopic records places important constraints on models describing the role of formation of the Antarctic ice sheet during the middle Miocene climatic transitions. Thus, HPC Hole 574A provides a valuable sequence for detailed study of climatic variability during an important time in the Earth's history, although we cannot provide a definitive explanation of the major oxygen isotopic event of the middle Miocene.

Grain-size distribution, carbon and calcium carbonate at DSDP Leg 63 Holes

Sand-silt-clay distribution was determined at Scripps on samples collected at the time the cores were split and described. The sediment classification used here is that of Shepard (1954); sand, silt, and clay boundaries are determined on the basis of the Wentworth (1922) scale. Thus the sand, silt, and clay fractions are composed of particles whose diameters range from 2000 to 62.5 µm, 62.5 to 3.91 µm, and less than 3.91 µm, respectively. This classification is applied regardless of sediment type and origin.

Grain-size, carbon and calcium carbonate at DSDP Leg 77 Holes

Sand-silt-clay distribution was determined on 10-cm**3 sediment samples collected at the time the cores were split and described.

Calcium carbonate, organic carbon, d13C and C/N composition of ODP Sites 186-1150 and 186-1151

Past changes in sea-surface productivity in the Oyashio Current are evaluated on the basis of abundances of biological constituents in sediments from Leg 186 sites. Organic carbon contents at Sites 1150 and 1151 are moderate (0.5 to 1.5 wt%) and have an algal origin as indicated by low C/N ratios (<10) and by carbon isotopic compositions ranging from -23.4 to -21.3. A decreasing trend in organic carbon contents, carbon isotope ratios, and C/N ratios occurs with depth at both sites, probably as a consequence of diagenetic degradation of organic matter. Mass accumulation rates (MARs) determined for organic carbon and carbonates at Sites 1150 and 1151 show an abrupt increase between ~5 and 7 Ma. Similar results have been reported for sites in the Indian Ocean and the Pacific Ocean for the same time interval. As it has been previously suggested, the observed increase in MAR for both carbonate and organic carbon at Leg 186 sites probably resulted from augmented nutrient supply either from continental sources or from a more vigorous ocean circulation.

Grain-size, carbona and calcium carbonate at DSDP Leg 58 Holes

Sand-silt-clay distribution was determined on 10-cm**3 sediment samples collected at the time the cores were split and described. The sediment classification used here is that of Shepard (1954), with the sand, silt, and clay boundaries based on the Wentworth (1922) scale. Thus the sand, silt, and clay fractions are composed of particles whose diameters are 2000 to 62.5 µm, 62.5 to 3.91 µm, and less than 3.91 µm, respectively. This classification is applied without regard to sediment type and origin; therefore, the sediment names used in this table may differ from those used elsewhere in this volume; e.g., a silt composed of nannofossils may be called a nannofossil ooze in a site chapter.