The influence of temperature and seawater carbonate saturation state on 13C-18O bond ordering in bivalve mollusks

The shells of marine mollusks are widely used archives of past climate and ocean chemistry. Whilst the measurement of mollusk delta 18O to develop records of past climate change is a commonly used approach, it has proven challenging to develop reliable independent paleothermometers that can be used to deconvolve the contributions of temperature and fluid composition on molluscan oxygen isotope compositions. Here we investigate the temperature dependence of 13C-18O bond abundance, denoted by the measured parameter Delta 47, in shell carbonates of bivalve mollusks and assess its potential to be a useful paleothermometer. We report measurements on cultured specimens spanning a range in water temperatures of 5 to 25 °C, and field collected specimens spanning a range of -1 to 29 °C. In addition we investigate the potential influence of carbonate saturation state on bivalve stable isotope compositions by making measurements on both calcitic and aragonitic specimens that have been cultured in seawater that is either supersaturated or undersaturated with respect to aragonite. We find a robust relationship between Delta 47 and growth temperature. We also find that the slope of a linear regression through all the Delta 47 data for bivalves plotted against seawater temperature is significantly shallower than previously published inorganic and biogenic carbonate calibration studies produced in our laboratory and go on to discuss the possible sources of this difference. We find that changing seawater saturation state does not have significant effect on the Delta 47 of bivalve shell carbonate in two taxa that we examined, and we do not observe significant differences between Delta 47-temperature relationships between calcitic and aragonitic taxa.

Influence of temperature and CO2 on the strontium and magnesium composition of coccolithophore calcite

Marine calcareous sediments provide a fundamental basis for palaeoceanographic studies aiming to reconstruct past oceanic conditions and understand key biogeochemical element cycles. Calcifying unicellular phytoplankton (coccolithophores) are a major contributor to both carbon and calcium cycling by photosynthesis and the production of calcite (coccoliths) in the euphotic zone, and the subsequent long-term deposition and burial into marine sediments. Here we present data from controlled laboratory experiments on four coccolithophore species and elucidate the relation between the divalent cation (Sr, Mg and Ca) partitioning in coccoliths and cellular physiology (growth, calcification and photosynthesis). Coccolithophores were cultured under different seawater temperature and carbonate chemistry conditions. The partition coefficient of strontium (DSr) was positively correlated with both carbon dioxide (pCO2) and temperature but displayed no coherent relation to particulate organic and inorganic carbon production rates. Furthermore, DSr correlated positively with cellular growth rates when driven by temperature but no correlation was present when changes in growth rates were pCO2-induced. Our results demonstrate the complex interaction between environmental forcing and physiological control on the strontium partitioning in coccolithophore calcite and challenge interpretations of the coccolith Sr / Ca ratio from high-pCO2 environments (e.g. Palaeocene-Eocene thermal maximum). The partition coefficient of magnesium (DMg) displayed species-specific differences and elevated values under nutrient limitation. No conclusive correlation between coccolith DMg and temperature was observed but pCO2 induced a rising trend in coccolith DMg. Interestingly, the best correlation was found between coccolith DMg and chlorophyll a production, suggesting that chlorophyll a and calcite associated Mg originate from the same intracellular pool. These and previous findings indicate that Mg is transported into the cell and to the site of calcification via different pathways than Ca and Sr. Consequently, the coccolith Mg / Ca ratio should be decoupled from the seawater Mg / Ca ratio. This study gives an extended insight into the driving factors influencing the coccolith Mg / Ca ratio and should be considered for future palaeoproxy calibrations.

Composition of bentonite-, smectite-rich- and ash beds from DSDP Leg 19 holes

Late Cenozoic ash deposits cored in Deep Sea Drilling Project Leg 19 in the far northwest Pacific and in the Bering Sea have altered to bentonite beds. Some bentonite layers were subsequently replaced by carbonate beds. A significant part of the Neogene volcanic history of land areas adjacent to the far north Pacific is represented by these diagenetic deposits. Bentonite beds are composed of authigenic smectite and minor amounts of clinoptilolite. Authigenic smectite has fewer illite layers than detrital smectite. Opal-A and opal-CT, abundant in Bering Sea sediment, are not found in ash or bentonite layers. The percentage of smectite in the total clay-mineral assemblage of ash beds is greater than that for adjacent terrigenous sediment, but the total amount of clay minerals in ash sequences is less than in surrounding deposits. Morphology of the 17-Å peak of smectite found in ash may represent newly formed, poorly crystalline smectite. Smectite becomes better crystallized as bentonite layers form. The percentage of smectite of the total clay-mineral assemblage in bentonite beds is greater than that in surrounding sediment, and, in contrast to ash beds, the total amount of clay minerals (mostly smectite) in bentonite layers is greater than in adjacent terrigenous sediment. Apparently, silica is not mobilized when volcanic ash layers transform to bentonite beds. Saponite-nontronite varieties of smectite and high Fe/Al and Ti/Al ratios distinguish bentonite beds derived from basaltic parent material from those beds formed from more silicic volcanic ash. These silicic ash beds produce bentonite composed mostly of montmorillonite. The basal sediment section at site 192 is rich with bentonite beds. Smectite in the upper part of this section (Eocene) was formed by low-temperature diagenesis of volcanic debris of intermediate or more silicic composition derived from arc or Pacific volcanoes. In contrast, smectite from the lowest 10 to 20 m of the sedimentary section (Cretaceous) is formed from either low-temperature or hydrothermal alteration of the underlying basaltic basement and associated pyroclastic debris. This near-basement smectite contains Mg and K acquired from sea water and Si, Al, Fe, Ti, and Mn released from the volcanic material.

Seawater carbonate chemistry, thickness and carbonate elemental composition of the test of juvenile sea urchins in a laboratory experiment

Continuous anthropogenic CO2 emissions to the atmosphere and uptake by the oceans will cause a reduction of seawater pH and saturation state (Omega) of CaCO3 minerals from which marine calcifiers build their shells and skeletons. Sea urchins use the most soluble form of calcium carbonate, high-magnesium calcite, to build their skeleton, spines and grazing apparatus. In order to highlight the effects of increased pCO2 on the test thickness and carbonate elemental composition of juvenile sea urchins and potential differences in their responses linked to the diet, we performed a laboratory experiment on juvenile Paracentrotus lividus, grazing on calcifying (Corallina elongata) and non-calcifying (Cystoseira amentacea, Dictyota dichotoma) macroalgae, under different pH (corresponding to pCO2 values of 390, 550, 750 and 1000 µatm). Results highlighted the importance of the diet in determining sea urchin size irrespectively of the pCO2 level, and the relevance of macroalgal diet in modulating urchin Mg/Ca ratio. The present study provides relevant clues both in terms of the mechanism of mineral incorporation and in terms of bottom-up processes (algal diet) affecting top-down ones (fish predation) in rocky subtidal communities

(Table 6) Selenium isotopic composition of sediment samples from ODP Site 185-1149

Multiple-collector inductively coupled plasma mass spectrometry has been used for the precise measurement of the isotopic composition of Se in geological samples. Se is chemically purified before analysis by using cotton impregnated with thioglycollic acid. This preconcentration step is required for the removal of matrix-interfering elements for hydride generation, such as transitional metals, and also for the quantitative separation of other hydride-forming elements, such as Ge, Sb, and As. The analyte is introduced in the plasma torch with a continuous-flow hydride generation system. Instrumental mass fractionation is corrected with a "standard-sample bracketing" approach. By use of this new technique, the minimum Se required per analysis is lowered to 10 ng, which is one order of magnitude less than the amount needed for the N-TIMS technique. The estimated external precision calculated for the 82Se/76Se isotope ratio is 0.25? (2 sigma), and the data are reported as delta notation (?) relative to our internal standard (MERCK elemental standard solution). Measurements of Se isotopes are presented for samples of standard solutions and geological reference materials, such as silicate rocks, soils, and sediments. The Se isotopic composition of selected terrestrial and extraterrestrial materials are also presented. An overall Se isotope variation of 8? has been observed, suggesting that Se isotopes fractionate readily and are extremely useful tracers of natural processes.