Chemical and Sr isotopic compositions of pore fluids and marine carbonates from ODP Hole 130-807A

The 87Sr/86Sr ratios and Sr concentrations in sediment and pore fluids are used to evaluate the rates of calcite recrystallization at ODP Site 807A on the Ontong Java Plateau, an 800-meter thick section of carbonate ooze and chalk. A numerical model is used to evaluate the pore fluid chemistry and Sr isotopes in an accumulating section. The deduced calcite recrystallization rate is 2% per million years (%/Myr) near the top of the section and decreases systematically in older parts of the section such that the rate is close to 0.1/age (in years). The deduced recrystallization rates have important implications for the interpretation of Ca and Mg concentration profiles in the pore fluids. The effect of calcite recrystallization on pore fluid chemistry is described by the reaction length, L, which varies by element, and depends on the concentration in pore fluid and solid. When L is small compared to the thickness of the sedimentary section, the pore fluid concentration is controlled by equilibrium or steady-state exchange with the solid phase, except within a distance L of the sediment-water interface. When L is large relative to the thickness of sediment, the pore fluid concentration is mostly controlled by the boundary conditions and diffusion. The values of L for Ca, Sr, and Mg are of order 15, 150, and 1500 meters, respectively. L_Sr is derived from isotopic data and modeling, and allows us to infer the values of L_Ca and L_Mg. The small value for L_Ca indicates that pore fluid Ca concentrations, which gradually increase down section, must be equilibrium values that are maintained by solution-precipitation exchange with calcite and do not reflect Ca sources within or below the sediment column. The pore fluid Ca measurements and measured alkalinity allow us to calculate the in situ pH in the pore fluids, which decreases from 7.6 near the sediment-water interface to 7.1+/-0.1 at 400-800 mbsf. While the calculated pH values are in agreement with some of the values measured during ODP Leg 130, most of the measurements are artifacts. The large value for L_Mg indicates that the pore fluid Mg concentrations at 807A are not controlled by calcite-fluid equilibrium but instead are determined by the changing Mg concentration of seawater during deposition, modified by aqueous diffusion in the pore fluids. We use the pore fluid Mg concentration profile at Site 807A to retrieve a global record for seawater Mg over the past 35 Myr, which shows that seawater Mg has increased rapidly over the past 10 Myr, rather than gradually over the past 60 Myr. This observation suggests that the Cenozoic rise in seawater Mg is controlled by continental weathering inputs rather than by exchange with oceanic crust. The relationship determined between reaction rate and age in silicates and carbonates is strikingly similar, which suggests that reaction affinity is not the primary determinant of silicate dissolution rates in nature.

Strontium isotope ratios of planktonic foraminifera from late Neogene sediment samples

A curve describing the variation of the strontium isotopic composition of seawater for the late Neogene (9 to 2 Ma) was constructed from 87Sr/86Sr analyses of marine carbonate in five Deep Sea Drilling Project (DSDP) sites: 502, 519, 588, 590, and 593. The strontium isotopic composition of the oceans increased between 9 and 2 Ma with several changes in slope. From 9 to 5.5 Ma, 87Sr/86Sr values were nearly constant at ~0.708925. Between 5.5 and 4.5 Ma, 87Sr/86Sr ratios increased monotonically at a rate of not, vert, similar 1 * 10**-4 per million years. The steep slope during this interval provides the potential for high resolution strontium isotope stratigraphy across the Miocene/Pliocene boundary. The rate of change of 87Sr/86Sr decreases to near zero again during the interval 4.5-2.5 Ma, and ratios average 0.709025. The relatively rapid increase of 87Sr/86Sr between 5.5 and 4.5 Ma must be related to changes in the flux or average 87Sr/86Sr ratios of the major inputs of Sr to the oceans. Quantitative modelling of these inputs suggests that the increase was most probably caused by an increase in the dissolved riverine flux of strontium to the oceans, an increase in the average 87Sr/86Sr composition of river water, or some combination of these parameters. Modelling of this period as a transient-state requires a pulse-like increase in the input of 87Sr to the oceans between 5.5 and 4.5 Ma. Alternatively, the 5.5-4.5 Ma period can be modelled as a simple transition from one steady-state to another if the oceanic residence time of strontium was eight times less than the currently accepted value of 4 Ma. During the time interval of steep 87Sr/86Sr increase, other geochemical and sedimentologic changes also occur including an increase in sediment accumulation rates, a drop in the calcite compensation depth (CCD), and a decrease in the delta13C of dissolved bicarbonate (i.e., "carbon shift"). The simplest mechanism to explain 87Sr/86Sr variation and these related geochemical changes is to invoke an increase in the dissolved chemical fluxes carried by rivers to the oceans. This, in turn, implies increased chemical denudation rates of the continents and shelves during the late Neogene. The increase in chemical weathering rates is attributed to increased exposure of the continents by eustatic regression, intensified glacial/interglacial cycles, and accelerated rates of global tectonism beginning at 5.5 Ma during the latest Miocene.

Geochemistry of pore water and sediments offshore Nicaragua and Costa Rica

Four volcanic ash-bearing marine sediment cores and one ash-free reference core were examined during research cruise RV Meteor 54/2 offshore Nicaragua and Costa Rica to investigate the chemical composition of pore waters related to volcanic ash alteration. Sediments were composed of terrigenous matter derived from the adjacent continent and contained several distinct ash layers. Biogenic opal and carbonate were only minor components. The terrigenous fraction was mainly composed of smectite and other clay minerals while the pore water composition was strongly affected by the anaerobic degradation of particulate organic matter via microbial sulphate reduction. The alteration of volcanic matter showed only a minor effect on major element concentrations in pore waters. This is in contrast to prior studies based on long sediment cores taken during the DSDP, where deep sediments always showed distinct signs of volcanic ash alteration. The missing signal of ash alteration is probably caused by low reaction rates and the high background concentration of major dissolved ions in the seawater-derived pore fluids. Dissolved silica concentrations were, however, significantly enriched in ash-bearing cores and showed no relation to the low but variable contents of biogenic opal. Hence, the data suggest that silica concentrations were enhanced by ash dissolution. Thus, the dissolved silica profile measured in one of the sediment cores was used to derive the in-situ dissolution rate of volcanic glass particles in marine sediments. A non-steady state model was run over a period of 43 kyr applying a constant pH of 7.30 and a dissolved Al concentration of 0.05 ?M. The kinetic constant (AA) was varied systematically to fit the model to the measured dissolved silica-depth profile. The best fit to the data was obtained applying AA = 1.3 * 10**-U9 mol of Si/cm**2/ s. This in-situ rate of ash dissolution at the seafloor is three orders of magnitude smaller than the rate of ash dissolution determined in previous laboratory experiments. Our results therefore imply that field investigations are necessary to accurately predict natural dissolution rates of volcanic glasses in marine sediments.

Seawater carbonate chemistry and Ruditapes decussatus biological processes during experiments, 2011

We investigated the effects of ocean acidification on juvenile clams Ruditapes decussatus (average shell length 10.24 mm) in a controlled CO2 perturbation experiment. The carbonate chemistry of seawater was manipulated by diffusing pure CO2, to attain two reduced pH levels (by -0.4 and -0.7 pH units), which were compared to unmanipulated seawater. After 75 days we found no differences among pH treatments in terms of net calcification, size or weight of the clams. The naturally elevated total alkalinity of local seawater probably contributed to buffer the effects of increased pCO2 and reduced pH. Marine organisms may, therefore, show diverse responses to ocean acidification at local scales, particularly in coastal, estuarine and transitional waters, where the physical-chemical characteristics of seawater are most variable. Mortality was significantly reduced in the acidified treatments. This trend was probably related to the occurrence of spontaneous spawning events in the control and intermediate acidification treatments. Spawning, which was unexpected due to the small size of the clams, was not observed for the pH -0.7 treatment, suggesting that the increased survival under acidified conditions may have been associated with a delay in the reproductive cycle of the clams. Future research about the impacts of ocean acidification on marine biodiversity should be extended to other types of biological and ecological processes, apart from biological calcification.

Ground-based electromagnetic (EM) and drill-hole ice and snow thickness and melt pond depth measurements during Polarstern cruise ARK-IX/4, ARK-XI/1, and ARK-XII

Drillhole-determined sea-ice thickness was compared with values derived remotely using a portable small-offset loop-loop steady state electromagnetic (EM) induction device during expeditions to Fram Strait and the Siberian Arctic, under typical winter and summer conditions. Simple empirical transformation equations are derived to convert measured apparent conductivity into ice thickness. Despite the extreme seasonal differences in sea-ice properties as revealed by ice core analysis, the transformation equations vary little for winter and summer. Thus, the EM induction technique operated on the ice surface in the horizontal dipole mode yields accurate results within 5 to 10% of the drillhole determined thickness over level ice in both seasons. The robustness of the induction method with respect to seasonal extremes is attributed to the low salinity of brine or meltwater filling the extensive pore space in summer. Thus, the average bulk ice conductivity for summer multiyear sea ice derived according to Archie's law amounts to 23 mS/m compared to 3 mS/m for winter conditions. These mean conductivities cause only minor differences in the EM response, as is shown by means of 1-D modeling. However, under summer conditions the range of ice conductivities is wider. Along with the widespread occurrence of surface melt ponds and freshwater lenses underneath the ice, this causes greater scatter in the apparent conductivity/ice thickness relation. This can result in higher deviations between EM-derived and drillhole determined thicknesses in summer than in winter.

Geochemical analysis of two sediment cores from the southern Mendeleev Ridge

We present results of an inorganic geochemical pore water and sediment study conducted on Quaternary sediments from the western Arctic Ocean. The sediment cores were recovered in 2008 from the southern Mendeleev Ridge during RV Polarstern Expedition ARK-XXIII/3. With respect to sediment sources and depositional processes, peaks in Ca/Al, Mg/Al, Sr/Al and Sr/Mg indicate enhanced input of both ice-rafted (mainly dolomite) and biogenic carbonate during deglacial warming phases. Distinct and repetitive brown layers enriched in Mn (oxyhydr)oxides occur mostly in association with these carbonate-rich intervals. For the first time, we show that the brown layers are also consistently enriched in scavenged trace metals Co, Cu, Mo and Ni. The bioturbation patterns of the brown layers, specifically well-defined brown burrows into the underlying sediments, support formation close to the sediment-water interface. The Mn and trace metal enrichments were probably initiated under warmer climate conditions. Both river runoff and melting sea ice delivered trace metals to the Arctic Ocean, but also enhanced seasonal productivity and organic matter export to the sea floor. As Mn (oxyhydr)oxides and scavenged trace metals were deposited at the sea floor, a co-occurring organic matter "pulse" triggered intense diagenetic Mn cycling at the sediment-water interface. These processes resulted in the formation of Mn and trace metal enrichments, but almost complete organic matter degradation. As warmer conditions ceased, reduced riverine runoff and/or a solid sea ice cover terminated the input of riverine trace metal and fresh organic matter, and greyish-yellowish sediments poor in Mn and trace metals were deposited. Oxygen depletion of Arctic bottom waters as potential cause for the lack of Mn enrichments during glacial intervals is highly improbable. While the original composition and texture of the brown layers resulted from specific climatic conditions (including transient Mn redox cycling at the sediment-water interface), pore water data show that early diagenetic Mn redistribution is still affecting the organic-poor sediments in several meters depth. Given persistent steady state diagenetic conditions, purely authigenic Mn-rich brown layers may form, while others may completely vanish. The degree of diagenetic Mn redistribution largely depends on the depositional environment within the Arctic Ocean, the availability of Mn and organic matter, and seems to be recorded by the Co/Mo ratios of single Mn-rich layers. We conclude that brown Arctic sediment layers are not necessarily synchronous features, and correlating them across different parts of the Arctic Ocean without additional age control is not recommended.