Methanol and ethanol analysis in marine sediment pore water

Low-molecular-weight (LMW) alcohols are produced during the microbial degradation of organic matter from precursors such as lignin, pectin, and carbohydrates. The biogeochemical behavior of these alcohols in marine sediment is poorly constrained but potentially central to carbon cycling. Little is known about LMW alcohols in sediment pore waters because of their low concentrations and high water miscibility, both of which pose substantial analytical challenges. In this study, three alternative methods were adapted for the analysis of trace amounts of methanol and ethanol in small volumes of saline pore waters: direct aqueous injection (DAI), solid-phase microextraction (SPME), and purge and trap (P&T) in combination with gas chromatography (GC) coupled to either a flame ionization detector (FID) or a mass spectrometer (MS). Key modifications included the desalination of samples prior to DAI, the use of a threaded midget bubbler to purge small-volume samples under heated conditions and the addition of salt during P&T. All three methods were validated for LMW alcohol analysis, and the lowest detection limit (60 nM and 40 nM for methanol and ethanol, respectively) was achieved with the P&T technique. With these methods, ambient concentrations of volatile alcohols were determined for the first time in marine sediment pore waters of the Black Sea and the Gulf of Mexico. A strong correlation between the two compounds was observed and tentatively interpreted as being controlled by similar sources and sinks at the examined stations.

Lead 210 and silicate profiles from sediments of the equatorial Pacific and South Atlantic

Particle mixing rates have been determined for 5 South Atlantic/Antarctic and 3 equatorial Pacific deep-sea cores using excess 210Pb and 32Si measurements. Radionuclide profiles from these siliceous, calcareous, and clay-rich sediments have been evaluated using a steady state vertical advection diffusion model. In Antarctic siliceous sediments210Pb mixing coefficients (0.04-0.16 cm**2/y) are in reasonable agreement with the 32Si mixing coefficient (0.2 or 0.4 cm**2/y, depending on 32Si half-life). In an equatorial Pacific sediment core, however, the 210Pb mixing coefficient (0.22 cm**2/y) is 3-7 times greater than the 32Si mixing coefficient (0.03 or 0.07 cm**2/y). The difference in 210Pb and 32Si mixing rates in the Pacific sediments results from: (1) non-steady state mixing and differences in characteristic time and depth scales of the two radionuclides, (2) preferential mixing of fine-grained clay particles containing most of the 210Pb activity relative to coarser particles (large radiolaria) containing the 32Si activity, or (3) the supply of 222Rn from the bottom of manganese nodules which increases the measured excess 210Pb activity (relative to 226Ra) at depth and artificially increases the 210Pb mixing coefficient. Based on 32Si data and pore water silica profiles, dissolution of biogenic silica in the sediment column appears to have a minor effect on the 32Si profile in the mixed layer. Deep-sea particle mixing rates reported in this study and the literature do not correlate with sediment type, sediment accumulation rate, or surface productivity. Based on differences in mixing rate among three Antarctic cores collected within 50 km of each other, local variability in the intensity of deep-sea mixing appears to be as important as regional differences in sediment properties.

Dating analysis from DSDP Hole 90-594

Date-32 is a fast and easily used computer program developed to date Quaternary deep-sea cores by associating variations in the earth's orbit with recurring oscillations in core properties, such as carbonate content or isotope composition. Starting with known top and bottom dates, distortions in the periodicities of the core properties due to varying sedimentation rates are realigned by fast Fourier analysis so as to maximise the spectral energy density at the orbital frequencies. This allows age interpolation to all parts of the core to an accuracy of 10 kyrs, or about 1.5% of the record duration for a typical Brunhes sequence. The influence of astronomical forcing is examined and the method is applied to provide preliminary dates in a high-resolution Brunhes record from DSDP Site 594 off southeastern New Zealand.

Seawater carbonate chemistry and swimming behaviors of the raphidophyte Heterosigma akashiwo in a laboratory experiment

We investigated the effects of pH on movement behaviors of the harmful algal bloom causing raphidophyte Heterosigma akashiwo. Motility parameters from >8000 swimming tracks of individual cells were quantified using 3D digital video analysis over a 6-h period in 3 pH treatments reflecting marine carbonate chemistry during the pre-industrial era, currently, and the year 2100. Movement behaviors were investigated in two different acclimation-to-target-pH conditions: instantaneous exposure and acclimation of cells for at least 11 generations. There was no negative impairment of cell motility when exposed to elevated PCO2 (i.e., low pH) conditions but there were significant behavioral responses. Irrespective of acclimation condition, lower pH significantly increased downward velocity and frequency of downward swimming cells (p < 0.001). Rapid exposure to lower pH resulted in 9% faster downward vertical velocity and up to 19% more cells swimming downwards (p < 0.001). Compared to pH-shock experiments, pre-acclimation of cells to target pH resulted in ~30% faster swimming speed and up to 46% faster downward velocities (all p < 0.001). The effect of year 2100 PCO2 levels on population diffusivity in pre-acclimated cultures was >2-fold greater than in pH-shock treatments (2.2 × 105 µm**2/s vs. 8.4 × 104 µm**2/s). Predictions from an advection-diffusion model, suggest that as PCO2 increased the fraction of the population aggregated at the surface declined, and moved deeper in the water column. Enhanced downward swimming of H. akashiwo at low pH suggests that these behavioral responses to elevated PCO2 could reduce the likelihood of dense surface slick formation of H. akashiwo through reductions in light exposure or growth independent surface aggregations. We hypothesize that the HAB alga's response to higher PCO2 may exploit the signaling function of high PCO2 as indicative of net heterotrophy in the system, thus indicative of high predation rates or depletion of nutrients.

Grain shape of sediment from the Weddell Sea

Very fine quartz sand was examined from Paleogene and Neogene sediments of ODP Sites 693, 694, 695, 696, and 697 to determine their grain roundness using Fourier analysis and SEM surface texture characteristics. The objective of this study was to identify grain roundness and surface texture characteristics unique to East (Site 693) and West (Sites 695, 696, and 697) Antarctica and to glacial regimes. Once identified, these distinguishing features could then be used to determine changes in source area and glacial conditions in the central Weddell Sea Basin (Site 694). Three end members of very fine quartz sand are recognized in the Oligocene to Pleistocene sediments of the Weddell Sea: angular, rounded, and intermediate. End member 1 (angular) consists of extremely angular grains with numerous fracture textures. Previous investigations suggested that these sands are derived from crystalline rocks that fractured during formation or deformation and/or were exposed to weathering by ice. In this study, however, the correlation of angularity with ice activity is problematical as the most angular sands were recovered in the lower Oligocene sediments of the South Orkney Microcontinent, a period of temperate climatic conditions. End member 3 (rounded) consists of rounded grains with chemically and mechanically produced surface textures. These sands are presumed to be derived from the Beacon-type rocks in East Antarctica and the sedimentary deposits of the Northern Antarctic Peninsula. End member 2 (intermediate) grains display crystalline nodes and grain embayments. They are thought to be derived from felsic intrusives, East Antarctic quartzites, basement metamorphics of the South Orkney Microcontinent, and/or the Andean intrusive series of West Antarctica. Unfortunately, no features unique to either the East or West Antarctic sediment sources or to glacial conditions could be isolated. Therefore, the objective of determining provenance changes and sediment erosion and transport mechanisms could not be achieved using this approach.

Morphometric data for Globigerinoides sacculifer and Globorotalia tumida (size and Fourier coefficients) and temperature proxy reconstructions (UK37' and Tex86H) from samples from ODP sites 165-999/165-1000 and 202-1241 spanning the last 10Ma

Sediment samples from both Site 165-999/165-1000 (Atlantic) and Site 202-1241 (Pacific) were chosen at 1Ma intervals over the period 0.3-9.3Ma. Samples were washed and sieved <150µm. Splits of the sediment fraction were picked completely to obtain, where possible, at least 30 specimens each of planktic foraminifer species Globigerinoides sacculifer and Globorotalia tumida, on which outline analysis (Fourier) was performed. Sea surface and thermocline temperatures were reconstructed from palaeoenvironmental proxies (UK37' and Tex86H respectively).

Table 1 Core site, fractional abundance of individual isoprenoid GDGTs and TEX86 values

TEXL86 and TEXH86 are organic palaeothermometers based on the lipids of Group 1 Crenarchaeota, recently proposed as a modified version of the original TEX86 index, but with significantly improved geographical coverage. Since few data from the global core top calibration are from the Pacific, this study was carried out to assess whether the global core top calibration is regionally biased or not. The result of principal components analysis of the fractional abundance of GDGTs, an analysis of variance (ANOVA) and the comparison of the residuals of TEXH 86 derived sea surface temperature (SST) estimates of the Pacific subset with that of the global data set suggest that the Pacific subset has a similar TEXH 86-SST relationship with the global data set. However, the regression line through the Pacific data and an ANOVA on the residuals of TEXL 86 derived SST estimates suggest otherwise. The contradictory findings are likely to stem from the large scatter in the Pacific TEXL 86 values in the mid temperature range. While regionality does not seem to exert a strong bias on TEXL 86 and TEXH 86 calibration, it appears that there is a strong need to resolve the large scatter in the global data set, especially in the mid and high latitudes, in order to improve the calibration for a better SST estimation.

Carbon/oxygen ratios, clay composition and gas-hydrate saturation of ODP Leg 164 sites

The analyses of downhole log data from Ocean Drilling Program (ODP) boreholes on the Blake Ridge at Sites 994, 995, and 997 indicate that the Schlumberger geochemical logging tool (GLT) may yield useful gas hydrate reservoir data. In neutron spectroscopy downhole logging, each element has a characteristic gamma ray that is emitted from a given neutron-element interaction. Specific elements can be identified by their characteristic gamma-ray signature, with the intensity of emission related to the atomic elemental concentration. By combining elemental yields from neutron spectroscopy logs, reservoir parameters including porosities, lithologies, formation fluid salinities, and hydrocarbon saturations (including gas hydrate) can be calculated. Carbon and oxygen elemental data from the GLT was used to determine gas hydrate saturations at all three sites (Sites 994, 995, and 997) drilled on the Blake Ridge during Leg 164. Detailed analyses of the carbon and oxygen content of various sediments and formation fluids were used to construct specialized carbon/oxygen ratio (COR) fan charts for a series of hypothetical gas hydrate accumulations. For more complex geologic systems, a modified version of the standard three-component COR hydrocarbon saturation equation was developed and used to calculate gas hydrate saturations on the Blake Ridge. The COR-calculated gas hydrate saturations (ranging from about 2% to 14% bulk volume gas hydrate) from the Blake Ridge compare favorably to the gas hydrate saturations derived from electrical resistivity log measurements.

Geographical variation in shell morphology of juvenile snails (Concholepas concholepas) along the physical-chemical gradient of the Chilean coast

Changes in phenotypic traits, such as mollusc shells, are indicative of variations in selective pressure along environmental gradients. Recently, increased sea surface temperature (SST) and ocean acidification (OA) due to increased levels of carbon dioxide in the seawater have been described as selective agents that may affect the biological processes underlying shell formation in calcifying marine organisms. The benthic snail Concholepas concholepas (Muricidae) is widely distributed along the Chilean coast, and so is naturally exposed to a strong physical-chemical latitudinal gradient. In this study, based on elliptical Fourier analysis, we assess changes in shell morphology (outlines analysis) in juvenile C. concholepas collected at northern (23°S), central (33°S) and southern (39°S) locations off the Chilean coast. Shell morphology of individuals collected in northern and central regions correspond to extreme morphotypes, which is in agreement with both the observed regional differences in the shell apex outlines, the high reclassification success of individuals (discriminant function analysis) collected in these regions, and the scaling relationship in shell weight variability among regions. However, these extreme morphotypes showed similar patterns of mineralization of calcium carbonate forms (calcite and aragonite). Geographical variability in shell shape of C. concholepas described by discriminant functions was partially explained by environmental variables (pCO2, SST). This suggests the influence of corrosive waters, such as upwelling and freshwaters penetrating into the coastal ocean, upon spatial variation in shell morphology. Changes in the proportion of calcium carbonate forms precipitated by C. concholepas across their shells and its susceptibility to corrosive coastal waters are discussed.