Petrophysical measurement of ODP Leg 122 and 123 samples (Tables 1, 2)

The capillary-pressure characteristics of 22 samples of lithified post-Paleozoic Indian-Ocean carbonates were compared to published data from older carbonate rocks (lower Paleozoic Hunton Group of Texas and Oklahoma). The Indian-Ocean samples are considerably more porous than are the Paleozoic samples, yet all of the Indian-Ocean samples fit readily into a descriptive petrofacies scheme previously established for the Hunton Group. The Indian-Ocean samples may be assigned to four petrophysical facies (petrofacies) based on the shapes of their capillary-pressure curves, their pore-throat-size distributions, their estimated recovery efficiency values (for nonwetting fluids), and the visual characteristics of their pore systems, as observed with a scanning-electron microscope. Petrofacies assignments for the Indian-Ocean samples are as follows. Petrofacies I includes six samples collected from the coarse basal portions of event deposits (primarily turbidites). These samples have large throats, leptokurtic throat-size distributions, low- to moderate recovery efficiency values, concave cumulative-intrusion capillary-pressure curves, and high porosity values. Petrofacies II includes two sedimentologically dissimilar samples that have medium-size throats, platykurtic throat-size distributions, moderate- to-high recovery efficiency values, gently sloping cumulative-intrusion capillary-pressure curves, and high porosity values. Petrofacies III includes two polymictic sandstones and a skeletal packstone that have small throats, polymodal throat-size distributions, moderate recovery efficiency values, gently sloping cumulative-intrusion capillary-pressure curves, and high porosity values. Petrofacies IV includes 11 samples, mostly recrystallized neritic carbonates, that have small throats, leptokurtic throat-size distributions, high recovery efficiency values, convex cumulative-intrusion capillary-pressure curves, and low porosity values. Comparison of petrofacies assignment to core-, thin-section-, and smear-slide data, and to inferred depositional setting, suggests that pore systems in most samples from Holes 765C and 766A result from primary depositional features, whereas pore systems in samples from Hole 761C and one sample from Hole 765C have been strongly influenced by diagenetic processes. For Hole 761C, prediction of petrophysical parameters should be most successful if based on diagenetic facies patterns. By contrast, the distribution of favorable reservoir facies and of permeability barriers in less highly altered rocks collected from Holes 765C and 766A is related to depositional patterns. Recovery efficiency is inversely related to both porosity and median throat size for the present data set. This relationship is similar to that observed for carbonates of the lower Paleozoic Hunton Group and the Ordovician Ellenburger dolomite, but opposite of that observed for some other ancient carbonates. The coarse deposits of the massive basal units of turbidites are petrophysically distinct and form a coherent petrophysical group (Petrofacies I) with substantial reservoir potential. Two samples assigned to Petrofacies I have extremely large throats (median throat size at least 4 ?m, and at least six times that of any other sample) and therefore high permeability values. These two samples come from thin, coarse turbidites that lack or have poorly developed fine divisions and are interpreted to have been deposited on channeled suprafan lobes in a proximal mid-fan setting. The restriction of extremely high permeability values to a single depositional facies suggests that careful facies mapping of deep-sea fans in a deliberate search for such coarse turbidites could dramatically enhance the success of exploration for aquifers or hydrocarbon reservoirs. Such reservoirs should have substantial vertical heterogeneity. They should have high lateral permeability values but low vertical permeability values, and reservoir sections should include numerous thin units having widely differing petrophysical characteristics.

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.

Experimental data of CO2, CO3, Omega calcite saturation, pH values, alpha and epsilon fractionation factors, and Dd18O calctite-water

The oxygen isotopic composition (d18O) of calcium carbonate of planktonic calcifying organisms is a key tool for reconstructing both past seawater temperature and salinity. The calibration of paloeceanographic proxies relies in general on empirical relationships derived from field experiments on extant species. Laboratory experiments have more often than not revealed that variables other than the target parameter influence the proxy signal, which makes proxy calibration a challenging task. Understanding these secondary or "vital" effects is crucial for increasing proxy accuracy. We present data from laboratory experiments showing that oxygen isotope fractionation during calcification in the coccolithophore Calcidiscus leptoporus and the calcareous dinoflagellate Thoracosphaera heimii is dependent on carbonate chemistry of seawater in addition to its dependence on temperature. A similar result has previously been reported for planktonic foraminifera, supporting the idea that the [CO3]2- effect on d18O is universal for unicellular calcifying planktonic organisms. The slopes of the d18O/[CO3]2- relationships range between -0.0243 per mil/(µmol/kg) (calcareous dinoflagellate T. heimii) and the previously published -0.0022 per mil/(µmol/kg) (non-symbiotic planktonic foramifera Orbulina universa), while C. leptoporus has a slope of -0.0048 per mil/(µmol/kg). We present a simple conceptual model, based on the contribution of d18O-enriched [HCO3]- to the [CO3]2- pool in the calcifying vesicle, which can explain the [CO3]2- effect on d18O for the different unicellular calcifiers. This approach provides a new insight into biological fractionation in calcifying organisms. The large range in d18O/[CO3]2- slopes should possibly be explored as a means for paleoreconstruction of surface [CO3]2-, particularly through comparison of the response in ecologically similar planktonic organisms.

Consistent increase in dimethyl sulfide (DMS) in response to high CO2 in five shipboard bioassays from contrasting NW European waters

The ubiquitous marine trace gas dimethyl sulfide (DMS) comprises the greatest natural source of sulfur to the atmosphere and is a key player in atmospheric chemistry and climate. We explore the short-term response of DMS production and cycling and that of its algal precursor dimethyl sulfoniopropionate (DMSP) to elevated carbon dioxide (CO2) and ocean acidification (OA) in five 96 h shipboard bioassay experiments. Experiments were performed in June and July 2011, using water collected from contrasting sites in NW European waters (Outer Hebrides, Irish Sea, Bay of Biscay, North Sea). Concentrations of DMS and DMSP, alongside rates of DMSP synthesis and DMS production and consumption, were determined during all experiments for ambient CO2 and three high-CO2 treatments (550, 750, 1000 µatm). In general, the response to OA throughout this region showed little variation, despite encompassing a range of biological and biogeochemical conditions. We observed consistent and marked increases in DMS concentrations relative to ambient controls (110% (28-223%) at 550 µatm, 153% (56-295%) at 750 µatm and 225% (79-413%) at 1000 µatm), and decreases in DMSP concentrations (28% (18-40%) at 550 µatm, 44% (18-64%) at 750 µatm and 52% (24-72%) at 1000 µatm). Significant decreases in DMSP synthesis rate constants (µDMSP /d) and DMSP production rates (nmol/d) were observed in two experiments (7-90% decrease), whilst the response under high CO2 from the remaining experiments was generally indistinguishable from ambient controls. Rates of bacterial DMS gross consumption and production gave weak and inconsistent responses to high CO2. The variables and rates we report increase our understanding of the processes behind the response to OA. This could provide the opportunity to improve upon mesocosm-derived empirical modelling relationships and to move towards a mechanistic approach for predicting future DMS concentrations.

Table 1. Pressure, temperature and isotope ratios between H2O and CO2 for all experiments

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on d13C values of CO2 to trace the migration of injected CO2 in the subsurface. More recently the use of d18O values of both CO2 and reservoir fluids has been proposed as a method for quantifying in situ CO2 reservoir saturations due to O isotope exchange between CO2 and H2O and subsequent changes in d18OH2O values in the presence of high concentrations of CO2. To verify that O isotope exchange between CO2 and H2O reaches equilibrium within days, and that d18OH2O values indeed change predictably due to the presence of CO2, a laboratory study was conducted during which the isotope composition of H2O, CO2, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50°C and up to 19 MPa) and varying CO2 pressures. Conditions typical for the Pembina Cardium CO2 Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that d18O values of CO2 were on average 36.4±2.2 per mil (1 sigma, n=15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5 per mil for the experimental temperatures of 50°C. By using 18O enriched water for the experiments it was demonstrated that changes in the d18O values of water were predictably related to the fraction of O in the system sourced from CO2 in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO2 is related to the total volumetric saturation of CO2 and water as a fraction of the total volume of the system, it is concluded that changes in d18O values of reservoir fluids can be used to calculate reservoir saturations of CO2 in CCS settings given that the d18O values of CO2 and water are sufficiently distinct.

Villefranche MedSeA mesocosm experiment 2013: perturbation studies and field studies

A joint mesocosm experiment took place in February/March 2013 in the bay of Villefranche in France as part of the european MedSeA project. Nine mesocosms (52 m**3) were deployed over a 2 weeks period and 6 different levels of pCO2 and 3 control mesocosms (about 450 µatm), were used, in order to cover the range of pCO2 anticipated for the end of the present century. During this experiment, the potential effects of these perturbations on chemistry, planktonic community composition and dynamics including: eucaryotic and prokaryotic species composition, primary production, nutrient and carbon utilization, calcification, diazotrophic nitrogen fixation, organic matter exudation and composition, micro-layer composition and biogas production were studied by a group of about 25 scientists from 8 institutes and 6 countries. This is one of the first mesocosm experiments conducted in oligotrophic waters. A blog dedicated to this experiment can be viewed at: http://medseavillefranche2013.obs-vlfr.fr.

Stareso MedSeA mesocosm experiment: field and perturbation studies 2012

A joint mesocosm experiment took place in June/July 2012 in Corsica (bay of Calvi, Stareso station;http://www.stareso.com/) as part of the european MedSeA project. Nine mesocosms (52 m**3) were deployed over a 20 days period and 6 different levels of pCO2 and 3 control mesocosms (about 450 µatm), were used, in order to cover the range of pCO2 anticipated for the end of the present century. During this experiment, the potential effects of these perturbations on chemistry, planktonic community composition and dynamics including: eucaryotic and prokaryotic species composition, primary production, nutrient and carbon utilization, calcification, diazotrophic nitrogen fixation, organic matter exudation and composition, micro-layer composition and biogas production were studied by a group of about 25 scientists from 8 institutes and 6 countries. This is one of the first mesocosm experiments conducted in oligotrophic waters. A blog dedicated to this experiment can be viewed at: http://medseastareso2012.wordpress.com/.

Mesozooplankton community development at elevated CO2

The increasing CO2 concentration in the atmosphere caused by burning fossil fuels leads to increasing pCO2 and decreasing pH in the world ocean. These changes may have severe consequences for marine biota, especially in cold-water ecosystems due to higher solubility of CO2. However, studies on the response of mesozooplankton communities to elevated CO2 are still lacking. In order to test whether abundance and taxonomic composition change with pCO2, we have sampled nine mesocosms, which were deployed in Kongsfjorden, an Arctic fjord at Svalbard, and were adjusted to eight CO2 concentrations, initially ranging from 185 µatm to 1420 µatm. Vertical net hauls were taken weekly over about one month with an Apstein net (55 µm mesh size) in all mesocosms and the surrounding fjord. In addition, sediment trap samples, taken every second day in the mesocosms, were analysed to account for losses due to vertical migration and mortality. The taxonomic analysis revealed that meroplanktonic larvae (Cirripedia, Polychaeta, Bivalvia, Gastropoda, and Decapoda) dominated in the mesocosms while copepods (Calanus spp., Oithona similis, Acartia longiremis and Microsetella norvegica) were found in lower abundances. In the fjord copepods prevailed for most of our study. With time, abundance and taxonomic composition developed similarly in all mesocosms and the pCO2 had no significant effect on the overall community structure. Also, we did not find significant relationships between the pCO2 level and the abundance of single taxa. Changes in heterogeneous communities are, however, difficult to detect, and the exposure to elevated pCO2 was relatively short. We therefore suggest that future mesocosm experiments should be run for longer periods.

Hydrocarbon concentrations from pressurized cores in the northern Gulf of Mexico

Two newly developed coring devices, the Multi-Autoclave-Corer and the Dynamic Autoclave Piston Corer were deployed in shallow gas hydrate-bearing sediments in the northern Gulf of Mexico during research cruise SO174 (Oct-Nov 2003). For the first time, they enable the retrieval of near-surface sediment cores under ambient pressure. This enables the determination of in situ methane concentrations and amounts of gas hydrate in sediment depths where bottom water temperature and pressure changes most strongly influence gas/hydrate relationships. At seep sites of GC185 (Bush Hill) and the newly discovered sites at GC415, we determined the volume of low-weight hydrocarbons (C1 through C5) from nine pressurized cores via controlled degassing. The resulting in situ methane concentrations vary by two orders of magnitudes between 0.031 and 0.985 mol kg**-1 pore water below the zone of sulfate depletion. This includes dissolved, free, and hydrate-bound CH4. Combined with results from conventional cores, this establishes a variability of methane concentrations in close proximity to seep sites of five orders of magnitude. In total four out of nine pressure cores had CH4 concentrations above equilibrium with gas hydrates. Two of them contain gas hydrate volumes of 15% (GC185) and 18% (GC415) of pore space. The measurements prove that the highest methane concentrations are not necessarily related to the highest advection rates. Brine advection inhibits gas hydrate stability a few centimeters below the sediment surface at the depth of anaerobic oxidation of methane and thus inhibits the storage of enhanced methane volumes. Here, computerized tomography (CT) of the pressure cores detected small amounts of free gas. This finding has major implications for methane distribution, possible consumption, and escape into the bottom water in fluid flow systems related to halokinesis.

Carbonate chemistry, community metabolism, PAR, temperature and salinity of One Tree Island reef

There are few in situ studies showing how net community calcification (Gnet) of coral reefs is related to carbonate chemistry, and the studies to date have demonstrated different predicted rates of change. In this study, we measured net community production (Pnet), Gnet, and carbonate chemistry of a reef flat at One Tree Island, Great Barrier Reef. Diurnal pCO2 variability of 289-724 µatm was driven primarily by photosynthesis and respiration. The reef flat was found to be net autotrophic, with daily production of ? 35 mmol C/m**2/d and net calcification of ? 33 mmol C/m**2/d . Gnet was strongly related to Pnet, which drove a hysteresis pattern in the relationship between Gnet and aragonite saturation state (Omega ar). Although Pnet was the main driver of Gnet, Omega ar was still an important factor, where 95% of the variance in Gnet could be described by Pnet and Omega ar. Based on the observed in situ relationship, Gnet would be expected to reach zero when Omega ar is 2.5. It is unknown what proportion of a decline in Gnet would be through reduced calcification and what would occur through increased dissolution, but the results here support predictions that overall calcium carbonate production will decline in coral reefs as a result of ocean acidification.

Effects of high CO2 levels on the ecophysiology of the diatom Thalassiosira weissflogii differ depending on the iron nutritional status

Iron availability in seawater, namely the concentration of dissolved inorganic iron ([Fe']), is affected by changes in pH. Such changes in the availability of iron should be taken into account when investigating the effects of ocean acidification on phytoplankton ecophysiology because iron plays a key role in phytoplankton metabolism. However, changes in iron availability in response to changes in ocean acidity are difficult to quantify specifically using natural seawater because these factors change simultaneously. In the present study, the availability of iron and carbonate chemistry were manipulated individually and simultaneously in the laboratory to examine the effect of each factor on phytoplankton ecophysiology. The effects of various pCO2 conditions (390, 600, and 800 µatm) on the growth, cell size, and elemental stoichiometry (carbon [C], nitrogen [N], phosphorus [P], and silicon [Si]) of the diatom Thalassiosira weissflogii under high iron ([Fe'] = 240 pmol/l) and low iron ([Fe'] = 24 pmol/l) conditions were investigated. Cell volume decreased with increasing pCO2, whereas intracellular C, N, and P concentrations increased with increasing pCO2 only under high iron conditions. Si:C, Si:N, and Si:P ratios decreased with increasing pCO2. It reflects higher production of net C, N, and P with no corresponding change in net Si production under high pCO2 and high iron conditions. In contrast, significant linear relationships between measured parameters and pCO2 were rarely detected under low iron conditions. We conclude that the increasing CO2 levels could affect on the biogeochemical cycling of bioelements selectively under the iron-replete conditions in the coastal ecosystems.