Bicarbonate uptake via an anion exchange protein is the main mechanism of inorganic carbon acquisition by the giant kelp Macrocystis pyrifera (Laminariales, Phaeophyceae) under variable pH

Macrocystis pyrifera is a widely distributed, highly productive, seaweed. It is known to use bicarbonate (HCO3-) from seawater in photosynthesis and the main mechanism of utilization is attributed to the external catalyzed dehydration of HCO3- by the surface-bound enzyme carbonic anhydrase (CAext). Here, we examined other putative HCO3- uptake mechanisms in M. pyrifera under pHT 9.00 (HCO3-: CO2 = 940:1) and pHT 7.65 (HCO3-: CO2 = 51:1). Rates of photosynthesis, and internal CA (CAint) and CAext activity were measured following the application of AZ which inhibits CAext, and DIDS which inhibits a different HCO3- uptake system, via an anion exchange (AE) protein. We found that the main mechanism of HCO3- uptake by M. pyrifera is via an AE protein, regardless of the HCO3-: CO2 ratio, with CAext making little contribution. Inhibiting the AE protein led to a 55%-65% decrease in photosynthetic rates. Inhibiting both the AE protein and CAext at pHT 9.00 led to 80%-100% inhibition of photosynthesis, whereas at pHT 7.65, passive CO2 diffusion supported 33% of photosynthesis. CAint was active at pHT 7.65 and 9.00, and activity was always higher than CAext, because of its role in dehydrating HCO3- to supply CO2 to RuBisCO. Interestingly, the main mechanism of HCO3- uptake in M. pyrifera was different than that in other Laminariales studied (CAext-catalyzed reaction) and we suggest that species-specific knowledge of carbon uptake mechanisms is required in order to elucidate how seaweeds might respond to future changes in HCO3-:CO2 due to ocean acidification.

Chemical composition of interstitial waters from sediments of brine-bearing deeps of the Red Sea

Data on concentrations of the major ions (Cl, SO4, Alk, Na, K, Ca, Mg, NH4) in interstitial waters from sediments of three brine-bearing deeps of the Red Sea rift zone are reported. Interstitial waters of the Atlantis-II Deep have the highest salinity (310.1 g/l), of the Discovery Deep - slightly lower (298.8 g/l), and of the Suakin Deep - the lowest (159.9 g/l). Interstitial waters of all three deeps are characterized by low, compared with sea water, absolute and relative concentrations of Mg and SO4 ions and have extremely low alkaline reserve (0.15-0.64 meq/l). Concentrations of K, Ca and especially Na and Cl ions, as compared with sea water, are highly increased. Interstitial waters from the deeps in study have high, compared with sea water, concentrations of NH4 (12-62 mg/l).

Interstitial-water geochemistry of Kerguelen Plateau sediments

This report synthesizes all of the interstitial-water chemistry studies associated with the Kerguelen Plateau phase of ODP Leg 119. Sediments were cored at six sites (49°24'S to 59°36'S) in water depths ranging from 564 to 4082 m. A total of 77 interstitial-water samples was recovered as part of the routine sampling protocol. In addition, a novel, highresolution pore-water sampling program was tested during Leg 119 that enabled us to pinpoint reaction zones and extend our data base to deeper, drier levels that were heretofore inaccessible. Data collected include interstitial-water sodium, potassium, calcium, magnesium, pH, alkalinity, sulfate, ammonia, phosphate, aqueous silica, salinity, chloride, oxidation-reduction potentials, and sediment chemistry. The northern sector (Sites 736 and 737) is characterized by the highest sedimentation rates (up to 140 m/m.y.) and thermal gradients (70°-98°C/km) encountered on the Kerguelen Plateau during Leg 119. Site 737 represents the most reactive sediment column cored on the Kerguelen Plateau. Major cation fluxes at Site 737 are the strongest measured during Leg 119. High dissolved calcium concentrations (141.5 mM) were encountered near the bottom of Hole 737B. Elevated temperatures promote silica diagenesis and the alteration of volcanic material below 300 mbsf, and a diagenetic front was discovered near 370 mbsf at Site 737. The southern portion of the Kerguelen Plateau (Sites 738 and 744) records the lowest sedimentation rates (less than 5 m/m.y.) and thermal gradients (43°C/km) of the three study areas. Major cation fluxes at the southern sites are the lowest that we measured on the Kerguelen Plateau. High-resolution sampling provided evidence for significant silica release to the pore waters during the weathering of basement basalt. The relatively low thermal gradient does not appear to be sufficient for the formation of the opal-CT and quartz chert beds and nodules that were encountered below 120 mbsf at Site 738. Sediment-accumulation rates on the Eastern Kerguelen Sediment Ridge (Sites 745 and 746) are intermediate to those of the northern and southern sites. Deposition below the regional CCD accounts for the nearly carbonate-free, siliceous sediments. Despite their low organic carbon contents (mean = 0.15%), sediments on the Eastern Kerguelen Sediment Ridge exhibit the highest pore-water alkalinity (6.77 mM), ammonium (0.50 mM), and phosphate (23 µM) concentrations measured on the Kerguelen Plateau. Major cation fluxes are intermediate to those calculated for the northern and southern sites. The Eastern Kerguelen Sediment Ridge interstitial waters are unusual, however, in that the downward flux of magnesium is greater than the upward flux of calcium.

Ion concentration and deduced chemical compounds of the GRIP and Dome Fuji ice cores, Greenland and Antarctica

We have proposed a method of deducing the chemical compounds found in deep polar ice cores by analyzing the balance between six major ions (Cl-, NO3-, SO4**2-, Na+, Mg2+, and Ca2+). The method is demonstrated for the Holocene and last glacial maximum regions of the Dome Fuji and GRIP ice cores. The dominant compounds depend only on the ion balance and the sequence of chemical reactions. In priority order, the principle salts are calcium sulfate, other sulfates, nitrate, chloride, and carbonate. The chemical abundances deduced by this method agree well with the results of Raman spectroscopy on individual salt inclusions. The abundances in the ice cores are shown to reflect differences in climatic periods (the acidic environment of the Holocene versus the reductive environment of the last glacial maximum) and regional conditions (the marine environment of Antarctica versus the continental environment of Greenland).

Geochemistry and Nd-Pb isotope ratios of sediments from the Lesser Antilles arc

The Lesser Antilles arc is a particularly interesting island arc because it is presently very active, it is located perpendicular to the South American continent and its chemical and isotopic compositions display a strong north-south gradient. While the presence in the south of a thick pile of sedimentary material coming from the old South American continent has long been suspected to explain the geochemical gradient, previous studies failed to demonstrate unambiguously a direct link between the arc lava compositions and the subducted sediment compositions. Here, we present new Nd, Sm, Th, U and Pb concentrations and Nd-Pb isotopic data for over 60 sediments from three sites located in the fore arc region of the Lesser Antilles arc. New data for DSDP Site 543 drill core located east of Dominica Island complement the data published by White et al. (1985, doi:10.1016/0016-7037(85)90082-1) and confirm their relatively uniform isotopic compositions (i.e., 206Pb/204Pb between 19.13 and 19.53). In contrast, data obtained on DSDP Site 144 located further south, on the edge of the South American Rise and on sediments from Barbados Island are much more variable (206Pb/204Pb ranges from 18.81 to 27.69). The very radiogenic Pb isotopic compositions are found in a 60 m thick black shale unit, which has no age equivalent in the Site 543 drill core. We interpret the peculiar composition of the southern sediments as being due to two factors, (a) the proximity of the South American craton, which contributes coarse grain old detrital material that does not travel far from the continental shelf, and (b) the presence of older sediments including the thick black shale unit formed during Oceanic Anoxic events 2 and 3. The north-south isotopic change known along the Lesser Antilles arc can be explained by the observed geographical changes in the composition of the subducted sediments. About 1% contamination of the mantle wedge by Site 543 sediments explains the composition of the northern islands while up to 10% sediments like those of Site 144 is required in the source of the southern island lavas. The presence of black shales in the subducted pile provides a satisfactory explanation for the very low Delta8/4 values that characterize the Lesser Antilles arc.

Biogeochemical measurements of cold seep sediments inhabit by vesicomyid clams in the Japan Deep Sea Trench

Vesicomyidae clams harbor sulfide-oxidizing endosymbionts and are typical members of cold seep communities associated with tectonic faults where active venting of fluids and gases takes place. We investigated the central biogeochemical processes that supported a vesicomyid clam colony as part of a locally restricted seep community in the Japan Trench at 5346 m water depth, one of the deepest seep settings studied to date. An integrated approach of biogeochemical and molecular ecological techniques was used combining in situ and ex situ measurements. During the cruise YK06-05 in 2006 with the RV Yokosuka to the Japan Trench, we investigated a clam colony inhabited by Abyssogena phaseoliformis (former known as Calyptogena phaseoliformis) and Isorropodon fossajaponicum (former known as Calyptogena fossajaponica). The targeted sampling and precise positioning of the in situ instruments were achieved with the manned research submersible Shinkai 6500 (JAMSTEC, Nankoku, Kochi, Japan). Sampling was first performed close to the rim of the JTC colony and then at the center. Immediately after sample recovery onboard, the sediment core was sub-sampled for ex situ rate measurements or preserved for later analyses. In sediment of the clam colony, low sulfate reduction (SR) rates (max. 128 nmol ml**-1 d**-1) were coupled to the anaerobic oxidation of methane (AOM). They were observed over a depth range of 15 cm, caused by active transport of sulfate due to bioturbation of the vesicomyid clams. A distinct separation between the seep and the surrounding seafloor was shown by steep horizontal geochemical gradients and pronounced microbial community shifts. The sediment below the clam colony was dominated by anaerobic methanotrophic archaea (ANME-2c) and sulfate-reducing Desulfobulbaceae (SEEP-SRB-3, SEEP-SRB-4). Aerobic methanotrophic bacteria were not detected in the sediment and the oxidation of sulfide seemed to be carried out chemolithoautotrophically by Sulfurovum species. Thus, major redox processes were mediated by distinct subgroups of seep-related microorganisms that might have been selected by this specific abyssal seep environment. Fluid flow and microbial activity was low but sufficient to support the clam community over decades and to build up high biomasses. Hence, the clams and their microbial communities adapted successfully to a low-energy regime and may represent widespread chemosynthetic communities in the Japan Trench.

Chemical and germanium isotopic compositions of sediments and sedimentary rocks from ODP Sites 129-801 and 185-1149

A new technique for the precise and accurate determination of Ge stable isotope compositions has been developed and applied to silicate rocks and biogenic opal. The analyses were performed using a continuous flow hydride generation system coupled to a MC-ICP-MS. Samples have been purified through anion- and cation-exchange resins to separate Ge from matrix elements and eliminate potential isobaric interferences. Variations of 74Ge/70Ge ratios are expressed as d74Ge values relative to our internal standard and the long-term external reproducibility of the data is better than 0.2? for sample size as low as 15 ng of Ge. Data are presented for igneous and sedimentary rocks, and the overall variation is 2.4? in d74Ge, representing 12 times the uncertainty of the measurements and demonstrating that the terrestrial isotopic composition of Ge is not unique. Co-variations of 74Ge/70Ge, 73Ge/70Ge and 72Ge/70Ge ratios follow a mass-dependent behaviour and imply natural isotopic fractionation of Ge by physicochemical processes. The range of d74Ge in igneous rocks is only 0.25? without systematic differences among continental crust, oceanic crust or mantle material. On this basis, a Bulk Silicate Earth reservoir with a d74Ge of 1.3+/-0.2? can be defined. In contrast, modern biogenic opal such as marine sponges and authigenic glauconite displayed higher d74Ge values between 2.0? and 3.0?. This suggests that biogenic opal may be significantly enriched in light isotopes with respect to seawater and places a lower bound on the d74Ge of the seawater to +3.0?.This suggests that seawater is isotopically heavy relative to Bulk Silicate Earth and that biogenic opal may be significantly fractionated with respect to seawater. Deep-sea sediments are within the range of the Bulk Silicate Earth while Mesozoic deep-sea cherts (opal and quartz) have d74Ge values ranging from 0.7? to 2.0?. The variable values of the cherts cannot be explained by binary mixing between a biogenic component and a detrital component and are suggestive of enrichment in the light isotope of diagenetic quartz. Further work is now required to determine Ge isotope fractionation by siliceous organisms and to investigate the effect of diagenetic processes during chert lithification.

(Table 1) Micro-inclusion counts and ion concentrations in the five GRIP ice-core sections

We provide the first direct evidence that a number of water-soluble compounds, in particular calcium sulfate (CaSO4 2H2O) and calcium carbonate (CaCO3), are present as solid, micron-sized inclusions within the Greenland GRIP ice core. The compounds are detected by two independent methods: micro-Raman spectroscopy of a solid ice sample, and energy-dispersive X-ray spectroscopy of individual inclusions remaining after sublimation. CaSO4 2H2O is found in abundance throughout the Holocene and the last glacial period, while CaCO3 exists mainly in the glacial period ice. We also present size and spatial distributions of the micro-inclusions. These results suggest that water-soluble aerosols in the GRIP ice core are dependable proxies for past atmospheric conditions.

Mean chemical characteristics and volcano signatures of ice cores from Belukha, the Everest and three Svalbard sites

Ice cores from outside the Greenland and Antarctic ice sheets are difficult to date because of seasonal melting and multiple sources (terrestrial, marine, biogenic and anthropogenic) of sulfates deposited onto the ice. Here we present a method of volcanic sulfate extraction that relies on fitting sulfate profiles to other ion species measured along the cores in moving windows in log space. We verify the method with a well dated section of the Belukha ice core from central Eurasia. There are excellent matches to volcanoes in the preindustrial, and clear extraction of volcanic peaks in the post-1940 period when a simple method based on calcium as a proxy for terrestrial sulfate fails due to anthropogenic sulfate deposition. We then attempt to use the same statistical scheme to locate volcanic sulfate horizons within three ice cores from Svalbard and a core from Mount Everest. Volcanic sulfate is <5% of the sulfate budget in every core, and differences in eruption signals extracted reflect the large differences in environment between western, northern and central regions of Svalbard. The Lomonosovfonna and Vestfonna cores span about the last 1000 years, with good extraction of volcanic signals, while Holtedahlfonna which extends to about AD1700 appears to lack a clear record. The Mount Everest core allows clean volcanic signal extraction and the core extends back to about AD700, slightly older than a previous flow model has suggested. The method may thus be used to extract historical volcanic records from a more diverse geographical range than hitherto.

Porewater concentrations, pH, single cell number, anaerobic oxidation of methane (AOM) rate, sulfate reduction (SR) rate of samples during METEOR cruise M76/3b at the REGAB cold seep site from the West African margin in 2008

The giant pockmark REGAB (West African margin, 3160 m water depth) is an active methane-emitting cold seep ecosystem, where the energy derived from microbially mediated oxidation of methane supports high biomass and diversity of chemosynthetic communities. Bare sediments interspersed with heterogeneous chemosynthetic assemblages of mytilid mussels, vesicomyid clams and siboglinid tubeworms form a complex seep ecosystem. To better understand if benthic bacterial communities reflect the patchy distribution of chemosynthetic fauna, all major chemosynthetic habitats at REGAB were investigated using an interdisciplinary approach combining porewater geochemistry, in situ quantification of fluxes and consumption of methane, as well bacterial community fingerprinting. This study revealed that sediments populated by different fauna assemblages show distinct biogeochemical activities and are associated with distinct sediment bacterial communities. The methane consumption and methane effluxes ranged over one to two orders of magnitude across habitats, and reached highest values at the mussel habitat, which hosted a different bacterial community compared to the other habitats. Clam assemblages had a profound impact on the sediment geochemistry, but less so on the bacterial community structure. Moreover, all clam assemblages at REGAB were restricted to sediments characterized by complete methane consumption in the seafloor, and intermediate biogeochemical activity. Overall, variations in the sediment geochemistry were reflected in the distribution of both fauna and microbial communities; and were mostly determined by methane flux.