Cloride and bromide concentrations and Br-/Cl- molar ratios in pore fluids at ODP Site 134-833

Other than halite diagenesis and organic matter degradation, Cl- and Br- are considered to be conservative in marine pore fluids. Consequently, Br-/Cl- ratios should remain constant during most diagenetic reactions. Nonetheless, Br-/Cl- molar ratios decrease to 0.00127 (~18% less than seawater value) in pore fluids from Site 833 in the Aoba Basin of the New Hebrides convergent margin despite the lack of halite diagenesis and little organic matter. Sediment at this site is largely volcanic ash, which becomes hydrated with depth as it converts to clay and zeolite minerals. These hydration reactions remove sufficient water to increase the concentrations of most solutes including Cl- and Br-. The resulting concentration gradients drive diffusion, but calculations indicate that diffusion does not decrease the Br-/Cl- ratio. Some Cl- may be leached from the ash, but insufficient amounts are available to cause the observed decrease in Br-/Cl- ratio. The limited source of Cl- suggests that proportionately more Br- than Cl- is lost from the fluids to the diagenetic solids. Similar nonconservative behavior of Cl- and Br- may occur during fluid circulation at ridge crests and flanks, thereby influencing the halide distribution in the crust.

Oceanography during TYDEMAN cruise DCM (DeepChlorMax) to the Equatorial Atlantic

The cruise with RV Tydeman was devoted to study permanently stratified plankton systems in the (sub)tropical ocean, which are characterised by a deep chlorophyll peak between 80 and 150 m. To minimise lateral effects by horizontal transport of nutrients and organic matter from river outflow and upwelling regions, stations were selected in the middle of the North Atlantic Ocean between the continents of America and Africa. (5 - 35° N and 50 - 15° W). Here the vertical distributions of light and nutrients control the abundance and growth of autotrophic algae in the thermically stratified water column. This phytoplankton is numerically dominated by the prokaryotic picoplankters Synechococcus spp. and Prochlorococcus spp., which are smaller than 2 ?m. The productivity of the 100 to 150 m deep euphotic zone can be high, because a high heterotrophic/autotrophic biomass ratio induces a rapid regeneration of nutrients and inorganic carbon. Primary grazers are mainly micro-organisms such as heterotrophic nannoflagellates and ciliates, which feed on the small algae and on bacteria. Heterotrophic bacteria can outnumber the autotrophic algae, because their number is related to the substrate pools of dissolved and particulate dead organic matter. These DOC and detritus pools reach equilibrium at a concentration, where the rate of their production (proportional to algal biomass) equals their mineralisation and sinking rate (proportional to the concentration and weight of POC and detritus). At a relatively low value of the weight-specific loss rates, the equilibrium concentration of these carbon pools and their load of bacteria can be high. The bacterial productivity is proportional to the mineralisation rate, which in a steady state can never be higher than the rate of primary production. Hence the ratio in turnover rate of bacteria and autotrophs tends to be reciprocally proportional to their biomass ratio.

n-fatty acids of shale partings in the Franciscan bedded cherts

Normal saturated fatty acid (n-fatty acid) in marine sediments from coastal and pelagic environments were analyzed. The coastal sediments contain both short-chained n-fatty acids with carbon numbers from 12 to 18 and long-chained acids from 22 to 32, whereas the pelagic sediments contain predominantly short-chained acids. The relative abundance of short-chained to long-chained n-fatty acids, expressed by the molar ratio C16/C26, can be an indicator to assess the depositional environment of sedimentary rocks. The ratio of long-chained n-fatty acids (C22-C32) to the total n-fatty acids also has the potential to discriminate sedimentary environments. The indicators based on the n-fatty acids were applied to the Franciscan bedded cherts. The result shows that the bedded cherts had deposited in continuous environments from the pelagic to the coastal. This is in harmony with the same inference based on major, trace and rare earth elements and normal paraffins.

Organic compounds in sediments and pore waters of ODP Sites 117-723 and 117-724

Total organic carbon, amino compounds, and carbohydrates were measured in pore waters and sediments of Pliocene to Pleistocene age from Sites 723 and 724 (ODP Leg 117) to evaluate (1) relationships between organic matter in the sediment and in the pore water, (2) the imprint of lithological variations on the abundance and contribution of organic substances, (3) degradation of amino compounds and carbohydrates with time and/or depth, and (4) the dependence of the ammonia concentration in the pore water on the degradation of amino compounds in the sediment. Total organic carbon concentrations (TOC) of the investigated sediment samples range from 0.9% to 8.7%, and total nitrogen concentrations (TN) from 0.1% to 0.5%. Up to 4.9% of the TOC is contributed by hydrolyzable amino acids (THAA) which are present in amounts between 1.1 and 21.3 µmol/g dry sediment and decrease strongly downhole. Hydrolyzable carbohydrates (THCHO) were found in concentrations from 1.3 to 6.6 ?mol/g sediment constituting between 0.1% and 2.0% of the TOC. Differences between the distribution patterns of monomers in Sites 723 and 724 indicate higher terrigenous influence for Site 724 and, furthermore, enhanced input of organic matter that is relatively resistant to microbial degradation. Lithologically distinct facies close to the Pliocene/Pleistocene boundary yield different organic matter compositions. Laminated horizons seem to correspond with enhanced amounts of biogenic siliceous material and minor microbiological degradation. Total amounts of dissolved organic carbon (DOC) in pore waters vary between 11 and 131 mg/L. Concentrations of DOC as well as of dissolved amino compounds and carbohydrates appear to be related to microbial activity and/or associated redox zones and not so much to the abundance of organic matter in the sediments. Distributions of amino acids and monosaccharides in pore waters show a general enrichment in relatively stable components in comparison to those of the sediments. Nevertheless, the same trend appears between amino acids present in the sediments from Sites 723 and 724 as well as between amino acids in pore waters from these two sites, indicating a direct relation between the dissolved and the sedimentary organic fractions. Different ammonia concentrations in the pore waters of Sites 723 and 724 seem to be related to enhanced release of ammonia from degradation of amino compounds in Site 723.

Distribution of Au and Pd in basalts and diabases in DSDP/ODP Hole 504B

Au contents have been determined in 77 samples of basalts and sheeted diabase dikes. Pd has been evaluated in 39 of the samples. The mean amount of Au is 3 parts per billion (ppb), fluctuating from 0.4 to 10 ppb. Au contents appear to be independent in type and intensity of alteration as well as with depth sub-bottom, although in the lower part of Hole 504B, 1900-2000 mbsf, Au contents are markedly decreased (mean: 1.1 ppb) and show a distinct correlation with a decrease in Zn contents. Pd contents vary from 2 to 360 ppb (mean: 37 ppb) Pd is higher in basalts (53.7 ppb) and lower in diabase dikes (30 ppb), especially in moderately or strongly altered ones (12.5 ppb).

Phytol and phytyldiol concentrations at DYFAMED time series station and sediment trap

Particulate samples from the water column were collected monthly from depths of 5-150 m, between May 1996 and March 1997, in the northwestern Mediterranean Sea (Ligurian Sea) as part of the DYFAMED project within the French JGOFS program. These samples were analyzed by gas chromatography-electron impact mass spectrometry for their phytol and 3-methylidene-3,7,11-trimethylhexadecan-1,2-diol (phytyldiol) content. The corresponding Chlorophyll Phytyl side chain Photodegradation Index, molar ratio of phytyldiol to phytol, was calculated and the mean amount of chlorophyll photodegraded within the euphotic zone estimated. Seasonal differences in the chlorophyll photodegradation process appear in the one-year study. The chlorophyll appeared more photodegraded in the surface water (generally more than 40% photodegraded at 5-10 m) than at the deep chlorophyll maximum (DCM) (40-50 m) observed in the summer stratified waters (about 20% photodegraded). This difference was attributed to the healthy state of the phytoplankton community (coincidence with the highest primary production levels) and to the lower intensity of irradiance at the DCM level. On the other hand, the bulk of the detrital chlorophyll (chlorophyll associated with phytodetritus, phaeopigments) undergoes photodegradation before it sinks out of the photic zone. However, in January (winter mixed water) the pigments exported towards the sea floor were less photodegraded. This is thought to result from a shorter period of residence of the pigments in the photic zone due to vertical convection and grazing activity of macrozooplankton (salps), which are producers of rapid sinking fecal pellets.

Part of the global DOC versus AOU (dissolved organic carbon/apparent oxygen utilization) data compilation, Ross Sea

Dissolved and particulate organic matter was measured during six cruises to the southern Ross Sea. The cruises were conducted during late austral winter to autumn from 1994 to 1997 and included coverage of various stages of the seasonal phytoplankton bloom. The data from the various years are compiled into a representative seasonal cycle in order to assess general patterns of dissolved organic matter (DOM) and particulate organic matter (POM) dynamics in the southern Ross Sea. Dissolved organic carbon (DOC) and particulate organic carbon (POC) were at background concentrations of approximately 42 and 3 µM C, respectively, during the late winter conditions in October. As the spring phytoplankton bloom progressed, organic matter increased, and by January DOC and POC reached as high as 30 and 107 µM C, respectively, in excess of initial wintertime conditions. Stocks and concentrations of DOC and POC returned to near background values by autumn (April). Approximately 90% of the accumulated organic matter was partitioned into POM, with modest net accumulation of DOM stocks despite large net organic matter production and the dominance of Phaeocystis antarctica. Changes in NO3 concentration from wintertime values were used to calculate the equivalent biological drawdown of dissolved inorganic carbon (DICequiv). The fraction of DICequiv drawdown resulting in net DOC production was relatively constant (ca. 11%), despite large temporal and spatial variability in DICequiv drawdown. The C : N (molar ratio) of the seasonally produced DOM had a geometric mean of 6.2 and was nitrogen-rich compared to background DOM. The DOM stocks that accumulate in excess of deep refractory background stocks are often referred to as "semi-labile" DOM. The "semi-labile" pool in the Ross Sea turns over on timescales of about 6 months. As a result of the modest net DOM production and its lability, the role DOM plays in export to the deep sea is small in this region.

Part of the global DOC versus AOU (dissolved organic carbon/apparent oxygen utilization) data compilation, BATS

The contributions of total organic carbon and nitrogen to elemental cycling in the surface layer of the Sargasso Sea are evaluated using a 5-yr time-series data set (1994-1998). Surface-layer total organic carbon (TOC) and total organic nitrogen (TON) concentrations ranged from 60 to 70 µM C and 4 to 5.5 µM N seasonally, resulting in a mean C : N molar ratio of 14.4±2.2. The highest surface concentrations varied little during individual summer periods, indicating that net TOC production ceased during the highly oligotrophic summer season. Winter overturn and mixing of the water column were both the cause of concentration reductions and the trigger for net TOC production each year following nutrient entrainment and subsequent new production. The net production of TOC varied with the maximum in the winter mixed-layer depth (MLD), with greater mixing supporting the greatest net production of TOC. In winter 1995, the TOC stock increased by 1.4 mol C/m**2 in response to maximum mixing depths of 260 m. In subsequent years experiencing shallower maxima in MLD (<220 m), TOC stocks increased <0.7 mol C/m**2. Overturn of the water column served to export TOC to depth (>100 m), with the amount exported dependent on the depth of mixing (total export ranged from 0.4 to 1.4 mol C/m**2/yr). The exported TOC was comprised both of material resident in the surface layer during late summer (resident TOC) and material newly produced during the spring bloom period (fresh TOC). Export of resident TOC ranged from 0.5 to 0.8 mol C/m**2/yr, covarying with the maximum winter MLD. Export of fresh TOC varied from nil to 0.8 mol C/m**2/yr. Fresh TOC was exported only after a threshold maximum winter MLD of ~200 m was reached. In years with shallower mixing, fresh TOC export and net TOC production in the surface layer were greatly reduced. The decay rates of the exported TOC also covaried with maximum MLD. The year with deepest mixing resulted in the highest export and the highest decay rate (0.003 1/d) while shallow and low export resulted in low decay rates (0.0002 1/d), likely a consequence of the quality of material exported. The exported TOC supported oxygen utilization at dC : dO2 molar ratios ranging from 0.17 when TOC export was low to 0.47 when it was high. We estimate that exported TOC drove 15-41% of the annual oxygen utilization rates in the 100-400 m depth range. Finally, there was a lack of variability in the surface-layer TON signal during summer. The lack of a summer signal for net TON production suggests a small role for N2 fixation at the site. We hypothesize that if N2 fixation is responsible for elevated N : P ratios in the main thermocline of the Sargasso Sea, then the process must take place south of Bermuda and the signal transported north with the Gulf Stream system.

Seawater carbonate chemistry, calcification and respiration duirng experiments with a pteropod Creseis acicula, 2010

Among marine calcifiers, shelled pteropods are expected to be particularly sensitive to ocean acidification, generated by the uptake of anthropogenic CO2 by the ocean, and the associated decrease of the seawater saturation state with respect to aragonite (omega aragonite). The few available studies have mostly focused on polar species although pteropods are also important components of temperate and tropical ecosystems. It is also unknown which parameter of the carbonate system controls calcification. Specimens of the temperate Mediterranean species Creseis acicula were maintained under seven different conditions of the carbonate chemistry, obtained by manipulating pH and total alkalinity, with the goal to disentangle the effects of pH and omega aragonite. Respiration, excretion as well as rates of net and gross calcification were not directly affected by a decrease in pH but decreased significantly with a decrease of omega aragonite. The decrease of gross calcification rates is consistent with that reported for polar species. Although the organisms were apparently able to maintain gross calcification rates under slightly undersaturated aragonite conditions, the clear net dissolution signal observed below saturation suggests that they are not able to build a shell in seawater corrosive to aragonite. The decrease in respiration and excretion, and the low O:N molar ratio, could be due to the short time that the organisms were allowed to acclimatize to their new environment.

Geochemistry of volcanivlastic sediments of ODP Sites 134-832 and 134-833

Volcaniclastic sediments of North Aoba Basin (Vanuatu) recovered during Ocean Drilling Program (ODP) Leg 134 show a mineralogical and chemical overprint of low grade hydrothermal alteration superimposed on the primary magmatic source compositions. The purpose of this study was to identify authigenic mineral phases incorporated in the volcaniclastic sediments, to distinguish authigenic chemical and mineralogical signals from the original volcaniclastic mineralogical and chemical compositions, and to determine the mechanism of authigenic minerals formation. Mineralogical, micro-chemical and bulk chemical analyses were utilized to identify and characterize authigenic phases and determine the original unaltered ash compositions. 117 volcaniclastic sediment samples from North Aoba Basin Sites 832 and 833 were analyzed. Primary volcaniclastic materials accumulated in North Aoba Basin can be divided into three types. The older basin-filling sequences show three different magmatic trends: high K, calc-alkaline, and low K series. The most recent accumulations are rhyodacitic composition and can be attributed to Santa Maria or Aoba volcanic emissions. Original depositional porosity of volcaniclastic sediments is an important factor in influencing distribution of authigenic phases. Finer-grained units are less altered and retain a bulk mineralogical and chemical composition close to the original pyroclastic rock composition. Coarser grained units (microbreccia and sandstones) are the major hosts of authigenic minerals. At both sites, authigenic minerals (including zeolites, clay minerals, Mg-carbonates, and quartz) exhibit complex zonation with depth that crosses original ash depositional boundaries and stratigraphic limits. The zeolite minerals phillipsite and analcime are ubiquitous throughout the altered intervals. At Site 832, the first zeolite minerals (phillipsite) occur in Pleistocene deposits as shallow as 146 meters below seafloor (mbsf). At Site 833 the first zeolite minerals (analcime) occur in Pleistocene deposits as shallow as 224 mbsf. The assemblage phillipsite + analcime + chabazite appears at 635 mbsf (Site 832) and at 376 mbsf (Site 833). Phillipsite + analcime + chabazite + thomsonite + heulandite are observed between 443 and 732 mbsf at Site 833. Thomsonite is no longer observed below 732 mbsf at Site 833. Heulandite is present to the base of the sections cored. The zeolite assemblages are associated with authigenic clay minerals (nontronite and saponite), calcite, and quartz. Chlorite is noticeable at Site 832 as deep as 851 mbsf. Zeolite zones are present but are less well defined at Site 832. Dolomite and rare magnesite are present below 940 m at Site 832. The coarse-grained authigenic mineral host intervals exhibit geochemical signatures that can be attributed to low grade hydrothermal alteration. The altered intervals show evidence of K2O, CaO, and rare earth elements mobilization. When compared to fine-grained, unaltered units, and to Santa Maria Island volcanics rocks, the altered zones are relatively depleted in rare earth elements, with light rare earth elements-heavy rare earth elements fractionation. Drilling at Site 833 penetrated a sill complex below 840 m. No sill was encountered at Site 832. Complex zonation of zeolite facies, authigenic smectites, carbonates and quartz, and associated geochemical signatures are present at both sites. The mineralogical and chemical alteration overprint is most pronounced in the deeper sections at Site 832. Based on mineralogical and chemical evidence at two locations less than 50 km apart, there is vertical and lateral variation in alteration of the volcaniclastic sediments of North Aoba Basin. The alteration observed may be activated by sill intrusion and associated expulsion of heated fluids into intervals of greater porosity. Such spatial variation in alteration could be attributed to the evolution of the basin axis associated with subduction processes along the New Hebrides Trench.

Hydrogen isotope composition of pore waters and interlayer water in sediments of ODP Leg 129 holes

Hydrogen isotope compositions have been measured on pore waters from sediments of Leg 129 sites in the Pigafetta and East Mariana basins (central western Pacific). Total water (pore + sorbed waters) contents and their dD have been analyzed for three samples that contain smectite but no zeolite so that sorbed water can be attributed to interlayer water. The H budget for pore and total waters implies that interlayer water is 20 per mil to 30 per mil depleted in D compared to pore water. Because the interlayer/total water molar ratio (0.25 to 0.5) in smectitic sediments is very high, interlayer water represents an important reservoir of D-depleted water in sediments. dD depth profiles for pore water at Sites 800 and 801 show breaks related to chert and radiolarite layers and are relatively vertical below. Above these chert units, pore waters are similar to modern seawater but below, they are between -10 per mil and -5.5 per mil. These values could represent little modified pre-Miocene seawater values, which were D-depleted because of the absence of polar caps, and were preserved from diffusive exchange with modern seawater by the relatively impermeable overlying chert layers. At Site 802, dD values of the pore waters show a decrease in the Miocene tuffs from 0 per mil values at the top to -8 per mil at 250 mbsf. Below, dD values are relatively uniform at about -8ë. Miocene tuffs are undergoing low water/rock alteration. A positive covariation of dD and Cl content of pore water in the tuffs suggests that the increase of dD values could result from secondary smectite formation. Low diffusive exchange coupled with D enrichment due to alteration of preglacial waters could explain the observed profile.