Deep ocean fluxes and their link to surface ocean processes and the biological pump

Intense studies of upper and deep ocean processes were carried out in the Northwestern Indian Ocean (Arabian Sea) within the framework of JGOFS and related projects in order to improve our understanding of the marine carbon cycle and the ocean’s role as a reservoir for atmospheric CO₂. The results show a pronounced monsoon-driven seasonality with enhanced organic carbon fluxes into the deep-sea during the SW Monsoon and during the early and late NE Monsoon north of 10°N. The productivity is mainly regulated by inputs of nutrients from subsurface waters into the euphotic zone via upwelling and mixed layer-deepening. Deep mixing introduces light limitation by carrying photoautotrophic organisms below the euphotic zone during the peak of the NE Monsoon. Nevertheless, deep mixing and strong upwelling during the SW Monsoon provide an ecological advantage for diatoms over other photoautotrophic organisms by increasing the silica concentrations in the euphotic zone. When silica concentrations fall below 2 μmol l⁻¹, diatoms lose their dominance in the plankton community. During diatom-dominated blooms, the biological pathway of uptake of CO₂ (the biological pump) appears to be more efficient than during blooms of other organisms, as indicated by organic carbon to carbonate carbon (rain) ratios. Due to the seasonal alternation of diatom and non-diatom dominated exports, spatial variations of the annual mean rain ratios are hardly discernible along the main JGOFS transect.Data-based estimates of the annual mean impact of the biological pump on the fCO₂ in the surface water suggest that the biological pump reduces the increase of fCO₂ in the surface water caused by intrusion of CO₂-enriched subsurface water by 50–70%. The remaining 30 to 50% are attributed to CO₂ emissions into the atmosphere. Rain ratios up to 60% higher in river-influenced areas off Pakistan and in the Bay of Bengal than in the open Arabian Sea imply that riverine silica inputs can further enhance the impact of the biological pump on the fCO₂ in the surface water by supporting diatom blooms. Consequently, it is assumed that reduced river discharges caused by the damming of major rivers increase CO₂ emission by lowering silica inputs to the Arabian Sea; this mechanism probably operates in other regions of the world ocean also.     

Microbial Biomass and Organic Nutrients in the Deep-Sea Sediments of the Central Indian Ocean Basin

In order to assess the impact of deep-sea mining on the in situ benthic life, we measured the microbial standing stock and concentration of organic nutrients in the deep-sea sediments of the Central Indian Ocean Basin in the Indian pioneer area. Sediments were collected using box core and grab samples during September 1996. The total bacterial numbers ranged from 10 10 -10 11 cells per g -1 dry weight sediment. There was a marginal decrease in the number of bacteria from surface to 30 cm depth, though the subsurface section registered a higher number than did the surface. The highest numbers were encountered at depths of 4-8 cm. The retrievable number of bacteria were two orders less in comparison with the direct total counts of bacteria. An almost homogeneous distribution of bacteria, total organic carbon, living biomass, and lipids throughout the depth of cores indicates active microbial and benthic processes in the deep sea sediments. On the other hand, a uniform distribution of total counts of bacteria, carbohydrates, and total organic carbon in all the cores indicates their stable nature and suggests that they can serve as useful parameters for long-term monitoring of the area after the benthic disturbance. Further studies on temporal variability in this region would not only verify the observed norms of distribution of these variables but would also help to understand restabilization processes after the simulated benthic disturbance.     

The influence of island generated eddies on the carbon dioxide system, south of the Canary Islands

Measurements of surface partial pressure of CO₂ and water column alkalinity, pH_T, nutrients, oxygen, fluorescence and hydrography were carried out, south of the Canary Islands during September 1998. Cyclonic and anticyclonic eddies were alternatively observed from the northwestern area to the central area of the Canary Islands. Nutrient pumping and vertical uplifting of the deep chlorophyll maximum by cyclonic eddies were also ascertained by upward displacement of dissolved inorganic carbon. A model was applied to determine the net inorganic carbon balance in the cyclonic eddy. The fluxes were determined considering both the diffusive and convective contributions from the upward pumping and the corresponding horizontal transport of water outside the area. An increase in the total inorganic carbon concentration in the upper layers inside the eddy field of 133 mmol C m^− 2 d^− 1 was determined. The upward flux of inorganic carbon decreased the effect of the increased primary production on the carbon dioxide chemistry. The reduced fCO₂ inside the cyclonic eddy, 15 μatm lower than that observed in non-affected surface water, was explained by thermodynamic aspects, biological activity, eddy upward pumping and diffusion and air–sea water exchange effects.     

Fluid–Sediment Interaction in a Marine Shallow-Water Hydrothermal System in the Wakamiko Submarine Crater, South Kyushu, Japan

The Wakamiko submarine crater is a small depression located in Kagoshima Bay, southwest Japan. Marine shallow‐water hydrothermal activity associated with fumarolic gas emissions at the crater sea floor (water depth 200 m) is considered to be related with magmatic activity of the Aira Caldera. During the NT05‐13 dive expedition conducted in August 2005 using remotely operated vehicle Hyper‐Dolphine (Japan Agency for Marine‐Earth Science and Technology), an active shimmering site was discovered (tentatively named the North site) at approximately 1 km from the previously known site (tentatively named the South site). Surface sediment (up to 30 cm) was cored from six localities including these active sites, and the alteration minerals and pore fluid chemistry were studied. The pore fluids of these sites showed a drastic change in chemical profile from that of seawater, even at 30 cm below the surface, which is attributed to mixing of the ascending hydrothermal component and seawater. The hydrothermal component of the North site is estimated to be derived from a hydrothermal aquifer at 230°C based on the hydrothermal end‐member composition. Occurrence of illite/smectite interstratified minerals in the North site sediment is attributed to in situ fluid–sediment interaction at a temperature around 150°C, which is in accordance with the pore fluid chemistry. In contrast, montmorillonite was identified as the dominant alteration mineral in the South site sediment. Together with the significant low potassium concentration of the hydrothermal end‐member, the abundant occurrence of low‐temperature alteration mineral suggests that the hydrothermal aquifer in the South site is not as high as 200°C. Moreover, the montmorillonite is likely to be unstable with the present pore fluid chemistry at the measured temperature (117°C). This disagreement implies unstable hydrothermal activity at the South site, in contrast to the equilibrium between the pore fluid and alteration minerals in the North site sediment. This difference may reflect the thermal and/or hydrological structure of the Wakamiko Crater hydrothermal system.     

Environmental geochemistry of the River Gomti: A tributary of the Ganges River

Water and sediment samples collected from the Gomti River, a tributary of the Ganges River system, during the postmonsoon season have been analyzed to estimate major elemental chemistry. Water chemistry of the River Gomti shows almost monotonous spatial distribution of various chemical species, especially because of uniform presence of alluvium Dun gravels throughout the basin. The river annually transports 0.34×10⁶ tonnes of total suspended material (TSM) and 3.0×10⁶ tonnes of total dissolved solids (TDS), 69 percent of which is accounted for by bicarbonate ions only. Samples collected downstream of the city of Lucknow show the influence of anthropogenic loadings for a considerable distance in the river water. Na⁺, Cl^–, and SO₄ ^2– concentrations build up downstream. The bed sediment chemistry is dominated by Si (36 percent), reflecting a high percentage of detrital quartz, which makes up about 74 percent of the mineralogy of the bed sediments in the River Gomti. The average Kjeldahl nitrogen concentration (234 g/g) indicates indirectly the amount of organic matter in the sediments. The Hg concentration in sediments has been found to be higher (average 904 ppb) than the background value. The suspended sediments are well sorted, very finely skewed, and extremely leptokurtic, indicating a low energy condition of flow in the Gomti River. The influence of chemical loads in the Gomti has been found to be small or nonexistent on the Ganges River, perhaps because the water discharge of the Gomti (1.57 percent) to the Ganges is quite low.     

Rate constants for the reactions of the NO3 radical with HCOOH/HCOO− and CH3COOH/CH3COO− in aqueous solution between 278 and 328 K

The kinetics of the aqueous phase reactions of NO₃ radicals with HCOOH/HCOO^– and CH₃COOH/CH₃COO^– have been investigated using a laser photolysis/long-path laser absorption technique. NO₃ was produced via excimer laser photolysis of peroxodisulfate anions (S₂O ₈ ^2– ) at 351 nm followed by the reactions of sulfate radicals (SO ₄ ^– ) with excess nitrate. The time-resolved detection of NO₃ was achieved by long-path laser absorption at 632.8 nm. For the reactions of NO₃ with formic acid (1) and formate (2) rate coefficients ofk ₁=(3.3±1.0)×10⁵ l mol^–1 s^–1 andk ₂=(5.0±0.4)×10⁷ l mol^–1 s^–1 were found atT=298 K andI=0.19 mol/l. The following Arrhenius expressions were derived:k ₁(T)=(3.4±0.3)×10¹⁰ exp[–(3400±600)/T] l mol^–1 s^–1 andk ₂(T)=(8.2±0.8)×10¹⁰ exp[–(2200±700)/T] l mol^–1 s^–1. The rate coefficients for the reactions of NO₃ with acetic acid (3) and acetate (4) atT=298 K andI=0.19 mol/l were determined as:k ₃=(1.3±0.3)×10⁴ l mol^–1 s^–1 andk ₄=(2.3±0.4)×10⁶ l mol^–1 s^–1. The temperature dependences for these reactions are described by:k ₃(T)=(4.9±0.5)×10⁹ exp[–(3800±700)/T] l mol^–1 s^–1 andk ₄(T)=(1.0±0.2)×10¹² exp[–(3800±1200)/T] l mol^–1 s^–1. The differences in reactivity of the anions HCOO^– and CH₃COO^– compared to their corresponding acids HCOOH and CH₃COOH are explained by the higher reactivity of NO₃ in charge transfer processes compared to H atom abstraction. From a comparison of NO₃ reactions with various droplets constituents it is concluded that the reaction of NO₃ with HCOO^– may present a dominant loss reaction of NO₃ in atmospheric droplets.     

Molecular and bulk isotopic analyses of organic matter in marls of the Mulhouse Basin (Tertiary, Alsace, France)

Contents of 13C in kerogens and carbonates in 21 samples from a core of the MAX borehole, Mulhouse Evaporite Basin, range from -27.3 to -23.5 and -3.7 to -1.8% vs PDB, respectively. Organic nitrogen in the same samples is enriched in 15N relative to atmospheric N2 by 12.2-15.7%. Hydrogen indices and delta values for kerogens vary systematically with facies, averaging 493 mg HC/g Corg and -25.7% in the most saline facies (dominated by inputs from aquatic sources) and 267 mg HC/g Corg and -23.7% in the least saline facies (50/50 aquatic/terrigenous). Values of delta were measured for individual aliphatic hydrocarbons from three samples representing three different organic facies. For all samples, terrigenous inputs were unusually rich in 13C, the estimated delta value for bulk terrigenous debris, apparently derived partly from CAM plants, being -22.5%. In the most saline facies, isotopic evidence indicates the mixing of 13C-depleted products of photosynthetic bacteria with 13C-enriched products of halotolerant eukaryotic algae. At lower salinities, a change in the producer community is marked by a decrease in the 13C content of algal lipids. The content of 13C in algal lipids increases in the least saline facies, due either to succession of different organisms or to decreased concentrations of dissolved CO2.     

Brønsted reactions on oxide mineral surfaces and the temperature-dependence of their dissolution rates

The pH-dependence of oxide dissolution rates is controlled by Brønsted acid-base reactions at the mineral surface. These reactions are rapid but depend explicitly on temperature, as do the subsequent slow rates of bond hydrolysis. The net result is that dissolution rates vary in a complicated fashion with temperature and solution pH. The enthalpy changes of acid-base reactions on oxide materials are sufficiently similar, however, that general statements can be made about their contribution. The enthalpy changes from proton adsorption to a hydroxyl functional group (SOH), or to a deprotonated functional group (SO ^–), are generally exothermic. The enthalpy changes become increasingly endothermic, however, as charge accumulates on the mineral surface and the charged species interact electrostatically. The result is that mineral dissolution rates are least sensitive to temperature, as measured with an Arrhenius-like rate law, at pH conditions near the Point of Zero Net Proton Charge.     

Palaeoclimatic studies in South Shetland Islands,Antarctica, based on numerous stratigraphic variables in lake sediments

The hitherto longest found lake sediment sequence on Byers Peninsula, Livingston Island, South Shetland Islands, was analysed with respect to lithology, chronology, diatoms, Pediastrum, pollen and spores, mosses, mineralogy, and sediment chemistry. During the ca. 5000 year long development the sediments were influenced by frequent tephra fall-outs. This volcanic impact played a major role in the lake's history during two periods, 4700–4600 and 2800–2500 BP, but was of importance during the lake's entire history with considerable influence on many of the palaeoenvironmentally significant indicators. The large and complex data set was analysed and zonated with different types of multivariate analysis. This resulted in a subdivision of the sequence into 8 time periods and 21 variables. Redundancy analysis (RDA) of this data set, both without and with the tephra periods, and with 4–6 of the variables as explanatory environmental variables, reveal that climatic/environmental signals are detectable. The palaeoclimatic picture that emerged out of the tephra noise suggests that the first 100 years were characterized by mild, humid conditions. This was followed by a less mild and humid climate until ca. 4000 BP when a gradual warming seems to have started, coupled with increased humidity. These mild and humid conditions seem to have reached an optimum slightly after 3000 BP. At ca. 2500 BP a distinct climatic deterioration occurred with colder and drier conditions and long seasons with ice cover. This arid, cold phase probably reached its optimum conditions at ca. 1500 BP, when slightly warmer conditions might have prevailed for a while. Except for the modern sample with rather mild climate, the last 1400 years seem to have been fairly arid and cold, and the effects of the frequent volcanic activity during this period is only vaguely seen in the records.     

Numerical study of droplet size dependent chemistry in oceanic,wintertime stratus cloud at southern mid-latitudes

Cloud droplet chemistry is modelled for the first 150 m of rise in a wintertime, mid-latitude, marine stratus cloud using observations made at and near the Cape Grim Baseline Station as a source of input parameters. The emphasis in this work was to study the variation in droplet chemistry as a function of both droplet size and nucleus composition, with a particular focus on the way in which oxidation of dissolved sulfur dioxide varied.At 150 m above the condensation level, solute concentration as a function of droplet size was found to increase by as much as 2 to 3 orders of magnitude for only a factor of 2 increase in droplet radius, primarily as a consequence of the 1/r dependence in the droplet growth equation. This type of size dependence exists at all levels in the model cloud, and has a significant influence on oxidation rate of sulfur dioxide in droplets growing on sulfate nuclei, oxidation by ozone being favoured in the smallest droplets, but oxidation by hydrogen peroxide being favoured in the larger droplets. Oxidation by ozone is favoured at all sizes in droplets formed on sea-salt nuclei as a result of the initially high alkalinity of these droplets, and in the cloud overall is calculated to be the more important oxidation pathway. Although based on a simplified chemical scheme, these results suggest that both size-dependent and nucleus-dependent chemistry of cloud droplets may need to be considered explicitly in cloud modelling work.Volume-weighted mean pH values in the range 5 to 6 were predicted from sensitivity studies in which input variables were varied over reasonable ranges, in agreement with two sets of bulk cloud-water pH data obtained by aircraft near Cape Grim.