Tidal and spatial variations of DI13C and aquatic chemistry in a temperate tidal basin during winter time

Here, the pelagic carbonate system and the ?13C signature of dissolved inorganic carbonate (DIC) were investigated in a tidal basin of the southern North Sea, the Jade Bay, with respect to tidal cycles and a transect towards the North Sea in winter time (January and November, 2010). Physical parameters, major and trace elements, and nutrient concentrations were considered, too. Primary production and pelagic organic matter respiration were negligible during winter time. Both, the compositional variations on the transects as well as during the tidal cycles indicate the mixing of North Sea with fresh water. The combined spatial co-variations of different parameters indicate an introduction of fresh water that was enriched in DI12C, metabolites (e.g., ammonia), protons, and dissolved redox-sensitive elements (e.g., Mn2+). During the January campaign, the discharge via the flood gates was limited due to ice cover of the hinterland drainage ditches, allowing for an observation of tidal variations without significant mixing contributions from surface water discharges. Considering a binary mixing model with North Sea and fresh water as end-members, the extrapolated fresh water end-member composition for this campaign is estimated to contain about 3.8 mmol/kg DIC , and enhanced concentrations of NH4+, Mn2+, and protons compared to North Sea water. The fast temporal response of dissolved geochemical tracers on tidal variations in the Jade Bay indicates a continuous supply of a fresh water component. The measured composition of fresh waters entering the Jade Bay via flood gates (end of October, 2010) did not match the values estimated by the binary mixing model. Therefore, the overall fresh water component likely is a mixture between sources originating from flood gates and (in January) dominating submarine groundwater discharge entering the Jade Bay. This model is consistent with the results obtained during the November campaign, when a more important contribution from flood gates is expected and a more variable fresh water end-member is estimated. The co-variations of the concentrations and the stable carbon isotope composition of DIC are applied to evaluate possible superimposed sink-source-transformation processes in the coastal waters and a general co-variation scheme is suggested.

Dissolved iron measured along surface transects of the CARUSO-EISENEX experiment

Measurements of Fe(II) and H2O2 were carried out in the Atlantic sector of the Southern Ocean during EisenEx, an iron enrichment experiment. Iron was added on three separate occasions, approximately every 8 days, as a ferrous sulfate (FeSO4) solution. Vertical profiles of Fe(II) showed maxima consistent with the plume of the iron infusion. While H2O2 profiles revealed a corresponding minima showing the effect of oxidation of Fe(II) by H2O2, observations showed detectable Fe(II) concentrations existed for up to 8 days after an iron infusion. H2O2 concentrations increased at the depth of the chlorophyll maximum when iron concentrations returned to pre-infusion concentrations (<80 pM) possibly due to biological production related to iron reductase activity. In this work, Fe(II) and dissolved iron were used as tracers themselves for subsequent iron infusions when no further SF6 was added. EisenEx was subject to periods of weak and strong mixing. Slow mixing after the second infusion allowed significant concentrations of Fe(II) and Fe to exist for several days. During this time, dissolved and total iron in the infusion plume behaved almost conservatively as it was trapped between a relict mixed layer and a new rain-induced mixed layer. Using dissolved iron, a value for the vertical diffusion coefficient Kz=6.7±0.7 cm**2/s was obtained for this 2-day period. During a subsequent surface survey of the iron-enriched patch, elevated levels of Fe(II) were found in surface waters presumably from Fe(II) dissolved in the rainwater that was falling at this time. Model results suggest that the reaction between uncomplexed Fe(III) and O2? was a significant source of Fe(II) during EisenEx and helped to maintain high levels of Fe(II) in the water column. This phenomenon may occur in iron enrichment experiments when two conditions are met: (i) When Fe is added to a system already saturated with regard to organic complexation and (ii) when mixing processes are slow, thereby reducing the dispersion of iron into under-saturated waters.

Chemistry of Late Quaternary sediments and their interstitial waters of sediment cores from the Nort-West African continental margin

In the sediments of the NW African continental margin the mainly biogenic carbonate constituents become increasingly diluted with terrigenous material as one approaches the coast, as indicated by the carbonate-CO2 content, the Al2O3/SiO2-ratios, and the presence of ammonia fixed to alumino-silicates, predominantly to illites. In the norther area of the investigation - off Cape Blanc and Cape Bojador . the terrigenous constituents are mainly quartz from the Sahara Desert, whereas in the south - off Senegal - more alumino-silicates as clay minerals are admixed with the carbonate constituents. The organic carbon content of the continental slope sediments off Senegal is higher than in samples of the continental rise or of the preservation of organic matter as a result of high production and relatively rapid sedimentation. The zone of manganese-oxide enrichment follows the redox potential of + 330 mV from the surface (0-5 cm) into the sediments (20-30 cm deep) at 2000--3000 m and 3700 m of water depths, respectively. At shallower water depths, low redox potentials preclude deposition of manganese oxides and cause their mobilization from the sediments. About 1/3 of the total sedimentary Zn and 1/4 of the Cu is associated with the carbonate mineral fraction, probably in calcium phosphate overgrowths as a result of the mineralization of phosphorus-containing organic matter. Besides the precipitation of calcium phosphate, the mineralization of organic matter mediated by bacterial sulfate reduction also results in calcium carbonate precipitation and the exchange of ammonia for potassium on illites. Because of these simultaneous reactions, the depth distribution of all mineralization constituents in the interstitial water can be determined using the actual molar carbon-to-nitrogen-to phosphorus ratios of the sedimentary organic matter. The amount of sulfide sulfur in this process indicates the predominance of bacterial sulfate reduction in the sediments off NW Africa. This process also preferentially decomposes nitrogen- and phosphorus-containing organic compounds so organic matter deficient in these elements is characteristic for the rapidly accumulating sediments than today, indicating there was increased production of organic carbon compounds and more favorable conditions of their preservations. During the last interglacial times conditions were similar to those to today. This differentiation with time has also been observed in sediments from the Argentine Basin and from slope off South India indicating perhaps world-wide environmental changes throughout Late Quaternary times.

Fluor and opal in surface sediment from the Bransfield Strait (Table 1)

The influence of biogenic opal sediment input (mainly diatom skeletons) on the fluorine budget of marine sediments will be shown for 24 sampling stations of the antarctic regions of Bransfield Strait, Powell Basin, South Orkney Plateau and northwestern Weddell Sea. 4 bulk samples, one from each sedimentation area, contain 9 to 28 wt.-% of biogenic opal , the clay fraction of the 24 samples investigated have 2 to 82 wt.-%. The fluorine concentration in the amorphous biogenic component is 15 ppm. 300 to 800 ppm of fluorine were measured in the clay fractions, 330 to 920 ppm in their lithogenic components. Biogenic opal causes a decrease in fluorine concentration of the sediment by a considerable amount: 6 to 56 % relative to the clay fraction, due to the proportions involved. Biogenic opal is therefore taken into account as a 'diluting' factor for the fluorine budget in marine sediments.

Water chemistry, and body temperature, swimming depth and stomach contents of Arctic char (Salvelinus alpinus) in inner Frobisher Bay, Canada

The influence of salinity, temperature and prey availability on the marine migration of anadromous fishes was determined by describing the movements, habitat use and feeding behaviours of Arctic char (Salvelinus alpinus). The objectives were to determine whether char are restricted to the upper water column of the inter-/subtidal zones due to warmer temperatures. Twenty-seven char were tracked with acoustic temperature/pressure (depth) transmitters from June to September, 2008/2009, in inner Frobisher Bay, Canada. Most detections were in surface waters (0-3 m). Inter-/subtidal movements and consecutive repetitive dives (maximum 52.8 m) resulted in extreme body temperature shifts (-0.2-18.1 °C). Approximately half of intertidal and subtidal detections were between 9-13 °C and 1-3 °C, respectively. Stomach contents and deep diving suggested feeding in both inter-/subtidal zones. We suggest that char tolerate cold water at depth to capture prey in the subtidal zone, then seek warmer water to enhance feeding/digestion physiology.

Sea surface productivity and temperature detected by coccolith accumulation rates from the southeastern Pacific off Chile

Recent coccoliths from 74 surface sediment samples recovered from the southeastern Pacific off Chile were examined quantitatively to investigate modern regional gradients of sea surface productivity and temperature. All findings are based on coccolith accumulation rates. Therefore an approach was designed to estimate recent sedimentation rates based on 210Pb and bulk chemistry analyses of the same set of surface samples. Highest total coccolith accumulation rates were found off north-central Chile, where seasonal upwelling takes place. Based on amultiple linear regression between calculated coccolith accumulation rates andWorld Ocean Atlas derived sea surface temperatures, a calibrationmodel to reconstruct annual average temperatures of the uppermost 75 mof thewater column is provided. Themodelwas cross-validated and the SST estimateswere compared with SST observed and SST estimates based on diatoms and planktonic foraminifera, showing a good correlation.

Global database of surface ocean particulate organic carbon export fluxes diagnosed from the 234Th technique

Through the processes of the biological pump, carbon is exported to the deep ocean in the form of dissolved and particulate organic matter. There are several ways by which downward export fluxes can be estimated. The great attraction of the 234Th technique is that its fundamental operation allows a downward flux rate to be determined from a single water column profile of thorium coupled to an estimate of POC/234Th ratio in sinking matter. We present a database of 723 estimates of organic carbon export from the surface ocean derived from the 234Th technique. Data were collected from tables in papers published between 1985 and 2013 only. We also present sampling dates, publication dates and sampling areas. Most of the open ocean Longhurst provinces are represented by several measurements. However, the Western Pacific, the Atlantic Arctic, South Pacific and the South Indian Ocean are not well represented. There is a variety of integration depths ranging from surface to 220m. Globally the fluxes ranged from -22 to 125 mmol of C/m**2/d. We believe that this database is important for providing new global estimate of the magnitude of the biological carbon pump.

Seawater carbonate chemistry and photosynthetic response of Emiliania huxleyi (CS-369) to UV radiation and elevated temperature duirng experiments, 2011

Changes in calcification of coccolithophores may affect their photosynthetic responses to both, ultraviolet radiation (UVR, 280-400 nm) and temperature. We operated semi-continuous cultures of Emiliania huxleyi (strain CS-369) at reduced (0.1 mM, LCa) and ambient (10 mM, HCa) Ca2+ concentrations and, after 148 generations, we exposed cells to six radiation treatments (>280, >295, >305, >320, >350 and >395 nm by using Schott filters) and two temperatures (20 and 25 °C) to examine photosynthesis and calcification responses. Overall, our study demonstrated that: (1) decreased calcification resulted in a down regulation of photoprotective mechanisms (i.e., as estimated via non-photochemical quenching, NPQ), pigments contents and photosynthetic carbon fixation; (2) calcification (C) and photosynthesis (P) (as well as their ratio) have different responses related to UVR with cells grown under the high Ca2+ concentration being more resistant to UVR than those grown under the low Ca2+ level; (3) elevated temperature increased photosynthesis and calcification of E. huxleyi grown at high Ca2+concentrations whereas decreased both processes in low Ca2+ grown cells. Therefore, a decrease in calcification rates in E. huxleyi is expected to decrease photosynthesis rates, resulting in a negative feedback that further reduces calcification.

Magnesium/Calcium ratios in benthic foraminifera from surface sediments

We used modern epibenthic foraminifer tests of Cibicidoides mundulus and Planulina wuellerstorfi from South Atlantic core top sediments in order to establish Mg/Ca-temperature relationships for the temperature range from 0 to 15°C. We obtained the following calibrations: Mg/Ca (mmol/mol) = 0.830*exp(0.145*BWT (°C)) for P. wuellerstorfi, and Mg/Ca (mmol/mol) = 0.627*exp(0.143*BWT (°C)) for C. mundulus. However, a number of tests, especially those bathed in North Atlantic Deep Water, revealed higher Mg/Ca ratios than predicted from the calibration. Our data suggest that d[CO3 2-] of bottom water exerts a significant control on dMg/Ca (temperature-corrected) of C. mundulus (dMg/Ca = 0.017*d[CO3 2-] -0.14), while dMg/Ca of P. wuellerstorfi is more likely to be governed by TCO2 (dMg/Ca = -0.007*TCO2 + 15). Since both d[CO3 2-] and TCO2 are closely linked to [CO3 2-], it is inferred that carbonate ion acts as secondary control, after temperature, on benthic shell Mg/Ca below -4°C. A drop in [CO3 2-] by 25 ?mol/kg at 4 km water depth, as suggested for the Last Glacial Maximum, would decrease Mg/Ca by up to 0.4 mmol/mol, which leads to an underestimation of bottom water temperature by -3.5°C. Therefore our results indicate that the Mg/Ca thermometer should be used cautiously for benthic foraminifers where changes in the carbonate chemistry are present in the paleoceanographic record.

Seawater carbonate chemistry and accumulation of radiotracers in squid, Loligo vulgaris during experiments, 2011

The anthropogenic release of carbon dioxide (CO2) into the atmosphere leads to an increase in the CO2 partial pressure (pCO2) in the ocean, which may reach 950 ?atm by the end of the 21st century. The resulting hypercapnia (high pCO2) and decreasing pH ("ocean acidification") are expected to have appreciable effects on water-breathing organisms, especially on their early-life stages. For organisms like squid that lay their eggs in coastal areas where the embryo and then paralarva are also exposed to metal contamination, there is a need for information on how ocean acidification may influence trace element bioaccumulation during their development. In this study, we investigated the effects of enhanced levels of pCO2 (380, 850 and 1500 ?atm corresponding to pHT of 8.1, 7.85 and 7.60) on the accumulation of dissolved 110mAg, 109Cd, 57Co, 203Hg, 54Mn and 65Zn radiotracers in the whole egg strand and in the different compartments of the egg of Loligo vulgaris during the embryonic development and also in hatchlings during their first days of paralarval life. Retention properties of the eggshell for 110mAg, 203Hg and 65Zn were affected by the pCO2 treatments. In the embryo, increasing seawater pCO2 enhanced the uptake of both 110mAg and 65Zn while 203Hg showed a minimum concentration factor (CF) at the intermediate pCO2. 65Zn incorporation in statoliths also increased with increasing pCO2. Conversely, uptake of 109Cd and 54Mn in the embryo decreased as a function of increasing pCO2. Only the accumulation of 57Co in embryos was not affected by increasing pCO2. In paralarvae, the CF of 110mAg increased with increasing pCO2, whereas the 57Co CF was reduced at the highest pCO2 and 203Hg showed a maximal uptake rate at the intermediate pCO2. 54Mn and 65Zn accumulation in paralarvae were not significantly modified by hypercapnic conditions. Our results suggest a combined effect of pH on the adsorption and protective properties of the eggshell and of hypercapnia on the metabolism of embryo and paralarvae, both causing changes to the accumulation of metals in the tissues of L. vulgaris.