The first building blocks of life could be produced in ultramafic-hosted hydrothermal systems considering the large amounts of hydrogen and methane generated by serpentinisation and ...Fischer–Tropsch-Type synthesis, respectively, in those systems. The purpose of this study was to detect and characterise organic molecules in hydrothermal fluids from ultramafic-hosted hydrothermal systems in the Mid-Atlantic Ridge (MAR) region. During the EXOMAR cruise 2005, fluids from the Rainbow (36°14′N) and the Lost City (30°N) hydrothermal fields were collected and treated by Stir Bar Sorptive Extraction (SBSE) and Solid Phase Extraction (SPE). The extracts were analysed by Thermal Desorption–Gas Chromatography–Mass Spectrometry (TD–GC–MS) and GC–MS, respectively. Compared to nearby deep seawater, hydrothermal fluids were clearly enriched in organic compounds, with a more diverse spectrum of molecules. We observed a very similar range of organic compounds in fluids from both sites, with a dominance of aliphatic hydrocarbons (C9–C14), aromatic compounds (C6–C16) and carboxylic acids (C8–C18). The occurrence of these compounds is supported by other field studies on serpentinites and sulfide deposits. Literature on thermodynamic data and experimental work has suggested the possible abiogenic origin of hydrocarbons and organic acids. In addition, it has been shown elsewhere that catalytic reactions producing hydrocarbons likely occur at both Lost City and Rainbow hydrothermal fields as suggested by the evolution of
δ
13C with increasing C number for methane, ethane, propane and butane. In order to investigate the origin of the organic molecules in the fluids, compound-specific carbon isotope ratio measurements were performed on n-alkanes and carboxylic acids, for which the
δ
13C values were in the range of −
46 to −
20‰ (vs. V-PDB). These preliminary data did not allow conclusive support or rejection of an abiogenic origin of the compounds. Indeed, predicting
δ
13C signatures in hydrothermal systems is likely to be complicated, due to differences in source
δ
13C signatures (i.e., of the C building blocks), and a variety of, mostly unknown, fractionation steps which may occur along the synthesis pathways. In addition, even though a fraction of the compounds detected in the fluids is likely abiotically produced, a dominance of biogenic sources and/or processes might hide their characteristic signature.
The KEOPS2 project aims to elucidate the role of natural Fe fertilisation on biogeochemical cycles and ecosystem functioning, including quantifying the sources and processes by which iron is ...delivered in the vicinity of the Kerguelen Archipelago, Southern Ocean. The KEOPS2 process study used an upstream high-nutrient, low-chlorophyll (HNLC), deep water (2500 m), reference station to compare with a shallow (500 m), strongly fertilised plateau station and continued the observations to a downstream, bathymetrically trapped recirculation of the Polar Front where eddies commonly form and persist for hundreds of kilometres into the Southern Ocean. Over the Kerguelen Plateau, mean particulate (1–53 μm) Fe and Al concentrations (pFe = 13.4 nM, pAl = 25.2 nM) were more than 20-fold higher than at an offshore (lower-productivity) reference station (pFe = 0.53 nM, pAl = 0.83 nM). In comparison, over the plateau dissolved Fe levels were only elevated by a factor of ~ 2. Over the Kerguelen Plateau, ratios of pMn / pAl and pFe / pAl resemble basalt, likely originating from glacial/fluvial inputs into shallow coastal waters. In downstream, offshore deep-waters, higher pFe / pAl, and pMn / pAl ratios were observed, suggesting loss of lithogenic material accompanied by retention of pFe and pMn. Biological uptake of dissolved Fe and Mn and conversion into the biogenic particulate fraction or aggregation of particulate metals onto bioaggregates also increased these ratios further in surface waters as the bloom developed within the recirculation structure. While resuspension of shelf sediments is likely to be one of the important mechanisms of Fe fertilisation over the plateau, fluvial and glacial sources appear to be important to areas downstream of the island. Vertical profiles within an offshore recirculation feature associated with the Polar Front show pFe and pMn levels that were 6-fold and 3.5-fold lower, respectively, than over the plateau in surface waters, though still 3.6-fold and 1.7-fold higher respectively than the reference station. Within the recirculation feature, strong depletions of pFe and pMn were observed in the remnant winter water (temperature-minimum) layer near 175 m, with higher values above and below this depth. The correspondence between the pFe minima and the winter water temperature minima implies a seasonal cycle is involved in the supply of pFe into the fertilised region. This observed association is indicative of reduced supply in winter, which is counterintuitive if sediment resuspension and entrainment within the mixed layer is the primary fertilising mechanism to the downstream recirculation structure. Therefore, we hypothesise that lateral transport of pFe from shallow coastal waters is strong in spring, associated with snow melt and increased runoff due to rainfall, drawdown through summer and reduced supply in winter when snowfall and freezing conditions predominate in the Kerguelen region.
We sampled a tidal creek (Ras Dege, Tanzania) during a 24-h cycle to document the variations in a suite of creek water column characteristics and to determine the relative influence of tidal and ...biological driving forces. Since the creek has no upstream freshwater inputs, highest salinity was observed at low tide, due to evaporation effects and porewater seepage. Total suspended matter (TSM) and particulate organic carbon (POC) showed distinct maxima at periods of highest water flow, indicating that erosion of surface sediments and/or resuspension of bottom sediments were an important source of particulate material. Dissolved organic carbon (DOC), in contrast, varied in phase with water height and was highest at low tide. Stable isotope data of POC and DOC displayed large variations in both pools, and similarly followed the variations in water height. Although the variation of δ13CDOC (−23.8 to −13.8‰) was higher than that of δ13CPOC (−26.2 to −20.5‰), due to the different end-member pool sizes, the δ13C signatures of both pools differed only slightly at low tide, but up to 9‰ at high tide. Thus, at low tide both DOC and POC originated from mangrove production. At high tide, however, the DOC pool had signatures consistent with a high contribution of seagrass-derived material, whereas the POC pool was dominated by marine phytoplankton. Daily variations in CH4, and partial pressure of CO2 (pCO2) were similarly governed by tidal influence and were up to 7- and 10-fold higher at low tide, which stresses the importance of exchange of porewater and diffusive fluxes to the water column. When assuming that the high dissolved inorganic carbon (DIC) levels in the upper parts of the creek (i.e. at low tide) are due to inputs from mineralization, δ13C data on DIC indicate that the organic matter source for mineralization had a signature of −22.4‰. Hence, imported POC and DOC from the marine environment contributes strongly to overall mineralization within the mangrove system. Our data demonstrate how biogeochemical processes in the intertidal zone appear to be prominent drivers of element concentrations and isotope signatures in the water column, and how pathways of dissolved and particulate matter transport are fundamentally different.
We examined phytoplankton community responses to natural iron fertilisation at 32 sites over and downstream from the Kerguelen Plateau in the Southern Ocean during the austral spring bloom in ...October–November 2011. The community structure was estimated from chemical and isotopic measurements (particulate organic carbon – POC; 13C-POC; particulate nitrogen – PN; 15N-PN; and biogenic silica – BSi) on size-fractionated samples from surface waters (300, 210, 50, 20, 5, and 1 μm fractions). Higher values of 13C-POC (vs. co-located 13C values for dissolved inorganic carbon – DIC) were taken as indicative of faster growth rates and higher values of 15N-PN (vs. co-located 15N-NO3 source values) as indicative of greater nitrate use (rather than ammonium use, i.e. higher f ratios). Community responses varied in relation to both regional circulation and the advance of the bloom. Iron-fertilised waters over the plateau developed dominance by very large diatoms (50–210 μm) with high BSi / POC ratios, high growth rates, and significant ammonium recycling (lower f ratios) as biomass built up. In contrast, downstream polar frontal waters with a similar or higher iron supply were dominated by smaller diatoms (20–50 μm) and exhibited greater ammonium recycling. Stations in a deep-water bathymetrically trapped recirculation south of the polar front with lower iron levels showed the large-cell dominance observed on the plateau but much less biomass. Comparison of these communities to surface water nitrate (and silicate) depletions as a proxy for export shows that the low-biomass recirculation feature had exported similar amounts of nitrogen to the high-biomass blooms over the plateau and north of the polar front. This suggests that early spring trophodynamic and export responses differed between regions with persistent low levels vs. intermittent high levels of iron fertilisation.
As part of the GEOTRACES Bonus-GoodHope (BGH) expedition (January–March 2008) in the Atlantic sector of the Southern Ocean, particulate organic carbon (POC) export was examined from the surface to ...the mesopelagic twilight zone using water column distributions of total 234Th and biogenic particulate Ba (Baxs). Surface POC export production was estimated from steady state and non steady state modelling of 234Th fluxes, which were converted into POC fluxes, using the POC/234Th ratio of large, potentially sinking particles (> 53 μm) collected via in situ pumps. Deficits in 234Th activities were observed at all stations from the surface to the bottom of the mixed layer, yielding 234Th export fluxes from the upper 100 m of 496 214 dpm m−2 d−1 to 1195 158 dpm m−2 d−1 for the steady state model and of 149 517 dpm m−2 d−1 to 1217 231 dpm m−2 d−1 for the non steady state model. Using the POC/234Thp ratio of sinking particles (ratios varied from 1.7 0.2 μmol dpm−1 to 4.8 1.9 μmol dpm−1) POC export production at 100 m was calculated to range between 0.9 0.4 and 5.1 2.1 mmol C m−2 d−1,assuming steady state and between 0.3 0.9 m−2 d−1 and 4.9 3.3 mmol C m−2 d−1, assuming non steady state. From the comparison of both approaches, it appears that during late summer export decreased by 56 to 16% for the area between the sub-Antarctic zone and the southern Antarctic Circumpolar Current Front (SACCF), whereas it remained rather constant over time in the HNLC area south of the SACCF. POC export represented only 6 to 54% of new production, indicating that export efficiency was, in general, low, except in the vicinity of the SACCF, where export represented 56% of new production. Attenuation of the POC sinking flux in the upper mesopelagic waters (100–600 m depth interval) was evidenced both, from excess 234Th activities and from particulate biogenic Ba (Baxs) accumulation. Excess 234Th activities, reflected by 234Th/238U ratios as large as 1.21 0.05, are attributed to remineralisation/disaggregation of 234Th-bearing particles. The accumulation of excess 234Th in the 100–600 m depth interval ranged from 458 633 dpm m−2 d−1 to 3068 897 dpm m−2 d−1, assuming steady state. Using the POC/234Thp ratio of sinking particles (> 53 μm), this 234Th accumulation flux was converted into a POC remineralisation flux which ranged between 0.9 1.2 mmol C m−2 d−1 and 9.2 2.9 mmol C m−2 d−1. Mesopelagic particulate biogenic Ba has been reported to reflect bacterial degradation of organic matter and to be related to oxygen consumption and bacterial carbon respiration. We observed that the highest Baxs contents (reaching up to > 1000 pM), in general, occurred between 200 and 400 m. Depth-weighted average mesopelagic Baxs (meso-Baxs) values were converted into respired C fluxes, which ranged between 0.23 and 6.4 mmol C m−2 d−1, in good agreement with 234Th-based remineralisation fluxes. A major outcome from this study is the observed significant positive correlation between POC remineralisation as estimated from meso-Baxs contents and from 234Th excess (R2 = 0.73; excluding 2 outliers). Remineralisation of POC in the twilight zone was particularly efficient relative to POC export resulting in negligible bathypelagic (> 600 m) POC export fluxes in the sub-Antarctic zone, the Polar Front zone and the northern Weddell Gyre, while the subtropical zone as well as the vicinity of the SACCF had significant deep POC fluxes.
In this study we report full‐depth water column profiles for nitrogen and oxygen isotopic composition (δ15N and δ18O) of nitrate (NO3−) during the GEOTRACES GA01 cruise (2014). This transect ...intersects the double gyre system of the subtropical and subpolar regions of the North Atlantic separated by a strong transition zone, the North Atlantic Current. The distribution of NO3− δ15N and δ18O shows that assimilation by phytoplankton is the main process controlling the NO3− isotopic composition in the upper 150 m, with values increasing in a NO3− δ18O versus δ15N space along a line with a slope of one toward the surface. In the subpolar gyre, a single relationship between the degree of NO3− consumption and residual NO3− δ15N supports the view that NO3− is supplied via Ekman upwelling and deep winter convection, and progressively consumed during the Ekman transport of surface water southward. The co‐occurrence of partial NO3− assimilation and nitrification in the deep mixed layer of the subpolar gyre elevates subsurface NO3− δ18O in comparison to deep oceanic values. This signal propagates through isopycnal exchanges to greater depths at lower latitudes. With recirculation in the subtropical gyre, cycles of quantitative consumption‐nitrification progressively decrease subsurface NO3− δ18O toward the δ18O of regenerated NO3−. The low NO3− δ15N observed south of the Subarctic Front is mostly explained by N2 fixation, although a contribution from the Mediterranean outflow is required to explain the lower NO3− δ15N signal observed between 600 and 1500 m depth close to the Iberian margin.
Key Points
Nitrate assimilation controls the nitrate isotopic composition in surface waters of the North Atlantic subpolar gyre
Nitrate isotopic composition reveals that nitrate is supplied from subpolar to subtropical gyre by Ekman transport and isopycnal mixing
N2 fixation and Mediterranean outflow have an impact on nitrate isotopic composition in the North Atlantic Ocean
We studied patterns in organic carbon pools and their origin in the Tana River Basin (Kenya), in February 2008 (dry season), September–November 2009 (wet season), and June–July 2010 (end of wet ...season), covering the full continuum from headwater streams to lowland mainstream sites. A consistent downstream increase in total suspended matter (TSM, 0.6 to 7058 mg l−1 and particulate organic carbon (POC, 0.23 to 119.8 mg l−1 was observed during all three sampling campaigns, particularly pronounced below 1000 m above sea level, indicating that most particulate matter exported towards the coastal zone originated from the mid and low altitude zones rather than from headwater regions. This indicates that the cascade of hydroelectrical reservoirs act as an extremely efficient particle trap. Although 7Be / 210Pbxs ratios/age of suspended sediment do not show clear seasonal variation, the gradual downstream increase of suspended matter during end of wet season suggests its origin is caused by inputs of older sediments from bank erosion and/or river sediment resuspension. During wet season, higher TSM concentrations correspond with relatively young suspended matter, suggesting a contribution from recently eroded material. With the exception of reservoir waters, POC was predominantly of terrestrial origin as indicated by generally high POC : chlorophyll a (POC : Chl a) ratios (up to ~41 000). Stable isotope signatures of POC (δ13CPOC ranged between −32 and −20‰ and increased downstream, reflecting an increasing contribution of C4-derived carbon in combination with an expected shift in δ13C for C3 vegetation towards the more semi-arid lowlands. δ13C values in sediments from the main reservoir (−19.5 to −15.7‰) were higher than those found in any of the riverine samples, indicating selective retention of particles associated with C4 fraction. Dissolved organic carbon (DOC) concentrations were highest during the end of wet season (2.1 to 6.9 mg l−1), with stable isotope signatures generally between −28 and −22‰. A consistent downstream decrease in % organic carbon (%OC) was observed for soils, riverine sediments, and suspended matter. This was likely due to better preservation of the organic fraction in colder high altitude regions, with loss of carbon during downstream spiraling. δ13C values for soil and sediment did not exhibit clear altitudinal patterns, but values reflect the full spectrum from C3-dominated to C4-dominated sites. Very low ratios of organic carbon to mineral surface area (OC : SA) were found in reservoir sediments and suspended matter in the lower Tana River, indicating that these are stable OC pools which have undergone extensive degradation. Overall, our study demonstrates that substantial differences occur in both the quantities and origin of suspended sediments and organic carbon along the river profile in this tropical river basin, as well as seasonal differences in the mechanisms causing such variations.
Although the Southern Ocean is considered a high-nutrient, low-chlorophyll (HNLC) area, massive and recurrent blooms are observed over and downstream of the Kerguelen Plateau. This mosaic of blooms ...is triggered by a higher iron supply resulting from the interaction between the Antarctic Circumpolar Current and the local bathymetry. Net primary production, N uptake (NO3− and NH4+), and nitrification rates were measured at eight stations in austral spring 2011 (October–November) during the KEOPS 2 cruise in the Kerguelen Plateau area. Natural iron fertilization stimulated primary production, with mixed layer integrated net primary production and growth rates much higher in the fertilized areas (up to 315 mmol C m−2 d−1 and up to 0.31 d−1 respectively) compared to the HNLC reference site (12 mmol C m−2 d−1 and 0.06 d−1 respectively). Primary production was mainly sustained by nitrate uptake, with f ratios (corresponding to NO3−-uptake / (NO3−-uptake + NH4+-uptake)) lying at the upper end of the observations for the Southern Ocean (up to 0.9). We report high rates of nitrification (up to ~ 3 μmol N L−1 d−1, with ~ 90 % of them < 1 μmol N L−1 d−1) typically occurring below the euphotic zone, as classically observed in the global ocean. The specificity of the studied area is that at most of the stations, the euphotic layer was shallower than the mixed layer, implying that nitrifiers can efficiently compete with phytoplankton for the ammonium produced by remineralization at low-light intensities. Nitrate produced by nitrification in the mixed layer below the euphotic zone is easily supplied to the euphotic zone waters above, and nitrification sustained 70 ± 30 % of the nitrate uptake in the productive area above the Kerguelen Plateau. This complicates estimations of new production as potentially exportable production. We conclude that high productivity in deep mixing system stimulates the N cycle by increasing both assimilation and regeneration.
In this study we test if calcite shells of the common mussel,
Mytilus edulis, contain barium in proportion to the water in which they grew. Similar to all bivalves analyzed to date, the Ba/Ca
shell ...profiles are characterized by a relatively flat background Ba/Ca
shell, interrupted by sharp Ba/Ca
shell peaks. Previous studies have focused on these Ba/Ca
shell peaks, but not on the background Ba/Ca
shell. We show that in both laboratory and field experiments, there is a direct relationship between the background Ba/Ca
shell and Ba/Ca
water in
M. edulis shells. The laboratory and field data provided background Ba/Ca partition coefficients (
D
Ba) of 0.10
±
0.02 and 0.071
±
0.001, respectively. This range is slightly higher than the
D
Ba previously determined for inorganic calcite, and slightly lower than foraminiferal calcite. These data suggest that
M. edulis shells can be used as an indicator of Ba/Ca
water, and therefore, fossil or archaeological
M. edulis shells could be used to extend knowledge of estuarine dissolved Ba throughputs back in time. Moreover, considering the inverse relationship between Ba/Ca
water and salinity, background Ba/Ca
shell data could be used as an estuary specific indicator of salinity. The cause of the Ba/Ca
shell peaks is more confusing, both the laboratory and field experiments indicate that they cannot be used as a direct proxy of Ba/Ca
water or phytoplankton production, but may possibly be caused by barite ingestion.
Southern Ocean biogeochemical processes have an impact on global marine primary production and global elemental cycling, e.g. by likely controlling glacial-interglacial pCO2 variation. In this ...context, the natural silicon isotopic composition (δ30Si) of sedimentary biogenic silica has been used to reconstruct past Si-consumption:supply ratios in the surface waters. We present a new dataset in the Southern Ocean from a IPY-GEOTRACES transect (Bonus-GoodHope) which includes for the first time summer δ30Si signatures of suspended biogenic silica (i) for the whole water column at three stations and (ii) in the mixed layer at seven stations from the subtropical zone up to the Weddell Gyre. In general, the isotopic composition of biogenic opal exported to depth was comparable to the opal leaving the mixed layer and did not seem to be affected by any diagenetic processes during settling, even if an effect of biogenic silica dissolution cannot be ruled out in the northern part of the Weddell Gyre. We develop a mechanistic understanding of the processes involved in the modern Si-isotopic balance, by implementing a mixed layer model. We observe that the accumulated biogenic silica (sensu Rayleigh distillation) should satisfactorily describe the δ30Si composition of biogenic silica exported out of the mixed layer, within the limit of the current analytical precision on the δ30Si. The failures of previous models (Rayleigh and steady state) become apparent especially at the end of the productive period in the mixed layer, when biogenic silica production and export are low. This results from (1) a higher biogenic silica dissolution:production ratio imposing a lower net fractionation factor and (2) a higher Si-supply:Si-uptake ratio supplying light Si-isotopes into the mixed layer. The latter effect is especially expressed when the summer mixed layer becomes strongly Si-depleted, together with a large vertical silicic acid gradient, e.g. in the Polar Front Zone and at the Polar Front.
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