Factors influencing the stable carbon isotopic composition of suspended and sinking organic matter in the coastal Antarctic sea ice environment

A high resolution time-series analysis of stable carbon isotopic signatures in particulate organic carbon (δ<sup>13</sup>C<sub>POC</sub>) and associated biogeochemical parameters in sea ice and surface waters provides an insight into the factors affecting δ<sup>13</sup>C<sub>POC</sub> in the coastal western Antarctic Peninsula sea ice environment. The study covers two austral summer seasons in Ryder Bay, northern Marguerite Bay between 2004 and 2006. A shift in diatom species composition during the 2005/06 summer bloom to near-complete biomass dominance of <i>Proboscia inermis</i> is strongly correlated with a large ~10 ‰ negative isotopic shift in δ<sup>13</sup>C<sub>POC</sub> that cannot be explained by a concurrent change in concentration or isotopic signature of CO<sub>2</sub>. We hypothesise that the δ<sup>13</sup>C<sub>POC</sub> shift may be driven by the contrasting biochemical mechanisms and utilisation of carbon-concentrating mechanisms (CCMs) in different diatom species. Specifically, very low δ<sup>13</sup>C<sub>POC</sub> in <i>P. inermis</i> may be caused by the lack of a CCM, whilst some diatom species abundant at times of higher δ<sup>13</sup>C<sub>POC</sub> may employ CCMs. These short-lived yet pronounced negative δ<sup>13</sup>C<sub>POC</sub> excursions drive a 4 ‰ decrease in the seasonal average δ<sup>13</sup>C<sub>POC</sub> signal, which is transferred to sediment traps and core-top sediments and consequently has the potential for preservation in the sedimentary record. This 4 ‰ difference between seasons of contrasting sea ice conditions and upper water column stratification matches the full amplitude of glacial-interglacial Southern Ocean δ<sup>13</sup>C<sub>POC</sub> variability and, as such, we invoke phytoplankton species changes as a potentially important factor influencing sedimentary δ<sup>13</sup>C<sub>POC</sub>. We also find significantly higher δ<sup>13</sup>C<sub>POC</sub> in sea ice than surface waters, consistent with autotrophic carbon fixation in a semi-closed environment and possible contributions from post-production degradation, biological utilisation of HCO<sub>3</sub><sup>−</sup> and production of exopolymeric substances. This study demonstrates the importance of surface water diatom speciation effects and isotopically heavy sea ice-derived material for δ<sup>13</sup>C<sub>POC</sub> in Antarctic coastal environments and underlying sediments, with consequences for the utility of diatom-based δ<sup>13</sup>C<sub>POC</sub> in the sedimentary record

Macronutrient and carbon supply, uptake and cycling across the Antarctic Peninsi shelf during summer

The West Antarctic Peninsula shelf is a region of high seasonal primary production which supports a large and productive food web, where macronutrients and inorganic carbon are sourced primarily from intrusions of warm saline Circumpolar Deep Water. We examined the cross-shelf modification of this water mass during mid-summer 2015 to understand the supply of nutrients and carbon to the productive surface ocean, and their subsequent uptake and cycling. We show that nitrate, phosphate, silicic acid and inorganic carbon are progressively enriched in subsurface waters across the shelf, contrary to cross-shelf reductions in heat, salinity and density. We use nutrient stoichiometric and isotopic approaches to invoke remineralization of organic matter, including nitrification below the euphotic surface layer, and dissolution of biogenic silica in deeper waters and potentially shelf sediment porewaters, as the primary drivers of cross-shelf enrichments. Regenerated nitrate and phosphate account for a significant proportion of the total pools of these nutrients in the upper ocean, with implications for the seasonal carbon sink. Understanding nutrient and carbon dynamics in this region now will inform predictions of future biogeochemical changes in the context of substantial variability and ongoing changes in the physical environment

Nutrient cycling in the Atlantic basin: the evolution of nitrate isotope signatures in water masses

A basin-wide transect of nitrate isotopes (δ15NNO3, δ18ONO3), across the UK GEOTRACES 40°S transect in the South Atlantic is presented. This data set is used to investigate Atlantic nutrient cycling and the communication pathways of nitrogen cycling processes in the global ocean. Intermediate waters formed in the subantarctic are enriched in δ15NNO3 and δ18ONO3 from partial utilization of nitrate by phytoplankton and distant denitrification processes, transporting heavy isotope signatures to the subtropical Atlantic. Water mass modification through the Atlantic is investigated by comparing data from 40°S (South Atlantic) and 30°N (North Atlantic). This reveals that nitrate in the upper intermediate waters is regenerated as it transits through the subtropical Atlantic, as evidenced by decreases in δ18ONO3. We document diazotrophy-producing high N:P particle ratios (18–21:1) for remineralization, which is further confirmed by a decrease in δ15NNO3 through the subtropical Atlantic. Thesemodifications influence the isotopic signatures of the North Atlantic Deep Water (NADW) which is subsequently exported from the Atlantic to the Southern Ocean. This study reveals the dominance of recycling processes and diazotrophy on nitrate cycling in the Atlantic. These processes provide a source of low δ15NNO3 to the Southern Ocean via the NADW, to counteract enrichment in δ15NNO3 from water column denitrification in the Indo/Pacific basins. We hence identify the Southern Ocean as a key hub through which denitrification and N2 fixation communicate in the ocean through deepwater masses. Therefore, the balancing of the oceanic N budget and isotopic signatures require time scales of oceanic mixing

Hydrogen isotope analysis of natural abundance and deuterium- enriched waters by reduction over chromium on-line to a dynamic dual inlet isotope-ratio mass spectrometer

This paper describes the application of a simple chromium reduction furnace which can be interfaced with a dual inlet isotope-ratio mass spectrometer thus providing the capacity for cheap, fast, accurate and precise measurement of deltaD(V-SMOW) by dynamic mass spectrometry. Measurements are precise to the order of less than or equal to0.5%. Mean 95% confidence intervals for the Vienna Standard Mean Ocean Water (V-SMOW) to Standard Light Antarctic Precipitation (SLAP) range are in the order of 2.5 parts per thousand and the system is linear over the range -428 to 23,000 parts per thousand. Memory effects do exist, but are small for natural abundance samples and can be minimised by careful planning of the analytical load