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Glacier meltwater supplies a significant amount of silicon (Si) and iron (Fe) sourced from weathered bedrock to downstream ecosystems. However, the extent to which these essential nutrients reach the ocean is regulated by the processes occurring within fjords, which act as conduits from glacial rivers and subglacial discharge and the ocean. One key – but understudied – component of biogeochemistry within fjords is benthic cycling, especially in regions of rapid deposition of reactive particulates at fjord heads. Here, we explore the benthic cycling of Si and Fe at four Patagonian fjord heads through geochemical analyses of sediment pore waters, including stable Si and Fe isotopes (δ30Si and δ56Fe respectively), and novel reaction-transport modelling for Si. A high diffusive flux of dissolved Fe from the fjord sediments compared to open ocean sediments is supported by both reductive and non-reductive dissolution of glacially-sourced reactive Fe phases, as reflected by the range of pore water stable Fe isotopes (δ56Fe from -2.7 to +0.8‰). In contrast, the diffusive flux of dissolved Si from the fjord sediments is relatively low. High pore water δ30Si (up to +3.3‰) observed near the Fe(II)-Fe(III) redox boundary is likely associated with the removal of dissolved Si by Fe(III) mineral phases, which, together with high sedimentation rates, contribute to the low diffusive flux of Si at the sampled sites. Our results suggest that early diagenesis promotes the release of dissolved Fe but suppresses the release of dissolved Si at glaciated fjord heads. The redox sensitive coupling of Si and Fe has significant implications for our understanding of how essential nutrients are transport along fjord systems.

Unprecedented and dramatic transformations are occurring in the Arctic in response to climate change, but academic, public, and political discourse has disproportionately focussed on the most visible and direct aspects of change, including sea ice melt, permafrost thaw, the fate of charismatic megafauna, and the expansion of fisheries. Such narratives disregard the importance of less visible and indirect processes and, in particular, miss the substantive contribution of the shelf seafloor in regulating nutrients and sequestering carbon. Here, we summarise the biogeochemical functioning of the Arctic shelf seafloor before considering how climate change and regional adjustments to human activities may alter its biogeochemical and ecological dynamics, including ecosystem function, carbon burial, or nutrient recycling. We highlight the importance of the Arctic benthic system in mitigating climatic and anthropogenic change and, with a focus on the Barents Sea, offer some observations and our perspectives on future management and policy.

The carbonate chemistry of Arctic Ocean seafloor and its vulnerability to ocean acidification remains poorly explored. This limits our ability to quantify how biogeochemical processes and bottom wa...

The Arctic Ocean is currently experiencing rapid oceanographic shifts and significant sea-ice loss as a result of regional atmospheric and oceanic warming. The Barents Sea is a notable example of these phenomena, having seen a near 40% decline of its April sea-ice extent since 1979, and a progressive northward expansion of Atlantic Water (i.e., Atlantification). Such changes affect primary productivity and nutrient cycling in ways that remain poorly understood. Longer ice-free periods and the inflow of warmer Atlantic Water are expected to lead to extended bloom seasons on short, near-future timescales and therefore increase nutrient uptake in upper water layers. The benthic recycling of nutrients is believed to play an important part in replenishing nutrient inventories in overlying waters thus maintaining high primary productivity over the continuously expanding growth season. Therefore, it is crucial to increase our understanding of nutrient dynamic controls in changing oceans to make more accurate predictions and decipher the complex feedbacks involved in these evolving environments. However, most efforts to constrain and quantify nutrient fluxes so far have been directed at silicon, nitrogen or iron. This study aims to provide specific insight into phosphorus (P) cycling through its response to OM fluctuations and coupling with iron cycling. An integrated data-model approach was used to investigate the dynamics of P cycling at the sediment-water interface across five locations along the 30°E meridian that were drilled in the framework of the ChAOS project in the Barents Sea. The model approach allowed to explore the sensitivity of P cycling to plausible ranges of reactive iron and OM inputs. Greater inputs of reactive iron were found to decrease benthic phosphate fluxes (JPO4) whereas greater inputs of OM increased phosphate return to the water column. The quality of these inputs is equally significant: JPO4 decreased when iron hydroxides were made more reactive and increased with more reactive OM. Our findings indicate that variation in climatically sensitive processes, such as burial of terrestrial sediments and iron cycling, could represent powerful feedbacks on JPO4 through adsorption/desorption mechanisms. Results also reveal significant oceanographic controls on JPO4, suggesting Atlantification of the Barents Sea will play into future phosphate availability.

In this study we evaluate the benthic fluxes of silicic acid along the West Antarctic Peninsula (WAP). Silicic acid (DSi) is one of the macronutrients essential in fuelling biological hotspots of diatom-dominated primary production along the WAP. Here we measure the concentration and stable silicon isotopic composition of DSi in porewater profiles, biogenic silica content (BSi) and diatom abundance from sediment cores collected along the WAP. We couple these measurements with reaction-transport modelling, to assess the DSi flux and the processes that release this key nutrient from the sediment into the overlying waters. Our results show that the benthic DSi flux is dominated by the diffusive flux, which is estimated to be equivalent to 26.7 ± 2.7 Gmol yr−1 for the WAP continental shelf. The DSi isotope profiles reveal the important impact of sedimentary processes on porewater DSi and suggest that biogenic silica dissolution is the main source of DSi in porewaters and consequently of the benthic fluxes. Our integrated data model assessment highlights the impact of surface productivity on sedimentary processes and the dynamic environment of core-top sediments where dissolution and reverse weathering reactions control DSi exchanges.

The Barents Sea is experiencing long-term climate-driven changes, e.g. modification in oceanographic conditions and extensive sea ice loss, which can lead to large, yet unquantified disruptions to ecosystem functioning. This key region hosts a large fraction of Arctic primary productivity. However, processes governing benthic and pelagic coupling are not mechanistically understood, limiting our ability to predict the impacts of future perturbations. We combine field observations with a reaction-transport model approach to quantify organic matter (OM) processing and disentangle its drivers. Sedimentary OM reactivity patterns show no gradients relative to sea ice extent, being mostly driven by seafloor spatial heterogeneity. Burial of high reactivity, marine-derived OM is evident at sites influenced by Atlantic Water (AW), whereas low reactivity material is linked to terrestrial inputs on the central shelf. Degradation rates are mainly driven by aerobic respiration (40–75%), being greater at sites where highly reactive material is buried. Similarly, ammonium and phosphate fluxes are greater at those sites. The present-day AW-dominated shelf might represent the future scenario for the entire Barents Sea. Our results represent a baseline systematic understanding of seafloor geochemistry, allowing us to anticipate changes that could be imposed on the pan-Arctic in the future if climate-driven perturbations persist. This article is part of the theme issue ‘The changing Arctic Ocean: consequences for biological communities, biogeochemical processes and ecosystem functioning’.

Biogeochemical cycling of silicon (Si) in the high latitudes has an important influence on the marine Si budget. The Barents Sea is divided aproximately equally into Arctic and Atlantic water (ArW and AW respectively) domains. However, increases in the temperature and inflow of AW across the Barents Sea opening is driving an expansion of the AW realm. While the sensitivity of pelagic processes pertaining to primary production is receiving increasingly more attention, less is known of the effect on the benthic Si cycle. This knowledge gap could prove integral, as the flux of Si across the sediment-water interface (SWI) from Arctic shelf sediments could be up to 20% higher than that of riverine sources. This benthic flux is largely controlled by early diagenetic processes in sediment pore waters, including biogenic silica (bSi) dissolution and authigenic precipitation.To improve our understanding of benthic Si dynamics in the Barents Sea and examine its sensitivity to future change, we analysed pore water and sediment samples from both the AW and ArW realms between 2017-2019 for dissolved silica (dSi) concentrations and stable silicon isotopic compositions. Moreover, to determine the composition and content of bSi, as well as Si sorbed onto metal oxides, we conducted a sequential digestion of surface sediment. Following this we coupled our analyses with reaction transport modelling to further improve our mechanistic understanding of the system and to quantitatively disentangle the relative importance of these diagenetic processes to pore water Si chemistry and benthic fluxes.Our work suggests that both interannual and spatial variability of dSi are increased in the southern, AW region of the Barents Sea. Benthic flux estimates for the southern sites have been found to more than double (~30 to 100 mmol m-2 yr-2) between cruise years, compared to a more consistent flux in the north (~80 mmol m-2 yr-2). Therefore, future Atlantification of the northern region may enance the variability of dSi supply from the benthos to bottom waters, with potential consequences for diatom productivity in the region.

Total phosphorus (TP) records reflect variations in input and burial of organic matter (OM) in coastal and shelf sediments . At Antarctic regions , TP levels are often derived from natural sources; however, with emergent human pressure at these regions, anthropogenic sources of TP may play an important role. At the Antarctic Peninsula , Admiralty Bay attracts great scientific and touristic interest, especially during austral summer months, thus being vulnerable to human activities. Currently, only scarce spatial distributions of TP are available for this key region, whereas no vertical distributions have been determined. To fill this gap, we investigated short ( sediment cores in ten areas along Admiralty Bay for TP contents. We produced the first TP vertical distributions and established site-specific background values (from 492 ± 13 to 932 ± 17 μg g −1 ), which are related to hydrodynamics, sedimentology , and natural inputs of P. We observed a gradual surface TP enrichment at all sites, mainly due to input of fresh OM. Benefiting from our background values, we employ the Phosphorus Pollution Index (PPI) to assess possible human impacts . Generally, the increase of PPI suggests natural inputs of P. However, PPI ≥ 1.3 found at the nearby Comandante Ferraz Research Station (Brazil) can be linked to recent (past 2–3 decades) treated sewage inputs in Martel Inlet. We suggest PPI as a proxy for preliminary assessments of anthropogenic impacts in coastal Antarctic regions experiencing increased human pressure.

The U37K′ proxy for past sea surface temperature (SST) is based on the unsaturation ratio of C37 alkenones. It is considered a diagenetically robust proxy, but biases have been invoked because the index can be altered by preferential degradation of the C37:3 alkenone, resulting in higher reconstructed SST. However, alkenone degradation rate constants are poorly constrained, making it difficult to evaluate the plausibility of such a bias. Therefore, we quantitatively assessed the effect of: (1) different alkenone degradation rate constants; (2) differential degradation factors between di- and tri-unsaturated C37 alkenones; (3) and initial U37K′ values on the U37K′ paleothermometer for two depositional environments (shelf and upper-slope), by means of a Reaction-Transport Model (RTM). RTM results reveal that preferential degradation of C37:3 can potentially alter the original signal of the U37K′ paleothermometer, but SST biases (ΔSST) are largely within U37K′ calibration error (ΔSST 1.5 °C are associated with marked downcore decreases in alkenone concentration. Consequently, we caution against the interpretation of U37K′ indices when extensive degradation results in very low alkenone concentrations (

The stable isotope composition of key chemical elements for life on Earth (e.g., carbon, hydrogen, nitrogen, oxygen, sulfur) tracks changes in fluxes and turnover of these elements in the biogeosphere. Over the past 15–20 years, the potential to measure these isotopic compositions for individual, source-specific organic molecules (biomarkers) and to link them to a range of environmental conditions and processes has been unlocked and amplified by increasingly sensitive, affordable and wide-spread analytical technology. Paleoenvironmental research has seen enormous step-changes in our understanding of past ecosystem dynamics. Vital to these paradigm shifts is the need for well-constrained modern and recent analogues. Through increased understanding of these environments and their biological pathways we can successfully unravel past climatic changes and associated ecosystem adaption. With this review, we aim to introduce scientists working in the field of Quaternary paleolimnology to the tools that compound-specific isotope analysis (CSIA) provides for the gain of information on biogeochemical conditions in ancient environments. We provide information on fundamental principles and applications of novel and established CSIA applications based on the carbon, hydrogen, nitrogen, oxygen and sulfur isotopic composition of biomarkers. While biosynthesis, sources and associated isotope fractionation patterns of compounds such as n-alkanes are relatively well-constrained, new applications emerge from the increasing use of functionalized alkyl lipids, steroids, hopanoids, isoprenoids, GDGTs, pigments or cellulose. Biosynthesis and fractionation are not always fully understood. However, although analytical challenges remain, the future potential of deeper insights into ecosystem dynamics from the study of these compounds is also emerging.

The present article describes integration of environmental monitoring and discharge data and interpretation using multivariate statistics, principal component analysis (PCA), and partial least squares (PLS) regression. The monitoring was carried out at the Peregrino oil field off the coast of Brazil. One sensor platform and 3 sediment traps were placed on the seabed. The sensors measured current speed and direction, turbidity, temperature, and conductivity. The sediment trap samples were used to determine suspended particulate matter that was characterized with respect to a number of chemical parameters (26 alkanes, 16 PAHs, N, C, calcium carbonate, and Ba). Data on discharges of drill cuttings and water-based drilling fluid were provided on a daily basis. The monitoring was carried out during 7 campaigns from June 2010 to October 2012, each lasting 2 to 3 months due to the capacity of the sediment traps. The data from the campaigns were preprocessed, combined, and interpreted using multivariate statistics. No systematic difference could be observed between campaigns or traps despite the fact that the first campaign was carried out before drilling, and 1 of 3 sediment traps was located in an area not expected to be influenced by the discharges. There was a strong covariation between suspended particulate matter and total N and organic C suggesting that the majority of the sediment samples had a natural and biogenic origin. Furthermore, the multivariate regression showed no correlation between discharges of drill cuttings and sediment trap or turbidity data taking current speed and direction into consideration. Because of this lack of correlation with discharges from the drilling location, a more detailed evaluation of chemical indicators providing information about origin was carried out in addition to numerical modeling of dispersion and deposition. The chemical indicators and the modeling of dispersion and deposition support the conclusions from the multivariate statistics. Integr Environ Assess Manag 2017;13:387-395. © 2016 SETAC.

Process-based, mechanistic investigations of organic matter transformation and diagenesis directly beneath the sediment–water interface (SWI) in Arctic continental shelves are vital as these regions are at greatest risk of future change. This is in part due to disruptions in benthic–pelagic coupling associated with ocean current change and sea ice retreat. Here, we focus on a high-resolution, multi-disciplinary set of measurements that illustrate how microbial processes involved in the degradation of organic matter are directly coupled with inorganic and organic geochemical sediment properties (measured and modelled) as well as the extent/depth of bioturbation. We find direct links between aerobic processes, reactive organic carbon and highest abundances of bacteria and archaea in the uppermost layer (0–4.5 cm depth) followed by dominance of microbes involved in nitrate/nitrite and iron/manganese reduction across the oxic-anoxic redox boundary (approx. 4.5–10.5 cm depth). Sulfate reducers dominate in the deeper (approx. 10.5–33 cm) anoxic sediments which is consistent with the modelled reactive transport framework. Importantly, organic matter reactivity as tracked by organic geochemical parameters ( n -alkanes, n -alkanoic acids, n -alkanols and sterols) changes most dramatically at and directly below the SWI together with sedimentology and biological activity but remained relatively unchanged across deeper changes in sedimentology. This article is part of the theme issue ‘The changing Arctic Ocean: consequences for biological communities, biogeochemical processes and ecosystem functioning’.

The present article describes integration of environmental monitoring and discharge data and interpretation using multivariate statistics, principal component analysis (PCA), and partial least squares (PLS) regression. The monitoring was carried out at the Peregrino oil field off the coast of Brazil. One sensor platform and 3 sediment traps were placed on the seabed. The sensors measured current speed and direction, turbidity, temperature, and conductivity. The sediment trap samples were used to determine suspended particulate matter that was characterized with respect to a number of chemical parameters (26 alkanes, 16 PAHs, N, C, calcium carbonate, and Ba). Data on discharges of drill cuttings and water-based drilling fluid were provided on a daily basis. The monitoring was carried out during 7 campaigns from June 2010 to October 2012, each lasting 2 to 3 months due to the capacity of the sediment traps. The data from the campaigns were preprocessed, combined, and interpreted using multivariate statistics. No systematic difference could be observed between campaigns or traps despite the fact that the first campaign was carried out before drilling, and 1 of 3 sediment traps was located in an area not expected to be influenced by the discharges. There was a strong covariation between suspended particulate matter and total N and organic C suggesting that the majority of the sediment samples had a natural and biogenic origin. Furthermore, the multivariate regression showed no correlation between discharges of drill cuttings and sediment trap or turbidity data taking current speed and direction into consideration. Because of this lack of correlation with discharges from the drilling location, a more detailed evaluation of chemical indicators providing information about origin was carried out in addition to numerical modeling of dispersion and deposition. The chemical indicators and the modeling of dispersion and deposition support the conclusions from the multivariate statistics. Integr Environ Assess Manag 2017;13:387-395. © 2016 SETAC.

Submitted by Gisele Mara Hadlich (gisele@ufba.br) on 2019-05-14T17:36:43Z No. of bitstreams: 1 apa.2014.070: 7170173 bytes, checksum: 313b74651054d4308b837a0de84344df (MD5) Approved for entry into archive by Jessica Alves (alves.jessica@ufba.br) on 2019-05-31T13:31:37Z (GMT) No. of bitstreams: 1 apa.2014.070: 7170173 bytes, checksum: 313b74651054d4308b837a0de84344df (MD5) Made available in DSpace on 2019-05-31T13:31:37Z (GMT). No. of bitstreams: 1 apa.2014.070: 7170173 bytes, checksum: 313b74651054d4308b837a0de84344df (MD5) Previous issue date: 2011 Classic hydrographical parameters and dissolved nutrients were measured during the Antarctic summers from 2009 to 2012. Physical and biological processes control the nutrient levels in Admiralty Bay, as well as upwelling of deep water from Brans eld Strait. Additional data on summer land run-o and wind speeds and directions is needed to get a better model for the factors that control the primary production of the area.

A fim de avaliar a origem, distribuição e possíveis mudanças na deposição da matéria orgânica (MO) na plataforma continental sul do Brasil, nove testemunhos de alta resolução foram coletados em mudbelts, distribuídos ao longo da plataforma continental média, entre 25 e 33°S. A avaliação dos marcadores moleculares mostrou-se muito útil para a compreensão da distribuição e variação no aporte da MO terrígena para a região de mudbelts no sul do Brasil. Os resultados de n-alcanos indicaram a predominância de fontes terrígenas. As semelhanças entre a maior parte dos testemunhos indicou uma fonte predominante, relacionada ao aporte do Rio da Prata, e que não apresentou grandes variações durante os últimos100 anos. O gradiente latitudinal nos valores da temperatura da superfície do mar (TSM), calculada a partir das alquenonas, está relacionado ao transporte de águas frias provenientes do sul, como a Água Subantártica de Plataforma e a Pluma do Rio da Prata, com menores temperaturas na região sul da área de estudo e aumento na direção norte. A presença da Frente Subtropical de Plataforma não influenciou a deposição da matéria orgânica terrígena. Os dois testemunhos coletados próximos à região de Itajaí, em Santa Catarina, distinguiram-se significativamente do restante, com as variações mais expressivas ao longo do tempo. Tais diferenças estão relacionadas à maior influência de fontes locais para esta região, em especial ao aporte fluvial do Rio Itajaí-Açu, o que permitiu observar mudanças no regime de chuva se impacto de ações antrópicas na região do Vale do Itajaí. In order to assess the origin, distribution and possible changes in organic matter (OM) deposition on the southern continental shelf of Brazil, nine high-resolution cores distributed along the middle continental shelf, between 25 and 33 °S were collected in mudbelt regions. The evaluation of molecular biomarkers showed to be very useful to understand the distribution and variation in the contribution of terrigenous OM to the mudbelt region in southern Brazil. The results of n-alkanes indicated the predominance of terrigenous sources. The similarity in most of the cores indicated a predominant source for terrigenous OM, related to the La Plata River outflow, which did not present great variations during the last 100 years. The latitudinal gradient in sea surface temperature (SST) values, calculated from alkenones, is related to the transport of cold water from the southern region, such as Sub-Antarctic Shelf Water and the La Plata River Plume, presenting lower temperatures in the southern region of the study area and an increase towards the north. The presence of the Subtropical Shelf Front did not influence the deposition of terrigenous organic matter. The two cores collected near the region of Itajaí, in Santa Catarina, differed significantly from the others, and presented the most expressive variations over time. Such differences are related to the greater influence of local sources for this region, especially the fluvial input from the Itajaí-Açu River, that presented variations related to changes in the rainfall regime and to the anthropic impact in the Itajaí Valley region.