Interannual variability in the summer dissolved organic matter inventory of the North Sea: Implications for the continental shelf pump

We present the distribution and C:N stoichiometry of dissolved organic matter (DOM) in the North Sea in two summers (August 2011 and August 2012), with supporting data from the intervening winter (January 2012). These data demonstrate local variability superimposed on a general pattern of decreasing DOM with increasing distance from land, suggesting concentrations of DOM are controlled on large spatial scales by mixing between the open North Atlantic and either riverine sources or high DOM productivity in nearshore coastal waters driven by riverine nutrient discharge. Given the large size and long residence time of water in the North Sea, we find concentrations are commonly modified from simple conservative mixing between two endmembers. We observe differences in dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) concentrations and land-ocean gradients between the two summers, leading to an estimated 10-20Tg difference in the DOC inventory between the two years, which is of the same order of magnitude as the annual uptake of atmospheric CO 2 by the North Sea system, and thus significant for the carbon budget of the North Sea. This difference is not consistent with additional terrestrial loading and is more likely to be due to balancing of mixing and in situ production and loss processes across the North Sea. Differences were particularly pronounced in the bottom layer of the seasonally stratifying northern North Sea, with higher DOC and C:N ratio in 2011 than in 2012. Using other data, we consider the extent to which these differences in the concentrations and C:N ratio of DOM could be due to changes in the biogeochemistry or physical circulation in the two years, or a combination of both. The evidence we have is consistent with a flushing event in winter 2011/12 exchanging DOM-rich, high C:N shelf waters, which may have accumulated over more than 1 year, with deep North Atlantic waters with lower DOC and marginally higher DON. We discuss the implications of these observations for the shelf sea carbon pump and the export of carbon-rich organic matter off the shelf and hypothesise that intermittent flushing of temperate shelf systems may be a key mechanism in the maintenance of the continental shelf pump, via the accumulation and subsequent export of carbon-rich DOM

Dissolved oxygen dynamics during a phytoplankton bloom in the Ross Sea polynya

The Ross Sea polynya is one of the most productive regions in the Southern Ocean. However, limited access and high spatio-temporal variability of physical and biological processes limit the use of conventional oceanographic methods to measure early season primary productivity. High-resolution observations from two Seagliders provide insights into the timing of a bloom in the southern Ross Sea polynya in December 2010. Changes in chlorophyll and oxygen concentrations are used to assess bloom dynamics. Using a ratio of dissolved oxygen to carbon, net primary production is estimated over the duration of the bloom showing a sensitive balance between net autotrophy and heterotrophy. The two gliders, observing spatially distinct regions during the same period, found net community production rates of -0.9±0.7 and 0.7±0.4 g C m-2 d-1. The difference highlights the spatial variability of biological processes and is probably caused by observing different stages of the bloom. The challenge of obtaining accurate primary productivity estimates highlights the need for increased observational efforts, particularly focusing on subsurface processes not resolved using surface or remote observations. Without an increased observational effort and the involvement of emerging technologies, it will not be possible to determine the seasonal trophic balance of the Ross Sea polynya and quantify the shelf's importance in carbon export

Determination of Arsenic, Mercury and Barium in herbarium mount paper using dynamic ultrasound-assisted extraction prior to atomic fluorescence and absorption spectrometry

A dynamic ultrasound-assisted extraction method using Atomic Absorption and Atomic Flourescence spectrometers as detectors was developed to analyse mercury, arsenic and barium from herbarium mount paper originating from the herbarium collection of the National Museum of Wales. The variables influencing extraction were optimised by a multivariate approach. The optimal conditions were found to be 1% HNO3 extractant solution used at a flow rate of 1 mL min-1. The duty cycle and amplitude of the ultrasonic probe was found to be 50% in both cases with an ultrasound power of 400 W. The optimal distance between the probe and the top face of the extraction chamber was found to be 0 cm. Under these conditions the time required for complete extraction of the three analytes was 25 min. Cold vapour and hydride generation coupled to atomic fluorescence spectrometry was utilized to determine mercury and arsenic, respectively. The chemical and instrumental conditions were optimized to provide detection limits of 0.01ng g-1 and 1.25 ng g-1 for mercury and arsenic, respectively. Barium was determined by graphite-furnace atomic absorption spectrometry, with a detection limit of 25 ng g-1. By using 0.5 g of sample, the concentrations of the target analytes varied for the different types of paper and ranged between 0.4–2.55 µg g-1 for Ba, 0.035–10.47 µg g-1 for As and 0.0046–2.37 µg g-1 for Hg

Discovery Prospects for a Supernova Signature of Biogenic Origin

Approximately 2.8 Myr before the present our planet was subjected to the debris of a supernova explosion. The terrestrial proxy for this event was the discovery of live atoms of 60Fe in a deep-sea ferromanganese crust. The signature for this supernova event should also reside in magnetite Fe3O4 microfossils produced by magnetotactic bacteria extant at the time of the Earth-supernova interaction, provided the bacteria preferentially uptake iron from fine-grained iron oxides and ferric hydroxides. Using estimates for the terrestrial supernova 60Fe flux, combined with our empirically derived microfossil concentrations in a deep-sea drill core, we deduce a conservative estimate of the ^{60}{Fe} fraction as 60Fe/Fe ~ 3.6 x 10^{-15}. This value sits comfortably within the sensitivity limit of present accelerator mass spectrometry capabilities. The implication is that a biogenic signature of this cosmic event is detectable in the Earth's fossil record.Comment: As it appears in Icaru

Ocean processes at the Antarctic continental slope

The Antarctic continental shelves and slopes occupy relatively small areas, but, nevertheless, are important for global climate, biogeochemical cycling and ecosystem functioning. Processes of water mass transformation through sea ice formation/melting and ocean-atmosphere interaction are key to the formation of deep and bottom waters as well as determining the heat flux beneath ice shelves. Climate models, however, struggle to capture these physical processes and are unable to reproduce water mass properties of the region. Dynamics at the continental slope are key for correctly modelling climate, yet their small spatial scale presents challenges both for ocean modelling and for observational studies. Cross-slope exchange processes are also vital for the flux of nutrients such as iron from the continental shelf into the mixed layer of the Southern Ocean. An iron-cycling model embedded in an eddy-permitting ocean model reveals the importance of sedimentary iron in fertilizing parts of the Southern Ocean. Ocean gliders play a key role in improving our ability to observe and understand these small-scale processes at the continental shelf break. The Gliders: Excellent New Tools for Observing the Ocean (GENTOO) project deployed three Seagliders for up to two months in early 2012 to sample the water to the east of the Antarctic Peninsula in unprecedented temporal and spatial detail. The glider data resolve small-scale exchange processes across the shelf-break front (the Antarctic Slope Front) and the front\u27s biogeochemical signature. GENTOO demonstrated the capability of ocean gliders to play a key role in a future multi-disciplinary Southern Ocean observing system

Governing processes for reactive nitrogen compounds in the atmosphere in relation to ecosystem climatic and human health impacts

Reactive nitrogen (Nr) compounds have different fates in the atmosphere due to differences in governing processes of physical transport, deposition and chemical transformation. Nr compounds addressed here include reduced nitrogen (NHx: ammonia (NH3) and its reaction product ammonium (NH4+)), oxidized nitrogen (NOy: nitrogen monoxide (NO) + nitrogen dioxide (NO2) and their reaction products) as well as organic nitrogen compounds (organic N). Pollution abatement strategies need to take into account these differences in the governing processes of these compounds when assessing their impact on ecosystem services, biodiversity, human health and climate. NOx (NO + NO2) emitted from traffic affects human health in urban areas where the presence of buildings increases the residence time in streets. In urban areas this leads to enhanced exposure of the population to NOx concentrations. NOx emissions have little impact on nearby ecosystems because of the small dry deposition rates of NOx. These compounds need to be converted into nitric acid (HNO3) before removal through deposition is efficient. HNO3 sticks quickly to any surface and is thereby either dry deposited or incorporated into aerosols as nitrate (NO3−). In contrast to NOx compounds, NH3 has potentially high impacts on ecosystems near the main agricultural sources of NH3 because of its large ground-level concentrations along with large dry deposition rates. Aerosol phase NH4+ and NO3− contribute significantly to background PM2.5 and PM10 (mass of aerosols with a diameter of less than 2.5 and 10 μm, respectively) with an impact on radiation balance as well as potentially on human health. Little is known quantitatively and qualitatively about organic N in the atmosphere, other than that it contributes a significant fraction of wet-deposited N, and is present in both gaseous and particulate forms in the atmosphere. Further studies are needed to characterize the sources, air chemistry and removal rates of organic N emissions

Carbon dioxide and ocean acidification observations in UK waters. Synthesis report with a focus on 2010–2015

Key messages: 1.1 The process of ocean acidification is now relatively well-documented at the global scale as a long-term trend in the open ocean. However, short-term and spatial variability can be high. 1.2 New datasets made available since Charting Progress 2 make it possible to greatly improve the characterisation of CO2 and ocean acidification in UK waters. 3.1 Recent UK cruise data contribute to large gaps in national and global datasets. 3.2 The new UK measurements confirm that pH is highly variable, therefore it is important to measure consistently to determine any long term trends. 3.3 Over the past 30 years, North Sea pH has decreased at 0.0035±0.0014 pH units per year. 3.4 Upper ocean pH values are highest in spring, lowest in autumn. These changes reflect the seasonal cycles in photosynthesis, respiration (decomposition) and water mixing. 3.5 Carbonate saturation states are minimal in the winter, and lower in 7 more northerly, colder waters. This temperature-dependence could have implications for future warming of the seas. 3.6 Over the annual cycle, North-west European seas are net sinks of CO2. However, during late summer to autumn months, some coastal waters may be significant sources. 3.7 In seasonally-stratified waters, sea-floor organisms naturally experience lower pH and saturation states; they may therefore be more vulnerable to threshold changes. 3.8 Large pH changes (0.5 - 1.0 units) can occur in the top 1 cm of sediment; however, such effects are not well-documented. 3.9 A coupled forecast model estimates the decrease in pH trend within the North Sea to be -0.0036±0.00034 pH units per year, under a high greenhouse gas emissions scenario (RCP 8.5). 3.10 Seasonal estimates from the forecast model demonstrate areas of the North Sea that are particularly vulnerable to aragonite undersaturation

Iron biogeochemistry across marine systems progress from the past decade

Based on an international workshop (Gothenburg, 14–16 May 2008), this review article aims to combine interdisciplinary knowledge from coastal and open ocean research on iron biogeochemistry. The major scientific findings of the past decade are structured into sections on natural and artificial iron fertilization, iron inputs into coastal and estuarine systems, colloidal iron and organic matter, and biological processes. Potential effects of global climate change, particularly ocean acidification, on iron biogeochemistry are discussed. The findings are synthesized into recommendations for future research areas

Seasonal ITCZ migration dynamically controls the location of the (sub)tropical Atlantic biogeochemical divide

Inorganic nitrogen depletion restricts productivity in much of the low-latitude oceans, generating a selective advantage for diazotrophic organisms capable of fixing atmospheric dinitrogen (N2). However, the abundance and activity of diazotrophs can in turn be controlled by the availability of other potentially limiting nutrients, including phosphorus (P) and iron (Fe). Here we present high-resolution data (∼0.3°) for dissolved iron, aluminum, and inorganic phosphorus that confirm the existence of a sharp north–south biogeochemical boundary in the surface nutrient concentrations of the (sub)tropical Atlantic Ocean. Combining satellite-based precipitation data with results from a previous study, we here demonstrate that wet deposition in the region of the intertropical convergence zone acts as the major dissolved iron source to surface waters. Moreover, corresponding observations of N2 fixation and the distribution of diazotrophic Trichodesmium spp. indicate that movement in the region of elevated dissolved iron as a result of the seasonal migration of the intertropical convergence zone drives a shift in the latitudinal distribution of diazotrophy and corresponding dissolved inorganic phosphorus depletion. These conclusions are consistent with the results of an idealized numerical model of the system. The boundary between the distinct biogeochemical systems of the (sub)tropical Atlantic thus appears to be defined by the diazotrophic response to spatial–temporal variability in external Fe inputs. Consequently, in addition to demonstrating a unique seasonal cycle forced by atmospheric nutrient inputs, we suggest that the underlying biogeochemical mechanisms would likely characterize the response of oligotrophic systems to altered environmental forcing over longer timescales