Beschreibung: The development of phosphate sensors suitable for long-term in situ deployments in natural waters, is essential to improve our understanding of the distribution, fluxes, and biogeochemical role of this key nutrient in a changing ocean. Here, we describe the optimization of the molybdenum blue method for in situ work using a lab-on-chip (LOC) analyzer and evaluate its performance in the laboratory and at two contrasting field sites. The in situ performance of the LOC sensor is evaluated using hourly time-series data from a 56-day trial in Southampton Water (UK), as well as a month-long deployment in the subtropical oligotrophic waters of Kaneohe Bay (Hawaii, USA). In Kaneohe Bay, where phosphate concentrations were characteristic of the dry season (0.13 ± 0.03 μM, n = 704), the in situ sensor accuracy was 16 ± 12% and a potential diurnal cycle in phosphate concentrations was observed. In Southampton Water, the sensor data (1.02 ± 0.40 μM, n = 1,267) were accurate to ±0.10 μM relative to discrete reference samples. Hourly in situ monitoring revealed striking tidal and storm derived fluctuations in phosphate concentrations in Southampton Water that would not have been captured via discrete sampling. We show the impact of storms on phosphate concentrations in Southampton Water is modulated by the spring-neap tidal cycle and that the 10-fold decline in phosphate concentrations observed during the later stages of the deployment was consistent with the timing of a spring phytoplankton bloom in the English Channel. Under controlled laboratory conditions in a 250 L tank, the sensor demonstrated an accuracy and precision better than 10% irrespective of the salinity (0–30), turbidity (0–100 NTU), colored dissolved organic matter (CDOM) concentration (0–10 mg/L), and temperature (5–20°C) of the water (0.3–13 μM phosphate) being analyzed. This work demonstrates that the LOC technology is mature enough to quantify the influence of stochastic events on nutrient budgets and to elucidate the role of phosphate in regulating phytoplankton productivity and community composition in estuarine and coastal regimes.

Beschreibung: A multitracer approach is applied to assess the impact of boundary fluxes (e.g., benthic input from sediments or lateral inputs from the coastline) on the acid-base buffering capacity, and overall biogeochemistry, of the North Sea. Analyses of both basin-wide observations in the North Sea and transects through tidal basins at the North-Frisian coastline, reveal that surface distributions of the δ13C signature of dissolved inorganic carbon (DIC) are predominantly controlled by a balance between biological production and respiration. In particular, variability in metabolic DIC throughout stations in the well-mixed southern North Sea indicates the presence of an external carbon source, which is traced to the European continental coastline using naturally occurring radium isotopes (224Ra and 228Ra). 228Ra is also shown to be a highly effective tracer of North Sea total alkalinity (AT) compared to the more conventional use of salinity. Coastal inputs of metabolic DIC and AT are calculated on a basin-wide scale, and ratios of these inputs suggest denitrification as a primary metabolic pathway for their formation. The AT input paralleling the metabolic DIC release prevents a significant decline in pH as compared to aerobic (i.e., unbuffered) release of metabolic DIC. Finally, long-term pH trends mimic those of riverine nitrate loading, highlighting the importance of coastal AT production via denitrification in regulating pH in the southern North Sea.

Beschreibung: A well documented, publicly available, global data set of surface ocean carbon dioxide (CO2) parameters has been called for by international groups for nearly two decades. The Surface Ocean CO2 Atlas (SOCAT) project was initiated by the international marine carbon science community in 2007 with the aim of providing a comprehensive, publicly available, regularly updated, global data set of marine surface CO2, which had been subject to quality control (QC). Many additional CO2 data, not yet made public via the Carbon Dioxide Information Analysis Center (CDIAC), were retrieved from data originators, public websites and other data centres. All data were put in a uniform format following a strict protocol. Quality control was carried out according to clearly defined criteria. Regional specialists performed the quality control, using state-of-the-art web-based tools, specially developed for accomplishing this global team effort. SOCAT version 1.5 was made public in September 2011 and holds 6.3 million quality controlled surface CO2 data points from the global oceans and coastal seas, spanning four decades (1968–2007). Three types of data products are available: individual cruise files, a merged complete data set and gridded products. With the rapid expansion of marine CO2 data collection and the importance of quantifying net global oceanic CO2 uptake and its changes, sustained data synthesis and data access are priorities

Beschreibung: As a response to public demand for a well-documented, quality controlled, publically available, global surface ocean carbon dioxide (CO2) data set, the international marine carbon science community developed the Surface Ocean CO2 Atlas (SOCAT). The first SOCAT product is a collection of 6.3 million quality controlled surface CO2 data from the global oceans and coastal seas, spanning four decades (1968–2007). The SOCAT gridded data presented here is the second data product to come from the SOCAT project. Recognizing that some groups may have trouble working with millions of measurements, the SOCAT gridded product was generated to provide a robust, regularly spaced CO2 fugacity (fCO2) product with minimal spatial and temporal interpolation, which should be easier to work with for many applications. Gridded SOCAT is rich with information that has not been fully explored yet (e.g., regional differences in the seasonal cycles), but also contains biases and limitations that the user needs to recognize and address (e.g., local influences on values in some coastal regions).

Beschreibung: The major geochemical characteristics of Red Sea brine are summarized for 11 brine-filled deeps located along the central graben axis between 19°N and 27°N. The major element composition of the different brine pools is mainly controlled by variable mixing situations of halite-saturated solution (evaporite dissolution) with Red Sea deep water. The brine chemistry is also influenced by hydrothermal water/rock interaction, whereas magmatic and sedimentary rock reactions can be distinguished by boron, lithium, and magnesium/calcium chemistry. Moreover, hydrocarbon chemistry (concentrations and δ 13 C data) of brine indicates variable injection of light hydrocarbons from organic source rocks and strong secondary (bacterial or thermogenic) degradation processes. A simple statistical cluster analysis approach was selected to look for similarities in brine chemistry and to classify the various brine pools, as the measured chemical brine compositions show remarkably strong concentration variations for some elements. The cluster analysis indicates two main classes of brine. Type I brine chemistry (Oceanographer and Kebrit Deeps) is controlled by evaporite dissolution and contributions from sediment alteration. The Type II brine (Suakin, Port Sudan, Erba, Albatross, Discovery, Atlantis II, Nereus, Shaban, and Conrad Deeps) is influenced by variable contributions from volcanic/ magmatic rock alteration. The chemical brine classification can be correlated with the sedimentary and tectonic setting of the related depressions. Type I brine-filled deeps are located slightly off-axis from the central Red Sea graben. A typical " collapse structure formation " which has been defined for the Kebrit Deep by evaluating seismic and geomorphological data probably corresponds to our Type I brine. Type II brine located in depressions in the northern Red Sea (i.e., Conrad and Shaban Deeps) could be correlated to " volcanic intrusion-/extrusion-related " deep formation. The chemical indications for hydrothermal influence on Conrad and Shaban Deep brine can be related to brines from the multi-deeps region in the central Red Sea, where volcanic/magmatic fluid/rock interaction is most obvious. The strongest hydrothermal influence is observed in Atlantis II brine (central multi-deeps region), which is also the hottest Red Sea brine body in 2011 (*68.2 °C).

Beschreibung: High-resolution multibeam bathymetry data collected with an autonomous underwater vehicle (AUV) complemented by compressed high-intensity radar pulse (Chirp) profiles and remotely operated vehicle (ROV) observations and sediment sampling reveal a distinctive rough topography associated with seafloor gas venting and/or near-subsurface gas hydrate accumulations. The surveys provide 1 m bathymetric grids of deep-water gas venting sites along the best-known gas venting areas along the Pacific margin of North America, which is an unprecedented level of resolution. Patches of conspicuously rough seafloor that are tens of meters to hundreds of meters across and occur on larger seafloor topographic highs characterize seepage areas. Some patches are composed of multiple depressions that range from 1 to 100 m in diameter and are commonly up to 10 m deeper than the adjacent seafloor. Elevated mounds with relief of 〉10 m and fractured surfaces suggest that seafloor expansion also occurs. Ground truth observations show that these areas contain broken pavements of methane-derived authigenic carbonates with intervening topographic lows. Patterns seen in Chirp profiles, ROV observations, and core data suggest that the rough topography is produced by a combination of diagenetic alteration, focused erosion, and inflation of the seafloor. This characteristic texture allows previously unknown gas venting areas to be identified within these surveys. A conceptual model for the evolution of these features suggests that these morphologies develop slowly over protracted periods of slow seepage and shows the impact of gas venting and gas hydrate development on the seafloor morphology.

Beschreibung: The coastal ocean is a crucial link between land, the open ocean and the atmosphere. The shallowness of the water column permits close interactions between the sedimentary, aquatic and atmospheric compartments, which otherwise are decoupled at long time scales (≅ 1000 yr) in the open oceans. Despite the prominent role of the coastal oceans in absorbing atmospheric CO2 and transferring it into the deep oceans via the continental shelf pump, the underlying mechanisms remain only partly understood. Evaluating observations from the North Sea, a NW European shelf sea, we provide evidence that anaerobic degradation of organic matter, fuelled from land and ocean, generates total alkalinity (AT) and increases the CO2 buffer capacity of seawater. At both the basin wide and annual scales anaerobic AT generation in the North Sea's tidal mud flat area irreversibly facilitates 7–10%, or taking into consideration benthic denitrification in the North Sea, 20–25% of the North Sea's overall CO2 uptake. At the global scale, anaerobic AT generation could be accountable for as much as 60% of the uptake of CO2 in shelf and marginal seas, making this process, the anaerobic pump, a key player in the biological carbon pump. Under future high CO2 conditions oceanic CO2 storage via the anaerobic pump may even gain further relevance because of stimulated ocean productivity.