Description: The role of the global surface ocean as a source and sink for atmospheric carbon dioxide and the flux strengths between the ocean and the atmosphere can be quantified by measuring the fugacity of CO2 (ƒCO2) as well as the dissolved inorganic carbon (DIC) concentration and its isotopic composition in surface seawater. In this work, the potential of continuous wave cavity ringdown spectroscopy (cw-CRDS) for autonomous underway measurements of ƒCO2 and the stable carbon isotope ratio of DIC [δ13C(DIC)] is explored. For the first time, by using a conventional air-sea equilibrator setup, both quantities were continuously and simultaneously recorded during a field deployment on two research cruises following meridional transects across the Atlantic Ocean (Bremerhaven, Germany–Punta Arenas, Chile). Data are compared against reference measurements by an established underway CO2 monitoring system and isotope ratio mass spectrometric analysis of individual water samples. Agreement within ΔƒCO2 = 0.35 μatm for atmospheric and ΔƒCO2 = 2.5 μatm and Δδ13C(DIC) =0.33‰ for seawater measurements have been achieved. Whereas “calibration-free” ƒCO2 monitoring is feasible, the measurement of accurate isotope ratios relies on running reference standards on a daily basis. Overall, the installed CRDS/equilibrator system was shown to be capable of reliable online monitoring of ƒCO2, equilibrium δ13C(CO2), δ13C(DIC), and pO2 aboard moving research vessels, thus making possible corresponding measurements with high spatial and temporal resolution.

Description: Tracing the origin of nutrients is a fundamental goal of food web research but methodological issues associated with current research techniques such as using stable isotope ratios of bulk tissue can lead to confounding results. We investigated whether naturally occurring delta C-13 patterns among amino acids (delta C-13(AA)) could distinguish between multiple aquatic and terrestrial primary production sources. We found that delta C-13(AA) patterns in contrast to bulk delta C-13 values distinguished between carbon derived from algae, seagrass, terrestrial plants, bacteria and fungi. Furthermore, we showed for two aquatic producers that their delta C-13(AA) patterns were largely unaffected by different environmental conditions despite substantial shifts in bulk delta C-13 values. The potential of assessing the major carbon sources at the base of the food web was demonstrated for freshwater, pelagic, and estuarine consumers; consumer delta C-13 patterns of essential amino acids largely matched those of the dominant primary producers in each system. Since amino acids make up about half of organismal carbon, source diagnostic isotope fingerprints can be used as a new complementary approach to overcome some of the limitations of variable source bulk isotope values commonly encountered in estuarine areas and other complex environments with mixed aquatic and terrestrial inputs.

Description: OS51C-1004 Dissolved radiogenic Nd isotopes (εNd), rare earth element (REE), Ba, and nutrient concentrations combined with oxygen isotopes retrieved along a section between Spitsbergen and Greenland at approximately 79°N during the ARK XXVII/1 cruise in 2012 were measured to characterize the origin and mixing of the water masses in the Fram Strait. Deep waters below 500 m are nearly constant in Nd concentration (CNd) around 16 pmol/kg and εNd signatures range from -9.5±0.2 to -10.9±0.2. The heavy REE to light REE ratio (HREE/LREE) ranges from 4 to 5. Ba concentrations range from 47 to 58 nmol/kg, increasing slightly with depth. These homogeneous signatures do not allow identification of distinct deep water masses. The upper 500 m of the water column close to the Western Svalbard margin including the shelf is relatively warm and saline (T ≤ 5.5°C, S ≤ 35.1) and shares characteristics of Atlantic Water (AW) including low CNd (~15 pmol/kg) and relatively unradiogenic εNd signatures (-12.2±0.2). This water is also characterized by HREE/LREE around 4 and CBa around 50 nmol/kg. Low salinity surface waters on the East Greenland shelf have unradiogenic εNd signatures similar to AW (-12.4±0.3) but in contrast to AW high CNd of up to 37 pmol/kg. At the same time the HREE/LREE ratio is relatively low (~3.5) and CBa reaches 73 nmol/kg. This suggests a significant freshwater contribution either from the McKenzie or the Lena rivers. Eastwards of these freshwater-influenced waters (at ~5°W), admixture of a Pacific component characterized by a more radiogenic εNd (-8.8±0.2) and high nutrient concentrations outcropping at surface was detected. Waters of the same origin are present on the East Greenland shelf at about 150 m depth. Based on these data we use mass balance calculations to determine the fractions of sea ice meltwater, Eurasian run-off, North American run-off, and Arctic seawater and compare these results with our εNd and REE data.

Description: Late Pliocene changes in the advection of Mediterranean Outflow Water (MOW) derivates were reconstructed at northeast Atlantic DSDP/ODP sites 548 and 982 and compared to records of WMDW at West Mediterranean Site 978. Neodymium isotope (εNd) values more positive than −10.5/−11 reflect diluted MOW derivates that spread almost continuously into the northeast Atlantic from 3.7 to 2.55 Ma, reaching Rockall Plateau Site 982 from 3.63 to 2.75 Ma. From 3.4 to 3.3 Ma average MOW temperature and salinity increased by 2°–4 °C and ~1 psu both at proximal Site 548 and distal Site 982. The rise implies a rise in flow strength, coeval with a long-term rise in both west Mediterranean Sea surface salinity by almost 2 psu and average bottom water salinity (BWS) by ~1 psu, despite inherent uncertainties in BWS estimates. The changes were linked with major Mediterranean aridification and a drop in African monsoon humidity. In contrast to model expectations, the rise in MOW salt discharge after 3.4 Ma did not translate into improved ventilation of North Atlantic Deep Water, since it possibly was too small to significantly influence Atlantic Meridional Overturning Circulation. Right after ~2.95 Ma, with the onset of major Northern Hemisphere Glaciation, long-term average bottom water temperature (BWT) and BWS at Site 548 dropped abruptly by ~5 °C and ~1–2 psu, in contrast to more distal Site 982, where BWT and BWS continued to oscillate at estimates of ~2 °C and 1.5–2.5 psu higher than today until ~2.6 Ma. We relate the small-scale changes both to a reduced MOW flow and to enhanced dilution by warmwaters of a strengthenedNorth Atlantic Current temporarily replacingMOWderivates at Rockall Plateau.

Description: Highlights • Stratigraphic framework over the Miocene-Pliocene boundary at IODP Site U1387. • Abrupt sedimentary changes over the Miocene-Pliocene boundary. • Clear hints for onset of Mediterranean Outflow after the Messinian Salinity Crisis. • Evidence of bottom water currents in contouritic sedimentation and elevated Zr/Al. • Quiet, hemipelagic sediment deposition during the Messinian in the Gulf of Cadiz. Abstract Integrated Ocean Drilling Program (IODP) Expedition 339 cored multiple sites in the Gulf of Cadiz in order to study contourite deposition resulting from Mediterranean Outflow water (MOW). One hole, U1387C, was cored to a depth of 865.6 meters below seafloor (mbsf) with the goal of recovering the Latest Miocene to Pliocene transition in order to evaluate the history of MOW immediately after the end of the Messinian Salinity Crisis. To understand this history, an accurate age model for the succession is needed, but is challenging to construct, because the Miocene-Pliocene boundary is not marked by a clear biostratigraphic event in the Atlantic and coring gaps occur within the recovered stratigraphic record. These limitations are overcome by combining a variety of chronostratigraphic datasets to construct an age-model that fits the currently available age indicators and demonstrates that coring in Hole U1387C did indeed recover the Miocene-Pliocene boundary at around 826 mbsf. This boundary is associated with a distinct and abrupt change in depositional environment. During the latest Messinian, hemipelagic sediments exhibiting precession-induced climate variability were deposited. These are overlain by Pliocene sediments deposited at a much higher sedimentation rate, with much higher and more variable XRF-scanning Zr/Al ratios than the underlying sediment, and that show evidence of winnowing, particle sorting and increasing grain size, which we interpret to be related to the increasing flow of MOW. Pliocene sedimentary cyclicity is clearly visible in both the benthic δ18O record and the Zr/Al data and is probably also precessionally controlled. Two contouritic bigradational sandy-beds are revealed above the third sedimentary cycle of the Pliocene. On the basis of these results, we conclude that sedimentation associated with weak Mediterranean-Atlantic exchange, began in the Gulf of Cadiz virtually at or shortly after the Miocene-Pliocene boundary.

Description: The stable carbon isotope composition of dissolved inorganic carbon (δ13C-DIC) can be used to quantify fluxes within the carbon system. For example, knowing the δ13C signature of the inorganic carbon pool can help in describing the amount of anthropogenic carbon in the water column. The measurements can also be used for evaluating modeled carbon fluxes, for making basin-wide estimates of anthropogenic carbon, and for studying seasonal and interannual variability or decadal trends in interior ocean biogeochemistry. For all these purposes, it is not only important to have a sufficient amount of data, but these data must also be internally consistent and of high quality. In this study, we present a δ13C-DIC dataset for the North Atlantic which has undergone secondary quality control. The data originate from oceanographic research cruises between 1981 and 2014. During a primary quality control step based on simple range tests, obviously bad data were flagged. In a second quality control step, biases between measurements from different cruises were quantified through a crossover analysis using nearby data of the respective cruises, and values of biased cruises were adjusted in the data product. The crossover analysis was possible for 24 of the 32 cruises in our dataset, and adjustments were applied to 11 cruises. The internal accuracy of this dataset is 0.017 ‰.

Description: Considerable interannual differences were observed in river water and sea-ice meltwater inventory values derived from d18O and salinity data in the Eurasian Basin along the continental margin of the Laptev Sea in the summers of 1993 and 1995, and in the summers of 2005 and 2006 during Nansen and Amundsen Basins Observational system (NABOS) expeditions. The annually different pattern in river and sea-ice meltwater inventories remain closely linked for all of the years studied, which indicates that source regions and transport mechanisms for both river water and sea-ice formation are largely similar over the relatively shallow Laptev Sea Shelf. A simple Ekman trajectory model for surface Lagrangian particles based solely on wind forcing can explain the main features observed between years with significantly different wind patterns and vorticities, and can also explain differences in river water distributions observed for years with a generally similar offshore wind setting. An index based on this simplified trajectory model is rather similar to the vorticity index, but reflects the hydrology on the shelf better for distinctive years. This index is not correlated with the Arctic Oscillation, but rather with a local mode of oscillation, which controls the outflow and distribution of the Eurasian Basin major freshwater source on an annual timescale.