Theoretical and experimental investigation of nickel isotopic fractionation in species relevant to modern and ancient oceans

Nickel plays a central role as an enzyme co-factor in the metabolism of methanogenic Archaea. Methanogens can fractionate Ni isotopes during assimilation, opening the possibility of using the stable isotopic composition of Ni as a biomarker. However, other sources of Ni isotopic variations need to be evaluated before one can establish Ni isotopes as an unambiguous tracer of methanogenesis in the rock record. Equilibrium exchange of Ni between the different species present in the ocean is a potential source of isotopic fractionation. Through controlled laboratory experiments and theoretical calculations, we quantify equilibrium Ni isotope fractionation between different species relevant to the modern and ancient ocean: Ni(H₂O)₆²⁺, Ni(H₂O)₁₈²⁺, NiOH(H₂O)₅⁺, Ni(OH)₂(H₂O)₄, NiCl(H₂O)₅⁺, cis-NiCl₂(H₂O)₄, trans-NiCl₂(H₂O)₄, NiHS(H₂O)₅⁺, Ni(HS)₂(H₂O)₄, NiSO₄(H₂O)₄, NiHCO₃(H₂O)₄⁺, NiCO₃(H₂O)₄, and organic ligands (crown ether and oxalic acid). The magnitude of ligand-controlled Ni isotopic fractionation, approximately 1.25‰/amu (2.5‰ for the ⁶⁰Ni/⁵⁸Ni ratio), is similar to that previously measured in cultures of methanogenic Archaea.     

Stratigraphy and optically stimulated luminescence (OSL) dating of a Quaternary sequence along the Dong Nai River, southern Vietnam

The pre-Holocene Cenozoic sequence outcrops in the terrestrial part of the eastern margin of the Mekong Basin. However, the stratigraphy of the sequence is still unclear. Its detailed stratigraphy and chronology were therefore studied along the Dong Nai River, southern Vietnam, and the lithofacies and the relations among the formations were investigated from the outcrops. The ages of the deposits were determined by using optically stimulated luminescence (OSL) dating.The Ba Mieu Formation was deposited about 176±52 ka during marine isotope stage (MIS) 7–6. The Thu Duc Formation was deposited about 97±27 ka during MIS 5. Both the Ba Mieu and Thu Duc formations are composed of fluvial and tidally influenced coastal deposits. The newly proposed Nhon Trach Formation was originally an eolian (blanket) deposit, but it has been partly reworked by fluvial processes. The Nhon Trach Formation was deposited about 10.9±4.7 ka, in the last part of the Pleistocene to the beginning of the Holocene. The OSL ages for the Ba Mieu, Thu Duc, and Nhon Trach formations are younger than the ages previously assigned to these formations.     

Optimization of dissolved urea measurements in coastal waters with the combination of a single reagent and high temperature

Urea is an unstable and intermediate organic nitrogenous compound present in coastal environments and is derived from the excretion of some aquatic organisms and wastewater discharges. Urea plays an important role in the nitrogen cycle, where it is utilized by algae, including diatoms. However, there are very limited relevant data on the production, consumption, and degradation of urea because of the lack of appropriate measurement techniques. The conventional method is based on the formation of a colored product when urea reacts with diacetyl monoxime in a sulfuric acid solution. We examined the optimal conditions for the formation of the colored product; specifically, we evaluated different temperatures (22–80 °C), reaction times, mixing ratios of color reagents, and sample storage times. Application of the single mixed color-developing reagent (COLDER) at 70 °C resulted in the optimal formation of the colored product within a short reaction time of 60 min. This method was then used to measure dissolved urea in different coastal environments. The concentrations detected were as follows: 0.65–0.72, 0.49–0.58, and 1.09–2.28 µM urea-N at coral reef, seagrass, and mangrove sites, respectively. Our results showed high precision (SD = 0.02, CV = 1.2%), a low detection limit (0.03 µM urea-N), and a high recovery rate (94–99%). In summary, this high-temperature procedure for urea measurements should be valuable for obtaining high-precision data that can further the understanding of urea dynamics and its role in coastal ecosystems.     

Seasonal variations in the nitrogen isotopic composition of settling particles at station K2 in the western subarctic North Pacific

Intensive observations using hydrographical cruises and moored sediment trap deployments during 2010 and 2012 at station K2 in the North Pacific Western Subarctic Gyre (WSG) revealed seasonal changes in δ ¹⁵N of both suspended and settling particles. Suspended particles (SUS) were collected from depths between the surface and 200 m; settling particles by drifting sediment traps (DST; 100–200 m) and moored sediment traps (MST; 200 and 500 m). All particles showed higher δ ¹⁵N values in winter and lower in summer, contrary to the expected by isotopic fractionation during phytoplankton nitrate consumption. We suggest that these observed isotopic patterns are due to ammonium consumption via light-controlled nitrification, which could induce variations in δ ¹⁵N(SUS) of 0.4–3.1 ‰ in the euphotic zone (EZ). The δ ¹⁵N(SUS) signature was reflected by δ ¹⁵N(DST) despite modifications during biogenic transformation from suspended particles in the EZ. δ ¹⁵N enrichment (average: 3.6 ‰) and the increase in C:N ratio (by 1.6) in settling particles suggests year-round contributions of metabolites from herbivorous zooplankton as well as TEPs produced by diatoms. Accordingly, seasonal δ ¹⁵N(DST) variations of 2.4–7.0 ‰ showed a significant correlation with primary productivity (PP) at K2. By applying the observed δ ¹⁵N(DST) vs. PP regression to δ ¹⁵N(MST) of 1.9–8.0 ‰, we constructed the first annual time-series of PP changes in the WSG. This new approach to estimate productivity can be a powerful tool for further understanding of the biological pump in the WSG, even though its validity needs to be examined carefully.     

Attenuation behaviour of tuffaceous sandstone and granite during microfracturing

Laboratory measurements of ultrasonic wave propagation in tuffaceous sandstone (Kimachi, Japan) and granite (Iidate, Japan) were performed during increasing fracturing of the samples. The fracturing was achieved by unconfined uniaxial compression up to and beyond the point of macrofracture of the specimen using a constant low strain rate. The observed variation of wave velocity (up to 40 per cent) due to the development of micro- and macrofractures in the rock is interpreted by rock models relating velocity changes to damage and crack density. The calculated density of the newly formed cracks reaches higher values for the sandstone than for the granite. Using the estimated crack densities, the attenuation behaviour is interpreted in terms of different attenuation mechanisms; that is, friction and scattering. Rayleigh scattering as described by the model of Hudson (1981 ) may explain the attenuation qualitatively if the largest plausible crack dimensions are assumed in modelling.     

Spatial distribution of turbulent diapycnal mixing along the Mindanao current inferred from rapid-sampling Argo floats

The Mindanao Current (MC) bridges the North Pacific low-latitude western boundary current system region and the Indonesian Seas by supplying the North Pacific waters to the Indonesian Throughflow. Although the previous study speculated that the diapycnal mixing along the MC might be strong on the basis of the water mass analysis of the gridded climatologic dataset, the real spatial distribution of diapycnal mixing along the MC has remained to be clarified. We tackle this question here by applying a finescale parameterization to temperature and salinity profiles obtained using two rapid-sampling profiling Argo floats that drifted along the MC. The western boundary (WB) region close to the Mindanao Islands and the Sangihe Strait are the two mixing hotspots along the MC, with energy dissipation rate ε and diapycnal diffusivity K_ρ enhanced up to?~?10^–6 W kg^?1 and?~?10^–3 m² s^?1, respectively. Except for the above two mixing hotspots, the turbulent mixing along the MC is mostly weak, with ε and K_ρ to be 10^–11–10^–9 W kg^?1 and 10^–6–10^–5 m² s^?1, respectively. Strong mixing in the Sangihe Strait can be basically attributed to the existence of internal tides, whereas strong mixing in the WB region suggests the existence of internal lee waves. We also find that water mass transformation along the MC mainly occurs in the Sangihe Strait where the water masses are subjected to strong turbulent mixing during a long residence time.

     

Physical properties and isotopic characteristics of landfast sea ice around the North Water (NOW) Polynya region

Abstract

An ice core sampling program was conducted during the North Water (NOW) Polynya Project 1998 Experiment in northern Baffin Bay during April‐May 1998. The physical properties of snow and sea ice as well as the microstructure and stable isotopic composition of first‐year landfast sea ice near the polynya were investigated. The thickness of sea ice at the sampling sites ranged between 147 and 194 cm with thinner snow cover during the period between mid‐April and late May. The ice was characterized as typical first‐year landfast sea ice, being composed of a thin granular ice layer at the top and an underlying columnar ice layer towards the bottom of the ice. The samples obtained at a site closer to the ice edge of the polynya contained a thin granular ice layer originating from frazil ice near the ice bottom. Formation of frazil ice was considered to be caused by turbulent processes induced by winds, waves and currents forced from the polynya and also mixing with water masses produced at the polynya.     

State Estimation of the North Pacific Ocean by a Four-Dimensional Variational Data Assimilation Experiment

A four-dimensional variational data assimilation system has been applied to an experiment to describe the dynamic state of the North Pacific Ocean. A synthesis of available observational records and a sophisticated ocean general circulation model produces a dynamically consistent dataset, which, in contrast to the nudging approach, provides realistic features of the seasonally-varying ocean circulation with no artificial sources/sinks for temperature and salinity fields. This new dataset enables us to estimate heat and water mass transports in addition to the qualification of water mass formation and movement processes. A sensitivity experiment on our assimilation system reveals that the origin of the North Pacific Intermediate Water can be traced back to the Sea of Okhotsk and the Bering Sea in the subarctic region and to the subtropical Kuroshio region further south. These results demonstrate that our data assimilation system is a very powerful tool for the identification and characterization of ocean variabilities and for our understanding of the dynamic state of ocean circulation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Vegetation and climate variability in East Asia driven by low-latitude oceanic forcing during the middle to late Holocene

At centennial to millennial timescales, little is known of C₃ and C₄ plant productivity’s responses to past regional climate changes and the dominant forcing factors during the Holocene, although large-scale changes in glacial-interglacial periods have been attributed to changes in aridity, temperature, and CO₂ concentration. We investigated the δ¹³C of TOC, C/N ratios, and pollen in samples from a wetland on Jeju Island, Korea. The bulk isotopic signal ranging from ?17‰ to ?29‰ was partitioned into C₃ and C₄ plant signals by using a binary mixing model and calculating separate organic carbon-accumulation rates for C₃ and C₄ plants (OCAR₃ and OCAR₄) during the last 6500 years. Pollen data indicated that the temperate deciduous broadleaved trees replaced grassland dominated by Artemisia, dry-tolerant grass, and further expanded in the maar. The long-term decreasing trend of Artemisia-dominated grassland was similar to those of δ¹³C values and OCAR₄. The multi-centennial to millennial variability superimposed on the gradual increasing trend of OCAR₃ was inversely correlated with those of the sea surface temperature (SST) in the western tropical Pacific (WTP) and El Niño-Southern Oscillation (ENSO) activity, suggesting that C₃ plants have stronger sensitivity to regional climate change driven by oceanic forcing. Our data suggest that vegetation changes in a coastal area in East Asia were affected by monsoonal changes coupled with SST in WTP and ENSO activity. The vegetation change on Jeju Island varied quite differently from change in the westerly pathway, suggesting only a weak influence from high-latitude-driven atmospheric circulation changes. We conclude that centennial- to millennial-scale climate changes in coastal regions of East Asia during the mid- to late-Holocene may have been mainly controlled by low-latitudinal oceanic forcing, including forcing by SST and ENSO activity.