Marine Chemistry最新文献

New seawater stable oxygen isotope (δ¹⁸O) samples were collected from the southeast Indian Ocean as part of the Coring to Reconstruct Ocean Circulation and Carbon dioxide Across 2 Seas (CROCCA-2S) expedition in November – December of 2018. These data fill a gap in the δ¹⁸O sampling coverage of the southern Indian basin, providing new insights into the hydrologic and oceanographic processes influencing the δ¹⁸O distribution of the region and its relationship to salinity in the upper ocean. Our surface ocean data (<100 m)—in combination with decades of observations from the broader south Indian Ocean—show distinct δ¹⁸O – salinity characteristics on either side of ∼85°E. The balance between evaporation and precipitation yields a strong, robust δ¹⁸O – salinity relationship west of 85°E (δ¹⁸O = 0.50(±0.01) * S – 17.2(±0.22)). However, within the mesoscale eddy field initiated by the Leeuwin Current further east (∼85–120°E), our observations fall along a mixing line between the southwest Indian Ocean and data collected from the Australian coastal margin, illustrating for the first time how the unique eastern boundary system of the south Indian Ocean drives regional-scale variability in the δ¹⁸O – salinity relationship of the surface ocean. A comparison between our observations in the shallow subsurface (100–1000 m) and those from neighboring surveys reinforces this upper ocean connection across the Indo-Australian basin. Antarctic Intermediate Water from the Indian Ocean can be isotopically distinguished from the more regional Tasman Intermediate Water occupying the South Australian Bight, suggesting exchange between the two regions is most prevalent at surface and mode water depths. In deeper waters (> ∼1500 m), we observe a notable 0.87‰ spread in δ¹⁸O. This variability may represent interactions between distinct deep water masses in the region, although additional data are needed to confirm. Overall, our data provide a new look at the hydrography and isotopic chemistry of the southeast Indian Ocean, emphasizing the impact of the region's mesoscale eddy field and its interconnectivity with neighboring basins.

Polysulfides (S_x²⁻) are important reduced sulfur species (RSS) that play a role in numerous environmental processes. A sound analytical method for the measurement of S_x²⁻ in euxinic waters is lacking. In this work, differential pulse voltammetry (DPV) at the Hg electrode was used to measure the presence of S_x²⁻ in a model seawater solution and an euxinic marine lake (Rogoznica Lake - RL Croatia), in which the concentration of RSS, mainly HS⁻, varies between 100 and 4000 μM. In the DPV, an adsorption phenomenon associated with S_x²⁻ reduction on Hg produces a characteristic current minimum at −1.0 V (vs. Ag/AgCl), the magnitude of which is proportional to the concentration of polysulfidic sulfur.

The DPV current minima were recorded in the model solution K₂S_x NaCl/NaHCO₃ (pH ∼ 8.2) in a concentration range from 10 to 100 μM of polysulfidic sulfur. Total RSS was measured by cyclic voltammetry, and sampled DC voltammetry showed the ratio between HS⁻ and S⁰ within the S_x²⁻. Using the same methodology, the presence of S_x²⁻ below the chemocline enriched by photoptrophic sulfur bacteria was measured in the euxinic layer of RL at concentrations of up to 70 μM of polysulfidic sulfur. The results suggest that euxinic RL samples can be considered as polydisperse solutions of S⁰ or of S-rich compounds that can change their physicochemical properties and speciation during sample manipulation. These changes can be detected by electrochemistry. Atomic force microscopy proved the release of bacterial cellular S⁰ during the acidification and purging step in the electrochemical measurements, which contributed to the voltammetric RSS signal.

The fate of microplastics (MPs) in the ocean is mostly driven by (i) photo-oxidation to smaller particles and dissolved constituents, which fuel the dissolved organic carbon pool (plastic-derived DOC, pDOC), and (ii) interactions with organic matter forming sinking aggregates (marine plastic snow). Two separate laboratory experiments were conducted to investigate the two pathways of MPs. In the first experiment, we measured potential rates of microbial pDOC utilization in bottle incubations over 15 days with microbial assemblages from coastal and offshore waters. Microbial utilization of pDOC was more efficient in the coastal (72% bioreactive pDOC) compared with the offshore experiment (32% bioreactive pDOC) 15 days. Changes in bacterial cell abundance and extracellular enzyme activities (glucosidase, peptidase, esterases) indicated that a fraction of pDOC was repackaged into microbial exopolymeric substances (EPS), stimulating growth of known EPS degrading bacteria within the phyla Verrucomicrobiota and Planctomycetota. Microbial EPS likely also played a key role in our second experiment that showed the formation of marine plastic snow in roller tanks with cultured cells of Emiliana huxleyi but not with cells of an Isocrysis sp. culture. Average sinking velocities of marine plastic snow were a factor of 1.2 lower compared with marine snow without MPs. Both aggregate types showed reduced sinking velocities in a density stratified sinking column. Our results from the two experiments on (i) microbial utilization of pDOC and (ii) the formation and sinking of marine plastic snow indicate potential effects of plastic-derived compounds on microbial elemental cycles (i.e., pDOC repackaged into EPS) with consequences for the efficiency of the biological carbon pump (i.e., marine plastic snow reduces carbon export) and the fate of plastic-derived compounds in the ocean.

The pronounced seasonal variation over the Bay of Bengal affects trace metals concentration and distribution. Trace metals distribution in the Bay of Bengal has been best characterized during spring and fall intermonsoon, while limited studies were conducted during the southwest monsoon. This study reports the full-depth profiles of trace metals, including dissolved iron, manganese, lead, cadmium, copper, and zinc (Fe, Mn, Pb, Cd, Cu, and Zn) in the Bay of Bengal (BoB) during southwest monsoon, from July to August 2013. At coastal and ocean scales, transect observations covering the entire water depth provided a comprehensive picture of the circulation and biogeochemical cycles of these elements in seawater during the southwest monsoon. Water samples were obtained from one station in the northeastern Indian Ocean (NR-1) and from three shallow coastal stations with maximum depths <60 m (BA-1, BA-3, and BA-5), as well as from three offshore stations with maximum depths exceeding 2000 m (MY-7, MY-9, and MY-11). In the surface layer (5 m depth), the trace metal concentrations at the shallow near-coastal station BA-5 were higher than those at the ocean station NR-1. Surface trace metal concentrations in offshore regions encompassing stations MY-11, MY-9, and MY-7 were relatively higher than those reported for other seasons in a similar salinity region, indicating seasonal variation associated with freshwater intrusion and coastal-derived input. Below the mixed layer depth, the trace metal/phosphate (P) ratio was higher than that previously reported in the eastern Indian Ocean, suggesting an input from continental margins and mildly reducing sediments, particularly for Fe, Mn, and Cu. Moreover, at intermediate depths (190–800 m), where the North Indian Central Water (NICW) is the main water mass, the Cd/P ratio (0.55 ± 0.11 nmol/μmol) deviated from the global trend (∼0.3 nmol/μmol) owing to oxygen-deficient conditions. Intriguingly, at some stations, specifically MY-9 and MY-7, the intermediate dFe concentrations were relatively higher than those at station NR-1 at the same depth. Continental margin sediment, water mass movement, and ventilation may control the transport of Fe from locations with high Fe concentrations, including near the continental shelf (station MY-11 in this study) and the Andaman Sea.

The radiocesium (¹³⁷Cs) distribution between dissolved and particulate phases was examined in river water and coastal seawater as a function of the ¹³⁷Cs sorption behavior on suspended particles. Dissolved ¹³⁷Cs activity concentrations in the Tomioka River (salinity <0.1), about 10 km south of Fukushima Dai-ichi Nuclear Power Plant, and in coastal seawater at Tomioka fishery port (salinity >30), Fukushima Prefecture, from June 2019 to October 2021 were 3.6–20 Bq/m³ (geometric mean 11 Bq/m³) and 2.4–86 Bq/m³ (13 Bq/m³), respectively. Although the suspended particle concentration was lower in the river than in seawater, the mean ¹³⁷Cs activity on suspended particles was 11,000 Bq/kg-dry in the river versus 3200 Bq/kg-dry in seawater. Proportions of ion-exchangeable, organically bound, and refractory fractions of ¹³⁷Cs on suspended particles were determined by sequential extraction. The ion-exchangeable fraction accounted for 0.3–2.0% (average: 1.2%) and 0.4–1.3% (0.8%) at the river and port sites, respectively. The organically bound fraction accounted for 0.3–4.8% (1.8%) and 0.1–5.5% (2.1%) at the river and port sites, respectively. In both areas, the refractory fraction accounted for >90% of ¹³⁷Cs. Therefore, the small labile ¹³⁷Cs fraction on suspended particles in coastal seawater indicates that the mobility of ¹³⁷Cs to marine biota is quite low.

Synopsis

This study is the first to examine radiocesium sorption forms on suspended particles in coastal seawater near the Fukushima Dai-ichi Nuclear Power Plant. It suggests immobility of ¹³⁷Cs in suspended particles being incorporated to marine biota.

Here, we explicitly define a half-cell reaction approach for pH calculation using the electrode couple comprised of the solid-state chloride ion-selective electrode (Cl-ISE) as the reference electrode and the hydrogen ion-selective ion-sensitive field effect transistor (ISFET) of the Honeywell Durafet as the hydrogen ion $\left(H^{+}\right)$-sensitive measuring or working electrode. This new approach splits and isolates the independent responses of the Cl-ISE to the chloride ion $\left({\mathrm{Cl}}^{-}\right)$ (and salinity) and the ISFET to $H^{+}$ (and pH), and calculates pH directly on the total scale $\left({\mathrm{pH}}_{\text{total}}^{\mathrm{EXT}}\right)$ in molinity (mol (kg-soln)⁻¹) concentration units. We further apply and compare ${\mathrm{pH}}_{\text{total}}^{\mathrm{EXT}}$ calculated using the half-cell and the existing complete cell reaction (defined by Martz et al. (2010)) approaches using measurements from two SeapHOx sensors deployed in a test tank. Salinity (on the Practical Salinity Scale) and pH oscillated between 1 and 31 and 6.9 and 8.1, respectively, over a six-day period.

In contrast to established Sensor Best Practices, we employ a new calibration method where the calibration of raw pH sensor timeseries are split out as needed according to salinity. When doing this, ${\mathrm{pH}}_{\text{total}}^{\mathrm{EXT}}$ had root-mean squared errors ranging between ±0.0026 and ±0.0168 pH calculated using both reaction approaches relative to ${\mathrm{pH}}_{\text{total}}$ of the discrete bottle samples $\left({\mathrm{pH}}_{\text{total}}^{\text{disc}}\right)$. Our results further demonstrate the rapid response of the Cl-ISE reference to variable salinity with changes up to ±12 (30 min)⁻¹. Final calculated ${\mathrm{pH}}_{\text{total}}^{\mathrm{EXT}}$ were ≤±0.012 pH when compared to ${\mathrm{pH}}_{\text{total}}^{\text{disc}}$ following salinity dilution or concentration. These results are notably in contrast to those of the few in situ field deployments over similar environmental conditions that demonstrated ${\mathrm{pH}}_{\text{total}}^{\mathrm{EXT}}$ calculated using the Cl-ISE as the reference electrode had larger uncertainty in nearshore waters. Therefore, additional work beyond the correction of variable temperature and salinity conditions in $\mathrm{pH}$ calculation using the Cl-ISE is needed to examine the effects of