Marine Chemistry最新文献

We present a new method for imaging dissolved manganese at millimeter scale by coupling DET (diffusive equilibrium in thin film) and colorimetric techniques. The method is an adaptation of the porphyrin approach for the measurement of dissolved Mn by substitution of Mn(II) and Mn(III) to Cd in the Cd(II)–POR complex. Optimization of the Cd-POR concentrations was required for transposition to 2D-DET. A commercial flatbed scanner and a hyperspectral camera were used for imaging. Using the hyperspectral camera, detection limit is about 5 μM and measuring range is up to 520 μM. The method was applied on the field in a tidal mudflat of the French Atlantic coast and in sediments inhabited by polychaetes. These first images allowed to precisely describe two-dimensional millimeter features such as burrows and highlighted the role of bioirrigation in benthic Mn fluxes. This new technique offers the possibility to investigate the reactivity of microenvironments towards dissolved Mn in two dimensions in a wide range of laboratory and in situ studies using a non-destructive tool.

This study investigated the redox speciation and mobility of V in the acid-extractable fraction of surface sediments from the Krka River estuary using an optimized IC-UV/Vis analytical method. The separation of V(IV) and V(V) redox species was done using anion-exchange based chromatographic method, while pseudo-total V concentrations were measured using HR ICP-MS analytical instrumentation. Extracted V concentrations from the sediment fraction (pH = 5, HCl) and determined pseudo-total V concentrations were used to calculate the Enrichment Factor (EF) and Risk Assessment Code (RAC), indicating potential anthropogenic influence and environmental risk. A simple PHREEQC model was developed to asses V speciation in the oxic bottom seawater layer simulating possible remobilization of the leached sediment phase. The results of the study show that minor fraction of V is present in the acid-extractable phase across the surface sediment of Krka River estuary. Higher V mobility is mostly observed at locations rich with clay minerals, terrigenous input, and carbonates. Anthropogenic influence was linked to higher enrichment but lower mobility, suggesting binding to less mobile sediment phases (reducible, organic and residual fractions). The predominance of reduced V(IV) species in the acid-extractable sediment fraction indicates a potentially low V toxicity risk in the sediments of Krka River estuary, even in cases of high potential remobilization of V. However, the model predicted complete oxidation of V(IV) to V(V) upon remobilization into the oxic bottom water layer. This highlights the complexity of V behavior in natural estuarine systems, where the toxicity risks of possible V remobilization still remain unclear. Results of this study demonstrate the need for the strengthening efforts in speciation of V in the mobile sediment phase to obtain a cohesive outlook on its potential toxicity and biogeochemical cycling.

Dissolved inorganic carbon (DIC) and particulate organic carbon (POC) dynamics in the world's estuaries have been studied extensively at monthly, seasonal, and annual time scales with particular focus on their concentrations and export fluxes to the coastal oceans. However, given the dynamic nature of the estuaries, the effect of tidal and diel cycles on the processes modulating DIC and POC dynamics remains obscure. To decipher the biogeochemical processes at tidal scale, DIC and POC concentrations and their carbon and nitrogen isotopic compositions were measured across the salinity gradient at every high and low tide for nine consecutive days (14–23 October 2019) in the Mahanadi estuary, a tropical estuary at the east coast of India. Showing contrasting differences across salinity gradient in DIC, POC and their isotopic compositions, DIC and POC were significantly different during high and low tide in the mixing zone only during spring duration. This showed the effect of spring-neap tidal cycle owing to water level fluctuations and mixing intensity in the estuarine mixing zone. Linear least-squares regression models indicated carbonate and/or silicate weathering by biogenic CO₂ to be the probable DIC source in the freshwater region of the estuary. Deviations of observed DIC concentrations and δ¹³C_DIC from the conservative mixing values suggested pronounced alteration of DIC source signature in the mixing zone. A process-based model approach aimed at delineating possible biogeochemical processes affecting DIC dynamics indicated calcite dissolution during low tide and calcite precipitation during high tide to be dominant processes in the mixing zone. Additionally, signatures of more than one simultaneous biogeochemical process modulating the DIC dynamics were also observed. POC pool in the mixing zone was largely influenced by its removal through rapid remineralization during both high and low tides. Graphical plots also showed that POC in the mixing zone and at the saline location was significantly affected by processes such as degradation, whereas it was only slightly affected in the freshwater region of the estuary. δ¹³C_POC, along with the C/N ratio of POM, indicated that C3 plants and/or their derived soil were the major source of POM in the freshwater, whereas the higher contribution of riverine POM and marine phytoplankton was observed in the mixing zone and saline location, respectively.

Radiotracers are highly sensitive tools for quantifying the rates of important biogeochemical processes and the fates of specific atoms and/or compounds within major global elemental cycles, especially those that are requisite for life. Important radiolabeled organosulfur compounds, like dimethylsulfide (DMS) and its precursor 3-dimethylsulfoniopropionate (DMSP), are not commercially available, but their well-documented use has been key in furthering our understanding of the marine sulfur cycle. [³⁵S]-DMSP obtained by chemical synthesis has been used extensively in radiotracer studies involving DMS and DMSP, but its synthesis has been restricted to 2 research groups. Presented here is a protocol for the chemical synthesis of [³⁵S]-DMSP from [³⁵S]-L-methionine, though the method could be used for other radiolabels (e.g. [¹⁴C], [³H]). The synthesis consists of 2 reaction steps, (1) the sequential oxidative deamination and decarboxylation of [³⁵S]-L-methionine to [³⁵S]-3-methylmercaptopropionate and (2) the methylation of [³⁵S]-methylmercaptopropionate to yield the product [³⁵S]-DMSP. The product is purified by liquid chromatography and two cation-resin exchanges. Average final [³⁵S]-DMSP yield was 5.34% (n = 16; range: 1.26% to 14.84%, excluding failures), although updated instrumentation could likely improve final yields. The objective of this work is to standardize the synthesis of [³⁵S]-DMSP to widen its availability and use among the community and hence facilitate increased understanding of the reduced sulfur and carbon cycles.

Radiocarbon (¹⁴C) is a widely used tool with applications that transcend disciplinary boundaries, including the marine chemistry field. The development of ¹⁴C measurement techniques and icebreaking research vessels especially encourage and support polar research using ¹⁴C. Research examining ¹⁴C in polar oceans in the context of climate change has led to considerable insight into the marine carbon cycle. A comprehensive review of the principles, applications, progress, and challenges of ¹⁴C will undoubtedly advance related polar research. This review compiled available literature on ¹⁴C in the polar oceans and summarizes current progresses in carbon cycling, glacial and ice sheet dynamics, water circulation, and ventilation. The impact of warming induced melting sea ice and glaciers on marine biogeochemical cycles, future environmental challenges and research directions have also been summarized. The limitations of existing ¹⁴C research in polar regions can be addressed through well-designed and continuous investigation, data and sample sharing, and the development of state-of-the-art ¹⁴C measurement techniques.

Platinum (Pt) is an emerging critical metal, but the long-term environmental impacts of anthropogenic Pt remain largely unknown. We report, for the first time, Pt input from three major German rivers (Ems, Weser and Elbe) into the southern North Sea. All three rivers were a major source of Pt, with a maximum of 6.3 pmol L⁻¹ in the Elbe endmember, compared to generally <1.0 pmol L⁻¹ in the North Sea samples. All samples measured in the North Sea were elevated in Pt (mean of ∼0.9 pmol L⁻¹) relative to typical open-ocean values (∼0.2–0.3 pmol L⁻¹ in the Atlantic and Pacific). Across the Weser and Elbe estuarine transect, an initial sharp drawdown of Pt concentrations at low salinity (S < 1.5) was observed, which correlated well with Fe and Mn concentrations, indicating adsorption and co-precipitation at low salinity. At higher salinities (S ≥ 3) Pt concentrations followed a more conservative distribution relative to salinity. In addition, we followed a 12 h tidal cycle in each of the rivers, which generally reflected an inverse correlation of Pt concentrations against salinity. This study indicates that Pt might be an emerging contaminant in the North Sea, requiring further study to define specific sources.

The Arabian Sea is one of the most productive regions in the global ocean. In the present study, relationship of Chl-a with environmental parameters have been studied in the Arabian Sea. The Autoregressive Integrated Moving Average with explanatory variable (ARIMAX) models namely ARIMAX (1,0,1), ARIMAX (2,0,3), ARIMAX (5,0,4), ARIMAX (7,0,6), ARIMAX (8,0,8), ARIMAX (11,0,9) and ARIMAX (12,0,11) were tested. After evaluation, ARIMAX (2,0,3) and ARIMAX (12,0,11) were identified as the best fit models and can be used to model Chl-a in the Arabian Sea. Wavelet coherence approach was applied to understand the relationship of Chl-a with rainfall, sensible heat flux, remote sensing at 443 nm, aerosol optical depth, black carbon deposition and calcite concentration. Two strips of high correlation in the frequency bands of 4–8 and 8–16 significant at 95% level were observed in each wavelet coherence diagram except for remote sensing reflectance at 443 nm and sensible heat flux.

Recurrent dissolved oxygen (DO) depletion is common in many estuaries and coastal areas worldwide. However, its impact on the accumulation of resistant dissolved organic carbon (DOC) remains controversial. To address how recurrent DO depletion affects the degradation and stability of marine DOC, a series of DOC degradation incubations in a particulate-dissolved coexisting system in April 2021 were conducted, followed by a field investigation in the East China Sea (ECS) in October. In the ECS, we found that DO ranged from 4.71 to 7.40 mg/L in the near-bottom waters, while the degradation index (DI), an indicator of amino acids molecules, increased from −0.78–2.84, suggesting an accumulation of labile DOC over DO depletion. This is further supported by the bacteria community composition that showed an increase in anaerobic metabolism families when DO <6.29 mg/L. Laboratory incubation revealed strong labile DOC release (∼ 243 ± 38 μmol/L) from particulate organic carbon (POC) over oxygen depletion, followed by significant DOC loss in either anoxic-oxic or oxic-oxic groups. The degraded original DOC was slightly less in the oxygen depletion-treated group compared to the oxic group, and the resistant proportion was estimated as 1% ∼ 8% after 1–14 days of anoxic treatments. The resistant DOC accumulation after DO alleviation for 30 days was much less in amount when compared to the big release of labile DOC over DO depletion (48 vs. 243 μmol/L) and we believed that the lack of observed resistant DOC accumulation in the field observation was due to the overlap of multiple anoxic-oxic cycling processes and the masking effect of newly labile DOC released from the POC.

Despite decades of mitigation efforts, eutrophication-induced algal blooms and hypoxia have not significantly decreased globally, possibly due to the legacy effects of eutrophication. The legacy effect has been more explored in inland waters and enclosed estuaries than in open coastal waters. Here, we reanalyzed cruise data from the East China Sea inner shelf to explore the effect of eutrophication on nutrient accumulations in high-saline bottom waters. Our dataset showed elevated nitrate (12.75 ± 6.51 μmol L⁻¹) and phosphate (0.85 ± 0.26 μmol L⁻¹) in high-salinity (salinity>34, temperature < 23 °C) bottom waters during the summer of 2006 to 2013. They were higher than those typically observed in the Taiwan Warm Current Bottom Water by approximately 5.45 ± 6.51, and 0.29 ± 0.26 μmol L⁻¹, respectively. Significant correlations of nitrate with apparent oxygen utilization (AOU) and elevated AOU suggested that organic matter decomposition contributed to increased nitrate in bottom waters under eutrophication conditions. Based on an end-member mixing estimation, we found that the organic matter decomposition accounted for 28% to 37% of the nutrient concentrations in the bottom waters, with a standard deviation of 20%. Results from our mass-balance model indicated that 40–74% of regenerated nutrients are flushed out of the model box set within 95% equilibrium time due to the advection of offshore waters, assuming a residence time of 46.0 to 13.9 days. Based on cruise results in June and August 2009, the net accumulation rates of nitrate, phosphate, and AOU in the Taiwan Warm Current Bottom Water were estimated to be 0.046, 0.0036, and 0.44 μmol L⁻¹ d⁻¹, respectively. Such nutrient accumulations in the water column and the residual nutrients in sediment are crucial legacy nutrients, potentially triggering algal blooms. Conversely, the flushing effect suggests a significant transport of nutrients and other chemical elements to the offshore and open ocean.