Marine Chemistry最新文献

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.

The Southern Ocean (SO) not only functions as an important carbon sink but also serves as a crucial source of intermediate and deep waters to lower latitudes. The Ross Sea and Amundsen Sea in the West Antarctic are highly productive regions of the Southern Ocean, critically vulnerable to climate change. Hence, comprehending the source-sink patterns of nutrients, particularly trace metals, in these regions is of paramount significance for understanding their ecological effect and the effect on elemental distribution in global ocean. Here, we reported the surface and vertical distributions of phytoplankton composition, Chlorophyll-a (Chl-a), particulate organic carbon (POC), macronutrients, and trace metals (TMs) in the Ross and Amundsen Seas. Deplete dissolved iron concentrations were observed in surface waters averaging 0.17 ± 0.09 nM. High POC and Chl-a were observed that corresponded to elevated Fe in shallow subsurface water (100–300 m), while low POC and Chl-a were found to associate with depleted iron (∼0.1 nM) throughout the upper water column down to 300 m. Sea-ice melting and islands were found to be possible external TMs sources in the Amundsen Sea offshore. Phytoplankton act as a sink for trace metals and regulate the elemental concentration and composition of water bodies, while also being influenced by environmental conditions such as temperature, salinity, and the mixing layer depth. Elemental consumptions in surface water were associated with diatom abundance in both Ross and Amundsen Seas. Based on elemental drawndown ratios in the surface mixed layer, the stoichiometries of the two major phytoplankton functional groups, diatoms and haptophytes, were estimated. Our observations offered insights into the relationships among iron supply, nutrients distribution patterns, and phytoplankton composition in the Southern Ocean.

Coastal marine settings are important in terms of geochemical cycles and biological productivity. Climate change is predicted to affect coastal environment via hypoxia and Submarine Groundwater Discharge (SGD). Appropriate proxies could help to better understand oxygenation history and the role of SGD in regulating hypoxia. This would also benefit prediction of potential outcomes of future environmental changes. The sensitivity of benthic foraminiferal shell chemistry to environmental conditions opens the possibility to use them as proxies of coastal hypoxia and SGD. We report here that the average Mn/Ca ratios in tests of living benthic foraminiferal shells in the Changjiang River Estuary (CJE) is 2.3 times higher during hypoxia periods than under well-mixed conditions. In addition, Ba/Ca ratios in living benthic foraminiferal shells co-varied well with radon-inferred SGD signals. Fluctuations of Mn/Ca and Ba/Ca ratios in tests of a single foraminiferal shell along successive chambers corresponds well with seasonal-scale variations of hypoxia and SGD. We suggest that Mn/Ca and Ba/Ca ratios within intra-tests of benthic foraminifer can provide a reliable proxy for past hypoxia and SGD trends.

Total alkalinity (TA) is the measure of water's ability to neutralize acids. Discrete TA samples are typically measured by acid titration, with one sample processed at a time, which is tedious and time-consuming. In this study, we assessed an automated titration system for TA batch measurements that included the washing procedure between each sample analysis; and evaluated the impact of various factors on the precision of TA measurement, including the sample mass, sample salinity, temperature variation, and the dilution effect from the residual washing water. The results showed that temperature variation within ±1 °C, salinity ranging from 0 to 40, sample mass from 20 to 30 g, and the residual washing water within 2 g did not affect the precision of TA measurement (±2 μmol/kg). In addition, the automated titration system encoded with Gran calculation managed to determine the negative TA as low as −100 μmol/kg. Our study suggests that the automated titration system with an auto-sampler is capable of high-precision TA batch measurements.