Marine Chemistry最新文献

A novel deterministic lateral displacement (DLD) method employing a pressure-driven flow for the continuous size-based separation of microplastic particles is presented in this paper. To induce the DLD effect, arrays of triangular posts were designed to enhance the sorting resolution and reduce the particles clogging. For the particles with a diameter larger than the critical diameter ($D_c$) in the DLD device, they move in bump mode with collision to microposts. While, the particles flow in zigzag mode if their sizes are below the $D_c$ value. The DLD microfluidic chip enables simplified fabrication process and shows property of label-free and high throughput. Numerical studies were conducted to discuss the $D_c$ values in the microchannel with horizontally symmetrical and asymmetrical posts, where $D_c$ was found smaller in the asymmetric horizontal flow, enabling higher separation sensitivity and resolution. Experiments were conducted to demonstrate the separation of 10 μm and 15 μm polystyrene microplastic particles, and different types of polystyrene and polyethylene microplastic particles by adjusting the flow rates. In order to achieve successful separation, the flow rates between the sheath flow and the sample solution were well matched. In this way, the proposed DLD microfluidic chip with horizontally asymmetrical triangular posts shows property of label-free, high throughput, capability to analyze microplastic particle selectively and sensitively, possibility of sorting nanoplastic particles.

The method of competitive ligand exchange followed by adsorptive cathodic stripping voltammetry (CLE-AdCSV) allows for the determination of dissolved iron (DFe) organic speciation parameters, i.e., ligand concentration (L_Fe) and conditional stability constant (log $K_{\mathrm{Fe}\prime L}^{\text{cond}}$). Investigation of DFe organic speciation by CLE-AdCSV has been conducted in a wide range of marine systems, but aspects of its application pose challenges that have yet to be explicitly addressed. Here, we present a set of observations and recommendations to work toward establishing best practice for DFe organic speciation measurements using the added ligand salicylaldoxime (SA). We detail conditioning procedures to ensure a stable AdCSV signal and discuss the processes at play during conditioning. We also present step-by-step guidelines to simplify CLE-AdCSV data treatment and interpretation using the softwares ECDSoft and ProMCC and a custom spreadsheet. We validate our application and interpretation methodology with the model siderophore deferoxamine B (DFO-B) in a natural seawater sample. The reproducibility of our application and interpretation methodology was evaluated by running duplicate titrations on 19 samples, many of which had been refrozen prior to the duplicate analysis. Nevertheless, 50% of the duplicate analyses agreed within 10% of their relative standard deviation (RSD), and up to 80% within 25% RSD, for both L_Fe and log $K_{\mathrm{Fe}\prime L}^{\text{cond}}$. Finally, we compared the sequential addition and equilibration of DFe and SA with overnight equilibration after simultaneous addition of DFe and SA on 24 samples. We found a rather good agreement between both procedures, with 60% of samples within 25% RSD for L_Fe (and 43% of samples for log $K_{\mathrm{Fe}\prime L}^{\text{cond}}$), and it was not possible to predict differences in L_Fe or log $K_{\mathrm{Fe}\prime L}^{\text{cond}}$ based on the method applied, suggesting specific association/dissociation kinetics for different ligand assemblages. Further investigation of the equilibration kinetics against SA may be helpful as a potential way to distinguish natural ligand assemblages.

Mineralogical and isotopically distinct authigenic carbonates from the zones of methane oxidation and methanogenesis in the cold-seep environment, from the Krishna-Godavari basin are investigated for major, trace, and rare earth element compositions. For this study, the elemental compositions of the ¹³C-depleted carbonate phase (δ¹³C < −45‰) developed under the influence of anaerobic methane oxidation in the shallow parts (<115mbfs) of a sediment core, are compared with those in isotopically heavier siderite (δ¹³C > +5‰) from the zone of microbial methanogenesis at the deeper sediment depths (115-197mbfs). Results showed both types of cold-seep carbonate in two geochemical regimes have a comparable range of concentrations of redox-sensitive (e.g. V, Cr, Co, Ni, Zn) and refractory elements (e.g. Sc, Cs, Ga, Zr, Hf, Ta, Th), indicating limited impacts of mineralogy and their genetic processes on the distribution of these elements. In contrast, the degree of enrichments of elements like Si, Al, Sr, Y, HREE, and U in those isotopically discrete seep carbonates were distinctly different. Such compositional variability in two types of authigenic carbonates is described in terms of their diverse formation mechanisms, mineralogical controls, and variable contributions of terrigenous materials.

Accurate spectrophotometric pH measurements in seawater are critical to documenting long-term changes in ocean acidity and carbon chemistry, and for calibration of autonomous pH sensors. The recent development of purified indicator dyes greatly improved the accuracy of spectrophotometric pH measurements by removing interfering impurities that cause biases in pH that can grow over the seawater pH range to > 0.01 above pH 8. However, some batches of purified indicators still contain significant residual impurities that lead to unacceptably large biases in pH for oceanic and estuarine climate quality measurements. While high-performance liquid chromatography (HPLC) is the standard method for verifying dye purity, alternative approaches that are simple to implement and require less specialized equipment are desirable. We developed a model to detect impurities in the pH indicator m-cresol purple (mCP) using a variant of the classification technique Soft Independent Modeling of Class Analogy (SIMCA). The classification model was trained with pure mCP spectra (350 nm to 750 nm at 1 nm resolution) at pH 12 and tested on independent samples of unpurified and purified mCP with varying levels of impurities (determined by HPLC) and measured on two different spectrophotometers. All the dyes identified as pure by the SIMCA model were sufficiently low in residual impurities that their apparent biases in pH were < 0.002 in buffered artificial seawater solutions at a salinity of 35 and over a pH range of 7.2 to 8.2. Other methods that can also detect residual impurities relevant to climate quality measurements include estimating the impurity absorption at 434 nm and assessing the apparent pH biases relative to a reference purified dye in buffered solutions or natural seawater. Laboratories that produce and distribute purified mCP should apply the SIMCA method or other suitable methods to verify that residual impurities do not significantly bias pH measurements. To apply the SIMCA method, users should download the data and model developed in this work and measure a small number of instrument standardization and model validation samples. This method represents a key step in the development of a measurement quality framework necessary to attain the uncertainty goals articulated by the Global Ocean Acidification Observing Network (GOA-ON) for climate quality measurements (i.e., ±0.003 in pH).

Using a ²²⁴Ra/²²⁸Th disequilibrium approach, we demonstrate in this study that benthic fluxes of dissolved inorganic phosphorus (DIP) in the seasonally hypoxic Yangtze River Estuary were largely manipulated by two counteracting processes: the decomposition of sedimentary organic matter and adsorption of DIP onto iron (Fe) oxides. The decomposition rate of sedimentary organic matter rose exponentially with bottom water dissolved oxygen (DO) concentration multiplied by the amplification factor of sediment surface area (ξ), a variable used to describe the intensity of bio-irrigation and physical reworking in the sediment deposit. In the summer of 2020, the Yangtze River catchment encountered the largest flood event in the past 20 years. As a result of enhanced physical reworking of the seabed, dissolved inorganic carbon (DIC) flux increased by approximately 4-fold as compared to the summer of 2019 (657 vs. 154 mmol m⁻² d⁻¹). DIP flux exhibited similar inter-annual variations to DIC flux, indicating that changes in the decomposition rate of sedimentary organic matter were the main cause of the inter-annual differences in DIP flux (1.5 mmol m⁻² d⁻¹ in 2020 vs. 0.3 mmol m⁻² d⁻¹ in 2019). On the other hand, benthic dissolved Fe fluxes declined exponentially with rising DO concentration because of re-oxidation of Fe²⁺ in porewater into Fe oxides. As a consequence, approximately 90% of DIP sourced from the decomposition of sedimentary organic matter was retained within the sediment when the bottom water was well oxygenated (DO >125 μmol l⁻¹). Our results imply that regeneration of sedimentary P and Fe may be efficient only within a very narrow redox window where DO concentrations are below a threshold value of ∼60 μmol l⁻¹, but bio-irrigation or physical reworking is still active.

Hydroxylamine is considered an indicator of nitrification, as it is both produced and consumed during the ammonium (NH₄⁺) oxidation process. In this study, to explore the site of active nitrification and elucidate the factors controlling nitrification, hydroxylamine concentrations in the seawater and porewater of the hypereutrophic Yatsu tidal flat, eastern Japan, were measured using the iodine oxidation method with a Sep-Pak C₁₈ cartridge. The concentrations over approximately 2 years indicated that nitrification was more active in the surface sediment than in seawater. This would support denitrification in the surface sediment via active nitrification–denitrification, which removes N. In addition, multiple linear regression analysis indicated that the concentration in porewater was positively correlated with the seawater parameters of nitrate (NO₃⁻) concentration, NH₄⁺ concentration, and temperature, while among porewater parameters, it was negatively correlated with the phosphate (PO₄³⁻) concentration and positively correlated with the NH₄⁺ concentration. These relationships between hydroxylamine concentration and environmental factors suggest that porewater nitrification increases with higher temperature and NH₄⁺ supply from seawater and porewater, as well as under oxic conditions. Our results demonstrate that hydroxylamine is a useful indicator of sediment nitrification in the hypereutrophic intertidal zone.

Understanding factors influencing seawater chemistry variability in coral reef environments is a major challenge to improve predictions of their evolution in the context of ocean acidification. In this study, autonomous sensors for current speed and direction, photosynthetically active radiation (PAR), temperature, salinity, dissolved oxygen (DO) and pH_T were deployed three times between 2021 and 2022 offshore and on three reef flat sites of the main fringing reef of La Reunion Island. Discrete sampling of seawater for DO, pH_T and total alkalinity (TA) at different times of the day complemented the monitoring. Diurnal variation of those variables on the reef flat was mainly driven by benthic community metabolism but hydrodynamics and reef geomorphology played also a key role. DO and pH_T variations were decoupled in time, especially at night when we observed DO rebounds while pH_T values were stationary. The reef flat was also largely TA depleted compared to offshore waters. We hypothesize that the strong offshore-alongshore current redirected TA depleted water exiting from reef channels into the reef flat. This seawater re-entrainment could also explain specific variations of DO and pH_T values. This result highlights the important role of reef geomorphology in modulating changes in seawater chemistry. Neglecting this phenomenon could lead to substantial errors in the estimation of carbonate budgets when using the Eulerian approach.

Considering that zinc (Zn) is essential for marine phytoplankton growth and cadmium (Cd) can replace Zn as a cofactor of mutual conversion and regulate the effect of carbonic anhydrase, we here presented the concentration, chemical speciation and relationship of Zn and Cd collected from three consecutive voyages (2019–2021) in summer coastal seawater of northern China. Dissolved Zn and Cd concentrations were determined using inductively coupled plasma mass–spectrometry (ICP–MS) and ranged from 0.37 to 3.09 μM and 1.88–13.66 nM, respectively. Natural labile Zn and Cd were determined using a highly automated electrochemical detection system and ranged from below detection limit-1.11 μM and below detection limit-5.23 nM, respectively. The speciation, distribution and interrelationships of Zn and Cd were compared with the distribution of the diatoms community, and studied by the correlation with pH and dissolved inorganic carbon (DIC). Finally, the Zn and Cd labile and inert chemical species concentrations were compared with those of the open sea and the coast. The results indicated that the dissolved Zn and Cd concentrations in surface seawater were higher than those in bottom seawater, possibly due to the dominance of exogenous inputs compared to phytoplankton uptake. Higher phytoplankton abundance was associated with lower natural labile Zn and Cd concentrations, but this was not the main factor affecting the distribution of natural labile Zn and Cd. Unlike the open ocean, there was no potential for Zn limitation of certain phytoplankton groups in this region, but both Zn and Cd played important roles in the fixation of carbon dioxide, and Cd might result in mitigating Zn uptake. Activities such as ocean currents, which bring limiting nutrient trace metals (e.g., Zn) from the coast into the open ocean, could regulate the structure of primary producers. This study has great potential for the investigation of the biogeochemical cycling of Zn and Cd and their role in marine carbon fixation in coastal seawater.

The goal of NASA's EXport Processes in the Ocean from RemoTe Sensing (EXPORTS) project is to develop a predictive understanding of the fate of global ocean primary productivity and export of carbon from the surface to the deep ocean. Thorium-234 (²³⁴Th, t_1/2 = 24.1 d) was used to measure sinking particle export from an anticyclonic eddy during the EXPORTS North Atlantic cruise (May 2021) at the Porcupine Abyssal Plain. The four-week sampling period was broken into three time periods (“epochs”) where 800 ²³⁴Th seawater samples were collected from over 50 CTD casts with high depth resolution over the upper 500 m. Size-fractioned particulate samples were collected to determine particulate organic carbon (POC) and biogenic silica (bSi) to ²³⁴Th ratios using in situ McLane pumps. A ²³⁴Th non-steady state model shows an eddy center epoch average progression of increasing ²³⁴Th export (∼2800 ± 300 (Epoch 1; standard deviation) to 4500 ± 700 (Epoch 3) dpm m⁻² d⁻¹) out of the top 110 m of the water column over the course of the cruise (29 d). This translates into an epoch average progression of ∼11 ± 1 to 14 ± 2 mmol C m⁻² d⁻¹ of sinking POC flux, and ∼ 3 ± 1 to 6 ± 1 mmol bSi m⁻² d⁻¹ of sinking bSi flux to deeper waters at 110 m. The overall efficiency of the biological carbon pump (amount of net primary production reaching 100 m below the euphotic zone) increases from ∼10% to ∼30% throughout the sampling period. The temporal trends discussed extensively in this paper show that POC and bSi export increase during diatom bloom evolution.

The dissolution of silicate minerals on the seafloor releases an important amount of dissolved silicon (dSi), which is necessary for maintaining high diatom production in Coastal and Continental Margin Zones (CCMZs). However, the dissolution of silicate minerals along the continental shelves is variable, which hinders our understanding of the marine Si cycle on both a regional and global scale. To understand the discrepancy of silicon (Si) released in different sediment matrices and its potential controlling factors, we investigated surface sediments of typical CCMZs of the Chinese marginal Seas using a continuous alkaline extraction technique, grain size and chemical (carbon and total nitrogen) analysis as well as a qualitative measurement of clay mineral composition by X-ray diffraction. The results showed that the amount of Si and aluminum (Al) leached from muddy sediments were 2 times greater than those released from sandy sediments. High dissolution rates (> 0.20 mg-SiO₂ g⁻¹ min⁻¹) of silicate minerals are caused by a large sediment-specific surface area. Further, our data showed that biogenic silica (bSi) with high Al content (Si:Al < 40) has low reactivity and that the source of Al incorporated in bSi is silicate minerals undergoing dissolution. We show that although the dissolution of silicate minerals is less active than that of bSi, it still potentially releases more bio-available Si and Al to seawater due to its dominant presence on the seafloor (70.3% − 99.0%wt). This study highlights silicate minerals as an important potential marine Si source and emphasizes the need for a better understanding of the roles of silicate minerals in the Si cycle of marginal seas in future studies.