Seawater System Research Articles

Apparent nitrous acid dissociation across environmentally relevant temperatures in freshwater and seawater

AbstractNitrite is a ubiquitous compound found across aquatic systems and an intermediate in both the oxidative and reductive metabolisms transforming fixed nitrogen in the environment. Yet, the abiotic cycling of nitrite is often overlooked in favor of biologically mediated reactions. Here we quantify the apparent acid dissociation constant (pKa) between nitrous acid and its conjugate base nitrite in both freshwater and seawater systems across a range of environmentally relevant temperatures (5–35°C) using potentiometric‐based titration. In freshwater, we measured a pKa,NBS of 3.14 at 25°C and a pKa,T of 2.87 for seawater at the same temperature. We quantify substantial effects of both salinity and temperature on the pKa, with colder and fresher water manifesting higher values and thus a greater proportion of protonated nitrite at any given pH. Because nitrous acid is unstable and decomposes to nitric oxide, the implications for the nitrous acid dissociation constant on ecosystem function are broad.

The selective occurrence of ripening effect makes the cotransport of various sized nanoplastics in seawater-saturated and freshwater-saturated porous media significantly different

We explored the coadsorption and cotransport (single, binary, and ternary systems) of varying sized (50, 200, and 500 nm) Polymethylmethacrylate (PMMA) nanoplastics (NPs) with different concentration ratios in freshwater-saturated and seawater-saturated porous media. It was found that ripening effect occurred selectively, with ripening more likely to occur in seawater relative to freshwater, resulting in significantly different cotransport and coadsorption of varying sized NPs in freshwater-saturated and seawater-saturated porous media. In freshwater, there was no obvious ripening effect happening. In both binary and ternary systems, as the concentration of coexisting PMMA NPs increased, the adsorption and retention of coexisting other sized PMMA NPs were inhibited due to competition for adsorption sites. In seawater, coexisting varying sized NPs promoted adsorption and retention of each other in saturated porous media due to increased roughness and ripening effect. The NP aggregate size and the increase in surface roughness of media grains brought about by the increase in size variety of NPs dominated the cotransport of varying sized NPs in seawater-saturated porous media. The findings of this study provide help for clarifying the fate of NPs presented in real environments in porous media of freshwater and seawater systems.

In situ construction of W-doped Co-P electrocatalyst by electrodeposition for boosting alkaline water/seawater hydrogen evolution reaction

The development of an efficient yet cost-effective non-precious electrocatalyst for the hydrogen evolution reaction (HER) in alkaline water and seawater systems remains a formidable obstacle to the large-scale production of hydrogen energy, stemming from the sluggish kinetics of electron transfer reactions during the HER process. In this article, an amorphous Co-P-W electrocatalyst on nickel foam is prepared using a brief cyclic voltammetry (CV) electrodeposition method. The optimized Co-P-W electrocatalyst exhibits excellent electrocatalytic performance for HER, which only requires overpotentials of 59 and 143 mV to achieve a current density of 10 mA cm−2 in alkaline water (1.0 M KOH) and alkaline seawater (1.0 M KOH + natural seawater), respectively, and remarkable stability and durability. The improved HER performance of the Co-P-W electrocatalyst is attributed to the introduction of W, which modulates the electronic structure of Co and P, optimizes the adsorption/dissociation of H2O, and reduces the charge transfer resistance of the Co-P electrocatalyst, thus improving the kinetics of the HER. Furthermore, the W-doping significantly enhances the hydrophilicity of the Co-P electrocatalyst, which favors rapid and thorough penetration of electrolytes into the electrocatalyst, facilitating the formation of a highly accessible reaction interface, ultimately resulting in excellent HER activity. Our findings demonstrate the feasibility of designing an efficient, durable, and scalable electrocatalyst to significantly boost HER efficiency for practical water electrolysis.

Carbon dioxide sequestration through mineralization from seawater: The interplay of alkalinity, pH, and dissolved inorganic carbon

Marine carbon dioxide removal technologies rely on the equilibration of the seawater with atmospheric CO2, where a pH increase can facilitate carbon dioxide removal either through increased absorption capacity of CO2, or precipitation of minerals. Here, we focus on explicitly defining the governing factors that influence seawater alkalinity with respect to CaCO3 mineralization and atmospheric CO2 uptake. We utilize an electrochemical setup and different water types, from near-shore Mediterranean seawater as well as Red Sea Salt water. The setup allows us to separate mineralization from alkalinity enhancement via an electrochemical membrane cell, and a second compartment with controlled environment, where the interplay of ion concentration, precipitation, pH, DIC concentration, and total alkalinity are evaluated. The effect of sparging additional carbon dioxide before, and after the precipitation of CaCO3 was evaluated while utilizing both a mild pH swing (from, ∼8.3 to ∼9.5), and a larger pH swing (from, ∼8.3 to ∼10.2). A thermodynamic model is presented defining the energy consumption to increase the pH, and the influence of Mg thereon is explicated. Furthermore, we detail theoretical aquatic chemistry simulations via PHREEQC to rationalize the observed intricate dynamics of the carbonate system in seawater. We end with a discussion of the implications of total alkalinity, pH, salt complexation, and carbon uptake capacity relevant to of all ocean alkalinity enhancement and marine based carbon dioxide removal systems, concluding that the carbon uptake capacity of water returned to the ocean must be verified in such technologies

Study of the efficacy of three depuration methods as a prerequisite for the hygiene-sanitary program in bivalve molluscs, from mariculture in Jurujuba, Niterói, Brazil

Depuration is a technique used to reduce microbial contamination of filtering molluscs, to levels acceptable by legislation for human consumption, by keeping the animals in tanks with clean water. The present study aimed to verify the effectiveness of three depuration methods on Perna mussels (Linnaeus, 1758), from commercial cultivation in Jurujuba, Niterói, Rio de Janeiro, Brazil, as a prerequisite for the National Safe Bivalve Molluscs Program (MoluBiS) aiming to satisfactory microbiological quality in bivalve molluscs. The depuration systems used were closed recirculated seawater systems with disinfection methods that use ozone, ultraviolet light (UV) and UV light associated to a chlorine-based compound. Thus, 80 animals were collected at once for experimental contamination with a strain of Escherichia coli, application of the three different depuration methods and subsequent bacteriological analysis of the mussels. After statistical analysis of the results, it was observed that in the depuration process using ozone for 10 min with 3.05 log, ultraviolet (UV) with 2.20 log, and ultraviolet (UV) combined with a sanitizing agent with 2.08 log, there was inactivation of E. coli in a relatively short time (24 h), allowing for the commercial sale of this mollusk in a reduced time. Therefore, it is necessary to implement depuration processes in the state of Rio de Janeiro to monitor sanitary conditions, so that the minimum requirements for guaranteeing the safety and quality of bivalve molluscs for human consumption are ensured.

Anchoring nanoscale zero-valent iron within bacterial cellulose particles for boosting efficient adsorption of Co(II) and Sr(II) from seawater: Dual system and varying adsorption mechanisms

Increasing attention has been paid to radioactive wastewater to direct discharge in Japan or accidental leaks. Strontium-90 (90Sr) and Cobalt-60 (60Co) are the most hazardous nuclides in waste discharged form nuclear reactors. Because of their high solubility and long half-lives, these radioisotopes can persist for hundreds of years before decaying to negligible levels. Herein, a green and biodegradable material nanoscale zero-valent iron (nZVI) supported by bacterial cellulose particles (BCP-nZVI) is constructed for the first time to adsorb Co2+ and Sr2+ in single and binary systems. BCP-nZVI shows superior adsorption capacities of Co2+ and Sr2+in a single system within a wide range of pH values from 5 to7, while the coexistence of Co2+ adsorption inhibits the Sr2+ in binary system. Pseudo-second-order dynamics model and Langmuir isothermal model can be indicated the BCP-nZVI adsorption progress with 107.10 mg/g (Co2+) and 64.96 mg/g (Sr2+) maximum adsorption capacity. BCP-nZVI has outstanding stability, allowing it to be stored for more than one month with compromising its performance. More importantly, BCP-nZVI exhibits exceptional removal efficiency of Co2+(92.53%) and Sr2+(58.62%) removal in natural seawater systems. The mechanism investigation illustrates the high adsorption capacity of BCP-nZVI for Co2+ is controlled by redox and hydroxyl complexation. While Sr2+ is controlled by hydroxyl complexed adsorption, thus it has weak against interference by cations like Na+, Ca2+, etc. BCP-nZVI exhibits the advantages of high adsorption capacity, wide pH range, strong stability, and good applicability in natural seawater, which has excellent potential for application in radioactive ions removal.

Machine learning-assisted optimization of food-grade spirulina cultivation in seawater-based media: From laboratory to large-scale production

The shortage of food and freshwater sources threatens human health and environmental sustainability. Spirulina grown in seawater-based media as a healthy food is promising and environmentally friendly. This study used three machine learning techniques to identify important cultivation parameters and their hidden interrelationships and optimize the biomass yield of Spirulina grown in seawater-based media. Through optimization of hyperparameters and features, eXtreme Gradient Boosting, along with the recursive feature elimination (RFE) model demonstrated optimal performance and identified 28 important features. Among them, illumination intensity and initial pH value were critical determinants of biomass, which impacted other features. Specifically, high initial pH values (>9.0) mainly increased biomass but also increased nutrient sedimentation and ammonia (NH3) losses. Both batch and continuous additions could decrease nutrient losses by increasing their availability in the seawater-based media. When illumination intensity exceeded 200 μmol photons/m2/s, it amplified the growth of Spirulina by mitigating the light attenuation caused by a high initial inoculum level and counteracted the negative effect of low temperature (<25 °C). In large-scale cultivation, production efficiency would be reduced if illumination was not maintained at a high level. High salinity and sodium bicarbonate (NaHCO3) addition promoted carbohydrate accumulation, but suitable dilution could keep the required protein content in Spirulina with relatively low media and production costs. These findings reveal the interactive influence of cultivation parameters on biomass yield and help us determine the optimal cultivation conditions for large-scale cultivation of Spirulina-based seawater system based on a developed graphical user interface website.

Impact of coagulation characteristics on the aggregation of microplastics in upper-ocean turbulence

The dynamics and aggregation of microplastics in marine environments are investigated through high-fidelity direct numerical simulations with Lagrangian point-particle tracking. The properties of microplastics and biogenic particles, including size, density, and concentration, align with scenarios typical of seawater systems. The stickiness nature of microplastics, induced by biofilm formation (biofouling), is modeled through coagulation efficiency (stickiness parameter), which represents the probability of aggregation following a collision event. Two main aspects are at the core of the present work: analyzing the mechanisms of collision and coalescence between microplastics and biogenic particles, along with their spatial distribution, and characterizing the emerging aggregates. The results indicate that particles stickiness, concentration and (especially) size impact on the collision and coalescence rates. Furthermore, microplastics exhibit a strong tendency to accumulate near biogenic particles, leading to the creation of hetero-aggregates whose tendency to sink supports the general hypothesis of “missing microplastics”. Particularly, in cases where microplastics and biogenic particles are evenly concentrated, microplastics primarily contribute to the formation of aggregates. The stickiness mainly determines the most complex and large aggregates, which are less than 1% of the total.

Frequency optimization of the AUV wireless charging system for minimum energy dissipation

With the growing demand for ocean exploration, research on docking technology is gaining popularity, resulting in the development of various types of docking systems. In contrast to traditional cable-based systems, this paper introduces a self-powered docking system designed for AUV recovery and recharging. To minimize energy loss in the self-powered system, an analysis of eddy current loss produced by the coils in the seawater is conducted, and a calculation method for determining the equivalent eddy current impedance is proposed. This allows for the transformation of energy loss analysis from the magnetic field to circuit analysis. Then the efficiency of the inductively coupled power transmission system in seawater is analyzed, and a frequency optimization method is proposed to minimize dissipated energy during the AUV battery charging process. Finally, the effectiveness of the frequency optimization method is validated through laboratory experiments. Moreover, the results of the sea trial confirm the feasibility of the optimal wireless charging system operating in a seawater environment.

A sulfhydryl-functionalized vinylene-linked covalent organic framework for promoting gold recovery by light-assistance

Gold, as one of the precious metals, has a wide range of applications and a high market demand. Recovering gold from secondary resources not only safeguards the natural environment but also optimizes resource utilization. Extensive efforts have been devoted to developing materials that can efficiently and selectively recover gold from solutions via adsorption in a rapid manner. In this study, we designed and prepared a vinylene-linked covalent organic framework (viCOF-mtd) through post-synthesis modification by sulfhydryl groups for efficient recovery of gold in aqueous solution. viCOF-mtd exhibits good porosity and structural stability, and possesses an attractive gold adsorption capacity up to 1249 mg g−1. By introducing light stimulation, the gold adsorption capacity of viCOF-mtd can be further enhanced to 3386 mg g−1 along with improved adsorption kinetics. The results of various structural and property characterization tests and density-functional theory (DFT) calculations confirm the presence of electrostatic interaction, S–Au coordination, and redox effects during the gold adsorption process. Notably, light stimulation can effectively increase the photogenerated electrons in viCOF-mtd, which enhance the redox effect on gold ions. Furthermore, viCOF-mtd exhibits remarkable adsorption selectivity towards gold even in the solutions with multiple competing ions and in the complex seawater system.

Impact of ionic strength on goethite colloids co-transported with arsenite (As3+) through a saturated sand column under anoxic condition: Experiment and mathematical modeling

The knowledge about co-transport of goethite and As3+ to investigate the effect of goethite colloids on As3+ transport under various degrees of seawater intrusion, particular extremely conditions, in groundwater environment is still limited. The main objective is to investigate the influence of seawater intrusion on the sorption, migration, and reaction of As3+and goethite colloids into sand aquifer media under anoxic conditions by using the bench-scale and reactive geochemical modeling. The research consisted of two parts as follows: 1) column transport experiments consisting of 8 columns, which were packed by using synthesis groundwater at IS of 0.5, 50, 200, and 400 mM referring to the saline of seawater system in the study area, and 2) reactive transport modeling, the mathematical model (HYDRUS-1D) was applied to describe the co-transport of As3+ and goethite. Finally, to explain the interaction of goethite and As3+, the Derjaguin-Landau-Verwey-Overbeek (DLVO) calculation was considered to support the experimental results and HYDRUS-1D model. The results of column experiments showed goethite colloids can significantly inhibit the mobility of As3+ under high IS conditions (>200 mM). The Rf of As3+ bound to goethite grows to higher sizes (47.5 and 65.0 μm for 200 and 400 mM, respectively) of goethite colloid, inhibiting As3+ migration through the sand columns. In contrast, based on Rf value, goethite colloids transport As3+ more rapidly than a solution with a lower IS (0.5 and 50 mM). The knowledge gained from this study would help to better understand the mechanisms of As3+ contamination in urbanized coastal groundwater aquifers and to assess the transport of As3+ in groundwater, which is useful for groundwater management, including the optimum pumping rate and long-term monitoring of groundwater quality.

Streamlining large-scale oceanic biomonitoring using passive eDNA samplers integrated into vessel's continuous pump underway seawater systems

Passive samplers are enabling the scaling of environmental DNA (eDNA) biomonitoring in our oceans, by circumventing the time-consuming process of water filtration. Designing a novel passive sampler that does not require extensive sample handling time and can be connected to ocean-going vessels without impeding normal underway activities has potential to rapidly upscale global biomonitoring efforts onboard the world's oceanic fleet. Here, we demonstrate the utility of an artificial sponge sampler connected to the continuous pump underway seawater system as a means to enable oceanic biomonitoring. We compared the performance of this passive sampling protocol with standard water filtration at six locations during a research voyage from New Zealand to Antarctica in early 2023. Eukaryote metabarcoding of the mitochondrial COI gene revealed no significant difference in phylogenetic α-diversity between sampling methods and both methods delineated a progressive reduction in number of Zero-Radius Operational Taxonomic Units (ZOTUs) with increased latitudes. While both sampling methods revealed comparable trends in geographical community compositions, distinct clusters were identified for passive samplers and water filtration at each location. Additionally, greater variability between replicates was observed for passive samplers, resulting in an increased estimated level of replication needed to recover 90 % of the biodiversity. Furthermore, traditional water filtration failed to detect three phyla observed by passive samplers and extrapolation analysis estimated passive samplers recover a larger number of ZOTUs compared to water filtration for all six locations. Our results demonstrate the potential of this passive eDNA sampler protocol and highlight areas where this emerging technology could be improved, thereby enabling large-scale offshore marine eDNA biomonitoring by leveraging the world's oceanic fleet without interfering with onboard activities.

Microscopic experimental study on the effects of NaCl concentration on the self-preservation effect of methane hydrates under 268.15 K

It is known that salt ions are abundant in the natural environment where natural gas hydrates are located; thus, it is essential to investigate the self-preservation effect of salt ions on methane hydrates. The dissociation behaviors of gas hydrates formed from various NaCl concentration solutions in a quartz sand system at 268.15 K were investigated to reveal the microscopic mechanism of the self-preservation effect under different salt concentrations. Results showed that as the salt concentration rises, the initial rate of hydrate decomposition quickens. Methane hydrate hardly shows self-preservation ability in the 3.35% (mass) NaCl and seawater systems at 268.15 K. Combined the morphology of hydrate observed by the confocal microscope with results obtained from in situ Raman spectroscopy, it was found that during the initial decomposition stage of gas hydrate below the ice point, gas hydrate firstly converts into liquid water and gas molecules, then turns from water to solid ice rather than directly transforming into solid ice and gas molecules. The presence of salt ions interferes with the ability of liquid water to condense into solid ice. The results of this study provide an important guide for the mechanism and application of the self-preservation effect on the storage and transport of gas and the exploitation of natural gas hydrates.

Studying the variation of the CO2 system in seawater of Bania's coast- Syria

Studying the variation of the CO2 system in seawater of Bania's coast- Syria

Information propagation of focus wave mode localized waves in anisotropic turbulent seawater

The evolution of the information transfer capability of an optical system for underwater focused wave mode localized wave (FWMLW) in anisotropic weakly turbulent absorbing seawater is studied. By developing the probability distribution function as well as the detection probability of the vortex modes carried by the FWMLW and the average bit error rate of the FWMLW underwater system, the information capacity of the FWMLW system with a pointing error is modeled. Through a numerical analysis of the effects of turbulent seawater and optical system parameters on the built light intensity, the detection probability, and the information capacity models, we find that the FWMLW system has an optimal delay time determined by the spectrum bandwidth when the spectrum bandwidth is greater than 1. The information capacity of the FWMLW system is higher than that of the X localized wave system under the same turbulent seawater channel condition, and FWMLW is a better optical signal source for vortex mode division multiplexing underwater systems than a Bessel–Gaussian beam.

Solid-state fermentation converts rice bran into a high-protein feed ingredient for Penaeus monodon

Fermented rice bran (FRB) was evaluated as an alternative protein source to soybean meal (SM) in practical diets for juvenile black tiger shrimp, Penaeus monodon. This feed ingredient was tested in a feeding trial to replace soybean meal in P. monodon diets at 0% (T0), 12.5% (T12.5), 25% (T25), 37.5% (T37.5), and 50% (T50). Five iso-nitrogenous and iso-caloric experimental diets containing 44% crude protein were fed to groups of juvenile shrimp (0.47 ± 0.002 g) randomly assigned to twenty 60-l rectangular tanks equipped with a recirculating seawater system. Each dietary treatment was run in 4 replicates, and the feeding trial lasted 50 days. Results show significant improvement in weight gain, specific growth rate, and protein efficiency ratio in treatment T12.5 and T25. Treatments with higher levels of SM replacement with FRB exhibited similar growth indices to those of the control group. Polynomial regression analysis indicates that the optimum replacement of soybean meal with FRB for optimum growth is 21.08%. The apparent dry matter and protein digestibility coefficients of FRB are 83.05 ± 0.02% and 87.20 ± 0.30%, respectively. There were no significant differences in the whole-body composition (dry matter, protein, lipid, ash) among treatments of shrimp fed with FRB replacement. The data suggest that FRB replacement of dietary soybean meal is feasible at 50% without affecting the growth performance but may promote growth at 21.08% replacement of P. monodon.

Effect of Welding Current on Corrosion Resistance of Heat-Affected Zones of HDR Duplex Stainless Steel.

This paper examines the corrosion behavior of the welding heat-affected zone (HAZ) of HDR (high chromium, duplex, corrosion-resistant) duplex stainless steel, which currently faces corrosion-related challenges in marine seawater systems. The corrosion behavior of the HAZ was studied using microstructure analysis, polarization curve experiments, and double-loop potentiodynamic reactivation experiments. The results show that (1) the covering welding current can promote the formation of austenite in the HAZ, and that the covering welding current has no strict correspondence with the formation of austenite; (2) increasing the welding gap properly can facilitate the formation of austenite; (3) increasing the covering welding current enhances the material's pitting resistance, and a covering welding current of 70 A, coupled with a covering welding current of 100 A, represents a reasonable choice in terms of achieving a stronger pitting resistance; (4) in terms of intergranular corrosion resistance, increasing the covering welding current is not conducive to the intergranular corrosion resistance of the material, as the covering current will promote the precipitation of the secondary phase at the grain boundary, thus reducing its intergranular corrosion resistance; and (5) reducing the welding current appropriately contributes to improving the stability of the grain boundary.

Use of tunicate meal (pleated sea squirt Styela plicata) protein as a partial replacement of menhaden fish meal protein in the diet of juvenile Black Sea Bass

AbstractObjectiveThe pleated sea squirt Styela plicata (subphylum Tunicata), an invasive marine invertebrate in coastal waters of southeastern North Carolina, was investigated as an alternative protein source to fish meal (FM) in the diet of juvenile Black Sea Bass Centropristis striata.MethodsSix different isoproteic and isolipidic diets were formulated to replace 0.0, 8.3, 16.7, 25.0, 33.3, and 41.6% of FM protein with tunicate meal (TM) protein by supplementing 0, 5, 10, 15, 20, and 25% TM in the diets. The experimental system consisted of eighteen 75‐L tanks supported by a recirculating seawater system in an indoor, climate‐controlled laboratory. Juveniles (average weight = 7.1 g) were stocked at a density of 15 fish/tank (N = 3 tanks/treatment) and were fed the test diets daily to apparent satiation for 55 days.ResultReplacement of FM protein with TM protein caused slight declines in dietary amino acid concentrations (notably arginine, methionine, and tryptophan) at higher replacement levels. At terminal sampling, no significant differences in survival (87–96%), percent body weight gain (157–228%), feed conversion ratio (1.50–1.71), or proximate composition were observed among dietary treatment groups. However, significant positive linear trends were found between incremental levels of TM and final fish weight, body weight gain, and specific growth rate. Whole‐body fatty acid composition reflected dietary levels.ConclusionResults indicate that TM protein can be used to replace at least 41.6% of the FM protein in the diet for juvenile Black Sea Bass without adverse effects on survival, growth, feed utilization, or whole‐body proximate composition.

Tuning d–p Orbital Hybridization of NiMoO4@Mo15Se19/NiSe2 Core‐Shell Nanomaterials via Asymmetric Coordination Interaction Enables the Water Oxidation Process

AbstractThe electrocatalytic performance of MoNi‐based nanomaterials undergo selenization has garnered significant interest due to their modified electronic structure, while still posses certain challenges for obtained bimetallic selenides. Here, a novel MoNi‐based electrocatalyst of NiMoO4@Mo15Se19/NiSe2 core‐shell nanomaterials is constructed to promote the desorption of OOH* which can facilitate the water oxidation process. NiMoO4@Mo15Se19/NiSe2 core‐shell nanoarrays show that the “cores” are mainly NiMoO4 nanorods while the “shells” are the bimetallic selenides nanoflakes, which are super architectures that can expand more active sites and accelerate the electron transfer. Moreover, the hybridization interaction between Ni 3d, Mo 4d, and Se 4p orbitals leads to an asymmetric distribution of electric clouds, which decreases the adsorption energy and transformation of oxygen‐containing species. Electrochemical data displays that the overpotentials of NiMoO4@Mo15Se19/NiSe2 core‐shell nanomaterials are only 195 mV, 220 mV, and 224 mV for oxygen evolution reaction (OER) in alkaline freshwater, alkaline simulated seawater, and alkaline natural seawater. The current density decay is negligible after 100 h stability at about 1.46 V with a three‐electrode system in alkaline natural seawater. The low cost and the unique MoNi‐based bimetallic selenides in this work provide a more constructive solution for designing efficient and stable OER catalysts in the future.

Investigation of the Influence Mechanism of CO2 Hydrate Formation in Seawater Systems in the Presence of Solid Promoters by Combining In Situ Raman Analysis with Macroscopic Experiments

Investigation of the Influence Mechanism of CO₂ Hydrate Formation in Seawater Systems in the Presence of Solid Promoters by Combining In Situ Raman Analysis with Macroscopic Experiments