Search

The antifouling booster biocides are frequently studied for toxic effects on the aquatic ecosystems. The present investigation proposes passive silicone rubber samplers as a collection method for biocides, once these methods can concentrate substances in aqueous matrices at very low levels. Through the passive sampler-water partition coefficient (Ksw) and the analyte chemical nature, we can optimize their extraction from the membrane to apply in the sample medium. We used the co-solvent method to determine the Ksw of three third-generation antifouling biocides, chlorothalonil, dichlofluanid, and dichlorooctylisothiazolinone (DCOIT), with log Ksw = 2.24, 4.01, and 2.38, respectively. Improving extraction also led to a recovery range higher than 70%, determinations were carried out by gas chromatography with an electron capture detector. Biocides concentration in seawater samples from Itaqui port (São Marcos Bay, northern Brazil) ranged from 0.058 to 0.72 µg L-1 for chlorothalonil, 0.001 to 0.008 µg L-1 for dichlofluanid, and 0.018 to 0.64 µg L-1 for DCOIT.

The quality of seawater is very important for the state of Qatar as it is a peninsula. This paper is focused on the analysis of several physicochemical parameters, such as pH, Conductivity, Total Dissolved Solids (TDS), Turbidity, Alkalinity (M), Total Hardness, Silica, Sulphate, Iron, Nitrate, Phosphate, and Temperature from different sampling sites along major coastal areas on the East Coast of Qatar--namely the Doha Corniche, Al Khor, and Mesaieed. The results revealed that Qatari coastal waters contained typical values of each physicochemical parameter analyzed and were clean and unaffected by the risks of polluted waters or large-scale algal blooming. Across all nine samples, the pH values of the different water samples ranged from 7.7-7.9. Across all nine samples, the conductivity ranged from 57,590 to 64,960 µS/cm. Across all nine samples, the TDS readings ranged from 41110 - 43380 ppm. Across all nine samples, the turbidity ranged from 1 to 2.65 NTU. Across all nine samples, the alkalinity ranged from 110 to 127 ppm as CaCO3. Across all nine samples, the hardness ranged from 6640 to 6515 ppm as CaCO3. Across all nine samples, the Silica levels ranged from 0.15 to 0.23 ppm as Si. Across all nine samples, the sulfate levels ranged from 2140 to 2145 ppm as SO4. Across all nine samples, the iron levels ranged from 0.03 to 0.1 ppm as Fe+3. Across all nine samples, the nitrate levels ranged from 3.2 to 6.6 ppm as NO3. Across all nine samples, the phosphate levels all read 0 ppm as PO4 (below the detection limit). Across all nine samples, the temperature levels ranged from 24 to 28.8°C. [ABSTRACT FROM AUTHOR]

Abstract Ionic diodes are components in ionic circuits for AC‐electricity driven desalination and ion extraction processes. Independent of the ionic diode type/mechanism, achieving ionic current rectification at high ionic strengths is challenging but important, for example in seawater desalination and treatment of brine. Here, the butylation of a molecularly rigid (glassy) polymer of intrinsic microporosity (PIM‐EA‐TB) is shown to give anionic diodes with ultrahigh rectification effects (associated with interfacial resistivity) even in high ionic strength aqueous 2 M NaCl solution. The effect is rationalised based on polymer structure affecting ion transport.

Amidoxime-functionalized hydrogels are one of most promising adsorbents for high-efficiency uranium (U) extraction from seawater, but bioadhesion on their surface seriously decreases their adsorption efficiency and largely shortens their service life. Herein, a semi-interpenetrating zwitterion–poly(amidoxime) (ZW-PAO) hydrogel was explored through introducing a PAO polymer into a poly [3-(dimethyl 4-vinylbenzyl amino) propyl sulfonate] (PDVBAP) polyzwitterionic (PZW) network via ultraviolet (UV) polymerization. Owing to the anti-polyelectrolyte effect of the PZW network, this ZW-PAO hydrogel can provide excellent super-hydrophilicity in seawater for high-efficiency U-adsorption from seawater. Furthermore, the ZW-PAO hydrogel had outstanding anti-biofouling performance for both highly enhanced U-adsorption and a relatively long working life in natural seawater. As a result, during only 25 days in seawater (without filtering bacteria), the U-uptake amount of this ZW-PAO hydrogel can reach 9.38 mg/g and its average rate can reach 0.375 mg/(g∙day), which is excellent among reported adsorbents. This work has explored a promising hydrogel for high-efficiency U-recovery from natural seawater and will inspire new strategy for U-adsorbing materials.

Solar-driven interfacial evaporation has emerged as an efficient and sustainable way to generate freshwater from seawater to address the crisis of drinkable water. Though rational designs of photothermal materials and structures are essential to the interfacial solar evaporation process, the salt accumulation remains a challenge to the long-term operation of seawater desalination. Here, we report a high-yield and low-cost natural sphagnum as solar steam generator with ultra-fast water transportation, unique microstructure to prevent salting out, and high evaporation rates. The carbonized sphagnum based photothermal evaporator exhibits a strong broad-band light absorption (>97.0 %). During the solar steam generation, a high evaporation rate of 3.53 kg m−2 h−1 was achieved under 1.0 sun illumination. More significantly, the 3D sphagnum evaporator shows excellent selective filtration of salt ions and cycling stability in actual sea water even high salinity solution (10 wt.% NaCl) for 7 days. This work provides an environmentally friendly and cost-effective photothermal material for large-scale seawater desalination, and treatment of waste water with high ions concentration.

The mineral content of seawater is a natural raw material to produce rich mineral sea salt. Rich mineral sea salt is a consumption salt with a NaCl content of

Abstract In this study, we investigated Ni2+, Zn2+, and Co2+ mineralogical incorporation and its effect on green rust transformation to magnetite. Mineral transformation experiments were conducted by heating green rust suspensions at 85 °C in the presence of Ni2+, Zn2+, or Co2+ under strict anoxic conditions. Transmission electron microscopy and powder X-ray diffraction showed the conversion of hexagonal green rust platelets to fine grained cubic magnetite crystals. The addition of Ni2+, Zn2+, and Co2+ resulted in faster rates of mineral transformation. The conversion of green rust to magnetite was concurrent to significant increases in metal uptake, demonstrating a strong affinity for metal sorption/co-precipitation by magnetite. Dissolution ratio curves showed that Ni2+, Zn2+, and Co2+ cations were incorporated into the mineral structure during magnetite crystal growth. The results indicate that the transformation of green rust to magnetite is accelerated by metal impurities, and that magnetite is a highly effective scavenger of trace metals during mineral transformation. The implications for using diagenetic magnetite from green rust precursors as paleo-proxies of Precambrian ocean chemistry are discussed. Graphical Abstract

This study is the first review of current research on microplastics (MPs) in the marine environments at the national scale in Indonesia from 2015 to 2022. This review was conducted to measure the environmental risk and highlight the waste management issue in Indonesian waters. Our literature study found that: (1) the MPs research was mainly conducted in the western part of Indonesia, especially in Java Island; (2) current research has primarily focused on coastal waters (98%) rather than the deep-sea area (2%); (3) the comparability of data is still hampered by difference in quality, about 67% of articles published have not carried out the polymer confirmation; (4) MPs concentrations reported on the articles that did not carry out the polymer identification tended to report higher MPs concentrations. Finally, we propose to have a standard guideline for MPs analysis at a national level and to do more research in the eastern part of Indonesia and deep-sea areas. Further research is required to fill research gaps on plastic distribution and density in deep-sea areas in the eastern part of Indonesia.

Nanosized vaterite, which exhibits characteristics such as high specific surface area, porosity, and biocompatibility, has attracted research attention for use as a drug delivery material. However, fatal drawbacks such as high costs, difficulty in mass production, and toxicity exist in conventional nanosized vaterite production owing to the use of a large amount of organic solvents to forcibly suppress the vaterite recrystallization and particle growth. Therefore, nanosized 100 % vaterite was produced in this study via indirect carbonation without using any organic solvent, which has rarely been achieved previously. Seawater, sucrose, ultrasonication, and aging—which facilitate vaterite production and particle size reduction—exhibited a synergistic effect in producing vaterite. To realize nanosized vaterite production via indirect carbonation, seawater was used as a solvent, sucrose was added when Ca was eluted, and CO2 bubbling was performed under ultrasonication. Furthermore, the CaCO3-containing suspension obtained after the carbonation was aged. Ultrasonic waves were required to generate nanosized vaterite and reducing size at the carbonation stage. This nanosized-vaterite-production strategy involving organic-solvent-free indirect carbonation is meaningful, in that it highlights the potential of synthesizing vaterite in an economically sound, environmentally friendly manner for use as a pharmaceutical raw material.

This paper adopts the fluid–structure coupling algorithm based on the acoustic fluid element, the fluid dynamic artificial boundary, and the consistent viscoelastic artificial boundary of solid media to establish a finite element model of the dynamic interaction of the reef-island–seawater system. Then, a numerical simulation of the seismic response of the reef-island site is carried out to study the seismic ground motion distribution patterns of the reef–seawater site and the reef-island–lagoon site. The innovation of this article is that the influence of reef–island topography and fluid–structure coupling is considered in the analysis when vertical ground motion is input. The results show that the slope angle of the bottom layer has a significant influence on the peak ground acceleration distribution and peak size on the island slope surface and the reef platform. For high-frequency input motion, a smaller reef platform width will induce a larger peak acceleration response on the reef platform. Seawater has a significant suppressive effect on vertical ground acceleration. The more high-frequency components of the input bedrock motion, the more obvious this suppression effect will be. The existence of the lagoon will amplify the maximum peak acceleration on the reef platform. According to the calculation results, lagoon terrain can amplify the maximum horizontal and vertical peak accelerations on the reef platform by about 19 and 6 times relative to the free-field results, respectively.

Seawater has been proposed as a reservoir for antibiotic-resistant bacteria and antibiotic resistance genes, thus representing a risk to public health. In this study, we evaluated the presence of antibiotic resistance determinants (bacteria and genes) in 77 seawater samples collected at different points along the coast of the Gulf of Valencia (Spain). Specifically, indicators of fecal contamination bacteria, Escherichia coli and Enterococcus sp., were isolated, and their antibiotic resistance profiles were analyzed through the use of the Sensititre® system, followed by the detection of the main antibiotic resistance genes (blaTEM, qnrS, tetW, sulI, and ermB). The highest frequencies of resistance in the E. coli isolates were detected for ampicillin (35.1%) and ciprofloxacin (17.5%), followed by sulfamethoxazole and trimethoprim (15.7%), while 23% of enterococci isolates showed resistance to a single antibiotic, 20% against tetracycline and 3% against daptomycin. Through PCR analysis, 93% of the E. coli strains showed the blaTEM and sulI resistance genes. Among the enterococci, the presence of the blaTEM gene was detected in 40% of the isolates, while the rest of the genes were present at very low rates. Among the water samples, 57% were positive for at least one of the tested genes, italic format with blaTEM being the most commonly found gene (47%), followed by the qnrS (33%) and sulI (23%) genes. These results show that seawater, in addition to being subjected to a high rate of fecal contamination, can contribute to the spread of antibiotic resistance.

In the last decade, plastic waste has become one of the main threats to marine ecosystems and their biodiversity due to its abundance and increased persistence. Microplastics can be classified as either primary, i.e., fabricated for commercial use, or secondary, i.e., resulting from the fragmentation/weathering processes of larger plastic pieces in the environment. In general, microplastics are detected in a number of aquatic organisms (e.g., fish, bivalves, mollusks, etc.) with alarming effects on their health. Therefore, the present work focuses on the detection and identification of microplastics in fish species (Dicentrarchus labrax, Sparus aurata) and mussels (Mytilus galloprovincialis) from aquaculture systems since these aquatic organisms are largely commercially available for consumption. In addition, seawater was also screened for the types of polymers present as well as their aging. The experimental protocol for biota samples contains a digestion step using Fenton’s reagent (0.05 M FeSO4⋅7H2O with 30% H2O2 at a volume ratio of 1:1) to remove organic material followed by filtration and a density separation step where the sample material was mixed with a saturated ZnCl2 solution to separate microplastic particles from heavier material. For seawater samples (sampled by a microplastic net sampler), only sieving on stainless steel sieves followed by filtration on silica filters was applied. Detection of microplastics and identification of their polymeric composition was achieved through the combined use of micro-Raman analysis, Attenuated Total Reflectance–Fourier Transform Infrared spectroscopy, and Scanning Electron Microscopy in tandem with Energy Dispersive X-ray spectroscopy. Microplastic abundance was 16 ± 1.7 items/individual in mussels and 22 ± 2.1 items/individual in sea bass, and 40 ± 3.9 items/individual in sea bream, with polyethylene (74.4%) being the most detected polymer type, while polyethylene-co-vinyl acetate (65%), polyvinyl-butyral (36.8%), polyvinyl alcohol (20%), and polybutyl methacrylate (15.8%) were also detected to a lesser extent. The microplastics isolated from seawater samples were films (30%), fragments (30%), and fibers (20%), while some of them were derived from foams (20%). Also, in most of these seawater-recovered microplastics, a relatively high degree of oxidation (carbonyl index > 0.31) was observed, which was further confirmed by the results of Energy Dispersive X-ray spectroscopy. Finally, the Scanning Electron Microscopy images showed various morphological characteristics (cracks, cavities, and burrs) on the surfaces of the microplastics, which were attributed to environmental exposure.

Benzo(a)pyrene, as the main polycyclic aromatic hydrocarbon pollutant in marine oil spill pollution, has negative effects on marine ecology and human health. A facile and sensitive method of rapid benzo(a)pyrene detection in seawater is essential for marine conservation. In this paper, a novel immunosensor is fabricated using a multi-walled carbon nanotubes-chitosan composite loaded with benzo(a)pyrene antibody. This immunosensor is based on a biosensing assay mechanism that uses multi-walled carbon nanotubes-chitosan composites as conductive mediators to enhance electron transfer kinetics. Then, potassium ferricyanide was used as an electrochemical probe to produce an electrochemical signal for the voltammetric behavior investigation of the immune response by differential pulse voltammetry. Under optimal experimental conditions, the peak current change was inversely proportional to the benzo(a)pyrene concentration in the range of 0.5 ng⋅ml−1 and 80 ng⋅ml−1 with a detection limit of 0.27 ng⋅ml−1. The immunosensor was successfully applied to assay BaP in seawater, and the recovery was between 96.6 and 100%, which exhibited a novel, sensitive and interference-resistant analytical method for real-time water environment monitoring. The results demonstrate that the proposed immunosensor has a great potential for application in the monitoring of seawater.

In this study, a facile and rapid microwave-assisted synthesis method was used to synthesize In2S3 nanosheets, ZnS nanosheets, and ZnIn2S4 nanosheets with sulfur vacancies. The two-dimensional semiconductor photocatalysts of ZnIn2S4 nanosheets were characterized by XRD, FESEM, BET, TEM, XPS, UV–vis diffuse reflectance, and PL spectroscopy. The ZnIn2S4 with sulfur vacancies exhibited an evident energy bandgap value of 2.82 eV, as determined by UV–visible diffuse reflectance spectroscopy, and its energy band diagram was obtained through the combination of XPS and energy bandgap values. ZnIn2S4 nanosheets exhibited about 33.3 and 16.6 times higher photocatalytic hydrogen production than In2S3 nanosheets and ZnS nanosheets, respectively, under visible-light irradiation. Various factors, including materials, sacrificial reagents, and pH values, were used to evaluate the influence of ZnIn2S4 nanosheets on photocatalytic hydrogen production. In addition, the ZnIn2S4 nanosheets revealed the highest photocatalytic hydrogen production from seawater, which was about 209.4 and 106.7 times higher than that of In2S3 nanosheets and ZnS nanosheets, respectively. The presence of sulfur vacancies in ZnIn2S4 nanosheets offers promising opportunities for developing highly efficient and stable photocatalysts for photocatalytic hydrogen production from seawater under visible-light irradiation.

We have demonstrated a two-step wet chemical approach for synthesizing ternary Ag/Ag2S/CdS heterostructures for efficient photocatalytic hydrogen evolution. The CdS precursor concentrations and reaction temperatures are crucial in determining the efficiency of photocatalytic water splitting under visible light excitation. In addition, the effect of operational parameters (such as the pH value, sacrificial reagents, reusability, water bases, and light sources) on the photocatalytic hydrogen production of Ag/Ag2S/CdS heterostructures was investigated. As a result, Ag/Ag2S/CdS heterostructures exhibited a 3.1-fold enhancement in photocatalytic activities compared to bare CdS nanoparticles. Furthermore, the combination of Ag, Ag2S, and CdS can significantly enhance light absorption and facilitate the separation and transport of photogenerated carriers through the surface plasma resonance (SPR) effect. Furthermore, the Ag/Ag2S/CdS heterostructures in seawater exhibited a pH value approximately 2.09 times higher than in de-ionized water without an adjusted pH value under visible light excitation. The ternary Ag/Ag2S/CdS heterostructures provide new potential for designing efficient and stable photocatalysts for photocatalytic hydrogen evolution.

Anthropogenic chemical contamination represents a key stressor of natural environments with pharmaceuticals comprising a particular group of emerging pollutants with the potential to induce biological responses in non-target organisms. Therefore, an analytical method based on ultra-high-performance liquid chromatography coupled to time-of-flight tandem mass spectrometry (UHPLC-TOF-MS) was developed for estuarine and seawaters, targeting 63 globally used pharmaceuticals (including amoxicillin, ciprofloxacin, sulfamethoxazole, trimethoprim and venlafaxine included in the Surface Water Watch List) from 8 therapeutic groups: antibiotics, analgesic, NSAIDs, antidepressants, β-blockers, lipid regulators, anticonvulsants and antihypertensive drugs. The method presents high selectivity and sensitivity, with the limits of detection ranging from 0.01 to 8.92 ng/L and the limits of quantification from 0.02 to 29.73 ng/L. Considering precision, the highest value was achieved for amoxicillin (20.9%) and the lower for ofloxacin (2.6%), while recoveries ranged from 80.6 to 112.6%. Overall, the quantification method was highly efficient for multi-residues quantification in such complex environmental samples.

High purity magnesium hydroxide has been synthesised from seawater with the addition of dolomite lime as reagent. High intensity ultrasound-assisted crystallization of magnesium hydroxide was carried out during precipitation with the intention to obtain fine particles of Mg(OH)2 as well as to prevent their agglomeration. Investigations were conducted on magnesium hydroxide samples in the form of sludge and voluminous powder. The composition, morphology, and properties of the product were determined by chemical, XRD, FTIR, and SEM/EDS analysis. The particle size distribution was detected by the laser light scattering method. The results showed that the mean particle size of magnesium hydroxide sludge was 5.75 µm, while voluminous powder was 7.58 µm. The morphology of magnesium hydroxide voluminous powder was in the form of aggregated filamentous (up to 300 nm in size) or flake structures.

The effect of temperature (from 288 to 308 K) and concentration of sulfide ions (up to 40 ppm) on the corrosion behavior of AISI 304L and AISI 316L stainless steels in seawater was studied with measurements of open-circuit potential, linear and potentiodynamic polarization, and electrochemical impedance spectroscopy. An increase in temperature and pollutant concentration negatively affects the corrosion stability of stainless steels at the open circuit (the resistance, compactness, and thickness of the surface layer decrease and the corrosion current increases), in the passive region (the passivation current increases, the depassivation potential decreases, and the passive potential region narrows), and in the transpassive potential region (the rate of metal dissolution increases). The occurrence of pitting corrosion on the surface of the samples was confirmed with optical microscopy and a non-contact 3D profilometer. A few large pits (depth 80–100 μm and width 100 μm) were formed on the surface of AISI 304L steel, while several smaller pits (depth 40–50 μm and width 50 μm) were formed on the surface of AISI 316L steel. With increasing temperature and sulfide ion concentration, the width, depth, and density of the pits increased on both steel samples. In the studied temperature and concentration range of sulfide ions, the AISI 316L steels exhibited higher corrosion resistance. Overall, the influence of sulfide ions on steel corrosion was more pronounced than the influence of temperature.

Amino- and carboxyl-functionalized carbon quantum dots (Amino-CQDs) were synthesized through fast and simple microwave treatment of a citric acid, ethylenediamine and ethylenediaminetetraacetic acid (EDTA) mix. The reproducible and stable optical properties from newly synthesized CQD dispersion with a maximum absorbance spectra at 330 nm and the symmetric emission maximum at 470 nm made the Amino-CQDs a promising fluorescence material for analytical applications. The highly aminated and chelate moieties on the CQDs was appropriate for a copper (Cu2+) cation sensor in the linear range from 1 × 10−4 mg/mL to 10 mg/mL with a limit of detection at 0.00036 mg/mL by static fluorescence quenching effects. Furthermore, Amino-CQDs demonstrated stable fluorescence parameters for assays in diluted alkali metal solution (Na+ and K+) and sea water. Finally, a visual sensor, based on Amino-CQDs, was successfully created for the 0.01–100 mg/mL range to produce a colorimetric effect that can be registered by computer vision software (Open CV Python).

Poor durability of reinforced concrete structures can lead to serious structural failures. An accurate model to observe the effects of aggressive agents like carbonation, sulfate ingress, and seawater solutions on the solid phase assemblage will help designers and specifiers better understand how cement behaves in these environments. This paper presents the first steps in developing such a model using the PHREEQC geochemical software by accounting for alkali binding and dissolution. It also presents the use of discrete solid phases (DSPs) to account for the solid-solution behaviour of siliceous hydrogarnet and magnesium silicate hydrate (M-S-H). A new thermodynamic description of the vaterite phase has also been developed for this work using the cemdata18 thermodynamic database. The predicted phase assemblages of cements in these environments here agree with previously published findings using a different thermodynamic model supported with experimental data.

Generation of hydrogen fuel at cathode during the electrolysis of seawater can be economically beneficial considering the vast availability of the electrolyte although it faces sluggishness caused by the anode reactions. In this regard a carbon nanosphere-protected CuO/Co3O4 (CCuU) composite was synthesized through heat treatment and was used as the cathode material for electrocatalytic seawater splitting. CCuU showed a significantly low overpotential of 73 mV@10 mA cm−2, Tafel slope of 58 mV dec−1 and relatively constant activity and morphology over a long time electrocatalytic study. A synergy within metal oxide centers was observed that boosted the proton-electron transfer at the active site. Moreover, the presence of carbon support increased the electroactive surface area and stability of the composite. The activity of the CCuU was studied for HER in KOH and alkaline NaCl solution to understand the activity. This work will pave the way for designing mesoporous non-precious electrocatalysts towards seawater electrocatalysis.

Water scarcity is the main issues in Indonesia especially for coastal areas. As a consequence, the water has high salinity of >50.000 ppm salt concentration where an appropriate treatment is necessary before consumed. In this case, desalination process could be carried out using inorganic silica membranes. However, during the process the pore of silica membranes were collapsed due to the directly contact of pores to water molecules for a long term performance. Thereby, in this work the innovation of membrane fabrication using carbon templated in silica matrices has been successfully fabricated. Literally, the carbon templates could be improving the membrane hydro-stability. The interlayer-free silica-pectin membrane was fabricated using TEOS as silica precursor and carbon templated from pectin apple. All membranes waere calcined in variance temperature of 300 and 400°C via Rapid Thermal Processing (RTP). The FTIR results show some functionalization of siloxane, silanol and a new bond of silica-carbon. Whereas, the SEM images show the membrane morphology that the membrane not dense and crack-free with thin film's thickness of ~ 1 μm. An excellent condition of interlayer-free silica-pectin membrane was obtained at pectin concentration of 2.5 %wt. (300°C) and 0.5 %wt. (400°C) with highest functionalization of siloxane and silica-carbon bonds. The existence of silica-carbon bonds were capable to enhancing the membrane hydro-stability. In addition, the carbon chains were contributed to form a smaller pores but also robust pore structures. Those fabricated membranes were shown a good promising due to fast and low cost fabrication with high quality to applicate in seawater desalination.

In this study, we investigated an alternative method for the chemical CO2 reduction reaction in which power ultrasound (488 kHz ultrasonic plate transducer) was applied to CO2-saturated (up to 3%) pure water, NaCl and synthetic seawater solutions. Under ultrasonic conditions, the converted CO2 products were found to be mainly CH4, C2H4 and C2H6 including large amount of CO which was subsequently converted into CH4. We have found that introducing molecular H2 plays a crucial role in the CO2 conversion process and that increasing hydrogen concentration increased the yields of hydrocarbons. However, it was observed that at higher hydrogen concentrations, the overall conversion decreased since hydrogen, a diatomic gas, is known to decrease cavitational activity in liquids. It was also found that 1.0 M NaCl solutions saturated with 2% CO2 + 98% H2 led to maximum hydrocarbon yields (close to 5%) and increasing the salt concentrations further decreased the yield of hydrocarbons due to the combined physical and chemical effects of ultrasound. It was shown that CO2 present in a synthetic industrial flue gas (86.74% N2, 13% CO2, 0.2% O2 and 600 ppm of CO) could be converted into hydrocarbons through this method by diluting the flue gas with hydrogen. Moreover, it was observed that in addition to pure water, synthetic seawater can also be used as an ultrasonicating media for the sonochemical process where the presence of NaCl improves the yields of hydrocarbons by ca. 40%. We have also shown that by using low frequency high-power ultrasound in the absence of catalysts, it is possible to carry out the conversion process at ambient conditions i.e., at room temperature and pressure. We are postulating that each cavitation bubble formed during ultrasonication act as a “micro-reactor” where the so-called Sabatier reaction -CO2+4H2→UltrasonicationCH4+2H2O - takes place upon collapse of the bubble. We are naming this novel approach as the “Islam-Pollet-Hihn process”.

Ammonium is a fundamental nutrient for phytoplankton growth in seawater and is a key component of the microbial loop. Ammonium measured in parallel with other nutrients is crucial in understanding the small temporal scale changes in oceanographic ecology. Despite the importance of measuring ammonium at sea, owing to its lability, there is no consensus on the best method. The lack of availability of certified reference materials for ammonium in seawater also makes it difficult to assess the accuracy and reproducibility of ammonium measurements. In this study we present a modified segmented flow analysis method using ortho-phthaldialdehyde (OPA) with fluorescence detection to measure ammonium at sea together with four other macro-nutrients (nitrate, nitrite, silicate and phosphate) in near real time. An in-house ammonium quality control (QC) material was produced to improve the accuracy and repeatability of the measurement at sea. The QC was prepared following two different methods and stored in two types of containers. The suitability of the in-house QC’s as a reference material were assessed onboard the RV Investigator in 2018 during two oceanographic voyages, including one on the repeat SR03 CLIVAR transect. This paper describes the production and assessment of the in-house QC for ammonium in seawater, providing groundwork for creating a short-term stable ammonium reference material for sea going voyages. The uncertainty of this method of ammonium measurement was found to be 0.10 μmol/L at ammonium concentration of 1.0 μmol/L. Results show that preparation of the QC inside a laminar flow cabinet and directly into 10 mL polypropylene sample tubes just prior to the commencement of the voyage improved its stability.

The release of mercury into the environment has adverse effects on humans and aquatic species, even at very low concentrations. Pyrene and its derivatives have interesting fluorescence properties that can be utilized for mercury (Hg2+) ion sensing. Herein, we reported the highly selective pyrene-functionalized silica nanoparticles (Pyr-NH@SiO2 NPs) for chemosensing mercury (Hg2+) ions in a seawater sample. The Pyr-NH@SiO2 NPs were synthesized via a two-step protocol. First, a modified Stöber method was adopted to generate amino-functionalized silica nanoparticles (NH2@SiO2 NPs). Second, 1-pyrenecarboxylic acid was coupled to NH2@SiO2 NPs using a peptide coupling reaction. As-synthesized NH2@SiO2 NPs and Pyr-NH@SiO2 NPs were thoroughly investigated by 1H-NMR, FTIR, XRD, FESEM, EDS, TGA, and BET surface area analysis. The fluorescent properties were examined in deionized water under UV-light illumination. Finally, the developed Pyr-NH@SiO2 NPs were tested as a chemosensor for Hg2+ ions detection in a broad concentration range (0–50 ppm) via photoluminescence (PL) spectroscopy. The chemosensor can selectively detect Hg2+ ions in the presence of ubiquitous ions (Na+, K+, Ca2+, Mg2+, Ba2+, Ag+, and seawater samples). The quenching of fluorescence properties with Hg2+ ions (LOD: 10 ppb) indicates that Pyr-NH@SiO2 NPs can be effectively utilized as a promising chemosensor for mercury ion detection in seawater environments.

Phosphotungstic acid (HPW) as a polyoxometalate was selected as the active component of the catalyst. The activated carbon supported different percentage of HPW catalysts were prepared by impregnation and were characterized by X-ray diffraction (XRD), nitrogen adsorption, Fourier transform infrared (FTIR), and scanning electron microscope (SEM). The results showed that the HPW retained the original Keggin structure after being supported on activated carbon, the specific surface of the HPW/C was much bigger than that of pure HPW. The catalytic performance of HPW/C in the hydrogen generation reaction by hydrolysis of sodium borohydride in seawater and in deionized water were studied. 2.5 wt.% HPW/C showed the fastest hydrolysis reaction rate and the biggest volume of hydrogen generated. As for hydrolysis of sodium borohydride, catalytic effect of HPW/C was better in seawater than in distilled water. HPW dispersed on activated carbon is a real promising catalytic system for the development of hydrogen generation by hydrolysis of NaBH4 in seawater.

The Mediterranean Sea is subjected to a high anthropic pressure, which determines direct or indirect discharges of persistent organic pollutants deriving from intensive industrial activities. These compounds could easily enter and contaminate the whole marine compartment, with possible transfers (and contamination) among water, sediment and biota. Based on the above-mentioned assumptions, in this work we studied the presence of 16 polycyclic aromatic hydrocarbons (PAHs) and 14 dioxin and non-dioxin-like polychlorinated biphenyls (PCBs) in the neritic protected marine area of the Southern Ligurian Sea, affected by the impact of human activities. The study was focused on the possible partition of micropollutants within seawater, sediment and zooplankton. Results showed that both seasonal and anthropic causes strongly affect contaminant transfer behaviors, with summertime periods more impacted by PAH and PCB contamination. Regarding the PAH contamination, low molecular weight congeners were mainly detected in the target matrices, revealing concentrations up to 1 µg/L in seawater (anthracene), 250 µg/Kg in sediments (benzo[b]fluoranthene) and 2.3 mg/Kg in carnivorous copepods. Concerning PCBs, only few congeners were detected in the matrices studied. To better understand the occurrence of preferential bioaccumulation pathways in zooplankton, partition studies were also performed in several taxa (hyperbenthic Isopoda, holoplanktonic crustacean copepods and ichthyoplankton) through the calculation of BAF values, observing that both living and feeding habits could influence the bioaccumulation process.

The determination of trace pollutants in seawater is challenging, and sampling is a crucial step in the entire analytical process. Passive samplers combine in situ sampling and preconcentration, thus limiting the tedious treatment steps of the conventional sampling methods. Their use to monitor water quality in confined marine environment could bring several advantages. In this work, the presence of organic contaminants at trace and ultra-trace levels was assessed in the Genoa Aquarium supply-and-treated water using Polar Organic Integrative Samplers (POCIS). Both untargeted gas chromatography-mass spectrometry and targeted liquid chromatography-tandem mass spectrometry were employed. The untargeted approach showed the presence of hydrocarbons, diphenyl sulfone and 2,4-di-tert-butyl-phenol. Only hydrocarbons were detected in all the samples. Nineteen emerging contaminants, belonging to different classes (pharmaceuticals, UV-filters, hormones and perfluorinated compounds), were selected for the target analysis. Thirteen analytes were detected, mainly in supply water, even though the majority of them were below the quantitation limit. It is worthy to note that two of the detected UV-filters had never been reported in seawater using the POCIS samplers. The comparison of the analytes detected in supply and treated water indicated a good performance of the Aquarium water treatment system in the abatement of seawater contaminants.

In this paper, a simple dispersive liquid-liquid microextraction for the extraction and pre-concentration of formaldehyde in seawater samples followed with spectrophotometric is proposed. Formaldehyde was derivatized in situ with acetyl acetone in the presence of ammonium acetate in a single step. Then it was collected into a mixture of ethanol (disperser solvent) and chloroform (extracting solvent). Experimental parameters which have an influence on the extraction, including type and volume of extracting and disperser solvent, pH of sample solution, the concentration of acetyl acetone and ammonium acetate, reaction time and temperature were evaluated and optimized. Under optimal experimental conditions, good linearity was observedin the range of 1-500 µg/Lfor the analyte with a limit of detection of 0.29 µg/L. The proposed method was applied to the analysis of real seawater samples. For spiked samples, good recoveries in the range of 97.7-101.5% were obtained. The relative standard deviations were below 2.1%. Using this method, formaldehyde content in seawater from several locations in Chabahar Bay (southeast Iran) were determined in the range of 1.4 to 4.8 µg/L.

The durability of alkali-activated steel electric arc furnace slag (EAFS) in a marine environment was evaluated with respect to the chemical composition of the alkaline activator. Two different alkaline activators have been used: a mixture of NaOH and Na2SiO3 solutions (Na-activator), as well as a mixture of KOH and K2SiO3 solutions (K-activator). The obtained results gave the insight into the influence of alkaline activator chemistry on the compressive strength and durability of alkali-activated slag (AAS), which was exposed to the damaging seawater environment. The porosity of AAS was found to be the most important factor with regards to the strength and durability of these materials in marine environment. Sodium based alkali-activated slag (Na-AAS) displayed lower porosity and higher compressive strength compared to potassium based AAS (K- -AAS). Lower porosity and thus a lower rate of water uptake by AAS matrix, i.e., the lower sorptivity was exhibited by the Na-AAS when compared to K-AAS. Hence, Na-AAS exhibited better durability in a marine environment.

Studies on the interaction between crude oil, brine, and rock systems showed that the composition of water injected into the oil reservoir influences the amount of oil recovered from such a reservoir. Therefore, researchers are now emphasizing the use of SmartWater for enhanced oil recovery (EOR). In this research, the capability of activated clay to be used for tuning the chemistry of seawater for subsequent production of SmartWater was investigated. Filter cakes were formed using bentonite and its blends with raw clay and activated clay (which was produced in-house using locally obtained clay samples). The capability of the cakes to control the transport properties of permeating seawater was evaluated in terms of ion rejection. The average rejection for the raw clay cake for Na+, K+, Mg2+, and Ca2+ is 4.45, 49.64, 53.33, and 94.43%, respectively. The rejection results for the mixed-matrix cake containing the activated clay were 6.38, 51.34, 86.19, and 78.09 for Na+, K+, Mg2+, and Ca2+, respectively. It was observed that the selectivity of the filter cake for Mg2+ and Ca2+ was reversed due to the addition of the activated clay. Thus, activated clay possesses some potentials for SmartWater production for an EOR application. [ABSTRACT FROM AUTHOR]

Determining air‐sea CO2 fluxes using pCO2 disequilibrium requires knowing the gas transfer velocity and air‐sea pCO2 difference. Most pCO2 measurements are made from ships, whose uncontaminated seawater intakes are located at >5‐m depth to prevent ingestion of air. However, there could be bias in determinations of CO2 fluxes if there is disagreement between pCO2 measurements at the surface and 5 m. Seawater measurements made at the near surface and 5 m in the eastern Equatorial Pacific Ocean show that precipitation can dilute surface seawater salinity and lower the pCO2 and dissolved inorganic carbon and raise pH of the same water, and that these changes in ocean chemistry are largely missed by measurements at 5 m. This finding implies that estimates of ocean CO2 uptake might be underestimated, since rain will lower surface ocean pCO2 in both source and sink regions and, hence, increase uptake in sink regions and decrease outgassing in source regions. Key Points: Simultaneous measurements at the ocean surface and at 5 m show significant differences in pCO2Rain affects surface ocean pCO2 by mainly by dilution but also by temperature changeRain‐induced changes in pCO2 could significantly bias the determination of global air‐sea CO2 fluxes [ABSTRACT FROM AUTHOR]

The Tonian Period followed a long interval of relative stasis and led into the climatic extremes and biological radiations of multicellular life during the Cryogenian and Ediacaran Periods, respectively. However, despite its pivotal situation, it remains relatively understudied, in large part due to the lack of robust age constraints. A combination of fossil evidence, radiometric ages, and isotopic constraints reveal that carbonate strata on the North China craton were deposited between ca. 980 and ca. 920 Ma, thereby filling a gap in marine archives. Here we present 87Sr/86Sr data from selected calcite microspar cements, which filled early diagenetic "molar tooth" cracks, along with data from demonstrably well-preserved bulk carbonate samples. These new data show that seawater 87Sr/87Sr rose in stages from -0.7052 at ca. 980 Ma to -0.7063 by ca. 920 Ma, after which a return to low values coincided with the eruption of the Dashigou large igneous province across the North China craton. We also present a new Neoproterozoic seawater 87Sr/86Sr curve, which reveals that the general trend toward higher 87Sr/87Sr during the Tonian Period was checked repeatedly by the input of less-radiogenic strontium from a series of eruptive events, both coincident with and prior to the main breakup of Rodinia. The weathering of Tonian volcanic provinces has been linked to higher carbon burial, glaciation, and oxygenation due to the high phosphorus content of flood basalts. Here we show that the weathering of major volcanic provinces affected material fluxes and ocean chemistry much earlier than previously envisaged. [ABSTRACT FROM AUTHOR]

The greenhouse world of the mid‐Cretaceous (~94 Ma) was punctuated by an episode of abrupt climatic upheaval: Oceanic Anoxic Event 2. High‐resolution climate records reveal considerable changes in temperature, carbon cycling, and ocean chemistry during this climatic perturbation. In particular, an interval of cooling has been detected in the English Chalk on the basis of an invasive boreal fauna and bulk oxygen‐isotope excursions registered during the early stages of Oceanic Anoxic Event 2—a phenomenon known as the Plenus Cold Event, which has tentatively been correlated with climatic shifts worldwide. Here we present new high‐resolution neodymium‐, carbon‐, and oxygen‐isotope data, as well as elemental chromium concentrations and cerium anomalies, from the English Chalk exposed at Dover, UK, which we evaluate in the context of >400 records from across the globe. A negative carbon‐isotope excursion that correlates with the original "Plenus Cold Event" is consistently expressed worldwide, and CO2 proxy records, where available, indicate a rise and subsequent fall in CO2 over the Plenus interval. However, variability in the timing and expression of cooling at different sites suggests that, although sea‐surface paleotemperatures may reflect a response to global CO2 change, local processes likely played a dominant role at many sites. Variability in the timing and expression of changes in water mass character, and problems in determining the driver of observed proxy changes, suggest that no single simple mechanism can link the carbon cycle to oceanography during the Plenus interval and other factors including upwelling and circulation patterns were locally important. As such, it is proposed that the Plenus carbon‐isotope event is a more reliable stratigraphic marker to identify the Plenus interval, rather than any climatic shifts that may have been overprinted by local effects. Key Points: This study is the first to review mechanistic interactions, and temporal leads and lags, between temperature, seawater chemistry, and CO2 within the Plenus intervalThe negative carbon‐isotope excursion during the Plenus interval was a global event driven by a CO2 increase, and appears decoupled from cooling and circulation changesCooling was not globally synchronous; local climatic and environmental responses to the CO2 change are more complex than previously understood [ABSTRACT FROM AUTHOR]

The accurate and precise determination of Li isotopic composition by MC‐ICP‐MS suffers from the poor performance of traditional column chromatography. Previously established chromatographic processes cannot completely remove Na in complex geological samples, which is currently interpreted to be a result of Na breakthrough. In this study, Na breakthrough during single‐column purification was found to differ between simply artificial Na‐containing sample solutions, where a little Na residue was found, and silicate rocks, where a large amount of breakthrough occurred. A revised two‐step column purification for Li using 0.5 and 0.3 mol l−1 HCl as eluents was designed to remove the Na. This modified method achieves high‐efficiency Li purification from Na and consequently avoiding high Na/Li ratio interference for subsequent MC‐ICP‐MS analyses. The proposed method was validated by the analysis of a series of reference materials, including Li2CO3 (IRMM‐016, ‐0.10‰), basalt (BCR‐2: 2.68‰; BHVO‐2: 4.39‰), andesite (AGV‐2: 6.46‰; RGM‐2: 2.59‰), granodiorite (GSP‐2: −0.87‰) and seawater (CASS‐5, 30.88‰). This work reports early Na appearance prior to the elution curves in chromatography and emphasises its influence for subsequent Li isotope measurement. Based on the findings, the established two‐step method would be more secure than single‐column chemistry for Li purification. [ABSTRACT FROM AUTHOR]

Marine habitat‐forming species often play critical roles on rocky shores by ameliorating stressful conditions for associated organisms. Such ecosystem engineers provide structure and shelter, for example, by creating refuges from thermal and desiccation stresses at low tide. Less explored is the potential for habitat formers to alter interstitial seawater chemistry during their submergence. Here, we quantify the capacity for dense assemblages of the California mussel, Mytilus californianus, to change seawater chemistry (dissolved O2, pH, and total alkalinity) within the interiors of mussel beds at high tide via respiration and calcification. We established a living mussel bed within a laboratory flow tank and measured vertical pH and oxygen gradients within and above the mussel bed over a range of water velocities. We documented decreases of up to 0.1 pH and 25 μmol O2 kg−1 internal to the bed, along with declines of 100 μmol kg−1 in alkalinity, when external flows were < 0.05 m s−1. Although California mussels often live in habitats subjected to much faster velocities, sizeable populations also inhabit bays and estuaries where such moderate flow speeds can occur > 95% of the time. Reductions in pH and O2 inside mussel beds may negatively impact resident organisms and exacerbate parallel human‐induced perturbations to ocean chemistry while potentially selecting for improved tolerance to altered chemistry conditions. [ABSTRACT FROM AUTHOR]

Electrocatalytic water splitting is a possible route to the expanded generation of green hydrogen; however, a long-term challenge is the requirement of fresh water as an electrolyzer feed. The use of seawater as a direct feed for electrolytic hydrogen production would alleviate fresh water needs and potentially open an avenue for locally generated hydrogen from marine hydrokinetic or off-shore power sources. One environmental limitation to seawater electrolysis is the generation of chlorine as a competitive anodic reaction. This work evaluates transition metal (W, Co, Fe, Sn, and Ru) doping of Mn-Mo-based catalysts as a strategy to suppress chlorine evolution while sustaining catalytic efficiency. Electrochemical evaluations in neutral chloride solution and raw seawater showed the promise of a novel Mn-Mo-Ru electrode system for oxygen evolution efficiency and enhanced catalytic activity. Subsequent stability testing in a flowing raw seawater flume highlighted the need for improved catalyst stability for long-term applications of Mn-Mo-Ru catalysts. This work highlights that elements known to be selective toward chlorine evolution in simple oxide form (e.g., RuO2) may display different trends in selectivity when used as isolated dopants, where Ru suppressed chlorine evolution in Mn-based catalysts.

Chromatographic development for the determination of pharmaceuticals in environmental water samples is particularly challenging when the analytes have significantly different physico-chemical properties (solubility, polarity, pKa) often requiring multiple chromatographic methods for each active component. This paper presents a method for the simultaneous determination of azithromycin, erythromycin (antibiotics), fluoxetine (anti-depressant) and sotalol (b-blocker) in surface waters by ultra-high-performance liquid chromatography coupled with ultra-high-resolution time-of-flight mass spectrometry. These pharmaceuticals—presenting a broad spectrum of polarity (0.24 ≤ log Kow ≤ 4.05)—were separated on a C-18 analytical column, after a simple filtration step for freshwater samples or after a liquid–liquid extraction with Methyl-tertio-butyl ether (MTBE) for seawater samples. The optimized separation method (in terms of nature of column and eluent, elution gradient, and of mass spectrometric parameters), enable one to reach limits of detection ranging between 2 and 7 ng L−1 and limits of quantification between 7 and 23 ng L−1 for the four targeted molecules, within a three minute run. This method was validated using samples collected from three different surface waters in Lebanon (freshwater and seawater) and analytical results were compared with those obtained in surface waters sampled in a French river, equivalent in terms of human activities. Using this method, we report the highest concentration of pharmaceuticals found in surface water (up to 377 ng L−1 and 268 ng L−1, respectively, for azithromycin and erythromycin, in the Litani river, Lebanon).

The potassium (K) sorption characteristics with three adsorbents, natural zeolite, ammonium acetate-treated zeolite, and manganese nodule, were studied and compared to see the potential use of manganese nodule as an alternative K adsorbent. In general, the Langmuir isotherm could fit the K sorption in the KCl solutions at different pH conditions better than the Freundlich isotherm. Based on the Langmuir parameters, the maximum K sorption was greater for the zeolite-based adsorbents (i.e., 40–42 mg g−1) than the manganese nodule (i.e., 2.0 mg g−1) at acidic conditions, while the manganese nodule (i.e., 9.7 mg g−1) showed better K sorption at neutral conditions. With the seawater samples, the zeolite-based adsorbents showed higher K recovery (4–14%) than the manganese nodule (0–8.8%). The K sorption on the zeolite-based adsorbents followed the pseudo-second-order kinetics and the K sorption rates were higher for the treated zeolite than the natural zeolite. The repeated sorption tests showed that the natural zeolite could potentially be reused up to three times without any significant loss of K sorption capacity, while the ammonium acetate-treated zeolite lost its K sorption capacity after the single sorption test. Overall, the results show that the manganese nodule may potentially be the alternative to zeolite for K recovery under certain conditions, yet the zeolite-based adsorbents are generally better than the manganese nodule. Thus, more studies to enhance the K recovery using zeolite, including surface modified zeolite, are recommended.