peer reviewed | Mercury (Hg) concentrations have significantly increased in oceans during the last century. This element accumulates in marine fauna and can reach toxic levels. Seafood consumption is the main pathway of methylmercury (MeHg) toxicity in humans. Here, we analyzed total Hg (T-Hg) concentrations in two oceanic squid species (Ommastrephes bartramii and Thysanoteuthis rhombus) of an increasing commercial interest off Martinique, French West Indies. Stable isotope ratios reveal a negative linear relationship between δ15N or δ13C in diamondback squid samples. No significant trend was observed between δ34S values and T-Hg concentrations, contrasting with the sulfate availability and sulfide abundance hypotheses. This adds to a growing body of evidence suggesting Hg methylation via sulfate-reducing bacteria is not the main mechanism driving Hg bioavailability in mesopelagic organisms. All squid samples present T-Hg levels below the maximum safe consumption limit (0.5 ppm), deeming the establishment of a commercial squid fishery in the region safe for human consumption.

Low sulfur fuel oils (LSFOs) with less than 0.5% sulfur content have been mandated for marine vessels by the International Maritime Organization since 2020. However, owing to the low dispersibility and high viscosity of LSFOs, their oceanic spills are difficult to clean using conventional response systems. In this study, we propose a superhydrophilic and hygroscopic ramie to clean spilled LSFO. To this end, a raw ramie fiber, which is intrinsically hydrophobic, was treated using a mild alkali to remove its waxy, rough, and gummy veneer and reveal a smooth surface. This substantially improved its hygroscopic nature, superhydrophilicity, and water-retention, while preserving its mechanical durability in dry and wet environments. The hygroscopic ramie exhibited underwater superoleophobicity and self-cleaning abilities against highly adhesive LSFOs. Two proofs-of-concept are demonstrated in this study—an oil-proof glove for maximizing oil repellency and a direct oil-scooping device for simple and continuous recovery of spilled oil with high efficiency.

The removal of organic pollutants presents a major challenge for drinking water treatment plants. The chemical oxygen demand (COD) is essentially the measure of oxidizable organic matter in source waters. In this study, we report that COD can efficiently be decreased by adding Fe(II)/Fe(III) and sulfite ion to the source water while purging it with air. In this process, oxygen is activated to oxidize the main constituents of COD, i.e. organic substrates, via the generation of reactive inorganic oxysulfur radical ions. In the end, the total amount of sulfur(IV) is converted to the non-toxic sulfate ion. It has been explored how the COD removal efficiency depends on the concentration of S(IV), the total concentration of iron species, the concentration ratio of Fe(II) and Fe(III), the purging rate and the contact time by using source water from a specific location (Királyhegyes, Hungary). The process has been optimized by applying the Response Surface Methodology (RSM). Under optimum conditions, the predicted and experimentally found COD removal efficiencies are in excellent agreement: 85.4% and 87.5%, respectively. The robustness of the process was tested by varying the optimum values of the parameters by ± 20%. It was demonstrated that the method is universally applicable because a remarkable decrease was achieved in COD, 62.0–88.5%, with source waters of various compositions acquired from 9 wells at other locations using the same conditions as in the case of Királyhegyes.

We investigated the biological response of soluble organic fraction (SOF) and water-soluble fraction (WSF) extracted from particulate matter (PM) emitted by an automotive diesel engine operating in a representative urban driving condition. The engine was fueled with ultra-low sulfur diesel (ULSD), and its binary blends by volume with 13% of butanol (Bu13), and with hydrotreated vegetable oil (HVO) at 13% (HVO13) and 20% (HVO20). Cytotoxicity, genotoxicity, oxidative DNA damage and ecotoxicity tests were carried out, and 16 polycyclic aromatic hydrocarbons (PAH) expressed as tbenzo(a)pyrene total toxicity equivalent (BaP-TEQ) were also analyzed. The Hepatocarcinoma epithelial cell line (HepG2) was exposed to SOF for 24 h and analyzed using comet assay, with the inclusion of formamidopyrimidine DNA glycosylase (FPG) and endonuclease III (Endo III) to recognize oxidized DNA bases. The WSF was evaluated through acute ecotoxicity tests with the aquatic microcrustacean Daphnia pulex (D. Pulex). Results showed that there was no cytotoxic activity for all tested SOF concentrations. Genotoxic responses by all the SOF samples were at same level, except for the HVO13 which was weaker in the absence of the enzymes. The addition of the FPG and Endo III enzymes resulted in a significant increase in the comet tail, indicating that the DNA damage from SOF for all tested fuel blends involves oxidative damage including a higher level of oxidized purines for ULSD and Bu13 in comparison with HVO blends, but the oxidized pyrimidines for HVO blends were slightly higher compared to Bu13. The WSF did not show acute ecotoxicity for any of the fuels. Unlike other samples, Bu13-derived particles significantly increase the BaP-TEQ. The contribution to the genotoxic activity and oxidative DNA from SOF was not correlated to BaP-TEQ, which means that the biological activity of PM might be affected also by other toxic compounds present in particulate phase.

Evidence suggests that the invasion of Spartina alterniflora (S. alterniflora) poses potentially serious risks to the stability of coastal wetlands, an ecosystem that is extremely vulnerable to both biological and non-biological threats. However, the effects and mechanisms of sulfur (S) in mediating the growth and expansion of S. alterniflora are poorly understood, particularly when sediments are contaminated with cadmium (Cd). A 6-month greenhouse study was conducted to evaluate the mediating effect of S on Cd tolerance and growth of S. alterniflora. Treatments consisted of a factorial combination of three S rates (applied as Na₂SO₄; 0, 500, 1000 mg kg⁻¹ dry weight (DW), as S₀, S₅₀₀, and S₁₀₀₀) and four Cd rates (applied as CdCl₂; 0, 1, 2, 4 mg kg⁻¹ DW, as Cd₀, Cd₁, Cd₂, and Cd₄). Results showed that although the exogenous S supply obviously increased Cd accumulation in roots (up to 71.22 ± 6.43 mg kg⁻¹ DW) due to the decrease of Fe concentration in iron plaque (down to 4.02 ± 1.18 mg g⁻¹ DW), biomass reduction and oxidative stress in plant tissues were significantly alleviated. The addition of S significantly up-regulated the concentration of compounds related to Cd tolerance, including proline and glutathione. Therefore, the translocation of Cd was restricted, and plant growth was not impacted. The present study demonstrated that the exogenous sulfur supply could promote the growth of S. alterniflora and enhance its tolerance to Cd. Therefore, under the effects of S. alterniflora, the increased fluctuations of S pool caused by the release and deposition of S might further exacerbate S. alterniflora expansion in Cd contaminated coastal wetlands.

The effectiveness and feasibility of the three biochar materials for remediation of arsenic (As) and lead (Pb) contaminated soil were explored in this study. Significant reduction of bioaccessibility and migration risks of both heavy metals have been explained mechanistically by incubation, column experiments and numerical simulation. Langmuir equation fitted As and Pb sorption isotherms better in the control and biochar (BC) amended soils, while Freundlich model was more suitable for iron modified biochar (Fe-BC) and sulfur/iron modified biochar (S/Fe-BC) amended soils, indicating that modified biochar promoted chemical adsorption process for As and Pb. For the three biochar materials, S/Fe-BC showed the best effects on reducing the bioavailability of As and Pb, with a decrease of 40.42%–64.21%. The reduction in bioaccessibility by metal portioning into available and non-available fractions was better for illustrating the mechanisms including adsorption, precipitation/coprecipitation and As(III) oxidation behind S/Fe-BC efficacy. Moreover, S/Fe-BC can effectively inhibit the leaching behavior of As and Pb under acid rain, which increased by 99.89% and 90.18%, respectively, compared with the control. The HYDRUS-1D modeling indicated that S/Fe-BC could continuously treat As (100 mg/L) and Pb (1000 mg/L) contaminated water for 16.22 years and 40.86 years, respectively, and ensure the groundwater quality criteria being met. Based on these insights, we believe that our study will provide meaningful information about the potentials of biochar derived materials for soil heavy metals’ remediation.

Laboratory experiments and point observations, for instance in wetlands, have shown evidence that microbial sulfate reduction (MSR) can lower sulfate and toxic metal concentrations in acid mine drainage (AMD). We here hypothesize that MSR can impact the fate of AMD in entire catchments. To test this, we developed a sulfur isotope fractionation and mass-balance method, and applied it at multiple locations in the catchment of an abandoned copper mine (Nautanen, northern Sweden). Results showed that MSR caused considerable, catchment-scale immobilization of sulfur corresponding to a retention of 27 ± 15% under unfrozen conditions in the summer season, with local values ranging between 13 ± 10% and 53 ± 18%. Present evidence of extensive MSR in Nautanen, together with previous evidence of local MSR occurring under many different conditions, suggest that field-scale MSR is most likely important also at other AMD sites, where retention of AMD may be enhanced through nature-based solutions. More generally, the developed isotope fractionation analysis scheme provides a relatively simple tool for quantification of spatio-temporal trends in MSR, answering to the emerging need of pollution control from cumulative anthropogenic pressures in the landscape, where strategies taking advantage of MSR can provide viable options.

It has been shown that chemical modification of chitosan with sulfur (S) functional groups could significantly enhance its chelating capability with heavy metals included Cd(II). However, a molecular level understanding has been lacking. Here, we carried out X-ray absorption fine structure (XAFS) and Fourier transformed infrared (FTIR) spectra studies to bridge this knowledge gap. The results indicate that both Cd–O/N and Cd–S bonds exist in the complex of Cd(II) with dithiocarbamate chitosan (DTC-CTS). S functional groups (dithiocarbamate) in DTC-CTS play the major role in complexation with Cd(II) and S content affects the adsorption mechanism. At low S content, Cd(II) is mainly adsorbed on DTC-CTS as an outer-sphere complex with two monodentate amino groups and two water molecules in tetrahedral configuration. At high S content, Cd adsorption dominantly occurs by formation of an inner-sphere complex with two bidentate mononuclear S ligands in tetrahedral configuration. This investigation provides information on the effectiveness and mechanisms of Cd(II) removal that is critical for evaluating modified chitosan applications for stabilization of Cd(II) in surface water, groundwater, soils and sediments.

The occurrence of veterinary antibiotics and hydro-chemical parameters in eleven natural springs in a livestock production area is evaluated, jointly with the characterization of their DOM fingerprint by Orbitrap HRMS. Tetracycline and sulfonamide antibiotics were ubiquitous in all sites, and they were detected at low ng L⁻¹ concentrations, except for doxycycline, that was present at μg L⁻¹ in one location. DOM analysis revealed that most molecular formulas were CHO compounds (49 %–68 %), with a remarkable percentage containing nitrogen and sulphur (16 %–23 % and 11 %–24 %, respectively). Major DOM components were phenolic and highly unsaturated compounds (~90 %), typical for soil-derived organic matter, while approximately 11 % were unsaturated aliphatic, suggesting that springs may be susceptible to anthropogenic contamination sources. Comparing the DOM fingerprint among sites, the spring showing the most different profile was the one with surface water interaction and characterized by having lower CHO and higher CHOS formulas and aliphatic compounds. Correlations between antibiotics and DOM showed that tetracyclines positively correlate with unsaturated oxygen-rich substances, while sulfonamides relate with aliphatic and unsaturated oxygen-poor compounds. This indicates that the fate of different antibiotics will be controlled by the type of DOM present in groundwater.