Partitioning between nitrate reduction pathways, denitrification and dissimilatory nitrate reduction to ammonium (DNRA) determines the fate of nitrate removal and thus it is of great ecological importance. Sulfide (S²⁻) is a potentially important factor that influences the role of denitrification and DNRA. However, information on the impact of microbial mechanisms for S²⁻ on the partitioning of nitrate reduction pathways in freshwater environments is still lacking. This study investigated the effects of long-term (108 d) S²⁻ addition on nitrate reduction pathways and microbial communities in the sediments of two different freshwater lakes. The results show that the increasing S²⁻ addition enhanced the coupling of S²⁻ oxidation with denitrification instead of DNRA. The sulfide-oxidizing denitrifier, Thiobacillus, was significantly enriched in the incubations of both lake samples with S²⁻ addition, which indicates that it may be the key genus driving sulfide-oxidizing denitrification in the lake sediments. During S²⁻ incubation of the Hongze Lake sample, which had lower inherent organic carbon (C) and sulfate (SO₄²⁻), Thiobacillus was more enriched and played a dominant role in the microbial community; while during that of the Nansi Lake sample, which had higher inherent organic C and SO₄²⁻, Thiobacillus was less enriched, but increasing abundances of sulfate reducing bacteria (Desulfomicrobium, Desulfatitalea and Geothermobacter) were observed. Moreover, sulfide-oxidizing denitrifiers and sulfate reducers were enriched in the Nansi Lake control treatment without external S²⁻ input, which suggests that internal sulfate release may promote the cooperation between sulfide-oxidizing denitrifiers and sulfate reducers. This study highlights the importance of sulfide-driven denitrification and the close coupling between the N and S cycles in freshwater environments, which are factors that have often been overlooked.

The microbiome has been described as an additional host “organ” with well-established beneficial roles. However, the effects of exposures to chemicals on both structure and function of the gut microbiome of fishes are understudied. To determine effects of benzo[a]pyrene (BaP), a model persistent organic pollutant, on structural shifts of gut microbiome in juvenile fathead minnows (Pimephales promelas), fish were exposed ad libitum in the diet to concentrations of 1, 10, 100, or 1000 μg BaP g⁻¹ food, in addition to a vehicle control, for two weeks. To determine the link between exposure to BaP and changes in the microbial community, concentrations of metabolites of BaP were measured in fish bile and 16S rRNA amplicon sequencing was used to evaluate the microbiome. Exposure to BaP only reduced alpha-diversity at the greatest exposure concentrations. However, it did alter community composition assessed as differential abundance of taxa and reduced network complexity of the microbial community in all exposure groups. Results presented here illustrate that environmentally-relevant concentrations of BaP can alter the diversity of the gut microbiome and community network connectivity.

This research was designed to investigate changes that can arise in an invertebrate organism due to stress caused by a strong prooxidant, graphene oxide (GO), and a potent antioxidant, vitamin C. The study aimed to investigate if vitamin C may support convalescence after chronic GO intoxication. We investigated the toxicity of chronic dietary graphene oxide administration in house cricket (Acheta domesticus) types: wild and selected for longevity (with a better developed antioxidant system, conducive to long life). Vitamin C was applied immediately after cessation of graphene oxide intoxication to check if it can support the remedial effect. The condition of cells, DNA stability, catalase activity, and the reproduction potential, measured as the Vitellogenin (Vg) protein expression level, were investigated in control and GO treated groups, recovery groups (-GO), and recovery groups with Vit. C (-GO + Vit.C). In this study vitamin C had no evident remedial effect on the house crickets exposed to graphene oxide. Most probably, the mechanism of vitamin C action, in case of intoxication with nanoparticles, is much more complicated. In the context of the results obtained, it is worth considering whether Vit. C, applied after GO intoxication, causes further disturbance of homeostasis in terms of the cells' redox potential.

In addition to endocrine disruption, bisphenol A (BPA) is known to induce inflammation through the activation of nuclear factor-κB (NF-κB). However, detailed studies on the mechanism of NF-κB activation by BPA have not been sufficiently conducted. In the present study, we observed that low concentrations of BPA (≤1 μM) upregulated the release of proinflammatory mediators, including nitric oxide (NO) and prostaglandin E₂ (PGE₂), as well as proinflammatory cytokines, including tumor necrosis factor (TNF)-α, interleukin (IL)-12, and IL-6. Molecular modeling predicted that BPA docked with the Toll-like receptor 4 (TLR4)/myeloid differentiation factor 2 (MD2) complex activates downstream molecules including myeloid differentiation primary response 88 (MyD88) and IL-1 receptor-associated kinase 4 (IRAK-4) and results in the upregulation of the NF-κB signaling pathway. Additionally, BPA increased morphological abnormalities and mortality in zebrafish larvae and enhanced the dispersal of macrophages and neutrophils in the whole body, thereby causing an endotoxemia-like disorder. However, a specific TLR4 inhibitor, TLR4-IN-C34, mitigated BPA-induced mortality and morphological abnormalities, which indicates that the TLR4/MD2 complex is a molecular target of BPA-induced immunotoxicity. Collectively, our results indicate that low concentrations of BPA, which is a potential agonist of the TLR4/MD2 complex, can intensify the immune response and eventually cause an endotoxemia-like disorder.

Cadmium (Cd) pollution is currently the most serious type of heavy metal pollution throughout the world. Previous studies have shown that Cd elevates the mortality of paddy field spiders, but the lethal mechanism remains to be explored profoundly. In the present study, we measured the activities of protective enzymes (acetylcholinesterase, glutathione peroxidase, phenol oxidase) and a heavy metal chelating protein (metallothionein) in the pond wolf spider Pardosa pseudoannulata after Cd exposure. The results indicated that Cd initially increased the enzyme activities and protein concentration of the spider after 10- and 20-day exposure before inhibiting them at 30-day exposure. Further analysis showed that the enzyme activities in the cephalothorax were inhibited to some extent. Since the cephalothorax region contains important venom glands, we performed transcriptome sequencing (RNA-seq) analysis of the venom glands collected from the spiders after long-term Cd exposure. RNA-seq yielded a total of 2826 differentially expressed genes (DEGs), and most of the DEGs were annotated into the process of protein synthesis, processing and degradation. Furthermore, a mass of genes involved in protein recognition and endoplasmic reticulum (ER) -associated protein degradation were down-regulated. The reduction of protease activities supports the view that protein synthesis and degradation in organelles and cytoplasm were dramatically inhibited. Collectively, our outcomes illustrate that Cd poses adverse effects on the expression of protective enzymes and protein, which potentially down-regulates the immune function in the venom glands of the spiders via the alteration of protein processing and degradation in the ER.

Marine canopies formed by seagrass and other coastal vegetated ecosystems could act as sinks of microplastics for being efficient particle traps. Here we investigated for the first time the occurrence of microplastic retention by marine canopies in a hydraulic flume under unidirectional flow velocities from 2 to 30 cm s⁻¹. We used as model canopy-forming species the seagrass Zostera marina with four canopy shoot density (0, 50, 100, 200 shoots m⁻²), and we used as microplastic particles industrial pristine pellets with specific densities from 0.90 to 1.34 g cm⁻³ (polypropylene PP; polystyrene PS; polyamide 6 PA; and polyethylene terephthalate PET). Overall, microplastics particles transported with the flow were retained in the seagrass canopies but not in bare sand. While seagrass canopies retained floating microplastics (PP) only at low velocities (<12 cm s⁻¹) due to a barrier created by the canopy touching the water surface, the retention of sinking particles (PS, PA, PET) occurred across a wider range of flow velocities. Our simulations revealed that less dense sinking particles (PS) might escape from the canopy at high velocities, while denser sinking particles can be trapped in scouring areas created by erosive processes around the eelgrass shoots. Our results show that marine canopies might act as potential barriers or sinks for microplastics at certain bio-physical conditions, with the probability of retention generally increasing with the seagrass shoot density and polymer specific density and decreasing with the flow velocity. We conclude that seagrass meadows, and other aquatic canopy-forming ecosystems, should be prioritized habitats in assessment of microplastic exposure and impact on coastal areas since they may accumulate high concentration of microplastic particles that could affect associated fauna.

This paper proposes a holistic approach to connect anthropogenic impacts to environmental remediation solutions. The eDPSIR (engineered-Drivers-Pressures-States-Impacts-Responses) framework aims at supporting the decision-maker in designing technological solutions for a contaminated coastal area, where the natural matrices need to be cleaned up. The eDPSIR is characterized by cause-effect relationships that are operationally implemented through three multidisciplinary toolboxes: (i) Toolbox 1, to connect driving forces with pressures, classifying the state of the system and allowing the identification of target contaminants and the extent of contamination; (ii) Toolbox 2, to quantify bioaccumulation also by identifying corresponding areas; (iii) Toolbox 3, to identify the most suitable remediation solutions for previously identified contaminated areas, named contamination scenarios. The eDPSIR was calibrated on the case study of the Mar Piccolo in Taranto (Southern Italy), one of the most complex and polluted areas in Europe. While the consolidated DPSIR allows for a strategic response by limiting the use of contaminated areas or reducing upstream pressures, the eDPSIR made it possible to structure with a semi-quantitative logic the problem of assisting the decision-makers in choosing the optimal technological remediation responses for each sediment scenario of contamination (heavy metal; organic compounds; mixed). Assisted natural attenuation was identified as the best remediation technology in terms of treatment effectiveness and smallest amount of impacts involved in the project actions. However, considering the scenario of mixed contamination, in-situ reactive capping reached a good rank with a value of the composite indicator equal to 99.5%; thermal desorption and stabilization/solidification recorded a value of 94.1% and 84.6%, respectively. The application of these toolboxes provides alternative means to interpret, manage, and solve different cases of global marine contaminated sites.

Uranyl carbonate (UC(VI)) is a stable form of uranyl (U(VI)) that widely coexists with amorphous colloidal silica (ACSi) and humic acid (HA) in carbonate-rich U-contaminated areas. In this context, the cotransport behavior and mechanism of UC(VI) with ACSi (100 mg L⁻¹) and HA colloids in saturated porous media were systematically investigated. It was found that the ACSi and strip-shaped HA have a strong adsorption capacity for UC(VI), and their adsorption distribution coefficient (Kd) is 4–5 orders of magnitude higher than that of quartz sand (QS). In the ternary system, UC(VI) was mainly existing in the colloid-associated form at low UC(VI) concentration (4.2 × 10⁻⁶ M). Compared with the individual transport of UC(VI), the presence of ACSi and strip-shaped HA in the binary system promotes the transport of low-concentration UC(VI) (4.2 × 10⁻⁶ M) but shows a hindering effect when UC(VI) = 2.1 × 10⁻⁵ M. When ionic strength (IS) increased from 0 to 100 mM, the individual transport of UC(VI) and ACSi was weakened owing to the masking effect and the compression of the electrical double layer, respectively; this weakening effect is more pronounced in the binary (UC(VI)–ACSi) system. Notably, the transport of UC(VI) and ACSi in the ternary system is independent of the changes in IS due to the surface charge homogeneity strengthening the electrostatic repulsion between HA and QS. The Derjaguin–Landau–Verwey–Overbeek theory and retention profiles reveal the co-deposition mechanism of ACSi and UC(VI) in the column under different hydrochemical conditions. The nonequilibrium two-site model and the mathematical colloidal model successfully described the breakthrough data of UC(VI) and ACSi, respectively. These results are helpful for evaluating the pollution caused by UC(VI) migration in an environment rich in HA and formulating corresponding effective control strategies.

Increased metal concentrations in aquatic habitats come as a result of both anthropogenic and natural sources. Emerging aquatic insects that play an indispensable role in these environments, transferring resources and energy to higher trophic levels in both aquatic and terrestrial habitats, may inadvertently also act as biovectors for metals and other contaminants. This study measured levels of 22 different metals detected in biofilm, aquatic and terrestrial life stages of Trichoptera and Odonata, as well as riparian spiders, to examine the uptake and transfer from freshwater to terrestrial ecosystems. We show that emerging insects transfer metals from aquatic to terrestrial ecosystems, however with large losses observed on the boundary of these two environments. Significantly lower concentrations of most metals in adult insects were observed in both hemimetabolous (Odonata) and holometabolous insect orders (Trichoptera). In holometabolous Trichoptera, however, this difference was greater between aquatic life stages (larvae to pupae) compared to that between pupae and adults. Trophic transfer may have also played a role in decreasing metal concentrations, as metal concentrations generally adhered to the following pattern: biofilm > aquatic insects > terrestrial invertebrates. Exceptions to this observation were detected with a handful of essential (Cu, Zn, Se) and non-essential metals (Cd, Ag), which measured higher concentrations in adult aquatic insects compared to their larval counterparts, as well as in aquatic and terrestrial predators compared to their prey. Overall, all metals were found to be bioavailable and biotransferred from contaminated waters to terrestrial invertebrates to some degree, suggesting that risks associated with metal-contaminated freshwaters could extend to terrestrial systems through the emergence of these potential invertebrate biovectors.

Although it is known that increases in ambient particulate matter (PM) levels are associated with elevated occurrence of adverse health outcomes, the understanding of the mechanisms of PM-related health effects is limited by our knowledge of how particle size and composition are altered subsequent to inhalation through respiratory-deposited processing. Here we present a particle-generated hydroxyl radical (·OH) study of the size-resolved particles as particles are inhaled in the human respiratory tract (RT), and we show that accumulation-mode particles are significant factors (71–75%) in ·OH generation of lung-deposited particles using Multiple-Path Particle Dosimetry (MPPD) model. The ability of PM to catalyze ·OH generation is mainly related to transition metals, particularly towards the upper regions of the RT (75%), and to quinones deeper in the lung (42–46%). Identification of this generation ability induced by chemical composition has shown that four potential sources (biomass burning, incomplete combustion, mobile & industry, and mineral dust) are responsible for ·OH generation. With ·OH-forming ability after PM inhalation implicated as the first step towards revealing the subsequent toxic processes, this work draws a connection between the detailed ·OH chemistry occurring on size-resolved particles and a possible toxicological mechanism based on chemical composition and sources.