The presence of abundant extracellular polymeric substances (EPS) play a vital role in affecting heteroaggregation process and toxicity of nanoparticles (NPs) to Microcystis aeruginosa. Interactions between n-CeO₂ and cyanobacteria with/without EPS and the toxicity of n-CeO₂ to M. aeruginosa were investigated in this study. Aggregation kinetics of n-CeO₂ under both soluble EPS (SEPS) and bound EPS (BEPS) indicated the presence of EPS could induced the formation of EPS-NPs aggregates. Heteroaggregation between cells and n-CeO₂ was confirmed through co-settling experiment and SEM-EDS observation. SEPS contributed to the observable heteroaggregation using spectral measurement. Heteroaggregation between cells and n-CeO2 under no BEPS was hardly obtained through spectral measurement, but SEM-EDS observation convinced this process. And the DLVO theory explained this heteroaggregation process under various EPS conditions, where the energy barrier decreased with gradual EPS extraction. In addition, the order for 96 h half growth inhibition concentration (IC₅₀) was Raw M9 > M9-SEPS > M9+BEPS > M9-BEPS. These results revealed that not all heteroaggregation between cell-NPs can lead to the NPs toxicity to cells. BEPS act more important role in buffering against the toxicity of NPs from ambient adverse factors, but SEPS increase the stability of NPs which could aggravate the adverse effects of NPs in the environment.

The effect of health status on the relationship between particulate matter (PM) and black carbon (BC) and cardiac autonomic function has not been examined sufficiently directly comparing patients with healthy participants.To evaluate the association patterns between size-fractioned indoor PM and BC and cardiac autonomic function in chronic obstructive pulmonary disease (COPD) patients and their healthy spouses.Twenty-four-hour heart rate variability (HRV) and heart rate (HR) was measured in eight pairs of stable COPD patients and their healthy spouses. Real-time size-fractioned indoor PM and BC levels were monitored on the same, and preceding, days. Mixed-effects models were used to estimate the changes in health indices and pollutants after controlling for potential confounding variables.Increases in size-fractioned PM and BC were associated with alterations in cardiac autonomic function in both COPD patients and their healthy spouses. However, the association patterns differed between the two groups. In COPD group, an IQR (13.65 μg/m3) increase in PM0.5 at 12-h moving average was associated with reductions of 14.62% (95% CI: -21.74%, -6.86%) in total power (TP) and 10.14% (95% CI: -16.11%, -3.76%) in high frequency (HF) power. In healthy volunteers, however, TP and HF declined immediately upon exposure to PM and then returned to normal levels gradually. In this group, an IQR increase in PM0.5 at 5 min moving average was associated a 20.30% (95% CI: -25.49%, -14.73%) reduction in TP and a 31.79% (95% CI: -36.48%, -26.72%) reduction in HF.Exposure to indoor PM and BC was associated with cardiac autonomic dysfunction in COPD patients and their healthy spouses. Exposure had a greater lagged effect on HRV in COPD patients than in healthy participants. These findings will aid the formulation of targeted measures to prevent the adverse effects of indoor air pollution for individuals with different health statuses.

Applying an electric field to stimulate the microbial reductive dechlorination of polychlorinated biphenyls (PCBs) represents a promising approach for bioremediation of PCB-contaminated sites. This study aimed to demonstrate the biocathodic film-facilitated reduction of PCB 61 in a sediment-based bioelectrochemical reactor (BER) and, more importantly, the characterizations of electrode-microbe interaction from microbial and electrochemical perspectives particularly in a time-dependent manner. The application of a cathodic potential (−0.45 V vs. SHE) significantly improved the rate and extent of PCB 61 dechlorination compared to the open-circuit scenario (without electrical stimulation), and the addition of an external surfactant further increased the dechlorination, with Tween 80 exerting more pronounced effects than rhamnolipid. The bacterial composition of the biofilms and the bioelectrochemical kinetics of the BERs were found to be time-dependent and to vary considerably with the incubation time and slightly with the coexistence of an external surfactant. Excellent correlations were observed between the dechlorination rate and the relative abundance of Dehalogenimonas, Dechloromonas, and Geobacter, the dechlorination rate and the cathodic current density recorded from the chronoamperometry tests, and the dechlorination rate and the charge transfer resistance derived from the electrochemical impedance tests, with respect to the 120 day-operation. After day 120, PCB 61 was resistant to further appreciable reduction, but substantial hydrogen production was detected, and the bacterial community and electrochemical parameters observed on day 180 were not distinctly different from those on day 120.

Secondary salinization represents a global threat to freshwater ecosystems. Salts, such as NaCl, can be toxic to freshwater organisms and may also modify the outcome of species interactions (e.g. host-parasite interactions). In nature, hosts and their parasites are embedded in complex communities where they face anthropogenic and biotic (i.e. predators) stressors that influence host-parasite interactions. As human populations grow, considering how anthropogenic and natural stressors interact to shape host-parasite interactions will become increasingly important. We conducted two experiments investigating: (1) the effects of NaCl on tadpole susceptibility to trematodes and (2) whether density- and trait-mediated effects of a parasite-predator (i.e. damselfly) and a host-predator (i.e. dragonfly), respectively, modify the effects of NaCl on susceptibility to trematode infection. In the first experiment, we exposed tadpoles to three concentrations of NaCl and measured parasite infection in tadpoles. In the second experiment, we conducted a 2 (tadpoles exposed to 0 g L−1 NaCl vs. 1 g L−1 NaCl) x 4 (no predator, free-ranging parasite-predator (damselfly), non-lethal host-predator (dragonfly kairomone), and free-ranging parasite-predator + dragonfly kairomone) factorial experiment. In the absence of predators, exposure to NaCl increased parasite infection. Of the predator treatments, NaCl only caused an increase in parasite infection in the presence of the parasite-predator. However, direct consumption of trematodes caused a reduction in overall infection in the parasite-predator treatment. In the dragonfly kairomone treatment, a reduction in tadpole movement (i.e. trematode avoidance behavior) led to an increase in overall infection. In the parasite-predator + dragonfly kairomone treatment, antagonistic effects of the parasite-predator (reduction in trematode abundance) and dragonfly kairomone (reduction in parasite avoidance behavior) resulted in intermediate parasite infection. Collectively, these findings demonstrate that NaCl can increase amphibian susceptibility to parasites, and underscores the importance of considering predator-mediated interactions in understanding how contaminants influence host-parasite interactions.

The Mediterranean Sea has been described as one of the most affected areas by marine litter in the world. Although effects on organisms from marine plastic litter ingestion have been investigated in several oceanic areas, there is still a lack of information from the Mediterranean Sea. The main objectives of this paper are to review current knowledge on the impact of marine litter on Mediterranean biodiversity, to define selection criteria for choosing marine organisms suitable for use as bioindicator species, and to propose a methodological approach to assessing the harm related to marine litter ingestion in several Mediterranean habitats and sub-regions. A new integrated monitoring tool that would provide the information necessary to design and implement future mitigation actions in the Mediterranean basin is proposed.According to bibliographic research and statistical analysis on current knowledge of marine litter ingestion, the area of the Mediterranean most studied, in terms of number of species and papers in the Mediterranean Sea is the western sub-area as well as demersal (32.9%) and pelagic (27.7%) amongst habitats.Applying ecological and biological criteria to the most threatened species obtained by statistical analysis, bioindicator species for different habitats and monitoring scale were selected. A threefold approach, simultaneously measuring the presence and effects of plastic, can provide the actual harm and sub-lethal effects to organisms caused by marine litter ingestion. The research revealed gaps in knowledge, and this paper suggests measures to close the gap. This and the selection of appropriate bioindicator species would represent a step forward for marine litter risk assessment, and the implementation of future actions and mitigation measures for specific Mediterranean areas, habitats and species affected by marine litter ingestion.

Silver nanoparticles (nAg), due to their biocidal properties, are common in medical applications and are used in more consumer products than any other engineered nanomaterial. This growing abundance, combined with their ability to translocate across the epithelium and bioaccumulate, suggests that internalized nAg may present a risk of toxicity to many organisms in the future. However, little experimentation has been devoted to cardiac responses to acute nAg exposure, even though nAg is known to disrupt ion channels even when ionic Ag+ does not. In this study, we examined the cardiac response to nAg exposure relative to a sham and an ionic AgNO3 control across cardiomyocyte survival and homeostasis, ventricular contractility, and intrinsic pacing rates of whole hearts. Our results suggest that nAg, but not Ag+ alone, inhibits force production by the myocardium, that Ag in any form disrupts normal pacing of cardiac contractions, and that these responses are likely not due to cytotoxicity. This evidence of nanoparticle-specific effects on physiology should encourage further research into nAg cardiotoxicity and other potential sublethal effects.

Small heterotrophic protists (flagellates and naked amoebae) are very abundant in soil and play a key role in maintaining soil services. Hence, knowledge on how xenobiotics affect these organisms is essential in ecosystem management. Cadmium (Cd) is an increasing environmental issue as both industrial deposition and recycling of heavy metal rich waste products have led to Cd enrichment of soils. Evaluation of toxicity of Cd to micro-organisms is often performed using a solution of pure Cd (e.g. CdCl) in liquid culture. This approach may be highly misleading as interactions between Cd and other substances, e.g. various ions or inherent soil components often strongly modify Cd toxicity. Hence, we compared the toxic effect of Cd to small heterotrophic protists in soil microcosms and liquid culture. We also evaluated how zinc (Zn) affects Cd toxicity, as Zn usually accompanies Cd in a ratio of c. 100:1, and is known to impede Cd toxicity. In the soil microcosms, we also monitored the primary food source of the protists, i.e. culturable bacteria, and used soil respiration as a proxy of soil functioning. Finally, we examined to what extent Cd actually sorbs to soil. We found 1) that c. 10³ times more Cd was required to obtain the same effect in the soil microcosms compared to the liquid culture, 2) that soil sorption explains why Cd, even though highly toxic in aqueous solutions, has very limited effect when applied to soil, and 3) (very surprisingly) that in our experimental systems Zn was as toxic as Cd. Our study suggests that Cd toxicity to soil protists will be small because most Cd in soil will be sorbed to the soil matrix and because the Zn:Cd ratio of 100:1 in most substances, incl. pollutants, will mean that lethal Zn effects will occur before Cd reaches toxic levels.

α, β and γ-hexachlorocyclohexane (HCH) are persistent and bioaccumulative pollutants and they were included in the Stockholm Convention on Persistent Organic Pollutants (POPs). Old lindane factories generated high amounts of wastes with HCH and other Chlorinated Organic Compounds (COCS). These were often dumped in the surroundings of the production sites, polluting soil and groundwaters with the associated risk of surface pollution. This is the case of the Sardas and Bailin landfills, located in Sabiñánigo (Huesca, Spain). Among the waste from lindane production, a liquid residue was detected in the landfill subsurfaces, forming a dense non-aqueous phase liquid (DNAPL) composed of HCH isomers, benzene and chlorobenzenes, with a high impact on groundwater pollution. In this study, six DNAPL samples obtained from the Bailin and Sardas landfills were analyzed by GC/MSD and GC/FID/ECD. Compounds were identified using mass spectra and the retention index from pure standards and literature information. Pure positional isomers of dichlorobenzene (DCB), trichlorobenzene (TCB), tetrachlorobenzene (TetraCB), HCH and pentachlorocyclohexene (PentaCX) were distinguished and quantified. In addition, heptachlorocyclohexane (HeptaCH) isomers, precursors of hexacholorocylohexene (HexaCX), were also identified and quantified in the DNAPL samples, although the corresponding isomers could not be discriminated. Information about PentaCX, HexaCx and HeptaCH identification is very limited in the literature. HCH contents in the DNAPL ranged from 22% to 30% in weight, the major isomers being lindane and δ-HCH, followed by α-HCH. The β isomer was the least abundant. HeptaCH contents were present in the same order of magnitude as HCHs in the DNAPL. PentaCXs and HexaCXs could have appeared as dehydrochlorination derivatives of HCHs and HeptaCHs, respectively. Two of the DNAPLs analyzed showed a higher content of TCBs and TetraCBs, associated with lower HCH and HeptaCH contents. Variations of these compounds in the DNAPL could be related to an alkaline dehydrochlorination in the landfill conditions.

This study aimed to develop a novel in-situ method to directly remove toxic hexavalent chromium anions from groundwater. The characteristics of Mg/Al-layered double hydroxides (LDH) involving in-situ synthesis and interlayer exchangeable anions can facilitate to remove Cr(VI) from solution. Two different methods of LDH preparation were employed to explore the adsorption efficiency of (di)chromates, such as traditional coprecipitation (CO₃-LDH) and innovative in-situ synthesis (in-situ-LDH). The synthesized LDH samples were characterized using scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and zeta potential. The results demonstrated that the adsorptive amount of Cr(VI) for the in-situ synthesis process dramatically increased with an increase in initial Cr(VI) concentrations from 100 mg/L to 900 mg/L. The kinetic study indicated that the constant rate (k₂) of the pseudo-second-order equation significantly decreased when the initial concentration of Cr(VI) exceeded 500 mg/L. The removal efficiency of Cr(VI) was slightly dependent on solution pH (5.0–12) values. The in-situ-LDH absorbent (339 mg/g) exhibited the significantly higher Langmuir maximum adsorption capacity than CO₃-LDH (246 mg/g). The primary adsorption mechanism was anion exchange; meanwhile, the adsorption-coupled reduction mechanism also played an integral role. The advanced in-situ synthetic method can be developed to efficiently remove toxic hexavalent chromium anions from groundwater.

Packed column experiments were conducted to investigate the transport and blocking behavior of surfactant- and polymer-stabilized engineered silver nanoparticles (Ag-ENPs) in saturated natural aquifer media with varying content of material < 0.063 mm in diameter (silt and clay fraction), background solution chemistry, and flow velocity. Breakthrough curves for Ag-ENPs exhibited blocking behavior that frequently produced a delay in arrival time in comparison to a conservative tracer that was dependent on the physicochemical conditions, and then a rapid increase in the effluent concentration of Ag-ENPs. This breakthrough behavior was accurately described using one or two irreversible retention sites that accounted for Langmuirian blocking on one site. Simulated values for the total retention rate coefficient and the maximum solid phase concentration of Ag-ENPs increased with increasing solution ionic strength, cation valence, clay and silt content, decreasing flow velocity, and for polymer-instead of surfactant-stabilized Ag-ENPs. Increased Ag-ENP retention with ionic strength occurred because of compression of the double layer and lower magnitudes in the zeta potential, whereas lower velocities increased the residence time and decreased the hydrodynamics forces. Enhanced Ag-ENP interactions with cation valence and clay were attributed to the creation of cation bridging in the presence of Ca2+. The delay in breakthrough was always more pronounced for polymer-than surfactant-stabilized Ag-ENPs, because of differences in the properties of the stabilizing agents and the magnitude of their zeta-potential was lower. Our results clearly indicate that the long-term transport behavior of Ag-ENPs in natural, silicate dominated aquifer material will be strongly dependent on blocking behavior that changes with the physicochemical conditions and enhanced Ag-ENP transport may occur when retention sites are filled.