Sewage sludge contains Ag₂S-NPs causing NP exposure of soil fauna when sludge is applied as soil amendment. Earthworm bioturbation is an important process affecting many soil functions. Bioturbation may be affected by the presence of Ag₂S-NPs, but the earthworm activity itself may also influence the displacement of these NPs that otherwise show little transport in the soil. The aim of this study was to determine effects of Ag₂S-NPs on earthworm bioturbation and effect of this bioturbation on the vertical distribution of Ag₂S-NPs. Columns (12 cm) of a sandy loamy soil with and without Lumbricus rubellus were prepared with and without 10 mg Ag kg⁻¹, applied as Ag₂S-NPs in the top 2 cm of the soil, while artificial rainwater was applied at ∼1.2 mm day⁻¹. The soil columns were sampled at three depths weekly for 28 days and leachate collected from the bottom. Total Ag measurements showed more displacement of Ag to deeper soil layers in the columns with earthworms. The application of rain only did not significantly affect Ag transport in the soil. No Ag was detected in column leachates. X-ray tomography showed that changes in macro porosity and pore size distribution as a result of bioturbation were not different between columns with and without Ag₂S-NPs. Earthworm activity was therefore not affected by Ag₂S-NPs at the used exposure concentration. Ag concentrations along the columns and the earthworm density allowed the calculation of the bioturbation rate. The effect on the Ag transport in the soil shows that earthworm burrowing activity is a relevant process that must be taken into account when studying the fate of nanoparticles in soils.

Biochar as a porous carbon material could be used for improving soil physical and chemical properties, while insufficient attention has been paid to potential risks induced by infiltration of heavy metals in the runoff water flowing through biochar-amended soil. Four different soil-biochar matrices with same volumes were constructed including soil alone (M1), biochar alone (M2), soil-biochar layering (M3) and soil-biochar mixing (M4). Leaching experiments were conducted with Pb, Cu, and Zn contaminated runoff water. Results showed that biochar amendment greatly improved the water permeation, and the infiltration rates in M2, M3, and M4 were 2.85–23.0 mm min⁻¹, being much higher than those in M1 (1.33–4.05 mm min⁻¹), though the rates decreased as the leaching volumes increased. However, biochar induced more Pb, Cu, and Zn infiltrated through soil-biochar matrix. After 350-L leaching, M1 retained about 95% Pb, 90% Cu, and 36% Zn, while M2 only retained 4.80% Pb, 17.4% Cu, and 4.01% Zn; about 30% Pb, 80% Cu, and 15% Zn were retained in M3 and M4. Notably, Zn was trapped first and then re-leached into the filtrate, which resulted in a much higher effluent Zn than the influent Zn at the later stage. However, the unit weight of biochar showed a higher capacity for retaining heavy metals compared to per unit of soil. Under the dynamic water flow, all benefits and disadvantages induced by biochar were weakened with its physical disintegration. Biochar as soil amendment can enhance plant growth via ameliorating soil structure, while it would pose risks to environment because of large penetration of heavy metals. If biochar was compacted to form a denser physical structure, perhaps more heavy metals could be retained.

The influence of anthropogenic outdoor sources on the geochemical composition of house dust material in large cities is poorly understood. In this study, we investigate the magnetic signature and the concentrations of potentially toxic elements (PTEs) in randomly selected house dust samples from the metropolitan area of Athens, the most populated city in Greece. Environmental magnetic measurements, including isothermal remanent magnetization and thermomagnetism, indicated that the main magnetic mineral is coarse-grained low-coercivity magnetite. Detailed microscopic observations of the magnetically extracted material revealed the presence of three different kinds of Fe-rich particles deriving from both combustion-related and non-exhaust vehicular sources: irregularly-shaped grains and spherules of Fe-oxides, and particles consisting of metallic Fe. Further study of the morphology of single anthropogenic magnetic spherules (size > 30 μm) identified the presence of magnetite spherical particles, typically formed by industrial combustion processes. Enrichment factors (EFs) for the PTEs calculated against the Athens urban soil showed that the house dusts were very highly enriched in Cd, Cu, Zn and significantly enriched in Pb (median EF values of 34.1, 26.2, 25.4 and 10.3, respectively). The oral bioaccessibility of PTEs in the house dust, evaluated using a simulated gastric solution (0.4 M glycine), was in the order Pb > Zn > Mn > Cd > Ni > Cu > Cr > Fe. Concentrations of Pb increased with the house age. Principal component and cluster analysis demonstrated the close association of anthropogenic Cu, Pb and Zn with the magnetic susceptibility of the house dusts. We conclude that both traffic-related and industrial sources trigger the occurrence of magnetic Fe/PTEs- rich particles in house dust. These results reinforce the use of environmental magnetism determinations for assessing anthropogenic contamination of PTEs in the indoor environment in large cities.

During their lifecycle, many engineered nanoparticles (ENPs) undergo significant transformations that may modify their toxicity, behaviour, and fate in the environment. Therefore, understanding the possible environmentally relevant transformations that ENPs may undergo as a result of their surroundings is becoming increasingly important. This work considers industrially produced ceria (CeO2) and focuses on a particle library consisting of seven zirconium-doped variants (Ce1-xZrxO2) where the Zr doping range is x = 0–1. The study assesses their potential transformation in the presence of environmentally relevant concentrations of phosphate. These ENPs have an important role in the operation of automotive catalysts and therefore may end up in the environment where transformations can take place. Samples were exposed to pH adjusted (c. 5.5) solutions made up of either 1 mM or 5 mM each of KH2PO4, citric acid and ascorbic acid and the transformed particles were characterised by means of DLS – size and zeta potential, UV/VIS, TEM, FT-IR, EDX and XRD. Exposure to the phosphate solutions resulted in chemical and physical changes in all ceria-containing samples to cerium phosphate (with the monazite structure). The transformations were dependent on time, ceria concentration in the particles (Ce:Zr ratio) and phosphate to ceria ratio. The presence of Zr within the doped samples did not inhibit these transformations, yet the pure end member ZrO2 ENPs showed no conversion to phosphate. The quite dramatic changes in size, structure and composition observed raise important questions regarding the relevant form of the materials to investigate in ecotoxicity tests, and for regulations based on one or more dimensions in the nanoscale.

This work evaluates the degradation of benzoic acid, a tracer from biomass burning, by different oxidation agents (Fe (III); H₂O₂; sunlight; and combinations of the previous ones) in model solutions and in real atmospheric waters. The extent of reactions was assessed by Ultraviolet–Visible and molecular fluorescence spectroscopies. The oxidation of benzoic acid occurred with the chemical oxidants Fe (III), H₂O₂, Fe (III) and H₂O₂ simultaneously in the presence of sunlight, and with Fe (III) and H₂O₂ simultaneously in the absence of light. The decrease of the pH value from neutral to acid for atmospheric waters generally increased the extent of oxidation. Sunlight was an important oxidation agent, and its combination with chemical oxidants increased the oxidation rate of benzoic acid, possibly due to the photogeneration of hydroxyl radicals. The results also suggested the occurrence of direct and indirect photolysis of benzoic acid in atmospheric waters. Moreover, the oxidation of benzoic acid produced new and more complex chromophoric compounds, which were then degraded. In addition, the nocturnal period is not sufficient for the full degradation of benzoic acid and of the intermediates formed by Fenton-like oxidation. The diurnal period may be enough for their full degradation through photo-Fenton-like oxidation, but this depends on the composition of the atmospheric waters, namely of the chromophoric content. Thus, this study highlights that benzoic acid from biomass burning, and its derivatives, may persist in atmospheric waters for periods of longer than one day, becoming available for other reactions, and may also affect the terrestrial and aquatic ecosystems through the wet depositions.

Atmospheric particulate matter (PM) pollution levels and human health risks resulting from exposure to non-anthropogenic pollution sources, such as coal mine-fires, are serious global issues. The toxicity of PM₁₀-bound metals and polycyclic aromatic hydrocarbons (PAHs) was assessed according to their non-cancer and cancer risks (CRs) at the mine-fire and in an adjacent city area. Health risks were estimated for inhalation, ingestion, and dermal absorption pathways. The non-cancer risks, presented in terms of the hazard index (HI) and hazard quotient (HQ), were found to be significant (>1) at all locations, except in the mining (for HQ-dermal) and city background area (for HQ-ingestion and HQ-dermal) in children and adults, respectively. The total CR was estimated to be highest at the city nearby the mine-fire area (3.31E-02 and 1.93E-02) followed by the mine-fire area (2.66E-02 and 1.71E-02) for children and adults, respectively. The total CR and CR via individual exposure routes were estimated to be in the high risk (10⁻³ ≤ CR < 10⁻¹) category at the mine-fire site and adjacent city area. For all exposures, CR levels were calculated to be higher than the acceptable range (from 1.00E-06 to 1.00E-04), except for the CR-inhalation level at the A5 location. Among all elements, Cd and BaPₑqᵤ were more significant for the CR at the coal mine-fire and the adjacent city area. Hence, this study concluded that non-anthropogenic sources, such as coal mine-fires, could be part for the significant health risk (carcinogenic and non-carcinogenic) levels in the study area.

Soil and sludge are important pools for microplastics (MPs), however standard separation methods for MPs from these pools are still missing. We tested the widely used methods for MPs extraction from water and sediment to six agriculture surface soils and three sewage sludges from municipal wastewater treatment plants and included an additional pre-digestion procedure with 30% H₂O₂ before floatation to remove soil or sludge organic matter (OM). Extraction efficiency of MPs were evaluated under different separation conditions, including floatation solution (NaCl, ZnCl₂, and NaI), filtration membrane, and oxidation solution. Results showed that H₂O₂ pre-digestion significantly increased MPs extraction in soil and sludge, especially the samples with high OM contents, particularly sludge. Floatation solution with higher densities recovered more MPs. The extra released MPs were mainly small fibrous MPs, probably because they are easily retained by aggregates. Our results provide an feasible separation method for MPs in soil and sludge, i.e., pre-digestion with 30% H₂O₂ at 70 °C, floatation with NaI solution, filtration through nylon membrane, and further oxidation with 30% H₂O₂ + H₂SO₄ or 30% H₂O₂ at 70 °C. About 420–1290 MP items/kg soil were detected in soil samples, while much higher numbers (5553–13460 MP items/kg) were found in sludge samples. The dominate morphology of MPs was white fiber with a size of 0.02–0.25 mm, while the main types of MPs, identified by a micro-Fourier transformed infrared spectroscopy (μ-FTIR), were polyethylene and polypropylene in soil samples and polyethylene, polyethylene terephthalate, and polyacrylonitrile in sludge samples.

Measurements of biological responses on living organisms are essential in aquatic biomonitoring. In freshwaters, Dreissena polymorpha is an invasive bivalve commonly used in ecotoxicological studies and considered as a model organism. However, D. polymorpha abundances are declining while another species colonizes most of the freshwaters: Dreissena rostriformis bugensis. This species has already been studied in ecophysiology but there is still a lack of data concerning its responses to stressors before its use as a bioindicator of environmental pollution. This study aims to compare the responses of the two species exposed to metal stress. Responses at different levels of biological organization were targeted with measurement of sub-cellular and individual biomarkers following an exposure of up to 7 days to cadmium at 10 μg.L−1. At the individual level, the scope for growth (SFG) was measured. It corresponds to the energy allocated to growth and reproduction. D. polymorpha exhibits variations in biomarker measurements as well as in the SFG in presence of Cd. D. r. bugensis shows no variation in its responses at the different targeted levels. According to the present results, energy metabolism seems to have an essential role for these species when facing a metal stress. Different energy allocation strategies were evidenced between the two species, although the link with biochemical biomarkers is more evident for D. polymorpha than for D. r. bugensis.

Nowadays Cylindrospermopsis raciborskii (C. raciborskii) and the metabolites produced, such as cylindrospermopsin (CYN), pose a serious threat to the ecosystem. Advanced oxidation technologies have been verified as constituting a very promising means to eliminate the risk from harmful algae. But so far little research has focused on the visible-light photocatalytic destruction of C. raciborskii cells and the degradation of their metabolites.In our study, N-doped TiO2 (N-TiO2) was used to degrade C. raciborskii and the degradation was compared with that of the Microcystis aeruginosa (M. aeruginosa). Results showed that although the photodegradation of C. raciborskii was more difficult than that of M. aeruginosa, the treatment with N-TiO2 was still satisfactory. After adding 200 mg/L N-TiO2, C. raciborskii cells (5 × 106 cells/mL) were completely destroyed within 20 h under visible light irradiation, and nearly 90% of the organic matter and CYN in the suspensions were also degraded, thereby markedly improving the water quality.The photocatalytic process starts with damage to the cell membrane resulting in the leakage of internal components. Subsequently, the leaked metabolites were oxidised by the reactive oxidizing species produced by N-TiO2. Thus, the application of N-TiO2 is a promising method for the treatment of C. raciborskii.

However the physiological stress in aquatic organisms associated with hydropower plants (HPP) ecosystems has been previously investigated, no studies have so far assessed it on biochemical level. Therefore this study evaluated an oxidative stress and toxicity in the gibel carp Carassius auratus gibelio associated with a small-scale HPP in the West Ukraine. A battery of liver, brain and blood markers was evaluated individuals inhabiting upstream and downstream of the dam of the small-scale Kasperivtci HPP (KHPP; an installed capacity of 7.5 MW), and from a reference site. Number of alterations were noted in fish from the KHPP impoundment facility including signs of oxidative stress (a decrease in superoxide dismutase (SOD) activity and an increase in protein carbonyls) and cytotoxicity (an increase in micronucleated erythrocytes and caspase-3 activity). No changes in DNA fragmentation in hepatocytes or brain cholinesterase activity were detected. As demonstrated by the integral stress index, fish associated with downstream of the dam revealed the greatest alterations reflected by the combined oppression of antioxidant system (SOD, catalase) and pro-oxidants (thiobarbituric acid reactive substances and oxyradicals), low concentration of metallothioneins, but high cathepsin D activity (as markers of lysosomal dysfunction and autophagy) and increased vitellogenin concentration in males (indicating an endocrine disruption). The study highlights that fish inhabiting ecosystems associated with HPP, particularly downstream of the dam, may face additional stresses with long-term effects yet to be evaluated.