International audience | This work investigates the physical-chemical evolution during artificial aging in water of four commercialized sunscreens containing TiO2-based nanocomposites. Sunscreens were analyzed in terms of mineralogy and TiO2 concentration. The residues formed after aging were characterized in size, shape, chemistry and surface properties. The results showed that a significant fraction of nano-TiO2 residues was released from all sunscreens, despite their heterogeneous behaviors. A stable dispersion of submicronic aggregates of nanoparticles was generated, representing up to 38 w/w% of the amount of sunscreen, and containing up to 30% of the total nano-TiO2 initially present in the creams. The stability of the dispersion was tested as a function of salt concentration, revealing that in seawater conditions, a major part of these nano-TiO2 residues will aggregate and sediment. These results were put in perspective with consumption and life cycle of sunscreens to estimate the amount of nano-TiO2 potentially released into AQUATIC environment. (C) 2011 Elsevier Ltd. All rights reserved.

Microplastics (MPs) in soil undergo different aging processes such as photoaging, mechanical abrasion and biodegradation, leading to alterations in the surface properties of MPs. In this study, we investigated the adsorption-desorption of chlorpyrifos (CPF) on pristine and UV light-aged low-density polyethylene (LDPE) and biodegradable (Bio) MPs that were derived from plastic mulch films. We also tested the bioconcentration of pristine and aged MPs (LDPE- and Bio-MPs aged under UV light and LDPE-MPs aged in three different soils) associated with CPF by earthworms (Lumbricus terrestris). The results showed that UV-aged MPs showed higher CPF adsorption capacities than pristine MPs, with the adsorption capacities at 184.9 ± 5.3, 200.5 ± 1.8, 193.0 ± 8.7, and 215.9 ± 1.1 μg g−1 for pristine LDPE-, UV-aged LDPE-, pristine Bio- and UV-aged Bio-MPs, respectively. The desorption rate of CPF from UV-aged LDPE-MPs within 48 h was lower than the desorption from pristine ones (28.8 ± 7.7% vs. 40.0 ± 3.9%), while both pristine and UV-aged Bio-MPs showed very low CPF desorption rates. A 4-day Petri dish experiment showed that UV-aged MPs were significantly less concentrated in earthworm casts than pristine counterparts (52% and 36% lower for UV-aged LDPE- and Bio-MPs), while UV-aged MPs with adsorbed CPF were concentrated significantly more than UV-aged MPs without CPF. Interestingly, LDPE-MPs aged in soil with a high carbon, nitrogen, and carbon-to-nitrogen ratio were significantly more concentrated in earthworm casts than pristine LDPE-MPs. In conclusion, UV-aged MPs acted as stronger vectors for CPF than pristine MPs. The bioconcentration of MPs differed significantly due to microplastic aging, as well as the combined effect with CPF. Moreover, LDPE-MPs aged in soil with enriched carbon and nitrogen were significantly concentrated in earthworm casts. Further studies on the environmental behaviours of aged MPs associated with other pollutants in soil, especially soils high in carbon and nitrogen, are needed.

The bacteria toxicity of nanoscale zero-valent iron (nZVI) can be changed during its application in water treatment but the toxicity mechanism is still not well understood, particularly under anaerobic conditions. Here, the toxicity of nZVI and its aging products towards Escherichia coli (E. coli) and the mechanisms of extracellular and intracellular reactive oxygen species (ROS) damage were deeply probed in the presence and absence of oxygen in ultrapure water. Under aerobic conditions, the ROS damage primarily caused by the generation of extracellular free •OH can be a major contributor to the toxicity of nZVI to E. coli. By contrast, in anaerobic nZVI treatment system, the intracellular •OH can be quenched by benzoic acid which is a cell permeable quencher and the electron spin resonance (ESR) signals of 5,5-dimethy-1-pyrroline (DMPO)- •OH were evidently observed in system with the addition of F⁻ which could desorb the surface •OH into solution. It indicated that the intracellular •OH adsorbed on the particle surface can also play an indispensable role in inactivating cells under anaerobic conditions. Moreover, nZVI can steeply decline the membrane potential, causing severe membrane disruption and therefore resulting in the stronger toxicity in anaerobic conditions. Furthermore, the chemical composition transformation of nZVI and generation of benign iron corrosion products (e.g., Fe₃O₄, γ-Fe₂O₃, γ-FeOOH) are mainly responsible for the reduced toxicity with the increasing aging time. These results provide insights into the extracellular and intracellular ROS damage occurred in aerobic and anaerobic nZVI treatment systems, offering more perspective to the risk assessment of nZVI application.

Expanding applications of metal-oxide nanoparticles (NPs) and increased environmental deposition of NPs followed by their interactions with edible crops threaten yields. This study demonstrates the effects of aging (45 days in soil) of four NPs (ZnO, CuO, Al₂O₃, TiO₂; 3.9–34 nm) and their corresponding metal oxide bulk particles (BPs; 144–586 nm) on cucumbers (Cucumis sativus L.) cultivated in sandy-clay-loam field soil and compares these with the phytotoxic effects of readily soluble metal salts (Zn²⁺, Cu²⁺, and Al³⁺). Data revealed the cell-to-cell translocations of NPs, their attachments to outer and inner cell surfaces, nuclear membranes, and vacuoles, and their upward movements to aerial parts. Metal bioaccumulations in cucumbers were found in the order: (i) ZnO-NPs > ZnO-BPs > Zn²⁺, (ii) CuO-NPs > CuO-BPs > Cu²⁺, (iii) Al³⁺> Al₂O₃-NPs > Al₂O₃-BPs and (iv) TiO₂-NPs > TiO₂-BPs. Aging of NPs in soil for 45 days significantly enhanced metal uptake (P ≤ 0.05), for instance aged ZnO-NPs at 1 g kg⁻¹ increased the uptake by 20.7 % over non-aged ZnO-NPs. Metal uptakes inhibited root (RDW) and shoot (SDW) dry weight accumulations. For Cu species, maximum negative impact (%) was exhibited by Cu²⁺ (RDW:SDW = 94:65) followed by CuO-NPs (RDW:SDW = 78:34) and CuO-BPs (RDW:SDW = 27:22). Aging of NPs/BPs at 1–4 g kg⁻¹ further enhanced the toxic impact of tested materials on biomass accumulations and chlorophyll formation. NPs also induced membrane damage of root tissues and enhanced levels of antioxidant enzymes. The results of this study suggest that care is required when aged metal-oxide NPs of both essential (Zn and Cu) and non-essential (Al and Ti) metals interact with cucumber plants, especially, when they are used for agricultural purposes.

Toxicokinetic studies appertain to the fundamental research of soil bioavailability. However, the research outcomes of aspects influencing uptake and elimination of hydrophobic organic compounds have not been summarized so far. In our review, a recapitulation of available toxicokinetic data (i.e. experimental conditions, if the steady state was reached, uptake and elimination rate constants, and bioaccumulation factors) is presented in well-arranged tables. Further, toxicokinetic models are overviewed in the schematic form. In the review, the required information could be quickly found and/or the experimental gaps easily identified. Generally a little is known about the effects of soil properties other than soil organic matter. Limited or no data are available about soil treatment, food supply during laboratory exposure, and metabolization in oligochaeta. The impact of these factors might be important especially for arable soils with typically low organic matter content but high consequences on humans. Besides these circumstances, other uncertainties between published studies have been found. Firstly, the scientific results are provided in heterogenous units: bioaccumulation factors as well as the rate constants are reported in dry or wet weight of soil and earthworms. The steady state is another critical factor because the time to reach the equilibrium is influenced not only by soil and compound characteristics but for example also by aging. Nevertheless, toxicokinetic studies bring irreplaceable information about the real situation in soil and our review help to define missing knowledge and estimate the scientific priorities.

Current understanding of biochar's effect on antibiotic resistance genes (ARGs) in soil is limited, and whether the effect could change after long-term field aging remains largely unknown. In this study, we employed high-throughput quantitative PCR to assess the effect of biochar amendment on soil resistome as affected by three years of field aging. Application of fresh biochar significantly elevated the number and abundance of ARGs in the manured soil, but did not show such effect under pakchoi cultivation. The presence of aged biochar caused a marked reduction of ARGs only in the planted manured soil. Results of principal coordinate analysis and structural equation modeling indicate that biochar's effect on soil ARG profile was changed by field aging through altering soil microbial composition. These results highlight the necessity of considering aging effect of biochar during its on-farm application to mitigate soil antibiotic resistance.

Nanoplastics are inevitably released into aquatic environments due to their extensive use and the continuous fragmentation of plastics. Therefore, it is imperative to understand the aggregation behaviours that determine the transport and fate of nanoplastics in aquatic environments. In this study, the effects of various metal cations, pH, aging and extracellular polymeric substances (EPS) on the aggregation of polystyrene nanoplastics (nano-PS) in aqueous solutions were systematically evaluated based on aggregation kinetics experiments and Derjaguin–Landau–Verwey–Overbeek (DLVO) theoretical calculation. The concentration, valence and hydration ability of metal cations jointly affected the aggregation of nano-PS. The critical coagulation concentration (CCC) of nano-PS was significantly higher than the ionic strengths in aquatic environments, indicating that the aggregation rate of nano-PS is relatively low in aquatic environments. The results of the aggregation kinetics experiments were consistent with DLVO theory, which showed that the energy barrier of nano-PS was dependent on electrostatic repulsion forces and van der Waals forces, and increased with pH. Nano-PS was artificially aged by UV-H₂O₂, which reduced the hydrophobic nature of the particle surfaces, consequently enhancing the stability of the nanoplastics. EPS (excreted from Chlorella pyrenoidosa) decreased the aggregation rates of nano-PS due to steric effects, which was confirmed by the extend DLVO model. Our results highlight the high stability of nano-PS in aquatic environments, which could help facilitate the evaluation of their environmental impact.

The increasing application of iron-based nanoparticles (NPs), especially high concentrations of zero-valent iron nanoparticles (nZVI), has raised concerns regarding their environmental behavior and potential ecological effects. In the environment, iron-based NPs undergo physical, chemical, and/or biological transformations as influenced by environmental factors such as pH, ions, dissolved oxygen, natural organic matter (NOM), and biotas. This review presents recent research advances on environmental transformations of iron-based NPs, and articulates their relationships with the observed toxicities. The type and extent of physical, chemical, and biological transformations, including aggregation, oxidation, and bio-reduction, depend on the properties of NPs and the receiving environment. Toxicities of iron-based NPs to bacteria, algae, fish, and plants are increasingly observed, which are evaluated with a particular focus on the underlying mechanisms. The toxicity of iron-based NPs is a function of their properties, tolerance of test organisms, and environmental conditions. Oxidative stress induced by reactive oxygen species is considered as the primary toxic mechanism of iron-based NPs. Factors influencing the toxicity of iron-based NPs are addressed and environmental transformations play a significant role, for example, surface oxidation or coating by NOM generally lowers the toxicity of nZVI. Research gaps and future directions are suggested with an aim to boost concerted research efforts on environmental transformations and toxicity of iron-based NPs, e.g., toxicity studies of transformed NPs in field, expansion of toxicity endpoints, and roles of laden contaminants and surface coating. This review will enhance our understanding of potential risks of iron-based NPs and proper uses of environmentally benign NPs.

Stable isotope 111Cd was spiked into sediments of different organic content levels for 3 days to 2 months. Bioavailability of spiked Cd to deposit-feeders, assessed by in vitro Cd solubilization, generally decreased with contact time but became comparable with that of background Cd after 2 months. This could be explained by the gradual transfer of Cd from the more mobile geochemical phase (carbonate associated phase) to more refractory phases (Fe–Mn oxide associated phase, and organic associated phase) within 2 months. The sedimentary organic content had a weak effect on Cd solubilization, while the distribution of Cd in carbonate or Fe–Mn oxide associated phase could have a larger influence on the solubilization of sedimentary Cd and its change with contact time. The observations in this study emphasize the need to consider Cd sequestration over time in sediments of various compositions, which would be useful in risk assessment of contaminated sediments.

Selective supercritical fluid extraction (SSFE) was used as a measurement of compound chemical accessibility and as a predictor of compound bioavailability from three natural soils and artificial analogues prepared to have comparable total organic carbon content. Soils spiked with phenanthrene, pyrene, PCB 153, lindane, and p,p′-DDT were aged for 0, 14, 28, or 56 days and then selectively extracted by supercritical fluid extraction. Compounds exhibited decreasing extractability with increasing pollutant–soil contact time and increasing total organic carbon content in tested soils. However, the different extractability of compounds from artificial and natural pairs having comparable TOC indicates the limitations of using TOC as an extrapolation basis between various soils. The comparison of extractability with bioaccumulation by earthworms (Eisenia fetida) previously published by Vlčková and Hofman (2012) showed that only for PAHs it was possible to predict their bioaccumulation by means of selective SFE.