International audience | In order to determine the mechanisms of the retention of 60Co, 85Sr and 134Cs in natural silica sand columns, desorption experiments were performed by changes of pH and ionic strength and by injection of natural organic matter (NOM). Injection of KCl (0.1 M) resulted in a high release of 60Co (60-100%) and 85Sr (72-100%) but a smaller release of 134Cs (31-66%). Only limited release of 60Co (66%) and 85Sr (71%) and no release of 134Cs were observed by injection of NOM. The different percentages of desorption were related to the chemical characteristics of the organic colloids previously retained in columns before the desorption step. The results evidenced different sorption processes on energetically heterogeneous surface sites. According to the initial conditions, the binding of the radionuclides to the solid phase resulted from weak and easily reversible sorption processes to strong association probably by inner sphere complexes. The rather weak release of 134Cs by KCl was attributed to the strong retention of 134Cs by clay coatings on the natural silica sand surfaces. © 2005 Elsevier Ltd. All rights reserved.

Corrosion is an environmental and economic global problem. “Smart” or stimuli-responsive colorimetric nanosensors for maritime coatings have been proposed as an asset to overcome the limitations of the current monitoring techniques by changing color in the presence of triggers associated with the early stages of corrosion. Layered double hydroxides (Zn–Al LDH; Mg–Al LDH) and silica mesoporous nanocapsules (SiNC) were used as precursor nanocarriers of active compounds: hexacyanoferrate ions ([Fe(CN)₆]³⁻) and phenolphthalein (PhPh), respectively. Additionally, the safer-by-design principles were employed to optimize the nanosensors in an eco-friendly perspective (e.g., regular vs. warm-washed SiNC-PhPh; immobilization using different carriers: Zn–Al LDH-[Fe(CN)₆]³⁻ vs. Mg–Al LDH-[Fe(CN)₆]³⁻). Therefore, the present study aims to assess the environmental behavior in saltwater and the toxic effects of the nanosensors, their nanocarriers, and the active compounds on the marine microalgae Tetraselmis chuii and the crustacean Artemia salina. Briefly, tested compounds exhibited no acute toxic effects towards A. salina (NOEC = 100 mg/L), apart from SiNC-PhPh (LC₅₀ = 2.96 mg/L) while tested active compounds and nanosensors caused significant growth inhibition on T. chuii (lowest IC₅₀ = 0.40 mg/L for SiNC-PhPh). The effects of [Fe(CN)₆]³⁻ were similar regardless of the nanocarrier choice. Regarding SiNC-PhPh, its toxicity can be decreased at least twice by simply reinforcing the nanocapsules washing, which contributes to the removal (at least partially) of the surfactants residues. Thus, implementing safe-by-design strategies in the early stages of research proved to be critical, although further progress is still needed towards the development of truly eco-friendly nanosensors.

The catalytic hydrogenolysis of a typical model compound of mulching film waste, polyethylene, was investigated as a potential way to improve economic efficiency of mulching film recycling. Nickel-based heterogeneous catalysts are proposed for polyethylene hydrogenolysis to produce liquid hydrocarbons. Among catalysts supported on various carriers, Ni/SiO₂ catalyst shows the highest activity which may due to the interactions between nickel and silica with the formation of nickel phyllosilicate. As high as 81.18% total gasoline and diesel range hydrocarbon was obtained from the polyethylene hydrogenolysis at relatively mild condition of 280 °C, and 3 MPa cold hydrogen pressure. The result is comparable to what have been reported in previous studies using noble metal catalysts. The gasoline and diesel range hydrocarbon are n-alkanes with a distribution at a range of C₄–C₂₂. The gas products are primarily CH₄ along with a small amount of C₂H₆ and C₃H₈. High yield of CH₄ as much as 9.68% was observed for the cleavage of molecule occurs along the alkane chain.

The excessive arsenic (As) accumulation in plant tissues enforced toxic impacts on growth indices. So, the utilization of As-contaminated food leads to risks associated with human health. For the reduction of As concentrations in foods, it is obligatory to fully apprehend the take up, accretion, transportation and toxicity mechanisms of As within plant parts. This metalloid impairs the plant functions by disturbing the metabolic pathways at physio-biochemical, cellular and molecular levels. Though several approaches were utilized to reduce the As-accumulation and toxicity in soil-plant systems. Recently, engineered nanoparticles (ENPs) such a zinc oxide (ZnO), silicon dioxide or silica (SiO₂), iron oxide (FeO) and copper oxide (CuO) have emerged new technology to reduce the As-accumulation or phytotoxicity. But, the mechanistic approaches with systematic explanation are missing. By knowing these facts, our prime focus was to disclose the mechanisms behind the As toxicity and its mitigation by ENPs in higher plants. ENPs relives As toxicity and its oxidative damages by regulating the transporter or defense genes, modifying the cell wall composition, stimulating the antioxidants defense, phytochelatins biosynthesis, nutrients uptake, regulating the metabolic processes, growth improvement, and thus reduction in As-accumulation or toxicity. Yet, As-detoxification by ENPs depends upon the type and dose of ENPs or As, exposure method, plant species and experimental conditions. We have discussed the recent advances and highlight the knowledge or research gaps in earlier studies along with recommendations. This review may help scientific community to develop strategies such as applications of nano-based fertilizers to limit the As-accumulation and toxicity, thus healthy food production. These outcomes may govern sustainable application of ENPs in agriculture.

Cropland contamination by toxic trace metal (loid)s (TTMs) has attracted increasing attention due to the serious consequential threat to crop quality and human health. Mitigation of plant TTM stress by silica amendment has been proposed recently. However, the relationship between the siliceous structure of phytoliths and TTMs in plants, and the environmental implications of phytolith-occluded trace metal (loid)s (PhytTMs) remain unclear. This study assessed the accumulation of five metal (loid)s, including lead (Pb), zinc (Zn), cadmium (Cd), copper (Cu) and arsenic (As), in the organic tissues and phytoliths of wheat grown in a mixed-TTM contaminated soil under both lightly and heavily contaminated conditions. The results show that the concentrations of plant TTMs and PhytTMs were significantly (p < 0.05) positively correlated, and higher in heavily contaminated wheats than those in lightly contaminated ones. The bio-enrichment factors between phytoliths and organic tissues were higher for As (1.83), Pb (0.27) and Zn (0.30) than for Cd (0.03) and Cu (0.14), implying that As, Pb and Zn were more readily co-precipitated with silicon (Si) in phytolith structures than Cd and Cu. Network analysis of the relationship between soil and plant elements with PhytTMs showed that severe contamination could impact the homeostasis of elements in plants by altering the translocation of TTMs between soils, plants, and phytoliths. The accumulation of TTMs in phytoliths was affected by the capacity of Si deposition in tissues and chelation of TTMs with silica, which could impact the role of PhytTMs in global biogeochemical TTM cycles.

Growing applications of nanoagrichemicals have resulted in their increasing accumulation in agricultural soils, which could modify soil properties and affect soil health. A greenhouse pot trial was conducted to determine the effects of three metallic nanoagrichemicals on several fundamental chemical properties of a rice paddy soil, including zinc oxide nanoparticles (ZnO NPs) and copper oxide nanoparticles (CuO NPs) at 100 mg/kg, and silicon oxide nanoparticles (SiO₂ NPs) at 500 mg/kg, as well as their bulk and ionic counterparts. The investigated soil amendments displayed significant and distinctive impact on the examined soil chemical properties relevant to agricultural production, including soil pH, redox potential, soil organic carbon (SOC), cation exchange capacity (CEC), and plant available As. For example, all amendments increased the bulk soil pH at day 47 to some extent, but the increase was substantially higher for SiO₃²⁻ (37.7%) than other amendments (5.8%–13.7%). Soil Eh was elevated markedly at day 47 after the addition of soil amendments in both the bulk soil (45.9%–74.4%) and rice rhizosphere soil (20.3%–68.9%). CuO NPs and Cu²⁺ generally exhibited greater impact on soil chemical properties than other agrichemicals. Significantly different responses to soil amendments were observed between bulk and rhizosphere soils, suggesting the essential role of plants in affecting soil properties and their responses to environmental disturbance. Overall, our results confirmed that the tested amendments could have remarkable impacts on the fundamental chemical properties of rice paddy soils.

Microplastics (MPs; <5 mm) released into freshwaters from anthropogenic sources accumulate in sediments, where they may pose an environmental threat to benthic organisms, such as nematodes. Several studies have examined the effects of nano- and microplastics on the nematode Caenorhabditis elegans, whereas reduced food availability was suggested as a possible explanation for the observed inhibitory effects. Therefore, this study should clarify whether micro-beads of different sizes (1.0 and 6.0 μm in diameter) and materials (polystyrene PS, silica) are able to interfere with the feeding of C. elegans on its bacterial diet (Escherichia coli), and, by this, lowering its consumption rate within 7 h of exposure. Moreover, it was examined whether an inhibited bacterial consumption was caused by a reduction of the nematode’s pumping rate, as a primary indicator of food ingestion. Bacterial consumption by C. elegans was significantly decreased in the presence of 1.0- and 6.0-μm PS beads (49–67% lower bacterial consumption compared to control), whereas in the presence of 1.0-μm silica beads feeding was not impeded. Interestingly, the pumping rate was significantly lower in the presence of non-ingestible 6.0-μm PS beads with 161 ± 16 pumps min⁻¹, while it was largely unchanged for nematodes exposed to ingestible 1.0-μm PS beads with 205 ± 12 pumps min⁻¹, compared to control conditions with 210 ± 18 pumps min⁻¹, respectively. As reduced bacterial consumption leads to generally lower energy reserves in C. elegans, these results allow to link observed inhibitory effects of MPs on the nematodes to a lower food availability. Such indirect, food-web related, effects of MPs should raise concern of ecological consequences in natural habitats, where temporal food deficiencies can occur. Consequently, disturbances in food availability and feeding efficiency should be regarded as important parameters in environmental risk assessments focusing on MPs.

Adsorption and fractionation of Pt, Pd and Rh (defined here as platinum group elements, PGEs) onto the representative inorganic microparticles, including Fe2O3, MnO2, CaCO3, SiO2, Al2O3 and kaolinite in seawater were investigated. The effects of macromolecular organic compounds (MOCs) as the representatives of organic matter, including humic acids (HA), bovine serum albumin (BSA) and carrageenan, on the adsorption were also studied considering that organic matter is ubiquitous in seawater and indispensable to marine biogeochemical cycles. In the absence of MOCs, the representative mineral particles Fe2O3 and MnO2 had the strongest interaction with PGEs. The adsorption of PGEs onto the representative biogenic particles SiO2 and CaCO3 and lithogenic particles Al2O3 and kaolinite was similar or weaker than onto the mineral particles. MOCs inhibited the interaction between PGEs and the particles except for Pt and Pd onto the biogenic particles in artificial seawater. This impediment may be closely related to the interaction between particles, MOCs and elements. The partition coefficient (log Kd) of Pt was similar (∼4.0) in the presence of MOCs, indicating that the complexation between Pt and MOCs was less important than hydrolysis or adsorption onto the acid oxide particle surface. Rh tended to fractionate onto the mineral and lithogenic particles in the presence of HA and carrageenan, while Pd was more likely to fractionate onto the biogenic particles. However, BSA enhanced the fractionation tendency of Pd onto the mineral particles. The results indicate that the adsorption behavior of Pd onto inorganic particles was significantly affected by the composition or the type of MOCs. Hence, the interaction between PGEs and inorganic particles may be greatly affected by the macromolecular organic matter in the ocean.

The silica-composited biochars (SBC) were synthesized by adding silica particulates into bamboo biomass during pyrolysis at 700 °C to examine the effect of silica addition on biochar stabilities and adsorption properties for tetracycline (TC). Silica addition increased the total pore volume and average pore diameter of biochar due to the abundant mesopores in SBC, but decreased specific surface area due to the blockage of biochar pore with silica particles. Biochar stability was obviously enhanced with silica addition due to the decreased atomic ratio of H/C and O/C, the reduced C loss amount after chemical oxidation treatment, and the increased thermal stability. The adsorption capacities of SBC for TC were greatly enhanced with silica addition and increased with the increasing silica addition amount, which can be attributed to the facilitating effect of π–π electron donor acceptor (EDA) interaction and pore-filling effect. In addition, silica addition can also effectively enhance the oxidation resistance of biochar for TC adsorption, since the decreased degree (δ) of TC adsorption amounts on the biochars after chemical oxidation decreased with the increasing silica addition level. The observed positive correlations between δ values and the corresponding C loss amount of biochars after chemical oxidation suggested that the high carbon stability was favorable for the maintenance of biochar adsorption capacity. These results can provide a new way to improve biochar stabilities, aging resistance, and adsorption properties for organic pollutants.

Antifouling booster biocides are chemicals used in protective paints to tackle the adhesion of fouling organisms to maritime artificial structures. However, they are also known to exert toxic effects on non-target organisms. Recent research developments have highlighted the potential use of engineered micro/nanomaterials (EMNMs) as carriers of antifouling booster biocides in order to control their release and to reduce the harmful effects on living biota. In the present study, we sought to assess the toxicity of two commercially-available booster biocides: (zinc pyrithione (ZnPT) and copper pyrithione (CuPT)); three unloaded engineered micro/nanomaterials (EMNMs); layered double hydroxides (LDH), silica nanocapsules (SiNC), polyurea microcapsules (PU); , and six novel EMNMs (loaded with each of the two biocides). The exposure tests were conducted on the larval stage (nauplii) of the brine shrimp Artemia salina and on two embryonic developmental stages of the European purple sea urchin Paracentrotus lividus. The findings indicate that the unloaded LDH and PU (i.e. both biocide-free EMNMs) have non/low toxic effects on both species. The unloaded SiNC, in contrast, exerted a mild toxic effect on the A. salina nauplii and P. lividus embryos. The free biocides presented different toxicity values, with ZnPT being more toxic than CuPT in the P. lividus assays. LDH-based pyrithiones demonstrated lower toxicity compared to the free forms of the state-of-the-art compounds, and constitute good candidates in terms of their antifouling efficacy.