Partie B | International audience | Incidental zinc sulfide nanoparticles (nano-ZnS) are spread on soils through organic waste (OW) recycling. Here we performed soil incubations with synthetic nano-ZnS (3 nm crystallite size), representative of the form found in OW. We used an original set of techniques to reveal the fate of nano-ZnS in two soils with different properties. 68 Zn tracing and nano-DGT were combined during soil incubation to discriminate the available natural Zn from the soil, and the available Zn from the dissolved nano-68 ZnS. This combination was crucial to highlight the dissolution of nano-68 ZnS as of the third day of incubation. Based on the extended X-ray absorption fine structure, we revealed faster dissolution of nano-ZnS in clayey soil (82% within 1 month) than in sandy soil (2% within 1 month). However, the nano-DGT results showed limited availability of Zn released by nano-ZnS dissolution after 1 month in the clayey soil compared with the sandy soil. These results highlighted: (i) the key role of soil properties for nano-ZnS fate, and (ii) fast dissolution of nano-ZnS in clayey soil. Finally, the higher availability of Zn in the sandy soil despite the lower nano-ZnS dissolution rate is counterintuitive. This study demonstrated that, in addition to nanoparticle dissolution, it is also essential to take the availability of released ions into account when studying the fate of nanoparticles in soil.

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.

The adsorption of microplastic (MPs) on aquifer media is affected by their own properties and environmental factors. Research results have shown that the adsorption capacity of MPs on the three media has the following order: fine sand > medium sand > coarse sand, and the adsorption equilibrium times are 8 h, 12 h and 24 h, respectively. The adsorption process has three stages (fast linear distribution, slow adsorption and equilibrium stability), and the action law is compounded by the pseudo-second-order kinetic equation. After adsorption, MPs were observed on the three media, and there were single existence and aggregation phenomena. The energy spectrum analysis indicates that elemental carbon (C) appears on the surface of the medium after the action occurs, and the surface of the media adsorbs MPs to varying degrees. According to the results of infrared spectroscopy, after action, the peak areas of the absorption peaks at 680-880 cm⁻¹ and 1450-1620 cm⁻¹ increase. The absorption peaks are mainly C–H out-of-plane bending vibrations from aromatic hydrocarbons and C–H stretching vibrations on the benzene ring skeleton. As the initial concentration increases, the equilibrium adsorption capacity increases linearly. The isothermal adsorption of MPs in porous media conforms to the Freundlich model. The adsorption process is also affected by different anions and cations. The higher the ionic strength of NH₄⁺ is, the weaker the electrostatic effect of negatively charged MPs, thereby increasing the adsorption capacity of microplastics on porous media. Ca²⁺ can promote the adsorption of MPs by the media through the formation of ternary complexes between cations, MPs and surface functional groups. The increase in SO₄²⁻ and HCO₃⁻ concentrations gradually inhibits the adsorption of MPs.

Nonylphenol (Noph) has garnered worldwide concern as a typical endocrine disruptor due to its toxicity, estrogenic properties, and widespread contamination. To better elucidate the interaction of Noph with ubiquitously existing microplastics (MPs) and the potential interdependence of their transport behaviors, batch adsorption and column experiments were conducted, paired with mathematical modeling. Compared with sand, MPs and soil colloids show stronger adsorption affinity for Noph due to the formation of hydrogen bonding and the larger numbers of interaction sites that are available on solid surfaces. Limited amount of soil-colloid coating on sand grains significantly influenced transport behaviors and the sensitivity to solution chemistry. These coatings led to a monotonic increase in Noph retention and a nonmonotonic MPs retention in single systems because of the altered physicochemical properties. The mobility of both MPs and Noph was enhanced when they coexisted, resulting from their association, increased electrostatic repulsion, and competition on retention sites. Limited release of MPs and Noph (under reduced ionic strength (IS) and increased pH) indicated strong interactions in irreversible retention. The retention and release of Noph were independent of IS and solution pH. A one-site model with a blocking term and a two-site kinetic model well described the transport of MPs and Noph, respectively. Our findings highlight the essential roles of coexisting MPs and Noph on their transport behaviors, depending on their concentrations, IS, and physicochemical properties of the porous media. The new knowledge from this study refreshes our understanding of the co-transport of MPs and organic contaminants such as Noph in the subsurface.

We investigated the competitive effects of different fractions of wastewater treatment plant effluent organic matter (EfOM) on adsorption of an organic micro pollutant (OMP), propranolol (PRO), in a fixed bed column packed with magnetic tyre char (MTC). The results showed that the presence of EfOM inhibited PRO adsorption in wastewater leading to decreased PRO adsorption capacity from 5.86 to 2.03 mg/g due to competitive effects and pore blockage by smaller EfOM fractions. Characterization of EfOM using size exclusion chromatography (LC-OCD) showed that the principal factor controlling EfOM adsorption was pore size distribution. Low molecular weight neutrals had the highest adsorption onto MTC while humic substances were the least interfering fraction. Effect of important parameters such as contact time, linear velocity and bed height/diameter ratio on MTC performance was studied in large-lab scale columns. Linear velocity and contact time were found to be effective in increasing adsorption capacity of PRO on MTC and delaying breakthrough time. Increase in linear velocity from 0.64 cm/min to 1.29 cm/min increased mass transfer and dispersion, resulting in considerable rise of adsorbed amount (5.86 mg/g to 22.58 mg/g) and increase in breakthrough time (15.8–62.7 h). Efficiency of non-equilibrium Hydrus model considering dispersion and mass transfer mechanism was demonstrated for real wastewater and scale up purposes. Ball milling for degradation of adsorbed PRO and regeneration of MTC resulted in 79% degradation of PRO was achieved after 5 h milling (550 rpm), while the addition of quartz sand increased the efficiency to 92%.

The unified bioaccessibility method (UBM) was harnessed to assess in vitro oral bioaccessibility pools of dialkyl phthalate congeners (with methyl, –ethyl, –butylbenzyl, –n-butyl, –2-ethylhexyl, and –n-octyl moieties) and bisphenol A at the 17 μg g⁻¹ level in beach sand contaminated with polyethylene microplastics. A variety of sample preparation approaches prior to the analysis of the UBM gastrointestinal extracts, including traditional methods (protein precipitation, liquid-liquid extraction, and solid-phase extraction) and dispersive liquid-liquid microextraction (DLLME) were comprehensively evaluated for clean-up and analyte enrichment. DLLME was chosen among all tested approaches on account of the high extraction efficiency (73–95%, excluding bis(2-ethylhexyl)phthalate and di-n-octyl phthalate), high sample throughput (∼7 min per set of samples), and environmental friendliness as demonstrated by the analytical eco-scale score of 83, and the green analytical procedure index pictogram with green/yellow labeling. The release of the less hydrophobic plastic-laden compounds (dimethyl phthalate, diethyl phthalate and bisphenol A) from the contaminated sample into the body fluids was significant, with bioaccessibility values ranging from 30 to 70%, and from 43 to 74% in gastric and gastrointestinal fluids, respectively, and with relative standard deviation < 17% in all cases. The majority of the compounds were leached during gastric digestion, likely as the combined action of the low pH and the gastric enzymes. The risk exposure analysis revealed that accumulation/concentration in the body fluids is potentially relevant for dimethyl phthalate, diethyl phthalate and bisphenol A, with relative accumulation ratios ranging from 1.1 ± 0.1 to 2.6 ± 0.4. The average daily intake values for the suite of compounds, corrected with the bioaccessibility fraction, ranged from 60 to 430 ng kg of body weight⁻¹·day⁻¹, in all cases, far below the tolerable daily intakes, thus indicating the lack of children health risk by ingestion of microplastic-laden sand with elevated concentrations of plasticizers.

Long term monitoring of atmospheric wet and dry depositions and associated nutrients fluxes was conducted on the coast of Japan facing the East China Sea continuously for 1 year and 2 months, with the origin of air mass investigated based on isotope analyses (Sr, Nd, and NO₃). During the same period, intensive observations of ocean conditions and the chemical composition of sinking particles collected using sediment traps were conducted to investigate the effects of atmospheric deposition-derived nutrients on phytoplankton blooms. Dry-deposition-derived nutrient inputs to the surface ocean were larger during autumn to spring than in summer due to the effect of continental air mass occasionally carrying Asian dust (yellow sand). However, these nutrients fluxes were limited (1.1–1.5 mg-N m⁻² day⁻¹ on average) and didn't appear to cause phytoplankton blooms through the year. Although average dissolved inorganic nitrogen (DIN) concentrations in rainwater were lower in oceanic air masses compared to continental air masses, wet-deposition-derived nutrient inputs to the surface ocean on rainy days during the summer (26.0 mg-N m⁻² day⁻¹ on average) were large due to higher precipitation from oceanic air masses. Wet-deposition-derived nutrients significantly increased nutrient concentrations in the surface ocean and seemed to cause phytoplankton blooms in the warm rainy season when nutrients in the surface were depleted due to increased stratification. The increase in phytoplankton biomass was reflected in increased particle sinking into the bottom layer, as well as changing chemical characteristics. The supply of flesh phytoplankton-derived labile organic matter into the bottom layer could be expected to promote rapid bacterial decomposition and contribute to the formation of hypoxic water masses in early summer when the ocean was strongly stratified. Atmospheric deposition-derived nutrients in East Asia will have important impacts on not only the oligotrophic outer ocean but also surrounding coastal areas in the warm rainy season.

Children in urban environments are exposed to potential harmful elements (PHEs) through variable exposure media. Playing activities in outdoor playgrounds have been considered of high concern due to children's exposure to sand-bound PHEs through unintentional or intentional sand ingestion. Furthermore, the affinity of magnetic particles with dust-bound PHEs in playgrounds has been reported. In this study, playground sands (PG sands) from public playgrounds in the city of Thessaloniki, N. Greece were sampled and the levels, the contamination degree, oral bioaccessibility and exposure assessment of PHEs were evaluated. In addition, low-cost and fast magnetic measurements (i.e. mass specific magnetic susceptibility, χₗf) were explored as potential pollution and health risk proxies. Mineralogically, siliceous PG sands dominated, while morphologically angular magnetic particles and Fe-rich “spherules” of anthropogenic origin were revealed and verified by enhanced χₗf values. The average total elemental contents exhibited a descending order of Mn > Ba > Cr > Zn > Ni > Pb > Cu > Co > As > Sn > Bi > Cd, however only Cd, Bi, Pb, Cr, As and Zn were presented anthropogenically enhanced. Notable increase on PHEs levels and finer sand fractions were observed with continuous sand use. Anthropogenically derived elements (i.e. Cd and Pb with high Igₑₒ values) exhibited higher bioaccessible fractions in PG sands and considered easily soluble in gastric fluids through ingestion. However, increased risks were found for specific PHEs (especially Pb) only in a worst case exposure scenario of an intentional sand ingestion (pica disorder). Statistical analysis results revealed a linkage of anthropogenic components with sand-bound magnetic particles. Moreover, the recorded high affinity of Pb contents (in an enhanced magnetized sub-set of PG sands) and bioaccessible Cd fractions with χₗf provide a preliminary indication on the successful applicability of low-cost and fast magnetic measurements in high impacted playground environments.

Bird guano and the faeces of marine mammals appear to be a significant yet undisclosed biotransporter of Endocrine Disrupting Compounds in the marine environment. The authors determined the concentration of bisphenol A (BPA), 4-tert-octylphenol (4-t-OP) and 4-nonylphenol (4-NP) removed from birds and seals in their droppings into the coastal zone of the Gulf of Gdansk (Southern Baltic Sea).The research was carried out on samples of bird guano collected during the breeding season and after in 2016 at nesting sites, as well as on faecal samples from grey seals (Halichoerus grypus grypus) living in the Seal Centre of the Marine Station in Hel between 2014 and 2018. Measurements were carried out using high performance chromatography with fluorescence detector. Results have shown that the presence of seabird habitats and grey seal colonies in the coastal zone of the Gulf of Gdansk can have an impact on the pollution of the seashore (beach sand, bottom sediment and surface seawater) with phenol derivatives. The concentrations of BPA, 4-t-OP and 4-NP ranged from 0.1 to 32.97 ng∙g⁻¹dw in sediment and beach sand, and from 0.23 to over 800 ng dm⁻³ in seawater. In the cases of bisphenol A and 4-tert-octylphenol safe concentration levels in the waters were exceeded. Bisphenol A concentrations were almost always found to be the highest. This was also noted in bird guano and seal faeces, although it was found to be much higher in the seal faeces - average 10149.79 ng g⁻¹ dw, than in bird guano. An experiment conducted to assess BPA, 4-t-OP, 4-NP leaching from bird guano and seal faeces into seawater, also confirmed the importance of animal excrement in the circulation of these compounds in the marine ecosystem. The highest % of leaching related to BPA was noted at 20 °C and reached 84%. The lowest % of leaching was for 4-nonylphenol (44%).

The release of fine particles from biochar materials applied in the environment may have important environmental implications, such as mobilization of environmental contaminants. In natural environments biochar fine particles can undergo various transformation processes, which may change their surface chemistry and consequently, the mobility of the particles. Here, we show that sulfide reduction can significantly alter the transport of wheat-straw- and pine-wood-derived biochar fine particles in saturated porous media. Counterintuitively, the sulfide-reduced biochar particles exhibited greater mobility in artificial groundwater than their non-reduced counterparts, even though reduction led to decrease of surface charge negativity and increase of hydrophobicity (from the removal of surface O-functional groups), both should favor particle deposition, as predicted based on extended Derjaguin–Landau–Verwey–Overbeek (XDLVO) theory. Using transport experiments conducted in single-cation background solutions containing K⁺, Mg²⁺ or Ca²⁺ under different pH conditions, we show that the surprisingly greater mobility of sulfide-reduced biochar particles was attributable to the removal of surface carboxyl groups during reduction, as this markedly alleviated particle deposition through cation bridging, wherein Ca²⁺ acted as the bridging agent in linking the surface O-functional groups of biochar particles and quartz sand. These findings show the critical roles of surface properties in dictating the mobility of biochar fine particles and call for further understanding of their transport properties, which apparently cannot be simply extrapolated based on the findings of other (engineered) carbonaceous nanomaterials.