International audience | This review investigates the impact of salinity on the fate of the active compounds of pesticides in a cultivated environment. Due to the over-exploitation of water resources and intensification of agriculture, salinity outbreaks are being observed more often in cultivated fields under pesticide treatments. Nevertheless, there is a poor understanding of the incidence of varying water salt loads on the behavior of pesticides’ active ingredients in soil and water bodies. The present review established that water salinity can affect the diffusion of pesticides’ active ingredients through numerous processes. Firstly, by increasing the vapor pressure and decreasing the solubility of the compounds, which is known as the salting-out effect, salinity can change the colligative properties of water towards molecules and the modification of exchange capacity and sorption onto the chemicals. It has also been established that the osmotic stress induced by salinity could inhibit the biodegradation process by reducing the activity of sensitive microorganisms. Moreover, soil properties like dissolved organic matter, organic carbon,clay content, and soil texture control the fate and availability of chemicals in different processes of persistence in water and soil matrix. In the same line, salinity promotes the formation of different complexes, such as between humic acid and the studied active compounds. Furthermore, salinity can modify the water flux due to soil clogging because of the coagulation and dispersion of clay particle cycles, especially when the change in salinity ranges is severe.

As a redox-sensitive element, manganese (Mn) plays a critical role in Cd mobilization, especially in paddy soil. In an anoxic environment, the precipitation of Mn(II)-hydroxides specifically favors Cd retention, while draining the paddy fields results in substantial remobilization of Cd. However, how the change in Mn redox states during the periodical transit of anoxic to oxic systems affects Cd mobility remains unclear. In this study, we demonstrate that the radical effect generated during the oxidation of Mn(II)-hydroxides exerts a significant effect on the oxidative dissolution of Cd during the aeration of paddy soils. The extractable Cd concentration decreased rapidly during the reduction phases but increased upon oxidation, while Cd availability produced the opposite effect with soil pe + pH and the extractable Mn concentration. Inhibiting the oxidation of Mn(II)-containing phases by microbes suppressed the production of hydroxyl free radicals (•OH) and Cd mobilization in the drainage phase. Analysis of X-ray absorption spectroscopy and sequential extraction demonstrated that the transformation from the Mn phase of Mn(II) to Mn(III/IV) determines Cd solubility. Altogether, the oxidization of Mn(II)-hydroxides was associated with the generation of significant amounts of •OH. The dissolution of Mn(II)- incorporating phases lead to a net release of Cd into soils during soil aeration.

Selenium (Se) is regarded as a trace element for humans, but it is toxic in excess. In natural environments, the mobility of Se is dominantly controlled by the Se oxyanions with high solubility such as selenite (Se(IV)). Se(IV) is often associated with the omnipresent ferrihydrite and coexisting organic matter. However, there is little information on the dynamic interactions among Se(IV), fulvic acid, and ferrihydrite. This study investigated the influence of fulvic acid on ferrihydrite-Se(IV) coprecipitates (Fh-Se) transformation for 8 days and the subsequent behavior of Se(IV) at varied pH (5.0, 7.5, and 10.0). Results showed that fulvic acid had different effects on Fh-Se transformation at varied pH values. Fh-Se transformation was promoted by fulvic acid at initial pH 5.0 whereas it was inhibited at initial pH 10.0. Interestingly, at initial pH 7.5, Fh-Se transformation was promoted at a low C/Fe ratio while it was suppressed at a high C/Fe ratio. Besides, fulvic acid induced the generation of more extractable Se(IV) at initial pH 5.0 and more coprecipitated Se(IV) at initial pH 7.5 and blocked the release of Se(IV) at initial pH 10.0. Fulvic acid possibly interacted with Se(IV) via carboxyl complexation and weakened the inhibition of Se(IV) on Fh-Se transformation. Thus, fulvic acid increased the transformation rate of Fh-Se. These findings help to uncover the environmental behavior of Se(IV) and organic matter during ferrihydrite transformation.

Lead (Pb) exposure is known to affect the health of children while soil Pb is an important contributor to human Pb exposure. To analyze the effects of both environmental and other factors, especially total and bioaccessible Pb in neighborhood soil, on school-aged urban children’s blood lead level (BLL), 75 children (6–11 years old) were recruited from an industry city in eastern China for BLL measurement and questionnaire survey. Soil samples were collected from their living neighborhoods and measured for total and bioaccessible Pb. The mean BLL was 4.82 μg dL⁻¹, with 42 out of 75 children having BLL exceeding the international guideline of 5 μg dL⁻¹. Low Pb contamination was observed in soil with total Pb ranging from 12.5 to 271 mg kg⁻¹ (mean 34.3 mg kg⁻¹). Based on the in vitro Solubility Bioaccessibility Research Consortium (SBRC) gastric fluid extraction, bioaccessible Pb in soil ranged from 0.40 to 79.1 mg kg⁻¹ (mean 7.58 mg kg⁻¹) with Pb bioaccessibility ranging from 1.74 to 68.1 (mean 19.9%). When BLL was correlated with total Pb in soil, insignificant linear relationship was observed (P > 0.05, correlation coefficient 95%CI = −0.047–0.40, R² = 0.07). However, when BLL was correlated with soil bioaccessible Pb or Pb bioaccessibility, much stronger linear relationships were observed (P < 0.01, correlation coefficient 95%CI = 0.28–0.64, R² = 0.16–0.20), suggesting that bioaccessible Pb was a much stronger predictor of BLL. In addition, strong associations were also observed between BLL and social factors such as house decoration, residence time, and personal habits, suggesting that both soil Pb contamination and social factors play important roles in elevating BLL for city children.

We investigated the influence of sulfate (SO₄²⁻) deposition and concentrations on the net formation and solubility of methylmercury (MeHg) in peat soils. We used data from a natural sulfate deposition gradient running 300 km across southern Sweden to test the hypothesis posed by results from an experimental field study in northern Sweden: that increased loading of SO₄²⁻ both increases net MeHg formation and redistributes methylmercury (MeHg) from the peat soil to its porewater. Sulfur concentrations in peat soils correlated positively with MeHg concentrations in peat porewater, along the deposition gradient similar to the response to added SO₄²⁻ in the experimental field study. The combined results from the experimental field study and deposition gradient accentuate the multiple, distinct and interacting roles of SO₄²⁻ deposition in the formation and redistribution of MeHg in the environment.

Cu nanoparticles (CuNPs) have been widely used in numerous products, and may become a potential threat to marine organisms, but their behavior in the marine environments and potential toxicity to marine organisms remain little known. In the present study, we investigated the behavior of CuNPs in seawater, as well as the toxicity and bioaccumulation of CuNPs and copper sulfate (CuSO4) in barnacle larvae (Balanus amphitrite), a dominant fouling invertebrate in marine environment. CuNPs tended to aggregate in natural seawater and released Cu ion rapidly into seawater. The aggregation and release were especially higher at a lower concentration of CuNPs, e.g., 94–96% of CuNPs were released as Cu ions at 20 μg/L after 24 h. The larger size of CuNPs (40 nm) tended to display a higher solubility than the 20 nm CuNPs did. Humic acids enhanced the aggregation and inhibited the dissolution of CuNPs, and had a protective effect on the survival of nauplii II at higher Cu concentrations (100–200 μg/L). Comparison of the lethal concentrations showed that CuNPs were generally less toxic to the two stages of barnacle larvae (nauplii II and VI) than the Cu ions. The calculated 48-h LC50 values for nauplii II were 189.5 μg/L, 123.2 μg/L, and 89.8 μg/L for 20 nm CuNPs, 40 nm CuNPs, and CuSO4, respectively. However, the lethal concentrations of Cu bioaccumulation in the barnacle larvae were comparable between CuNPs and Cu ions when expressed by the actual tissue Cu bioaccumulation. Barnacle larval settlement decreased with an increase of Cu concentrations of both CuNPs and CuSO4, and was significantly inhibited at 100 μg/L CuSO4 and 150 μg/L CuNPs. Our results indicated that the toxicity of CuNPs could not be solely explained by the released Cu ions, and both CuNPs and the released Cu ion contributed to their toxicity and bioaccumulation in barnacle larvae.

The effluents from nuclear mining processes contain relatively high content of radionuclides (such as uranium), which may seriously threaten the environment and human health. Herein, a novel adsorbent, porous hydroxyapatite, was prepared and proven highly efficient for removal of uranyl ions (U(VI)) given its high U(VI) uptake capacity of 111.4 mg/g, fast adsorption kinetics, and the potential stabilization of adsorbed U(VI). A nearly complete removal of U(VI) was achieved by porous HAP under optimized conditions. Langmuir model could well describe the adsorption equilibrium. The data fit well with pseudo-second-order kinetic model, suggesting that U(VI) adsorption is primarily attributed to chemisorption with porous HAP. Intraparticle diffusion analysis showed that the intraparticle diffusion is the rate-limiting step for U(VI) adsorption by porous HAP. After removal by porous HAP, the adsorbed U(VI) ions were incorporated into tetragonal autunite, which has a low solubility (log Ksp: −48.36). Our findings demonstrate that the porous HAP can effectively remediate uranium contamination and holds great promise for environmental applications.

The predominance of natural organic matter (NOM) in nonlinear sorption of nonionic organic compounds (NOCs) is a fundamental behavior that controlling the fate, transfer and bioavailability of NOCs in natural environment. There is a debate, i.e., whether the nonlinear sorption is captured by nonlinear partition mechanism or adsorption mechanism. The debate has been going on for decades because characteristics of nonlinear partition are still unknown due to the lack of an adsorbent that can partition NOCs nonlinearly. We find a resin ADS-21, with specific surface area undetectable (<0.5 m² g⁻¹) but high sorption capacity for NOCs (up to 1000 mg g⁻¹ for phenol as an example), is an ideal adsorbent for examining characteristics of nonlinear partitioning. This resin has nonlinear isotherms for phenols and anilines but linear isotherms for polycyclic aromatic hydrocarbons and nitrobenzenes. The observed positively linear relationship of sorption capacities of NOCs with NOCs solubility in water or octanol, could be one of the characteristics of nonlinear partition. Moreover, competitive sorption and no desorption hysteresis could be observed for the nonlinear partition. Hydrogen-bonding of phenols and anilines with ADS-21 is responsible for nonlinear partition, competitive sorption and isotherm nonlinearity. These evidences would be supportive for understanding nonlinear partition and the nonlinear sorption of NOCs by NOM.

Solvent stabilizer 1,4-dioxane, an emerging recalcitrant groundwater contaminant, was commonly added to chlorinated solvents such as trichloroethene (TCE), and the impact of co-disposal on contaminant transport processes remains uncertain. A series of batch equilibrium experiments was conducted with variations of 1,4-dioxane and TCE composition to evaluate aqueous dissolution of the two components and their sorption to aquifer sediments. The solubility of TCE increased with increasing amounts of 1,4-dioxane, indicating that 1,4-dioxane acts as a cosolvent causing solubility enhancement of co-contaminants. The solubilization results compared favorably with predictions using the log-linear cosolvency model. Equilibrium sorption coefficients (Kd and Kf) were also measured for different 1,4-dioxane and TCE compositions, and the findings indicate that both contaminants adsorb to aquifer sediments and TCE Kd values increased with increasing organic matter content. However, the Kd for TCE decreased with increases in 1,4-dioxane concentration, which was attributed to cosolvency impacts on TCE solubility. These findings further advance our understanding of the mass-transfer processes controlling groundwater plumes containing 1,4-dioxane, and also have implications for the remediation of 1,4-dioxane contamination.

In order to exhaustively investigate the physical and chemical mechanisms of heavy metal immobilization in sludge incineration residue (SIR)-based magnesium potassium phosphate cement (MKPC), this work investigated the influence of Pb²⁺ and Zn²⁺ on the compressive strength and microstructure of SIR-based MKPC, and the efficiency of Pb and Zn immobilization. Taking the difference of Ksp (solubility product) of different heavy metal compounds as the entry point, the physical and chemical mechanisms of Pb and Zn immobilization, and the competitive mechanism between coexisting ions, were comprehensively analyzed. It was discovered that Pb²⁺ is in the form Pb₃(PO₄)₂, and Zn²⁺ is immobilized in the form Zn₂(OH)PO₄ [Zn₃(PO₄)₂ is preferentially formed, when the pH > 7, Zn₃(PO₄)₂ is converted to Zn₂(OH)PO₄]. The low solubility of heavy metal phosphates is the main reason that Pb²⁺ and Zn²⁺ are well immobilized. The preferential formation of Pb₃(PO₄)₂ (Kₛₚ = 8 × 10⁻⁴³) and Zn₃(PO₄)₂ (Kₛₚ = 9.0 × 10⁻³³) reduced the amount of MgKPO₄·6H₂O (Kₛₚ = 2.4 × 10⁻¹¹), resulting in a decrease in compressive strength. Besides, coexisting Pb²⁺ and Zn²⁺ has a competitive effect: Pb²⁺ will weaken the immobilization efficiency of Zn²⁺. The new exploration of these mechanisms provide a theoretical basis for rationally adjusting the Magnesia/Phosphate ratio to enhance the compressive strength and improve the efficiency of heavy metals immobilization.