Low pH and aluminum (Al)-toxicity often coexist in acidic soils. Citrus sinensis seedlings were treated with nutrient solution at a pH of 2.5, 3.0, 3.5 or 4.0 and an Al concentration of 0 or 1 mM for 18 weeks. Thereafter, malate, citrate, isocitrate, acid-metabolizing enzymes, and nonstructural carbohydrates in roots and leaves, and release of malate and citrate from roots were measured. Al concentration in roots and leaves increased under Al-toxicity, but it declined with elevating nutrient solution pH. Al-toxicity increased the levels of glucose, fructose, sucrose and total soluble sugars in leaves and roots at each given pH except for a similar sucrose level at pH 2.5–3.0, but it reduced or did not alter the levels of starch and total nonstructural carbohydrates (TNC) in leaves and roots with the exception that Al improved TNC level in roots at pH 4.0. Levels of nonstructural carbohydrates in roots and leaves rose with reducing pH with a few exceptions with or without Al-toxicity. A potential model for the possible role of root organic acid (OA) metabolism (anions) in C. sinensis Al-tolerance was proposed. With Al-toxicity, the elevated pH upregulated the OA metabolism, and increased the flow of carbon to OA metabolism, and the accumulation of malate and citrate in roots and subsequent release of them, thus reducing root and leaf Al and hence eliminating Al-toxicity. Without Al-toxicity, low pH stimulated the exudation of malate and citrate, an adaptive response of Citrus to low pH. The interactive effects of pH and pH on OA metabolism were different between roots and leaves.

To investigate the removal characteristics of ammonium-nitrogen (NH₄⁺-N), nitrite-nitrogen (NO₂⁻-N), nitrate-nitrogen (NO₃⁻-N), and total nitrogen from groundwater by a degradable composite active medium, kinetics, thermodynamics, and equilibrium adsorption, experiments were performed using scoria and degrading bacteria immobilized on scoria. Removal of NH₄⁺-N, NO₂⁻-N, and NO₃⁻-N was conducted in adsorption experiments using different times, initial concentrations, pH values, and groundwater chemical compositions (Ca²⁺, Mg²⁺, HCO₃⁻, CO₃²⁻, Fe²⁺, Mn²⁺, and SO₄²⁻). The results showed that the removal of nitrogen by the composite active medium was obviously better than that of scoria alone. The removal rates of NH₄⁺-N (C₀ = 5 mg/L), NO₂⁻-N (C₀ = 5 mg/L), and NO₃⁻-N (C₀ = 100 mg/L) by the composite active medium within 1 h were 96.05%, 82.40%, and 83.16%, respectively. The adsorption kinetics were well fitted to a pseudo-second order model, whereas the equilibrium adsorption agreed with the Freundlich model. With changes in the pH, variation in the removal could be attributed to the combined effect of hydrolysis and competitive ion adsorption, and the optimum pH was 7. Different concentration conditions, hardness, alkalinity, anions, and cations showed different promoting and inhibiting effects on the removal of nitrogen. A careful examination of ionic concentrations in adsorption batch experiments suggested that the sorption behavior of nitrogen onto the immobilized medium was mainly controlled by ion exchange. The degrading bacteria on the scoria surface were eluted and analyzed by metagenomic sequencing. There were significant differences in the number of operational taxons, relative abundances, and community diversity among degrading bacteria after adsorption of the three forms of nitrogen. The relative abundance of degrading bacteria was highest after NO₃⁻-N removal, and the diversity was highest after NO₂⁻-N removal. Pseudomonas and Serratia were the dominant genera that could efficiently remove NH₄⁺-N and NO₂⁻-N.

In this study, we examined the removal of arsenite (As(III)) and arsenate (As(V)) by perilla leaf-derived biochars produced at 300 and 700 °C (referred as BC300 and BC700) in aqueous environments. Results revealed that the Langmuir isotherm model provided the best fit for As(III) and As(V) sorption, with the sorption affinity following the order: BC700-As(III) > BC700-As(V) > BC300-As(III) > BC300-As(V) (QL = 3.85–11.01 mg g⁻¹). In general, As removal decreased (76–60%) with increasing pH from 7 to 10 except for the BC700-As(III) system, where notably higher As removal (88–90%) occurred at pH from 7 to 9. Surface functional moieties contributed to As sequestration by the biochars examined here. However, significantly higher surface area and aromaticity of BC700 favored a greater As removal compared to BC300, suggesting that surface complexation/precipitation dominated As removal by BC700. Arsenic K-edge X-ray absorption near edge structure (XANES) spectroscopy demonstrated that up to 64% of the added As(V) was reduced to As(III) in BC700- and BC300-As(V) sorption experiments, and in As(III) sorption experiments, partial oxidation of As(III) to As(V) occurred (37–39%). However, XANES spectroscopy was limited to precisely quantify As binding with sulfur species as As2S3-like phase. Both biochars efficiently removed As from natural As-contaminated groundwater (As: 23–190 μg L⁻¹; n = 12) despite in the presence of co-occurring anions (e.g., CO3²⁻, PO4³⁻, SO4²⁻) with the highest levels of As removal observed for BC700 (97–100%). Overall, this study highlights that perilla leaf biochars, notably BC700, possessed the greatest ability to remove As from solution and groundwater (drinking water). Significantly, the integrated spectroscopic techniques advanced our understanding to examine complex redox transformation of As(III)/As(V) with biochar, which are crucial to determine fate of As on biochar in aquatic environments.

Recent efforts have been directed towards better understanding the persistency and toxicity of ionic liquids (ILs) in the context of the “benign-by-design” approach, but the assessment of their bioaccumulation potential remains neglected. This paper reports the experimental membrane partitioning of IL cations (imidazolium, pyridinium, pyrrolidinium, phosphonium), anions ([C(CN)3]-, [B(CN)4]-, [FSO2)2N]-, [(C2F5)3PF3]-, [(CF3SO2)2N]-) and their combinations as a measure for estimating the bioconcentration factor (BCF). Both cations and anions can have a strong affinity for phosphatidylcholine bilayers, which is mainly driven by the hydrophobicity of the ions. This affinity is often reflected in the ecotoxicological impact. Our data revealed that the bioconcentration potential of IL cations and anions is much higher than expected from octanol-water-partitioning based estimations that have recently been presented. For some ILs, the membrane-water partition coefficient reached levels corresponding to BCFs that might become relevant in terms of the “B” (bioaccumulation potential) classification under REACH. However, this preliminary estimation need to be confirmed by in vivo bioconcentration studies.

Bisphenol F (BPF), an environmental estrogen, is used as a monomer in plastic industry and its environmental fate and decontamination are emerging concern. This study focused on the kinetics, influencing factors and pathways of its oxidation by MnO₂. At pH 5.5, about 90% of BPF was oxidized in 20min in a solution containing 100μM MnO₂ and 4.4μM BPF. The reaction was pH-dependent, following an order of pH 4.5>pH 5.5>pH 8.6>pH 7.5>pH 6.5>pH 9.6. Humic acids inhibited the reaction at low (≤pH 5.5) and high pH (≥pH 8.6) at high concentrations. In addition, metal ions and anions also suppressed the reaction, following the order Mn²⁺>Ca²⁺>Mg²⁺>Na⁺ and HPO₄ ²⁻>Cl⁻>NO₃ ⁻≈SO₄ ²⁻, respectively. A total of 5 products were identified, from which a tentative pathway was proposed.

Multivariate statistical techniques are efficient ways to display complex relationships among many objects. An attempt was made to study the data of trace elements in groundwater using multivariate statistical techniques such as principal component analysis (PCA), Q-mode factor analysis and cluster analysis. The original matrix consisted of 17 trace elements estimated from 55 groundwater samples colleted in 27 wells located in a coastal area in Shenzhen, China. PCA results show that trace elements of V, Cr, As, Mo, W, and U with greatest positive loadings typically occur as soluble oxyanions in oxidizing waters, while Mn and Co with greatest negative loadings are generally more soluble within oxygen depleted groundwater. Cluster analyses demonstrate that most groundwater samples collected from the same well in the study area during summer and winter still fall into the same group. This study also demonstrates the usefulness of multivariate statistical analysis in hydrochemical studies. Multivariate statistical analysis was used to investigate relationships among trace elements and factors controlling trace element distribution in groundwater.

Acidification in variable charge soils is on the rise due to increased acid deposition and use of nitrogenous fertilizers. The associated low pH and cation exchange capacity make the soils prone to depleted base cations and increased levels of Al³⁺. Consequently, Al toxicity to plants and soil infertility decrease crop yield. This study was designed to investigate the effect of Pseudomonas fluorescens on the acidification of two Ultisols. The simulated acidification experiment demonstrated that the pH of bacteria-treated soil was higher than that of control under similar conditions, suggesting that the adhered bacteria inhibited soil acidification. This observation was attributed to the association of organic anions (RCOO⁻ or RO⁻) on bacteria with H⁺ to form neutral molecules (RCOOH or ROH) and reducing the activity of H⁺ in solution. The bacteria also inhibited the increase in soil soluble Al and exchangeable Al during soil acidification. The adhesion of bacteria on the soils increased soil effective cation exchange capacity (ECEC) and exchangeable base cations at each pH compared to control. The release of exchangeable base cations from bacteria-treated soil, and the decrease in soil ECEC and exchangeable base cations with decreasing pH confirmed that protonation of organic anions on adhered bacteria was mainly responsible for the inhibition of soil acidification. The change of zeta potential of the bacteria with pH and the ART-FTIR analysis at various pH provided more evidence for this mechanism. Therefore, the bacteria in variable charge soils played an important role in retarding soil acidification.

After the exploitation of coal mines in the 19th and 20th centuries in northern France, many mining slag heaps (SH) were left without any particular management or monitoring. Currently, the influence of these SHs on the quality of surrounding wetlands is hardly known.The purpose of this work is to determine the water quality in the neighbourhood of two SHs located near the city of Douai and its influence on the distribution of aquatic invertebrates in local wetlands. Our approach involves (1) the spatial and temporal characterization of the water composition (anions, major elements, sulphide, DOC and alkalinity) and of the biological diversity (aquatic invertebrates) and (2), based on this chemical and biological screening, the establishment of relationships between water quality and biodiversity distribution through multivariate data analysis. The results clearly indicate that substantial leaching from the slag heaps occurs, given the very high concentrations of dissolved sulphates (in the range of 2 g L⁻¹). While the pH remains weakly basic, indicating that the leaching water has been neutralized by the highly carbonated regional substratum, high levels of biodegradable organic matter and sulphate contents have been noticed. They sporadically cause significant drops in dissolved oxygen and the occurrence of dissolved sulphides that massively reduce biodiversity, qualitatively and quantitatively. In Summer, oxygen saturation is generally lower due to the higher rate of organic matter degradation, and the risk of anoxic episodes therefore increases. Finally, as wetlands are vulnerable environments, these preliminary results suggest that monitoring and management of these sites must be attempted quickly to avoid the degradation of those valuable habitats.

Nano zero valent iron/Ni bimetal materials (nZVI/Ni) were prepared by borohydride reduction method to remediate toxic Cr(Ⅵ) contaminated in soil leachate. nZVI/Ni was characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS). Different factors including pH value of soil leachate, reaction time, temperature, humic acid and coexisting anions (SO42-, NO3−, HCO3−, CO32-) were studied to analyze the reduction rate. Results showed that the reduction rate of Cr(Ⅵ) could reach 99.84% under the condition of pH of 5 and temperature of 303 K. pH values and temperature of soil leachate had a significant effect on the reduction efficiency, while humic acid had inhibition effect for the reduction reaction. SO42-, HCO3− and CO32- had inhibition effect for reduction rate, while NO3− barely influenced the reduction process of nZVI/Ni. Moreover, Langumir-Hinshelwood first order kinetic model was studied and could describe the reduction process well. The thermodynamic studies indicated that the reaction process was endothermic and spontaneous. Activation energy was 143.80 kJ mol−1, showing that the reaction occurred easily. Therefore, the study provides an idea for nZVI/Ni further research and practical application of nZVI/Ni in soil remediation.

Ionic mixtures, measured as specific conductivity, have been increasingly concerned because of their toxicities to aquatic organisms. However, identifying protective values of specific conductivity for aquatic organisms is challenging given that laboratory test systems cannot examine more salt-intolerant species nor effects occurring in streams. Large data sets used for deriving field-based benchmarks are rarely available. In this study, a field-based method for small data sets was used to derive specific conductivity benchmark, which is expected to prevent the extirpation of 95% of local taxa from circum-neutral to alkaline waters dominated by a mixture of SO42− and HCO3− anions and other dissolved ions. To compensate for the smaller sample size, species level analyses were combined with genus level analyses. The benchmark is based on extirpation concentration (XC95) values of specific conductivity for 60 macroinvertebrate genera estimated from 296 sampling sites in the Hun-Tai River Basin. We derived the specific conductivity benchmark by using a 2-point interpolation method, which yielded the benchmark of 249 μS/cm. Our study tailored the method that was developed by USEPA to derive aquatic life benchmark for specific conductivity for basin scale application, and may provide useful information for water pollution control and management.