International audience | The ability of the free ion activity model (FIAM), the terrestrial biotic ligand model (TBLM), the diffusive gradients in thin films (DGT) technique and a plant-based biotest, the RHIZOtest, to predict root copper (Cu) concentration in field-grown durum wheat (Triticum turgidum durum L) was assessed on 44 soils varying in pH (3.9-7.8) and total Cu (32-184 mg kg(-1)). None of the methods adequately predicted root Cu concentration, which was mainly correlated with total soil Cu. Results from DGT measurements and even more so FIAM prediction were negatively correlated with soil pH and over-estimated root Cu concentration in acidic soils. TBLM implementation improved numerically FIAM prediction but still failed to predict adequately root Cu concentration as the TBLM formalism did not considered the rhizosphere alkalisation as observed in situ. In contrast, RHIZOtest measurements accounted for rhizosphere alkalisation and were mainly correlated with total soil Cu.

The ammonia stomatal compensation point of plants is determined by leaf temperature, ammonium concentration ([NH4+]apo) and pH of the apoplastic solution. The later two depend on the adjacent cells metabolism and on leaf inputs and outputs through the xylem and phloem. Until now only empirical models have been designed to model the ammonia stomatal compensation point, except the model of Riedo et al. (2002. Coupling soil-plant-atmosphere exchange of ammonia with ecosystem functioning in grasslands. Ecological Modelling 158, 83e110), which represents the exchanges between the plant’s nitrogen pools. The first step to model the ammonia stomatal compensation point is to adequately model [NH4+]apo. This [NH4+]apo has been studied experimentally, but there are currently no process-based quantitative models describing its relation to plant metabolism and environmental conditions. This study summarizes the processes involved in determining the ammonia stomatal compensation point at the leaf scale and qualitatively evaluates the ability of existing whole plant N and C models to include a model for [NH4+]apo.

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.

Significant concerns have been raised regarding to the pollution of antibiotics in recent years due to the abuse of antibiotics and their high detection rate in water. Herein, a novel super adsorbent, boronic acid-modified bacterial cellulose microspheres with a size of 415 μm in diameter was prepared through a facile water-in-oil emulsion method. The adsorbent was characterized by atomic force microscopy, scanning electron microscopy, and fourier transform infrared spectroscopy analyses to confirm its properties. The microspheres were applied as packing materials for the adsorption of tetracycline (TC) from an aqueous solution and hoggery sewer via the reversible covalent interaction between cis-diol groups in TC molecules and the boronic acid ligand. TC adsorption performance had been systemically investigated under various conditions, including the pH, temperature, TC concentration, contact time, and ionic strength. Results showed that the adsorption met pseudo-second-order, Elovich kinetic model and Sips, Redlich-Peterson isothermal models. And the adsorption process was spontaneous and endothermic, with the maximum TC adsorption capacity of 614.2 mg/g. After 18 adsorption-desorption cycles, the adsorption capacity remained as high as 84.5% compared with their original adsorption capacity. Compared with other reported adsorption materials, the microspheres had high adsorption capacity, a simple preparation process, and excellent recovery performance, demonstrating great potential in application on TC removal for water purification and providing new insights into the antibiotic's adsorption behavior of bacterial cellulose-based microspheres.

The ionic strength of infiltration water changes with the seasonal alternation of irrigation sources. In this study, reactivity changes of birnessite-coated sand with the fluctuations of ionic strength of infiltration water (i.e. from groundwater to rainwater) and the involved mechanism were investigated through column experiments. Birnessite-coated sand was less reactive in groundwater than in rainwater because of the higher cation content and higher pH of groundwater. The cations in the groundwater were adsorbed on birnessite-coated sand and then desorbed in presence of a dilute aqueous solution represented by rainwater. The reactivity of the passivated birnessite-coated sand was recovered instantaneously, and approximately one-third of the pristine reactivity was restored. During recovery, Na⁺ desorption and lincomycin (LIN) removal both exhibited a two-stage reaction pattern. The LIN removal correlated with Na⁺ desorption (r = 0.99) so that the reactive sites that were binding 5.602 μmol of Na⁺ became available for 1 μmol of LIN removal. These results suggest that the reactivity of manganese oxides toward organic contaminant is associated with the ionic strength of infiltration water and indicate that the partial reactivity can be naturally restored.

The effects of combined biochar and double inhibitor application on gaseous nitrogen (N; nitrous oxide [N₂O] and ammonia [NH₃]) emissions and N leaching in paddy soils remain unclear. We investigated the effects of biochar application at different rates and double inhibitor application (hydroquinone [HQ] and dicyandiamide [DCD]) on NH₃ and N₂O emissions, N leaching, as well as rice yield in a paddy field, with eight treatments, including conventional urea N application at 280 kg N ha⁻¹ (CN); reduced N application at 240 kg N ha⁻¹ (RN); RN + 7.5 t ha⁻¹ biochar (RNB1); RN + 15 t ha⁻¹ biochar (RNB2); RN + HQ + DCD (RNI); RNB1 + HQ + DCD (RNIB1); RNB2 + HQ + DCD (RNIB2); and a control without N fertilizer. When compared with N leaching under RN, biochar application reduced total N leaching by 26.9–34.8% but stimulated NH₃ emissions by 13.2–27.1%, mainly because of enhanced floodwater and soil NH₄⁺-N concentrations and pH, and increased N₂O emission by 7.7–21.2%, potentially due to increased soil NO₃⁻-N concentrations. Urease and nitrification inhibitor addition decreased NH₃ and N₂O emissions, and total N leaching by 20.1%, 21.5%, and 22.1%, respectively. Compared with RN, combined biochar (7.5 t ha⁻¹) and double inhibitor application decreased NH₃ and N₂O emissions, with reductions of 24.3% and 14.6%, respectively, and reduced total N leaching by up to 45.4%. Biochar application alone or combined with double inhibitors enhanced N use efficiency from 26.2% (RN) to 44.7% (RNIB2). Conversely, double inhibitor application alone or combined with biochar enhanced rice yield and reduced yield-scaled N₂O emissions. Our results suggest that double inhibitor application alone or combined with 7.5 t ha⁻¹ biochar is an effective practice to mitigate NH₃ and N₂O emission and N leaching in paddy fields.

Trivalent chromium [Cr(III)] and tannins serve as necessary substances in leather processing and coexist in tannery site, which lead to the chromium contamination in site soil when disposed improperly. However, coexisting tannins are very likely to complex with Cr(III) and affect its properties, ultimately changing the mobility of chromium in soil. In this study, tannic acid (TA) was selected to investigate the complexation with Cr(III) and the influence on the solubility and sorption of Cr(III) in soils. Then, the transport behavior and mechanism of Cr(III)-TA complexes in soil was clarified. Dialysis results showed that the increase of TA concentration and solution pH promoted the formation of complexed Cr(III). The results of UV–Vis absorption spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations indicated that the adjacent ionized phenolic hydroxyls in TA functioned as the binding sites with Cr(III) to form the Cr–O bonds and the degree of complexation increased with pH. The Cr(III)-TA complexes had higher solubility than free Cr(III) at pH ≥ 6.0. Batch sorption experiments demonstrated that the sorption capacity of Cr(III)-TA to soils with different pH was always lower than that of free Cr(III). These reasons led to the stronger mobility of Cr(III)-TA in soil columns than Cr(III). Our research reveals that the enhanced mobility of Cr(III) in soils coexisting with TA.

Although pollutants pose environmental and human health risks, the majority are not routinely monitored and regulated. Organic pollutants emanate from a variety of sources, and can be classified depending on their chemistry and environmental fate. Classification of pollutants is important because it informs fate processes and apposite removal technologies. The occurrence of emerging contaminants (ECs) in water bodies is a source of environmental and human health concern globally. Despite being widely reported, data on the occurrence of ECs in South Africa are scarce. Specifically, ECS in wastewater in the Northern Cape in South Africa are understudied. In this study, various ECs were screened in water samples collected from three wastewater treatment plants (WWTPs) in the province. The ECs were detected using liquid chromatography coupled to high resolution Orbitrap mass spectrometry following Oasis HLB solid-phase extraction. The main findings were: (1) there is a wide variety of ECs in the WWTPs, (2) physico-chemical properties such as pH, total dissolved solids, conductivity, and dissolved organic content showed reduced values in the outlet compared to the inlet which confirms the presence of less contaminants in the treated wastewater, (3) specific ultraviolet absorbance of less than 2 was observed in the WWTPs samples, suggesting the presence of natural organic matter (NOM) that is predominantly non-humic in nature, (4) most of the ECs were recalcitrant to the treatment processes, (5) pesticides, recreational drugs, and analgesics constitute a significant proportion of pollutants in wastewater, and (6) NOM removal ranged between 35 and 90%. Consequently, a comprehensive database of ECs in wastewater in Sol Plaatje Municipality was created. Since the detected ECs pose ecotoxicological risks, there is a need to monitor and quantify ECs in WWTPs. These data are useful in selecting suitable monitoring and control strategies at WWTPs.

Contaminant vulnerability in the critical zones like groundwater (GW)-seawater (SW) continuum along the entire Gujarat coast was investigated for the first time through an extensive water monitoring survey. The prime focus of the study was to evaluate whether or not: i) seawater intrusion induced metal load translates to toxicity; ii) in the coastal groundwater, metal distribution follows the pattern of other geogenic and anthropogenic contaminants like NO₃- and F-; and iii) what future lies ahead pertaining to metal fate in association with saturation conditions of the coastal aquifers. The spatial distribution of contaminants depicts that the Gulf of Khambhat area is highly contaminated. Ecological risk assessment (ERA) indicates that the Gujarat coast is experiencing a high ecological risk compared to the southeast coast of India. Investigation results revealed that metals, pH, NO₃, and CO₃ are more vulnerable at the SW-GW mixing interface. An increase in pH is reflected in fewer ionic species of metals in the GW. Salinity ingress due to seawater intrusion (SWI) reduces the toxicities of all trace metals except Cu, attributed to the increase of Ca in GW, leading to dissociation of CuCO₃. Reactive species are dominant for Zn and Cd; and M-CO₃ ligands are dominant for Cu and Pb owing to the undersaturation of dolomite and calcite in the aquifer system. SWI tends to increase the metal load but the toxicity of metals varies with the density of industries, anthropogenic activities, changes in the mixing-induced saturation conditions, and intensive salt production across the coast. Multivariate analysis confirmed that the hydrogeochemical processes change due to GW-SW mixing and dictates over natural weathering. The ecological risk index (ERI) for the Arabian sea is experiencing moderate (300 ≥ ERI>150) to high ecological risk (ERI >600). Children population is likely to encounter a high health risk through ingestion and dermal exposure than adults. Overall, the study emphasizes the complexity of toxicity-related health impacts on coastal communities and suggests the dire need for frequent water monitoring along the coastal areas for quick realization of sustainable development goals.

Xiangjiang (XJ) is a typical urban inland river that serves as a drinking water source, which may be affected by the currently used organochlorine pesticides (CUOCPs) originating from agricultural activities in the vicinity. On this basis, this study comprehensively explored the occurrence and distribution characteristics of CUOCPs in surface water and sediments under long-term precipitation and subsequent floods. Considering the low concentration of CUOCPs in water, a technique combining high-throughput organic analysis with high-volume solid phase extraction (High-throat/Hi-volume SPE) was introduced for effective analysis of CUCOPs. The results showed that the concentration of CUOCPs in the water and sediments of XJ ranged from 2.33 to 6.40 ng L⁻¹ (average of 3.93 ± 1.15 ng L⁻¹) and from 1.52 to 21.2 ng g⁻¹ (average of 6.60 ± 4.31 ng g⁻¹ dw), respectively. The distribution of CUOCPs in water was consistent throughout XJ, but that in sediments was not uniform, indicating a stronger impact of floods on water than on sediments. Water-sediment partition coefficients were generally >2 L g⁻¹, showing a tendency of CUOCP dominance in sediments. The results of principal component analysis and cluster analysis showed that the occurrence of CUOCPs is significantly affected by exogenous disturbance, which could be flood events; meanwhile, clusters of CUOCPs were found in both water and sediments in the source-limited middle reaches in urban areas. Redundancy analysis (RDA) showed that CUOCP occurrences were not positively correlated with nutrient elements (nitrogen and phosphorus), but related to pH and dissolved oxygen (DO), indicating complex sources.