Fluoride (F) is an emerging pollutant that originates from multiple sources and adversely affects plant growth and nutrient bioavailability in soil. This greenhouse study investigated the effects of soil F (0, 10, 20, 50, 100, 200 mg kg⁻¹) on morpho-physiological growth characteristics of wheat, soil F contents, and bioavailability and uptake of F, phosphorus (P), sulphur (S), potassium (K), calcium (Ca), magnesium (Mg), aluminium (Al), iron (Fe), manganese (Mn), silicon (Si) and zinc (Zn) by wheat. Higher F significantly reduced plant height and number of leaves particularly at early growth stages and increased visible leaf injury index. Powdery mildew infestation coincided with leafy injury and was higher in elevated soil F treatments. Fluoride treatments (>50 mg kg⁻¹) significantly increased water (H₂O)- and calcium chloride (CaCl₂)-extractable F contents in soil. Water-extractable soil F contents from soil in all concentration were higher than CaCl₂-extractable F. This increased F bioavailability resulted in significantly higher F uptake and accumulation in live leaves, dead leaves and grains of wheat which followed order: live leaves > dead leaves > grains. Leaf injury index and number of dead leaves correlated significantly positively with soil H₂O- and CaCl₂-extractable F contents. Patterns of nutrient (P, K, S) and trace metals (Al, Ca, Mg, Fe, Mn, Si, Zn) varied significantly with F concentrations and between live and dead leaves, and grains except for Zn. Dead leaves generally had higher nutrients and trace metals than live leaves and grains. Fluoride contents in live leaves, dead leaves and grains showed positive correlations with nutrient elements but negative with trace metals. Number of dead leaves correlated negatively with Al, Ca, Fe, Mg, S and Si but positively with P and Zn contents in dead leaves whereas leaf injury index showed positive correlation with Fe, K, P, Si, Zn, S but negative with Al, Ca and Mg contents. These observations provided evidence of higher F uptake and associated impairment in nutrient and trace metal accumulation which caused leaf injury accompanied by powdery mildew infestation in wheat. However, further research in the region is required to confirm the relationship between F pollution, leaf injury and trace metal accumulation in crops under field conditions.

Present study reports the laboratory and field scale application of different organic and inorganic amendments to immobilize cadmium (Cd) and lead (Pb) in a co-contaminated alluvial paddy soil. For that purpose, lime, biochar, Fe-biochar and two composite amendments (CA) composed of biochar, lime, sepiolite and zeolite (CA1: composite amendment 1) and manure, lime and sepiolite (CA2: composite amendment 2) were firstly tested in an incubation experiment to ameliorate Cd and Pb co-contaminated alluvial soil. It was observed that liming and CA2 elevated the soil pH and reduced DTPA extractable Cd and Pb in the incubated soil leading to higher metal immobilization. Therefore, efficiency of lime and CA2 was further investigated in field conditions with mid rice as the test crop to evaluate field scale immobilization and precise application rate for the tested soil type. DTPA and CaCl₂ extractable Cd (46 and 51%) and Pb (68 and 70%) in field soil were decreased with applied treatments. Speciation of Cd and Pb also promoted conversion of metal exchangeable contents to less-available forms. Activated functional groups on amendments’ surface (_OH bonding, C_O and CO, -O-H, Si–O–Si, carboxylic and ester groups) sequestered metals by precipitation, adsorption, ion exchange or electro static attributes. Application of lime at 2400 kg/acre (T4) and CA2 at 1200 kg/acre was more effective in reducing rice shoot and grains metal contents. Moreover, obtained results in terms of pH, extractable content, speciation and yield, and microanalysis of amendments highlights the remarkable efficiency of lime and composite amendment to sorb Cd and Pb providing the key evidence of these amendments for metals immobilization and environmental remediation. Considering these results, lime and CA2 are potential amendments for co-contaminated rice field especially in context of alluvial soil.

Urbanization and industrialization have elevated metal concentrations in soils. However, systematic investigation on their availability in regional soils under industrial impacts is lacking. In this study, 230 paired soil-rice samples were collected from two areas in Southeast China, with low and high industrial impacts. Classic equilibrium-based CaCl₂ and EDTA extraction methods, and dynamic-based diffusive gradients in thin-films (DGT) technique were used to study metal availability in soils, with the results being compared with metal concentrations in soils and rice grains. Generally, Cd, Ni, Cu, Zn, Cr and Pb concentrations in soils exceeded the Chinese Soil Quality Standard (GB15618-2018), whereas only Cd and Ni in some rice grains exceeded the Chinese Safety Guidelines. CaCl₂ and EDTA extractions, DGT method and soil total metal concentrations provided good predication of grain Cd (R = 0.51–0.66, p < 0.01), whereas only CaCl₂ and DGT tests provided good predication of grain Ni (R = 0.36–0.47, p < 0.01). Overall, CaCl₂ extraction best predicted Cd and Ni accumulation in rice grains, explaining 66% of grain Cd and 47% of grain Ni. The extraction rate of available Cd was higher than that of Ni, indicating higher Cd availability than Ni, consistent with the parameters (response time, Tc, and desorption rate, k–₁) from DIFS (DGT-induced flux in soils) model and bioconcentration factor values. This study showed that, at regional scale, CaCl₂ extraction method is efficient in predicting Cd and Ni accumulation in rice grains from contaminated soils.

Soot nanoparticles (SNPs) produced from incomplete combustion have strong impacts on aquatic environments as they eventually reach surface water, where their environmental fate and transport are largely controlled by aggregation. This study investigated the aggregation kinetics of SNPs in the presence of macromolecules including fulvic acid (FA), humic acid (HA), alginate polysaccharide, and bovine serum albumin (BSA, protein) under various environmentally relevant solution conditions. Our results showed that increasing salt concentrations induced SNP aggregation by suppressing electrostatic repulsion and that CaCl2 exhibited stronger effect than NaCl in charge neutralization, which is in agreement with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The aggregation rates of SNPs were variously reduced by macromolecules, and such stabilization effect was the greatest by BSA, followed by HA, alginate, and FA. Steric repulsion resulting from macromolecules adsorbed on SNP surfaces was mainly responsible for enhancing SNP stability. Such steric repulsion appeared to be affected by macromolecular structure, as BSA having a more compact globular structure on SNP surfaces imparted long-range steric repulsive forces and retarded the SNP aggregation rate by 10–100 times. In addition, alginate was shown to enhance SNP aggregation by ∼10 times at high CaCl2 concentrations due to alginate gel formation via calcium bridging. The results may bear strong significance for the fate and transport of SNPs in both natural and controlled environmental systems.

Municipal solid wastes (MSW) can be composted to become an organic fertilizer. However, besides plant nutrients, it can also contain high concentration of some toxic metals than can pollute agricultural soils, contaminate food, animals and human being. A greenhouse experiment was carried out for two purposes: i) to evaluate the concentrations of cadmium, copper, chromium, nickel, lead and zinc in four Brazilian MSW composts, and, ii) to know which is the best solution for extracting those metals in phytoavailable form from the composts. In order to evaluate the phytoavailability of metals, they were extracted with six chemical extractants: i) water, ii) 0.05 mol L⁻¹ Ca(NO₃)₂, iii) 0.1 mol L⁻¹ HCl, iv) 0.005 mol L⁻¹ DTPA at pH 7.3, v) 0.05 mol L⁻¹ CaCl₂ and vi) Mehlich 3 solution. In addition, lettuces were cultivated as a test plant in pots containing 1.8 kg of MSW compost as substrate. Fifty-six days later, lettuce plants were harvested. New lettuces were then planted for a second cycle, and then harvested after fifty-six days. Semi-total concentration of metals in composts and total in plants was also determined through an extraction with nitric-perchloric acid. Semi–total concentration of Cd and Pb exceeded the intervention limits from Brazil in the four studied composts, and lettuce plants were polluted by those two elements. Therefore, compost made of MSW must be characterized before being used for agricultural soils. Copper and nickel in phytoavailable were effectively extracted with the strongest chelating agents used, HCl and Mehlich 3, probably because most metal is bound to organic matter in the compost. Cadmium, chromium, lead and zinc were no efficiently extracted with any of the tested extractants.

Bisphenol A (BPA) is a widely concerned endocrine disrupting chemical and hard to be removed through conventional wastewater treatment processes. In this study, we developed a TiO2 decorated titanate nanotubes composite (TiO2/TNTs) and used for photocatalytic degradation of BPA. TEM and XRD analysis show that the TiO2/TNTs is a nano-composite of anatase and titanate, with anatase acting as the primary photocatalytic site and titanate as the skeleton. TiO2/TNTs exhibited excellent photocatalytic reactivity and its easy-settling property leaded to good reusability. After 5 reuse cycles, TiO2/TNTs also could photo-degrade 91.2% of BPA with a high rate constant (k1) of 0.039 min⁻¹, which was much better than TiO2 and TNTs. Higher pH facilitated photocatalysis due to more reactive oxygen species produced and less material aggregation. The presence of NaCl and CaCl2 showed negligible effects on BPA degradation, but NaHCO3 caused an inhibition effect resulting from consumption of ·OH. Humic acid inhibited degradation mainly due to blockage of the active sites of TiO2/TNTs. Degradation pathway was well interpreted through theoretical calculation. Hydroxyl radical played the dominate role in BPA photodegradation, and the atoms of BPA with high Fukui index based on density-functional theory (DFT) calculation are the radical easy-attacking (f⁰) sites. Considering the good photocatalytic reactivity, reusability, stability and settle property, TiO2/TNTs promises to be an efficient alternative for removal of organic compounds from wastewaters.

Continual efforts have been made to determine a simple and universal method of estimating heavy metal phytoavailability in terrestrial systems. In the present study, a mechanism-based multi-surface model (MSM) was developed to predict the partition of Ni(II) in soil–solution phases and its bioaccumulation in wheat (Triticum aestivum L.) in 19 Chinese soils with a wide range of soil properties. MSM successfully predicted the Ni(II) dissolution in 0.01 M CaCl2 extracting solution (R2 = 0.875). The two-site model for clay fraction improved the prediction, particularly for alkaline soils, because of the additional consideration of edge sites. More crucially, the calculated dissolved Ni(II) was highly correlated with the metal accumulation in wheat (R2 = 0.820 for roots and 0.817 for shoots). The correlation coefficients for the MSM and various chemical extraction methods have the following order: soil pore water > MSM ≈ diffuse gradient technique (DGT) > soil total Ni > 0.43 M HNO3 > 0.01 M CaCl2. The results suggested that the dissolved Ni(II) calculated using MSM can serve as an effective indicator of the bioavailability of Ni(II) in various soils; hence, MSM can be used as an supplement for metal risk prediction and assessment besides chemical extraction techniques.

Understanding of the interaction of graphene with natural polysaccharides (e.g., alginate) is crucial to elucidate its environmental fate. We investigated the impact of alginate on the agglomeration and stability of ¹⁴C-labeled few-layer graphene (FLG) in varying concentrations of monovalent (NaCl) and divalent (CaCl₂) electrolytes. Enhanced agglomeration occurred at high CaCl₂ concentrations (≥5 mM) due to the alginate gel networks formation in the presence of Ca²⁺. FLG enmeshed within extended alginate gel networks was observed under transmission electron microscope and atomic force microscope. However, background Na⁺ competition for binding sites with Ca²⁺ at the alginate surfaces shielded the gelation of alginate. FLG was readily dispersed by alginate under environmentally relevant ionic strength conditions (i.e., <200 mM Na⁺ and <5 mM Ca²⁺). In comparison with the bare FLG, the slow sedimentation of the alginate-stabilized FLG (158 μg/L) caused continuous exposure of this nanomaterial to freshwater snails, which ingested 1.9 times more FLG through filter-feeding within 72 h. Moreover, surface modification of FLG by alginate significantly increased the whole-body and intestinal levels of FLG, but reduced the internalization of FLG to the intestinal epithelial cells. These findings indicate that alginate will act as a stabilizing agent controlling the transport of FLG in aqueous systems. This study also provides the first evidence that interaction of graphene with natural polysaccharides affected the uptake of FLG in the snails, which may alter the fate of FLG in aquatic environments.

Microplastics are an emerging contaminants of concern in aquatic environments. The aggregation behaviors of microplastics governing their fate and ecological risks in aquatic environments is in need of evaluation. In this study, the aggregation behavior of polystyrene microspheres (micro-PS) in aquatic environments was systematically investigated over a range of monovalent and divalent electrolytes with and without natural organic matter (i.e., Suwannee River humic acid (HA)), at pH 6.0, respectively. The zeta potentials and hydrodynamic diameters of micro-PS were measured and the subsequent aggregation kinetics and attachment efficiencies (α) were calculated. The aggregation kinetics of micro-PS exhibited reaction- and diffusion-limited regimes in the presence of monovalent or divalent electrolytes with distinct critical coagulation concentration (CCC) values, followed the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The CCC values of micro-PS were14.9, 13.7, 14.8, 2.95 and 3.20 mM for NaCl, NaNO3, KNO3, CaCl2 and BaCl2, respectively. As expected, divalent electrolytes (i.e., CaCl2 and BaCl2) had stronger influence on the aggregation behaviors of micro-PS as compared to monovalent electrolytes (i.e., NaCl, NaNO3 and KNO3). HA enhanced micro-PS stability and shifted the CCC values to higher electrolyte concentrations for all types of electrolytes. The CCC values of micro-PS were lower than reported carbonaceous nanoparticles CCC values. The CCC[Ca2+]/CCC [Na+] ratios in the absence and presence of HA at pH 6.0 were proportional to Z−2.34 and Z−2.30, respectively. These ratios were in accordance with the theoretical Schulze–Hardy rule, which considers that the CCC is proportional to z−6–z−2. These results indicate that the stability of micro-PS in the natural aquatic environment and the possibility of significant aqueous transport of micro-PS.

Although the aggregation of graphene oxide (GO) has been widely researched, the influence of the GO size on the homoaggregation behavior and its interaction with environmental media are still unexplored. In this work, critical coagulation concentration (CCC) values for GO with different sizes, from micro to nanosheet, were measured with NaCl and CaCl₂ electrolytes, and the results indicated that GO with the largest size presented the smallest CCC value. Aluminum oxide (Al₂O₃) was selected as a natural solid particle representative to mimic the interaction between GO and environmental media. Batch experiments were conducted in solution with different pH and ionic strength. Results indicated that the attachment capacity of large GO onto Al₂O₃ particles was greater than that of small GO. The experimental data were well fitted with Freundlich model. The electrostatic attraction and hydrogen-bonding interaction dominated the interaction process between GO and Al₂O₃. These findings are important for better understanding in the environmental fate and transport of GO.