Mercury (Hg) and methylmercury (CH3Hg) bind strongly to micro and nano (NP) particles and this partitioning impacts their fate and bioaccumulation into food webs, and, as a result, potential human exposure. This partitioning has been shown to influence the bioavailability of inorganic Hg to methylating bacteria, with NP-bound Hg being more bioavailable than particulate HgS, or organic particulate-bound Hg. In this study we set out to investigate whether the potential interactions between dissolved ionic Hg (HgII) and CH3Hg and NPs was due to incorporation of Hg into the core of the cadmium selenide and sulfide (CdSe; CdS) nanoparticles (metal exchange or surface precipitation), or due purely to surface interactions. The interaction was assessed based on the quenching of the fluorescence intensity and lifetime observed during HgII or CH3Hg titration experiments of these NP solutions. Additional analysis using inductively coupled plasma mass spectrometry of CdSe NPs and the separated solution, obtained after HgII additions, showed that there was no metal exchange, and X-ray photoelectron spectroscopy confirmed this and further indicated that the Hg was bound to cysteine, the NP capping agent. Our study suggests that Hg and CH3Hg adsorbed to the surfaces of NPs would have different bioavailability for release into water or to (de)methylating organisms or for bioaccumulation, and provides insights into the behavior of Hg in the environment in the presence of natural or manufactured NPs.

As one of the most cost-effective and sustainable methods for contaminants' removal, sequestration and/or detoxification, phytoremediation has already captured comprehensive attention worldwide. Nevertheless, the accurate effects of various spatial pattern in enhancing phytoremediation efficiency is not yet clear, especially for the polluted mining areas. This study designed nine planting patterns (monocropping, double intercropping and triple intercropping) of three indigenous plant species (Setaria viridis (L.), Echinochloa crus-galli (L.) and Phragmites australis (Cav.) Trin. ex Steud.) to further explore the effects of plants spatial pattern on phytoremediation efficiency. Considering the uncertainties of the residual contaminants' concentration (RCC) caused by soil anisotropy, permeability and land types, the interval transformation was introduced into the plant uptake model to simulate the remediation efficiency. Then multi-criteria decision analysis (MCDA) were applied to optimal the planting patterns, with the help of criteria of (a) the amount of heavy metal absorption; (b) the concentration of residual contaminant in soil; (c) root tolerance of heavy metals; (d) the total investment cost. Results showed that (1) the highest concentrations of Zn, Cd, and Pb of the polluted area were 7320.02, 14.30, 1650.51 mg kg⁻¹ (2) During the 180 days simulation, the highest RMSE of residue trace metals in soil are 3.02(Zn), 2.67(Pb), 2.89(Cd), respectively. (3) The result of IMCDA shows that the planting patterns of Setaria viridis, Echinochloa crus-galli and Phragmites australis in alternative a9 (269 mg kg⁻¹ year⁻¹) had the highest absorption rate of heavy metals compared with a7 (235 mg kg⁻¹ year⁻¹) and a2 (240 mg kg⁻¹ year⁻¹). After 20 years of remediation, the simulated RCC in a9 is far below the national standard, and the root toxicity is 0.12 (EC ≤ EC₂₀). In general, the optimal alternative derived from interval residual contaminant concentration can effectively express the dynamic of contaminant distribution and then can be effectively employed to evaluate the sustainable remediation methods.

The aim of this study was to assess the effect of major cations (Ca²⁺, Mg²⁺, Na⁺, K⁺, and H⁺) on cadmium toxicity to the springtail Folsomia candida. Survival of the animals was determined after seven days exposure to different cadmium concentrations in an inert sand-solution medium, in different experimental setups with modification of the cation concentrations. Among the cations tested, Ca²⁺ and Mg²⁺ had protective effects on the toxicity of cadmium to the springtails while Na⁺, K⁺, and H⁺ showed less competition with free cadmium ions for binding to the uptake sites of the collembolans. Toxicity predicted with a biotic ligand model agreed well with the observed values. Calculated conditional binding constants and the fraction of biotic ligands occupied by cadmium to show 50% effects were similar to values reported in the literature. The results emphasize the important role of solution chemistry in determining metal toxicity to soil invertebrates.

In the present study, the competitive adsorption of Cu²⁺, Pb²⁺, and Cd²⁺ by a novel natural adsorbent (i.e., argillaceous limestone) modified with chitosan (C-AL) was investigated. The results demonstrated that both intraparticle diffusion and chemisorption marked significant contributions to the Cu²⁺ adsorption process by both raw argillaceous limestone (R-AL) and C-AL in mono-metal adsorption systems. Antagonism was found to be the predominant competitive effect for Cu²⁺, Pb²⁺ and Cd²⁺ adsorptions by C-AL in the multi-metal adsorption system. The three-dimensional simulation and FTIR analysis revealed that the presence of Cu²⁺ suppressed Pb²⁺ and Cd²⁺ adsorptions, while the effect of Cd²⁺ on Cu²⁺ and Pb²⁺ adsorptions was insignificant. The spectroscopic analyses evidenced that amide groups in C-AL played a crucial role in metal adsorption. The preferential adsorptions of Pb²⁺ > Cu²⁺ > Cd²⁺ were likely due to the different affinities of the metals to the lone pair of electrons on the N atom from the amide groups and/or the O atoms from the –OH and -COO⁻ groups on C-AL. The interactions between C-AL and metal ions and between various metal species influenced their competitive adsorption behaviors. C-AL exhibited a superior metal adsorption capacity in comparison with that the capacities of other natural adsorbents reported during the last decade, suggesting its potential practical applications.

Atmospheric particulate matter (PM) pollution levels and human health risks resulting from exposure to non-anthropogenic pollution sources, such as coal mine-fires, are serious global issues. The toxicity of PM₁₀-bound metals and polycyclic aromatic hydrocarbons (PAHs) was assessed according to their non-cancer and cancer risks (CRs) at the mine-fire and in an adjacent city area. Health risks were estimated for inhalation, ingestion, and dermal absorption pathways. The non-cancer risks, presented in terms of the hazard index (HI) and hazard quotient (HQ), were found to be significant (>1) at all locations, except in the mining (for HQ-dermal) and city background area (for HQ-ingestion and HQ-dermal) in children and adults, respectively. The total CR was estimated to be highest at the city nearby the mine-fire area (3.31E-02 and 1.93E-02) followed by the mine-fire area (2.66E-02 and 1.71E-02) for children and adults, respectively. The total CR and CR via individual exposure routes were estimated to be in the high risk (10⁻³ ≤ CR < 10⁻¹) category at the mine-fire site and adjacent city area. For all exposures, CR levels were calculated to be higher than the acceptable range (from 1.00E-06 to 1.00E-04), except for the CR-inhalation level at the A5 location. Among all elements, Cd and BaPₑqᵤ were more significant for the CR at the coal mine-fire and the adjacent city area. Hence, this study concluded that non-anthropogenic sources, such as coal mine-fires, could be part for the significant health risk (carcinogenic and non-carcinogenic) levels in the study area.

Huelva is a highly industrialized city in SW Spain hosting, among others, a Cu smelter, a phosphate fertilizer plant, a power plant, and oil refineries. This study aims to evaluate metal concentrations in lichens as bioindicators of atmospheric pollution in the impacted urban areas. Xanthoria parietina species from Huelva and nearby villages, as well as reference samples from remote, non-contaminated urban areas, were analyzed for trace elements (V, Cr, Mn, Co, Ni, Cu, Zn, Sr, As, Cd, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm, Er, Tm, Yb, Lu, Pb, Th, U) using Inductively Coupled Plasma-Mass Spectrometry; and for major elements (Ca, K, Mg, P, and S) by Inductively Coupled Plasma-Optical Emission Spectrometry after acid digestion.The metal composition of X. parietina exhibits spatial distribution patterns with extremely elevated concentrations (Co, Ni, Cu, Zn, As, Cd, Sb, Ba, Pb, U, and S) in the surroundings of the industrial estates to <1 km distance. Mean concentrations were significantly lower in the urban areas >1 km from the pollution sources. However, air pollution persists in the urban areas up to 4 km away, as the mean concentrations of Cu, Zn, As, Cd, Sb and S remained considerably elevated in comparison to the reference samples. Though rigorous source apportionment analysis was not the aim of this study, a good positive correlation of our results with metal abundances in ambient particulate matter and in pollution sources points to the Cu smelter as the main source of pollution. Hence, the severe air pollution affecting Huelva and nearby urban areas may be considered a serious health risk to local residents.

Land degradation by salinization and sodification changes soil function, destroys soil health, and promotes bioaccumulation of heavy metals in plants, but little is known about their fundamental mechanisms in shaping microbial communities and regulating microbial interactions. In this study, we explored the impact of saline-alkaline (SA) stress on soil bacterial and fungal community structures in different Cd-contaminated soils of Dezhou, Baoding, Xinxiang, Beijing and Shenyang cities from the North China Plain, China. Increased soil salinity and alkalinity enhanced Cd availability, indicated by significant increases in available Cd2+ in soil solution of 34.1%–49.7%, soil extractable Cd of 32.0–51.6% and wheat root Cd concentration of 24.5%–40.2%, as well as decreased activities of antioxidative enzymes of wheat root when compared with CK (no extra neutral or alkaline salts added). Soil bacteria were more active in response to the SA stress than fungi, as the significant structural reorganization of soil bacterial microbiota rather than fungal microbiota between SA and CK treatments was illustrated by principal component analysis. Adding neutral and alkaline salts enriched oligotrophic and haloalkaliphilic taxa in the Sphingobacteriaceae, Cellvibrionaceae, and Caulobacteraceae bacterial families, but decreased some Acidobacteria such as subgroup 6_norank, which was a sensitive biomarker that responded only to Cd contamination in CK-treated soils. Conversely, fungi were more sensitive to soil differences than bacteria: the composition of the fungal community was significantly different among different soil types. Phylogenetic molecular ecological network (pMEN) analysis further indicated that the microbial community structure and network interactions were altered to strengthen the adaptability of microorganisms to SA stress; the changes in structure and network interactions were proposed to contribute to competitive interactions. Most of the keystone genera identified in SA-treated soils, such as Blastococcus, Gemmatimonas, RB41, or Candida, had relatively low abundances (<1%), indicating their disproportionate ecological roles in triggering resistance or tolerance to SA stress and Cd toxicity.

Proper management of waste crop residues has been an environmental concern for years. Yellow mealworms (larvae of Tenebrio molitor Linnaeus, 1758) are major insect protein source. In comparison with normal feed wheat bran (WB), we tested five common lignocellulose-rich crop residues as feedstock to rear mealworms, including wheat straw (WS), rice straw (RS), rice bran (RB), rice husk (RH), and corn straw (CS). We then used egested frass for the production of biochar in order to achieve clean production. Except for WS and RH, the crop residues supported mealworms’ life activity and growth with consumption of the residues by 90% or higher and degraded lignin, hemicellulose and cellulose over 32 day period. The sequence of degradability of the feedstocks is RS > RB > CS > WS > RH. Egested frass was converted to biochar which was tested for metal removal including Pb(II), Cd(II), Cu(II), Zn(II), and Cr(VI). Biochar via pyrolysis at 600 °C from RS fed frass (FRSBC) showed the best adsorption performance. The adsorption isotherm fits the Langmuir model, and kinetic analysis fits the Pseudo-Second Order Reaction. The heavy metal adsorption process was well-described using the Intra-Particle Diffusion model. Complexation, cation exchange, precipitation, reduction, deposition, and chelation dominated the adsorption of the metals onto FRSBC. The results indicated that crop residues (WS, RS, RB, and CS) can be utilized as supplementary feedstock along with biochar generated from egested frass to rear mealworms and achieve clean production while generating high-quality bioadsorbent for environment remediation and soil conditioning.

Measurement of solute-transport parameters through soils for a wide range of solute- and soil-types is time-consuming, laborious, expensive and practically impossible. So, indirect methods for estimating the transport parameters by pedo-transfer functions are now advancing. This study developed and evaluated an Artificial Neural Network (ANN) model for estimating the transport velocity (V), dispersion coefficient (D) and retardation factor (R) of NaAsO₂, Pb(NO₃)₂, Cd(NO₃)₂, C₉H₉N₃O₂ and CaCl₂ from the basic soil properties. Breakthrough data of the solutes were measured in 14 agricultural soils of Bangladesh by time-domain reflectometry (TDR) in repacked soil columns under unsaturated steady-state water-flow conditions. The transport parameters of the chemicals were determined by analyzing the solute breakthrough data. Bulk density (γ), organic carbon (OC), clay (C) content, pH, median grain diameter (D₅₀) and uniformity coefficient (Cᵤ) of the soils were determined. An ANN model for V, D and R was developed by using data of eight soils, validated/tested with the data of five soils and verified with the data of one soil. Clay content and bulk density of the soils were the most sensitive input variables to the ANN model followed by other soil properties (OC, C, pH, D₅₀ and Cᵤ). The model reliably predicted V, D and R with relative root-mean-square error (RRMSE) of 0.028–0.363, mean error (ME) of – 0.00004 to 0.0005, bias error (BOE%) of 0–0.003 and modeling efficiency (EF) of >0.99. Thus, the ANN model can significantly enhance prediction of pollution transport through soils in terms of cost and effort.

Enhancing metals phytoextraction using gentile mobilizing agents might be an appropriate approach to increase the phytoextraction efficiency and to shorten the phytoremediation duration. The effect of sulfur-impregnated organoclay (SIOC) on the redistribution of potentially toxic elements (PTEs) among their geochemical fractions in soils and their plant uptake has not yet been studied. Therefore, our aim is to investigate the role of different SIOC application doses (1%, 3% and 5%) on operationally defined geochemical fractions (soluble + exchangeable; bound to carbonate; manganese oxide; organic matter; sulfide; poorly- and well-crystalline Fe oxide; and residual fraction) of Cd, Cr, Cu, Ni, Pb, and Zn, and their accumulation by pea (Pisum sativum) and corn (Zea mays) in a greenhouse pot experiment using a polluted floodplain soil. The SIOC caused a significant decrease in soil pH, and an increase in organic carbon and total sulfur content in the soil. The addition of SIOC increased significantly the soluble + exchangeable fraction and bioavailability of the metals. The SIOC leads to a transformation of the residual, organic, and Fe-Mn oxide fractions of Cd, Cu, Ni, and Zn to the soluble + exchangeable fraction. The SIOC addition increased the potential mobile (non-residual) fraction of Cr and Pb. The SIOC increased the sulfide fraction of Cr, Ni, and Zn, while it decreased the same fraction for Cd, Cu, and Pb. The effect of SIOC on the redistribution of metal fractions increased with enhancing application dosages. Pea accumulated more metals than corn with greater accumulation in the roots than shoots. Application of the higher dose of SIOC promoted the metals accumulation by roots and their translocation to shoots of pea and corn. Our results suggest the potential suitability of SIOC for enhancing the phytomanagement of PTEs polluted soils and reducing the environmental risk of these pollutants.