Knowledge of distribution of toxic metal in crop is essential for studying toxic metal uptake, transportation and bioaccumulation, and it is important for environmental pollution monitoring. In this study, the macro spatial distribution of chromium in rice leaves was visualized by re-heating dual-pulse laser-induced breakdown spectroscopy (DPLIBS) and chemometric methods. After the optimization of two important parameters (delay time and energy ratio) in DPLIBS, chromium prediction model was established based on global spectra. The global model achieved acceptable performance while slight overfitting for model was found because of numerous irrelevant variables. Feature variables including emissions from chromium and other elements were successfully selected by the values of regression coefficient in partial least square regression model. Best performance was achieved by using the feature variables and support vector machine, with correlation coefficient of prediction of 0.959, root mean square error of prediction of 13.4 mg/kg and residual predictive deviation of 3.6. Finally, the distribution of chromium in rice leaves was visualized with the best prediction model. The distribution image showed that chromium distributed approximately symmetrically along the vein and was likely to be accumulated in leaf apex. The preliminary results provide an approach for investigating the macro spatial distribution of elements in crops, which is important for environmental protection and food safety.

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.

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.

The release of hexavalent chromium [Cr(VI)] into water bodies poses a major threat to the environment and human health. However, studies of the biological response to Cr(VI) are limited. In this study, a toxic bacterial mechanism of Cr(VI) was investigated using Pannonibacter phragmitetus BB (hereafter BB), which was isolated from chromate slag. The maximum Cr(VI) concentrations with respect to the resistance and reduction by BB are 4000 mg L−1 and 2500 mg L−1, respectively. In the BB genome, more genes responsible for Cr(VI) resistance and reduction are observed compared with other P. phragmitetus strains. A total of 361 proteins were upregulated to respond to Cr(VI) exposure, including enzymes for Cr(VI) uptake, intracellular reduction, ROS detoxification, DNA repair, and Cr(VI) efflux and proteins associated with novel mechanisms involving extracellular reduction mediated by electron transfer, quorum sensing, and chemotaxis. Based on metabolomic analysis, 174 metabolites were identified. Most of the upregulated metabolites are involved in amino acid, glucose, lipid, and energy metabolisms. The results show that Cr(VI) induces metabolite production, while metabolites promote Cr(VI) reduction. Overall, multi-enzyme expression and metabolite production by BB contribute to its high ability to resist/reduce Cr(VI). This study provides details supporting the theory of Cr(VI) reduction and a theoretical basis for the efficient bioremoval of Cr(VI) from the environment.

As a useful heavy metal ion, chromium has seen its applications in various fields. While it is also a toxic contaminant in water and may cause serious threats to the environment and human health. To develop a novel material with good adsorption capacity and easy solid-liquid separation strategy was necessary and significant. In this paper, the β-cyclodextrin (β-CD) functionalized three-dimensional structured graphene foam (CDGF) was successfully synthesized with the facile and one-step hydrothermal method. The SEM, BET, XRD, FT-IR and XPS analysis were carried out and the results confirmed the successfully grafting of β-CD onto GF. The batch adsorption of Cr(VI) was also taken out and the CDGF possessed good selectivity compared with other metal ions at pH = 3. The adsorption capacity reduced gradually as the initial pH of the Cr(VI) solution grew higher, which was because the anionic species of Cr(VI) were partial to the positively charged surface of CDGF. The easy separation strategy of the CDGF was also demonstrated and the CDGF could be taken out easily with a tweezer after the adsorption of Cr(VI), which significantly simplified the separation procedure and reduced time. By comparing the FT-IR and XPD analysis results, the adsorption mechanism was explored and the hydroxyl groups on CDGF played the main role in the adsorption process. This work brings a novel material for the adsorption of Cr(VI) from water and provides an innovative direction for the easy and fast solid-liquid separation strategy in the adsorption and other application fields.

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.

The binding of metal ions with humic acid (HA) plays an important role in the aggregation of HA and the migration of metal ions in the environments. The effects of common cations (Na⁺, Mg²⁺, Ca²⁺ and Al³⁺) and heavy metal ions (Ag⁺, Cd²⁺, Cu²⁺, Cr³⁺ and Eu³⁺) on the aggregation of HA were investigated systematically by aggregation kinetics, spectroscopic techniques and molecular dynamic (MD) simulations. The critical coagulation concentration (CCC) of mono-, di- and trivalent cations could be predicted by the Schulze-Hardy rule. The aggregation of HA in the presence of Na⁺ and Ag⁺ was mainly due to the reduction of repulsive force and the hydrogen bonds between HA molecules. While the complexation of di- and trivalent cations with carboxylic/phenolic groups, or the cation-π interactions enhanced the intra- or inter-molecular bridges in HA and then contributed greatly to the aggregation of HA. Heavy metal ions could easily pass through the electric double-layer of HA compared with common cations. MD simulations further signified the strong aggregation ability of HA molecules in solutions containing high valence metal ions. These findings are important for understanding not only how the influence of metal ions on the aggregation of HA, but also the conditions which ions more efficient for aggregation.

Metal contamination in aquatic environments is a severe global concern to human health and aquatic ecosystems. This study used several risk assessment indices, to evaluate metal (Cu, Zn, Pb, Cd and Cr) environmental risk of riverine surface sediments across the rural-urban interface of the rapidly developing Wen-Rui Tang River watershed in eastern China. Risk assessments were determined for 38 sites based on the potential ecological risk index (RI), consensus-based sediment quality guidelines (SQGs) and risk assessment code (RAC). Land-use cluster analysis showed that sediments were severely contaminated, especially for Cd, whose concentrations were ∼100 times higher than background levels and had a high proportion in the bioaccessible fraction. According to RI, ErCd was identified with extremely high risk potential, resulting in the highest ecological risk of Cluster 4 (industrial). Similarly, risk within Cluster 4 (industrial) was also ranked highest by SQGs assessment due to the high proportion of industrial land use. Zinc was determined with high risk due to its high concentration compared to its effect range medium (ERM) value. Discrepancies in predicting environmental risks from metals among the three indices were mainly attributed to the contrasting definitions of these metrics. Environmental risk uncertainty derived from spatial variation was further estimated by Monte Carlo simulation and ranked as: Zn > Cd > Cr > Pb > Cu. This comprehensive environmental risk assessment provides important information to guide remediation strategies for management of metal contamination at the watershed scale.

In modern society, the intense vehicle traffic and the lack of effective mitigating strategies may adversely impact freshwater systems. Road-deposited sediments (RDS) accumulate a variety of toxic substances which are transported into nature during hydrologic events, mainly affecting water bodies through stormwater runoff. The aim of this study was to evaluate the RDS metal enrichment ratio between the end of wet season and the middle of the dry season for Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn in samples from Natal, Brazil. Twenty RDS, drainage system and river sediment samples were collected in the wet and dry seasons using a stainless-steel pan, brush and spatula. In the laboratory, the samples were submitted to acid digestion and heavy metal concentrations were measured by atomic absorption spectrometry (AAS). A consistent RDS enrichment by heavy metals in dry season samples was followed by an increase in the finest particle size fraction (D < 63 μm). Maximum concentrations were 5, ND, 108, 23810, 83, ND, 77 and 150 mg kg⁻¹ for Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn, respectively. The RDS enrichment ratio was Cr(1.3 ×), Cu(2.6 ×), Fe(3.3 ×), Mn(1.5 ×), Pb(1.5 ×) and Zn(2.1 ×). The Geo-accumulation Index values showed that RDS were moderately polluted for Cu and slighted polluted for Zn and Pb. Principal Component Analysis (PCA) showed that the accumulation of toxic heavy metals decreased according to water flow.

Metal flux measurements inform the mobility, potential bioavailability and risk of toxicity for metals in contaminated sediments and therefore is an important approach for sediment quality assessment. The binding and release of metals that contribute to the net flux is strongly influenced by the presence and behaviors of benthic organisms. Here we studied the effects of bioturbation on the mobility and efflux of metals from multi-metal contaminated sediments that inhabited by oligochaete worms or both worms and bivalves. Presence of bivalves enhanced the release of Mn, Co, Ni and Zn but not for copper and chromium, which is likely due to the high affinities of copper and chromium for the solid phase. Metals in the overlying water were primarily associated with fractions smaller than 10 kDa, and the fractionation of all metals were not affected by the presence of the bivalve. Metal fluxes attributed to different processes were also distinguished, and the bioturbation induced effluxes were substantially higher than the diffusive effluxes. Temporal variabilities in the total net effluxes of Mn, Co, Ni and Zn were also observed and were attributed to the biological activities of the bivalves. Overall, the present study demonstrated that the response of different metals to the same bioturbation behavior was different, resulting in distinct mobility and fate of the metal contaminants.