Supported carbon quantum dots (CQDs), used as fluorescent sensors for the detection of metal ions, have rarely been used to remove heavy metals from water. Nitrogen-doped CQDs immobilized in hydrophilic silica hydrogels exhibited a more superior sensitivity and selectivity for the detection of Re(VII) and Cr(VI) than other metal ions, including Fe(III), Fe(II), Zn(II), Cu(II) and Mn(II). For the first time, low limits of detection (LOD) of 2.3 μM for Re(VII) detection and 65 nM for Cr(VI) detection were reported by a facile method. Based on the high selectivity of fluorescent silica hydrogels for Re(VII) and Cr(VI) detection, the removal of Re(VII) and Cr(VI) by graphene oxide (GO) in water was monitored with the hydrogels used as a turn-off fluorescent sensing platform. The consistent results of the sorption isotherms of each metal on GO, which were obtained from the fluorescence spectra and by UV absorption, further verified the possibility of monitoring metal removal by fluorescence detection. Remarkably, GO removed 1186 mg/g of Re(VII) but only 178 mg/g of Cr(VI). The density functional theory (DFT) calculations indicated that both Re(VII) and Cr(VI) formed stable bonds with silica hydrogels, confirming that the interactions between the metal ions and the substrate would promote the fluorescence quenching of the supported CQDs. On the other hand, Re(VII) interacted more strongly with the carboxyl groups of GO than Cr(VI). In addition, a real-time detection system was designed to alarm the service life of a GO filter used for Re(VII) removal.

In health-oriented air pollution control, it is vital to rank the contributions of different emission sources to the health risks posed by hazardous components in airborne fine particulate matters (PM₂.₅), such as trace metals. Towards this end, we investigated the PM₂.₅-associated metals in two densely populated regions of China, the Yangtze River Delta (YRD) and Pearl River Delta (PRD) regions, across land-use gradients. Using the positive matrix factorization (PMF) model, we performed an integrated source apportionment to quantify the contributions of the major source categories underlying metal-induced health risks with information on the bioaccessibility (using simulated lung fluid) and speciation (using synchrotron-based techniques) of metals. The results showed that the particulate trace metal profiles reflected the land-use gradient within each region, with the highest concentrations of anthropogenically enriched metals at the industrial sites in the study regions. The resulting carcinogenic risk that these elements posed was higher in the YRD than in the PRD. Chromium was the dominant contributor to the total excessive cancer risks posed by metals while manganese accounted for a large proportion of non-carcinogenic risks. An elevated contribution from industrial emissions was found in the YRD, while traffic emissions and non-traffic combustion (the burning of coal/waste/biomass) were the common dominant sources of cancer and non-cancer risks posed by metals in both regions. Moreover, the risk-oriented source apportionment of metals did not mirror the mass concentration-based one, suggesting the insufficiency of the latter to inform emission mitigation in favor of public health. While providing region-specific insights into the quantitative contribution of major source categories to the health risks of PM₂.₅-associated trace metals, our study highlighted the need to consider the health protection goal-based source apportionment and emission mitigation in supplement to the current mass concentration-based framework.

Odontarrhena muralis is one of the most promissing plant species for Ni phytomining, and soil amendments can further increase its Ni phytoextraction ability. Here we investigated whether Ni phytomining/phytoremediation using this Ni hyperaccumulator can benefit from applying citric acid to a serpentine soil that is naturally enriched in Ni (>1000 mg kg⁻¹). Synchrotron micro X-ray fluorescence (μ-SXRF) was used to image Ni and other metal distributions in whole fresh leaves of O. muralis. Leaf Ni accumulation in plants grown on citric acid-amended soil increased up to 55% while Co, Cr, Fe, Mn, and Zn concentrations were 4-, 14-, 6-, 7- and 1.3-fold higher than the control treatment. O. muralis presented high bioconcentration factors (leaf to soil concentration ratio) to Ni and Zn whereas Cr was seemingly excluded from uptake. The μ-SXRF images showed a uniform distribution of Ni, preferential localization of Co in the leaf tip, and clear concentration of Mn in the base of trichomes. The citric acid treatments strongly increased the Co fluoerescence intensity in the leaf tip and altered the spatial distribution of Mn across the leaf, but there was no difference in Ni fluorescence counts between the trichome-base region and the bulk leaf. Our data from a serpentine soil suggests that citrate treatment enhances Ni uptake, but Co is excreted from leaves even in low leaf concentrations, which can make Co phytoming using O. muralis unfeasible in natural serpentine soils.

A large amounts of arable land is facing a high risk of hexavalent chromium (Cr(VI)) pollution, which requires remediation using a low toxic agent. In this study, the remediation effect of amorphous iron pyrite (FeS₂₍ₐₘ₎) on Cr(VI) in Cr(VI)-contaminated soil was evaluated by systematically analyzing the variation of the leachability, bioaccessibility, phytotoxicity, and long-term stability of the remediated soil. The effectiveness of FeS₂₍ₐₘ₎ on the leachability was assessed by alkaline digestion and the toxicity characteristic leaching procedure (TCLP); the effect on the bioaccessibility was evaluated via the physiologically based extraction test (PBET) and the Tessier sequential extraction; the effect on the phytotoxicity was assessed via phytotoxicity bioassay (seed germination experiments) based on rape (Brassica napus L.) and cucumber (Cucumis Sativus L.), and the long-term stability of the Cr(VI)-remediated soil was appraised using column tests with groundwater and acid rain as the influents. The results show that FeS₂₍ₐₘ₎, with a stoichiometry of 4× exhibited a high efficiency in the remediation of Cr(VI) and decreased its leachability and bioaccessibility during the 30-day remediation period. In addition, seed germination rate, accumulation and translocation of Cr, and root and shoot elongation of rape and cucumber of remediated soil are not significantly different from those of clean soil, illustrating that FeS₂₍ₐₘ₎ is suitable for remediating Cr(VI) contaminated arable soil. The stabilization of Cr(VI) in contaminated soil using FeS₂₍ₐₘ₎ was maintained for 1575 days. The long-term effectiveness was further confirmed by the increasing amount of free Fe and Mn in the effluent and the decreasing redox potential. In summary, FeS₂₍ₐₘ₎ has an excellent efficiency for the remediation of Cr(VI), demonstrating it is a very promising alternative for use in the contaminated arable soil.

Chromium (Cr) is a toxic element among which hexavalent chromium [Cr(VI)] is more toxic than trivalent chromium [Cr(III)]. Chromium can be reduced or oxidized in soil because soil is a complex medium and various soil components affect redox reaction of Cr in soil. Therefore, Cr speciation in hydroponics and soil was compared and Cr uptake and speciation by lettuce grown in the media were evaluated. Higher phytotoxicity was found in Cr(III) spiked soil than in Cr(VI) spiked soil, while Cr toxicity was higher in Cr(VI) treated hydroponics than Cr(III) treated hydroponics. Chromium was mainly accumulated in lettuce roots as Cr(III), and more Cr was translocated from roots to shoots grown in Cr(VI) treated hydroponics than Cr(III) treated hydroponics. Accumulation of Cr in roots grown in Cr(III) treated nutrient solution reduced Fe, K, Ca, Mg, and P uptake in lettuce. Chromium valence state was Cr(III) in lettuce leaves and roots grown in both Cr(III) and Cr(VI) treated hydroponics and soil. Chromium speciation in hydroponically grown lettuce roots was Cr(III) coordinated with 6 oxygens in the first shell and 2 or 4 carbons in the second shell as analyzed by X-ray absorption spectroscopy (XAS), which was similar to chromium acetate. The valence state of Cr in Cr(III) and Cr(VI) treated nutrient solution was not changed, while Cr(VI) was reduced to Cr(III) in Cr(VI) spiked soil by soil organic matter. Spiking of Cr(III) induced reduction of Mn in soil, which resulted in an increase of bioavailable Mn concentration in the Cr(III) spiked soil. Therefore, the increased phytotoxic effect for lettuce in Cr(III) spiked soil can be attributed to the reduction of Mn and subsequent release of Mn(II). For Cr(III) contaminated soil, Mn speciation should be considered, and bioavailable Mn concentration should be monitored although Cr existed as Cr(III) in soil.

A facile method was developed to fabricate porous tube-like ZnS by sulfurizing rod-like ZIF-L with thioacetamide (TAA) at different durations and the formation mechanism of the porous tube-like ZnS was discussed in detail. The series of sulfide products (ZS-X) were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), solid-state nuclear magnetic resonance spectroscopy (SSNMR), transmission electron microscopy (TEM), UV–visible diffuse-reflectance spectroscopy (UV–vis DRS). The photocatalytic performances of ZS-X toward Cr(VI) reduction and organic pollutant degradation were explored. It was discovered that ZS-3 (porous tube-like ZnS) exhibited excellent activities under UV light and displayed good reusability and stability after several experimental cycles. In addition, Cr(VI) reduction and organic pollutant degradation were investigated under different pH values and existence of different foreign ions. The photocatalytic activities of ZS-3 were tested toward the matrix of Cr(VI) and reactive red X–3B. The mechanism was proposed and verified by both electrochemical analysis and electron spin resonance (ESR) measurement.

Fungi have an exceptional capability to flourish in presence of heavy metals and pesticide. However, the mechanism of bioremediation of pesticide (lindane) and multimetal [mixture of cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni), lead (Pb), zinc (Zn)] by a fungus is little understood. In the present study, Aspergillus fumigatus, a filamentous fungus was found to accumulate heavy metals in the order [Zn(98%)>Pb(95%)>Cd(63%)>Cr(62%)>Ni(46%)>Cu(37%)] from a cocktail of 30 mg L⁻¹ multimetal and lindane (30 mg L⁻¹) in a composite media amended with 1% glucose. Particularly, Pb and Zn uptake was enhanced in presence of lindane. Remarkably, lindane was degraded to 1.92 ± 0.01 mg L⁻¹ in 72 h which is below the permissible limit value (2.0 mg L⁻¹) for the discharge of lindane into the aquatic bodies as prescribed by European Community legislation. The utilization of lindane as a cometabolite from the complex environment was evident by the phenomenal growth of the fungal pellet biomass (5.89 ± 0.03 g L⁻¹) at 72 h with cube root growth constant of fungus (0.0211 g¹/³ L⁻¹/³ h⁻¹) compared to the biomasses obtained in case of the biotic control as well as in presence of multimetal complex without lindane. The different analytical techniques revealed the various stress coping strategies adopted by A. fumigatus for multimetal uptake in the simultaneous presence of multimetal and pesticide. From the Transmission electron microscope coupled energy dispersive X-ray analysis (TEM-EDAX) results, uptake of the metals Cd, Cu and Pb in the cytoplasmic membrane and the accumulation of the metals Cr, Ni and Zn in the cytoplasm of the fungus were deduced. Fourier-transform infrared spectroscopy (FTIR) revealed involvement of carboxyl/amide group of fungal cell wall in metal chelation. Thus A. fumigatus exhibited biosorption and bioaccumulation as the mechanisms involved in detoxification of multimetals.

Microplastic pollution is a major global environmental problem in both aquatic and terrestrial environments. Pesticides are frequently applied to agricultural soil to reduce the effects of pests on crops, but may also affect the degradation of plastics. In this study, we generated microplastics from polyethylene (PE) film and biodegradable poly(butylene adipate-co-terephthalate) (PBAT) film and determined (1) the effect of prothioconazole on degradation of the microplastics, and (2) the adsorption and release characteristics of heavy metals (Cr, Cu, As, Pb, Ba, and Sn) by the microplastics during degradation process. Changes of surface functional groups and morphologies were measured by FTIR and SEM, while metal concentrations were determined by ICPMS. Prothioconazole was found to promote plastic degradation. PBAT degraded faster and adsorbed more heavy metals from the soil than PE. Whether the microplastics adsorb or release heavy metals depended on the metal and their concentrations. Prothioconazole inhibited the adsorption of Cr, As, Pb and Ba by microplastics, promoted the adsorption of Cu, and had no significant effect for Sn. These results can help to assess the ecological risk of microplastic pollution from plastic mulch when combined with heavy metals.

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.