Southwestern China contains the largest and most well-developed karst region in the world, and the potentially toxic elements (PTEs) content in the soils of the region is remarkably high. To explore the internal and external control factors and sources of soil PTEs enrichment in this area and to provide a basis for the treatment of PTE pollution, 113 soil samples were collected from Hengxian County, a karst region in Guangxi Province, southwestern China. The importance of eighteen influencing factors including parent material, weathering, physicochemical properties, topography and human activities were quantitatively analyzed by (partial) redundancy analysis. The sources of PTEs were identified using the Pb isotope ratio and absolute principal component score/multiple linear regression (APCS-MLR) model. The contents of all soil PTEs were higher than the corresponding background values of Guangxi soils. The contents in Cu, Zn, Cd, Hg and Pb were the highest in the soil from carbonate rock. The factor group of geological background and weathering explained 26.5% for the accumulation and distribution of soil PTEs and the influence of physicochemical properties was less than 2% but increased to 25.6% through interaction with weathering. Fe (47.1%), Al (42.1%), Mn (22%), chemical index of alteration (12.8%) and clay (11.9%) were the key factors affecting the soil PTEs, while the influence of human activities was weak. Pb isotope ratio and APCS-MLR classified 62.8–74% of soil PTEs as derived from natural sources, whereas 18.23% and 18.95% were derived from industrial activities and agricultural practice/traffic emissions, respectively. The Pb isotope ratio showed that the natural sources account for up to 90% of the Pb in the soil from carbonate rock, the highest contribution among the studied soils. The results of the study can provide background information on the soil PTEs contamination in the karst areas of China and other areas worldwide.

Intensive anthropogenic activity has triggered serious heavy metal contamination of soil. Land use and land cover (LULC) changes bear significant impacts, either directly or indirectly, on the distribution of heavy metal in soils. A total of 180 samples were acquired from various land covers at different depths, namely surface soils (020 cm) and subsurface soils (20–40 cm). Spatial interpolation, geographically weighted regression (GWR) and self-organizing map (SOM) were used to discern how variations in the spatial distributions of soil heavy metals were caused by human activities for different land uses, and how these pollutants contributed to environmental risks. The medium concentrations of Cd, Cr, Cu, Pb and Zn in surface soil all exceeded the corresponding local background values in flat cropland and developed area soil. The overall ecological risk level of the study varied from low to medium. The GWR model indicated that the land use intensity had a certain influence on the accumulation of heavy metals in the surface soil. K-means clustering of the SOM revealed that the type of LULC also contributed to the redistribution of heavy metals in the surface soil.

In this study, samples of soil and particulate matter obtained from the highly industrialized region of Ostrava, Czech Republic, are used for the toxicity evaluation of the selected metal(loid)s (Cd, Cr, Cu, Ni, Pb, Zn, As). We investigated the samples from sites supposedly affected the most by the local pollution sources using mineralogical techniques (XRD, SEM/EDS) to understand the solid speciation of the contaminants as the crucial factor affecting their release. Although the bulk composition was defined by common silicates and oxides that are rather resistant to leaching, the presence of tiny Ni, Pb, and/or Zn sulfate-like droplets indicated a potential increase of the solubility of these metals. In vitro tests simulating gastric and lung fluids were used to assess the exposure risk for humans, as well as metal(loid) bioaccessibility. Based on the results, the potential risk for the observed age group (3-year-old children) could be recognized, particularly in the cases of As, Pb and Cd for both oral and inhalation exposure. Arsenic exhibits high bioaccessibility (7.13–79.7%, with the median values of 10.6 and 15.6 for SGL and SLF, respectively), high daily intake (1.4- to 8.5-fold higher than the tolerable daily intake) and high concentrations in atmospheric PM₁₀ (2.5 times the tolerable concentration in air). In contrast, Ni exceeded tolerable concentrations in the atmosphere up to 20-fold, but its bioaccessibility remained relatively low (0.1–22%), and Ni did not pose a major threat to human health. Cadmium, Pb and As originating from industrial activities and domestic heating have been suggested to be the most important pollutants (tolerable daily intake was exceeded by up to 74-, 34- and 8-fold for Cd, Pb and As, respectively).

Atmospheric nitrogen (N) deposition is believed to accelerate dissolved organic carbon (DOC) production and could lead to increased heavy metal mobility into water resources. We sampled intact soil cores from the Isle of Skye with low background N deposition history and having Serpentine rock known for its higher heavy metal concentrations including zinc (Zn), copper (Cu), nickel (Ni) and lead (Pb). The effects of 16 (16kgN) and 32 kg N ha⁻¹ year⁻¹ (32kgN), and liming with 32kgN (32kgN+Lime) on soil solution chemistry and heavy metal mobilization were investigated over the 15-month study. Nitrogen in deposition load was added at five ammonium (NH₄⁺) to nitrate (NO₃⁻) ratios of 9:1, 5:1, 1:1, 1:5 and 1:9 along NO₃⁻dominance. We found significant effects of load on Cu and NH₄⁺/NO₃⁻ ratio on pH, DOC and Zn in soil solution. However, under lime and ratio experimental factors, liming significantly influenced pH, DOC, Cu and Pb, and NH₄⁺/NO₃⁻ ratio pH, DOC, Ni and Zn whereas interactions between lime and ratio was significant for Ni and Cu. pH and DOC increased with N load, liming and NO₃⁻ dominance, and both correlated significantly positively. Liming under NH₄⁺ dominance enhanced DOC production due to supply of base cations in lime. Mobilization of Cu, Ni and Pb was driven by DOC concentrations and, therefore, increased with load, liming and NO₃⁻ dominance in deposition. However, in contrast, low pH and high NH₄⁺ dominance was associated with Zn mobilization in soil solution. On the contrary, despite of some patterns, heavy metals in soil HNO₃ extracts were devoid of any load, lime and NH₄⁺/NO₃⁻ ratio effects. Our study suggests that the effects of N load and forms in deposition on sites with high accumulated loads of metals need to be better quantified through soil solution partitioning models.

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.

Atmospheric heavy metal contamination is becoming a serious threat to environmental and human health in Chinese megacities. This study evaluated the concentrations of arsenic (As), cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) and Pb isotopic compositions in herbarium and native bryophytes collected from Guangzhou from 1932 to 2018. Relatively low mean metal concentrations were measured for bryophytes collected in the 1930s. The highest mean concentrations of Cd (0.72 ± 0.32 mg/kg), Cu (28.1 ± 9.8 mg/kg), Pb (125.9 ± 62.4 mg/kg) and Zn (273 ± 130 mg/kg) were found in the bryophytes from 1979 to 2000, following the commencement of the Reform and Opening-Up Program in 1978. The mean Pb concentrations (74.7 ± 6.3 mg/kg) decreased sharply from 2001 onwards, following the cessation of leaded petrol across the Chinese mainland in 2000. However, these values are still higher than those in 1950–1978, corresponding to a significant increase in atmospheric Pb emissions from coal combustion, nonferrous metal smelting and motor vehicle petrol consumption in China in the 2000s. The lead isotopic ratios of bryophyte archives (²⁰⁶Pb/²⁰⁷Pb 1.141–1.229, ²⁰⁸Pb/²⁰⁷Pb 2.376–2.482) indicate that lithogenic input and anthropogenic input arising from leaded petrol and industrial emissions have been the main sources of atmospheric heavy metal deposition in the city of Guangzhou over the past 85 years. Herbarium bryophyte can be utilised to reconstruct temporal and spatial shifts in atmospheric heavy metal deposition to better understand and manage the current air quality in Chinese megacities.

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.

Amendment with sewage sludge or biosolids can increase soil fertility but may also transfer biosolid-borne pollutants to the soil and the possible effects on the soil ecosystem are poorly understood, especially long-term effects. A long-term experiment was therefore established to assess the effects of repeated applications of different types of biosolids (fresh domestic, dried domestic and fresh industrial sludges) in field conditions. Nine years of sludge application led to changes in soil chemical and biological properties and generally contributed little to soil nutrient status. However, soil concentrations of potentially toxic elements (PTEs) were elevated by amendment, especially with industrial biosolids. Soil fauna are usually used to decipher the underlying effects of biosolid applications on the soil ecosystem. Here, collembolans (50.9%), nematodes (41.6%) and enchytraeid worms (7.50%) were collected and differentiated into different ecological and trophic groups and their body lengths and PTE concentrations in the body tissues were investigated. The animals showed different responses to the biosolids at population and individual levels. There were substantial changes in epigeic collembolan communities and bacterivorous nematodes increased significantly after biosolid amendment. Biosolid-borne PTEs were major factors and Redundancy (RDA) analysis indicates that collembolan communities were strongly influenced by zinc (Zn). The three groups of soil animals showed similar trends in accumulation of PTEs in the sequence cadmium (Cd) > Zn > copper (Cu), and the bioaccumulation factor (BAF) values of the PTEs were significantly higher in the industrial sludge treatment than in other two treatments with a similar trend of decreasing body length of nematodes. The results indicate that it is potentially risky to use industrial biosolids in the long term, and different species and ecological groups of collembolans and different trophic groups of nematodes should be examined when assessing soil health.

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.

This work has been conducted as an integrated approach to study the behavior of soils to the metals from sludge amendment. Bureau Commun Reference (BCR) methodology was used as an appropriate tool to harvest precious information about heavy metals evolution versus depth before and after sludge treatments. This three-step extraction procedure (i.e., BCR) may clarify the leaching or retention of heavy metals from the amended soils, as well as their risk level. Our results indicated that sludge applications has shown an increasing flux of heavy metals towards amended soils, of which Pb was the most abundant. Heavy metals mobility in control and amended soils showed that main influencing factors are pH and total organic carbon, especially for copper mobility. Almost all of the metals decreased with soil depth, except for Ni. Speciation of heavy metals in sludges showed that about 45% of Pb, Cu and Ni were associated with residual fraction; Cd was mainly bound to reducible fraction. Speciation forms in the control soil indicated that short term application of sludge has remobilized a fraction of heavy metals into their most labile forms (i.e., exchangeable and reducible fraction). Multivariate statistical analysis suggested that Cd, Zn, Pb and Cu preferentially accumulated in organic-rich surface horizons and clay layers where adsorption played an important role as a determining mechanism. Nevertheless, adsorption did not appear to be directly controlled by high pH values (pH > 7). From Cluster Analysis (CA), one can easily recognize that Pb, Zn and Cu movement in soil profiles were significantly affected by pH, especially residual fraction, labile fraction and reducible fraction.