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.

Fulvic acid (FA) significantly influences the bioavailability and fate of heavy metals in environments, while its acid-base characters and metal binding processes are still unclear. Here, spectroscopic techniques combined with multiple models (e.g., NICA-Donnan model) and two-dimensional correlation spectroscopy (2D COS) were applied to explore the proton and copper binding properties of FA sub-fractions (FA3-FA13). The charge densities, average contents of carboxylic and phenolic groups, average dissociation constants pKa1 and pKa2 of sub-fractions ranged 0–16 meq∙g∙C−1, 5.03–9.58 meq∙g∙C−1, 2.52–4.67 meq∙g∙C−1, 4.15–4.33 and 8.52–9.72, respectively. FA sub-fractions had a relatively narrow distribution of carboxyl group and a broad distribution of phenolic group. FA sub-fractions also exhibited roughly two phenolic hydroxyl groups per every 1–3 phenyl rings. Differential absorbance spectra (DAS) derived Gaussian bands were associated to the inter-chromophore interactions, the changes of molecular conformations and functional groups with copper addition. Differential spectra slopes (DSlope275-295&325-375) were more significant with higher copper concentration and copper amounts bonded to carboxylic groups. UV–Vis and fluorescence spectra with 2D heterospectral COS revealed the copper binding heterogeneities and sequential orders of chromophores and fluorophores, quantitatively confirming by the order of conditional stability constants (log KCu: 4.64–5.56). Salicylic-/polyhydroxyphenolic, hydroxyl and amino groups were strongly associated to the basic units for fluorophores. Sequential changes followed the order of humic-like→fulvic-like materials for FA3/FA5, humic-like→fulvic-like→tryptophan-like materials for FA7, and humic-like→tryptophan-like→fulvic-like→tyrosine-like materials for FA9/FA13. Spectroscopic techniques combined with various models (especially for 2D COS) are beneficial to elucidate the binding heterogeneity and sensitivity for metal-organic matters at the functional group level.

The Gulf of Mexico (GoM) is exposed to a diversity of contaminants, such as hydrocarbons and heavy metal(oid)s, either from natural sources or as a result of uncontrolled coastal urbanisation and industrialisation. To determine the effect of these contaminants on the marine biota along the Mexican GoM, the biological responses of the shoal flounder Syacium gunteri, naturally exposed, were studied. The study area included all the Mexican GoM, which was divided into three areas: West-southwest (WSW), South-southwest (SSW) and South-southeast (SSE). The biological responses included the global DNA methylation levels, the expression of biomarker genes related to contaminants (cytochrome P450 1A, glutathione S-transferase, glutathione reductase, glutathione peroxidase, catalase, and vitellogenin), histopathological lesions and PAH metabolites in bile (hydroxynaphthalene, hydroxyphenanthrene, hydroxypyrene and Benzo[a]pyrene). The correlation between the biological responses and the concentration of contaminants (hydrocarbons and metal(oid)s), present in both sediments and organisms, were studied. The shoal flounders in WSW and SSW areas presented higher DNA hypomethylation, less antioxidative response and biotransformation gene expression and a higher concentration of PAH metabolites in bile than SSE area; those responses were associated with total hydrocarbons and metals such as chromium (Cr). SSE biological responses were mainly associated with the presence of metals, such as cadmium (Cd) and copper (Cu), in the tissue of shoal flounders. The results obtained on the physiological response of the shoal flounder can be used as part of a permanent active environmental surveillance program to watch the ecosystem health of the Mexican GoM.

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).

Recently polymer inclusion membranes (PIMs) have been proposed as materials for passive sampling, nonetheless a theoretical base to describe the mass transfer process through those materials, under such conditions of monitoring, has not been elucidated. Under the assumption that: (i) the transport of the metal ion occurs at steady state conditions, (ii) the concentration gradients are linear, and (iii) the kinetics of the chemical reactions in the extraction process on the membrane are elemental; an equation for the passive sampling of copper (II) using a PIM system containing Kelex-100 as carrier is derived. The prediction capacity of this sampler under different conditions of temperature, metal concentration, flow velocity, ionic strength and pH is analyzed as well. Among the dependencies of the PIM on the physicochemical conditions, effects of concentration, temperature and flow velocity tend to increment copper (II) flux across the membrane, being the parameter temperature the one with the most pronounced effect at T ≥ 30 °C. Ionic strength had no great effect on passive sampler response, however the sampler is dependent on the acidity of the medium. The comparable metal ion concentrations estimated from the PIM sampler to those obtained by direct measurements of the sampling medium suggest that PIMs can be robust materials when used as passive sampler devices.

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.

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.

Anthropogenic activities have significantly changed the stoichiometry and concentrations of nutrients in coastal waters. Silicon (Si) has become a potential limiting nutrient due to disproportionate nitrogen, phosphorus, and silicate inputs into these areas. The disrupted nutrient ratios can cause changes to metal sensitivity and accumulation in marine diatoms, an important group of eukaryotic phytoplankton that requires silicon for growth. In this study, we examined the effects of Si availability on the metal sensitivity in the diatom P. tricornutum. We found that Si starvation dramatically compromised its cadmium, copper, and lead tolerances. Interestingly, multiple lines of evidence indicated that Si-enriched cells had higher metal adsorption and influx rates than Si-starved cells. Yet Si-enriched cells also had a greater ability to respond to and counteract metal toxicity via elevated expression of membrane and vacuolar metal transporters and greater antioxidant activities which scavenge reactive oxygen species created by metal stress.