Shellfish constitute an important component of human diet, especially for those living in coastal regions. Shellfish have attracted extensive attention due to high enrichment of heavy metals. The aims of this study were to investigate the levels of trace elements in shellfish from coastal waters of Shenzhen, China and to assess human intake risks. Nine elements, including chromium (Cr), copper (Cu), iron (Fe), zinc (Zn), manganese (Mn), selenium (Se), cadmium (Cd), arsenic (As) and lead (Pb) were measured in 216 shellfish samples from eight species. Their concentrations (based on wet weight) were: Cr (0.28–21.4 mg kg⁻¹), Cu (1.40–158 mg kg⁻¹), Fe (16.5–5387 mg kg⁻¹), Zn (11.1–847 mg kg⁻¹), Mn (1.33–422 mg kg⁻¹), Se (0.15–11.8 mg kg⁻¹), Cd (0.02–18.4 mg kg⁻¹), Pb (<LOQ-10.9 mg kg⁻¹) and As (2.24–95.5 mg kg⁻¹), relatively greater than those reported in shellfish from other locations of China. Crassostrea ariakensis and Babylonia areolata were found to enrich As and Cd, respectively. The target hazard quotient (THQ) values of Cd and As were more than 1, suggesting considerable health risks from the consumption of shellfish of this zone. To our knowledge, this is the first study to assess the human risk exposure to trace elements via shellfish consumption in South China.

In aquatic environments, organisms such as freshwater mussels are likely exposed to complex contaminant mixtures related to industrial, agricultural, and urban activities. With growing interest in understanding the risk that chemical mixtures pose to mussels, this investigation focused on the effects of various waterborne contaminants (ammonia, chloride, copper, and potassium) and selected binary mixtures of these chemicals following a fixed-ratio design to Villosa iris glochidia and juvenile Lampsilis fasciola. In individual exposures, 48-h EC50 values were determined for V. iris glochidia exposed to ammonia chloride (7.4 [95% confidence interval (CI) 6.6–8.2] mg N/L), ammonia sulfate (8.4 [7.6–9.1] mg N/L), copper sulfate (14.2 [12.9–15.4] μg Cu2+/L), potassium chloride (12.8 [11.9–13.7] mg K+/L), potassium sulfate (10.1 [8.9–11.2] mg K+/L), and sodium chloride (480.5 [435.5–525.5] mg Cl−/L). The 7-d LC50 values for juvenile L. fasciola were determined for potassium sulfate (45.0 [18.8–71.2] mg K+/L), and sodium chloride (1738.2 [1418.6–2057.8] mg Cl−/L). In Ontario these waterborne contaminants have been reported to co-occur, with concentrations exceeding the EC10 for both life stages at some locations. Data from binary mixture exposures for V. iris glochidia (chloride-ammonia, chloride-copper, and copper-ammonia) and juvenile L. fasciola (chloride-potassium) were analyzed using a regression-based, dose-response mixture analysis modeling framework. Results from the mixture analysis were used to determine if an additive model for mixture toxicity [concentration addition (CA) or independent action (IA)] best described the toxicity of each mixture and if deviation towards dose-ratio (DR) or dose-level (DL) synergism/antagonism (S/A) occurred. For all glochidia binary mixture exposures, CA was the best fit model with DL deviation reported for the chloride-copper mixture and DR deviation reported for the copper-ammonia mixture. Using the model deviation ratio (MDR), the observed toxicity in all three glochidia mixture exposures were adequately described by both CA (mean = 0.71) and IA (mean = 0.97) whereas the juvenile mixture exposure was only adequately described by CA (mean = 0.64; IA mean = 0.05).

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) are cancerogenic organic pollutants that priority controlled by Stockholm Convention with globally 183 signatories now. Secondary nonferrous smelting plants are confirmed to be important sources in China due to its large industrial activities and high emissions of PCDD/Fs. It is important to prioritize source to achieve source emission reduction by conducting field monitoring on typical case plants. Here, the emission profiles and levels of PCDD/Fs were investigated in 25 stack gas samples collected from three secondary copper production (SeCu), two secondary zinc production (SeZn) and two secondary lead production (SePb). Both average mass concentration and toxic equivalency quantity (TEQ) concentrations of PCDD/Fs all generally decreased in the order: SeCu > SeZn > SePb. It is noteworthy that the mean TEQ concentration in stack gas from SeCu with oxygen-enrich melting furnace technology, at 2.7 ng I-TEQ/Nm³, was much higher than the concentrations of other smelting processes. The average emission factors and annual release amounts of PCDD/Fs from SeCu, SePb and SeZn investigated were 28.4, 1.5, 10.4 μg I-TEQ/t and 1.03, 0.023, 0.17 g I-TEQ/year, respectively. The ratios of 2,3,7,8-TCDF to 1,2,3,7,8-PeCDF and OCDD to 1,2,3,7,8,9-HxCDD varied to large extent for three metal smelting, which could be used as diagnostic ratios of tracing specific PCDD/Fs sources. Addition of copper-containing sludge into the raw materials might lead to higher PCDD/Fs emissions. It is important to emphasize and reduce the PCDD/Fs emissions from oxygen-enrich melting furnace from secondary copper productions.

Heavy metals (HMs) in an aquatic environment mainly affects fish, and thus, fish are convenient pollution bio-indicators. In this study, the toxic effects of HM mixture (chromium (Cr), cadmium (Cd), copper (Cu)) in 0 mg/L to 3.2 mg/L concentration range was investigated in Cyprinus carpio (28 days). HM accumulation, histopathology, oxidative stress, and gut microbial changes were evaluated. HMs accumulated in the order of Cr > Cu > Cd, primarily in the kidneys and finally scales. Reactive oxygen species generation increased in all exposure groups up to day 14, with maximum generation at 3.2 mg/L mixture, which later decreased on day 28 in all. Malondialdehydeand and superoxide dismutase levels increased from day 7 to 28 with increased HM concentrations, while total protein showed an inverse trend. Gill histopathology showed major changes such as uplifted and disintegrated primary lamella, and secondary lamella shortening. The kidneys were characterized by glomerular necrosis, Bowman’s capsule expansion, and tubular space dilatation. Proteobacteria and Firmicutes abundance increased up to 59.4% and 99.16% in 0.8 mg/L and 3.2 mg/L treatment groups, respectively. This study provided a better understanding on the physiology and gut microbiota alteration in C. carpio under multiple HM stress.

Concentrations of As, Cd, Cr, Cu, Hg, Pb, and Zn in sediment samples and muscle tissue of the European perch were analyzed using inductively-coupled plasma optical emission spectrometry (ICP-OES), with the aim to assess the potential ecological (RI) and human health risk, and the degree of contamination (Cd) of three types of reservoirs in Serbia, based on their purpose: electricity generation (Vlasina, Perućac, Zaovine, and Međuvršje), drinking water supply (Garaši), and recreation (Lake Sava). The concentrations of the studied elements were higher in sediments than in fish. However, the levels of Cd in fish caught in Vlasina, Zaovine, and Međuvršje, Hg in Perućac and Garaši, and Pb in Lake Sava exceeded the maximum allowed concentrations. The pollution load index (PLI) indicated that sediments in all six reservoirs were contaminated, but Cd was low; a moderate contamination with Cd was observed in Vlasina, Perućac, and Zaovine, Cr in Zaovine and Međuvršje, and Cu in Međuvršje. A low RI was recorded for all studied reservoirs. Cd was found to be the primary contamination and ecological risk factor. Total target hazard quotient (THQ) and target carcinogenic risk factor (TR) were higher for fishers operating in these reservoirs than for the general population. Higher values of PLI, Cd, RI, and TR were observed in electricity generation reservoirs. Results indicated that this type of reservoirs suffer from higher anthropogenic pressure and/or have a worse pollution management policy compared with other types of reservoirs included in this study, especially the drinking water supply reservoir.

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.

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).