Humic acid (HA) plays vital roles in regulating the environmental behaviors of metals and thus their toxicity to biota. However, the inner relation between metal bioavailability to soil organisms and the presence of HA with different molecular weight (Mw) is not well documented. In this study, we separated HAs into four fractions with Mw range of 5-30k Da, and discussed their ability to alleviating the toxicity of Cd and Pb to earthworm. The bioaccumulation capacities (Cₘₐₓ) increased in order of: UF1<UF2<UF3<UF4, which is in line with the variations of bioavailable concentrations of Cd and Pb in soil. Variations of Mw and binding capacities of HA determine the accumulation behavior in soil solution. The unsatisfactory of biotic ligand model fitting and the differences in fractions of the total biotic ligand sites (f) in earthworm bound by Cd and Pb suggested that only free species of Cd could be considered as biological available to earthworm, while the Pb–HAs complexes have potential ability to interact with earthworm membrane. Antioxidant enzymes are effective biomarkers, and HA with lower Mw play more important roles in restricting the toxicity of soil Cd and Pb to earthworm. These results reveal the different mechanism for HA controlling metal bioavailability between Cd and Pb in soil environment.

Human-induced temperature changes influence coastal regions, both via thermal pollution and ocean warming, which exerts profound effects on the chemistry of metals and the physiology of organisms. However, it remains unknown whether the increased temperature of discharged water or ocean warming, as a result of climate change, lead to an increase of human health risks associated with the consumption of sea foods. In this study, the influence of temperature on metal accumulation by oysters was studied in individuals collected from a coastal area affected by the thermal water discharge of the Houshi Power Plant, China. The bioaccumulation factor (BAF) and oral bioavailability (OBA) of metals in oysters was determined. Elevated temperatures led to an increase in BAF for Cu, Zn, Hg, and Cd (p < 0.05), but no change was observed for As and Pb (p > 0.05). The OBA for Cd, As, and Pb correlated positively to elevated temperatures (p < 0.05). However, for Cu and Zn, OBA was negatively correlated with increasing temperature (p < 0.05). As, Pb, and Cd in the trophically available metal (defined as a sum of heat-stable proteins, heat-denaturable proteins, and organelles) was significantly elevated at the highest temperature seawater site (site A) compared to the lowest seawater site (site B). Thus, the irregular variation of OBA for each metal may be the result of variations in the subcellular distribution of metals and the protein quality influenced by the increased temperature. Moreover, the increased temperature and increased the hazard quotient values of As and Cd (p < 0.05 for As, n = 6, p < 0.05 for Cd, n = 6), which provided an indication of the potential risks of the consumption of oysters or other seafood to future warming under climate change scenarios.

Lead intoxication is an important threat to human health and a large number of wildlife species. Animals are exposed to several sources of lead highlighting hunting ammunition and lead that is bioavailable in topsoil. Disentangling the role of each in lead exposure is an important conservation issue, particularly for species potentially affected by lead poisoning, such as vultures. The identification of lead sources in vultures and other species has been classically addressed by means of stable-isotope comparisons, but the extremely varied isotope signatures found in ammunition hinders this identification when it overlaps with topsoil signatures. In addition, assumptions related to the exposure of individual vultures to lead sources have been made without knowledge of the actual feeding grounds exploited by the birds. Here, we combine lead concentration analysis in blood, novel stable isotope approaches to assign the origin of the lead and GPS tracking data to investigate the main foraging grounds of two Iberian griffon vulture populations (N = 58) whose foraging ranges differ in terms of topsoil lead concentration and intensity of big game hunting activity. We found that the lead signature in vultures was closer to topsoil than to ammunition, but this similarity decreased significantly in the area with higher big game hunting activity. In addition, attending to the individual home ranges of the tracked birds, models accounting for the intensity of hunting activity better explained the higher blood lead concentration in vultures than topsoil exposure. In spite of that, our finding also show that lead exposure from topsoil is more important than previously thought.

Tea plants (Camellia sinensis (L.) O. Kuntze) can hyperaccumulate fluoride (F). The accumulation of F in tea leaves may induce serious health problems in tea consumers. It has been reported that selenium (Se) could reduce the accumulation of heavy metals in plants. Thus, the aim of this study was to investigate whether exogenous Se could reduce F accumulation in tea plant. The results showed that Se treatment could decrease F content in tea leaves, increase F accumulation in roots, decrease the proportion of water-soluble F in tea leaves and increase the Se content. Low F levels promoted the accumulation of Se in tea plants. Se treatment could modulate F-induced oxidative injury by decreasing malondialdehyde level and increasing the activities of superoxide dismutase, peroxidase and catalase. Moreover, Se inhibited F-induced increase in leaf iron, calcium, aluminum, leaf and root magnesium and lead contents. These results showed that Se application could decrease F content and increase Se content in tea leaves, which may be served as a novel strategy for production of healthy tea.

Rice is the world’s most consumed and in-demand grain. Ecuador is one of the main rice-consuming countries in Latin America, with an average per capita consumption of 53.2 kg per year. Rice cultivation takes place under flooding conditions, which favors the mobilization and subsequent accumulation of heavy metals in the plant. This study’s principal objective was to evaluate the contamination of cadmium (Cd) and lead (Pb) in the rice cultivation system in the province of Guayas. To this end, extensive sampling of water, soil and rice grains was carried. Water samples were analyzed to determine physicochemical properties and concentrations of dissolved Cd and Pb. Physicochemical properties, total organic carbon (TOC), total content of nitrogen (N), iron (Fe), manganese (Mn), phosphorus (P), bioavailable phosphorus (P mehlich), Cd and Pb were determined in soil samples. In addition, to understand the dynamics of Cd and Pb mobility and bioavailability, an extraction of six randomly selected soil samples was carried out. The concentration values of the total Cd and Pb content in the rice cultivation system did not exceed the maximum recommended limit for soil, water and rice grains. However, 85% of the total Cd was in the soluble or exchangeable fraction of the soil, while the Pb was strongly bound to crystalline iron oxyhydroxides. It was established that the TOC, N, Fe, and P mehlich have a significant correlation (p < 0.05) with the overall concentration of Cd and Pb in the rice farming soil. The Cd and Pb present in rice do not represent a dietary health risk to the population of Ecuador.

Being signaling molecules, nitric oxide (NO) and hydrogen sulfide (H₂S) can mediate a wide range of physiological processes caused by plant metal toxicity. Moreover, legume-rhizobium symbiosis has gained increasing attention in mitigating heavy metal stress. However, systematic regulatory mechanisms used for the exogenous application of signaling molecules to alter the resistance of legume-rhizobium symbiosis under metal stress are currently unknown. In this study, we examined the exogenous effects of sodium nitroprusside (SNP) as an NO donor additive and sodium hydrosulfide (NaHS) as a H₂S donor additive on the phytotoxicity and soil quality of alfalfa (Medicago sativa)-rhizobium symbiosis in lead/cadmium (Pb/Cd)-contaminated soils. Results showed that rhizobia inoculation markedly promoted alfalfa growth by increasing chlorophyll content, fresh weight, and plant height and biomass. Compared to the inoculated rhizobia treatment alone, the addition of NO and H₂S significantly reduced the bioaccumulation of Pb and Cd in alfalfa-rhizobium symbiosis, respectively, thus avoiding the phytotoxicity caused by the excessive presence of metals. The addition of signaling molecules also alleviated metal-induced phytotoxicity by increasing antioxidant enzyme activity and inhibiting the level of lipid peroxidation and reactive oxygen species (ROS) in legume-rhizobium symbiosis. Also, signaling molecules improved soil nutrient cycling, increased soil enzyme activities, and promoted rhizosphere bacterial community diversity. Both partial least squares path modeling (PLS-PM) and variation partitioning analysis (VPA) identified that using signaling molecules can improve plant growth by regulating major controlling variables (i.e., soil enzymes, soil nutrients, and microbial diversity/plant oxidative damage) in legume-rhizobium symbiosis. This study offers integrated insight that confirms that the exogenous application of signaling molecules can enhance the resistance of legume-rhizobium symbiosis under metal toxicity by regulating the biochemical response of the plant-soil system, thereby minimizing potential health risks.

The Tharsis mine is presently abandoned, but the past intense exploitation has left large dumps and other sulphide-rich mining wastes in the area generating acid mine drainages (AMD). The main goal of this work is to study the effect of hydrogeochemical processes, hydrological regime and the waste typology on the physicochemical parameters and dissolved concentrations of pollutants in a deeply AMD-affected zone. Extreme leachates are produced in the area, reaching even negative pH and concentrations of up to 2.2 g/L of As and 194 g/L of Fe. The results of the comparison of ore grades of sulphide deposits with dissolved concentrations in waters shows that Pb is the least mobile element in dissolution probably due to the precipitation of Pb secondary minerals and/or its coprecipitation on Fe oxyhydroxysulphates. Arsenic, Cr, and V are also coprecipitated with Fe minerals. Seasonal patterns in metal contents were identified: elements coming from the host rocks, such as Al, Mn and Ni, show their maximum values in the dry period, when dilution with freshwater is lower and the interaction of water-rock processes and evaporation is higher. On the other hand, As, Cr, Fe, Pb and V show minimum concentrations in the dry period due to intense Fe oxyhydroxysulphate precipitation. In this sense, large sulphide rich waste heaps would be a temporal sink of these elements (i.e. Pb, As, Cr and V) in the dry period, and a significant source upon intense rainfalls.

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.

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.

Microplastics are known to be associated with co-contaminants, but little is understood about the mechanisms by which these chemicals are transferred from ingested plastic to organisms. This study simulates marine avian gastric conditions in vitro to examine the bioaccessibility of authigenic metals (Fe, Mn) and trace metals (Co, Pb) that have been acquired by polyethylene microplastic pellets from their environment. Specifically, different categories of pellet were collected from beaches in Cornwall, southwest England, and exposed to an acidified saline solution of pepsin (pH ∼ 2.5) at 40 °C over a period of 168 h with extracted metal and residual metal (available to dilute aqua regia) analysed by ICP-MS. For Fe, Mn and Co, kinetic profiles consisted of a relatively rapid initial period of mobilisation followed by a more gradual approach to quasi-equilibrium, with data defined by a diffusion model and median rate constants ranging from about 0.0002 (μg L⁻¹)⁻¹ h⁻¹ for Fe to about 7 (μg L⁻¹)⁻¹ h⁻¹ for Co. Mobilisation of Pb was more complex, with evidence of secondary maxima and re-adsorption of the metal to the progressively modified pellet surface. At the end of the time-courses, maximum total concentrations were 38.9, 0.81, 0.014 and 0.10 μg g⁻¹ for Fe, Mn, Co and Pb, respectively, with maximum respective percentage bioaccessibilities of around 60, 80, 50 and 80. When compared with toxicity reference values for seabirds, the significance of metals acquired by microplastics from the environment and exposed to avian digestive conditions is deemed to be low, but studies of a wider range of plastics and metal associations (e.g. as additives) are required for a more comprehensive risk assessment.