There is a lack of appropriate models to delineate the toxicity of rare earth elements (REEs) while taking into account the factors that affect bioavailability. Here, standardized wheat (Triticum aestivum L.) root elongation tests were conducted to examine the impact of exposure conditions (i.e., varying Ca, Mg, Na, K and pH levels) on Y and Ce toxicity. Cation competition and electrostatic theory were examined for their applicability in explaining the observed variations in toxicity. Only Ca2+ and Mg2+ significantly alleviated the toxicity of Y3+ and Ce3+, while Na+, K+ and H+ showed no significant effects. Based on the cation competition, the derived binding constants for the hypothetical biotic ligands of wheat logKCaBL, logKMgBL, logKYBL, and logKCeBL were 3.87, 3.59, 6.70, and 6.48, respectively. The biotic ligand model (BLM) succeeded in predicting toxicities of Y and Ce, with more than 93% of the variance in toxicity explained. Given the BLM requires large data sets for deriving model parameters, attempts were further made to explore a simpler electrostatic based model to quantify REEs toxicity. The results demonstrated that the predictive capacity of the electrostatic approach, which considers ion activities at the plasma membrane surface, was comparable to that of BLM with at least 87% of the variations in toxicity explained. This suggested that the electrostatic theory can serve as a surrogate to BLM in modeling Y and Ce toxicities. Therefore, we recommend the BLM and electrostatic-based model as effective approaches to incorporate bioavailability in quantifying REEs toxicity in the presence of various levels of other major cations.

The binding of metal ions with humic acid (HA) plays an important role in the aggregation of HA and the migration of metal ions in the environments. The effects of common cations (Na⁺, Mg²⁺, Ca²⁺ and Al³⁺) and heavy metal ions (Ag⁺, Cd²⁺, Cu²⁺, Cr³⁺ and Eu³⁺) on the aggregation of HA were investigated systematically by aggregation kinetics, spectroscopic techniques and molecular dynamic (MD) simulations. The critical coagulation concentration (CCC) of mono-, di- and trivalent cations could be predicted by the Schulze-Hardy rule. The aggregation of HA in the presence of Na⁺ and Ag⁺ was mainly due to the reduction of repulsive force and the hydrogen bonds between HA molecules. While the complexation of di- and trivalent cations with carboxylic/phenolic groups, or the cation-π interactions enhanced the intra- or inter-molecular bridges in HA and then contributed greatly to the aggregation of HA. Heavy metal ions could easily pass through the electric double-layer of HA compared with common cations. MD simulations further signified the strong aggregation ability of HA molecules in solutions containing high valence metal ions. These findings are important for understanding not only how the influence of metal ions on the aggregation of HA, but also the conditions which ions more efficient for aggregation.

Elemental concentrations of ambient aerosols are commonly sampled over 12–24 h, and the low time resolution puts a great limit on current understanding about the temporal variations and source apportionment based on receptor models. In this work, hourly-resolved concentrations of eighteen elements in PM₂.₅ at an urban site in Nanjing, a megacity in Yangtze River Delta of east China, were obtained by using a Xact 625 ambient metals monitor from 12/12/2016 to 12/31/2017. The influence of traffic activities was clearly reflected by the spikes of crustal elements (e.g., Fe, Ca, and Si) in the morning rush hour, and the firework burning and sandstorm events during the sampling periods were tracked by sharp enrichment of Ba, K and Fe, Ca, Si, Ti in PM₂.₅, respectively. To evaluate the advantage of hourly-resolved elements data in identifying impacts from specific emission sources, positive matrix factorization (PMF) analysis was performed with the 1-h data set (PMF₁₋ₕ) and 23-h averaged data (PMF₂₃₋ₕ), respectively. The 4- and 6-factor PMF₂₃₋ₕ solutions had similar factor profiles and consistent factor contributions as the corresponding PMF₁₋ₕ solutions. However, due to the limit in inter-sample variability, PMF analysis with 23-h average data misclassified some major (e.g., K, Fe, Zn, Ca, and Si) and trace (e.g., Pb) elements in factor profiles, resulting in different absolute factor contributions between PMF₂₃₋ₕ and PMF₁₋ₕ solutions. These results suggested the use of high time-resolved data to obtain valid and robust source apportionment results.

The ultra-high Cd polluted environment is a special habitat in nature. Analysis of the biological adaptation and resistance mechanism of Auxenochlorella protothecoides UTEX234 to ultra-high Cd stress would offer some inspiring understanding on Cd detoxification mechanism and help discovering highly active bioremediation agents. In this study, integrated analyses of the transcriptome, multi-physiological and biochemical data and fatty acid profilings of UTEX2341 were performed for the first time. It was found that exogenous Ca ions could alleviate Cd stress. Manganese-dependent superoxide dismutase and peroxidase also participated in intracellular detoxification. And non-enzymatic antioxidants rather than one specific enzymatic antioxidant were suggested to be used as “core antioxidants”, which witnessed better performance in Cd detoxification. In addition, Cd stress improved sixteen alkane value and biofuel yield and quality.

This study investigated the effects of pollution emissions on the bioreactivity of PM2.5 during Asian dust periods. PM2.5 during the sampling period were 104.2 and 85.7 μg m−3 in Xi'an and Beijing, respectively, whereas PM2.5 which originated from the Tengger Desert was collected (dust background). Pollution conditions were classified as non-dust days, pollution episode (PE), dust storm (DS)-1, and DS-2 periods. We observed a significant decrease in cell viability and an increase in LDH that occurred in A549 cells after exposure to PM2.5 during a PE and DS-1 in Xi'an and Beijing compared to Tengger Desert PM2.5. Positive matrix factorization was used to identify pollution emission sources. PM2.5 from biomass and industrial sources contributed to alterations in cell viability and LDH in Xi'an, whereas vehicle emissions contributed to LDH in Beijing. OC, EC, Cl−, K+, Mg2+, Ca, Ti, Mn, Fe, Zn, and Pb were correlated with cell viability and LDH for industrial emissions in Xi'an during DS. OC, EC, SO42−, S, Ti, Mn, and Fe were correlated with LDH for vehicle emissions in Beijing during DS. In conclusion, the dust may carry pollutants on its surface to downwind areas, leading to increased risks of particle toxicity.

Epidemiological studies and animal experiments have suggested that exposure to Di-(2-ethylhexyl) phthalate (DEHP) is strongly associated with an increase in blood pressure. However, the mechanisms that result in the detrimental effects of DEHP exposure on blood pressure are unclear. In our study, mice were orally exposed to DEHP dosages of 0.1, 1, 10 mg/kg/day for 6 weeks. The results showed that DEHP could induce a significant increase in systolic blood pressure (SBP) and heart rate, and a significant thickening of the ventricular wall. To explore the underlying mechanism, we measured the level of: angiotensin converting enzyme (ACE); bradykinin B2 receptor (BK2R); endothelial nitric oxide synthase (eNOS); bradykinin and Ca²⁺ in cardiac cytoplasm as well as in serum nitric oxide (NO). The results suggested that DEHP could induce an increase in ACE levels, and a decrease in bradykinin levels. Moreover, BK2R, Ca²⁺, eNOS and NO decreased when mice were exposed to 10 mg/kg/day DEHP. Interestingly, 5 mg/kg/day angiotensin converting enzyme inhibitor (ACEI) treatment inhibited the increase in blood pressure, and inhibited the decrease in the levels of BK2R, Ca²⁺, eNOS, and NO, that were induced by DEHP exposure. Our results suggest that DEHP might increase blood pressure by activating ACE expression, and inhibiting the bradykinin-NO pathway.

The gut microbiota is important for maintaining homeostasis of the host. Gut microbes represent the initial site for toxicant processing following dietary exposures to environmental contaminants. The diet is the primary route of exposure to polychlorinated biphenyls (PCBs), which are absorbed via the gut, and subsequently interfere with neurodevelopment and behavior. Developmental exposures to PCBs have been linked to increased risk of neurodevelopmental disorders (NDD), including autism spectrum disorder (ASD), which are also associated with a high prevalence of gastrointestinal (GI) distress and intestinal dysbiosis. We hypothesized that developmental PCB exposure impacts colonization of the gut microbiota, resulting in GI pathophysiology, in a genetically susceptible host. Mouse dams expressing two heritable human mutations (double mutants [DM]) that result in abnormal Ca²⁺ dynamics and produce behavioral deficits (gain of function mutation in the ryanodine receptor 1 [T4826I-RYR1] and a human CGG repeat expansion [170–200 CGG repeats] in the fragile X mental retardation gene 1 [FMR1 premutation]). DM and congenic wild type (WT) controls were exposed to PCBs (0–6 mg/kg/d) in the diet starting 2 weeks before gestation and continuing through postnatal day 21 (P21). Intestinal physiology (Ussing chambers), inflammation (qPCR) and gut microbiome (16S sequencing) studies were performed in offspring mice (P28–P30). Developmental exposure to PCBs in the maternal diet caused significant mucosal barrier defects in ileum and colon (increased secretory state and tight junction permeability) of juvenile DM mice. Furthermore, PCB exposure increased the intestinal inflammatory profile (Il6, Il1β, and Il22), and resulted in dysbiosis of the gut microbiota, including altered β-diversity, in juvenile DM mice developmentally exposed to 1 mg/kg/d PCBs when compared to WT controls. Collectively, these findings demonstrate a novel interaction between PCB exposure and the gut microbiota in a genetically susceptible host that provide novel insight into environmental risk factors for neurodevelopmental disorders.

The present study aims to investigate the spatial distribution and associated various geochemical mechanisms responsible for fluoride (F⁻) contamination in groundwater of unconfined aquifer system along major rivers in Sindh and Punjab, Pakistan. The concentration of F⁻ in groundwater samples ranged from 0.1 to 3.9 mg/L (mean = 1.0 mg/L) in Sindh and 0.1–10.3 mg/L (mean = 1.0 mg/L) in Punjab, respectively with 28.9% and 26.6% of samples exhibited F⁻ contamination beyond WHO permissible limit value (1.5 mg/L). The geochemical processes regulated F⁻ concentration in unconfined aquifer mainly in Sindh and Punjab were categorized as follows: 1) minerals weathering that observed as the key process to control groundwater chemistry in the study areas, 2) the strong correlation between F⁻ and alkaline pH, which provided favorable environmental conditions to promote F⁻ leaching through desperation or by ion exchange process, 3) the 72.6% of samples from Sindh and Punjab were dominated by Na⁺- Cl⁻ type of water, confirmed that the halite dissolution process was the major contributor for F⁻ enrichment in groundwater, 4) dolomite dissolution was main process frequently observed in Sindh, compared with Punjab, 5) the arid climatic conditions promote evaporation process or dissolution of evaporites or both were contributing to the formation of saline groundwater in the study area, 6) the positive correlation observed between elevated F⁻ and fluorite also suggested that the fluorite dissolution also played significant role for leaching of F⁻ in groundwater from sediments, and 7) calcite controlled Ca2⁺ level and enhanced the dissolution of F-bearing minerals and drive F⁻ concentration in groundwater. In a nut shell, this study revealed the worst scenarios of F⁻ contamination via various possible geochemical mechanisms in groundwater along major rivers in Sindh and Punjab, Pakistan, which need immediate attention of regulatory authorities to avoid future hazardous implications.

China continues to suffer from severe acid deposition, despite the government implying a series of policies to control air pollution. In this study, rainwater samples were collected from 2011 to 2016 in Sichuan province to measure the pH values and the concentrations of nine inorganic ions (SO₄²⁻, NO₃⁻, NH₄⁺, Cl⁻, Na⁺, Ca²⁺, K⁺, Mg²⁺, and F⁻), and then to investigate their spatiotemporal variations. Besides, the dominant sources for the acidic ions in the precipitation were also revealed by statistical model. The results showed that the rainwater continued to be highly acidic, and the Volume-Weighted Mean (VWM) pH value was calculated to be 5.18 during 2011 and 2016. NH₄⁺, Ca²⁺, NO₃⁻, and SO₄²⁻ were the dominant water-soluble inorganic ions, accounting for 79.2% of the total ions on average. The remarkable decrease in NO₃⁻ and SO₄²⁻ concentrations (from 75.9 to 54.3 μeq L⁻¹ and from 285 to 145 μeq L⁻¹, respectively) resulted in an increase in the pH value of rainwater from 5.24 in 2011 to 5.70 in 2016. The concentrations of SO₄²⁻, NO₃⁻, F⁻, Na⁺, and K⁺ showed remarkably seasonal variation, with the highest value observed in winter, followed by spring and autumn, and the lowest value observed in summer. High VWM concentration of these ions in winter were mainly due to adverse meteorological conditions (e.g., rare rainfall, lower planetary boundary height, and stagnant air) and intensive anthropogenic emissions. SO₄²⁻, NO₃⁻, and F⁻ ions peaked in the southeastern Sichuan province, which is a typical industrial region. NH₄⁺ concentrations decreased from 268 μeq L⁻¹ in the east to 10.4 μeq L⁻¹ in the western Sichuan province, which could be related to the development of agriculture in the eastern Sichuan province. Ca²⁺ peaked in southeastern Sichuan province due to intensive construction activities and severe stone desertification. On the basis of Positive Matrix Factorization (PMF) analysis, four sources of inorganic ions in rainwater were identified, including anthropogenic source, crust, biomass burning, and aging sea salt aerosol. Geographically Weighted Regression (GWR) was used to find the spatial correlations between the socio-economic factors and ions in the rainwater. At the regional scale, the influence of fertilizer consumption and Gross Agricultural Production (GAP) on NH₄⁺ increased from east to west; moreover the influence of Gross Industrial Production (GIP) on SO₄²⁻ and NO₃⁻ also increased.

Bogota registers frequent episodes of poor air quality from high PM₁₀ concentrations. It is one of the main Latin American megacities, located at 2600 m in the tropical Andes, but there is insufficient data on PM₁₀ source contribution. A characterization of the chemical composition and the source apportionment of PM₁₀ at an urban background site in Bogota was carried out in this study. Daily samples were collected from June 2015 to May 2016 (a total of 311 samples). Organic carbon (OC), elemental carbon (EC), water soluble compounds (SO₄²⁻, Cl⁻, NO₃⁻, NH₄⁺), major elements (Al, Fe, Mg, Ca, Na, K, P) and trace metals (V, Cd, Pb, Sr, Ba, among others) were analyzed. The results were interpreted in terms of their variability during the rainy season (RS) and the dry season (DS). The data obtained revealed that the carbonaceous fraction (∼51%) and mineral dust (23%) were the main PM₁₀ components, followed by others (15%), Secondary Inorganic Compounds (SIC) (11%) and sea salt (0.4%). The average concentrations of soil, SIC and OC were higher during RS than DS. However, peak values were observed during the DS due to photochemical activity and forest fires. Although trace metals represented <1% of PM₁₀, high concentrations of toxic elements such as Pb and Sb on RS, and Cu on DS, were obtained. By using a PMF model, six factors were identified (∼96% PM₁₀) including fugitive dust, road dust, metal processing, secondary PM, vehicles exhaust and industrial emissions. Traffic (exhaust emissions + road dust) was the major PM₁₀ source, accounting for ∼50% of the PM₁₀. The results provided novel data about PM₁₀ chemical composition, its sources and its seasonal variability during the year, which can help the local government to define control strategies for the main emission sources during the most critical periods.