A massive and dense textured layer (ca. 35–50 cm thick) of hardpan was uncovered at the top layer, which capped the unweathered sulfidic Cu-Pb-Zn tailings in depth and physically supported gravelly soil root zones sustaining native vegetation for more than a decade. For the purpose of understanding functional roles of the hardpan layer in the cover profile, the present study has characterized the microstructures of the hardpan profile at different depth compared with the tailings underneath the hardpans. A suit of microspectroscopic technologies was deployed to examine the hardpan samples, including field emission-scanning electron microscopy coupled with energy dispersive spectroscopy (FE-SEM-EDS), X-ray diffraction (XRD) and synchrotron-based X-ray absorption fine structure spectroscopy (XAFS). The XRD and Fe K-edge XAFS analysis revealed that pyrite in the tailings had been largely oxidised, while goethite and ferrihydrite had extensively accumulated in the hardpan. The percentage of Fe-phyllosilicates (e.g., biotite and illite) decreased within the hardpan profile compared to the unweathered tailings beneath the hardpan. The FE-SEM-EDS analysis showed that the fine-grained Ca-sulfate (possibly gypsum) evaporites appeared as platelet-shaped that deposited around pyrite, dolomite, and crystalline gypsum particles, while Fe-Si gels exhibited a needle-like texture that aggregated minerals together and produced contiguous coating on pyrite surfaces. These microstructural findings suggest that the weathering of pyrite and Fe-phyllosilicates coupled with dolomite dissolution may have contributed to the formation of Ca-sulfate/gypsum evaporites and Fe-Si gels. These findings have among the first to uncover the microstructure of hardpan formed at the top layer of sulfidic Cu-Pb-Zn tailings, which physically capped the unweathered tailings in depth and supported root zones and native vegetation under semi-arid climatic conditions.

Ground-level ozone (O3) concentrations have been elevating in the last century. While there has been a notable progress in understanding O3 effects on vegetation, O3 effects on ecological stoichiometry remain unclear, especially early in the oxidative stress. Ethyelenediurea (EDU) is a chemical compound widely applied in research projects as protectant of plants against O3 injury, however its mode of action remains unclear. To investigate O3 and EDU effects early in the stress, we sprayed willow (Salix sachalinensis) plants with 0, 200 or 400 mg EDU L−1, and exposed them to either low ambient O3 (AOZ) or elevated O3 (EOZ) levels during the daytime, for about one month, in a free air O3 controlled exposure (FACE); EDU treatment was repeated every nine days. We collected samples for analyses from basal, top, and shed leaves, before leaves develop visible O3 symptoms. We found that O3 altered the ecological stoichiometry, including impacts in nutrient resorption efficiency, early in the stress. The relation between P content and Fe content seemed to have a critical role in maintaining homeostasis in an effort to prevent O3-induced damage. Photosynthetic pigments and P content appeared to play an important role in EDU mode of action. This study provides novel insights on the stress biology which are of ecological and toxicological importance.

Ants accumulate heavy metals and respond to pollution with modification in species composition, community structure, altered behaviour and immunity. However, the levels of heavy metals in ants’ nests and explicit individual-level responses towards heavy metals have not been revealed. We found that red wood ants Formica lugubris accumulate high and correlated values of such heavy metals as Al, Cd, Co, Cu, Fe, Ni, Pb and Zn both in ants and nest material near cobalt smelter in Finland. Relative differences in metal concentrations were higher in nests than in ants. The highest values were obtained for elements such as Co (36.6), Zn (14.9), Cd (9.7), Pb (8.5), Cu (7.4), Ni (6.4), As (4.7), Cr (2.9) and Fe (2.4) in nest material, and Co (32.7), Cd (6.3), Pb (6), Fe (2.8), Ni (2.9) and Zn (2.1) in ants. In industrial and reference areas, ants have no differences in size, but differed in dry and residual body mass. In polluted areas, F. lugubris had less melanised heads, but not thoraxes. The sensitivity of cuticular colouration in red wood ants subjected to heavy metal pollution might be related to metal-binding properties of melanins. The overall results are useful for the improvement of biomonitoring techniques using ants as indicators of industrial contamination and for further discovery of novel ecotoxicological biomarkers.

Arsenic (As) remediation in contaminated water using nanoparticles is promising. However, the fate and transport of As associated with nano-adsorbents in natural environment is poorly understood. To investigate the fate of adsorbed As on nano-TiO₂ in changed redox condition from oxic to anoxic, we added the As(V)-TiO₂ suspension in groundwater to an autoclaved soil column which inoculated a sulfate-reducing bacterium, Desulfovibrio vulgaris DP4. The dissolved As(V) in effluent increased to 798 μg/L for the biotic column and to 1510 μg/L for the abiotic control, and dissolved As(III) was observed only in biotic column. The total As (dissolved plus particulate) in the biotic column effluent (high to 2.5 mg/L) was substantially higher than the abiotic control (1.5 mg/L). Therefore SRB restrained the release of dissolved As, and facilitated the transport of particulate As. Micro-XRF analysis suggested that the nano-TiO₂ with As was mainly retained in the influent front and that its transport was negligible. Our pe-pH calculation and XANES analysis demonstrated that generated secondary iron minerals containing magnetite and mackinawite mainly were responsible for dissolved As retention, and then transported with As as particulate As. The results shed light on the mobilization of adsorbed As on a nano-adsorbent in an anoxic environment.

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.

High arsenic groundwater generally coexists with elevated Fe2+ concentrations (mg L−1 levels) under reducing conditions, but an explanation for the extremely high arsenic (up to ∼2690) concentrations at very low Fe2+ (i.e., μg L−1 levels) in groundwater of Datong Basin remains elusive. Field groundwater investigation and laboratory microcosm experiments were implemented in this study. The field groundwater was characterized by weakly alkaline (pH 7.69 to 8.34) and reducing conditions (Eh −221.7 to −31.9 mV) and arsenic concentration averages at 697 μg L−1. Acinetobacter (5.9–51.3%), Desulfosporosinus (4.6–30.2%), Brevundimonas (3.9–19%) and Pseudomonas (3.2–14.6%) were identified as the dominant genera in the bacterial communities. Bacterially mediated arsenate reduction, Fe(III) reduction, and sulfate reduction are processes occurring (or having previously occurred) in the groundwater. Results from incubation experiment (27 d) revealed that nitrate, arsenate, and Fe(III)/sulfate reduced sequentially with time under anoxic conditions, while Fe(III) and sulfate reduction processes had no obvious differences, occurring almost simultaneously. Moreover, low Fe2+ concentrations were attributed to initially high pH conditions, which relatively retarded Fe(III) reduction. In addition, arsenic behavior in relation to groundwater redox conditions, matrices, and solution chemistry were elaborated. Bacterial arsenate reduction process proceeded before Fe(III) and sulfate reduction in the incubation experiment, and the total arsenic concentration (dominated by arsenite) gradually increased from ∼7 to 115 μg L−1 as arsenate was reduced. Accordingly, bacterially mediated reductive desorption of arsenate is identified as the main process controlling arsenic mobility, while Fe(III) reduction coupled with sulfate reduction are secondary processes that have also contributed to arsenic enrichment in the study site. Overall, this study provide important insights into the mechanism controlling arsenic mobility under weakly alkaline and reducing conditions, and furnishes that arsenate reduction by bacteria play a major role leading to high accumulation of desorbed arsenite in groundwater.

Soil contamination due to atmospheric deposition of metals originating from smelters is a global environmental problem. A common problem associated with this contamination is the discrimination between anthropic and natural contributions to soil metal concentrations: In this context, we investigated the characteristics of soil contamination in the surrounding area of a world class smelter. We attempted to combine several approaches in order to identify sources of metals in soils and to examine contamination characteristics, such as pollution level, range, and spatial distribution. Soil samples were collected at 100 sites during a field survey and total concentrations of As, Cd, Cr, Cu, Fe, Hg, Ni, Pb, and Zn were analyzed. We conducted a multivariate statistical analysis, and also examined the spatial distribution by 1) identifying the horizontal variation of metals according to particular wind directions and distance from the smelter and 2) drawing a distribution map by means of a GIS tool. As, Cd, Cu, Hg, Pb, and Zn in the soil were found to originate from smelter emissions, and As also originated from other sources such as abandoned mines and waste landfill. Among anthropogenic metals, the horizontal distribution of Cd, Hg, Pb, and Zn according to the downwind direction and distance from the smelter showed a typical feature of atmospheric deposition (regression model: y = y0 + αe−βx). Lithogenic Fe was used as an indicator, and it revealed the continuous input and accumulation of these four elements in the surrounding soils. Our approach was effective in clearly identifying the sources of metals and analyzing their contamination characteristics. We believe this study will provide useful information to future studies on soil pollution by metals around smelters.

Thallium (Tl) is a well-recognized hazardous toxic heavy metal that has been reported to have embryotoxicity and fetotoxicity. However, little is known about its association with preterm birth (PTB) in humans. We aimed to evaluate the predictors of Tl exposure and assessed its relation with PTB. The study population included 7173 mother-infant pairs from a birth cohort in Wuhan, China. Predictors of Tl concentrations were explored using linear regression analyses, and associations of Tl exposure with risk of PTB or gestational age at birth were estimated using logistic regression or generalized linear models. The geometric mean and median values of urinary Tl concentrations were 0.28 μg/L (0.55 μg/g creatinine) and 0.29 μg/L (0.53 μg/g creatinine). We found that maternal urinary Tl concentrations varied by gestational weight gain, educational attainment, multivitamin and iron supplementations. Women with Tl concentrations higher than 0.80 μg/g creatinine were at higher risk of giving birth prematurely versus those with Tl concentrations lower than 0.36 μg/g creatinine [adjusted odds ratio (95% confidence interval (CI)): 1.55 (1.05, 2.27)], and the association was more pronounced in PTB with premature rupture of membranes (PROM) rather than in PTB without PROM. About 3-fold increase in creatinine-corrected Tl concentrations were associated with 0.99-day decrease in gestational length (95% CI: −1.36, −0.63). This is the first report on the associations between maternal Tl exposure and the risk of PTB.

Acceleration of Fe³⁺/Fe²⁺ cycle and simultaneous reduction of particle size with enhanced stability is extremely important for iron-based heterogeneous Fenton catalysts. In this work, Fe⁰-Fe₂O₃ composite nanoparticles embedded ordered mesoporous carbon hybrid materials (Fe⁰-Fe₂O₃/OMC) were rationally designed as efficient heterogeneous Fenton catalysts. Because of the confinement and reduction of OMC, highly dispersed Fe⁰-Fe₂O₃ active species with diameter of ∼8 nm were generated by an optimized carbothermic reduction process. In addition, Fe⁰-Fe₂O₃/OMC possesses ordered mesoporous structure with uniform mesopore, high surface area and pore volume. For comparison, two other catalysts, including solely Fe⁰ nanoparticles supported on ordered mesoporous carbon (Fe⁰/OMC) and solely Fe₂O₃ nanoparticles supported on ordered mesoporous carbon (Fe₂O₃/OMC) were also prepared. The Fenton catalytic performance of synthesized catalysts was evaluated by using H₂O₂ as oxidizing agent to degrade Acid Orange II (AOII). The results show that almost 98.1% of 100 mg L⁻¹ AOII was removed by Fe⁰-Fe₂O₃/OMC in condition of neutral pH and nearly room temperature, which is much higher than those of compared catalysts. The enhanced catalytic activity of Fe⁰-Fe₂O₃/OMC for AOII removal is due to the efficient electron transfer between the Fe⁰ and iron oxide and the accelerated Fe³⁺/Fe²⁺ cycle. The stability and reusability of the catalyst was also investigated, which showed a good performance even after five consecutive runs. The as-synthesized catalyst is proved to be an attractive candidate in heterogeneous Fenton chemistry and practical application.

World soils are subjected to a number of anthropogenic global change factors. Although many previous studies contributed to understand how single global change factors affect soil properties, there have been few studies aimed at understanding how two naturally co-occurring global change drivers, nitrogen (N) deposition and increased precipitation, affect critical soil properties. In addition, most atmospheric N deposition and precipitation increase studies have been simulated by directly adding N solution or water to the forest floor, and thus largely neglect some key canopy processes in natural conditions. These previous studies, therefore, may not realistically simulate natural atmospheric N deposition and precipitation increase in forest ecosystems. In a field experiment, we used novel canopy applications to investigate the effects of N deposition, increased precipitation, and their combination on soil chemical properties and the microbial community in a temperate deciduous forest. We found that both soil chemistry and microorganisms were sensitive to these global change factors, especially when they were simultaneously applied. These effects were evident within 2 years of treatment initiation. Canopy N deposition immediately accelerated soil acidification, base cation depletion, and toxic metal accumulation. Although increased precipitation only promoted base cation leaching, this exacerbated the effects of N deposition. Increased precipitation decreased soil fungal biomass, possible due to wetting/re-drying stress or to the depletion of Na. When N deposition and increased precipitation occurred together, soil gram-negative bacteria decreased significantly, and the community structure of soil bacteria was altered. The reduction of gram-negative bacterial biomass was closely linked to the accumulation of the toxic metals Al and Fe. These results suggested that short-term responses in soil cations following N deposition and increased precipitation could change microbial biomass and community structure.