This study aimed at evaluating the interactive effects of acetaminophen (AC; 400 mg kg−1) and silicon dioxide nanomaterial (nano-SiO2;3 mg kg−1) on soil-grown barley. After 14 days of growth, plant growth, evaluated in terms of fresh and dry weight, was greatly inhibited by AC, independently of being or not co-treated with nano-SiO2. Plants growing under high levels of AC did not show any increase in malondialdehyde (MDA) nor thiols contents, though levels of superoxide anion (O2.-) and hydrogen peroxide (H2O2) were increased in leaves and roots, respectively. When plants were co-treated with nano-SiO2, reactive oxygen species (ROS) content remained unchanged, but lipid peroxidation (LP) was diminished and the thiol redox network was up-regulated in roots. The evaluation of the response of the antioxidant system showed that AC affected both non-enzymatic and enzymatic components in an organ-specific manner: proline levels and superoxide dismutase (SOD) activity were enhanced, whilst catalase (CAT) activity decreased in leaves; ascorbate content and CAT activity were diminished in roots. In response to the nano-SiO2 co-treatment, this pattern was not vastly altered, despite for ascorbate peroxidase (APX), whose activity was greatly enhanced in both organs. Overall, combining biometric, biochemical and molecular approaches, this study revealed that, although AC impaired plant growth and development, it did not trigger a harsh oxidative stress condition. Maybe by this reason, the ameliorating potential of nano-SiO2 was not so evident; yet, nano-SiO2 was able to reduce LP and to stimulate thiol content and APX activity, possibly as a defense mechanism against AC-induced stress.

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.

Nitrogen (N) deposition and biological N fixation (BNF) are main external N inputs into terrestrial ecosystems. However, few studies have simultaneously quantified the contribution of these two external N inputs to global NPP and consequent C sequestration. Based on literature analysis, we estimated new net primary production (NPP) due to external N inputs from BNF and N deposition and the consequent C sinks in global boreal, temperate and tropical forest biomes via a stoichiometric scaling approach. Nitrogen-induced new NPP is estimated to be 3.48 Pg C yr⁻¹ in global established forests and contributes to a C sink of 1.83 Pg C yr⁻¹. More specifically, the aboveground and belowground new NPP are estimated to be 2.36 and 1.12 Pg C yr⁻¹, while the external N-induced C sinks in wood and soil are estimated to be 1.51 and 0.32 Pg C yr⁻¹, respectively. BNF contributes to a major proportion of N-induced new NPP (3.07 Pg C yr⁻¹) in global forest, and accounts for a C sink of 1.58 Pg C yr⁻¹. Compared with BNF, N deposition only makes a minor contribution to new NPP (0.41 Pg C yr⁻¹) and C sinks (0.25 Pg C yr⁻¹) in global forests. At the biome scale, rates of N-induced new NPP and C sink show an increase from boreal forest towards tropical forest, as mainly driven by an increase of BNF. In contrast, N deposition leads to a larger C sink in temperate forest (0.11 Pg C yr⁻¹) than boreal (0.06 Pg C yr⁻¹) and tropical forest (0.08 Pg C yr⁻¹). Our estimate of total C sink due to N-induced new NPP approximately matches an independent assessment of total C sink in global established forests, suggesting that external N inputs by BNF and atmospheric deposition are key drivers of C sinks in global forests.

Given its wide distribution in the natural environment and global transport potential, mercury (Hg) is regarded as a ubiquitous pollutant. In this study, we carried out nation-wide sampling campaigns across China to investigate the distribution of Hg in agricultural soils. Concentrations of Hg in the soils collected in 2011 and 2016 ranged from 0.04 to 0.69 and 0.06–0.78 mg kg−1, respectively. Based on the data from 2016, the reserve of Hg in the surface arable soils (0–20 cm) in China was 4.1 × 104 metric tons and Chinese cultivated soils accounted for 63.4–364 metric tons of Hg released to the global atmosphere. The soil Hg concentrations were significantly higher than the reference background level, highlighting the impacts of anthropogenic activities. The vertical distribution pattern showed a clear enrichment at the surface and a decrease with depth of the soils. Comparison of calculated geo-accumulation indexes among individual provinces showed that Northwest China had higher levels of Hg contamination than other regions of China, likely due to long-term energy related combustions in the area. Soil Hg level showed strong positive correlations with organic matter contents of soil, as well as the mean annual precipitation and temperature of the sampling locations. The non-carcinogenic human health risks of soil Hg were below the threshold level, but the general risk to the ecosystem was considerable. The increases in Hg accumulation from 2011 to 2016 at provincial level were found to relate to coal combustion, power generation and per capita GDP. This examination of energy consumption and socioeconomic drivers for China's soil Hg reserve increase is critical for direct Hg control by guiding policy-making and targets of technology development in era of rapid economic growth.

Satellite-based aerosol optical depth (AOD) is now comprehensively applied to estimate ground-level concentrations of fine particulate matter (PM2.5). This study aimed to construct the AOD-PM2.5 estimation models over Taiwan. The AOD-PM2.5 modeling in Taiwan island is challenging owing to heterogeneous land use, complex topography, and humid tropical to subtropical climate conditions with frequent cloud cover and prolonged rainy season. The AOD retrievals from the MODerate resolution Imaging Spectroradiometer (MODIS) onboard the Terra and Aqua satellites were combined with the meteorological variables from reanalysis data and high resolution localized land use variables to estimate PM2.5 over Taiwan island from 2005 to 2015. Ten-fold cross validation was carried out and the residuals of the estimation model at various locations and seasons are assessed. The cross validation (CV) R2 based on monitoring stations were 0.66 and 0.66, with CV root mean square errors of 14.0 μg/m3 (34%) and 12.9 μg/m3 (33%), respectively, for models based on Terra and Aqua AOD. The results provided PM2.5 estimations at locations without surface stations. The estimation revealed PM2.5 concentration hotspots in the central and southern part of the western plain areas, particularly in winter and spring. The annual average of estimated PM2.5 concentrations over Taiwan consistently declined during 2005–2015. The AOD-PM2.5 model is a reliable and validated method for estimating PM2.5 concentrations at locations without monitoring stations in Taiwan, which is crucial for epidemiological study and for the assessment of air quality control policy.

The prevalence of allergic diseases has increased in the past few decades. Bio-aerosol proteins and their chemical modifications, such as 3-nitrotyrosine (3-NT), in the atmosphere have been attracting attention due to their promotive effects on allergies. 3-NT is generated from the amino acid, tyrosine, through a reaction with ozone (O3) and nitrogen dioxide (NO2). However, the underlying mechanisms have not yet been elucidated in detail. Therefore, we measured 3-NT and evaluated the relationships among 3-NT and various pollutants such as sulfur dioxide (SO2), NOx (NO + NO2), ozone (O3), PM7, total suspended particulate matter (TSP) containing proteins, humidity, and temperature. 3-NT positively correlated with O3, SO2, humidity, and temperature, and negatively correlated with NOx. A multiple regression analysis showed that 3-NT positively associated with O3, humidity, and PM7. O3 positively associated with 3-NT and PM7, and negatively associated with NOx and humidity. These results suggest that 3-NT is generated from PM proteins through a reaction with O3 under high humidity conditions, and that the measurement of 3-NT is important and useful for the research of O3.

The negative effect of carbonate on the rate and extent of bioreduction of aqueous U(VI) has been commonly reported. The solution pH is a key chemical factor controlling U(VI)ₐq species and the Gibbs free energy of reaction. Therefore, it is interesting to study whether the negative effect can be diminished under specific pH conditions. Experiments were conducted using Shewanella putrefaciens under anaerobic conditions with varying pH values (4–9) and bicarbonate concentrations ([CO32−]T, 0–50 mmol/L). The results showed a clear correlation between the pH-bioreduction edges of U(VI)ₐq and the [CO32−]T. The specific pH at which the maximum bioreduction occurred (pHₘbᵣ) shifted from slightly basic to acidic pH (∼7.5–∼6.0) as the [CO32−]T increased (2–50 mmol/L). At [CO32−]T = 0, however, no pHₘbᵣ was observed in terms of increasing bioreduction with pH (∼100%, pH > 7). In the presence of [CO32−]T, significant bioreduction was observed at pHₘbᵣ (∼100% at 2–30 mmol/L [CO32−]T, 93.7% at 50 mmol/L [CO32−]T), which is in contrast to the previously reported infeasibility of bioreduction at high [CO32−]T. The pH-bioreduction edges were almost comparable to the pH-biosorption edges of U(VI)ₐq on heat-killed cells, revealing that biosorption is favorable for bioreduction. The end product of U(VI)ₐq bioreduction was characterized as insoluble nanobiogenic uraninite by HRTEM. The redox potentials of the master complex species of U(VI)ₐq, such as (UO2)4(OH)7+, (UO2)2CO3(OH)3−, and UO2(CO3)34−, were calculated to obtain insights into the thermodynamic reduction mechanism. The observed dynamic role of pH in bioreduction suggests the potential for bioremediation of uranium-contaminated groundwater containing high carbonate concentrations.

The hydrological and pollution processes are an important science problem for aquatic ecosystem. In this study, the samples of river water, reservoir water, shallow groundwater, deep groundwater, and precipitation in mining area are collected and analyzed. δD and δ¹⁸O are used to identify hydrological process. δ¹⁵N-NO₃⁻ and δ¹⁸O-NO₃⁻ are used to identify the sources and pollution process of NO₃⁻. The results show that the various water bodies in Fenhe River Basin are slightly alkaline water. The ions in the water mainly come from rock weathering. The concentration of SO₄²⁻ is high due to the impact of coal mining activity. Deep groundwater is significantly less affected by evaporation and human activity, which is recharged by archaic groundwater. There are recharge and discharge between reservoir water, river water, soil water, and shallow groundwater. NO₃⁻ is the main N species in the study area, and forty-six percent of NO₃⁻-N concentrations exceed the drinking water standard of China (NO₃⁻-N ≤ 10 mg/L content). Nitrification is the main forming process of NO₃⁻. Denitrification is also found in river water of some river branches. The sources of NO₃⁻ are mainly controlled by land use type along the riverbank. NO₃⁻ of river water in the upper reaches are come from nitrogen in precipitation and soil organic N. River water in the lower reaches is polluted by a mixture of soil organic N and fertilizers.

Polybrominated diphenyl ethers (PBDEs) and their hydroxylated (OH) and methoxylated (MeO) structural analogues have been found widely distributed in aquatic ecosystems, and may exhibit potential adverse effects to humans due to their bioaccumulative behavior through food chain. Fishmeal is an important animal feed applied around the world and is generally of marine origin. However, the levels and sources of PBDEs in fishmeal have not been thoroughly evaluated and their structural analogues have not been reported to date. The present study collected ninety-two fishmeal samples from world main fishmeal producing area to determine 27 PBDEs, 10 MeO-PBDEs and 11 OH-PBDEs. The concentrations of Σ₂₇PBDEs, Σ₁₀MeO-PBDEs and Σ₁₁OH-PBDEs were in the ranges of 0.1–1498 (mean: 75.8), 1.14–881 (37.4) and 1.00–47.5 (8.17) ng/g lipid, respectively. PBDEs were found primarily correlated with the historically commercial production, meaning higher production of certain commercial product in a country, higher corresponding PBDE congeners in local fishmeal. A market shift from penta- and octa-formulations toward deca-formulation was observed. BDE209 was identified as a major congener in fishmeal. Both the MeO-PBDEs and the OH-PBDEs were influenced by fishmeal producing areas (p < 0.001). High MeO-PBDEs were identified in the Southeast Asian fishmeal, which might be due to the suitable environmental conditions for the generation of bromoperoxidase-contained algae in local area. The ratio of two major MeO-PBDE congeners, 6-MeO-BDE47/2′-MeO-BDE68, were generally >1 in the northern hemisphere and <1 in the southern hemisphere in the present study, which was consistent with the results obtained from previous published papers. Both MeO-PBDEs and OH-PBDEs were in accordance with the specialties of naturally produced halogenated compounds.

Continual efforts have been made to determine a simple and universal method of estimating heavy metal phytoavailability in terrestrial systems. In the present study, a mechanism-based multi-surface model (MSM) was developed to predict the partition of Ni(II) in soil–solution phases and its bioaccumulation in wheat (Triticum aestivum L.) in 19 Chinese soils with a wide range of soil properties. MSM successfully predicted the Ni(II) dissolution in 0.01 M CaCl2 extracting solution (R2 = 0.875). The two-site model for clay fraction improved the prediction, particularly for alkaline soils, because of the additional consideration of edge sites. More crucially, the calculated dissolved Ni(II) was highly correlated with the metal accumulation in wheat (R2 = 0.820 for roots and 0.817 for shoots). The correlation coefficients for the MSM and various chemical extraction methods have the following order: soil pore water > MSM ≈ diffuse gradient technique (DGT) > soil total Ni > 0.43 M HNO3 > 0.01 M CaCl2. The results suggested that the dissolved Ni(II) calculated using MSM can serve as an effective indicator of the bioavailability of Ni(II) in various soils; hence, MSM can be used as an supplement for metal risk prediction and assessment besides chemical extraction techniques.