Natural birnessite-like minerals are commonly enriched in various transitional metals (TMs), which greatly modify the mineral structure and properties. However few studies are yet conducted systematically on the effects of TM doping on birnessite reactivity towards Cr(III) oxidation. In the present study, the transformation behaviors of Cr(III) on Co-, Ni-, V-containing birnessites were investigated. Co and Ni doping generally decrease the mineral crystalline sizes and hydrodynamic sizes (DH) while V-doping greatly decreases the crystalline sizes but not the DH, owing to particle aggregation. Co and Ni firstly decrease and then increase the mineral zeta potentials (ζ) at pH4 while V decreases ζ. Electrochemical specific capacitances for Co-containing birnessites are gradually reduced, while those for Ni-doped birnessites are slightly reduced and for V-doped birnessites increased, which have a positively linear relationship with the amounts of Cr(III) oxidized by these samples. Cr(III) removal efficiencies from solution by these Co-, Ni- and V-containing birnessites are 26–51%, ∼62–72% and ∼96–100%, respectively, compared to ∼92% by pure birnessite. Cr(III) oxidation kinetics analysis demonstrates the gradual decrease of Mn(IV) and concurrent increase of Mn(III) and the adsorption of mainly Cr(III) on mineral surfaces. A negatively linear relationship exists between birnessite lateral sizes and the proportions of Mn(IV/III) consumed to oxidize Cr(III). Apparent initial Cr(III) oxidation rate (kobs) for Co-containing birnessites are greatly reduced, while those for Ni-doped samples moderately decreased and for V-doped samples first increased and then decreased. A positively or negatively linear relationship exists between kobs or the amount of Mn(II) released and the mineral Mn(IV) content respectively. Cr(III) oxidation probably initiates from layer edge sites of Ni-doped birnessites but the vacancies of Co- and V-containing birnessites. These results provide insights into the reaction mechanisms of Cr(III) with natural birnessite-like minerals.

It is of environmental significance to study the leaching performance of additives from microplastics (MPs) and further evaluate the toxicity of leachate to microalgae. Here, we investigated the effects of accelerated aging on characteristics, leaching, and toxicity of commercial lead chromate pigmented MPs. Results show that aging of MPs caused surface cracks and fragmentation, increased their surface area and carbonyl contents, and promoted the release of lead chromate pigment. Chromium (Cr) and lead (Pb) tend to leach under acidic condition, rather than neutral and alkali environment. Aging treatment facilitates the leaching performance and a high concentration of NaCl solution also favors the leaching process. Toxicology experiments demonstrate that only high concentration of leachate (>10 μg L⁻¹) exerted significant inhibitory influence (p < 0.005) on cell photosynthesis of Microcystis aeruginosa. The growth inhibition of algal cells remarkably increased with increasing leachate concentrations. We observed more inhibiting effects on cell growth and photosynthesis using the leachates of aged MPs. Longer aging time leads to more release of Cr and Pb, rendering higher toxicity to microalgae. These novel findings will benefit us from assessing the leaching behavior of additives in MPs and their toxicological risks to aquatic organisms.

Few studies specifically address the possible associations between multiple-metal exposures and liver damage among the occupational population. This study aimed to explore the cross-sectional relationships of plasma metals with liver function parameters. For 571 on-the-spot workers in the manganese-exposed workers healthy cohort (MEWHC), we determined liver function parameters: total bilirubin (TBILI), direct bilirubin (DBILI), indirect bilirubin (IBILI), alanine transaminase (ALT) and aspartate transaminase (AST). Total concentrations of 22 plasma metals were measured by ICP-MS. The LASSO (least absolute shrinkage and selection operator) penalized regression model was applied for selecting plasma metals independently associated with liver function parameters. Multiple linear regression analyses and restricted cubic spline (RCS) were utilized for identifying the exposure-response relationship of plasma metals with liver function parameters. After adjusting for covariates and selected metals, a 1-SD increase in log-10 transformed levels of iron was associated with increases in the levels of TBILI, DBILI and IBILI by 20.3%, 12.1% and 23.7%, respectively; similar increases in molybdenum for decreases in levels of TBILI, DBILI and IBILI by 6.1%, 2.6% and 8.3%, respectively. The effect of a 1-SD increase in plasma copper corresponded decreases of 3.2%, 3.4% and 5.0% in TBILI, AST and ALT levels, respectively. The spline analyses further clarified the non-linear relationships between plasma iron and bilirubin whilst negative linear relationships for plasma molybdenum and bilirubin. Plasma iron was positively whilst plasma molybdenum was negatively associated with increased serum bilirubin levels. Further studies are needed to validate these associations and uncover the underlying mechanisms.

Pesticides often occur as mixtures of complex compounds in water environments, while most of studies only focus on the toxic effects of individual pesticides with little attention to the joint toxic effects. In the present study, we aimed to the mixture toxicity of beta-cypermethrin (BCY) and thiacloprid (THI) to zebrafish (Danio rerio) employing multiple toxicological endpoints. Results displayed that the 96-h LC50 values of BCY to D. rerio at various developmental stages ranged from 2.64 × 10 (1.97 × 10–3.37 × 10) to 6.03 × 103 (4.54 × 103–1.05 × 104) nM, which were lower than those of THI ranging from 2.97 × 104 (1.96 × 104–4.25 × 104) to 2.86 × 105 (2.19 × 105–5.87 × 105) nM. Mixtures of BCY and THI exhibited synergistic response in embryonic zebrafish. Meanwhile, the enzyme activities of antioxidants (CAT and SOD) and detoxification enzyme (CarE), endogenous T-GSH and MDA contents, as well as gene expressions (tsh, crh, cxcl and bax) involved in oxidative stress, cellular apoptosis, immune system and endocrine system were obviously changed in the mixture exposure compared with the respective BCY or THI treatment. Consequently, the increased toxicity of pesticide mixture suggested that the toxicological data acquired from individual pesticide tests might underrate the toxicity risk of pesticides that actually arise in the real environment. Taken together, our present study provided evidence that mixture exposure of BCY and THI could induce additional toxic effect compared with their respective individual pesticides on D. rerio, offering valuable insights into the toxic mechanism of pesticide mixture.

Silver nanoparticles (AgNPs) are expected to enter aquatic systems, but there are limited data on how they might affect microbial communities in pathogen impaired streams. We examined microbial community responses to citrate-AgNP (10.9 ± 0.7 nm) and polyvinylpyrrolidone (PVP)–AgNP (11.0 ± 0.7 nm) based on microbial concentration and enzyme activity in sediment from a pathogen impaired stream. Addition of each nanoparticle to sediment caused at least a 69% decrease in microbial concentration (1,264 ± 93.6 to 127 ± 29.5 CFU/g) and a 62% decrease in β-glucosidase activity (11.7 ± 2.1 to 1.3 ± 0.3 μg/g/h). Each AgNP reduced alkaline phosphatase activity but their effects were not statistically significant. Sediment exposed to 0.108 mg Ag/kg of AgNO₃ resulted in a 92% decrease in microbial concentration and a reduced enzyme activity which was not statistically significant. Measured total silver in sediments treated with AgNPs which exhibited significant inhibition effects on the microbial community ranged from 0.19 ± 0.02 to 0.39 ± 0.13 mg Ag/kg. These concentrations tested in this study are much lower than the expected concentrations (2–14 mg Ag/kg) in freshwater sediments. The results of this study demonstrate that AgNPs can alter microbial community activity and population size, which may lead to false negative fecal indicator bacteria detection and enumeration using methods that rely on β-glucosidase activity. We conclude that the presence of AgNPs in impaired streams and recreational waters can influence pathogen detection methods, potentially affecting public health risk estimates.

The emission of mercury (Hg) from cropland soil greatly affects the global Hg cycle. Combinations of different crop cultivars and planting densities will result in different light transmittance under canopies, which directly affects the solar and heat radiation flux received by the soil surface below crops. In turn, this might lead to differences in the soil–air total gaseous mercury (TGM) exchange under different cropping patterns. However, soil–air TGM exchange fluxes in croplands under differing canopies have been poorly investigated. Here, a one-year observation of TGM exchange flux was conducted for cropland soils covering five different crop cultivars and three planting densities in North China Plain using the dynamic flux chamber method. The results showed that light transmittance under the canopies was the key control on soil–air TGM exchange fluxes. High light transmittance can enhance soil TGM emission rates and increase the magnitude of diurnal variations in soil–air TGM exchange fluxes. Furthermore, we found that there were piecewise–function relationships (Peak function–constant equation) between light transmittance under the different canopies and the numbers of days after crop sowing. The soil–air TGM exchange fluxes showed a parabolic response to changes in light transmittance under the different canopies. A second-order model was established for the response relationship between soil–air TGM exchange flux and soil Hg concentration, total solar radiation above the canopy, and numbers of days after sowing. The estimated annual average soil–air TGM exchange flux was 5.46 ± 21.69 ng m⁻² h⁻¹ at corn–wheat rotation cropland with 30 cm row spacing using this second-order model. Our results might a data reference and a promising foundation for future model development of soil–air TGM exchange in croplands under different crop cultivars and planting densities.

Next to the city of Huelva (SW of Spain), around 100 Mt of phosphogypsum (PG) are stored in stacks on the salt-marshes of the Tinto River estuary covering a surface of about 1000 ha. Due to the high content of ²³⁸U series natural radionuclides of the PG, its acidic nature (pH about 3), and the fact that PG stacks were disposed without any kind of isolation from the substrate, they could produce a potential radioactive impact into the underlying sediments.The aim of this work is to assess the pollution of the underlying sediments by natural radionuclides coming from the PG stacks. To this end, seven cores were taken, and PG and sediments samples collected at different depths were analysed. The activity concentrations of the main long half-live natural radionuclides of interest were determined by applying both gamma-ray and alpha-particle spectrometry radiometric techniques.The results of this study showed that the first decimeters of salt-marsh sediment act as a “barrier” for the radionuclides coming from the PG stacks decreasing rapidly its activity concentration in depth, affecting mainly sediments located in the first 20 cm below the contact due to mixing processes. While ²³⁰Th, ²²⁶Ra and ²¹⁰Pb pollution is mainly restricted to the first 20 cm of sediments, U-isotopes can reach higher depths (up to around 50 cm) by leaching processes due to their lower reactivity and higher concentration in the polluted leachates. The obtained results have high relevance for the design of the perimeter channel which is projected to build in the restoration project, suggesting that should has around 1 m deep under the base of the PG stacks, to ensure the full collection of polluting leachates, and to prevent their release into the estuary of the Tinto River.

Herein, a new peroxymonosulfate (PMS) activation system was established using a biochar (BC)-supported Co₃O₄ composite (Co₃O₄-BC) as a catalyst to enhance chloramphenicols degradation. The effects of the amount of Co₃O₄ load on the BC, Co₃O₄-BC amount, PMS dose and solution pH on the degradation of chloramphenicol (CAP) were investigated. The results showed that the BC support could well disperse Co₃O₄ particles. The degradation of CAP (30 mg/L) was enhanced in the Co₃O₄-BC/PMS system with the apparent degradation rate constant increased to 5.1, 19.4 and 7.2 times of that in the Co₃O₄/PMS, BC/PMS and PMS-alone control systems, respectively. Nearly complete removal of CAP was achieved in the Co₃O₄-BC/PMS system under the optimum conditions of 10 wt% Co₃O₄ loading on BC, 0.2 g/L Co₃O₄-BC, 10 mM PMS and pH 7 within 10 min. The Co₃O₄/BC composites had a synergistic effect on the catalytic activity possibly because the conducting BC promoted electron transfer between the Co species and HSO₅⁻ and thus accelerated the Co³⁺/Co²⁺redox cycle. Additionally, over 85.0 ± 1.5% of CAP was still removed in the 10th run. Although both SO₄⁻ and OH were identified as the main active species, SO₄⁻ played a dominant role in CAP degradation. In addition, two other chloramphenicols, i.e., florfenicol (FF) and thiamphenicol (TAP), were also effectively degraded with percentages of 86.4 ± 1.3% and 71.8 ± 1.0%, respectively. This study provides a promising catalyst Co₃O₄-BC to activate PMS for efficient and persistent antibiotics degradation.

The co-contamination of arsenic (As) and cadmium (Cd) in soils is a common problem. Selenium (Se) can reduce the uptake of As and Cd in plants, and in practice, the alternate wetting and drying is a common culture mode in rice production. However, it is unknown whether Se can efficiently reduce As and Cd concentrations in crops suffering from a high-level contamination of As and Cd under different soil water conditions. In this study, we assessed the efficiency and risks of selenite [Se(IV)], in a pot experiment, to reduce the uptake of As and Cd in a rice plant (YangDao No 6) growing in a heavily contaminated soil by As and Cd (pH 7.28) under different soil water conditions. The results showed that Se(IV) failed to control the grain total As and Cd concentrations within their individual limited standard (0.2 mg kg⁻¹) despite that Se(IV) significantly reduced the grain total As and Cd concentrations. The soil drying treatment alone could reduce the accumulation of arsenite [As(III)] in the grains, but additional Se(IV) stimulated the accumulation of As(III) in the grains under soil drying conditions. In addition, the addition of Se(IV) enhanced the As and Cd concentrations in the shoots and/or roots of rice plants under certain conditions. The above results all suggested that the utilization of Se(IV) in a high contaminated soil by As and Cd cannot well control the total concentrations of As and Cd in plants. In this study, the available concentrations of As and Cd in the rhizosphere soil, the rhizosphere soil pH, the formation of root iron/manganese plaques and the concentrations of essential elements in the grains were monitored, and the related mechanisms on the changes of these parameters were also discussed. This study will give a guideline for the safe production of rice plants in a heavily co-contaminated soil by As and Cd.