Ecotoxicity and Risk to Zooplankton of a Novel Insecticide Used in Rice Paddies in a Simulated Ecosystem.

Diamide insecticides are widely used in rice paddies and pose a potential threat to aquatic organisms. However, the risk research related to their application in major rice-producing areas is very limited, especially mesocosm research to simulate the impact on aquatic ecosystems of long-term exposure, as well as exposure analysis based on local models and local scenarios. To assess potential risks from a novel diamide insecticide (tetrachlorantraniliprole) to aquatic nontarget organisms in the field over long-term exposure, an outdoor mesocosm study was performed, and the environmental concentrations were predicted by the multimedia paddy-pond model (TOPRICE). The mesocosm experiment showed that tetrachlorantraniliprole mainly stayed in the aqueous phase after entering the water body. Although the chemical dissipated quickly in the aqueous phase (half-life of 0.79-1.5 days), it showed toxic effects on zooplankton communities. Cladocerans, represented by Simocephalus vetulus, were most sensitive to tetrachlorantraniliprole stress. Significant short-term toxicity to cladocerans occurred in all treatment groups, but all recovered within 8 weeks except for the highest concentration group (30.0 µg /L). Based on the ecological recovery results, 7.74 µg tetrachlorantraniliprole/L (nominal concentration, 10.0 µg /L) is suggested to be the no-observed-ecological-adverse-effect concentration (NOEAEC) for the zooplankton community. When this NOEAEC was compared with predicted environmental concentrations (PECs; the PECs in natural ponds simulated by the TOPRICE model for 148 application scheme combinations in major rice-producing areas), a relatively high risk of applying tetrachlorantraniliprole during the rice tillering stage was found. The present study makes a positive contribution to the hypothesis that the current Tier 1 approaches for global acute risk assessment have a sufficient protective effect for assessing the risk of tetrachlorantraniliprole to aquatic organisms. Also, the present results should help us to gain a fuller understanding of the ecological risk of diamide insecticides in aquatic ecosystems and their rational application schemes. Environ Toxicol Chem 2024;43:429-439. © 2023 SETAC.

Transformation of zinc oxide nanoparticles in the presence of aluminum oxide with pre-sorbed phosphorus ligands.

Naturally occurring oxides could react with zinc oxide (ZnO) nanoparticles (NPs) and then change its transformation and toxicity to ecological receptors. The reaction may be affected by a variety of environmental factors, yet the relevant processes and mechanisms are limitedly investigated. Natural prevalent ligands, as an important factor, can sorb on natural oxide minerals and change its surface property, finally affecting ZnO NP transformation. This study investigated the interactions of ZnO NPs with phosphorus ligands (i.e., phytate and orthophosphate) pre-sorbed γ-alumina (γ-Al2O3) via batch experiments and multi-technique analyses. A limited amount of aqueous Zn2+ is observed when the concentration of ZnO NPs is relatively low (<64.8 mg L-1) in the presence of phytate pre-sorbed γ-Al2O3. Solid Zn(II) species includes binary/ternary surface Zn(II) complexes on γ-Al2O3 with minor amounts of zinc phytate precipitates. As the concentration of ZnO NPs increases, surface Zn(II) complexes gradually transform into zinc phytate and Zn-Al layered double hydroxide (Zn-Al LDH) precipitates. The quantitative analysis indicates that, as the concentration of ZnO NPs increases from 32.4 to 388.8 mg L-1, the proportion of Zn(II) species as binary/ternary surface complexes decreases from 81.9 to 30.2%; and the proportion as zinc phytate and Zn-Al LDH increases from 17.9 to 27.6% and 0 to 43.8%, respectively. The pre-sorption of orthophosphate can also inhibit ZnO NP transformation into Zn-Al LDH precipitates on γ-Al2O3. This study suggests that natural ligands pre-existed on natural oxide minerals could greatly influence the solubility, stability, transformation, and fate of easily dissoluble metal oxides (e.g., ZnO) in the environments.

Effects and mechanisms of Al substitution on the catalytic ability of ferrihydrite for Mn(II) oxidation and the subsequent oxidation and immobilization of coexisting Cr(III).

Al(III)-substituted ferrihydrite existing in natural soils is more common than pure ferrihydrite; however, the effects of Al(III) incorporation on the interaction between ferrihydrite, Mn(II) catalytic oxidation, and coexisting transition metal (e.g., Cr(III)) oxidation remain elusive. To address this knowledge gap, Mn(II) oxidation on synthetic Al(III)-incorporated ferrihydrite and Cr(III) oxidation on the previously formed Fe-Mn binaries were investigated in this study via batch kinetic studies combined with various spectroscopic analyses. The results indicate that Al substitution in ferrihydrite barely changes its morphology, specific surface area, or the types of surface functional groups, but increases the total amount of hydroxyl on the ferrihydrite surface and enhances its adsorption capacity toward Mn(II). Conversely, Al substitution inhibits electron transfer in ferrihydrite, thereby weakening its electrochemical catalysis on Mn(II) oxidation. Thus, the contents of Mn(III/IV) oxides with higher Mn valence states decrease, whereas those of lower Mn valence states increase. Furthermore, the number of hydroxyl radicals formed during Mn(II) oxidation on ferrihydrite decreases. These inhibitions of Al substitution on Mn(II) catalytic oxidation subsequently cause decreased Cr(III) oxidation and poor Cr(VI) immobilization. Additionally, Mn(III) in Fe-Mn binaries is confirmed to play a dominant role in Cr(III) oxidation. This research facilitates sound decision-making regarding the management of Cr-contaminated soil environments enriched with Fe and Mn.

A systematic review and meta-analysis of Comaneci/Cascade temporary neck bridging devices for the treatment of intracranial aneurysms.

Background: The temporary neck bridging devices represented by Comaneci and Cascade are a type of promising endovascular device for the treatment of intracranial bifurcation or wide-necked aneurysms. This systematic review and meta-analysis aim to assess the efficacy and safety of Comaneci/Cascade devices for the treatment of intracranial aneurysms. Methods: We performed a systematic literature search on articles in PubMed, Embase, and Web of Science that evaluated the efficacy and safety of Comaneci/Cascade devices for endovascular treatment of intracranial aneurysms, based on the Preferred Reporting Items for Systematic Reviews and Meta Analytics (PRISMA) guideline. We extracted the characteristics and treatment related information of patients included in the study, recorded the rate of technical success, procedural related complications, and angiographic outcomes. The angiographic outcome was evaluated based on Raymond Roy classification, and adequate occlusion was defined as Raymond Ray I + II. Results: Nine studies comprising 253 patients with 255 aneurysms were included. Among them, eight studies were conducted in Europe, one study was conducted in the USA. All these studies were retrospective. 206 aneurysms (80.78%) were ruptured. The vast majority of patients with ruptured aneurysms did not receive antiplatelet therapy. The rate of technical success was 97.1% (95% CI, 94.9 to 99.3%, I2 = 0%). The rate of periprocedural clinical complications was 10.9% (95% CI, 5.4 to 22.1%, I2 = 54%). The rate of complete occlusion (RR1) and adequate occlusion (RR1 + RR2) on immediate angiography after the procedure were 77.7% (95% CI, 72.7 to 83.2%, I2 = 35%) and 98% (95% CI, 95.9 to 100%, I2 = 0%) respectively. The rate of complete occlusion (RR1) and adequate occlusion (RR1 + RR2) on the last follow-up angiography were 81.2% (95% CI, 69.2 to 95.2%, I2 = 81%) and 93.7% (95% CI, 85.6 to 100%, I2 = 69%) respectively, with follow-up range from 3 to 18 months. 22/187 (11.76%) cases of aneurysms progressed during the follow-up period. 39/187 (20.86%) cases of aneurysms received additional treatment during the follow-up period. No fatal complications occurred during the treatment. Conclusion: The Comaneci/Cascade device can be used as an auxiliary treatment for intracranial aneurysms, with a good occlusion effect, but the incidence of complications still needs to be monitored.

Hepatic Steatosis and Fibrosis in Chronic Inflammatory Bowel Disease.

Background and Purpose: Chronic inflammatory bowel diseases (IBD) frequently affect extraintestinal organs including the liver. Since limited evidence suggests the presence of liver disease in IBD patients, we studied the frequency of hepatic steatosis and fibrosis in these patients and characterized disease-related factors. Methods: In this retrospective, cross-sectional, hospital-based, single-center study, consecutive patients with Crohn's disease (CD) and ulcerative colitis (UC) were included who had undergone routine abdominal ultrasound including transhepatic elastography. Hepatic steatosis was diagnosed by hyperechogenicity on B-mode ultrasound and by measuring controlled attenuation parameter (CAP). Hepatic fibrosis was assumed if transhepatic elastography yielded a stiffness > 7 kPa. Results: 132 patients (60% CD) with a median disease duration of 10 years were included. Steatosis assessed by B-mode ultrasound and CAP correlated well. Of the IBD patients, 30.3% had non-alcoholic fatty liver (NAFL). Factors associated with NAFL were age, BMI, duration of disease, as well as serum activities of aspartate-aminotransferase (AST) and gamma-glutamyl-transpeptidase (GGT). In multivariate analysis, only disease duration was independently associated with hepatic steatosis. Hepatic fibrosis was found in 10 (8%) of all IBD patients, predominantly in patients with CD (10/11). Conclusions: Pure hepatic steatosis is common in both CD and UC, whereas hepatic fibrosis occurs predominantly in CD patients. Association of disease duration with NAFLD suggests a contribution of IBD-related pathogenetic factors. Longitudinal studies are needed to better understand the impact of IBD on hepatic disorders.

The Controlled Synthesis of Birnessite Nanoflowers via H2O2 Reducing KMnO4 For Efficient Adsorption and Photooxidation Activity.

Birnessite nanoflowers composed of layers have been proven to be the strongest adsorbent and oxidant in the surface environment. However, the current synthesis methods of birnessite nanoflowers are suffering from long reaction time and high reaction temperature. Based on these, this paper explores a new method for the rapid and controlled synthesis of layered manganese oxides. The method relies on the molar ratios of KMnO4 and H2O2 redox reacting species to drive the production of birnessite nanoflowers under acidic conditions. The molar ratios of KMnO4 and H2O2 are the key to the crystal structure of the as-prepared. It was found that when the molar ratios of KMnO4 and H2O2 is from 1:1.25 to 1:1.90, the sample is birnessite nanoflowers, and when the ratio is increased to 1:2.0, the sample is a mixture of birnessite nanoflowers and feitknechtite nanoplates. Among the as-prepared samples, BF-1.85 (molar ratios of KMnO4 and H2O2 is 1:1.85) shows the highest capacity for Pb2+ adsorption (2,955 mmol/kg) and greatest degradation efficiency of phenol and TOC. The method proposed herein is economical and controllable, and it yields products with high efficiency for the elimination of inorganic and organic pollutants.

Kinetics of Mn(II) adsorption and catalytic oxidation on the surface of ferrihydrite.

Mn(II) adsorption-oxidation on iron (Fe) oxides (e.g., ferrihydrite) occurs in various soils and sediments, significantly affecting the toxicities and bioavailabilities of Mn and other associated elements. However, the detailed processes of Mn(II) adsorption-oxidation on ferrihydrite remain elusive. In this study, the Mn(II) (2 mM) adsorption-oxidation kinetics on different masses of ferrihydrite (0.25, 0.50, 1.00, and 1.25 g) at pH 7 were determined using batch kinetic studies combined with X-ray diffraction, transmission electron microscopy, and wet chemistry analyses. The results indicated that the low-concentration Mn(II) adsorption-oxidation on ferrihydrite occurred in two steps. First, Mn(II) was adsorbed onto ferrihydrite, where it was partially oxidized by the catalytic effect of ferrihydrite, within ~0-60 min; subsequently, the remaining Mn(II) underwent autocatalytic oxidation on the previously generated Mn (oxyhydr)oxides. The initial adsorption-oxidation behaviors of Mn(II) on the ferrihydrite surface determined the kinetics of Mn(II) removal and oxidation, and therefore the amounts and types of Mn (oxyhydr)oxides formed. Furthermore, the specific characteristics of Mn(II) adsorption-oxidation on ferrihydrite showed a strong dependence on the Fe/Mn molar ratio. When this ratio was below 16.35, the initial process was dominated by Mn(II) adsorption onto ferrihydrite, with slight oxidation generating hausmannite (~0-60 min), followed by the catalytic oxidation of Mn(II) on the formed hausmannite, generating manganite or groutite. Conversely, when the Fe/Mn molar ratio was above 32.7, the reactions primarily involved Mn(II) adsorption onto ferrihydrite with minor oxidation to form Mn(III/IV) (oxyhydr)oxides (~0-60 min), followed by the autocatalytic oxidation of Mn(II) on the freshly-generated Mn(III/IV) (oxyhydr)oxides, forming Mn(III) (oxyhydr)oxides, i.e., feitknechtite. These results provide further insight into the interaction between Fe and Mn, Mn(II) removal, and Mn (oxyhydr)oxide formation in the environment.

Modeling coupled kinetics of arsenic adsorption/desorption and oxidation in ferrihydrite-Mn(II)/manganese (oxyhydr)oxides systems.

The speciation and mobility of As are controlled by both Fe and Mn (oxyhydr)oxides through a series of surface complexation and redox reactions occurring in the environment, which is also complicated by the solution chemistry conditions. However, there is still a lack of quantitative tools for predicting the coupled kinetic processes of As reactions with Fe and Mn (oxyhydr)oxides. In this study, we developed a quantitative model for the coupled kinetics of As adsorption/desorption and oxidation in ferrihydrite-Mn (oxyhydr)oxides and ferrihydrite-Mn(II)-O2 systems. This model also accounted for the variations in solution chemistry conditions and binding site heterogeneity. Our model suggested that Mn (oxyhydr)oxide and ferrihydrite mainly served as an oxidant and an adsorbent, respectively, when they coexisted. Among the three types of binding sites of ferrihydrite, the adsorbed As(V) was mainly distributed on the nonprotonated bidentate sites. Our model quantitatively showed that the oxidation rates of different reaction systems varied significantly. The rates of As(III) oxidation were enhanced with higher pH values and higher molar ratios of Mn(II)/As(III) in the ferrihydrite-Mn(II)-O2 system. This study provides a modeling framework for predicting the kinetic behavior of As when multiple adsorption/desorption and oxidation reactions are coupled in the environment.

Characterisation of hexagonal birnessite with a new and rapid synthesis method-comparison with traditional synthesis.

Birnessite is one of the most important manganese oxides that can control the geochemical behaviors of pollutants or can be applied to form industrial products. Many studies have been conducted on the synthesis of hexagonal birnessite because different synthesis methods can affect the structural, morphological, and physicochemical properties of hexagonal birnessite. However, there are still some defects in these synthesis methods. Therefore, a new synthesis method that is rapid, simple, and low-cost was proposed in this study involving the reduction of KMnO4 by H2O2 in a H2SO4 solution without controlling the pH, temperature and pressure. Using a series of XRD, chemical composition, AOS, SSA, SEM, FTIR, and TGA analyses, Bir-H2O2 was found to have lower crystallinity than Bir-HCl. However, the AOS and SSA of Bir-H2O2 were 3.87 and 103 m2 g-1 higher than those of Bir-HCl, i.e., 3.70 and 22 m2 g-1, respectively. Moreover, both Bir-H2O2 and Bir-HCl had similar particle morphology and thermal stability; in addition, the maximum adsorption content of Pb2+ on Bir-H2O2 (∼3006 mmol kg-1) was ∼30% greater than that on Bir-HCl (∼2285 mmol kg-1) at pH 5.5; this indicated that the adsorption of Pb2+ on Bir-H2O2 was better and belonged to a pseudo-second-order model. All the abovementioned results indicate that Bir-H2O2 synthesized herein using the proposed synthesis method can have large application value.

Efficient catalytic As(III) oxidation on the surface of ferrihydrite in the presence of aqueous Mn(II).

Arsenic is a carcinogenic element that exists primarily as arsenate [As(V)] and arsenite [As(III)] in the nature environment, with As(III) being more toxic and mobile of the two species. In addition, ferrihydrite, which is widely distributed in soils and aquatic environments, can catalyze the oxidation of Mn(II) and accelerate the formation of high-valence Mn, which can significantly influence the speciation, toxicity, and mobility of As when these species co-exist. In this context, we herein explored the mechanism of As(III) oxidation in the presence of ferrihydrite and Mn(II) using a kinetic approach combined with multiple spectroscopic techniques, including X-ray absorption near edge spectroscopy, in situ horizontal attenuated total-reflectance Fourier transform infrared spectroscopy, and in situ quick scanning X-ray absorption spectroscopy. Our results indicate that efficient As(III) oxidation by dissolved O2 occurs on the surface of ferrihydrite in the presence of aqueous Mn(II). Compared with As(III) oxidation in the presence of ferrihydrite and Mn oxides (i.e., Mn oxides/hydroxides), the degree of As(III) oxidation in the ferrihydrite-Mn(II) system was significantly higher, and the majority of generated As(V) was adsorbed on the mineral (i.e., ferrihydrite) surface. Furthermore, As(III) oxidation was enhanced upon increasing both the molar ratio of Mn(II)/As(III) and the solution pH. The greater As(III) oxidation by O2 in the ferrihydrite-Mn(II) system was mainly attributed to the formation of a strong oxidant of the instantaneous intermediate Mn(III) species via Mn(II) oxidation under catalysis by the ferrihydrite surface. Moreover, As(III) oxidation occurred mainly on the ferrihydrite surface and was accompanied by the regeneration of Mn(II), thereby rendering it recyclable. These results therefore provide new insights into the mechanism of As(III) oxidation on the surfaces of Fe oxides (i.e., Fe oxides/hydroxides) in the presence of aqueous Mn(II) as well as the new details regarding the electron transfer mechanisms between the As(III)-Mn(II, III)-O2 species at the ferrihydrite surface, and could lead to novel approaches for As(III) contaminant remediation in the environment.