Relationships between high-concentration toxic metals in sediment and evolution of microbial community structure and carbon-nitrogen metabolism functions under long-term stress perspective.

Microorganisms are highly sensitive to toxic metal pollution and play an important role in the material cycling and energy flow of the water ecosystem. Herein, 13 sediment samples from Junchong Reservoir (Guangxi Province, China) were collected in December 2021. The spatial distribution of pollution levels for toxic metals and the effects of toxic metals on the composition, functional characteristics, and metabolism of microorganisms were investigated. The results demonstrated that the area is a proximate area to industrial zones with severity of toxic metal pollution. Their mean concentrations of As, Cu, Zn, and Pb were up to 128.79 mg/kg, 57.62 mg/kg, 594.77 mg/kg, and 97.12 mg/kg respectively. There was a strong correlation between As, Cu, Zn, and Pb, with the highest correlation coefficient reaching 0.94. As the level of toxic metal pollution increases, the diversity and abundance of microorganisms gradually decrease. Compared to those with lower pollution levels, the Shannon index in regions with higher pollution levels decreases by up to 0.373, and the Chao index decreases by up to 143.507. However, the relative abundance of Bacteroidota, Patescibacteria, and Chloroflexi increased by 23%, 20%, and 5%, respectively, indicating their higher adaptability to toxic metals. Furthermore, microbial carbon and nitrogen metabolism were also affected by the presence of toxic metals. FAPROTAX analysis demonstrated an abundant reduction of ecologically functional groups associated with carbon and nitrogen transformations under high toxic metal pollution levels. KEGG pathway analysis indicated that carbon fixation and nitrogen metabolism pathways were inhibited with increasing toxic metal concentrations. These findings would contribute to a better understanding of the effects of toxic metal pollution on sediment microbial communities and function, shedding light on the ecological consequences of toxic metal contamination.

Simultaneous removing algal and its extracellular organic matters by Mg/Al-layered double hydroxide /La-montmorillonite.

Rapid and effective simultaneous removal of algal and extracellular organic matter (EOM) is essential for algal blooms water emergency treatment. In this study, a composite material was prepared by physical and chemical interaction between La-montmorillonite (La-MMT) and Mg/Al-layered double hydroxide (LDHs), and its removal effect of algal and extracellular organic matters (EOM) was investigated. The results showed that the removal rate of chlorophyll a (chl-a) was 96.8% within 2 h when the LDHs/La-MMT2:1 dosage was 1.0 g/L. Three-dimensional fluorescence characteristic spectra and parallel factor analysis showed that the removal of EOM by composite material mainly reflected in the removal of humus-like substances. The reaction heat of composite material for the algal solution was -32.7 J/g. Zeta potential changed from -25.7 mV to -16.9 mV, the main treatment mechanisms of composite material were surface adsorption, complexation precipitation, charge neutralisation, and ion exchange. These findings herein proposed that composite material was a potential and proper treating agent for removing algal cells and EOM from algal blooms water.

The changes in iron ions concentration and organic matter composition during the surface microlayer membrane formation process in freshwater.

The surface microlayer membrane (SMM) is a complex and unique water body ecosystem. The SMM has a significant effect on water quality and the water ecological system. However, despite the long-lasting interest in the SMM formation process and its environmental effect mechanism in freshwater, studies on it are still scarce. This paper studied the changes in iron ions concentration and organic matter composition during the SMM formation process. Our results revealed that the iron ions enriched in the SMM, at a concentration of up to 8.02 µg/mL, exist in the form of Fe3+. The main organic matter is polysaccharides and proteins in the SMM. Additionally, the microbial community structure revealed that the changes in iron ion morphology in water and the SMM was a significant association with the presence of Aeromonas and Zoogloea. The rapid enrichment process of iron ions and organic matter in the aquatic surface microlayer is involved in the rapid formation of early SMM. Obviously, these findings provide new insights and a basis for the SMM of freshwater.

Ecological risk assessment of heavy metals in riverine sediments of rural area driven by urbanization.

Rural revitalization denotes the gathering of large populations in rural areas and the subsequent gradual urbanization. Rural environments have been deteriorated by heavy metals (HMs) over the last few years. Without the existence of large-scale industries, the accumulation of HMs in sediments due to population aggregation in rural environments needs to be scientifically confirmed. Therefore, in this study we first understand the sediment pollution in rural environments in China and across the globe, and subsequently investigate HMs in sediments in rural micro water. The study area, Sichuan Province, China, was divided into two areas, namely, sparsely populated areas (SPA) and densely populated areas (DPA). Eight typical HMs (As, Zn, Ni, Hg, Cd, Cr, Cu, and Pb) were selected to target in riverine sediments, and the content and spatial distribution characteristics were analyzed. The results indicate that As, Hg, Cd, and Pb concentrations in sediments were higher than background values (BVs), with high concentration sample sites located in the DPA. In addition, the geo-accumulation index (Igeo), pollution load index (PLI) and potential ecological risk index (RI) were used to quantitatively evaluate the pollution characteristics of HMs in sediments, revealing that the sediments exhibited high As and Hg pollution in the DPA (PLI = 1.09). In general, mild (RI = 48.76) and moderate (RI = 154.92) HM pollution was observed in the sediments of the SPA and DPA, respectively, based on the high PLI (> 1.0) and RI (> 150) values. Correlation analysis and principal component analysis (PCA) indicate that the Cd in the sediment generally originated from geogenic sources, while the other elements (Zn, As, Cu, Cr, Hg, Ni and Pb) were primarily linked to anthropogenic sources. Finally, the results demonstrate that population aggregation will lead to the enrichment of HMs.

In situ prepared Chlorella vulgaris-supported nanoscale zero-valent iron to remove arsenic (III).

Nanoscale zero-valent iron (nZVI) has a high removal affinity toward arsenic (As). However, the agglomeration of nZVI reduces the removal efficiency of As and, thus, limit its application. In this study, we report an environmentally friendly novel composite of Chlorella vulgaris-supported nanoscale zero-valent iron (abbreviated as CV-nZVI) that exhibits a fast and efficient removal of As(III) from As-contaminated water. Scanning electron microscopy-energy-dispersive spectroscopy (SEM-EDS), X-ray diffractometry (XRD), attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR), and X-ray photoelectron spectroscopy (XPS) were used to characterize and analyze the CV-nZVI. These results indicated that the stabilization effect of C. vulgaris reduced the nZVI agglomeration and enhanced the reactivity of nZVI. The experiments showed a removal efficiency of 99.11% for As(III) at an optimum pH of 7.0. The adsorption kinetics and isotherms followed the pseudo-second-order kinetic model and Langmuir adsorption isotherm with the superior maximum adsorption capacities of 34.11 mg/g for As(III). The FTIR showed that the As(III) was adsorbed on the CV-nZVI surface by complexation reaction, and XPS indicated that oxidation reaction was also involved. After five reuse cycles, the removal efficiency of As(III) by CV-nZVI was 32.93%, suggesting that the CV-nZVI had some reusability and regeneration. Overall, this work provides a practical and highly efficient approach for As remediation in As-contaminated water, and simultaneously resolves the agglomeration problems of nZVI nanoparticles.

Convergent evolution of plant pattern recognition receptors sensing cysteine-rich patterns from three microbial kingdoms.

The Arabidopsis thaliana Receptor-Like Protein RLP30 contributes to immunity against the fungal pathogen Sclerotinia sclerotiorum. Here we identify the RLP30-ligand as a small cysteine-rich protein (SCP) that occurs in many fungi and oomycetes and is also recognized by the Nicotiana benthamiana RLP RE02. However, RLP30 and RE02 share little sequence similarity and respond to different parts of the native/folded protein. Moreover, some Brassicaceae other than Arabidopsis also respond to a linear SCP peptide instead of the folded protein, suggesting that SCP is an eminent immune target that led to the convergent evolution of distinct immune receptors in plants. Surprisingly, RLP30 shows a second ligand specificity for a SCP-nonhomologous protein secreted by bacterial Pseudomonads. RLP30 expression in N. tabacum results in quantitatively lower susceptibility to bacterial, fungal and oomycete pathogens, thus demonstrating that detection of immunogenic patterns by Arabidopsis RLP30 is involved in defense against pathogens from three microbial kingdoms.

A novel scheme to improve the photo-Fenton performance of iron oxychloride by carbon: Three existent states and roles of carbon in the degradation of tetracycline in water.

The photo-Fenton process is promising for sincerely treating contaminated water. In this work, carbon-decorated iron oxychloride (C-FeOCl) is synthesized as a photo-Fenton catalyst for removing tetracycline (TC) from water. Three actual states of carbon are identified and their different roles in enhancing photo-Fenton performance are revealed. All carbon on/in FeOCl, including graphite carbon, carbon dots and lattice carbon, enhance visible light adsorption. More importantly, a homogeneous graphite carbon on the outer surface of FeOCl accelerates the transportation-separation of photo-excited electrons along the horizontal direction of FeOCl. Meanwhile, the interlayered carbon dots offer a FeOC bridge in helping the transportation-separation of photo-excited electrons along the vertical direction of FeOCl. In this way, C-FeOCl acquires isotropy in conduction electrons to ensure an efficient Fe(II)/Fe(III) cycle. These interlayered carbon dots extend the layer spacing (d) of FeOCl to about 1.10 nm, exposing the internal iron centers. The lattice carbon significantly increases the amounts of coordinatively unsaturated iron sites (CUISs) in activating hydrogen peroxide (H2O2) to hydroxyl radical (OH). Density functional theory (DFT) calculations confirm this activation on inner and external CUISs with a significantly low activation energy of about 0.33 eV.

Regulating Lewis acidity and local electron density of iron-based metal organic frameworks via cerium doping for efficient photo-Fenton process.

The photo-Fenton performance of Fe-based metal organic frameworks (Fe-MOFs) largely depends on the amount and the local electron density of metal coordinately unsaturated sites (M CUSs). However, a majority of Fe active sites are fully bound by organic ligands leading to decreased Fe CUSs. Additionally, the symmetrical electronic distribution of iron-oxo (Fe-O) clusters and the fast electron-hole recombination are unbeneficial for the directional electron transfer and the following electron accumulation on Fe CUSs. Herein, the structure of Fe-O clusters onto the framework of MIL-88B was controllably regulated via change of Ce doping amount, among which Fe0.8Ce0.2-MIL-88B exhibited highest removal efficiency of tetracycline (TC). That was mainly ascribed to the following two points: for one, the induced ligand missing defects ameliorated the pore structures and generated more M CUSs; for another, the lower electronegativity of Ce than Fe and the role of ligand missing defects as electron trap state collectively increased the local electron density at Fe CUSs. As a result, the increased M CUSs provided more active sites for H2O2 coordination and the highly concentrated electrons density at Fe CUSs afforded the substantial electron donation towards robust H2O2 dissociation into ∙OH. Furthermore, the increased mesoporous size favored highly-efficient utilization of ∙OH. This work provides a facile strategy to improve photo-Fenton performance of Fe-MOFs.

Steady release-activation of hydrogen peroxide and molecular oxygen towards the removal of ciprofloxacin in the FeOCl/CaO2 system.

Difficult storage of hydrogen peroxide (H2O2), low production of reactive oxygen species (ROS), and inefficient Fe(II)/Fe(III) recycling limit the application of the Fenton-like process. Calcium peroxide (CaO2) based iron oxychloride (FeOCl) system was developed for solving these deficiencies, and ciprofloxacin (CIP) was effectively degraded within 20 min treatment. 0.33 mmol/L H2O2 and 2.4 mg/L dissolved oxygen (DO) were produced via CaO2. Quenching experiments and electron paramagnetic resonance results confirmed that hydroxyl radicals (·OH) and superoxide anion (·O2-) worked as the main ROS. Density functional theory (DFT) calculations and experimental results suggested that H atoms of H2O2 adsorbed on FeOCl favored the activation of H2O2 into ·OH and DO into ·O2-, and electrophilic Cl and O coordination in FeOCl contributed to the cycle of Fe(II)/Fe(III). ·OH and·O2- were responsible for CIP degradation, and toxicity assessments demonstrated that the developed system reduced the hazard of treated solution. Clarity of FeOCl/CaO2 system triple roles, including H2O2 and O2 production, activation into ROS, and Fe(II)/Fe(III) recycling, facilitates the efficient utilization of O2 in Fenton-like system.

Highly dispersed of Ag/AgCl nanoparticles on exfoliated FeOCl nanosheets as photo-Fenton catalysts for pollutants degradation via accelerating Fe(II)/Fe(III) cycle.

In this work, Ag/AgCl/FeOCl (Ag-Fe) catalysts were successfully prepared via multistep routes in which Ag was uniformly anchored to the enriched Cl sites provided by exfoliated FeOCl nanosheets. Among these Ag-Fe catalysts, 5% Ag-Fe exhibited the highest pseudo first-order kinetic constant 0.1056 min-1 for photo-Fenton degradation of Rhodamine B (RhB), which was 11 times higher than that of FeOCl (0.0096 min-1). Ag-Fe catalysts exposed more coordinatively unsaturated Fe active sites to coordinate with H2O2 due to the cleavage of Fe-Cl bond. The exposed coordinatively unsaturated Fe(III) active sites could capture the photoinduced electrons and reduce them to Fe(II), which boosted the separation efficiency of photogenerated charge carriers. Meanwhile, the photogenerated electrons of Ag0 transferred to the FeOCl, promoting the reduction of Fe(III) to Fe(II). In addition, the intensified visible light adsorption (SPR effect) was achieved after introducing Ag/AgCl nanoparticles on exfoliated FeOCl. Hydroxyl radicals (·OH) and holes (h+) were determined as the main reactive oxidative species (ROS) in the photo-Fenton degradation process.

Preparation of a novel clay loaded with Fe (VI) for degradation of cefazolin: performance, pathway, and mechanism.

Cephalosporin antibiotics, a group of widely prescribed antibiotics, are frequently detected in wastewater effluent and in the natural aquatic environment. Materials have been sought to effectively degrade the antibiotics. In this study, a novel high-iron clay was prepared with potassium ferrate and montmorillonite via a strong alkaline in situ synthesis method. Degradation of cefazolin sodium (CFZ) by this novel Fe (VI)-clay was investigated. The optimal conditions for the degradation of CFZ were determined using a single factor experiment and response surface optimization method. We found that 89.84% removal efficiency was obtained in 137 min when pH value was 5.16 and Fe (VI)-clay dosage was 0.79 g. The CFZ degradation mechanism was studied by computations on the Frontier Electron Density (FED) in combination with spectroscopic and mass spectroscopic analysis. The spectroscopic characteristics of the products at different stages showed that the oxidation decomposition reaction occurred during the degradation of CFZ by Fe (VI)-clay. Furthermore, FED calculation combined with GC-MS results showed that the degradation pathways of CFZ by the Fe (VI)-clay was mainly the cleavage of ß-lactam, thiadiazole, tetrazole, and dihydrothiazine rings.

The geochemical behavior of trace metals and nutrients in submerged sediments of the Three Gorges Reservoir and a critical review on risk assessment methods.

Permanently submerged sediment samples (SS) were collected in the center stream of eleven tributaries of Changjiang (Yangtze River) and at eight confluence zones in the Three Gorges Reservoir (TGR) in May and December of 2017. The work showed that aqua regia digestion is a simpler, more reliable and robust method compared to total digestion with hydrofluoric acid (HF) for the determination of trace metals (TMs) in sediment for risk assessment purpose. Our study revealed a remarkable accumulation of TMs at the confluence zones and a trend of their gradual increase toward this zone. The presence of iron and manganese (oxy)hydroxides combined with hydrodynamic conditions created by the Three Gorges Dam (TGD) and its operation are believed to play a crucial role. This work also found that concentrations of [Formula: see text] in May sediment were significantly higher than those in December, which could have been caused by both the cyclic hydrodynamic conditions and the warmer water. TOC and TP were both very low in the sediment. Although TN was 2 times higher than the Lowest Effect Level suggested by the Ontario Ministry of Environment, it is uncertain if it reflects a natural background level or due to anthropogenic activities. A critical discussion is made by comparing the conclusions obtained when using different TMs risk assessment models. Necessary precautions are highly recommended when performing this exercise. In this study, no significant risk from either TMs or nutrients was identified.

Effect of ferric ions on the anaerobic bio-dissolution of jarosites by Acidithiobacillus ferrooxidans.

Large amounts of jarosites are produced during zinc hydrometallurgy and bioleaching, as well as in acid sulfate soils and acid mine drainage environments. As such, understanding the behavior of jarosite dissolution is important for analyzing the iron cycle process and promoting the control and treatment of jarosites. In general, soluble ferric ions and jarosites coexist in acid environments; however, the relationship between soluble ferric ions and jarosites under anaerobic reductive conditions is still not well understood. In this study, the effect of adding Fe3+ on the promotion of the bio-dissolution of jarosites using Acidithiobacillus ferrooxidans is investigated. With the addition of 12 mM Fe3+, the efficiency and maximum rate of jarosite bio-dissolution were found to reach 84.1% and 2.66 mmol/(L·d), respectively. The addition of Fe3+ at concentrations higher than 12 mM did not further improve the jarosite bio-dissolution. These results indicate that the mechanisms underlying these improvements include: (i) the reduction of the zeta potential due to the compression of the diffusion layer of the electric double layer by Fe3+; (ii) bacteria growth enhancement and the stabilization of the pH of cultures via the reduction of soluble Fe3+. Based on these observations, this study serves to promote the development of jarosite bio-dissolution using Acidithiobacillus ferrooxidans and challenges the idea that soluble Fe3+ suppresses the bio-dissolution reaction of solid Fe3+ substances such as jarosite when soluble ferric ions and jarosite coexist.

Anaerobic reductive bio-dissolution of jarosites by Acidithiobacillus ferrooxidans using hydrogen as electron donor.

Jarosites are secondary iron-hydroxyl-sulfate minerals and widely occur in bioleaching, acid mine drainage, and acid sulfate soil environments. Anaerobic reductive dissolution of jarosites is yet to be methodically examined. In this study, we explored the bio-dissolution of jarosites by Acidithiobacillus ferrooxidans (At. ferrooxidans) by using hydrogen in batch experiments. After bio-dissolution by At. ferrooxidans for 22 d, ferrous ion concentrations reached 10.07 mM (biologically produced jarosites), 7.68 mM (potassium jarosite), and 1.45 mM (lead jarosite). Strengthening the dissolved jarosites by decreasing the initial pH (pH < 2.0) or by adding citric acid (1, 5, and 10 mM) was inefficient for bio-dissolution owing to restricted cellular activity. The pathways of bio-dissolution should include direct contact bio-dissolution and indirect bio-dissolution and relate to the solubility of jarosites in a bio-dissolution system. The results demonstrate that anaerobic reductive bio-dissolution of jarosites by At. ferrooxidans using hydrogen shows potential. This study also provides opportunities to contribute to the development of the bioleaching field via the aerobic/anaerobic cycle using a single strain to control and reuse jarosites in situ.

The Botrytis cinerea Xylanase BcXyl1 Modulates Plant Immunity.

Botrytis cinerea is one of the most notorious pathogenic species that causes serious plant diseases and substantial losses in agriculture throughout the world. We identified BcXyl1 from B. cinerea that exhibited xylanase activity. Expression of the BcXyl1 gene was strongly induced in B. cinerea infecting Nicotiana benthamiana and tomato plants, and BcXyl1 deletion strains severely compromised the virulence of B. cinerea. BcXyl1 induced strong cell death in several plants, and cell death activity of BcXyl1 was independent of its xylanase activity. Purified BcXyl1 triggered typically PAMP-triggered immunity (PTI) responses and conferred resistance to B. cinerea and TMV in tobacco and tomato plants. A 26-amino acid peptide of BcXyl1 was sufficient for elicitor function. Furthermore, the BcXyl1 death-inducing signal was mediated by the plant LRR receptor-like kinases (RLKs) BAK1 and SOBIR1. Our data suggested that BcXyl1 contributed to B. cinerea virulence and induced plant defense responses.

A Verticillium dahliae Pectate Lyase Induces Plant Immune Responses and Contributes to Virulence.

Verticillium dahliae is a wide-host-range fungal pathogen that causes soil-borne disease in hundreds of dicotyledonous hosts. In search of V. dahliae Vd991 cell death-inducing proteins, we identified a pectate lyase (VdPEL1) that exhibited pectin hydrolytic activity, which could induce strong cell death in several plants. Purified VdPEL1 triggered defense responses and conferred resistance to Botrytis cinerea and V. dahliae in tobacco and cotton plants. Our results demonstrated that the mutant VdPEL1rec lacking the enzymatic activity lacked functions to induce both cell death and plant resistance, implying that the enzymatic activity was necessary. In addition, VdPEL1 was strongly induced in V. dahliae infected Nicotiana benthamiana and cotton roots, and VdPEL1 deletion strains severely compromised the virulence of V. dahliae. Our data suggested that VdPEL1 contributed to V. dahliae virulence and induced plant defense responses. These findings provide a new insight for the function of pectate lyase in the host-pathogen interaction.

Column bioleaching copper and its kinetics of waste printed circuit boards (WPCBs) by Acidithiobacillus ferrooxidans.

Application of bioleaching process for metal recovery from electronic waste has received an increasing attention in recent years. In this work, a column bioleaching of copper from waste printed circuit boards (WPCBs) by Acidithiobacillus ferrooxidans has been investigated. After column bioleaching for 28d, the copper recovery reached at 94.8% from the starting materials contained 24.8% copper. Additionally, the concentration of Fe(3+) concentration varied significantly during bioleaching, which inevitably will influence the Cu oxidation, thus bioleaching process. Thus the variation in Fe(3+) concentration should be taken into consideration in the conventional kinetic models of bioleaching process. Experimental results show that the rate of copper dissolution is controlled by external diffusion rather than internal one because of the iron hydrolysis and formation of jarosite precipitates at the surface of the material. The kinetics of column bioleaching WPCBs remains unchanged because the size and morphology of precipitates are unaffected by maintaining the pH of solution at 2.25 level. In bioleaching process, the formation of jarosite precipitate can be prevented by adding dilute sulfuric acid and maintaining an acidic condition of the leaching medium. In such way, the Fe(2)(+)-Fe(3+) cycle process can kept going and create a favorable condition for Cu bioleaching. Our experimental results show that column Cu bioleaching from WPCBs by A. ferrooxidans is promising.

Bioleaching waste printed circuit boards by Acidithiobacillus ferrooxidans and its kinetics aspect.

In this paper, H(+) consumption and metal recovery, during the process of bioleaching waste printed circuit boards (WPCBs) by Acidithiobacillus ferrooxidans (A. ferrooxidans), were discussed in detail. When the WPCBs concentration was 15g/L, Cu (96.8%), Zn (83.8%), and Al (75.4%) were recovered after 72h by A. ferrooxidans. Experimental results indicated that metal recovery rate was significantly influenced by acid. Based on experimental results, the kinetics of the H(+) consumption and metal recovery on bioleaching WPCBs were represented by reaction kinetic equations. The kinetic of H(+) consumption could be described by the second-order kinetic model. The metal recovery belongs to the second-order model with adding acid, which was changed to the shrinking core model with precipitate production.