Non-targeted metabolomics reveals the stress response of a cellulase-containing penicillium to uranium

Human industrial activities have caused environmental uranium (U) pollution, resulting in uranium(VI) had radiotoxicity and chemical toxicity. Here, a cellulase-producing Penicillium fungus was screened and characterized by X-ray fluorescence (XRF), and Fourier transform infrared reflection (FT-IR), as well as by GC/MS metabolomics analysis, to study the response to uranium(VI) stress. The biomass of Penicillium decreased after exposure to 100 mg/L U. Uranium combined with carboxyl groups, amino groups, and phosphate groups to form uranium mineralized deposits on the surface of this fungal strain. The α-activity concentration of uranium in the strain was 2.57×10⁶ Bq/kg, and the β-activity concentration was 2.27×10⁵ Bq/kg. Metabolomics analysis identified 118 different metabolites, as well as metabolic disruption of organic acids and derivatives. Further analysis showed that uranium significantly affected the metabolism of 9 amino acids in Penicillium. These amino acids were related to the TCA cycle and ABC transporter. At the same time, uranium exhibited nucleotide metabolism toxicity to Penicillium. This study provides an in-depth understanding of the uranium tolerance mechanism of Penicillium and provides a theoretical basis for Penicillium to degrade hyper-enriched plants.     

Assessing the role of mineral particles in the atmospheric photooxidation of typical carbonyl compound

Mineral particles are ubiquitous in the atmosphere and exhibit an important effect on the photooxidation of volatile organic compounds (VOCs). However, the role of mineral particles in the photochemical oxidation mechanism of VOCs remains unclear. Hence, the photooxidation reactions of acrolein (ARL) with OH radical (OH) in the presence and absence of SiO₂ were investigated by theoretical approach. The gas-phase reaction without SiO₂ has two distinct pathways (H-abstraction and OH-addition pathways), and carbonyl-H-abstraction is the dominant pathway. In the presence of SiO₂, the reaction mechanism is changed, i.e., the dominant pathway from carbonyl-H-abstraction to OH-addition to carbonyl C-atom. The energy barrier of OH-addition to carbonyl C-atom deceases 21.33 kcal/mol when SiO₂ is added. Carbonyl H-atom of ARL is occupied by SiO₂ via hydrogen bond, and carbonyl C-atom is activated by SiO₂. Hence, the main product changes from H-abstraction product to OH-adduct in the presence of SiO₂. The OH-adduct exhibits a thermodynamic feasibility to yield HO₂ radical and carboxylic acid via the subsequent reactions with O₂, with implications for O₃ formation and surface acidity of mineral particles.     

Gangba sheep in the Tibetan plateau: Validating their unique meat quality and grazing factor analysis

Gangba sheep are known for having typical sensory characteristics attributed to free range conditions and grazing on wild plants. The genuine Gangba mutton was selected as the experimental group, and the commercial Tibetan mutton was selected as the control group, the nutritive composition of basic chemical components, amino acids and fatty acids in mutton were investigated to correlate its unique meat quality and eating satisfaction. The results showed that fatty acids were significantly higher (P<0.05) in Gangba mutton than in commercial mutton, and the higher content of flavoring amino acids (glutamic acid and aspartame) were primarily responsible for the taste attributes umami of meat juices. Moreover, the trace elements analysis in mutton and grazing factors (forage, water source and soil) were conducted, to explain the source of essential trace elements in mutton. The concentrations of essential trace elements show that the Gangba mutton was a valuable source for highly available Cu and Zn in human nutrition, and well managed with few detected of toxicity metal. The concentrations of essential trace elements in mutton are closely related to the trace elements in environmental grazing factors. In conclusion, the congenital grazing conditions (a highly mineralized water resource, natural forages and clean soils) were shown to contribute to the unique meat characteristics of Gangba sheep.     

Induced transformation of antimony trioxide by Mn(II) oxidation and their co-transformed mechanism

Antimony (Sb) is a toxic and carcinogenic element that often enters soil in the form of antimony trioxide (Sb₂O₃) and coexists with manganese (Mn) in weakly alkaline conditions. Mn oxides such as birnessite have been found to promote the oxidative dissolution of Sb₂O₃, but few researches concerned the co-transformations of Sb₂O₃ and Mn(II) in environment. This study investigated the mutual effect of abiotic oxidation of Mn(II) and the coupled oxidative dissolution of Sb₂O₃. The influencing factors, such as Mn(II) concentrations, pH and oxygen were also discussed. Furthermore, their co-transformed mechanism was also explored based on the analysis of Mn(II) oxidation products with or without Sb₂O₃ using XRD, SEM and XPS. The results showed that the oxidative dissolution of Sb₂O₃ was enhanced under higher pH and higher Mn(II) loadings. With a lower Mn(II) concentration such as 0.01 mmol/L Mn(II) at pH 9.0, the improved dissolution of Sb₂O₃ was attributed to the generation of dissolved intermediate Mn(III) species with strong oxidation capacity. However, under higher Mn(II) concentrations, both amorphous Mn(III) oxides and intermediate Mn(III) species were responsible for promoting the oxidative dissolution of Sb₂O₃. Most released Sb (∼72%) was immobilized by Mn oxides and Sb(V) was dominant in the adsorbed and dissolved total Sb. Meanwhile, the presence of Sb₂O₃ not only inhibited the removal of Mn(II) by reducing Mn(III) to Mn(II) but also affected the final products of Mn oxides. For example, amorphous Mn oxides were formed instead of crystalline Mn(III) oxides, such as MnOOH. Furthermore, rhodochrosite (MnCO₃) was formed with the high Mn(II)/Sb₂O₃ ratio_, but without being observed in the low Mn(II)/Sb₂O₃ ratio. The results of study could help provide more understanding about the fate of Sb in the environment and the redox transformation of Mn.     

Hygroscopic properties of sodium and potassium salts as related to saline mineral dusts and sea salt aerosols

Mineral dust,soil,and sea salt aerosols are among the most abundant primary inorganic aerosols in the atmosphere,and their hygroscopicity affects the hydrological cycle and global climate.We investigated the hygroscopic behaviors of six Na-and K-containing salts commonly found in those primary organic aerosols.Their hygroscopic growths as a function of relative humidity(RH) agree well with thermodynamic model prediction.Temperature dependence of deliquescence RH(DRH) values for five of those sal...     

Simultaneous adsorption of As(Ⅲ) and Pb(Ⅱ) by the iron-sulfur codoped biochar composite:Competitive and synergistic effects

Simultaneous elimination of As(Ⅲ) and Pb(Ⅱ) from wastewater is still a great challenge.In this work,an iron-sulfur codoped biochar (Fe/S-BC) was successfully fabricated in a simplified way and was applied to the remediate the co-pollution of As(Ⅲ) and Pb(Ⅱ).The positive enthalpy indicated that the adsorption in As-Pb co-pollution was an endothermic reaction.The mechanism of As(Ⅲ) removal could be illustrated by surface complexation,oxidation and precipitation.In addition to precipitation and com...     

Photocatalytic reduction of Cr(VI) over cinder-based nanoneedle in presence of tartaric acid: Synergistic performance and mechanism

Cr(VI) is a common heavy metal ion, which will seriously harm human body and environment. Therefore, the removal of Cr(VI) has become an attractive topic. In this work, cinder was used as a raw material to synthesize a nanoneedle material: γ-([email protected]) (γ[email protected]). The physicochemical properties of γ[email protected] were thoroughly characterized, and its effectiveness as a catalyst for photocatalytic reduction of Cr(VI) was evaluated. The results showed that Cr(VI) could be efficiently reduced by γ[email protected] in the presence of tartaric acid (TA) under visible light. The variable factors on the reaction were investigated in detail, and the results showed that under optimal conditions (γ[email protected] 0.4 g/L, TA 0.6 g/L, pH 2), Cr(VI) was completely reduced within 7 min. Besides, scavenger experiments and EPR proved that O₂^{? —} and CO₂^{? —} played a significant role in the photocatalytic reduction of Cr(VI). TA acts as a sacrificial agent to trap the holes and generate strong reducing free radicals: CO₂^{? —}. Dissolving O₂ could react with electrons to generate O₂^{? —}. This work discussed the performance and mechanism of photocatalytic reduction of Cr(VI) in detail, which provided a new idea for the resource utilization of solid waste and the treatment of heavy metal sewage.     

Transformation mechanism and fate of dissolved organic nitrogen (DON) in a full-scale drinking water treatment

Dissolved organic nitrogen (DON) has attracted much attention in drinking water treatment due to its potential to produce nitrogenous disinfection by-products (N-DBPs). This work was designed to explore the transformation and fate of DON and dissolved inorganic nitrogen (DIN) in drinking water treatment. The changes of DON and formation of N-DBPs were evaluated along the water treatment route (i.e., pre-ozonation and biological-contact oxidation, delivery pipes’ transportation, coagulation-sedimentation, sand filtration, post-ozonation, biological activated carbon, ultrafiltration and disinfection) of drinking water treatment plant (DWTP). The transformation mechanism of DON was comprehensively investigated by molecular weight fractionation, three-dimensional fluorescence, LC-OCD (Liquid Chromatography-Organic Carbon Detection), total free amino acids. A detailed comparison was made between concentrations and variations of DON and DIN affected by seasons in the drinking water treatment. Regardless of seasonal variation in raw water concentration, the DON removal trends between different treatment processes remain constant in the present study. Compared to other treatment processes, pre-ozonation and coagulation-sedimentation exhibited the dominant DON removal in different seasons, i.e., 11.13%-14.45% and 14.98%-22.49%, respectively. Contrary, biological-contact oxidation and biological activated carbon negatively impacted the DON removal, in which DON increased by 1.76%-6.49% in biological activated carbon. This may be due to the release of soluble microbial products (SMPs) from bacterial metabolism, which was further validated by the rise of biopolymers in LC-OCD.     

Root-associated (rhizosphere and endosphere) microbiomes of the Miscanthus sinensis and their response to the heavy metal contamination

The plant root-associated microbiomes, including both the rhizosphere and the root endosphere microbial community, are considered as a critical extension of the plant genome. Comparing to the well-studied rhizosphere microbiome, the understanding of the root endophytic microbiome is still in its infancy. Miscanthus sinensis is a pioneering plant that could thrive on metal contaminated lands and holds the potential for phytoremediation applications. Characterizing its root-associated microbiome, especially the root endophytic microbiome, could provide pivotal knowledge for phytoremediation of mine tailings. In the current study, M. sinensis residing in two Pb/Zn tailings and one uncontaminated site were collected. The results demonstrated that the metal contaminant fractions exposed strong impacts on the microbial community structures. Their influences on the microbial community, however, gradually decreases from the bulk soil through the rhizosphere soil and finally to the endosphere, which resulting in distinct root endophytic microbial community structures compared to both the bulk and rhizosphere soil. Diverse members affiliated with the order Rhizobiales was identified as the core microbiome residing in the root of M. sinensis. In addition, enrichment of plant-growth promoting functions within the root endosphere were predicted, suggesting the root endophytes may provide critical services to the host plant. The current study provides new insights into taxonomy and potential functions of the root-associated microbiomes of the pioneer plant, M. sinensis, which may facilitate future phytoremediation practices.     

A novel approach to estimate and control denitrification performance in activated sludge systems with respirogram technology

Respirogram technology has been widely applied for aerobic process, however, the response of respirogram to anoxic denitrification is still unclear. To reveal such response may help to design a new method for the evaluation of the performance of denitrification. The size distribution of flocs measured at different denitrification moments demonstrated a clear expansion of flocs triggered by denitrification, during which higher specific endogenous and quasi-endogenous respiration rates (SOUR_e and SOUR_q) were also observed. Furthermore, SOUR_q increases exponentially with the specific denitrification rate (SDNR), suggesting that there should be a maximum SDNR in conventional activated sludge systems. Based on these findings, an index R_q/t, defined as the ratio of quasi-endogenous (OUR_q) to maximum respiration rate (OUR_t), is proposed to estimate the denitrification capacity that higher R_q/t indicates higher denitrification potential, which can be readily obtained without complex measurement or analysis, and it offers a novel and promising respirogram-based approach for denitrification estimation and control by taking measures to extend anoxic time to maintain its value at a high level within a certain range.     

Simultaneous oxidation of Mn(II) and As(III) on cupric oxide (CuO) promotes As(III) removal at circumneutral pH

Oxidation of Mn(II) or As(III) by molecular oxygen is slow at pH < 9, while they can be catalytically oxidized in the presence of oxide minerals and then removed from contaminated water. However, the reaction mechanisms on simultaneous oxidation of Mn(II) and As(III) on oxide mineral surface and their accompanied removal efficiency remain unclear. This study compared Mn(II) oxidation on four common metal oxides (γ-Al₂O₃, CuO, α-Fe₂O₃ and ZnO) and investigated the simultaneous oxidation and removal of Mn(II) and As(III) through batch experiments and spectroscopic analyses. Among the tested oxides, CuO and α-Fe₂O₃ possess greater catalytic activity toward Mn(II) oxidation. Oxidation and removal kinetics of Mn(II) and As(III) on CuO indicate that O₂ is the terminal electron acceptor for Mn(II) and As(III) oxidation on CuO, and Mn(II) acts as an electron shuttle to promote As(III) oxidation and removal. The main oxidized product of Mn(II) on CuO is high-valent MnO_x species. This newly formed Mn(III) or Mn(IV) phases promote As(III) oxidation on CuO at circumneutral pH 8 and is reduced to Mn(II), which may be then released into solution. This study provides new insights into metal oxide-catalyzed oxidation of pollutants Mn(II) and As(III) and suggests that CuO should be considered as an efficient material to remediate Mn(II) and As(III) contamination.     

Evaluation of joint toxicity of heavy metals and herbicide mixtures in soils to earthworms (Eisenia fetida)

It is widely acknowledged that a simplified and robust approach to evaluating thecombined effects of chemical mixtures is critical for ecological risk assessment(ERA) of contaminated soil. The earthworm( Eisenia fetida) was used as a model to study the combined effects of polymetallic contamination and the herbicide siduron in field soil using a microcosm experiment. The responses of multiple biomarkers, including the activities of catalase(CAT), superoxide dismutase(SOD), glutathione reductase(...     

Distinctive differences in the granulation of saline and non-saline enriched anaerobic ammonia oxidizing (AMX) bacteria

The growing interest in the anaerobic ammonium oxidizing (AMX) process in treating high nitrogen containing wastewaters and a comprehensive study into the granulation mechanism of these bacteria under diverse environmental conditions over the years have been unequal. To this effect, the distinctive differences in saline adapted AMX (S_AMX) and non-saline adapted AMX (NS_AMX) granules are presented in this study. It was observed that substrate utilisation profiles, granule formation mechanism, and pace towards granulation differed marginally for the two adaptation conditions. The different microbial dominant aggregation types aided in splitting the 471 days operated lab-scale SBRs into three distinct phases. In both reactors, phase III (granules dominant phase) showed the highest average nitrogen removal efficiency of 87.9% ± 4.8% and 85.6% ± 3.6% for the S_AMX and NS_AMX processes, respectively. The extracellular polymeric substances (EPS) quantity and major composition determined its role either as a binding agent in granulation or a survival mechanism in saline adaptation. It was also observed that granules of the S_AMX reactor were mostly loosely and less condensed aggregates of smaller sub-units and flocs while those of the NS_AMX reactor were compact agglomerates. The ionic gradient in saline enrichment led to an increased activity of the Na⁺/K⁺ – ATPase, hence enriched granules produced higher cellular adenosine triphosphate molecules which finally improved the granules active biomass ratio by 32.96%. Microbial community showed that about three to four major known AMX species made up the granules consortia in both reactors. Proteins and expression of functional genes differed for these different species.     

Assessing the factors impacting the bioaccessibility of mercury (Hg) in rice consumption by an in-vitro method

Mercury (Hg) in rice is drawing mounting concern since methylmercury (MeHg) was found capable of accumulating in rice. In-vitro bioaccessibility is a feasible and reliable method to assess the health effects of Hg in rice and has been utilized in a number of studies. This study was done to investigate the impact of cultivar, planting location, and cooking on the total mercury (THg) and MeHg bioaccessibility of rice, for which multiple statistical analysis methods were used to analyze the significance of their effects. The THg concentrations of rice samples taken from non-Hg contaminated areas of China were all below 15 ng/g and their MeHg concentrations were below 2 ng/g. Cooking could significantly reduce the MeHg bioaccessibility of rice because the MeHg was mainly combined with protein and the protein will be denatured during the cooking process, and then the denatured MeHg is difficult to be dissolved into the liquid phase. Indica- and japonica-type rice cultivars did not show significant differentiation in either the concentration of Hg or its bioaccessibility. However, the glutinous rice type differed significantly from the above rice types, and it showed greater bioaccessibility of THg and MeHg due to its distinct protein contents and starch properties. Planting location can affect the Hg concentration in rice and THg bioaccessibility but has a limited impact on MeHg bioaccessibility. Based on these results, two macro factors (rice cultivar, planting location) are presumed to impact Hg bioaccessibility by how they affect micro factors (i.e., Hg forms).     

Kinetic and mechanism studies of the ozonolysis of three unsaturated ketones

Reaction rate constants and products of 1-octen-3-one,3-octen-2-one and 4-hexen-3-one with ozone were studied in a 100-L fluorinated ethylene propylene(FEP) Teflon film bag using absolute rate method at 298 ± 1 K and atmospheric pressure.The rate constants were(1.09 ± 0.12) × 10^-17,(3.48 ± 0.36) × 10^-17 and(5.70±0.60) × 10^-17 cm³/(molecule·sec),respectively.According to the obtained rate constants,the effects of carbonyl were discussed.The carbonyl gro...     

Phase transformation of Cr(VI)-adsorbed ferrihydrite in the presence of Mn(II): Fate of Mn(II) and Cr(VI)

Ferrihydrite is an important sink for the toxic heavy metal ions, such as Cr(VI). As ferrihydrite is thermodynamically unstable and gradually transforms into hematite and goethite, the stability of Cr(VI)-adsorbed ferrihydrite is environmentally significant. This study investigated the phase transformation of Cr(VI)-adsorbed ferrihydrite at different pH in the presence of aqueous Mn(II), as well as the fate of Mn(II) and Cr(VI) in the transformation process of ferrihydrite. Among the ferrihydrite transformation products, hematite was dominant, and goethite was minor. The pre-adsorbed Cr(VI) inhibited the conversion of ferrihydrite to goethite at initial pH 3.0, whereas little amount of adsorbed Mn(II) favored the formation of goethite at initial pH 7.0. After the aging process, Cr species in solid phase existed primarily as Cr(III) in the presence of Mn(II) at initial pH 7.0 and 11.0. The aqueous Mn concentration was predominantly unchanged at initial pH 3.0, whereas the aqueous Mn(II) was adsorbed onto ferrihydrite or form Mn(OH)₂ precipitates at initial pH 7.0 and 11.0, promoting the immobilization of Cr(VI). Moreover, the oxidation of Mn(II) occurred at initial pH 7.0 and 11.0, forming Mn(III/IV) (hydr)oxides.     

Water-lifting and aeration system improves water quality of drinking water reservoirs: Biological mechanism and field application

Reservoirs have been served as the major source of drinking water for dozens of years. The water quality safety of large and medium reservoirs increasingly becomes the focus of public concern. Field test has proved that water-lifting and aeration system (WLAS) is a piece of effective equipment for in situ control and improvement of water quality. However, its intrinsic bioremediation mechanism, especially for nitrogen removal, still lacks in-depth investigation. Hence, the dynamic changes in water quality parameters, carbon source metabolism, species compositions and co-occurrence patterns of microbial communities were systematically studied in Jinpen Reservoir within a whole WLAS running cycle. The WLAS operation could efficiently reduce organic carbon (19.77%), nitrogen (21.55%) and phosphorus (65.60%), respectively. Biolog analysis revealed that the microbial metabolic capacities were enhanced via WLAS operation, especially in bottom water. High-throughput sequencing demonstrated that WLAS operation altered the diversity and distributions of microbial communities in the source water. The most dominant genus accountable for aerobic denitrification was identified as Dechloromonas. Furthermore, network analysis revealed that microorganisms interacted more closely through WLAS operation. Oxidation-reduction potential (ORP) and total nitrogen (TN) were regarded as the two main physicochemical parameters influencing microbial community structures, as confirmed by redundancy analysis (RDA) and Mantel test. Overall, the results will provide a scientific basis and an effective way for strengthening the in-situ bioremediation of micro-polluted source water.