Dynamic nano-Ag colloids cytotoxicity to and accumulation by Escherichia coli: Effects of Fe3+, ionic strength and humic acid

Released Ag ions or/and Ag particles are believed to contribute to the cytotoxicity of Ag nanomaterials, and thus, the cytotoxicity and mechanism of Ag nanomaterials should be dynamic in water due to unfixed Ag particle:Ag⁺ ratios. Our recent research found that the cytotoxicity of PVP-Ag nanoparticles is attributable to Ag particles alone in 3 hr bioassays, and shifts to both Ag particles and released Ag⁺ in 48 hr bioassays. Herein, as a continued study, the cytotoxicity and accumulation of 50 and 100 nm Ag colloids in Escherichia coli were determined dynamically. The cytotoxicity and mechanisms of nano-Ag colloids are dynamic throughout exposure and are derived from both Ag ions and particles. Ag accumulation by E. coli is derived mainly from extracellular Ag particles during the initial 12 hr of exposure, and thereafter mainly from intracellular Ag ions. Fe³⁺ accelerates the oxidative dissolution of nano-Ag colloids, which results in decreasing amounts of Ag particles and particle-related toxicity. Na⁺ stabilizes nano-Ag colloids, thereby decreasing the bioavailability of Ag particles and particle-related toxicity. Humic acid (HA) binds Ag⁺ to form Ag⁺-HA, decreasing ion-related toxicity and binding to the E. coli surface, decreasing particle-related toxicity. HA in complex conditions showed a stronger relative contribution to toxicity and accumulation than Na⁺ or Fe³⁺. The results highlighted the cytotoxicity and mechanism of nano-Ag colloids are dynamic and affected by environmental factors, and therefore exposure duration and water chemistry should be seriously considered in environmental and health risk assessments.     

Recent advances in catalytic decomposition of ozone

Ozone (O₃), as a harmful air pollutant, has been of wide concern. Safe, efficient, and economical O₃ removal methods urgently need to be developed. Catalytic decomposition is the most promising method for O₃ removal, especially at room temperature or even subzero temperatures. Great efforts have been made to develop high-efficiency catalysts for O₃ decomposition that can operate at low temperatures, high space velocity and high humidity. First, this review describes the general reaction mechanism of O₃ decomposition on noble metal and transition metal oxide catalysts. Then, progress on the O₃ decomposition performance of various catalysts in the past 30 years is summarized in detail. The main focus is the O₃ decomposition performance of manganese oxides, which are divided into supported manganese oxides and non-supported manganese oxides. Methods to improve the activity, stability, and humidity resistance of manganese oxide catalysts for O₃ decomposition are also summarized. The deactivation mechanisms of manganese oxides under dry and humid conditions are discussed. The O₃ decomposition performance of monolithic catalysts is also summarized from the perspective of industrial applications. Finally, the future development directions and prospects of O₃ catalytic decomposition technology are put forward.     

Effect of substituents in hydroxyl radical-mediated degradation of azo pyridone dyes: Theoretical approaches on the reaction mechanism

Understanding the degradation behavior of azo dyes in photocatalytic wastewater treatment is of fundamental and practical importance for their application in textile-processing and other coloration industries. In this study, quantum chemistry, as density functional theory, was used to elucidate different degradation pathways of azo pyridone dyes in a hydroxyl radical (HO^?)-initiated photocatalytic system. A series of substituted azo pyridone dyes were synthesized by changing the substituent group in the para position of the benzene moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The effect of dye molecular structure on the photocatalytic degradation reaction mechanism was analyzed and quantification of substituent effects on the thermodynamic and kinetics parameters was performed. Potential energy surface analysis revealed the most susceptible reaction site for the HO^? attack. The calculated reaction barriers are found to be strongly affected by the nature of substituent group with a good correlation using Hammett σ_p constants and experimentally determined reaction rates. The stability of pre-reaction complexes and transition state complexes were analyzed applying the distortion-interaction model. The increased stability of the transition state complexes with the distancing from the substituent group has been established.     

Metabolomic modulations in a freshwater microbial community exposed to the fungicide azoxystrobin

An effective broad-spectrum fungicide, azoxystrobin (AZ), has been widely detected in aquatic ecosystems, potentially affecting the growth of aquatic microorganisms. In the present study, the eukaryotic alga Monoraphidium sp. and the cyanobacterium Pseudanabaena sp. were exposed to AZ for 7 days. Our results showed that 0.2–0.5 mg/L concentrations of AZ slightly inhibited the growth of Monoraphidium sp. but stimulated Pseudanabaena sp. growth. Meanwhile, AZ treatment effectively increased the secretion of total organic carbon (TOC) in the culture media of the two species, and this phenomenon was also found in a freshwater microcosm experiment (containing the natural microbial community). We attempted to assess the effect of AZ on the function of aquatic microbial communities through metabolomic analysis and further explore the potential risks of this compound. The metabonomic profiles of the microcosm indicated that the most varied metabolites after AZ treatment were related to the citrate cycle (TCA), fatty acid biosynthesis and purine metabolism. We thereby inferred that the microbial community increased extracellular secretions by adjusting metabolic pathways, which might be a stress response to reduce AZ toxicity. Our results provide an important theoretical basis for further study of fungicide stress responses in aquatic microcosm microbial communities, as well as a good start for further explorations of AZ detoxification mechanisms, which will be valuable for the evaluation of AZ environmental risk.     

微生物菌剂对堆肥功能微生物重构的影响

堆肥产品不仅可以作为有机肥或土壤改良剂,还可以在包气带土层防护地下水污染的过程中起到微生物载体的作用.在堆肥中接种菌剂能够加速堆肥进程,促进堆肥材料的腐熟,但是也有研究认为接种剂与堆肥土著微生物的竞争会导致菌剂无法发挥作用.为了阐明菌剂与土著微生物之间的相互作用,采用宏蛋白质组学方法,分析餐厨垃圾堆肥接菌组（木质纤维素混合菌剂）和对照组（未接菌）中功能微生物群落和碳水化合物代谢途径的变化.结果表明:接菌组中假单胞菌目（Pseudomonadales）和散囊菌纲（Eurotiomycetes）菌群的相对丰度比对照组分别提高了12.5%和22.0%,成为优势细菌和真菌,二者在碳水化合物代谢活性上也成为优势菌群.菌剂主要是由芽孢杆菌目（Bacillales）和散囊菌纲的曲霉（Aspergillus）组成,曲霉因具有堆肥系统所需的木质纤维素分解能力而成为优势真菌,而菌剂中的芽孢杆菌虽然数量较多,但是缺乏堆肥系统所需的功能而无法成为优势细菌.餐厨垃圾中易降解物质分解过程中产生的有机酸会导致酸性环境,对照组中能够适应酸性环境的芽孢杆菌目和酵母菌纲（Saccharomycetes）是优势群落,添加菌剂后,堆肥系统中土著的假单胞菌目和散囊菌纲具有较高的碳水化合物代谢活性和多种有机酸转化通路,因此在与菌剂中的芽孢杆菌目和土著的芽孢杆菌及酵母菌的竞争中成为优势菌群.研究显示,外源菌剂与土著微生物之间以及各土著微生物之间都会发生竞争作用,能否成为优势菌群取决于是否适应堆肥底物新陈代谢的变化,因此只要选择好菌剂的功能和接种时机,菌剂就能够发挥原有的作用.      

土壤微生物群落结构对生活源和工业源再生水灌溉的差异化响应

为研究不同来源再生水灌溉对土壤微生物群落结构的影响,以地下水灌溉土壤为对照,采用Illumina MiSeq高通量测序技术对长期利用生活源和工业源再生水灌溉的土壤微生物群落结构进行分析,进一步探究土壤环境因子及其相互作用对微生物群落结构的影响.结果表明,与地下水灌溉相比,长期生活源再生水灌溉可显著提高土壤中TOC、 DOC、 Eh、 NH~+_4-N和TP的含量,长期工业源再生水灌溉导致Cd、 Cr、 Cu、 Pb和Zn在表层土壤大量累积.再生水灌溉显著增加了土壤中Acidobacteria和Planctomycetes的相对丰度,降低了Firmicutes和Tectomicrobia的相对丰度,且不同来源再生水对土壤中功能微生物的影响不同,生活源再生水灌溉可显著增加Chloroflexi和Nitrospirae的相对丰度,而工业源再生水灌溉对Actinobacteria具有显著的抑制作用.db-RDA分析结果表明,生活源再生水灌溉土壤菌群主要受TN、 TP、 DOC和Eh影响(P0.05),工业源再生水灌溉土壤菌群主要受重金属影响(P0.05).长期再生水灌溉可改变土壤环境因子间的相互作用,进而影响微生物群落结构,生活源再生水灌溉土壤中微生物主要受DOC、 TN和TP等营养物质含量的增加和氧化还原条件的改变控制,工业源再生水灌溉土壤中微生物与重金属的积累显著相关.     

汶川地震重灾区泥石流灾损土地利用及生态修复模式——以北川县都坝河小流域为例

汶川地震诱发了大量泥石流灾害,灾损土地利用和生态修复是灾区产业重建面临的重要课题。以北川县都坝河小流域为研究对象,通过调查灾损土地禀赋、灾害特征、土地需求,采取多因素耦合和关键因子限制分析法,探讨灾害胁迫条件下的经济活动与生态修复之间的互馈作用,结果表明：（1）流域新增土地供给源主要为泥石流灾损土地,土地资源化利用受灾害、聚落和产业结构控制;（2）灾损土地根据成因划分为沟口堆积型、沟道冲淤型以及岸坡侵蚀型,三者的肥力、安全性及交通条件等特征具有显著差异;（3）基于“因灾分区、耕地优先、产业共建、美居造景”的原则,建立了灾损土地的利用方式和生态修复模式,并选取杨家沟进行验证,沟域灾损土地利用方式为生态林地、产业林地及优质耕地,分别占比28.5%、56.3%、15.2%,生态修复措施主要为提高土地安全度、提升植被覆盖率和增强水保功能。该研究建立的震区土地利用和生态修复模式可有力协调人地矛盾、发展绿色经济和提升人居环境。     

水动力对沉积物-水界面氧通量产生机制的影响

选取三峡库区支流御临河为研究对象,测量了5个水动力条件（平均流速为0.00,0.03,0.07,0.12,0.20m/s）下沉积物-水界面（SWI）氧通量的变化及水动力条件对SWI氧通量产生机制的影响.结果表明,随着平均流速的升高,SWI氧通量增加,由0.00m/s时的1.197mmol/（m²·h）增加为0.20m/s时的43.981mmol/（m²·h）,溶解氧穿透深度增加,氧进入沉积物更深处并被微生物和还原性物质所利用,沉积物耗氧量上升;当平均流速较低时,沉积物耗氧量以生物耗氧量为主,在0.00m/s与0.03m/s时生物耗氧量为氧通量的85.3%与57.7%;当水体平均流速较高,化学耗氧量与其他耗氧量中的化学过程耗氧量在氧通量中的比重逐步提高.     

不同基质生物炭对厌氧处理餐厨垃圾效能及微生态的影响

探究了剩余污泥（SS）、餐厨垃圾（FW）、玉米芯（CC）、甘蔗渣（BG）4种不同基质生物炭对厌氧生物处理餐厨垃圾效能的影响,对厌氧污泥的关键酶活性、微生物群落分布以及代谢途径等微生态进行了分析.结果表明,厌氧反应器分别加入4种生物炭后,COD平均去除率分别提高了29.49%、23.16%、29.42%、40.32%;傅里叶红外分析表明,投加SS生物炭组出水中羟基、酰胺基以及C-O-C伸缩振动峰减弱.4个厌氧反应器中厌氧污泥的乙酸激酶活性分别为0.40,0.42,0.96,0.98 μmol/g,表明投加CC与BG生物炭促进了餐厨垃圾的厌氧水解酸化过程;厌氧污泥胞外聚合物的蛋白质/多糖之比分别为0.415、0.56、1.89、2.8,投加CC、BG生物炭提高了污泥的稳定性.4个厌氧反应器中拟杆菌门、变形菌门、厚壁菌门为主要菌群,投加BG生物炭促进了变形菌门与厚壁菌门的生长;对于古细菌而言,甲烷杆菌属与甲烷丝菌属为优势种群,SS组的甲烷杆菌属丰度最高（53.48%）,而BG组中甲烷丝菌属丰度最高（42.72%）.KEGG功能分析表明古菌及细菌均以碳水化合物代谢、氨基酸代谢为主;而投加BG与SS生物炭后,微生物膜运输水平得到了提高.     

不同裂解温度稻壳生物炭对阿特拉津的吸附行为及机制

为探究不同裂解温度下稻壳生物炭的结构和性质差异及其对阿特拉津（AT）的吸附作用机制和构-效关系,以稻壳为原料在300、500和700℃下制备稻壳生物炭（分别记为RH300、RH500、RH700）,通过电镜扫描、元素分析仪、比表面积分析仪和傅里叶变换红外光谱分析仪等对3种稻壳生物炭进行结构表征分析,并采用批量等温吸附法研究稻壳生物炭对AT的吸附特性.结果表明:裂解温度由300℃升至700℃时,稻壳生物炭中w（C）由48.81%升至64.67%,w（H）、w（N）和w（O）则由3.22%、1.45%和34.66%分别降至0.89%、0.92%和16.29%,原子比H/C、O/C和（O+N）/C值均降低.可见,随着裂解温度升高,稻壳生物炭的芳香性增强,亲水性和极性降低,且比表面积和孔体积增大,平均孔径减小.3种稻壳生物炭对AT的吸附均可用Freundlich和Langmuir两种等温吸附模型进行较好地拟合（R≥0.948,P < 0.01）,吸附作用及非线性程度与生物炭的比表面积（SSA）、芳香性（H/C）、亲水性（O/C）和极性〔（O+N）/C〕呈良好的指数关系,大小表现为RH700 > RH500 > RH300.稻壳生物炭对AT的吸附机制主要包括分配作用和表面吸附,分配作用强度与生物炭的极性和炭化程度有关;而表面吸附作用与AT的分子大小有关,3种稻壳生物炭对AT的表面吸附除表面覆盖外,还存在多层平铺、毛细管现象和孔隙填充等.研究显示,裂解温度是影响生物炭吸附有机污染物的重要因素,在综合考虑成本和制备工艺的同时,适当提高裂解温度可增强生物炭对有机污染物的吸附作用.