One-electron standard reduction potentials of nitroaromatic and cyclic nitramine explosives

Extensive studies have been conducted in the past decades to predict the environmental abiotic and biotic redox fate of nitroaromatic and nitramine explosives. However, surprisingly little information is available on one-electron standard reduction potentials (E^o(R-NO₂/R-NO₂⁻)). The E^o(R-NO₂/R-NO₂⁻) is an essential thermodynamic parameter for predicting the rate and extent of reductive transformation for energetic residues. In this study, experimental (linear free energy relationships) and theoretical (ab initio calculation) approaches were employed to determine E^o(R-NO₂/R-NO₂⁻) for nitroaromatic, (caged) cyclic nitramine, and nitroimino explosives that are found in military installations or are emerging contaminants. The results indicate a close agreement between experimental and theoretical E^o(R-NO₂/R-NO₂⁻) and suggest a key trend: E^o(R-NO₂/R-NO₂⁻) value decreases from di- and tri-nitroaromatic (e.g., 2,4-dinitroanisole) to nitramine (e.g., RDX) to nitroimino compound (e.g., nitroguanidine). The observed trend in E^o(R-NO₂/R-NO₂⁻) agrees with reported rate trends for reductive degradation, suggesting a thermodynamic control on the reduction rate under anoxic/suboxic conditions.     

硫自养反硝化系统运行效能和微生物群落结构研究

启动了单质硫自养反硝化反应器并研究其脱氮性能,通过血清瓶批式实验测定了污泥的反硝化活性,并采用扫描电镜和高通量测序手段揭示了系统内微生物群落结构特征.结果表明,SBR反应器进水NO₃^--N浓度为80mg/L,随水力停留时间由12h逐渐缩短为6h,反应器的自养脱氮性能逐渐增强,稳定期反应器的总无机氮去除率达99.1%,总无机氮去除负荷平均值为0.158kg N/（m³·d）;SBR周期内NO₂^--N浓度最大值为13.3mg/L,NO₃^--N还原为NO₂^--N过程pH值由7.38降低至6.94,NO₂^--N还原为N₂过程pH值基本不变;批式实验结果表明,硫自养反硝化和异养反硝化NO₃^--N去除速率分别为0.515,0.196kg N/（kg VSS·d）,硫自养反硝化污泥NO₂^--N降解速率为0.117kg N/（kg VSS·d）,污泥同时具有自养反硝化和异养反硝化活性;扫描电镜显示,污泥中存在大量的杆状细菌和球状菌;污泥中主要的硫反硝化细菌分别为Thiobacillus、Sulfurimonas和Thermomonas属,其相对丰度分别为14.5%、7.6%和6.0%.     

石英ESR法在河流沉积物源示踪中的探讨及应用

使用石英ESR法示踪河流沉积物源是一种新方法和新理论的探索。本文从拟解决的科学问题出发,在着重分析石英ESR信号强度和CI值物源示踪理论基础之上,讨论了该方法在亚洲现代沙尘沉降物源示踪和地质历史时期风尘堆积物源示踪研究中的有效性,结合ESR测年可覆盖整个第四纪时期的特性,认为石英ESR法不仅可以为物源示踪提供良好的年代框架约束,而且还可以较好的反映地质历史时期沉积物质来源在不同时空尺度上的变化特征。随后,通过对指导思想、研究思路以及长江流域不同河段和主要支流的地质地貌背景、岩石类型分布、水系组合特征以及"源-汇"系统之间物质剥蚀-堆积过程的可通达性等方面的综合论述与分析,讨论了石英ESR法在河流沉积物源示踪上的有效性及其在研究长江流域水系发育历史和沉积演化过程中的可行性。     

A simple method to harness DC (direct current) electrical energy generated by bacterial activity

We developed a new system for collecting electrons generated by bacterial activity to supply DC (direct current) electrical energy. This system used eight titanium sub-electrodes (surface area of each sub-electrode: 189 cm²) connected to one central main titanium electrode (surface area of electrode: 1571 cm²). The distance between each sub-electrode and the main electrode was 30 cm. In an initial experiment, we collected electrons during composting cattle excreta, which was mixed with a commercially available microbial compost activator/starter. We analysed the relationships between the composting temperature and electrical current and voltage. Electrons were effectively collected and used successfully to obtain DC electrical energy. Generation of a stable voltage of approximately 0.5 V was clearly observed. This voltage was not related to compost temperature; however, the generated electrical current increased and decreased with compost temperature. The method was then used in a second experiment to collect electrons generated by bacterial activity in an agricultural field (area: 48 m²). Electrons in the field were effectively collected, and we measured a stable voltage of approximately 1.1 V and a stable current of approximately 0.7 mA. The system has the advantages of being simple, easily maintained, inexpensive, and applicable to large-scale agricultural fields.     

Dechlorination of 2,2＇,4,4＇,5,5＇-hexachlorobiphenyl by thermal reaction with activated carbon-supported copper or zinc

Activated carbon （AC）-supported copper or zinc made from ion exchange resin （IRCu-C and IRZn-C） have an increased metal load of 557.3 mg·g^-1 and 502.8 mg·g^-1 compared to those prepared by the traditional method involving impregnation with AC and copper （II） citrate or zinc citrate solution （LaCu-C and LaZn-C） of 12.9 mg·g^-1 and 46.0 mg·g^-1 respectively. When applied to decompose 2,2＇,4,4＇,5,5＇-hexachlorobiphenyl at 250 ℃, IRCu-C achieved higher activity of 99.0% decomposition efficiency than LaCu-C of 84.7%, IRZn-C of 90.5% and LaZn-C of 62.7%. When the reaction temperature rose to 350 ℃, all the four kinds of reactants can decompose PCB- 153 with efficiency above 90%. Further, X-ray photoelec- tron spectroscopy characterization of IRCu-C before and after the reaction indicated transformation of 19.1% of Cu atoms into Cu^2＋, illustrating that Cu is the active ingredient or electron donor promoting the decomposition of PCB- 153. The mechanism underlying this process differs from a traditional H donor. However, there is no significant change on the surface of IRZn-C before and after the reaction, suggesting that Zn acts as catalyst during the process of PCB-153 decomposition.     

Size fractionation and characterization of nanocolloidal particles in soils

A protocol was developed to fractionate soil particles down to the nanocolloid scale by combining sieving, sedimentation, centrifugation, and cross-flow filtration (CFF). The validity of the method and the performance of the CFF system were tested by characterizing fractions using laser granulometry, electron microscopy, and chemical analysis. The 0.1-μm-pore-size membrane CFF system effectively retained nanocolloids (<0.1 μm) as shown by laser granulometry and observed directly by transmission electron microscopy. However, environmental scanning electron microscopy images of freeze-dried colloids were very different from their TEM counterparts, suggesting that sample preparation influenced microscopy imaging. Chemical analysis of Cu, Cd, and organic carbon in each fraction showed that the concentrations of these components increased as particle size decreased, indicating colloids and nanocolloids play an important role in retaining trace metals. Particle-size fractionation combined with chemical analysis and electron microscopy can provide insight into the nature and properties of nanocolloids in soil.     

Enhanced catalytic oxidation of 2,4-dichlorophenol via singlet oxygen dominated peroxymonosulfate activation on CoOOH@Bi2O3 composite

• Bi₂O₃ cannot directly activate PMS. • Bi₂O₃ loading increased the specific surface area and conductivity of CoOOH. • Larger specific surface area provided more active sites for PMS activation. • Faster electron transfer rate promoted the generation of reactive oxygen species. • ¹O₂ was identified as dominant ROS in the CoOOH@Bi₂O₃/PMS system. Cobalt oxyhydroxide (CoOOH) has been turned out to be a high-efficiency catalyst for peroxymonosulfate (PMS) activation. In this study, CoOOH was loaded on bismuth oxide (Bi₂O₃) using a facile chemical precipitation process to improve its catalytic activity and stability. The result showed that the catalytic performance on the 2,4-dichlorophenol (2,4-DCP) degradation was significantly enhanced with only 11 wt% Bi₂O₃ loading. The degradation rate in the CoOOH@Bi₂O₃/PMS system (0.2011 min⁻¹) was nearly 6.0 times higher than that in the CoOOH/PMS system (0.0337 min⁻¹). Furthermore, CoOOH@Bi₂O₃ displayed better stability with less Co ions leaching (16.4% lower than CoOOH) in the PMS system. These phenomena were attributed to the Bi₂O₃ loading which significantly increased the conductivity and specific surface area of the CoOOH@Bi₂O₃ composite. Faster electron transfer facilitated the redox reaction of Co (III) / Co (II) and thus was more favorable for reactive oxygen species (ROS) generation. Meanwhile, larger specific surface area furnished more active sites for PMS activation. More importantly, there were both non-radical (¹O₂) and radicals (SO₄⁻•, O₂⁻•, and OH•) in the CoOOH@Bi₂O₃/PMS system and ¹O₂ was the dominant one. In general, this study provided a simple and practical strategy to enhance the catalytic activity and stability of cobalt oxyhydroxide in the PMS system.     

Isolation,identification, and the degradation characteristics of a BDE-47 degrading strain北大核心CSCD

In an effort to remove BDE-47 residues from the environment, a bacterial strain that is capable of utilizing BDE-47 as the sole carbon source was isolated and screened from soil collected from an e-waste recycling area in Tianjin to analyze the degradation properties. The strain was preliminarily identified as Enterobacter sp. according to a 16S rDNA gene sequence analysis. The strain degraded 35.8% of 525 μg/L of BDE-47 in 35 d when the initial concentration of bacteria was 7.1 × 105 cells/ mL. The product of the biodegradation of BDE-47 was BDE-28. The biodegradation of BDE-47 fit well with first-order kinetics, and its degradation kinetics was ln Ct = - 0.104t + 6.22. With the addition of an electron acceptor, such as Fe3+, SO4 2- and NO3 -, the BDE-47 degradation rate was significantly increased to 49.8%, 59.1%, and 67.3%, respectively. The above results revealed that the strain could degrade BDE-47, which is of importance in the application of environmental bioremediation of BDE-47. © 2018 Science Press. All rights reserved.     

Enhancement of extracellular Cr(VI) reduction for anammox recovery using hydrazine: performance,pathways, and mechanism

● N₂H₄ addition enhanced and recovered anammox performance under Cr(VI) stress. ● N₂H₄ accelerated electron transfer of Cr(VI) reduction for detoxification. ● N₂H₄ enhanced anammox metabolism for activity recovery from Cr(VI) inhibition. ● Extracellular Cr(VI) reduction to less toxic Cr(III) was the dominant mechanism. The hexavalent chromium (Cr(VI)) would frequently impose inhibition to anaerobic ammonium oxidation (anammox) process, hindering the efficiency of nitrogen removal in wastewater treatment. Hydrazine (N₂H₄), which is an intermediate product of anammox, participates in intracellular metabolism and extracellular Cr(VI) reduction. However, the roles of N₂H₄-induced intracellular metabolism and extracellular reduction in nitrogen removal under Cr(VI) stress remain unclear. The addition of 3.67 mg/L of N₂H₄ increased the anammox activity by 17%. As an intermediate, N₂H₄ enhanced anammox metabolism by increasing the heme c content and electron transfer system activity. As a reductant, N₂H₄ accelerated the reduction of c-Cyts-mediated extracellular Cr(VI) to the less toxic Cr(III). Extracellular Cr(III) accounts for 74% of the total Cr in a Cr(VI)-stressed anammox consortia. These findings highlight that N₂H₄-induced extracellular Cr(VI) reduction is the dominant mechanism for the survival of anammox consortia. We also found that N₂H₄ increased the production of extracellular polymeric substances to sequester excessive Cr(VI) and produced Cr(III). Taken together, the study findings suggest a potential strategy for enhancing nitrogen removal from ammonium-rich wastewater contaminated with Cr(VI).     

青岛大气颗粒物的扫描电镜研究和污染源识别

应用扫描电镜－X射线能谱对青岛市大气颗粒物定性分析。单个颗粒物分析和多个颗粒物复合分析的结果,为污染源识别和相对重要性的估计提供了重要信息:青岛市大气颗粒物的来源,主要有土壤扬尘和燃煤飞灰、硫酸钙和其他硫酸盐类的二次颗粒物、有机物质颗粒物、天然海盐、工业钡盐与其他类型的工业排放。