The thermal transformation mechanism of chlorinated paraffins: An experimental and density functional theory study

The increasing production and usage of chlorinated paraffins(CPs) correspondently increase the amount of CPs that experience thermal processes. Our previous study revealed that a significant amount of medium-chain chlorinated paraffins(MCCPs), short-chain chlorinated paraffins(SCCPs) as well as aromatic and chlorinated polycyclic aromatic hydrocarbons(Cl-PAHs) were formed synergistically during the thermal decomposition of CP-52(a class of CP products).However, the transformation mechanisms of CP-52 to these compounds are still not very clear.This article presents a mechanistic analysis on the decomposition of CP-52 experimentally and theoretically. It was found that CP-52 initially undergoes dehydrochlorination and carbon chain cleavage and it transformed into chlorinated and unsaturated hydrocarbons. Cyclization and aromatization were the most accessible pathways at low temperatures(200–400°C), both of which produce mostly aromatic hydrocarbons. As the temperature exceeds 400°C, the hydrocarbons could decompose into small molecules, and the subsequent radical-induced reactions become the predominant pathways, leading to the formation of Cl-PAHs. The decomposition of CP-52 was investigated by using density functional theory and calculations demonstrating the feasibility and rationality of PCB and PCN formation from chlorobenzene. The results improve the understanding of the transformation processes from CP-52 to SCCPs and Cl-PAHs as well as provide data for reducing their emissions during thermal-related processes.     

Application of interface material and effects of oxygen gradient on the performance of single-chamber sediment microbial fuel cells (SSMFCs)

Single-chamber sediment microbial fuel cells(SSMFCs) have received considerable attention nowadays because of their unique dual-functionality of power generation and enhancement of wastewater treatment performance. Thus, scaling up or upgrading SSMFCs for enhanced and efficient performance is a highly crucial task. Therefore, in order to achieve this goal, an innovative physical technique of using interface layers with four different pore sizes embedded in the middle of SSMFCs was utilized in this study.Experimental results showed that the performance of SSMFCs employing an interface layer was improved regardless of the pore size of the interface material, compared to those without such layers. The use of an interface layer resulted in a positive and significant effect on the performance of SSMFCs because of the effective prevention of oxygen diffusion from the cathode to the anode. Nevertheless, when a smaller pore size interface was utilized, better power performance and COD degradation were observed. A maximum power density of 0.032 mW/m~2 and COD degradation of 47.3% were obtained in the case of an interface pore size of 0.28 μm. The findings in this study are of significance to promote the future practical application of SSMFCs in wastewater treatment plants.     

Enzyme-electrolytic degradation of dichloromethane: Efficiency, kinetics and mechanism

Enzymatic electrolysis cell(EEC) has advantages over microbial electrolysis cell(MEC) due to the needless of microbe inoculation and high-efficiency of enzymatic reaction. In this study, an EEC was first applied to achieve the effective degradation of halogenated organic pollutants and dichloromethane(CH_2Cl_2) was utilized as a model pollutant. The results indicate that the degradation efficiency of CH_2Cl_2 after 2 hr reaction in the EEC was almost100%, which was significantly higher than that with enzyme(51.1%) or current(19.0%). The current induced the continuous regeneration of reduced glutathione(GSH), thus CH_2Cl_2 was degraded under the catalysis of GSH-dependent dehalogenase through stepwise dechlorination, and successively formed monochloromethane(CH_3Cl) and methane(CH_4). The kinetic result shows that with a current of 15 mA, the maximum specific degradation rate of CH_2Cl_2(3.77 × 10~(-3) hr~(-1)) was increased by 5.7 times. The optimum condition for CH_2Cl_2 dechlorination was also obtained with pH, current and temperature of 7.0, 15 mA and 35°C,respectively. Importantly, this study helps to understand the behavior of enzymes and the fate of halogenated organic pollutants with EEC, providing a possible treatment technology for halogenated organic pollutants.     

One-step synthesis of Cu(II) metal–organic gel as recyclable material for rapid, efficient and size selective cationic dyes adsorption

Efficient removal of non-biodegradable and hazardous dyes from wastewater remains a hot research topic. Herein, a rationally designed a Cu(Ⅱ)-based metal–organic gel(Cu-MOG) with a nanoporous 3 D network structure prepared via a simple one-step mixing method was successfully employed for the removal of cationic dyes. The Cu-MOG exhibited high efficiency, with an adsorption capacity of up to 650.32 mg/g, and rapid adsorption efficiency, with the ability to adsorb 80% of Neutral Red within 1 min. The high adsorption efficiency was attributed to its large specific surface area, which enabled it to massively bind cationic dyes through electrostatic interaction, and a nanoporous structure that promoted intra-pore diffusion. Remarkably, the Cu-MOG displayed size-selective adsorption, based on adsorption studies concerning dyes of different sizes as calculated by density functional theory. Additionally, the adsorption performance of the Cu-MOG still maintained removal efficiency of 100% after three regeneration cycles. These results suggested that the Cu-MOG could be expected to be a promising and competitive candidate to conveniently process wastewater.     

长期施肥下水稻根际和非根际土壤微生物碳源利用特征

以红壤丘陵区典型稻田长期定位施肥试验土壤为研究对象,选取不施肥(CK)、化肥(NPK)、秸秆还田+化肥(NPKS)、30%有机肥+化肥(LOM)和60%有机肥+化肥(HOM)这5种处理,研究长期不同施肥条件下水稻根际和非根际土壤微生物碳源利用特征.基于~(18)O-H_2O示踪的结果表明,土壤微生物量碳(MBC)和微生物生长速率(CGrowth)均以HOM处理最高,CK处理最低.根际土中,土壤微生物基础呼吸速率以HOM最高,CK和NPK最低;微生物碳源利用效率(CUE)以NPK最高,LOM和HOM最低.非根际土中,不同施肥处理的基础呼吸速率和CUE均无显著差异. MicroResp~(TM)结果显示,非根际土中微生物对外源碳源代谢能力高于根际土.施用有机物料(秸秆或有机肥)均能提高微生物对羧酸类、氨基酸、碳水化合物的代谢速率,且土壤微生物利用羧酸类碳源的活性最高,其次为氨基酸类和碳水化合物类碳源,对复杂化合物的代谢速率较低. RDA分析表明,微生物对不同碳源代谢情况的聚类总体以根际土与非根际土分开,CK与施肥处理分开,且NPK与NPKS相对聚集,LOM与HOM相对聚集,NPK、NPKS与LOM、HOM分开,即不同施肥处理显著改变土壤微生物对外源碳源代谢特征.结果表明,施肥未改变微生物CUE和基础呼吸速率,但有外源碳源输入(如根系分泌物)的情况下,施用有机物料增加基础呼吸、降低CUE.     

不同类型秸秆对污泥厌氧消化特性及细菌群落结构的影响

为促进污水处理厂污泥及农作物秸秆的资源化利用,探讨不同类型秸秆（玉米、小麦、水稻）对污泥厌氧消化特性、产气效果及细菌群落结构的影响,在中温〔（35±1）℃〕下,研究了污泥与秸秆按不同质量比（1:0、1:0.5、1:1、1:1.5）联合厌氧消化对污泥C/N（碳氮比）和厌氧消化环境中pH、ρ（NH₄+-N）、ρ（VFAs）（VFAs为挥发性脂肪酸）、日均沼气产量及φ（CH₄）、细菌群落的特征变化,以未添加秸秆的污泥厌氧消化为CK（对照）.结果表明:不同类型秸秆的添加对厌氧消化体系的pH、ρ（NH₄+-N）、ρ（VFAs）均产生显著影响,秸秆的加入明显提高了厌氧消化体系的产气量.联合厌氧消化可通过优化厌氧消化底物的C/N,从而增加ρ（VFAs）和φ（CH₄）.其中,污泥与玉米秸秆质量比为1:1.5时对厌氧消化的促进作用最为显著;其沼气日产量为2 303.08 mL,比CK（536.15 mL）提高了3倍以上,而沼气中φ（CH₄）最高为54.49%,比CK（37.07%）提高46.99%.此外,不同类型秸秆的添加也可通过改变细菌群落结构从而促进秸秆降解,增加ρ（VFAs）和提高沼气产量,特别是添加秸秆后,Bacteroidetes会逐渐取代Proteobacteria成为主要的产酸菌种,从而导致ρ（VFAs）增加.研究显示,污泥与秸秆联合厌氧消化可改善污泥营养结构,改变细菌群落结构,提高沼气产量.      

青霉菌与生物炭复合修复土壤砷污染的研究

采用随机区组设计,分别对添加不同量的青霉菌和生物炭的砷污染土壤进行培养,通过测定土壤中的As~(3+)、As~(5+)及总砷含量,探究了青霉菌与生物碳复合修复对砷污染土壤中有效砷的钝化率及土壤中砷的价态转化的影响,同时对土壤中的微生物数量进行区系分析,建立了微生物数量与有效砷含量之间的关系.结果显示,随着青霉菌接菌量与生物炭施用量的增加,土壤中总砷含量不会发生变化,有效砷含量从17.74 mg·kg~(-1)下降到12.69 mg·kg~(-1),有效砷的钝化率可达到27.6%左右.而两种价态的砷(As~(5+)、As~(3+))之间没有发生转化,约27%的As~(5+)会被青霉菌与生物炭固定,但As~(3+)在土壤中的含量基本保持不变.在有效砷含量下降的同时,土壤中放线菌的含量基本不变,但土壤中细菌的总量有所上升.结果表明,青霉菌与生物碳复合修复可以降低有效砷的含量,并使砷污染土壤中的微生物环境有所改善,对砷污染土壤显示出较好的修复性能.     

生态工程综合治理系统对农业小流域氮磷污染的治理效应

以典型农业小流域——开慧河流域源区为研究对象,基于研究区农业面源污染的主要排放特征,建立以生态湿地为主的小流域面源污染生态工程综合治理系统,重点探讨其对水体氮磷污染物的去除效果.结果表明,畜禽养殖业是开慧河流域源区水体氮磷污染物的主要来源,需要重点防控.组合生态湿地处理工程对农村分散式生活与养殖混合废水总氮(TN)、总磷(TP)的平均去除率为87. 1%和90. 9%;多级人工湿地拦截工程对农田排水与分散式养殖混合废水TN、TP的平均去除率为85. 7%和84. 9%;景观型生态湿地净化工程对末端汇水区水体中TN、TP的去除率在27. 1%～67. 4%和13. 3%～81. 5%之间.整个生态工程综合治理系统对流域TN和TP污染物的总拦截量分别为5 292 kg·a~(-1)和1 054 kg·a~(-1),占研究区农业面源TN、TP总污染负荷的35. 3%和43. 6%.因此,构建的生态工程综合治理系统对流域农业面源氮磷污染具有较好的治理效应,适合在我国南方小流域水环境治理中推广应用.     

基于GIS格网化分析支撑的旅游空间规划技术方法研究——以青岛市为例

空间规划是支撑旅游地发展规划的核心章节,目前主要依靠规划者经验判断,主观性较强,缺乏客观方面的信息数据支持。论文将GIS格网化与旅游资源评价模型相结合,提出了旅游资源单体采集、旅游资源格网化及其空间分析方法,并融合旅游资源群评价模型、旅游功能区识别模型、旅游线路和空间发展轴线识别模型予以支撑,形成了标准化的旅游资源采集、评价到空间识别的集成技术方法;并以青岛市为例,识别出了旅游资源集群及其发展潜力、旅游功能区和空间拓展轴线,确立了“一心、一带、三轴、五区”的空间发展格局。论文初步探讨了GIS格网化空间分析方法在区域旅游规划中的应用,能够补充传统定性评价方法客观性不足的缺陷,实现复杂旅游资源数据的单体评价、旅游资源集群评价、旅游功能区识别、旅游线路和空间发展轴线优选的系列化分析技术路线,可为延伸旅游规划深度、提高规划精度提供科学参考。     

Simultaneous quantification of fifty-one odor-causing compounds in drinking water using gas chromatography-triple quadrupole tandem mass spectrometry

A wide range of compounds with various structural features can cause taste and odor(TO)problems in drinking water. It would be desirable to determine all of these compounds using a simple analytical method. In this paper, a sensitive method combining liquid–liquid extraction(LLE) with gas chromatography-triple quadrupole tandem mass spectrometry(GC–MS/MS)was established to simultaneously analyze 51 odor-causing compounds in drinking water,including organic sulfides, aldehydes, benzenes, phenols, ethers, esters, ketones, nitrogenous heterocyclic compounds, 2-methylisoborneol and geosmin. Three deuterated analogs of target analytes, dimethyl disulfide-d6, benzaldehyde-d6 and o-cresol-3,4,5,6-d4,were used to correct the variations in recovery, and five isotope-labeled internal standards(4-chlorotoluene-d4, 1, 4-dichlorobenzene-d4, naphthalene-d8, acenaphthene-d10, phenanthrene-d10 respectively) were used prior to analysis to correct the variations arising from instrument fluctuations and injection errors. The calibration curves of the target compounds showed good linearity(R2 0.99, level = 7),and method detection limits(MDLs) below 1/10 of the odor threshold concentrations were achieved for most of the odorants(0.10–20.55 ng/L). The average recoveries of most of the analytes in tap water samples were between 70% and 120%, and the method was reproducible(RSD 20%, n = 7). Additionally, concentrations of odor-causing compounds in water samples collected from three drinking water treatment plants(DWTPs) were analyzed by this method.According to the results, dimethyl trisulfide, dimethyl disulfide and indole were considered to be the key odorants responsible for the swampy/septic odor. 2-Methylisoborneol and geosmin were detected as the main odor-causing compounds for musty/earthy odor in DWTP B.