Characterization of a new smog chamber for evaluating SAPRC gas-phase chemical mechanism

A new state-of-the-art indoor smog chamber facility (CAPS-ZJU) has been constructed and characterized at Zhejiang University, which is designed for chemical mechanism evaluation under well-controlled conditions. A series of characterization experiments were performed to validate the well-established experimental protocols, including temperature variation pattern, light spectrum and equivalent intensity (J_NO2), injection and mixing performance, as well as gases and particle wall loss. In addition, based on some characterization experiments, the auxiliary wall mechanism has been setup and examined. Fifty chamber experiments were performed across a broad range of experimental scenarios, and we demonstrated the ability to utilize these chamber data for evaluating SAPRC chemical mechanism. It was found that the SAPRC-11 can well predict the O₃ formation and NO oxidation for almost all propene runs, with 6 hr Δ(O₃ – NO) model error of –3% ± 7%, while the final O₃ was underestimated by ~20% for isoprene experiments. As for toluene and p-xylene experiments, it was confirmed that SAPRC-11 has significant improvement on aromatic chemistry than earlier version of SAPRC-07, although the aromatic decay rate was still underestimated to some extent. The model sensitivity test has been carried out, and the most sensitive parameters identified are the initial concentrations of reactants and the light intensity as well as HONO offgasing rate and O₃ wall loss rate. All of which demonstrated that CAPS-ZJU smog chamber could derive high quality experimental data, and could provide insights on chamber studies and chemical mechanism development.     

Surface characterization of metal oxides-supported activated carbon fiber catalysts for simultaneous catalytic hydrolysis of carbonyl sulfide and carbon disulfide

The sol–gel method was used to synthesize a series of metal oxides-supported activated carbon fiber (ACF) and the simultaneous catalytic hydrolysis activity of carbonyl sulfide (COS) and carbon disulfide (CS₂) at relatively low temperatures of 60°C was tested. The effects of preparation conditions on the catalyst properties were investigated, including the kinds and amount of metal oxides and calcination temperatures. The activity tests indicated that catalysts with 5 wt.% Ni after calcining at 400°C (Ni(5)/ACF(400)) had the best performance for the simultaneous catalytic hydrolysis of COS and CS₂. The surface and structure properties of prepared ACF were characterized by scanning electron microscope-energy disperse spectroscopy (SEM-EDS), Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), carbon dioxide-temperature programmed desorption (CO₂-TPD) and diffuse reflectance Fourier transform infrared reflection (DRFTIR). And the metal cation defects were researched by electron paramagnetic resonance (EPR) method. The characterization results showed that the supporting of Ni on the ACF made the ACF catalyst show alkaline and increased the specific surface area and the number of micropores, then improved catalytic hydrolysis activity. The DRFTIR results revealed that -OH species could facilitate the hydrolysis of COS and CS₂; -COO and -C–O species could facilitate the oxidation of catalytic hydrolysate H₂S. And the EPR results showed that high calcination temperature conditions provide more active reaction center for the COS and CS₂ adsorption.     

水环境中溶解性有机物溯源分析及分子结构表征概述

溶解性有机物(DOM)是地球上最大的碳基化合物反应性储层之一,涉及各种生物地化反应并且在污染物溶解度、毒性、生物利用度、流变性和分布中发挥重要作用。本文介绍了当前用于表征水环境中DOM的策略和工具,探讨了当前研究在技术限制(预处理过程复杂、仪器分辨率低、数据处理困)、结构复杂性、结构多变性等方面存在的诸多局限性。分析认为:已有研究主要侧重于溯源分析和分子结构特征解析,未来研究应该在不同的结构层面和角度开展,加强多学科融合、数据库创建、对照实验和协同工作。     

农业排水沟渠硝态氮吸收动力学特征及相关性分析

为揭示农业排水沟渠NO_3~--N吸收动态变化特征,选择溴化钠(Na Br)为保守示踪剂、硝酸钾(KNO3)为添加营养盐,于2016年10月至2017年4月在合肥地区某一源头溪流开展5次示踪试验,并以TASCC方法和Michaelis-Menten(M-M)方程模拟NO_3~--N吸收动力学特征,结果表明,背景浓度条件下排水沟渠完全混合子渠段U_(amb)和V_(f-amb)的变化范围分别为11.40~69.13μg·(m~2·s)~(-1)[均值为34.45μg·(m~2·s)-1]、0.07~0.43 mm·s~(-1)(均值为0.24 mm·s~(-1)),相应地Sw-amb变化范围为92.51~405.74 m(均值为199.06 m),明显小于排水沟渠长度(也就是2.5 km),表明沟渠具有较强的NO_3~--N滞留潜力.M-M方程较好地拟合了NO_3~--N吸收动力学特征,参数Umax变化范围为158~1 280μg·(m~2·s)~(-1)[均值为631.13μg·(m~2·s)~(-1)],Km变化范围为0.16~5.52 mg·L~(-1)(均值为1.46 mg·L~(-1)).相关分析表明,Sw-amb与NO_3~--Namb呈显著负相关、Uamb与NO_3~--Namb呈极显著正相关,其它螺旋指标与NO_3~--N背景浓度的相关性均不明显;水文因素对NO_3~--N滞留影响也不显著,而沟渠槽道地貌特征指标Фw、ФA与大部分螺旋指标都呈显著相关性,表明槽道地貌特征对NO_3~--N滞留影响相对较为重要.     

高效重金属捕集剂EDTC的结构表征及对酸性络合铜的去除特性研究

以乙二胺和二硫化碳为反应物,无水乙醇和去离子水的混合溶液为溶剂,制备了一种巯基类重金属捕集剂N,N-双(二硫代羧基)乙二胺(EDTC),采用紫外光谱、红外光谱和元素分析对其结构进行表征,重点研究了其对EDTA络合铜、柠檬酸络合铜和酒石酸铜3种酸性模拟络合铜的去除性能及螯合沉淀物的溶出特性,并探讨了EDTC脱除络合铜的机理.研究结果表明,处理50 mg·L-1的含铜废水,p H值范围为3~9,EDTC投加量为mEDTC/mCu=8(质量比),反应时间3 min,PAM投加量为1 mg·L-1,此时出水Cu2+浓度均低于0.25 mg·L-1,去除率达到99.5%以上.螯合沉淀物在弱酸性和弱碱性条件下很稳定,不易产生二次污染.红外光谱图分析结果表明,EDTC与Cu会发生螯合反应,即EDTC直接脱出络合铜中Cu2+,并与Cu2+生成难溶的螯合产物EDTC-Cu,进而有效地去除废水中Cu.     

A multiscale hierarchical Markov transition matrix model for generating and analyzing thematic raster maps

A model is described for generating hierarchically scaled spatial pattern as represented in a thematic raster map. The model involves a series of Markov transition matrices, one for each level in the scaling hierarchy. In full generality, the model allows the transition matrices to be different at each level, potentially making available a large number of parameters for landscape characterization. The model is self-similar when the transition matrices are all equal. A method is presented for fitting the model to data that take the form of a single-resolution thematic raster map. Explicit analytic solutions are obtained for the fitted parameters. The fitting method is based on a relationship between the hierarchical transitions in the model and spatial transitions at varying distance scales in the data map, a categorical analogy of the geostatistical variogram.     

淀粉/凹凸棒粘土复合吸附絮凝材料的研究

采用接枝聚合法在硅烷化凹凸棒粘土(OATP)表面接枝淀粉,制备淀粉/凹凸棒粘土(ATP)复合吸附絮凝材料.采用傅里叶变换红外光谱(FT-IR)、扫描电子显微镜(SEM)对淀粉/ATP进行了表征,并对其制备条件进行了优化.结果表明,当淀粉质量分数(相对OATP质量)为100%,聚合反应时间为3 h,引发剂质量分数为0.003%,反应温度为60℃时,制备的淀粉/ATP对镉离子的最大吸附容量可达到36.78 mg/g.与ATP、OATP相比,淀粉/ATP对镉离子的吸附容量增大了2倍以上.复合材料具有比OATP更强的捕获能力,所形成的絮凝体大而密实,比淀粉絮凝剂具有更好的沉降性能.     

Removal of arsenate with hydrous ferric oxide coprecipitation：Effect of humic acid

Insights from the adverse effect of humic acid(HA) on arsenate removal with hydrous ferric oxide(HFO) coprecipitation can further our understanding of the fate of As(V) in water treatment process. The motivation of our study is to explore the competitive adsorption mechanisms of humic acid and As(V) on HFO on the molecular scale. Multiple complementary techniques were used including macroscopic adsorption experiments, surface enhanced Raman scattering(SERS), extended X-ray absorption fine structure(EXAFS) spectroscopy, flow-cell attenuated total reflectance Fourier transform infrared(ATR-FTIR) measurement, and charge distribution multisite complexation(CDMUSIC) modeling. The As(V) removal efficiency was reduced from over 95% to about 10% with the increasing HA concentration to 25 times of As(V) mass concentration. The SERS analysis excluded the HA-As(V) complex formation. The EXAFS results indicate that As(V) formed bidentate binuclear surface complexes in the presence of HA as evidenced by an As-Fe distance of 3.26–3.31 ?. The in situ ATR-FTIR measurements show that As(V) replaces surface hydroxyl groups and forms innersphere complex. High concentrations of HA may physically block the surface sites and inhibit the As(V) access. The adsorption of As(V) and HA decreased the point of zero charge of HFO from 7.8 to 5.8 and 6.3, respectively. The CD-MUSIC model described the zeta potential curves and adsorption edges of As(V) and HA reasonably well.     

INTEGRATING LANDSCAPE ASSESSMENT AND HYDROLOGIC MODELING FOR LAND COVER CHANGE ANALYSIS1

ABSTRACT: Significant land cover changes have occurred in the watersheds that contribute runoff to the upper San Pedro River in Sonora, Mexico, and southeast Arizona. These changes, observed using a series of remotely sensed images taken in the 1970s, 1980s, and 1990s, have been implicated in the alteration of the basin hydrologic response. The Cannonsville subwatershed, located in the Catskill/Delaware watershed complex that delivers water to New York City, provides a contrast in land cover change. In this region, the Cannonsville watershed condition has improved over a comparable time period. A landscape assessment tool using a geographic information system (GIS) has been developed that automates the parameterization of the Soil and Water Assessment Tool (SWAT) and KINEmatic Runoff and EROSion (KINEROS) hydrologic models. The Automated Geospatial Watershed Assessment (AGWA) tool was used to prepare parameter input files for the Upper San Pedro Basin, a subwatershed within the San Pedro undergoing significant changes, and the Cannonsville watershed using historical land cover data. Runoff and sediment yield were simulated using these models. In the Cannonsville watershed, land cover change had a beneficial impact on modeled watershed response due to the transition from agriculture to forest land cover. Simulation results for the San Pedro indicate that increasing urban and agricultural areas and the simultaneous invasion of woody plants and decline of grasslands resulted in increased annual and event runoff volumes, flashier flood response, and decreased water quality due to sediment loading. These results demonstrate the usefulness of integrating remote sensing and distributed hydrologic models through the use of GIS for assessing watershed condition and the relative impacts of land cover transitions on hydrologic response.     

Preparation and characterization of mixed hydroxy-Fe-Al pillared montmorillonite with large basal spacing

IntroductionMontmorilloniteisaclaymineralwithsubstantialisomorphicsubstitution .Mesoporouspillaredmontmorillonitecanbepreparedbyintroducinggallerytemplates ,suchasquaternaryammoniumcationandlongchainamine .Thusformedorgano montmorilloniteshaveimprovedcapa…