硫化纳米零价铁(S-nZVI)对水体中镉的去除研究

由于矿山开采、工业废水排放及农业施肥等人类活动,使得我国镉污染日益突出.本研究采用液相还原法制备硫化纳米零价铁(S-nZVI),研究其对Cd的去除行为.考察了不同硫化剂、合成方法、S/Fe比(物质的量比)及pH对Cd去除的影响,并采用扫描电子显微镜(SEM)、拉曼光谱(Raman)、X-射线衍射(XRD)等技术对反应前后的材料进行表征,结合批实验结果探讨Cd的去除机理.结果表明,采用一步法以硫化钠(Na_2S)为硫化剂合成的S-nZVI对Cd的去除效率远高于其它方法,去除容量可达385.6 mg·g~(-1).反应120 min后,S-nZVI对Cd的去除率随S/Fe比的增加而升高,S-nZVI反应体系受pH影响较小.材料表征结果显示,S-nZVI颗粒由Fe~0、Fe_3O_4、FeS组成,其中,FeS的含量随S/Fe比的升高而增加.S-nZVI对Cd的去除机理主要是Cd将FeS中的Fe置换,与S结合形成稳定的CdS.     

纳米铁锰氧化物对钒的吸附特性研究

为寻求处理土壤和地下水钒污染的吸附剂,采用模拟实验,开展了纳米铁锰氧化物(MnFe_2O_4)对五价钒(V~(5+))的吸附特征研究,分析了纳米铁锰氧化物浓度、pH值、时间、温度和初始钒浓度等因素对MnFe_2O_4吸附V~(5+)的影响,以揭示纳米铁锰氧化物的吸附动力学及热力学等特征,并通过扫描电镜(SEM)和红外光谱(IR)等表征方法分析了纳米铁锰氧化物吸附V~(5+)的机理.结果表明,在初始钒溶液为100 mg·L~(-1),MnFe_2O_4加入量为0.1 g,pH=4,温度为25℃的条件下,吸附过程在24 h达到平衡,且此条件下有最大吸附值和吸附率,分别为15.14 mg·g~(-1)和60.54%.纳米铁锰氧化物吸附钒的动力学过程符合伪二级动力学模型,等温吸附线符合Langmuir模型.热力学研究表明,升高温度有利于吸附,吸附过程为吸热过程.由扫描电镜结果可知,纳米铁锰氧化物有较大的比表面积,可提供较多的活性位点.因此,纳米铁锰氧化物可作为一种吸附材料用于钒污染废水处理.     

亚热带河口陆基养虾塘水体CDOM三维荧光光谱平行因子分析

利用三维荧光光谱平行因子分析(EEMs-PARAFAC)技术,对我国亚热带地区闽江、木兰溪、九龙江河口滨海陆基养虾塘水体的有色溶解性有机质(CDOM)进行了组分及来源分析.研究表明从养虾塘水体CDOM荧光光谱中解析出4个有效PARAFAC荧光组分,包括2种类蛋白质物质和2种类腐殖酸物质,其中类蛋白质组分是河口陆基养虾塘水体中CDOM的主要组成部分.水体的荧光指数FI和自生源指标BIX表明河口区滨海陆基养虾塘水体中CDOM的强自生来源贡献.而腐殖化指标HIX表明养殖塘水体具有弱腐殖化特征.类蛋白质组分与类腐殖质组分之间可能具有相同的来源属性和地化行为,盐度与CDOM呈现极显著负相关,而DOC与CDOM中类腐殖质组分(C2、C3)呈现显著正相关.本研究为进一步揭示养虾塘水体CDOM的光化学性质提供了科学依据.     

模拟酸雨淋溶条件下紫壤淋出液中溶解性有机质的三维荧光特性

运用三维荧光技术分析了模拟酸雨淋溶紫壤淋出液中溶解性有机质（dissolved organic matter,DOM）的组分与酸度及淋溶量的关系.研究结果表明,模拟酸雨淋溶紫壤淋出液中DOM荧光峰主要为类胡敏酸和类富里酸,荧光峰的中心位于Ex/Em=305—370 nm/420—450 nm和Ex/Em=260—270...     

河口区有色溶解有机物(CDOM)三维荧光光谱的影响因素

结合在厦门湾九龙江口的现场调查与实验室分析,对目前河口区CDOM三维荧光光谱(excitation-emission matrix spectroscopy,EEMS)分析的一些影响因素(主要是离子强度、浓度效应、不同孔径滤膜过滤)进行了探讨.结果表明,CDOM的EEMS与样品中离子强度关系不大,说明在河口区河海水混合过程中,仅仅由于水体盐度的变化不会造成CDOM光学特征的明显变化.河端CDOM的荧光强度随物理稀释倍数的增大成相应比例的减小,稀释对EEMS的影响仅仅体现在荧光强度上,显示河口区的CDOM样品不存在荧光淬灭效应.九龙江口河流端样品中共含有类腐殖质(C、A)及类蛋白质(T1、T2)4种荧光团,随着混合样品中海水体积分数的增大,样品荧光强度逐渐降低,代表海洋来源的类腐殖质荧光峰M逐渐显露,T1峰逐渐高于A峰.这说明从河端至外海CDOM的组成结构发生了一系列的变化,来源上逐渐完成了以陆源为主到海源为主的转变;性质上逐渐完成了以类腐殖质荧光团为主到类蛋白质荧光团为主的转变.在中、高盐度区,0.2μm的Millipore聚碳酸酯滤膜可以很好地去除水体散射对EEMS的干扰,EEMS(0.2μm)比EEMS(0.7μm)更为规则,各峰的显示更加清晰.不同荧光基团的划分更加容易.无论高、中、低盐度站位,0.7μm滤膜过滤的样品,其CDOM荧光强度都要略高于0.2μm滤膜过滤的样品,2种不同孔径滤膜过滤对CDOM荧光测定带来的差异不可忽略.     

Correction model for CO detection in the coal combustion loss process in mines based on GWO-SVM

Accurate detection of CO gas is crucial to the prevention of coal combustion. Tuneable diode laser absorption spectroscopy (TDLAS) is a reliable method for CO detection during coal combustion. The influences of temperature and pressure cause changes in the line strength and linewidth of the index gases’ absorption spectra, leading to sizable measurement errors. To correct the distortion of the CO absorption spectrum caused by temperature and pressure fluctuation, a compensation model based on the grey wolf optimizer–support vector machine (GWO–SVM) was proposed. The results were compared with those of the single SVM, the back propagation neural network (BPNN), and multiple regression analysis (MRA). MRA was revealed to result in the lowest accuracy, which indicated that MRA is not ideal for compensation in TDLAS. The hyperparameter selection of the SVM had the disadvantages of randomness and blindness, which led to instability and large errors. The BPNN achieved better correction in the training stage, but severe overfitting occurred in the testing stage. The modified results revealed that the GWO–SVM model had higher accuracy and stability than the other models. It effectively inhibited the effects of temperature and pressure on the measured concentration and greatly improved the measurement accuracy. The equipment is thus suitable for CO gas detection with the aim to preventing coal combustion loss, and it can be further applied to loss prevention in other process fields.     

Adsorption behavior of condensed phosphate on aluminum hydroxide

Sodium pyrophosphate （pyro-P, Na4P2OT）, sodium tripolyphosphate （tripoly-P, Na3P3O10）, and sodium hexametaphosphate （meta-P, （NaPO3）6） were selected as the model compounds of condensed phosphate to investigate the adsorption behavior of condensed phosphate on aluminum hydroxide. The adsorption was found to be endothermic and divisible into two stages： （1） fast adsorption within 1 h; and （2） slow adsorption between 1 and 24 h. The modified Freundlich model simulated the fast adsorption stage well; the slow adsorption stage was described well by the first-order kinetics. The activation energies of pyro-P, tripoly-P, and meta-P adsorption on aluminum hydroxide were determined to be 20.2, 22.8 and 10.9 kJ/mol P adsorbed, respectively, in the fast adsorption stage and to be 66.3, 53.5 and 72.5 kJ/mol P adsorbed, respectively, in the slow adsorption stage. The adsorption increased the negative charge of the aluminum hydroxide surface. Transmission electron microscopy and energy dispersive X-ray analysis analyses provided evidence that the adsorption was not uniform on the surface and that the small crystals contributed more to the fast adsorption than the normal sites did. The results from X-ray fluorescence spectrometry and X-ray photoelectron spectroscopy tests also revealed the uneven adsorption of condensed phosphate as a function of the penetration depth. More condensed phosphates were adsorbed on the outer surface of aluminum hydroxide than in its inner parts.     

Detection of intermediates in the TiO2-assisted photodegradation of Rhodamine B under visible light irradiation

The photocatalytic degradation of dye Rhodamine B （RhB） in the presence of TiO2 nanostdpe or P25 under visible light irradiation was investigated. The degradation intermediates were identified using Infrared spectra （IR spectra）, ^1H nuclear magnetic resonance （^1HNMR） spectra, and gas chromatography-mass spectroscopy （GC-MS）. The IR and the ^1HNMR results showed that the large conjugated chromophore structure of RhB was efficiently destroyed under visible light irradiation in both the photocatalytic systems （TiO2 nanostfipe or P25 and Rhodamine B systems）. GC-MS results showed that the main identified intermediates were ethanediotic acid, 1,2-benzenedicarboxylic acid, 4-hydroxy benzoic acid and benzoic acid, which were almost the same in the TiO2 nanostdpes and P25 systems. This work provides a good insight into the reaction pathway（s） for the TiO2-assisted photocatalytic degradation of dye pollutants under visible light irradiation.     

恒能量同步荧光光谱法测定水体中多环芳烃

建立了胶束溶液中多环芳烃混合物同时测定的恒能量同步荧光分析法,方法简便快速,无需对混合物进行分离,就可实现11种组分的同时鉴别和定量测定,方法的检出限在1.3×10-11～4×10-9g/mL,标准偏差为1.03～1.73,方法应用于分析河水样、污水样中的多环芳烃的效果良好,回收率分别为77.88%～120.13%、6...     

粉煤灰对废水中的石油样品的吸附去除

用紫外分光光度法分析经粉煤灰处理后含油废水中的油样含量。考察了pH值,粉煤灰使用量,接触时间,废水中油样的初始浓度,温度等因素对粉煤灰除油率的影响。结果表明：用石油醚溶解的油样紫外光最佳吸收波长为272．5nm;中性条件下,粉煤灰对废水中的油样有较好的去除率;粉煤灰使用量增大、接触时间增加、温度升高有利于粉煤灰对油样的吸附去除;废水中油样含量越高,粉煤灰对其去除率越低。