西安市冬季道路扬尘中有机质组成特征及其氧化潜势

道路是城市人群户外活动暴露大气颗粒物的主要场所,道路颗粒物中含有的某些氧化活性物质是诱导产生活性氧,进而危害人体健康的重要组分.探索西安市道路扬尘中水溶性(WSM)和甲醇溶性组分(MSM)中有机质组成特征及其氧化潜势(OP),并基于平行因子分析(PARAFAC)研究了有机组分以及分布状况,还分析有机质类型与OP之间的相关性.结果表明,西安市道路扬尘中水不溶性组分含有更多的发色团有机物质,其总浓度平均值为(4.71±1.27)×10⁴ R.U.,是WSM的12倍[(3.96±1.10)×10³ R.U.],其中低氧化性类腐殖质(HULIS)是主要有机质(占总有机质的34.8%～43.7%).聚类分析结果显示西安市道路扬尘中有机质的重要来源为燃料燃烧和工业生产.扬尘氧化毒性(以DTT计)的平均值是(0.34±0.08) pmol·(min·μg)^-1,其中水不溶性组分提供了扬尘颗粒物总氧化毒性的70%,是水溶性组分的2.4倍.扬尘颗粒物氧化毒性的主要前驱物为金属元素,特殊类型的有机物质也是重要氧化毒性前驱物质之一,其中发色团...     

Rapid discrimination of plastic packaging materials using MIR spectroscopy coupled with independent components analysis (ICA)

Plastic packaging wastes increased considerably in recent decades, raising a major and serious public concern on political, economical and environmental levels. Dealing with this kind of problems is generally done by landfilling and energy recovery. However, these two methods are becoming more and more expensive, hazardous to the public health and the environment. Therefore, recycling is gaining worldwide consideration as a solution to decrease the growing volume of plastic packaging wastes and simultaneously reduce the consumption of oil required to produce virgin resin. Nevertheless, a major shortage is encountered in recycling which is related to the sorting of plastic wastes. In this paper, a feasibility study was performed in order to test the potential of an innovative approach combining mid infrared (MIR) spectroscopy with independent components analysis (ICA), as a simple and fast approach which could achieve high separation rates. This approach (MIR-ICA) gave 100% discrimination rates in the separation of all studied plastics: polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polystyrene (PS) and polylactide (PLA). In addition, some more specific discriminations were obtained separating plastic materials belonging to the same polymer family e.g. high density polyethylene (HDPE) from low density polyethylene (LDPE). High discrimination rates were obtained despite the heterogeneity among samples especially differences in colors, thicknesses and surface textures. The reproducibility of the proposed approach was also tested using two spectrometers with considerable differences in their sensitivities. Discrimination rates were not affected proving that the developed approach could be extrapolated to different spectrometers. MIR combined with ICA is a promising tool for plastic waste separation that can help improve performance in this field; however further technological improvements and developments are required before it can be applied at an industrial level given that all tests presented here were performed under laboratory conditions.     

溶解性有机物在土壤含水层处理系统中的变化

通过实验室模拟土壤含水层处理(SAT)的土壤柱系统研究了二级处理出水中溶解性有机物(DOM)的荧光特性在SAT系统中的变化.利用XAD树脂将二级处理出水中的DOM分为5个部分:疏水性有机酸(HPO-A),疏水性中性有机物(HPO-N),过渡亲水性有机酸(TPI-A),过渡亲水性中性有机物(TPI-N)和亲水性有机物(HPI).结果表明,TPI-N中的类芳香族蛋白质荧光物质在SAT系统中优先去除.经过SAT系统处理后,类芳香族蛋白质荧光物质和类溶解性微生物代谢产物荧光物质在HPO-A,HPO-N,TPI-A和HPI中的相对含量升高.各组分中带有3~5个稠合苯环的荧光物质,以及激发波长/发射波长(λex/λem)=390~410nm/456~476nm的类腐殖酸荧光物质在SAT系统中的去除率低于相应组分中以溶解性有机碳(DOC)表征的整体有机物的去除率.不同组分中的其他荧光物质在SAT系统中去除行为不同.     

三维荧光光谱结合荧光区域指数分析方法评估堆肥腐熟度

评估堆肥腐熟度是确保堆肥产品质量的重要保证. 采用三维荧光光谱结合荧光区域指数分析方法快速评估菜粕和稻糠堆肥过程中的腐熟度. 结果表明:菜粕和稻糠堆肥可在16 d内完成一次发酵,其中第7～14天为高温期(>50 ℃,共8 d);随后,堆体进入降温期,第16天降至32 ℃. 堆肥初期(第0～6天)DOC(溶解性有机碳)、DON(溶解性有机氮)质量浓度和EC(电导率)先稳定在一个较低的水平;在堆肥高温期(第7～14天),ρ(DOC)、 ρ(DON)和EC则分别迅速升至10.47 mg/L、7.52 mg/L和5.76 mS/cm. 堆肥腐熟度相关指标〔即ρ(DOC)、 ρ(DON)和EC〕与FRI(荧光区域指数)方法中P_Ⅲ,n、P_Ⅴ,n、P_Ⅴ,n/P_Ⅲ,n指标的变化趋势一致,并且具有极显著相关性(R>0.942,P<0.01);而与P_Ⅰ,n变化趋势相反,也具有显著的相关性(R<-0.871,P<0.05). 因此,P_Ⅲ,n、P_Ⅴ,n、P_Ⅴ,n/P_Ⅲ,n与P_Ⅰ,n可以用于表征堆肥腐熟度.      

滇池典型陆生和水生植物溶解性有机质组分的光谱分析

应用紫外-可见光谱、傅里叶红外光谱与三维荧光光谱,对采自滇池外海及湖滨农田的2种典型陆生植物(玉米、紫茎泽兰)和5种水生植物(芦苇、水红花、水葫芦、眼子菜、茭草)所提取的DOM(溶解性有机质)组分进行了光谱分析. 结果表明,陆生与水生植物DOM的紫外-可见光谱曲线基本类似,吸光度均随波长的增加而降低. 陆生植物DOM的SUVA₂₅₄(单位溶解性有机碳浓度下波长254 nm处吸收系数)值大于水生植物,表明滇池外源输入的DOM腐殖化程度大于内源. 植物叶中DOM的A₂₅₀/A₃₆₅(A₂₅₀、A₃₆₅分别为波长250和365 nm处的紫外吸光度比值)小于茎,表明叶中DOM的芳香性和分子量都大于茎. 陆生与水生植物DOM均有相似的红外特征峰带,其中—COO-、—CH₂、—CO、—OH、—NH₂的特征峰明显,表明它们是构成陆生和水生植物DOM的主要官能团. 三维荧光光谱分析表明,陆生植物茎的DOM中含有类富里酸物质,而叶的DOM中含有类腐殖酸物质. 水生植物除了水葫芦叶的DOM中含有类腐殖酸物质外,其他样品无论茎、叶都含有类富里酸物质. 除水葫芦叶外,同种植物茎的DOM中存在类色氨酸物质,而叶中不存在.      

Analysis of particulates by Raman microprobe†

We describe a new technique of local analysis of heterogeneous samples which is analogous to the electron or ion microprobe but is based on molecular spectra of materials to characterize the different components of a microscopic sample and (or) to obtain images giving their surface distribution.

The sample is illuminated by a laser beam causing characteristic Raman lines of the different components to be emitted. Using these Raman lines, the components can then be detected, identified and located. For this purpose, the microscopic area of the preparation which is illuminated is analysed by a conventional optical microscope coupled with a tunable band pass filter and a multichannel or monochannel detection system.

One main advantage of this technique is the ability to study samples not under vacuum but in air, under a controlled atmosphere or even inside a transparent matrix. Normal Raman spectra can be obtained from particles of 1 μm size and larger, and are the basis for the qualitative identification of molecular constituents. The technique has been applied to molecular microanalysis of matter in the particulate form (i.e., Airborne particles—stack particulates, flyash, asbestos minerals, defects and inclusions in industrial materials,...). It is especially interesting for organic materials which are not detected by other methods. Different examples illustrate this technique.     

Surface characterization of acid-oxidized multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWNTs) oxidized with sulfuric acid, nitric acid, and the mixture of sulfuric and nitric acids were characterized by thermogravimetric analysis (TGA), Raman spectroscopy, elemental analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. The TGA data showed that the MWNTs were more resistant to oxidation than C₆₀ or activated carbon fibers. Catalyst particles could be removed by the oxidants containing sulfuric acid, and thus indicative of the tip opening of MWNTs. The sulfuric acid had a propensity to create defect sites and introduce the surface oxides at those defects that already exist or be newly generated on MWNTs. However, the acid mixture could open the caps of MWNTs but preserve the structure homogeneity. The treatment with nitric acid gave rise to the highest bulk oxygen content in MWNTs, while the most abundant surface oxides were provided by sulfuric acid oxidation. In addition, nitric acid exhibited the best ability to transform the phenolic groups into carboxyl groups.     

Application of an inclusion complex for determination of dithianon residues in water and fruits

A 3,3′-benzidine/β-cyclodextrin fluorescence derivative (BCDFD) was prepared and characterized by means of elemental analysis and ¹H NMR. An inclusion complex was formed between BCDFD and the pesticide dithianon based on the internal cavity of β-cyclodextrin (β-CD), and the binding constant (K_S ) of the inclusion complex was investigated. The inclusion complex could be applied for the determination of dithianon residues. Based on this, a sensitive method for the determination of dithianon was established. The linear dynamic range was from 0.63 to 12.5?mg?L^?1 with a correlation coefficient of 0.9927. The limit of detection for an aqueous solution of standard and the relative standard deviation (RSD) were 10.6?µg?L^?1 and 0.76%, respectively. The proposed method has been successfully applied for the determination of dithianon residues in water and fruit samples with satisfactory results, and recoveries in the range of 96.0–108% were obtained. The method is rapid, direct, economical, and sensitive for dithianon analysis.     

Dissipation of fluvalinate and characterisation of its degradation products on chickpea crop by mass spectroscopy

Fluvalinate was applied on chickpea crop at (i) 0.056, (ii) 0.112 and (iii) 0.56 kg a.i. ha^‐1 to evaluate its rate of dissipation. Two major degradation products of fluvalinate formed on the crop were identified and characterised as phenoxybenzoic acid and 2‐[2‐chloro‐4‐(trifluoromethyl)anilino]‐3‐methylbutanoic acid. They were estimated in day‐5 and day‐10 samples of chickpea crop as their methyl esters by gas liquid chromatography.     

河流底泥中溶解性有机物的释放途径及影响因素研究

以沈阳市新开河底泥为研究对象,考察了河流底泥中溶解性有机物（DOM）的释放途径,并分析了时间、温度、pH值、底泥粒径、盐度和上覆水体中溶解性有机碳（DOC）浓度对河流底泥DOM释放的影响.此外,还研究了底泥释放对上覆水体中DOM的光谱学特性的影响.结果表明,对底泥DOM释放影响程度最高的是间隙水的混合作用,其次是底泥表层静态释放,而悬浮颗粒释放对底泥DOM释放的影响程度较小.底泥DOM的释放量随温度,pH值,底泥粒径,盐度的增大而增大.上覆水体DOC浓度较高时,DOM由上覆水体向底泥迁移.扰动作用能够影响底泥DOM的迁移.类富里酸荧光物质和类芳香族蛋白质荧光物质是底泥DOM中的主要荧光物质.河流底泥DOM向上覆水体释放的主要是激发波长分别为280~300nm和320~380nm的荧光物质.并且,扰动作用促进了荧光物质由底泥向上覆水体的释放.