不同垃圾渗滤液组合处理工艺中DOM的变化特征

为了快速表征垃圾渗滤液处理过程中有机物的特性变化,分别采用紫外光谱和三维荧光光谱对2种垃圾渗滤液处理工艺不同单元溶解性有机物(DOM)的变化进行了系统分析。结果表明,二级RO和厌氧+好氧+MBR+NF+RO工艺对渗滤液COD和NH3-N的去除率分别为98.7%、99.0%和98.8%、98.6%。随着处理过程的进行,2个处理工艺中DOM的SUVA254、E253/E203分别由0.74、0.33和0.46、0.12下降至0.015、0.014和0.010、0.012,有机物的芳香性和不饱和性下降,脂肪链芳香烃化合物开始增加。不同处理阶段渗透液DOM三维荧光光谱表明,随着处理过程的进行,类富里酸和类蛋白物质的含量逐渐下降,芳构化程度开始降低。其中二级RO系统对渗滤液中类富里酸物质的去除效果较好,而厌氧-好氧-MBR-NF-RO工艺中,类酪氨酸物质主要通过微生物降解去除,NF和RO膜对类富里酸和类腐殖酸物质的截留效果较好。     

乌梁素海沉积物孔隙水中溶解有机质的荧光及紫外光谱研究

运用紫外可见光吸收光谱与荧光光谱研究乌梁素海沉积物孔隙水中溶解有机质的来源、结构及腐殖化程度。r_(A，C)、HIX、SUVA₂₈₀和SUVA₂₅₄等被用于表征DOM的腐殖化程度和芳香构化程度及结构，f_450/500用于指示DOM的来源。研究结果表明：腐殖化程度最高的点为湖泊东部的W4样点，腐殖化程度最低的为总排干影响区域的W1样点。E_253/203表明湖泊入口处沉积物孔隙水中有机质主要为不可取代的芳香环结构。荧光指数f_450/500为1.57～1.82之间。总体而言，f_450/500的值更接近于1.6，处于2个端源中间，说明乌梁素海DOM中的腐殖质主要来源于陆源输入。相关分析的结果表明， DOM的不同来源对其腐殖化程度产生影响。随着腐殖化值的增大，DOM的来源由生物源向陆源过渡。     

SBR-混凝处理渗滤液过程中有机物的变化特征

考察了SBR-混凝组合工艺对垃圾渗滤液中溶解性有机物(DOM)不同分子量区间物质及组分腐殖酸(HA)、富里酸(FA)和亲水性有机物(Hy I)的去除效果,同时利用傅里叶红外光谱及三维荧光光谱对处理过程中DOM各组分变化特性进行了分析。结果表明,组合工艺对表观分子量为2 000~4 000及2 000的DOM去除率分别为89.3%和72.1%;对渗滤液DOM组分HA、FA和Hy I的去除率分别为-52.0%、73.1%和77.1%。红外光谱显示,DOM各组分都含有醇、羧酸、脂等多种有机物,SBR对糖、醇、羧酸等去除效果较好,而混凝对脂肪族及芳香族化合物去除效果较好;三维荧光光谱分析表明,经组合工艺处理,DOM各组分荧光峰强度及复杂化程度明显降低,且SBR工艺对色氨酸等类蛋白物质去除效果较好,混凝工艺对类腐殖酸、类富里酸等大分子物质的去除效果较好。     

氯消毒对城市污水中DOM的三维荧光特性影响

在城市污水二级出水氯消毒过程中,通过对溶解性有机物(DOM)的三维荧光光谱(3DEEM)分析及反应过程中三卤甲烷(THMs)生成量的连续测定,分析各类荧光物质随加氯反应时间的变化规律,探讨其与THMs生成量之间的关系,以此来推测THMs的主要前驱物质。结果表明,加氯后0～6 h内,各反应时间点三维荧光光谱图的等高线的密集程度较原二级出水明显降低,荧光峰的荧光强度减少40%～70%,说明DOM与氯发生反应,芳香构造化程度及不饱程度降低,从而失去荧光特性。其中,简单芳香族蛋白质(酪氨酸类)、腐殖酸类及富里酸类物质在加氯前后荧光强度变化较大,是生成THMs的主要前驱物质。THMs的生成量随反应时间的增加呈现明显的上升趋势,15 min内各类荧光特性有机物的荧光强度减少约50%左右,同时生成了50.17%的THMs。     

鸡粪堆肥水溶性有机物转化特性研究

采用离子色谱和三维荧光光谱,分别对鸡粪堆肥不同阶段水溶性有机物(DOM)中典型小分子有机酸、磷酸和荧光有机物进行了研究。分析显示,所研究的7种酸(乙酸、琥珀酸、苹果酸、草酸、柠檬酸、酒石酸及磷酸)中,苹果酸的含量最高(1 000 mg/L),草酸的浓度最低(3 mg/L),琥珀酸和柠檬酸未检测到。随着堆肥的进行,各种酸的含量先上升而后下降,堆肥结束降至最低;堆肥过程样品所有荧光峰强度之和与COD达到显著相关(R=0.917,P0.05),类蛋白荧光峰强度与总荧光峰强度的比值不断降低,而类富里酸荧光峰强度与总荧光峰强度的比值不断上升。结果表明,堆肥过程小分子有机酸主要出现在堆肥中期;类蛋白荧光强度或类富里酸荧光强度与总荧光强度之比可以有效表征堆肥腐熟过程。     

转运站垃圾渗滤液的深度处理及其荧光分析

采用电Fenton法对北京市某垃圾转运站垃圾渗滤液进行深度处理,运用三维荧光光谱技术对电Fenton法氧化前后溶解性有机物(DOM)的荧光特性进行了分析。结果表明,电Fenton法可使COD去除率达到88%以上,NH3-N及色度的去除率接近或等于100%。通过三维荧光特性的测定表明,电Fenton法对大分子的类富里酸有很好的去除效果。     

不同密度沉水植物腐解过程中水体DOM变化特征

选取白洋淀淀区的泥、水以及晒干的优势沉水植物金鱼藻、轮藻为研究对象,设置6个密度梯度模拟实验,分别于实验进行的50 d和100 d采集水样,运用紫外和荧光光谱技术研究沉水植物腐解阶段水体中溶解性有机质(DOM)的变化。结果显示,同步荧光光谱中,类蛋白峰荧光强度的变化不具规律性,类腐殖质峰荧光强度随密度的增加呈上升趋势,I2/I1的值随着密度的增加或时间的推移均逐渐增大;三维荧光光谱中,随着密度的增加,类富里酸荧光峰A和C的强度逐渐增加,而类色氨酸荧光峰T1的强度变化不大,腐解植物的密度大于3 kg/m3时各组均产生了类海洋腐殖质荧光峰B且强度随密度的增加逐渐增强,C峰的强度与水样中的COD和TP呈显著正相关;紫外光谱测定中,A253/A203的值随着密度的增加或时间的推移而逐渐增大,水体中的芳香族化合物也增多。     

猪场沼液处理过程中溶解性有机质的光谱学特征

猪场沼液无序排放会导致严重的水环境问题,探索猪场沼液处理过程中有机物变化的检测方法,可以为养殖废水处理和排放管控提供技术支撑。利用三维荧光光谱法和紫外—可见分光光度法对猪场沼液处理过程中溶解性有机物(DOM)的光学参数进行分析。结果表明:猪场沼液DOM的三维荧光图谱显示其主要存在类腐殖质、类色氨酸和类酪氨酸3类物质,以类腐殖质物质为主;经AO处理后猪场沼液中的类色氨酸物质部分转化为类酪氨酸物质;经序批式生物膜反应器(SBBR,由SBBR1和SBBR2组成)工艺处理后,类色氨物质全部被分解转化。猪场沼液经SBBR2和氧化塘处理后,DOM浓度和各荧光组分含量有所升高,需要进一步调试优化。DOM在254nm处的光吸收系数(A254)、各特征荧光峰强度以及特征荧光峰总强度与TN、溶解性有机碳(DOC)均具有显著正相关性,因此利用猪场沼液DOM的光谱学特征,不仅可以指示废水中DOM成分的转化状况,也可作为判断工艺流程处理效果的依据,还能较好地表征TN和DOC,具有广泛的应用前景。     

生物强化组合工艺处理河水的三维荧光及生物多样性分析

通过对受污染地表水进行生物滤池-臭氧预氧化-生物活性炭滤池工艺处理,考察生物强化条件下该项工艺对河水中主要污染物的净化效果,并采用EEM光谱技术进行了溶解性有机物变化和去除规律分析,利用PCR-DGGE技术进行各单元中微生物多样性对比分析。结果表明,生物强化组合工艺系统出水水质主要指标已达到/接近地表水环境质量标准(GB 3838-2002)Ⅳ类限值,生物强化滤池填料中微生物多样性指数和物种数均高于其他工艺单元。受污染河水DOM中主要的荧光物质有类芳香族蛋白质(荧光峰A、B和E)及类腐殖酸(荧光峰C)及类富里酸(荧光峰D),其中,A峰、B峰与E峰的中心位置分别位于225/340 nm、275/336 nm和225/298 nm,各特征荧光峰强度发生明显改变表明,污水中溶解性有机物的含量随系统处理过程而变化。     

光谱与呼吸图谱联用判定河流污染状态与自净能力

河流污染状态一般采用化学水质或生物等指标单独描述,目前尚缺少简便易行且可同时从化学与生物角度进行定量描述的指标。针对这一问题,采用三维荧光光谱、紫外吸收光谱与呼吸图谱联用的分析方法研究了纳污河、自然水体与污水处理厂各处理单元水样的溶解性有机物(DOM)的空间分布特征与河流微生物的呼吸特征。结果表明,光谱法可快速对河流有机污染物的种类进行辨别,而呼吸图谱具有识别河流自净能力的特点,其中类色氨酸(T峰与D峰)、类酪氨酸(S峰)、腐殖质(C峰)、富里酸(A峰)是指示不同污染程度的重要指标。通过呼吸图谱与荧光光谱联用(T峰)可快速对污染程度和自净能力进行区分,从而为河流的管理与自净能力的恢复提供参考。     

大气二氧化硫浓度的光学测定方法

介绍了测定二氧化硫浓度的几种光学方法 ,指出了目前一些化学方法的局限性 ,特别对紫外荧光法的原理、二氧化硫的吸收光谱以及荧光光谱进行分析探讨 ,设计了实验分析系统 ,得出该方法具有操作简单、灵敏度高、可实时在线的智能化优点 ,将会成为今后研究的主导方向。     

共振能量转移同步荧光猝灭法测定水体中孔雀石绿

采用L-半胱氨酸、巯基乙酸为稳定剂水相合成Cd Te量子点,且以Cd Te量子点为能量供体、孔雀石绿为能量受体建立荧光共振能量转移体系,从而实现孔雀石绿含量的同步荧光猝灭法测定。结果表明,当固定波长差为220 nm时,Cd Te量子点的同步荧光最大发射波长位于323 nm。在最优实验条件下,体系的同步荧光淬灭强度与孔雀石绿的浓度在0.5~10.0μmol/L范围内呈良好的线性关系,相关系数为0.9995,方法的检出限为10 nmol/L。该方法用于实际水样中孔雀石绿含量的测定,加标回收率为94%~105%。     

Comparative analysis of the structure of carbon materials relevant in combustion

The determination of the structure of carbon materials is an analytical problem that join the research scientific communities involved in the chemical characterization of heavy fuel-derived products (heavy fuel oils, coal-derived fuels, shale oil, etc.) and of carbon materials (polycyclic aromatic compounds, tar, soot) produced in many combustion processes.

The knowledge of the structure of these “difficult” fuels and of the carbon materials produced by incomplete combustion is relevant to research for the best low-environmental impact operation of combustion systems; but an array of many analytical and spectroscopic tools are necessary, and often not sufficient, to attempt the characterization of such complex products and in particular to determine the distribution of molecular masses.

In this paper the size exclusion chromatography using N-methyl-pyrrolidinone as eluent has been applied for the characterization of different carbon materials starting from typical carbon species, commercially available like polyacenaphthylene, carbon black, naphthalene pitch up to combustion products like soot and soot extract collected in fuel-rich combustion systems. Two main fractions were detected, separated and molecular weights (MWs) determined by comparison with polystyrene standards: a first fraction consisted of particles with very large molecular masses (>100 000 u); a second fraction consisted of species in a relatively small MW range (200–600 u). The distribution of these fractions changes in dependence on the carbon sample characteristics.

Fluorescence spectroscopy applied on the fractions separated by size-exclusion chromatography has been used and comparatively interpreted giving indications on the differences and similarities in chemical structure of such different materials.     

Toxic interaction mechanism of two fluoroquinolones with serum albumin by spectroscopic and computational methods

To evaluate the toxicity of two fluoroquinolones (FQs), ciprofloxacin (CPFX), and enrofloxacin (ENFX), at the protein level, their binding modes with bovine serum albumin (BSA) were characterized by multiple spectroscopic and molecular docking methods under simulated physiological conditions. On the basis of fluorescence spectra, we concluded that both FQs greatly quenched the fluorescence intensity of BSA, which was attributed to the formation of a moderately strong complex mainly through electrostatic interactions. Besides, CPFX posed more of an affinity threat than ENFX. The molecular docking methods further illustrated that both CPFX and ENFX could bind into the subdomain IIIA of BSA and interact with Arg 508 and Lys 437, the positively charged residues in protein. Furthermore, as shown by the synchronous fluorescence, UV-Visible absorption and circular dichroism data, both CPFX and ENFX could lead to the conformational and microenvironmental changes of BSA, which may affect its physiological function.     

不同来源溶解态腐殖酸与Cu2+作用的荧光特性

利用三维荧光等高线图以及其所确定的荧光峰荧光强度随溶液化学条件的变化，研究不同来源溶解态腐殖酸与Cu²⁺作用的荧光特性。研究结果表明：溶解态天然腐殖酸中主要存在二类发射荧光的有机物官能团能与Cu²⁺发生络合作用。位于激发波长和发射波长分别为271～281 nm和335～351 nm的荧光峰1所代表的有机物官能团是与Cu²⁺发生络合配位的主要点位；pH值为4～6时，其络合受pH值影响较显著；而受溶液离子强度影响较小。位于激发波长和发射波长分别为223～246 nm和335～371 nm的荧光峰2所代表的有机物官能团与Cu²⁺的络合作用受溶液pH值影响较小，受溶液离子强度影响较显著。溶解态商品腐殖酸荧光峰1′所代表的有机物官能团与Cu²⁺的络合作用荧光特性，与天然腐殖酸荧光峰1所代表的有机物官能团和Cu²⁺络合作用荧光特性相似，在pH值为3～7时，其络合受pH值影响较显著。     

A rapid and sensitive fluoroimmunoassay based on quantum dot for the detection of chlorpyrifos residue in drinking water

A rapid and sensitive indirect competitive fluorescence-linked immunosorbent assay (cFLISA) method based on quantum dots as the fluorescence label coupled with secondary antibody (Ab₂) for the detection of chlorpyrifos in drinking water has been developed. The cFLISA method allowed for chlorpyrifos determination in a liner working range of 15.2–205.5 ng mL^?1. The 50 % inhibition value (IC₅₀) and the limit of detection (LOD) of the cFLISA were 50.2 ng mL^?1 and 8.4 ng mL^?1, while the IC₅₀ and the LOD of the conventhional enzyme linked immunosorbent assay (ELISA) were 95.3 ng- mL^?1 and 16.2 ng mL^?1, respectively. When the concentrations of chlorpyrifos were 200, 100 and 50 ng mL^?1, the recoveries ranged from 90.8 % to 108.2 % with a coefficient of variation (CV) of 7.5 %–15.2 %. In water sample analysis, the results of cFLISA were similar to those obtained from a cELISA and a high performance liquid chromatography (HPLC) method, while the detection time by cFLISA was reduced 0.5 h compared with ELISA. It showed that cFLISA could be used as a new screening method for the detection of pesticide residue.     

Effects of ozone on chlorophyll and quantum yield of tobacco (Nicotiana tabacum L.) varieties

Plants of Bel-W3 and of seven commercial tobacco varieties (Nicotiana tabacum L.) were exposed to two relatively low ozone concentrations (90 or 135 ppb) for 20 consecutive days, for 8 h per day. Ozone caused necrotic and chlorotic spots, acceleration of leaf senescence, depression of photosynthetic mechanism, chlorophyll diminution and greater destruction of chl a than of chl b. The higher sensitivity of chl a was also confirmed by exposure of segments of leaves in test tubes to high ozone concentration (>1000 ppb) as well as by bubbling of ozone in extracts of chlorophyll in vitro. The quantum yield (QY) of photosynthesis was positively correlated with the chlorophyll content and negatively correlated with the visible injury and the chl b/a ratio.     

荧光染色法测定活性污泥中的活性生物量

活性污泥中活性微生物量是表征污染物去除能力的重要指标。探索了荧光染色法直接检测活性细菌的原理和测定方法,结果表明,大肠杆菌、唾液链球菌和铜绿假单胞杆菌的活菌细胞浓度与荧光光强的线性相关度都超过0.95;在惰性颗粒物浓度为20 mg/L到60 mg/L的范围内,其对荧光光强的影响可通过线性关系修正;搅拌速度为1 000 r/min且搅拌10 min时前处理效果最好。     

Interaction of tebuconazole with bovine serum albumin: determination of the binding mechanism and binding site by spectroscopic methods

Abstract

This study investigates the interaction between tebuconazole and bovine serum albumin (BSA) in a physiological buffer (pH = 7.4) using the fluorescence quenching method to obtain the apparent binding constants (K) and number of binding sites (n) in the interaction between tebuconazole and BSA. The results revealed that tebuconazole can quench the intrinsic fluorescence of BSA through a static quenching procedure. It also shows that the thermodynamic parameters of enthalpy change (ΔH) and entropy change (ΔS) are negative, indicating that the interaction of tebuconazole with BSA is mainly driven by van der Waals forces and hydrogen bonds. The process of binding was a spontaneous process in which Gibbs free energy change was negative. The distance of r between the donor (BSA) and acceptor (tebuconazole) was calculated to be 0.68?nm based on Forster’s non-radiative energy transfer theory. Analysis of synchronous fluorescence, three-dimensional fluorescence and circular dichroism (CD) spectra demonstrates that tebuconazole can induce conformational changes of BSA.