藻类的三维荧光光谱辨别及算法研究

采用三维荧光技术分析了栅藻,微囊藻和小环藻的色素组成.通过对3种藻的特殊激发谱线的分析,采用435,485,525,630nm作为叶绿素a、叶绿素b、叶绿素c与藻蓝胆素的特征激发波长,采用684nm作为发射波长,建立了3种藻叶绿素浓度与藻密度的荧光强度矩阵方程.根据水样的标准荧光光谱和4个激发波长可以计算出每种藻类的叶绿素浓度与藻密度.     

渤海油类测试中标准油的选择研究

本文对渤海油类测试中标准油的选择进行研究。选取5种原油,11种成品油,1种人工配制油。荧光光谱技术:分别记录310nm、290nm、250nm激发波长时荧光发射谱;室内模拟水中溶解/分散油、沉积物中油的荧光发射谱,获得各类型油的最佳荧光发射波长、发射特性及光谱指纹图。 记录并剖析了渤海海区各站位水体中溶解/分散油、沉积物中油的各波长荧光发射谱。参照ASTM(美国试验与材料学会)溢油鉴别原则,进行了峰形,峰位,指纹综合分析,认为在渤海海区油污染测试中,可用20号重柴油作标准油。     

污染扩散的示踪剂罗丹明—B的试验

荧光分光光度计激发光为552nm,狭缝宽为10nm;发射光为578nm,狭缝宽为10nm时,可准确测定示踪剂罗丹明-B 的浓度,方法简捷,最低检出限为0.15μg/l。     

流动注射荧光检测法测定河水中溶解的腐殖质

河水中溶解的腐殖质是构成溶解有机碳的主要成分,一般由腐殖酸和灰黄霉酸组成。这些物质的定量测定是河流管理的重要依据之一。目前测定腐殖质的方法主要是紫外吸收测定法和荧光测定法。最近W.A.McCrum建立了一种流动注射荧光检测法,该方法是由Brun和Millburn设计的自动分析仪发展而来的。手工操作可采用简易的单线流动注液系统,自动分析可采用由集合管组成的自动连续流动注液系统。检测器是装有高压液相色谱流动池的荧光分光光度计。通过样品的荧光响应(激发波长270nm,发射波长460nm)与技术级腐殖酸标准的荧光响应比较而测定。 测定腐殖质时使用含有柠檬酸钠-酒石酸钾钠络合物的硼酸钠缓冲液(pH10.5),柠檬酸钠-酒石酸钾钠络合物能消除三价铁的干扰并防止金属氢氧     

分子荧光光度法直接测定水中十二烷基本磺酸钠

本文用分子荧光光度法直接测定水中十二烷基苯磺酸钠的含量,不需显色与萃取。本法简便、快速、最大激发波长为EX=230nm,最大发射波长EM=290nm。检出限达32μg/L,回收率为100～101%。     

冰封期前后河流底泥中溶解性有机物组分的荧光特性的变化

以沈阳市新开河为研究对象,考察了冰封期前、后河流底泥中溶解性有机物(DOM)组分荧光特性的变化.按照DOM在XAD树脂上的吸附特性将其分为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:HPO-A是河流底泥中的主要DOM组分,在冰封期前、后分别占溶解性有机碳(DOC)的41.2%~69.5%和38.9%~63.9%.冰封期前河流底泥中的DOM及HPO-A、HPI的DOC值均高于冰封期后.三维荧光光谱结果显示,冰封期前、后河流底泥DOM组分中含有类腐殖酸荧光物质,类富里酸荧光物质,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,并且类芳香族蛋白质荧光物质在各DOM组分中的含量最高.冰封期后HPO-A、HPI中荧光物质的含量低于冰封期前.同步荧光光谱结果显示,在冰封期河流底泥DOM组分中激发波长分别为285~295 nm和330~350 nm的荧光物质向水体释放,导致其在底泥DOM组分中相对含量的显著降低.     

污水氯和二氧化氯消毒过程中溶解性有机物变化的三维荧光光谱解析

采用三维荧光光谱（3DEEM）技术对污水在氯和二氧化氯消毒过程中溶解性有机物（DOM）的变化进行了初步解析.结果表明,与饮用水、地表水等不同,生物处理出水含有较多的芳香族蛋白质和溶解性微生物代谢产物,且其中的腐殖质主要为生物源,芳香性较弱.在氯和二氧化氯消毒后,污水DOM中的芳香族蛋白质和微生物代谢产物类物质的荧光峰发生蓝移,即峰值的激发或发射波长减少了几个nm,这可能由芳香环结构的破坏引起;而腐殖质类物质的荧光峰发生红移,即峰值的激发或发射波长增加了几个到二十几个nm,此现象与地表水相反,可能与腐殖质的来源不同有关.与遗传毒性的变化类似,氨氮对水样氯消毒后的荧光变化有明显影响,但对二氧化氯消毒后的荧光变化无明显影响.     

海上溢油鉴别方法的研究——用荧光分光光度法对各种类型的石油进行分类的研究

对各种类型的原油及成品油的分类的研究是用荧光分光光度法进行的。 首先,我们以无荧光环已烷为溶剂配制了浓度分别为1/1万,1/2万和1/10万的标准油溶液。 我们用日立650—60型荧光分光光度计进行了测空,在激发波长340nm,对发射波长300—500nm进行扫描。 检查了约七十种原油,发现它们按荧光光谱的峰值比440/385可分为六类(3—8类)。对深色成品油(重紫油,船用紫油和用过的润滑油)来说,可用它们的谱图和440/385峰值比来鉴定其类似性。但对淡色成品油(汽油,灯油,轻油和新的润滑油)则必须用特殊操作进行分析。 本法可以当做一种鉴定手段应用于鉴别排放到海洋中的原油和成品油的种类和类似性。     

河口区溶解有机物三维荧光光谱的平行因子分析及其示踪特性

利用激发发射矩阵荧光光谱(EEMs)并结合平行因子分析(PARAFAC),研究了九龙江口有色溶解有机物(CDOM)的荧光组分特征及其河口动力学行为,并探讨其作为河口区有机污染示踪指标的可行性.利用PARAFAC模型识别出九龙江口CDOM由2类4个荧光组分组成,即类腐殖质荧光组分C1(240,310/382nm)、C2(230,250,340/422nm)、C4(260,390/482nm)及类蛋白质荧光组分C3(225,275/342nm).模型结果表明,传统寻峰法指认的短波类腐殖质A峰区域(240～290/380～480nm)实际上并非一个单独的荧光峰,而是若干荧光组分的组合,并且它与传统上指认的长波区海源类腐殖质M峰、陆源类腐殖质C峰之间存在内在联系.包含M峰的C1组分在河口区随盐度增加呈稀释降低趋势,表明M峰并不能被认为是海洋来源的专有特征峰.类腐殖质组分C1和C2在盐度6的河口最大浑浊带区表现出一定的添加行为,之后在河口混合过程中呈保守行为,而类腐殖质荧光组分C4则在整个河口混合过程中都呈保守行为.类蛋白质荧光组分C3在河口混合过程中呈不保守行为,并且在总荧光组分中所占比例在高盐度区呈上升趋势.EEM-PARAFAC不仅可示踪九龙江不同支流DOM的特征,并且还可很好地示踪九龙江口的有机污染程度.     

荧光溶解性有机质EEMs的新旧自组织映射图解析方法比较研究

目前,对地表水体荧光溶解性有机质(Fluorescent Dissolved Organic Matter,FDOM)三维激发发射矩阵(Excitation-Emission Matrices,EEMs)数据的解析仍旧存在挑战.本文结合原始EEMs和从中分离的荧光平行因子分析(Parallel Factor Analysis,PARAFAC)组分,利用自组织映射图(Self-Organizing Maps,SOM),开展了基于传统EEMs-SOM和新型PARAFAC-SOM神经网络模型的复杂荧光数据解析能力对比研究,以此探索和改进EEMs多元解析方法技术体系.模型以已发表论文原始数据为基础构建,研究对象为南太湖重要入湖河流东苕溪水系.结果显示:EEMsSOM模型需依赖常规"摘峰法"对各荧光峰做出主观判断,不能有效识别重叠荧光峰,且人为割裂多激发共发射荧光物质峰之间的联系,从而弱化分析结果的实际环境意义,但神经元的模式荧光光谱可视化效果较佳,且操作简便,耗时较少;PARAFAC-SOM模型克服了上述缺陷,可清除EEMs中的噪声或无用信息,大幅降低输入变量数(从1742个降至4个),缩减运算时间,较大地改善了输出结果的准确性,获得无损可靠且实际环境意义较强的结果,但该法的PARAFAC预处理要求较高,工作量较大;两类模型解析结论大体一致,对前期研究进行了全新的阐述和补充,且生动揭示了FDOM在多级河流水体中的空间赋存变化规律及河流的动态污染过程.综上,推荐在今后研究中综合使用两类优势互补的模型以实现对EEMs的深度解析.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.