改良型AO法组合工艺中有机物的三维荧光分析

采用三维荧光(EEM)光谱技术,对上海竹园第二污水处理厂改良型AO法组合工艺运行过程中的各种溶解性有机物(DOM)进行分析,并对比研究传统好氧活性污泥法曝气池出水和A/O脱氮工艺硝化池出水DOM的EEM光谱的迁移变化特性.结果表明,各种DOM中主要的荧光物质有类蛋白质(荧光峰A和B)及类腐殖质(荧光峰C),经改良型AO法组合工艺处理后,荧光峰的强度降低了14％～60％,同时类蛋白质和腐殖质的结构也发生了变化；腐殖酸溯源表明DOM中的腐殖酸以微生物代谢产生的带有荧光基团的腐殖酸类为主.     

沸石生物联合吸附再生工艺中溶解性有机物的特性变化

利用三维荧光技术(EEM)和凝胶过滤色谱法(GFC)研究了沸石生物联合吸附再生(ZCS)工艺中溶解性有机物(DOM)在系统中的变化规律.结果表明,生活污水DOM中主要的荧光物质有类蛋白质(荧光峰A和B)和类腐殖质(荧光峰C),经ZCS工艺处理后,荧光峰B较峰A的强度降低更多,说明类蛋白质的组成结构发生了变化;荧光峰C削...     

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。     

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。     

沈阳市黑臭水体溶解性有机物组分及其光学特征

以沈阳市5条黑臭水体作为研究对象,其中支流I和支流II为重度黑臭,支流III、IV和V为轻度黑臭。运用三维荧光光谱结合平行因子方法对黑臭水体中水溶性有机物(DOM)组分进行了表征,并通过与光谱数据相结合的方法,建立了DOM各组分最大荧光强度(F_(max))与归一化遥感反射率的一元线性回归方程。三维荧光分析结果显示,DOM分为2个类别3种不同组分,分别为类蛋白荧光组分C1(235nm/360nm)、类腐殖质荧光组分C2(220nm/430nm)和C3(255nm/520nm)。水体光谱分析结果表明:在250～800 nm处,有色可溶性有机物吸收系数(a_g)、总悬浮物吸收系数(a_p)曲线均随着波长的增大逐渐减小,空间变化特征明显;在特征波长440 nm处,轻度黑臭水体的有色可溶性有机物吸收系数总体上大于重度黑臭水体,重度黑臭水体总悬浮物吸收系数总体大于轻度黑臭水体。与正常水体相比,在可见光波段,沈阳市黑臭水体遥感反射率普遍较低,出现3个反射峰和1个反射谷。但支流I与其他黑臭水体不同,表面呈白灰色,导致其遥感反射率(R_(rs))呈现与正常水体类似的明显的波峰和波谷,是一类特殊的黑臭水体。线性回归分析表明,由归一化遥感反射率比值R_(688)/R_(555)与DOM组分最大荧光强度所建立的线性模型估算精度最理想。R_(688)/R_(555)与轻度黑臭水体DOM组分F_(max)的拟合程度好于重度黑臭水体。进一步研究表明,R_(688)/R_(555)与色氨酸类物质拟合程度较好,与腐殖质类物质没有明显的线性关系。     

基于三维荧光光谱特征峰的水体有机污染物综合指标检测

对来源不同一的32个水样进行三维荧光光谱的测定,并用5种典型有机物的荧光特征峰A(腐殖酸类)、C(腐殖酸类)、B(络氨酸类)、T1(色氨酸类)、T2(色氨酸类)进行了单一和组合式建模,发现对于来源不同一的水体的总有机含碳量(TOC)、化学耗氧量(COD)的检测采用这种提取特征峰建模的效果并不理想.该研究说明,依据典型特...     

基于三维荧光光谱技术解析不同微生物法净化黑臭水体的效果

应用曝气、菌剂+曝气、生物促生剂+曝气、菌剂+生物促生剂+曝气4种微生物技术净化黑臭水体,分别考察了进水中溶解性有机物(DOM)的特征和来源及出水中DOM的特征和效果,采用三维荧光(EEM)光谱技术与平行因子(PARAFAC)模型相结合的方式对进出水DOM进行了分析。结果表明,不同处理方式下进出水DOM的不同组分荧光峰强度变化存在较明显的差异,经过菌剂和生物促生剂联合处理之后,对类腐殖质等难降解物质削减效果最好。FI、HIX和BIX指数分析表明各处理水样中的DOM整体处于较强的自生源特征。利用主成分分析法(PCA)对影响黑臭水体DOM的主要因素及其贡献量研究发现:第1主成分表现为陆源类腐殖质和生物源类腐殖质共存的现象,对水体中DOM的贡献率为54.98%;第2主成分反映了以微生物代谢过程为代表的内源污染,对水体中DOM的贡献率为26.56%。因此,利用三维荧光分析能够较好的反映水中DOM的去除情况,易于实时在线监测,对黑臭水治理具有重要意义。     

垃圾渗滤液处理工艺中有机污染物的三维荧光光谱

利用荧光发射和三维荧光光谱研究了三峡库区某垃圾堆场的渗滤液及其处理工艺出水溶解性有机质(DOM)的荧光光谱特性。堆场渗滤液的DOM含有类酪氨酸、色氨酸及紫外区类富里酸，特征荧光峰中心位于E_x/E_m=275 nm/305 nm，为高激发波长类酪氨酸，与前人的研究结果并不一致，这可能与垃圾的堆放期有关。渗滤液和各处理工艺出水的荧光指数f_450/500均大于1.9，表明腐殖质主要为微生物源。渗滤液在处理前后荧光峰特征和强度均发生明显改变，类蛋白荧光强度与DOC值变化趋势基本一致。生化处理工艺中，类蛋白荧光强度降低了66.4%～95.5%，紫外区类富里酸荧光强度只降低了28.8%，显示类蛋白质具有良好的可生化性，而类富里酸相对较难生化降解。三维荧光光谱能反映渗滤液处理过程中污染物的种类、性质和数量等变化信息，能快速地进行定性分析、定量评价。     

沉积物中溶解性有机质的垂直分布光谱特性

采用紫外光谱和三维荧光光谱结合平行因子分析(PARAFAC)方法对瀛湖沉积物中溶解有机质(dissolved organic matters,DOM)垂直分布的光谱特性进行了分析,利用荧光指数(fluorescence index,FI)、腐殖化指数(humification index,HIX)和生物源指数(biological index,BIX)解析了沉积物中DOM荧光组分、空间分布特征和来源。紫外光谱结果表明:瀛湖沉积物的UV254值在0.14~0.30之间,最大值出现在深度10~11 cm处,深层(20 cm以下深度)沉积物UV254值趋于稳定。A250/A365比值在3.69~9.98之间,均值为5.36,表明瀛湖沉积物DOM以富里酸为主。三维荧光光谱结合平行因子分析结果表明:沉积物DOM包含3类4个荧光组分,即类腐殖质组分(C1和C2)、类蛋白组分(C3和C4),其中,类腐殖质组分的荧光强度约占全部组分荧光强度的60.7%;随着深度的增加,3个采样点的类蛋白质组分(C3和C4)的荧光强度均呈现下降趋势。FI、HIX和BIX都表明瀛湖沉积物DOM的来源主要是由沉积物中自生微生物活动产生。其中,FI在1.73~2.10范围内,BIX处于0.72~0.96范围内,HIX在1.39~4.72范围内。     

基于三维荧光光谱-平行因子分析法的工业园区污水溶解性有机物溯源与归趋

本研究以某工业园区内的污水处理厂为研究对象,使用紫外-可见光谱和三维荧光光谱对11个进水管道和水处理各工艺段的水样进行检测,结合平行因子分析法探究了污水厂水体中主要污染物的来源和类别,最后对水质参数和各组分进行了相关性分析.紫外-可见光谱、三维荧光光谱结合平行因子分析结果表明,污水主要有5种荧光组分,其中C1,C2,C...     

掺碘二氧化钛薄膜自组装制备、表征及光催化性能

通过自组装技术在低温液相反应体系中制备出大尺寸纳米二氧化钛及其掺碘薄膜。使用XRD、TEM、荧光发射光谱仪、激光拉曼光谱仪等手段对样品进行表征，发现掺I^5＋后的二氧化钛薄膜在可见光区也表现出明显的响应，而且合成的I^5＋／TiO2纳米薄膜在TEMggNT其晶型显示为金红石型，并且碘掺杂后样品的拉曼光谱强度减弱，峰位蓝移且宽化。掺杂I^5＋原溶液浓度为2mmol／L时，其可见光下光催化效果最优，5h后降解率可达到95％，较未掺杂的TiO2纳米薄膜提高了40％，I^5＋掺杂明显提高了TiO2对甲基橙溶液的光催化降解效率。     

Can time-weighted average concentrations be used to assess the risks of metsulfuron-methyl to Myriophyllum spicatum under different time-variable exposure regimes?

We tested the effects of the herbicide metsulfuron-methyl on growth of the submerged macrophyte Myriophyllum spicatum under laboratory conditions using different exposure scenarios. The exposures of each scenario were comparable in the concentration × time factor, viz., the same 21-d time-weighted average (TWA) concentrations but variable in peak exposure concentrations (ranging from 0.1 to 21 000 ng ai L⁻¹) and exposure periods (1, 3, 7, 14 or 21 d). To study recovery potential of the exposed M. spicatum plants we continued the observation on shoot and root growth for another 21 d in herbicide-free medium so that the total observation period was 42 d. Non-destructive endpoints, length and number of new shoots and roots, were determined weekly from day 14 onwards. Destructive endpoints, dry-weight (DW) of main shoots, new shoots and new roots, were measured at the end of the experiment (t = 42 d).Metsulfuron-methyl exposure in particular inhibited new tissue formation but was not lethal to main shoots. On days 21 and 42 after start exposure, EC₁₀/EC₅₀ values for new tissues expressed in terms of peak concentration (=measured concentration during exposure periods of different length) showed large differences between exposure scenarios in contrast to EC₁₀/EC₅₀ values for days 21 and 42 expressed in terms of 21-d and 42-d TWA concentrations, respectively. At the end of the experiment (day 42), 42-d TWA EC_x values were remarkably similar between exposure scenarios, while a similar trend could already be observed on day 21 for 21-d TWA EC_x values. For the macrophyte M. spicatum and exposure to the herbicide metsulfuron-methyl the TWA approach seems to be appropriate to use in the risk assessment. However, the data from the toxicity experiment suggest that on day 21 also the absolute height of the pulse exposure played a (minor) role in the exposure - response relationships observed.     

电极-SBBR处理含铜有机污水

采用电极一SBBR系统去除Cu^2＋，考察了电流强度，IA竞争离子（阴离子SO4^2-、NO3^-、CL^-和阳离子Zn^2＋、Ph^2＋）、初始含Cu^2＋量及溶液pH值对除铜效除果的影响。结果表明，当电流强度为40mA时Cu^2＋去除率最高为98％。投加阴（SO4^2-、NO3^-、Cl^-）、阳（Zn^2＋、Pb^2＋）离子均会引起出水Cu^2＋浓度的增加，且Cl^-和Ph^2＋含量分别为45mg／L和30mg／L时对Cu^2＋去除的影响更为显著。进水Cu^2＋浓度为30mg／L时，Cu^2＋去除率最高为98．48％，当进水Cu^2＋≥70mg／L时，出水Cu^2＋浓度不能达标。酸性（pH4．0～4．5）与碱性（pH9．0～10．0）条件均不利于Cu^2＋的去除，且酸性条件的负面影响更显著．当pH为4．5～7．5时．Cu^2＋去除率最高为97．78％。     

The role of endogenous nitric oxide in melatonin-improved tolerance to lead toxicity in maize plants

Melatonin (MT) and nitric oxide (NO) are known as scavengers of free radicals and an antioxidant against biotic and abiotic stresses in plant defense systems. However, whether NO interplays role in MT-induced antioxidant defense remains to be determined in the plants exposed to lead (Pb) toxicity. So, two experiments were designed to evaluate the role of NO in MT-mediated tolerance of maize plants to Pb stress. In the initial experiment, prior to starting different treatments, a solution of 0.05- or 0.10-mM MT was sprayed every other day for a period of 10 days to the leaves of maize plants exposed to Pb stress (0.1-mM PbCl₂). Pb toxicity significantly caused reduction in plant biomass (both fresh and dry), PSII maximum efficiency (F_v/F_m), total chlorophyll, leaf potassium (K), calcium (Ca), and leaf water potential, but it resulted in increased levels of proline, hydrogen peroxide (H₂O₂), malondialdehyde (MDA), electron leakage (EL), leaf Pb, and endogenous NO. An addition experiment was set up to further understand whether NO played role in mitigation of Pb toxicity in maize plants by MT using scavengers of NO and cPTIO combined with the MT treatments. MT-induced tolerance to Pb toxicity was totally eliminated by cPTIO by reversing endogenous NO. The present results clearly indicated that MT mediated the endogenous NO to improve tolerance of maize plants to Pb toxicity. This evidence was also supported by the increases of H₂O₂ and MDA and reduces some antioxidant enzyme activities tested as well as the plant growth inhibition and increased leaf Pb content by application of MT combined with cPTIO.

     

三维电极法处理钻井废水影响因素分析

采取电化学法处理某钻井废水,考察了三维电极系统处理钻井废水时,废水浓度、电流密度、处理时间、电解质浓度和pH值对废水COD降解率的影响,实验结果表明,三维电极法处理钻井废水效果显著;增大电流密度、提高电解质浓度和延长处理时间能使COD去除率提高;最佳pH值为9。正交实验得到最优水平组合为A2B3C2D3E4,在此条件下COD去除率为86.56%。     

Air quality in Yanbu,Saudi Arabia

Yanbu, on the Red Sea, is an affluent Saudi Arabian industrial city of modest size. Substantial effort has been spent to balance environmental quality, especially air pollution, and industrial development. We have analyzed six years of observations of criteria pollutants O₃, SO₂, particles (PM_2.5 and PM₁₀) and the known ozone precursors—volatile organic compounds (VOCs) and nitrogen oxides (NO_x). The results suggest frequent VOC-limited conditions in which ozone concentrations increase with decreasing NO_x and with increasing VOCs when NO_x is plentiful. For the remaining circumstances ozone has a complex non-linear relationship with the VOCs. The interactions between these factors at Yanbu cause measurable impacts on air pollution including the weekend effect in which ozone concentrations stay the same or even increase despite significantly lower emissions of the precursors on the weekends. Air pollution was lower during the Eids (al-Fitr and al-Adha), Ramadan and the Hajj periods. During Ramadan, there were substantial night time emissions as the cycle everyday living is almost reversed between night and day. The exceedances of air pollution standards were evaluated using criteria from the U.S. Environmental Protection Agency (EPA), World Health Organization (WHO), the Saudi Presidency of Meteorology and Environment (PME) and the Royal Commission Environmental Regulations (RCER). The latter are stricter standards set just for Yanbu and Jubail. For the fine particles (PM_2.5), an analysis of the winds showed a major impact from desert dust. This effect had to be taken into account but still left many occasions when standards were exceeded. Fewer exceedances were found for SO₂, and fewer still for ozone. The paper presents a comprehensive view of air quality at this isolated desert urban environment.

Implications: Frequent VOC-limited conditions are found at Yanbu in Saudi Arabia that increase ozone pollution if NO_x is are reduced. In this desert environment, increased nightlife produces the highest levels of VOCs and NO_x at night rather than the day. The effects increase during Ramadan. Fine particles peak twice a day—the morning peak is caused by traffic and increases with decreasing wind, potentially representing health concerns, but the larger afternoon peak is caused by the wind, and it increases with increasing wind speeds. These features suggest that exposure to pollutants must be redefined for such an environment.     

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。     

Ambient TSP concentration and dustfall in major cities of China: Spatial distribution and temporal variability

Based on environmental monitoring data in 93 major cities and meteorological records at 398 weather stations in China from 1981 to 2007, total suspended particle (TSP) concentration, the intensity of dustfall, and sand and dust storm frequency (F_d) were analysed. During the past 27 years, the annual average TSP concentration (C_TSP) in 93 cities was 402 μg m^?3. Annual average C_TSP decreased from the north to the south and from inland to the coast areas with a peak value of 628.8 μg m^?3 in Lanzhou. In the 1980s, 1990s and 2000s, annual average C_TSP was 628.7, 319.2, and 250.1 μg m^?3, respectively. Annual average intensity of dustfall (I_d) was 240.5 t km^?2 a^?1, decreased from northern to southern China and from inland to the coast areas with the maximum value of 717.2 t km^?2 a^?1 in Baotou. In the 1980s, 1990s and 2000s, annual average I_d was 334.8, 220.9, 146 t km^?2 a^?1 respectively. Annual average I_d in the Loess Plateau region was commonly higher than 200 t km^?2 a^?1. The annual average F_d decreased from arid regions in northwestern China to humid areas in southeastern China with two sand and sand storm centers existing in Xinjiang Taklamakan Desert and western Inner Mongolia. The annual average F_d in the 1980s, 1990s, 2000s was 16, 8, 6 days respectively, decreased steadily from 18 days in 1981–5 days in 2007. Annual average I_d had a positive linear relation to annual average C_TSP (R² = 0.96). Annual average F_d had a positive relation with annual average C_TSP (R² = 0.97) as well as annual average I_d (R² = 0.94). TSP was the chief pollutant influencing Air Pollution Index (API) in northern China in spring and winter seasons. Sand and dust storm might be a major factor affecting the temporal variability and spatial distribution of TSP and dustfall in China.     

钝化剂在烟草植物修复铅镉污染土壤中的作用简

重金属钝化剂可以改变土壤中重金属的形态，降低其在土壤中的有效浓度、植物毒性及生物有效性，影响污染土壤中植物的生长及其对重金属的吸收。在温室盆栽条件下研究了施加羟基磷灰石（HA）、纳米羟基磷灰石（nHA）、纳米零价铁（nFe⁰）和纳米TiO₂（nTiO₂）对烟草植物修复铅镉污染土壤的作用。结果表明，HA降低土壤中Pb、Cd的有效性、促进烟草生长、增加了烟草叶、茎、根中Cd的吸收量和根系中Pb的吸收量，有利于Pb、Cd的钝化和植物修复。nHA也可以降低土壤中Pb、Cd的有效性，增加了烟草叶中Cd的吸收量，有利于Pb、Cd的钝化和Cd的植物提取。nFe⁰和nTiO₂对于土壤Pb和Cd的钝化作用和植物修复均没有显著影响。综合来看，HA最适合应用于烟草植物修复铅镉污染土壤。     

Spectroscopic study of the degradation of antibiotics and the generation of representative EfOM oxidation products in ozonated wastewater

This study examined effects of ozonation on thirteen fluoroquinolone, macrolide and lincosamide antibiotics present in municipal wastewater. Transformations of effluent organic matter (EfOM) caused by ozonation were characterized using absorbance/fluorescence spectroscopy and high performance size exclusion chromatography (HPSEC). Concentrations of aldehydes and carboxylic acids generated via the oxidation of EfOM were also determined. The absorbance and fluorescence of ozonated wastewater decreased with increasing ozone dose or treatment time. HPSEC data showed that these phenomena corresponded to the oxidation of all EfOM fractions, with some preference towards the degradation of the EfOM molecules with high apparent molecular weight. The removal of antibiotics and production of aldehydes and carboxylic acids were strongly correlated with the changes in both EfOM absorbance and fluorescence. Applications of a model describing the concurrent degradation of trace level contaminants and relative changes of EfOM emission allowed achieving a good fitting between the experimental and modeled ΔC/C₀ vs. ΔA/A₀ and ΔC/C₀ vs. ΔF/F₀ data.