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。     

城市污水处理过程中DOM的三维荧光光谱及紫外谱图特性

利用三维荧光光谱法和紫外分光光度法对城市污水处理过程中溶解性有机物(DOM)的光谱特性等进行研究。结果表明,污水中的类蛋白质物质较易被降解,类腐殖酸物质属于较难生物降解物质。且在λ_(Ex)/λ_(Em)为(290~295)nm/(325~330)nm处出现新荧光峰,推测其可能是溶解性微生物代谢产物或是被原荧光峰覆盖的难降解有机物所发射荧光形成的。FI值在2.03~2.16,表明DOM主要是生物来源且芳香度较低。紫外谱图在190~230 nm和250~290 nm分别存在着明显的吸收带和吸收平台。在好氧处理后,紫外谱图中的吸收带发生了红移且其吸收强度逐渐增大。通过SUVA、UV_(253)/UV_(203)值和Zeta电位在生物处理过程中的变化,表明DOM经过生物降解,芳香构造程度化逐渐增大,所含苯环的取代程度降低,逐渐稳定。污水处理过程中TOC、UV_(254)与λ_(Ex)/λ_(Em)位于(230~235)nm/(340~350)nm的类蛋白质所发射的荧光强度、荧光峰荧光强度和之间均有很强的正相关性。     

紫外辐射加速磺胺嘧啶生物降解的机理

采用紫外光解与生物降解耦合的方法可以明显提高磺胺嘧啶(SD)的生物降解速率。经过分析,发现SD在紫外光解过程中首先生成对氨基苯磺酸(p-aminobenzenesulfonic acid, ABS)和2-氨基嘧啶(2-aminopyrimidine, 2-AP),而ABS很快分解为苯胺(aniline, An)和SO42-。其中2-AP不能加速苯胺的生物降解,反而具有一定的生物抑制。而苯胺可以提高其生物降解速率。按比例同时将2-AP和An加入到SD溶液中,其生物降解速率与紫外光解耦合生物降解时相近,是单独生物降解速率的2倍。这是因为苯胺在生物氧化过程中,可以提供足够的电子并通过共基质作用加速SD的初始单加氧反应。     

Quantifying interactions between propranolol and dissolved organic matter (DOM) from different sources using fluorescence spectroscopy

Beta blockers are widely used pharmaceuticals that have been detected in the environment. Interactions between beta blockers and dissolved organic matter (DOM) may mutually alter their environmental behaviors. To assess this potential, propranolol (PRO) was used as a model beta blocker to quantify the complexation with DOM from different sources using the fluorescence quenching titration method. The sources of studied DOM samples were identified by excitation–emission matrix spectroscopy (EEMs) combined with fluorescence regional integration analysis. The results show that PRO intrinsic fluorescence was statically quenched by DOM addition. The resulting binding constants (log K _oc) ranged from 3.90 to 5.20, with the surface-water-filtered DOM samples claiming the lower log K _oc and HA having the highest log K _oc. Log K _oc is negatively correlated with the fluorescence index, biological index, and the percent fluorescence response (P _i,n) of protein-like region (P _I,n) and the P _i,n of microbial byproduct-like region (P _II,n) of DOM EEMs, while it is correlated positively with humification index and the P _i,n of UVC humic-like region (P _III,n). These results indicate that DOM samples from allochthonous materials rich in aromatic and humic-like components would strongly bind PRO in aquatic systems, and autochthonous DOM containing high protein-like components would bind PRO more weakly.     

Effect of textile auxiliaries on the biodegradation of dyehouse effluent in activated sludge

The textile industry is confronted with serious environmental problems associated with its immense wastewater discharge, substantial pollution load, extremely high salinity, and alkaline, heavily coloured effluent. Particular sources of recalcitrance and toxicity in dyehouse effluent are two frequently used textile auxiliaries; i.e. dye carriers and biocidal finishing agents. The present experimental work reports the observation of scientific and practical significance related with the effect of two commercially important textile dye carriers and two biocidal finishing agents on biological activated sludge treatment at a textile preparation, dyeing and finishing plant in Istanbul. Respirometric measurements of the dyehouse effluent spiked with the selected textile chemicals were carried out for the assessment of the "readily biodegradable COD fraction" of the wastewater. The respirometric data obtained to visualize the effect of the selected textile auxiliaries on biomass activity was evaluated by an adopted activated sludge model. Results have indicated that the tested biocides did not exert any significant inhibitory effect on the treatment performance of the activated sludge reactor at the concentrations usually encountered in the final, total dyehouse effluent. The situation with the dye carriers was inherently different; one dye carrier appeared to be highly toxic and caused serious inhibition of the microbial respirometric activity, whereas the other dye carrier, also known as the more ecological alternative, i.e. the "Eco-Carrier", appeared to be biodegradable. Finally, the respirometric profile obtained for the Eco-Carrier was described by a simplified respirometric model.     

矿化垃圾反应床处理垃圾渗滤液出水中的水溶性有机物

以矿化垃圾反应床处理垃圾渗滤液出水(以下简称尾水)为研究对象,采用国际上最常用的树脂联用法,对其进行梯度分离表征.研究结果表明,憎水性腐殖质对尾水COD和溶解性有机碳(DOC)的贡献分别为42.55%和45.12%,准亲水性物质对尾水中COD和DOC的贡献分别为34.89%和37.14%,憎水性腐殖质和准亲水性物质是尾水中水溶性有机物(DOM)的重要组成部分.近紫外区域吸光度分析发现,尾水中含有大量带共轭双键或苯环的有机物质,这些物质从尾水中去除后,尾水在近紫外区域的吸光度明显下降.分子量分布显示.尾水中DOM的分子量主要集中在2 000 u以下.元素分析和红外光谱结果显示,胡敏酸(HA)和富里酸(FA)带有苯环结构,存在醇羟基或酚羟基及羧酸官能团;准亲水性物质含有较多的羧酸官能团,另外存在一定置的羟基官能团,同时还可能含有三键和双键的结构.     

城市污水处理厂出水低浓度污染物的生物降解研究

由于城市污水处理厂出水中含有的低浓度污染物的性能稳定而不易被去除,为探索一种快速、直接的低浓度污染物的深度处理方法,通过采用富二价阳离子斜发沸石作载体的生物沸石曝气滤池对某城市污水厂二级处理出水中的低浓度污染物的去除进行了实验研究,研究结果表明,当污水厂二级处理出水水质年平均指标NH3-N、COD、BOD5、TP及浊度分别为27.4 mg/L、57.2 mg/L、20.4 mg/L、1.7 mg/L和16 NTU时,采用两级生物沸石曝气滤池串联工艺,在第一级生物沸石曝气滤池装填3 m生物沸石,水力停留时间1 h,气水比为2∶1;第二级生物沸石曝气滤池装填2 m生物沸石,水力停留时间为0.5 h,气水比为1∶1,最终出水年平均指标NH3-N 0.13 mg/L、COD 7.55 mg/L(CODMn)、BOD50.78 mg/L、TP0.6 mg/L、浊度为0.13 NTU,出水水质可满足热力发电厂循环冷却补充水的水质要求.此种方法为污水处理厂的出水提供了经济有效的回用途径。     

Monitoring the photochemical degradation of triclosan in wastewater by UV light and sunlight using solid-phase microextraction

Photo solid-phase microextraction (photo-SPME) is applied for the first time to study the photochemical behavior of an emerging pollutant, triclosan, in real contaminated wastewater samples using a solar simulator. In this study, water samples are extracted by SPME and then, the fiber coating is irradiated for a selected time. This on-fiber procedure, so-called photo-SPME, followed by gas chromatography-mass spectrometry makes it possible to study photodegradation kinetics and the generation of byproducts. Several photoproducts were identified in the real samples including the 2,8-dichlorodibenzo-p-dioxin, dichlorophenols and a compound tentatively identified as other DCDD congener or a dichlorohydroxydibenzofuran. Accordingly, it was possible to postulate main photodegradation mechanisms. Photo-SPME demonstrated slower kinetics in wastewater than in spiked ultrapure water probably due to the presence of dissolved organic matter. This technique was extensively compared with conventional aqueous photodegradation showing high similarity. The influence of pH on the triclosan photolysis and on the triclosan-dioxin conversion was also investigated in wastewater. Photodegradation of triclosan and formation of 2,8-DCDD occurred independently of sample pH. This study represents an advance in the use of photo-SPME to understand the photochemical fate of environmental organic pollutants and demonstrates its clear advantages with real samples.     

LC-OCD分析活性焦吸附-生物降解去除稠油废水中DOC的历程

采用液相色谱-有机碳测定仪(LC-OCD)分析活性焦吸附-生物降解去除稠油废水中溶解性有机碳的历程。结果表明,稠油废水中的溶解性有机物,除含有大量矿物油和有机表面活性剂外,还含有微量生物聚合物和少量腐殖酸及腐殖酸的降解产物;活性焦吸附-生物降解工艺对稠油废水中DOC的去除率为85.6%,其中HOC和CDOC分别占40.8%和44.8%。HOC和CDOC总去除率分别为92.73%和80%,活性焦吸附去除42.4%DOC,其中预吸附和后吸附分别去除24.0%和18.4%,预吸附主要去除HOC和OA,后吸附主要去除NEU。生物降解去除43.2%的DOC,主要是HOC、NEU、OA和BP。活性焦吸附-生物降解降解稠油废水容易去除的DOC是HOC、OA、BP和NEU,比较难去除的DOC为HS和BB。     

In situ measurements of volatile aromatic hydrocarbon biodegradation rates in groundwater

Benzene and alkylbenzene biodegradation rates and patterns were measured using an in situ microcosm in a crude-oil contaminated aquifer near Bemidji, Minnesota. Benzene-D6, toluene, ethylbenzene, o-, m- and p-xylenes and four pairs of C₃- and C₄-benzenes were added to an in situ microcosm and studied over a 3-year period. The microcosm allowed for a mass-balance approach and quantification of hydrocarbon biodegradation rates within a well-defined iron-reducing zone of the anoxic plume. Among the BTEX compounds, the apparent order of persistence is ethylbenzene > benzene > m,p-xylenes > o-xylene ≥ toluene. Threshold concentrations were observed for several compounds in the in situ microcosm, below which degradation was not observed, even after hundreds of days. In addition, long lag times were observed before the onset of degradation of benzene or ethylbenzene. The isomer-specific degradation patterns were compared to observations from a multi-year study conducted using data collected from monitoring wells along a flowpath in the contaminant plume. The data were fit with both first-order and Michaelis-Menten models. First-order kinetics provided a good fit for hydrocarbons with starting concentrations below 1 mg/L and Michaelis-Menten kinetics were a better fit when starting concentrations were above 1 mg/L, as was the case for benzene. The biodegradation rate data from this study were also compared to rates from other investigations reported in the literature.     

Ozonation effects on emerging micropollutants and effluent organic matter in wastewater: characterization using changes of three-dimensional HP-SEC and EEM fluorescence data

The degradation of effluent organic matter (EfOM) in a municipal wastewater treated by ozonation was characterized using the methods of high-performance size-exclusion chromatography (HP-SEC) and excitation/emission matrix (EEM) fluorescence combined with parallel factor analysis (PARAFAC). The removal of 40 diverse trace-level contaminants of emerging concern (CEC) present in the wastewater was determined as well. Ozonation caused a rapid decrease of the absorbance and fluorescence of the wastewater, which was associated primarily with the oxidation of high and low apparent molecular weight (AMW) EfOM fractions. PARAFAC analysis also showed that components C1 and C2 decreased prominently in these conditions. The EfOM fraction of intermediate molecular weight ascribable to a terrestrial humic-like component (C3) tended to be less reactive toward ozone. Relative changes of EEM fluorescence were quantified using F _max values of PARAFAC-identified components (∆F/F ⁰ _max). Unambiguous relationships between ∆F/F ⁰ _max values and the extent of the degradation of the examined CECs (∆C/C₀) were established. This allowed correlating main parameters of the ∆C/C₀ vs. ∆F/F ⁰ _max relationships with the rates of oxidation of these CECs. The results demonstrate the potential of online measurements of EEM fluorescence for quantitating effects of ozonation on EfOM and micropollutants in wastewater effluents.

     

Monitoring laboratory-scale bioventing using synchronous scan fluorescence spectroscopy: analysis of the vapor phase

Bioventing is an improved method of soil remediation that is being used with increasing frequency. In this paper, we refine techniques to measure the progress of petroleum hydrocarbon decomposition by monitoring vapor phase composition with synchronous scan fluorescence spectroscopy (SSFS). Analysis of the vapor phase has advantages compared to standard extraction techniques that require extensive sample handling and clean up. For comparison, hydrocarbon contamination in the soil was measured by analysis of Soxhlet extractions with gas chromatography-mass spectrometry (GC-MS). Comparison of the GC-MS and SSFS data showed that changes in hydrocarbon composition measured in the vapor phase provide an accurate measure of decomposition reactions taking place in the soil.     

UV Fourier transform measurements of tropospheric O3, NO2, SO2, benzene, and toluene.

Using the differential optical absorption spectroscopy (DOAS) technique and a Fourier transform spectrometer, NO2, SO2, O3, benzene. and toluene were measured during three measurement campaigns held in Brussels in 1995, 1996, and 1997. The O3 concentrations could be explained as the results of the local photochemistry and the dynamical properties of the mixing layer. NO2 concentrations were anti-correlated to the O3 concentrations, as expected. SO2 also showed a pronounced dependence on car traffic. Average benzene and toluene concentrations were, respectively 1.7 ppb and between 4.4 and 6.6 pbb, but high values of toluene up to 98.8 ppb were observed. SO2 concentrations and to a lesser extent, those of NO2 and 03, were dependent on the wind direction. Ozone in Brussels has been found to be influenced by the meteorological conditions prevailing in central Europe. Comparisons with other measurements have shown that 03 and SO2 data are in general in good agreement, but our NO2 concentrations seem to be generally higher.     

城市污水生化处理水UV/O3法深度处理效果及影响因素研究

研究城市污水生化处理水的深度处理技术及其影响因素,对于减轻环境污染和实现废水回用具有重要理论意义和实用价值。考察了UV／O3法对城市污水生化处理水深度处理的效果及其影响因素。结果表明,由于UV／O3过程具有氧化能力强,反应无选择性等优点,使其在城市污水生化处理水深度处理方面较普通O3氧化更具有优势,50min时CODCr去除率达到90％以上,达到了深度处理的目的。对于难氧化有机物,UV／O3法处理时几乎大部分都被氧化分解残留量很少,而O3法处理时仍有较多难氧化有机物残留。UV／O3法处理城市污水生化处理水时,在pH=6～9时,CODCr去除率随pH的升高而降低,表明较低pH（pH=5）有利CODCr的去除。有机污泥对CODCr去除率基本没有影响。但无机悬浮物SiO2对CODCr去除率影响较大,投加70mg／L的SiO2后CODCr氧化速率和去除率有较明显下降。随溶液碱度的增加,CODCr的去除率下降,碱度越高对CODCr去除的影响也越明显。     

Treatment of cork boiling wastewater using chemical oxidation and biodegradation

Three cultures were enriched from cork boiling wastewater using tannic acid as the selective carbon substrate, at 25 degrees C and pH 7.2, 25 degrees C and pH 4.7 and 50 degrees C and pH 4.7. The enrichment culture obtained at neutral pH was composed of five culturable isolates, whereas from each acidic enrichment two bacterial strains were isolated. Mesophilic isolates were Gram negative bacteria belonging to the genera Klebsiella, Pseudomonas, Stenotrophomonas and Burkholderia. Thermophilic isolates were members of the genus Bacillus. Despite the capability of the enrichment cultures to use tannic acid as single carbon and energy source, those cultures were unable to reduce the total polyphenols or the total organic carbon content of cork boiling wastewater. In order to increase the bioavailability of the organic carbon in cork boiling wastewater, biodegradation was preceded by Fenton oxidation. It was demonstrated that the combined process, using small amounts of Fenton reagents and biodegradative inoculum added almost simultaneously to cork boiling wastewater, leads to TOC reductions of more than 90%.     

UV treatment of microorganisms on artificially-contaminated surfaces using excimer and microwave UV lamps

An XeBr excilamp having a peak emission at 283 nm, and microwave UV lamps with peak emissions at 253.7 nm that also generate ozone, have been tested for ability to eradicate high populations of microbial vegetative cells and spores (of bacteria and fungi) artificially added to filter surfaces. The study examined the energy required to completely eradicate large populations on filter surfaces. It was found that both the excilamp and microwave UV lamps were effective at killing large populations on surfaces with killing efficiency dependant on the type of organism, and, whether present in its vegetative or spore forms. The main killing factor is UV radiation following short treatment times. It is considered that for longer irradiation periods that are required to facilitate complete destruction of surface microorganisms, ozone and other oxidising species produced by microwave UV lamps would act to enhance microbial destruction.     

Daily surface UV exposure and its relationship to surface pollutant measurements

For the past 30 years, the stratospheric ozone layer has decreased in the Northern Hemisphere. The main effect of this ozone decrease was an expected increase in the UV radiation at the Earth's surface, but there has been no clear evidence of an increasing urban trend in surface UV. This study shows that specific air pollutants can reduce the increased surface levels of UV radiation and offers an explanation for why the expected surface UV increases have not been observed, especially in urban regions. A U.S. Environmental Protection Agency (EPA) UV monitoring site at the University of California at Riverside combined with air pollution data from a site operated by the California Air Resources Board in Rubidoux, CA, provided the basis of this study. The 1997 South Coast Ozone Study (SCOS-97) provided three key ingredients: black carbon, PM10 concentrations, and collocated radiometric measurements. The Total Ozone Mapping Spectrometer (TOMS) satellite data were used to provide the stratospheric ozone levels that were included in the statistical model. All of these input parameters would be used to test this study's hypothesis: the expected increase of surface UV radiation, caused by decreases in stratospheric ozone, can be masked by increases in anthropogenic emissions. The values for the pollutants were 7:00 a.m.-5:00 p.m. averages of the instrument's values taken during summer 1997. A statistical linear regression model was employed using the stratospheric ozone, black carbon, PM10, and surface ozone concentrations, and the sin (theta) and cos (theta). The angle theta is defined by theta = 2pi (Julian date/365). This model obtained a coefficient of determination of 0.94 with an uncertainty level (p value) of less than 0.3% for all of the variables in the model except ground-level ozone. The final model, regressed against a data set from a remote, western North Carolina site, resulted in a coefficient of determination of 0.92. The model shows that black carbon can reduce the Diffey-weighted UV levels that reach the surface by as much as 35%, depending on the season.     

Triclocarban: UV photolysis,wastewater disinfection,and ecotoxicity assessment using molecular biomarkers

Triclocarban (TCC) is an antibacterial agent found in pharmaceuticals and personal care products (PPCP). It is potentially bioaccumulative and an endocrine disruptor, being classified as a contaminant of emerging concern (CEC). In normal uses, approximately 96% of the used TCC can be washed down the drain going into the sewer system and eventually enter in the aquatic environment. UV photolysis can be used to photodegrade TCC and ecotoxicity assays could indicate the photodegradation efficiency, since the enormous structural diversity of photoproducts and their low concentrations do not always allow to identify and quantify them. In this work, the TCC was efficiently degraded by UVC direct photolysis and the ecotoxicity of the UV-treated mixtures was investigated. Bioassays indicates that Daphnia similis (48 h EC₅₀ = 0.044 μM) was more sensitive to TCC than Pseudokirchneriella subcapitata (72 h IC₅₀ = 1.01 μM). TCC and its photoproducts caused significant effects on Eisenia andrei biochemical responses (catalase and glutathione-S-transferase); 48 h was a critical exposure time, since GST reached the highest activity values. UVC reduced the TCC toxic effect after 120 min. Furthermore, TCC was photodegraded in domestic wastewater which was simultaneously disinfected for total coliform bacterial (TCB) (360 min) and Escherichia coli (60 min).

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Graphical abstract TCC degradation and ecotoxicological assessment

     

Degradation of bisphenol A using UV and UV/H2O2 processes

Bisphenol A (BPA; 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol) is a substance typically used in the plastic industry. It is used in the production of epoxy resins, polycarbonate, or fire retardants or as a stabilizer and an antioxidant in numerous types of plastics. Bisphenol A is introduced into the environment via municipal and industrial wastewater. Because of its hydrophobic properties, BPA has the potential for sorption on activated sludge during the biological wastewater treatment processes. This study investigated the degradation of BPA by means of UV-radiation and in the UV/H2O2 process with the presence and absence of hydrocarbonate ions (HCO3(-)) as hydroxyl radicals (OH*) scavengers. The calculated value of quantum yield was equal to 0.18, and the value of BPA rate constant with hydroxyl radicals was equal to 3.3 x 10(9) M(-1) s(-1).     

Resolving the variability of CDOM fluorescence to differentiate the sources and fate of DOM in Lake Taihu and its tributaries

Taihu Basin is the most developed area in China, which economic development has resulted in pollutants being produced and discharged into rivers and the lake. Lake Taihu is located in the center of the basin, which is characterized by a complex network of rivers and channels. To assess the sources and fate of dissolved organic matter (DOM) in surface waters, we determined the components and abundance of chromophoric dissolved organic matter (CDOM) within Lake Taihu and 66 of its tributaries, and 22 sites along transects from two main rivers. In Lake Taihu, there was a relative less spatial variation in CDOM absorption a_CDOM(355) with a mean of 2.46 ± 0.69 m⁻¹compared to the mean of 3.36 ± 1.77 m⁻¹ in the rivers. Two autochthonous tryptophan-like components (C1 and C5), two humic-like components (C2 and C3), and one autochthonous tyrosine-like component (C4) were identified using the parallel factor analysis (PARAFAC) model. The C2 and C3 had a direct relationship with a_CDOM(355), dissolved organic carbon (DOC), and chemical oxygen demand (COD). The separation of lake samples from river samples, on both axes of the Principal Component Analysis (PCA), showed the difference in DOM fluorophores between these various environments. Components C1 and C5 concurrently showed positive factor 1 loadings, while C4 was close to the negative factor 1 axis. Components C2 and C3 showed positive second factor loadings. The major contribution of autochthonous tryptophan-like components to lake samples is due to the autochthonous production of CDOM in the lake ecosystems. The results also showed that the differences in geology and associated land use control CDOM dynamics, such as the high levels of CDOM with terrestrial characteristics in the northwestern upstream rivers and low levels of CDOM with increased microbial characteristics in the southwestern upstream rivers. Most of river samples from the downstream regions in the eastern and southeastern plains had a similar relative abundance of humic-like fluorescence, with less of the tryptophan-like and more of the tyrosine-like contributions than did samples from upstream regions.