北京市温榆河-北运河水系水质空间分布特征研究

采用水体三维荧光光谱(3D-EEMs)结合平行因子分析(PARAFAC)方法,研究了温榆河-北运河水系溶解性有机物(DOM)的荧光组分及其空间分布特征,并对沿岸污水处理厂、支流、干流的水质参数及其DOM组分之间的相互作用进行了分析。结果表明:温榆河-北运河水系干流溶解性有机碳(DOC)浓度与各支流接近,总磷浓度从上游到下游逐渐降低,氨氮和总磷污染严重。水体DOM共存在2类(4种)荧光组分,包括类腐殖质组分(类腐殖酸,C1;类富里酸,C2)和类蛋白组分(类色氨酸,C3;微生物代谢产物,C4)。污水处理厂出水汇入各支流后,水体DOM中的类腐殖质组分的比例上升。荧光比例显示,各河流DOM以C3组分为主,占比为24.76%~40.27%。水体荧光指数(1.58~1.72)、自生源指数(0.96~1.17)及腐殖化指数(0.74~0.81)计算结果指明,该水体的DOM组成具有内源和外源的双重特性,整体腐殖化程度低且自生源特性强。DOC与C1、C2和C4组分呈现极显著正相关,表明荧光组分可用于动态跟踪河流有机物;总氮与C1、C2组分呈极显著正相关,说明类腐殖质组分会对氮污染物浓度产生重要影响;总磷与自生源指数呈显著负相关(P＜0.05),表现为DOM腐殖化程度越高,总磷浓度越低。     

厌氧-缺氧-好氧处理工艺的污水处理厂进出水的毒性评价

为了准确评估厌氧-缺氧-好氧（A²/O）处理工艺对废水毒性的削减效率，采用斑马鱼胚胎急性毒性实验、发光细菌急性毒性实验和小鼠L929细胞毒性实验进行测试，结合理化指标，通过毒性当量（TU）法、平均毒性（AvTx）法、毒性指数（TxPr）法、最敏感测试（MST）法和潜在生态毒性效应（PEEP）法对常州市6家污水处理厂（生活污水、综合废水、化工废水、制药废水）进水和出水的生物毒性进行了评价。结果表明，斑马鱼胚胎的毒性敏感程度最高，3种受试生物的毒性评价结果具有较好的一致性。理化达标的污水处理厂出水仍存在一定的生物毒性效应，出水毒性较大的是综合污水处理厂，排入受纳水体后可能会对周围的生态环境产生潜在的生态风险。A²/O处理工艺对各污水处理厂进水的毒性削减较好，其中对制药废水的毒性削减最高，AvTx、TxPr、MST和PEEP的毒性削减率分别为99.45%、99.64%、99.48%和69.66%。与AvTx、TxPr、MST法相比，PEEP法能够更综合地评价废水毒性。     

磨盘山水库溶解性有机质光谱特性及来源分析

结合紫外可见吸收光谱与三维荧光光谱法，利用平行因子分析方法研究哈尔滨市磨盘山水库水体中的溶解性有机质（DOM）。结果表明，水体DOM吸收系数α355平均值为（4.71±0.66）m-1，表明水库中有色溶解性有机质（CDOM）较高；水库水体DOM存在3个荧光组分，分别为类腐殖质C1（345 nm、440 nm）、类腐殖质C2（285 nm、405 nm）和类富里酸组分C3（275 nm、475 nm）；C1、C3呈现显著的正相关性，自生源指数与C1呈显著的负相关性；类腐殖质的荧光强度在深层水体中逐渐增加，且深层水体的腐殖化程度较高，较为稳定；水库中心水体中DOM的自生源特征较其他区域明显，浮游植物和细菌的有机体降解产物增加。     

城市雨水管网沉积物不同分子量溶解性有机质空间分布及光谱特征

采用超滤法、紫外-可见吸收光谱和三维荧光光谱分析法研究了北京市西城区4个典型功能区(居民区、文教区、交通区、商业区)雨水管网表层沉积物中不同分子量溶解性有机质(DOM)的分布特征和光谱特性。结果表明:雨水管网沉积物DOM以小分子量组分为主,约占整体水平的60%~70%。通过分析还发现,沉积物中小分子量(小于3k Da)DOM主要是类蛋白物质,而腐殖类物质主要集中在DOM的大分子量(大于10k Da)区域,微生物活动对小分子量DOM贡献作用显著,由此可见,DOM的分子组成和结构特性在一定程度上可以作为雨水管网沉积物DOM主成分和来源的衡量指标。4个功能区DOM腐殖化水平较低,表现出随分子量增大DOM腐殖化程度升高的规律。     

GC-MS分析碱法草浆造纸废水中的有机污染物组成

碱法草浆造纸废水在酸性条件下经乙醚萃取--K-D浓缩器浓缩,采用气相色谱-质谱(GC-MS)联用仪对其有机污染物进行了分析研究.结果表明,该废水中共含有29种有机物,其中主要为有机酸类,占有机物总量的50.84%.其次为难降解的呋喃类和毒性较大的苯环类有机物,它们分别占有机物总量的25.12%和13.53%.     

城市垃圾填埋场渗滤液中污染物检测与分析

垃圾渗滤液水质复杂,危害性大,对其无害化处理尚未得到很好解决。溶解性有机物(DOM)是导致渗滤液处理难以达标的主导性污染物。采用GC-MS技术可将渗滤液中DOM标识划分为亲水性和疏水性两类物质,为DOM的针对性处理提供了新的思路。采用ICP-AES从渗滤液中检测出美国环境保护局颁布的13种优先污染重金属中的11种,其含量大幅超标。废弃的电子材料、颜料涂料、电池以及药物等物质的不分类收集是导致渗滤液中重金属浓度超标、毒性增强的主要原因。在垃圾渗滤液处理领域,认为BOD5/COD小于0.3就不可以采用生物法处理的传统观点已经不符合实验与工程现实。通过检测与分析,掌握了垃圾渗滤液的水质特性与污染源头,能够为制定切实可行的处理方案提供借鉴。     

七虎林河流域上游溶解性有机质光谱特性分析

七虎林河源头区地表腐殖质随着径流的冲刷进入水体，形成了天然有机质(NOM),其中，溶解性有机质(DOM)易对河流水质造成影响。为了研究七虎林河中DOM的时空分布特征及其对水质的影响，开展了6次采样，分析了水体及土壤吸收光谱和荧光光谱特征参数，利用平行因子(PARAFAC)算法解析了水体DOM的特性及来源。结果表明：七虎林河上游水体五日生化需氧量(BOD₅)、高锰酸盐指数(COD_Mn)、化学需氧量(COD)、可溶性有机碳(DOC)的浓度分别为1.4 mg/L±0.2 mg/L、6.1 mg/L±3.0 mg/L、21 mg/L±8 mg/L、7.0 mg/L±3.2 mg/L,BOD₅/COD平均值为0.08,说明流域内水体DOM的可生化性差，对水质影响较小。光谱特征参数紫外吸收系数(SUVA₂₅₄)、荧光指数(FI)、腐殖化指数(HIX)、生物源指数(BIX)分析结果表明，七虎林河上游云山水库库上林区河段DOM的物质组成与水库及库下河段差异显著。库上河段DOM的芳香碳含量更高、分子量更大、自生源组分...     

Profiling and monitoring of DOM in brewery wastewater and treated wastewater

Dissolved organic matter (DOM) in raw and treated wastewater from two breweries in Thailand was profiled and monitored for the purpose of water reclamation. The wastewater and the effluent from the use of an upflow anaerobic sludge blanket (UASB) and activated sludge (AS) were collected and analyzed through a resin fractionation method using the fluorescent excitation?Cemission matrix (FEEM) technique. The results revealed that the major organic fractions in the brewery wastewater were hydrophobic acid (HPOA) and hydrophilic base (HPIB), accounting for 65% of total dissolved organic carbon (DOC) mass for brewery A and 56% of total DOC mass for brewery B. The FEEM results indicated that the organic matter in the wastewaters of both breweries were mainly composed of tryptophan-like substances, represented by peaks C (230 nm_Ex/340?C365 nm_Em) and D (265?C295 nm_Ex/315?C390 nm_Em), and humic-like substances, represented by peaks E (290 nm_Ex/400 nm_Em), F (330?C335 nm_Ex/395?C410 nm_Em), and G (255?C265 nm_Ex/435?C455 nm_Em). The analysis revealed that the reduction of DOM occurred mostly during the UASB treatment where most of the DOM reduction resulted from the removal of the HPOA and HPIB fractions. The HPOA fraction, a group of humic-like substances, is of particular concern when reclaiming treated brewery wastewater, and although it was reduced by more than 80% of its initial amount, it was still a dominant DOM fraction in the effluents.     

Changes in the sorption and rate of 17β-estradiol biodegradation by dissolved organic matter collected from different water sources

The potential biodegradation and subsequent transformation of 17β-estradiol (E2) to estrone (E1) were examined in the presence of various dissolved organic matter (DOM) isolated from effluent, river and lake waters. In addition, estrogenicity was estimated in association with the removal of E2 via its sorption onto DOM and biodegradation. The more biodegradable lake-derived DOM promoted more extensive transformation of E2 into E1 than the effluent organic matter through a biodegradation process. Overall, under all conditions, biodegradation dominated the removal of E2 in water. The increased dissolved organic carbon (DOC) concentrations in river and lake-derived DOM (e.g. 6.5 mg C L(-1)) reduced the removal of E2 by decreasing its biodegradation due to the moderate sorption of E2 onto DOM. The effluent organic matter showed greater removal of E2 via biodegradation, as well as significantly high sorption. This was associated with a large amount of hydrophobic fulvic acid (FA)- and humic acid (HA)-like organic components, as shown by the small increase in the specific UV absorbance at 254 nm (SUVA(254)). An increase in the DOC concentration reduced the removal of E2, resulting in high estrogenicity. The present study suggests that both organic composition and DOC concentration influenced the removal of E2 and, therefore, should be fully considered when assessing estrogenicity and its impacts on the aquatic environment.     

Chemical speciation studies on DU contaminated soils using flow field flow fractionation linked to inductively coupled plasma mass spectrometry (FlFFF-ICP-MS)

Flow field flow fractionation (FlFFF) in combination with inductively coupled plasma mass spectrometry (ICP-MS) was used to study the chemical speciation of U and trace metals in depleted uranium (DU) contaminated soils. A chemical extraction procedure using sodium pyrophosphate, followed by isolation of humic and fulvic substances was applied to two dissimilar DU contaminated sample types (a sandy soil and a clay-rich soil), in addition to a control soil. The sodium pyrophosphate fractions of the firing range soils (Eskmeals and Kirkcudbright) were found to contain over 50% of the total U (measured after aqua regia digestion), compared to approximately 10% for the control soil. This implies that the soils from the contaminated sites contained a large proportion of the U within more easily mobile soil fractions. Humic and fulvic acid fractions each gave characteristic peak maxima for analytes of interest (Mn, Fe, Cu, Zn, Pb and U), with the fulvic acid fraction eluting at a smaller diameter (approximately 2.1 nm on average) than the humic fraction (approximately 2.4 nm on average). DU in the fulvic acid fraction gave a bimodal peak, not apparent for other trace elements investigated, including natural U. This implies that DU interacts with the fulvic acid fraction in a different way to all other elements studied.     

An HPLC method development for the assessment of degradation products of anthraquinone dye

The behavior of metsulfuron-methyl and its residues in an artificial pond was studied using a ¹⁴C isotopic tracer technique. Throughout the experimental period, the majority of metsulfuron-methyl residues were sustained in the pond water. Furthermore, the metsulfuron-methyl residues were just found in the surface layer of the sediment, and the transfer distance of these residues had only reached 9?C12 cm by the end of the experiment. The extract residues of metsulfuron-methyl in sediment were slightly higher than those of the bound residues (BR) during the initial experiment stage, while the BR dominated the surface sediment after 45 days. Finally, the metsulfuron-methyl residues could be combined with humus in the surface sediment, and the distribution of metsulfuron-methyl residues in fulvic acid was significantly higher than that in humic acid.     

Comparison of dissolved organic matter fractions in a secondary effluent and a natural water

This research compared the structural and chemical characteristics among dissolved organic matter (DOM) fractions within the same source and among different origins. Samples taken from the Taiping Wastewater Treatment Plant (TWTP) (Harbin, China) and from the Songhuajing River (SR), Heilongjiang Province, China were chosen to represent waters containing DOM of wastewater origin and of natural-water origin, respectively. DOM was fractionated using XAD resins into five fractions: hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N) and hydrophilic fraction (HPI). The SR fractions were more UV-sensitive and more reactive with chlorine in formation of trihalomethanes (THMs) than the TWTP secondary effluent (TSE) fractions. The aromatic character peaks in the Fourier-transform infrared (FT-IR) spectra of SR fractions were clearer than those of TSE fractions. On the other hand, the peaks of carbohydrates in TSE fractions were more prominent in comparison with SR fractions. In addition, the amide-2 peak was present in the spectra of all the five TSE fractions but not visible in the spectra of SR fractions. The fluorescence results showed that SR DOM fractions contained more fulvic acid-like fluorescent compounds while TSE DOM fractions had higher amounts of protein-like fluorescent components.     

DBP Levels in Chlorinated Drinking Water: Effect of Humic Substances

Chlorination is the most widely used technique for disinfection of drinking water. A consequence of chlorination is the formation of Disinfection By-Products (DBPs). The formation of DBPs in drinking water results from the reaction of chlorine with naturally occurring organic materials, principally humic and fulvic acids. This paper focuses on the effect of humic substances on the formation of twenty-four compounds belonging to different categories of DBPs. This investigation was conducted in two water treatment plants in Greece, Menidi and Galatsi, from July 1999 to April 2000. Humic substances were determined by the diethylaminoethyl (DEAE) method with subsequent UV measurement. The techniques used for the determination of DBPs were liquid-liquid extraction, gas chromatography and mass spectrometry. The concentrations of DBPs were generally low. Total trihalomethanes (TTHMs) ranged from 5.1 to 24.6 microg L(-1), and total haloacetic acids (HAAs) concentration ranged from 8.6 to 28.4 microg L(-1), while haloaketones (HKs) and chloral hydrate (CH) occurred below 1 microg L(-1). The content of humic substances was found to influence the formation of DBPs and especially TTHMs, trichloroacetic acid (TCA), dibromoacetic acid (DBA), CH, 1,1-dichloropropanone (1.1-DCP) and 1,1,1-trichloropropanone (1,1,1-TCP). Seasonal variation of TTHMs and HAAs generally followed that of humic substances content with peaks occurring in autumn and spring. The trends of 1,1-DCP, 1,1,1-TCP and CH formation seemed to be in contrast to TTHMs and HAAs. Trends of formation of individual compounds varied in some cases, probably due to influence of parameters other than humic substances content. Statistical analysis of the results showed that the concentrations of TTHMs, CH, 1,1-DCP, 1,1,1-TCP, TCA and DBA are strongly affected from humic substances content (at 0.01 confidence level). The opposite is true for dichloroacetic acid (DCA) concentration. Humic substances also vary to a statistically significant degree during different months, as well as the concentrations of TTHMs, CH, 1,1-DCP, 1,1,1-TCP, TCA and DCA. The variance of DBA was not statistically significant. Regarding the effect of sampling station, humic substances content showed no statistically significant difference between the two raw water sources studied.     

Multistep, microvolume resin fractionation combined with 3D fluorescence spectroscopy for improved DOM characterization and water quality monitoring

Conventionally, resin fractionation (RF) method has been widely used to characterize dissolved organic matter (DOM) found in different source waters based on general and broad DOM fractions grouping. In this study, a new refined method using multistep, microvolume resin fractionation combined with excitation emission matrix fluorescence spectroscopy (MSM-RF-EEMS) was developed for further isolation and characterization of subfractions within the primary DOM fractions separated from using the conventional RF method. Subsequently, its feasibility in indicating the occurrence of urban pollution in source waters was also assessed. Results from using the new MSM-RF-EEMS method strongly illustrated that several organic subfractions still exist within the regarded primary pure hydrophobic acid (HoA) fraction including the humic- and fulvic-like organic matters, tryptophan- and tyrosine-like proteins. It was found that by using the MSM-RF-EEMS method, the organic subfractions present within the primary DOM fraction could be easily identified and characterized. Further validation on the HoA fraction using the MSM-RF-EEMS method revealed that the constant association of EEM peak T1 (tryptophan) fraction could specifically be used to indicate the occurrence of urban pollution in source water. The correlation analysis on the presence of EEM peak T2 (tyrosine) fraction could be used as a supplementary proof to further verify the presence of urban pollution in source waters. These findings on using the presence of EEM peaks T1 and T2 within the primary HoA fraction would be significant and useful for developing a sensory device for online water quality monitoring.     

The simultaneous modelling of metal ion and humic substance transport in column experiments

Pulsed column experiments using Co, fulvic acid and porous sediment packing, along with up/down-flooding experiments using Eu, humic acid and intact sandstone blocks have been performed. The elution of metal and humic and their distribution along the sandstone columns have been measured. A mixed equilibrium and kinetic coupled chemical transport model has been used to simulate the results. In both cases, one exchangeable and one non-exchangeable component have been used to simulate the interaction of metal and humic substance. For the pulsed experiments, a simple equilibrium approach was used to model humic sorption, while a two component, kinetic model was required for the sandstone columns.     

Penetration of polar brominated DBPs through the activated carbon columns during total organic bromine analysis

Total organic bromine (TOBr) is a collective parameter representing all the brominated organic disinfection byproducts (DBPs) in water samples. TOBr can be measured using the adsorption-pyrolysis method according to Standard Method 5320B. This method involves that brominated organic DBPs are separated from inorganic halides and concentrated from aqueous solution by adsorption onto the activated carbon (AC). Previous studies have reported that some commonly known brominated DBPs can partially penetrate through the AC during this adsorption step. In this work, the penetration of polar brominated DBPs through AC and ozone-modified AC was explored with two simulated drinking water samples and one chlorinated wastewater effluent sample. Polar brominated DBPs were selectively detected with a novel precursor ion scan method using electrospray ionization-triple quadrupole mass spectrometry. The results show that 3.4% and 10.4% of polar brominated DBPs (in terms of total ion intensity) in the chlorinated Suwannee River fulvic acid and humic acid samples, respectively, penetrated through the AC, and 19.6% of polar brominated DBPs in the chlorinated secondary wastewater effluent sample penetrated through the AC. The ozone-modification of AC minimized the penetration of polar brominated DBPs during the TOBr analysis.     

Heat shock protein 47 stress responses in Chinese hamster ovary cells exposed to raw and reclaimed wastewater

As wastewater reclamation and reuse becomes more widespread, risks of exposure to treated wastewater increase. Moreover, an unlimited number of pollutants can be identified in wastewater. Therefore, comprehensive toxicity assessment of treated wastewater is imperative. The objective of this study was to perform a comprehensive toxicity assessment of wastewater treatment systems using stress response bioassays. This powerful tool can comprehensively assess the toxicity of contaminants. In this study, samples from conventional activated sludge treatment, membrane bioreactors (MBRs) with different pore sizes and sludge retention times (SRTs), rapid sand filtration, coagulation, nano-filtration (NF) and reverse osmosis (RO) were investigated. The results of stress response bioassays confirmed that the secondary effluent showed higher stress response than influent indicating that biological treatment generates toxic compounds. The results obtained from molecular weight fractionation of water samples demonstrated that organic matter with a higher molecular weight fraction (>0.1 μm) causes toxicity in secondary effluent. Furthermore, supernatant from MBR reactors showed toxicity regardless of SRT. On the other hand, stress response was not detected in MBR permeates except for an MBR equipped with a larger pore size membrane (0.4 μm) and with a short SRT (12 days). While rapid sand filtration could not remove the toxic compounds found in secondary effluent, coagulation tests, operated at an appropriate pH, were effective for reducing stress response in the secondary effluent. Experimental findings also showed that stress response was not detected in cases of NF and RO permeate subsequent to MBR treatment.