固相萃取—高效液相色谱法测定水中痕量酚

研究了水中7种痕量酚类物质的前处理方法和采用高效液相色谱（HPLC）分析的色谱条件。用Waters Oasis HLB固相萃取小柱预分离和富集水中的酚,采用Agilent ZORBAX-C18分析柱进行色谱分离,以乙腈和0．1mol／L的磷酸作为流动相进行线性梯度洗脱,流速为1．5mL／min。各组分均在其最大紫外吸收波长下进行检测。结果表明,7种酚在13min之内能够很好地分离,回收率为80％～104％,相对标准偏差为2．4％～8．5％,色谱最低检测浓度达0．1～0．4mg／L,方法检出限为0．1～0．4μg／L。     

超高效液相色谱-高分辨质谱法测定水体中青霉素残留

采用超高效液相色谱-高分辨质谱法(UPLC-HRMS)同时测定水体中7种青霉素残留。水样经Oasis HLB固相萃取小柱富集和净化后,用反向C18色谱柱分离,以0.1%的甲酸水溶液和乙腈溶液为流动相进行梯度洗脱,采用电喷雾离子源正离子模式进行检测。7种青霉素类化合物在1.0~20.0μg/L的线性范围内,相关系数r均大于0.99,检出限为1~10 ng/L。实际水样加标回收率为91.15%~106.36%,相对标准偏差为2.30%~8.47%,均小于10%。该方法具有简单快速、准确度高等特点,可以实现水体中7种目标青霉素残留的测定。     

利用气质联用技术对木材进行分类和鉴别

采用气质联用技术(GC-MS)对不同类及不同产地的同类木材进行分析,结果发现:不同类木材的总离子流图差别非常明显,相关系数非常小;而同类木材总离子流图基本相同,相关系数较高,并且都含有相同的特征峰.上述实验结果表明,鉴别木材有2种有效方法:一是利用相关系数,即相关系数大于0.900的可认为是同类木材;二是根据特征成分,即每种木材在其总离子流图中都有一组特征峰.     

HPLC-PDA detection of cylindrospermopsin--opportunities and limits

The cyanobacterial hepatotoxic alkaloid cylindrospermopsin (CYL) is of increased concern to public health due to the spreading of its main producer, Cylindrospermopsis raciborskii, around the globe. Here we present results of an evaluation of the possibility to analyse environmental samples for their content of CYL based on HPLC with photo diode array detection as an alternative to costly LC-MS approaches. A gradient from 0% to 50% aqueous methanol (+0.05% trifluoroacetic acid) in 20 min proved to be highly reproducible with respect to peak height, peak area, and retention time of purified CYL. Good linearity of peak area response was found for 1-300 ng CYL on column. For a good performance the duration of equilibration prior to individual runs was crucial. Extraction from cell material (culture and bloom) was efficiently done with pure water in one extraction step and CYL contents determined matched well with results previously obtained by LC-MS. When different seston matrices were added to cultured cells to mimic realistic environmental samples, however, peaks eluting close to CYL in chromatograms restrained the performance. The data presented show a limitation of HPLC-PDA analysis for trace amounts of CYL in environmental samples but also underline the potential of an inexpensive and fast analysis for various purposes.     

An assessment of estrogenic organic contaminants in Canadian wastewaters

A suite of 30 primarily estrogenic organic wastewater contaminants was measured in several influent/effluent wastewater samples from four municipal wastewater treatment plants and effluents from one bleached kraft pulp mill (BKME) using an ultra-trace analytical method based on gas chromatography-high resolution mass spectroscopy (GC-HRMS). In vitro recombinant yeast assay detection of the estrogenic equivalent (EEq) on whole and solid phase extracted (SPE) and fractionated wastewater was also performed. 19-norethindrone was the most frequently detected and abundant (26-224 ng/L) of all the synthetic estrogens/progesterones in the influent samples. 17alpha-ethinylestradiol was the more frequently detected synthetic estrogen/progesterone in the effluents occurring at or below 5 ng/L with some sporadic occurrences of up to 178 ng/L. The greatest levels of steroidal estrogens in municipal effluents were E1>E2>E3 which were all <20 ng/L. Nonylphenol and di(2-ethylhexyl) phthalate were found to be the highest non-steroidal synthetic compounds surveyed in both municipal influent and effluent samples, both occurring at 6-7 microg/L in municipal effluents. BKME contained relatively large amounts of the plant sterol stigmasterol (4 microg/L) but low amounts of fecal sterols, and steroidal estrogens (E2 only at 6 ng/L) when compared to the municipal effluents. In vitro EEq in the wastewater surveyed ranged from 9-106 ng E2/L and ranked from municipal influent>municipal effluent approximately BKME, with most of the estrogenicity fractionating in the 100% methanol SPE fraction followed by a secondary amount in the diethyl ether (for municipal) or methyl-tert butyl ether (for BKME) SPE fractions. Most correlations between chemical and in vitro estrogenic equivalency were weak (p>0.05 in most cases). Unexpected inverse correlations between in vitro estrogenic activity and concentrations of the estrogenic contaminant bisphenol A were found which likely contributed to the weakness of these correlations. A modified toxicity identification and evaluation procedure was continued with the SPE extracts from the more potent 100% methanol SPE fractions of municipal effluent. High performance liquid chromatography band elution retention times, based on in vitro estrogen detection, indicated that steroidal estrogens such as E2 were responsible for most of the estrogenicity of the samples. Subsequent collection and GC-MS analysis of active bands did not confirm the presence of steroidal estrogens, but expanded the possibility of phthalate esters (i.e. dibutyl phthalate) and natural sterols (i.e. beta-sitosterol) contributing to the overall estrogenic load.     

化学生物絮凝工艺去除城市污水中重金属的研究

采用化学生物絮凝工艺处理上海市的低浓度城市污水，考察了对污水中重金属的去除效果，探讨了化学生物絮凝工艺反应的实质。平行对比试验结果显示：化学生物絮凝工艺中存在着化学和生物的协同作用，是一种深度集成的污水强化一级处理工艺。在相同的加药量下，该工艺在减少絮凝产物中铝含量的同时，可去除部分有害重金属元素且效果优于化学强化一级处理工艺。对铝的去除率比单一的化学絮凝工艺提高了106％；在重金属元素去除方面，对铬和锰的去除率提高了10％～15％，对镍元素的吸附量也有一定的提高。但是该工艺在处理高浓度污水时，处理效果会受到重金属浓度的制约。     

城市污水生物—生态处理工艺的能效分析

采用生物—生态组合工艺处理城市污水,其中生物单元采用连续流一体化生物反应器(CIBR),生态单元采用波形潜流人工湿地。根据原水水质和生态单元处理效能的季节性变化,通过调整CIBR生物单元的运行工况,实现了对城市污水的高效、低耗、稳定、达标处理。该系统的出水水质全年可稳定地达到《城镇污水处理厂污染物排放标准》(GB 18918—2002)的一级A标准,处理能耗平均为0.362(kW.h)/m3,在达到相同处理效果的基础上,比A2/O工艺和Bardenpho工艺分别降低了37.69%和57.91%。该组合工艺的节能原理是建立在生物单元变工况运行与生态单元低能耗脱氮除磷共同作用基础上的。     

The assessment of particle association and UV disinfection of wastewater using indigenous spore-forming bacteria

Studies have shown that association between particles and coliform bacteria in wastewater influence the inactivation of these microorganisms by ultraviolet (UV) irradiation. This research investigated the potential use of indigenous aerobic spore-forming (ASF) bacteria for studying the particle - microorganism interaction and its effect on UV disinfection of protozoan pathogens, such as Giardia spp. and Cryptosporidium spp., present in effluents from full-scale municipal wastewater treatment plants. The effect of particle - ASF association was determined by homogenizing wastewater effluent samples before and after exposure to controlled UV doses delivered by a bench-scale collimated beam apparatus. Particle association between Bacillus subtilis spores added to wastewater and wastewater particles was also assessed. The results indicate that spores are not significantly associated with wastewater particulate matter and particle association does not significantly affect the inactivation of indigenous spores present in wastewater by UV radiation in this study.     

城市污水脱氮除磷技术与展望

介绍了国内外城市污水的脱氮除磷现状,探讨了城市污水脱氮除磷技术的发展趋势,同时提出较为高效、经济且资源化的城市污水脱氮除磷工艺,对城市污水脱氮除磷技术的发展进行了展望。     

Selected organic pesticides, behavior and removal from domestic wastewater by chemical and physical processes

A study was conducted to evaluate the effectiveness of chemical and physical wastewater treatment processes in removing selected organic pesticides from domestic wastewater. A 3785 m³ day⁻¹ (1 MGD) nominal capacity pilot plant consisting of biological, chemical and physical units was used for the study. Biologically treated domestic wastewater was subjected to chemical coagulation, multimedia filtration, and activated carbon adsorption. Eight sequences of treatment processes were studied. Influent and effluent samples were analyzed for selected chlorinated hydrocarbon pesticides and chlorophenoxy herbicides using EC-GC. Confirmatory tests such as TLC, extraction of p-value and CPU-MS-GC were applied on selected samples. Results of the study provided qualitative and quantitative evaluation of the performance of the treatment processes studied. Qualitatively characteristic profiles consisting of a limited number of refractory organic residues were detected as peaks on EC chromatograms of extracts from each treatment unit. Thirteen compounds were confirmed in the biologically treated wastewater. These included DDT and its metabolites, aldrin, dieldrin, and 2,4-D alkyl esters and salts. Concentration levels of these compounds in wastewaters were at the ng l⁻¹ (part per trillion) level. Chemical coagulation with alum-lime or lime-ferric chloride was found to effect slight reduction of the organic residues detected on EC chromatograms. Quantitatively only DDT compounds were more completely removed by chemical treatment. Multimedia filters had no discernible effect in removing organic residues from biologically and chemically treated wastewater. Activated carbon columns were found to be the most effective means for removing the refractory organic residues detected. However, breakthrough of some organic residues was noted after usage of the carbon for over 1 year. The overall results of the study showed that application of several sequences of treatment processes on domestic wastewater can produce a high quality effluent which is virtually free from EC detectable organic residues.     

Historical trends in occurrence and atmospheric inputs of halogenated volatile organic compounds in untreated ground water used as a source of drinking water

Analyses of samples of untreated ground water from 413 community-, non-community- (such as restaurants), and domestic-supply wells throughout the US were used to determine the frequency of detection of halogenated volatile organic compounds (VOCs) in drinking-water sources. The VOC data were compiled from archived chromatograms of samples analyzed originally for chlorofluorocarbons (CFCs) by purge-and-trap gas chromatography with an electron-capture detector (GC-ECD). Concentrations of the VOCs could not be ascertained because standards were not routinely analyzed for VOCs other than trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113). Nevertheless, the peak areas associated with the elution times of other VOCs on the chromatograms can be classified qualitatively to assess concentrations at a detection limit on the order of parts per quadrillion. Three or more VOCs were detected in 100% (percent) of the chromatograms, and 77.2% of the samples contained 10 or more VOCs. The maximum number of VOCs detected in any sample was 24. Modeled ground-water residence times, determined from concentrations of CFC-12, were used to assess historical trends in the cumulative occurrence of all VOCs detected in this analysis, as well as the occurrence of individual VOCs, such as CFC-11, carbon tetrachloride (CCl(4)), chloroform and tetrachloroethene (PCE). The detection frequency for all of the VOCs detected has remained relatively constant from approximately 1940 to 2000; however, the magnitude of the peak areas on the chromatograms for the VOCs in the water samples has increased from 1940 to 2000. For CFC-11, CCl(4), chloroform and PCE, small peaks decrease from 1940 to 2000, and large peaks increase from 1940 to 2000. The increase in peak areas on the chromatograms from analyses of more recently recharged water is consistent with reported increases in atmospheric concentrations of the VOCs. Approximately 44% and 6.7% of the CCl(4) and PCE detections, respectively, in pre-1940 water, and 68% and 62% of the CCl(4) and PCE detections, respectively, in water recharged in 2000 exceed solubility equilibrium with average atmospheric concentrations. These exceedences can be attributed to local atmospheric enrichment or direct contaminant input to ground-water flow systems. The detection of VOCs at concentrations indicative of atmospheric sources in 100% of the samples indicates that untreated drinking water from ground-water sources in the US recharged within the past 60 years has been affected by anthropogenic activity. Additional inputs from a variety of sources such as spills, underground injections and leaking landfills or storage tanks increasingly are providing additional sources of contamination to ground water used as drinking-water sources.     

农家乐污水中溶解性有机质的三维荧光特性研究

采用三维荧光光谱(3DEEM)技术考察了农家乐污水中溶解性有机质的三维荧光特性.结果表明,农家乐污水中的有机污染物荧光峰以类蛋白质荧光峰为主,其中高激发波长类色氨酸荧光峰Peak T最强,其次是低激发波长类色氨酸荧光峰Peak S和低激发波长类酪氨酸荧光峰Peak D;综合性农家乐污水的Peak S和Peak D荧光强度比以餐饮为主的农家乐污水的要强.农家乐污水经受纳水体稀释和净化后,类蛋白质荧光强度仍远高于地表水的.其对受纳水体的污染不容忽视.     

Synergistic effect of the sequential use of UV irradiation and chlorine to disinfect reclaimed water

The effectiveness of UV and chlorination, used individually and sequentially, was investigated in killing pathogenic microorganisms and inhibiting the formation of disinfection by-products in two different municipal wastewaters for the source water of reclaimed water, which were from a microfilter (W1) and membrane bioreactor (W2) respectively. Heterotrophic plate count (HPC), total bacteria count (TBC), and total coliform (TC) were selected to evaluate the efficiency of different disinfection processes. UV inactivation of the three bacteria followed first-order kinetics in W1 wastewater, but in W2 wastewater, the UV dose-response curve trailed beyond approximately 10 mJ/cm² UV. The higher number of particles in the W2 might have protected the bacteria against UV damage, as UV light alone was not effective in killing HPC in W2 wastewater with higher turbidity. However, chlorine was more effective in W2 than in W1 for the three bacteria inactivation owing to the greater formation of inorganic and organic chloramines in W1 wastewater. Complete inactivation of HPC in W1 wastewater required a chlorine dose higher than 5.5 mg/L, whereas 4.5 mg/L chlorine gave the equivalent result in W2 wastewater. In contrast, sequential UV and chlorine treatment produced a synergistic effect in both wastewater systems and was the most effective option for complete removal of all three bacteria. UV disinfection lowered the required chlorine dose in W1, but not in W2, because of the higher chlorine consumption in W2 wastewater. However, UV irradiation decreased total trihalomethane formation during chlorination in both wastewaters.     

Modeling the elution of organic chemicals from a melting homogeneous snow pack

Organic chemicals are often released in peak concentrations from melting snow packs. A simple, mechanistic snowmelt model was developed to simulate and predict the elution of organic substances from melting, homogeneous snow, as influenced by chemical properties and snow pack characteristics. The model calculates stepwise the chemical transport along with the melt water flow in a multi-layered snow pack, based on chemical equilibrium partitioning between the individual bulk snow phases. The model succeeds in reproducing the elution behavior of several organic contaminants observed in previously conducted cold room experiments. The model aided in identifying four different types of enrichment of organic substances during snowmelt. Water soluble substances experience peak releases early during a melt period (type 1), whereas chemicals that strongly sorb to particulate matter (PM) or snow grain surfaces elute at the end of melting (type 2). Substances that are somewhat water soluble and at the same time have a high affinity for snow grain surfaces may exhibit increasing concentrations in the melt water (type 3). Finally, elution sequences involving peak loads both at the beginning and the end of melting are simulated for chemicals that are partially dissolved in the aqueous melt water phase and partially sorbed to PM (type 4). The extent of type 1 enrichment mainly depends on the snow depth, whereby deeper snow generates more pronounced concentration peaks. PM influences the elution behavior of organic chemicals strongly because of the very large natural variability in the type and amount of particles present in snow. Urban and road-side snow rich in PM can generate type 2 concentration peaks at the end of the melt period for even relatively water soluble substances. From a clean, melting snow pack typical for remote regions, even fairly hydrophobic chemicals can be released in type 1 mode while being almost completely dissolved in the aqueous melt water phase. The model provides a mechanistic understanding of the processes that lead to chemical peak releases during snowmelt.     

水温对太湖流域城镇污水厂除污效果影响的调研

对太湖流域三个城市的6座城镇污水处理厂的污水水温变化及运行效果进行了分析,探索了温度对污水厂生物处理效果的影响规律。结果表明:江苏省太湖流域污水处理厂污水水温变化范围是9.6～31℃,年平均值为(20.3±6.0)℃;污水水温12℃的年概率约为9%;气温变化速率约为水温变化速率的1.7倍。污水水温对COD和TP的去除效果影响不明显;但污水水温降至15℃左右时,低温对活性污泥硝化反硝化性能的抑制作用开始逐渐增强,因此太湖流域大多数城镇污水处理厂采取了应对低温的各项强化措施。     

Biological degradation of pharmaceuticals in municipal wastewater treatment: proposing a classification scheme

A simple classification scheme is suggested to characterize the biological degradation of micropollutants such as pharmaceuticals, musk fragrances and estrogens during wastewater treatment. The scheme should be a basis for the discussion about potential removal efficiencies. Hence, the biological degradation of 25 pharmaceuticals, hormones and fragrances was studied in batch experiments at typical concentration levels using activated sewage sludge originating from nutrient-eliminating municipal wastewater treatment plants. Since pseudo first-order degradation kinetics was observed for all compounds down to ng L(-1) levels, the removal rates can be predicted for various reactor configurations. Therefore dilution of wastewater (e.g. by extraneous water) is expected to reduce the degree of biological removal. Wastewater segregation and treatment at the source are therefore to be favoured for elimination of persistent micropollutants over centralized end-of-pipe treatment. For reactor configurations typical for nutrient removal in municipal wastewater, the derived formula for predicting removal allows the identification of three groups of micropollutants according to their degradation constant k(biol): compounds with k(biol)<0.1 L g(SS)(-1)d(-1) are not removed to a significant extent (<20%), compounds with k(biol)>10 L g(SS)(-1)d(-1) transformed by >90% and in-between moderate removal is expected. Based on the degradation of a heterogeneous group of 35 compounds (including literature data), state of the art biological treatment schemes for municipal wastewater are not efficient in degrading pharmaceuticals: only 4 out of 35 compounds are degraded by more than 90% while 17 compounds are removed by less than 50%.     

A policy framework for trans‐boundary wastewater issues along the Green Line,the Israeli–Palestinian border

The annual discharges of municipal wastewater across the Green Line (the Israeli–Palestinian border) are causing a bi‐national conflict with political, environmental, and economic dimensions. This paper surveys the current scope of wastewater facilities in Palestinian communities and discusses the immense challenges to achieving sustainable wastewater treatment facilities. Current Israeli water policy hinders effective regional solutions to trans‐boundary wastewater issues. This paper proposes a less confrontational approach to solve common problems. The better management of bi‐national wastewater resources could establish sustainable trans‐boundary sanitation facilities. This would bring a range of benefits to health, the environment, and socio‐economic life.     

Evaluation of on-site biological treatment for landfill leachates and its impact: A size distribution study

A cost effective and widely applied approach for landfill leachate disposal is to discharge it to a municipal wastewater treatment plant (WWTP). The recalcitrant nature of leachate organics and the impact on the downstream WWTPs were comprehensively investigated in this study. Size fractionation by ultrafiltration (UF) and microfiltration (MF) was employed in conjunction with various analyses (TOC, COD, nitrogen species and UV₂₅₄ absorbance) on raw and biologically treated landfill leachates to provide insight into biological treatability. Overall, landfill leachate organics showed bio-refractory properties. Less than half of the organic matter, measured as total organic carbon (TOC), could be removed in the biological processes examined. Size distribution data showed that the <1 thousand Daltons (kDa) fraction is dominant in most untreated and treated landfill leachates, indicating difficulties for membrane treatment. Also, most removal occurred for the <1 kDa fraction in the biological processes, while the intermediate size fractions increased slightly. This may be caused by bio-flocculation and/or partial degradation of larger molecular weight fractions. Organic nitrogen was investigated in this study as one of the first explorations for landfill leachates. Organic nitrogen in landfill leachates was more bio-refractory than other organic matter. UV quenching by landfill leachates was also investigated since it interferes with the UV disinfection at WWTPs. The combination of activated carbon and activated sludge (PACT) showed some effectiveness for reducing UV quenching, indicating that carbon adsorption is a potential method for removal of UV quenching substances. Fourier transform Infrared (FT/IR) data showed that aromatic groups are responsible for the UV quenching phenomenon.     

城镇污水处理工艺对紫外线消毒RED的影响

使用准平行紫外光束仪测定了重庆市3个采用不同处理工艺的城镇污水处理厂终沉池出水中粪大肠菌群(FC)的紫外线响应曲线,考察了不同处理工艺对紫外线消毒等效生物验证剂量(RED)的影响.结果表明,在15mJ/CM2的紫外线辐照剂量下,3个污水处理厂终沉池出水中的FC未发生光复活和暗复活现象;运用虚拟变量回归分析法对3个水样的试验数据进行统计分析,发现3个水样属于同一个样本空间,表明不同的二级污水处理工艺对紫外线消毒效果没有显著影响;基于数据合并处理的结果,建议新建的城镇二级污水处理厂的紫外线消毒反应器的进水FC浓度设计值取5.0×106MPN/L,以对应1.0×104和1.0×103MPN/L的两个排放标准,REDmsz分别为25和36mJ/cm2.     

Operating strategies for variable-flow sequencing batch reactors

Sequencing batch reactors (SBRs) are variable‐volume, non‐steady‐state, suspended‐growth biological wastewater treatment reactors. The treatment process is characterised by a repeated treatment cycle consisting of a series of sequential process phases: fill, react, settle, decant and idle. The design and operation of an SBR must take into account (1) the biological process requirement for treating influent wastewater and (2) the hydraulic requirement to enable throughput of the water through the reactor without compromising on the quality of biological treatment. During routine operation, the priority between the process and hydraulic consideration can change depending on the influent flow rate and its rate of change. The importance of the interaction between these considerations will vary depending on the fill strategy and the cycle time control strategy. Where flow‐proportional cycle times are utilised to optimise the treatment process, the operating strategy must be capable of accurately adjusting the intercycle phase times to prevent loss of biological treatment or volumetric capacity. This paper considers various operating strategies and describes the specific strategy used at the SBR at Avonmouth wastewater treatment works.