Assessing the removal of pharmaceuticals and personal care products in a full-scale activated sludge plant

Purpose

This study aimed to investigate the removal mechanisms of pharmaceutical active compounds (PhACs) and musks in a wastewater treatment plant (WWTP). Biological removal and adsorption in the activated sludge tank as well as the effect of UV radiation used for disinfection purposes were considered when performing a mass balance on the WWTP throughout a 2-week sampling campaign.

Methods

Solid-phase extraction (SPE) was carried out to analyse the PhACs in the influent and effluent samples. Ultrasonic solvent extraction was used before SPE for PhACs analysis in sludge samples. PhAC extracts were analysed by LC-MS. Solid-phase microextraction of liquid and sludge samples was used for the analysis of musks, which were detected by GC-MS. The fluxes of the most abundant compounds (13 PhACs and 5 musks) out of 79 compounds studied were used to perform the mass balance on the WWTP.

Results

Results show that incomplete removal of diclofenac, the compound that was found in the highest abundance, was observed via biodegradation and adsorption, and that UV photolysis was the main removal mechanism for this compound. The effect of adsorption to the secondary sludge was often negligible for the PhACs, with the exceptions of diclofenac, etofenamate, hydroxyzine and indapamide. However, the musks showed a high level of adsorption to the sludge. UV radiation had an important role in reducing the concentration of some of the target compounds (e.g. diclofenac, ibuprofen, clorazepate, indapamide, enalapril and atenolol) not removed in the activated sludge tank.

Conclusions

The main removal mechanism of PhACs and musks studied in the WWTP was most often biological (45%), followed by adsorption (33%) and by UV radiation (22%). In the majority of the cases, the WWTP achieved >75% removal of the most detected PhACs and musks, with the exception of diclofenac.     

杭州某污水处理厂活性污泥中三氯生含量测定

采用快速溶剂萃取(ASE)进行样品前处理,用高效液相色谱检测了杭州某污水处理厂活性污泥中的三氯生(TCS)含量。在单因素基础上,通过正交实验得出ASE萃取最佳条件为甲醇作萃取剂,萃取时间2min,萃取次数4次,萃取温度80℃,冲洗体积70%。在色谱柱为Hypersil ODS2C18柱、流动相为甲醇/水(体积比95∶5)溶液、流量为1.0mL/min条件下检测。该方法的检出限为0.1μg/mL,线性范围为5~100μg/mL,方法的回收率为93.89%~105.62%,相对标准偏差(RSD)小于6%。该方法简单快速,灵敏度高,适用于活性污泥中TCS的检测。     

Assessment of the importance of sorption for steroid estrogens removal during activated sludge treatment

Distribution coefficients (K(d)) between water and activated sludge particles (f(oc)=27.7+/-0.1%) were measured for the steroid estrogens (SE), estrone (E1), 17beta-estradiol (E2) and 17alpha-ethinylestradiol (EE2) in batch experiments. Experimental concentration levels ranged from environmentally realistic low ng/l to the high microg/l. In this range K(d)s were independent of their water concentration. The experimentally obtained K(d)s (with 95% confidence intervals) were 402+/-126 l/kg, 476+/-192 l/kg and 584+/-136 l/kg for E1, E2 and EE2, respectively. K(d)s were used to estimate the fraction of the total SE concentration that is expected to be sorbed in the activated sludge treatment tanks of a typical STP assuming equilibrium conditions. Assuming a suspended solids concentration of 4 g/l dissolved solids (ds), it was estimated that 61+/-9%, 66+/-13% and 70+/-6% of the total concentration of E1, E2 and EE2, respectively, would be sorbed during activated sludge treatment. The fraction of the SEs that was expected to be sorbed to suspended sludge particles in the effluents from a typical Danish STP was estimated to be only 0.20+/-0.06%, 0.24+/-0.10% and 0.29+/-0.07% of the total concentration of E1, E2 and EE2, respectively, at a suspended solids concentration of 5 mg/lds. For a typical STP the removal of steroid estrogens with excess sludge was estimated to be only 1.5-1.8% of the total loading if equilibrium conditions exists. Sorption is therefore not important for the fate of SEs in STPs compared to biodegradation.     

DS-EBPR颗粒污泥和絮状污泥除磷效能

为提高反应器的稳定性,同时对硫循环协同反硝化生物除磷（DS-EBPR）颗粒污泥和絮体污泥的脱氮除磷效果以及物质转化规律进行对比研究,实验采用序批式活性污泥反应器（SBR）分别培养DS-EBPR絮体污泥和颗粒污泥。结果表明：GSBR（颗粒污泥SBR）乙酸根平均去除率和磷平均去除率均高于FSBR（絮体污泥SBR）;且GSBR中PHA（聚羟基脂肪酸）的作用机制相比于FSBR明显优于glycogen（糖原）,表明GSBR具有更好的功能微生物富集作用;反应器运行过程中poly-S（聚硫颗粒）储存形式的转变表明DS-EBPR系统中poly-S的转化形式并不是根据反应阶段固定的,而是根据系统能量供需状态变化的,且对比硫循环转化效果显示GSBR的能量利用效率高于FSBR。     

Fe0还原、芬顿氧化及其耦合技术去除染料厂剩余污泥中的AOX

染料废水中含有大量难生物降解的卤代有机物合成中间体,合成卤代有机物在废水的生物处理过程中容易被吸附到剩余污泥中,如不能妥善处理会引起生态健康风险。研究了零价铁还原、芬顿氧化及其组合技术对染料企业剩余污泥中AOX（可吸附有机卤代物）的去除效果,优化了处理条件,解析了去除机理。结果表明,铁粉投加量为5 g·L-1,厌氧反应30 d时,零价铁还原对污泥中AOX降解率仅为24.7%;Fe2+投加量0.059 mol·L-1,H2O2投加量0.89 mol·L-1,芬顿氧化1.5 h时,污泥中AOX去除率提高至73.7%;投加2 g·L-1的铁粉,还原30 d后再进行芬顿反应,则污泥中AOX去除率可达到90.3%。GC-MS分析结果表明,污泥中的主要AOX物质为2,6-二氯-4-硝基苯胺,该物质经过零价铁还原与芬顿氧化组合工艺处理后,比直接芬顿氧化能得到更有效的去除。     

The occurrence and removal of selected pharmaceutical compounds in a sewage treatment works utilising activated sludge treatment

Pharmaceutical substances have been detected in sewage effluents as well as receiving waters in many parts of the world. In this study, the occurrence and removal of a number of drug compounds were studied within a large sewage treatment plant in the south of England. Samples were processed using solid phase extraction and analysed using gas chromatography-mass spectrometry (GC-MS). The results demonstrate that ibuprofen, paracetamol, salbutamol and mefenamic acid were present in both the influent and effluent of the works while propranolol-HCl was not found above the limit of quantification in any sample. Elimination rates were circa 90% for each compound but several hundred nanograms per litre were still present in the final effluent.     

A comparison of five rapid direct toxicity assessment methods to determine toxicity of pollutants to activated sludge

Five rapid direct toxicity assessment methods were used in three European partner countries to determine the toxicity of single toxicants, mixed toxicants and real industrial wastes. The final aim was to protect microbial degradation of organic wastes in biological treatment processes and hence enhance the quality of treated effluents to be discharged to the environment. Nitrification inhibition, Respirometry, Adenosine triphosphate luminescence and Enzyme inhibition were tested utilising activated sludge as the testing matrix. The Vibrio fischeri toxicity test was used as a surrogate to compare the various microbial bioassays. The IC50 (toxicant concentration eliciting a 50% inhibitory effect) was determined for a number of pollutants including single toxicants Cd, Cr, Cu, Zn, 3,5-dichlorophenol, toluene and linear alkylbenzenesulphonate (LAS); a standard mixture of metals and LAS; a standard mixture of organics and LAS, and 16 industrial effluents. The V. fischeri bioassay was also chosen in order to assess quality control of toxicant preparation during testing in the different laboratories of the partner countries. Comparisons of sensitivity, cost of implementation, cost per test, relevance, and ease of use were made. The most sensitive bioassays were V. fischeri and Nitrification inhibition, however, this depended in the main on the pollutant and mixtures tested. It is recommended that during assessment of wastewater toxicity a suite of tests be used rather than reliance on one particular test.     

降雨过程对污水处理厂无机颗粒物特性及活性污泥的影响

取消初沉池的污水处理厂,粒径小于200 μm细微无机颗粒物将直接进入生化池,或悬浮或沉积,进而影响生化池的运行。以山地城市某污水处理厂为例,跟踪监测了夏季2个月的6次降雨过程中旋流沉砂池进出水无机颗粒物的粒径和浓度,并同期测定了生化池活性污泥浓度以及污泥MLVSS/MLSS比值。研究发现：旱季旋流沉砂池进出、水中的无机颗粒物平均粒径分别为65.25 μm及54.14 μm,浓度均值分别为146 mg·L-1及128 mg·L-1,无机颗粒去除率12.33%;降雨旋流沉砂池进出、水中的无机颗粒物峰值平均粒径分别为140.48 μm及94.54 μm,峰值平均浓度分别为2 167 mg·L-1及1 591 mg·L-1,无机颗粒去除率26.58%;旋流沉砂池对粒径≥200 μm颗粒的去除较稳定,对细微无机颗粒物的去除效率约10%。研究进一步发现,降雨中颗粒物浓度分别与雨前晴天数及平均雨强呈线性正相关关系。通过核算生化池无机颗粒物的物料平衡关系,得知研究期间生化池累积无机颗粒物总量410.25 t,其中399.45 t沉积在底部,其余悬浮于活性污泥混合液中。活性污泥MLVSS/MLSS由0.52降至0.40,MLVSS由1 410 mg·L-1降至930 mg·L-1,污泥活性下降,系统运行效能受到影响。     

Evaluation of a respirometric test method to determine the heterotrophic yield coefficient of activated sludge bacteria

The heterotrophic yield coefficient of activated sludge bacteria is an important parameter in the field of wastewater degradation kinetics and the determination of degradation kinetics of defined chemicals. With the help of easily biodegradable organic compounds like glucose and acetate the respiration kinetics of degrading activated sludge bacteria was studied. The results of the respiration analysis were transformed to examine the degradation and respiration kinetics of municipal wastewaters at different food to microorganism ratios (F/M ratios). It was proved that the heterotrophic yield coefficient of aerobically degrading activated sludge bacteria could reliably be determined and that the heterotrophic yield coefficient was independent of the F/M ratio over a wide range.     

Maximum nitrogen removal in the step-feed activated sludge process.

This paper presents a mathematical framework that can be used to determine the flow distributions for a step-feed activated sludge process that result in maximum nitrogen removal. The model indicates that nitrogen removal efficiency in a step-feed activated sludge process is highly dependent on the ultimate biochemical oxygen demand (BOD(L))-to-total Kjeldahl nitrogen (TKN) ratio of the wastewater. For typical domestic wastewater, which has a relatively high BOD(L)-to-TKN ratio, the step-feed process will outperform the Modified Ludzack-Ettinger process for nitrogen removal, when the flow to each step is optimally distributed. Using plant-specific water quality data and operating conditions from a 1-year period, nitrogen removal performance for four step-feed activated sludge plants operated by the Sanitation Districts of Los Angeles County (California) was calculated using the developed model. The calculated nitrogen removal efficiencies match well with the actual plant performance data. These results validate the model as a useful tool for predicting nitrogen removal in a step-feed activated sludge process. Other analyses revealed that improvements in nitrogen removal at existing facilities are achievable by adjusting the split of primary effluent flow to each anoxic zone several times during the day. The timing of the adjustments and the optimal flow splits can be determined from data on diurnal fluctuations in BOD(L) and TKN concentrations. An example is provided to illustrate the application of such an operating strategy and the potential enhancement of nitrogen removal.     

剩余污泥水解酸化液磷去除的影响因素研究

城市污水厂剩余污泥水解酸化后可产生高浓度挥发性有机酸(VFAs),其中的乙酸和丙酸是增强生物除磷(EBPR)工艺的有利基质.但水解酸化液中含有大量的磷,如不进行处理就作为碳源回用到污水处理工艺中,势必增加除磷负荷.利用鸟粪石沉淀法可以去除污水中的磷.对城市污水厂剩余污泥水解酸化液形成鸟粪石的影响因素进行了试验研究.结果表明,在最佳工艺条件下,正磷和总磷的去除率分别可达92.5%和83.8%.     

固定化活性污泥实现短程硝化反硝化处理畜禽废水

以畜禽废水为处理对象,通过分别控制水力停留时间(HRT)、溶解氧(DO)、pH值、温度和碳氮比(C/N)等影响亚硝化的主要单因子,以使固定化活性污泥颗粒实现短程硝化反硝化反应,在连续流运行模式下进行废水脱氮实验,实验结果表明,单因子HRT为10 h,溶解氧为4 mg/L,pH值为8.5,温度为30℃,碳氮比为10时,对TN和COD的去除率分别为81.98%、93.79%;87.32%、98.35%;83.82%、93.93%;85%、97%;85.37%、97.28%,达到了理想的去除效果。     

污水处理工程--两段式活性污泥工艺

我国中小城市的污水处理通常有如下特点(1 )工业废水所占比重较大,甚至超过50 %,致使要处理的城市污水的污染物浓度较高,污染物负荷变化较大 ;(2)城市财政状况比较紧张,可用于建设污水处理厂的资金有限.两段式活性污泥工艺是对传统活性污泥工艺的改进,在好氧处理之前采用一个缺氧或厌氧段,用于有机物的水解酸化或生物除磷.两段式工艺有以下优点处理效率高、工程投资和日常运行费用低,更适合我国国情.本文以两个工程项目为例,论述了两段式活性污泥工艺的工程设计与实际应用.山东省招远市污水处理厂于1999年7月投入运行,处理后排放水中的污染物指标低于设计值.蓬莱市污水处理厂工程即将竣工,设计处理能力20000m3 /d,工程总投资约1200万元,远远低于目前国内的平均水平.     

NaCl盐度对耐盐活性污泥沉降性能及脱氮的影响

针对海水冲厕工程的实施,采用序批式活性污泥反应器(SBR)处理实际含盐生活污水,考察了盐度对耐盐活性污泥沉降性能及脱氮效能的影响。研究发现,经过长期盐度驯化后的污泥系统也会出现丝状菌污泥膨胀。在经过10 g/L盐度长期驯化的污泥系统中,污泥容积指数(SVI)随着盐度的升高而降低,盐度升高使丝状菌减少,污泥絮体变小变密实。但是,盐度降低时会引发更严重的污泥膨胀,导致污泥流失。对脱氮性能的研究表明,硝化菌的耐盐能力较强。当盐度由10 g/L改变为0、5、15、20 g/L时,氨氮去除率依然可以维持在99%以上。但亚硝酸盐积累率无论是盐度升高或降低时都升高,这表明驯化后污泥中的亚硝酸氧化菌(NOB)对盐度变化的耐受能力比氨氧化菌(AOB)弱,无论盐度升高或降低都会对其产生较大的影响。     

活性污泥系统中微型动物与水质净化效果的相关分析

活性污泥系统中微型动物的种类、数量和变化情况与活性污泥状况和出水水质密切相关.在某大型炼油厂污水处理车间曝气池活性污泥系统中,通过微生物镜检监测出30多种微型动物.实验研究发现,固着型纤毛虫的种类最多,出现频率也较高.对微型动物密度与曝气池出水水质和污泥指标的相关性分析表明,小口钟虫可作为曝气池混合液DO浓度的指示生物,小口钟虫密度越大,DO浓度越高;小口钟虫、八钟虫和转轮虫可作为曝气池出水COD的指示生物,其数量增加是水质净化程度提高的标志.