A review on pharmaceuticals removal from waters by single and combined biological,membrane filtration and ultrasound systems

Contaminants of emerging concern (CEC) such as pharmaceuticals commonly found in urban and industrial wastewater are a potential threat to human health and have negative environmental impact. Most wastewater treatment plants cannot efficiently remove these compounds and therefore, many pharmaceuticals end up in aquatic ecosystems, inducing problems such as toxicity and antibiotic-resistance. This review reports the extent of pharmaceutical removal by individual processes such as bioreactors, advanced oxidation processes and membrane filtration systems, all of which are not 100% efficient and can lead to the direct discharge of pharmaceuticals into water bodies. Also, the importance of understanding biotransformation of pharmaceutical compounds during biological and ultrasound treatment, and its impact on treatment efficacy will be reviewed. Different combinations of the processes above, either as an integrated configuration or in series, will be discussed in terms of their degradation efficiency and scale-up capabilities. The trace quantities of pharmaceutical compounds in wastewater and scale-up issues of ultrasound highlight the importance of membrane filtration as a concentration and volume reduction treatment step for wastewater, which could subsequently be treated by ultrasound.     

厌氧处理结合超声空化高效破解剩余污泥

为了提高超声空化破解剩余污泥的效率,进而提高污泥的可生化性能,提出先进行短时间的厌氧处理,再进行超声空化的破解方案;并对厌氧0~6 d的污泥进行了超声破解实验研究.实验结果显示:随着厌氧时间的增加,污泥自身性质发生较大改变,如化学需氧量(COD)、肽聚糖浓度大幅度增加,p H值明显降低等;对厌氧污泥进行破解,其破解效果优于新鲜污泥:对厌氧6 d的污泥进行破解,其COD浓度是新鲜污泥的99.3倍,是新鲜污泥破解后的9.5倍.厌氧处理可以降低污泥的破解难度,在较大程度上提高超声空化强度,该工艺可以实现高效破解剩余污泥的目的.     

不同pH值下胞外聚合物对污泥脱水性能及束缚水含量的影响

研究了不同pH值下污泥脱水性能和束缚水含量的变化,通过测定污泥调理过程中各层胞外聚合物( S-EPS、LB-EPS和TB-EPS)中蛋白质和多糖的含量、S-EPS中有机官能团以及有机酸的含量,探讨了胞外聚合物对污泥脱水性能及束缚水含量的影响.酸性条件下,污泥的脱水性能明显好于中性条件,并且pH值为3.03时,污泥滤饼含水率( WC)和毛细吸水时间( CST)均降至最低,分别为60.8%和25.4 s;碱性条件下,污泥中束缚水的含量明显增加,WC和CST均大幅升高,污泥脱水性能恶化.酸碱的加入导致污泥中TB-EPS含量降低,LB-EPS和S-EPS含量升高,并且EPS各层组均与WC、CST以及束缚水含量具有很强的相关性,其中S-EPS与污泥脱水性能以及束缚水含量的相关性最显著.酸碱调理过程中,部分EPS水解生成有机酸等小分子有机物,S-EPS中有机官能团的总量和种类都有明显增多.     

Determination of Chlorophenols in Sewage Sludge and Soil by High-Performance Liquid Chromatography–Tandem Mass Spectrometry with Ultrasonic-Assisted and Solid-Phase Extraction

Chlorophenols are a category of toxic pollutants that are ubiquitously present in the environment. This paper presents a reliable and feasible method for the determination of five chlorophenols in sewage sludge and soil using liquid chromatography–tandem mass spectrometry (LC-MS/MS). The pretreatment involved ultrasonic-assisted extraction and solid-phase extraction purification with hydrophilic–lipophilic balance cartridges. LC-MS/MS equipped with an electrospray ionization source operated in negative mode was used for detection, and multitude reaction monitoring mode was applied for data acquisition. The pretreatment and working conditions of LC-MS/MS were optimized to achieve satisfactory results. The intra-batch accuracies were 100.5–113.4% with relative standard deviations?≤?15.6% for the chlorophenols in sewage sludge and 71.3–102.7% with relative standard deviations?≤?14.0% for those in soil. The inter-batch accuracies were 86.1–100.5% (relative standard deviations?≤?33.6%) for sewage sludge samples and 70.5–112.5% (relative standard deviations?≤?28.2%) for soil samples, respectively. This method has been applied to the determination of chlorophenols in sewage sludge of wastewater treatment plants and soil collected from Guangzhou, China. Parachlorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, and pentachlorophenol were detected in some sewage sludge samples, with concentrations from 0.51 to 13.20?ng/g. In addition, parachlorophenol, 2,3,4,6-tetrachlorophenol, and pentachlorophenol were found in all the soil samples with concentrations from 0.33 to 5.21?ng/g. The chromatographic behavior, on-filter adsorption behavior, and the relationship between optimal collision energies and degree of chlorination of the chlorophenols was investigated. This method will be conducive to environmental research focusing on pollution investigation of chlorophenols in the environment.     

Pressurised hot water extraction followed by simultaneous derivatization and headspace solid-phase microextraction and gas chromatography-tandem mass spectrometry for the determination of aliphatic primary amines in sewage sludge

In this paper we describe an environmentally friendly and sensitive method for the determination of ten primary amines in sewage sludge. The method is based on pressurised hot water extraction (PHWE) followed by simultaneous derivatization with pentafluorobenzaldehyde (PFBAY) and headspace solid-phase microextraction (HS-SPME) and subsequent gas-chromatography ion-trap tandem mass spectrometry (GC-IT-MS-MS) analysis. The influence of the main factors on the PHWE of sludge was optimized by a central composite design. For all species the optimal conditions were water at pH 4 as the extracting solvent, an extraction temperature of 100 °C and an extraction time of 15 min. The separation and detection of the ten amines by GC-IT-MS-MS took just 10 min and the entire process took approximately 1 h. Repeatability and reproducibility between days, expressed as RSD (%) (n = 5), were less than 19 and 24%, respectively. The average limit of detection (LOD) was of 65 μg kg⁻¹ s (range found 9-135) and the average limit of quantification (LOQ) was of 230 μg kg⁻¹ (range found 50-450) of dry weight (d.w.). Under optimized conditions we used this method to determine the compounds in industrial and municipal sewage sludge samples and in sludge from a potable water treatment plant. Methylamine and isobutylamine showed the highest levels in one of the industrial sewage sludge samples (404 and 543 mg kg⁻¹ (d.w.), respectively). To our knowledge, this paper presents for the first time the determination of ten primary amines in sewage sludge samples using PHWE.     

A new sample preparation method for determination of acidic drugs in sewage sludge applying microwave assisted solvent extraction followed by gas chromatography-mass spectrometry

This paper presents a new sample preparation procedure for determination of selected acidic pharmaceuticals (ibuprofen, naproxen, ketoprofen, and diclofenac) in sewage sludge using microwave assisted solvent extraction, dispersive matrix extraction (DME) followed by the conventionally applied solid phase extraction (SPE), derivatization, and gas chromatography-mass spectrometry. The recoveries calculated from analytical data of spiked sludge samples changed in the range of 80-105% ± 15% for the four pharmaceuticals in mixed and activated sludge depending on the efficiency of the clean-up procedure. The measured concentration values of ibuprofen and naproxen were identical in the mixed and the activated sludge samples. However, ketoprofen and diclofenac showed about twice as high concentration in activated sludge than in the mixed one independently of the applied extraction method. The typical concentration ranges of ibuprofen, naproxen, ketoprofen and diclofenac in sewage sludge were 10-30 ng/g, 30-50 ng/g, 50-130 ng/g, and 50-140 ng/g respectively.     

蠕虫减量剩余活性污泥反应器的CFD数值模拟

构建以序批式反应器(SBR)为主体工艺并联合蠕虫反应器的生活污水处理系统,在保证系统出水水质达标的前提下,蠕虫对SBR产生的剩余活性污泥摄食减量约23%(以质量计)。利用ANSYS FLUENT 16.0软件提供的欧拉两相流模型和标准k-ε湍流模型,对蠕虫反应器内部速度场、含气率以及湍流强度等进行了计算流体动力学(CFD)数值模拟。模拟结果表明,蠕虫反应器内曝气量约为0.2m₃/h、 蠕虫投放在P2位置即蠕虫密度为1.63g/dm₃时,蠕虫反应器内部流场适合蠕虫减量污泥,减质最高达23%,与试验结果基本吻合。通过响应曲面法(BBD)进行试验,所得污泥减量率与BBD预测值基本相符,进一步佐证了数值模拟结果的可靠性。因此,利用CFD数值模拟可以指导蠕虫反应器优化运行,从而为蠕虫减量污泥系统的放大设计及工程应用奠定基础。     

Determination of non-steroidal anti-inflammatory drugs in sewage sludge by direct hollow fiber supported liquid membrane extraction and liquid chromatography–mass spectrometry

In this study, a three-phase hollow fiber liquid-phase microextraction (HF-LPME) method combined with liquid chromatography–mass spectrometry was developed for direct determination of four non-steroidal anti-inflammatory drugs (ketoprofen, naproxen, diclofenac and ibuprofen) in sewage sludge. The drugs were extracted from non-spiked and spiked slurry samples with different amounts of sludge into an organic phase and then back-extracted into an aqueous phase held in the lumen of the hollow fiber. High enrichment factors ranging from 2761 to 3254 in pure water were achieved. In sludge samples, repeatability and inter-day precision were tested with relative standard deviation values between 10–18% and 7–15%, respectively. Average concentrations of 29 ± 9, 138 ± 2, 39 ± 5 and 122 ± 7 ng/g were determined in dried sludge from Källby sewage treatment plant (Sweden) for ketoprofen, naproxen, diclofenac and ibuprofen, respectively.     

Hollow fiber liquid phase microextraction as a preconcentration and clean-up step after pressurized hot water extraction for the determination of non-steroidal anti-inflammatory drugs in sewage sludge

A method for the quantitative determination of non-steroidal anti-inflammatory drugs (NSAIDs) in sewage sludge was developed and validated. The target compounds were extracted using pressurized hot water extraction (PHWE) and then purified and preconcentrated by three-phase hollow fiber liquid phase microextraction (HF-LPME) followed by LC–ESI-MS analysis. The PHWE was optimized with regard to the pH of solvent as well as other operational parameters. The optimum conditions were 0.01 M NaOH as the extraction solvent, temperature of 120 °C, pressure of 100 bar, static time 5 min, 5 cycles, flush volume 90% and purge time 60 s. Spike recoveries for sludge samples spiked at 200 ng g⁻¹ were in the range of 101–109% but for the native drugs in non-spiked sludge samples, recoveries were 38.9%, 59.8%, 90.3% and 47.8% for ketoprofen, naproxen, diclofenac and ibuprofen, respectively. Donor phase pH, ionic strength and extraction time were optimized for HF-LPME after PHWE. The optimum conditions were 2 h extraction at pH 1.5 without salt addition. Enrichment factors in the range of 947–1213 times were achieved (extraction recoveries were 23.6–30.3%) for HF-LPME after PHWE. The matrix effect on the ionization of drugs in LC–ESI-MS was also investigated. The results show that there is a smaller matrix effect (−8.9% to +14.6%) in comparison with other published values obtained using solid phase extraction (SPE) for clean-up after pressurized liquid extraction (PLE). Method detection limits (MDLs) and method quantification limits (MQLs) for different drugs were in the range of 0.4–3.7 ng g⁻¹ and 1.5–12.2 ng g⁻¹ in dried sludge samples, respectively. The characteristics of the proposed method were compared with those of other published works. The considerably lower ion suppression/enhancement and minimum use of organic solvents (a few microliters of di-n-hexyl ether) in the sample preparation step are two highlighted advantages of the proposed method in comparison with previously published works. The method was applied to determine NSAIDs in sewage sludge from Källby wastewater treatment plant (Lund, Sweden) in April, June, August and October 2010. The highest concentration level was recorded for ibuprofen in the April sewage sludge sample (588 ng g⁻¹) and all of the selected NSAIDs were detected in all the samples analyzed.     

丙烯腈-丁二烯-苯乙烯树脂废水的生化处理研究

对兰州石化公司ABS生产装置生产的丙烯腈丁二烯苯乙烯 (ABS)树脂废水水质进行了分析和处理技术研究。通过试验筛选出两株ABS树脂废水高效降解菌ABS 2、ABS 5及其激活剂JH 6 ,可将絮凝处理后ABS树脂废水的生化需氧量与化学需氧量的比值由 38%提高到 4 9% ,提高了废水可生化性 ,强化了ABS树脂废水通过活性污泥法进行处理的效果 ,加快了废水处理启动速度 ,提高了处理效率。静态试验、动态试验及动态扩试等系统性试验表明 ,投加高效菌及其激活剂强化活性污泥法可在水力停留时间 8h内使ABS树脂废水化学需氧量由 770mg/L降至 12 0mg/L以下 ,实现达标排放。由色谱分析推断 ,处理后的水中残余成分主要为低聚物。