Occurrence and reduction of pharmaceuticals in the water phase at Swedish wastewater treatment plants

During the last decade, several screening programs for pharmaceuticals at Swedish wastewater treatment plants (WWTPs) have been conducted by research institutes, county councils, and wastewater treatment companies. In this study, influent and effluent concentrations compiled from these screening programs were used to assess the occurrence and reduction of non-antibiotic pharmaceuticals for human usage. The study is limited to full-scale WWTPs with biological treatment. Based on the data compiled, a total of 70 non-antibiotic pharmaceuticals have been detected, at concentrations ranging from a few ng/L to several μg/L, in the influent water. The influent concentrations were compared with the sale volumes and for many pharmaceuticals it was shown that only a small fraction of the amount sold reaches WWTPs as dissolved parent compounds. Pharmaceuticals with low reduction degrees at traditional WWTPs were identified. Further comparison based on the biological treatment showed lower reduction degrees for several pharmaceuticals in trickling filter plants compared with activated sludge plants with nitrogen removal.     

载锰污泥活性炭催化臭氧氧化草酸废水的研究

为研究在催化臭氧化过程中,载锰污泥活性炭对草酸废水降解的催化效果,以及为污泥的资源化探索一条新途径,本实验采用连续流臭氧氧化实验,通过单因素实验方法考察了载锰污泥活性炭催化臭氧化反应的主要影响因素及最佳反应条件,同时对催化臭氧化反应机理进行了探讨。结果表明:在臭氧浓度为5.0 mg/L,载锰污泥活性炭投加量为100 mg/L,pH值为3.5的最佳反应条件下,60 min内草酸的去除率最高达91.2%。叔丁醇对草酸降解具有抑制作用,催化臭氧化反应符合羟基自由基的反应机制。该方法的处理效果较为明显,对评价催化臭氧法的效果具有较明显的参考价值。     

A comparison of BNR activated sludge systems with membrane and settling tank solid-liquid separation.

Installing membranes for solid-liquid separation into biological nutrient removal (BNR) activated sludge (AS) systems makes a profound difference not only to the design of the membrane bio-reactor (MBR) BNR system itself, but also to the design approach for the whole wastewater treatment plant (WWTP). In multi-zone BNR systems with membranes in the aerobic reactor and fixed volumes for the anaerobic, anoxic and aerobic zones (i.e. fixed volume fractions), the mass fractions can be controlled (within a range) with the inter-reactor recycle ratios. This zone mass fraction flexibility is a significant advantage of MBR BNR systems over BNR systems with secondary settling tanks (SSTs), because it allows changing the mass fractions to optimise biological N and P removal in conformity with influent wastewater characteristics and the effluent N and P concentrations required. For PWWF/ADWF ratios (fq) in the upper range (fq approximately 2.0), aerobic mass fractions in the lower range (f(maer) < 0.60) and high (usually raw) wastewater strengths, the indicated mode of operation of MBR BNR systems is as extended aeration WWTPs (no primary settling and long sludge age). However, the volume reduction compared with equivalent BNR systems with SSTs will not be large (40-60%), but the cost of the membranes can be offset against sludge thickening and stabilisation costs. Moving from a flow unbalanced raw wastewater system to a flow balanced (fq = 1) low (usually settled) wastewater strength system can double the ADWF capacity of the biological reactor, but the design approach of the WWTP changes away from extended aeration to include primary sludge stabilisation. The cost of primary sludge treatment then has to be offset against the savings of the increased WWTP capacity.     

Pre-ozonation in the activated sludge process: fate of nitrogen species

The objective of this research was to include ozonation prior to an activated sludge treatment and investigate the effect on the nitrogen species, their fate and the consequences of this oxidation upon the biomass. Three parallel treatment systems were used: the base system, where feed went directly to the activated sludge reactor, and two others, where the influent was ozonated at two different dosages, 15 and 25 mg/L of influent, prior to the biological reactors. The results from the ozonation chamber show a high oxidation capacity of the entering ammonia and organic nitrogen, proportional to the ozone dose. The oxidation product was nitrate. No de-nitrification was expected because a high oxygen concentration (4 mg/L) was maintained in the reactors. The reactors receiving ozonated influent showed a lower assimilation of nitrogen by the biomass. The sludge nitrogen content resulted in 11, 9.3 and 7.4% dry-weight corresponding to no-ozone, low ozone and high ozone dosages, respectively. In spite of the lower ammonia available in the ozonated flows, the corresponding reactors showed a higher specific nitrification rate. The ozonated system also performed better in terms of chemical oxygen demand (COD) and biochemical oxygen demand (BOD5) removals, besides showing a higher true biomass yield coefficient.     

Effects of silver nanoparticles on biological nitrogen removal processes

The effects of silver (Ag) nanoparticles (NPs) on activated sludge in a biological nitrogen removal (BNR) process were investigated under aerobic and anoxic conditions. We show that nitrification was more vulnerable to Ag NPs exposure than denitrification at the same Ag NPs concentration. In continuous operation of the BNR process, a higher inhibitory effect on nitrification was attributed to a smaller size of Ag NPs. About 70-90% of the Ag NPs supplied were embedded in the sludge matrix but 10-30% of the Ag NPs remained in the supernatant. This indicates that significant amounts of Ag NPs could be discharged from wastewater treatment plants and potentially impact on aquatic ecosystems.     

A pilot study on a step-feeding anoxic/oxic activated sludge system.

A four stage pilot plant of step-feed biological nutrient removal (BNR) was employed to investigate reactor performance and process stability. The results obtained showed that step-feed BNR is efficient and cost-effective for nitrogen and carbonaceous removal from municipal wastewater. The total average removal efficiencies of COD, NH3-N, TN and TP could reach as high as 89.5, 97.8, 73 and 75%, respectively, with 50% of return activated sludge (RAS), 9 h of hydraulic retention time (HRT) and 20 d of sludge retention time (SRT). Step-feed BNR is an alternative and effective technology of nutrient removal for municipal wastewater treatment.     

Biological nutrient removal in membrane bioreactors: denitrification and phosphorus removal kinetics.

The impact of including membranes for solid liquid separation on the kinetics of nitrogen and phosphorus removal was investigated. To achieve this, a membrane bioreactor (MBR) biological nutrient removal (BNR) activated sludge system was operated. From batch tests on mixed liquor drawn from the MBR BNR system, denitrification and phosphorus removal rates were delineated. Additionally the influence of the high total suspended solids concentrations present in the MBR BNR system and of the limitation of substrate concentrations on the kinetics was investigated. Moreover the ability of activated sludge in this kind of system to denitrify under anoxic conditions with simultaneous phosphate uptake was verified and quantified.The denitrification rates obtained for different mixed liquor (ML) concentrations indicate no effect of ML concentration on the specific denitrification rate. The denitrification took place at a single specific rate (K(2)) with respect to the ordinary heterotrophic organisms (OHOs, i.e. non-PAOs) active mass. Similarly, results have been obtained for the P removal process kinetics: no differences in specific rates were observed for different ML or substrate concentrations. From the P removal batch tests results it seems that the biological phosphorus removal population (PAO) consists of 2 different sets of organisms denitrifying PAO and aerobic PAO.     

Occurrence of levofloxacin, clarithromycin and azithromycin in wastewater treatment plant in Japan.

Residual pharmaceutical products in sewage and other water environments have recently become a serious social problem in advanced countries. Among these pharmaceutical products, antibiotics have attracted special attention due to their serious impact on the ecosystem and connections to the emergence of drug-resistant bacteria. Our research intended to develop a new method to analyse the three antibiotics estimated to be released out of the body in large amounts in Japan; levofloxacin (LVFX), clarithromycin (CAM) and azithromycin (AZM), and survey the state of pollution in the sewerage. The concentrations of the water-phase antibiotics LVFX, CAM and AZM were measured in each process of activated sludge process in six wastewater treatment plants. Liquid chromatography tandem mass spectrometry (LC/MS/MS) was used to analyse solutions of the antibiotics after pretreatment with a solid phase extraction. The limits of quantification and the average recoveries for these antibiotics in the influent were 1.2 to 29 ng/L and 46 to 93%, respectively. In the influent, LVFX, CAM and AZM were detected at concentrations of 552, 647 and 260 ng/L, respectively, while their removal efficiencies were 42, 43 and 49%, respectively. Although the CAM and AZM concentrations decreased as the treatment progressed, it was shown that the LVFX concentration increased in activated sludge reactors in some cases. Despite differences in octanol-water partition coefficients among LVFX, CAM and AZM, their removal efficiency showed no major difference. This indicates that this removal phenomenon cannot be explained by simple adsorption by the activated sludge.     

Comparison of linear alkylbenzene sulfonates removal in conventional activated sludge systems and membrane bioreactors.

The potential of a membrane bioreactor (MBR) and a conventional activated sludge (CAS) system to remove polar micropollutants was evaluated using linear alkylbenzene sulfonates (LAS) as model components. Removal efficiencies over 97% were achieved in both reactor systems. The appearance of biological breakdown metabolites and the respirometric response of the sludges to LAS addition indicated that LAS removal was due to biodegradation, rather than sorption phenomena. The effect of operational variables, such as hydraulic retention time, LAS composition and hydrophobicity of the membrane used in the MBR, was negligible in the range tested. A stepwise increase in LAS influent concentration resulted in higher residual effluent concentrations but did not change the procentual removal efficiency. Because an increase in LAS and SPC effluent concentration occurred to a larger extent in the CAS than in the MBR under similar operating conditions, MBRs may turn out to be be more robust with respect to biological degradation of micropollutants than CAS.     

Boosting nitrification by membrane-attached biofilm.

Nitrification is a key step for reliable biological nitrogen removal. In order to enhance nitrification in the activated sludge (AS) process, membrane-attached biofilm (MAB) was incorporated in a conventional activated sludge tank. Simultaneous organic carbon removal and nitrification of the MAB incorporated activated sludge (AS + MAB) process was investigated with continuous wastewater treatment. The effluent TOC concentration of AS and the AS + MAB processes were about 6.3 mg/L and 7.9 mg/L, respectively. The TOC removal efficiency of both AS and AS + MAB were above 95% during the wastewater treatment, indicating excellent organic carbon removal performance in both processes. Little nitrification occurred in the AS process. On the contrary, successful nitrification was obtained with the AS + MAB process with nitrification efficiency of about 90%. The volumetric and surface nitrification rates were about 0.14 g/Ld and 6.5 g/m2d, respectively. The results clearly demonstrated that nitrification in the conventional AS process was boosted by MAB. Furthermore, the microfaunal population in the AS + MAB process was different from that in the AS process. The high concentration of rotifers in the AS + MAB process was expected to decrease the generation of excess sludge in the process.     

Application of vibration milling for advanced wastewater treatment and excess sludge reduction

As a new sludge reduction technology with a phosphorus removal mechanism, a vibration milling technology that uses iron balls have been applied to the wastewater treatment process. Three anaerobic-aerobic cyclic activated sludge processes: one without sludge disintegration; one disintegrated sludge by ozonation; and the other disintegrated sludge with the vibrating ball mill were compared. Ozonation achieved the best sludge reduction performance, but milling had the best phosphorus removal. This is because iron was mixed into the wastewater treatment tank due to abrasion of the iron balls, leading to settling of iron phosphates. Thus, the simple means of using iron balls as the medium in a vibrating ball mill can achieve both a sludge reduction of half and excellent phosphorus removal. Material balances in the processes were calculated and it was found that carbon components in disintegrated sludge were more resistant to biological treatment than nitrogen.     

Model-based evaluation of struvite recovery from an in-line stripper in a BNR process (BCFS).

Phosphate removal and recovery can be combined in BNR processes. This may be realised by struvite precipitation from the supernatant of the sludge in anaerobic compartments. This can be beneficial for either improving bio-P removal effluent quality or lowering the influent COD/P ratio required for bio-P removal. For this reason, a patented BNR process, BCFS, was developed and applied in The Netherlands. Several questions relating to P-recovery and behaviour of the system remain unclear and need to be ascertained. For this purpose, a modelling technique was employed in this study. With the help of a previous developed model describing carbon oxidation and nutrient removal, three cases were fully simulated. The simulations demonstrated that there was an optimal stripping flow rate and P-recovery would increase in costs and bio-P activity might be negatively affected due to decreased bio-P efficiency if this value was exceeded. The simulations indicated that the minimal COD(biod)/P ratio required for the effluent standard (1 g P/m3) could be lowered from 20 to 10 with 36% of P-recovery. A simulation with dynamic inflow revealed that the dynamic influent loads affected slightly the anaerobic supernatant phosphate concentration but the effluent phosphate concentration would not be affected with regular P-recovery.     

臭氧-非均相Fenton工艺在焦化废水处理中的应用研究

通过对江苏沙钢集团厂区现有的焦化废水处理工艺进行深入的调研后,合理优化现有处理单元,采用增加前处理以及末端深度处理环节的方式,达到提高污染去除效率的目的。通过现场中试实验,获取改良工艺对焦化废水去除效果的最优工况参数。中试实验的工艺路线为“破乳→隔油→臭氧催化Fenton→气浮→EGSB→BACT→臭氧催化Fenton→气浮”,在前处理段臭氧浓度设置为100mg/L、深度处理单元臭氧浓度设置为50mg/L、BACT段分流比为1∶1、污泥回流比为1∶1时,工艺运行稳定后,在COD进水浓度为4100~5600mg/L时,系统对COD去除率可稳定达到95%以上,在氨氮进水浓度为250~310mg/L时,系统对氨氮去除率可稳定达到91%以上。     

CASS工艺生物脱氮除磷效果分析

对CASS工艺脱氮除磷效果进行了试验研究,重点研究了温度和回流比对脱氮效果的影响,曝气量对除磷效果的影响。研究结果表明,水温在30℃时系统脱氮效果最好,此时NH3-N去除率在80%左右,TN去除率在70%左右;污泥回流比为25%、50%、100%和200%时,TN去除率分别为50%、58%、62%和70%,增加回流比可以提高脱氮效率;好氧区DO维持在2mg/L和4 mg/L时,TP去除率分别为82%和37%。     

林可霉素高浓度有机废水处理技术

采用厌氧颗粒和好氧活性污泥分别对内循环厌氧反应器(IC)和间歇式活性污泥法(SBR)进行污泥接种培养,研究水解酸化-IC-SBR工艺在林可霉素生产废水处理方面的运行效果。结果表明:在进水COD的质量浓度为6 000~9 000 mg/L,IC和SBR反应器中有机负荷分别为0.82 kg/(kg.d)和0.26 kg/(kg.d)左右的情况下,IC和SBR反应器分别运行60 d和7 d,COD平均去除率分别达到91%和61%,出水COD的质量浓度在300 mg/L以下,达到GB 8978—1996《污水综合排放标准》二级标准。     

Development of MBR with reduced operational and maintenance costs.

To reduce MBR O&M costs, a new MBR process that conducts efficient simultaneous biological nitrogen and phosphorus removal (BNR) was developed. In the development of this process, various approaches were taken, including reduction of power demand, chemical consumption and sludge disposal costs. To address power demand reductions, air supply requirements for membrane cleaning were reduced. The process adopted an improved membrane that requires less air for cleaning than conventional membranes. It also introduced cyclic aeration, which alternately supplies washing air to the two series of membrane units. Adoption of biological phosphorus removal eliminated chemical costs for phosphorus removal and contributed to the reduction of sludge disposal costs. By combining these technologies, compared to conventional MBR processes, an approximately 27% reduction in O&M costs was achieved.     

Biological treatment of sludge digester liquids.

Nitrogen removal in side stream processes offers a good potential for upgrading wastewater treatment plants (WWTPs) that need to meet stricter effluent standards. Removing nutrients from these internal process flows significantly reduces the N-load to the main treatment plant. These internal flows mainly result from the sludge processing and have a high temperature and a high concentration of ammonia. Therefore, the required reactor volumes as well as the required aerobic SRT are small. Generally, biological treatment processes are more economical and preferred over physical-chemical processes. Recently, several biological treatment processes have been introduced for sludge water treatment. These processes are available now on the activated sludge market (e.g. SHARON, ANAMMOX and BABE processes). The technologies differ in concept and in the limitations guiding the application of these processes for upgrading WWTPs. This paper reviews and compares different biological alternatives for nitrogen removal in side streams. The limitations for selecting a technology from the available ones in the activated sludge market are noted and analysed. It is stressed that the choice for a certain process is based on more aspects than pure process engineering arguments.     

Re-use of winery wastewaters for biological nutrient removal.

The aim of this study was to evaluate the feasibility of the re-use of the winery wastewater to enhance the biological nutrient removal (BNR) process. In batch experiments it was observed that the addition of winery wastewater mainly enhanced the nitrogen removal process because of the high denitrification potential (DNP), of about 130 mg N/g COD, of the contained substrates. This value is very similar to that obtained by using pure organic substrates such as acetate. The addition of winery wastewater did not significantly affect either phosphorus or COD removal processes. Based on the experimental results obtained, the optimum dosage to remove each mg of N-NO3 was determined, being a value of 6.7 mg COD/mg N-NO3. Because of the good properties of the winery wastewater to enhance the nitrogen removal, the viability of its continuous addition in an activated sludge pilot-scale plant for BNR was studied. Dosing the winery wastewater to the pilot plant a significant increase in the nitrogen removal was detected, from 58 to 75%. The COD removal was slightly increased, from 89 to 95%, and the phosphorus removal remained constant.     

Pilot-scale studies on biological treatment of hypersaline wastewater at low temperature.

In order to investigate the feasibility of biological treatment of hypersaline wastewater produced from toilet flushing with seawater at low temperature, pilot-scale studies were established with plug-flow activated sludge process at low temperature (5-9 degrees C) based on bench-scale experiments. The critical salinity concentration of 30 g/L, which resulted from the cooperation results of the non-halophilic bacteria and the halophilic bacteria, was drawn in bench-scale experiments. Pilot-scale studies showed that high COD removal efficiency, higher than 80%, was obtained at low temperature when 30 percent seawater was introduced. The salinity improved the settleability of activated sludge, and average sludge value dropped down from 38% to 22.5% after adding seawater. Seawater salinity had a strong negative effect on notronomonas and nitrobacter growth, but much more on the nitrobacter. The nitrification action was mainly accomplished by nitrosomonas. Bench-scale experiments using two SBRs were carried out for further investigation under different conditions of salinities, ammonia loadings and temperatures. Biological nitrogen removal via nitrite pathway from wastewater containing 30 percent seawater was achieved, but the ammonia removal efficiency was strongly related not only to the influent ammonia loading at different salinities but also to temperature. When the ratio of seawater to wastewater was 30 percent, and the ammonia loading was below the critical value of 0.15 kgNH4+-N/(kgMLSS.d), the ammonia removal efficiency via nitrite pathway was above 90%. The critical level of ammonia loading was 0.15, 0.08 and 0.03 kgNH4+-N/(kgMLSS.d) respectively at the different temperature 30 degrees C, 25 degrees C and 20 degrees C when the influent ammonia concentration was 60-80 mg/L and pH was 7.5-8.0.     

Biomass adaptation to complex substrate degradation in membrane bioreactors: appropriated operating conditions.

The aim of this work is to analyse the biological performances of two immersed membranes bioreactors focusing on the biomass adaptation to complex substrate degradation and the performance in term of permeate quality. Two influents were selected: a synthetic complex influent (acetate/Viandox, MBR1) and a real seafood processing wastewater (surimi product, MBR2). The MBR systems were operated for long periods without any sludge extraction except for sampling. Organic matter removal, sludge production and quality of the treated wastewater were analysed and studied. COD removal efficiencies after a period of biomass adaptation were higher than 97% and 95% for the synthetic and real wastewater respectively. In both cases, the COD of the treated wastewater was lower than 50 mg.L(-1). In spite of salt concentration in the real wastewater a biomass adaptation process occurs. In the overall operational period, a 0.058 gCOD P.gCOD T(-1) and a 0.12 gCOD P.gCOD T(-1) observed sludge yields were obtained for the MBR1 and MBR2 respectively. These values are approximately 5 to 10 times lower than those measured in conventional activated sludge process. These results showed that the presence of particular and some of non-easily degradable compounds in the influent of MBR2 didn't limit the performance of MBR in term of COD removal achieved. The results have also confirmed the excellent permeate quality for water reuse from MBRs systems.