Mass flows of perfluorinated compounds (PFCs) in central wastewater treatment plants of industrial zones in Thailand

Perfluorinated compounds (PFCs) are fully fluorinated organic compounds, which have been used in many industrial processes and have been detected in wastewater and sludge from municipal wastewater treatment plants (WWTPs) around the world. This study focused on the occurrences of PFCs and PFCs mass flows in the industrial wastewater treatment plants, which reported to be the important sources of PFCs. Surveys were conducted in central wastewater treatment plant in two industrial zones in Thailand. Samples were collected from influent, aeration tank, secondary clarifier effluent, effluent and sludge. The major purpose of this field study was to identify PFCs occurrences and mass flow during industrial WWTP. Solid-phase extraction (SPE) coupled with HPLC-ESI-MS/MS were used for the analysis. Total 10 PFCs including perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluoropropanoic acid (PFPA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorohexane sulfonate (PFHxS), perfluoronanoic acid (PFNA), perfluordecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA) were measured to identify their occurrences. PFCs were detected in both liquid and solid phase in most samples. The exceptionally high level of PFCs was detected in the treatment plant of IZ1 and IZ2 ranging between 662-847 ng L⁻¹ and 674-1383 ng L⁻¹, respectively, which greater than PFCs found in most domestic wastewater. Due to PFCs non-biodegradable property, both WWTPs were found ineffective in removing PFCs using activated sludge processes. Bio-accumulation in sludge could be the major removal mechanism of PFCs in the process. The increasing amount of PFCs after activated sludge processes were identified which could be due to the degradation of PFCs precursors. PFCs concentration found in the effluent were very high comparing to those in river water of the area. Industrial activity could be the one of major sources of PFCs contamination in the water environment.     

Chlorination of chlortoluron: kinetics, pathways and chloroform formation

Chlortoluron chlorination is studied in the pH range of 3-10 at 25 ± 1 °C. The chlorination kinetics can be well described by a second-order kinetics model, first-order in chlorine and first-order in chlortoluron. The apparent rate constants were determined and found to be minimum at pH 6, maximum at pH 3 and medium at alkaline conditions. The rate constant of each predominant elementary reactions (i.e., the acid-catalyzed reaction of chlortoluron with HOCl, the reaction of chlortoluron with HOCl and the reaction of chlortoluron with OCl⁻) was calculated as 3.12 (± 0.10) × 10⁷ M⁻² h⁻¹, 3.11 (±0.39) × 10² M⁻¹ h⁻¹ and 3.06 (±0.47) × 10³ M⁻¹ h⁻¹, respectively. The main chlortoluron chlorination by-products were identified by gas chromatography-mass spectrometry (GC-MS) with purge-and-trap pretreatment, ultra-performance liquid chromatography-electrospray ionization-MS and GC-electron capture detector. Six volatile disinfection by-products were identified including chloroform (CF), dichloroacetonitrile, 1,1-dichloropropanone, 1,1,1-trichloropropanone, dichloronitromethane and trichloronitromethane. Degradation pathways of chlortoluron chlorination were then proposed. High concentrations of CF were generated during chlortoluron chlorination, with maximum CF yield at circumneutral pH range in solution.     

Use of fugacity model to analyze temperature-dependent removal of micro-contaminants in sewage treatment plants

Effluents from sewage treatment plants (STPs) are known to contain residual micro-contaminants including endocrine disrupting chemicals (EDCs) despite the utilization of various removal processes. Temperature alters the efficacy of removal processes; however, experimental measurements of EDC removal at various temperatures are limited. Extrapolation of EDC behavior over a wide temperature range is possible using available physicochemical property data followed by the correction of temperature dependency. A level II fugacity-based STP model was employed by inputting parameters obtained from the literature and estimated by the US EPA’s Estimations Programs Interface (EPI) including EPI’s BIOWIN for temperature-dependent biodegradation half-lives. EDC removals in a three-stage activated sludge system were modeled under various temperatures and hydraulic retention times (HRTs) for representative compounds of various properties. Sensitivity analysis indicates that temperature plays a significant role in the model outcomes. Increasing temperature considerably enhances the removal of β-estradiol, ethinyestradiol, bisphenol, phenol, and tetrachloroethylene, but not testosterone with the highest biodegradation rate. The shortcomings of BIOWIN were mitigated by the correction of highly temperature-dependent biodegradation rates using the Arrhenius equation. The model predicts well the effects of operating temperature and HRTs on the removal via volatilization, adsorption, and biodegradation. The model also reveals that an impractically long HRT is needed to achieve a high EDC removal. The STP model along with temperature corrections is able to provide some useful insight into the different patterns of STP performance, and useful operational considerations relevant to EDC removal at winter low temperatures.     

Estrogen receptor mediated activity in bankside groundwater, with flood suspended particulate matter and floodplain soil - an approach combining tracer substance, bioassay and target analysis

Bankside groundwater is widely used as drinking water resource and, therefore, contamination has to be avoided. In the European Union groundwater protection is explicit subject to Water Framework Directive. While groundwater pollution may originate from different sources, this study investigated on impacts via flood events.Groundwater was sampled with increasing distance to the river Rhine near Karlsruhe, Germany. Samples were HPLC-MS-MS analyzed for the river contaminant carbamazepine to indicate river water infiltration, giving permanent presence in 250 m distance to the river (14-47 μg L⁻¹). Following a flood event, concentrations of about 16-20 μg L⁻¹ could also be detected in a distance of 750 m to the river. Furthermore, estrogenic activity as determined with the Yeast Estrogen Screen assay was determined to increase up to a 17β-ethinylestradiol equivalent concentration (E-EQ) = 2.9 ng L⁻¹ near the river, while activity was initially measured following the flood with up to E-EQ = 2.6 ng L⁻¹ in 750 m distance. Detections were delayed with increasing distance to the river indicating river water expansion into the aquifer.Flood suspended matter and floodplain soil were fractionated and analyzed for estrogenic activity in parallel giving up to 1.4 ng g⁻¹ and up to 0.7 ng g⁻¹, respectively. Target analysis focusing on known estrogenic active substances only explained <1% of measured activities.Nevertheless, river water infiltration was shown deep into bankside groundwater, thus, impacting groundwater quality. Therefore, flood events have to be in the focus when aiming for groundwater and drinking water protection as well as for implementation of Water Framework Directive.     

Contamination of nonylphenolic compounds in creek water, wastewater treatment plant effluents, and sediments from Lake Shihwa and vicinity, Korea: comparison with fecal pollution

Nonylphenolic compounds (NPs), coprostanol (COP), and cholestanol, major contaminants in industrial and domestic wastewaters, were analyzed in creek water, wastewater treatment plant (WWTP) effluent, and sediment samples from artificial Lake Shihwa and its vicinity, one of the most industrialized regions in Korea. We also determined mass discharge of NPs and COP, a fecal sterol, into the lake, to understand the linkage between discharge and sediment contamination. Total NP (the sum of nonylphenol, and nonylphenol mono- and di-ethoxylates) were 0.32-875 μg L⁻¹ in creeks, 0.61-87.0 μg L⁻¹ in WWTP effluents, and 29.3-230 μg g⁻¹ TOC in sediments. Concentrations of COP were 0.09-19.0 μg L⁻¹ in creeks, 0.11-44.0 μg L⁻¹ in WWTP effluents, and 2.51-438 μg g⁻¹ TOC in sediments. The spatial distributions of NPs in creeks and sediments from the inshore region were different from those of COP, suggesting that Lake Shihwa contamination patterns from industrial effluents differ from those from domestic effluents. The mass discharge from the combined outfall of the WWTPs, located in the offshore region, was 2.27 kg d⁻¹ for NPs and 1.00 kg d⁻¹ for COP, accounting for 91% and 95% of the total discharge into Lake Shihwa, respectively. The highest concentrations of NPs and COP in sediments were found in samples at sites near the submarine outfall of the WWTPs, indicating that the submarine outfall is an important point source of wastewater pollution in Lake Shihwa.     

Occurrence and distribution of pharmaceuticals in surface water, suspended solids and sediments of the Ebro river basin, Spain

The occurrence of 43 pharmaceuticals belonging to predominant therapeutic classes and their distribution in surface water, suspended solids and sediments has been investigated in the Ebro river basin in the Northeast of Spain. WWTP effluents were found to be a main source of contamination and the spatial distribution was affected by the river flow at the sampling point and corresponding dilution factor, resulting in higher concentrations and higher loads in small tributary rivers than in the Ebro river. The study showed that some compounds are preferentially found bound to suspended solids and not detected in river water. Generally, compounds with basic characteristics (pKa > 7) showed higher tendency to bind to suspended solids. The sediment samples generally presented lower concentrations than suspended solids.     

固硫灰渣深度处理焦化废水的实验研究

选用同硫灰渣深度处理经生化处理后焦化废水,采用分光光度计法评价焦化废水的处理效果,采用XRD、XRF、SEM和IR等分析材料的成分、结构和微观形貌等.结果表明,固硫灰渣用量60 g/L、吸附时间15 min,焦化废水的脱色率可达94.22%,COD从原水的76.01 mg/L降低到处理后的5.76 mg/L,NH+4-...     

低剂量臭氧的直接通加对活性污泥的活性、微生物种群及污泥减量化的影响

研究构建了2个容积为1.1 L的好氧活性污泥反应器（即1号和2号反应器）1,号反应器每天直接通加低剂量臭氧（投加量为0.01 g O3/g TSS）,不加臭氧的2号反应器作为对照平行运行,均采用每天换一次人工污水的充/排式操作。运行71 d的结果表明2,个反应器对人工污水COD的处理效果基本相同。反应器运行40 d后1,号反应器的污泥浓度比2号反应器的污泥浓度低1 400～1 700 mg/L并可稳定在8 200 mg/L,污泥减量化效果明显。低剂量臭氧的直接通加明显降低了胞内ATP浓度,并影响了微生物的抗氧化活性,2号反应器的平均超氧化物歧化酶和过氧化氢酶酶活比1号反应器分别高了24.3%和9.5%。PCR-DGGE对两反应器微生物种群的分析结果表明：Uncultured gammaproteobacteria bacteri-um、Nannocystis exedens和Uncultured actinobacterium为1号反应器的主要种群;而2号反应器的主要种群为Uncultured bacte-rium和Uncultured gammaproteobacteria bacterium。     

大宝山矿区水体和沉积物中重金属的污染评价

分别于丰水期和枯水期对广东省大宝山矿区铁龙拦泥坝至凉桥河段水体中溶解态的重金属进行了调查,应用EPA推荐的健康风险评价模型发现,水体中非致癌物通过饮水途径所导致平均个人年风险排列顺序是Cu〉Pb〉Zn,最大值的平均个人年风险在丰水期和枯水期的平均值分别是2.14×10-7 a-1和4.13×10-7 a-1,小于国际防辐射委员会（ICRP）推荐的最大可接受平均个人年风险5.0×10-5a-1。致癌物Cd的平均个人年风险在丰水期和枯水期的平均值分别是3.52×10-4 a-1和4.53×10-4 a-1,大于ICRP推荐的最大可接受值,同时也大于非致癌物3～4个数量级。另外,通过对枯水期沉积物的重金属总量分析,发现凉桥槽对坑支流受水体pH的影响,导致其沉积物重金属的浓度最高。根据Long和Macdonald利用生物效应数据库法建立的沉积物质量基准,发现除冷水泾外,其他采样点的平均效应中值指数（mERMQ）值都大于1.5,可见沉积物中的重金属会对当地底栖生物产生毒害作用。     

不同营养水平下悬浮细菌数量对生物粘泥性质的影响

循环水系统中的微生物有悬浮态和附着态,悬浮细菌的存在对附着态生物粘泥的生长及特性有明显影响。通过向模拟循环冷却水系统中投加不同数量初始悬浮细菌,考察在营养水平不同的情况下,悬浮细菌数量对生物粘泥化学组成和脱氢酶活性的影响。结果表明,营养水平不同,初始悬浮细菌数量对生物粘泥的化学组成和脱氢酶活性的影响程度不同;在不同营养水平下,应分别控制初始悬浮细菌数量。贫营养下,初始悬浮细菌数量应控制在6×105个/mL左右;中营养下,初始悬浮细菌数量应控制在1×105～2.6×105个/mL之间;富营养下,初始悬浮细菌数量应控制在0.11×105～2.6×105个/mL之间最不利于生物粘泥的生长。