Occurrence and removal of titanium at full scale wastewater treatment plants: implications for TiO2 nanomaterials

Titanium dioxide nanoparticles increasingly will be used in commercial products and have a high likelihood of entering municipal sewage that flows to centralized wastewater treatment plants (WWTPs). Treated water (effluent) from WWTPs flows into rivers and lakes where nanoparticles may pose an ecological risk. To provide exposure data for risk assessment, titanium concentrations in raw sewage and treated effluent were determined for 10 representative WWTPs that use a range of unit processes. Raw sewage titanium concentrations ranged from 181 to 1233 μg L(-1) (median of 26 samples was 321 μg L(-1)). The WWTPs removed more than 96% of the influent titanium, and all WWTPs had effluent titanium concentrations of less than 25 μg L(-1). To characterize the morphology and presence of titanium oxide nanoparticles in the effluent, colloidal materials were isolated via rota-evaporation, dialysis and lyophilization. High resolution transmission electron microscopy and energy dispersive X-ray analysis indicated the presence of spherical titanium oxide nanoparticles (crystalline and amorphous) on the order of 4 to 30 nm in diameter in WWTP effluents. This research provides clear evidence that some nanoscale particles will pass through WWTPs and enter aquatic systems and offers a methodological framework for collecting and analyzing titanium-based nanomaterials in complex wastewater matrices.     

The simultaneous stripping of arsenic and selenium from wastewaters using hollow-fibre supported liquid membranes

The extraction of total arsenic and selenium using hollow-fibre supported liquid membranes (HFSLMs), with specific interest in the optimal conditions for the extraction in wastewater, is reported. The extraction time, type of liquid membrane, sample and donor pH and stirring rate were optimised, and thereafter, the developed method was tested in real wastewater samples. The optimal HFSLMs adopted, after optimisation tests, comprised of Aliquat 336, 0.8 M NaOH, 200 rpm and 80 min as the extractant, stripping phase, stirring rate and reaction time, respectively. The developed method had reasonable-to-high extraction efficiencies in real wastewater samples with the final effluent recording as high as 73 and 78 % removal efficiencies for Se and As, respectively. Considering the initial concentrations found in the samples, use of this developed method could bring down the concentrations to levels admissible by the United States Environmental Protection Agency (US-EPA) and World Health Organisation (WHO).     

Bacterial biosensors for rapid and effective monitoring of biodegradation of organic pollutants in wastewater effluents

Significant amounts of toxic substances which are hazardous to animals, plants, microorganisms, and other living organisms including humans are released annually into aquatic and terrestrial environments, mostly from improper wastewater discharges. Early detection of such pollutants in wastewater effluents and proper monitoring before their final release into the environment is therefore necessary. In this study, two whole-cell bacterial biosensors were constructed by transforming competent cells of Shigella flexneri and Shigella sonnei with pLUX plasmids and evaluated for their potential to monitor wastewater samples undergoing degradation by measuring bioluminescence response using a microplate luminometer. Both bacterial biosensors were found to be extremely sensitive to the wastewater samples, with different patterns, concomitant with those of the COD removals demonstrated at the different days of the degradation. Generally higher bioluminescence values were obtained at the later days of the degradation period compared to the initial values, with up to 571.76% increase in bioluminescence value obtained at day 5 for 0.1% (v/v) effluent concentration. Also, a steady decrease in bioluminescence was observed for the bacterial biosensors with increasing time of exposure to the wastewater effluent for all the sampling days. These biosensor constructs could therefore be applicable to indicate the bioavailability of pollutants in a way that chemical analysis cannot, and for in situ monitoring of biodegradation. This has great potential to offer a risk assessment strategy in predicting the level of bioremediation required during municipal wastewater treatment before their final discharge into the aquatic milieu.     

Penetration of polar brominated DBPs through the activated carbon columns during total organic bromine analysis

Total organic bromine (TOBr) is a collective parameter representing all the brominated organic disinfection byproducts (DBPs) in water samples. TOBr can be measured using the adsorption-pyrolysis method according to Standard Method 5320B. This method involves that brominated organic DBPs are separated from inorganic halides and concentrated from aqueous solution by adsorption onto the activated carbon (AC). Previous studies have reported that some commonly known brominated DBPs can partially penetrate through the AC during this adsorption step. In this work, the penetration of polar brominated DBPs through AC and ozone-modified AC was explored with two simulated drinking water samples and one chlorinated wastewater effluent sample. Polar brominated DBPs were selectively detected with a novel precursor ion scan method using electrospray ionization-triple quadrupole mass spectrometry. The results show that 3.4% and 10.4% of polar brominated DBPs (in terms of total ion intensity) in the chlorinated Suwannee River fulvic acid and humic acid samples, respectively, penetrated through the AC, and 19.6% of polar brominated DBPs in the chlorinated secondary wastewater effluent sample penetrated through the AC. The ozone-modification of AC minimized the penetration of polar brominated DBPs during the TOBr analysis.     

Partitioning and sources of PAHs in wastewater receiving streams of Tianjin,China

Polycyclic aromatic hydrocarbons (PAHs) partitioning among dissolved phase, suspended particulate matter, pore water, and sediment was studied in one moderately contaminated river (Yongding New River) and two highly contaminated drainage canals (South Drainage Canal and North Drainage Canal) of Tianjin, China. PAHs concentrations in sediment (ranged from 0.2 to 195 μg/g) showed positive relations with both total organic carbon contents (ranged from 0.7% to 31.1%, dw) and black carbon contents (ranged from 0.1% to 2.1%, dw) in the sediments. Moreover, most of the measured organic carbon normalized partition coefficients of PAHs in the three streams were 0.76 to 1.54 log units higher than the predicted values. These indicated that strong and nonlinear sorption of PAHs by carbonaceous geosorbents such as black carbon (BC) existed in the streams, and BC was an important part of the carbonaceous particles controlling the partitioning of PAHs in the sediments of this study. PAH component ratio analyses suggested that PAHs in the three streams, effluent samples from wastewater treatment plants, and soil samples by the riverbank had similar main sources, which is coal/petroleum combustion. We suggested the transportation and transformation of both carbonaceous particles and PAHs during wastewater treatment process, surface runoff, etc, should be studied further in order to make decisions on PAHs controlling measures.     

Quantitative analyses of selected polychlorinated biphenyl (PCB) congeners in water,soil, and sediment during winter and spring seasons from Msunduzi River,South Africa

The lack of information and the need for knowledge on the organic pollutants within the area of KwaZulu-Natal together with the global problem of water supply have prompted our investigation into the analyses of eight polychlorinated biphenyl (PCB) congeners in the Msunduzi River of KwaZulu-Natal, South Africa. Soil, sediment, and water samples were collected at ten different sites along the river during winter and spring seasons. Soil and sediment samples were extracted using ultra sonication with dichloromethane while water samples were liquid-liquid extracted using dichloromethane. All sample extracts were cleaned-up using a multi-layer silica gel column and analyzed with gas chromatography-mass spectrometry. Quality assurance measures were also determined. The percentage recoveries for water were 53–128 for all the PCBs analyzed, while sediment recoveries ranged between 69 and 105%. The highest total concentrations of the PCBs in sediment were 214.21–610.45 ng/g dw at the Du Toit sampling site and 30.86–444.43 ng/g dw basis at the wastewater treatment inlet for winter and spring, respectively. Soil PCB concentrations were 76.53–397.75 ng/g dw at the Msunduzi Town sampling site and 20.84–443.49 ng/g (dry weight) at the Du Toit sampling site for winter and spring, respectively. In addition, high PCB concentrations were found in effluent of the wastewater treatment inlet compared to other sampling sites, which ranged between 0.68–22.37 and 2.53–35.69 ng/mL for winter and spring seasons, respectively. In all the sampling sites selected for this study, Du Toit afforded the highest PCB concentration levels and the lowest was after chlorination at the Darvill wastewater treatment plant. The results presented are new and it is the first study of organic pollutants such as PCBs that has been carried out on this river.     

Prediction of the effluent from a domestic wastewater treatment plant of CASP using gray model and neural network

When a domestic wastewater treatment plant (DWWTP) is put into operation, variations of the wastewater quantity and quality must be predicted using mathematical models to assist in operating the wastewater treatment plant such that the treated effluent will be controlled and meet discharge standards. In this study, three types of gray model (GM) including GM (1, N), GM (1, 1), and rolling GM (1, 1) were used to predict the effluent biochemical oxygen demand (BOD), chemical oxygen demand (COD), and suspended solids (SS) from the DWWTP of conventional activated sludge process. The predicted results were compared with those obtained using backpropagation neural network (BPNN). The simulation results indicated that the minimum mean absolute percentage errors of 43.79%, 16.21%, and 30.11% for BOD, COD, and SS could be achieved. The fitness was higher when using BPNN for prediction of BOD (34.77%), but it required a large quantity of data for constructing model. Contrarily, GM only required a small amount of data (at least four data) and the prediction results were analogous to those of BPNN, even lower than that of BPNN when predicting COD (16.21%) and SS (30.11%). According to the prediction, results suggested that GM could predict the domestic effluent variation when its effluent data were insufficient.     

Heat shock protein 47 stress responses in Chinese hamster ovary cells exposed to raw and reclaimed wastewater

As wastewater reclamation and reuse becomes more widespread, risks of exposure to treated wastewater increase. Moreover, an unlimited number of pollutants can be identified in wastewater. Therefore, comprehensive toxicity assessment of treated wastewater is imperative. The objective of this study was to perform a comprehensive toxicity assessment of wastewater treatment systems using stress response bioassays. This powerful tool can comprehensively assess the toxicity of contaminants. In this study, samples from conventional activated sludge treatment, membrane bioreactors (MBRs) with different pore sizes and sludge retention times (SRTs), rapid sand filtration, coagulation, nano-filtration (NF) and reverse osmosis (RO) were investigated. The results of stress response bioassays confirmed that the secondary effluent showed higher stress response than influent indicating that biological treatment generates toxic compounds. The results obtained from molecular weight fractionation of water samples demonstrated that organic matter with a higher molecular weight fraction (>0.1 μm) causes toxicity in secondary effluent. Furthermore, supernatant from MBR reactors showed toxicity regardless of SRT. On the other hand, stress response was not detected in MBR permeates except for an MBR equipped with a larger pore size membrane (0.4 μm) and with a short SRT (12 days). While rapid sand filtration could not remove the toxic compounds found in secondary effluent, coagulation tests, operated at an appropriate pH, were effective for reducing stress response in the secondary effluent. Experimental findings also showed that stress response was not detected in cases of NF and RO permeate subsequent to MBR treatment.     

Effect of process conditions on the analysis of free and conjugated estrogen hormones by solid-phase extraction–gas chromatography/mass spectrometry (SPE–GC/MS)

Simultaneous analysis of 11 free estrogen hormones and five conjugated estrogens in water and municipal wastewater was studied. The analytical method was developed and tested for different types of solid-phase extraction adsorbents, eluents, sample containers and storage conditions, derivatization, and matrix effects. Varian Bond Elut C-18 solid-phase extraction adsorbent cartridge was selected based on its high recoveries for both free and conjugated estrogens. Sample storage conditions, as well as selection and pretreatment of sample container materials, can affect the trace level analysis of estrogens. Silanization of glassware is observed to provide low relative standard deviation (RSD) in the analysis and less percentage loss due to contacting with sample container materials. Light exposure during the test can significantly impact the results. The derivatized samples stored at −20°C for at least 6 days showed less than 10.5% average RSD in the analysis. The recovery efficiency in clean water varies from 72% to 101% for free estrogens and 78% to 82% for conjugated estrogens. The method detection limits (MDL) for most of the compounds range from 30 to 870 ng/L using a sample volume of 200 mL. With a sample volume of 3 L, the most sensitive compound produces a MDL of 0.03 ng/L. Dilute methanol is used to wash the loaded cartridge as a cleanup step in order to remove interfering species during analysis of wastewater samples. Using the optimized analytical methods, the concentration level of free estrogens in the influent and effluent municipal wastewaters is tested.     

Quality of wastewater reuse in agricultural irrigation and its impact on public health

This study is planned to perform a sanitary survey of the largest sewage treatment plant in Riyadh, KSA, fortnightly for 6 months to examine its effluent quality as an example for the growing dependence on reuse of treated municipal wastewater in agricultural irrigation purposes to cope with increasing water shortage. The biological and physico-chemical parameters of 12 wastewater samples from the plant were examined using standard methods. The physico-chemical analysis indicated that the surveyed municipal wastewater treatment plant contained some of the studied parameters, such as turbidity, total suspended solids, biochemical oxygen demand, chemical oxygen demand and residual chlorine above the maximum permissible wastewater limits set by the Saudi Standards. However, heavy metal concentrations in all samples were lower than the recommended standards. Total and faecal coliform counts were above the permissible limits indicating poor sanitation level. Fifty percent of all wastewater samples were contaminated with faecal coliforms but, surprisingly, Escherichia coli were only detected in 8.3 % of the samples. Regular monitoring and enhancement of microbial and physico-chemical parameters of the wastewater quality served by different wastewater treatment plants for reuse in agricultural irrigation is recommended to preserve the environment and public health.     

Fish scales as indicators of wastewater toxicity from an international water channel Tung Dhab drain

The effect of wastewater exposure on scales and chromatophores of freshwater fish Channa punctatus was studied using wastewater dilutions (60–100%) from an international water channel Tung Dhab drain at an interval of 15 and 30 days. The exposed fish showed significant alterations such as uprooted and damaged lepidonts and dispersal of chromatophores. These observations strongly suggest that fish scales can be successfully employed as indicators of wastewater pollution.     

Source to sink tracking of selected human pharmaceuticals from two Oslo city hospitals and a wastewater treatment works

The occurrence of twenty pharmaceutical compounds was quantitatively determined in effluents from two major Oslo city hospitals, Rikshospitalet and Ullev?l, along with influent, sludge and final effluent from the city's VEAS wastewater treatment works (WTW). Composite hospital effluents were collected over a twelve week period and were showed to contain paracetamol, metoprolol, diclofenac, ibuprofen, 17beta-Estradiol, estriol, estrone, oxytetracycline, tetracycline, doxycycline, chlorotetracycline, demeclocycline, trimethoprim, ciprofloxacin, sulfamethoxazole, cyclophosphamide and ifosfamide. Three pharmaceuticals were not detected above the limit of detection; cefuroxime, 17alpha-ethinylestradiol and meclocycline. Composite influent, sludge and effluent samples were collected from VEAS WTW over a seven week period. The influent into VEAS WTW contained all of the same selected substances detected in the hospital effluents, except for oxytetracycline, chlorotetracycline, demeclocycline, cyclophosphamide and ifosfamide. The percentage of pharmaceuticals entering the works from the hospitals was <10% for all of the selected compounds. VEAS sludge samples contained a different profile of substances reflecting their physico-chemical properties. Hydrophobic antibiotics, such as oxytetracycline, tetracycline and ciprofloxacin, were detected in all of the collected sludge samples. Their absence in the collected influent samples suggests that they enter the works bound to effluent particles, with the dissolved fraction observed in the hospital effluents partitioning onto particulate matter within the sewerage network. The final effluent from VEAS WTW contained reduced concentrations of many pharmaceuticals, including paracetamol, ibuprofen and sulfamethoxazole. For other compounds, such as metoprolol, diclofenac and trimethoprim, there were often higher concentrations in the effluent than the influent. These effluent concentrations represent median inputs varying from low g day(-1) (e.g. paracetamol and ibuprofen) to nearly 200 g day(-1) (e.g. metoprolol and trimethoprim) into Oslofjord. A simple risk assessment showed that the antibiotic ciprofloxacin may at times pose an acute risk to the Oslofjord aquatic environment.     

Long-term reclaimed water application effects on phosphorus leaching potential in rapid infiltration basins

Rapid infiltration basins (RIBs) are effective tools for wastewater treatment and groundwater recharge, but continuous application of wastewater can increase soil P concentrations and subsequently impact groundwater quality. The objectives of this study were to (1) investigate the effects of reclaimed water infiltration rate and "age" of RIBs on soil P concentrations at various depths, and (2) estimate the degree (percentage) of sorption equilibrium reached between effluent P and soil attained during reclaimed water application to different RIBs. The study was conducted in four contrasting cells of a RIB system with up to a 25 year history of secondary wastewater application. Soil samples were collected from 0 to 300 cm depth at 30 cm intervals and analyzed for water extractable phosphorus (WEP) and oxalate extractable P, Al, and Fe concentrations. Water extractable P and P saturation ratio (PSR) values were generally greater in the cells receiving reclaimed water compared to control soils, suggesting that reclaimed water P application can increase soil P concentrations and the risk of P movement to greater depths. Differences between treatment and control samples were more evident in cells with longer histories of reclaimed water application due to greater P loading. Data also indicated considerable spatial variability in WEP concentrations and PSR values, especially within cells from RIBs characterized by fast infiltration rates. This occurs because wastewater-P flows through surface soils much faster than the minimum time required for sorption equilibrium to occur. Studies should be conducted to investigate soil P saturation at deeper depths to assess possible groundwater contamination.     

水中汞监测存在的问题与解决办法

利用中日合作 (JICA)项目资金 ,对测定地表水中汞存在的主要问题 ,如水样的保存和处理 ,水样的消解 ,测汞的冷原子吸收法和原子荧光法等进行了研究。通过对 33个环境监测站的样品考核 ,发现测定结果与标准值相比 ,偏高的数据达 75 %以上。提出了用 1%H2 SO4 和 0 1%K2 Cr2 O7保存水样最好 ;高锰酸钾 -过硫酸钾消解法适用于消解含有机物、悬浮物和组成复杂的废水样 ,高锰酸钾 -硫酸消解法适用于消解被有机物轻度污染的废水 ,溴酸钾 -溴化钾消解法适用于消解地表水和含较少有机物的生活污水及工业废水。研究表明 :尤以硫酸 -高锰酸钾 -过硫酸钾消解体系消解地表水和废水效果良好。对冷原子吸收法和原子荧光法中影响汞测定的因素 ,如空白值高、干扰物的消除、载气种类和流量、反应瓶体积和气液比以及反应时间等提出了详尽的解决方法     

GC-MS identification of gaseous volatiles in wastewater

Gaseous volatiles from wastewater samples taken from a local sewage treatment plant were air-stripped and trapped onto Tenax GC. These volatiles were then thermally desorbed and subsequently analyzed using a gas chromatograph coupled to a mass spectrometer (GC-MS). The results show that saturated aliphatic and aromatic hydrocarbons were the most dominant compounds found in the sewage gaseous volatiles. Other compounds found were chlorinated hydrocarbons, organic acids, sulfides and phenols. A wide variety of gaseous volatiles were found in the raw wastewater, the primary clarifier effluent, the pre-aeration wastewater and the sludge samples. A comparison of the gas chromatograms for the pre- and post-aeration wastewater shows that many odorous gaseous volatiles were removed during the aeration process in the treatment plant.     

运用热带爪蟾胚胎测定工业废水的发育毒性

采用热带爪蟾胚胎测定江苏省常州市8家典型行业工业废水的发育毒性，结果显示：各行业工业废水对爪蟾胚胎的发育均有不同程度的影响，而印染、啤酒、电镀和化工行业出水的发育毒性更强。试验表明，理化指标并不能完全反映工业废水的综合毒性，而热带爪蟾胚胎可有效地表征其发育毒性。比较各行业工业废水的毒性，初步探讨热带爪蟾胚胎用于工业废水毒性检测的可行性。     

Monitoring of pharmaceutically active compounds on the Guadalquivir River basin (Spain): occurrence and risk assessment

Guadalquivir River (South of Spain) is among the major freshwater sources of the European Atlantic basin. Until now scientific efforts have been focused on contamination by heavy metals and some priority pollutants in Guadalquivir River. However, the presence of "emerging contaminants", such as pharmaceutically active compounds, has not yet been studied. In this work the occurrence and risk assessment of sixteen pharmaceutically active compounds, belonging to different therapeutic groups, in Guadalquivir River during its course through Seville city are reported. Wastewater effluents from four wastewater treatment plants discharging into Guadalquivir River and river water samples were analyzed. All studied pharmaceutically active compounds, except sulfamethoxazole, trimethoprim, estrone and clofibric acid, were detected in effluent wastewaters at concentration levels up to 28.9 μg L(-1). Among the pharmaceutically active compounds found in effluent wastewater, seven were present in Guadalquivir River samples at concentration levels up to 0.75 μg L(-1), which indicated an important dilution from effluent discharge. Environmental risk assessment reveals that potential ecotoxicological risk cannot be expected on Guadalquivir River at measured concentration levels. Only, the lipid regulator gemfibrozil showed a medium risk for the environment. The risk for acute toxic effects in the environment with the current use of active pharmaceutical ingredients is unlikely. However, the results do not rule out the potential for chronic environmental effects.     

Influence of different textile fibers on characterization of dyeing wastewater and final effluent

Textile industry needs to recover and reuse its wastewater as to fulfil the demand of increasingly strict regulations. The characterization of dyeing wastewater samples according to textile fiber and final textile effluent enables the application of different treatment methods. This study aims to characterize dyeing wastewater in black color of polyamide, polyester, and viscose fibers and final textile effluent. Samples were collected and characterized completely for major pollution indicator parameters. Dyeing wastewater of polyester showed higher values for some parameters, e.g., 4994.44% (49,944,400 mg L^?1 and 917 NTU) of turbidity and 4100.00% of phenol when compared to dyeing wastewater of other fibers. Other parameters such as pH, alkalinity, color, phosphorus, nitrogen, sulfides, chlorides, oil and grease, dissolved solids, and chemical and biochemical oxygen demand were also assessed. In addition to individual characterization, this study also presents a correlation of the contribution of each parameter to the final textile effluent. Although dyeing wastewater of polyamide contributes the most in terms of quantity for the final effluent, this study revealed that dyeing wastewater of polyester influenced the most on the final composition of the textile wastewater when evaluating color, turbidity, total iron, biochemical oxygen demand, chemical oxygen demand, phenol, mercury, oil and grease, and total phosphorus. The present study is focused on bringing new insights to provide future research with other strategies to improve the treatment of dyeing wastewater. In addition, some suggestions are also given for wastewater treatments according to type of textile fiber.     

A Characterization of Selected Endocrine Disruptor Compounds in a Portuguese Wastewater Treatment Plant

Anthropogenic compounds that are able to disrupt the endocrine system of wildlife species are a major cause for concern and have led to a demand for new screening methods. The identification and quantification of endocrine disruptor compounds at wastewater treatment plant is of major interest to assess the endocrine activity of wastewater treatment plant discharges into the environment. This study consists of a preliminary survey of concentrations of previously selected endocrine disruptor compounds, undertaken to establish environmental concentrations and to support a biological program assay exposing freshwater fish to them. Selected endocrine disrupting chemicals (APEs, bisphenol A and 17 β-estradiol) were measured in samples from a wastewater treatment plant located in Lisbon (Portugal), using recent commercial enzyme-linked immunosorbent assay kits and also LC-MS/MS. The results show that the wastewater treatment plant treatment process is efficient on the removal of target endocrine disruptor compounds. However, environmentally significant concentrations are still present in the treated effluent. The results also show that enzyme-linked immunosorbent assay kit is suitable for routine analysis of the selected compounds. The results are also useful since the wastewater treatment plant is located in a Mediterranean region, which results in an effluent with its own characteristics.