Removal of pharmaceuticals in sewage treatment plants in Italy

A listing of "priority pharmaceuticals" for human use in Italy resulted in the selection of 26 pharmaceuticals, belonging to 11 therapeutic classes. They were analyzed by liquid chromatography-tandem mass spectrometry, their occurrence was assessed in six sewage treatment plants (STPs), and the loads and the removal rates (RR) were studied. Total loads ranged from 1.5 to 4.5 g/day/1000 inhabitants in influents and 1.0 and 3.0 g/day/1000 inhabitants in effluents. Total RR in STPs were mostly lower than 40%. Pharmaceuticals could be divided into three groups according to their behavior in STPs: one group with RR higher in summer than in winter, one group with RR similar in summer and winter, and a last group not removed. Last, we studied the distribution and fate of residual pharmaceuticals in the surface waters receiving the effluents of the STPs and identified degradation and sorption as the major factors affecting attenuation. Ciprofloxacin, ofloxacin, sulfamethoxazole (antibiotics), atenolol (cardiovascular drug), ibuprofen (antiinflammatory), furosemide, hydrochlorothiazide (diuretics), ranitidine (gastrointestinal drug), and bezafibrate (lipid regulator) were the most abundant residual drugs, thus those of environmental concern.     

Organophosphorus flame retardants and plasticizers in Swedish sewage treatment plants

The levels, distribution, and possible sources of 12 organophosphorus flame retardants and plasticizers, some of which are reported to be toxic to aquatic organisms, were investigated in samples of influents, effluents, and sludge from 11 Swedish sewage treatment plants (STPs). The organophosphorus compounds (OPs) studied were poorly removed from the wastewater; especially the chlorinated OPs tended to pass through the STPs without being removed or degraded, while alkyl-OPs, such as tributyl phosphate (TBP), were more successfully removed. In both influents and effluents, tris(2-butoxyethyl) phosphate and TBP were the most prominent substances followed by tris(2-chloroisopropyl) phosphate (TCPP). The highest concentration of any individual OP detected in the influents was 52 microg L(-1) (TBP). Ethylhexyl diphenyl phosphate and TCPP dominated in all sludge samples. A budget calculation comparing the annual amount of OPs in the influent received by Swedish STPs with the known amount of OPs imported indicated that approximately 15% is emitted to STPs. Of the total amount of OPs reaching the STPs annually, 49% is degraded, 50% (27 tons) is emitted to the recipients, and only 1% ends up in the sludge. The concentrations of most OPs were quite similar among the sampled STPs, indicating that the data may be applicable in other STPs.     

Fluorochemical mass flows in a municipal wastewater treatment facility

Fluorochemicals have widespread applications and are released into municipal wastewater treatment plants via domestic wastewater. A field study was conducted at a full-scale municipal wastewater treatment plant to determine the mass flows of selected fluorochemicals. Flow-proportional, 24 h samples of raw influent, primary effluent, trickling filter effluent, secondary effluent, and final effluent and grab samples of primary, thickened, activated, and anaerobically digested sludge were collected over 10 days and analyzed by liquid chromatography electrospray-ionization tandem mass spectrometry. Significant decreases in the mass flows of perfluorohexane sulfonate and perfluorodecanoate occurred during trickling filtration and primary clarification, while activated sludge treatment decreased the mass flow of perfluorohexanoate. Mass flows of the 6:2 fluorotelomer sulfonate and perfluorooctanoate were unchanged as a result of wastewater treatment, which indicates that conventional wastewater treatment is not effective for removal of these compounds. A net increase in the mass flows for perfluorooctane and perfluorodecane sulfonates occurred from trickling filtration and activated sludge treatment. Mass flows for perfluoroalkylsulfonamides and perfluorononanoate also increased during activated sludge treatment and are attributed to degradation of precursor molecules.     

Pathogenic bacteria in sewage treatment plants as revealed by 454 pyrosequencing

This study applied 454 high-throughput pyrosequencing to analyze potentially pathogenic bacteria in activated sludge from 14 municipal wastewater treatment plants (WWTPs) across four countries (China, U.S., Canada, and Singapore), plus the influent and effluent of one of the 14 WWTPs. A total of 370,870 16S rRNA gene sequences with average length of 207 bps were obtained and all of them were assigned to corresponding taxonomic ranks by using RDP classifier and MEGAN. It was found that the most abundant potentially pathogenic bacteria in the WWTPs were affiliated with the genera of Aeromonas and Clostridium. Aeromonas veronii, Aeromonas hydrophila, and Clostridium perfringens were species most similar to the potentially pathogenic bacteria found in this study. Some sequences highly similar (>99%) to Corynebacterium diphtheriae were found in the influent and activated sludge samples from a saline WWTP. Overall, the percentage of the sequences closely related (>99%) to known pathogenic bacteria sequences was about 0.16% of the total sequences. Additionally, a platform-independent Java application (BAND) was developed for graphical visualization of the data of microbial abundance generated by high-throughput pyrosequencing. The approach demonstrated in this study could examine most of the potentially pathogenic bacteria simultaneously instead of one-by-one detection by other methods.     

Occurrence of natural and synthetic glucocorticoids in sewage treatment plants and receiving river waters

This paper first reports the occurrence of sixglucocorticoids (prednisone, prednisolone, cortisone, cortisol, dexamethasone, and 6alpha-methylprednisolone) in sewage treatment plants (STPs) and receiving rivers by establishing a method for analyzing glucocorticoids in complex environmental waters. For the various types of aqueous matrices considered, the absolute recoveries were from 73 to 99%, and limits of quantification were below 0.2 ng/L. Among the seven STPs studied, the average concentrations of prednisone, prednisolone, cortisone, cortisol, dexamethasone, and 6alpha-methylprednisolone in influents were, respectively, 2.6 +/- 2.1, 3.0 +/- 1.6, 30 +/- 21, 39 +/- 26, 1.2 +/- 0.70, and 0.62 +/- 0.65 ng/L, and their percent removals were 99 +/- 3.1, 78 +/- 8.8, 99 +/- 1.2, 98 +/- 2.5, 99 +/- 1.8, and 100 +/- 0%, respectively. The lower removal of prednisolone was found to be due to its relatively low efficiency of biodegradation, especially in anoxic and aerobic units. The frequently detected glucocorticoids in effluents were prednisolone, cortisol, and cortisone with average concentrations 0.56 +/- 0.06, 0.50 +/- 0.33, and 0.26 +/- 0.10 ng/ L. In the receiving waters, the Tonghui and Qing Rivers, the concentrations of these compounds in some samples were much higher than those in their corresponding STP effluents; these differences depended on the sampling date, suggesting that there was random discharging of untreated wastewaters into these rivers. In addition, the ratio between the combined concentrations of two natural glucocorticoids (cortisol and cortisone) and the concentration of one synthetic glucocorticoid, prednisolone, was found to be a potential index to reflect the wastewater discharging.     

Simultaneous determination of lincomycin and five macrolide antibiotic residues in honey by liquid chromatography coupled to electrospray ionization mass spectrometry (LC-MS/MS).

A sensitive and specific method based on high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), for the simultaneous determination of lincomycin and five macrolide antibiotics in honey, was developed and validated. The analytes were extracted with Tris buffer 0.1 M, pH 10.5, and cleaned-up by a single solid-phase extraction step on OASIS HLB column. The chromatographic separation of analytes was performed on a Synergi Hydro-RP reversed-phase column using a gradient programme of aqueous 0.01 M ammonium acetate, pH 3.5, and acetonitrile as the mobile phase, at a flow rate 0.25 ml min-1. The detection of analytes was achieved by positive ionization electrospray in multiple reaction-monitoring mode. Two characteristic transitions were monitored for each substance. The following analytical parameters were validated according to the guidelines laid down by European Commission Decision 2002/657/EC (European Commission 2002): linearity, specificity, decision limit (CCalpha), detection capability (CCbeta), repeatability, within-laboratory reproducibility, recovery and ruggedness.     

Isolation of iron-oxidizing bacteria from corroded concretes of sewage treatment plants

Thirty-six strains of iron-oxidizing bacteria were isolated from corroded concrete samples obtained at eight sewage treatment plants in Japan. All of the strains isolated grew autotrophically in ferrous sulfate (3.0%), elemental sulfur (1.0%) and FeS (1.0%) media (pH 1.5). Washed intact cells of the 36 isolates had activities to oxidize both ferrous iron and elemental sulfur. Strain SNA-5, a representative of the isolated strains, was a gram-negative, rod-shaped bacterium (0.5-0.6x0.9-1.5 microm). The mean G+C content of its DNA was 55.9 mol%. The pH and temperature optima for growth were 1.5 and 30 degrees C, and the bacterium had activity to assimilate 14CO2 into the cells when ferrous iron or elemental sulfur was used as a sole source of energy. These results suggest that SNA-5 is Thiobacillus ferrooxidans strain. The pHs and numbers of iron-oxidizing bacteria in corroded concrete samples obtained by boring to depths of 0-1, 1-3, and 3-5 cm below the concrete surface were respectively 1.4, 1.7, and 2.0, and 1.2 x 10(8), 5 x 10(7), and 5 x 10(6) cells/g concrete. The degree of corrosion in the sample obtained nearest to the surface was more severe than in the deeper samples. The findings indicated that the levels of acidification and corrosion of the concrete structure corresponded with the number of iron-oxidizing bacteria in a concrete sample. Sulfuric acid produced by the chemolithoautotrophic sulfur-oxidizing bacterium Thiobacillus thiooxidansis known to induce concrete corrosion. Since not only T. thiooxidans but also T. ferrooxidans can oxidize reduced sulfur compounds and produce sulfuric acid, the results strongly suggest that T. ferrooxidans as well as T. thiooxidans is involved in concrete corrosion.     

Calculation methods to perform mass balances of micropollutants in sewage treatment plants. application to pharmaceutical and personal care products (PPCPs)

Two different methods are proposed to perform the mass balance calculations of micropollutants in sewage treatment plants (STPs). The first method uses the measured data in both liquid and sludge phase and the second one uses the solid-water distribution coefficient (Kd) to calculate the concentrations in the sludge from those measured in the liquid phase. The proposed methodologies facilitate the identification of the main mechanisms involved in the elimination of micropollutants. Both methods are applied for determining mass balances of selected pharmaceutical and personal care products (PPCPs) and their results are discussed. In that way, the fate of 2 musks (galaxolide and tonalide), 3 pharmaceuticals (ibuprofen, naproxen, and sulfamethoxazole), and 2 natural estrogens (estrone and 17beta-estradiol) has been investigated along the different water and sludge treatment units of a STP. Ibuprofen, naproxen, and sulfamethoxazole are biologically degraded in the aeration tank (50-70%), while musks are equally sorbed to the sludge and degraded. In contrast, estrogens are not removed in the STP studied. About 40% of the initial load of pharmaceuticals passes through the plant unaltered, with the fraction associated to sludge lower than 0.5%. In contrast, between 20 and 40% of the initial load of musks leaves the plant associated to solids, with less than 10% present in the final effluent. The results obtained show that the conclusions concerning the efficiency of micropollutants removal in a particular STP may be seriously affected by the calculation method used.     

Species identification by genotyping and determination of antibiotic resistance in Campylobacter jejuni and Campylobacter coli from humans and chickens in Sweden

Campylobacter is today the most common cause of human bacterial enteritis in Sweden, as well as in most other industrialized countries. Common sources of infection are undercooked chicken meat, unpasteurized milk and contaminated drinking water. One aim with our present study was to identify the species Campylobacter jejuni and Campylobacter coli strains from humans and chickens using a polymerase chain reaction/restriction enzyme analysis (PCR/REA) method, as well as traditional hippurate hydrolysis test. Another aim was to investigate the antibiotic resistance pattern of the human domestic C. jejuni/C. coli isolates from infected patients and isolates from healthy Swedish chicken, as well as isolates from humans infected abroad. If discrimination between C. jejuni and C. coli was based on testing for hippurate hydrolysis, 95% of the human domestic strains and 88% of the chicken strains were identified as C. jejuni. Based on genotyping by PCR/REA, 100% of the human domestic strains and 98% of the chicken strains were attributed to C. jejuni. The E-test and disc diffusion methods were used for phenotypic antibiotic resistance studies. The two methods gave similar results. Most Swedish C. jejuni/C. coli isolates both from humans and chickens were sensitive to doxycycline and erythromycin, which are antibiotics used to treat human infection. Only 7% of the human domestic strains and 2% of the chicken strains were resistant to the quinolones tested. As a comparison, more than 94% of strains isolated from travelers to Asia and southern Europe showed antibiotic resistance to one or more drugs.     

Removal of two polycyclic musks in sewage treatment plants: freely dissolved and total concentrations

In the current study, the removal of slowly degradable hydrophobic chemicals in sewage treatment plants (STPs) has been evaluated with emphasis on the combination of free and total concentration data. Free and total concentrations of two polycyclic musks were determined in each compartment of four STPs. The free concentration of the polycyclic musks remains virtually constant throughout all the compartments of the STPs with values between 0.21 and 0.57 microg/L for AHTN and between 0.79 and 2.0 microg/L for HHCB. Total concentrations of these fragrances are highly dependent on the volatile solids in a given compartment resulting in much more variation with values between 0.42 and 92 microg/L for AHTN and between 1.25 and 258 microg/L for HHCB. It is concluded that free concentrations of these hydrophobic chemicals in the compartments of STPs are mostly biodegradation mediated, while total concentrations are mediated by the concentration of solids. The combination of measurements of free and total concentrations can improve estimations regarding removal efficiency and removal pathways.     

Liquid chromatography-tandem mass spectrometry method for the determination of anthelmintics in alfalfa plants

A simple and inexpensive liquid chromatography-tandem mass spectrometric method for the determination of anthelmintics in alfalfa plants (Medicago sativa L.) was developed and validated. Anthelmintics in plant leaves and stems (green chops) were extracted with methanol/acetonitrile (7:3, v/v) followed by a concentration and clean-up step using solid-phase extraction (Strata-X, 500?mg, 6?ml cartridge). After drying with nitrogen gas, the adsorbed analytes were eluted with methanol/acetonitrile (50:50, v/v) mixture followed by 100% acetonitrile. Chromatographic separation was achieved on an Atlantis T-3 (2.1?×?100?mm?×?3?µm) analytical column with a Phenomenex guard cartridge (C8, 4?×?3?mm) attached to a Waters triple quadrupole mass spectrometer operated in positive electrospray ionisation mode with selected reaction monitoring. Samples were analysed using gradient elution at a flow rate of 0.35?ml?min^–1. The mobile phase consisted of a 10?mM ammonium formate solution in (A) water/acetonitrile (90:10, v/v) and (B) methanol/acetonitrile (50:50, v/v). The method was validated for levamisole, fenbendazole, fenbendazole sulphoxide and fenbendazole sulphone at 10, 20 and 40?µg?kg^–1 and for eprinomectin at 20, 40 and 80?µg?kg^–1. Limits of quantification (LOQ) were 10?µg?kg^–1 for all analytes except eprinomectin, which had an LOQ of 20?µg?kg^–1. The overall mean recovery in green plants was between 74.2% and 81.4% with repeatabilities ranging from 2.2% to 19.1% and reproducibilities in the range 3.8–8.7%. The validated method was applied to plant samples in a study on the behaviour of anthelmintic drugs in a soil, plant and water system.     

分散固相萃取-气相色谱-串联质谱法同时测定草莓及土壤中5种杀菌剂

目的 建立分散固相萃取-气相色谱-串联质谱分析法同时检测5种不同类型杀菌剂(五氯硝基苯、百菌清、氟吡菌酰胺、肟菌酯、咪鲜胺)的含量。方法 样品经10 mL乙酸乙酯提取, N-丙基乙二胺与C18(50 mg: 50 mg)分散固相萃取混合净化。采用多反应监测模式进行定性, 外标法进行定量分析。结果 5种杀菌剂在1~1000 μg/L浓度范围内呈线性, 相关系数为0.9802~0.9996。空白样品在10、100和200 μg/kg添加浓度下的回收率为84%~119%, 相对标准偏差为1%~17%(n=3), 方法定量限为最小添加浓度10 μg/kg。结论 该方法能够满足土壤和草莓样品中痕量杀菌剂检测的要求。     

QuEChERS-超高效液相色谱-串联质谱法同时快速测定肉类食品中多种抗生素残留

目的建立能同时检测肉类食品中20种磺胺和8种喹诺酮类抗生素残留的Qu ECh ERS-超高效液相色谱-串联质谱法(UPLC-MS/MS)。方法样品加1%甲酸乙腈提取,经分散固相萃取净化后,采用Waters C18(2.1 mm×100 mm,1.7μm)色谱柱分离,梯度洗脱,采用电喷雾-正离子多反应监测模式,外标法定量。结果 28种抗生素在各自浓度范围内线性关系良好,相关系数(r)为0.997 5~0.999 6,检出限(LOD)为0.17~0.91μg/kg(S/N=3),磺胺类抗生素回收率在70.9%~115.2%之间,RSD在2.8%~15.9%(n=6)之间;喹诺酮类抗生素回收率在71.3%~112.3%之间,RSD在2.5%~14.6%(n=6)之间。结论建立的方法准确、快速、灵敏度高,可对动物源性食品中多种抗生素残留进行快速分析。     

湿法消解-电感耦合等离子体质谱法同时测定水生蔬菜中5种元素

目的　建立湿法消解/电感耦合等离子体质谱法（inductively coupled plasma mass spectrometry, ICP-MS）测定8种水生蔬菜中5种元素的方法。方法　样品在混合酸（硝酸+高氯酸=4+1, V/V）介质中消解,消解后,将消化液用水转移至25 mL容量瓶,并用ICP-MS同时测定水生蔬菜中总As、Cd、Cr、Ni和Pb这5种元素的含量。结果　5种元素的标准曲线线性范围可达0μg/L~200μg/L,相关系数：0.9992~0.9998,检出限：0.009 μg/L~0.025μg/L,定量限：0.030μg/L~0.083μg/L,回收率：89.4%~112.6%,RSD(n=11)：1.20%~1.86%。80份水生蔬菜样品中5种元素的含量均低于国家标准规定的食品中污染物限量。水生蔬菜不同种类间,5种元素的含量有显著差异。结论　湿法消解/ICP-MS方法直观、快速、准确、可靠,适于水生蔬菜中多元素同时测定。     

超高效液相色谱–质谱联用法定量测定奶茶中的 3种毒品成分

目的建立超高效液相色谱质谱联用法测定奶茶中苯丙胺、甲基苯丙胺和氯胺酮的分析方法。方法样品经甲醇超声提取处理,利用超高效液相色谱质谱联用法, 4.0 min内完成样品的上机分析。结果方法在0.1～50.0 ng/mL范围内,线性良好,相关系数r大于0.999。仪器检出限在0.008～0.027 ng/mL之间,定量限在0.028～0.089 ng/mL之间。三水平加标回收率在80.7%～112.0%之间。高浓度样品分析后, 3种毒品无明显仪器残留。使用本方法分析市售奶茶样品,未检出3种毒品。结论本方法灵敏、快速、线性范围宽、选择性好、前处理简单,适用于奶茶中3种毒品的准确定量检测。     

Quantitative determination of fluorinated alkyl substances by large-volume-injection liquid chromatography tandem mass spectrometry-characterization of municipal wastewaters

A quantitative method was developed for the determination of fluorinated alkyl substances in municipal wastewater influents and effluents. The method consisted of centrifugation followed by large-volume injection (500 microL) of the supernatant onto a liquid chromatograph with a reverse-phase column and detection by electrospray ionization and tandem mass spectrometry. The fluorinated analytes studied include perfluoroalkyl sulfonates, fluorotelomer sulfonates, perfluorocarboxylates, and select fluorinated alkyl sulfonamides. Recoveries of the fluorinated analytes from wastewater treatment plant (WWTP) raw influents and final effluent were in the ranges of 82-100% and 86-100%, respectively. The lower limit of quantitation was 0.5 ng/L depending on the analyte. The method was applied to flow-proportional composites of raw influent and final effluent collected over a 24 h period from 10 WWTPs nationwide. Fluorinated alkyl substances were observed in wastewater at all treatment plants, and each plant exhibited unique distributions of fluorinated alkyl substances despite similarities in treatment processes. In 9 out of the 10 plants sampled, at least one class of fluorinated alkyl substances exhibited increased concentrations in the effluent as compared to the influent concentrations. In some instances, decreases in certain fluorinated analyte concentrations were observed and attributed to sorption to sludge.     

五种秋葵营养成分及活性物质含量的分析比较

通过测定浏阳本地秋葵、红秋葵、绿五星、早生五角、台湾五福等五个品种秋葵的营养成分及活性物质含量,以比较不同品种间的差异。结果表明,五种秋葵嫩果荚的灰分、粗脂肪、粗蛋白、总糖、多糖、总黄酮含量分别处于4.33⁶.53、1.54².05、1.96².46、64.35⁶8.64、2.60².87、1.66¹.97 g·100 g-1的范围之间,变异系数分别为14.36%、9.62%、10.22%、2.38%、3.95%、7.36%;五种秋葵嫩果籽的灰分、粗脂肪、粗蛋白、总糖、多糖、总黄酮含量分别处于4.50⁵.95、15.05¹7.37、22.73²5.36、20.48²5.03、1.20¹.59、2.03².20 g·100 g-1的范围之间,变异系数分别为11.67%、4.91%、4.21%、8.19%、9.47%、2.89%;五种秋葵嫩果荚的营养成分以总糖为主,其次为灰分,粗蛋白、粗脂肪含量最少;五种秋葵嫩果籽主要含粗脂肪、粗蛋白、多糖,三者含量均衡;五种秋葵嫩果荚的多糖含量均高于嫩果籽,总黄酮含量低于嫩果籽（p<0.05）;秋葵嫩果荚、嫩果籽的多糖、总黄酮含量均高于老果荚与老果籽（p<0.05）。      

UV-B辐射对植物营养及生物活性物质的影响研究进展

UV-B辐射作为一种重要的代谢调控手段,其辐射作用与植物体内多种组成成分的合成、积累及代谢密切相关,因此研究UV-B对植物体内主要营养物质及生物活性物质的影响具有重要意义。本文综述了近年来有关UV-B辐射（Ultraviolet-B radiation）对植物体内的基础营养物质（碳水化合物、脂类、蛋白质）和主要生物活性物质（氨基酸、多酚类、萜类、生物碱）影响的研究进展,并对领域内现有问题进行分析,对后续研究重点进行展望。以期指导后续有关UV-B的调控作用研究,为农业生产及农作物品质提升研究提供理论依据。      

Arbutin determination in medicinal plants and creams

A simple flow injection (FI) manifold with spectrophotometric detection was fabricated and tested for arbutin determination. It is based on the measurement of a red-coloured product at 514 nm formed by the complexation reaction between arbutin and 4-aminoantipyrine (4-AP) in the presence of hexacyanoferrate (III) in an alkaline medium. On injecting 300 μL standard solutions at various concentrations of arbutin into the FI system under optimum conditions, a linear calibration graph over the range of 1.0–30.0 μg mL⁻¹ arbutin was established. It is expressed by the regression equation y  = 0.2188 ± 0.0036 x  + 0.1019 ± 0.0366 ( r ²   = 0.9990, n  = 5). The detection limit (3σ) and the limit of quantitation (10σ) were 0.04 μg mL⁻¹ and 0.13 μg mL⁻¹, respectively. The RSD of intraday and interday precisions were found to be 1.2–1.4% and 1.7–2.7%, respectively. The method was successfully applied in the determination of arbutin in four selected fruits and three commercial whitening cream extracts with the mean recoveries of the added arbutin over the range of 96.2–99.0%. No interference effects from some common excipients used in commercial whitening creams were observed. The method is simple, rapid, selective, accurate, reproducible and relatively inexpensive.