Occurrence of pharmaceutical compounds in wastewater process streams in Dublin,Ireland

The aim of this work is to establish baseline levels of pharmaceuticals in three wastewater treatment plant (WWTP) streams in the greater Dublin region to assess the removal efficiency of the selected WWTPs and to investigate the existence of any seasonal variability. Twenty compounds including several classes of antibiotics, acidic and basic pharmaceuticals, and prescribed medications were selected for investigation using a combination of membrane filtration, solid phase extraction (SPE) cleanup, and liquid chromatography–electrospray ionization tandem mass spectrometry. Fourteen of the selected compounds were found in the samples. Increased effluent concentrations, compared to influent concentrations, for a number of compounds (carbamazepine, clotrimazole, propranolol, nimesulide, furosemide, mefenamic acid, diclofenac, metoprolol, and gemfibrozil) were observed. The detected concentrations were generally below toxicity levels and based on current knowledge are unlikely to pose any threat to aquatic species. Mefenamic acid concentrations detected in both Leixlip and Swords effluents may potentially exert ecotoxicological effects with maximum risk quotients (i.e., ratio of predicted exposure concentration to predicted no effect concentration) of 4.04 and 1.33, respectively.     

Simultaneous determination of selected endocrine disrupter compounds in wastewater samples in ultra trace levels using HPLC-ES-MS/MS

An analytical procedure for the simultaneous determination of six selected endocrine disrupter compounds (EDCs: diltiazem, progesterone, benzyl butyl phthalate (BBP), estrone, carbamazepine (Cbz), acetaminophen) was developed by liquid chromatography electrospray ionization tandem mass spectrometry (HPLC-ES-MS/MS). All of the parameters for HPLC and ES-MS/MS systems including mobile phase composition, flow rate, and sample injection volume were optimized to obtain not only the best separation of species interested but also low detection limits. Reverse phase chromatography coupled to ES-MS/MS was used for the separation and detection of EDCs. Formic acid (0.10% ) and 5.0 mM ammonium formate were selected as mobile phase composition in gradient elution. Detection limits for diltiazem, progesterone, BBP, estrone, Cbz, and acetaminophen were found to be 0.13, 0.12, 0.04, 0.13, 0.12, and 0.05 ng/mL, respectively. Influent and effluents from three different wastewater treatment plants located in Ankara, i.e., rotating flat-sheet membrane unit, pilot type flat-sheet membrane unit located at METU Campus and samples from Ankara central wastewater treatment plant were analyzed for their EDCs contents under the optimum conditions.     

GC/FTIR-FID测定石化废水中挥发性有机物

所述石化废水中挥发性有机物分析方法 ,以 GC分离 ,FTIR定性 ,FID定量。水样前处理采用大吹脱体积 ,两级捕集的吹脱捕集技术。为解决剖析分析无标样定量问题 ,成功地实现了 GC/FTIR-FID匹配联机 ,使得未知组分定性定量一次完成。方法变异系数低于 5% ,回收率高于 90 % ,最低检出浓度可达 0 .0 0 5mg/L     

LC-MS/MS法测定沉积物中磺胺类和四环素类抗生素

沉积物样品用乙腈-柠檬酸缓冲溶液提取后经HLB-SPE柱净化,采用LC-MS/MS法在MRM模式下测定17种磺胺类和4种四环素类抗生素,通过优化测定条件,使方法在0. 500μg/kg～100μg/kg范围内线性良好。方法检出限为0. 15μg/kg～1. 2μg/kg,2个质量比水平的加标回收率为44. 1%～125%,试验5次结果的RSD 16. 0%。将该方法用于测定厦门近岸海域沉积物中抗生素,共有6种磺胺类和4种四环素类抗生素检出,测定值为0. 3μg/kg～26. 2μg/kg。     

Identification and quantification of bisphenol A by gas chromatography and mass spectrometry in a lab-scale dual membrane system

Endocrine disruptor contamination is an emerging issue of concern in the field of water quality engineering. In this study, a lab-scale microfiltration (MF) and reverse osmosis (RO) based water reclamation system was set up to monitor and evaluate the removal of bisphenol A (BPA), which is a known oestrogenic compound. The identification and quantification of BPA were performed by using gas chromatography coupled with mass spectrometry. It was noted that the detection method used in this study was able to achieve an average recovery ranging from 88.2 to 94.1% of BPA with standard deviations of less than 10% in different spiked samples. The detection limit of the analytical protocol was determined at 20 ng L(-1). Based on the analytical protocol, it was noted that a low level of BPA (1.18-3.04 microg L(-1)) could be detected in feed water (effluent of an activated sludge treatment system) to the dual membrane water reclamation system. The results obtained suggested that BPA could be easily chlorinated by sodium hypochlorite with a dosage of 4 to 5 mg L(-1) and a contact time of 1 to 2 min. In this lab-scale study, a satisfactory removal of BPA was readily obtained by RO and BPA was abated to an undetectable level in the product water. It was noted that the RO rejection characteristic of BPA was not sensitive to the variations in raw feed water characteristics experienced in this study. In addition, it was noted that BPA concentration present in raw feed water did not exert any significant impact on RO performance in terms of BPA rejection. The results of this study demonstrated that membrane technology could be effectively used for BPA removal.     

Determination of six anti-infectives in wastewater using tandem solid-phase extraction and liquid chromatography-tandem mass spectrometry

A rugged and specific method based on tandem solid-phase extraction and liquid chromatography-tandem mass spectrometry for the determination of anti-infectives in raw sewage and wastewater plant effluents was developed. Analyte recoveries from spiked effluents ranged from 68 to 104%. Two specific selected reaction monitoring transitions and their peak area ratios were used to avoid false positives and confirm the presence of the targeted substances. Detection limits allowed low nanogram per litre detection (0.3-22 ng L(-1)). The method was successfully applied to real samples from the Montréal wastewater treatment plant. All the studied anti-infectives were found in the wastewater samples in concentrations ranging from 39 to 276 ng L(-1). Mean flows of anti-infectives were estimated from effluent concentrations and it was found that large amounts (>118 g day(-1) up to 830 g day(-1)) are discharged in the receiving waters of the St Lawrence River.     

A new catalytic oxidation method for sensitive quantification of bromate in flours and bottled water using AgNPs

In this paper, a simple and sensitive spectrophotometric method for the determination of nanomolar level of bromate, based on the catalytic effect of silver nanoparticles on the oxidation of acid red 14 by potassium bromate, is described. The reaction rate was monitored spectrophotometrically by measuring the decrease in absorbance of acid red 14 at 516 nm. The detection limit of the method was 8 ng/mL, and the linear range was between 15 and 130 ng/mL. The effects of acidity, concentration of reactants and reaction time, and external ions were also discussed. The optimum reaction conditions were fixed, and some kinetic parameters determined. The relative standard deviation for the determination of bromate at the concentration of 50 ng/mL was calculated to be 0.996 % (n?=?10). The method has been successfully applied to the determination of bromate in flours and bottled waters.     

Determination of organophosphorus fire retardants and plasticizers in wastewater samples using MAE-SPME with GC-ICPMS and GC-TOFMS detection

Determination of organophosphorus fire retardants and plasticizers at trace levels in wastewater is described. In this work, microwave assisted extraction (MAE) and solid-phase microextraction (SPME) are used for sample preparation to extract and preconcentrate the analytes, followed by analysis by gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS) for phosphorus-specific detection. Gas chromatography coupled to time of flight mass spectrometry (GC-TOF-MS) was used to confirm the organphosphorus fire retardants in wastewater. The detection limits of organophosphorus fire retardants (OPFRs) were 29 ng L(-1) for tri-n-butyl phosphate (TnBP), 45 ng for L(-1) for tris(2-butoxyethyl)phosphate (TBEP), and 50 ng L(-1) for tris(2-ethylhexyl)phosphate (TEHP). Optimized extraction conditions were performed at 65 degrees C for 30 min and with 10% NaCl. Application of MAE during the sample preparation prior to the SPME allowed the detection of tris(2-ethylhexyl) phosphate, which has been difficult to determine in previous work. Application of the method to wastewater samples resulted in detecting 3.1 microg L(-1) P from TnBP, 5.0 microg L(-1) P from TBEP, and 4.0 microg L(-1) P from TEHP. The presence of these compounds were also confirmed by SPME-GC-TOF-MS.     

Examination of the operator and compensator tank role in urban wastewater treatment using activated sludge method

No doubt, operator is one of the main fundaments in wastewater treatment plants. By identifying the inadequacies, the operator could be considered as an important key in treatment plant. Several methods are used for wastewater treatment that requires spending a lot of cost. However, all investments of treatment facilities are useable when the expected efficiency of the treatment plant was obtained. Using experienced operator, this goal is more easily accessible. In this research, the wastewater of an urban community contaminated with moderated, diluted and highly concentrated pollution has been treated using surface and deep aeration treatment method. Sampling of these pilots was performed during winter 2008 to summer 2009. The results indicate that all analyzed parameters were eliminated using activated sludge and surface aeration methods. However, in activated sludge and deep aeration methods in combination with suitable function of operator, more pollutants could be eliminated. Hence, existence of operator in wastewater treatment plants is the basic principle to achieve considered efficiency. Wastewater treatment system is not intelligent itself and that is the operator who can organize even an inefficient system by its continuous presence. The converse of this fact is also real. Despite the various units and appropriate design of wastewater treatment plant, without an operator, the studied process cannot be expected highly efficient. In places frequently affected by the shock of organic and hydraulic loads, the compensator tank is important to offset the wastewater treatment process. Finally, in regard to microbial parameters, existence of disinfection unit is very useful.     

An alternative method for the determination of estrogens in surface water and wastewater treatment plant effluent using pre-column trimethylsilyl derivatization and gas chromatography/mass spectrometry

A procedure using pre-column trimethylsilyl derivatization and gas chromatography/ mass spectrometry (GC/MS) was developed and applied in determining trace estrogens in complex matrix. Main conditions were optimized, including pH value, salinity of water sample, elution reagents, clean procedure, derivative solvent and temperature. The optimized method was used to determine steroid estrogens in surface water and effluents of wastewater treatment plant (WWTP). Low detection limits of 0.01, 0.03, 0.03, 0.07, 0.09 and 0.13 ng/l for DES, E1, E2, EE2, E3 and E(V), respectively were obtained under optimism condition. No apparent interferences appeared in chromatography in comparison with ultrapure water blank. Mean recovery ranged from 72.6% to 111.0% with relative standard deviation of 1.1-4.6% for spiked surface water, and from 66.6% to 121.1% with relative standard deviation of 1.5-4.7% for spiked effluent of WWTP. The results suggested that the optimized method provides a robust solution for the determination of trace steroid estrogens in complex matrix.     

Simultaneous quantification of Bi(III) and U(VI) in environmental water samples with a complicated matrix containing organic compounds

Trace amounts of bismuth(III) and uranium(VI) can be simultaneously determined in a single scan by adsorptive cathodic stripping voltammetry in the presence of cupferron as a complexing agent. Optimal conditions were found to be: 0.1 mol?L^?1 acetate buffer (pH 5.3), 5?×?10^?5?mol?L^?1 cupferron, accumulation potential of ?0.25 V, and accumulation time of 30 s. The linear range of Bi(III) and U(VI) was observed over the concentration range from 2?×?10^?9 to 2?×?10^?7?mol?L^?1 and from 1?×?10^?8 to 5?×?10^?7?mol?L^?1, respectively. The influence of the main components of real water samples such as foreign ions and organic substances (surface active substances, humic substances) was precisely investigated. The method was applied to the simultaneous measurements of bismuth and uranium in natural water samples.     

Feasibility of detection and quantification of gas-phase carbonyls in indoor environments using PFBHA derivatization and solid-phase microextraction (SPME)

Solid-phase microextraction (SPME) was evaluated for the detection and quantification of the gas-phase carbonyls: citronellal, glyoxal, methylglyoxal, and beta-ionone. Prepared air samples containing the carbonyl compounds were collected at a flow rate of 2.8 L min(-1) in an impinger containing a 25% reagent water/75% methanol collection liquid. The aqueous samples were then derivatized with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA), extracted with a PDMS/DVB coated SPME fiber, and analyzed by GC-MS. Detection limits with a sample air volume of 76 L were calculated to be 0.03 ppbv, 0.34 ppbv, 0.12 ppbv, and 0.28 ppbv for citronellal, glyoxal, methylglyoxal, and beta-ionone, respectively.     

Simultaneous analysis of endosulfan, chlorpyrifos, and their metabolites in natural soil and water samples using gas chromatography-tandem mass spectrometry

Analysis of endosulfan, chlorpyrifos, and their nonpolar metabolites in extracts from environmental aqueous and soil samples was performed using a gas chromatography-tandem mass spectrometry (GC–MS/MS) technique. Full-scan GC–MS analysis showed poor sensitivity for some of the metabolites (endodiol and endosulfan ether). A multisegment MS/MS method was developed and MS/MS parameter isolation time, excitation time, excitation voltage, and maximum excitation energy were optimized for chosen precursor ions to enhance selectivity and sensitivity of the analysis. The use of MS/MS with optimized parameters quantified analytes with significantly higher accuracy, and detection limits were lowered to ~1/6th compared with the full-scan method. Co-eluting compounds, chlorpyrifos and chlorpyrifos oxon, were also analyzed successfully in the MS/MS mode by choosing exclusive precursor ions. Analysis of soil and water phase samples from contaminated soil slurry bioreactors showed that the MS/MS method could provide more reliable estimates of these pesticide and metabolites (especially those present in low concentrations) by annulling interferences from soil organic matter.     

Screening and quantification of emerging contaminants in Periyar River,Kerala (India) by using high-resolution mass spectrometry (LC-Q-ToF-MS)

The presence of emerging contaminants (ECs) in different aquatic systems may contribute to hazardous effects on aquatic organisms and subsequently on human health. In the present work, liquid chromatography coupled to a quadrupole time of flight mass spectrometer (LC-Q-ToF-MS) was used to identify and quantify a series of ECs in Periyar River in Aluva region, Kerala, India. The water samples were pre concentrated using solid-phase extraction (SPE) prior to analysis. The compounds were probed in both positive and negative ionization mode using electro spray ionization (ESI). Method validations were performed for linearity, limit of detection (LOD), limit of quantification (LOQ), accuracy, and precision (intraday and inter day). The ECs were quantified using standard calibration curve. The identified nine ECs include pharmaceuticals, personal care products, steroids, surfactants, and phthalate. A relatively high concentration was observed in the case of 2-dodecyl benzene sulfonic acid (1012 ng/l) and low concentration was observed for lignocaine (4.3 ng/l; since this is below LOQ, the value is only approximate). In addition, we have identified another 28 organic compounds using the technique of non-target analysis out of which seven compounds fall in the category of surfactants. Being the first report on ECs in Periyar River, the data is very important as this river is one of the biggest and important rivers of Kerala having several purification units for drinking water in the province.     

固相微萃取-毛细管气相色谱法快速同步分析水中硝基苯类及氯苯类化合物

固相微萃取是一种快速、简便、集萃取浓缩进样于一体的样品前处理技术,具有分析时间短、灵敏度高、无需有机溶剂的优点。文章用固相微萃取富集水中9种硝基苯类及5种氯苯类化合物,毛细管气相色谱ECD检测器分离分析,整个分析过程只需25min,检出限可达0.0002~0.02μg/L,已用于地表水、海水与工厂废水中硝基苯类及氯苯类化合物含量的测定。     

Screening of dioxin-like compounds in bio-composts and their materials: chemical analysis and fractionation-directed evaluation of AhR ligand activities using an in vitro bioassay

Application of the dioxin responsive-chemical activated luciferase gene expression (DR-CALUX) bioassay to three compost products (kitchen garbage compost, treated sludge compost, and poultry manure compost) and their organic waste materials was performed for the screening of dioxin-like compounds. Phased sample preparation was conducted for the bioassay to yield separate crude, acid-stable, and carbon column fractions. Chemical analyses were also conducted for polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polyaromatic hydrocarbons (PAHs). Their determined WHO-PCDD/PCDF/dl-PCB-TEQ values were compared to the DR-CALUX results expressed as CALUX-TEQ to ascertain their contributions to overall activity. Overall all three compost products were polluted to a low level by persistent PCDD/PCDF/dl-PCBs in a few pg/g WHO-TEQ concentration range. The organic crude fraction showed non-persistent CALUX-TEQ values 2-4 orders of magnitude higher than those of WHO-TEQ. For the acid-resistant fractions of all samples, persistent CALUX-TEQ values were 1-8-fold higher than WHO-PCDD/PCDF/dl-PCB-TEQ values. Both TEQs correlated well for this fraction, which confirms the availability of CALUX for estimation of the actual WHO-TEQ level of the samples using reflux method with 44% sulfuric acid/silica gel, although the compost and material samples examined in this study contained much lower levels of WHO-TEQ: less than 1 pg/g in almost all cases. Additional carbon column treatment enhanced the potency and efficacy of CALUX activity in the three compost samples, which showed 1.6-4.4 times higher values of CALUX-TEQ than those obtained for the acid-resistant fraction. Although further DR-CALUX data collection for compost samples will be necessary, DR-CALUX is useful as a rapid screening method for monitoring dioxin-like compounds in compost.     

Study of odor compounds in gaseous effluents generated during production of poultry feather and viscera meal using headspace solid phase microextraction

This work reports the screening and characterization of odor compounds in gaseous effluents generated during the production of poultry feather and viscera meal, the by-products of the poultry meat industry. Chemical analysis was carried out by solid phase microextraction in the headspace (HS-SPME) mode. Exhaust air of thermal processing of poultry feather and viscera were sampled online from a bench-scale digester, condensed, and collected in sampling flasks. Both volatile and semivolatile organic compounds present in the condensed gases were extracted under agitation at constant temperature. The extracts were analyzed with a gas chromatograph coupled to a mass spectrometric detector (GC/MSD). The identification of compounds was carried out by comparing the mass spectra obtained with those from the Wiley library and quantification was accomplished through authentic analytical standards. For the determination of the best extraction conditions and analysis, extraction fibers of different coatings and polarities were tested: divinylbenzene/carboxen/polydimethyilsiloxane (DVB/CAR/PDMS), carbowax/divinylbenzene (CW/DVB), and polydimethylsiloxane (PDMS) and chromatography columns of different polarities: DB-WAX (polar) and DB-5 (nonpolar). The best extraction conditions and analysis of the compounds of interest were obtained by the use of the SPME fiber with DVB/CAR/PDMS coating and analysis by GC/MSD with polar capillary column. Several carboxylic acids were identified, as well as mercaptans, amines, and aldehydes of great environmental importance.