Simultaneous Analysis of Natural Free Estrogens and Their Conjugates in Wastewater by GC‐MS

A solid‐phase extraction (SPE)‐gas chromatography (GC)‐mass spectrometry (MS) analytical method was developed for the simultaneous analysis of natural free estrogens and their conjugates in wastewater samples. Natural free estrogens and their conjugates in wastewater were successfully separated by the oasis hydrophilic‐lipophilic balance solid phase extraction (Oasis HLB SPE) method, and the conjugates were initially enzyme hydrolyzed by β‐glucuronidase or arylsulfatase from Helix pomatia prior to derivatization. N‐methyl‐N‐(tert‐butyldimethylsilyl)trifluoroacetamide (MTBSTFA) plus 1% tert‐butyldimetheylchlorosilane (TBDMCS) was chosen as the derivatization reagent, and the most appropriate conditions of derivatization were determined to be at 95°C for 90 min. The recovery ratios of nine target chemicals were determined by spiking them in 1 L of ultra‐purified water or the influent of a wastewater treatment plant (WWTP). The recovery ratios of six out of nine for the analytes ranged from 73.3–114.9% with relative standard deviations (RSD) from 1.6–19.9%. The established method was successfully applied to environmental wastewater samples which were collected from one municipal wastewater treatment plant (WWTP) in Osaka, Japan, for the determination of natural free estrogens and their conjugates. In the influent sample, E1, E2, E1‐3S, E3‐3S, and E1‐3G were detected at concentrations of 16.6, 9.6, 8.2, 21.9, and 3.2 ng L^–1, respectively. However, only E1 was detected at a high concentration of 44 ng L^–1 in the effluent sample, suggesting that it is the dominant natural free estrogen in the effluent.     

Removal of Natural Free Estrogens and their Conjugates in a Municipal Wastewater Treatment Plant

Removal of natural free estrogens and estrogen conjugates in a municipal wastewater treatment plant (WWTP) was investigated and analyzed by GC‐MS, in which estrogen conjugates were first transformed to their corresponding free estrogens with an acid solvolysis procedure before their analysis. Natural free estrogens, E1‐3‐sulfate (E1‐3S), and E3‐3‐sulfate (E3‐3S) were detected with high concentrations in both the influent and effluent of the primary settling tank (PS), while no estrogen glucuronides were detected in any of the monitored wastewater samples. Regarding their removal efficiencies, all were almost completely removed, except for E1 with only a minor decrease. The estrogenic/androgenic removal of the same WWTP was also evaluated with estrogen receptor (androgen receptor) (ER (AR))‐binding assays, in which the removal efficiencies for E2 equivalents (EEQ) or testosterone equivalents (TEQ) were 68.5 and 72.2%. In addition, the chemically calculated EEQ from natural estrogens were about 20.6–39.3% that of the ER‐binding assay, in which E3 contributed the biggest proportion in both the influent and PS, while the calculated value of E1 increased from only 6.7% in the influent to as high as 20.6% in the effluent.     

Fate of Lignin in the Process of Aerobic Biological Treatment of Paper Mill Wastewater

Although lignin is known to be not readily biodegradable the concentration of dissolved lignin decreased during aerobic biological treatment of paper mill wastewater performed in sequencing batch reactors (SBR). Systematic lab scale batch tests were conducted to clarify whether the observed removal of lignin was the result of biodegradation or adsorption onto the activated sludge. For the batch tests, sludge samples were taken from sequencing batch reactors operated at solid retention times (SRT) of 10, 15, 20, 30, and 40 days, respectively. The amount of lignin present in the bulk liquid and in the sludge samples was quantified by an analytical procedure comprising pyrolysis, gas chromatography and mass spectrometry (py‐GC/MS analysis). It was found that lignin adsorbs onto the activated sludge by up to 30%[TH]w/w. This demonstrates the sludge excellent adsorption properties. The ultimate removal of lignin is achieved by sludge wasting. The highest overall removal rate was found when sludge was used from the SBR run at SRT of 20 days.     

Problems and Solutions in Pesticide Analysis Using Solid‐phase Extraction (SPE) and Gas Chromatography Ion‐trap Mass Spectrometry Detection (GC‐MS)

In the present study an analytical method was tested for the determination of selected pesticides and metabolites using solid‐phase extraction (SPE) and gas chromatography ion‐trap mass spectrometry (GC‐MS). The extraction efficiency of C18, Isolut ENV+, and Lichrolut EN for SPE was compared for trifluralin, fenitrothion, endosulfan, propargite, 2,4‐D, 3‐methyl‐4‐nitrophenol, 2‐(4‐tert‐butylphenoxy)cyclohexanol, endosulfan sulfate, and 2,4‐dichlorophenol. Isolut ENV+ and C18 showed good results as sorbents and acetone as an elution solvent for SPE for the selected pesticides. Recoveries varied between 36% and 176% with a relative standard deviation of 2...18%. Because of coextracts from the SPE materials, recovery values higher than 100% were obtained for fenitrothion, endosulfan sulfate, and 2,4‐D with C18 as well as for endosulfan sulfate and 3‐methyl‐4‐nitrophenol with Isolut ENV+. A standard addition method was used to verify the occurrence of coextracts in the sample after SPE.     

Quantification of Diclofenac in Hospital Effluent and Identification of Metabolites and Degradation Products

In this study the occurrence of diclofenac and sub‐products in effluent emerging from the University Hospital at the Federal University of Santa Maria was investigated. One metabolite was identified and, in aqueous solution, three degradation products. The quantification was conducted by means of HPLC‐DAD, and the determination of metabolite and degradation products by LC–ESI–MS/MS–QTrap. For the HPLC‐DAD method, a 70:30 mixture of methanol/sodium phosphate was used in isocratic mode. For the LC–ESI–MS/MS–QTrap determinations, a mobile phase, where phase A was an ammonium acetate solution 5 × 10^?3 mol L^?1, and phase B was methanol (5 × 10^?3 mol L^?1)/ammonium acetate (9:1, v/v), on gradient mode. The LDs for the HPLC and LC–MS/MS methods, respectively, were 2.5 and 0.02 µg L^?1, the LQs, 8.3 and 0.05 µg L^?1, and the linear range from 10 up to 2000 µg L^?1 and 0.05 up to 10 µg L^?1. As expected, the LC–ESI–MS/MS–QTrap method was more sensitive and less laborious. The metabolite 4′‐hydroxy‐diclofenac was identified. Photolysis was used for the degradation studies and three products of diclofenac were identified (m/z of 214, 286 and 303) in aqueous solution. These results notwithstanding, no degradation products of diclofenac were found in the hospital effluent.     

Distribution Study of U,V, Mo,and Zr in Different Sites of Lakes Van and Hazar,River and Seawater Samples by ICP‐MS

The aim of this study is to investigate the concentrations of U, Th, V, Mo, and Zr in natural waters taken from Turkey. Among these water species, Lake Van is the largest soda lake and the fourth largest closed basin on Earth. The water samples were collected from 51 locations between 2008 and 2009. The inductively coupled plasma‐MS was used for determinations. The obtained U and Zr concentrations are in the range of 37–110 µg L^?1 and 17–78 µg L^?1 in Lake Van and 0.53–0.81 µg L^?1 and 0.15–0.19 µg L^?1 in Lake Hazar, respectively. The concentration of uranium in other studied waters varies from the lowest 0.09 µg L^?1 in Tigris (Dicle) river to the highest 4.0 µg L^?1 in Mediterranean Sea water. Mean Mo and V concentrations in the studied water samples were found to be in ranges of 0.1–17 and 2.7–113 µg L^?1, respectively. The obtained highest U concentration in Lake Van correlates with the highest Mo and Zr levels compared to the Lake Hazar and river waters. These results imply that there is a young occurrence of uranium minerals around Lake Van. It is concluded that there is about 50.000 ton of uranium in Lake Van water.     

Occurrence of the Antimicrobials Sulfamethoxazole and Trimethoprim in Hospital Effluent and Study of Their Degradation Products after Electrocoagulation

In this study, an investigation was carried out into the occurrence of sulfamethoxazole (SMX) and trimethoprim (TMP) in the effluent of the university hospital (HUSM) of the UFSM. The degradation of these antimicrobials by the electrocoagulation (EC) process was also examined, in both the aqueous solution and hospital effluent, and a study was conducted in order to identify the subproducts formed. The experiments were optimized through factorial planning and, also, checked by response surface methodology. The best conditions for EC (achieving 58.0% of chemical oxygen demand (COD) reduction) were obtained by using 13 mA cm^?2, 500 mg L^?1 of NaCl, and 30 mm of interelectrode distance. The quantification of SMX (27.8 µg L^?1) and TMP (6.65 µg L^?1) in the hospital effluent, and the identification of the degradation products were carried out through liquid chromatography‐mass spectrometry quadrupole linear and ion trapping with electrospray ionization (LC‐ESI‐MS/MS_QTrap). Removals of 88.0% (degradation only) and 33.0% (adsorption only) were achieved for aqueous solutions of SMX and TMP, respectively, under optimized conditions. In hospital effluent samples, fortified with additions of SMX and TMP, corresponding removals of 16.0% (degradation) and 28.0% (adsorption) were achieved. This suggests that the EC process is efficient in degrading SMX in aqueous solution, although the same was not the case with TMP. The degradation products of SMX were identified (m/z 256.0 and 288.5); however, only the latter is mentioned in the literature. Toxicological aspects were not considered in this study.     

The Effects of Different Substrates on Ammonium Removal in Constructed Wetlands: A Comparison of Their Physicochemical Characteristics and Ammonium‐Oxidizing Prokaryotic Communities

A vertical flow constructed wetland (VFCW) filled with natural zeolite had higher ammonium removal (82.4–94.0%) than another VFCW filled with volcanic rock (51.3–69.4%) treating piggery wastewater under any of three recirculation ratios. To reveal the underling reasons, physicochemical characteristics and ammonium‐oxidizing prokaryotes (AOPs) of two substrates were determined. The calculated maximum ammonium adsorption of zeolite (11.6 mg g^?1) was remarkably higher than that of volcanic rock (0.21 mg g^?1), mainly because the former contains two cationic binding crystalline species, and montmorillonite. Quantitative analyses indicated that ammonium‐oxidizing archaea (AOA) are the dominant AOP of zeolite and ammonium‐oxidizing bacteria (AOB) are the dominant AOP of volcanic rock respectively. Diversity and phylogenetic analysis further showed that both AOB and AOA communities were significantly different between two substrates. Nitrosospira‐like AOB (92.6%) and sediment/soil clade AOA (71.4%) were the main components of AOB and AOA in natural zeolite, whereas Nitrosomonas‐like AOB (76.1%) and water/sediment clade AOA (77.1%) dominated the AOB and AOA in volcanic rock. These results suggest that the substrates show high selectivity to AOP community. Thus, in addition to physicochemical characteristics, the AOP of substrates is very likely to affect ammonium removal in VFCWs.     

Analysis of hydrodynamic conditions in adjacent free and heterogeneous porous flow domains

The existence of a free‐flow domain (e.g. a liquid layer) adjacent to a porous medium is a common occurrence in many environmental and petroleum engineering problems. The porous media may often contain various forms of heterogeneity, e.g. layers, fractures, micro‐scale lenses, etc. These heterogeneities affect the pressure distribution within the porous domain. This may influence the hydrodynamic conditions at the free–porous domain interface and, hence, the combined flow behaviour. Under steady‐state conditions, the heterogeneities are known to have negligible effects on the coupled flow behaviour. However, the significance of the heterogeneity effects on coupled free and porous flow under transient conditions is not certain. In this study, numerical simulations have been carried out to investigate the effects of heterogeneous (layered) porous media on the hydrodynamics conditions in determining the behaviour of combined free and porous regimes. Heterogeneity in the porous media is introduced by defining a domain composed of two layers of porous media with different values of intrinsic permeability. The coupling of the governing equations of motion in free and porous domains has been achieved through the well‐known Beavers and Joseph interfacial condition. Of special interest in this work are porous domains with flow‐through ends. They represent the general class of problems where large physical domains are truncated to smaller sections for ease of mathematical analysis. However, this causes a practical difficulty in modelling such systems. This is because the information on flow behaviour, i.e. boundary conditions at the truncated sections, is usually not available. Use of artificial boundary conditions to solve these problems effectively implies the imposition of conditions that do not necessarily match with the solutions required for the interior of the domain. This difficulty is resolved in this study by employing ‘stress‐free boundary conditions’ at the open ends of the domains, which have been shown to provide accurate results by a number of previous workers. Copyright © 2005 John Wiley & Sons, Ltd.