Study on the removal of hormones from domestic wastewaters with lab-scale constructed wetlands with different substrates and flow directions.

Eight wastewater samples from a university campus were analysed between May and July of 2014 to determine the concentration of 14 natural and synthetic steroid hormones. An on-line solid-phase extraction combined with ultra-high performance liquid chromatography coupled with mass spectrometry (on-line SPE-UHPLC-MS/MS) was used as extraction, pre-concentration and detection method. In the samples studied, three oestrogens (17ß-estradiol, estrone and estriol), two androgens (boldenone and testosterone), three progestogens (norgestrel, progesterone and norethisterone) and one glucocorticoid (prednisone) were detected. The removal of hormones was studied in primary and secondary constructed wetland mesocosms. The porous media of the primary constructed wetlands were palm tree mulch. These reactors were used to study the effect of water flow, i.e. horizontal (HF1) vs vertical (VF1). The latter was more efficient in the removal of 17ß-estradiol (HF1: 30%, VF1: 50%), estrone (HF1: 63%, VF1: 85%), estriol (100% both), testosterone (HF1: 45%, VF1: 73%), boldenone (HF1:-77%, VF1: 100%) and progesterone (HF1: 84%, VF1: 99%). The effluent of HF1 was used as influent of three secondary constructed wetland mesocosms: two double-stage vertical flow constructed wetlands, one with gravel (VF2gravel) and one with palm mulch (VF2mulch), and a mineral-based, horizontal flow constructed wetland (HFmineral). VF2mulch was the most efficient of the secondary reactors, since it achieved the complete removal of the hormones studied with the exception of 17ß-estradiol. The significantly better removal of BOD and ammonia attained by VF2mulch suggests that the better aeration of mulch favoured the more efficient removal of hormones.

Optimization and application of fabric phase sorptive extraction coupled to ultra-high performance liquid chromatography tandem mass spectrometry for the determination of cytostatic drug residues in environmental waters.

Every year, hundreds of tons of organic pollutants reach the environment through effluents released from wastewater treatment plants worldwide, and many of these compounds have harmful effects on the aquatic ecosystem. A new class of emerging pollutants of high concern is cytostatic drugs, which are designed to treat different types of cancers by attacking cells. Environmental concentrations of cytostatic drugs are known to be in the range of ngL-1, and for this reason, it is imperative to develop analytical methods of extraction and preconcentration to allow for subsequent instrumental analysis of these drugs. In this work, a rapid, simple and green method for the analysis of seven cytostatic drug compounds that are commonly used in anti-cancer therapies was developed using a novel extraction process based on a powerful miniaturized technique, fabric phase sorptive extraction (FPSE) coupled to ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). The major parameters that affect the extraction process were optimized. The new method shows good linearity, with a relative standard deviation (RSD) of less than 12%. Relative recoveries higher than 40% were obtained for the studied compounds, and the detection limit of the method was within the values at which these compounds are usually found in environmental water (0.20ngL-1 to 80ngL-1). The Limit of Quantification ranged from 0.68 to 267ngL-1. Significant suppression of the signal due to the matrix effect, a common shortcoming attributed to interference from the extraction process as well as the use of ionization mode, was not observed. Subsequently, the method was applied to real wastewater samples from an effluent obtained from a hospital area and three wastewater treatment plants located in Gran Canaria Island, Spain.

Analytical methodologies for the determination of endocrine disrupting compounds in biological and environmental samples.

Endocrine-disruptor compounds (EDCs) can mimic natural hormones and produce adverse effects in the endocrine functions by interacting with estrogen receptors. EDCs include both natural and synthetic chemicals, such as hormones, personal care products, surfactants, and flame retardants, among others. EDCs are characterised by their ubiquitous presence at trace-level concentrations and their wide diversity. Since the discovery of the adverse effects of these pollutants on wildlife and human health, analytical methods have been developed for their qualitative and quantitative determination. In particular, mass-based analytical methods show excellent sensitivity and precision for their quantification. This paper reviews recently published analytical methodologies for the sample preparation and for the determination of these compounds in different environmental and biological matrices by liquid chromatography coupled with mass spectrometry. The various sample preparation techniques are compared and discussed. In addition, recent developments and advances in this field are presented.

Determination and assessment of estradiol-mimicking compounds in the dissolved and particulate phases of wastewater treatment plant samples.

During the last two decades, a large number of publications have clearly shown that anthropogenic compounds that disrupt the endocrine system of wildlife species are a major cause for concern, and this concern has led to a demand for new screening methods. In this work, we have optimized and applied a new method to identify endocrine-disrupting chemicals (EDCs), such as nonylphenol, octylphenol, and their corresponding ethoxylates, 17alpha-ethynylestradiol, bisphenol-A, 17beta-estradiol, and estriol, in sewage samples. For the extraction and preconcentration of all analytes from the dissolved and particulate phases, we used SPE and ultrasonic assisted extraction, respectively. Identification and quantification were achieved by HPLC with fluorescence detection. Satisfactory LODs (between 0.5 and 7.6 ng/L in the dissolved phase and 12.3 and 21.4 ng/g in the particulate phase) and analyte recoveries (between 67 and 102%) were achieved for the target compounds. The optimized method was applied to the determination of EDCs in liquid sewage samples collected from July 2009 to July 2010 from a wastewater treatment plant in Las Palmas de G.C. (Spain). Concentrations of EDCs ranged from <10 to nearly 1300 ng/L in the dissolved phase, and from 0.1 to 7.7 microg/g in the suspended particulate matter.

Analysis of anti-inflammatory, analgesic, stimulant and antidepressant drugs in purified water from wastewater treatment plants using SPE-LC tandem mass spectrometry.

This work presents an effective sample preparation method for the evaluation of seven pharmaceutical compounds belonging to different therapeutic classes in purified water from wastewater treatment plants (WWTPs). The target compounds include caffeine (stimulant), nicotine (stimulant), atenolol (beta blocker), metamizole (anti-inflammatory and analgesic), fluoxetine (antidepressant), paraxanthine (stimulant) and clofibric acid (lipid regulator). Solid-phase extraction (SPE) and liquid chromatography-mass spectrometry (LC-MS) were selected as extraction and detection techniques, respectively. A detailed study of the experimental conditions of extraction was performed. Under optimal conditions, recoveries obtained were in the range of 21% to 100%, and the relative standard deviations were below 12%. The detection and quantification limits of the method were in the range 2.2-97.4 and 21.1-324.7 ng L(-1), respectively. The developed method was successfully applied to evaluate the presence of these pharmaceutical compounds in wastewaters samples from wastewater treatment plants located on the Gran Canaria Island (Spain). Most of the compounds were detected at concentrations up to 12.31 µg L(-1) in the WWTP influents that were studied.

Analytical methodologies for the determination of nitroimidazole residues in biological and environmental liquid samples: a review.

Nitroimidazoles (NDZs) are antiprotozoal drugs that are typically used in veterinary and human medicine. NDZs and their metabolites are believed to possess genotoxic, carcinogenic and mutagenic properties, and this is (one reason) why their use has been banned within the European Union. Hence, the determination of trace residues of these substances in edible animal tissues has been of growing concern over the past few years. Even, though there has been a need to develop sensitive and reliable analytical methods to study the residues of these compounds in different matrices, available methodologies in environmental samples are rather limited. These and other pharmaceutical compounds have become one of the most important new classes of environmental pollutants that have been detected in wastewater-treatment-plant (WWTP) effluents, receiving waters, drinking water and groundwater. A compilation of the most representative analytical methodologies for the determination of NDZ residues during the last decade is presented in this paper. Its scope is the two main areas which require their determination, namely biological and environmental matrices. A detailed explanation of both areas, including sample treatment and detection systems, and future trends is presented, focusing on the difficulties of confirming analytes at low concentration levels.

Use of polyoxyethylene surfactants for the extraction of organochlorine pesticides from agricultural soils.

Two non-ionic surfactant mixtures (POLE and Polyoxyethylene 10 Cetyl ether, POLE and Polyoxyethylene 10 Stearyl ether) have been used for microwave-assisted extraction of six organochlorine pesticides from agricultural soils prior to being determined by HPLC-UV. An experimental design was applied for the determination of variables which affect to recovery and to optimize the extraction parameters, surfactant concentration and volume, microwave time and power. Under the optimized conditions, the method was applied to different soil samples in order to analyze the influence of soil characteristics on the pesticides extraction. The results obtained indicate that most of these compounds can be recovered in good yields with RSD lower than 10% and detection limit ranged between 80 and 800 ng g(-1) for the pesticides studied. The proposed method was applied to a reference soil sample and to aged soils.

An approach to the application of microwave-assisted micellar extraction and liquid chromatography with ultraviolet detection to the extraction and determination of organophosphorus pesticides in tomato samples.

Microwave-assisted micellar extraction methodology was applied to extract a mixture of 8 organophosphorus pesticides from the cuticle of tomato samples prior to analysis by liquid chromatography with ultraviolet detection. This technique provided very good results and was simple, fast, and environmentally friendly. The pesticides under study were extracted using the nonionic surfactants polyoxyethylene 10 lauryl ether (POLE) and oligoethylene glycol monoalkyl ether (Genapol X-080). The optimal extraction variables to be applied were determined for each surfactant and then compared. POLE proved to be the most suitable for the extraction, with recoveries over 70% in the majority and relative standard deviation values under 4.8%. After validation using a tomato sample enriched with a certified mixture, the proposed method was applied to the analysis of organophosphorus pesticides in lettuce and pepper samples.