Critical evaluation of the determination of pharmaceuticals, personal care products, phenolic endocrine disrupters and faecal steroids by GC/MS and PTV-GC/MS in environmental waters

An analytical method is described for the determination of a broad range of emerging and priority pollutants, together with sewage molecular markers in environmental waters. The step-by-step study of the GC/MS analyses focuses on the effects of experimental variables using a large volume injection (LVI) technique [a programmed temperature-vaporising (PTV) inlet], the evaluation of a clean-up step using classical and newer sorbents (i.e. Al-N, Fl, NH₂, PSA, Si, CN and DIOL), and the revision of how organic matter [i.e. humic acids (HA) content] affects method performance. Reproducibility and recoveries from spiked coastal water samples at different analyte concentrations (100, 250 and 500 ng L⁻¹) as well as with different levels of spiked humic acids (2, 10 and 20 mg L⁻¹) are reported indicating a good performance of the extraction procedure with low levels of HA (<10 mg L⁻¹). The presence of HA is a critical parameter during the solid-phase extraction (SPE) procedures. Of the clean-up sorbents tested, CN and DIOL proved most efficient in cleaning-up the extracts with recoveries in the range of 66-77% and 100-114%, respectively for the selected analytes. Both GC/MS and PTV-GC/MS instrumental configurations were tested using final sewage effluents, riverine, estuarine and coastal water samples. However, limited applicability of the PTV inlet is reported for environmental applications, affording only a modest improvement in chromatographic signal-to-noise ratios.     

Development and optimization of the SPE procedure for determination of pharmaceuticals in water samples by HPLC‐diode array detection

This paper focuses on the investigation of different types of SPE sorbents for the preconcentration of eight veterinary pharmaceuticals from water samples. The pharmaceuticals studied were sulfamethazine, sulfadiazine, sulfaguanidine, trimethoprim, oxytetracycline, enrofloxacin, norfloxacin and penicillin G/procaine. Five different SPE materials (Strata‐X, Strata‐X‐C, Strata SDB‐L, Strata C8 and Strata C18) from Phenomenex were compared with Oasis HLB with a view to obtaining the best cartridges for all pharmaceuticals investigated. Extraction efficiency was determined by HPLC with diode array detection (DAD). HPLC‐DAD separation and quantification of the selected pharmaceuticals were carried out under gradient elution by a binary mixture of 0.01 M oxalic acid and ACN based on cyano modified column (LiChrosphere 100 CN) from Merck. Strata‐X provided the best results in the preconcentration of 100 mL water samples, yielding average pharmaceutical recoveries of higher than 90%, except for sulfaguanidine (76.1%). The developed Strata‐X‐HLPC‐DAD method was validated and applied, for the efficient investigation of reverse osmosis/nanofiltration membranes and for the removal of these eight pharmaceuticals from the production wastewater samples. NF90 and XLE membranes were shown to be the best for the rejection of all investigated pharmaceuticals.     

Selection of suitable operating conditions to minimize the gradient equilibration time in the separation of drugs by Ultra-High-Pressure Liquid Chromatography with volatile (mass spectrometry-compatible) buffers

Reversed phase gradient elution is the method of choice for pharmaceuticals analysis since it allows reducing the analysis time while improving both the quality of the separation and the detection limits. The current trends are towards faster separations which can be achieved thanks to equipments withstanding ultra-high pressures and/or high temperatures. Under such conditions, gradient separations can be carried out within a few minutes or even a few tens of seconds. A long equilibration time in addition to the gradient time can be therefore very detrimental. In this work, we investigated the extent to which the gradient equilibration time can be reduced and which parameters mainly affect the retention variability of ionizable compounds when using volatile buffers. We first found out an excellent repeatability between run-to-run experiments whatever the equilibration time and the operating conditions. We then pointed out the key operating parameters which allow achieving reproducible runs when varying the equilibration time between runs. With a view of reducing the equilibration time, the effects of various conditions were examined. The latter include the type of additive for mobile phase pH adjustment, the initial eluent composition, the type of stationary phase, the temperature and the flow-rate. Although much remains to be understood about the equilibration process, our study allows making progress in the knowledge of this phenomenon. Based on the present results, a beneficial effect of both temperature and flow-rate was highlighted and operating conditions leading to faster column equilibration are suggested.     

Structured emulsion-based delivery systems: Controlling the digestion and release of lipophilic food components

There is a need for edible delivery systems to encapsulate, protect and release bioactive and functional lipophilic constituents within the food and pharmaceutical industries. These delivery systems could be used for a number of purposes: controlling lipid bioavailability; targeting the delivery of bioactive components within the gastrointestinal tract; and designing food matrices that delay lipid digestion and induce satiety. Emulsion technology is particularly suited for the design and fabrication of delivery systems for lipids. In this article we provide an overview of a number of emulsion-based technologies that can be used as edible delivery systems by the food and other industries, including conventional emulsions, nanoemulsions, multilayer emulsions, solid lipid particles, and filled hydrogel particles. Each of these delivery systems can be produced from food-grade (GRAS) ingredients (e.g., lipids, proteins, polysaccharides, surfactants, and minerals) using relatively simple processing operations (e.g., mixing, homogenizing, and thermal processing). The structure, preparation, and utilization of each type of delivery system for controlling lipid digestion are discussed. This knowledge can be used to select the most appropriate emulsion-based delivery system for specific applications, such as encapsulation, controlled digestion, and targeted release.     

Rapid automated screening, identification and quantification of organic micro-contaminants and their main transformation products in wastewater and river waters using liquid chromatography-quadrupole-time-of-flight mass spectrometry with an accurate-mass database

In this study we have developed and evaluated an analytical method for a rapid automated screening and confirmation of a large number of organic micro-contaminants (almost 400) and also the quantification of the positive findings in water samples of different types (surface and wastewaters) using liquid chromatography-electrospray quadrupole-time-of-flight mass spectrometry (LC-QTOFMS) based on the use of an accurate-mass database. The created database includes data not only on the accurate masses of the target ions but also on the characteristic in-source fragment ions, isotopic pattern and retention time data. This customized database was linked to commercially available software which extracted all the potential compounds of interest from the LC-QTOFMS raw data of each sample and matched them against the database to search for targeted compounds in the sample. The detailed fragmentation information has also been used as a powerful tool for the automatic identification of unknown compounds and/or transformation products with similar structures to those of known organic contaminants included in the database. The database can be continually enlarged. To confirm identification of compounds which have no fragment ions (or fragments with low intensity/relative abundance) from in-source CID fragmentation or isomers which are not distinguished within full single mass spectra, a "Targeted MS/MS" method is developed. Thereafter, these compounds can be further analyzed using the collision energy (CE) in QTOF-MS/MS mode. Linearity and limits of detection were studied. Method detection limits (MDLs) in effluent wastewater and river waters were, in most cases, lowers or equal to 5 and 2 ng/L, respectively. Only 15 compounds had MDLs between 5 and 50 ng/L in effluent wastewater matrix. We obtained a linearity of the calibration curves over two orders of magnitude. The method has been applied to real samples and the results obtained reveal that most of the pharmaceutically active compounds contained in the created database were present in the water samples with concentrations in the range of ng/L and μg/L levels and in most of the samples between 2 and 15 pesticides of the 300 contained in the database were also detected. In addition to the compounds included in the database, some degradation products were found, thus revealing the method as a useful tool for the analysis of organic micro-contaminants in waters.     

Access to pyridines via cascade nucleophilic addition reaction of 1,2,3-triazines with activated ketones or acetonitriles

We studied the cascade nucleophilic addition reactions of 1,2,3-triazines with activated acetonitriles or ketones,which were used to construct highly substituted pyridines that are not easily accessed by conventional methods.The strategy addressed some structural diversity issues currently facing medicinal chemistry,and the resulting pyridines could be used as convenient precursors for the synthesis of related pharmaceuticals.In particular,our method was applied to the syntheses of the marketed drug etoricoxib and several biologically important molecules in a few steps.     

Ultrasound‐assisted extraction method for the simultaneous determination of emerging contaminants in freshwater sediments

Sediments are the fate of several emerging organic contaminants, such as pharmaceuticals, personal care products and hormones, and therefore an important subject in environmental monitoring studies. In the present work, a simple and sensitive method was developed, validated and applied for the simultaneous extraction of atenolol, caffeine, carbamazepine, diclofenac, ibuprofen, naproxen, propranolol, triclosan, estrone, 17‐β‐estradiol and 17‐α‐ethinylestradiol using ultrasound‐assisted extraction from freshwater sediment samples followed by solid‐phase extraction clean‐up and liquid chromatography with tandem mass spectrometry detection. The solvent type and extraction pH were evaluated to obtain the highest recoveries of the compounds. The best method shows absolute recoveries between 54.0 and 94.4% at 50 ng/g concentration. The method exhibits good precision with relative standard deviation ranging from 1.0–16%. The detection and quantification limits ranged from 0.006–0.067 and 0.016–0.336 ng/g, respectively. The developed method was successfully applied to freshwater sediment samples collected from different sites in Jundiaí River basin of São Paulo State, Brazil. The compounds atenolol, caffeine, propranolol and triclosan were detected in all the sampling sites with concentrations of 13.8, 41.0, 28.5 and 176 ng/g, respectively.     

Preliminary selection of clay minerals for the removal of pharmaceuticals,bisphenol A and triclosan in acidic and neutral aqueous solutions

Pharmaceuticals, personal care products and endocrine disruptors demonstrate huge potential to cause adverse ecological health effects at very low concentration in aquatic environment. There is a need to improve current purification technologies used in sewage and drinking-water treatment plants. This article aims at providing new insights into the recent development of natural and modified clay-based sorbents for the removal of aqueous contaminants such as pharmaceuticals and personal care products. The removal of six widely used pharmaceuticals: ibuprofen, diclofenac, ketoprofen, carbamazepine, as well as endocrine disrupting chemicals – bisphenol A and a bactericidal agent, triclosan – was examined by sorption onto eight adsorbents. Sorption was performed using natural and modified clay minerals – montmorillonite (Mt), vermiculite (VER), bentonite (B), kaolinite (K), commercial acid activated montmorillonites K10 and K30, and two carbonaceous-mineral nanocomposites, MtG5%T, BAlG3%C. This study showed that among the tested natural clays, vermiculite is the most promising sorbent for the removal of pharmaceuticals in purification processes. Among the modified clay minerals, the best results were achieved for carbonaceous bentonite and two acid activated montmorillonites K10 and K30. However, the removal of acidic pharmaceuticals on montomorillonite K10 and carbonaceous bentonite was strongly dependent on the pH value. In the case of vermiculite and acid-modified montmorillonite K30, the sorption of the selected compounds was not significantly affected by pH, which is crucial in wastewater treatment. The sorption constant divided by the specific surface area (K_d/A) is proposed to assess whether the surface area or chemical properties of the materials control the sorption process. K_d/A values were relatively high in the case of vermiculite, so it should be noticed that individual and specific surface properties of vermiculite were of crucial importance for sorption.     

化学计量学-动力学分光光度法同时测定两种糖皮质类激素

在碱性介质中,高锰酸钾能将糖皮质类激素(醋酸泼尼松和地塞米松)氧化,而本身被还原成绿色的锰酸钾,基于这一反应,本文提出了同时测定醋酸泼尼松和地塞米松的化学计量学-动力学分光光度法.研究发现反应体系在610 nm处有一个吸收峰,实验以该波长为检测波长,优化实验条件.在该条件下,检测醋酸泼尼松和地塞米松的线性范围分别为0....