Fluoroquinolones in soil—risks and challenges

Fluoroquinolones (FQs) are among the most important antibacterial agents used in human and veterinary medicine. Because of the growing practice of adding manure and sewage sludge to agricultural fields these drugs end up in soils, where they can accumulate and have adverse effects on organisms. This paper presents an overview of recent developments in the determination of FQs in solid environmental matrices and describes the risks and challenges (persistence, fate, effects, and remediation) which result from their presence in soil. Figure Pathways into the environment for FQs     

Assessment of the occurrence and distribution of pharmaceuticals in a Mediterranean wetland (L'Albufera, Valencia, Spain) by LC-MS/MS

The distribution of 17 pharmaceuticals between water and the solid phase (sediments and soils) was studied by utilizing solid-phase extraction (SPE) and liquid chromatography?Ctandem mass spectrometry (LC-MS/MS). Two extraction procedures for soils and sediments, prior to the SPE, one based on pressurized liquid extraction (PLE) with hot water and the other on methanol/water ultrasonic extraction, were compared. Absolute recoveries were 71.2?C99.3% [relative standard deviation (RSD) <21.4%)] for water, and the method detection limits (MDLs) ranged from 0.3 to 10?ng?L^?1. Recoveries were 35.4?C105.3% (RSDs <19.1%) and 42.1?C97.8% (RSDs <14%) for soil and sediment samples, respectively, using PLE and 20.2?C86.5% (RSDs <25.1%) and 30.3?C97.4% (RSDs <19.1%) using ultrasonic extraction. Fifteen of the 17 pharmaceuticals were present in the L??Albufera water at concentrations up to 17???g?L^?1. Oxytetracycline and tetracycline were not detected. In sediments, only tetracycline, norfloxacin and diclofenac were not found. The other studied pharmaceuticals were present in the range from less than the method quantification limit (MQL) to 35.83?ng?g^?1. Among the 17 target compounds, ofloxacin, ciprofloxacin, norfloxacin, trimethoprim, clofibric acid and diclofenac were not detected in soil samples. The average concentrations ranged from less than the MQL for ibuprofen to 34.91?ng?g^?1 for tetracycline. These results indicate that pharmaceuticals could survive the wastewater treatment processes, which could lead to their dissemination in water environments.     

Photo-induced magnetic bistability in a controlled assembly of anisotropic coordination nanoparticles

Anisotropic coordination nanoparticles of the photomagnetic network Cs(I)(2)Cu(II)(7)[Mo(IV)(CN)(8)](4) are obtained through a surfactant-free high-yield synthetic procedure in water. These particles are organised as Langmuir-Blodgett films with a preferential orientation of the nano-objects within the film that exhibit a magnetic bistability below 20 K with a very large coercivity due to an efficient photo-transformation.     

Highly efficient and stereoselective synthesis of beta-glycolipids

beta-Galactosylceramide and glycolipid analogues were prepared in high yield and with complete chemo and stereoselectivity by reaction of alpha-iodo glycosides with stannyl ceramides, formed in situ. TBAI was used to activate both the iodogalactose and the stannyl ether.     

Energy Transfer in Aminonaphthalimide‐Boron‐Dipyrromethene (BODIPY) Dyads upon One‐ and Two‐Photon Excitation: Applications for Cellular Imaging

Aminonaphthalimide–BODIPY energy transfer cassettes were found to show very fast (k_EET≈10¹⁰–10¹¹ s^?1) and efficient BODIPY fluorescence sensitization. This was observed upon one‐ and two‐photon excitation, which extends the application range of the investigated bichromophoric dyads in terms of accessible excitation wavelengths. In comparison with the direct excitation of the BODIPY chromophore, the two‐photon absorption cross‐section δ of the dyads is significantly incremented by the presence of the aminonaphthalimide donor [δ≈10 GM for the BODIPY versus 19–26 GM in the dyad at λ_exc=840 nm; 1 GM (Goeppert–Mayer unit)=10^?50 cm⁴ s molecule^?1 photon^?1]. The electronic decoupling of the donor and acceptor, which is a precondition for the energy transfer cassette concept, was demonstrated by time‐dependent density functional theory calculations. The applicability of the new probes in the one‐ and two‐photon excitation mode was demonstrated in a proof‐of‐principle approach in the fluorescence imaging of HeLa cells. To the best of our knowledge, this is the first demonstration of the merging of multiphoton excitation with the energy transfer cassette concept for a BODIPY‐containing dyad.     

1H and 13C assignments of cyclo[N-(Lys-Phe)-Orn-Val], a semicyclic imide tetrapeptide from Burkholderia cepacia

The rhizobacteria Burkholderia cepacia biosynthesized the new tetrapeptide Cyclo[N-(Lys-Phe)-Orn-Val] (1), a 2,5-diketopiperazine, and the known siderophore azurechelin (salicylic acid). The structure of 1 was established by means of IR, UV, 1H and 13C NMR, double dimension experiments and MS.     

A route to regioselectively functionalized carbazoles, dibenzofurans, and dibenzothiophenes through anionic cyclization of benzyne-tethered aryllithiums

The treatment of 2-fluorophenyl 2-iodophenylamines, ether, and thioether, easily prepared from commercially available products, with 3.3 equiv of t-BuLi and further reaction with selected electrophiles gives rise to functionalized carbazole, dibenzofuran, and dibenzothiophene derivatives in a direct and regioselective manner. The process involves an anionic cyclization on a benzyne-tethered aryllithium intermediate.     

Differentiation of Spanish brandies according to their metal content

Eleven metals, namely, aluminium, calcium, cadmium, copper, iron, lead, magnesium, manganese, potassium, sodium and zinc were determined in twenty samples of Sherry brandies and twelve samples of Penedés brandies by applying atomic spectrometry techniques. Flame atomic absorption spectrometry was used for quantitating calcium, copper, iron, magnesium, manganese and zinc; atomic emission spectrometry to determine potassium and sodium; and graphite furnace atomic absorption spectrometry to analyse aluminium, cadmium and lead. A chemometric approach was followed to study the discrimination between brandies from Sherry or Penedés according to the metal profile.     

Optimization of LC-MS/MS using triple quadrupole mass analyzer for the simultaneous analysis of carbosulfan and its main metabolites in oranges

This paper describes an analytical method involving a simple solvent extraction for the simultaneous liquid chromatography coupled to quadrupole tandem mass spectrometry (LC-MS/MS) determination of carbosulfan, its most toxic metabolite -carbofuran -, and its other main metabolites - 3-hydroxycarbofuran, 3-ketocarbofuran, 3-hydroxy-7-phenolcarbofuran, 3-keto-7-phenolcarbofuran, 7-phenolcarbofuran and dibutylamine - in oranges. Chromatography was performed on a Zorbax Bonus-RP (150 mm × 2.1 mm, 5 μm). The mobile phase was a ternary gradient water-methanol-acetonitrile with 1.0 mM ammonium acetate at flow rate of 0.2 ml min⁻¹. The LC separation and MS/MS optimization were studied to select the most appropriate operating conditions. The method developed has also been validated. The limits of quantification (LOQs) were from 1 μg kg⁻¹ for carbofuran to 10 μg kg⁻¹ for 3-keto-7-phenolcarbofuran. Extracts spiked with carbosulfan and its metabolites, at LOQ level, yielded average recoveries in the range 60-94%, with relative standard deviations (R.S.D.s) less than 15%. Calibration curves for carbosulfan and its metabolites (range LOQ-1000LOQ) were linear, with coefficients of correlations better than 0.990. The method was successfully applied to establish the primary degradation products in oranges treated with carbosulfan. The LC-MS/MS method developed is simple, rapid, and suitable for the quantification and confirmation of carbosulfan and seven of its main metabolites in orange at levels lower than 10 μg kg⁻¹.     

Study of the performance of three LC-MS/MS platforms for analysis of perfluorinated compounds

The analytical suitabilities of three different liquid chromatography–tandem mass spectrometry (LC-MS/MS) systems, (1) triple quadrupole (QqQ), (2) conventional 3D ion trap (IT), and (3) quadrupole–linear IT (QqLIT), to determine trace levels of perfluorinated compounds (PFCs) in fish and shellfish were compared. Sample preparation was performed using alkaline extraction and solid-phase-extraction cleanup. This evaluation was focused on both quantitative (sensitivity, precision, and accuracy) and qualitative (identification capabilities) aspects. In the three instruments, the former facet was evaluated using selected reaction monitoring (SRM), which is the standard mode for quantitative LC-MS/MS analysis. Accuracy was similar in the three systems, with recoveries always over 70 %. Precision was better for the QqLIT and QqQ systems (7–15%) than for the IT system (10–17%). The QqLIT (working in SRM mode) and QqQ systems offered a linear dynamic range of at least 3 orders of magnitude, whereas that of the IT system was 2 orders of magnitude. The QqLIT system achieved at least 20-fold higher sensitivity than the QqQ system, and this was at least tenfold higher sensitivity than for the IT system. In the IT system, identification was based on sensitive full mass range acquisition and MS ⁿ fragmentation and in the QqLIT system, it was based on the use of an information-dependent-acquisition scan function, which allows the combination of an SRM or MS full scan acting as the survey scan and an enhanced product ion scan followed by MS³ as the dependent scan in the same analysis. Three instruments were applied to monitor the content in fish and shellfish (anchovies, swordfish, tuna, mussels, and oysters) obtained from Valencia and Barcelona markets (Spain). The eight target PFCs were detected at mean concentrations in the range from 10 ng ?kg^-1 (perfluoro-7-methyloctanoic acid and perfluoro-1-decanesulfonate) to 4,200 ng ?kg^-1 (perfluoropentanoic acid). Furthermore, perfluoroheptanoic and perfluoroundecanoic acids (not covered as target analytes) were identified in some samples.