Improved coupled-column liquid chromatographic method for the determination of glyphosate and aminomethylphosphonic acid residues in environmental waters

An existing method for the determination of glyphosate and its main metabolite aminomethylphosphonic acid (AMPA) in water has been improved. It is based on precolumn derivatization with the fluorescent reagent 9-fluorenylmethylcloroformate (FMOC) followed by large-volume injection in a coupled-column LC system using fluorescence detection (LC-LC-FD). The derivatization step was slightly modified by changing parameters such as volume and/or concentration of sample and reagents to decrease the limits of quantification (LOQ) of glyphosate and AMPA to 0.1 microg/l. Additionally, the use of Amberlite IRA-900 for preconcentration of glyphosate, prior to the derivatization step, was investigated; the LOQ of glyphosate was lowered to 0.02 microg/l. Drinking, surface and ground water spiked with glyphosate and AMPA at 0.1-10 microg/l concentrations were analysed by the improved LC-LC-FD method. Recoveries were 87-106% with relative standard deviations lower than 8%. Drinking and ground water spiked with glyphosate at 0.02 and 0.1 microg/l were analysed after preconcentration on the anion-exchange resin with satisfactory recoveries (94-105%) and precision (better than 8%).     

The speciation of rhodium(III) in hydrochloric acid media by capillary zone electrophoresis

A fast and effective method to study the aquation of rhodium(III) chlorocomplex in hydrochloric solutions using capillary zone electrophoresis (CZE) is developed. At least five species, some of which seem to be oligomeric, are formed in solution during the aquation process at pH>1. The fast hydration of RhCl₆³⁻ makes this species impossible to detect. The first species detected in the optimised conditions is RhCl₅(H₂O)²⁻ although RhCl₄(H₂O)₂⁻ is the main species during the first stage of the aquation process. When equilibrium is reached either RhCl₃(H₂O)₃ or a cationic complex, RhCl₂(H₂O)₄⁺, is formed as the main species. Matrix Assisted Laser Desorption Ionisation Time of Flight Mass Spectrometry (MALDI-TOF MS) is used as a novel technique to elucidate the structure of the rhodium aqua/chloro complexes formed in solution. Results obtained by CZE are confirmed by spectrophotometry.     

Leaf volatiles and secretory cells of Alpinia zerumbet (Pers.) Burtt et Smith (Zingiberaceae)

Plant leaves are commonly used in folk medicine and food industry. Their volatile composition is an important determinant in such applications. However, to properly assess the quality of volatiles, proper analytic tools must be utilised. Accordingly, the static headspace technique was used to evaluate the main volatiles emitted from in vitro-grown Alpinia zerumbet plants cultured with indole-3-acetic acid, thidiazuron, benzyladenine or kinetin, under standard physical conditions, as compared to those of field-grown donor plants. Although the leaf aroma of the donor plants was found to be a complex mixture, mainly consisting of sabinene, α and γ-terpinene, 1,8-cineole and caryophyllene, volatile analyses from most of the in vitro samples only revealed the presence of sabinene and caryophyllene. Many alkanes were found in the aromas after treating plantlets with cytokinins. Histochemical analysis of leaf sections was also carried out. Secretory cells found in the epidermis and mesophyll showed a strong positive reaction to lipophilic compounds using Oil red and Nile blue reagents. These findings demonstrated how in vitro conditions may alter the quality of volatiles in micropropagation systems, while leaf anatomy analysis revealed a large quantity of oil cells in the mesophyll as a constant feature responsible for the production of volatile compounds in both donor and in vitro-grown plants.     

Sensitivity enhancement for the analysis of naproxen in tap water by solid-phase extraction coupled in-line to capillary electrophoresis

SPE coupled in-line to CE, as the strategy to enhance the concentration sensitivity in CE, has been used to enrich naproxen in tap water samples. In this study, a microcartridge containing an octadecyl silica (C18) sorbent was placed near the inlet within the separation capillary column. The optimum conditions were obtained when naproxen in an acidic aqueous solution (pH 3.5) was loaded into the capillary at 930 mbar for 30 min, and 20 mM ammonium acetate in methanol/water (70:30 v/v) was used as both an elution solution and a separation BGE. Under these conditions, the sensitivity was enhanced 1820-fold with respect to normal hydrodynamic injection, and the LOD achieved was 0.2 microg/L. To show the capability of the in-line SPE-CE method, tap water samples were analysed after a pretreatment consisting in an off-line C18-SPE procedure. The recovery of this procedure was higher than 80%. Under these conditions, naproxen could be detected at a concentration of 10 ng/L; so the potential of the procedure for the sensitive analysis of this type of drugs in water samples was demonstrated. Afterwards, these results were compared with those previously obtained for naproxen in water samples using different sample stacking techniques.     

Assays on the simultaneous determination and elimination of chloroanisoles and chlorophenols from contaminated cork samples

A method for the simultaneous determination of the chloroanisoles and chlorophenols in cork samples with gas chromatography has been evaluated in view to its application. All the stages of the suggested procedure have been submitted to an in-depth examination using spiked ground corks. The recoveries of the method, which involves a simultaneous extraction with n-pentane followed by a second extraction using an aqueous basic solution where the phenolic derivates are transferred and, subsequently, derivatised, have been satisfactory for the all analytes at the studied spiking concentration levels. Good precision data and limits of detection between 1 ng/g and 2 ng/g were obtained for almost all compounds. As real samples, naturally contaminated cork slabs taken from different sources have been analysed, showing the presence of 2,4,6-trichloroanisole (TCA) and, in lesser extent, its direct precursor, 2,4,6-trichlorophenol (TCP). Removal studies have been performed by washing these tainted cork slabs with different solutions: Milli-Q water, sodium hydroxide and commercial products. Sodium hydroxide solutions have led to better analyte elimination, and the complete removal of TCP from the cork has been accomplished together with 72% of TCA reduction has been achieved.     

Development of a selective optical sensor for Cr(VI) monitoring in polluted waters

An optical sensor is described for the sensitive and selective determination of the Cr(VI) ion in aqueous solutions. The optode membrane is prepared by incorporating Aliquat 336 as an ionophore and a chromoionophore (4',5'-dibromofluorescein octadecyl ester) in a poly(vinyl chloride) (PVC) membrane containing ortho-nitrophenyloctyl ether (o-NPOE) as a plasticizer. The response to Cr(VI) is indicated by co-extraction of the target species and of hydrogen ions into the bulk of the membrane yielding large absorbance changes which can easily be measured in the visible spectral range. The optode membrane shows a reversible response in the concentration range of 1.1x10(-5)-1.0x10(-3) M and has been shown to be more selective towards the HCrO4(-) ion than other anions with a selectivity pattern HCrO4(-) > SCN- approximately = ClO4(-) > NO3(-) approximately = I- approximately = NO2(-) > H2PO4(-) approximately = Cl- approximately = SO4(2-). The sensing method developed has successfully been applied to the determination of Cr(VI) in spiked river water as well as in electroplating rinse waters.     

Effects of supplemental UV-A on the development, anatomy and metabolite production of Phyllanthus tenellus cultured in vitro

Phyllanthus tenellus is widely used for its antiviral, analgesic and hepatoprotective properties. Although the production of several chemical classes of secondary metabolites is influenced by UV radiation, particularly phenolic compounds, we also know that UV radiation can result in anatomical and developmental damage. However, the morphological, anatomical and phytochemical changes in response to UV-A exposure are generally understudied in the Phyllanthaceae. Therefore, we evaluated the effects of UV-A radiation on plant development and leaf anatomy, as well as the production of secondary metabolites and the contents of carotenoids and chlorophylls a and b, in P. tenellus. To accomplish this, in vitro cultures of P. tenellus were maintained for 60 days under white light (WL) and WL plus UV-A radiation. Results showed different phenotypic responses under additional UV-A, such as high phenolic metabolite production, increasing dimensions of abaxial epidermis and thickness of palisade parenchyma. Compared to plants cultured under WL, UV-A radiation caused damage to plant morphogenesis, including a reduced number of branches and shoots, consequently reducing the rate of proliferation. On the other hand, geraniin, ellagic acid and carotenoid contents increased after UV-A exposure, indicating that this light source is an important resource for inducing phenolic compounds.     

Determination of pharmaceutical compounds in sewage sludge using a standard addition method approach

An analytical method for the simultaneous determination of eight pharmaceutical compounds in biosolids from urban wastewater treatment plants (WWTPs) was developed and validated. The compounds evaluated were non-steroidal anti-inflammatory drugs (naproxen, diclofenac, and ibuprofen), lipid regulators (clofibric acid), and antibiotics (sulfathiazole, sulfapyridine, sulfamethazine, and sulfamethoxazole). Ultrasound assisted extraction with a water–methanol solvent mixture (1:1, v:v) was performed and the compounds were then determined by liquid chromatography coupled with tandem mass spectrometry. The design of the method was based on the application of the standard addition calibration methodology to reduce matrix interferences. Validation procedures were conducted with rabbit excrements as blank samples. Recoveries of the target analytes ranged from 76 to 131% in spiked samples at 50, 200 or 1000 ng g^?1 dry weight (dw). The relative standard deviations were in the range of 5–15% and the method detection limits ranged from 2 to 12 ng g^?1dw. The method was applied to monitor pharmaceutical concentrations in biosolids from different WWTPs over an eight-month period (May to December 2011). Diclofenac, sulfapyridine and ibuprofen were detected in most of the samples whereas sulfamethazine and ibuprofen were the pharmaceuticals found in the highest concentrations (>200 ng g^?1 dw on average).     

Exploring the Porosity in Ceramics at the nm Scale: From Understanding Historical Ceramics to Innovative Materials Design

Ceramics are complex objects and a rich source of information: they constitute a large part of the staple memory of past and present human activities. A deep understanding of traditional ceramics is an essential key to designing new ceramic materials. The demanding synthesis of ceramics with fine-tuned properties, such as enhanced mechanical, electrical, optical or magnetic characteristics, must be associated with cutting-edge analysis procedures in order to improve the engineering process. In this context, we describe a neutron-based non-destructive approach to investigating the nanoporosity of an historical pottery matrix as an effective investigation technique for exploring both traditional and advanced ceramic materials.     

Preconcentration of the herbicide glyphosate and its metabolite AMPA by immobilised metal ion affinity chromatography (IMAC)

A method based on Immobilised Metal Ion Affinity Chromatography (IMAC) using a chelating resin (Spheron Oxine 1000) loaded with Pd(II) is evaluated for the extraction and preconcentration of glyphosate and AMPA from natural water samples. The efficiency of the metal-loaded resin in retaining glyphosate and AMPA and the ability of different reagents to recover them is investigated. The most effective elution solution for the recovery of both analytes from the resin is found to be a mixture of 0.1 M HCI and 1 M NaCl. The effect of flow rate, analyte concentration, and sample volume is evaluated. The optimised experimental conditions are then used in the extraction of the analytes from spiked natural waters. The use of the Pd loaded resin led to recoveries ranging from 80-90% for glyphosate and 60-80% for AMPA.