Montserrat López-Mesas

Rapid decolourization and mineralization of the azo dye C.I. Acid Red 14 by heterogeneous Fenton reaction

The decolourization and mineralization of a solution of an azo dye using a catalyst based on Fe(II) supported on Y Zeolite (Fe(II)-Y Zeolite) and adding hydrogen peroxide (heterogeneous Fenton process) have been studied. The catalyst was prepared by ion exchange, starting from a commercial ultra-stable Y Zeolite. All experiments were performed on a laboratory scale set-up. The effects of different parameters such as initial concentration of the dye, initial pH of the solution of the dye, H(2)O(2) concentration, temperature and ratio of amount of catalyst by amount of solution on the decolourization efficiency of the process were investigated. A percentage of colour removal of 99.3±0.2% and a mineralization degree of 84±5% of the solution of the dye were achieved in only 6 min of contact time between the catalyst and the solution, under the following conditions: initial concentration of the dye of 50 ppm, pH 5.96, 8.7 mM of H(2)O(2), T of 80°C and catalyst concentration of 15 g/L. Moreover, the catalyst Fe(II)-Y Zeolite can be easily filtered from the solution, does not leach any iron into the solution (avoiding any secondary contamination due to the metal) and its effectivity can be reproduced after consecutive experiments.

Development and validation of a simple determination of urine metabolites (oxalate, citrate, uric acid and creatinine) by capillary zone electrophoresis.

Oxalate, citrate, uric acid and creatinine are important urine markers for the evaluation and treatment of urolithiasic patients. They have been traditionally analysed by enzymatic and chromatographic techniques which present practical drawbacks, mainly in the sample pre-treatment step. The purpose of this study was to evaluate those markers in urine samples, by an easy multi-analyte assay using capillary zone electrophoresis. The four urine metabolites were determined, at 25 degrees C, by using a 50 cm x 75 microm capillary in 50 mmol l(-1) phosphate buffer (pH 6.5), at constant voltage of -30 kV and UV detection at 195 nm (for oxalate and citrate) or 30 kV and 234 nm (for creatinine and uric acid). The sample pre-treatment was minimum, 5- and 20-fold dilution of the urine sample and acidification to pH 3-4. Validation parameters (linear range, sensitivity, accuracy, precision and detection limits) were statistically comparable to those obtained with the official methods normally used in the clinical practice. The effect of freezing as a conservation method of urine samples is also discussed in terms of recoveries of the analytes. The analytical method developed is highly useful as a diagnostic tool for detecting metabolic renal disorders due to its simplicity, time consuming, easy automation, cost efficiency and analytical effectiveness, accomplishing with the clinical requirements.

Biological treatment of a textile effluent after electrochemical oxidation of reactive dyes.

In this work, a synthetic textile effluent containing a reactive dye (C.I. Reactive Orange 4) was treated in an electrochemical cell with titanium covered by platinum oxide (Ti/PtOx) electrodes to remove color. The discolored effluent was mixed with other textile mill process effluents (scouring, bleaching, washing, etc.), according to the rate of each effluent in the mill, and was submitted to biological treatment (activated sludge plant). Two biological plants were run simultaneously to evaluate the influence of oxidant products generated during the electrochemical treatment. The final chemical oxygen demand (COD) removal in both plants was 65 to 72%. The yield of the activated sludge plants was not affected by the addition of 10% of the discolored dyeing effluent (even when oxidants products were not removed), which indicates that the previous electrochemical treatment do not produce inhibition effects on the biological plant. However, in the case of direct addition of the discolored effluent, the biological treatment plant required a longer adaptation period. In addition, the electrolytic respirometry tests showed that all the biodegradable organic matter was removed, which implies that the yield in organic matter removal was the maximum possible for this type of treatment.

Hyperspectral imaging based method for fast characterization of kidney stone types

The formation of kidney stones is a common and highly studied disease, which causes intense pain and presents a high recidivism. In order to find the causes of this problem, the characterization of the main compounds is of great importance. In this sense, the analysis of the composition and structure of the stone can give key information about the urine parameters during the crystal growth. But the usual methods employed are slow, analyst dependent and the information obtained is poor. In the present work, the near infrared (NIR)-hyperspectral imaging technique was used for the analysis of 215 samples of kidney stones, including the main types usually found and their mixtures. The NIR reflectance spectra of the analyzed stones showed significant differences that were used for their classification. To do so, a method was created by the use of artificial neural networks, which showed a probability higher than 90% for right classification of the stones. The promising results, robust methodology, and the fast analytical process, without the need of an expert assistance, lead to an easy implementation at the clinical laboratories, offering the urologist a rapid diagnosis that shall contribute to minimize urolithiasis recidivism.

Molecularly imprinted polymer-liquid chromatography/fluorescence for the selective clean-up of hydroxylated polycyclic aromatic hydrocarbons in soils

Hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs), a group of metabolites produced during the biodegradation of PAHs by microorganisms, are known to be difficult to analyze from complex environmental or biological matrices. In the field of contaminated soils, where OH-PAHs are less studied, a new method was compared to a common method for the analysis of monohydroxylated PAH metabolites: 2-naphthol, 2-hydroxyfluorene, 9-phenanthrol and 1-hydroxypyrene. After optimizing the microwave assisted extraction (MAE) step, the obtained extracts, containing the OH-PAHs together with the corresponding PAHs, were purified by molecularly imprinted polymers (MIPs). MIPs showed an effective selectivity for the hydroxylated derivatives studied (and not for native PAHs), which allowed their identification and quantification by HPLC/FLD. By this method, good limits of detection (0.003–0.014 μg g−1) and limits of quantification (0.010–0.044 μg g−1) were achieved. On the other hand, following the common method, the sample extract was concentrated by evaporation, silylated, and analyzed by GC/MS. The new method was more sensitive for all OH-PAHs and the analysis showed fewer matrix effects due to the use of MIP clean-up. In the present work the advantages and disadvantages of the new method are shown, as well as the possible application to soil biodegradation studies.

Minimum handling method for the analysis of phosphorous inhibitors of urolithiasis (pyrophosphate and phytic acid) in urine by SPE-ICP techniques.

Pyrophosphate (PPi) and phytic acid (IP6) are natural phosphorous compounds with growing interest in the biomedical field due to their ability as potential inhibitors of urolithiasis among others. Existing methodologies for their evaluation show inconveniences mainly associated with sample treatment, matrix interferences and lack of resolution. The objective of the present work is the validation of a new method to determine both inhibitors in urine samples selectively and its application to the diagnosis of lithiasic patients. After urine purification by an off-line anion exchange solid phase extraction (SPE), based in an appropriate acidic elution gradient, the phosphorous compounds were analyzed by (31)P measurements by inductively coupled plasma mass spectrometry (ICP-MS) in the purified urine extracts. Linear range and limit of detection obtained were adequate for the analysis of the physiological amounts of the compounds in urine. The method was successfully applied to human urine samples, resulting in adequate accuracy and precision and allowing for the analysis of phosphorus inhibitors of urolithiasis in urine. The method simplicity and high sample throughput leads to a clear alternative to current determinations of the mentioned species in urine. Moreover, PPi and IP6 concentrations found in patients suffering from oxalocalcic urolithiasic were significantly lower than those for healthy controls, supporting the fact that the risk for oxalocalcic urolithiasis increases when urinary phosphorus inhibitors decrease. Thus, speciation of phosphorus inhibitors of urolithiasis in urine of stone formers can be performed, which is of unquestionable value in diagnostic, treatment and monitoring of urolithiasis.

High precision mapping of kidney stones using μ-IR spectroscopy to determine urinary lithogenesis

Evolution of urinary lithiasis is determined by the metabolism and life-style of the related patient. The appropriate classification of the stone is mandatory for the identification of the lithogenic process. In this study, cros-sections from a single stone of each of the most frequent urolithiasis types (calcium oxalate mono and dihydrate and carbonate apatite) have been selected and imaged using IR microspectroscopy. Moreover, the use of high definition sFTIR (synchrotron source) has revealed hidden information to the conventional FTIR. This work has demonstrated that minor components become key factors on the description of the stages of stone formation. Intensity map for COM (1630 cm(-1) peak). The high spatial definition achieved is key for the precise description of the kidney stone history.

Determination of Oxalate Content in Herbal Remedies and Dietary Supplements Based on Plant Extracts

Lifestyle, especially diet, is a prominent risk factor that affects the formation of calcium oxalate stones. Urinary oxalate excretion is directly related to the amount of oral intake and intestinal absorption rate of oxalate. This work evaluated the possibility of increasing oxalate ingestion, which could lead to secondary hyperoxaluria, associated with the intake of herbal remedies and dietary supplements containing plant extracts. A wide variety of 17 commercially available drugs and dietary supplements were analyzed using ion chromatography. The results showed remarkable differences in oxalate contents of the extracts. Total oxalate concentrations ranged from 0.03 to 2.2 mg/g in solid samples and from 0.005 to 0.073 mg/mL in liquid samples. The selected herbal remedies and dietary supplements containing plant extracts represent only a low risk for calcium oxalate stone formers, if the recommended daily dose is not exceeded.

Hollow fibre liquid phase micro-extraction by facilitated anionic exchange for the determination of flavonoids in faba beans (Vicia faba L.)

INTRODUCTION Flavonoids are polyphenolic compounds found ubiquitously in foods of plant origin. They are commonly extracted from plant materials with ethanol, methanol, water, their combination or even with acidified extracting solutions. The disadvantages of these methods are the use of high quantity of organic solvent, the possible loss of analytes in the different steps and the laborious process of the techniques. In addition, the complexity of the phenolic mixtures present in plant materials requires a preliminary clean-up and fractionation of the crude extracts. OBJECTIVE To develop a hollow fibre liquid phase micro-extraction (HF-LPME) method for a one step clean-up and pre-concentration of flavonoids. METHODOLOGY Two flavonoids (catechin and rutin) has been extracted by HF-LPME and analysed by HPLC. The related driving force for the liquid membrane has been studied by means of facilitated and non-facilitated transport. Different ionic and non-ionic water insoluble compounds [trioctylamine (TOA), tributyl phosphate (TBP), trioctylphosphine oxide (TOPO) and methyltrioctylammonium chloride (aliquat 336)] were used as carriers. The liquid membrane was constituted by a solution of n-decanol in the presence or absence of carriers. RESULTS Maximum enrichment factors were obtained with n-decanol/aliquat 336 (20%) as organic liquid membrane, sodium hydroxide (NaOH) (0.1 M) as donor solution, sodium chloride (NaCl) (2 M) as acceptor solution and 3 h as extraction time. Under these conditions, good results for validation parameters were obtained [for linearity, limit of detection (LOD), limit of quantitation (LOQ) and repeatability]. CONCLUSIONS The developed method is simple, effective and has been successfully applied to determine catechin and rutin in ethanolic extracts of faba beans.

Molecularly imprinted polymer for the removal of diclofenac from water: Synthesis and characterization

Contaminants of Emerging Concerns (CECs) have been introduced as one type of recalcitrant pollutant sources in water. In this study, the non-steroidal anti-inflammatory drug diclofenac (DCF) has been removed from water solutions using Molecularly Imprinted Polymer (MIP), synthetized via bulk polymerization with allylthiourea (AT) as the functional monomer and using DCF as template (MIP-DCF). DCF detection has been performed by UV spectrophotometer. From the kinetic study in batch mode, approximately 100% of removal is observed by using 10mg of MIP-DCF, with an initial concentration of 5mg/L of DCF at pH7, within 3min and agitated at 25°C. In continuous flow mode study, using a cartridge pre-packed with 10mg of MIP-DCF, a high adsorption capacity of 160mgDCF/g MIP was obtained. To study the porosity of MIPs, scanning electron microscopy (SEM) has been used. In order to characterize the chemical interaction between monomer and template, the pre-polymerization mixture for MIP and DCF has also been studied by 1H NMR. One of the chemical shift observed has been related to the formation of a complex between amine protons of thiourea group of AT with carboxylic acid on DCF. In conclusion, the developed MIP works as a good adsorbent for DCF removal, and is selective to DCF in the presence of indomethacin and ibuprofen.