Misused terms in analytical chemistry with emphasis on ultrasound application

A wide number of analytical terms have been applied erroneously for many years by analytical chemists, and they apply at present yet, by considering the time makes their use correct. The question is, may precedents validate the present use of incorrect scientific terms? Misused terms are found along the analytical process, starting with giving the name of the sample to the exiguous fraction of the original sample that reaches the detector or the high-resolution equipment after sample pretreatment and sample preparation. All the steps of the analytical process are considered in this article, with special emphasis on sample preparation and, within this, on the use of ultrasound, mainly for assisting extraction more unequivocally named as leaching or lixiviation. A call of attention in this respect is considered by the author to be of help to the analytical community

Analytical methods in wineries: is it time to change?

A review of the methods for the most common parameters determined in wine—namely, ethanol, sulfur dioxide, reducing sugars, polyphenols, organic acids, total and volatile acidity, iron, soluble solids, pH, and color—reported in the last 10 years is presented here. The definition of the given parameter, official and usual methods in wineries appear at the beginning of each section, followed by the methods reported in the last decade divided into discontinuous and continuous methods, the latter also are grouped in nonchromatographic and chromatographic methods because of the typical characteristics of each subgroup. A critical comparison between continuous and discontinuous methods for the given parameter ends each section. Tables summarizing the features of the methods and a conclusions section may help users to select the most appropriate method and also to know the state-of-the-art of analytical methods in this area

Determination of Arsenic, Mercury and Barium in herbarium mount paper using dynamic ultrasound-assisted extraction prior to atomic fluorescence and absorption spectrometry

A dynamic ultrasound-assisted extraction method using Atomic Absorption and Atomic Flourescence spectrometers as detectors was developed to analyse mercury, arsenic and barium from herbarium mount paper originating from the herbarium collection of the National Museum of Wales. The variables influencing extraction were optimised by a multivariate approach. The optimal conditions were found to be 1% HNO3 extractant solution used at a flow rate of 1 mL min-1. The duty cycle and amplitude of the ultrasonic probe was found to be 50% in both cases with an ultrasound power of 400 W. The optimal distance between the probe and the top face of the extraction chamber was found to be 0 cm. Under these conditions the time required for complete extraction of the three analytes was 25 min. Cold vapour and hydride generation coupled to atomic fluorescence spectrometry was utilized to determine mercury and arsenic, respectively. The chemical and instrumental conditions were optimized to provide detection limits of 0.01ng g-1 and 1.25 ng g-1 for mercury and arsenic, respectively. Barium was determined by graphite-furnace atomic absorption spectrometry, with a detection limit of 25 ng g-1. By using 0.5 g of sample, the concentrations of the target analytes varied for the different types of paper and ranged between 0.4–2.55 µg g-1 for Ba, 0.035–10.47 µg g-1 for As and 0.0046–2.37 µg g-1 for Hg

Extraction of wood compounds by use of subcritical fluids

A study of the extraction of oak wood compounds with subcritical water-ethanol mixtures as extractant, with an ethanol content between 0-60%, is reported. Identification and characterisation of the extracted compounds have been made by spectrophotometry and gas chromatography with either flame ionisation or mass detectors. Extraction was performed statically manner by use of a single cycle or repeated cycles. All variables affecting the extraction process were studied and optimised. Extraction time and temperature are 60 min and 200ºC, respectively. Comparison of the extract thus obtained with commercial extracts showed the former to be rich in compounds characteristic of the commercial extracts. The method enables manipulation of the extract composition by changing the temperature and water/ethanol ratio used. It is faster than the traditional procedures for obtaining wood extracts

Two-parameter determination in vinegar by a flow injection-pervaporation system

A flow-injection method (FI) for the sequential determination of ethanol and acetic acid in vinegar is reported. The determination of ethanol is based on the oxidation of the pervaporated ethanol by Cr2O7K2. The acetic acid is determined by an acid-base reaction with Thymol Blue as the indicator. Both reactions are monitored photometrically at 600 nm using a single detector. Optimisation studies and assessment of the sequential FI method are also reported. The linear determination range is between 0-12 % (v/v) for ethanol and 0-10 % (grams of acetic acid in 100 ml) for acetic acid. The sample throughput of the sequential manifold is 7 per hour. The new method has been applied to vinegar samples and the results obtained are in excellent agreement with those from the reference methods used in Spain

Semiautomatic flow-injection method for the determination of volatile acidity in wines

A flow-injection (FI) method based on analytical pervaporation was assessed for its routine use in the determination of volatile acidity in winery laboratories. The new method was compared with both the official method and the Mathieu method, which is most often used in Spanish wineries, by testing 30 different wines, including young and aged, and sweet and dry wines from Montilla-Moriles appellation d´origine. The robustness of the new method was established and then all three methods were studied in terms of range of linearity and regression of the calibration curve, repeatability, reproducibility, sensitivity, detection and quantification limits (LOD and LQ, respectively) and time of analysis. The FI method surpasses the Mathieu method in reproducibility and both the Mathieu and official methods in LOD and LQ and sensitivity; it also requires less personnel involvement and shorter analysis time. The statistical criteria established by the “Office International de la Vigne et du Vin” were applied to the data and the results obtained indicated that the differences between the analytical parameters of the 3 methods are not significant and can be applied indistinctly. The correlation of the methods was studied by taking them 2 by 2, and the corresponding equations, coefficients and deviations confirmed the statistical results. Thus, the new method can be used in winery laboratories with clear advantages over its 2 counterparts (the routine and official methods)

Determination of ethanol in beverages by flow injection, pervaporation and density measurements

A fast, clean and easy to automate flow injection-pervaporation method for the determination of ethanol in different beverages using density measurements is proposed. The method is based on separation of the ethanol from the sample using a pervaporation module, thus obtaining in the acceptor chamber of the pervaporator a water-alcohol mixture, the density of which is measured. After optimisation by either the univariate or multivariate approach as required, a linear range between 0-40% was established. Then, the assessment of the method versus a reference one was studied in terms of repeatability (0.12% v/v), reproducibility (0.32% v/v), detection limit (0.11% v/v) and traceability. The sample throughput was 15 samples h-1. The method was in agreement with the reference methods used in the European Union

Superheated liquids for the extraction of solid residues from winemaking processes

Solid residues from winemaking process have been subjected to extraction with superheated water-ethanol mixtures. Identification and characterisation of the extracted compounds have been made by spectrophotometry, gas chromatography with either flame ionisation or mass detectors and high performance liquid chromatography with UV detection. The extraction has been performed in a static manner by single or repetitive cycles. All variables affecting the extraction process have been studied and optimised. The extraction time and temperature are 65 min and 210ºC, respectively. Two phases constitute the extract: an aqueous phase, which is rich in phenol compounds and an oily phase, mainly formed by fatty acids. The method allows manipulation of the extract composition by changing the applied pressure, temperature, water-ethanol ratio and pH. The method is faster than the traditional extraction procedures for obtaining valuable compounds from these residues

Sequential Spectrophotometric determination of methanol and iron in vinegar by a flow injection-pervaporation method

An easily automatable sequential flow-injection-pervaporation method is proposed for the photometric determination of methanol and iron in vinegar. The method is based on separation of the methanol from the sample matrix by pervaporation followed by its oxidation to formaldehyde with permanganate, decolouration of the latter with S2O5-2 and subsequent reaction of formaldehyde with p-rosaniline to yield a violet reaction product with maximum absorption at 567 nm. Iron is determined by an existing method based on reaction with thiocyanate in acidic medium and monitoring at 508 nm. After optimisation by either the univariate or multivariate approaches, as required, the linear range was established for methanol (4-1000 mg L-1) and iron (0.18-20 mg L-1); The proposed method was then compared with reference methods for methanol and iron in terms of repeatability (2.452 mg L-1 and 0.245 mg L-1, respectively), reproducibility (4.435 mg L-1 and 0.356 mg L-1, respectively), detection limit (LOD=82 and 0.234 mg L-1, respectively) and traceability. The throughput was nine samples per hour