Ion mobility spectrometry as a fast analytical tool in benzalkonium chloride homologs determination.

Abstract A novel procedure is proposed for the determination by ion mobility spectrometry (IMS) of C 12 , C 14 and C 16 benzalkonium chloride (BAC) homologs. The proposed method requires minimum sample treatment and the measurement was made in less than one minute. A high sensitivity was obtained for BAC determination by IMS with limit of detection values from 37 to 69 µg L −1 . Accuracy of the proposed methodology was evaluated through the analysis of aqueous and alcoholic samples spiked with BAC at concentration levels from 0.002% to 20% (w/v), providing recovery values from 91% to 104%. BAC was determined in sanitary alcohols, nasal sprays, postharvest products, algaecides, and treated s…

Flame atomic absorption analysis of gold in jewelry samples

A new procedure is proposed for the determination of gold by flame atomic absorption in jewelry samples. The method is based on the acid digestion of 10 mg of sample in a microwave oven and on the on-line dilution, using a three-way valve. The dynamic range of the technique is extended to 100 mg/l gold solutions and using a weighted bracketing method for the treatment of the results, accuracy errors lower than 2% can be found in the analysis of real samples as compared with those obtained by fire assay. The method is very fast and implies only little damage to the jewelry samples.

Physicochemistry of the Atmosphere

Determination of arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid in cereals by hydride generation atomic fluorescence spectrometry

Abstract A fast, sensitive and simple non-chromatographic analytical method was developed for the speciation analysis of toxic arsenic species in cereal samples, namely rice and wheat semolina. An ultrasound-assisted extraction of the toxic arsenic species was performed with 1 mol L− 1 H3PO4 and 0.1% (m/v) Triton XT-114. After extraction, As(III), As(V), dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA) concentrations were determined by hydride generation atomic fluorescence spectrometry using a series of proportional equations corresponding to four different experimental reduction conditions. The detection limits of the method were 1.3, 0.9, 1.5 and 0.6 ng g− 1 for As(III), As(V)…

Flow injection-spectrophotometric determination of cresol compounds in water by reaction withp-aminophenol

A spectrophotometric method has been developed for the simultaneous determination ofo-cresol andm-cresol in water by reaction withp-aminophenol (PAP). Three different methodologies have been assayed; (i) batch analysis, after reaction in an alkaline medium in the presence of dissolved molecular oxygen as oxidizing agent, (ii) a stopped-flow procedure, carried out in the presence of KIO4 and (iii) a flow injection method based on the same approach. The batch procedure requires 22 min for the full development of colour witho-cresol and 12 min form-cresol. In the stopped-flow mode, using KIO4 and a reaction time of 12 min, better sensitivity can be obtained for both compounds and limits of det…

Validated fast procedure for trace element determination in basil powder

Abstract An inductively coupled plasma optical emission spectroscopic (ICP-OES) method has been developed and fully validated for trace element determination in basil samples. The method involves the previous sample digestion, under pressure, with a mixture of HNO 3 , HCl and H 2 O 2 inside a microwave oven, 42 elements were studied and 33 elements (Al, As, Ba, Ca, Cr, Co, Cu, Fe, Pb, Li, Mg, Mn, Mo, Ni, K, Se, Na, Sr, Tl, Ti, V, Zn, Sc, Y, La, Ce, Nd, Tb, Ho, Er, Tm, Yb, Lu) were determined quantitatively in basil leaves obtained from Morocco and Spain. The method provided recovery percentages from 89% to 113% for spiked concentrations at mg kg −1 and μg kg −1 . Accurate results were found…

Elemental fingerprint of wines from the protected designation of origin Valencia

Abstract Inductively coupled plasma optical emission (ICP-OES), in combination with different chemometric approaches, has been used to verify the origin of different red wine samples from Utiel-Requena, Jumilla, Yecla and Valencia protected designation of origin (PDO). The ability of multivariate analysis methods, such as hierarchical cluster analysis (HCA), principal component analysis (PCA), classification and regression trees (CARTs) and discriminant analysis (DA), to achieve wine classification from their elemental contents has been investigated. The calculations were performed using 38 variables (contents of Al, Ba, Be, Ca, Cd, Ce, Co, Cr, Cu, Dy, Er, Eu, Fe, Gd, Ho, K, La, Li, Lu, Mg,…

The use of topological models in analytical chemistry

In the present paper, the possible analytical applications of two toplogical models, the DARC model and the group contribution model, are discussed. Both models are applied to obtain calibration laws, which relate UV and IR characteristics with the chemical structure of ethylene oxide condensates. The group contribution model is also applied to determine the contribution of each part of the different compounds involved in a chemical interaction process, having established the sensitization parameters of benzodiazepines and anionic surfactants from the micellar enhancement fluorescence.

Elemental composition of seasoning products

The elemental composition of seasoning products, like spices garlic and onion, has been reviewed paying special attention to methods proposed in the literature to determine specific elements or as much as possible components of these products which are widespread used in food preservation or food flavouring and can contribute to the intake of both, essential and toxic elements. Sample treatment and metal speciation aspects have been critically revised concerning onion, garlic and pepper (the most commonly studied products).

Fluorimetric determination of 1-naphthol and mixtures of carbaryl and 1-naphthol in micellar media

The interaction of 1-naphthol with different types of anionic, cationic and non-ionic surfactants has been studied spectrofluorimetrically in order to obtain a sensitivity enhancement in the determination of this compound. At neutral pH, cetyl trimethyl ammonium bromide (CTAB) provides a 2-fold sensitivity enhancement of 1-naphthol and exhibits a weak interaction with carbaryl. In strong alkaline medium carbaryl is hydrolyzed to 1-naphthol and in the presence of CTAB micells, a 5-fold sensitivity enhancement and a limit of detection of 0.2 μg·ml−1 with a 101±3% percentage of recovery is obtained. These facts permit the development of an accurate method for the fluorimetric analysis of 1-nap…

On-line microwave oven digestion flame atomic absorption analysis of solid samples

Abstract A manifold has been developed for on-line microwave oven digestion and flame atomic absorption spectrometric (FAAS) determination of metallic elements in solid samples. The use of a closed flow system permits sample treatment before analysis by FAAS, the direct injection of slurries avoids a filtration step and the interconnection of two conventional rotary injection valves allows the rapid introduction of samples and standards. The determination of lead in sewage sludge was employed as a test system for the proposed on-line sample digestion manifold. The procedure has a limit of detection of 0.2 μg Pb g−1.

Determination of PAHs in airborne particles by accelerated solvent extraction and large-volume injection-gas chromatography-mass spectrometry.

Abstract A sensitive and automated method is presented for the determination of polycyclic aromatic hydrocarbons (PAHs) in airborne particulate matter. The procedure includes extraction of PM10-bound PAHs by accelerated solvent extraction (ASE) followed by gel permeation chromatography (GPC) clean-up, and large-volume programmable temperature vaporizer (PTV–LV) injection coupled to GC–MS. The limit of detection (LOD) of the whole method, based on a signal-to-noise ratio (S/N) of 3:1, ranged from 0.26 pg m−3 to 3 pg m−3 when air volumes of 760 m3 are collected. The hexane–acetone mixture (1:1, v/v) gave the best recoveries when ASE parameters were fixed at 125 °C, 1500 psi, and a total time …

The use of emulsions in the preparation of samples and standards for analysis by atomic-absorption spectroscopy determination of Cu and Fe in mibk extracts of their apdc complexes

The use of aqueous/organic emulsions is shown to give advantages in the AAS determination of Cu and Fe extracted as their pyrrolidinedithiocarbamate complexes into methyl isobutyl ketone. The emulsions are more stable than the extracts, and the standards can be prepared from aqueous solutions by emulsification, but without extraction.

High performance liquid chromatography—atomic fluorescence spectrometric determination of arsenic species in beer samples

Abstract A method has been developed for the direct determination of As(III), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA) and As(V) in beers by hydride generation—atomic fluorescence spectrometry after separation of arsenic species by high performance liquid chromatography. Compounds were separated by anion-exchange chromatography with isocratic elution using KH 2 PO 4 /K 2 HPO 4 as mobile phase with elution times of 1.67, 2.08, 6.52 and 10.72 min for As(III), DMA, MMA and As(V), respectively. Parameters affecting the hydride generation of all arsenic species were studied and the best conditions were established as a reaction coil of 150 cm, for a sample injected volume of 100 …

PLS-UV spectrophotometric method for the simultaneous determination of paracetamol, acetylsalicylic acid and caffeine in pharmaceutical formulations

A simple and fast analytical procedure is proposed for the simultaneous determination of paracetamol, acetylsalicylic acid and caffeine in pharmaceuticals by means the partial least square treatment of the spectrophotometric absorbance data between 216 and 300 nm, taken at 5 nm intervals. The method involves the use of 8 standard mixtures of the three compounds assayed, considered at two concentration levels, and the measurement of the absorbance of samples in a 20% (v/v) ethanol in water solution previously filtered. In the analysis of real and synthetic samples precise and accurate values were obtained by the aforementioned procedure, providing in all cases variation coefficients and accu…

Extension of the dynamic range of flame atomic absorption spectrometry using flow injection analysis with variable-volume dilution chambers

Abstract A simple and inexpensive procedure is proposed for the extension of the dynamic range of flame atomic absorption spectrometry measurements using on-line dilution. The proposed methodology is based on the use of a manifold with two coupled dilution chambers and a zone injection system. The samples are prediluted in a closed system which includes a variable-volume mixing chamber (10–120 ml) and two injection valves. The samples are injected through one of these valves, and the other is employed to take 100 μl of prediluted samples which are then passed through a new dilution chamber (volume 1–10 ml) and aspirated by the nebulizer of the instrument. A third injection valve mounted in …

Analytical methods to determine cocaine contamination of banknotes from around the world

Abstract The presence of cocaine in a significant number of UK pounds (Xxxx), Euros (€) and North American banknotes ($) in general circulation requires appropriate tools to do determinations. This article discusses the-state-of-the-art in the analysis of cocaine on banknotes. We summarize the usual extraction methods of currency samples and compare them, especially with respect to avoiding sample damage. We critically discuss analytical methods, namely gas chromatography (GC) and liquid chromatography (LC), capillary electrophoresis (CE), immunoassay, thermal desorption tandem mass spectrometry (TD-MS2) and ion-mobility spectrometry (IMS). We also review cocaine levels on banknotes around …

Application of point-to-point matching algorithms for background correction in on-line liquid chromatography–Fourier transform infrared spectrometry (LC–FTIR)

A new background correction method for the on-line coupling of gradient liquid chromatography and Fourier transform infrared spectrometry has been developed. It is based on the use of a point-to-point matching algorithm that compares the absorption spectra of the sample data set with those of a previously recorded reference data set in order to select an appropriate reference spectrum. The spectral range used for the point-to-point comparison is selected with minimal user-interaction, thus facilitating considerably the application of the whole method. The background correction method has been successfully tested on a chromatographic separation of four nitrophenols running acetonitrile (0.08…

Determination of critical eluent composition for polyethylenglycols using on-line liquid chromatography-Fourier transform infrared spectrometry.

In this work, it has been extended to methanol:water mobile phases, the use of a background correction method for on-line LC-FTIR measurements named Univariate background correction based on the use of a reference spectra matrix (UBC-RSM) and absorbance ratios. It permits to overcome the problem related to spectral changes occurring during the gradient elution, which in the past limited the on-line coupling of LC and FTIR to isocratic elutions. The combined use of the aforementioned background correction technique in on-line isocratic and gradient LC-FTIR, and partial least squares (PLS) has been applied for the search of the critical conditions for polymers. Polyethylenglycol (PEG) has bee…

Implementation of multicommutation principle with flow-through multioptosensors

Abstract For the first time, the combination of multicommutation concept with flow-through multioptosensors is exploited and a biparameter multicommutated UV sensor is developed. A very easy-operated and automated sensing device is proposed here and demonstrated to be useful in the routine analysis by applying it to the determination of two widely used pharmaceuticals chosen as model analytes: salicylamide and caffeine. The particulated solid phase used performs two functions: (a) states selectivity conditions by itself in the flow cell and (b) provides appropriate separation of the analytes in the on-line precolumn, thus making possible the sequential arrival of the analytes to the detecti…

Evaluation of nutritional parameters in infant formulas and powdered milk by Raman spectroscopy

It has been made a critical evaluation of the application of near infrared Fourier transform-Raman spectroscopy for the simultaneous determination of the most important nutritional parameters such as energetic value, carbohydrate, protein and fat contents of infant formula and powdered milk samples based on the use of partial least squares (PLS) regression analysis. A highly heterogeneous population of 23 samples, covering a wide range of infant food formula and powdered milk, were obtained from the Spanish market. Raman spectra, obtained by excitation with a Nd:YAG laser at 1064 nm, show no disturbing fluorescence effects; therefore sample spectra can be recorded without any previous prepa…

Micellar fluorescence enhancement of carbamate pesticides

Abstract Different studies have been carried out on the interaction of carbamate pesticides, such as carbofuran and carbaryl, with nonionic and anionic surfactants. Micellar fluorescence enhancements (MEF) of 15–20 for carbofuran in the presence of fatty alcohol ethylene oxide condensates, and of 3.7–8.6 in the presence of anionic surfactants at neutral pH have been obtained. Carbaryl does not interact with surfactants, but when it is hydrolysed to 1-naphthol, MEF values of the order of 2 are obtained in the presence of nonylphenol ethylene oxide condensates. The experimental parameters have been optimized in order to obtain maximum fluorescence. The mechanisms involved in the fluorescence …

Flow injection-FTIR determination of dithiocarbamate pesticides

A flow injection Fourier transform infrared spectrometric procedure has been developed for the determination the dithiocarbamate pesticides Ziram and Thiram in solid samples. All the operations involved, such as extraction, filtration and measurement, were integrated in the experimental set-up in order to avoid excessive manipulation of samples and standards. Ultrasonic assisted and mechanical extraction were evaluated for the solubilization of the analytes and, additionally, the effect of carrier flow rate, sample loop volume and the ratio between sample mass and volume of solvent employed were studied. Quantitative extractions with chloroform were obtained for both Ziram and Thiram, after…

Electrothermal Atomic Absorption Determination of Chromium in Sediments

Abstract An electrothermal atomic absorption spectrometric method has been developed to determine total chromium concentration in natural sediment samples. Samples were mineralized by dry ashing at 550°C and fused at 1100°C for 30 min with lithium metaborate. Dissolved samples were injected in graphite tubes, mineralized at 1100°C, and atomized at 2600°C. Standard addition calibration made unnecessary the use of chemical modifiers. The method provided a limit of detection from 23 to 45 ng liter −1 . The relative standard deviation for chromium determination was between 3 and 14%. Results obtained for a standard reference material agree well with the certified value. A series of natural samp…

On-line solvent recycling: a tool for the development of clean analytical chemistry in flow injection Fourier transform infrared spectrometry. Determination of ketoprofen

Abstract A flow injection strategy has been developed for the direct determination of ketoprofen in pharmaceuticals by Fourier transform infrared spectrometry also incorporating a distillation unit which allows the carbon tetrachloride employed to dissolve samples and standards and used as a carrier to be recovered on-line. The system developed permits a drastic reduction of reagent consumption and easy and fast sampling and cleaning of the measurement cell. For the quantification of ketoprofen in pharmaceuticals the carbonyl bands at 1712 and 1666 cm −1 were employed and the developed method provided a 3 σ limit of detection of 0.04 mg ml −1 , a dynamic range up to 10 mg ml −1 and typical …

Passive exposure to nicotine from e-cigarettes

A procedure based on the use of ion mobility spectrometry (IMS), after liquid-liquid microextraction (LLME), has been successfully employed for the determination of passive exposure to nicotine from cigarette and e-cigarette smoking. Nicotine has been determined in exhaled breath and oral fluids of both, active and passive smokers. The aforementioned studies, made in closed environments, evidenced that the exhaled breath after conventional blend cigarette smoke provides nicotine levels of the order of 220 ng per puff, in the case of experienced smokers, being exhaled only 32 ng in the case of e-cigarettes. On the other hand, the nicotine amount in oral fluids of passive vapers was between 8…

Is lithium implicated in tobacco addiction?

IntroductionTobacco is a source of mineral elements that can affect human health in various ways, such as lithium, which is used as a psychiatric medication. Lithium salts are used as mood-stabilizing drugs and indicated in the treatment of manic-depressive psychosis.ObjectiveStudying the lithium content in tobacco over the smokers’plasma content and evaluate the potential role of lithium in tobacco addiction.MethodsA total of 18 different tobacco products (cigarettes, smokeless and water pipe tobacco) and 125 plasma samples (45 from smokers, 10 from ex-smokers and 70 from non-smokers) were collected to determinate the lithium content. Tobacco samples were digested with nitric acid and lith…

Speciation of tetraalkyllead compounds by flow injection — atomic absorption spectrophotometry

The on-line demetallation of alkyllead compounds, with iodine, and further emulsification, provides a fast determination of total lead content in liposoluble matrices, such as gasolines. It can be carried out in a double channel manifold, using a magnetically well stirred dilution chamber for the emulsification of the samples, previous to their analysis by flame atomic absorption spectrophotometry. On the other hand, the different behaviour of tetraethyllead (TEL) and tetramethyllead (TML) can be employed for speciation of both compounds in the sample. The effect of the flow injection parameters on the sensitivity and accuracy has been studied and the figures of merit of the proposed method…

Conductimetric study of struvite crystallization in water as a function of pH

Abstract The main objective of this work was to investigate the best pH for phosphorus removal from synthetic aqueous solutions using chemical precipitation of struvite, at constant temperature. The experimental approach, developed in the present study, consisted to precipitate struvite in synthetic wastewater containing PO 4 3− , NH 4 + and Mg 2+ ions in an equal molar ratio, using a stirred tank with continuous monitoring by conductimetry, at 25 °C. Different laboratory experiments were used to evaluate the effects of pH in the range of 8.5 till 11.8, on size, shape, and purity of the precipitated crystals. Struvite crystals were characterized by Infrared spectroscopy (FTIR), scanning ele…

A chemical status predictor. A methodology based on World-Wide sediment samples.

As a consequence of the limited resources of underdeveloped countries and the limited interest of the developed ones, the assessment of the chemical quality of entire water bodies around the world is a utopia in the near future. The methodology described here may serve as a first approach for the fast identification of water bodies that do not meet the good chemical status demanded by the European Water Framework Directive (WFD). It also allows estimating the natural background (or reference values of concentration) of the areas under study using a simple criterion. The starting point is the calculation the World-Wide Natural Background Levels (WWNBLs) and World-Wide Threshold Values (WWTVs…

Fourier transform infrared analysis of paint solvents

Abstract The composition of solvent mixtures employed in the paint industry was determined by Fourier transform infrared spectrometry. A procedure based on the use of the ratio between the absorbance of characteristic bands of each component permits the ratio between two solvents in a binary mixture to be determined, independently of the thickness of the sample film. Typical mixtures of xylol with butan-1-ol and with butyl acetate (xylol=mixture of o-, m- and p-xylenes) were used as model systems to develop the proposed procedure and the accuracy was determined using synthetic formulations. Another possible application of the procedure is the characterization of azeotropic mixtures.

Recent developments in flow-analysis vibrational spectroscopy

Abstract This review deals with developments in the new century on the use of vibrational spectroscopy techniques for detection in flow-injection analysis (FIA) systems. To provide a picture of the evolution, highlights and future developments in this field, we revisited Fourier transform infrared (FTIR), in the mid-IR and near-IR ranges, and FT-Raman spectrometry applications using different approaches, from classical FIA to modern (sequential injection analysis (SIA) or multicommutation). We used the analytical abstracts database for 2000–06 for the literature search, but we based this review very much on the experience of our team in this field.

Science based calibration for the extraction of 'analyte-specific' HPLC-DAD chromatograms in environmental analysis

Multivariate science based calibration (SBC) has been applied to the resolution of overlapped peaks in liquid chromatography with diode array detection (LC-DAD). Complex river water samples spiked with 11 pharmaceutical substances resulted in poorly resolved chromatograms containing additional peaks from interfering matrix compounds and a change in the background absorbance due to the mobile phase gradient. Applying the present multivariate approach it was possible to resolve all 11 analytes from overlapping peaks, obtaining linear calibration lines (R2 > 0.96). Recovery percentages on spiked samples ranged between 74.6 and 113.5%, which are quite satisfactory taking into account the low co…

Efficiency of the microwave-assisted extraction of hydrocarbons and pesticides from sediments

Abstract A mixture of toluene and water is proposed for the microwave-assisted extraction of organic pollutants, hydrocarbons and pesticides, from marine sediments. The effect of experimental conditions, such as microwave power and irradiation time, on the extraction of linear, unresolved and polycyclic aromatic hydrocarbons as well as PCBs and DDTs has been evaluated using real marine sediment samples. Values found by Soxhlet and ultrasonic extraction were employed to evaluate the efficiency of the microwave-assisted extraction. Analytical determinations were carried out by gas chromatography using FID, ECD and MS detectors. For 2 g of a dry sediment, an extraction time of 6 min with 10 ml…

Flow-injection spectrophometric determination of propoxur with p-aminophenol

Abstract The spectrophotomeric determination of propoxur [2-(1-methyxlthoxy)phenyl methyl carbamate] was carried out with p -aminophenol (PAP) in a flow system. The method involves the on-line hydrolysis with NaOH of propoxur to 2-isopropoxyphenol and the oxidation of PAP to its relative quinone imine with KIO 4 and the reaction between the phenolate and the quinone imine. A four-channel flow manifold was employed to carry out all the different steps of the reaction considered, monitoring the indo dye formed at 600 nm. The developed procedure provides a typical calibration line of A = 0.000 7 + 1.8 × 10 3 C ( A = absorbance; C = concentration in M) with a regression coefficient of 0.9998 an…

Preliminary results about the breath of passive smokers and vapers based on the use of portable air monitoring devices

Abstract Preliminary studies were made on the effect of both, classical smoking and electronic cigarettes (ECs) vaping, based on the quality of the indoor air and the breath of passive smokers. Portable air monitoring devices were used to evaluate carbon monoxide (CO), carbon dioxide (CO2), particulate materials (PM), formaldehyde and volatile organic compounds (VOCs) in indoor air and breath of active and passive smokers and vapers. As preliminary results, it can be observed that the major part of PMs liberated in classical smoking and ECs vaping correspond to the lowest size, which is the most dangerous for human health. However, the number of smallest PMs formed during vaping is around 5…

On-line gradient liquid chromatography–Fourier transform infrared spectrometry determination of sugars in beverages using chemometric background correction

Abstract An on-line gradient reversed phase liquid chromatography–Fourier transform infrared spectrometry (LC–FTIR) method was developed for the determination of fructose, glucose, sucrose and maltose in beverages. Improved chromatographic resolution was obtained using a linear gradient from 75 to 55% (v/v) acetonitrile in water in 15 min. Changes in the background spectra were corrected employing “univariate background correction based on the use of a reference spectra matrix” (UBC-RSM) and using the ratio of absorbance (AR) at 2256 and 2253 cm −1 for the identification of the eluent spectra within the RSM. The method provided limits of detection in the order of 0.75 mg ml −1 . The precisi…

Chromium speciation in liquid matrices: a survey of the literature

A thorough review of the literature published (1983 - March 1999) on chromium speciation in liquid samples is presented, and analytical techniques used in the 404 articles are summarized. The discussion focuses on atomic spectrometric techniques, which are mainly employed for chromium speciation in liquid matrices (134 articles). Details on the type of pretreatment, species, samples, techniques and analytical features of the methodologies proposed are given.

Trace elemental composition of curry by inductively coupled plasma optical emission spectrometry (ICP-OES)

A methodology based on inductively coupled plasma optical emission spectrometry (ICP-OES) after microwave-assisted acid digestion was developed to determine the content of traces elements in curry samples from the Spanish market. The methodology was validated in terms of accuracy by the analysis of citrus and tomato leaf reference materials achieving comparable results with the certified values. The trace metal content of curry samples was compared with data available from previously published reports concerning Indian samples, especially in terms of heavy metal composition, in order to guarantee the quality of the commercially available spices in the European countries. Values found for th…

Determination of carbonates in waters by on-line vapor generation FTIR

Abstract An electrically heated gas-permeation unit (GPU) has been employed for the vapor-generation Fourier transform infrared (FTIR) determination of total carbonate in waters. The developed method is based on the simultaneous injection of 100 μ l sample and 100 μ l nitric acid in a two-channel manifold with a merging zone, which provides the generation of CO 2 through the GPU, heated at 90°C, from which CO 2 is swept by a stream of N 2 to a long-path infrared gas cell. Absorbance measurements were made in the range from 2500 to 2150 cm −1 and the corresponding flow injection recordings were obtained as a function of time. The areas of these peaks are interpolated in a calibration equatio…

Uptake and translocation monitoring of imidacloprid to chili and tomato plants by molecularly imprinting extraction - ion mobility spectrometry

Abstract The degradation of imidacloprid in soil and its uptake and translocation to chili and tomato plants was evaluated, as a proof of concept, of the possibilities of the combination of molecularly imprinted polymers (MIPs) and ion mobility spectrometry (IMS) for a fast and sensitive bioprocesses monitoring tool. To do it, a method based on the selective extraction of imidacloprid from soil and plant materials was developed. In the selected conditions, the MIP-IMS procedure provided a recovery of imidacloprid in soil and plant samples from 102 to 114%, for spiked concentration levels from 0.2 to 2.0 μg g−1. Precision of the methodology, expressed as the relative standard deviation (RSD)…

The use of near-infrared spectrometry in the olive oil industry.

The enormous possibilities offered by near-infrared (NIR) spectroscopy for the (on/in/at-line) quality control process of olive fruits, pastes, and oils are summarized throughout this paper. Special attention has been paid to the combination of NIR and chemometric treatments for the on-line analysis of olive fruits and also for the quality parameters evaluation on olive oils and pastes which can enhance the production of a high quality olive oil and the selection of olive fruit with superior properties. The implementation of NIR sensors in olive mills with successful results has also been reviewed and the commercial olive fruit and oil analyzers highlighted.

Pesticide Industries Air Quality

Determination of nitrogen in hydrolyzed protein formulations by continuous vapour phase FTIR.

An on-line system with vapour generation (VG) and Fourier transform infrared (FTIR) spectrometric detection has been developed for the determination of free ammonium and organic nitrogen in agrochemical formulations containing hydrolyzed proteins. Commercial samples were digested, in batch mode, with sulphuric acid and the obtained solution was alkalinized on-line to transform the NH(4)(+) to NH(3) that was continuously monitored by FTIR. Free ammonium was determined in the same system after simple dilution of undigested samples with water. Different gas phase separators were assayed in order to introduce gaseous NH(3) into a home made IR gas cell of 10 cm pathlength, where the correspondin…

Comparative study of different approaches for the flow injection-fourier transform infrared determination of toluene in gasolines.

Abstract A single channel flow injection manifold has been employed to carry out the direct determination of toluene in gasolines by FT—IR without any sample pretreatment and by using different strategies. Toluene can be directly determined by measuring the absorbance at 728 cm −1 , using a base line established between 835 and 575 cm −1 ; and in this case a limit of detection of 0.01% (v/v) can be obtained with a dynamic range up to 2% (v/v). In some cases it could be convenient to determine toluene by derivative flow-injection FT—IR in order to avoid matrix interferences in the analysis of some types of gasolines. Carrying out the first order derivative FI—FT—IR measurements on the 728 cm…

Microwave muffle furnace assisted decomposition of vegetable samples for flame atomic spectrometric determination of Ca, Mg, K, Fe, Mn and Zn

Calcium, magnesium, potassium, iron, manganese and zinc can be accurately determined in vegetable samples by flame atomic absorption and flame emission spectrophotometry after a previous dry ashing of the sample in a microwave muffle furnace. This treatment is carried out in 45 min using a new accessory developed by us to obtain high temperatures on a domestic microwave oven. Sample ashes, obtained in the muffle, are diluted with nitric acid and the obtained slurry is introduced directly into an air-C2H2 flame for the analysis of Fe, Mn, and Zn, or injected into a double-channel FIA manifold to determine Ca, Mg and K. The obtained results agree with those certified and also with those obtai…

Seafood freshness determination through vapour phase Fourier transform infrared spectroscopy.

Abstract A new vapour-phase manifold has been developed to determine trimethylamine (TMA) in fish and cephalopod samples by Fourier transform infrared (FT-IR) spectroscopy. Samples were treated off-line for 1 h with trichloroacetic acid (TCA), filtered and washed. The obtained extracts were aspirated and alkalinized with NaOH 2.0 M, in an on-line system. TMA was separated from the solution in a gas phase separator and then transported by means of a nitrogen carrier into a home made 10 cm pathlength IR gas cell, where the corresponding FT-IR spectra were acquired by accumulating 30 scans per spectrum with 2 cm−1 nominal resolution. The method was applied to the determination of TMA in natura…

FTIR TENTATIVE CHARACTERIZATION OF HUMIC ACIDS EXTRACTED FROM ORGANIC MATERIALS

Turkish humic acids, extracted from different materials, were characterized by their infrared spectra and by means of acidity measurements. The information obtained is of great interest to ascertain the nature and origin of humic acid samples.

Low-temperature phosphorescence of 1,4-benzodiazepines

Abstract A highly sensitive method for the low-temperature phosphorescence determination of a series of 1,4-benzodiazepines has been developed. Oxazepam has been used as a test molecule to study the effects of instrumental parameters, such as time decay, gate time, excitation and emission slits, and ordinate, on the phosphorescence spectra. The corresponding analytical parameters have been established for different concentration levels. Under the best sensitivity conditions a limit of detection of 16 parts per trillion (ppt) for oxazepam, 3.8 ppt for medazepam, 2 ppt for prazepam, 5 × 10 −3 ppt for diazepam, and 0.09 ppt for lorazepam could be obtained. The proposed method is thus the most …

Preliminary results on the influence of car characteristics on their gases emissions using gas sensors

Abstract A method, based on the use of monitoring portable sensors, has been successfully employed for the determination of the composition of car exhausts from 11 diesel and 5 gasoline cars. These emissions include nitrogen oxides (NOx), carbon monoxide (CO), carbon dioxide (CO2) and volatile organic compounds (VOCs). The measures were taken in different places where each car was parked. In this study it has been tried to correlate the emitted gases with some of the car characteristics, such as the power (varied from 68 to 143 HP), the number of kilometers traveled and the age of the car (between 2 and 19 years). Results found show a significant variation of the emission values, which rang…

Stopped-flow Fourier-transform infra-red spectrometric speciation of glycolic and lactic acids in cosmetic formulations

The dermatological activity of cosmetic formulations containing alpha-hydroxyacids depends on their different chemical forms, and it is therefore useful to determine these species in the finished products. In the present report a new procedure for studying the protonation equilibria of glycolic and lactic acids by stopped-flow Fourier-transform infra-red (FTIR) spectrometry is described. The procedure was validated for use in the speciation of glycolic and lactic acids in cosmetic formulations, with preferential attention given to glycolic acid, which is the most widely used. Species of these alpha-hydroxyacids can be approximately determined at different pHs and the total content of each a…

Multivariate data analysis and bivariate regression studies applied to comparison of two multi-elemental methods for analysing wine samples

Two inductively coupled plasma mass spectrometry (ICP-MS) methods which permit multi-elemental analysis in wine samples have been compared following two strategies. First, a multivariate tool based on principal component analysis (PCA) was employed for a global (all analytes) qualitative comparison of the two methods. A single plot based on the confidence limits of the Q and T2 PCA model statistics corresponding to the ‘standard’ method results (calibration set) was used to check the comparability of the ‘candidate’ method (test samples). The residual matrix (after test matrix interpolation into the PCA model) gives qualitative information about the nature of the main errors. This approach …

Organochlorinated pesticides in sediments from the Lake Albufera of Valencia (Spain).

Bottom sediment samples from 121 sites of the Lake Albufera of Valencia were analyzed. Dieldrin, endrin, heptachlor and op'-DDT were not detected (0.01 ng g(-1)) in 88-93% of the sites. Aldrin and HCB concentration ranges were between0.01 and 0.1 ng g(-1) in 86% and 94% of the sites, respectively. Heptachlor-epoxide and lindane 95% confidence intervals were 0.2-0.5 and 0.06-0.12, respectively. The greatest average concentration corresponds to pp'-DDE, pp'-DDD and pp'-DDT. The sum of six isomers and derivatives of the DDT average concentration reaches 2.1 ng g(-1), as opposed to 2.7 ng g(-1) for the sum of 13 pesticides considered. In the site with a major contamination, 27.0 ng g(-1) of pp'…

Slurries Introduction in Flow Injection Atomic Absorption Spectroscopic Analysis of Sewage Sludges

Abstract The direct introduction of slurries in flow Injection-flame atomic absorption spectroscopy has been studied using a single-channel manifold. The influence of flow Injection parameters on the sensitivity and accuracy of this procedure has been established. A method has been developed for the determination of copper, manganese, and lead In sewage sludge where batch digestion of the samples In a microwave oven is carried out before dilution. Both sensitivity and limit of detection of the flow Injection analysis procedure are adequate for the analysis of actual samples (the limit of detection was 0.06, 0.05, and 0.3 ppm for copper, manganese, and lead, respectively). The accuracy of th…

Comparison of two partial least squares infrared spectrometric methods for the quality control of pediculosis lotions.

Two vibrational spectroscopy procedures have been developed and compared for the direct and simultaneous determination of piperonyl butoxide and tetramethrin, the active ingredients of alcoholic capillary lotions, for hair pediculosis diseases. Nine lotions, purchased from the Spanish market, were analyzed using both, attenuated total reflectance (ATR) and transmission FT-IR measurements, and based on the use of partial least squares (PLS) multivariate calibration. A reduced set of 15 matched standards (11 for calibration and 4 for validation) was employed using both measurement modes. The spectral wave number ranges between 1757 and 1712 cm(-1) was selected to determine tetramethrin by bot…

Determination of lecithin and soybean oil in dietary supplements using partial least squares-Fourier transform infrared spectroscopy.

Lecithin and soybean oil in dietary supplements were determined by Fourier transform infrared spectrometry transmission measurements in dichloromethane in combination with a partial least squares (PLS) regression. Two different PLS models were developed, using 16 synthetic mixtures of analytes in dichloromethane, making measurements in the spectral range from 931.8 to 1252.3 cm(-1) for lecithin and from 911.4 to 1246.9 cm(-1) and 1695.3 to 1774.5 cm(-1) for soybean oil. Seven products from the Spanish market with lecithin concentrations between 21.1% and 99.1% and soybean oil concentrations between 0% and 37.2% were analyzed by the proposed method and the data was compared to a chromatograp…

Spectrophotometric determination of phenol and resorcinol by reaction with p-aminophenol

Abstract Based on the reaction with p-aminophenol, a series of procedures have been developed for the spectrophotometric determination of phenol and resorcinol. Three basic approaches have been studied: (i) a batch procedure, using the dissolved oxygen as oxidant, (ii) a stopped-flow procedure by use of KIO4 as oxidant and (iii) a flow injection (FI) procedure developed in the presence of KIO4. Phenol can be accurately determined at 626 nm, in the stopped-flow mode, after a reaction time of 45 min in 0.005M NaOH, 0.004M KIO4 and 500 μg/ml of PAP. The development of a manifold, which incorporates a sample parking, is a convenient approach which makes it possible to measure, in the stopped-fl…

Separation of motor oils, oily wastes and hydrocarbons from contaminated water by sorption on chrome shavings

In this paper, the ability of chrome shavings to remove motor oils, oily wastes and hydrocarbons from water has been studied. To determine amount of hydrocarbons sorbed on tanned wastes, a FT-NIR methodology was used and a multivariate calibration based on partial least squares (PLS) was employed for data treatment. The light density, porous tanned waste granules float on the surface of water and remove hydrocarbons and oil films. Wastes fibers from tannery industry have high sorption capacity. These tanned solid wastes are capable of absorbing many times their weight in oil or hydrocarbons (6.5-7.6g of oil and 6.3g of hydrocarbons per gram of chrome shavings). The removal efficiency of the…

Determination of biochemical parameters in human serum by near-infrared spectroscopy

NIR offers multiple advantages for serum analysis, permitting a fast and direct determination of several parameters simultaneously, with low sample handling and without the need for reagents during the measurement step. The aim of this paper was to provide an evaluation of this technique in a real world scale, for the simultaneous determination of several parameters and based on a considerable number of samples. Direct near infrared (NIR) absorbance measurements were used to determine the concentration of clinical parameters in human serum that are required in routine biochemical tests. Total protein, albumin, total cholesterol, high-density lipoprotein (HDL cholesterol), low-density lipopr…

Some observations on the determination of the methyl parathion-parathion ratio in binary mixtures by infrared spectroscopy

Abstract The determination of the methyl parathion/parathion ratio in binary mixtures has been carried out by infrared spectroscopy using a simple and easy model for the treatment of the spectra obtained from sample thin films using sodium chloride windows. The model is based on the use of two bands, one at 974 cm−1, characteristic of parathion, and other at 1348 cm−1, common to both compounds. From the spectra of pure parathion samples and mixtures of known composition of methyl parathion and parathion, two constants have been obtained. These constants relate the absorption of each compound at 1348 cm−1 to the absorption of parathion at 974 cm−1. Eighteen synthetic samples have been analyz…

Environmental impact of Recover cotton in textile industry

A comparative evaluation of the life cycle assessment (LCA) of Recover cotton, obtained from recycled garments, and virgin one, cultivated from traditional and organic crops, has been made based on the quantification of environmental impact categories, such as abiotic depletion, global warming, water use, acidification and eutrophication potential. LCA data reported in the literature for the steps of cultivation, ginning/cutting, and dyeing were compared in order to clearly show the environmental advantages of moving from traditional practices, to organic cultivation and the use of Recover cotton, a novel procedure that involves the production of cotton yarns from coloured and well characte…

Eucalyptol-based green extraction of brown alga Zonaria tournefortii

Abstract A green extraction method, based on the use of 1,8-cineole (eucalyptol) as biosolvent, has been developed to prepare crude extracts from the brown alga Zonaria tournefortii characterized by chemical composition, particularly dominated by phenolic compounds derived from phloroglucinol. The main advantage of the developed technique are the recovery of eucalyptol, based on multistep liquid-liquid extraction with distilled water, followed by centrifugation and elimination of the aqueous phase, and the complete recycling of biosolvent by steam distillation. A comparative study between the proposed green extract and the conventional extract, prepared by solvent maceration using the mixtu…

Essential oil counterfeit identification through middle infrared spectroscopy

Abstract Infrared spectroscopy (FTIR) has been employed for a fast quality control of commercial essential oils from different plant species. 47 samples were obtained from Algerian and Spanish market and directly measured, without any previous treatment, by attenuated total reflectance Fourier transform Infrared spectroscopy (ATR-FTIR), in the wavenumber region between 4000 and 550 cm−1. Pure essential oils were obtained by hydro- and steam-distillation extraction methods and their ATR spectra obtained. Results found evidenced the presence of solvents in some commercial formulations and permitted a rapid authentication of pure essential oils correctly extracted from those diluted. The propo…

The use of mathematical models in the characterization of ethylene oxide condensate Surfactants by infrared and ultraviolet spectroscopy

A topological treatment of the surfactant molecules (DARC system) and a group contribution model were applied to study the correlation between structures of ethylene oxide condensates with nonylsphenol and tert-octylphenol and their spectral characteristics such as extinction coefficient of the molecular absortion band. Using the experimental values of the spectral characteristics of an unknown smaple of an ethylene oxide condensate surfactant and the information parameters, previously determined by the mathematical treatment of a key population, it is possible to obtain their average condensation degree.

Fluorimetric determination of binding constants between micelles and chemical systems

Abstract A fluorimetric method is adapted to determine the binding constants (K) between different systems and micelles. The method is based on the variation of the fluorescence of the system in the presence of increasing amounts of a surfactant agent. This method permits the determination of binding constants in strong acid or alkaline media. The binding constants of 1-naphthol and 2-(4-alkylamino-2 hydroxyphenyl)benzo-X azoles (X being an O or an S atom, PAS-O and PAS-S) with cationic, anionic, and nonionic surfactants have been determined by the proposed method. Values from 49,100 M−1 for the interaction between PAS-S and CTAB in basic medium to 10 M−1 for the interaction of 1-naphthol w…

Simultaneous determination of hydride and non-hydride forming elements by inductively coupled plasma optical emission spectrometry

e percentagens de recuperacao entre 97 e 103%. A aplicabilidade do sistema foi demonstrada na determinacao simultânea de Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Zn, As, Bi, Sb, Se e Te em amostras certificadas para elementos tracos, NIST 1549 (leite em po desnatado), NIST 1570a (folhas de espinafre), DORM-2 (musculo de cacao) e TORT-2 (hepatopâncreas de lagosta). Os resultados obtidos foram concordantes com os teores certificados. The operating characteristics of a dual nebulization system were studied including instrumental and chemical conditions for the hydride generation and analytical figures of merit for both, hydride and non hydride forming elements. Analytical performance of the neb…

Pollutants and Air Pollution

Spectrophotometric determination of ethiofencarb in waters by reaction with p-aminophenol

An automatized procedure has been developed for the spectrophotometric determination of ethiofencarb in water by reaction with p-aminophenol after alkaline hydrolysis to obtain the corresponding phenol sulphone. The hydrolyzed samples are continuously introduced into different manifolds at the same time as 300 mg/l p-aminophenol, 0.004 mol/l KIO4 and 0.04 mol/l NaOH solutions. The absorbance is measured at 638 nm after a reaction time of 6 min in stop flow. This absorbance band corresponds to the indo dye obtained from the reaction between the phenol sulphone of ethiofencarb and the quinoneimine form of the p-aminophenol and it permits a matrix-free spectrophotometric determination of ethio…

Non-chromatographic speciation of inorganic arsenic in mushrooms by hydride generation atomic fluorescence spectrometry

Abstract A non-chromatographic speciation method has been developed for the determination of inorganic arsenic in cultivated and wild mushroom samples from different origins. The ultrasound-assisted extraction of the toxic arsenic species As (III) and As (V) was performed for 10 min with 1 mol l −1 H 3 PO 4 and 0.1% (m/v) Triton X-100. After phase separation the residue was washed with 0.1% (w/v) EDTA and centrifuged. As (III) and As (V) were determined by hydride generation atomic fluorescence spectrometry. Speciation was made using proportional equations corresponding to two different measurement conditions, (i) directly feeding sample extracts diluted with HCl and (ii) after reduction wi…

Evaluation of infrared spectroscopy as a screening tool for serum analysis

Abstract The application of attenuated total reflectance Fourier transform infrared (ATR-FT-IR) spectroscopy to the determination of clinical parameters in serum using partial least squares (PLS) has been evaluated as a point-of-care diagnostic tool. In this study the effect of using an increased size of the calibration set and the influence of the origin of samples and their interyear variation on the prediction capability of the method were considered. PLS-ATR-FT-IR provides a green, fast and cheap point-of-care tool for the determination of total protein. Albumin, glucose, urea, HDL, LDL and total cholesterol were predicted with relative errors between 15 and 32%. The analytical predicti…

Near-infrared diffuse reflectance spectroscopy and neural networks for measuring nutritional parameters in chocolate samples.

Abstract A rapid and non-destructive method has been developed for the characterization of chocolate samples based on diffuse reflectance near-infrared Fourier transform spectroscopy (DRIFTS) and artificial neural networks (ANNs). This methodology provides a potentially useful alternative to time-consuming chemical methods of analysis. To assess its utility, 36 chocolate samples purchased from the Spanish market were analyzed for the determination of the main nutritional parameters like carbohydrates, fat, proteins, energetic value and cocoa content. Direct triplicate measurements of each sample were carried out by DRIFTS. Cluster hierarchical analysis was used for selecting calibration and…

Recent advances in on-line liquid chromatography - infrared spectrometry (LC-IR)

We review advances in isocratic and gradient liquid chromatography hyphenated on-line with infrared spectrometry (LC-IR). We place special emphasis on chemometric background correction and other applications of chemometric algorithms used to improve the sensitivity and the resolution of LC-IR signals. We also comment on recent technical advances, (e.g., dedicated flow-cells and new light sources) and review applications in the technological, cosmetics, environmental and food sectors.

Determination of total phenolic compounds in compost by infrared spectroscopy

Abstract Middle and near infrared (MIR and NIR) were applied to determine the total phenolic compounds (TPC) content in compost samples based on models built by using partial least squares (PLS) regression. The multiplicative scatter correction, standard normal variate and first derivative were employed as spectra pretreatment, and the number of latent variable were optimized by leave-one-out cross-validation. The performance of PLS-ATR-MIR and PLS-DR-NIR models was evaluated according to root mean square error of cross validation and prediction (RMSECV and RMSEP), the coefficient of determination for prediction ( R pred 2 ) and residual predictive deviation (RPD) being obtained for this la…

Immobilization of vegetable tannins on tannery chrome shavings and their use for the removal of hexavalent chromium from contaminated water

Abstract Chestnut (C) and mimosa (M) tannins immobilized on chrome shavings (CS) as an adsorbent have been proposed to be an efficient and economical alternative in hexavalent chromium removal from aqueous solutions. The adsorption of hexavalent chromium onto chrome shavings-tannin (CS-T) adsorbents was performed using batch equilibrium technique at 25 ± 2 °C. The effect of pH is highly important especially in the case of high concentrations of hexavalent chromium. The maximum chromium uptake was obtained at pH 4. Two hours of contact time are enough to reach equilibrium. Sorption of chromium on CS-T was found to follow a pseudo-second order kinetic model (with correlation coefficients grea…

Authentication of Alicante’s Mountain cherries protected designation of origin by their mineral profile

Abstract Chemometric analysis of inductively coupled plasma optical emission spectroscopy (ICP-OES) data was employed to verify the origin of cherry samples of different areas of Spain: Aragon, Caceres, Castellon, Huesca and Alicante’s Mountain Protected Geographic Indication (PGI). The ability of multivariate analysis methods, such as discriminant analysis (DA), was used to achieve cherry classification from their mineral content. The study was performed using 22 variables (concentrations of Al, As, B, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Se, Sr, Ti and Te) and 23 variables (concentrations of Al, As, B, Ba, Be, Bi, Ca, Cd, Cr, Cu, Fe, K, Li, Mg, Mo, Na, Ni, Pb, Se, Sr…

Determination of insolubles in diesel lubricating oil by FIA-visible spectrometry

Insolubles determination is one of the parameters usually recommended to evaluate the residual life of oil because their presence at elevated levels in diesel lubricating oil changes the viscosity, prematurely clogs filters and is one of the major factors in causing abrasive engine wear. The proposed method employs visible spectrophotometric detection in association with flow injection analysis. The results obtained by this method were compared with the ones obtained by Fourier transform infrared spectrometry (FT-IR) since this is the most employed method for insolubles determination. The proposed method presented a linear response from 0 to 3% (w/w) of insolubles in pentane (ASTM D-893). T…

Inductively coupled plasma optical emission spectroscopy determination of trace element composition of argan oil.

A methodology based on inductively coupled plasma optical emission spectroscopy (ICP-OES) after microwave assisted acid digestion has been developed to determine the trace element content of Moroccan argan oil. Limit of detection values equal or lower than few mg/kg were obtained for all elements under study. To assure the accuracy of the whole procedure, recovery studies were carried out on argan oil samples spiked at different concentration levels from 10 to 200 µg/L. Quantitative average recovery values were obtained for all elements evaluated, demonstrating the suitability of this methodology for the determination of trace elements in argan oil samples. Aluminum, calcium, chromium, iro…

Ion mobility spectrometry and high resolution mass-spectrometry as methodologies for rapid identification of the last generation of new psychoactive substances

A new drug trafficking trend has been observed in the last years by the introduction in the black market of new psychoactive substances (NPS) in order to difficult competent authority controls. In this study, ion mobility spectrometry (IMS) and high-resolution mass-spectrometry (HRMS) were proposed as vanguard and rearguard methodologies for the rapid identification of the last generation of NPS in seizures. The combined use of IMS and HRMS has been evaluated through the analysis of 24 NPS seized from 2016 to 2018 in Valencia (Spain) to demonstrate the utility of this approach. The characteristic reduced mobility (K0) values for seized NPS were determined and mass-mobility relationships wer…

Mid-infrared and Raman spectrometry for quality control of pesticide formulations

This article deals with recent developments in the use of vibrational spectrometry for the quantitative analysis of active components in commercial pesticide formulations. We review the techniques, such as Fourier transform infrared (FTIR) and FT-Raman spectrometries, and measurement modes, such as stopped flow or flow injection. FTIR is being used increasingly in the determination of pesticides in agrochemical products because of its relatively short analysis time. However, FT-Raman spectrometry provides direct analysis of solid and aqueous samples. It is therefore clear that these techniques enable fast, non-destructive, precise and accurate measurements, so vibrational spectrometry appea…

Fourier transform infrared analysis of commercial formulations for Varroa treatment

A comparative study has been carried out between univariate and multivariate calibration strategies for the simultaneous determination of camphor, thymol, menthol and eucalyptol in commercial formulations used for Varroa treatment. Absorbance peak heights of the transmission mid-infrared (MIR) spectra of individual monoterpenes, prepared in dichloromethane, were measured at 1737, 1151, 1022 and 980 cm−1 (corrected with a base-line at 1933 cm−1) for camphor, thymol, menthol and eucalyptol, respectively. Data were processed using the proportional equations approach in univariate mode. For multivariate calibration, partial least squares (PLS) regression based on a classical 42 design for stand…

Flow injection flame atomic spectrometric determination of iron, calcium, magnesium, sodium and potassium in ceramic materials by using a variable-volume injector

A series of different ceramic materials, such as porcelain, feldspar, kaolin, varnish, clay and stoneware have been analyzed. Iron, calcium and magnesium have been determined in these materials by flame atomic absorption and sodium and potassium by flame emission. The use of a variable-volume injector enables one to carry out these analyses in a flow system (after fusion of samples with lithium metaborate) and does not require different dilutions for the determination of each type of sample considered, nor the use of different flow injection manifolds. The developed procedure provides a limit of detection of 100 μg/l for Na, 70 μg/l for Ca, 50 μg/l for both Fe and K and 8 μg/l for Mg. The c…

Analytical methodologies for chromium speciation in solid matrices: a survey of literature

The analytical literature about chromium speciation in solid samples has been surveyed. From 451 articles published on the speciation of chromium from 1983 to 1997, the methodologies to do speciation in solids after sample pretreatment are discussed, through consideration of the types of samples and their dissolution, the analytical techniques employed for chromium measurement, and the figures of merit of the 86 papers reported in the Analytical Abstracts data base.

Optimization of a microwave-assisted extraction large-volume injection and gas chromatography–ion trap mass spectrometry procedure for the determination of polybrominated diphenyl ethers, polybrominated biphenyls and polychlorinated naphthalenes in sediments

Abstract A sensitive and rapid method for the determination of polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and polychlorinated naphthalenes (PCNs) in sediment samples is proposed. The method involving microwave-assisted extraction (MAE) and large-volume injection (LVI) gas chromatography (GC)–ion trap mass spectrometry (ITMS), and the experimental conditions were optimized using the statistical design of experiments (DOE). A Plackett–Burman (P–B) design was chosen to estimate the influence of five factors, such as resonance excitation voltage (EV), isolation time (IT), excitation time (ET), ion source temperature (IST) and electron energy (EE) on the analytical r…

Non-chromatographic speciation

We evaluate the main strategies for screening trace-element species in most types of sample to establish their strengths and weaknesses, as they offer fast, sensitive and cheaper alternatives to classical methods involving chromatography. We consider the principles of non-chromatographic speciation analysis, based on the different behaviors of chemical species before measurement by atomic and molecular spectrometry and electroanalytical methods, so as to give an update on the literature in this field of research.

Analytical Process

Simple variable-volume injector for flow-injection systems

Abstract A simple and versatile variable-volume injector is described for the introduction of samples in flow-injection systems. The device delivers precisely and reproducibly (usually r.s.d.

Simultaneous Kinetic Determination of Carbamate Pesticides after Derivatization withp-Aminophenol by Using Partial Least Squares

Abstract A method has been developed for the fast spectrophotometric determination of propoxur, carbaryl, and ethiofencarb in water samples using injection analysis in the stopped-flow mode. The method is based on the reaction between p -aminophenol and the phenolic compounds obtained from the pesticides, after a previous hydrolysis with 0.05 M NaOH at room temperature for 15 min. The partial least-squares treatment of the spectrophotometry kinetic data provides a simultaneous determination of the three carbamate pesticides assayed with a relative accuracy error lower than 5% in complex mixtures also containing formetanate, which is only partially hydrolyzed under the experimental condition…

Fast authentication of tea tree oil through spectroscopy

Two new procedures, based on infrared spectroscopy in the near infrared (NIR) and mid infrared (MIR), have been developed for the authentication of tea tree oil (TTO) commercial samples. Infrared measurements were made on untreated samples by transmission NIR and attenuated total reflectance (ATR) followed by partial least square discriminant analysis (PLS-DA). These methods offer a fast and low cost alternative to enantiomeric two-dimensional gas chromatography coupled to mass detection usually employed to discriminate between authentic and non-authentic samples. In these studies, a set of 267 samples, including authentic and non-authentic labelled tea tree oil samples, were used to build …

Headspace–mass spectrometry determination of benzene, toluene and the mixture of ethylbenzene and xylene isomers in soil samples using chemometrics

A simple and fast method has been developed for the determination of benzene, toluene and the mixture of ethylbenzene and xylene isomers (BTEX) in soils. Samples were introduced in 10 mL standard glass vials of a headspace (HS) autosampler together with 150 microL of 2,6,10,14-tetramethylpentadecane, heated at 90 degrees C for 10 min and introduced in the mass spectrometer by using a transfer line heated at 250 degrees C as interface. The volatile fraction of samples was directly introduced into the source of the mass spectrometer which was scanned from m/z 75 to 110. A partial least squares (PLS) multivariate calibration approach based on a classical 3(3) calibration model was build with m…

Extraction of polycyclic aromatic hydrocarbons from cookies: a comparative study of ultrasound and microwave-assisted procedures.

The chromatographic determination of 15 polycyclic aromatic hydrocarbons (PAHs) in cookies has been improved in order to obtain a fast method with a low limit of detection through the combination of microwave-assisted extraction (MAE), oil saponification and solid-phase extraction clean-up before the injection of purified extracts in a C18 201TP52 (5 microm, 250 x 2.1 mm) column. Using acetonitrile-water as mobile phase, with a 50% to 95% w/w acetonitrile gradient for a fixed flow of 0.250 ml min(-1), 15 PAHs were separated in 45 min. The column temperature was maintained at 15 degrees C; and fluorimetric detection was made at a fixed excitation wavelength of 264 nm and emission measurement…

Exposure of heat-not-burn tobacco effect on the quality of air and expiratory plume

Abstract The increasing interest to avoid the consumption of regular tobacco has lead in the development of several types of devices to decrease the effects of this practice on active and bystanders. In this work, the impact of the use of new heat-not-burn (HnB) devices has been evaluated and compared with that of regular cigarettes and electronic cigarettes (e-cigs). Portable monitoring devices were employed for CO, CO2, particulate matter (PM) and volatile organic compounds (VOCs) to evaluate the quality of indoor air and expiratory plume of both, active and passive, users during these practices. It can be noticed that the levels of VOCs in active HnB smokers expiratory air are five times…

Rapid hydrolysis of benzodiazepines to benzophenones in a microwave oven

Abstract A microwave oven is used to carry out the complete hydrolysis of diazepam to the corresponding benzophenone in only 10 min, at 650 W, with good recovery. The reaction yield is evaluated by first-derivative UV spectrophotometry.

A comparative study of flame atomic-absorption methods for determination of zinc in serum and blood plasma

Seven selected methods for determination of zinc in blood plasma by flame atomic-absorption spectroscopy have been compared. Analytical characteristics such as sensitivity, detection limit, precision, analytical recovery, accuracy and physical interferences were studied. Two of the seven methods are recommended as the most suitable for the purpose.

Searching the most appropriate sample pretreatment for the elemental analysis of wines by inductively coupled plasma-based techniques.

Different sample preparation methods were evaluated for the simultaneous multielement analysis of wine samples by inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). Microwave-assisted digestion in closed vessel, thermal digestion in open reactor, and direct sample dilution were considered for the determination of Li, Be, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Y, Mo, Cd, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Tl, Pb, and Bi in 12 samples of red wine from Valencia and Utiel-Requena protected designation of origin. ICP-MS allows the determination of 17 elements in most…

Analytical Approaches for the Evaluation of Food Protected Designation of Origin

Abstract The state of the art analytical methodologies used to authenticate the origin and composition of foods will be presented in the frame of the protected designation of origin for European labels. The aforementioned labels guarantee the origin and good production practices in the elaboration of foods for human consumption. Target analytes and analytical procedures, together with the chemometric tools used to discriminate foods from different areas or production methods, will be presented and critically discussed. Examples of some of the most commonly evaluated foods in the scientific literature will be also included.

A clean analytical method for the spectrophotometric determination of formetanate incorporating an on-line microwave assisted hydrolysis step

Abstract A fast and completely automated procedure is proposed for the spectrophotometric determination of formetanate in waters by means of its reaction with p-aminophenol (PAP). The method involves the on-line alkaline hydrolysis of formetanate to m-aminophenol (MAP) and its reaction, in the presence of KIO 4 as oxidant agent, with the quinoneimine form of PAP, to form a blue indophenol dye which absorbs at 576 nm. The on-line hydrolysis can be carried out in a 6 m reaction coil located inside the cavity of a domestic microwave oven operated at 650 W, or in a 4 m reaction coil located inside the cavity of a Microdigest 301 microwave system operated at 60 W and allows us, in both cases, a …

Determination of arsenic compounds in beverages by high-performance liquid chromatography-inductively coupled plasma mass spectrometry.

Arsenic compounds including arsenous acid (As(III)), arsenic acid (As(V)), dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA) were separated by high-performance liquid chromatography (HPLC) and detected by inductively coupled plasma mass spectrometry (ICP-MS). A Hamilton PRX-100 anionic-exchange column and a pH 8.5 K(2)HPO(4)/KH(2)PO(4) 5.0x10(-3)molL(-1) mobile phase were used to achieve arsenic speciation. The separation of arsenic species provided peaks of As(III) at 2.75min, DMA at 3.33min, MMA at 5.17min and As(V) at 12.5min. The detection limits, defined as three times the standard deviation of the lowest standard measurements, were found to be 0.2, 0.2, 0.3 and 0.5ngmL(-1) f…

Determination of aluminum at the parts per billion level by solvent extraction and flame atomic emission spectrometry

A new method for the determination of aluminum at the parts per billion level, by N 2 O/ C 2 H 2 flame emission spectrometry with prior solvent extraction with acetylacetone or 8-hydroxyquinoline in 4-methylpentan-2-one, has been performed. The influence of extraction conditions and instrumental parameters on the sensitivity, precision, and dynamic range of the emission calibration curves have been studied. The limit of detection is between 5 and 10 ppb for both ligands, the variation coefficient being 0.2 and 3% at levels of 75 and 25 ppb, respectively. The method has been applied to the determination of Al in water and the results obtained are compared with those found by the standard add…

Determination of vinegar acidity by attenuated total reflectance infrared measurements through the use of second-order absorbance-pH matrices and parallel factor analysis

Univariate (zero-order), multivariate (first-order) and multiway (second-order) calibrations were assayed for the determination of vinegar acidity using a mechanized procedure based upon vibrational spectroscopy and the emerging multicommutation methodology. The second-order methodology relies on the use of a flow system based on multicommutation and binary sampling. The flow network comprises a set of three-way solenoid valves, computer-controlled to provide facilities to handle the sample and to generate a time-dependent pH gradient using two carrier solutions. The procedure is based on the volumetric fraction variation approach that maintains the same volume of sample solution and dynami…

Preliminary Results on the Use of Leather Chrome Shavings for Air Passive Sampling

A new passive sampler based on low-density polyethylene (LDPE) layflat tube filled with chrome shavings from tannery waste residues was evaluated to determine volatile organic compounds (VOCs) in indoor and outdoor areas. VOCs were directly determined by head space-gas chromatography-mass spectrometry (HS-GC-MS) without any pretreatment of the sampler and avoiding the use of solvents. Limit of detection values ranging from 20 to 75 ng sampler−1and good repeatability values were obtained for VOCs under study with relative standard deviation values from 2.8 to 9.6% except for carbon disulfide for which it was 22.5%. The effect of the amount of chrome shavings per sampler was studied and resul…

Removal of hexavalent chromium from wastewaters by bone charcoal

The adsorption of hexavalent chromium onto bone charcoal was studied as a function of time, amount of charcoal, pH, concentration of chromium and sample volume. The cross interference with other elements was also investigated. Tests were carried out with solutions of chromium(VI) at concentrations between 5 and 25 mg · L–1. Chromium removal efficiencies higher than 90% were achieved at pH = 1 using 2 g of bone charcoal and a stirring time in the order of 30 min. Acid and alkaline pretreatments of bone charcoal did not improve the sorption capacity of bone charcoal against Cr(VI). The presence of other ions had practically no influence on the chromium removal. The presence of a matrix of tan…

The importance of incorporating a waste detoxification step in analytical methodologies

The introduction of a waste detoxification step in the analytical process was highlighted using, as example, the determination of copper in pesticide formulations using electrogravimetry, flame atomic absorption spectroscopy and inductively coupled plasma optical emission spectroscopy. This quantitative study showed the improvement of the previously mentioned analytical methods, from a green perspective, after addition of electrodeposition or neutralization steps to the analytical process. Based on this, the application of the eco-scale and the Green Certificate to the evaluation of these methodologies allows the method to be moved from the B and C classes to the A class.

Influence of the differentiation system on the analytical parameters for the spectrophotometric determination of clonazepam in urine

Abstract Electronic and mathematical differentiation of the ultraviolet visible spectra were compared from the study of the analytical parameters of the direct determination of clonazepam in urine samples. Third-order derivative spectra were used. The mathematical differentiation provides higher sensitivity, a lower limit of detection, and better accuracy and precision than the electronic one. The use of a diode array instrument provides lower sensitivity than that found using a conventional spectrometer; however, the limit of detection obtained in both cases is of the same order.

Direct FIA—AS determination of potassium and magnesium in cement samples by use of the slurries approach

A direct procedure has been developed for the flame atomic determination of potassium and magnesium in cement samples. A 50-mg sample is dispersed in 25 ml of 0.13M nitric acid; 100 mul of this slurry is injected in a double channel FIA manifold simultaneously with 100 mul of a 10% (w/v) lanthanum solution. This procedure allows the rapid extraction of potassium and magnesium by leaching of the sample; nitric acid is not necessary if only potassium must be determined and the sample can be diluted with only distilled water. Aqueous standards are used. The manifold employed includes a well-stirred mixing chamber, which provides an adequate on-line dilution of the sample, in order to obtain em…

Interaction of diazepam with surfactants. Spectrophotometric and spectrofluorometric study

Abstract The interaction of diazepam with non-ionic, anionic and cationic surfactants has been studied spectrophotometrically and fluorometrically. It has been verified that the absorption spectrum of diazepam is not modified in micellar medium. However, a dramatic five-fold increase in fluorescence sensitivity is observed in the presence of sodium lauryl sulphate (SDS). The experimental conditions, temperature, pH and surfactant concentration have been optimized to improve the fluorometric determination of diazepam and a detection limit of 0,04 ppmhas been obtained.

Trace-element composition and stable-isotope ratio for discrimination of foods with Protected Designation of Origin

We review the literature on authentication of foods with Protected Designation of Origin (PDO) from their trace-element composition or stable-isotope ratios in order to evaluate the state of the art of this field and to identify the main parameters of analytical techniques and chemometric-data treatments that permit accurate discrimination of samples of different geographical origins and with different characteristics.

Partial least squares modelization of energy dispersive X-ray fluorescence.

As a proof of concept, a green methodology has been developed for the energy dispersive X-ray fluorescence (ED-XRF) determination of calcium, potassium, iron, magnesium, aluminum, chromium, strontium, phosphorus and nickel in the peel of untreated kaki fruit (Diospyros kaki. L) samples. ED-XRF spectra of fifty-six kakis purchased in the local area of LLombay (Valencia) were obtained directly from samples without any previous treatment and without sample damage just after cleaning the fruit with distilled water. Inductively Couple Plasma Optical Emission Spectrometry (ICP-OES) was used as a reference method to determine the mineral elements after microwave assisted acid digestion. XRF spectr…

Microwave-assisted extraction of polybrominated diphenyl ethers and polychlorinated naphthalenes concentrated on semipermeable membrane devices

Abstract Microwave-assisted extraction (MAE) has been evaluated as an alternative to dialysis for the extraction of polybrominated diphenyl ethers (PBDEs) and polychlorinated naphthalenes (PCNs) sampled by semipermeable membrane devices (SPMDs), using gas chromatography coupled to tandem mass spectrometry (GC–MS–MS). For MAE optimization a two level full factorial design 2 3 , plus a centre point, which involves 11 randomized runs was used. The results showed that the temperature had a significant influence on the extraction of the nine PBDEs and four PCNs tested. Also, the solvent volume had a positive influence on the extraction of PBDEs and PCNs, but only in latter compounds, it achieves…

Kinetic, isotherm and thermodynamic studies of the adsorption of methylene blue dye onto agro-based cellulosic materials

AbstractThe purpose of this work is to establish the optimal experimental conditions for the removal of methylene blue (MB-as model basic dye) from aqueous solution by adsorption onto four agro-based materials, namely, cedar sawdust, pine sawdust, wheat straw, and Provence cane Arundo donax. Results show that an increase in acidity or ionic strength of the medium has generally a negative effect on the discoloration yield. From the data of pH effect, there is no need to change the initial pH of the MB solution to be treated. Equilibrium was reached after 20−30 min of agitation when cedar sawdust, pine sawdust, and Provence cane are used as adsorbents. However, in the case of wheat straw, an …

Fourier transform infrared determination of CO 2 evolved from carbonate in carbonated apatites

A quantitative method based on FTIR has been developed to determine carbonate in synthetic apatites. The method measures the evolved CO2 after reaction of 50 mg apatite with 2 mL of hydrochloric acid (0.5 M) in a reaction vessel, heated to 40 degrees C. The CO2 evolved was swept by a carrier of nitrogen to a laboratory-made infrared gas cell of 39 mm pathlength and 490 microL volume. The signals were recorded as a function of time and the areas of the chemigram peaks obtained from the measurements in the wavenumber range of 2,500-2,150 cm(-1), were interpolated using a calibration curve. The method can be used to study apatites with carbonate contents below 0.2% with a sampling frequency of…

Analytical methods for clinical diagnostics

Micellar enhanced fluorimetric determination of carbendazim in natural waters

Abstract A micellar enhanced flow-injection fluorimetric method was developed for the determination of carbendazim in natural water samples. The method is based on the direct injection of 500 μ1 of water into a three-channel flow manifold in which the samples are merged with a buffer solution and subsequently with a surfactant solution. Two alternative procedures were used: one based on the use of sodium dodecyl sulphate micelles in 0.1 M HCl, which permits a 2.6-fold enhancement of the sensitivity found in the absence of micelles to be obtained, and the other based on the use of cetyltrimethylammonium bromide in 0.1 M NaOH, which provides a 11.6-fold enhancement of sensitivity and a limit …

Surfactant Association: Recent Theoretical and Experimental Developments

A theoretical model describing the association of ionic surfactants into rod-shaped micelles is combined with an approximate formula for the viscosity increase induced by rod-shaped aggregates. It is shown that most of the thermodynamic parameters of the association model can be obtained from viscosity measurements. The approach is applied to micellar solutions of hexadecylpyridinium salts. The pronounced effect of counter-ion concentration on the growth of rod-shaped micelles can be attributed to a slightly higher degree of counter-ion association in the cylindrical part than in the end portions. An attempt is made to explain the finding that the degree of counter-ion association is virtua…

Determination of tea tree oil terpenes by headspace gas chromatography mass spectrometry

An alternative procedure was developed for determining quality control of terpenes in tea tree oil commercial samples. The method is based on static headspace gas chromatography mass spectrometry measurements. Absolute limits of detection ranged from 1 ng for p-cymene to 71 ng for terpinen-4-ol. The accuracy of the developed methodology was evaluated by comparing the obtained eucalyptol and terpinen-4-ol concentrations with those provided for a certified sample and by comparing the developed procedure with literature tea tree oil analysis methodology. In the same way, spiked commercial samples provided recovery values ranging between 94% and 100% for all the target analytes with relative st…

A multicommuted flow system with solenoid micro-pumps for paraquat determination in natural waters.

A flow system designed with solenoid micro-pumps is proposed for the determination of paraquat in natural waters. The procedure involves the reaction of paraquat with dehydroascorbic acid followed by spectrophotometric measurements. The proposed procedure minimizes the main drawbacks related to the standard chromatographic procedure and to flow analysis and manual methods with spectrophotometric detection based on the reaction with sodium dithionite, i.e. high solvent consumption and waste generation and low sampling rate for chromatography and high instability of the reagent in the spectrophotometric procedures. A home-made 10-cm optical-path flow cell was employed for improving sensitivit…

Vapor-phase introduction of alkyltin compounds in atomic absorption spectrophotometry

Abstract Different systems for the introduction of alkyltin compounds in atomic absorption spectrophotometry using the vapor-phase introduction approach have been compared. Samples and standards were introduced in both quartz cell and flame atomizer using a vertical and a horizontal reactor. The better sensitivity was obtained with the quartz cell and the horizontal reactor.

Microwave-assisted extraction of OCPs, PCBs and PAHs concentrated by semi-permeable membrane devices (SPMDs)

Abstract Microwave-assisted extraction (MAE) has been evaluated as an alternative to dialysis for extraction of some water-borne hydrophobic contaminants sampled by semi-permeable membrane devices (SPMDs). Seven organochlorine pesticides (OCPs), 11 polychlorinated biphenyls (PCBs) and 13 polycyclic aromatic hydrocarbons (PAHs) were accumulated in SPMDs at nanogram levels and extracted with three 3-min irradiation cycles with 33 mL of a solvent mixture hexane–water (10:1,v/v) in each cycle. The developed MAE method gave for all analytes investigated statistically comparable extraction yields with those found by dialysis carried out with a total volume of 250 mL hexane for 48 h at room temper…

Determination of the relative quantum yields of the conformational species of autoassociating polypeptide gramicidin A in organic solvent using combined fluorescence spectroscopy and high performance liquid chromatography

Abstract A simple, novel method is proposed for the accurate determination of the relative quantum yields of each of the interconverting conformational species of the autoassociating polypeptide gramicidin A in organic solution. The method is based on fitting the experimental results obtained independently from fluorescence emission spectroscopy and high performance liquid chromatography. The fluorescence parameters obtained are discussed in terms of the structural features of the individual conformational species. The advantages of this approach and its possible application to other different organic solvents or to other autoassociating polypeptides are also considered.

Geographical traceability of “Arròs de Valencia” rice grain based on mineral element composition

The geographical traceability of rice grain samples involves the use of analytical methodologies that allow their differentiation on the basis of the rice composition, thus confirming their authenticity. In this paper, trace element determination of rice samples by inductively coupled plasma optical emission spectroscopy (ICP-OES) has been addressed to achieve a complete geographical origin classification. Samples (107) from Spain including Valencia, Tarragona, Murcia and Extremadura, Japan, Brazil and India were employed as training set whereas the validation set was formed by 46 samples of the aforementioned geographical origins. Data were processed by linear discriminant analysis (LDA), …

Green Spectroscopy: A Scientometric Picture

ABSTRACT The state of the art of green spectroscopy, as a sustainable and friendly alternative to the classical spectrometric methods of analysis, has been established from the evaluation of the scientific literature published about this topic in the frame of the so-called Green Chemistry paradigm. Special attention has been paid to the fact that keywords like Green Analytical Chemistry, environmentally friendly, or clean analytical method or sustainable analytical chemistry are far from being commonly used in analytical studies. In spite of this fact there are numerous studies that provide direct analytical methodologies, or a reduction of reagents consumption or waste generation, the recy…

Direct determination of calcium, magnesium, sodium and potassium in water by flow injection flame atomic spectroscopy, using a dilution chamber

A simple procedure to carry out the direct analysis of calcium, magnesium, sodium and potassium in water by flow injection analysis (FIA) using flame atomic absorption spectroscopy (AAS) or flame photometry (FP) has been developed, using a well stirred dilution chamber to extend the calibration range, and both a double injector and the merging zone technique to add a lanthanum solution to samples and standards. The results obtained in the analysis of real samples agree with those found by a batch flame atomic procedure. The use of the dilution chamber makes it possible to carry out the calibration using the dilution profile of a single concentrate standard for each element, and an empirical…

Chemometric determination of arsenic and lead in untreated powdered red paprika by diffuse reflectance near-infrared spectroscopy.

It has been evaluated the potential of near-infrared (NIR) diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) as a way for non-destructive measurement of trace elements at microg kg(-1) level in foods, with neither physical nor chemical pre-treatment. Predictive models were developed using partial least-square (PLS) multivariate approaches based on first-order derivative spectra. A critical comparison of two spectral pre-treatments, multiplicative signal correction (MSC) and standard normal variate (SNV) was also made. The PLS models built after using SNV provided the best prediction results for the determination of arsenic and lead in powdered red paprika samples. Relativ…

Flow injection flame atomic absorption analysis of Fe and Mn in cement samples

A new procedure has been developed for the determination of Fe and Mn in cements. It consists in dispersing 50 mg of the solid sample in 25 ml of 0.15 mol/l HNO3 and 0.12 mol/l HCl solution. Acid slurries are heated at 50°C for 10 min and then different volumes of the slurry are injected into a water carrier stream. This previous acid treatment leaches the elements to be determined and permits the use of acid solutions as standards. For the Mn determination, the use of a single line flow injection manifold provides a limit of detection of 0.03 mgl−1 and a dynamic range up to 6 mgl−1. For the determination of Fe, the on-line dispersion of samples, using a well stirred mixing chamber, increas…

Preliminary studies about thermal degradation of edible oils through attenuated total reflectance mid-infrared spectrometry

Abstract Degradation of edible oils during their heating process has been evaluated through the determination of cis -unsaturation and trans -fatty acids together with free fatty acids as a function of time and temperature heating. Two types of cooking oils, sunflower and seed (mixture of different seeds non-detailed), were heated at three different temperatures (147, 171 and 189 °C) during a total time of 1920 min (32 h) shared out in four sessions of 8 h each one, and samples were studied from their spectra obtained by Fourier transform infrared spectrometry using attenuated total reflectance measurements. A critical comparison between different multivariate calibration models built based…

Trace analysis by ion mobility spectrometry: From conventional to smart sample preconcentration methods. A review.

Ion mobility spectrometry (IMS) is a rapid and high sensitive technique widely used in security and forensic areas. However, a lack of selectivity is usually observed in the analysis of complex samples due to the scarce resolution of the technique. The literature concerning the use of conventional and novel smart materials in the pretreatment and preconcentration of samples previous to IMS determinations has been critically reviewed. The most relevant strategies to enhance selectivity and sensitivity of IMS determinations have been widely discussed, based in the use of smart materials, as immunosorbents, aptamers, molecularly imprinted polymers (MIPs), ionic liquids (ILs) and nanomaterial. …

PLS-NIR determination of total sugar, glucose, fructose and sucrose in aqueous solutions of fruit juices

Abstract An analytical procedure has been developed for the direct determination of sugars in fruit juice samples. The method is based on the partial least-squares (PLS) treatment of first derivative near infrared (NIR) spectroscopic data obtained between 1200 and 2450 nm, using 1 mm pathlength cell and a multicomponent calibration set, including seven binary mixtures and 10 ternary mixtures of glucose, fructose and sucrose. The limit of detection values found are of the order of 0.2 g/100 ml for total sugar and 0.2, 0.4 and 0.5 g/100 ml for glucose, fructose and sucrose, respectively. Relative standard deviation values obtained vary from 0.4% to 2.3% for six independent measurements of ind…

Spectrophotometric determination of carbaryl by on-line elution after its preconcentration onto polyurethane foam.

Abstract An analytical methodology has been developed for the UV-spectrophotometric determination of carbaryl in waters after its preconcentration onto a polyether type polyurethane foam followed by on-line elution. The aforementioned strategy offers an easy way for in-field sampling and to improve the analytical sensitivity. Several chemical and flow variables (mass of sorbent, sample flow rate, sample volume and carrier flow rate) were studied to ensure the best performance of the system. Recovery studies, carried out on natural water samples spiked with known amounts of carbaryl at concentration levels between 250 and 500 μg l−1, provided recovery percentages between 94 and 105%. A detec…

Rapid microwave assisted hydrolysis of formetanate

Abstract A fast microwave-assisted hydrolysis procedure has been developed for the derivatization of formetanate previously to the flow-injection spectrophotometric determination of m -aminophenol by reaction with p -aminophenol. Formetanate is quantitatively hydrolyzed with 0.1 M NaOH in 150 s using a closed polyetrafluoroethylene reactor with 115 ml internal volume and a radiation power of 390 W. The above procedure has been applied, as a previous step, for the flow-injection spectrophotometric determination of formetanate in spiked water samples and accurate and precise results have been found. The method permits to obtain a limit of detection of 0.025 mg 1 −1 of formetanate. The relativ…

Rapid determination of lead in petrol by atomic absorption spectrometry of emulsified samples

Supercritical fluid chromatography in drug analysis: A literature survey

The applications of supercritical fluid chromatography to the analysis of drugs have been carefully revised from the literature compiled in the Analytical Abstracts until March 1994. Easy-to-read tables provide useful information about the state-of-the-art and possibilities offered by SFC in pharmaceutical analysis. The tables comprise extensive data about samples analyzed, pharmaceutical principles determined, solvents used and sample quantity injected, supercritical fluids and modifiers employed, injection system, instrumentation, experimental conditions for chromatographic separations (density, pressure, flow, temperature), characteristics of columns employed (type, support, length, diam…

FIA—FT—IR determination of ibuprofen in pharmaceuticals

A method has been developed for the determination of Ibuprofen (2-[4-isobutylphenyl]-propionic acid) in pharmaceuticals by FT-IR, using the carbonyl band which this compound presents at 1710 cm(-1) in carbon tetrachloride solutions. Samples are dissolved in carbon tetrachloride. In this solvent the excipients are not soluble and so the drug can be directly determined without any additional treatment. The use of a simple FIA manifold permits one to carry out this analysis with a low consumption of reagent and the FT-IR provides a continuous monitoring of the spectral base-line which permits an accurate determination of the maximum in the absorbance band. Also, the FIA system permits easy and…

Some observations on the use of matrix modifiers in the determination of aluminum by electrothermal atomic absorption spectrophotometry

Abstract Some evidence demonstrating that the use of matrix modifiers is necessary to obtain good calibration lines in the determination of aluminum by graphite furnace atomic absorption spectrophotometry is provided. It was found that the most sensitive results were obtained when Mg(NO 3 ) 2 was used instead of NH 4 H 2 PO 4 .

Direct ATR-FTIR determination of sucrose in beet root.

A simple and fast procedure has been developed for the direct determination of sucrose in beet root samples through attenuated total reflectance Fourier transform infrared absorbance measurements (ATR-FTIR) at 1056 cm(-1) with a baseline established between 1187 and 887 cm(-1). The method only requires a previous crushing or liquefaction of samples and it is free from matrix effects and from the interference of minoritary sugars and fermentation molecules. Aqueous solutions of sucrose can be used as standards and recovery values from 101 to 103% were found for spiked concentration levels from 3.5 to 10.5% (w/w). The limit of detection provided by this method corresponds to 0.15% (w/w) of su…

Atomic fluorescence spectrometric determination of trace amounts of arsenic and antimony in drinking water by continuous hydride generation

A highly sensitive and simple method has been developed for the determination of As(III), total As, Sb(III) and total Sb in drinking water samples by continuous hydride generation and atomic fluorescence spectrometry (HGAFS). For As determination, water samples aspirated in a carrier of 2 mol l(-1) HCl were merged with a reducing NaBH(4) 3%(m/v) solution, with sample and NaBH(4) flow rates of 12.5 and 1.5 ml min(-1) respectively. The hydride generated in a 170 cm reaction coil was transported to the detector with an Ar flow of 400 ml min(-1), and a limit of detection between 5 and 20 ng l(-1) was obtained. For Sb determination, 2.5 mol l(-1) HCl and 2%(m/v) NaBH(4) were employed, with respe…

Microwave-assisted extraction of pyrethroid insecticides from soil

Abstract An analytical method has been developed for the microwave-assisted extraction of synthetic pyrethroid insecticide residues in soils and their determination by gas chromatography with electron capture detector (ECD) and mass spectrometry (MS) detector. Clean soil samples were spiked with nine pyrethroids: tetramethrin, cyfluthrin, flucythrinate, deltamethrin, bifenthrin, permethrin, cypermethrin and fluvalinate were used for this study. Concentration levels were 50 ng g −1 for all the compounds studied except to sumitrin for which a 10 μg g −1 was evaluated. Two grams of sample were treated in a closed PTFE reactor with 10 mL toluene and 1 mL water and irradiated at 700 W during 9 m…

Quantitative Vibrational Spectrometry in the 21st Century: A Scientometric Evaluation

Abstract The state of the art of research on vibrational spectrometry–based quantitative methodologies was evaluated from the literature compiled in Analytical Abstracts from 1980. Medium and near infrared, Raman spectrometry, and photoacoustic methods of analysis were considered. The evolution of the number of published papers, the distribution of the literature as a function of the different application fields in which the vibrational methods were employed, and a study of the impact on this area of chemometric and automation studies clearly shows that, from the 1990s until now, the importance of vibrational spectrometry in application analysis has grown to reach maturity. This field provi…

Some observations on the determination of total heavy metals in sewage sludge by atomic absorption spectrophotometry after a pressurized acid digestion

Abstract An economical and simple method for the flame atomic absorption spectrometric determination of Cd, Pb, Ni, Cu, Fe, and Zn in sewage sludges is described. Samples are treated with concentrated HNO 3 in a thermal oven using Pyrex glass tubes hermetically sealed with Bakelite screw caps. The effect of the digestion parameters, such as digestion time, acid volume, sample mass, and temperature, were studied. The precision and accuracy of this procedure were evaluated by the analysis of two BCR (Community Bureau of Reference, European Communities) certified sewage sludge samples (CRM 146 and 144).

Management of tannery wastewaters: treatment of spent chrome tanning bath and vegetable tanning effluents

Abstract In this work, a chain of treatment processes was proposed and described in order to reach better management of mineral and vegetable tannery wastewaters. First, chromium was precipitated from the spent chrome tanning bath by sodium hydroxide (NaOH) and then reformulated to form a complex of basic chromium sulfate which was tested successfully in mineral tanning process. On the other hand, the supernatant recovered after precipitation of chromium with NaOH was used to dilute vegetable tanning wastewaters characterized by a high concentration of polyphenols (about 2,574 mg/L). Diluted effluent was then treated by liming and tangential microfiltration using a ceramic membrane based on…

Determination of uranium in tap water by ICP-MS

A fast and accurate procedure has been developed for the determination of uranium at microg L(-1) level in tap and mineral water. The method is based on the direct introduction of samples, without any chemical pre-treatment, into an inductively coupled plasma mass spectrometer (ICP-MS). Uranium was determined at the mass number 238 using Rh as internal standard. The method provides a limit of detection of 2 ng L(-1) and a good repeatability with relative standard deviation values (RSD) about 3% for five independent analyses of samples containing 73 microg L(-1) of uranium. Recovery percentage values found for the determination of uranium in spiked natural samples varied between 91% and 106%…

Research on Spectroscopy in Morocco from 1984 to 2006

Abstract The evolution of spectroscopy‐based research activity in Morocco was evaluated on the basis of publications that have appeared in the Science Citation Index, Expanded (SCI), during the cumulative period 1984–2006 (September). The most active research groups, and their universities or centers, were identified in this subject from their scientific production in the first years of this century. The preference to publish in specific journals, the main areas of interest to Moroccan authors, and the spectroscopy techniques most commonly employed for their studies were also appraised. This scientometric study was undertaken to introduce a group of papers in a special issue of Spectroscopy…

Mineral profiles of legumes and fruits through partial least squares energy dispersive X-ray fluorescence

Abstarct Energy dispersive X-ray fluorescence (ED-XRF) has been employed for the determination of mineral elements in 15 varieties of legumes and 14 cherry samples. ED-XRF signals directly obtained from pulverized samples were modelized by partial least squares (PLS) using Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) of a selected number of samples, after microwave assisted acid digestion, as reference data. Models were built to predict the concentration of Al, Ca, Cu, Fe, K, Mg, P, Sr and Zn. Average concentrations predicted were 6, 930, 7, 40, 6400, 990, 2100, 4 and 15 μg g−1 for Al, Ca, Cu, Fe, K, Mg, P, Sr and Zn, respectively with relative errors from 7 till 26%. …

Classification of persimmon fruit origin by near infrared spectrometry and least squares-support vector machines

Abstract The main objective of this work has been the authentication by Fourier transform near infrared (FT-NIR) spectrometry of the origin of persimmon fruits cultivated in different regions of Spain. In order to achieve this goal, 166 persimmon samples from 7 different regions of Spain were analyzed by FT-NIR spectrometry. By splitting the spectral data in training and independent test sets, a classification model was built using least squares support vector machines chemometric technique. Orthogonal signal correction and principal component analysis were performed prior to conduct the classification strategy. The verified model was applied for the prediction of the origin of 50 samples f…

On-line gel permeation chromatography–attenuated total reflectance–Fourier transform infrared determination of lecithin and soybean oil in dietary supplements

Gel permeation chromatography (GPC) with attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectrometry detection has been proposed for the simultaneous determination of lecithin and soybean oil in dietary supplements. The method involves the extraction of analytes with dichloromethane in an ultrasound water bath and the injection of 2 ml of centrifuged and filtered extracts into the system integrated by two Envirogel GPC columns (19 mm x150 mm, 19 mm x 300 mm) coupled on-line. Dichloromethane was used as mobile phase. A method has been developed to select the most appropriated wavenumber to be used for the determination of each considered compound from the calculation of a…

Trace element determination in sediments: a comparative study between neutron activation analysis (NAA) and inductively coupled plasma-mass spectrometry (ICP-MS)

An inductively coupled plasma-mass spectrometry (ICP-MS) method has been employed for trace element determination in five real sediment samples and a standard reference material. These samples were mineralized by dry ashing at 550°C and fused at 1100°C for 30 min with lithium metaborate. Dissolved samples were measured by a semiquantitative methodology with external calibration and with Rh as an internal standard. More than 50 elements have been measured. As a reference technique, a direct analysis of the solid samples was carried out by neutron activation analysis. Results obtained by ICP-MS have been compared with those obtained by neutron activation analysis (NAA) by applying the paired …

Some observations on the sensitivity of flow-injection techniques for atomic absorption spectrophotometry

Abstract Different strategies for coupling flow-injection manifolds to atomic absorption spectrometers in order to obtain better sensitivity are compared. Using a T-connector interface, different carriers and flow compensation solvents have been assayed in an attempt to improve the sensitivity of flow-injection analysis. Manganese and copper determinations in sewage sludge have been used as a test system and the analytical parameters of both batch and flow-injection methods are compared.

Indoor and outdoor determination of pesticides in air by ion mobility spectrometry.

Abstract The use of ion mobility spectrometry (IMS) has been evaluated as analytical methodology to detect and evaluate the occupational exposure to pesticides. The developed IMS methodology was used, in positive and negative modes, to determine the presence of pesticides in air and to evaluate possible inhalation exposures of workers and users based on active sampling on Teflon membranes and direct thermal desorption IMS. The negative IMS mode was used to determine bensulfuron, clorpyrifos, diniconazole, diuron, flutolanil and imidacloprid, while the positive mode was employed to evaluate formetanate, metalaxyl, metamitrone, metribuzin, paclobutrazol and pirimicarb. The IMS measurements pr…

Spectroscopic and chromatographic study of the interaction of nonionic micelles with the aluminum-morin complex

Abstract The interaction of the aluminum-morin system with different nonionic surfactants has been studied spectrophotometrically and by high-performance liquid chromatography. It has been found that ethylene oxide-propylene oxide condensate surfactants sensitize the spectrophotometric determination of aluminum with morin more than ethylene oxide condensate surfactants. Binding ratio parameters for the different surfactants with free morin have been also estimated from the analysis of chromatographic vacant peaks.

Determination of edible oil parameters by near infrared spectrometry

Abstract A chemometric method has been developed for the determination of acidity and peroxide index in edible oils of different types and origins by using near infrared spectroscopy (NIR) measurements. Different methods for selecting the calibration set, after an hierarchical cluster analysis, were applied. After discrimination of olive oils from maize, seed and sunflower, the prediction capabilities of partial least squares (PLS) multivariate calibration of NIR data were evaluated. Several preprocessing alternatives (first derivative, multiplicative scatter correction, vector normalization, constant offset elimination, mean centering and standard normal variate) were investigated by using…

Sampling and analysis of pesticides in ambient air.

Developments in the sampling and determination of pesticides in ambient air have been discussed and data on the occurrence of pesticides in atmosphere have been presented. Developments in active sampling methods were reviewed and the different materials used for trapping pesticides from gas and particulate phases were discussed. Likewise, the use and developments of passive air samplers were reviewed. This article pays special attention to the analysis of pesticides trapped from ambient air, and recapitulate the procedures for extraction, clean-up and determination of these substances. Improvements in sampling procedures, analytical methods and monitoring activities are necessary to advance…

Fast determination of fish mineral profile. Application to Vietnamese panga fish

A methodology, based on inductively coupled plasma optical emission spectrometry after microwave-assisted digestion with HNO3/H2O2, was developed to determine the mineral profile of panga fish samples imported from Vietnam. A total of 42 essential and toxic elements were studied in seven samples taken from the local market. Preliminary studies were focused on selecting the best wavelength and the required dilution of samples in order to provide the highest sensitivity to maximize the number of analytes to be determined without spectral or matrix interferences. Adequate accuracy was assured by the analysis of certified reference material TORT-2. Mercury was also determined by a direct method…

A review of non-chromatographic methods for speciation analysis.

This manuscript overviews relevant scientific literature concerning speciation of trace elements by using non-chromatographic methods. The main principles of the different strategies proposed in the published works and their advantages and drawbacks are discussed in order to provide to the readers an appropriate picture of the state-of the-art of fast and cheap methodologies available to obtain information about the presence of different chemical forms of trace elements in environmental, clinical and food samples. A selection of the methods proposed for the speciation of the different elements studied was also provided together with their main features.

Adulteration detection of argan oil by inductively coupled plasma optical emission spectrometry

Abstract The singularity of the trace element profile of argan oil has been demonstrated by means of inductively coupled plasma optical emission measurement in combination with different chemometric approaches. The ability of multivariate analysis methods; such as hierarchical cluster analysis (HCA), principal component analysis (PCA), classification trees using Chi -squared Automatic Interaction Detector (CHAID) and discriminant analysis (DA) to achieve edible oils classification based on its type or variety from their elemental content have been investigated. The calculations were performed using 16 variables (contents of Na, Mg, Al, K, Ca, Ti, Fe, Co, Ni, Cu, Zn, Cd, Pr, Sm, Er and Bi at…

Continuous monitoring of photocatalytic treatment by flow injection. Degradation of dicamba in aqueous TiO2 dispersions

The possible use of flow injection (FI) to monitor the photocatalytic mineralization of dicamba (3,6-dichloro-2-methoxybenzoic acid) present at the trace level in aqueous solutions containing TiO2 suspensions has been evaluated. Experiments were performed in a stirred photochemical reactor equipped with a simple FI manifold, integrating an online filtration unit able to perform the monitoring of the UV absorbance of the irradiated solution every 4 min. The light source used was a medium pressure mercury lamp (125 W). During the initial steps of the reaction the formation of UV absorbing intermediates, which completely disappear in less than 80 min, was evidenced. Additional HPLC, DOC and ch…

Literature survey of the on-line preconcentration in flow-injection atomic spectrometric analysis

The literature on the use of “on-line” preconcentration in flow injection atomic spectrometric analysis is reviewed, taking into account its application both in flame and electrothermal atomic absorption methods as well as in plasma emission spectrometry. The basis of the different preconcentration approaches, such as liquid-liquid extraction, column preconcentration and “on-line” precipitation are discussed. The literature survey reveals the analytical performance of the developed methodologies.

Chromium speciation using activated alumina microcolumns and sequential injection analysis-flame atomic absorption spectrometry

Abstract A new procedure has been developed for chromium speciation in water by sequential injection analysis and flame atomic absorption spectrometry. The method involves the online retention of Cr(VI) anionic species and Cr(III) cationic species on alumina microcolumns, prepared by packing activated alumina in polytetrafluoroethylene tubes, followed by selective elution of Cr(VI) with 2 mol l −1 NH 4 OH and of Cr(III) with 0.2 mol l −1 HNO 3 . Studies were carried out on the effect of retention and elution conditions for both Cr species. The limit of detection values, established as the concentration corresponding to three times the standard deviation of blank measurements divided by the …

Non-chromatographic speciation of mercury in mushrooms

A fast, sensitive and cheap procedure has been developed for the determination of inorganic mercury (i-Hg) and organic mercury (o-Hg) in mushroom samples. The procedure is based on the use of cold vapour atomic fluorescence spectrometry (CV-AFS). The method involves the extraction of total mercury (t-Hg) with diluted HCl, followed by measurements of the corresponding Hg vapour under two different conditions: (i) directly to determine i-Hg, and (ii) after oxidation with a mixture KBr/KBrO3 to determine t-Hg. o-Hg was estimated from the difference between t-Hg and i-Hg. Previous studies were focused on the assessment of different reagents for mercury extraction and breakdown of organomercury …

Non-destructive and clean prediction of aviation fuel characteristics through Fourier transform-Raman spectroscopy and multivariate calibration

Abstract The combination of Fourier transform (FT)-Raman spectroscopy and partial least squares (PLS) regression is proposed to be used in off-line kerosene quality control. Here, six important physico-chemical properties have been studied: Abel flash point, initial boiling point (IBP), 10% of distilled sample, final boiling point (FBP), total percentage of aromatic compounds (% aromatics) and viscosity. The Raman spectra were obtained directly from standard 2 ml glass vials ( 12 mm ×32  mm), using a Bruker RFS 100 FT-Raman spectrometer, equipped with a 1064 nm Nd:YAG laser and a Ge detector, in back-scattering mode and accumulating 25 scans (150 s acquisition time) with a laser power of 30…

Removal of Hexavalent Chromium from Aqueous Solutions Using Biopolymers

AbstractTwo biopolymers were prepared by reaction of chestnut and quebracho tannins with gelatin extracted from untanned hide wastes. Obtained biopolymers were evaluated as adsorbents for removing ...

Metal speciation in solid matrices

The literature on metal ion speciation in solid matrices is reviewed, taking into account its applications in the analysis of soil, sediment, biological materials, foodstuff and other solid samples. The pretreatment methods of various solid materials required for carrying out speciation studies have been highlighted. The basis of the methods of separation of different species from matrices, such as sequential extraction, selective extraction, etc. is discussed. The instrumental techniques used for the characterization of different chemical species in solid matrices have been mentioned. The literature survey reveals the analytical details of the developed methodologies, and these have been e…

The Challenges of Air Protection and Control

Direct determination of ethanol and methanol in liquid samples by means of vapor phase-Fourier transform infrared spectroscopy

Abstract A FTIR procedure is proposed for the direct determination of methanol and ethanol in liquid samples, such as alcoholic beverages and eau-de-cologne, based on vapor generation from small injected volumes of untreated samples into a heated Pyrex glass reactor in which, at a temperature of 80°C, ethanol and methanol are volatilized and introduced into a long-path IR gas cell by means of a N2 carrier flow. The IR spectra obtained present two characteristic ethanol bands (1050 and 880 cm−1) and a single characteristic methanol band (1030 cm−1). The measurement of the area of the transient recording obtained for the wavenumber range between 1025–950 and 950–820 cm−1 allows us the determi…

Green Analytical Chemistry

We discuss the origins and the fundamentals of Green Analytical Chemistry (GAC), based on the literature published about clean, environmentally-friendly or GAC methods. We pay special attention to the strategies and the tools available to make sample-pretreatment and analytical methods greener. We consider that the main principles are to replace toxic reagents, to miniaturize and to automate methods, making it possible to reduce dramatically the amounts of reagents consumed and wastes generated, so reducing or avoiding side effects of analytical methods. We also consider on-line decontamination or passivation of wastes to be of special interest in making analytical chemistry sustainable.

Cocaine abuse determination by ion mobility spectrometry using molecular imprinting

A cocaine-based molecular imprinted polymer (MIP) has been produced by bulk polymerization and employed as selective solid-phase extraction support for the determination of cocaine in saliva samples by ion mobility spectrometry (IMS). The most appropriate conditions for washing and elution of cocaine from MIPs were studied and MIPs were characterized in terms of analyte binding capacity, reusability in water and saliva analysis, imprinting factor and selectivity were established and compared with non-imprinted polymers. The proposed MIP-IMS method provided a LOD of 18μgL-1 and quantitative recoveries for blank saliva samples spiked from 75 to 500μgL-1 cocaine. Oral fluid samples were collec…

Date-rape evidence through fast determination of γ-butyrolactone in adulterated beverages.

Abstract An infrared spectroscopy (IR) based methodology has been developed to determine γ-butyrolactone (GBL) in adulterated beverages. The proposed method permits the direct screening of GBL in beverages and involves a minimum sample treatment requiring less than 2 min for quantitative determination of GBL. Sensitivity of IR method was improved by using liquid-liquid extraction (LLE) providing detection limits of 0.023 mg g−1. Accuracy of the proposed methodology was evaluated through the analysis of soft beverages and alcoholic cocktails spiked with GBL at concentration levels ranging from 0.075 to 10 mg g−1 providing recovery values from 91 to 100%. GBL was determined in twelve blind-sp…

Passive Sampling of Atmospheric Organic Contaminants

The state of the art of passive sampling monitoring studies of atmospheric contaminants is reviewed in this chapter. The following passive samplers were considered: badge-type diffusive samplers; diffusive tubes; semi-permeable membrane devices; Radiello samplers; solid-phase microextraction fibers; polyurethane foam disks; XAD-2 passive air samplers; stir-bar samplers; polymer-coated glass surfaces; versatile, easy and rapid atmospheric monitor; and vegetation. A summary of the passive samplers used, sampling times, sampling rates, and analyte concentrations found is provided for different organic compounds, such as: carbonyl compounds, volatile compounds, polycyclic aromatic hydrocarbons,…

Prediction of organic carbon and total nitrogen contents in organic wastes and their composts by Infrared spectroscopy and partial least square regression

Middle and near infrared (MIR and NIR) were employed to determine organic carbon (OC) and total nitrogen (TN) in different soil organic amendments including wastes, composts and mixtures of composts and organic wastes. Prediction models based on partial least squares (PLS) regression from the spectra of untreated samples were built. Different spectra preprocessing strategies were adopted and the best number of latent variable was evaluated using leave-one-out cross-validation. Attenuated total reflectance (PLS-ATR-MIR) and diffuse reflectance (PLS-DR-NIR) models were built and evaluated from root mean square error of cross validation and prediction (RMSECV and RMSEP), coefficients of determ…

Comparative study of reflectance cells for PLS-FTIR determination of sugars in soft drinks

A comparative study has been carried out between a horizontal Attenuated Total Reflectance (h-ATR) cell and a Cylindrical Internal Reflection (CIR) cell (CIRCLE cell). Both cells were employed for the determination of glucose, fructose, sucrose and total sugar in soft drinks and fruit juices using absorbance measurements at two resolution values (4 and 8 cm–1). Data were processed by Partial Least Squares regression (PLS). Using a resolution of 4 cm–1, mean relative errors of prediction from 0.6% to 1.3% were obtained using the horizontal-ATR and from 0.6% to 2.8% using the CIRCLE cell resulting in a limit of detection from 0.03% in the case of sucrose to 0.21% for total sugar for the h-ATR…

Direct derivative spectrophotometric determination of carbaryl and carbofuran in water samples

Abstract Derivative absorption spectrophotometry has been applied to the direct determination of carbaryl and carbofuran in water samples. The use of the third derivative for carbaryl and the fourth derivative for carbofuran reduces the matrix effect and the seventh derivative provides, in both cases, accurate results for the determination of these pesticides, even working at low dilution levels of the samples. A limit of detection of 4 ppb and a variation coefficient of 0.1% have been obtained for the determination of carbaryl. Carbofuran can be determined with a limit of detection of 5 ppb and a variation coefficient of 0.02%.

Removal of trivalent chromium from tannery waste waters using bone charcoal

International audience; The ability of bone charcoal to remove Cr(III) from aqueous solutions by adsorption has been investigated. The adsorbent used was first characterised and then the adsorption was studied as a function of time and amount of charcoal. Tests were carried out with synthetic solutions whose Cr concentrations (500 mg L-1) were similar to those found in some effluents of Moroccan tannery industries. Cr removal efficiencies higher than 90% were obtained at pH 3.5 using 3 g of bone charcoal and a stirring time of about 30 min. Results of Cr removal by all sieved fractions of bone charcoal had shown the same interesting capabilities for Cr(III) retention. The cross interference…

Smartphone determination of fat in cured meat products

Abstract A method has been developed to determine the fat content in different cold meat products by image processing using the camera of a mobile phone. Salchichon , chorizo , salami and cured ham pictures were taken with a Meizu M2 Mini mobile phone camera under fixed lighting conditions of the light emitting diode flash of the mobile phone. Images were treated with Matlab to obtain the mean pixels of average red, green and blue camera values colours (RGB) of the pixels and different data pretreatments were taken into account to correlate colour parameters with fat content values determined in a series of commercially available samples by the Soxhlet method. RGB values were used as input …

Total content of As, Sb, Se, Te and Bi in Spanish vegetables, cereals and pulses and estimation of the contribution of these foods to the Mediterranean daily intake of trace elements

Abstract As, Sb, Se, Te and Bi were quantified in vegetables, pulses and cereals, in order to increase the available information on the presence of these elements in the Mediterranean daily intake. Samples were dry ashed and the ashes dissolved with diluted HCl. Hydride generation atomic fluorescence spectrometry was used for quantification. Limits of detection (LOD) ranged from 0.2 to 1.7 ng g−1 and the accuracy was assessed by the analysis of three certified reference materials, Rice Flour (NIST 1568a), Tomato Leaves (NIST 1573) and Cabbage (IAEA 359). Good concordance between results found and certified values were always observed. As, Sb, Se, Te and Bi levels varied in samples analysed …