Quality control of Metamitron in agrochemicals using Fourier transform infrared spectroscopy in the middle and near range
Abstract Two vibrational spectrometry-based methodologies were developed for Metamitron determination in pesticide formulations. Fourier transform-middle infrared (FT-MIR) procedure was based on the extraction of Metamitron by CHCl 3 and latter determination by peak area measurement between 1556 and 1533 cm −1 , corrected with a two points baseline established from 1572 to 1514 cm −1 . Fourier transform-near infrared (FT-NIR) determination was made after the extraction of Metamitron in acetonitrile and measuring the peak area between 6434 and 6394 cm −1 corrected using a two points baseline defined between 6555 and 6228 cm −1 . Repeatability, as relative standard deviation, of 5 independent…
Near infrared determination of Diuron in pesticide formulations
Abstract A simple, fast and environmentally friendly near infrared (NIR)-based methodology was developed for Diuron determination in pesticide formulations. This methodology was based on the pesticide extraction with acetonitrile and subsequent transmittance measurement determination by peak area measurement between 2021 and 2047 nm, corrected with a single point baseline established at 2071 nm. The repeatability, as relative standard deviation of five independent analysis of a 15.3 mg g −1 Diuron standard was 0.03% and the limit of detection 0.013 mg g −1 . The reagent consumption was clearly reduced in front of a chromatographic reference procedure from 39.1 ml acetonitrile per sample, re…
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…
Comparison of two vibrational procedures for the direct determination of mancozeb in agrochemicals.
The direct determination of mancozeb in agrochemicals has been made by diamond attenuated total reflectance (ATR) Fourier transform infrared spectroscopy in the middle range (DATR-MIR) and diffuse reflectance infrared Fourier transform spectroscopy in the near range (DR-NIR) methods using in both cases a previous identification of the samples using a dendrographic classification and an appropriate partial least squares (PLS) calibration established from a set of nine external standards and optimized for each type of sample. It was analyzed a heterogeneous population of 11 samples obtained from the Spanish market, containing different co-formulated products, such as fosetyl-Al, copper oxychl…
Testing of the region of Murcia soils by near infrared diffuse reflectance spectroscopy and chemometrics.
A partial least squares near infrared (PLS-NIR) method has been developed for the determination of several physicochemical parameters in soils from different locations of the Region of Murcia. The method was based on the proper chemometric treatment of diffuse reflectance spectra of soil samples. Reflectance spectra were scanned from samples stored in glass vials in the NIR region between 800 and 2600 nm, averaging 36 scans per spectrum at a resolution of 8 cm(-1). Models were built using reference data of 39 samples selected from a dendrogram obtained after hierarchical cluster analysis of NIR spectra of soils and prediction parameters were established from a validation set of 109 addition…
Partial least squares X-ray fluorescence determination of trace elements in sediments from the estuary of Nerbioi-Ibaizabal River.
The feasibility of partial least squares (PLS) regression modeling of X-ray fluorescence (XRF) spectra of estuarine sediments has been evaluated as a tool for rapid trace element content monitoring. Multivariate PLS calibration models were developed to predict the concentration of Al, As, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sn, V and Zn in sediments collected from different locations across the estuary of the Nerbioi-Ibaizabal River (Metropolitan Bilbao, Bay of Biscay, Basque Country). The study was carried out on a set of 116 sediment samples, previously lyophilized and sieved with a particle size lower than 63 microm. Sample reference data were obtained by inductively coupled plasma mass …
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.
Quality control Fourier transform infrared determination of diazepam in pharmaceuticals
A quality control procedure has been developed for the determination of diazepam in pharmaceuticals using Fourier transform infrared (FTIR) spectroscopy. The method involves the off-line extraction of diazepam with chloroform by sonication and direct determination in the extracts through peak area measurement in the interval between 1672 and 1682 cm(-1) using a baseline correction defined between 1850 and 1524 cm(-1). For standardization it was used an external calibration line established from standard solutions of diazepam in chloroform. The method provides a limit of detection of 0.04 mg per tablet (n=5), a relative standard deviation (R.S.D.) of 0.5% for 5 independent measurements of a …
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…
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…
Characterization of estuarine sediments by near infrared diffuse reflectance spectroscopy
It has been developed a partial least squares near infrared (PLS-NIR) method for the determination of estuarine sediment physicochemical parameters. The method was based on the chemometric treatment of first order derivative reflectance spectra obtained from samples previously lyophilized and sieved through a lower than 63 μm grid. Spectra were scanned from 833 to 2976 nm, averaging 36 scans per spectrum at a resolution of 8 cm-1, using chromatographic glass vials of 9.5 mm internal diameter as measurement cells. Models were built using reference data of 31 samples selected through the use of a hierarchical cluster analysis of NIR spectra of sediments obtained from the Ria de Arousa estuary…
Univariate near infrared methods for determination of pesticides in agrochemicals
Abstract It has been developed a general strategy for the determination of pesticides in agrochemicals by Fourier transform near infrared (FT-NIR) spectroscopy. The methodology is based on previous extraction of the active principles through sonication with acetonitrile and direct determination by transmission measurements, using glass vials as measurement cells and univariate calibration at selected wavenumbers as a function of the pesticide to be analyzed. Chlorsulfuron, metamitron, iprodione, pirimicarb, procymidone and tricyclazole were used as test molecules and data obtained by FT-NIR for 20 samples containing one of these active principles compare well with those found by reference l…
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…
Determination of the energetic value of fruit and milk-based beverages through partial-least-squares attenuated total reflectance-Fourier transform infrared spectrometry
Abstract The estimation of important nutritional parameters, such as carbohydrates content and energetic value (calories) in commercially available fruit juice and flavour milk shakes has been made by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) using a partial-least-square (PLS) calibration approach. A highly heterogeneous population of 65 samples obtained from the Spanish market, covering fruit juices, flavour milk shakes and milk-added fruit juices was used. The spectral range and the size of the calibration set for building the PLS model have been evaluated. Considering a calibration set comprised of 27 samples, selected via hierarchical cluster analys…
Determination of Olive Oil Parameters by Near Infrared Spectrometry
Publisher Summary Near infrared (NIR) covers the region between 780 and 2500 nm, and based on the absorption, transmission or reflection of the light, NIR spectroscopy provides a fast and non-destructive technique which is very useful for the simultaneous determination of several compounds in the same sample. Food NIR spectra comprise broad bands corresponding to overtones and combinations of vibrational modes involving C–H, O–H, and N–H chemical bonds, providing a great amount of information which properly treated by chemometrics is useful for classification and for the quantification of many parameters. The olive oil extraction process starts in the harvesting and transport of olive fruit…
New cut-off criterion for uninformative variable elimination in multivariate calibration of near-infrared spectra for the determination of heroin in illicit street drugs.
A new cut-off criterion has been proposed for the selection of uninformative variables prior to chemometric partial least squares (PLS) modelling. After variable elimination, PLS regressions were made and assessed comparing the results with those obtained by PLS models based on the full spectral range. To assess the prediction capabilities, uninformative variable elimination (UVE)-PLS and PLS were applied to diffuse reflectance near-infrared spectra of heroin samples. The application of the proposed new cut-off criterion, based on the t-Students distribution, provided similar predictive capabilities of the PLS models than those obtained using the original criteria based on quantile value. H…
Direct determination of Mancozeb by photoacoustic spectrometry
Abstract A solvent free, fast and environmentally friendly photoacoustic-infrared-based methodology (PAS-FTIR) was developed for the determination of Mancozeb in agrochemicals. This methodology was based on the direct measurement of the transmittance spectra of solid samples and a multivariate calibration model to determine the active ingredient concentration. The proposed partial least squares (PLS) model was made using nine standards prepared by mixing different amounts of kaolin and Mancozeb, with concentrations between 5.43 and 88.10% (w/w). A hierarchical cluster analysis was made in order to classify the samples in terms of similarity in the PAS-FTIR spectra. From their spectra differ…
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…
HPLC determination of oxadiazon in commercial pesticide formulations
A simple, fast and precise high performance liquid chromatographic (HPLC) procedure has been developed for the determination of oxadiazon in emulsifiable concentrated pesticide formulations. 20 µL of diluted sample in acetonitrile were injected in a Kromasil C18 (250 ×am injetados em uma coluna Kromasil C18 4.6 mm, 5 µm) column, using acetonitrile:water (80:20) as mobile phase at 1 mL min-1 flow rate and oxadiazon determined by absorbance measurement at 292 nm. A theoretical limit of detection of 0.02 µg mL-1, a limit of quantification of 0.047 µg mL-1, corresponding to a 0.02 and 0.07% m/v in the original sample, and a relative standard deviation of 0.08% for three replicate analysis of sa…
First‐Derivative Fourier‐Transform Infrared Determination of Oxadiazon in Commercial Herbicide Formulations
Abstract A Fourier‐transform infrared (FTIR) method has been developed for the quantification of oxadiazon in herbicide formulations. The method involves the extraction of the active ingredient by sonication of the samples with CHCl3 and direct measurement of the peak area values in first‐order derivate spectra from 1770 cm−1 to 1774 cm−1 corrected with a baseline point located at 1950 cm−1 and after a 5‐point smoothing. A limit of detection (3 s) of 0.03 mg g−1 and a typical relative standard deviation (RSD) of 1.3% were found. Results obtained were comparable with those found by liquid chromatography with UV detection. The proposed method involves a 7‐times reduction in solvent consumptio…
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…
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…
Fourier transform infrared spectrometric strategies for the determination of Buprofezin in pesticide formulations
Abstract Two different strategies for Buprofezin determination, an off-line extraction and stopped-flow determination and an automated procedure, based on the on-line extraction of Buprofezin samples with chloroform and flowing action analysis–fourier transform infrared (FIA–FT-IR) spectrometric measurement of the extracts, have been developed. For the treatment of the off-line extraction mode, data a three-factor partial least squares (PLSs) calibration was developed, using the region from 1465.7 to 1342.3 cm−1 with a single point baseline defined at 2051.9 cm−1 and based on the use of chloroform solutions of Buprofezin. The method provides a R.S.D. On the other hand, the recommended FIA m…
Nondestructive Direct Determination of Heroin in Seized Illicit Street Drugs by Diffuse Reflectance near-Infrared Spectroscopy
A new method has been developed for the fast and nondestructive direct determination of heroin in seized street illicit drugs using partial least-squares regression analysis of diffuse reflectance near-infrared spectra. Data were obtained from untreated samples placed in standard glass chromatography vials. A heterogeneous population of 31 samples, previously analyzed by a reference method, was employed to build the calibration model and to have a separated validation set. Based on the use of zero-order data for a calibration set of 21 samples, after standard normal variate and quadratic linear removed baseline correction (detrending), in the wavelength range from 1111 to 1647 nm, 8 PLS fac…
Validated, non-destructive and environmentally friendly determination of cocaine in euro bank notes.
A non-destructive, fast and environmentally friendly procedure has been developed for cocaine determination in euro bank notes. Cocaine was extracted with 15 ml methanol by vortex agitation during 5 min. The extract was evaporated and reconstituted in 0.5 ml methanol. GC-MS-MS analysis was performed using as precursor ion m/z 182.2, with an excitation energy voltage of 1.60 eV, being the product ions measured m/z 150.2 and 82.0. A limit of detection of 0.15 ng per note and a repeatability of 6%, established from the relative standard deviation, of a 1 ng ml(-1) level, were achieved. Recoveries of 101+/-2 and 98+/-3% were obtained for samples spiked with 100 and 10 microg respectively. Resul…
Automated Fourier Transform near Infrared Determination of Buprofezin in Pesticide Formulations
An automated procedure has been developed for Fourier transform near infrared (FT-NIR) determination of buprofezin in pesticide formulations. This methodology is based on on-line pesticide extraction with acetonitrile from solid samples and its determination by using peak area absorbance measurements between 2147 and 2132 nm, corrected with a horizontal baseline established at 2091 nm. The repeatability, as a relative standard deviation of five independent analyses of 18.9 mg g−1 of buprofezin, was 0.06% and the limit of detection 5 mg L−1. The reagent consumption was clearly reduced compared with a chromatographic reference procedure from 40.4 mL acetonitrile per sample, required by high …
Use of reflectance infrared spectroscopy for monitoring the metal content of the estuarine sediments of the Nerbioi-Ibaizabal River (Metropolitan Bilbao, Bay of Biscay, Basque Country).
Multivariate partial least-squares (PLS) calibration models have been developed for the spatial and seasonal simultaneous monitoring of 14 trace elements (Al, As, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sn, V, and Zn) in sediments from 117 samples taken in the estuary of the Nerbioi-Ibaizabal River. Models were based on the chemometric treatment of diffuse reflectance near-infrared (NIR) and attenuated total reflectance (ATR) mid infrared (MIR) spectra, obtained from samples previously lyophilized and sieved with a particle size lower than 63 microm. Vibrational spectra were scanned in both, NIR and MIR regions. Developed PLS models, based on the interaction between trace elements and organic m…
Estuarine sediment quality assessment by Fourier-transform infrared spectroscopy
Partial least squares Fourier-transform infrared (PLS-FTIR) models were developed for the quality assessment of estuarine sediments through the evaluation of several physico-chemical parameters. Models were based on the chemometric treatment of attenuated total reflection (ATR) spectra directly obtained from samples previously lyophilized and sieved through a lower than 63 μm grid. Spectra were scanned from 3997 to 523 cm-1, averaging 36 scans per spectrum with a nominal resolution of 8 cm-1. Models were built using reference data obtained for sediment samples collected from Ria de Arousa estuary. Hierarchical cluster classification of sediment ATR spectra was employed for the establishment…
Vibrational spectroscopy provides a green tool for multi-component analysis
Abstract Based on the literature published in the past decade, we focus on the possibilities offered by vibrational-spectroscopy-based techniques to make multi-component analysis of samples independently of their physical state. We discuss the main chemometric tools proposed for developing calibration models and solving problems derived from spectroscopic non-idealities (e.g., highly overlapped spectral bands or the presence of spectral non-linearity), and the benefits provided by vibrational-spectroscopy-based multi-component analysis in industry. Our main objective is to show that vibrational spectroscopy provides fast analytical methods that enable non-destructive analysis and permits, i…