This study determined the levels of total mercury in Spanish samples of baby food, fast food, and daily meal, which people of different ages consume, to evaluate potential toxicological risks through the contribution to the tolerable daily intake (TDI). The total mercury concentrations were determined in thirteen commercial baby foods for infants 6 to 12 months old, six types of fast foods prepared for children, and nine canteen menus prepared for adults. Samples were analyzed using a direct mercury analyzer, and the following concentration ranges were found: baby food (0.57-41.9 µg kg-1), fast food (0.54-68 µg kg-1), and adult menus (0.43-638 µg kg-1). The recovery of different amounts of spiked mercury ranged from 98.6 to 104.9%, and the method’s accuracy was checked with an analysis of different certified reference materials. The limits of detection and quantification obtained were 0.1 and 0.3 µg kg-1, respectively, with a relative standard deviation of up to 11%. The contribution of the samples to the TDI varied as follows: baby food (0.3-28%), fast food (0.5-102%), and adult menus (0.3-396%). Therefore, it was concluded that total mercury daily intake does not pose risks for Spanish children and adults if tuna is not included on their menu.

Alcohol-based gel hand sanitizers became very popular during the COVID-19 (coronavirus disease 2019) pandemic. In Brazil, several irregular factories emerged requiring an efficient control by the police and regulatory agencies to guarantee product quality. This problem required a method to determine ethanol content, which led to the development of two methods employing mid and near infrared spectroscopy associated with chemometrics. Partial least squares (PLS) models were built and presented satisfactory results with mean absolute percentage error of prediction and root mean square error of prediction (RMSEP) of 1.12 and 0.76% (m/m), respectively, for mid-infrared (MIR) and 1.83 and 1.18% (m/m) for near-infrared (NIR). The analysis of commercial and seized samples of hand sanitizers showed that only 7 out of 34 samples had an ethanol content of 70% (m/m) or higher. This result reinforces the need for constant vigilance by authorities to ensure that the products have the required specifications.

The present manuscript makes an extensive review of the scientific approaches developed in the last decade involving infrared and Raman spectroscopy combined with chemometrics for solving several issues in the investigation of the most relevant forensic traces, such as questioned documents and currency, explosives, gunshot residues, illicit drugs and body fluids. In addition, current trends, main challenges and the adequate use of several chemometric techniques are discussed. Principal component analysis (PCA) was found to be the most used technique. This unsupervised approach, however, has sometimes been misunderstood as a classification technique. Discriminant analysis techniques are widely employed, leaving a range of possibilities for application of class-modeling techniques, particularly in cases of problems regarding only one target class. In addition, increasingly complex dataset structures frequently require nonlinear approaches or flexible techniques such as multivariate curve resolution-alternating least squares (MCR-ALS). Results reporting, however, still lack reliable quality parameters and sample representativeness, posing a significant challenge to the solution of forensic problems. Regarding the analytical techniques, Raman has been playing an important role, especially in the area of questioned documents and of body fluids. Portable and hyperspectral imaging infrared spectrometers have also been showing significant potential in forensic applications.

Abstract The liquid-liquid extraction of free fatty acids (FFA) from residual oils and fats for biodiesel production, employing methanol as the solvent, has been optimized using process simulation and response surface methodology. The parameters investigated were temperature, number of stages and solvent-to-feed ratio (S/F). Responses evaluated were FFA mass fraction in the oil-rich phase ( w FFA B) and total cost, using yellow and brown greases as the raw materials. Quadratic and linear models were fitted for w FFA B and cost responses, respectively. The optimal conditions satisfying technical ( w FFA B ≤ 0.5%) and economic (minimum cost, including capital and operation costs, except for raw material cost) criteria were 321 K, 6 stages, S/F = 1.27, w FFA B = 0.41%, cost = $84.93/ton (yellow grease), and 318 K, 6 stages, S/F = 1.32, w FFA B = 0.49%, cost = $102.89/ton (brown grease).

PET - poly (ethylene terephthalate) - bottle surfaces were exposed to chemical agents and evaluated with middle infrared spectroscopy (MIR) and near infrared hyperspectral imaging (HSI-NIR). Images (928-2.524 nm) were acquired at different times from bottle surfaces exposed to alkaline, acidic and ethanolic media. Savitzky-Golay smoothing (2nd order polynomial and 5-point window) combined with Standard Normal Variate (SNV) was used for pre-processing data. Scores from principal component analysis (PCA) on images showed discrimination of PET according to exposure time, particularly when employing NaOH. After the first two hours of chemical exposure, significant contribution of the (-C-O + OH) combination band indicated formation of glycol ethylene on the PET surface, which was confirmed from PCA loading plots. MIR reflectance spectra ranged from 4.000 to 650 cm-1. Changes in spectral intensities could be associated with depolymerization of PET when exposed to NaOH. These were confirmed with PCA and attributed to the carboxylate group of terephthalate.

Near infrared spectroscopy in-line monitoring and modelling of soybean oil methanolysis has been done using multivariate curve resolution alternating least squares (MCR-ALS) with correlation constraint. This constraint allows for quantitation of the methyl ester formed with little calibration effort and the MCR model provides additionally a general description (qualitative and quantitative) of the rest of components in the process. Due to the complexity of this process, which shows components with severe kinetic and spectral overlap, suitably designed multiset analysis strategies were adopted to improve the recovery of concentration profiles of the methyl ester. To assess the temperature and catalyst concentration effects on the kinetic reaction, five batches with different temperatures (20, 44 and 55 °C) and catalyst concentrations (0.75 and 1 m/m%) were produced. The concentration profiles of methyl ester obtained by MCR-ALS for each batch was the starting information used to develop a simplified kinetic model and calculate the activation energy.

Dois fragmentos de pinturas rupestres pertencentes a dois sítios arqueológicos brasileiros, sendo um no estado do Piauí (Sítio Toca da Extrema II) e outro no estado do Rio Grande do Norte (Sítio arqueológico Xique-Xique), foram analisados por LIBS (espectroscopia de emissão em plasma induzido por laser). Um instrumento construído no laboratório (laser Nd:YAG, 1064 nm, 5,2 ns), contendo um policromador echelle, foi empregado para a aquisição dos espectros. Estudos preliminares envolvendo uma pintura realizada sobre uma tela de madeira contendo diferentes camadas de material foram realizados para determinar a melhor energia do pulso de laser. Para cada fragmento de pintura, foram realizados 8 pulsos sucessivos em 16 locações diferentes, sendo 8 locações sobre a pintura e 8 sobre o substrato. Neste trabalho, foi demonstrado que a utilização de técnicas multivariadas é indispensável devido à grande complexidade dos espectros obtidos durante estudo de profundidade de amostras arqueológicas.

Laser-induced breakdown spectroscopy (LIBS) was employed in the study of two fragments of prehistoric rock wall paintings found at two Brazilian sites: in Piauí State (Toca Extrema II) and in Rio Grande do Norte State (Xique-Xique). A time-resolved echellebased LIBS system assembled in the laboratory (laser Nd:YAG, 1064 nm, 5.2 ns) was employed for spectral acquisition. Preliminary depth profile studies were carried out in surrogate samples of a multilayer painting on wood to determine the best energy for the laser pulse. For each fragment of wall painting, the depth profile composition was investigated by firing 8 successive laser shots at each of 16 locations (8 in the area of pigment and 8 in the area of substrate). It is demonstrated in this work that the use of multivariate techniques is compulsory due to the high complexity of the spectral data obtained from depth profile studies of the archaeological samples.

Neste trabalho, a espectroscopia no infravermelho médio foi utilizada para investigar o efeito da quantidade (25 ou 40%) e do tipo de plastificante (di-2-etilhexil ftalato (DOP), di-2-etilhexil sebacato (DOS) e 2-nitrofenil octil éter (NPOE)) na resposta analítica de uma fase sensora de poli(cloreto de vinila) (PVC) para a determinação de hidrocarbonetos clorados (clorobenzeno (ClB), tricloroetileno (TCE) e triclorobenzeno(TCB)) em água. Foi observado que os filmes com 40% de plastificante geraram maior sensibilidade e menores limites de detecção que aqueles preparados com 25%, embora esses últimos sejam de manipulação mais fácil. Um comportamento similar foi também observado para fases sensoras preparadas com os plastificantes NPOE e DOS. Com o uso da fase sensora de PVC-DOS e um tempo de extração de 60 min, foram obtidos limites de detecção de 0,3, 0,6 e 0,5 mg L-1 para clorobenzeno, tricloroetileno e triclorobenzeno, respectivamente.

In this work, mid-infrared spectroscopy has been employed to investigate the effect of amount (25 or 40%) and type of plasticiser (di-2-ethylhexyl sebacate (DOS), di-2-ethylhexyl phthalate (DOP) and 2-nitrophenyl octyl ether (NPOE)) on the analytical response of a poly(vinylchloride) (PVC) sensing phase for the determination of the chlorinated hydrocarbons (chlorobenzene (ClB), trichloroethylene (TCE) and trichlorobenzene (TCB)) in water. It was observed that films with 40% of plasticiser provided higher sensitivity and lower limits of detection than those with 25%, although the later films are easier to handle. A similar behaviour was also observed for sensing phases prepared with the plasticisers NPOE and DOS. By employing a DOS-based PVC sensing phase and extraction time of 60 min, limits of detection of 0.3, 0.6, and 0.5 mg L-1 were obtained for chlorobenzene, trichloroethylene and trichlorobenzene, respectively.

The simultaneous determination of two or more active components in pharmaceutical preparations, without previous chemical separation, is a common analytical problem. Published works describe the determination of AZT and 3TC separately, as raw material or in different pharmaceutical preparations. In this work, a method using UV spectroscopy and multivariate calibration is described for the simultaneous measurement of 3TC and AZT in fixed dose combinations. The methodology was validated and applied to determine the AZT+3TC contents in tablets from five different manufacturers, as well as their dissolution profile. The results obtained employing the proposed methodology was similar to methods using first derivative technique and HPLC.

Neste trabalho descreve-se a composição mineral das folhas de Lippia alba (Mill.) que são utilizadas na preparação de chá utilizado na medicina popular. Assim, as folhas da espécie foram coletadas em cidades brasileiras e as amostras foram digeridas usando ácido nítrico e peróxido de hidrogênio em placa aquecedora e, em seguida, foram analisadas empregando espectrometria de emissão óptica com plasma acoplado indutivamente (ICP OES). Para avaliação da exatidão foi utilizado o material de referência certificado, folhas de maçã - NIST SRM 1515. Os resultados demonstraram que cálcio, magnésio e fósforo têm conteúdo médio de 1.950, 2.856 e 2.335 mg 100 g-1 e variações de concentrações de 767-3.887, 314-8.591 e 247-9.214 mg 100 g-1, respectivamente. Os micro-elementos, bário, zinco, cobre, ferro, manganês e níquel têm conteúdos médios de 2,16; 2,95; 0,94; 11,2; 4,25 e 0,09 mg 100 g-1, para variações de concentrações de 0,66-7,1; 1,35-6,3; 0,33-1,7; 0,98-34; 0.82-7,4 e 0,03-0,15 mg 100 g-1, respectivamente. Os dados foram também avaliados usando análise de componentes principais (PCA).

Leaves of Lippia alba (Mill.) N.E. Brown are used for the preparation of tea infusions that are employed in folk medicine. In this paper, the mineral composition of Lippia alba (Mill.) leaves, collected from different Brazilian cities, was evaluated. The samples were digested using nitric acid and hydrogen peroxide on a hot plate and were analyzed using inductively coupled plasma optical emission spectrometry (ICP OES). SRM 1515 apple leaves from NIST were used for checking accuracy. The results demonstrated that calcium, magnesium and phosphorus have average contents of 1,950, 2,856 and 2,335 mg 100 g-1, respectively, and concentration ranges of 767-3,887, 314-8,591 and 247-9,214 mg 100 g-1, respectively. The microelements barium, zinc, copper, iron, manganese and nickel have average contents of 2.16, 2.95, 0.94, 11.2, 4.25 and 0.09 mg 100 g-1, respectively, and concentration ranges of 0.66-7.1, 1.35-6.3, 0.33-1.7, 0.98-34, 0.82-7.4 and 0.03-0.15 mg 100 g−1, respectively. The data were also evaluated using principal component analysis (PCA).

Neste artigo, é proposta uma nova técnica para transferência de calibração, que combina o Algoritmo das Projeções Sucessivas (APS) para seleção de variáveis robustas com a técnica de sub-amostragem e agregação de modelos conhecida como subagging. A técnica proposta tem por objetivo construir modelos de Regressão Linear Múltipla (RLM) que sejam robustos com respeito a diferenças na resposta instrumental de dois espectrômetros (primário e secundário). Para isso, um pequeno conjunto de amostras de transferência, com espectros adquiridos no instrumento secundário, é empregado para guiar o procedimento de seleção de variáveis. A eficiência da técnica proposta é demonstrada em um estudo de caso envolvendo a determinação por FT-IR da massa específica e duas temperaturas de destilação (T10%, T90%) em amostras de gasolina e a determinação por NIR de umidade em amostras de milho. Em termos do erro quadrático médio de predição no espectrômetro secundário, os modelos RLM gerados pela abordagem APS-subagging forneceram resultados melhores que os obtidos por Mínimos Quadrados Parciais empregando Padronização Direta por Partes. Em particular, o uso de subagging resultou em uma redução mais sistemática do erro de predição com a inclusão progressiva de amostras de transferência.

This paper proposes a new technique for calibration transfer, which combines the Successive Projections Algorithm (SPA) for robust variable selection with the subsampling and model aggregation technique known as subagging. The proposed technique is aimed at building Multiple Linear Regression (MLR) models that are robust with respect to differences in the instrumental response of two spectrometers (primary and secondary). For this purpose, a small set of transfer samples with spectra acquired at the secondary instrument is employed to guide the variable selection procedure. The efficiency of the proposed technique is demonstrated in a case study concerning the FT-IR determination of specific mass and two distillation temperatures (T10%, T90%) for gasoline samples and the NIR determination of moisture in corn samples. In terms of the root-mean-square error of prediction at the secondary spectrometer, the MLR models obtained according to the SPA-subagging approach provided better results in comparison with Partial Least Squares employing Piecewise Direct Standardization. In particular, the use of subagging resulted in a more systematic reduction in the prediction error with the progressive inclusion of transfer samples.

As leishmanioses são zoonoses em expansão no Brasil, tendo o cão importância na transmissão e dispersão da doença, principalmente em áreas de leishmaniose visceral. O objetivo desta pesquisa foi avaliar a soroprevalência de leishmaniose em cães domiciliados na zona urbana de Cuiabá. Para a pesquisa foram selecionados quatro bairros de Cuiabá, sendo um em cada regional administrativa. A amostragem canina foi definida estatisticamente, considerando-se a prevalência de 8,4%. Dos 468 cães analisados, 16 foram reagentes na imunofluorescência indireta, obtendo-se uma prevalência geral de 3,4%. Não foi observada predisposição racial, sexual e etária para a ocorrência da leishmaniose canina. Os principais fatores de risco identificados na ocorrência da infecção canina na Cidade de Cuiabá, foram a localização dos cães no peridomicílio, bem como a proximidade das residências de matas, evidenciando mudanças na ocorrência da doença no ambiente urbano.

Leishmaniases are zoonoses that are undergoing expansion in Brazil. Dogs are of importance regarding transmission and dispersion of the disease, especially in areas presenting visceral leishmaniasis. The aim of this study was to evaluate the seroprevalence of leishmaniasis among domestic dogs in the urban area of Cuiabá. For this investigation, four districts of Cuiabá were selected, one in each administrative region. The dog sampling was defined statistically, taking the prevalence to be 8.4%. Among the 468 dogs examined, 16 presented an indirect immunofluorescence reaction, thus resulting in an overall prevalence of 3.4%. There was no predisposition towards canine leishmaniasis occurrences in relation to breed, sex or age. The main risk factors for occurrences of canine infection identified in the city of Cuiabá were the presence of dogs living in areas surrounding homes and the proximity of homes to forests. Thus, there have been changes in leishmaniasis occurrences within the urban environment.

Optical chemical sensors with detection in the near and mid infrared region are reviewed. Fundamental concepts of infrared spectroscopy and optical chemical sensors are briefly described, before presenting some aspects on optical chemical sensors, such as synthesis of NIR and IR reagents, preparation of new materials as well as application in determinations of species of biological, industrial and environmental importance.

This paper is a translation of an IUPAC document by K. Danzer, M. Otto and L. A. Currie (Pure Appl. Chem., 2004, 76(6), 1215-1225). Its goal is to establish a uniform and meaningful standard for terminology (in Portuguese), notation, and formulation concerning multispecies calibration in analytical chemistry. Calibration in analytical chemistry refers to the relation between sample domain and measurement domain (signal domain) expressed by an analytical function x = f s (Q) representing a pattern of chemical species Q and their amounts or concentrations x in a given test sample and a measured function y = f (z) that may be a spectrum, chromatogram, etc. Simultaneous multispecies analyses are carried out mainly by spectroscopic and chromatographic methods in a more or less selective way. For the determination of n species Qi (i=1,2, ..., n), at least n signals must be measured which should be well separated in the ideal case. In analytical practice, the situation can be different.

Neste trabalho, foi avaliada a composição mineral da farinha de trigo consumida no Brasil. Na etapa de amostragem foram coletadas 54 amostras em 15 cidades, incluindo as principais cidades brasileiras como: São Paulo, Rio de Janeiro, Salvador, Porto Alegre, Recife e outras. Os elementos determinados foram: cálcio, cobre, magnésio, manganês, ferro, fósforo, potássio e zinco. As amostras foram digeridas usando acido nítrico e peróxido de hidrogênio em sistema aberto. A técnica analítica empregada foi a espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES). A validação do método (incluindo digestão e determinação) foi confirmada usando um material de referência certificado de farinha de trigo fornecido pelo National Institute of Standards & Technology (NIST). Considerando as 54 amostras analisadas, os resultados demonstraram que os macronutrientes: cálcio, magnésio, potássio e fósforo encontram-se em média de 0,27; 0,35; 1,71 e 1,92 mg g-1, com variação da concentração de 0,11-1,96; 0,19-0,51; 0,76-3,16 e 0,81-7,15 mg g-1, respectivamente. Os micronutrientes: cobre, ferro, manganês e zinco encontram-se em média de 1,84; 37,82; 8,25 e 9,41 µg g-1, com a variação de concentração de 1,00-2,80; 10,46-146,58; 3,89-14,74 e 5,07-13,93 µg g-1, respectivamente. Os resultados foram também avaliados usando as técnicas de análise multivariadas: análise de componente principal (PCA) e análise de agrupamento hierárquico (HCA).

In the present paper, the mineral composition of wheat flour consumed in Brazil was evaluated. In the sampling step 54 samples were collected in 15 cities, including principal Brazilian cities such as: São Paulo, Rio de Janeiro, Salvador, Porto Alegre, Recife and others. The elements determinate were: calcium, copper, magnesium, manganese, iron, phosphorus, potassium and zinc. The samples were digested using nitric acid and hydrogen peroxide in open system. The analytical technique employed was Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES). The method validation (including digestion and determination) was performed using a certified reference material of wheat flour furnished by National Institute of Standards & Technology (NIST). Considering the 54 samples analyzed, the results demonstrated that the macronutrients: calcium, magnesium, potassium and phosphorus have average contents of 0.27, 0.35, 1.71 and 1.92 mg g-1, for concentration ranges of 0.11-1.96, 0.19-0.51, 0.76-3.16 and 0.81-7.15 mg g-1, respectively. The micronutrients: copper, iron, manganese and zinc have average contents of 1.84, 37.8, 8.2 and 9.4 µg g-1, for concentration ranges of 1.00-2.80, 10.5-146.6, 3.9-14.7 and 5.1-13.9 µg g-1, respectively. The results were also evaluated using the multivariate analysis techniques: principal component analysis (PCA) and hierarchical cluster analysis (HCA).