Magnetic solid phase extraction as a nonchromatographic method for the quantification of ultratrace inorganic arsenic in rice by inductively coupled plasma-optical emission spectrometry (ICP OES).

An alternative analytical method was developed for the quantification of inorganic arsenic (iAs) in rice by ICP OES. Iron nanoparticles modified with an organophosphorus compound were used as the solid phase for MSPE of iAs from the plant matrix. The MSPE procedure was performed using 4 mL of a buffer solution with pH 4.0, 20 mg of the nanomaterial, and a 15-min extraction time. The total As (tAs) by ICP OES was also quantified using the same MSPE procedure after solubilization of the samples by a block digester. The accuracy of tAs and iAs quantification was verified using CRM NIST 1568b (97 % and 101 % recovery, respectively). The precision (RSD < 15 %) and LOD and LOQ (1.08 and 3.70 µg kg-1, respectively) of the proposed method were satisfactory. The rice samples had tAs contents between 0.090 and 0.295 mg kg-1 and iAs mass fractions between 0.055 and 0.109 mg kg-1.

Selenium in Brazil nuts: An overview of agronomical aspects, recent trends in analytical chemistry, and health outcomes.

Se is an essential element in mammals. We review how its bioavailability in soil and the ability of plants to accumulate Se in foods depends on the soil Se profile (including levels and formats), besides to describe how the various selenoproteins have important biochemical functions in the body and directly impact human health. Owing to its favorable characteristics, the scientific community has investigated selenomethionine in most nut matrices. Among nuts, Brazil nuts have been highlighted as one of the richest sources of bioavailable Se. We summarize the most commonly used analytical methods for Se species and total Se determination in nuts. We also discuss the chemical forms of Se metabolized by mammals, human biochemistry and health outcomes from daily dietary intake of Se from Brazil nuts. These findings may facilitate the understanding of the importance of adequate dietary Se intake and enable researchers to define methods to determine Se species.

Non-chromatographic arsenic speciation analyses in wild shrimp (Farfantepenaeus brasiliensis) using functionalized magnetic iron-nanoparticles.

A new iron-magnetic nanomaterial functionalized with organophosphorus compound was used as solid-phase for arsenic speciation analysis in seafood samples by ICP-MS. The procedure was optimized using chemometric tools and the variables pH = 4.0, 15 min extraction time, and 20 mg of mass of material were obtained as the optimum point. The inorganic arsenic (iAs) extracted using nanoparticles presented concentrations between 20 and 100 µg kg-1 in the evaluated samples. The method was validated for accuracy using CRMs DOLT-5 and DORM-4. It was possible to reuse the same magnetic nanomaterial for 6 successive cycles, and we obtained a detection limit of 16.4 ng kg-1. The proposed method is suitable for the use of inorganic speciation of As, presenting good accuracy, precision, relatively low cost, and acquittance to green chemistry principles.

Rapid and Low Cost Determination of Total Mercury in Cat Foods by Photochemical Vapor Generation Coupled to Atomic Absorption Spectrometry.

A rapid and low-cost method for determination of total mercury (THg) in cat food was developed based on photochemical vapor generation (PVG) coupled to cold vapor atomic absorption spectrometry (CVAAS). Cat food samples with ingredients based on tuna fish and other seafood were investigated. Organic acid precursor and concentration for radical generation and Hg photoreduction, sample UV irradiation time, and carrier gas flow were optimized. Highest PVG efficiency was achieved using 10% v v-1 formic acid, 4-s UV irradiation time, and a carrier gas flow of 50 mL min-1. The calibration function presented a correlation coefficient of 0.99. Accuracy was confirmed by analysis of Certified Reference Materials with recoveries of 93-110% and relative standard deviation lower than 6%. Under optimized conditions, a procedural detection limit of 0.28 µg kg-1 was obtained. Determination of THg in 10 samples of cat food purchased in local markets revealed a concentration range of 0.035-0.388 mg kg-1. Highest concentrations were found in cat foods. Only one sample presented a concentration close to the regulatory limit of the European Commission Directive. Assuming the estimated daily food intake (EDI) calculated in a range of 0.0021 to 0.023 mg of THg per day per kg body weight, it is concluded that it remains below that considered lethal for cats. The methodology is efficient, simple, low cost, and fit for purpose.

Chemometric tools applied to optimize a fast solid-phase microextraction method for analysis of polycyclic aromatic hydrocarbons in produced water.

Chemometric tools are powerful strategies to efficiently optimize many processes. These tools were employed to optimize a fast-solid phase microextraction procedure, which was used for the analysis of polycyclic aromatic hydrocarbons (PAHs) in oil-based produced water using a Headspace-Solid Phase Microextraction technique (HS-SPME/GC-MS). This optimization was achieved with a 24 factorial design approach, where the final conditions for this extraction procedure were 10 µg L-1, 1 h, 92 °C (at headspace), and 0.62 mol L-1 for PAHs concentration, fiber exposition to headspace, temperature, and NaCl concentration, respectively. The limit of detection (LOD) in this protocol ranged from 0.2 to 41.4 ng L-1, while recovery values from 67.65 to 113.10%. Besides that, relative standard deviation (RSD) were lower than 8.39% considering high molecular weight compounds. Moreover, the proposed methodology in this work does not require any previous treatment of the sample and allows to quantify a higher number of PAHs. Notably, naphthalene was the major PAHs compound quantified in all samples of the produced water at 99.99 µg L-1. Altogether, these results supported this methodology as a suitable analytical strategy for fast determination of PAHs in produced water from oil-based industry.

Evaluation of different strategies for determination of selenomethionine (SeMet) in selenized yeast by asymmetrical flow field flow fractionation coupled to inductively coupled plasma mass spectrometry (AF4-ICP-MS).

This manuscript exemplifies the prospective use of asymmetrical flow field flow fractionation (AF4) coupled to inductively coupled plasma mass spectrometry (ICP-MS) as a simple tool for chemical speciation of selenomethionine (SeMet) in selenized yeast. Several popular sample preparation methods were evaluated for their suitability to determine selenomethionine (SeMet) in selenized yeast by AF4-ICP-MS. These included water, methanesulfonic acid (MSA), formic acid (FA) and alkaline extractions. Alkaline extraction (using sodium dodecyl sulfate buffer) provided the best recovery/determination conditions for SeMet based on analysis of NRC certified reference material (CRM) SELM-1 since it minimized hydrolysis of the protein peptide bonds optimally required for the AF4 separation. The analytical performance of three different AF4 membranes (5, 10 and 500 kDa regenerated cellulose) was also evaluated. No significant difference in the recovery of SeMet was observed when using 5 and 10 kDa RC membranes, whereas the 500 kDa membrane resulted in a significant loss. The proposed method presents appropriate instrument and intra-assay precisions of 4.4-9.2% and 3.8% RSD, respectively, a detection limit of 0.49 µg L-1 SeMet as Se and good linearity with correlation coefficients (R) between 0.996 - 0.999. This is the first report of use of AF4-ICP-MS for species specific quantitation of SeMet in selenized yeast demonstrating its efficient use as an alternative method to other traditional chromatographic techniques.

The concentration of polyphenolic compounds and trace elements in the Coffea arabica leaves: Potential chemometric pattern recognition of coffee leaf rust resistance.

Coffee (Coffea arabica L.) is an important commodity, involving about 500 million people from the cultivation of the coffee trees to final consumption of infusions of the ground roasted coffee beans. In contrast to a considerable amount of research performed on green coffee beans, there are relatively few studies regarding the chemical constituents of coffee leaves. Hemileia vastatrix is a parasite, specific to coffee plants and causes coffee leaf rust, which is a very destructive disease. Some coffee plants have natural resistance which is mainly linked to a gene and specific host resistance response. An increase in flavonoid production may be related to fungal disease resistance, with the levels and flavonoid types being an early physiological response to rust infection. Trace inorganic elements can be related to many roles in the defense response of higher plants and can be used as a biomarker for some diseases. To address this, coffee leaves from 16 different cultivars of Coffea arabica were harvested from Minas Gerais, Brazil (susceptible and resistant to rust) and their polyphenolic compounds were extracted using the QuEChERS technique and quantitated by HPLC-ESI-MS. The same leaves were decomposed using an acid mixture in a block digester and the content of Al, Cu, Mg, Mn, Ni, Sn and Zn was quantitated by ICP-OES. Principal component analysis (PCA) was applied and we could establish a relation between polyphenolic and trace element concentration in the leaves with resistance to rust infection. On this basis in this preliminary study we were able to separate the resistant from the susceptible cultivars. The main compounds responsible for this differentiation were the content of chlorogenic acid and magnesium in the leaves. The content of polyphenolic compounds was lower in susceptible cultivars and a diametric effect was observed between Mn and Mg concentrations. This study shows potential for the discrimination of resistant and susceptible coffee trees based on the analyses of both trace element and polyphenolic concentration.

Investigation of a rapid infrared heating assisted mineralization of soybean matrices for trace element analysis.

A fast sample preparation procedure based on use of infrared (IR) assisted heating for mineralization of soybean derived samples has been developed for their subsequent multielement analysis by inductively coupled plasma optical emission spectrometry (ICP-OES) and flame atomic absorption spectrometry (FAAS). A cold finger was examined for refluxing of acid vapors to determine its impact on efficiency and economy of digestion. The optimized procedure, based on 1 g subsamples, 8 mL of HNO3 (65% w/w) and exposure of the mixture to a 500 W IR source for 5 min without refluxing, permitted accurate determination of all analytes in NIST SRM 1568b (rice flour). Detection limits using ICP-OES were (µg/kg) 97, 1.0, 39, 185, 0.47 and 1200 for Ca, Cu, Fe, K, Mn and P, respectively, and 18 for Zn by FAAS. The IR-assisted digestion approach provided a low cost, easy to use system having great potential for implementation in routine analysis of trace elements in soybean and similar matrices.

Comparison between boiling and vacuum cooking (sous-vide) in the bioaccessibility of minerals in bovine liver samples.

Only some of ingested nutrients are available for absorption by the organism. The foods generally are submitted to some heat processing that may interfere in the bioaccessibility of nutrients. There are no studies of the influence of cooking under vacuum (sous vide) on the bioaccessibility of minerals. This study evaluated the in vitro bioaccessibility of Ca, Cu, Fe, K, Mg and Zn in bovine liver samples after traditional cooking in water and using the sous vide procedure. All heat treatments of bovine liver promoted the increase of the bioaccessibility of Ca, Cu, Fe, K and Mg, except for Zn when the effect was the opposite. The sous vide method provided higher bioaccessibility of these minerals than cooking in boiling water, except for K when both methods presented equivalent values. Samples of raw liver and liver cooked using sous vide method presented the following percentage of bioaccessible fraction, respectively: 39.7% and 95.8% (Ca), 8.78% and 26.9% (Cu), 8.80% and 39.5% (Fe), 30.2% and 42.6% (K), 26.4% and 43.9% (Mg), 24.8% and 36.3% (Zn). Thus, under the aspect of improvement availability of studied minerals by organism, the sous-vide technique was the most suitable to cook bovine liver.

A new approach to mineralization of flaxseed (Linum usitatissimum L.) for trace element analysis by flame atomic absorption spectrometry.

A new approach to the analysis of Cu, Fe, Mn and Zn in flaxseed was developed based on infrared-assisted acid digestion. Quantitation by flame atomic absorption spectrometry yields results in agreement with those arising from aggressive total decomposition using conventional microwave-assisted (MW) digestions. A full factorial design in two levels was applied to evaluate the impact of significant variables for all elements to determine optimal experimental conditions. A desirability function revealed these to be: 2.0g sample mass, 8mL of HNO3 and 8min of heating time in the IR system. Precision better than 10% (RSD) was obtained, superior to that of a combined IR-MW approach. Sample preparation based on IR-assisted digestion provides a rapid and inexpensive alternative to other conventional techniques for the analysis of complex samples and is able to accommodate relatively large masses of sample, alleviating potential homogeneity issues as well as enhancing detection power.

Optimization of a cloud point extraction procedure with response surface methodology for the quantification of dissolved iron in produced water from the petroleum industry using FAAS.

The characterization of inorganic elements in the produced water (PW) samples is a difficult task because of the complexity of the matrix. This work deals with a study of a methodology for dissolved Fe quantification in PW from oil industry by flame atomic absorption spectrometry (FAAS) after cloud point extraction (CPE). The procedure is based on the CPE using PAN as complexing agent and Triton X-114 as surfactant. The best conditions for Fe extraction parameters were studied using a Box-Behnken design. The proposed method presented a LOQ of 0.010µgmL-1 and LOD of 0.003µgmL-1. The precision of the method was evaluated in terms of repeatability, obtaining a coefficient of variation of 2.54%. The accuracy of the method was assessed by recovery experiments of Fe spiked that presented recovery of 103.28%. The method was applied with satisfactory performance to determine Fe by FAAS in PW samples.

Development of a wet digestion method for paints for the determination of metals and metalloids using inductively coupled plasma optical emission spectrometry.

Paints, a complex matrix, have a variable composition that is dependent on the application. In this work, a new wet digestion procedure for the determination of Al, As, Ba, Cd, Cr, Cu, Mn, Ni, Pb, Sn, Sr, Ti and Zn in paint samples using inductively coupled plasma optical emission spectrometry (ICP OES) has been developed. An experimental design approach was employed to determine the optimal conditions for achieving complete solubilization and/or decomposition in the sample preparation method. An efficient sample preparation was developed that consisted of a pre-digestion step at 40°C for 20 min using 1 mL of HNO3 to eliminate organic solvents followed by digestion at 120°C for 3h using 5 mL of HCl and 1 mL of HF in a block digestion. The proposed procedure promotes the complete solubilization of different bases of paints at low temperature and atmospheric pressure. The accuracy was determined by addition/recovery tests and comparing the results with those obtained using the ASTM D335-85a standard sample preparation method. The limits of quantification were 1.78, 0.11, 0.006, 0.006, 0.01, 0.04, 0.006, 0.006, 0.02, 0.07, 0.30, 1.30 and 0.30 mg kg(-1) for Al, As, Ba, Cd, Cr, Cu,Mn, Ni, Pb, Sn, Sr, Ti and Zn, respectively. The proposed method was applied for the analysis of inorganics via the ICP OES of paints with different colors and bases used to cover wall surfaces.

Chemometric characterization of alembic and industrial sugar cane spirits from cape verde and ceará, Brazil.

Sugar cane spirits are some of the most popular alcoholic beverages consumed in Cape Verde. The sugar cane spirit industry in Cape Verde is based mainly on archaic practices that operate without supervision and without efficient control of the production process. The objective of this work was to evaluate samples of industrial and alembic sugar cane spirits from Cape Verde and Ceará, Brazil using principal component analysis. Thirty-two samples of spirits were analyzed, twenty from regions of the islands of Cape Verde and twelve from Ceará, Brazil. Of the samples obtained from Ceará, Brazil seven are alembic and five are industrial spirits. The components analyzed in these studies included the following: volatile organic compounds (n-propanol, isobutanol, isoamylic, higher alcohols, alcoholic grade, acetaldehyde, acetic acid, acetate); copper; and sulfates.