UV-Vis spectrophotometry coupled to chemometric analysis for the performance evaluation of atrazine photolysis and photocatalysis.

In this study, a spectrophotometric-chemometric (Spec-Chem) approach was applied as an alternative to chromatography to monitor ATZ and by-products after photolytic and photocatalytic oxidation aiming to unveil the ATZ degradation mechanism. Spec-Chem is an accessible, easy-to-operate, low-cost analytical approach to monitor atrazine (ATZ) and by-products, and its applicability was validated by HPLC, the reference technique for the evaluation of pollutant degradation mechanisms. The chromatographic (DChro) and spectrophotometric (DSpec) data found 95% and 57% ATZ removal after 30 min, respectively, proving that the DSpec erroneously induces a 38% loss in removal efficiency. When DSpec was treated by multivariate curve resolution (MCR) analysis for providing chemometric data (DChem), it found ATZ removal and hydroxyatrazine (HAT) formation statistically equal to DChro (t-test, p = 0.05). After unraveling the ATZ degradation mechanism using Spec-Chem, a new hypothesis for the kinetic calculation of ATZ degradation was presented, where the concentrations of ATZ and HAT were used to find k and R2 values representative for the ATZ degradation mechanism. The values found for k were compatible with the literature under similar conditions of ATZ degradation, and the linear correlation coefficients (R2 = 0.99) showed an optimal fit for the proposed hypothesis. Thus, Spec-Chem was successfully applied to unravel the mechanism of photocatalytic degradation of ATZ in the presence of TiO2, while k was obtained by the new hypothesis proposed that considered ATZ and HAT concentration as parameters of kinetic interest. Therefore, the importance of monitoring quantitatively ATZ and HAT were provided in this study, providing new information for the scientific community.

Determination of melamine in milk by fluorescence spectroscopy and second-order calibration.

Melamine is a compound commonly used in the manufacturing of plastic and flame retardant products, but due to its solubility on water and high nitrogen content, it is also used to adulterate milk to mask adulteration by dilution in protein content tests. This work proposes a quick method using excitation-emission matrix (EEM) fluorescence spectroscopy and second-order calibration methods (PARAFAC and U-PLS/RBL) for the identification and quantification of melamine in milk. The proposed method uses a single clean-up step with acetic acid, resulting in a quick, low-cost, and environmentally friendly procedure, in agreement with green chemistry principles. Both PARAFAC and U-PLS/RBL were capable of detecting melamine in milk above 120.6 and 146.5 ppm respectively, adequate for adulterations above 2% in volume, with RMSEPs of 68.6 and 81.9 ppm, respectively.

Activated carbon production from industrial yeast residue to boost up circular bioeconomy.

This work aims to obtain activated carbon (AC) from yeast residue to boost up bioeconomy. In this way, carbon was prepared from yeast biomass produced by the ethanol industry and after beta-glucan extraction. Carbon was activated with CO2, water vapor, and a combination of both using an experimental design. The best conditions to produce AC were activation with CO2 for 30 min at 850 °C and CO2 flow of 0.09 L/min, set by experimental design and desirability function to optimize the yield, surface area, and microporosity. Thus, for physical activation with water vapor employing the optimized conditions, it was possible to achieve a yield of 56.6% (m/m) for AC with 1144 m2/g of surface area and mean micropore volume of 0.53 cm3/g. The maximum AC surface area reached 1616 ± 567 m2/g with a yield of 21 ± 1%. The prepared ACs were characterized by elemental analysis, X-ray diffractometry, infrared spectroscopy, thermogravimetry analysis, pHPZC, and potentiometric titration to determine the main functional groups of sorption sites. The carbon obtained from the desirability condition was used to remove dipyrone from synthetic aqueous effluent with an experimental sorption capacity of 88 ± 4 mg/g, being the phenomenon described by the Freundlich isotherm model.

A simple voltammetric electronic tongue for the analysis of coffee adulterations.

This work presents a simple and low-cost analytical approach to detect adulterations in ground roasted coffee by using voltammetry and chemometrics. The voltammogram of a coffee extract (prepared as simulating a home-made coffee cup) obtained with a single working electrode is submitted to pattern recognition analysis preceded by variable selection to detect the addition of coffee husks and sticks (adulterated/unadulterated), or evaluate the shelf-life condition (expired/unexpired). Two pattern recognition methods were tested: linear discriminant analysis (LDA) with variable selection by successive projections algorithm (SPA), or genetic algorithm (GA); and partial least squares discriminant analysis (PLS-DA). Both LDA models presented satisfactory results. The voltammograms were also evaluated for the quantitative determination of the percentage of impurities in ground roasted coffees. PLS and multivariate linear regression (MLR) preceded by variable selection with SPA or GA were evaluated. An excellent predictive power (RMSEP = 0.05%) was obtained with MLR aided by GA.

Flow-batch miniaturization.

This study introduces the first micro-flow-batch analyzer (µFBA). A simple, low-cost, deep urethane-acrylate photo-resist ultraviolet-lithographic technique was used in its development. Details of the microfabrication process are presented including; the use of two superimposed photo-masks to improve the micro-channel and stop chamber border definition, as well as integration of an LED/phototransistor photometric pair, while using an open nylon-thread (fishing line) micro-mixing system for solutions homogenization. The system was used for photometric determination of Fe(II) in oral solution iron supplements employing the well-known 1,10-phenanthroline method, with instantaneously prepared micro-chamber calibration solutions. All analytical processes were accomplished by simply changing the timing parameters in the control software. It must be emphasized here that there was no outside preparation of the standard calibration solutions; the mixing was all done in-chamber/in-line, with all solutions maintained flowing while being proportioned for the measurement processes. The µFBA results were acceptable when compared to the reference method, and comparable to normal flow-batch systems. It was possible both to project and build a low-cost probe with high sample throughput (about 120 h(-1)), low relative standard deviations (about 1.1%), and reduced reagent consumption (30 times less than the reference method). The µFBA system based on urethane-acrylate presented satisfactory physical and chemical properties while keeping the flexibility, versatility, robustness, and multi-task characteristics of normal flow-batch analyzers. The µFBA system contributes to the advance of micro-analytical instrumentation, while realizing the basic principles of "Green Chemistry".

Nickel sorption capacity of ground xylem of Quercus ilex trees and effects of selected ligands present in the xylem sap.

In this work the influence of four different ligands present in the xylem sap of Quercus ilex (histidine, citric, oxalic and aspartic acids) on Ni(II) adsorption by xylem was investigated. Grinded xylem was trapped in acrylic columns and solutions of Ni(II), in the absence and presence of the four ligands prepared in KNO(3) 0.1molL(-1) at pH 5.5, were percolated through the column. Aliquots of solutions were recovered in the column end for Ni determination by graphite furnace atomic absorption spectrometry (GFAAS). The experimental data to describe Ni sorption by xylem in both the presence and absence of ligands was better explained by the Freundlich isotherm model. The decreasing affinity order of ligands for Ni was: oxalic acid>citric acid>histidine>aspartic acid. On the other hand, the Ni(II) adsorption by xylem increased following the inverse sequence of ligands. Potentiometric titrations of acidic groups were carried out to elucidate the sorption site groups available in Q. ilex xylem. The potentiometric titration has shown three sorption sites: pK(a) 2.6 (57.7% of the sorption sites), related to monobasic aliphatic carboxylic acids or nitrogen aromatic bases, pK(a) 8.1 (9.6%) and pK(a) 9.9 (32.7%), related to phenolic groups.

Coconut coir as biosorbent for Cr(VI) removal from laboratory wastewater.

A high cost-effective treatment of sulphochromic waste is proposed employing a raw coconut coir as biosorbent for Cr(VI) removal. The ideal pH and sorption kinetic, sorption capacities, and sorption sites were the studied biosorbent parameters. After testing five different isotherm models with standard solutions, Redlich-Peterson and Toth best fitted the experimental data, obtaining a theoretical Cr(VI) sorption capacity (SC) of 6.3 mg g(-1). Acid-base potentiometric titration indicated around of 73% of sorption sites were from phenolic compounds, probably lignin. Differences between sorption sites in the coconut coir before and after Cr adsorption identified from Fourier transform infrared spectra suggested a modification of sorption sites after sulphochromic waste treatment, indicating that the sorption mechanism involves organic matter oxidation and chromium uptake. For sulphocromic waste treatment, the SC was improved to 26.8+/-0.2 mg g(-1), and no adsorbed Cr(VI) was reduced, remaining only Cr(III) in the final solution. The adsorbed material was calcinated to obtain Cr(2)O(3,) with a reduction of more than 60% of the original mass.

Soil calcium and pH monitoring sensor system.

An agrarian sensorial system based on temperature, moisture, and all solid-state ion-selective potentiometric sensors was developed with the objective of monitoring the behavior of H+ and Ca2+ ions in soil and in real conditions, contributing with a new tool that tries to complement the current precision agriculture technology. The evaluation of the sensorial system to pH monitoring presented a good correlation between the results obtained by the system and the standard methodology, allowing us to notice the soil buffer capacity at different soil depths. With regard to calcium, the sensor system also presented an agreement between its results and those obtained by flame atomic absorption spectrometry, using a calibration model based on multiple linear regressions that allows the correct determination of Ca2+ concentrations in soil depths where the relative moisture is different. In this way, using well-known potentiometric sensors in a complex, discontinued, and heterogeneous matrix, such as soil, the sensorial system proved to be a useful task for agrochemical field applications.

Flow injection potentiometric system for the simultaneous determination of inositol phosphates and phosphate: phosphorus nutritional evaluation on seeds and grains.

A simple flow injection potentiometric (FIP) system, which uses a tubular cobalt electrode, has been developed for phosphorus nutritional evaluation of seeds and grains. Inorganic phosphorus, P(i), is determined using a 1 x 10(-2) mol.L(-1) potassium phthalate buffer solution adjusted at pH 4. A sensitivity of 47 mV/decade and an operating range from 10 to 1000 mg.L(-1) (1 x 10(-4)-1 x 10(-2) M) of dihydrogen phosphate are obtained. The inositol phosphates amount, which is referred to the organic phosphorus, P(org), is directly determined from extracts using a 1 x 10(-2) mol.L(-1) Tris-HCl buffer solution adjusted at pH 8. A sensitivity of 127 mV/decade and an operating range of 10-1000 mg.L(-1) (2.5 x 10(-4)-5 x 10(-3) M) of P(org) (expressed as inositol hexakisphosphoric acid monocalcium) are achieved. Some samples of seed and grain are analyzed by an ICP-OES and a spectrophotometric method to compare results to the developed flow system; no significant differences at the 95% confidence level are observed using a paired t test. Other samples such as animal nursing feed, soybean meal, and corn are also analyzed with the proposed FIP system, showing a good correlation to the ICP-OES values.

In-soil potassium sensor system.

A potentiometric sensor system based on potassium ion-selective electrodes was developed for agricultural purposes. Sensors were built using PVC ion-selective membranes over an inner solid contact prepared with graphite-epoxy composites. A copper plate was used as a reference electrode. A two-stage electronic circuit composed of current and voltage amplifiers was designed to interface the sensors to a distributed data acquisition system. Three ion-selective sensors and three off-the-shelf temperature sensors and their associated circuits were mounted in a PVC tube to set up a soil probe. The electronic controls were placed in an airtight box fixed at the upper part of the probe. The system was evaluated in the field, where the sensors presented sensibility within the range of 69-71 mV dec(-)(1). Extracts of soil samples were analyzed by a current flame photometry approach, and the results, compared with the probe measurements, showed a linear relationship (r (2) = 0.992 and 0.995, respectively, to 5 and 20 cm depths), which implies viability and instrumentation reliability for agricultural applications.