Study and voltammetric determination of fipronil in bovine lactose-free milk by differential pulse voltammetry using a carbon paste electrode.

A novel voltammetric screening method has been developed for the rapid determination of fipronil (FPN) residues in lactose-free milk samples with the use of a carbon-paste electrode (CPE) by differential-pulse voltammetry (DPV). Cyclic voltammetry indicated the occurrence of an irreversible anodic process at approximately +0.700 V (vs. Ag|AgCl, 3.0 mol L-1 KCl) in a 0.100 mol L-1 NaOH supporting electrolyte prepared as a 30% (v/v) ethanol-water solution. Quantification of FPN was carried out by DPV and analytical curves were constructed. In the absence of a matrix, the limits of detection (LOD) and quantification (LOQ) were 0.568 mg L-1 and 1.89 mg L-1, respectively. In the presence of a lactose-free skim milk matrix, the values of LOD and LOQ were 0.331 mg L-1 and 1.10 mg L-1. The recovery percentages for three different concentrations of FPN in lactose-free skim milk samples ranged between 95.3% and 109%. All assays could be conducted with milk samples without any prior extraction steps or pre-concentration of FPN, making this novel method rapid, simple, and relatively cheap.

Evaluation of imazalil dissipation/migration in postharvest papaya using low-temperature partition extraction and GC-MS analysis.

Methods involving solid-liquid extraction with low-temperature partition and analysis by gas chromatography coupled to mass spectrometry (GC-MS) were validated to investigate the dissipation/migration of residues of the postharvest fungicide imazalil in papaya skin, pulp, and seeds. The fruits were stored for 23 days (14 °C). Every two days, fruits from the control group and those treated with imazalil had their skin, outer pulp, inner pulp, and seeds separated and then analyzed by GC-MS. After the 23rd day, about 70% of the imazalil had dissipated. Most of the remaining residue was found in the skin; however, the small amount migrating into the pulp was above the maximum residue levels allowed by the regulatory agencies. Imazalil residue was also detected in seeds at concentrations lower than the LOQ (0.025 mg kg-1). Mass loss was the only quality parameter that showed a significant difference between the fruits of the control and study groups.

Microextraction technique associated with gas chromatography-mass spectrometry for determining pesticide residues in urine.

Urine is one of the biological matrices most used for detecting human contamination, as it is representative and easily obtained via noninvasive sampling. This study proposes a fast, accurate, and ecological method based on liquid-liquid microextraction with low-temperature partition (µLLE/LTP). It was validated to determine nine pesticides (lindane, alachlor, aldrin, chlorpyrifos, dieldrin, endrin, DDT, bifenthrin, and permethrin) in human urine, in association with gas chromatography coupled with mass spectrometry (GC-MS). The technique was optimized through a factorial design. The best conditions for the simultaneous extraction of the analytes comprised the addition of 600 µL of water and 600 µL of acetonitrile (extracting solvent) to a 500-µL urine sample, followed by vortexing for 60 s. By freezing the samples for 4 h, it was possible to extract the pesticides and perform the extract clean-up simultaneously. The parameters selectivity, linearity, limit of detection (LOD), limit of quantification (LOQ), precision, and accuracy were used to appraise the performance of the method. Good values of selectivity and linearity (R2 > 0.990), LOQ (0.39-1.02 µg L-1), accuracy (88-119% recovery), and precision (%CV ≤ 15%) were obtained. The µLLE/LTP-GC-MS method was applied to authentic urine samples collected from volunteers in Southeast Brazil.

Influence of Homogenization in the Physicochemical Quality of Human Milk and Fat Retention in Gastric Tubes.

BACKGROUND: The retention of human milk nutrients in gastric tubes used to feed premature infants is a challenge to be overcome. RESEARCH AIMS: To evaluate (1) the performance of six homogenizers (mixing processor, piston valve, ultrasonic bath, ultraturrax, stirring mixer, and ultrasound probe) for the fat retention reduction in gastric tubes; (2) the influence of the best homogenization conditions on the fatty acid and protein profiles of human milk; and (3) the cost/benefit ratio for the inclusion of homogenization as a new step in human milk processing. METHODS: The influence of different levels and times of homogenization on reducing fat retention of human milk in probes was evaluated in this comparative prospective cross-sectional study. After homogenization, human milk flowed through a gavage and infusion pump apparatus used for feeding. Fat content was quantified before and after feeding. The techniques that reduced fat globule sizes and/or promoted a lower percentage of fat holding were evaluated for efficiency, variations in the fatty acid and protein profiles, and energy density and operating costs. RESULTS: Homogenization led to a reduction in fat retention in feeding probes. The mixer processor and the ultrasound probe reduced fat retention by 99.23% (SD = 0.07) and 99.95% (SD = 0.02), respectively, and did not negatively influence fatty acid and protein profiles. The mixer processor demonstrated low energy density and low cost for human milk processing. CONCLUSION: Homogenization promoted reduced fat retention in the feed probe and could help maintain fat nutrients of human milk during enteral feeding.

Direct determination of boscalid in grape samples by differential pulse voltammetry using a carbon paste electrode.

A new methodology to determine directly the fungicide boscalid (BSC) was developed and successfully applied in red grape 100% juice, peel extracts, pulp and purple grape seeds (Vitis labrusca L.) with a working carbon paste electrode (CPE) without sample preparation. Cyclic voltammetry (CV) indicated the presence of an irreversible cathodic process of BSC at -1.21 V vs. Ag|AgCl (KCl 3.0 mol L-1) in a solution of 0.100 mol L-1 HCl/acetone 70 : 30 (v/v). This behavior was also observed using Square Wave Voltammetry (SWV). The Differential Pulse Voltammetry (DPV) technique proved to be more sensitive and with higher selectivity for BSC quantification. The influence of pH on the reduction of BSC was investigated in Britton-Robinson Buffer (BRB), 0.01 mol L-1 (pH 2.00-12.00). The limit of detection (LOD) values obtained from calibration curves for different samples were as follows: 0.107 mg L-1 for deionized water; 0.146 mg L-1 for red grape 100% juice; 0.922 mg kg-1 for peel extracts; 0.818 mg kg-1 for grape pulp and 0.691 mg kg-1 for grape seeds. The corresponding Limit of Quantification (LOQ) values for the same samples were as follows: 0.358 mg L-1; 0.486 mg L-1; 2.87 mg kg-1; 2.73 mg kg-1 and 2.51 mg kg-1, respectively. In addition, the recovery rates for the different concentration levels in the investigated range varied between 97.13 and 103.4%. All tests performed with the samples did not require extraction or pre-concentration steps of BSC, resulting in a fast, simple and cheap methodology.

Determination of quinclorac by adsorptive stripping voltammetry in rice samples without sample pretreatment.

A novel voltammetric method with practically no sample pretreatment was developed for determination of Quinclorac (QNC) in rice samples by using a working Carbon Paste Electrode (CPE) modified with ionic liquid, with deposition potential (ED) of -1.43 V for 30 s in NaOH 0.01 mol L-1. The systematic influence of cations and anions of imidazole ionic liquids on the composition of CPE has evaluated. The best electrode composition was 65% (w/w) of graphite powder, 30% (w/w) of mineral oil and 5.0% (w/w) of C4min+BF4- ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate). The matrices analyzed were deionized water and extracts of upland rice: white, brown, peel and seed. The limits of quantification ranged between 0.954 mg kg-1 and 3.61 mg kg-1. The recovery percentages of QNC in rice samples ranged between 90% and 121%. The simplicity and good analytical frequency enable the proposed method to be used to obtain preliminary information on the presence of QNC, prior to the implementation of more detailed, costly and elaborate quantitative analyses. The technique can be applied in the study and evaluation of sorption mechanisms, metabolization of the herbicide in plants and its persistence and degradation in the environment.

The efficacy of washing strategies in the elimination of fungicide residues and the alterations on the quality of bell peppers.

Food safety problems caused by pesticide residues in vegetables have become a top issue to raise public concern. In this study, bell peppers were grown in an experimental field and sprayed with two systemic (azoxystrobin and difenoconazole) and one contact (chlorothalonil) fungicides. Ozone (ozonated water and water continuously bubble with ozone) or conventional domestic (washing with distilled water, detergent, acetic acid, sodium bicarbonate, and sodium hypochlorite solutions) procedures were investigated to identify the most effective way to remove fungicide residues in bell peppers. The residues in the fruits and the washing solutions were determined by solid-liquid extraction with a low-temperature partition (SLE/LTP) and liquid-liquid extraction with a low-temperature partition (LLE/LTP), respectively, and analyzed by gas chromatography. Water continuously bubbled with ozone a concentration of 3 mg L-1 was the most efficient treatment with removal of fungicides residues ranging from 67% to 87%. However, similar treatment at a lower concentration (1 mg L-1) did not only efficiently removed fungicide residues (between 53% and 75%) but also preserving the quality of the fruit along a storage time of 13 days. Among the conventional solutions, sodium bicarbonate at 5% showed good efficiency removing between 60% and 81% of the fungicide residues from bell peppers, affecting the color quality of the fruit. Overall, the most affected physicochemical parameters in bell peppers after the treatments were weight loss, color, and vitamin C content.

Building robust models for identification of adulteration in olive oil using FT-NIR, PLS-DA and variable selection.

Being a product with a high market value, olive oil undergoes adulterations. Therefore, studies that make the verification of the authenticity of olive oil more efficient are necessary. The aim of this study was to develop a robust model using FT-NIR and PLS-DA to discriminate extra virgin olive oil samples and build individual models to differentiate adulterated extra virgin olive oil samples. The best PLS-DA-OPS classification model for olive oils showed specificity (Spe) and accuracy (Acc) values higher than 99.7% and 99.9%. For the classification of adulterants, PLS-DA-OPS models presented values of Spe at 96.0% and Acc above 95.5% for varieties. For the blend, the best PLS-DA-GA model presented Acc and Spe values greater than 98.2% and 98.8%. Reliable and robust models have been built, allowing differentiation from seven adulterants to genuine extra virgin olive oils.

Proposal of a controlled release of citrate by solubility equilibrium.

Some substances at high concentrations in both the body and the environment can be toxic. The remediation of contaminated environments, for example by metals in toxic concentrations is a fairly current problem. In this way, organic acids of low molecular weight, because they are biodegradable, constitute an alternative potentially for their use in phytoremediation processes. Among these acids, citric acid was chosen to be used in this work due to its suitable binder behaviour, with high stability constants. The purpose of this work was to develop a controlled release of citrate that allows its release to the soil solution to pre-defined concentrations by the system and that this concentration is maintained even if the binder is consumed in the complexation of metals, diluted or percolated. In this way, the system has an additional feature, compared to the conventional controlled release system. The presence of calcium citrate allowed for a slower release of citrate compared to citrate soluble salts or even with calcium citrate directly in solution. The Noyes-Whitney model allowed to explain the effects of pellet sizes and percentages of agar-agar. The pH of the receptor solution and the calcium concentrations used in the preparation of the gels influenced the equilibrium concentration of the citrate, demonstrating the independence of the controlled release process in relation to other variables in the solution. The controlled release system proposed in this work is a promising and very useful system for phytoextraction processes.

Use of ozone and detergent for removal of pesticides and improving storage quality of tomato.

The efficiencies of two conventional domestic procedures (immersion in pure water and detergent solution at 0.25 and 1%) and two treatments using ozone (immersion in water with bubbling O3 and immersion in ozonated water, both at 1 and 3 mg L-1) were evaluated for the removal of residues of the fungicides azoxystrobin, chlorothalonil and difenoconazole in tomatoes. The fungicides were sprayed on the fruits at the recommended concentration for the crop. The residues in the tomatoes and in the washing solutions were determined by extraction with low-temperature partition techniques and analysis by gas chromatography. More concentrated solutions were more effective in removing pesticide residues. The water bubbled with ozone at 3 mg L-1 was the most efficient treatment for the removal of fungicides, reaching a reduction of 70-90% of the residues. However, the treatments with the lowest concentration of ozone had lower loss of fruit mass during storage.

Environmental remediation processes by zero valence copper: reaction mechanisms.

Recent studies have shown Cu(0) as a promising material for the removal of organic and inorganic pollutants. However, there is no review addressing the studies performed. This fact may be related to the toxicity of the particles and the copper released in solution that has not motivated researchers, which entails in a reduced number of publications. However, studies point out how to solve the problem of Cu deposition in support materials. In this work, a detailed review of Cu(0) applications was performed. The specific focus was the reaction mechanisms related to adsorption, oxidation, and reduction processes. Initially, the resources that allow the understanding of the reaction mechanism, such as characterization techniques and the experimental conditions for investigation of the species involved in the process, were presented. The studies were evaluated separately, showing the mechanisms involved only with the application of Cu(0) in pure and isolated form and in association with oxidizing or reductive agents, combined with irradiation sources and ultrasonic waves and in the form supported in polymer matrices. It was verified that by the proposed reaction mechanisms, the exclusive participation of Cu(0), being the removal process, explained only by the redox behavior of copper. Therefore, the review showed the need for future research regarding the redox behavior of the contaminants.

Characterization and evaluation of sorption potential of the iron mine waste after Samarco dam disaster in Doce River basin - Brazil.

The Fundão dam collapsed releasing 60 million tons of mining waste into the environment. The mining wastes should be better studied, since some of them are deposited on the alluvial plains soil and at the bottom of the rivers, like sediments, of the region affected. Thus, this work aims to perform the chemical, physical and adsorptive characterization of the samples colleted in region de Paracatu de Baixo. The mining waste has uneven surface, with sizes ranging from 2 to 200 µm, pHPCZ in 6.0. Are composed predominantly by kaolinite, goethite, hematite, gibbsite and quartz. It has been classified as non-hazardous residues. The adsorption studies showed the mining waste have a low Cationic Exchange Capacity. The sorption process was occurs by ion exchange and the kinetics follows the pseudo second order model (R2 > 0.78). The process is endothermic (ΔH in 29.33 kJ mol-1) and spontaneous (ΔG in -24.7 kJ mol-1 at 25 °C). The Langmuir model presented a better fit (R2 > 0.995) to the experimental data. Therefore, the methylene blue can be used as a cation model to predict the behavior of cationic species on the mining waste, with maximum adsorption capacity of 4.42 mg g-1 at 25 °C.

Pesticide residue removal in classic domestic processing of tomato and its effects on product quality.

This study was undertaken to evaluate the effectiveness of several household practices (washing with water or acidic, alkaline, and oxidizing solutions, and peeling) in minimizing pesticide residue contamination of tomatoes, as well as the impact on the quality of the treated fruit. Tests were performed using two systemic fungicides (azoxystrobin and difenoconazole) and one contact fungicide (chlorothalonil). Solid-liquid extraction with low temperature partition (SLE/LTP) and liquid-liquid extraction with low temperature partition (LLE/LTP) were used to prepare the samples for pesticides determination by gas chromatography. Washing the tomatoes with water removed approximately 44% of chlorothalonil, 26% of difenoconazole, and 17% of azoxystrobin. Sodium bicarbonate (5%) and acetic acid (5%) solutions were more efficient, removing between 32 and 83% of the residues, while peeling removed from 68 to 88% of the pesticides. The washing solutions altered some fruit quality parameters, including acidity and chroma, and also caused weight loss. Acetic acid (0.15 and 5%) and hypochlorite (1%) solutions had the greatest effect on these parameters.

Effects of ozone fumigation treatment on the removal of residual difenoconazole from strawberries and on their quality.

The effect of ozone fumigation on the reduction of difenoconazole residue on strawberries was studied. Strawberries were immersed in 1.0 L of aqueous solution containing 400 µL of the commercial product (250 g L(-1) of difenoconazole) for 1 min. Then, they were dried and exposed to ozone gas (O3) at concentrations of 0.3, 0.6 and 0.8 mg L(-1) for 1 h. The ozone fumigation treatments reduced the difenoconazole residue on strawberries to concentrations below 0.5 mg kg(-1), which corresponds to a 95% reduction. The strawberries treated with ozone and the control group, which was not treated with ozone, were stored at 4°C for 10 days. Some characteristics of the fruit were monitored throughout this period. Among these, pH, weight loss and total color difference did not change significantly (P > 0.05). The fumigation with ozone significantly affected the soluble solids, titratable acidity and ascorbic acid content (vitamin C) of the strawberries preventing a sharp reduction of these parameters during storage.

Evaluation of a high sensitivity PbO(2) pH-sensor.

In this paper, a new high sensitivity potentiometric pH-electrode with a response in the acid region is proposed. It consists of a PbO(2)-paraffin matrix deposited on graphite. Its simple construction and studies of some variables at 0.5molL(-1) ionic strength are reported. A direct relationship between the electric potential difference and the solution pH was observed for pH values ranging from 1.2 to 7.5. A slope greater than 100mV/decade and a conditional electric potential of about 1250mV were obtained. The results presented a high correlation with those from a conventional glass pH-electrode in complex matrix samples.