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.

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.

Ozone as degradation agent of pesticide residues in stored rice grains.

This work aimed to study the kinetics of bifenthrin and deltamethrin residues degradation in rice grains under exposure to ozone and evaluate the effect of ozonization on rice grains marketing standards. The grains sprayed with pesticides were exposed to ozone at a concentration of 3 mg L-1 and continuous flow of 1.0 L min-1 for defined periods of up to 10 h. Residues of pesticides were extracted from grains using solid liquid extraction method with low-temperature partition analyzed by gas chromatography with electron capture detection (SLE/LTP-GC/ECD). Data from residual concentrations of bifenthrin and deltamethrin, due to the ozone exposure period, were adjusted to kinetic models of zero order, first order and second order. It was observed that ozone was effective in the degradation bifenthrin and deltamethrin residues, removing 91.9% of bifenthrin and 92.7% of deltamethrin. The kinetic model that best fitted deltamethrin and bifenthrin residues degradation data by ozone, was the one of first order. The marketing standards evaluated were the water content and yield. It was observed the ozone did not alter the rice grains water content and yield.

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.

Leaching and persistence of ametryn and atrazine in red-yellow latosol.

This study evaluated the mobility and persistence of atrazine and ametryn in red-yellow latosols using polyvinyl chloride columns with a diameter of 100 mm and a height of 15 cm. The assays simulated 60-mm rainfall events at 10-day intervals for 70 days. The persistence and leaching were evaluated for these two herbicides. The analytes obtained from the samples were quantified by gas chromatography using flame ionization detection. Compared with ametryn, atrazine showed a greater potential to reach depths below 15 cm over 30 days of simulated rain. Ametryn, however, showed greater persistence in soil at 70 days after application. The persistence of atrazine and ametryn in soil under sunlight was 10 and 144 days respectively. Atrazine was more susceptible to sunlight than ametryn because sunlight favored atrazine degradation in hydroxyatrazine. The results indicate that in red-yellow latosol, atrazine has a high leaching potential in short term, but that ametryn is more persistent and has a high leaching potential in long term.

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 the composition of street cocaine seized in two regions of Brazil.

This work evaluates cocaine purity and the concentration ranges of adulterants and inorganic constituents for 31 street cocaine samples seized in two different regions of Brazil from July 2008 to May 2010. Cocaine and adulterants, such as caffeine, lidocaine and benzocaine, were quantified by Gas chromatography-mass spectrometry (GC-MS), and the inorganic constituents were determined by Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES) and ion chromatography (IC). The cocaine concentrations in the samples seized in the Amazonas state (AM samples) ranged from 154 to 978mgg(-1), and these samples did not contain any of the adulterants studied. The cocaine concentrations in the samples seized in the Minas Gerais state (MG samples) ranged from 63.9 to 753mgg(-1). Caffeine was the main adulterant found in 76% of the MG samples, ranging in concentration from 5.5 to 645.3mgg(-1). Lidocaine was found in 66.7% of the MG samples, with concentrations ranging from 16.3 to 576.7mgg(-1). Benzocaine was found in only one MG sample, at a concentration of 84.8mgg(-1). Fourteen elements were identified by ICP-OES, and a wide variation was observed in the concentrations of Ca, Mg, Na, P, Al, Fe, Mn and Zn. Pearson Product-moment Correlations between the analytes allowed the constituents to be associated with the chemicals used in the manufacturing of cocaine and with some common diluents. The study of the purity of cocaine and the presence and concentration of adulterants and inorganic constituents is important because the latter can have deleterious effects on health.

Determination of maleic hydrazide residues in garlic bulbs by HPLC.

In recent years, the release of information about the preventative and curative properties of garlic on different diseases and their benefits to human health has led to an increase in the consumption of garlic. To meet the requirements of international markets and reach competitiveness and profitability, farmers seek to extend the offer period of fresh garlic by increasing post-harvest life. As a result, the use of maleic hydrazide (1,2-dihydropyridazine-3,6-dione) [MH], a plant growth regulator, has been widespread in various garlic growing regions of the world. The present work was undertaken to develop and validate a new analytical procedure based on MH extraction from garlic previously frozen by liquid nitrogen and submitted to low temperature clean-up. The applicability of the method by analysis of garlic samples from a commercial plantation was also demonstrated. The influence of certain factors on the performance of the analytical methodology were studied and optimized. The approach is an efficient extraction, clean-up and determination alternative for MH residue-quantification due to its specificity and sensitivity. The use of liquid nitrogen during the sample preparation prevents the degradation of the analyte due to oxidation reactions, a major limiting factor. Moreover, the method provides good linearity (r(2): 0.999), good intermediate precision (coefficient of variation (CV): 8.39%), and extracts were not affected by the matrix effect. Under optimized conditions, the limit of detection (LOD) (0.33 mg kg(-1)) was well below the maximum residue level (MRL) set internationally for garlic (15 mg kg(-1)), with excellent rates of recovery (over 95%), good repeatability and acceptable accuracy (CV averaged 5.74%), since garlic is a complex matrix. The analytical performance of the methodology presented was compared with other techniques already reported, with highly satisfactory results, lower LOD and higher recoveries rates. In addition, the extraction process is simple, not expensive, easily executable and requires lower volumes of organic solvent. The proposed methodology removes the need of extensive typical laboratory extraction procedures, reducing the amount of time needed for pesticide analysis and increasing sample throughput. Adopting this method gives food safety laboratories the potential to increase cost savings by a suitable technique in routine testing to determine MH residues in garlic.

Optimization and validation of liquid-liquid extraction with low temperature partitioning for determination of carbamates in water.

Using a 2(3) experimental design, liquid-liquid extraction with low temperature partitioning (LLE-LTP) was optimized and validated for analysis of three carbamates (aldicarb, carbofuran and carbaryl) in water samples. In this method, 2.0 mL of sample is placed in contact with 4.0 mL of acetonitrile. After agitation, the sample is placed in a freezer for 3 h for phase separation. The organic extract is analyzed by high performance liquid chromatography with ultraviolet detection (HPLC-UV). For validation of the technique, the following figures of merit were evaluated: accuracy, precision, detection and quantification limits, linearity, sensibility and selectivity. Extraction recovery percentages of the carbamates aldicarb, carbofuran and carbaryl were 90%, 95% and 96%, respectively. Even though extremely low volumes of sample and solvent were used, the extraction method was selective and the detection and quantification limits were between 5.0 and 10.0 microg L(-1), and 17.0 and 33.0 microg L(-1), respectively.

Low-temperature clean-up method for the determination of pyrethroids in milk using gas chromatography with electron capture detection.

This paper describes a new gas-chromatography with electron capture detection (GC-ECD) method for determination of some pyrethroids in milk samples. The extraction of the pyrethroids was carried out by liquid-liquid extraction with clean-up by precipitation at low temperature, without additional stages for removal of fat interferences. The method was efficient with recoveries of 93.0+/-0.1% for cipermethrin and 84.0+/-0.3% for deltamethrin. The quantification limits were 0.75 microg L(-1) for both pyrethroids. The method was simple, of easy execution, and used only small quantities of organic solvent. After optimization and validation, the method was used for the determination of residues of the pyrethroids cipermethrin and deltamethrin in milk and in lactea drink commercialized in Viçosa (MG, Brazil). Some samples presented contamination with deltamethrin at levels below the maximum contamination limits established by the FAO.