Diethylene glycol is an extremely toxic substance to humans. Recently, cases of beer contamination in Brazil have raised awareness of the need for developing simple screening methods to evaluate this type of compound. This research developed a liquid-liquid extraction with low-temperature partitioning technique to determine diethylene glycol in beer via gas chromatography. Employing a flame-ionization detector simplifies the method, lowers its cost and therefore, it can be used as screening step to assess the possibility of contamination. A gas chromatograph coupled to a mass spectrometer would be used only for a confirmatory analysis. The optimized method was validated for the main figures of merit, and it proved to be adequate, with good values of recovery rate (94-106%), limit of detection (3.0 mg L-1), and quantification (10.0 mg L-1). Accuracy, in terms of repeatability and intermediate accuracy, showed variation coefficients lower than or equal to 20%. This method was applied to 28 samples of beers marketed in Brazil, and diethylene glycol was found above the limit of detection in three of them (10.7%). These results were confirmed by a gas chromatograph coupled to a mass spectrometer, which showed the reliability of the screening method for determining diethylene glycol in beer samples.

Ozone and hypochlorite are used for the disinfection of water and is essential to monitor these. In this paper, methods based on digital images were developed to determine these analytes in waters using the malachite green dye. The oxidation of the reagent with ozone was very fast and with hypochlorite occurred in 10 min in pseudo-first-order kinetics. New software called ICCA was developed for the capture and processing of red, green and blue (RGB) data, which is planned for digital image analysis. In addition, the recently proposed parameters analytical resolution and N9 were used to define some study conditions. An evaluation of different response functions and white correction of the webcam were done, having thrown some light on the subject to this theme. Their optimization showed a linear range from 0.6 mg L-1 to 5.0/6.0 mg L-1 (O3/Cl, respectively). The figures of merit were similar for both. The methods were validated and the recoveries achieved were between 85.0 and 96.0% (ozone) and 101.0 and 119.0% (hypochlorite).

Nitrate is an abundant ion that is present in many industrialized products and the environment. Various analytical methods have been described using the Griess-Ilosvay reagent for the determination of nitrate in different matrices after its reduction to nitrite, in most cases with metallic cadmium as the reducer. This work proposes a new method using aluminum spheres coated with a copper film for this reduction. To optimize the method, it was important to evaluate the conditions for the deposition of the copper film on the aluminum spheres, using a Doehlert matrix. The optimized method provided an analytical range from 2.0 to 100 µmol L-1, with a coefficient of determination of 0.9996 and a standard deviation of residuals (sres) of 7.59 x 10-4. The Limits of Detection and Quantification were 0.59 and 2.0 µmol L-1 respectively. The method was applied using mineral water samples and was shown to provide repeatability less than 6.98% and accuracy obtained through recovery essays between 81.1 and 104.6% for the determination of nitrate in this type of sample.

The liquid-liquid extraction with low-temperature partitioning technique (LLE/LTP) was miniaturized to determine the pesticides chlorpyrifos, bifenthrin, λ-cyhalothrin, and deltamethrin in a biological matrix, by gas chromatography. The method was proposed for fetal-bovine serum samples (500 μL), by using a full factorial design (23) with one center point. The evaluated factors included the volume of water added to the sample (1000 μL), volume of extraction solvent (500 μL) and stirring time (60 s) – a cleanup step was not necessary. The method was validated for the main figures of merit. The results indicated that the LLE/LTP/GC/ECD miniaturized method was efficient in extracting pesticides from blood-serum samples (75 to 115%). It showed both selectivity and sensitiveness, with limits of quantification (LOQ) ranging from 8 at 17 μg L-1;. Once validated, the method was applied to blood-serum samples of rural workers from a city in the Brazilian state of Minas Gerais. In that case, the presence of chlorpyrifos was detected in two of the samples.

Birnessite type manganese oxide (δ-MnO2) was synthesized for use in degradation of the cationic dye methylene blue in aqueous solution. The material was characterized using infrared spectroscopy, X-ray diffraction, and Brunauer-Emmett-Teller (BET) surface area calculations. The removal of the dye from aqueous solutions was evaluated considering the effects of the following variables: pH, manganese oxide concentration, contact time, and temperature. UV-Vis spectroscopy analyses indicated achievement of 99 and 95% removal of methylene blue (7 mg L-1) at pH 2.0 and 4.0, respectively, after 120 min of contact with the birnessite (100 mg L-1). At higher pH of 6.0 and 8.0, removals of around 99 and 80%, respectively, were obtained after a longer time of 1860 min. Analyses of total organic carbon (TOC) revealed that 80% reduction of organic matter was obtained at pH 4.0. The method of multivariate curve resolution-alternating least squares (MCR-ALS) was used together with UV-Vis spectroscopy to evaluate the removal process, confirming the degradation of methylene blue. Thionine (λmax = 601 nm) was identified as one of the byproducts of N-demethylation of methylene blue. The results indicated that the degradation process started with N-demethylations of the methylene blue molecule.

The method is based on the adsorptive accumulation of complex molybdenum(VI) with 8-hydroxyquinoline, using voltammetric square wave cathodic stripping voltammetry. The composition and concentration of the supporting electrolyte, frequency (Hz), amplitude (mV) and deposition time (s), were optimized by factorial design in relation to current reduction of molybdenum(VI). The optimum methodology provided the following values for the process variables: scan increase (0.5 mV), pulse amplitude (127 mV), frequency (96 Hz), adsorption time (80 s) and drop size (0.60 mm2), the concentration of KNO3 (2.0 mol L-1), acetate buffer (0.5 mol L-1) and 8-hydroxyquinoline (0.01 mol L-1). The results obtained after optimization showed a linear response in the range from 1.0 to 6.0 mg L-1 and limits of detection and quantification, respectively equal to 0.02 and 0.08 mg L-1. The molybdenum contained in the samples were determined using the optimized methodology, with values consistent with the values determined by atomic emission spectrometry with inductively coupled plasma (ICP-AES).

Resumo O processo desenvolvimento de projetos e orçamentos de empreendimentos públicos é realizado de forma fragmentada pelos stakeholders. Essa situação contribui para diversas inadequações de obras, principalmente relacionadas a custos e prazos. O presente trabalho tem como objetivo propor melhorias ao referido processo, utilizando como referencial teórico o Target Value Design (TVD). Para realização do trabalho, utilizou-se a pesquisa qualitativa, tendo como estratégia de pesquisa o estudo de caso múltiplo. Foram estudadas quatro instituições públicas, compostas de setores de desenvolvimento de projetos, orçamentos e fiscalização de obra. A proposta de investigação abrange os seguintes participantes: cliente; gestor; projetista (arquiteto e engenheiro); orçamentista; e fiscal de obra. A coleta de dados foi realizada com 17 participantes. Como resultado o trabalho apresenta um modelo de processo para o desenvolvimento de projetos de empreendimentos públicos (PDP).

Abstract The design and budget development process of public projects is done in a fragmented way by the stakeholders. This situation contributes to several inadequacies in construction projects, related mainly to costs and deadlines. The aim of this paper is to propose improvements to the process, based on Target Value Design (TVD). The investigation was done through qualitative research, and the research strategy used was a multiple case study. It involved four public institutions, comprising project the development, budget and inspection sectors. The study included the following participants: clients, managers, designers (architect and engineer), budgeters, and works inspectors. Seventeen participants were interviewed during the study. This paper presents a design development process model for public projects (DDP).

Clomazone exhibits high water solubility, low sorption in soil colloids, and therefore can leach and contaminate deep layers of soil profile and groundwater. In this work, the effect of the incorporation of sugarcane bagasse biochar in leaching and bioavailability of clomazone in red latosol was evaluated. Soil samples amended with 1% (m/m) biochar were placed in different depths (0-1, 0-2.5 and 0-5 cm) on the top of polyvinyl chloride (PVC) columns filled with soil. Clomazone-based herbicide was applied, and rainfall was simulated on top of the columns. A validated chromatographic method, together with a greenhouse bioassay, were used to quantify and to evaluate the mobility and availability of clomazone along the columns. The incorporation of sugarcane bagasse biochar in the superficial layers at the column tops increased herbicide sorption, reduced its leaching and bioavailability in soil and scaled down the environmental risk of clomazone avoiding contamination of underground aquifer reservoirs.

Two types of manganese oxide were investigated for the removal/degradation of Orange G (OG) dye in aqueous solution. One manganese oxide (pyrolusite) was obtained commercially and the other (birnessite) was prepared according to the polyol method by means of the oxidation of MnII hydroxide by H2O2. Both materials were characterized by X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), and nitrogen adsorption/desorption at 77 K. The effects of agitation time, pH, and MnO2 dose on the degradation of OG by the birnessite and pyrolusite were evaluated. Approximately 90 and 99% decoloration of OG (10 mg L-1) was obtained after 30 min of stirring with 0.20 g L-1 of birnessite or pyrolusite, respectively. The decoloration and increased intensity of absorbance bands in the UV-visible spectrum were indicative of a degradation process that followed pseudo-first order kinetics. The findings demonstrated the high efficiency of different types of manganese oxides for removal of this organic pollutant from waters.

Abstract Biochar is a carbonaceous material that has excellent potential as a fertilizer and soil conditioner. However, there is a lack of information concerning the effects of the amount and particle size of this pyrogenic material on the soil sorption capacity. In this work, evaluation was made of changes in clomazone (CMZ) sorption in a Red Latosol following soil conditioning using different percentages (0.25, 0.5, and 1% w/w) of sugarcane biochar in three particle sizes (<106, 106-508, and 508-610 µm). The conditioned soils presented apparent sorption coefficients (Kd) up to 1300 times higher than that of pure soil, besides changes in the behavior of CMZ sorption. The biochar particle size and percentage influenced sorption of the herbicide as well as its retention in the amended soil during desorption processes. Both sorption and desorption Freundlich constants were linearly correlated with the external surface area of the biochar present in the soil.

Effluents from pulp mills have a high organic load and can still contain high organic bio-recalcitrant material that is harmful to the aquatic environment, even after undergoing biological treatment in effluent treatment plants. This study presents a novel treatment method tested on effluents (prior to and after biotreatment) from a Brazilian kraft pulp mill, based on hydroxyl radical production and hydrogen peroxide obtained by plasma generated by high-voltage electrolysis. These species present significant oxidation potential that could enable the complete breakdown of the organic matter. From the application of plasma to treat pulp mill effluent for a 7-hour period, it was obtained a chemical oxygen demand (COD) removal between 88.2 and 99.7%, total organic carbon (TOC) removal of 90.3 to 95.6%, and a color removal of 95.0 to 98.0%. The final pH of the treated effluent was 11.6 to 11.9. The results obtained in this study showed that the high-tension plasma treatment, applied on effluent from kraft pulp mills before and after biological treatment, can be an attractive alternative.

A new method has been developed to determine trace levels of organophosphorus pesticide parathion-methyl in water samples by using dispersive liquid-liquid microextraction (DLLME), followed by gas chromatograph coupled with electron capture detector (GC/ECD) analysis. The optimized and validated method showed high extraction recovery (101.1%), high enrichment factor (57.3), low limits of detection and quantification, 0.083 and 0.250 µg L-1, respectively. The established DLLME-GC/ECD method has been successfully applied for the evaluation of the photodegradation of the parathion-methyl by UV254nm radiation in different conditions of pH and temperature. The parathion-methyl photodegradation at pH 3 and 35 °C achieved > 99.5% after 120 min of exposition. For this condition, it was observed the kinetic rate of 0.0515 min-1, the quantum yield of 1.22 × 10-5 mol Einstein-1 and a half-life time of 13.46 min. All experimental conditions tested proved to be strongly influenced by pH and temperature. The application of the optimized process in distilled and drinking water spiked with parathion-methyl provided residues of this pesticide at levels below the maximum permitted by Brazilian legislation, which is 9.0 µg L-1.

Abstract Soil erosion is a major problem observed in terrestrial ecosystems. Monitoring and identifying potential areas for erosion becomes extremely important for the better management of these areas. The main aim of this study was to develop a Geographic Information System script tool based on the universal soil loss equation (USLE), which calculates soil loss in three large agricultural sub-basins. Algorithms were implemented in the graphical interface of ModelBuilder and later in Python programming language, thus allowing the creation of a specific script to calculate soil loss in an automatic way. The "USLE Paracatu Watershed" script was validated and proved to be effective in estimating erosion in the three sub-basins with an average processing time of half second per km2. This can be added via "ArcToolbox" toolbox in ArcGIS software, so that the user only has to add the variables of the USLE equation and the software will process the algorithms in an automatic way, generating the final map with the soil loss value (t/ha.year). The friendly interface of the script allows it to be used in any area, only requiring the user to enter the updated data of parameters that compose the equation.

Resumo: A sarcotesta, camada mucilaginosa presente nas sementes de mamão, afeta negativamente o seu processo germinativo e sua retirada tem sido realizada manualmente. O uso do hipoclorito de sódio pode ser uma alternativa à remoção manual da sarcotesta. Objetivou-se avaliar o efeito de diferentes concentrações de cloro ativo (0, 2, 4, 6 e 8%), durante 24 horas de imersão, em diferentes proporções (10:200, 50:200, 100:200, 200:200, 300:200, 400:200, 500:200 e 600:200) entre sementes (número) e volume (mL) da solução de hipoclorito de sódio respectivamente, visando identificar a melhor combinação para a retirada efetiva da sarcotesta de maneira a contribuir no processo germinativo. Foram avaliados o teste de germinação e a primeira contagem. Empregou-se o delineamento estatístico inteiramente casualizado com quatro repetições. Para as variáveis quantitativas, que apresentaram efeito significativo pelo teste F a 5% de probabilidade, foi realizada a análise de regressão. A imersão de sementes de mamão na proporção de 10 sementes por 200 mL de solução de NaOCl (10:200, ou seja, 20 mL de solução por semente), na concentração de 2% de cloro ativo por 24 horas, pode ser uma alternativa para a retirada da sarcotesta em sementes recém-colhidas, pois, além da retirada efetiva da sarcotesta, favorece a germinação.

Abstract: Sarcotesta, a mucilaginous layer found in papaya seeds, negatively affects the germination of papaya seeds and its removal has been manually performed. The use of sodium hypochlorite can be an alternative to manual removal of sarcotesta in papaya seeds. The objective of this study was to evaluate the effect of different active chlorine concentrations (0, 2, 4, 6 and 8%) during 24 hours of immersion, in different proportions (10:200, 50:200, 100:200, 200:200, 300:200, 400:200, 500:200 and 600:200) of seeds number and solution volume (mL) to identify the best combination for an effective remotion of sarcotesta to improve the germination process. Germination test and first count were performed. A completely randomized design with four replications was used. Regression analysis was performed for quantitative variables with significant effect by F-test at 5% probability. Papaya seeds immersion in the ratio of 10 seeds per 200 mL of NaOCl solution (10:200, i.e. 20 mL of solution per seed), at a 2% sodium hypochlorite concentration during 24 hours of imbibition, can be used as an alternative for sarcotesta remotion for freshly harvested papaya seeds, because besides the effective remotion of sarcotesta, this technique improves the germination process.

A new method for the extraction of pesticide residues from soil was developed, optimized, validated and applied to real samples. The technique consisted of combining single-drop microextraction and solid-liquid extraction with low temperature partitioning (SLE/LTP-SDME) followed by analysis using gas chromatography with electron capture detection (GC/ECD). This method was used to determine the presence of alachlor, methyl parathion, trifluralin, endrin, lindane, dieldrin and dichloro-diphenyl-trichloroethane (4,4’-DDT) in soil samples. Recoveries ranging from 67.2 to 122.5% were achieved, coefficients of variation (repeatability) were lower than 22.4% and limits of detection ranged from 0.18 to 0.59 µg kg-1. Recovery from soils fortified with different concentrations of the pesticides ranged from 61.5 to 123.5%. The new method combines the primary advantages of the two techniques: purification of the sample using SLE/LTP and preconcentration using SDME. The new method also enables the determination of low volatility compounds without requiring the sample to be heated.