Activated Carbons Produced from Mixtures of Synthetic Polymers by Physical and Chemical Activation: Application on MCPA Removal

The production of AC was achieved using the most common industrial and consumer solid waste, namely PET, alone or blended with other synthetic polymer such PAN. The PET-PAN mixture (1:1 W/W %) was subjected to carbonization, with a pyrolysis yield off 31.9%, between that obtained with PET (16.9%) or PAN (42.6%) separately. By mixing PET, as a raw material, with PAN (different ratio), an improvement in the final yield of the AC production, for the same activation time, with CO2, was found.

Liquid Mixtures Involving Hydrogenated and Fluorinated Alcohols: Thermodynamics, Spectroscopy, and Simulation

This article reports a combined thermodynamic, spectroscopic, and computational study on the interactions and structure of binary mixtures of hydrogenated and fluorinated substances that simultaneously interact through strong hydrogen bonding. Four binary mixtures of hydrogenated and fluorinated alcohols have been studied, namely, (ethanol + 2,2,2-trifluoroethanol (TFE)), (ethanol + 2,2,3,3,4,4,4-heptafluoro-1-butanol), (1-butanol (BuOH) + TFE), and (BuOH + 2,2,3,3,4,4,4-heptafluoro-1-butanol). Excess molar volumes and vibrational spectra of all four binary mixtures have been measured as a function of composition at 298 K, and molecular dynamics simulations have been performed. The systems display a complex behavior when compared with mixtures of hydrogenated alcohols and mixtures of alkanes and perfluoroalkanes. The combined analysis of the results from different approaches indicates that this results from a balance between preferential hydrogen bonding between the hydrogenated and fluorinated alcohols and the unfavorable dispersion forces between the hydrogenated and fluorinated chains. As the chain length increases, the contribution of dispersion increases and overcomes the contribution of H-bonds. In terms of the liquid structure, the simulations suggest the possibility of segregation between the hydrogenated and fluorinated segments, a hypothesis corroborated by the spectroscopic results. Furthermore, a quantitative analysis of the infrared spectra reveals that the presence of fluorinated groups induces conformational changes in the hydrogenated chains from the usually preferred all-trans to more globular arrangements involving gauche conformations. Conformational rearrangements at the CCOH dihedral angle upon mixing are also disclosed by the spectra.

Production of activated carbons from single and mixtures of synthetic polymers

The production of activated carbons (ACs) involves two main steps: the carbonization of the carbonaceous of raw materials at temperatures below 1073 K in the absence of oxygen and the activation had realized at the temperature up to 1173 but the most useful temperature at 1073 K. In our study we used the most common industrial and consumer solid waste, namely PET, alone or blended with other synthetic polymer PAN. By mixing the two polymers in different ratios, an improvement of the yield of the AC production was found and some textural properties were enhanced by comparison with the AC prepared using each polymer separately. When all the samples were exposed through the carbonization process with a pyrolysis the mixture of PAN-PET (1:1w/w) yield around 31.9%, between that obtained with PET (16.9%) or PAN (42.6%) separately. The combine activation, with CO2 at 1073 K, allow ACs with a lower burn-off degree isothermally, when compared with those attained with PET or PAN alone, but with similarly chemicals or textural properties. The resultant ACs are microporous in their nature, as the activation time increase, the PET-PAN mixture AC are characterized by a better developed porous structure, when associated with the AC prepared from PAN. The AC prepared from PET-PAN mixture are characterized by basic surface characteristics, with a pHpzc around 10.5, which is an important characteristic for future applications on acidic pollutants removals from liquid or gaseous phase. In this study we had used the FTIR methods to determine the main functional groups in the surface of the activated carbons. The adsorbents prepared from PAN fibres presents an IR spectrum with similar characteristics to those obtained with PET wastes, but with fewer peaks and bands with less intensity, in particular for the PAN-8240 sample. This can be reflected by the stretching and deformation modes of NH bond in the range 3100 – 3300 cm-1 and 1520 – 1650 cm-1, respectively. Also, stretching mode associated to C–N, C=N, can contributed to the profile of IR spectrum around 1170 cm-1, 1585 – 1770 cm-1. And the TGA methods was used to study the loses of the precursors mass according to the excessive of the temperature. The results showed that, there were different decreasing of the mass of each precursors. PAN degradation started at almost 573 K and at 1073 K, PAN preserve more than 40% of the initial mass. PET degradation started at 650 K, but at 1073 K, it has lost 80% of the initial mass. However, the mixture of PET-PAN (1:1w/w) showed a thermogravimetric profile between the two polymers tested individually, with a final mass slightly less than 30%. From a chemical point of view, the carbonisation of PET mainly occurs in one step between 650 and 775 K.

Sugarcane herbicide leaching risk evaluation in Guarany Aquifer.

he region of Ribeirão Preto, São Paulo State, Brazil, is located over recharge area of the Guarany aquifer, the most important source of groundwater in the South Central region of the country. This region is also the most important sugarcane producing area of the country which produces a large amount of the ethanol. This study was conducted to determine the potential risk of herbicide groundwater contamination. The leaching risk potential of herbicides to groundwater was conducted using the weather simulator ?Weather Generator? (WGEN) coupled with the model ?Chemical Movement Trough Layered Soils? (CMLS94). The following herbicides were evaluated in clayey and sandy soils (Typic Haplorthox and Typic Quartzipsamment soils) found in the region: ametryn (N-ethyl-N\'-(1- methylethyl)-6-(methylthio)-1,3,5-triazine-2,4-diamine), atrazine (6-chloro-N-ethyl-N\'-(1-methylethyl)-1,3,5-triazine- 2,4-diamine), clomazone (2-[(2-chlorophenyl)methyl]-4,4-dimethyl-3-isoxazolidinone), diuron (3,4-dichlorophenyl)- N,N-dimethylurea), halosulfuron (3-chloro-5-[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl], hexazinone (3- cyclohexyl-6-(dimethylamino)-1-methyl-1,3,5-triazine-2,4 (1H,3H)-dione), imazapic ((±)-2-[4,5-dihydro-4-methyl-4- (1-methylethyl)-5-oxo-1H-imidazol-2-yl]-5-methyl-3-pyridinecarboxylic acid), imazapyr ((±)-2-[4,5-dihydro-4-methyl- 4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3-pyridinecarboxylic acid), MCPA (4-chloro-2-methylphenoxy)acetic acid), metribuzin (4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)-one), MSMA (Amonosodium salt of MAA), paraquat (1,1\'-dimethyl-4,4\'-bipyridinium ion), pendimethalin (N-(1-ethylpropyl)-3,4-dimethyl-2,6- dinitrobenzenamine), picloram (4-amino-3,5,6-trichloro-2-pyridinecarboxylic acid), simazine (6-chloro-N,N\'-diethyl- 1,3,5-triazine-2,4-diamine), sulfentrazone [N-[2,4-dichloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxo-1H- 1,2,4-triazol-1-yl]phenyl]methanesulfonamide], and tebuthiuron [N-[5-(1,1-dimethylethyl)-1,3,4-thiadiazol-2-yl]-N,N\'- dimethylurea]. Results obtained by our simulation study have shown that the herbicides picloram, tebuthiuron, and metribuzin have the highest leaching potential, in either sandy or clayey soils, with picloram reaching the root zone of sugarcane at 0.6m in less than 150 days.

Decomposition of organic matter in the presence of the herbicide clomazone.

Clomazone (2-(2-chlorophenyl) methyl-4.4-dimethyl-3-isoxazolidinone) is a post emergence herbicide widely used in rice fields in Rio Grande do Sul (Brazil) with high activity against Gramineae at the recommended application rate of 700 g/ha. The presence of this chemical in the water may affect microorganisms responsible for the decomposition of organic matter. Thus, a disturbe in the trophic chain sustained by the decompositors could happen. In the present work the decomposition rate of organic matter (Typha latifolia) exposed to several concentrations of a clomazone formulation: 0 (control), 25.0, 62.0, 156.0, 390.0 and 976.0mg/L on the basis of the active ingredient was evaluated. Five litter bags containing about 3.0g of pieces of T. latifolia leaves wereplaced in aquariums with 15 of reconstituted water. In cach aquarium were added 500g of sediment from the same place of the plant collection, as a source of decompositors microorganisms. The results relative tothe control, showed that the decomposition rate in the highest and lowest dose was reduced in 50.05 and 1,28%, respectively, after 80 days.

Toxicity of the herbicide clomazone on duckweed Lemna valdiviana.

The duckweed Lemna valdiviana is commonly founded colonizing small shallow waters (lakes on the lowland in south Brazil. This organism may have been affected by herbicide input into lakes from aerial application and/or drainage office paddy fields. Clomazone (2- (2-chlorophenyl) methyl-4.4-dimethyl-3-isoxazolidinone) is one of the herbicides more fiequentely used as post-emergence in rice paddies. For this work assays were carried as EC50(96h) semi-statics with aseptic culture. The sterile fronds were abtained from material harvest on the paddy fields, and the concentration of Clomazone ranged from 14.0 to 229.0 mg/l. two procedures were considered: diluted in water and sprayed applicated Clomazone. The observed phytotoxic effects were evaluated by growth rate (kt), duplication time (Td), frond yield, plant yield, mortality, chlorophyll a and b and protochlorophyll concentration. The EC50 values obtained to sprayed Clomazone (Kt=31.7; Td=31.9) were significantly small than to diluted Clomazone (Kt=46.4; td=47.3). These dadta suggest that aerial route is more hazardous than diluted procedure. Presence of chlorotic, necrotic, abnormal and died frond were common at the 114.0 and 229.0 mg/l treatment. Recuperation test corroborated the evidence that the sprayed procedure were more deleterious and L. valdiviana doesn't recovery his reproductive ability at the 114.0 and 229.0 mg/l treatment.

Risk assessment of the herbicide clomazone in the aquatic life.

Clomazone (2-(2-chlorophenyl)methyl-4.4-dimethyl-3-isoxazolidinone) is a post emergence herbicide widely used in rice fields in Rio Grande do Sul (Brazil) with high activity against Gramineae at the recommended application rate(AR).of 700g/ha. The herbicide input into the aquatic ecosystem may occur by aerial application or water drainage. The presence of this chemical in the water may affect non-target organisms leading to impairments in the aquatic food chain. Studies were conducted in this work to evaluate the risk of Clomazone using the estimated mean affective concentration (EC50) for the microalgae Selenastrum capricornutum(96h), the duckweed Lemna valdiviana(96h) and the crustacean Daphnia similis(48h). The EC50 values were 11.2; 31.7 and 13.8 mg/l, respectively. According to the obtained data, and considering a direct input of the herbicide in a 10cm column water, the estimated maximum application rate that doesn't cause acute effects is 5.3 AR for S. capricornutum, 6.5 AR for D. similis and 15.0 AR for L. valdiviana. The estimated maximum application rate that doesn't cause chronic effects is 2.0 AR for D. similis, 1.6 AR for S. capricornutum and 4.5 AR for L. valviana.

Investigation of the mechanism of resistance to glyphosate herbicide in hairy fleaban.

The resistance of weeds to herbicides is a consequence of one or more mechanisms in the plant, responsible for not allowing the herbicide to act properly at the active site.

Resistance characterization of Italian ryegrass (Lolium multiflorum) biotypes to clethodim herbicide.

2016

Geographic distribution of ryegrass resistent to the clethodim herbicide in Rio Grande do Sul.

2016

Monitoring of glyphosate residues in herbicide tolerant soybeans from eight production areas of Brazil - 2005/2006 and 2006/2007 harvest seasons.

2008

Sugarcane herbicide leaching risk evaluation in Guarany Aquifer.

2008

Tebuthiuron herbicide bioconcentration in sugarcane plants.

2008

Crystal engineering of co-crystals and host-guest systems for environmentally friendly applications: sunscreens stabilization, pollutant sequestering and herbicide reformulation.

Solid state engineered materials have proven to be useful and suitable tools in the quest of new materials. In this thesis different crystalline compounds were synthesized to provide more sustainable products for different applications, as in cosmetics or in agrochemistry, to propose pollutants removal strategy or to obtain materials for electrocatalysis. Therefore, the research projects presented here can be divided into three main topics: (i) sustainable preparation of solid materials of widely used active ingredients aimed at the reduction of their occurrence in the natural environment. The systems studied in this section are cyclodextrins host-guest compounds, obtained via mechanochemical and slurry synthesis. The first chemicals studied are sunscreens inclusion complexes, that proved to have enhanced photostability and desired photoprotection. The same synthetic methods were applied to obtain inclusion complexes of bentazon, a herbicide often found to leach in groundwaters. The resulting products showed to have desired water solubility properties. The same herbicide was also adsorbed on amorphous calcium phosphate nanoparticles, to obtain a biocompatible formulation of this agrochemical. This herbicide could benefit by the adsorption on nanoparticles for what concerns its kinetic release in different media as well as its photostability. (ii) Sustainable synthesis of co-crystals based on polycyclic aromatic hydrocarbons, for the proposal of a sequestering method with a resulting material with enhanced properties. The co-crystallization via mechanochemical means proved that these pollutants can be sequestered via simple solvent-free synthesis and the obtained materials present better photochemical properties when compared to the starting co-formers. (iii) Crystallization from mild solvents of nanosized materials useful for the application in electrocatalysis. The study of compounds based on nickel and cobalt metal ions resulted in the obtainment of 2D and 1D coordination polymers. Moreover, solid solutions were obtained. These crystals showed layered structures and, according to preliminary results, they can be exfoliated.

Seemingly unrelated linear regression for contaminated data based on Gaussian mixtures

In this thesis, new classes of models for multivariate linear regression defined by finite mixtures of seemingly unrelated contaminated normal regression models and seemingly unrelated contaminated normal cluster-weighted models are illustrated. The main difference between such families is that the covariates are treated as fixed in the former class of models and as random in the latter. Thus, in cluster-weighted models the assignment of the data points to the unknown groups of observations depends also by the covariates. These classes provide an extension to mixture-based regression analysis for modelling multivariate and correlated responses in the presence of mild outliers that allows to specify a different vector of regressors for the prediction of each response. Expectation-conditional maximisation algorithms for the calculation of the maximum likelihood estimate of the model parameters have been derived. As the number of free parameters incresases quadratically with the number of responses and the covariates, analyses based on the proposed models can become unfeasible in practical applications. These problems have been overcome by introducing constraints on the elements of the covariance matrices according to an approach based on the eigen-decomposition of the covariance matrices. The performances of the new models have been studied by simulations and using real datasets in comparison with other models. In order to gain additional flexibility, mixtures of seemingly unrelated contaminated normal regressions models have also been specified so as to allow mixing proportions to be expressed as functions of concomitant covariates. An illustration of the new models with concomitant variables and a study on housing tension in the municipalities of the Emilia-Romagna region based on different types of multivariate linear regression models have been performed.