Development, validation, and application of a method for the GC-MS analysis of fipronil and three of its degradation products in samples of water, soil, and sediment

A method for the identification and quantification of pesticide residues in water, soil, and sediment samples has been developed, validated, and applied for the analysis of real samples. The specificity was determined by the retention time and the confirmation and quantification of analyte ions. Linearity was demonstrated over the concentration range of 20 to 120 µg L(-1), and the correlation coefficients varied between 0.979 and 0.996, depending on the analytes. The recovery rates for all analytes in the studied matrix were between 86% and 112%. The intermediate precision and repeatability were determined at three concentration levels (40, 80, and 120 µg L(-1)), with the relative standard deviation for the intermediate precision between 1% and 5.3% and the repeatability varying between 2% and 13.4% for individual analytes. The limits of detection and quantification for fipronil, fipronil sulfide, fipronil-sulfone, and fipronil-desulfinyl were 6.2, 3.0, 6.6, and 4.0 ng L(-1) and 20.4, 9.0, 21.6, and 13.0 ng L(-1), respectively. The method developed was used in water, soil, and sediment samples containing 2.1 mg L(-1) and 1.2% and 5.3% of carbon, respectively. The recovery of pesticides in the environmental matrices varied from 88.26 to 109.63% for the lowest fortification level (40 and 100 µg kg(-1)), from 91.17 to 110.18% for the intermediate level (80 and 200 µg kg(-1)), and from 89.09 to 109.82% for the highest fortification level (120 and 300 µg kg(-1)). The relative standard deviation for the recovery of pesticides was under 15%.

A stability-indicating LC method for difloxacin in the presence of degradation products

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Stability study and degradation kinetics of ceftazidime in pharmaceutical preparations

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Evaluation and degradation chemistry of orbifloxacin using LC-MS

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Aplicação de doses de vinhaça sob desenvolvimento vegetativo de pastagem degradada e propriedades físicas do solo

The experiment was conducted in the experimental field of the University of GoiásUEG, UNU Ipameri - GO with the objective of evaluating the effect of different doses of vinasse on the vegetative development of degraded pasture and soil physical properties in two seasons. The pasture used in the experiment was in a state of degradation, and had eight years of formation. The experimental design was randomized blocks consisted of eight treatments and four blocks, totaling 32 experimental units. We evaluated the following soil physical properties: density the soil, particle density, total porosity, infiltration velocity, soil water. We also evaluated the following parameters of vegetative development of grassland: green and dry mass of shoots, effective depth of the root system, the grass height. The results were submitted to analysis of variance at 5% significance level and after we performed regression testing. The vinasse promoted significant effect on all parameters related to vegetative development of both grazing during the rainy season as in the dry. In this case, a model that best fit the dataset vegetative pasture was quadratic. It appeared that the vinasse different doses did not cause changes in the physical properties of the soil.

Comportamento do carbono orgânico e de atributos químicos, físicos e microbiológicos de um solo arenoso em área de conversão pastagem - Eucalipto

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Ecology, stable isotopes, and management of grassland songbirds at National Park Service properties on the Great Plains

Grassland ecosystems have been severely reduced and grassland bird populations have experienced consistent declines. National Park Service (NPS) properties on the Great Plains provide breeding habitat for grassland songbirds, though little is known about the quality of this habitat. A short-term study on songbirds at three NPS properties complemented current monitoring, providing an among park comparison addressing grassland bird productivity and fidelity relative to NPS property size. During 2008-2009, I assessed avian species richness, and estimated bird density and grassland songbird nest success. Bird species richness was greatest at small and medium sites, while number of nesting obligate species was greatest at the large site. Species-specific densities varied among sites, with few grassland obligates occurring at all three sites. Nest success estimates for grassland obligates were highest at the small site and lower at the large site. Another method to quantify habitat quality is assessment of breeding site fidelity. Current extrinsic markers used in monitoring site fidelity are inadequate for small birds; stable isotope analyses provide an alternative. I compared two techniques for assigning stable isotope tissue origin and measured grassland songbird site fidelity. My method of assigning origin provided site-specific variances of expected stable isotope values, an improvement over the most commonly used method. Fidelity tended to be higher at the large site, which may indicate a more robust breeding community of grassland birds. The small size of two of my sites precluded large sample sizes and made strong inferences difficult. To quantify how scientists cope with weak inference, I conducted a literature review. Strong inference was rarely observed, and most authors of weak-inference papers provided specific management recommendations. I suggest that adaptive management is an ideal method to resolve uncertainty from weak inference. Managers should consider my results within the context of regional and global management and the extent to which their unit might aide songbird conservation.

Comparative degradation of ZnO- and SnO(2)-based polycrystalline non-ohmic devices by current pulse stress

The degradation behaviour of SnO(2)-based varistors (SCNCr) due to current pulses (8/20 mu s) is reported here for the first time in comparison with the ZnO-based commercial varistors (ZnO). Puncturing and/or cracking failures were observed in ZnO-based varistors possessing inferior thermo-mechanical properties in comparison with that found in a SCNCr system free of failures. Both systems presented electric degradation related to the increase in the leakage current and decrease in the electric breakdown field, non-linear coefficient and average value of the potential barrier height. However, it was found that a more severe degradation occurred in the ZnO-based varistors concerning their non-ohmic behaviour, while in the SCNCr system, a strong non-ohmic behaviour remained after the degradation. These results indicate that the degradation in the metal oxide varistors is controlled by a defect diffusion process whose rate depends on the mobility, the concentration of meta-stable defects and the amount of electrically active interfaces. The improved behaviour of the SCNCr system is then inferred to be associated with the higher amount of electrically active interfaces (85%) and to a higher energy necessary to activate the diffusion of the specific defects.

Range extensions and conservation of some threatened or little known Brazilian grassland birds

Populations of grassland birds are declining in Brazil due to profound alterations to grassland habitats. In this paper, we present recent records and range extensions for 12 threatened or little known Brazilian grassland species: Ocellated Crake Micropygia schomburgkii, Sickle-winged Nightjar Eleothreptus anomalus, Campo Miner Geositta poeciloptera, Rufous-sided Pygmytyrant Euscarthmus rufomarginatus, Sharp-tailed Grass-tyrant Culicivora caudacuta, Cocktailed Tyrant Alectrurus tricolor, Cinereous Warbling-finch Poospiza cinerea, Black-masked Finch Coryphaspiza melanotis, Tawny-bellied Seedeater Sporophila hypoxantha, Marsh Seedeater S. palustris, Chestnut Seedeater S. cinnamomea and Black-bellied Seedeater S. melanogaster. We also comment on the biogeography and conservation of these species.

Unexpected toxicity decrease during photoelectrochemical degradation of atrazine with NaCl

This report shows an unexpected toxicity decrease during atrazine photoelectrodegradation in the presence of NaCl. Atrazine is a pesticide classified as endocrine disruptor occurring in industrial effluents and agricultural wastewaters. We therefore studied the effects of the degradation method, electrochemical and electrochemical photo-assisted, and of the supporting electrolyte, NaCl and Na2SO4, on the residual toxicity of treated atrazine solutions. We also studied the toxicity of treated atrazine solutions using Results show that at initial concentration of 20 mg L-1, atrazine was completely removed in up to 30 min using 10 mA cm(-2) electrolysis in NaCl medium, regardless of the electrochemical method used. The total organic carbon removal by the photo-assisted method was 82% with NaCl and 95% with Na2SO4. The solution toxicity increased during sole electrochemical treatment in NaCl, as expected. However, the toxicity unexpectedly decreased using the photo-assisted method. This finding is a major discovery because electrochemical treatment with NaCl usually leads to the formation of toxic chlorine-containing organic degradation by-products.

Phenol degradation in an anaerobic fluidized bed reactor packed with low density support materials

The objective of this research was to study phenol degradation in anaerobic fluidized bed reactors (AFBR) packed with polymeric particulate supports (polystyrene - PS, polyethylene terephthalate - PET, and polyvinyl chloride - PVC). The reactors were operated with a hydraulic retention time (HRT) of 24 h. The influent phenol concentration in the AFBR varied from 100 to 400 mg L-1, resulting in phenol removal efficiencies of similar to 100%. The formation of extracellular polymeric substances yielded better results with the PVC particles; however, deformations in these particles proved detrimental to reactor operation. PS was found to be the best support for biomass attachment in an AFBR for phenol removal. The AFBR loaded with PS was operated to analyze the performance and stability for phenol removal at feed concentrations ranging from 50 to 500 mg L-1. The phenol removal efficiency ranged from 90-100%.

Interference of inorganic ions on phenol degradation by the Fenton reaction

The addition of Cu2+ ions to the classical Fenton reaction (Fe2+ plus H2O2 at pH 3) is found to accelerate the degradation of organic compounds. This synergic effect causes an approximately 15 % additional reduction of the total organic carbon (TOC), representing an overall improvement of the efficiency of the mineralization of phenol. Although Fe2+ exhibits a high initial rate of degradation, the degradation is not complete due to the formation of compounds refractory to the hydroxyl radical. The interference of copper ions on the degradation of phenol by the Fenton reaction was investigated. In the presence of Cu2+, the degradation is slower, but results in a greater reduction of TOC at the end of the reaction (t = 120 min). In the final stages of the reaction, when the Fe3+ in the solution is complexed in the form of ferrioxalate, the copper ions assume the role of the main catalyst of the degradation.

Influence of light, temperature and metallic ions on biodiesel degradation and corrosiveness to copper and brass

Corrosion is a relevant issue regarding the problem of biodiesel compatibility with polymers and metals. This work aims to evaluate the influence of the natural light incidence and temperature in the corrosion rate of brass and copper immersed in commercial biodiesel as well as biodiesel degradation after the contact with metallic ions. The characterization of corrosion behavior was performed by weight loss measurements according to ASTM G1 and ASTM G31. The experiments according to ASTM G1 were performed at room temperature in light presence and absence. Experiments were also conducted at 55 degrees C in order to compare with ASTM G31 that is also performed at that temperature. The biodiesel degradation was characterized by water content, oxidation stability, viscosity as well as XRF, IR and Raman spectroscopies. The results of ASTM G1 tests showed that the thickness loss for both metals determined at room temperature is slightly higher when there is light incidence and these values significantly decrease for the highest temperature. The results of ASTM G31 tests indicated that air bubbling along with higher temperature affects mostly immersed samples. Biodiesel in contact with metals shows significant degradation in its properties as evidenced by increasing water content, higher viscosity and lower oxidation stability. (C) 2012 Elsevier Ltd. All rights reserved.

Mechanistic Implications of Zinc(II) Ions on the Degradation of Phenol by the Fenton Reaction

A study of the interference of Zn2+ ions on phenol degradation by Fenton reaction (Fe2+/Fe3(+) + H2O2) is reported. One of the first intermediates formed in the reaction, catechol, can reduce Fe3+ to Fe2+ and, in the presence of H2O2 initiates an efficient catalytic redox cycle. In the initial stages of the reaction, this catechol-mediated cycle becomes the principal route of thermal degradation of phenol and its oxidation products. The Zn2+ ion addition enhances the persistence time of catechol, probably by stabilization of the corresponding semiquinone radical via complexation.

Impact of Land Degradation on Soil Microbial Biomass and Activity in Northeast Brazil

Land degradation causes great changes in the soil biological properties. The process of degradation may decrease soil microbial biomass and consequently decrease soil microbial activity. The study was conducted out during 2009 and 2010 at the four sites of land under native vegetation (NV), moderately degraded land (LDL), highly degraded land (HDL) and land under restoration for four years (RL) to evaluate changes in soil microbial biomass and activity in lands with different degradation levels in comparison with both land under native vegetation and land under restoration in Northeast Brazil. Soil samples were collected at 0-10 cm depth. Soil organic carbon (SOC), soil microbial biomass C (MBC) and N (MBN), soil respiration (SR), and hydrolysis of fluorescein diacetate (FDA) and dehydrogenase (DHA) activities were analyzed. After two years of evaluation, soil MBC, MBN, FDA and DHA had higher values in the NV, followed by the RL. The decreases of soil microbial biomass and enzyme activities in the degraded lands were approximately 8-10 times as large as those found in the NV. However, after land restoration, the MBC and MBN increased approximately 5-fold and 2-fold, respectively, compared with the HDL. The results showed that land degradation produced a strong decrease in soil microbial biomass. However, land restoration may promote short- and long-term increases in soil microbial biomass.