Evaluation of the generation of reactive oxygen species and antibacterial activity of honey as a function of its phenolic and mineral composition.

The antibacterial activity (ABA) of honey is associated with the generation of reactive oxygen species (ROS), where polyphenols (PFs) play a key role due to their pro-oxidant action modulated by metallic cations. In this work, the contents of PFs, H2O2, OH radicals, Cu, Fe, Mn, Zn, and ABA against Staphylococcus epidermidis and Pseudomonas aeruginosa were determined in honeys from central Chile. Then, their relationships were evaluated through partial least squares regression. The average contents of phenolic acids, flavonoids and metals in honey ranged from 0.4 to 4 µg/g, 0.3-1.5 µg/g and 3-6 µg/g, respectively. All honeys showed accumulation of H2O2 (1-35 µg/g) and OH radicals. The PLS showed that gallic acid, p-coumaric acid, chrysin, kaempferol, Fe, and Mn stimulate the generation of ROS. Quercetin, Cu, and Zn showed marginal antioxidant effects. PFs favor the ABA of honey against both bacteria and H2O2 against S. epidermidis.

Effect of surfactants on the sorption-desorption, degradation, and transport of chlorothalonil and hydroxy-chlorothalonil in agricultural soils.

The fungicide chlorothalonil (CTL) and its metabolite hydroxy chlorothalonil (OH-CTL) constitute a risk of soil and water contamination, highlighting the need to find suitable soil remediation methods for these compounds. Surfactants can promote the bioavailability of organic compounds for enhanced microbial degradation, but the performance depends on soil and surfactant properties, sorption-desorption equilibria of contaminants and surfactants, and possible adverse effects of surfactants on microorganisms. This study investigated the influence of five surfactants [e.g., Triton X-100 (TX-100), sodium dodecyl sulphate (SDS), hexadecyltrimethylammonium bromide (HDTMA), Aerosol 22 and Tween 80] on the sorption-desorption, degradation, and mobility of CTL and OH-CTL in two volcanic and one non-volcanic soil. Sorption and desorption of fungicides depended on the sorption of surfactants on soils, surfactants' capacity to neutralize the net negative charge of soils, surfactants' critical micellar concentration, and pH of soils. HDTMA was strongly adsorbed on soils, which shifted the fungicide sorption equilibria by increasing the distribution coefficient (Kd) values. Contrarily, SDS and TX-100 lowered CTL and OH-CTL sorption on soils by decreasing the Kd values, which resulted in an efficient extraction of the fungicide compounds from soil. SDS increased the degradation of CTL, especially in the non-volcanic soil (DT50 values were 14 and 7 days in natural and amended soils, with final residues <7% of the initial dose), whereas TX-100 enabled an early start and sustenance of OH-CTL degradation in all soils. CTL and OH-CTL stimulated soil microbial activities without noticeable deleterious effects of the surfactants. SDS and TX-100 also reduced the vertical transport of OH-CTL in soils. Results of this study could be extended to soils in other regions of the world because the tested soils represent widely different physical, chemical, and biological properties.

Electro-kinetic washing of a soil contaminated with quinclorac and subsequent electro-oxidation of wash water.

This work deals with the remediation of a soil that has been enriched with Quinclorac (QNC), one of the herbicides most used in Chile for weed control in rice fields. Quinclorac damages the microflora and macrofauna of soils and is toxic to some susceptible crops, which results in economic loses during crop rotation. Furthermore, Quinclorac a potential contaminant of water resources and soils, given its high mobility and persistence. This has created the need to lower its concentrations in soils intensively cultivated. In this study, an electro-kinetic soil washing system (EKSW) for mobilizing this pesticide in the soil was explored. The performance of this technology was compared by assessing the effect of direct (DP) and reverse (RP) polarity during 15 days under potentiostatic conditions and applying an electric field of 1 V cm-1 between electrodes. Among the main results, the highest removal of QNC was obtained through the EKSW-RP process, which also contributed to the prevention of acidity and alkaline fronts in the soil, compared to the EKSW-DP system. In both cases, the highest accumulation of QNC occurred in the cathodic well by mobilizing the non-ionized contaminant through the electroosmotic flow (EOF) from anode to cathode. After the treatment with EKSW, the wash water accumulated in the anodic and cathodic wells, which contained an important concentration of pesticide, was subjected to electro-oxidation (EO) by applying different current densities (j). The high generation of •OH on the surface of a boron-doped diamond electrode (BDD) allowed for the complete degradation and mineralization of QNC and its major intermediate compounds to CO2. The results of this study show that the application of both coupled stages in this type of remediation technologies would enable the removal of QNC from the soil without altering its chemical and physical properties, constituting an environmentally friendly process.

Relationship among the minor constituents, antibacterial activity and geographical origin of honey: A multifactor perspective.

Some minor constituents of honey samples were determined through a fluorometric-chemical characterization method and related multifactorially with their antibacterial activity against Staphylococcus aureus and Pseudomonas aeruginosa and with their geographical origin. Rotated principal component analysis identified five significant components in honey: three related to antibacterial activity and linked to phenolic compounds; Maillard products; proteins; the concentration of H2O2 at 3 and 24 h of incubation; and a tyrosine-containing entity. On the other hand, five constituents (phenolic compounds were the most relevant) allowed the classification of honey samples by geographical origin with 87% certainty. The results showed that phenolic compounds and Maillard products are related to the sustained production of H2O2 over time, which in turn boosts the antibacterial activity of honey. Native flora could promote this capability. The results showed the effect of geographic origin on the content of the analyzed minor constituents of honey, particularly phenolic compounds.

Matrix solid-phase dispersion associated to gas chromatography for the assessment in honey bee of a group of pesticides of concern in the apicultural field.

A method based on matrix solid-phase dispersion (MSPD) associated to gas chromatography-flame photometric detection (GC-FPD), GC-electron capture detection (GC-ECD) and GC-mass spectrometry (GC-MS) for confirmation purposes, was developed for the determination of a representative group of twelve pesticides in honeybee with particular concern in the apicultural field (fipronil, thiamethoxam, acetamiprid, acrinathrin, metamidophos, dimetoathe, diazinon, chlorpyrifos, methidathion, profenophos, azinphos methyl and coumaphos). Factors influencing the extraction efficiency of MSPD were investigated and optimized through response surface method. The use of octadecylsilyl (C18) sorbent combined with a florisil clean-up and acetonitrile-methanol (99:1) elution was the optimal condition for the extraction of the selected pesticides. Under this condition the recovery of pesticides at the limit of quantification of the method (0.007 to 0.050 µg g-1) ranged from 68 to 102% with RSDs for within-laboratory reproducibility ≤20%. The proposed method was applied to the analysis of honeybees collected in 68 field hives from areas of great apicultural and agricultural development in central Chile. In 65% of these samples eight different pesticides were detected. Pesticides most frequently found were chlorpyrifos (34% of the samples, <0.017-0.067 µg g-1), acrinathrin (32% of the samples, <0.020-0.026 µg g-1) and diazinon (10% of the samples at values <0.015 µg g-1). The incidence of these pesticides in bees can be related to their high employ in central Chile, use to combat the varroosis in hives and hydrophobicity.

Degradation kinetics of chlorpyrifos and diazinon in volcanic and non-volcanic soils: influence of cyclodextrins.

The intensive use of insecticides such as chlorpyrifos (CPF) and diazinon (DZN) in the agricultural activities worldwide has produced contamination of soils and/or transport to non-target areas including their distribution to surface and groundwaters. Cyclodextrins (CDs) have been proposed as an alternative in remediation technologies based on the separation of contaminants from soils because they could allow a higher bioavailability for their degradation with a low environmental impact. In this work, the degradation pattern of CPF and DZN and the formation and dissipation of the major degradation products 3,5,6-trichloro-2-pyridinol (TCP) and 2-isopropyl-6-methyl-4-pyrimidinol (IMPH) was established in four agricultural volcanic and non-volcanic soils belonging to Andisol, Ultisol, and Mollisol orders. Both pesticides were highly adsorbed in these soils, consequently, with a greater probability of contaminating them. In contrast, the adsorption of their two main metabolites was low or null; therefore, they are potential groundwater contaminants. The degradation processes were studied in the natural and amended soils with ß-cyclodextrin (ß-CD) and methyl-ß-cyclodextrin (Mß-CD) for CPF and DZN, respectively. A slow degradation of CPF and DZN was obtained for volcanic soils with observable residues until the end of the incubation time (150-180 days). In Mollisols, the higher degradation rate of CPF was favored by the neutral to basic pH, and for DZN it was related to the lower adsorption and higher bioavailability. The amendment of soils with CDs produced slower degradation rates which led to a greater concentration of the compounds at the end of the incubation time. This effect was more pronounced for DZN. The exception was the Andisol, with no significant changes for both compounds regarding the unamended soil. No residues of TCP were observed for this soil in both conditions during the whole incubation time; nevertheless, the accumulation of TCP was significant in the Ultisol and Mollisols, but the concentrations were lower for the amended soils. The accumulation of IMPH was important in Mollisol amended soils; however, their residues were observed in the volcanic soils during the whole incubation period in the natural and amended soils. An important enhancement of the microbial activity occurred in the system ß-CD/CPF in Mollisols, without a more effective degradation of the insecticide. The opposite effect was observed in the system Mß-CD/DZN mainly in the oxidative activity in all soils. The higher degradation of DZN and IMPH in natural Mollisols was related to the higher hydrolytic and oxidative activities. The stability of the inclusion complexes formed could play an important role for explaining the results obtained with the amendments.

Influence of selected cyclodextrins in sorption-desorption of chlorpyrifos, chlorothalonil, diazinon, and their main degradation products on different soils.

Cyclodextrins (CDs) can improve the apparent solubility and bioavailability of a variety of organic compounds through the formation of inclusion complexes; accordingly, they are suitable for application in innovative remediation technologies of contaminated soils. However, the different interactions in the tertiary system CD/contaminant/soil matrix can affect the bioavailability of the inclusion complex through the possible sorption of CD and CD complex in the soil matrix, as well as with the potential of the sorbed CD to form the complex, concurrent with the desorption processes. This work focuses in changes produced by three different CDs in soil sorption-desorption processes of chlorpyrifos (CPF), diazinon (DZN), and chlorothalonil (CTL), and their major degradation products, 3,5,6-trichloro-2-pyridinol (TCP), 2-isopropyl-6-methyl-4-pyrimidinol, and hydroxy-chlorothalonil (OH-CTL). Cyclodextrins used were ß-cyclodextrin (ß-CD), methyl-ß-cyclodextrin (Mß-CD), and 2-hydroxypropyl-ß-cyclodextrin (HPß-CD). The studied soils belong to the orders Andisol, Ultisol, and Mollisol with different organic matter contents, mineral composition, and pH. The apparent sorption constants were significantly lower for the three pesticides in the presence of all CDs. The highest displacement of sorption equilibria was produced by the influence of Mß-CD, with the most pronounced effect for CPF, a pesticide strongly sorbed on soils. The same was obtained for TCP and OH-CTL, highlighting the need to assess the risk of generating higher levels of groundwater contamination with polar metabolites if degradation rates are not controlled. The highest desorption efficiency was obtained for the systems CPF-ß-CD, DZN-Mß-CD, and CTL-Mß-CD. Since the degree of adsorption of the complex is relevant to obtain an increase in the bioavailability of the contaminant, a distribution coefficient for the complexed pesticide in all CD-soil-pesticide system was estimated by using the apparent sorption coefficients, the stability constant for each CD-pesticide complex, and the distribution coefficients of free pesticide.

Sorption-desorption behavior of pesticides and their degradation products in volcanic and nonvolcanic soils: interpretation of interactions through two-way principal component analysis.

Sorption-desorption behavior of six pesticides and some degradation products was assessed on seven agricultural volcanic and nonvolcanic soils belonging to Andisol, Ultisol, Mollisol, and Alfisol orders. The global interpretation of sorption data was performed by principal component analysis. Results showed exceptionally high sorption of glyphosate and aminomethylphosphonic acid (AMPA) (the breakdown product) on volcanic soils (K f > 1500 µg(1 - 1 / n) mL(1 / n) g(-1)) related mainly to contents of amorphous aluminum oxides (Andisols) and crystalline minerals (Ultisols). The lower sorption on nonvolcanic soils was associated to low organic matter contents and lack of significant minerals. Metsulfuron-methyl and 3,5,6-trichloro-2-pyridinol (metabolite of chlorpyrifos) were weakly to substantially sorbed on Andisols and Ultisols, but the first one was not sorbed at pH > 6.4, including nonvolcanic soils. The metabolite of diazinon, 2-isopropyl-4-methyl-6-hydroxypyrimidine, was weakly sorbed on all soils (K f = 0.4 to 3.6 µg(1 - 1 / n) mL(1 / n) g(-1)). Acidic compounds would be lixiviated in Mollisols and Alfisols, but they could leach also in Andisols and Ultisols if they reach greater depths. Atrazine and deethylatrazine sorption was related to organic carbon content; therefore, they were weakly retained on nonvolcanic soils (K f = 0.7 to 2.2 µg(1 - 1 / n) mL(1 / n) g(-1)). Chlorpyrifos was highly sorbed on all soils reaching K OC values of >8000. Finally, the significant retention of chlorothalonil and diazinon on Mollisols and Alfisols in spite of their low OC contents showed the contribution of clay minerals in the sorption process.

Determination of imidacloprid in water samples via photochemically induced fluorescence and second-order multivariate calibration.

This paper presents a new method for the determination of imidacloprid in water samples; one of the most widely used neonicotinoid pesticides in the farming industry. The method is based on the measurement of excitation-emission spectra of photo-induced fluorescence (PIF-EEMs) associated with second-order multivariate calibration with a parallel factor analysis (PARAFAC) and unfolded partial least squares coupled to residual bilinearization (U-PLS/RBL). The second order advantage permitted the determination of imidacloprid in the presence of potential interferences, which also shows photo-induced fluorescence (other pesticides and/or unexpected compounds of the real samples). The photoreaction was performed in 100-µl disposable micropipettes. As a preliminary step, solid phase extraction on C18 (SPE-C18) was applied to concentrate the analyte and diminish the limit of detection. The LOD was approximately 1 ng mL(-1), which is suitable for detecting imidacloprid in water according to the guidelines established in North America and Europe. The PIF-EEMs coupled to PARAFAC or U-PLS/RBL was successfully applied for the determination of imidacloprid in different real water samples, with an average recovery of 101±10%.

Determination of glyphosate and aminomethylphosphonic acid in aqueous soil matrices: a critical analysis of the 9-fluorenylmethyl chloroformate derivatization reaction and application to adsorption studies.

The assessment of the environmental fate of glyphosate and its degradation product (aminomethylphosphonic acid) is of great interest given the widespread use of the herbicide. Studies of adsorption-desorption and transport processes in soils require analytical methods with sensitivity, accuracy, and precision suitable for determining the analytes in aqueous equilibrium solutions of varied complexity. In this work, the effect of factors on the yield of the derivatization of both compounds with 9-fluorenylmethyl chloroformate for applying in aqueous solutions derived from soils was evaluated through factorial experimental designs. Interference effects coming from background electrolytes and soil matrices were established. The whole method had a linear response up to 640 ng/mL (R(2) > 0.999) under optimized conditions for high-performance liquid chromatography with fluorescence detection. Limits of detection were 0.6 and 0.4 ng/mL for glyphosate and aminomethylphosphonic acid, respectively. The relative standard deviation was 4.4% for glyphosate (20 ng/mL) and 5.9% for aminomethylphosphonic acid (10 ng/mL). Adsorption of compounds on four different soils was assessed. Isotherm data fitted well the Freundlich model (R(2) > 0.97). Kf constants varied between 93 ± 3.1 and 2045 ± 157 for glyphosate and between 99 ± 4.1 and 1517 ± 56 (µg(1-1/) (n)  mL(1/) (n) ( ) g(-1) ) for aminomethylphosphonic acid, showing the broad range of applicability of the proposed method.

Determination of heavy polycyclic aromatic hydrocarbons of concern in edible oils via excitation-emission fluorescence spectroscopy on nylon membranes coupled to unfolded partial least-squares/residual bilinearization.

Seven heavy polycyclic aromatic hydrocarbons (PAHs) of concern on the US Environmental Protection Agency priority pollutant list (benzo[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3-c,d]-pyrene) were simultaneously analyzed in extra virgin olive oil. The analysis is based on the measurement of excitation-emission matrices on nylon membrane and processing of data using unfolded partial least-squares regression with residual bilinearization (U-PLS/RBL). The conditions needed to retain the PAHs present in the oil matrix on the nylon membrane were evaluated. The limit of detection for the proposed method ranged from 0.29 to 1.0 µg kg(-1), with recoveries between 64 and 78 %. The predicted U-PLS/RBL concentrations compared favorably with those measured using high-performance liquid chromatography with fluorescence detection. The proposed method was applied to ten samples of edible oil, two of which presented PAHs ranging from 0.35 to 0.63 µg kg(-1). The principal advantages of the proposed analytical method are that it provides a significant reduction in time and solvent consumption with a similar limit of detection as compared with chromatography.

Characterization of the atrazine sorption process on Andisol and Ultisol volcanic ash-derived soils: kinetic parameters and the contribution of humic fractions.

Atrazine sorption was studied in six Andisol and Ultisol soils. Humic and fulvic acids and humin contributions were established. Sorption on soils was well described by the Freundlich model. Kf values ranged from 2.2-15.6 µg(1-1/n)mL(1/n)g⁻¹. The relevance of humic acid and humin was deduced from isotherm and kinetics experiments. KOC values varied between 221 and 679 mLg⁻¹ for these fractions. Fulvic acid presented low binding capacity. Sorption was controlled by instantaneous equilibrium followed by a time-dependent phase. The Elovich equation, intraparticle diffusion model, and a two-site nonequilibrium model allowed us to conclude that (i) there are two rate-limited phases in Andisols related to intrasorbent diffusion in organic matter and retarded intraparticle diffusion in the organo-mineral complex and that (ii) there is one rate-limited phase in Ultisols attributed to the mineral composition. The lower organic matter content of Ultisols and the slower sorption rate and mechanisms involved must be considered to assess the leaching behavior of atrazine.

Feasibility of the determination of polycyclic aromatic hydrocarbons in edible oils via unfolded partial least-squares/residual bilinearization and parallel factor analysis of fluorescence excitation emission matrices.

The possibility of simultaneously determining seven concerned heavy polycyclic aromatic hydrocarbons (PAHs) of the US-EPA priority pollutant list, in extra virgin olive and sunflower oils was examined using unfolded partial least-squares with residual bilinearization (U-PLS/RBL) and parallel factor analysis (PARAFAC). Both of these methods were applied to fluorescence excitation emission matrices. The compounds studied were benzo[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene and indeno[1,2,3-c,d]-pyrene. The analysis was performed using fluorescence spectroscopy after a microwave assisted liquid-liquid extraction and solid-phase extraction on silica. The U-PLS/RBL algorithm exhibited the best performance for resolving the heavy PAH mixture in the presence of both the highly complex oil matrix and other unpredicted PAHs of the US-EPA list. The obtained limit of detection for the proposed method ranged from 0.07 to 2 µg kg(-1). The predicted U-PLS/RBL concentrations were satisfactorily compared with those obtained using high-performance liquid chromatography with fluorescence detection. A simple analysis with a considerable reduction in time and solvent consumption in comparison with chromatography are the principal advantages of the proposed method.

Screening of edible oils for polycyclic aromatic hydrocarbons using microwave-assisted liquid-liquid and solid phase extraction coupled to one- to three-way fluorescence spectroscopy analysis.

The potential of microwave-assisted liquid-liquid and solid phase extraction coupled with fluorescence spectroscopy and employing one- to three-way spectral data was assessed in terms of their capacity for the rapid detection of heavy polycyclic aromatic hydrocarbons (PAHs) in olive and sunflower oils. Tocopherols and pigments groups (chlorophyll and pheophytin) present in oil matrices were the main interference compounds in the detection of PAHs using fluorescence spectroscopy. Partial spectral overlap and inner-filter effects were observed in the emission range of the analytes. The effectiveness of removing these interferences using solid phase extraction (silica, C18 and graphitized carbon black) was examined. Solid phase extraction with silica was the most effective method for the removal of pigments and tocopherol and allowed for the detection of PAHs in edible oils using fluorescence spectroscopy. The limit of detection was observed to depend on the use of one-, two- or three-way fluorescence spectral data in the range of 0.8 to 7.0 µg kg(-1). The individual recoveries of PAHs following the microwave-assisted L-L extraction and SPE with silica were assessed using HPLC-FD with satisfactory results.

Metsulfuron-methyl sorption/desorption behavior on volcanic ash-derived soils. effect of phosphate and pH.

Metsulfuron-methyl sorption/desorption behavior was studied through batch sorption experiments in three typical volcanic ash-derived soils belonging to Andisol and Ultisol orders. Their distinctive physical and chemical properties are acidic pH and variable surface charge. Organic matter content and mineral composition affected in different ways sorption of metsulfuron-methyl (K(OC) ranging from 113 to 646 mL g(-1)): organic matter and iron and aluminum oxides mainly through hydrophilic rather than hydrophobic interactions in Andisols, and Kaolinite group minerals, as major constituents of Ultisols, and iron and aluminum oxides only through hydrophilic interactions. The Freundlich model described metsulfuron-methyl behavior in all cases (R(2) > 0.992). K(f) values (3.1-14.4 microg(1-1/n) mL(1/n) g(-1)) were higher than those reported for different class of soils including some with variable charge. Hysteresis was more significant in Ultisols. A strong influence of pH and phosphate was established for both kinds of soil, intensive soil fertilization and liming being the most probable scenario for leaching of metsulfuron-methyl, particularly in Ultisols.

Modeling the sorption kinetic of metsulfuron-methyl on Andisols and Ultisols volcanic ash-derived soils: kinetics parameters and solute transport mechanisms.

Metsulfuron-methyl sorption kinetic was studied in Andisol and Ultisol soils in view of their distinctive physical and chemical properties: acidic pH and variable surface charge. Different kinetic models were applied to the experimental results. The pseudo-second-order model fitted sorption kinetics data better than the pseudo-first-order model. The rate constant and the initial rate constant values obtained through this model demonstrated the different behavior of metsulfuron-methyl in both kinds of soils, both parameters being the highest for Andisol. The application of Elovich equation, intraparticle diffusion model and a two-site nonequilibrium model (TSNE) allowed to conclude that: (i) the high organic matter content is the governing factor for Andisols where mass transfer across the boundary layer, and in a lesser degree, intraparticle diffusion were the two processes controlling sorption kinetic and (ii) the mineral composition was more relevant in Ultisols where rate was controlled almost exclusively by intraparticle diffusion into macropores and micropores. The slower sorption rate on Ultisols, the mechanism involved and the lower sorption capacity of this kind of soils must be taken into account to assess leaching behavior of this herbicide.

Survey of organophosphorus pesticide residues in virgin olive oils produced in Chile.

Dimethoate, diazinon, parathion methyl, pirimiphos methyl, malathion, fenthion, chlorpyriphos, methidathion and azinphos methyl were determined in 71 olive oil samples produced in Chile from different varieties of olives (arbequina, frantoio, picual, lechino and blend) at three different harvest periods (2007, 2008 and 2009). The target pesticides were determined using a validated analytical method based on microwave-assisted liquid-liquid and solid-phase extraction with subsequent GC-FPD detection and GC-MS/MS for confirmation purposes. In 79% of the samples, five of the nine pesticides tested were detected with a frequency of one pesticide per sample. The highest detection rates were observed for the residues of chlorpyriphos and diazinon. The average concentration of chlorpyriphos, diazinon, azinphos methyl and methidathion were 0.084, 0.057, 0.024 and 0.010 µg g(-1), respectively. Higher contents of organophosphorus pesticides (OPPs) were found in regions where intensive agriculture is practiced. However, the levels of OPPs were reassuringly low and indicate that olive oil produced and exported from Chile does not currently represent any risk for consumers.

Molecular and crystalline structures of three (S)-4-alkoxycarbonyl-2-azetidinones containing long alkyl side chains from synchrotron X-ray powder diffraction data.

The (S)-4-alkoxo-2-azetidinecarboxylic acids are optically active beta-lactam derivatives of aspartic acid, which are used as precursors of carbapenem-type antibiotics and poly-beta-aspartates. The crystal structures of three (S)-4-alkoxo-2-azetidinecarboxylic acids with alkyl chains with 10, 12 and 16 C atoms were solved using parallel tempering and refined against the X-ray powder diffraction data using the Rietveld method. The azetidinone rings in the three compounds display a pattern of asymmetrical bond distances and an almost planar conformation; these characteristics are compared with periodic solid-state, gas-phase density-functional theory (DFT) calculations and MOGUL average bond distances and angles from the CSD. The compounds pack along [001] as corrugated sheets separated by approximately 4.40 A and connected by hydrogen bonds of the type N-H...O.

Microwave-assisted extraction at atmospheric pressure coupled to different clean-up methods for the determination of organophosphorus pesticides in olive and avocado oil.

An effective extraction method was devised for the determination of organophosphorus pesticides (OPPs) in olive and avocado oil samples, using atmospheric pressure microwave-assisted liquid-liquid extraction (APMAE) and solid-phase extraction or low-temperature precipitation as clean-up step. A simple glass system equipped with an air-cooled condenser was designed as an extraction vessel. The pesticides were partitioned between acetonitrile and oil solution in hexane. Analytical determinations were carried out by gas chromatography-flame photometric detection and gas chromatography-tandem mass spectrometry, using a triple quadrupole mass analyzer, for confirmation purposes. Several factors influencing the extraction efficiency were investigated and optimized through fractional factorial design and Doehlert design. Under optimal conditions the recovery of pesticides from oil at 0.025 microg g(-1) ranged from 71% to 103%, except for fenthion in avocado oil, with RSDs < or = 13% (n=5). The LOQ for the entire method ranged from 0.004 to 0.015 microg g(-1). Finally, the proposed method was successfully applied to the extraction and determination of the selected pesticides in 20 commercially packed extra virgin olive oils and four commercially packed avocado oils produced in Chile. Detectable residues of different OPPs were observed in 85% of samples.

Sorption behavior of bensulfuron-methyl on andisols and ultisols volcanic ash-derived soils: contribution of humic fractions and mineral-organic complexes.

Bensulfuron-methyl sorption was studied in Andisol and Ultisol soils in view of their characteristic physical and chemical properties, presenting acidic pH and variable charge. Humic and fulvic acids (HA and FA) and humin (HUM) contributions were established. Sorption was studied by using two synthetic sorbents, an aluminum-silicate with iron oxide coverage and the same sorbent coated with humic acid. Freundlich model described Bensulfuron-methyl behavior in all sorbents (R(2) 0.969-0.998). K(f) for soils (8.3-20.7 microg(1-1/n) mL(1/n) g(-1)) were higher than those reported in the literature. Organic matter, halloysite or kaolinite, and specific surface area contributed to the global process. The highest K(f) for HA, FA and HUM were 539.5, 82.9, and 98.7 microg(1-1/n) mL(1/n) g(-1). Model sorbents described the participation of variable charge materials with high adsorption capacity. The constant capacitance model was used to assess effects of Bensulfuron-methyl adsorption on the distribution of SOH, SOH(2)(+) and SO(-) sites of sorbents.