Selective modification of clay minerals for the adsorption of herbicides widely used in olive groves

Ground and surface water contamination by herbicides applied to olive groves in Spain and other Mediterranean countries is demanding strategies to prevent and remediate the environmental problems repeatedly caused by such herbicides. In this study, six different organic cations (L-carnitine, spermine, hexadimethrine, tyramine, phenyltrimethylammonium, and hexadecyltrimethylammonium) were incorporated into Na-rich Wyoming montmorillonite (SWy-2) and Ca-rich Arizona montmorillonite (SAz-1) at two different loadings (50% and 100% of the cation exchange capacity of the clays) as a strategy to enhance the affinity of the clay minerals for three herbicides widely used in olive groves: terbuthylazine, diuron, and MCPA. The modified montmorillonites were characterized and tested as adsorbents of the herbicides through batch adsorption tests. At the experimental conditions used, some of the modified montmorillonites removed more than 95% of the herbicide initially present in aqueous solution, whereas the unmodified clays removed less than 15%. All three herbicides displayed very strong affinities for SAz-1 exchanged with hexadecyltrimethylammonium cations, particularly when these were incorporated at 100% of the cation exchange capacity of the clay mineral. Terbuthylazine and diuron also displayed very strong affinities for SWy-2 exchanged with L-carnitine and spermine, respectively. The chemical characteristics of the organic cation greatly influenced the adsorptive properties of the resultant organoclay. The herbicides were in general reversibly adsorbed by the modified clays. The results indicate that some of the tested modified clays could be suitable for the removal of the assayed herbicides from contaminated water and also as possible supports for the design of slow release formulations of such herbicides to attenuate their environmental impact when used in high-risk scenarios such as olive groves.     

A General Approach to Model Movement in (Highly) Fragmented Patch Networks

Landscape heterogeneity can often be represented as a series of discrete habitat or resource patches surrounded by a matrix of non-habitat. Understanding how animals move in such networks of patches is important for many theoretical and applied questions. The probability of going from one patch to another is affected in a non-trivial way by the characteristics and location of other patches in the network. Nearby patches can compete as possible destinations, and a particular patch can be shadowed by neighboring patches. We present a way to account for the effects of the spatial configuration of patches in models of space use where individuals alternate between spending time in a patch and moving to other patches in the network. The approach is based on the original derivation of Ovaskainen and Cornell (J Appl Probab 40:557–580, 2003) for a diffusion model that considered all possible ways in which an individual leaving a particular patch can eventually reach another patch before dying or leaving the patch network. By replacing the theoretical results of Ovaskainen and Cornell by other appropriate functions, we provide generality and thus make their approach useful in contexts where diffusion is not a good approximation of movement. Furthermore, we provide ways to estimate time spent in the non-habitat matrix when going from patch to patch and implement a method to incorporate the effect of the history of previous visits on future patch use. We present an MCMC way to fit these models to data and illustrate the approach with both simulated data and data from sheep moving among seasonally flooded meadows in northern Patagonia.Supplementary materials accompanying this paper appear online.     

Ozone Biomonitoring with Bel-W3 Tobacco Plants in the City of Valencia (Spain)

A biomonitoring study using the ozone-sensitive bioindicator plant Nicotiana tabacum cv. Bel-W3 was conducted in the city of Valencia (eastern Spain) and surrounding areas in 2002. Plants were exposed to ambient air at seven sites, including four traffic-exposed urban sites, a large urban garden and a suburban and a rural station, for six consecutive 2-week periods using highly standardised methods. Foliar injury was registered at all stations in at least one of the exposure periods. The urban stations submitted to intense traffic showed lower ozone injury than the less traffic-exposed stations. Strong changes in the intensity of ozone injury were observed for the different exposure periods. Leaf injury was significantly related to both mean ozone values (24 and 12 h means) and cumulative exposure indices (AOT20, AOT40). However, correlation strength was moderate (r _s?=?0.39 to 0.58), suggesting that the plant response to ozone was modified by environmental factors. The use of sensitive bioindicators like tobacco Bel-W3 in cities provides complementary information to that of continuously operating air quality monitors, as the impact of ambient ozone levels is directly measured.     

Fatty acid effect on hydroxypropyl methylcellulose-beeswax edible film properties and postharvest quality of coated 'Ortanique' mandarins

The objective of this work was to investigate the effect of fatty acid (FA) type and content on mechanical properties, water vapor permeability and oxygen permeability of hydroxypropyl methycellulose (HPMC)-beeswax (BW) stand-alone edible films. The effect of these films formed as coatings on the postharvest quality of 'Ortanique' mandarins was also studied. Selected FAs were stearic acid (SA), palmitic acid (PA), and oleic acid (OA), using BW/FA ratios of 1:0.5 and 1:0.2 (w/w). HPMCBW coatings reduced weight and firmness loss of 'Ortanique' mandarins, without compromising flavor quality compared to uncoated mandarins. Coatings containing OA provided the best weight loss control at both concentrations tested; however, when the BW/OA ratio was 1:0.5, the coatings increased fruit internal CO2, ethanol, and acetaldehyde contents of 'Ortanique' mandarins, therefore reducing flavor compared to the rest of the coatings studied. Although barrier and mechanical properties might be used to understand coating performance, differences observed between film oxygen permeability and coating permeability indicate that permeance should be measured on the coated fruit.     

Recombinant human lactoferrin and iron transport across Caco-2 monolayers: effect of heat treatment on the binding to cells

Recombinant human lactoferrin (rhLF) from Aspergillus awamori bound to Caco-2 cell membranes in a saturable manner. The dissociation constant for the apo form was (Kd)=2.2 x 10(-7) M; however, the specific binding of the iron-saturated rhLF and of lactoferrin from human milk (hLF) was too low to calculate the binding parameters. Recombinant human lactoferrin subjected to heat treatment did not lose the ability to bind to cell membranes except at high temperature and long time treatments (85 and 89 degrees C for 40 min) for which there was a slight decrease in the binding. No significant differences have been found in the transport of iron bound to rhLF or to hLF across Caco-2 cell monolayers. Nevertheless, the amount of iron-saturated hLF transported across Caco-2 monolayers was significantly higher than that of rhLF. For both lactoferrins, the amount of intact protein in the lower chamber was about 4.5% of the total radioactivity transported, indicating the degradation of lactoferrin in the passage across Caco-2 cells.     

Influence of glycosidic linkages and molecular weight on the fermentation of maltose-based oligosaccharides by human gut bacteria

A structure-function study was carried out to increase knowledge of how glycosidic linkages and molecular weights of carbohydrates contribute toward the selectivity of fermentation by gut bacteria. Oligosaccharides with maltose as the common carbohydrate source were used. Potentially prebiotic alternansucrase and dextransucrase maltose acceptor products were synthesized and separated into different molecular weights using a Bio-gel P2 column. These fractions were characterized by matrix-assisted laser desorption/ionization time-of-flight. Nonprebiotic maltooligosaccharides with degrees of polymerization (DP) from three to seven were commercially obtained for comparison. Growth selectivity of fecal bacteria on these oligosaccharides was studied using an anaerobic in vitro fermentation method. In general, carbohydrates of DP3 showed the highest selectivity towards bifidobacteria; however, oligosaccharides with a higher molecular weight (DP6-DP7) also resulted in a selective fermentation. Oligosaccharides with DPs above seven did not promote the growth of "beneficial" bacteria. The knowledge of how specific structures modify the gut microflora could help to find new prebiotic oligosaccharides.     

Responses of Biochemical Markers in the Fish Prochilodus lineatus Exposed to a Commercial Formulation of Endosulfan

Among the most extensively used compounds for the pest control in Argentinean crops is the organochlorine endosulfan. The sublethal effects of the commercial endosulfan formulation on hematology and lipid peroxidation (LPO) of the neotropical fish Prochilodus lineatus were investigated. Firstly, we calculated acute toxicity (LC₅₀) in order to define sublethal concentrations (0, 1.2, and 2.4 ??g L^?1). Hematological and oxidative stress responses were assessed at 24, 48, and 96 h. Endosulfan exposure significantly diminished the hemoglobin concentration, mean cell hemoglobin, and total plasma protein and increased white blood cells count and plasma glucose after 96 h. Exposed fish showed an alteration of the differential leukocytes count, evidenced by more thrombocytes and monocytes and less lymphocytes and neutrophils. Endosulfan increased LPO levels in intestine, liver, and brain in both sublethal concentrations. The present results suggest that endosulfan produces biochemical and physiological alterations, including immunological disorders, and it is a good inductor of oxidative stress in P. lineatus.     

Bioaccumulation of Copper by Zea mays: Impact on Root, Shoot and Leaf Growth

In the present study, the growth and the Cu²⁺accumulation by roots, shoots and leaves of Zea mays were examined using copper sulphate in the range of 10^?4 to 10^?2 M. Plants of Z. mays did not show inhibition of growth in the presence of 10^?4 to 10^?2 M Cu²⁺; however, it was observed growth effects on root when different Cu²⁺ solution concentrations were used. Only the seedlings exposed to 10^?2 M exhibited substantial root growth reduction, yielding only 56% of length with respect to the control. Seedlings exposed to 10^?4 M Cu²⁺ exhibited 16% and 42% growth increase in shoots and leaves, respectively, when compared with the controls. The seedlings treated with 10^?3 and 10^?2 M Cu²⁺ were inhibited in shoot and leaf growth. The fresh weights in roots, shoots and leaves significantly decreased at 10^?2 M Cu²⁺. The tolerance index, based on root length, was not significantly different for the three different treatments with copper. However, the total accumulation rate was very low at 10^?4 and 10^?3 M compared to 10^?2 Cu treatments. The capacity of copper accumulation by roots, shoots and leaves of Z. mays plants increased concomitant to the copper concentration, arriving to 382 times more in roots, 157 in shoots and only 16 in leaves, all compared to the controls. Cu could be accumulated by roots, shoots and leaves when the initial concentrations were 10^?3 and 10^?4 M. However, when it was 10^?2 M, the metal could not be accumulated by leaf and shoot levels; the roots could increase their copper accumulation capacity three times compared to the control. Z. mays has potential ability to accumulate Cu without being overly sensitive to Cu toxicity.     

Chemometrical analysis of capillary electrophoresis casein fractions for predicting ripening times of milk mixture cheese

The effect of the ripening time on the proteolytic process in cheeses manufactured from mixtures of cow's and ewe's milk during a 167-day ripening period was monitored by capillary electrophoresis of the pH 4.6-insoluble fraction. Totals of 21 and 16 peaks were recognized and matched in the electropherograms obtained with a fused-silica capillary and a neutral capillary (hydrophilically coated), respectively. These peaks corresponded to intact bovine and ovine caseins and their hydrolysis products (e.g., alpha(s1)-casein, gamma-caseins). In 167-day-old cheeses, bovine alpha(s0)-casein (alpha(s1)-casein 9P) had been completely degraded and 6% of the residual bovine alpha(s1)-casein remained intact. Breakdown of the beta-casein fraction was lower than that of the alpha(s)-casein fraction. Finally, partial least-squares regression and principal component regression were used to predict the ripening time in cheeses. The root-mean-square errors in prediction by cross-validation were <7.8 days in all cases.