QuEChERS: a sample preparation for extraction of carbaryl from rat feces

Carbamate compounds are an important group of cholinesterase inhibitors. There is a need for creating awareness regarding the risks of the inadequate carbamate use in the residential areas due to potential adverse human effects. Carbaryl is a commonly used pesticide worldwide. A simple, fast, and high-throughput method was developed employing liquid chromatography with fluorescence detector to determine carbaryl residues in rat feces. The extraction was performed by using a rapid, easy, cheap, effective, reliable, and safe (QuEChERS) method, using acetonitrile as the extracting solvent. The parameters for the performance of the extraction method were optimized, such as ratio of mass of sample per volume of extraction solvent, QuEChERS content, and cleanup columns. Linear response was obtained for all calibration curves (solvent and matrix-matched) over the established concentration range (5–500 μg/L) with a correlation coefficients higher than 0.999. The achieved recovery was 97.9% with relative standard deviation values of 1.1% (n = 4) at 167 μg/kg fortified concentration level and the limits of detection and quantification were 27.7 and 92.3 µg/kg, respectively.     

Analytical solutions for reactive transport under an infiltration-redistribution cycle

Transport of reactive solute in unsaturated soils under an infiltration-redistribution cycle is investigated. The study is based on the model of vertical flow and transport in the unsaturated zone proposed by Indelman et al. [J. Contam. Hydrol. 32 (1998) 77], and generalizes it by accounting for linear nonequilibrium kinetics. An exact analytical solution is derived for an irreversible desorption reaction. The transport of solute obeying linear kinetics is modeled by assuming equilibrium during the redistribution stage. The model which accounts for nonequilibrium during the infiltration and assumes equilibrium at the redistribution stage is termed partial equilibrium infiltration-redistribution model (PEIRM). It allows to derive approximate closed form solutions for transport in one-dimensional homogeneous soils. These solutions are further applied to computing the field-scale concentration by adopting the Dagan and Bresler [Soil Sci. Soc. Am. J. 43 (1979) 461] column model. The effect of soil heterogeneity on the solute spread is investigated by modeling the hydraulic saturated conductivity as a random function of horizontal coordinates. The quality of the PEIRM is illustrated by calculating the critical values of the Damk?hler number which provide the achievable accuracy in estimating the solute mass in the mobile phase. The distinguishing feature of transport during the infiltration-redistribution cycle as compared to that of infiltration only is the finite depth of solute penetration. For irreversible desorption, the maximum solute penetration W/theta(r) is determined by the amount of applied water W and the residual water content theta(r). For sorption-desorption kinetics, the maximum depth of penetration z(r)(e, infinity ) also depends on the ratio between the rate of application and the column-saturated conductivity. It is shown that z(r)(e, infinity ) is bounded between the depths W/(theta(r)+K(d)) and W/theta(r) corresponding to the maximum solute penetration for equilibrium transport and for irreversible desorption, respectively. This feature of solute penetration explains the unusual phenomena of plume contraction after an initial period of spreading [Lessoff, S.C., Indelman, P., Dagan, G., 2002. Solute transport in infiltration-redistribution cycles in heterogeneous soils. In Raats, P.A.C., Smiles, D.,Warrick, A.W. (Eds), Environmental Mechanics: Water, Mass and Energy Transport in the Biosphere. American Geophysical Union, pp. 133-144]. Unlike transport under equilibrium conditions, when the solute is completely concentrated at the front, the solute under nonequilibrium conditions is spread out behind the front. Heterogeneity leads to additional spreading of the plume.     

Ozone stress and antioxidant substances in Trifolium repens and Centaurea jacea leaves

Ozone-sensitive (NC-S clone) and resistant plants (NC-R clone) of Trifolium repens and Centaurea jacea were exposed to moderate ozone concentrations in ambient air. The aim of this study was the investigation of the relation between ozone-sensitivity and leaf concentrations of antioxidants (ascorbic acid, total phenolics and total antioxidant capacity). NC-R clone showed the highest concentrations of antioxidants with 50-70% more ascorbic acid than NC-S. NC-R had about 5 times more ascorbic acid in the young leaves and 9 times more in the old leaves than Centaurea. In a fumigation experiment with acute ozone stress (100 nl L(-1)) the antioxidant levels changed profoundly. The ozone-injured leaves of NC-S had 6-8 times more total phenolics than uninjured leaves. Generally older leaves had lower antioxidant concentrations and were more prone to ozone injury than younger leaves. Ascorbic acid concentrations were closer related to the appearance of visible ozone injury than the other antioxidative parameters.     

Macrodispersion by diverging radial flows in randomly heterogeneous porous media

Radial flow takes place in a heterogeneous porous formation where the transmissivity T is modelled as a stationary random space function (RSF). The steady flow is driven by a given rate, and the mean velocity is radial. A pulse-like of a tracer is injected in the porous formation, and the thin plume spreads due to the fluctuations of the velocity which results a RSF as well. Transport is characterized by the mean front, and by the second spatial moment of the plume. We are primarily interested in tracer macrodispersion modelling. With the neglect of pore-scale dispersion, macrodispersion coefficients are computed at the second order of approximation, without neglecting the head-gradient fluctuations. Although transport is non-ergodic at the source, it is shown that ergodicity is achieved at small distances from the source. This is due to the fact that close to the source local velocities are quite large, and therefore solute particles become uncorrelated very soon. Under ergodic conditions, we compare macrodispersion mechanism in radial flows with that occurring in mean uniform flows. At short distances the spreading effect is highly enhanced by the large variability of the flow field, whereas at large distances transport exhibits a lesser dispersion due to the reduction of velocities. This supports the explanation provided by Indelman and Dagan (1999) to justify why the macrodispersivity is found smaller than that pertaining to mean uniform flows. The model is tested against a tracer transport experiment (Fernàndez-Garcia et al., 2004) by comparing the theoretical and experimental breakthrough curves. The accordance with real data, that is achieved without any fitting to concentration values, strengthens the capability of the proposed model to grasp the main features of such an experiment, the approximations as well as experimental uncertainties notwithstanding.     

Sixty years of habitat decline: impact of land-cover changes in northern Italy on the decreasing ortolan bunting <Emphasis Type="Italic">Emberiza hortulana</Emphasis>

Habitat loss and degradation are main global threats to biodiversity, and land-use changes in agriculture-dominated landscapes are crucial for an important portion of biodiversity, especially in Europe. We evaluated the effects of land-use changes (1954–2012) on a threatened species, the ortolan bunting, in an agricultural area crucial for its conservation in Italy. We built a distribution model for ortolan bunting in current landscapes and then re-projected it to past scenarios (1954 and 1999–2000). We evaluated the most important land-use changes occurred and estimated their effects on habitat suitability. Bunting occurrence was mostly affected by the extent of grassland (positively; used as foraging/breeding ground), shrubland (quadratic effect; perches/shelter), forest and urbanized land (negatively), and by solar radiation (positively) and slope (quadratic), consistent with other studies carried out especially in southern Europe. The potential distribution of the species was much larger in the past: the estimated decline in suitable habitat is 44–72 % (since 1999–2000/1954), coherent with historical data suggesting strong decline and contraction. Changes in suitability (1954–2012) were mostly associated with changes in the cover of forest, vineyards and abandoned areas (negatively), and shrubland (positively). Land-use/land-cover changes are the main drivers of species occurrence and of habitat decline. The heterogeneous landscape of hilly/low-mountain sites in this area, characterized by a mix of habitats offering complementary resources to ortolan buntings and other species of conservation concern, is currently threatened by abandonment and intensification, but its maintenance may be promoted by a correct definition of Rural Development Programme measures.     

Influence of fenamidone, indoxacarb, pyraclostrobin, and deltamethrin on the population of natural yeast microflora during winemaking of two sardinian grape cultivars

The influence of fenamidone ((S)-1-anilino-4-methyl-2-methylthio-4-phenylimidazolin-5-one), pyraclostrobin (methyl 2-[1-(4-chlorophenyl)pyrazol-3-yloxymethyl]-N-methoxycarbanilate), indoxacarb (methyl 7-Chloro-2,5-dihydro-2-[[(methoxycarbonyl) [4- (trifluoromethoxy) phenyl] amino] carbonyl] indeno[1,2-e][1,3,4] oxadiazine-4a(3H)-carboxylate), and deltamethrin ([cyano-[3-(phenoxy)phenyl]methyl] 3-(2,2-dibromoethenyl)-2,2-dimethylcyclopropane-1-carboxylate) on spontaneous fermentation carried out by natural yeast grapes microflora, was studied during the wine-making process. Aliquots of pesticide standard solutions were added to the grapes before crushing, to reach a concentration equal or half the maximum residue limit (MRL). Vinifications were performed, with maceration (R), or without maceration (W). During the wine-making process, samples were taken at the beginning (one hour after grapes crushing), at the middle and at the end of the spontaneous fermentation process. At half the MRL concentration, deltamethrin affected Pichia sp. population with a decrease of almost 50 %, while fenamidone decreased Candida sp., Candida stellata at 83, and 36%, respectively. Metschnikowia pulcherrima population decreased in all samples when compared to the control. Experiments at MRL levels showed a strong reduction for all non-Saccharomyces yeast species, when grapes had been treated with pyraclostrobin, fenamidone, and deltamethrine, except for Candida sp. which was found to have been affected only by fenamidone residues. Growth zone inhibition test showed only an in vitro activity of pyraclostrobin over Kloeckera spp., C. stellata, and M. pulcherrima. Microvinification experiments produced wines with no differences concerning S. cerevisiae population as well as production of ethanol and residual sugars. Experiments showed that at the end of the fermentation process pesticides were adsorbed by the lees and grape skins, and no pesticides residue was detectable in wine.     

New thiol adsorbent grafted on silica gel: synthesis,characterization and employment for heavy metal adsorptions

Silica gel surface has been modified in two reaction steps: (i) the silylating agent 3-mercaptopropyltrimetoxysilane was firstly immobilized to give a surface Sil-SH and (ii) this precursor incorporated an ethylene sulfide molecule to obtain the surface denoted Sil-SSH. This material was characterized by elemental analysis, IR spectroscopy, thermogravimetry, solid state 13C and 29Si NMR, and surface area measurement. These materials were employed as adsorbents for divalent heavy cations from aqueous solutions at room temperature and the isotherms were adjusted to a modified Langmuir equation. The maxima number of moles adsorbed were 1.0, 1.5, 1.6, 2.2, 2.4 and 3.3 mmol g(-1) for Co, Cu, Ni, Cd, Pb, and Hg, respectively.     

Reach and messages of the world's largest ivory burn

Recent increases in ivory poaching have depressed African elephant populations. Successful enforcement has led to ivory stockpiling. Stockpile destruction is becoming increasingly popular, and most destruction has occurred in the last 5 years. Ivory destruction is intended to send a strong message against ivory consumption, both in promoting a taboo on ivory use and catalyzing policy change. However, there has been no effort to establish the distribution and extent of media reporting on ivory destruction events globally. We analyzed media coverage of the largest ivory destruction event in history (Kenya, 30 April 2016) across 11 nation states connected to ivory trade. We used an online‐media crawling tool to search online media outlets and subjected 5 of the largest print newspapers (by circulation) in 5 nations of interest to content analysis. Most online news on the ivory burn came from the United States (81% of 1944 articles), whereas most of the print news articles came from Kenya (61% of 157 articles). Eighty‐six to 97% of all online articles reported the burn as a positive conservation action, whereas 4–50% discussed ivory burning as having a negative impact on elephant conservation. Most articles discussed law enforcement and trade bans as effective for elephant conservation. There was more relative search interest globally in the 2016 Kenyan ivory burn than any other burn in 5 years. Ours is the first attempt to track the reach of media coverage relative to an ivory burn and provides a case study in tracking the effects of a conservation‐marketing event.     

Cross-sectional biomonitoring study of pesticide exposures in Queensland,Australia, using pooled urine samples

A range of pesticides are available in Australia for use in agricultural and domestic settings to control pests, including organophosphate and pyrethroid insecticides, herbicides, and insect repellents, such as N,N-diethyl-meta-toluamide (DEET). The aim of this study was to provide a cost-effective preliminary assessment of background exposure to a range of pesticides among a convenience sample of Australian residents. De-identified urine specimens stratified by age and sex were obtained from a community-based pathology laboratory and pooled (n = 24 pools of 100 specimens). Concentrations of urinary pesticide biomarkers were quantified using solid-phase extraction coupled with isotope dilution high-performance liquid chromatography–tandem mass spectrometry. Geometric mean biomarker concentrations ranged from <0.1 to 36.8 ng/mL for organophosphate insecticides, <0.1 to 5.5 ng/mL for pyrethroid insecticides, and <0.1 to 8.51 ng/mL for all other biomarkers with the exception of the DEET metabolite 3-diethylcarbamoyl benzoic acid (4.23 to 850 ng/mL). We observed no association between age and concentration for most biomarkers measured but noted a “U-shaped” trend for five organophosphate metabolites, with the highest concentrations observed in the youngest and oldest age strata, perhaps related to age-specific differences in behavior or physiology. The fact that concentrations of specific and non-specific metabolites of the organophosphate insecticide chlorpyrifos were higher than reported in USA and Canada may relate to differences in registered applications among countries. Additional biomonitoring programs of the general population and focusing on vulnerable populations would improve the exposure assessment and the monitoring of temporal exposure trends as usage patterns of pesticide products in Australia change over time.     

Darcian preferential water flow and solute transport through bimodal porous systems: Experiments and modelling

Soils often exhibit a variety of small-scale heterogeneities such as inter-aggregate pores and voids which partition flow into separate regions. In this paper a methodological approach is discussed for characterizing the hydrological behaviour of a heterogeneous clayey–sandy soil in the presence of structural inter-aggregate pores. For the clay soil examined, it was demonstrated that, coupling the transfer function approach for analyzing BTCs and water retention data obtained with different methods from laboratory studies captures the bimodal geometry of the porous system along with the related existence of fast and slow flow paths. To be effectively and reliably applied this approach requires that the predominant effects of the soil hydrological behaviour near saturation be supported by accurate experimental data of both breakthrough curves (BTCs) and hydraulic functions for high water content values. This would allow the separation of flow phases and hence accurate identification of the processes and related parameters.