No abstract

Surface and ground waters Vineyards s u m m a r y A multi-residual analytical method based on solid phase extraction (SPE) followed by liquid chromatography-electrospray ionisation-mass spectrometry (LC-MS) was developed to monitor pesticides in natural waters. Fifty-eight compounds, including herbicides, fungicides, insecticides and some of their degradation products, were surveyed to evaluate the quality of natural waters throughout the winegrowing region of La Rioja (Rioja DOCa). Ninety-two sampling points were selected, including surface and ground waters that could be affected by agricultural activities covering the region's three sub-areas. Different parameters that may affect the efficiency of the SPE procedure were optimised (sorbent type, elution solvent and sample volume), and matrix-matched standards were used to eliminate the variable matrix effect and ensure good quantification. The developed method allows the determination of target compounds below the level established by the European Union for waters for human use with suitable precision (relative standard deviations lower than 18%) and accuracy (with recoveries over 61%). Forty compounds included in this study (six insecticides, 12 herbicides, 16 fungicides and six degradation products) were detected in one or more samples. The herbicides terbuthylazine, its metabolite desethyl terbuthylazine, fluometuron and ethofumesate and the fungicides pyrimethanil and tebuconazole were the compounds most frequently detected in water samples (present in more than 60% of the samples). Concentrations above 0.1 lg L À1 were detected for 37 of the compounds studied, and in several cases recorded values of over 18 lg L À1 . The results reveal the presence of pesticides in most of the samples investigated. In 64% of groundwaters and 62% of surface waters, the sum of compounds detected was higher than 0.5 lg L À1 (the limit established by EU legislation for the sum of all pesticides detected in waters for human use).

Changes in activity and structure of the soil microbial community after application of azoxystrobin or pirimicarb and an organic amendment to an agricultural soil

Different strategies are now being optimized to prevent water from agricultural areas being contaminated by pesticides. The aim of this work was to optimize the adsorption of non-polar (tebuconazole, triadimenol) and polar (cymoxanil, pirimicarb) pesticides by soils after applying the biosorbent spent mushroom substrate (SMS) at different rates. The adsorption isotherms of pesticides by three soils and SMS-amended soils were obtained and the adsorption constants were calculated. The distribution coefficients (K d) increased 1.40-23.1 times (tebuconazole), 1.08-23.7 times (triadimenol), 1.31-42.1 times (cymoxanil), and 0.55-23.8 times (pirimicarb) for soils amended with biosorbent at rates between 2 and 75 %. Increasing the SMS rates led to a constant increase in adsorption efficiency for non-polar pesticides but not for polar pesticides, due to the increase in the organic carbon (OC) content of soils as indicated by K OC values. The OC content of SMS-amended soils accounted for more than 90 % of the adsorption variability of non-polar pesticides, but it accounted for only 56.3 % for polar pesticides. The estimated adsorption of SMS-amended soils determined from the individual adsorption of soils and SMS was more consistent with real experimental values for non-polar pesticides than for polar pesticides. The results revealed the use of SMS as a tool to optimize pesticide adsorption by soils in dealing with specific contamination problems involving these compounds.

An important problem encountered during the preservation of paintings and other artworks is the fading of the original colors due to exposure of the colorants to light. This fact is clearly evidenced in some of Vincent Van Gogh's paintings in which an organic red, eosin or geranium lake, is present.The identification of eosin and the characterization of its degradation products in paintings represents a challenge because of (i) the generally low concentration of the pigment remaining after an aging period of ca 100 years, (ii) the scarcity of the paint micro samples available for analysis and the difficulty of obtaining additional ones and (iii) the complexity of the degradation behavior of eosin when it is mixed with organic or inorganic pigments, binding media or varnish.

Eosin is a synthetic organic colorant prone to fading under the influence of light. On the basis of the growing interest in the understanding of the discoloration mechanism of eosin-based lakes, this study compares the ability of two ultrafast and ultrasensitive mass spectrometry techniques to detect eosin derivatives in complex matrices, such as oil media without the use of conventional separation columns or additional sample preparation protocols. Direct analysis in real time mass spectrometry (DART-MS) and direct infusion electrospray ionization mass spectrometry (DI-ESI-MS) were used to characterize the degradation pathway of eosin in oil media. The analysis protocols developed in this study are applied to discern the degradation mechanism of the lake pigment eosin (comprising the molecule per se complexed to an inorganic substrate) dispersed in linseed oil to create an oil paint. The analysis of oil paints by high resolution MS without an extraction methodology that modifies the system chemistry allowed us to identify the degradation forms without causing any additional fragmentation. Both techniques revealed the primary photodegradation pathway of eosin in linseed oil, and DI-ESI-MS provided additional information on the native conformation of the lake.

No abstract

A study has been conducted on the leaching of two fungicides, tebuconazole and cymoxanil, in a soil amended with spent mushroom substrate (SMS), with an evaluation of how different factors influence this process. The objective was based on the potential use of SMS as a biosorbent for immobilizing pesticides in vulnerable soils, and the need to know how it could affect the subsequent transport of these retained compounds. Breakthrough curves (BTCs) for C-fungicides, non-incubated and incubated over 30days, were obtained in columns packed with an unamended soil (S), and this soil amended with SMS at rates of 5% (S+SMS5) and 50% (S+SMS50) under saturated and saturated-unsaturated flows. The highest leaching of tebuconazole (>50% of the total C added) was found in S when a saturated water flow was applied to the column, but the percentage of leached fungicide decreased when a saturated-unsaturated flow was applied in both SMS-amended soils. Also a significant decrease in leaching was observed for tebuconazole after incubation in the column, especially in S+SMS50 when both flows were applied. Furthermore, cymoxanil leaching was complete in S and S+SMS when a saturated flow was applied, and maximum peak concentrations were reached at 1pore volume (PV), although BTCs showed peaks with lower concentrations in S+SMS. The amounts of cymoxanil retained only increased in S+SMS when a saturated-unsaturated flow was applied. A more relevant effect of SMS for reducing the leaching of fungicide was observed when cymoxanil was previously incubated in the column, although mineralization was enhanced in this case. These results are of interest for extending SMS application on the control of the leaching of fungicides with different physicochemical characteristics after different ageing times in the soil and water flow conditions applied.