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.     

Effect of compost application rate on carbon degradation and retention in soils

We investigated the effect of a single compost application at two rates (50 and 85Mgha(-1)) on carbon (C) degradation and retention in an agricultural soil cropped with maize after 150d. We used both C mass balance and soil respiration data to trace the fate of compost C. Our results indicated that compost C accumulated in the soil after 150d was 4.24Mgha(-1) and 6.82Mg C ha(-1) for 50 and 85Mg ha(-1) compost rate, respectively. Compost C was sequestered at the rate of 623 and 617g C kg(-1) compost TOC for 50 and 85Mgha(-1) compost dose, respectively. These results point to a linear response between dose of application and both C degradation and retention. The amount of C sequestered was similar to the total recalcitrant C content of compost, which was 586g C kg(-1) compost TOC, indicating that, probably, during the short experiment, the labile C pool of compost (414g C kg(-1) of compost TOC) was completely degraded. Soil respiration measured at different times during the crop growth cycle was stable for soils amended with compost (CO2 flux of 0.96+/-0.11g CO2 m(-2) h(-1) and 1.07+/-0.10g CO2 m(-2) h(-1), respectively, for 50 and 85Mgha(-1)), whereas it increased in the control. The CO2 flux due to compost degradation only, though not statistically significant, was always greatest for the highest compost doses applied (0.22+/-0.40g CO2 m(-2) h(-1) and 0.33+/-0.25g CO2 m(-2) h(-1) for the 50 and 85Mgha(-1) compost dose, respectively). This seems to confirm the highest C degradation for the 85Mgha(-1) compost dose as a consequence of the presence of more labile C. Unlike other studies, the results show a slight increase in the fraction of carbon retained with the increase in compost application rate. This could be due to the highly stable state of the compost prior to application, although it could also be due to sampling uncertainty. Further investigations are needed to better explain how the compost application rate affects carbon sequestration, and how characterization into labile and recalcitrant C can predict the amount of C sequestered in the soil.     

Reduced activity of alkaline phosphatase due to host–guest interactions with humic superstructures

Nuclear Magnetic Resonance (NMR) spectroscopy was applied to directly study the interactions between the alkaline phosphatase enzyme (AP) and two different humic acids from a volcanic soil (HA-V) and a Lignite deposit (HA-L). Addition of humic matter to enzyme solutions caused signals broadening in ¹H-NMR spectra, and progressive decrease and increase of enzyme relaxation (T₁ and T₂) and correlation (τ_C) times, respectively. Spectroscopic changes were explained with formation of ever larger weakly-bound humic–enzyme complexes, whose translational and rotational motion was increasingly restricted. NMR diffusion experiments also showed that the AP diffusive properties were progressively reduced with formation of large humic–enzyme complexes. The more hydrophobic HA-L affected spectral changes more than the more hydrophilic HA-V. ¹H-NMR spectra also showed the effect of progressively greater humic–enzyme complexes on the hydrolysis of an enzyme substrate, the 4-nitrophenyl phosphate disodium salt hexahydrate (p-NPP). While AP catalysis concomitantly decreased NMR signals of p-NPP and increased those of nitrophenol, addition of humic matter progressively and significantly slowed down the rate of change for these signals. In agreement with the observed spectral changes, the AP catalytic activity was more largely inhibited by HA-L than by HA-V. Contrary to previous studies, in which humic–enzyme interactions were only indirectly assumed from changes in spectrophotometric behavior of enzyme substrates, the direct measurements of AP behavior by NMR spectroscopy indicated that humic materials formed weakly-bound host–guest complexes with alkaline phosphatase, and the enzyme catalytic activity was thereby significantly inhibited. These results suggest that the role of extracellular enzymes in soils may be considerably reduced when they come in contact with organic matter dissolved in the soil solution.     

Behavior of fenhexamid in soil and water

A study was conducted to investigate fenhexamid (FEX) behavior in soil and in water. FEX proved to be rather stable at acid pH but showed slight degradation at neutral and alkaline pH. After 101 days of FEX spiking of a soil sample, 94% at pH 4, 12% at pH 7 and 23% at pH 9 of the active ingredient was still present. In natural water the rate of FEX disappearance appeared to be slow which may be due to abiotic rather than biotic processes. The soil degradation tests showed low persistence of the active ingredient if a good microflora activity is guaranteed (DT₅₀ about 1 day). Moreover, in absence of microorganisms, FEX proved to be stable. Humidities of 25 and 50% of Water Holding Capacity (WHC) influenced in equal measure the rate of degradation. From the same soil, a bacterium was isolated and identified as Bacillus megaterium, which was able to metabolize FEX with the hydroxylation of the cyclohexane ring. Moreover, FEX showed an elevated affinity for humic acid (73%), smectite (31%), and ferrihydrite(20%) and low affinity for vermiculite (11%) and kaolinite (7%).     

Behavior of fenhexamid in soil and water

A study was conducted to investigate fenhexamid (FEX) behavior in soil and in water. FEX proved to be rather stable at acid pH but showed slight degradation at neutral and alkaline pH. After 101 days of FEX spiking of a soil sample, 94% at pH 4, 12% at pH 7 and 23% at pH 9 of the active ingredient was still present. In natural water the rate of FEX disappearance appeared to be slow which may be due to abiotic rather than biotic processes. The soil degradation tests showed low persistence of the active ingredient if a good microflora activity is guaranteed (DT(50) about 1 day). Moreover, in absence of microorganisms, FEX proved to be stable. Humidities of 25 and 50% of Water Holding Capacity (WHC) influenced in equal measure the rate of degradation. From the same soil, a bacterium was isolated and identified as Bacillus megaterium, which was able to metabolize FEX with the hydroxylation of the cyclohexane ring. Moreover, FEX showed an elevated affinity for humic acid (73%), smectite (31%), and ferrihydrite(20%) and low affinity for vermiculite (11%) and kaolinite (7%).     

Biogas from the organic fraction of municipal solid waste: Dealing with contaminants for a solid oxide fuel cell energy generator

The present work investigates electricity production using a high efficiency electrochemical generator that employs as fuel a biogas from the dry anaerobic digestion of the organic fraction of municipal solid waste (OFMSW).The as-produced biogas contains several contaminants (sulfur, halogen, organic silicon and aromatic compounds) that can be harmful for the fuel cell: these were monitored via an innovative mass spectrometry technique that enables for in-line and real-time quantification.A cleaning trap with activated carbons for the removal of sulfur and other VOCs contained in the biogas was also tested and monitored by observing the different breakthrough times of studied contaminants.The electrochemical generator was a commercial Ni anode-supported planar Solid Oxide Fuel Cell (SOFC), tested for more than 300 h with a simulated biogas mixture (CH₄ 60 vol.%, CO₂ 40 vol.%), directly fed to the anode electrode. Air was added to promote the direct internal conversion of CH₄ to H₂ and CO via partial oxidation (POx).The initial breakthrough of H₂S from the cleaning section was also simulated and tested by adding ～1 ppm(v) of sulfur in the anode feed; a full recovery of the fuel cell performance after 24 h of sulfur exposure (～1 ppm(v)) was observed upon its removal, indicating the reliable time of anode exposure to sulfur in case of exhausted guard bed.     

Validation and global uncertainty of a gas chromatographic with mass spectrometry method for fenamidone analysis in grapes and wines

Fenamidone is an imidazolinone fungicide recently introduced in viticulture practices. This work reports the validation and assessment of global uncertainty of a gas chromatographic with mass spectrometry method to analyze fenamidone in grapes and wines. This method consists in a simple and fast liquid-liquid extraction step followed by chromatographic determination. Limits of detection for fenamidone in grapes and wines were, respectively, 0.05 mg/kg and 0.06 mg/L, precision was below 9.4% and average recovery was 89 ± 5%. In the concentration range from 0.05 to 1.00 mg/kg (or mg/L) of fenamidone, global uncertainty calculated following the EURACHEM/CITAC rules, and also by the Horwitz function, was below 25%. The EURACHEM/CITAC global uncertainty budget used gave lower estimates than those obtained from the Horwitz function.     

Regional assessment of climate change impacts on maize productivity and associated production risk in Switzerland

A simple model of yield was used along with climate scenarios to assess the impact of climate change on grain maize productivity and associated economic risk in Switzerland. In a first application, changes in the precipitation regime alone were shown to affect the distribution of yield considerably, with shifts not only in the mean but also in the standard deviation and the skewness. Production risk was found to respond more markedly to changes in the long-term mean than in the inter-annual variability of seasonal precipitation amounts. In a further application, yield projections were generated with respect to a full climate scenario, with the emission pathway as specified in the IPCC A2 scenario. Anticipation of the sowing date was found to reduce the negative impact of climate change on yield stability, but was not sufficient to ensure average productivity levels comparable to those observed at present. We argued that this was caused by the reduction in the duration of the growing season, which had a stronger impact than suggested by previous studies. Assuming no change in price relations, the results also revealed a strong increase in production risk with climate change, with more than a doubling in the probability of yield falling short of a critical threshold as compared to today’s situation.     

Benthic vegetation,chlorophyllα and physical-chemical variables in a protected zone of a Mediterranean coastal lagoon (Lesina,Italy)

Phytoplankton and benthic vegetation biomass undergoes spatial-temporal changes in relation to their life cycle, but also to meteorological conditions, physical-chemical variables, organic input and internal dynamism. The main aim of this work was to observe the effect of all environmental variables on the vegetative dynamic process in a protected zone of a Mediterranean costal lagoon (Lesina lagoon, SE Italy). Seven samplings were performed from 2010 to 2012 at 30 sites for nutrient and chlorophyll analyses, while TOC measurements and wet biomass evaluation were performed at 10 sites. Temperature, salinity and oxygen saturation were also measured by multiparametric probe and a visual census for vegetation was performed. Sites close to freshwater inflow were characterized by lower temperature and salinity, and high nitrate, with maxima of 191.05 μM in May 2010 and more than 250 μM in October 2010. Silicates drastically decreased from May 2010 (87.57 μM) to July 2010 (6.15 μM) and increased again in October (74.99 μM). Chl a concentrations were not on average higher than 6 mg m^?3, but peaks of 20 mg m^?3 were observed during May 2011 and May 2012. Benthic vegetation wet biomass collected in 2010 was approximately twice that collected in 2012, with a maximum of 27,554 g m^?2 and a dominance of macroalgae (70 % in May 2010 and 40 % in August 2010). During period 2010, a simultaneous and drastic decreasing of both mean values of wet biomass and chl a was observed from May to October 2010. During period 2012 a shift of vegetation biomass was shown from May (phytoplankton prevalence) to August 2012, with angiosperm prevalence (more than 30 %).