Residues of pirimiphos-methyl in cereals and processed fractions following post harvest spray application

The aim of this work was to comparatively assess the persistence of pirimiphos methyl residues in cereals and in their milling fractions after spray application in post harvest. An analytical method, based on a slightly modified QuEChERS extraction followed by liquid chromatography tandem mass spectrometry (LC-MS/MS) determination was validated: mean recovery was in the range 73% to 92% depending on the spiking level, and precision as RSD ranged from 11% to 16%. The analysis of treated samples revealed that pirimiphos-methyl residues were highly persistent and that no differences could be observed between wheat, durum wheat and oat. As far as the impact of the milling process on residues is concerned, pirimiphos methyl contamination was significantly reduced during both cleaning and processing, and most of the contamination was related to outer kernel fractions.     

Arsenic uptake and speciation and the effects of phosphate nutrition in hydroponically grown kikuyu grass (Pennisetum clandestinum Hochst)

Background

This work focuses on the accumulation and mobility properties of arsenic (As) and the effects of phosphate (P) on its movement in Pennisetum clandestinum Hochst (kikuyu grass), grown hydroponically under increasing arsenate (As(V)) concentrations. The uptake of both ions and the relative kinetics show that phosphate is an efficient competitive inhibitor of As(V) uptake. The P/As uptake rate ratios in roots indicate that P is taken up preferentially by P/As transporters. An arsenite (As(III)) efflux from roots was also found, but this decreased when the arsenate concentration in the solution exceeded 5???M.

Methods

Increases in both arsenite and arsenate concentrations in roots were observed when the arsenate concentration in the solution was increased, and the highest accumulation of As(III) in roots was found when plants were grown at 5???M As(V). The low ratios of As accumulated in shoots compared to roots suggest limited mobility of the metalloid within Kikuyu plants.

Results

The results indicate that arsenic resistance in kikuyu grass in conditions of moderate exposure is mainly dependent on the following factors: 1) phosphate nutrition: P is an efficient competitive inhibitor of As(V) uptake because of the higher selectivity of membrane transporters with respect to phosphate rather than arsenate; and 2) a detoxification mechanism including a reduction in both arsenate and arsenite root efflux.

Conclusions

The As tolerance strategy of Kikuyu limits arsenate uptake and As translocation from roots to shoots; therefore, this plant cannot be considered a viable candidate for use in the phytoextraction of arsenic from contaminated soils or water.     

Volatile chlorinated hydrocarbons in Antarctic superficial snow sampled during Italian ITASE expeditions

In order to detect the presence of some volatile chlorinated hydrocarbons (VCHCs) and to understand their transport and deposition mechanism, superficial snow was sampled during two Italian ITASE (International Trans Antarctic Scientific Expedition) expeditions: the first traverse was carried out in 1998/1999 from Terra Nova Bay to Dome Concordia; the second traverse was carried out in 2001/2002 through Adélie, George V, Oates and Northern Victoria Lands. Some VCHCs (chloroform; 1,1,1-trichloroethane; tetrachloromethane; 1,1,2-trichloroethylene; tetrachloroethylene) were analysed using a highly sensitive and selective hyphenated technique composed of a purge-and-trap injector coupled to a gas chromatograph with a mass spectrometric detector (PTI-GC-MS) operating in SIM mode. Investigated VCHCs were present in all analysed snow samples with concentration levels of several units, tens, or sometimes hundreds of ng kg(-1). VCHC snow concentration levels remained approximately constant with changing distance from the coast and the comparison between fresh and aged snow did not show any substantial differences; on the basis of this evidence marine aerosol and dry deposition may be rejected as principal VCHC transport and deposition mechanism hypotheses. VCHC concentration levels in Antarctic snow samples were comparable to or greater than those found in snow from temperate zones.     

Photochemical reaction of peroxynitrite and carbon dioxide could account for up to 15 % of carbonate radicals generation in surface waters

The carbonate radical (CO ₃ ^?· ) is a photoinduced transient species occurring in surface waters. The carbonate radical can transform both natural compounds and xenobiotics. For instance, it can react with electron-rich substrates such as anilines, phenols and organic sulfur compounds. Here we used the APEX software to assess photochemical reactions, including the formation rates of transient species, based on water chemistry and depth, under summertime irradiation conditions. We found that the reaction between peroxynitrite and carbon dioxide is a potentially significant source of CO ₃ ^?· in sunlit surface waters, and could account for up to 10–15 % of the total CO ₃ ^?· formation. The peroxynitrite pathway to CO ₃ ^?· would be most significant at pH 7–8 and would be enhanced in waters with elevated nitrate and low alkalinity. Therefore, the proposed process could add to the known photochemical sources of CO ₃ ^?· in surface-water environments.     

The 2007 crisis and Greek wildfires: a multivariate analysis of suppression times

Shifts in government priorities in response to the 2007 global recession have affected wildfire management and natural disaster funding arrangements, leading to a reduced effectiveness of fire suppression actions and increasing fire vulnerability. Our study investigates the role of local socioeconomic contexts on fire suppression effectiveness under economic expansion and recession in a Mediterranean region (Attica, Greece) strongly affected by 2007 crisis and displaying a persistently high density of peri-urban wildfires. Basic characteristics of wildfires (spatial distribution, intensity, and land use preferences) were investigated in the study area over two consecutive 8-year time intervals characterized by economic expansion (2000–2007) and recession (2008–2015). An integrated approach based on multivariate statistics and artificial neural networks was implemented to evaluate latent relationships between fire suppression time, wildfire characteristics, and socioeconomic dynamics. Controlling for wildfires’ characteristics over the two time intervals, fire time length increased under crisis—mainly for small and medium-sized fires—possibly as an indirect response to reduced effectiveness of forest land management. Local contexts and political decisions influenced by economic downturns are relevant factors shaping wildfires’ severity in the Mediterranean region. With recession, local contexts vulnerable to wildfires require more effective fire prevention measures, sustainable forest management, and regional planning.     

A screening model for fate and transport of biodegradable polyesters in soil

A numerical model for predicting the fate and transport of biodegradable polyester residues in soil, following successive applications of mulch film, was developed and applied. The polymer, applied on surface soil, was assumed to be converted into by-products (monomers), according to a first order kinetics with constant K(1deg). The monomers released were assumed to sorb on soil organic matter (according to a first-order kinetics with constant K(s)), to be leached with the seepage water, through vertical advection and hydrodynamic dispersion, and biodegraded (according to a first-order kinetics with constant K(b)). Results suggested that, to assess a possible build-up of mulch film (as a polymer) on the surface soil, the degradation constant K(1deg) relating the polymer conversion to by-products should be known, whereas the biodegradation constant K(b) indicates there is no danger of groundwater pollution. Likewise, on the basis of by-product concentration in deep soil, soil pollution should not occur.     

Satellite-based indices in the analysis of land cover for municipalities in the province of Siena, Italy

Territorial indicators based on the satellite measured reflected or emitted energy can provide valuable information on the spatial evolution of a territory. Information regarding land use, biomass coverage and radiant temperature were obtained from remotely obtained measurements for each municipality in the Province of Siena. Remotely sensed data were combined into different indices to compare characteristics of land cover between territories and create an information base for continued study. A classification was performed on a municipal level and land use classes were grouped together and a general index of use pressure was created. A vegetation index was used to compare biomass densities. A radiant temperature index was calculated using measure thermal infrared emissions. The results of these analyses allowed researchers to examine the intra and inter-municipal spatial heterogeneity within the Province. A comparison between the results of each index was made and the problems related to the use of such indices were examined.     

TG, FT-IR and NMR characterization of n-C16H34 contaminated alumina and silica after mechanochemical treatment

This paper deals with the application of mechanochemistry to model systems composed of alumina or silica artificially contaminated with n-C16H34. The mechanochemical treatment was carried out by means of a ring mill for times ranging from 10 to 40h. Thermogravimetry and infrared and nuclear magnetic resonance spectroscopies were used for the characterization of the mechanochemical products. The results have indicated that, in the case of alumina, almost all the contaminant n-C16H34 undergoes a complex oxidative reaction path whose end products are strongly held on the surface. These end products are most likely made of crosslinked, partially oxidized hydrocarbon chains bond to the solid surface via COO(-) groups. In the case of silica, the hydrocarbon undergoes a different, equally complex reaction path, but to a lower extent. In this case the end products are most probably carbonylic compounds and graphitic carbon. Then, for both solid matrices, the mechanochemical treatment promotes significant modification of the chemical nature of the polluting hydrocarbon with end products much more difficult to remove from the surface. As the systems studied are models of sites contaminated by aliphatic hydrocarbon, the results are worthy of consideration in relation to the mobility of the contaminants in the environment.     

Environmental and biological monitoring of iridium in the city of Rome

The use of iridium in the latest catalytic converters to further reduce nitrogen oxide emission in the exhaust of lean-burn engines could result in increased atmospheric levels of this element in high-density vehicle traffic areas. The objective of this study is to assess environmental Ir pollution and its urinary levels in workers and an urban control group. Environmental monitoring inside a tram consisted in air samplings of total suspended particles (TSP), PM10 and PM2.5 carried out during November 2005. Urinary Ir levels were evaluated in 64 municipal tram drivers and in 58 administrative employees as controls. Quantification of Ir in air samples and urine was performed by means of Sector Field Inductively Coupled Plasma Mass Spectrometry. Means+/-standard deviation of Ir levels in TSP, in PM10 and PM2.5 fractions were 1.43+/-1.66, 0.44+/-0.27 and 0.36+/-0.19 pg m(-3), respectively. No statistically significant differences were observed among urinary Ir values in the exposed subjects and control group. The Ir levels in Rome air are still sufficiently low, even if the increased use of new Ir-based catalysts could be of some concern in the near future. The results of our study are of interest as they are a first attempt to explore airborne levels and urinary concentrations of Ir in an urban context at medium-high density of vehicle traffic. Particular attention should be given to the fact that Ir was found in the finest dust particles as the effects of fine particles containing Ir have not yet been studied.