Decomposition of carboxymethyl cellulose based on nano-knife principle

The traditional degradation of organic pollutants is based on the sacrifice of chemical or biological reagents. In this study, a purely physical technique was developed to break the chemical bonds and consequently decompose macromolecules in aqueous solution. Assisted with a high-speed mechanical blade, refined quartz sand grains with particularly sharp nanoscale edges can act as ‘nano-knives', which are able to cut the long chain of carboxymethyl cellulose(CMC, as a model molecule). High performance size exclusion chromatography measurements evidenced that the original CMC molecules(41,000 Da) were decomposed into a series of smaller molecules(460, 1000, 2200, 21,000, 27,000 and 31,000 Da). Consequently, the initial viscosity of the CMC solution(2 g/L) rapidly decreased by approximately 50% after 3 min treatment by the nano-knife materials along with the mechanical blade. Fourier transform infrared(FTIR) spectra indicated that the original functional groups were still present and new functional groups were not produced after shearing. The intensity of the main functional groupβ-1-4-glycosidic bond(wavenumber 1062 cm-1) was observed to markedly decrease after shearing. These results indicated that the long-chain CMC was cleaved into short-chain CMC. A degradation mechanism was proposed whereby the cutting force generated by the rapid motion of the nano-knives may be responsible for the breakage of β-1-4-glycosidic bonds in the macromolecular cellulose backbone. These results provide support for a potentially more affordable and environment-friendly strategy for physical-based decomposition of recalcitrant organic pollutants from aqueous solution without the need of chemical or biological reagents.     

Photodegradation of the pure and formulated alpha-cypermethrin insecticide gives different products

Alpha-cypermethrin is a broad-spectrum insecticide widely used in the treatment of rice crops, mainly commercialized as a CONTEST^® formulation. The photodegradation of alpha-cypermethrin and of the commercial formulation has not yet been systematically investigated in paddy water under natural conditions. Here, paddy water solutions of alpha-cypermethrin and CONTEST^® formulation at 5.0 mg L^?1 were irradiated under simulated sunlight for 10 days. Hydrolysis experiments were carried out on the same solutions preserved in the dark. Analysis by ultra-high-performance liquid chromatography–tandem mass spectrometry was developed for the identification of photodegradation products. Results show that degradation of pure alpha-cypermethrin and the formulation counterpart produces both common and different photodegradation products. Five out eleven photodegradation products were identified for the first time, in particular three in the alpha-cypermethrin paddy water solution and four in the formulation. Our findings underline the importance of carrying out photodegradation experiments directly on the commercial formulation, since degradation products could be different from the pure insecticide.     

Chemical and mineralogical transformations caused by weathering in anti-tank DU penetrators ("the silver bullets") discharged during the Kosovo war

A depleted-uranium penetrator, shot in 1999 at Djakovica, Western Kosovo, and there collected in June 2001, shows evident alteration processes, perceivable as black and yellow coatings. XRD indicates that the black coating mostly consists of uraninite, UO2, with possible presence of other more oxidized uranium forms, such as U3O8. The yellow material is mostly amorphous, with variable weak diffraction lines, due to minor embedded uraninite grains, or possibly to schoepite, UO3 x 2H2O. SEM-EDS reveals only uranium. Whereas uraninite does not show any crystal shape, the yellow material recrystallizes to flattened pseudo-hexagonal prisms, approximately 2-10 microm wide and 1-4 microm long. Raman spectra of the yellow material have peaks at 3474 and 3222 cm(-1), indicative for OH groups, plus at 812 and 744 cm(-1), indicative for UO2(2+) uranyl ions. Based on the different data, the yellow material covering the depleted-uranium dart is an oxidized corrosion product, containing uranyl ions and hydroxyls and/or water molecules, akin to schoepite. Therefore, the Djakovica dart shows evident oxidation and leaching processes, progressively releasing mobile uranium forms. As uranium will be progressively dispersed far from the impact sites, at a rate controlled by the presence of effective fixing mechanisms, we feel necessary to maintain long term geochemical control of water pollution within the battlefield surroundings.     

Urban ecosystem services: tree diversity and stability of tropospheric ozone removal

Urban forests provide important ecosystem services, such as urban air quality improvement by removing pollutants. While robust evidence exists that plant physiology, abundance, and distribution within cities are basic parameters affecting the magnitude and efficiency of air pollution removal, little is known about effects of plant diversity on the stability of this ecosystem service. Here, by means of a spatial analysis integrating system dynamic modeling and geostatistics, we assessed the effects of tree diversity on the removal of tropospheric ozone (O3) in Rome, Italy, in two years (2003 and 2004) that were very different for climatic conditions and ozone levels. Different tree functional groups showed complementary uptake patterns, related to tree physiology and phenology, maintaining a stable community function across different climatic conditions. Our results, although depending on the city-specific conditions of the studied area, suggest a higher function stability at increasing diversity levels in urban ecosystems. In Rome, such ecosystem services, based on published unitary costs of externalities and of mortality associated with O3, can be prudently valued to roughly US$2 and $3 million/year, respectively.     

Disaster management and mitigation: the telecommunications infrastructure

Among the most typical consequences of disasters is the near or complete collapse of terrestrial telecommunications infrastructures (especially the distribution network–the 'last mile') and their concomitant unavailability to the rescuers and the higher echelons of mitigation teams. Even when such damage does not take place, the communications overload/congestion resulting from significantly elevated traffic generated by affected residents can be highly disturbing. The paper proposes innovative remedies to the telecommunications difficulties in disaster struck regions. The offered solutions are network-centric operations-cap able, and can be employed in management of disasters of any magnitude (local to national or international). Their implementation provide ground rescue teams (such as law enforcement, firemen, healthcare personnel, civilian authorities) with tactical connectivity among themselves, and, through the Next Generation Network backbone, ensure the essential bidirectional free flow of information and distribution of Actionable Knowledge among ground units, command/control centres, and civilian and military agencies participating in the rescue effort.     

A flux-based assessment of the effects of ozone on foliar injury, photosynthesis, and yield of bean (Phaseolus vulgaris L. cv. Borlotto Nano Lingua di Fuoco) in open-top chambers

Stomatal ozone uptake, determined with the Jarvis' approach, was related to photosynthetic efficiency assessed by chlorophyll fluorescence and reflectance measurements in open-top chamber experiments on Phaseolus vulgaris. The effects of O₃ exposure were also evaluated in terms of visible and microscopical leaf injury and plant productivity. Results showed that microscopical leaf symptoms, assessed as cell death and H₂O₂ accumulation, preceded by 3-4 days the appearance of visible symptoms. An effective dose of ozone stomatal flux for visible leaf damages was found around 1.33 mmol O₃ m⁻². Significant linear dose-response relationships were obtained between accumulated fluxes and optical indices (PRI, NDI, ΔF/F_m^′). The negative effects on photosynthesis reduced plant productivity, affecting the number of pods and seeds, but not seed weight. These results, besides contributing to the development of a flux-based ozone risk assessment for crops in Europe, highlight the potentiality of reflectance measurements for the early detection of ozone stress.     

Inorganic pigments made from the recycling of coal mine drainage treatment sludge

Continuous industrial development increases energy consumption and, consequently, the consumption of fossil fuels. Coal mineral has been used in Brazil as a solid fuel for thermoelectric generators for several years. However, coal exploitation affects the environment intensely, mainly because Brazilian coal contains excess ash and pyrite (iron disulfide). According to the local coal industry syndicate, the average annual coal run per mine is 6 million ton/year; 3.5 million ton/year are rejected and disposed of in landfills. Besides pyrite, Brazilian coal contains Mn, Fe, Cu, Pb, Zn, Ge, Se, and Co. Additionally, the water used for coal beneficiation causes pyrite oxidation, forming an acid mine drainage (AMD). This drainage solubilizes the metals, transporting them into the environment, making treatment a requirement. This work deals with the use of sedimented residue from treated coal mine drainage sludge to obtain inorganic pigments that could be used in the ceramic industry. The residue was dried, ground and calcined ( approximately 1250 degrees C). The calcined pigment was then micronized (D(50) approximately 2mum). Chemical (XRF), thermal (DTA/TG), particle size (laser), and mineralogical (XRD) analyses were carried out on the residue. After calcination and micronization, mineralogical analyses (XRD) were used to determine the pigment structure at 1250 degrees C. Finally, the pigments were mixed with transparent glaze and fired in a laboratory roller kiln (1130 degrees C, 5min). The results were promising, showing that brown colors can be obtained with pigments made by residues.     

Impact of varying soil structure on transport processes in different diagnostic horizons of three soil types

When soil structure varies in different soil types and the horizons of these soil types, it has a significant impact on water flow and contaminant transport in soils. This paper focuses on the effect of soil structure variations on the transport of pesticides in the soil above the water table. Transport of a pesticide (chlorotoluron) initially applied on soil columns taken from various horizons of three different soil types (Haplic Luvisol, Greyic Phaeozem and Haplic Cambisol) was studied using two scenarios of ponding infiltration. The highest infiltration rate and pesticide mobility were observed for the Bt₁ horizon of Haplic Luvisol that exhibited a well-developed prismatic structure. The lowest infiltration rate was measured for the Bw horizon of Haplic Cambisol, which had a poorly developed soil structure and a low fraction of large capillary pores and gravitational pores. Water infiltration rates were reduced during the experiments by a soil structure breakdown, swelling of clay and/or air entrapped in soil samples. The largest soil structure breakdown and infiltration decrease was observed for the Ap horizon of Haplic Luvisol due to the low aggregate stability of the initially well-aggregated soil. Single-porosity and dual-permeability (with matrix and macropore domains) flow models in HYDRUS-1D were used to estimate soil hydraulic parameters via numerical inversion using data from the first infiltration experiment. A fraction of the macropore domain in the dual-permeability model was estimated using the micro-morphological images. Final soil hydraulic parameters determined using the single-porosity and dual-permeability models were subsequently used to optimize solute transport parameters. To improve numerical inversion results, the two-site sorption model was also applied. Although structural changes observed during the experiment affected water flow and solute transport, the dual-permeability model together with the two-site sorption model proved to be able to approximate experimental data.     

Comparison of seasonal variations of ozone exposure and fluxes in a Mediterranean Holm oak forest between the exceptionally dry 2003 and the following year

Ozone and energy fluxes have been measured using the eddy covariance technique, from June to December 2004 in Castelporziano near Rome (Italy), and compared to similar measurements made in the previous year. The studied ecosystem consisted in a typical Mediterranean Holm oak forest. Stomatal fluxes have been calculated using the resistance analogy and by inverting the Penmann-Monteith equation. Results showed that the average stomatal contribution accounts for 42.6% of the total fluxes. Non-stomatal deposition proved to be enhanced by increasing leaf wetness and air humidity during the autumnal months. From a comparison of the two years, it can be inferred that water supply is the most important limiting factor for ozone uptake and that prolonged droughts alter significantly the stomatal conductance, even 2 months after the soil water content is replenished. Ozone exposure, expressed as AOT40, behaves similarly to the cumulated stomatal flux in dry conditions whereas a different behaviour for the two indices appears in wet autumnal conditions. A difference also occurs between the two years.