Experimental and theoretical investigations for mitigating NaAlH4 reactivity risks during postulated accident scenarios involving exposure to air or water

Experimental and theoretical studies were conducted to investigate the pyrophoricity and water-reactivity risks associated with employing sodium alanate (NaAlH₄) complex metal hydride in on-board vehicular hydrogen (H₂) storage systems. The ignition and explosivity of NaAlH₄ upon exposure to oxidizers in air or water were attributed to the spontaneous formation of stable hydroperoxyl intermediates on the NaAlH₄ surface and/or H₂ production, as well as the large driving force for NaAlH₄ conversion to favorable hydroxide products predicted by atomic and thermodynamic modeling. The major products from NaAlH₄ exposure to air: NaAl(OH)₄, gibbsite and bayerite Al(OH)₃, and Na₂CO₃ observed by XRD, were identified to be formed by surface-controlled reactions. The reactivity risks were significantly minimized, without compromising de-/re-hydrogenation cyclability, by compacting NaAlH₄ powder into wafers to reduce the available surface area. These core findings are of significance to risk mitigation and H₂ safety code and standard development for the safe use of NaAlH₄ for on-board H₂ storage in light-duty vehicles.     

Soil C and N models that integrate microbial diversity

Industrial agriculture is yearly responsible for the loss of 55–100 Pg of historical soil carbon and 9.9 Tg of reactive nitrogen worldwide. Therefore, management practices should be adapted to preserve ecological processes and reduce inputs and environmental impacts. In particular, the management of soil organic matter (SOM) is a key factor influencing C and N cycles. Soil microorganisms play a central role in SOM dynamics. For instance, microbial diversity may explain up to 77 % of carbon mineralisation activities. However, soil microbial diversity is actually rarely taken into account in models of C and N dynamics. Here, we review the influence of microbial diversity on C and N dynamics, and the integration of microbial diversity in soil C and N models. We found that a gain of microbial richness and evenness enhances soil C and N dynamics on the average, though the improvement of C and N dynamics depends on the composition of microbial community. We reviewed 50 models integrating soil microbial diversity. More than 90 % of models integrate microbial diversity with discrete compartments representing conceptual functional groups (64 %) or identified taxonomic groups interacting in a food web (28 %). Half of the models have not been tested against an empirical dataset while the other half mainly consider fixed parameters. This is due to the difficulty to link taxonomic and functional diversity.     

Catalytic activities and mechanism of formaldehyde oxidation over gold supported on MnO<Subscript>2</Subscript> microsphere catalysts at room temperature

MnO₂ microspheres with various surface structures were prepared using the hydrothermal method, and Au/MnO₂ catalysts were synthesized using the sol-gel method. We obtained three MnO₂ microspheres and Au/MnO₂ samples: coherent solid spheres covered with wire-like nanostructures, solid spheres with nanosheets, and hierarchical hollow microspheres with nanoplatelets and nanorods. We investigated the properties and catalytic activities of formaldehyde oxidation at room temperature. Crystalline structures of MnO₂ are the main factor affecting the catalytic activities of these samples, and γ-MnO₂ shows high catalytic performance. The excellent redox properties are responsible for the catalytic ability of γ-MnO₂. The gold-supported interaction can change the redox properties of catalysts and accelerate surface oxygen species transition, which can account for the catalytic activity enhancement of Au/MnO₂. We also studied intermediate species. The dioxymethylene (DOM) and formate species formed on the catalyst surface were considered intermediates, and were ultimately transformed into hydrocarbonate and carbonate and then decomposed into CO₂. A proposed mechanism of formaldehyde oxidation over Au/MnO₂ catalysts was also obtained.     

Trends in the development of Estonian coastal land cover and landscapes caused by natural changes and human impact

The structure of coastal land cover in Estonia is intricate and exhibits considerable differences from site to site. The diverse geomorphology of the seashores is one of the key factors affecting the speed and magnitude of land cover changes. Likewise, the history of human inhabitance on the coast has also shaped the character of land cover. The Estonian coastal zone has experienced abrupt and radical changes in land ownership and its related land use during the last century. The main objectives of this paper are: 1) to give an overview of land use and the trends of development of land cover pattern along different parts of the Estonian coast; and 2) to analyze the relationships of natural and human processes and their cumulative impact on the evolution of coastal land cover pattern in Estonia. This study is based on results obtained during fieldwork in the study areas and on the analysis of large-scale (1:10,000) historical maps. In agriculturally dominant coastal areas, the traditional open landscape of fields and grassland at the beginning of the 20th century had been replaced by woodland and grasslands with shrubs by the start of the 21st century. Expansion of reed beds in areas of former seashore grasslands is another striking phenomenon. The structure of land cover on forested coasts has been fairly stable during the last 100 years. Areas of urban sprawl are characterised by dramatic changes in land cover structure. Rapidly increasing population and expanding settlements imposes on the ecological balance of the fragile dune forests in the coastal zone.     

Chitosan-polypropylene imine dendrimer hybrid: a new ecological biomordant for cochineal dyeing of wool

The classical use of synthetic dyes is causing issues of environmental pollution and heath risk. As a consequence natural dyes are gaining interest, but the use of natural dyes still includes toxic reagents such as metals as mordants and acids to enhance color and yield. Therefore, we designed a new chitosan-polypropylene imine dendrimer hybrid at 0–2000 mg/L to treat wool before dyeing with cochineal. We compared dye exhaustion, color depth, color characteristics, and color fastness of the new process with dyed pristine and metal mordanted wool. Results show that wool pretreatment improved dye exhaustion from 48 to 88 %, shifted saturation point toward lower dye concentration from 3000 to 1000 mg/L, and improved color depth from 13.68 for pristine wool and 15.17 for metal mordanted wool to 23.89 for the new process.     

Carbonization of waste PVC to develop porous carbon material without further activation

Efficient removal of chlorine from PVC achieved by two-stage heat-treatment (280 and 410 degrees C) provided chlorine-free isotropic pitch containing additive. The pitch was stabilized and carbonized into porous carbons with surface areas of approximately 300 m2/g. Resultant porous carbons showed three pore structures of supermicropore, micropore and mesopore. The generation of CO2 from the decomposition of the CaCO3 additive in waste PVC is responsible for the development of porous structures. The surface area of the carbonized product increased after the removal of CaO.     

Temporal and spatial distributions of sediment total organic carbon in an estuary river

Understanding temporal and spatial distributions of naturally occurring total organic carbon (TOC) in sediments is critical because TOC is an important feature of surface water quality. This study investigated temporal and spatial distributions of sediment TOC and its relationships to sediment contaminants in the Cedar and Ortega Rivers, Florida, USA, using three-dimensional kriging analysis and field measurement. Analysis of field data showed that large temporal changes in sediment TOC concentrations occurred in the rivers, which reflected changes in the characteristics and magnitude of inputs into the rivers during approximately the last 100 yr. The average concentration of TOC in sediments from the Cedar and Ortega Rivers was 12.7% with a maximum of 22.6% and a minimum of 2.3%. In general, more TOC accumulated at the upper 1.0 m of the sediment in the southern part of the Ortega River although the TOC sedimentation varied with locations and depths. In contrast, high concentrations of sediment contaminants, that is, total polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs), were found in sediments from the Cedar River. There was no correlation between TOC and PAHs or PCBs in these river sediments. This finding is in contradiction to some other studies which reported that the sorption of hydrocarbons is highly related to the organic matter content of sediments. This discrepancy occurred because of the differences in TOC and hydrocarbon source input locations. It was found that more TOC loaded into the southern part of the Ortega River, while almost all of the hydrocarbons entered into the Cedar River. This study suggested that the locations of their input sources as well as the land use patterns should also be considered when relating hydrocarbons to sediment TOC.     

Effects of sediment burial disturbance on macro and microelement dynamics in decomposing litter of <Emphasis Type="Italic">Phragmites australis</Emphasis> in the coastal marsh of the Yellow River estuary,China

From April 2008 to November 2009, a field decomposition experiment was conducted to investigate the effects of sediment burial on macro (C, N) and microelement (Pb, Cr, Cu, Zn, Ni, and Mn) variations in decomposing litter of Phragmites australis in the coastal marsh of the Yellow River estuary. Three one-off sediment burial treatments [no sediment burial (0 mm year^?1, S₀), current sediment burial (100 mm year^?1, S₁₀), and strong sediment burial (200 mm year^?1, S₂₀)] were laid in different decomposition sites. Results showed that sediment burials showed significant influence on the decomposition rate of P. australis, in the order of S₁₀ (0.001990 day^?1)?≈?S₂₀ (0.001710 day^?1)?>?S₀ (0.000768 day^?1) (p?<?0.05). The macro and microelement in decomposing litters of the three burial depths exhibited different temporal variations except for Cu, Zn, and Ni. No significant differences in C, N, Pb, Cr, Zn, and Mn concentrations were observed among the three burial treatments except for Cu and Ni (p?>?0.05). With increasing burial depth, N, Cr, Cu, Ni, and Mn concentrations generally increased, while C, Pb, and Zn concentrations varied insignificantly. Sediment burial was favorable for C and N release from P. australis, and, with increasing burial depth, the C release from litter significantly increased, and the N in litter shifted from accumulation to release. With a few exceptions, Pb, Cr, Zn, and Mn stocks in P. australis in the three treatments evidenced the export of metals from litter to environment, and, with increasing burial depth, the export amounts increased greatly. Stocks of Cu and Ni in P. australis in the S₁₀ and S₂₀ treatments were generally positive, evidencing incorporation of the two metals in most sampling times. Except for Ni, the variations of C, N, Pb, Cr, Cu, Zn, and Mn stocks in P. australis in the S₁₀ and S₂₀ treatments were approximated, indicating that the strong burial episodes (S₂₀) occurred in P. australis marsh in the future would have little influence on the stocks of these elements. With increasing burial depths, the P. australis was particularly efficient in binding Cu and Ni and releasing C, N, Pb, Cr, Zn, and Mn, implying that the potential eco-toxic risk of Pb, Cr, Zn, and Mn exposure might be very serious. This study emphasized the effects of different burials on nutrient and metal cycling and mass balance in the P. australis marsh of the Yellow River estuary.     

Improved traceability of Shiga-toxin-producing <Emphasis Type="Italic">Escherichia coli</Emphasis> using CRISPRs for detection and typing

Among strains of Shiga-toxin-producing Escherichia coli (STEC), seven serogroups (O26, O45, O103, O111, O121, O145, and O157) are frequently associated with severe clinical illness in humans. The development of methods for their reliable detection from complex samples such as food has been challenging thus far, and is currently based on the PCR detection of the major virulence genes stx1, stx2, and eae, and O-serogroup-specific genes. However, this approach lacks resolution. Moreover, new STEC serotypes are continuously emerging worldwide. For example, in May 2011, strains belonging to the hitherto rarely detected STEC serotype O104:H4 were identified as causative agents of one of the world’s largest outbreak of disease with a high incidence of hemorrhagic colitis and hemolytic uremic syndrome in the infected patients. Discriminant typing of pathogens is crucial for epidemiological surveillance and investigations of outbreaks, and especially for tracking and tracing in case of accidental and deliberate contamination of food and water samples. Clustered regularly interspaced short palindromic repeats (CRISPRs) are composed of short, highly conserved DNA repeats separated by unique sequences of similar length. This distinctive sequence signature of CRISPRs can be used for strain typing in several bacterial species including STEC. This review discusses how CRISPRs have recently been used for STEC identification and typing.