Improvement of the Derjaguin-Broekhoff-de Boer theory for capillary condensation/evaporation of nitrogen in mesoporous systems and its implications for pore size analysis of MCM-41 silicas and related materials

In this work, we propose an improvement of the classical Derjaguin-Broekhoff-de Boer (DBdB) theory for capillary condensation/evaporation in mesoporous systems. The primary idea of this improvement is to employ the Gibbs-Tolman-Koenig-Buff equation to predict the surface tension changes in mesopores. In addition, the statistical film thickness (so-called t-curve) evaluated accurately on the basis of the adsorption isotherms measured for the MCM-41 materials is used instead of the originally proposed t-curve (to take into account the excess of the chemical potential due to the surface forces). It is shown that the aforementioned modifications of the original DBdB theory have significant implications for the pore size analysis of mesoporous solids. To verify our improvement of the DBdB pore size analysis method (IDBdB), a series of the calcined MCM-41 samples, which are well-defined materials with hexagonally ordered cylindrical mesopores, were used for the evaluation of the pore size distributions. The correlation of the IDBdB method with the empirically calibrated Kruk-Jaroniec-Sayari (KJS) relationship is very good in the range of small mesopores. So, a major advantage of the IDBdB method is its applicability for small mesopores as well as for the mesopore range beyond that established by the KJS calibration, i.e., for mesopore radii greater than similar to4.5 nm. The comparison of the IDBdB results with experimental data reported by Kruk and Jaroniec for capillary condensation/evaporation as well as with the results from nonlocal density functional theory developed by Neimark et al. clearly justifies our approach. Note that the proposed improvement of the classical DBdB method preserves its original simplicity and simultaneously ensures a significant improvement of the pore size analysis, which is confirmed by the independent estimation of the mean pore size by the powder X-ray diffraction method.

DEVELOPMENT OF A CONDENSED PHASE VELOCITY MAP IMAGING APPARATUS: DISSOCIATION PHOTODYNAMICS OF NITROGEN DIOXIDE AT 355 NM

The photochemistry of the polar regions of Earth, as well as the interstellar medium, is driven by the effect of ultraviolet radiation on ice surfaces and on the materials trapped within them. While the area of ice photochemistry is vast and much research has been completed, it has only recently been possible to study the dynamics of these processes on a microscopic level. One of the leading techniques for studying photoreaction dynamics is Velocity Map Imaging (VMI). This technique has been used extensively to study several types of reaction dynamics processes. Although the majority of these studies have utilized molecular beams as the main medium for reactants, new studies showed the versatility of the technique when applied to molecular dynamics of molecules adsorbed on metal surfaces. Herein the development of a velocity map imaging apparatus capable of studying the photochemistry of condensed phase materials is described. The apparatus is used to study of the photo-reactivity of NO2 condensed within argon matrices to illustrate its capabilities. A doped ice surface is formed by condensing Ar and NO2 gas onto a sapphire rod which is cooled using a helium compressor to 20 K. The matrix is irradiated using an Nd:YAG laser at 355 nm, and the resulting NO fragment is state-selectively ionized using an excimer-pumped dye laser. In all, we are able to detect transient photochemically generated species and can collect information on their quantum state and kinetic energy distribution. It is found that the REMPI spectra changes as different sections of the dissociating cloud are probed. The rotational and translational energy populations are found to be bimodal with a low temperature component roughly at the temperature of the matrix, and a second component with much higher temperature, the rotational temperature showing a possible population inversion, and the translational temperature of 100-200 K. The low temperature translational component is found to dominate at long delay times between dissociation and ionization, while at short time delays the high temperature component plays a larger role. The velocity map imaging technique allows for the detection of both the axial and radial components of the translational energy. The distribution of excess energy over the rotational, electronic and translational states of the NO photofragments provides evidence for collisional quenching of the fragments in the Ar-matrix prior to their desorption.

Microbial nitrogen dynamics in organic and mineral soil horizons along a latitudinal transect in western Siberia

Soil N availability is constrained by the breakdown of N-containing polymers such as proteins to oligopeptides and amino acids that can be taken up by plants and microorganisms. Excess N is released from microbial cells as ammonium (N mineralization), which in turn can serve as substrate for nitrification. According to stoichiometric theory, N mineralization and nitrification are expected to increase in relation to protein depolymerization with decreasing N limitation, and thus from higher to lower latitudes and from topsoils to subsoils. To test these hypotheses, we compared gross rates of protein depolymerization, N mineralization and nitrification (determined using N-15 pool dilution assays) in organic topsoil, mineral topsoil, and mineral subsoil of seven ecosystems along a latitudinal transect in western Siberia, from tundra (67 degrees N) to steppe (54 degrees N). The investigated ecosystems differed strongly in N transformation rates, with highest protein depolymerization and N mineralization rates in middle and southern taiga. All N transformation rates decreased with soil depth following the decrease in organic matter content. Related to protein depolymerization, N mineralization and nitrification were significantly higher in mineral than in organic horizons, supporting a decrease in microbial N limitation with depth. In contrast, we did not find indications for a decrease in microbial N limitation from arctic to temperate ecosystems along the transect. Our findings thus challenge the perception of ubiquitous N limitation at high latitudes, but suggest a transition from N to C limitation of microorganisms with soil depth, even in high-latitude systems such as tundra and boreal forest.

Characterization of the effect of nitrogen deficiency on above-ground plant phenotypes in relation to root complexity in maize

Nitrogen (N) is an essential plant nutrient in maize production, and if considering only natural sources, is often the limiting factor world-wide in terms of a plant’s grain yield. For this reason, many farmers around the world supplement available soil N with synthetic man-made forms. Years of over-application of N fertilizer have led to increased N in groundwater and streams due to leaching and run-off from agricultural sites. In the Midwest Corn Belt much of this excess N eventually makes its way to the Gulf of Mexico leading to eutrophication (increase of phytoplankton) and a hypoxic (reduced oxygen) dead zone. Growing concerns about these types of problems and desire for greater input use efficiency have led to demand for crops with improved N use efficiency (NUE) to allow reduced N fertilizer application rates and subsequently lower N pollution. It is well known that roots are responsible for N uptake by plants, but it is relatively unknown how root architecture affects this ability. This research was conducted to better understand the influence of root complexity (RC) in maize on a plant’s response to N stress as well as the influence of RC on other above-ground plant traits. Thirty-one above-ground plant traits were measured for 64 recombinant inbred lines (RILs) from the intermated B73 & Mo17 (IBM) population and their backcrosses (BCs) to either parent, B73 and Mo17, under normal (182 kg N ha-1) and N deficient (0 kg N ha-1) conditions. The RILs were selected based on results from an earlier experiment by Novais et al. (2011) which screened 232 RILs from the IBM to obtain their root complexity measurements. The 64 selected RILs were comprised of 31 of the lowest complexity RILs (RC1) and 33 of the highest complexity RILs (RC2) in terms of root architecture (characterized as fractal dimensions). The use of the parental BCs classifies the experiment as Design III, an experimental design developed by Comstock and Robinson (1952) which allows for estimation of dominance significance and level. Of the 31 traits measured, 12 were whole plant traits chosen due to their documented response to N stress. The other 19 traits were ear traits commonly measured for their influence on yield. Results showed that genotypes from RC1 and RC2 significantly differ for several above-ground phenotypes. We also observed a difference in the number and magnitude of N treatment responses between the two RC classes. Differences in phenotypic trait correlations and their change in response to N were also observed between the RC classes. RC did not seem to have a strong correlation with calculated NUE (ΔYield/ΔN). Quantitative genetic analysis utilizing the Design III experimental design revealed significant dominance effects acting on several traits as well as changes in significance and dominance level between N treatments. Several QTL were mapped for 26 of the 31 traits and significant N effects were observed across the majority of the genome for some N stress indicative traits (e.g. stay-green). This research and related projects are essential to a better understanding of plant N uptake and metabolism. Understanding these processes is a necessary step in the progress towards the goal of breeding for better NUE crops.

Porous PLGA microspheres effectively loaded with BSA protein by electrospraying combined with phase separation in liquid nitrogen

Polymer microspheres loaded with bioactive particles, biomolecules, proteins, and/or growth factors play important roles in tissue engineering, drug delivery, and cell therapy. The conventional double emulsion method and a new method of electrospraying into liquid nitrogen were used to prepare bovine serum albumin (BAS)-loaded poly(lactic-co-glycolic acid) (PLGA) porous microspheres. The particle size, the surface morphology and the internal porous structure of the microspheres were observed using scanning electron microscopy (SEM). The loading efficiency, the encapsulation efficiency, and the release profile of the BSA-loaded PLGA microspheres were measured and studied. It was shown that the microspheres from double emulsion had smaller particle sizes (3-50 m), a less porous structure, a poor loading efficiency (5.2 %), and a poor encapsulation efficiency (43.5%). However, the microspheres from the electrospraying into liquid nitrogen had larger particle sizes (400-600 m), a highly porous structure, a high loading efficiency (12.2%), and a high encapsulation efficiency (93.8%). Thus the combination of electrospraying with freezing in liquid nitrogen and subsequent freeze drying represented a suitable way to produce polymer microspheres for effective loading and sustained release of proteins.

Excess deaths during the 2004 heatwave in Brisbane, Australia

The paper examines whether there was an excess of deaths and the relative role of temperature and ozone in a heatwave during 7–26 February 2004 in Brisbane, Australia, a subtropical city accustomed to warm weather. The data on daily counts of deaths from cardiovascular disease and non-external causes, meteorological conditions, and air pollution in Brisbane from 1 January 2001 to 31 October 2004 were supplied by the Australian Bureau of Statistics, Australian Bureau of Meteorology, and Queensland Environmental Protection Agency, respectively. The relationship between temperature and mortality was analysed using a Poisson time series regression model with smoothing splines to control for nonlinear effects of confounding factors. The highest temperature recorded in the 2004 heatwave was 42°C compared with the highest recorded temperature of 34°C during the same periods of 2001–2003. There was a significant relationship between exposure to heat and excess deaths in the 2004 heatwave estimated increase in non-external deaths: 75 [(95% confidence interval, CI: 11–138; cardiovascular deaths: 41 (95% CI: −2 to 84)]. There was no apparent evidence of substantial short-term mortality displacement. The excess deaths were mainly attributed to temperature but exposure to ozone also contributed to these deaths.

Nitrogen fertilizer rate management as a nitrous oxide mitigation strategy: Development of a nitrous oxide emission reduction protocol (NERP)

Nitrous oxide (N2O) is a potent agricultural greenhouse gas (GHG). More than 50% of the global anthropogenic N2O flux is attributable to emissions from soil, primarily due to large fertilizer nitrogen (N) applications to corn and other non-leguminous crops. Quantification of the trade–offs between N2O emissions, fertilizer N rate, and crop yield is an essential requirement for informing management strategies aiming to reduce the agricultural sector GHG burden, without compromising productivity and producer livelihood. There is currently great interest in developing and implementing agricultural GHG reduction offset projects for inclusion within carbon offset markets. Nitrous oxide, with a global warming potential (GWP) of 298, is a major target for these endeavours due to the high payback associated with its emission prevention. In this paper we use robust quantitative relationships between fertilizer N rate and N2O emissions, along with a recently developed approach for determining economically profitable N rates for optimized crop yield, to propose a simple, transparent, and robust N2O emission reduction protocol (NERP) for generating agricultural GHG emission reduction credits. This NERP has the advantage of providing an economic and environmental incentive for producers and other stakeholders, necessary requirements in the implementation of agricultural offset projects.

Nitrogen fertilizer management for nitrous oxide (N2O) mitigation in intensive corn (Maize) production: an emissions reduction protocol for US Midwest agriculture

Nitrous oxide (N2O) is a major greenhouse gas (GHG) product of intensive agriculture. Fertilizer nitrogen (N) rate is the best single predictor of N2O emissions in row-crop agriculture in the US Midwest. We use this relationship to propose a transparent, scientifically robust protocol that can be utilized by developers of agricultural offset projects for generating fungible GHG emission reduction credits for the emerging US carbon cap and trade market. By coupling predicted N2O flux with the recently developed maximum return to N (MRTN) approach for determining economically profitable N input rates for optimized crop yield, we provide the basis for incentivizing N2O reductions without affecting yields. The protocol, if widely adopted, could reduce N2O from fertilized row-crop agriculture by more than 50%. Although other management and environmental factors can influence N2O emissions, fertilizer N rate can be viewed as a single unambiguous proxy—a transparent, tangible, and readily manageable commodity. Our protocol addresses baseline establishment, additionality, permanence, variability, and leakage, and provides for producers and other stakeholders the economic and environmental incentives necessary for adoption of agricultural N2O reduction offset projects.

Nitrogen pools and fluxes in grassland soils sequestering carbon

Carbon sequestration in agricultural, forest, and grassland soils has been promoted as a means by which substantial amounts of CO2 may be removed from the atmosphere, but few studies have evaluated the associated impacts on changes in soil N or net global warming potential (GWP). The purpose of this research was to ( 1) review the literature to examine how changes in grassland management that affect soil C also impact soil N, ( 2) assess the impact of different types of grassland management on changes in soil N and rates of change, and (3) evaluate changes in N2O fluxes from differently managed grassland ecosystems to assess net impacts on GWP. Soil C and N stocks either both increased or both decreased for most studies. Soil C and N sequestration were tightly linked, resulting in little change in C: N ratios with changes in management. Within grazing treatments N2O made a minor contribution to GWP (0.1-4%), but increases in N2O fluxes offset significant portions of C sequestration gains due to fertilization (10-125%) and conversion (average = 27%). Results from this work demonstrate that even when improved management practices result in considerable rates of C and N sequestration, changes in N2O fluxes can offset a substantial portion of gains by C sequestration. Even for cases in which C sequestration rates are not entirely offset by increases in N2O fluxes, small increases in N2O fluxes can substantially reduce C sequestration benefits. Conversely, reduction of N2O fluxes in grassland soils brought about by changes in management represents an opportunity to reduce the contribution of grasslands to net greenhouse gas forcing.

Shoot growth dynamics and photosynthetic response to increased nitrogen availability in the alpine willow salix-glauca

Plants subjected to increases in the supply of resource(s) limiting growth may allocate more of those resources to existing leaves, increasing photosynthetic capacity, and/or to production of more leaves, increasing whole-plant photosynthesis. The responses of three populations of the alpine willow, Salix glauca, growing along an alpine topographic sequence representing a gradient in soil moisture and organic matter, and thus potential N supply, to N amendments, were measured over two growing seasons, to elucidate patterns of leaf versus shoot photosynthetic responses. Leaf-(foliar N, photosynthesis rates, photosynthetic N-use efficiency) and shoot-(leaf area per shoot, number of leaves per shoot, stem weight, N resorption efficiency) level measurements were made to examine the spatial and temporal variation in these potential responses to increased N availability. The predominant response of the willows to N fertilization was at the shoot-level, by production of greater leaf area per shoot. Greater leaf area occurred due to production of larger leaves in both years of the experiment and to production of more leaves during the second year of fertilization treatment. Significant leaf-level photosynthetic response occurred only during the first year of treatment, and only in the dry meadow population. Variation in photosynthesis rates was related more to variation in stomatal conductance than to foliar N concentration. Stomatal conductance in turn was significantly related to N fertilization. Differences among the populations in photosynthesis, foliar N, leaf production, and responses to N fertilization indicate N availability may be lowest in the dry meadow population, and highest in the ridge population. This result is contrary to the hypothesis that a gradient of plant available N corresponds with a snowpack/topographic gradient.

Excess length of stay due to central line–associated bloodstream infection in intensive care units in Argentina, Brazil, and Mexico

Objective.To estimate the excess length of stay in an intensive care unit (ICU) due to a central line–associated bloodstream infection (CLABSI), using a multistate model that accounts for the timing of infection. Design.A cohort of 3,560 patients followed up for 36,806 days in ICUs. Setting.Eleven ICUs in 3 Latin American countries: Argentina, Brazil, and Mexico. Patients.All patients admitted to the ICU during a defined time period with a central line in place for more than 24 hours. Results.The average excess length of stay due to a CLABSI increased in 10 of 11 ICUs and varied from −1.23 days to 4.69 days. A reduction in length of stay in Mexico was probably caused by an increased risk of death due to CLABSI, leading to shorter times to death. Adjusting for patient age and Average Severity of Illness Score tended to increase the estimated excess length of stays due to CLABSI. Conclusions.CLABSIs are associated with an excess length of ICU stay. The average excess length of stay varies between ICUs, most likely because of the case‐mix of admissions and differences in the ways that hospitals deal with infections.