X-ray and ultraviolet photoelectron spectroscopy studies of the interaction of carbon monoxide with oxygen adsorbed on silver covered with potassium, caesium or barium

X-ray and He(II) ultraviolet photoelectron spectroscopy studies of the interaction of CO with oxygen on potassium-, caesium- and barium-covered Ag surfaces have shown the formation of carbonate at 300 K. While on a caesium-covered surface only carbonate formation takes place, on the potassium- and barium-covered surfaces molecularly chemisorbed CO is also formed. The variation of the surface concentrations of carbon and oxygen with temperature has been examined and a reaction sequence for the interaction of CO with adsorbed oxygen on potassium-, caesium- and barium-covered Ag surfaces is suggested.

Sustainable me - a pharmacist’s role in reducing the carbon footprint of healthcare delivery

Introduction Climate change has been described as the most significant global health threat of the 21st century. Already, negative impacts on human health and wellbeing are being observed. These impacts present enormous challenges for the healthcare sector and the time has come for healthcare professionals to demonstrate leadership in addressing these challenges. Since any unsustainable organizational practices of healthcare organisations may ultimately have a negative impact on human health, there is an implicit moral obligation for these organisations and the people who work in them, to deliver healthcare more sustainably. If one considers that in 2010 pharmaceuticals comprised 22% of the carbon footprint of the NHS England (equating to 4.4 million tonnes of CO2 emissions) and 3% of England’s total carbon footprint (NHS Sustainable Development Unit, 2012), by reducing the carbon footprint of pharmaceuticals used in their healthcare organisations, pharmacists can have a significant impact on reducing the organisation’s total carbon footprint and ultimately on the public’s health. Aims The engagement of pharmacists with sustainability initiatives in the workplace has been largely unreported in international and national pharmacy journals. This paper aims to highlight the important role that pharmacists can play in helping to reduce the carbon footprint of healthcare delivery. Methods Literature was reviewed to identify areas where pharmacists could influence the more sustainable use of pharmaceuticals in their organisations. Discussion Much of the carbon footprint of pharmaceuticals is embedded carbon from their manufacture and delivery. Through efficient inventory management practices, pharmacists can reduce the number of orders and potentially reduce the number of deliveries required. Pharmacists can also help to reduce the amount of pharmaceutical waste generated. Of the waste that is generated, they can help improve the segregation of waste streams to increase the amount of non-contaminated packaging waste that is recycled and reduce the amount of pharmaceutical waste being incinerated or ending up in landfill. Reference NHS Sustainable Development Unit. (2012). Sustainability in the NHS Health Check 2012. NHS Sustainable Development Unit. Cambridge, UK: NHS Sustainable Devlopment Unit.

Climate response to physiological forcing of carbon dioxide simulated by the coupled Community Atmosphere Model (CAM3.1) and Community Land Model (CLM3.0)

Increasing concentrations of atmospheric CO2 decrease stomatal conductance of plants and thus suppress canopy transpiration. The climate response to this CO2-physiological forcing is investigated using the Community Atmosphere Model version 3.1 coupled to Community Land Model version 3.0. In response to the physiological effect of doubling CO2, simulations show a decrease in canopy transpiration of 8%, a mean warming of 0.1K over the land surface, and negligible changes in the hydrological cycle. These climate responses are much smaller than what were found in previous modeling studies. This is largely a result of unrealistic partitioning of evapotranspiration in our model control simulation with a greatly underestimated contribution from canopy transpiration and overestimated contributions from canopy and soil evaporation. This study highlights the importance of a realistic simulation of the hydrological cycle, especially the individual components of evapotranspiration, in reducing the uncertainty in our estimation of climatic response to CO2-physiological forcing. Citation: Cao, L., G. Bala, K. Caldeira, R. Nemani, and G.Ban-Weiss (2009), Climate response to physiological forcing of carbon dioxide simulated by the coupled Community Atmosphere Model (CAM3.1) and Community Land Model (CLM3.0).

Interaction of carbon monoxide with transition metal surfaces

XPS studies of the interaction of carbon monoxide with surfaces of Fe, Co and Ni indicate that at 300 K, the disproportionation reaction is prominent up to exposures of 103 L giving rise to high surface concentrations of carbon. At higher exposures and higher temperatures, dissociation of carbon monoxide accompanied by the formation of surface oxide layers becomes more prominent. In the case of copper, disproportionation is prominent up to 104 L even at 500 K followed by dissociation at higher exposures. These results are also supported by Auger spectroscopic studies.

Limitations of soil microbial biomass carbon as an indicator of soil pollution in the field

The size of the soil microbial biomass carbon (SMBC) has been proposed as a sensitive indicator for measuring the adverse effects of contaminants on the soil microbial community. In this study of Australian agricultural systems, we demonstrated that field variability of SMBC measured using the fumigation-extraction procedure limited its use as a robust ecotoxicological endpoint. The SMBC varied up to 4-fold across control samples collected from a single field site, due to small-scale spatial heterogeneity in the soil physicochemical environment. Power analysis revealed that large numbers of replicates (3-93) were required to identify 20% or 50% decreases in the size of the SMBC of contaminated soil samples relative to their uncontaminated control samples at the 0.05% level of statistical significance. We question the value of the routine measurement of SMBC as an ecotoxicological endpoint at the field scale, and suggest more robust and predictive microbiological indicators.

Productivity, carbon assimilation and intra-annual change in tropical reef platform seagrass communities of the Torres Strait, north-eastern Australia

Detailed data on seagrass distribution, abundance, growth rates and community structure information were collected at Orman Reefs in March 2004 to estimate the above-ground productivity and carbon assimilated by seagrass meadows. Seagrass meadows were re-examined in November 2004 for comparison at the seasonal extremes of seagrass abundance. Ten seagrass species were identified in the meadows on Orman Reefs. Extensive seagrass coverage was found in March (18,700 ha) and November (21,600 ha), with seagrass covering the majority of the intertidal reef-top areas and a large proportion of the subtidal areas examined. There were marked differences in seagrass above-ground biomass, distribution and species composition between the two surveys. Major changes between March and November included a substantial decline in biomass for intertidal meadows and an expansion in area of subtidal meadows. Changes were most likely a result of greater tidal exposure of intertidal meadows prior to November leading to desiccation and temperature-related stress. The Orman Reef seagrass meadows had a total above-ground productivity of 259.8 t DW day-1 and estimated carbon assimilation of 89.4 t C day-1 in March. The majority of this production came from the intertidal meadows which accounted for 81% of the total production. Intra-annual changes in seagrass species composition, shoot density and size of meadows measured in this study were likely to have a strong influence on the total above-ground production during the year. The net estimated above-ground productivity of Orman Reefs meadows in March 2004 (1.19 g C m-2 day-1) was high compared with other tropical seagrass areas that have been studied and also higher than many other marine, estuarine and terrestrial plant communities.

Cyclic Peptide Disulfides - Solution And Solid-State Conformation Of Boc-Cys-Pro-Aib-Cys-S-S-Bridge-Nhme,A Disulfide-Bridged Peptide Helix

The solution and solid-state conformations of the peptide disulfide Boc-Cys-Pro-Aib-Cys-NHMe have been determined by NMR spectroscopy and X-ray diffraction. The Cys(4) and methylamide NH groups are solvent shielded in CDCI3 and (CD,),SO, suggesting their involvement in intramolecular hydrogen bonding. On the basis of known stereochemical preferences of Pro and Aib residues, a consecutive @-turn structure is favored in solution. X-ray diffraction analysis reveals a highly folded 310 helical conformation for the peptide, with the S-S bridge lying approximately parallel to the helix axis, linking residues 1 and 4. The backbone conformational angles are Cys(1) 4 = -121.1', $ = 65.6"; Pro(2) 4 = -58.9', 4 = -34.0'; Aib(3) 4 = -61.8', $ = -17.9'; Cys(4) 4 = -70.5', $ = -18.6'. Two intramolecular hydrogen bonds are observed between Cys(1) CO--HN Cys(4) and Pro(2) CO--HNMe. The disulfide bond has a right-handed chirality, with a dihedral angle (xss) of 82'.

Long-term trends in fertility of soils under continuous cultivation and cereal cropping in southern Queensland. IX. Simulation of soil carbon and nitrogen pools using CENTURY model

Cultivation and cropping of soils results in a decline in soil organic carbon and soil nitrogen, and can lead to reduced crop yields. The CENTURY model was used to simulate the effects of continuous cultivation and cereal cropping on total soil organic matter (C and N), carbon pools, nitrogen mineralisation, and crop yield from 6 locations in southern Queensland. The model was calibrated for each replicate from the original datasets, allowing comparisons for each replicate rather than site averages. The CENTURY model was able to satisfactorily predict the impact of long-term cultivation and cereal cropping on total organic carbon, but was less successful in simulating the different fractions and nitrogen mineralisation. The model firstly over-predicted the initial (pre-cropping) soil carbon and nitrogen concentration of the sites. To account for the unique shrinking and swelling characteristics of the Vertosol soils, the default annual decomposition rates of the slow and passive carbon pools were doubled, and then the model accurately predicted initial conditions. The ability of the model to predict carbon pool fractions varied, demonstrating the difficulty inherent in predicting the size of these conceptual pools. The strength of the model lies in the ability to closely predict the starting soil organic matter conditions, and the ability to predict the impact of clearing, cultivation, fertiliser application, and continuous cropping on total soil carbon and nitrogen.

No-tillage and nitrogen application affects the decomposition of 15N-labelled wheat straw and the levels of mineral nitrogen and organic carbon in a Vertisol

No-tillage (NT) practice, where straw is retained on the soil surface, is increasingly being used in cereal cropping systems in Australia and elsewhere. Compared to conventional tillage (CT), where straw is mixed with the ploughed soil, NT practice may reduce straw decomposition, increase nitrogen immobilisation and increase organic carbon in the soil. This study examined 15N-labelled wheat straw (stubble) decomposition in four treatments (NT v. CT, with N rates of 0 and 75 kg/ha.year) and assessed the tillage and fertiliser N effects on mineral N and organic C and N levels over a 10-year period in a field experiment. NT practice decreased the rate of straw decomposition while fertiliser N application increased it. However, there was no tillage practice x N interaction. The mean residence time of the straw N in soil was more than twice as long under the NT (1.2 years) as compared to the CT practice (0.5 years). In comparison, differences in mean residence time due to N fertiliser treatment were small. However, tillage had generally very little effect on either the amounts of mineral N at sowing or soil organic C (and N) over the study period. While application of N fertiliser increased mineral N, it had very little effect on organic C over a 10-year period. Relatively rapid decomposition of straw and short mean residence time of straw N in a Vertisol is likely to have very little long-term effect on N immobilisation and organic C level in an annual cereal cropping system in a subtropical, semiarid environment. Thus, changing the tillage practice from CT to NT may not necessitate additional N requirement unless use is made of additional stored water in the soil or mineral N loss due to increased leaching is compensated for in N supply to crops.

The Context-integrity of the global carbon regime: The relevance and impact of the World Trade Organization

In the study of the integrity of the global carbon regime there are a number of institutions that must be considered for their impacts on this system. In particular, the subject matter of this chapter is concerned with the main international institution for trade, the World Trade Organization (the WTO). Otherwise stated, this chapter is concerned with how the institutional integrity of the global carbon regime aligns with the values and policy objectives of the WTO. This is done with a view to consider whether the global carbon regime aligns with these values and objectives in a way demonstrative of context-integrity. This alignment is not a single-sided undertaking and, therefore, it is essential that the underlying values of the WTO themselves align with the global carbon regime. I suggest this is particularly crucial given the importance of the objectives of the climate change regime, and the scientific predictions of the current climate projections.

Metabolite mobilization in the stem galls of Parthenium hysterophorus induced by Epiblema strenuana inferred from the signatures of isotopic carbon and nitrogen and concentrations of total non-structural carbohydrates

Parthenium hysterophorus L. (Asteraceae) is a weed of national significance in Australia. Among the several arthropod agents introduced into Australia to control populations of P. hysterophorus biologically, Epiblema strenuana Walker (Lepidoptera: Tortricidae) is the most widespread and abundant agent. By intercepting the normal transport mechanisms of P. hysterophorus, the larvae of E. strenuana drain nutrients, other metabolic products, and energy, and place the host plant under intense metabolic stress. In this study, determinations of total non-structural carbohydrates (TNC) levels and carbon and nitrogen isotope ratios of fixed products in different parts of the plant tissue, including the gall, have been made to establish the function of gall as a sink for the nutrients. Values of δ13C and δ15N in galls were significantly different than those in proximal and distal stems, whereas the TNC levels were insignificant, when measured in the total population of P. hysterophorus, regardless of plant age. However, carbon, nitrogen, and TNC signatures presented significant results, when assayed in different developmental stages of P. hysterophorus. Carbon isotope ratios in galls were consistently more negative than those from the compared plant organs. Nitrogen isotope ratios in galls, on the contrary, were either similar to or less negative than the compared plant organs, especially within a single host-plant stage population (i.e., either rosette, preflowering, or flowering stage). TNC levels varied within compared plant populations. The stem distal to the gall functioned more efficiently as a nodal channel than the stem proximal to the gall, especially in the translocation of nitrogenous nutrients. Our findings indicate that the gall induced by E. strenuana functions as a sink for the assayed nutrients, although some variations have been observed in the patterns of nutrient mobilization. By creating a sink for the nutrients in the gall, E. strenuana is able to place the overall plant metabolism under stress, and this ability indicates E. strenuana has the necessary potential for use as a biological-control agent.

Estimation of red blood cell lifespan from alveolar carbon monoxide measurements

Measurement of alveolar carbon monoxide (CO) presents a facile technique to estimate the lifespan, L, of red blood cells (RBCs) in vivo. Several recent studies employ this technique and calculate L (in days) using the expression, L = 13.8 (Hb)/P-CO(end), where (Hb) is the concentration (in g/dL) of hemoglobin in blood, and P-CO(end) is the endogenous production of CO (in ppm). Implicit in this calculation is the assumption that the fraction, f, of endogenous CO production due to RBC turnover is a constant equal to 0.7, which yields the expected RBC lifespan, L approximate to 120 days, in normal controls. In anemic patients, however, enhanced RBC turnover may increase f substantially above 0.7. The above expression then overestimates L. Here, we deriv an alternative tive expression, L = 3390[Hb]/322P(CO (end)-110, that accounts explicitly for the dependence of f on the rate of RBC turnover and thereby provides more accurate estimates of L without requiring additional measurements. Using the latter expression, we recalculate L from recent measurements on hepatitis C virus infected patients undergoing treatment with ribavirin. We find that our estimates of L in these patients (39 +/- 13 days) are significantly lower than current estimates (46 +/- 14 days), indicating that ribavirin affects RBC survival more severely than expected from current studies. Our expression for L is simple to employ in a clinical setting and would render the broadly applicable technique of alveolar CO measurement for the estimation of RBC lifespan more accurate.

Renormalization of the phonon spectrum in semiconducting single-walled carbon nanotubes studied by Raman spectroscopy

In situ Raman experiments together with transport measurements have been carried out in single-walled carbon nanotubes as a function of electrochemical top gate voltage (Vg). We have used the green laser (EL=2.41 eV), where the semiconducting nanotubes of diameter ~1.4 nm are in resonance condition. In semiconducting nanotubes, the G−- and G+-mode frequencies increase by ~10 cm−1 for hole doping, the frequency shift of the G− mode is larger compared to the G+ mode at the same gate voltage. However, for electron doping the shifts are much smaller: G− upshifts by only ~2 cm−1 whereas the G+ does not shift. The transport measurements are used to quantify the Fermi-energy shift (EF) as a function of the gate voltage. The electron-hole asymmetry in G− and G+ modes is quantitatively explained using nonadiabatic effects together with lattice relaxation contribution. The electron-phonon coupling matrix elements of transverse-optic (G−) and longitudinal-optic (G+) modes explain why the G− mode is more blueshifted compared to the G+ mode at the same Vg. The D and 2D bands have different doping dependence compared to the G+ and G− bands. There is a large downshift in the frequency of the 2D band (~18 cm−1) and D (~10 cm−1) band for electron doping, whereas the 2D band remains constant for the hole doping but D upshifts by ~8 cm−1. The doping dependence of the overtone of the G bands (2G bands) shows behavior similar to the dependence of the G+ and G− bands.

Low temperature electrical transport properties of carbon matrix containing iron nanoparticles

We present a comparative study of the low temperature electrical transport properties of the carbon matrix containing iron nanoparticles and the films. The conductivity of the nanoparticles located just below the metal-insulator transition exhibits metallic behavior with a logarithmic temperature dependence over a large temperature interval. The zero-field conductivity and the negative magnetoresistance, showing a characteristic upturn at liquid helium temperature, are consistently explained by incorporating the Kondo relation and the two dimensional electron-electron interaction. The films, in contrast, exhibit a crossover of the conductivity from power-law dependence at high temperatures to an activated hopping law dependence in the low temperature region. The transition is attributed to changes in the energy dependence of the density of states near the Fermi level. The observed magnetoresistance is discussed in terms of quantum interference effect on a three-dimensional variable range hopping mechanism.

Synthesis and Characterization of Carbon-Coated LiNi1/3Co1/3Mn1/3O2 in a Single Step by an Inverse Microemulsion Route

Layered LiNi1/3Co1/3Mn1/3O2, which is isostructural to LiCoO2, is considered as a potential cathode material. A layer of carbon coated on the particles improves the electrode performance, Which is attributed to an increase of the grain connectivity and also to protection of metal oxide from chemical reaction. The present work involves in situ synthesis of carbon-coated submicrometer-sized particles of LiNi1/3Co1/3Mn1/3O2 in an inverse microemulsion medium in the presence of glucose. The precursor obtained from the reaction is heated in air at 900 degrees C for 6 h to get crystalline LiNi1/3Co1/3Mn1/3O2. The carbon coating is found to impart porosity as well as higher surface area in relation to bare samples of the compound. The electrochemical characterization studies provide that carbon-coated LiNi1/3Co1/3Mn1/3O2 samples exhibit improved rate capability and cycling performance. The carbon coatings are shown to suppress the capacity fade, which is normally observed for the bare compound. Impedance spectroscopy data provide additional evidence for the beneficial effect of a carbon coating on LiNi1/3Co1/3Mn1/3O2 particles.