Permeation of binary gas mixtures in ultramicroporous membranes

High-quality nanometer thick ultramicroporous membranes were prepared from silica sol-gel processes and tested for the permeation of binary gas mixtures of He, H-2, CO2, and CH4 across different temperature and partial pressure regimens. Pore size distribution by molecular probing showed that the majority of pore sizes had dimensions below 2.9 Angstrom. In 50:50 binary mixtures, the fluxes of gases increased as a function of temperature, indicating an activated transport mechanism. The ultramicroporous membranes showed high selectivities at 150 degreesC for He/CO2 (30), He/CH4 (93), H-2/CO2 (10), and H-2/CH4 (9) with lower selectivities for CO2/CH4 (5). High activation energies (E-a) were observed for the permeance of 50:50 binary mixtures containing He and H-2 of 22.1-27.5 and 17.6-23.1 kJ.mol(-1), respectively. The E-a for the permeance of the total mixture approached the E-a for the permeance of the molecule with the smaller kinetic diameter (He or H-2).

Geographical variation in carbon dioxide fluxes from soils in agro-ecosystems and its implications for life-cycle assessment

1. Exchange of carbon dioxide (CO2) from soils can contribute significantly to the global warming potential (GWP) of agro-ecosystems. Due to variations in soil type, climatic onditions and land management practices, exchange of CO2 can differ markedly in different geographical locations. The food industry is developing carbon footprints for their products necessitating integration of CO2 exchange from soils with other CO2 emissions along the food chain. It may be advantageous to grow certain crops in different geographical locations to minimize CO2 emissions from the soil, and this may provide potential to offset other emissions in the food chain, such as transport. 2. Values are derived for the C balance of soils growing horticultural crops in the UK, Spain and Uganda. Net ecosystem production (NEP) is firstly calculated from the difference in net primary production (NPP) and heterotrophic soil respiration (Rh). Both NPP and Rh were estimated from intensive direct field measurements. Secondly, net biome production (NBP) is calculated by subtracting the crop biomass from NEP to give an indication of C balance. The importance of soil exchange is discussed in the light of recent discussions on carbon footprints and within the context of food life-cycle assessment (LCA). 3. The amount of crop relative to the biomass and the Rh prevailing in the different countries were the dominant factors influencing the magnitude of NEP and NBP. The majority of the biomass for lettuce Lactuca sativa and vining peas Pisum sativum, was removed from the field as crop; therefore, NEP and NBP were mainly negative. This was amplified for lettuces grown in Uganda (-16·5 and -17 t C ha-1 year-1 compared to UK and Spain -4·8 to 7·4 and -5·1 to 6·3 t C ha-1 year-1 for NEP and NBP, respectively) where the climate elevated Rh. 4. Synthesis and applications. This study demonstrates the importance of soil emissions in the overall life cycle of vegetables. Variability in such emissions suggests that assigning a single value to food carbon footprints may not be adequate, even within a country. Locations with high heterotrophic soil respiration, such as Spain and Uganda (21·9 and 21·6 t C ha-1 year-1, respectively), could mitigate the negative effects of climate on the C costs of crop production by growth of crops with greater returns of residue to the soil. This would minimize net CO2 emissions from these agricultural ecosystems.

A new regime for high rate growth of nanocrystalline diamond films using high power and CH4/H2/N2/O2 plasma

In this work, we report high growth rate of nanocrystalline diamond (NCD) films on silicon wafers of 2 inches in diameter using a new growth regime, which employs high power and CH4/H2/N2/O2 plasma using a 5 kW MPCVD system. This is distinct from the commonly used hydrogen-poor Ar/CH4 chemistries for NCD growth. Upon rising microwave power from 2000 W to 3200 W, the growth rate of the NCD films increases from 0.3 to 3.4 μm/h, namely one order of magnitude enhancement on the growth rate was achieved at high microwave power. The morphology, grain size, microstructure, orientation or texture, and crystalline quality of the NCD samples were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction, and micro-Raman spectroscopy. The combined effect of nitrogen addition, microwave power, and temperature on NCD growth is discussed from the point view of gas phase chemistry and surface reactions. © 2011 Elsevier B.V. All rights reserved.

Hurricane disturbance and recovery of energy balance, CO2 fluxes and canopy structure in a mangrove forest of the Florida Everglades

Eddy covariance (EC) estimates of carbon dioxide (CO2) fluxes and energy balance are examined to investigate the functional responses of a mature mangrove forest to a disturbance generated by Hurricane Wilma on October 24, 2005 in the Florida Everglades. At the EC site, high winds from the hurricane caused nearly 100% defoliation in the upper canopy and widespread tree mortality. Soil temperatures down to -50 cm increased, and air temperature lapse rates within the forest canopy switched from statically stable to statically unstable conditions following the disturbance. Unstable conditions allowed more efficient transport of water vapor and CO2 from the surface up to the upper canopy layer. Significant increases in latent heat fluxes (LE) and nighttime net ecosystem exchange (NEE) were also observed and sensible heat fluxes (H) as a proportion of net radiation decreased significantly in response to the disturbance. Many of these impacts persisted through much of the study period through 2009. However, local albedo and MODIS (Moderate Resolution Imaging Spectro-radiometer) data (the Enhanced Vegetation Index) indicated a substantial proportion of active leaf area recovered before the EC measurements began 1 year after the storm. Observed changes in the vertical distribution and the degree of clumping in newly emerged leaves may have affected the energy balance. Direct comparisons of daytime NEE values from before the storm and after our measurements resumed did not show substantial or consistent differences that could be attributed to the disturbance. Regression analyses on seasonal time scales were required to differentiate the storm's impact on monthly average daytime NEE from the changes caused by interannual variability in other environmental drivers. The effects of the storm were apparent on annual time scales, and CO2 uptake remained approximately 250 g C m-2 yr-1 lower in 2009 compared to the average annual values measured in 2004-2005. Dry season CO2 uptake was relatively more affected by the disturbance than wet season values. Complex leaf regeneration dynamics on damaged trees during ecosystem recovery are hypothesized to lead to the variable dry versus wet season impacts on daytime NEE. In contrast, nighttime CO2 release (i.e., nighttime respiration) was consistently and significantly greater, possibly as a result of the enhanced decomposition of litter and coarse woody debris generated by the storm, and this effect was most apparent in the wet seasons compared to the dry seasons. The largest pre- and post-storm differences in NEE coincided roughly with the delayed peak in cumulative mortality of stems in 2007-2008. Across the hurricane-impacted region, cumulative tree mortality rates were also closely correlated with declines in peat surface elevation. Mangrove forest-atmosphere interactions are interpreted with respect to the damage and recovery of stand dynamics and soil accretion processes following the hurricane.

Controls on sensible heat and latent energy fluxes from a short-hydroperiod Florida Everglades marsh

Little is known of energy balance in low latitude wetlands where there is a year-round growing season and a climate best defined by wet and dry seasons. The Florida Everglades is a highly managed and extensive subtropical wetland that exerts a substantial influence on the hydrology and climate of the south Florida region. However, the effects of seasonality and active water management on energy balance in the Everglades ecosystem are poorly understood. An eddy covariance and micrometeorological tower was established in a short-hydroperiod Everglades marsh to examine the dominant environmental controls on sensible heat (H) and latent energy (LE) fluxes, as well as the effects of seasonality on these parameters. Seasonality differentially affected H and LE fluxes in this marsh, such that H was principally dominant in the dry season and LE was strongly dominant in the wet season. The Bowen ratio was high for much of the dry season (1.5–2.4), but relatively low (H and LE fluxes across nearly all seasons and years (). However, the 2009 dry season LE data were not consistent with this relationship () because of low seasonal variation in LE following a prolonged end to the previous wet season. In addition to net radiation, H and LE fluxes were significantly related to soil volumetric water content (VWC), water depth, air temperature, and occasionally vapor pressure deficit. Given that VWC and water depth were determined in part by water management decisions, it is clear that human actions have the ability to influence the mode of energy dissipation from this ecosystem. Impending modifications to water management under the Comprehensive Everglades Restoration Plan may shift the dominant turbulent flux from this ecosystem further toward LE, and this change will likely affect local hydrology and climate.

Effects of Simulated Drought on the Carbon Balance of Everglades Short-Hydroperiod Marsh

Hydrology drives the carbon balance of wetlands by controlling the uptake and release of CO2 and CH4. Longer dry periods in between heavier precipitation events predicted for the Everglades region, may alter the stability of large carbon pools in this wetland's ecosystems. To determine the effects of drought on CO2 fluxes and CH4 emissions, we simulated changes in hydroperiod with three scenarios that differed in the onset rate of drought (gradual, intermediate, and rapid transition into drought) on 18 freshwater wetland monoliths collected from an Everglades short-hydroperiod marsh. Simulated drought, regardless of the onset rate, resulted in higher net CO2 losses net ecosystem exchange (NEE) over the 22-week manipulation. Drought caused extensive vegetation dieback, increased ecosystem respiration (Reco), and reduced carbon uptake gross ecosystem exchange (GEE). Photosynthetic potential measured by reflective indices (photochemical reflectance index, water index, normalized phaeophytinization index, and the normalized difference vegetation index) indicated that water stress limited GEE and inhibited Reco. As a result of drought-induced dieback, NEE did not offset methane production during periods of inundation. The average ratio of net CH4 to NEE over the study period was 0.06, surpassing the 100-year greenhouse warming compensation point for CH4 (0.04). Drought-induced diebacks of sawgrass (C3) led to the establishment of the invasive species torpedograss (C4) when water was resupplied. These changes in the structure and function indicate that freshwater marsh ecosystems can become a net source of CO2 and CH4 to the atmosphere, even following an extended drought. Future changes in precipitation patterns and drought occurrence/duration can change the carbon storage capacity of freshwater marshes from sinks to sources of carbon to the atmosphere. Therefore, climate change will impact the carbon storage capacity of freshwater marshes by influencing water availability and the potential for positive feedbacks on radiative forcing.

Radiation fluxes, soil heat flux, air temperature, soil temperature, soil moisture and vegetation at dwarf shrubs and wet sedges in Kytalyk, NE Siberia

Vegetation changes, such as shrub encroachment and wetland expansion, have been observed in many Arctic tundra regions. These changes feed back to permafrost and climate. Permafrost can be protected by soil shading through vegetation as it reduces the amount of solar energy available for thawing. Regional climate can be affected by a reduction in surface albedo as more energy is available for atmospheric and soil heating. Here, we compared the shortwave radiation budget of two common Arctic tundra vegetation types dominated by dwarf shrubs (Betula nana) and wet sedges (Eriophorum angustifolium) in North-East Siberia. We measured time series of the shortwave and longwave radiation budget above the canopy and transmitted radiation below the canopy. Additionally, we quantified soil temperature and heat flux as well as active layer thickness. The mean growing season albedo of dwarf shrubs was 0.15 ± 0.01, for sedges it was higher (0.17 ± 0.02). Dwarf shrub transmittance was 0.36 ± 0.07 on average, and sedge transmittance was 0.28 ± 0.08. The standing dead leaves contributed strongly to the soil shading of wet sedges. Despite a lower albedo and less soil shading, the soil below dwarf shrubs conducted less heat resulting in a 17 cm shallower active layer as compared to sedges. This result was supported by additional, spatially distributed measurements of both vegetation types. Clouds were a major influencing factor for albedo and transmittance, particularly in sedge vegetation. Cloud cover reduced the albedo by 0.01 in dwarf shrubs and by 0.03 in sedges, while transmittance was increased by 0.08 and 0.10 in dwarf shrubs and sedges, respectively. Our results suggest that the observed deeper active layer below wet sedges is not primarily a result of the summer canopy radiation budget. Soil properties, such as soil albedo, moisture, and thermal conductivity, may be more influential, at least in our comparison between dwarf shrub vegetation on relatively dry patches and sedge vegetation with higher soil moisture.

Oxygen, pH and calcium dynamics and fluxes at the thallus surface under ambient (8.1) and low (7.8) seawater pH and across a range of irradiances

Presently, an incomplete mechanistic understanding of tropical reef macroalgae photosynthesis and calcification restricts predictions of how these important autotrophs will respond to global change. Therefore, we investigated the mechanistic link between inorganic carbon uptake pathways, photosynthesis and calcification in a tropical crustose coralline alga (CCA) using microsensors. We measured pH, oxygen (O2), and calcium (Ca2+) dynamics and fluxes at the thallus surface under ambient (8.1) and low (7.8) seawater pH (pHSW) and across a range of irradiances. Acetazolamide (AZ) was used to inhibit extracellular carbonic anhydrase (CAext), which mediates hydrolysis of HCO3-, and 4,4' diisothiocyanatostilbene-2,2'-disulphonate (DIDS) that blocks direct HCO3- uptake by anion exchange transport. Both inhibited photosynthesis, suggesting both diffusive uptake of CO2 via HCO3- hydrolysis to CO2 and direct HCO3- ion transport are important in this CCA. Surface pH was raised approximately 0.3 units at saturating irradiance, but less when CAext was inhibited. Surface pH was lower at pHSW 7.8 than pHSW 8.1 in the dark, but not in the light. The Ca2+ fluxes were large, complex and temporally variable, but revealed net Ca2+ uptake under all conditions. The temporal variability in Ca2+ dynamics was potentially related to localized dissolution during epithallial cell sloughing, a strategy of CCA to remove epiphytes. Simultaneous Ca2+ and pH dynamics suggest the presence of Ca2+/H+ exchange. Rapid light-induced H+ surface dynamics that continued after inhibition of photosynthesis revealed the presence of a light-mediated, but photosynthesis-independent, proton pump. Thus, the study indicates metabolic control of surface pH can occur in CCA through photosynthesis and light-inducible H+ pumps. Our results suggest that complex light-induced ion pumps play an important role in biological processes related to inorganic carbon uptake and calcification in CCA.