Enthalpies and entropies of proton and cadmium adsorption onto Bacillus subtilis bacterial cells from calorimetric measurements

We used titration calorimetry to measure the bulk heats of proton and Cd adsorption onto a common Gram positive soil bacterium Bacillus subtilis at 25.0 °C. Using the 4-site non-electrostatic model of Fein et al. [Fein, J.B., Boily, J.-F., Yee, N., Gorman-Lewis, D., Turner, B.F., 2005. Potentiometric titrations of Bacillus subtilis cells to low pH and a comparison of modeling approaches. Geochim. Cosmochim. Acta69 (5), 1123-1132.] to describe the bacterial surface reactivity to protons, our bulk enthalpy measurements can be used to determine the following site-specific enthalpies of proton adsorption for Sites 1-4, respectively: −3.5 ± 0.2, −4.2 ± 0.2, −15.4 ± 0.9, and −35 ± 2 kJ/mol, and these values yield the following third law entropies of proton adsorption onto Sites 1-4, respectively: +51 ± 4, +78 ± 4, +79 ± 5, and +60 ± 20 J/mol K. An alternative data analysis using a 2-site Langmuir-Freundlich model to describe proton binding to the bacterial surface (Fein et al., 2005) resulted in the following site-specific enthalpies of proton adsorption for Sites 1 and 2, respectively: −3.6 ± 0.2 and −35.1 ± 0.3 kJ/mol. The thermodynamic values for Sites 1-3 for the non-electrostatic model and Site 1 of the Langmuir-Freundlich model of proton adsorption onto the bacterial surface are similar to those associated with multifunctional organic acid anions, such as citrate, suggesting that the protonation state of a bacterial surface site can influence the energetics of protonation of neighboring sites. Our bulk Cd enthalpy data, interpreted using the 2-site non-electrostatic Cd adsorption model of Borrok et al. [Borrok, D., Fein, J.B., Tischler, M., O’Loughlin, E., Meyer, H., Liss, M., Kemner, K.M., 2004b. The effect of acidic solutions and growth conditions on the adsorptive properties of bacterial surfaces. Chem. Geol.209 (1-2), 107-119.] to account for Cd adsorption onto B. subtilis, yield the following site-specific enthalpies of Cd adsorption onto bacterial surface Sites 2 and 3, respectively: −0.2 ± 0.4 and +14.4 ± 0.9 kJ/mol, and the following third law entropies of Cd adsorption onto Sites 2 and 3, respectively: +57 ± 4 and +128 ± 5 J/mol K. The calculated enthalpies of Cd adsorption are typical of those associated with Cd complexation with anionic oxygen ligands, and the entropies are indicative of inner sphere complexation by multiple ligands. The experimental approach described in this study not only yields constraints on the molecular-scale mechanisms involved in proton and Cd adsorption reactions, but also provides new thermodynamic data that enable quantitative estimates of the temperature dependence of proton and Cd adsorption reactions.     

Geospatial Information Integration for Authoritative and Crowd Sourced Road Vector Data

This article describes results from a research project undertaken to explore the technical issues associated with integrating unstructured crowd sourced data with authoritative national mapping data. The ultimate objective is to develop methodologies to ensure the feature enrichment of authoritative data, using crowd sourced data. Users increasingly find that they wish to use data from both kinds of geographic data sources. Different techniques and methodologies can be developed to solve this problem. In our previous research, a position map matching algorithm was developed for integrating authoritative and crowd sourced road vector data, and showed promising results ( Anand et al. 2010 ). However, especially when integrating different forms of data at the feature level, these techniques are often time consuming and are more computationally intensive than other techniques available. To tackle these problems, this project aims at developing a methodology for automated conflict resolution, linking and merging of geographical information from disparate authoritative and crowd‐sourced data sources. This article describes research undertaken by the authors on the design, implementation, and evaluation of algorithms and procedures for producing a coherent ontology from disparate geospatial data sources. To integrate road vector data from disparate sources, the method presented in this article first converts input data sets to ontologies, and then merges these ontologies into a new ontology. This new ontology is then checked and modified to ensure that it is consistent. The developed methodology can deal with topological and geometry inconsistency and provide more flexibility for geospatial information merging.     

U.S. National Forests adapt to climate change through Science–Management partnerships

Developing appropriate management options for adapting to climate change is a new challenge for land managers, and integration of climate change concepts into operational management and planning on United States national forests is just starting. We established science–management partnerships on the Olympic National Forest (Washington) and Tahoe National Forest (California) in the first effort to develop adaptation options for specific national forests. We employed a focus group process in order to establish the scientific context necessary for understanding climate change and its anticipated effects, and to develop specific options for adapting to a warmer climate. Climate change scientists provided the scientific knowledge base on which adaptations could be based, and resource managers developed adaptation options based on their understanding of ecosystem structure, function, and management. General adaptation strategies developed by national forest managers include: (1) reduce vulnerability to anticipated climate-induced stress by increasing resilience at large spatial scales, (2) consider tradeoffs and conflicts that may affect adaptation success, (3) manage for realistic outcomes and prioritize treatments that facilitate adaptation to a warmer climate, (4) manage dynamically and experimentally, and (5) manage for structure and composition. Specific adaptation options include: (1) increase landscape diversity, (2) maintain biological diversity, (3) implement early detection/rapid response for exotic species and undesirable resource conditions, (4) treat large-scale disturbance as a management opportunity and integrate it in planning, (5) implement treatments that confer resilience at large spatial scales, (6) match engineering of infrastructure to expected future conditions, (7) promote education and awareness about climate change among resource staff and local publics, and (8) collaborate with a variety of partners on adaptation strategies and to promote ecoregional management. The process described here can quickly elicit a large amount of information relevant for adaptation to climate change, and can be emulated for other national forests, groups of national forests with similar resources, and other public lands. As adaptation options are iteratively generated for additional administrative units on public lands, management options can be compared, tested, and integrated into adaptive management. Science-based adaptation is imperative because increasing certainty about climate impacts and management outcomes may take decades.     

In situ measurements of contributions to the global electrical circuit by a thunderstorm in southeastern Brazil

The global electrical circuit, which maintains a potential of about 280 kV between the earth and the ionosphere, is thought to be driven mainly by thunderstorms and lightning. However, very few in situ measurements of electrical current above thunderstorms have been successfully obtained. In this paper, we present dc to very low frequency electric fields and atmospheric conductivity measured in the stratosphere (30–35 km altitude) above an active thunderstorm in southeastern Brazil. From these measurements, we estimate the mean quasi-static conduction current during the storm period to be 2.5 ± 1.25 A. Additionally, we examine the transient conduction currents following a large positive cloud-to-ground (+ CG) lightning flash and typical − CG flashes. We find that the majority of the total current is attributed to the quasi-static thundercloud charge, rather than lightning, which supports the classical Wilson model for the global electrical circuit.     

Land surface coupling in regional climate simulations of the West African monsoon

Coupling of the Community Land Model (CLM3) to the ICTP Regional Climate Model (RegCM3) substantially improves the simulation of mean climate over West Africa relative to an older version of RegCM3 coupled to the Biosphere Atmosphere Transfer Scheme (BATS). Two 10-year simulations (1992–2001) show that the seasonal timing and magnitude of mean monsoon precipitation more closely match observations when the new land surface scheme is implemented. Specifically, RegCM3–CLM3 improves the timing of the monsoon advance and retreat across the Guinean Coast, and reduces a positive precipitation bias in the Sahel and Northern Africa. As a result, simulated temperatures are higher, thereby reducing the negative temperature bias found in the Guinean Coast and Sahel in RegCM3–BATS. In the RegCM3–BATS simulation, warmer temperatures in northern latitudes and wetter soils near the coast create excessively strong temperature and moist static energy gradients, which shifts the African Easterly Jet further north than observed. In the RegCM3–CLM3 simulation, the migration and position of the African Easterly Jet more closely match reanalysis winds. This improvement is triggered by drier soil conditions in the RegCM3–CLM3 simulation and an increase in evapotranspiration per unit precipitation. These results indicate that atmosphere–land surface coupling has the ability to impact regional-scale circulation and precipitation in regions exhibiting strong hydroclimatic gradients.     

Preparing for climate change in Washington State

Climate change is expected to bring potentially significant changes to Washington State’s natural, institutional, cultural, and economic landscape. Addressing climate change impacts will require a sustained commitment to integrating climate information into the day-to-day governance and management of infrastructure, programs, and services that may be affected by climate change. This paper discusses fundamental concepts for planning for climate change and identifies options for adapting to the climate impacts evaluated in the Washington Climate Change Impacts Assessment. Additionally, the paper highlights potential avenues for increasing flexibility in the policies and regulations used to govern human and natural systems in Washington.     

Public health impacts of climate change in Washington State: projected mortality risks due to heat events and air pollution

Illness and mortality related to heat and worsening air quality are core public health concerns associated with climate change projections. We examined the historical relationship between age- and cause-specific mortality rates from 1980 through 2006 and heat events at the 99th percentile of humidex values in the historic period from January 1, 1970 to December 31, 2006 in the greater Seattle area (King, Pierce and Snohomish counties), Spokane County, the Tri-Cities (Benton and Franklin counties) and Yakima County; the relative risks of mortality during heat events were applied to population and climate projections for Washington State to calculate number of deaths above the baseline (1980–2006) expected during projected heat events in 2025, 2045 and 2085. Three different warming scenarios were used in the analysis. Relative risks for the greater Seattle area showed a significant dose-response relationship between heat event duration and daily mortality rates for non-traumatic deaths for persons ages 45 and above, typically peaking at four days of exposure to humidex values above the 99th percentile. The largest number of projected excess deaths in all years and scenarios for the Seattle region was found for age 65 and above. Under the middle warming scenario, this age group is expected to have 96, 148 and 266 excess deaths from all non-traumatic causes in 2025, 2045 and 2085, respectively. We also examined projected excess deaths due to ground-level ozone concentrations at mid century (2045–2054) in King and Spokane counties. Current (1997–2006) ozone measurements and mid-twenty-first century ozone projections were coupled with dose-response data from the scientific literature to produce estimates overall and cardiopulmonary mortality. Daily maximum 8-h ozone concentrations are forecasted to be 16–28% higher in the mid twenty-first century compared to the recent decade of 1997–2006. By mid-century in King County the non-traumatic mortality rate related to ozone was projected to increase from baseline (0.026 per 100,000; 95% confidence interval 0.013–0.038) to 0.033 (95% CI 0.017–0.049). For the same health outcome in Spokane County, the baseline period rate of 0.058 (95% CI 0.030–0.085) was estimated increase to 0.068 (95% CI 0.035–0.100) by mid-century. The cardiopulmonary death rate per 100,000 due to ozone was estimated to increase from 0.011 (95% CI 0.005–0.017) to 0.015 (0.007–0.022) in King County, and from 0.027 (95% CI 0.013–0.042) to 0.032 (95% CI 0.015–0.049) in Spokane County. Public health interventions aimed at protecting Washington’s population from excessive heat and increased ozone concentrations will become increasingly important for preventing deaths, especially among older adults. Furthermore, heat and air quality related illnesses that do not result in death, but are serious nevertheless, may be reduced by the same measures.     

Lander radioscience for obtaining the rotation and orientation of Mars

The paper presents the concept, the objectives, the approach used, and the expected performances and accuracies of a radioscience experiment based on a radio link between the Earth and the surface of Mars. This experiment involves radioscience equipment installed on a lander at the surface of Mars. The experiment with the generic name lander radioscience (LaRa) consists of an X-band transponder that has been designed to obtain, over at least one Martian year, two-way Doppler measurements from the radio link between the ExoMars lander and the Earth (ExoMars is an ESA mission to Mars due to launch in 2013). These Doppler measurements will be used to obtain Mars’ orientation in space and rotation (precession and nutations, and length-of-day variations). More specifically, the relative position of the lander on the surface of Mars with respect to the Earth ground stations allows reconstructing Mars’ time varying orientation and rotation in space.Precession will be determined with an accuracy better by a factor of 4 (better than the 0.1% level) with respect to the present-day accuracy after only a few months at the Martian surface. This precession determination will, in turn, improve the determination of the moment of inertia of the whole planet (mantle plus core) and the radius of the core: for a specific interior composition or even for a range of possible compositions, the core radius is expected to be determined with a precision decreasing to a few tens of kilometers.A fairly precise measurement of variations in the orientation of Mars’ spin axis will enable, in addition to the determination of the moment of inertia of the core, an even better determination of the size of the core via the core resonance in the nutation amplitudes. When the core is liquid, the free core nutation (FCN) resonance induces a change in the nutation amplitudes, with respect to their values for a solid planet, at the percent level in the large semi-annual prograde nutation amplitude and even more (a few percent, a few tens of percent or more, depending on the FCN period) for the retrograde ter-annual nutation amplitude. The resonance amplification depends on the size, moment of inertia, and flattening of the core. For a large core, the amplification can be very large, ensuring the detection of the FCN, and determination of the core moment of inertia.The measurement of variations in Mars’ rotation also determines variations of the angular momentum due to seasonal mass transfer between the atmosphere and ice caps. Observations even for a short period of 180 days at the surface of Mars will decrease the uncertainty by a factor of two with respect to the present knowledge of these quantities (at the 10% level).The ultimate objectives of the proposed experiment are to obtain information on Mars’ interior and on the sublimation/condensation of CO₂ in Mars’ atmosphere. Improved knowledge of the interior will help us to better understand the formation and evolution of Mars. Improved knowledge of the CO₂ sublimation/condensation cycle will enable better understanding of the circulation and dynamics of Mars’ atmosphere.     

Apatite as a monitor of late-stage magmatic processes at Volcán Irazú, Costa Rica

Apatite phenocrysts from the 1963 and 1723 eruptions of Irazú volcano (Costa Rica) record a volatile evolution history that confirms previous melt inclusion studies, and provides additional information concerning the relative and absolute timing of subvolcanic magmatic events. Measurements of H, Cl, and F by secondary ion mass spectrometry reveal multiple populations of apatite in both 1723 and 1963 magmas. Assuming nominal apatite/melt partition coefficients allows us to compare the pattern of melt inclusions and apatites in ternary space, demonstrating the fidelity of the record preserved in apatite, and revealing a complex history of magma mixing with at least two components. The preservation of heterogeneous populations of apatite and of internally heterogeneous crystals requires short timescales (days to years) for these magmatic processes to occur.     

Sedimentary and faunal events revealed by a revised correlation of post‐glacial Hirnantian (Late Ordovician) strata in the Welsh Basin,UK

The discovery of a previously unrecognized unconformity and of new faunas in the type Llandovery area underpins a revised correlation of Hirnantian strata in mid Wales. This has revealed the sedimentary and faunal events which affected the Lower Palaeozoic Welsh Basin during the global rise in sea level that followed the end‐Ordovician glacial maximum and has allowed their interpretation in the context of local and global influences. In peri‐basinal shelfal settings the onset of post‐glacial deepening is recorded by an unfossiliferous, transgressive shoreface sequence (Cwm Clyd Sandstone and Garth House formations) which rests unconformably on Rawtheyan rocks, deformed during an episode of pre‐Hirnantian tectonism. In the deep water facies of the basin centre, this same sequence boundary is now recognized as the contact between fine‐grained, re‐sedimented mudstones and an underlying regressive sequence of turbidite sandstones and conglomerates; it is at a level lower than previously cited and calls into question the established lithostratigraphy. In younger Hirnantian strata, graptolites associated with the newly recognized Ystradwalter Member (Chwefri Formation) demonstrate that this distal shelf unit correlates with the persculptus graptolite‐bearing Mottled Mudstone Member of the basinal succession. Together these members record an important macrofaunal recolonization of the Welsh Basin and mark a key event in the post‐glacial transgression. Further deepening saw the establishment of a stratified water column and the imposition of anoxic bottom water conditions across the basin floor. These post‐glacial Hirnantian events are consistent with the re‐establishment of connections between a silled Welsh Basin and the open Iapetus Ocean. However, a comparison with other areas suggests that each event records a separate deepening episode within a pulsed glacio‐eustatic transgression, while also reflecting changes in post‐glacial climate and patterns of oceanic circulation and associated biotic flux. British Geological Survey © NERC 2009. All rights reserved.