Quantitative localized proton-promoted dissolution kinetics of calcite using scanning electrochemical microscopy (SECM)

Scanning electrochemical microscopy (SECM) has been used to determine quantitatively the kinetics of proton-promoted dissolution of the calcite (101̅4) cleavage surface (from natural “Iceland Spar”) at the microscopic scale. By working under conditions where the probe size is much less than the characteristic dislocation spacing (as revealed from etching), it has been possible to measure kinetics mainly in regions of the surface which are free from dislocations, for the first time. To clearly reveal the locations of measurements, studies focused on cleaved “mirror” surfaces, where one of the two faces produced by cleavage was etched freely to reveal defects intersecting the surface, while the other (mirror) face was etched locally (and quantitatively) using SECM to generate high proton fluxes with a 25 μm diameter Pt disk ultramicroelectrode (UME) positioned at a defined (known) distance from a crystal surface. The etch pits formed at various etch times were measured using white light interferometry to ascertain pit dimensions. To determine quantitative dissolution kinetics, a moving boundary finite element model was formulated in which experimental time-dependent pit expansion data formed the input for simulations, from which solution and interfacial concentrations of key chemical species, and interfacial fluxes, could then be determined and visualized. This novel analysis allowed the rate constant for proton attack on calcite, and the order of the reaction with respect to the interfacial proton concentration, to be determined unambiguously. The process was found to be first order in terms of interfacial proton concentration with a rate constant k = 6.3 (± 1.3) × 10–4 m s–1. Significantly, this value is similar to previous macroscopic rate measurements of calcite dissolution which averaged over large areas and many dislocation sites, and where such sites provided a continuous source of steps for dissolution. Since the local measurements reported herein are mainly made in regions without dislocations, this study demonstrates that dislocations and steps that arise from such sites are not needed for fast proton-promoted calcite dissolution. Other sites, such as point defects, which are naturally abundant in calcite, are likely to be key reaction sites

A repurposing strategy for Hsp90 inhibitors demonstrates their potency against filarial nematodes

Novel drugs are required for the elimination of infections caused by filarial worms, as most commonly used drugs largely target the microfilariae or first stage larvae of these infections. Previous studies, conducted in vitro, have shown that inhibition of Hsp90 kills adult Brugia pahangi. As numerous small molecule inhibitors of Hsp90 have been developed for use in cancer chemotherapy, we tested the activity of several novel Hsp90 inhibitors in a fluorescence polarization assay and against microfilariae and adult worms of Brugia in vitro. The results from all three assays correlated reasonably well and one particular compound, NVP-AUY922, was shown to be particularly active, inhibiting Mf output from female worms at concentrations as low as 5.0 nanomolar after 6 days exposure to drug. NVP-AUY922 was also active on adult worms after a short 24 h exposure to drug. Based on these in vitro data, NVP-AUY922 was tested in vivo in a mouse model and was shown to significantly reduce the recovery of both adult worms and microfilariae. These studies provide proof of principle that the repurposing of currently available Hsp90 inhibitors may have potential for the development of novel agents with macrofilaricidal properties

Proof-of-concept of a data-driven approach to estimate the associations of comorbid mental and physical disorders with global health-related disability

Objective: The standard method of generating disorder-specific disability scores has lay raters make rankings between pairs of disorders based on brief disorder vignettes. This method introduces bias due to differential rater knowledge of disorders and inability to disentangle the disability due to disorders from the disability due to comorbidities. Methods: We propose an alternative, data-driven, method of generating disorder-specific disability scores that assesses disorders in a sample of individuals either from population medical registry data or population survey self-reports and uses Generalized Random Forests(GRF) to predict global (rather than disorder-specific) disability assessed by clinician ratings or by survey respondent self-reports. This method also provides a principled basis for studying patterns and predictors of heterogeneity in disorder-specific disability. We illustrate this method by analyzing data for 16 disorders assessed in the World Mental Health Surveys(n=53,645).Results: Adjustments for comorbidity decreased estimates of disorder-specific disability substantially. Estimates were generally somewhat higher with GRF than conventional multivariable regression models. Heterogeneity was nonsignificant. Conclusions: The results show clearly that the proposed approach is practical, and that adjustment is needed for comorbidities to obtain accurate estimates of disorder-specific disability. Expansion to a wider range of disorders would likely find more evidence for heterogeneity

Response of ocean ecosystems to climate warming

Author Posting. © American Geophysical Union, 2004. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 18 (2004): GB3003, doi:10.1029/2003GB002134.We examine six different coupled climate model simulations to determine the ocean biological response to climate warming between the beginning of the industrial revolution and 2050. We use vertical velocity, maximum winter mixed layer depth, and sea ice cover to define six biomes. Climate warming leads to a contraction of the highly productive marginal sea ice biome by 42% in the Northern Hemisphere and 17% in the Southern Hemisphere, and leads to an expansion of the low productivity permanently stratified subtropical gyre biome by 4.0% in the Northern Hemisphere and 9.4% in the Southern Hemisphere. In between these, the subpolar gyre biome expands by 16% in the Northern Hemisphere and 7% in the Southern Hemisphere, and the seasonally stratified subtropical gyre contracts by 11% in both hemispheres. The low-latitude (mostly coastal) upwelling biome area changes only modestly. Vertical stratification increases, which would be expected to decrease nutrient supply everywhere, but increase the growing season length in high latitudes. We use satellite ocean color and climatological observations to develop an empirical model for predicting chlorophyll from the physical properties of the global warming simulations. Four features stand out in the response to global warming: (1) a drop in chlorophyll in the North Pacific due primarily to retreat of the marginal sea ice biome, (2) a tendency toward an increase in chlorophyll in the North Atlantic due to a complex combination of factors, (3) an increase in chlorophyll in the Southern Ocean due primarily to the retreat of and changes at the northern boundary of the marginal sea ice zone, and (4) a tendency toward a decrease in chlorophyll adjacent to the Antarctic continent due primarily to freshening within the marginal sea ice zone. We use three different primary production algorithms to estimate the response of primary production to climate warming based on our estimated chlorophyll concentrations. The three algorithms give a global increase in primary production of 0.7% at the low end to 8.1% at the high end, with very large regional differences. The main cause of both the response to warming and the variation between algorithms is the temperature sensitivity of the primary production algorithms. We also show results for the period between the industrial revolution and 2050 and 2090.J. L. Sarmiento and R. Slater were supported by the NOAA Office of Global Programs grant NA56GP0439 to the Carbon Modeling Consortium for model development and by NSF grant OCE00973166 for model and observational interpretations as part of the JGOFS Synthesis and Modeling Project. R. Barber was supported by NSF grant OCE 0136270 as part of the JGOFS Synthesis and Modeling Project. S. Doney and J. Kleypas wish to thank the Community Climate System Model science team and the Climate Simulation Laboratory at NCAR and acknowledge support from NOAA-OGP grant NOAA-NA96GP0360S. Spall is funded through the UK Department for Environment, Food and Rural Affairs contract PECD 7/12/37

Mining a Sea of Data: Deducing the Environmental Controls of Ocean Chlorophyll

Chlorophyll biomass in the surface ocean is regulated by a complex interaction of physiological, oceanographic, and ecological factors and in turn regulates the rates of primary production and export of organic carbon to the deep ocean. Mechanistic models of phytoplankton responses to climate change require the parameterization of many processes of which we have limited knowledge. We develop a statistical approach to estimate the response of remote-sensed ocean chlorophyll to a variety of physical and chemical variables. Irradiance over the mixed layer depth, surface nitrate, sea-surface temperature, and latitude and longitude together can predict 83% of the variation in log chlorophyll in the North Atlantic. Light and nitrate regulate biomass through an empirically determined minimum function explaining nearly 50% of the variation in log chlorophyll by themselves and confirming that either light or macronutrients are often limiting and that much of the variation in chlorophyll concentration is determined by bottom-up mechanisms. Assuming the dynamics of the future ocean are governed by the same processes at work today, we should be able to apply these response functions to future climate change scenarios, with changes in temperature, nutrient distributions, irradiance, and ocean physics

Turbulence and Fossil Turbulence in Oceans and Lakes

Turbulence is defined as an eddy-like state of fluid motion where the inertial-vortex forces of the eddies are larger than any of the other forces that tend to damp the eddies out. Energy cascades of irrotational flows from large scales to small are non-turbulent, even if they supply energy to turbulence. Turbulent flows are rotational and cascade from small scales to large, with feedback. Viscous forces limit the smallest turbulent eddy size to the Kolmogorov scale. In stratified fluids, buoyancy forces limit large vertical overturns to the Ozmidov scale and convert the largest turbulent eddies into a unique class of saturated, non-propagating, internal waves, termed fossil-vorticity-turbulence. These waves have the same energy but different properties and spectral forms than the original turbulence patch. The Gibson (1980, 1986) theory of fossil turbulence applies universal similarity theories of turbulence and turbulent mixing to the vertical evolution of an isolated patch of turbulence in a stratified fluid as its growth is constrained and fossilized by buoyancy forces. These theories apply to the dynamics of atmospheric, astrophysical and cosmological turbulence.Comment: 31 pages, 11 figures, 2 tables, see http://www-acs.ucsd.edu/~ir118 Accepted for publication by the Chinese Journal of Oceanology and Limnolog

Pathways between Primary Production and Fisheries Yields of Large Marine Ecosystems

The shift in marine resource management from a compartmentalized approach of dealing with resources on a species basis to an approach based on management of spatially defined ecosystems requires an accurate accounting of energy flow. The flow of energy from primary production through the food web will ultimately limit upper trophic-level fishery yields. In this work, we examine the relationship between yield and several metrics including net primary production, chlorophyll concentration, particle-export ratio, and the ratio of secondary to primary production. We also evaluate the relationship between yield and two additional rate measures that describe the export of energy from the pelagic food web, particle export flux and mesozooplankton productivity. We found primary production is a poor predictor of global fishery yields for a sample of 52 large marine ecosystems. However, chlorophyll concentration, particle-export ratio, and the ratio of secondary to primary production were positively associated with yields. The latter two measures provide greater mechanistic insight into factors controlling fishery production than chlorophyll concentration alone. Particle export flux and mesozooplankton productivity were also significantly related to yield on a global basis. Collectively, our analyses suggest that factors related to the export of energy from pelagic food webs are critical to defining patterns of fishery yields. Such trophic patterns are associated with temperature and latitude and hence greater yields are associated with colder, high latitude ecosystems

The handbook for standardised field and laboratory measurements in terrestrial climate-change experiments and observational studies

Climate change is a worldwide threat to biodiversity and ecosystem structure, functioning, and services. To understand the underlying drivers and mechanisms, and to predict the consequences for nature and people, we urgently need better understanding of the direction and magnitude of climate‐change impacts across the soil–plant–atmosphere continuum. An increasing number of climate‐change studies is creating new opportunities for meaningful and high‐quality generalisations and improved process understanding. However, significant challenges exist related to data availability and/or compatibility across studies, compromising opportunities for data re‐use, synthesis, and upscaling. Many of these challenges relate to a lack of an established “best practice” for measuring key impacts and responses. This restrains our current understanding of complex processes and mechanisms in terrestrial ecosystems related to climate change