How do mineral coatings affect dissolution rates? An experimental study of coupled CaCO3 dissolution—CdCO3 precipitation

Coupled CaCO₃ dissolution-otavite (CdCO₃) precipitation experiments have been performed to 1) quantify the effect of mineral coatings on dissolution rates, and 2) to explore the possible application of this coupled process to the remediation of polluted waters. All experiments were performed at 25°C in mixed-flow reactors. Various CaCO₃ solids were used in the experiments including calcite, aragonite, and ground clam, mussel, and cockle shells. Precipitation was induced by the presence of Cd(NO₃)₂ in the inlet solution, which combined with aqueous carbonate liberated by CaCO₃ dissolution to supersaturate otavite. The precipitation of an otavite layer of less than 0.01 μm in thickness on calcite surfaces decreases its dissolution rate by close to two orders of magnitude. This decrease in calcite dissolution rates lowers aqueous carbonate concentrations in the reactor such that the mixed-flow reactor experiments attain a steady-state where the reactive fluid is approximately in equilibrium with otavite, arresting its precipitation. In contrast, otavite coatings are far less efficient in lowering aragonite, and ground clam, mussel, and cockle shell dissolution rates, which are comprised primarily of aragonite. A steady-state is only attained after the precipitation of an otavite layer of 3-10 μm thick; the steady state CaCO₃ dissolution rate is 1-2 orders of magnitude lower than that in the absence of otavite coatings. The difference in behavior is interpreted to stem from the relative crystallographic structures of the dissolving and precipitating minerals. As otavite is isostructural with respect to calcite, it precipitates by epitaxial growth directly on the calcite, efficiently slowing dissolution. In contrast, otavite’s structure is appreciably different from that of aragonite. Thus, it will precipitate by random three dimensional heterogeneous nucleation, leaving some pore space at the otavite-aragonite interface. This pore space allows aragonite dissolution to continue relatively unaffected by thin layers of precipitated otavite. Due to the inefficiency of otavite coatings to slow aragonite and ground aragonite shell dissolution, aragonite appears to be a far better Cd scavenging material for cleaning polluted waste waters.     

Modelling chemistry in the nocturnal boundary layer above tropical rainforest and a generalised effective nocturnal ozone deposition velocity for sub-ppbv NOx conditions

Measurements of atmospheric composition have been made over a remote rainforest landscape. A box model has previously been demonstrated to model the observed daytime chemistry well. However the box model is unable to explain the nocturnal measurements of relatively high [NO] and [O₃], but relatively low observed [NO₂]. It is shown that a one-dimensional (1-D) column model with simple O₃-NO_x chemistry and a simple representation of vertical transport is able to explain the observed nocturnal concentrations and predict the likely vertical profiles of these species in the nocturnal boundary layer (NBL). Concentrations of tracers carried over from the end of the night can affect the atmospheric chemistry of the following day. To ascertain the anomaly introduced by using the box model to represent the NBL, vertically-averaged NBL concentrations at the end of the night are compared between the 1-D model and the box model. It is found that, under low to medium [NO_x] conditions (NO_x?<?1 ppbv), a simple parametrisation can be used to modify the box model deposition velocity of ozone, in order to achieve good agreement between the box and 1-D models for these end-of-night concentrations of NO_x and O₃. This parametrisation would could also be used in global climate-chemistry models with limited vertical resolution near the surface. Box-model results for the following day differ substantially if this effective nocturnal deposition velocity for ozone is implemented; for instance, there is a 9% increase in the following days peak ozone concentration. However under medium to high [NO_x] conditions (NO_x > 1 ppbv), the effect on the chemistry due to the vertical distribution of the species means no box model can adequately represent chemistry in the NBL without modifying reaction rate coefficients.     

Ordinary chondrite-related giant (>800 μm) cosmic spherules from the Transantarctic Mountains, Antarctica

In order to identify the parent bodies of cosmic spherules (melted micrometeorites) with porphyritic olivine (PO) and cryptocrystalline (CC) textures, we measured the oxygen isotopic composition of 15 giant (>800 μm) cosmic spherules recovered in the Transantarctic Mountains, Antarctica, with IR-laser fluorination/mass spectrometry, and we conducted a characterization of their petrographic and magnetic properties. Samples include 6, 8 and 1 spherules of PO, CC and barred olivine (BO) textural types, respectively. Eleven spherules (∼70% of the total: 4/6 PO and 6/8 CC, and the BO spherule) are related to ordinary chondrites based on oxygen isotopic compositions. Olivines in ordinary chondrite-related spherules have compositions Fa_8.5-11.8, they are Ni-poor to Ni-rich (0.04-1.12 wt.%), and tend to be richer in CaO than other spherules (0.10-0.17 wt.%). Ordinary-chondrite related spherules also have high magnetite contents (∼2-12 wt.%). One PO and one CC spherules are related to previously identified ¹⁷O-enriched cosmic spherules for which the parent body is unknown. One CC spherule has an oxygen isotopic signature relating it to CM/CR carbonaceous chondrites. The majority of PO/CC cosmic spherules derive from ordinary chondrites; this result exemplifies how the texture of cosmic spherules is not only controlled by atmospheric entry heating conditions but also depends on the parent body, whether be it through orbital parameters (entry angle and velocity), or chemistry, mineralogy, or grain size of the precursor.     

Global energy balance and regional hydrology: A Burgundian case study

Accurate measures of global atmospheric energy balance collected since the International Geophysical Year (1957-1958) show statistically significant relationships to regional monthly growing season discharge in east central France (also North Carolina, Texas, and Yucatan). The relationships are frequently curvilinear. Transfer functions can be calculated to reconstruct prehistoric and historic regional hydrological balance and project future effects. An astronomical climatology model is used to estimate past global energy balance. The projections appear to fit sediment, diatom, and pollen records. General circulation model estimates of greenhouse warming are used to drive future hydrological balance determinations.     

Assessment of NMR Logging for Estimating Hydraulic Conductivity in Glacial Aquifers

Glacial aquifers are an important source of groundwater in the United States and require accurate characterization to make informed management decisions. One parameter that is crucial for understanding the movement of groundwater is hydraulic conductivity, K. Nuclear magnetic resonance (NMR) logging measures the NMR response associated with the water in geological materials. By utilizing an external magnetic field to manipulate the nuclear spins associated with ¹H, the time-varying decay of the nuclear magnetization is measured. This logging method could provide an effective way to estimate K at submeter vertical resolution, but the models that relate NMR measurements to K require calibration. At two field sites in a glacial aquifer in central Wisconsin, we collected a total of four NMR logs and obtained measurements of K in their immediate vicinity with a direct-push permeameter (DPP). Using a bootstrap algorithm to calibrate the Schlumberger-Doll Research (SDR) NMR-K model, we estimated K to within a factor of 5 of the DPP measurements. The lowest levels of accuracy occurred in the lower-K (K < 10⁻⁴ m/s) intervals. We also evaluated the applicability of prior SDR model calibrations. We found the NMR calibration parameters varied with K, suggesting the SDR model does not incorporate all the properties of the pore space that control K. Thus, the expected range of K in an aquifer may need to be considered during calibration of NMR-K models. This study is the first step toward establishing NMR logging as an effective method for estimating K in glacial aquifers.     

The 2dF Galaxy Redshift Survey: the nature of the relative bias between galaxies of different spectral type

We present an analysis of the relative bias between early- and late-type galaxies in the Two-degree Field Galaxy Redshift Survey (2dFGRS) – as defined by the η parameter of Madgwick et al., which quantifies the spectral type of galaxies in the survey. We calculate counts in cells for flux-limited samples of early- and late-type galaxies, using approximately cubical cells with sides ranging from 7 to  42 h ⁻¹ Mpc  . We measure the variance of the counts in cells using the method of Efstathiou et al., which we find requires a correction for a finite volume effect equivalent to the integral constraint bias of the autocorrelation function. Using a maximum-likelihood technique we fit lognormal models to the one-point density distribution, and develop methods of dealing with biases in the recovered variances resulting from this technique. We then examine the joint density distribution function,   f (δ_E, δ_L)  , and directly fit deterministic bias models to the joint counts in cells. We measure a linear relative bias of ≈1.3, which does not vary significantly with ℓ. A deterministic linear bias model is, however, a poor approximation to the data, especially on small scales  (ℓ≤ 28  h ⁻¹ Mpc)  where deterministic linear bias is excluded at high significance. A power-law bias model with index   b ₁≈ 0.75  is a significantly better fit to the data on all scales, although linear bias becomes consistent with the data for  ℓ≳ 40  h ⁻¹ Mpc  .     

Bio-cultural refugia—Safeguarding diversity of practices for food security and biodiversity

Food security for a growing world population is high on the list of grand sustainability challenges, as is reducing the pace of biodiversity loss in landscapes of food production. Here we shed new insights on areas that harbor place specific social memories related to food security and stewardship of biodiversity. We call them bio-cultural refugia. Our goals are to illuminate how bio-cultural refugia store, revive and transmit memory of agricultural biodiversity and ecosystem services, and how such social memories are carried forward between people and across cohorts. We discuss the functions of such refugia for addressing the twin goals of food security and biodiversity conservation in landscapes of food production. The methodological approach is first of its kind in combining the discourses on food security, social memory and biodiversity management. We find that the rich biodiversity of many regionally distinct cultural landscapes has been maintained through a mosaic of management practices that have co-evolved in relation to local environmental fluctuations, and that such practices are carried forward by both biophysical and social features in bio-cultural refugia including; genotypes, artifacts, written accounts, as well as embodied rituals, art, oral traditions and self-organized systems of rules. Combined these structure a diverse portfolio of practices that result in genetic reservoirs—source areas—for the wide array of species, which in interplay produce vital ecosystem services, needed for future food security related to environmental uncertainties, volatile financial markets and large scale conflicts. In Europe, processes related to the large-scale industrialization of agriculture threaten such bio-cultural refugia. The paper highlights that the dual goals to reduce pressures from modern agriculture on biodiversity, while maintaining food security, entails more extensive collaboration with farmers oriented toward ecologically sound practices.