Influence of liquid structure on diffusive isotope separation in molten silicates and aqueous solutions

Molecular diffusion in natural volcanic liquids discriminates between isotopes of major ions (e.g., Fe, Mg, Ca, and Li). Although isotope separation by diffusion is expected on theoretical grounds, the dependence on mass is highly variable for different elements and in different media. Silicate liquid diffusion experiments using simple liquid compositions were carried out to further probe the compositional dependence of diffusive isotopic discrimination and its relationship to liquid structure. Two diffusion couples consisting of the mineral constituents anorthite (CaAl₂Si₂O₈; denoted AN), albite (NaAlSi₃O₈; denoted AB), and diopside (CaMgSi₂O₆; denoted DI) were held at 1450 °C for 2 h and then quenched to ambient pressure and temperature. Major-element as well as Ca and Mg isotope profiles were measured on the recovered quenched glasses. In both experiments, Ca diffuses rapidly with respect to Si. In the AB-AN experiment, D_Ca/D_Si ≈ 20 and the efficiency of isotope separation for Ca is much greater than in natural liquid experiments where D_Ca/D_Si ≈ 1. In the AB-DI experiment, D_Ca/D_Si ≈ 6 and the efficiency of isotope separation is between that of the natural liquid experiments and the AB-AN experiment. In the AB-DI experiment, D_Mg/D_Si ≈ 1 and the efficiency of isotope separation for Mg is smaller than it is for Ca yet similar to that observed for Mg in natural liquids.The results from the experiments reported here, in combination with results from natural volcanic liquids, show clearly that the efficiency of diffusive separation of Ca isotopes is systematically related to the solvent-normalized diffusivity - the ratio of the diffusivity of the cation (D_Ca) to the diffusivity of silicon (D_Si). The results on Ca isotopes are consistent with available data on Fe, Li, and Mg isotopes in silicate liquids, when considered in terms of the parameter D_cation/D_Si. Cations diffusing in aqueous solutions display a similar relationship between isotopic separation efficiency and D_cation/D_H2O, although the efficiencies are smaller than in silicate liquids. Our empirical relationship provides a tool for predicting the magnitude of diffusive isotopic effects in many geologic environments and a basis for a more comprehensive theory of isotope separation in liquid solutions. We present a conceptual model for the relationship between diffusivity and liquid structure that is consistent with available data.     

Low level wind maxima and temperature inversions over the northern great plains

Discriminant analysis is employed with kite sounding data from Drexel, Nebraska in an attempt to clarify the interaction between the wind shear and temperature inversions in the planetary boundary layer. The mean height of the inversion layer and a measure of the vertical wind shear either above or below the wind maximum combine in a statistically significant function to discriminate between cases when the level of the wind maximum is coincident either with the top or with the base of the inversion near sunrise.     

Mixing and biological production at eddy margins in the eastern Gulf of Alaska

We performed a multi-day shipboard experiment in June 2001 to test whether combining water from within an anticyclonic mesoscale eddy in the eastern Gulf of Alaska with water from outside could result in enhanced phytoplankton growth and to determine how mixing might influence planktonic assemblages. Initially, the eddy had lower standing stocks of algal pigments (chlorophyll a [chl a] and accessory pigments), nutrients, phytoplankton, and particulate organic carbon/nitrogen compared to waters outside of the eddy. The eddy possessed a greater diversity and abundance of coastal diatoms while the outside waters had a greater proportion of oceanic species, including the endemic pennate diatom, Nitzschia cylindroformis. After one week of incubation, rates of primary production were significantly higher in the mixed water compared to both the eddy and outside treatments. Pigment concentrations (except chl c₃, alloxanthin, and zeaxanthin) and the proportion of large diatoms (mainly Pseudo-nitzschia spp.) and heterotrophic dinoflagellates were greater in the mixed water than would be expected from the simple combination of inside and outside waters. Nutrient limitation (most likely by trace metals) appeared to be less severe in the mixed water. Chl a was enhanced in the mixed water, particularly when compared to the eddy water. The mixing of eddy and outside water masses stimulated primary production by ∼20%, but more importantly, the mixing resulted in a distinct planktonic assemblage. The biomass enrichment was short-lived, indicating that the maintenance of elevated chl a would require further mixing events in a physical setting that also permits an accumulation of biomass. We note that submesoscale processes, including the intensification of ageostrophic circulation that elicits strong vertical mixing in the presence of strain, might explain observed patterns of high phytoplankton standing stocks at the inner edges of Haida eddies in the field.     

Groundwater residence time in a dissected and weathered sandstone plateau: Kulnura–Mangrove Mountain aquifer,NSW, Australia

Groundwater residence time in the Kulnura–Mangrove Mountain aquifer was assessed during a multi-year sampling programme using general hydrogeochemistry and isotopic tracers (H₂O stable isotopes, δ¹³C_DIC, ³H, ¹⁴C and ⁸⁷Sr/⁸⁶Sr). The study included whole-rock analysis from samples recovered during well construction at four sites to better characterise water–rock interactions. Based on hydrogeochemistry, isotopic tracers and mineral phase distribution from whole-rock XRD analysis, two main groundwater zones were differentiated (shallow and deep). The shallow zone contains oxidising Na–Cl-type waters, low pH, low SC and containing ³H and ¹⁴C activities consistent with modern groundwater and bomb pulse signatures (up to 116.9 pMC). In this shallow zone, the original Hawkesbury Sandstone has been deeply weathered, enhancing its storage capacity down to ～50 m below ground surface in most areas and ～90 m in the Peats Ridge area. The deeper groundwater zone was also relatively oxidised with a tendency towards Ca–HCO₃-type waters, although with higher pH and SC, and no ³H and low ¹⁴C activities consistent with corrected residence times ranging from 11.8 to 0.9 ka BP. The original sandstone was found to be less weathered with depth, favouring the dissolution of dispersed carbonates and the transition from a semi-porous groundwater media flow in the shallow zone to fracture flow at depth, with both chemical and physical processes impacting on groundwater mean residence times.

Detailed temporal and spatial sampling of groundwater revealed important inter-annual variations driven by groundwater extraction showing a progressive influx of modern groundwater found at >100 m in the Peats Ridge area. The progressive modernisation has exposed deeper parts of the aquifer to increased NO₃^? concentrations and evaporated irrigation waters. The change in chemistry of the groundwater, particularly the lowering of groundwater pH, has accelerated the dissolution of mineral phases that would generally be inactive within this sandstone aquifer triggering the mobilisation of elements such as aluminium in the aqueous phase.     

Metabolic Responses of Estuarine Microbial Communities to Discharge of Surface Runoff and Groundwater from Contrasting Landscapes

Groundwater discharge is increasingly recognized as a significant source of nutrient input to coastal waters, relative to surface water inputs. There remains limited information, however, on the extent to which nutrients and organic matter from each of these two flowpaths influence the functional responses of coastal microbial communities. As such, this study determined dissolved organic carbon (DOC) and nutrient concentrations of surface water runoff and groundwater from both an urbanized and a relatively pristine forested drainage basin near Myrtle Beach, South Carolina, and quantified the changes in production rates and biomass of phytoplankton and bacterioplankton in response to these inputs during two microcosm incubation experiments (August and October, 2011). Rainwater in the urbanized basin that would otherwise enter the groundwater appeared to be largely rerouted into the surface flowpath by impervious surfaces, bypassing ecosystem buffers and filtration mechanisms. Surface runoff from the developed basin was most enriched in nutrients and DOC and yielded the highest production rates of the various source waters upon addition to coastal waters. The metabolic responses of phytoplankton and bacterioplankton were generally well predicted as a function of initial chemical composition of the various source waters, though more so with bacterial production. Primary and bacterial productivities often correlated at reciprocal time points (24-h measurement of one with the 72-h measurement of the other). These results suggest human modification of coastal watersheds enhances the magnitude of dissolved constituents delivered to coastal waters as well as alters their distributions between surface and groundwater flowpaths, with significant implications for microbial community structure and function in coastal receiving waters.     

Factors influencing nitrate within a low-gradient agricultural stream

In low-gradient agricultural streams, the proportion of land use devoted to agriculture, the sinuosity of the stream and the time of year influence the concentration of nitrate in the stream waters. Land use influences the source of nitrate and also the morphology of the stream. Greater agricultural land use weakly correlated (r = 0.67) to higher nitrate concentrations. Streams in agricultural areas have been straightened, which decreases the sinuosity. As a stream meanders and becomes more sinuous, the potential for lateral hyporheic flow increases, which can enhance a stream system’s ability to remove nitrate. Logically, higher sinuous streams should remove more nitrate and likely sulfate as there is a greater potential for lateral hyporheic flows. To test this hypothesis, nitrate and sulfate were monitored. Mass fluxes of nitrate along six stream segments with varying sinuosity values were calculated and statistically analyzed to assess if differences in mass fluxes along the segments existed. Along the segments, there are statistically significant differences in the mass fluxes of nitrate [F(5,174) = 4.777; p = 0.001]. Stream segments with higher sinuosity index values exhibited a loss or lower gain in nitrate and sulfate than lower sinuosity index segments. The data suggest that stream segments with high sinuosity indices provide greater stream distance and increased hyporheic interaction within the streambed. Additionally, the more sinuous segments provide for an increase in lateral hyporheic flow beneath meander lobes. These additional hyporheic flows lead to enhanced denitrification in low-gradient agricultural streams. Seasonal differences were also noted. August through October experienced the lower nitrate concentrations as compared to June and July which exhibited the highest nitrate concentrations.     

The 2dF Galaxy Redshift Survey: a targeted study of catalogued clusters of galaxies

We have carried out a study of known clusters within the 2dF Galaxy Redshift Survey (2dFGRS) observed areas and have identified 431 Abell, 173 APM and 343 EDCC clusters. Precise redshifts, velocity dispersions and new centroids have been measured for the majority of these objects, and this information is used to study the completeness of these catalogues, the level of contamination from foreground and background structures along the cluster's line of sight, the space density of the clusters as a function of redshift, and their velocity dispersion distributions. We find that the Abell and EDCC catalogues are contaminated at the level of about 10 per cent, whereas the APM catalogue suffers only 5 per cent contamination. If we use the original catalogue centroids, the level of contamination rises to approximately 15 per cent for the Abell and EDCC catalogues, showing that the presence of foreground and background groups may alter the richness of clusters in these catalogues. There is a deficiency of clusters at     that may correspond to a large underdensity in the Southern hemisphere. From the cumulative distribution of velocity dispersions for these clusters, we derive a space density of     clusters of     This result is used to constrain models for structure formation; our data favour low-density cosmologies, subject to the usual assumptions concerning the shape and normalization of the power spectrum.     

The 2dF Galaxy Redshift Survey: luminosity functions by density environment and galaxy type

We use the 2dF Galaxy Redshift Survey to measure the dependence of the b _J-band galaxy luminosity function on large-scale environment, defined by density contrast in spheres of radius  8  h ⁻¹ Mpc  , and on spectral type, determined from principal component analysis. We find that the galaxy populations at both extremes of density differ significantly from that at the mean density. The population in voids is dominated by late types and shows, relative to the mean, a deficit of galaxies that becomes increasingly pronounced at magnitudes brighter than   M _{b J}−5log₁₀ h ≲−18.5  . In contrast, cluster regions have a relative excess of very bright early-type galaxies with   M _{b J}−5log₁₀ h ≲−21  . Differences in the mid- to faint-end population between environments are significant: at   M _{b J}−5log₁₀ h =−18  early- and late-type cluster galaxies show comparable abundances, whereas in voids the late types dominate by almost an order of magnitude. We find that the luminosity functions measured in all density environments, from voids to clusters, can be approximated by Schechter functions with parameters that vary smoothly with local density, but in a fashion that differs strikingly for early- and late-type galaxies. These observed variations, combined with our finding that the faint-end slope of the overall luminosity function depends at most weakly on density environment, may prove to be a significant challenge for models of galaxy formation.