Surface chemistry and reactivity of biogenic silica

The surface chemistry of cultured diatoms was compared to that of biosiliceous material in Southern Ocean sediments, using potentiometric titrations and aluminum adsorption experiments. Aerosil 200, a well-studied synthetic amorphous silica, served as reference solid. Surface charge development and aluminum adsorption on cultured diatom shells were comparable to Aerosil. The surface chemical properties of biosiliceous material buried to depths of 15-25 cm in Southern Ocean sediments, however, deviated markedly from those of the cultured diatoms. In pH range 4-8.5, the surface charge density was systematically lower for biogenic silica from the sediments. In addition, the aluminum adsorption edge on the biosiliceous sediments was shifted to higher pHs by about 0.4 units. The results indicate that ionizable surface silanol groups on diagenetically altered diatom shells are less abundant and, possibly, less acidic than on freshly cultured diatoms. The observed differences in surface chemical structure are consistent with the progressive loss of reactivity, or aging, of biogenic silica which promotes its preservation in sediments.     

Flow dynamics at the origin of thin clayey sand lacustrine turbidites: Examples from Lake Hazar,Turkey

Turbidity currents and their deposits can be investigated using several methods, i.e. direct monitoring, physical and numerical modelling, sediment cores and outcrops. The present study focused on thin clayey sand turbidites found in Lake Hazar (Turkey) occurring in eleven clusters of closely spaced thin beds. Depositional processes and sources for three of those eleven clusters are studied at three coring sites. Bathymetrical data and seismic reflection profiles are used to understand the specific geomorphology of each site. X‐ray, thin sections and CT scan imagery combined with grain‐size, geochemical and mineralogical measurements on the cores allow characterization of the turbidites. Turbidites included in each cluster were produced by remobilization of surficial slope sediment, a process identified in very few studies worldwide. Three types of turbidites are distinguished and compared with deposits obtained in flume studies published in the literature. Type 1 is made of an ungraded clayey silt layer issued from a cohesive flow. Type 2 is composed of a partially graded clayey sand layer overlain by a mud cap, attributed to a transitional flow. Type 3 corresponds to a graded clayey sand layer overlain by a mud cap issued from a turbulence‐dominated flow. While the published experimental studies show that turbulence is damped by cohesion for low clay content, type 3 deposits of this study show evidence for a turbulence‐dominated mechanism despite their high clay content. This divergence may in part relate to input variables, such as water chemistry and clay mineralogy, that are not routinely considered in experimental studies. Furthermore, the large sedimentological variety observed in the turbidites from one coring site to another is related to the evolution of a sediment flow within a field‐scale basin made of a complex physiography that cannot be tackled by flume experiments.     

Origin and evolution of the Steamboat Springs siliceous sinter deposit, Nevada, U.S.A.

Siliceous hot spring deposits from Steamboat Springs, Nevada, U.S.A., record a complex interplay of multiple, changing, primary environmental conditions, fluid overprinting and diagenesis. Consequently these deposits reflect dynamic geologic and geothermal processes. Two surface sinters were examined—the high terrace, and the distal apron-slope, as well as 13.11 m (43 ft) of core material from drill hole SNLG 87-29. The high terrace sinter consists of vitreous and massive-mottled silica horizons, while the distal deposit and core comprise dominantly porous, indurated fragmental sinters. Collectively, the three sinter deposits archive a complete sequence of silica phase diagenetic minerals from opal-A to quartz. X-ray powder diffraction analyses and infrared spectroscopy of the sinters indicate that the distal apron-slope consists of opal-A and opal-A/CT mineralogy; the core yielded opal-A/CT and opal-CT with minor opal-A; and the high terrace constitutes opal-C, moganite, and quartz. Mineralogical maturation of the deposit produced alternating nano–micro–nano-sized silica particle changes. Based on filament diameters of microbial fossils preserved within the sinter, discharging thermal outflows fluctuated between low-temperatures (< 35 °C, coarse filaments) and mid-temperatures ( 35–60 °C, fine filaments). Despite transformation to quartz, primary coarse and fine filaments were preserved in the high terrace sinter. AMS ¹⁴C dating of pollen from three horizons within core SNLG 87-29, from depths of 8.13 to 8.21 m (26′8″ to 26′11″), 10.13 to 10.21 m (33′3″ to 33′6″), and 14.81 to 14.88 m (48′7″ to 48′10″), yielded dates of 8684 ± 64 years, 11,493 ± 70 years and 6283 ±60 years, respectively. In the upper section of the core, the stratigraphically out-of-sequence age likely reflects physical mixing of younger sinter with quartzose sinter fragments derived from the high terrace. Within single horizons, mineralogical and morphological components of the sinter matrix were spatially patchy. Overall, the deposit was modified by sub-surface flow of alkali-chloride thermal fluids depositing a second generation of silica, and periodically, by acidic steam condensate formed during periods when the water table was low. Local faulting produced considerable fracturing of the sinter. Hence, the Steamboat Springs sinter experienced a complex history of primary and secondary hydrothermal, geologic and diagenetic events, and their inter-relationships and effects are locked within the physical, chemical and biological signatures of the deposit.     

Scaling of the Vertical Spreading of a Plume of a Passive Tracer in a Rough-Wall Neutral Boundary Layer

The influence of surface roughness on the dispersion of a passive scalar in a rough wall turbulent boundary layer has been studied using wind-tunnel experiments. The surface roughness was varied using different sizes of roughness elements, and different spacings between the elements. Vertical profiles of average concentration were measured at different distances downwind of the source, and the vertical spread of the plume was computed by fitting a double Gaussian profile to the data. An estimate of the integral length scale is derived from the turbulence characteristics of the boundary layer and is then used to scale the measured values of plume spread. This scaling reduces the variability in the data, confirming the validity of the model for the Lagrangian integral time scale, but does not remove it entirely. The scaled plume spreading shows significant differences from predictions of theoretical models both in the near and in the far field. In the region immediately downwind of the source this is due to the influence of the wake of the injector for which we have developed a simple model. In the far field we explain that the differences are mainly due to the absence of large-scale motions. Finally, further downwind of the source the scaled values of plume spread fall into two distinct groups. It is suggested that the difference between the two groups may be related to the lack of dynamical similarity between the boundary-layer flows for varying surface roughness or to biased estimates of the plume spread.     

Evaluation of a high-resolution regional climate simulation over Greenland

A simulation of the 1991 summer has been performed over south Greenland with a coupled atmosphere–snow regional climate model (RCM) forced by the ECMWF re-analysis. The simulation is evaluated with in-situ coastal and ice-sheet atmospheric and glaciological observations. Modelled air temperature, specific humidity, wind speed and radiative fluxes are in good agreement with the available observations, although uncertainties in the radiative transfer scheme need further investigation to improve the model’s performance. In the sub-surface snow-ice model, surface albedo is calculated from the simulated snow grain shape and size, snow depth, meltwater accumulation, cloudiness and ice albedo. The use of snow metamorphism processes allows a realistic modelling of the temporal variations in the surface albedo during both melting periods and accumulation events. Concerning the surface albedo, the main finding is that an accurate albedo simulation during the melting season strongly depends on a proper initialization of the surface conditions which mainly result from winter accumulation processes. Furthermore, in a sensitivity experiment with a constant 0.8 albedo over the whole ice sheet, the average amount of melt decreased by more than 60%, which highlights the importance of a correctly simulated surface albedo. The use of this coupled atmosphere–snow RCM offers new perspectives in the study of the Greenland surface mass balance due to the represented feedback between the surface climate and the surface albedo, which is the most sensitive parameter in energy-balance-based ablation calculations.     

A comprehensive model inter-comparison study investigating the water budget during the BALTEX-PIDCAP period

Summary A comparison of 8 regional atmospheric model systems was carried out for a three-month late summer/early autumn period in 1995 over the Baltic Sea and its catchment area. All models were configured on a common grid using similar surface and lateral boundary conditions, and ran in either data assimilation mode (short term forecasts plus data assimilation), forecast mode (short term forecasts initialised daily with analyses) or climate mode (no re-initialisation of model interior during entire simulation period). Model results presented in this paper were generally post processed as daily averaged quantities, separate for land and sea areas when relevant. Post processed output was compared against available analyses or observations of cloud cover, precipitation, vertically integrated atmospheric specific humidity, runoff, surface radiation and near surface synoptic observations. The definition of a common grid and lateral forcing resulted in a high degree of agreement among the participating model results for most cases. Models operated in climate mode generally displayed slightly larger deviations from the observations than the data assimilation or forecast mode integration, but in all cases synoptic events were well captured. Correspondence to near surface synoptic quantities was good. Significant disagreement between model results was shown in particular for cloud cover and the radiative properties, average precipitation and runoff. Problems with choosing appropriate initial soil moisture conditions from a common initial soil moisture field resulted in a wide range of evaporation and sensible heat flux values during the first few weeks of the simulations, but better agreement was shown at later times. Received September 8, 2000 Revised April 3, 2001     

Tracer experiments with turbulently dispersed air ions

Unipolar air ions released into the wind constitute a tracer which can be measured with high resolution. An ion source produces a cloud with homogeneous charge density, insensitive to source strength, dependent on time since formation only. It is well suited for tracing concentration changes due to turbulence, less suited for cloud size tracing. A tight array of 8 sensors has been used to examine turbulently dispersed ions. High-resolution records are presented and discussed. The highest concentrations measured could be undiluted source material. The frequency distribution within a plume did not differ from that in a multitude of puffs. The distribution seems to be log-normal with a geometric standard deviation of about 2.45. The time resolution used corresponds to volume resolutions of 40, 225, and 650 cm³. Sample size had no apparent effect.     

Storm-damaged saline-contaminated boreholes as a means of aquifer contamination

Saline water from a storm surge can flow down storm-damaged submerged water supply wells and contaminate boreholes and surrounding aquifers. Using data from conventional purging techniques, aquifer test response analysis, chemical analysis, and regression analysis of chloride/silica (Cl/Si) ratio, equations were derived to estimate the volume of saline water intrusion into a well and a porous media aquifer, the volume of water needed to purge a well shortly following an intrusion event, and the volume of water needed after delay of several or more months, when the saline plume has expanded. Purging time required is a function of volume of water and pumping rate. The study site well is located within a shoreline community of Lake Pontchartrain, St. Tammany Parish, in southeastern Louisiana, United States, which was impacted by two hurricane storm surges and had neither been rehabilitated nor chlorinated prior to our study. Chemical analysis of water samples in fall 2005 and purging of well and aquifer in June 6, 2006, indicated saline water had intruded the well in 2005 and the well and aquifer in 2006. The volume of water needed to purge the study well was approximately 200 casing volumes, which is significantly greater than conventionally used during collection of water samples for water quality analyses.     

A comparison of boundary layer diffusion schemes in unstable conditions over land

We compare the results of a local and a nonlocal scheme for vertical diffusion in the atmospheric boundary layer with observations at the 200 m tower at Cabauw. This is done for a 12 h period during daytime on 31 May 1978, which is characterised by strong insolation, clear skies, moderately strong winds and weak advection. The local diffusion scheme uses an eddy diffusivity determined independently at each point along the vertical based on local vertical gradients of wind and virtual potential temperature, similar to the usual approach in atmospheric models. The nonlocal scheme determines an eddy diffusivity profile based on a diagnosed boundary-layer height and a turbulent velocity scale. It also incorporates nonlocal (vertical) transport effects for heat and moisture. The boundary-layer diffusion schemes are forced with the locally observed fluxes for heat and moisture. The outputs of the scheme are compared with the observed mean structure along the Cabauw tower, and the radiosonde profile at a nearby location (De Bilt). Overall, the nonlocal scheme transports moisture away from the surface more rapidly than the local scheme, and deposits the moisture at higher levels. The local scheme tends to saturate the lowest model levels unrealistically in comparison with the observations. We also compare the outputs of the two diffusion schemes with the results of a transilient model simulation. Subsequently, we study the impact on the model behaviour by varying important parameters in both diffusion schemes and we investigate the sensitivity to uncertainty in the environmental conditions. Finally, we study the interaction of the diffusion schemes with a simple surface flux scheme.     

Biomass Burning in Southern Africa: Individual Particle Characterization of Atmospheric Aerosols and Savanna Fire Samples

Ambient atmospheric aerosols and savanna fireparticulate emission samples from southern Africa werecharacterised in terms of particle classes and theirnumber abundance by electron probe X-ray microanalysis(EPXMA). About ten particle classes were identifiedfor each sample. The major classes werealuminosilicates and sea salts for ambient coarse(2–10 m equivalent aerodynamic diameter (EAD))samples, and K-S and S-only particles for ambient fine(<2 m EAD) samples. The K-S particles are oneof the major products of biomass burning. The EPXMAresults were found to be consistent with the resultsfrom bulk analyses on a sample by sample basis. Forsavanna fire fine samples, quantitative EPXMA revealedthat many particles had a composition of simple saltssuch as KCl. Some particles had a deviatingcomposition in the sense that more ionic species wereinvolved in sustaining the balance between cations andanions, and they were composite or mixed salts.Because of extensive processing during the atmospherictransport, the composition of the K-S particles in theambient samples was different from K₂SO₄,and such particles were enriched with S. The finepyrogenic KCl particles and the fine sea-saltparticles were much depleted in chlorine.