Elemental,infra-red spectrophotometric and electron spin resonance investigations of non-chemically isolated humic material

Naturally occurring organic material from a lake in the southeastern United States was isolated by ultrafiltration and analyzed by i.r. spectrophotometry and electron spin resonance spectrometry, and for its elemental composition without chemical pretreatment. The results of the study indicate the isolate is an apparent high molecular weight fulvic acid with associated, hydrated Mn²⁺ ion which does not appear strongly bound to the organic moiety.     

Analysis of the Time-Dependent Chemical Evolution of Titan Haze Tholin

Haze particles exert a significant influence over the thermodynamics and radiation absorption properties of the Titan haze, as well as its complex organic chemistry. Characterization of both the molecular and the submicrometer components of the haze is therefore vital for understanding the global properties of Titan. We have carried out a Titan tholin synthesis experiment and measured the time variation of the infrared spectrum of the product as a thin film developed. Also, to examine the possibility of oxygen contamination, we compared the infrared spectrum of the tholin film with that of a tholin film exposed to dry air and laboratory air. The objective of this study is to understand the chemical processes related to how simple organic molecules are processed into more complex haze particles. The progressive development of features characteristic of amines, aromatic and aliphatic hydrocarbons, and nitriles in the experimental mixture is clear. Of particular interest is the formation of aromatic rings after only a few seconds of glow discharge, indicating that these compounds appear to be intermediates between simple haze molecules and microphysical aerosols. The early dominance of aromatic ring structures is accompanied during the later stages of the experiment by the appearance of nitrile and amine compounds. This time-dependent succession of chemical structures provides vital clues to the possible chemical formation pathways of Titan haze aerosols.     

Localized thermal anomalies in haloclines of coastal Yucatan sinkholes

A temperature spike is reported in the haloclines of three Yucatan sinkholes along a 1 km NW-SE transect from 5 to 4 km inland from the Caribbean coast. The temperature spike decreases in magnitude from 3.5 degrees C to 0.2 degrees C, approaching the coast. The anomaly does not vary diurnally and does not extend down into the underlying sea water. These conditions are inconsistent with explanations such as radiation absorption within the halocline, in situ microbially mediated sulfate reduction within the halocline and the underlying sea water, and sulfide oxidation by photosynthetic purple and green bacteria within the halocline. One explanation consistent with the shape and halocline location of the temperature spike involves a localized sea water convection cell operating near the coast. Cold sea water from the Caribbean Sea enters the coastal limestone at depths of a few hundred meters and heats up because of the geothermal gradient, buoyantly rising in vertical fractures within the unconfined aquifer. Blocked by the less dense fresh water, the movement stops in the halocline where the warm sea water mixes with brackish water. The convection cycle would be completed by the coastward movement of cooling brackish water. The observed temperature anomalies could possibly be snapshots of this warm layer moving coastward.     

Observations of Boundary-Layer Wind-Tunnel Flow over Isolated Ridges of Varying Steepness and Roughness

Boundary-layer wind-tunnel flow is measured over isolated ridges of varyingsteepness and roughness. The steepness/roughness parameter space is chosento produce flows that range from fully attached to strongly separated. Measurementsshow that maximum speedup at the hill crest is significantly lower than predictedby linear theory and that recovery in the lee of the hill is much slower for stronglyseparated flow over steep terrain. The measurements also show that behaviour ofthe mean and turbulent components of the flow on the downwind side of the ridgeis fundamentally different between separated and non-separated flows. This suggeststhe dominance of much increased turbulence time and length scales in the lee of thehill in association with a production mechanism that scales with the hill length ratherthan the proximity to the surface as on the windward side of the hill crest.     

Effects of sediment iron mineral composition on microbially mediated changes in divalent metal speciation: Importance of ferrihydrite

Dissimilatory metal reducing bacteria (DMRB) can influence geochemical processes that affect the speciation and mobility of metallic contaminants within natural environments. Most investigations into the effect of DMRB on sediment geochemistry utilize various synthetic oxides as the Fe^III source (e.g., ferrihydrite, goethite, hematite). These synthetic materials do not represent the mineralogical composition of natural systems, and do not account for the effect of sediment mineral composition on microbially mediated processes. Our experiments with a DMRB (Shewanella putrefaciens 200) and a divalent metal (Zn^II) indicate that, while complexity in sediment mineral composition may not strongly impact the degree of “microbial iron reducibility,” it does alter the geochemical consequences of such microbial activity. The ferrihydrite and clay mineral content are key factors. Microbial reduction of a synthetic blend of goethite and ferrihydrite (VHSA-G) carrying previously adsorbed Zn^II increased both [Zn^II-aq] and the proportion of adsorbed Zn^II that is insoluble in 0.5 M HCl. Microbial reduction of Fe^III in similarly treated iron-bearing clayey sediment (Fe-K-Q) and hematite sand, which contained minimal amounts of ferrihydrite, had no similar effect. Addition of ferrihydrite increased the effect of microbial Fe^III reduction on Zn^II association with a 0.5 M HCl insoluble phase in all sediment treatments, but the effect was inconsequential in the Fe-K-Q. Zinc k-edge X-ray absorption spectroscopy (XAS) data indicate that microbial Fe^III reduction altered Zn^II bonding in fundamentally different ways for VHSA-G and Fe-K-Q. In VHSA-G, ZnO₆ octahedra were present in both sterile and reduced samples; with a slightly increased average Zn-O coordination number and a slightly higher degree of long-range order in the reduced sample. This result may be consistent with enhanced Zn^II substitution within goethite in the microbially reduced sample, though these data do not show the large increase in the degree of Zn-O-metal interactions expected to accompany this change. In Fe-K-Q, microbial Fe^III reduction transforms Zn-O polyhedra from octahedral to tetrahedral coordination and leads to the formation of a ZnCl₂ moiety and an increased degree of multiple scattering. This study indicates that, while many sedimentary iron minerals are easily reduced by DMRB, the effects of microbial Fe^III reduction on trace metal geochemistry are dependent on sediment mineral composition.     

The relationship of total dissolved solids measurements to bulk electrical conductivity in an aquifer contaminated with hydrocarbon

A recent conceptual model links higher bulk conductivities at hydrocarbon impacted sites to higher total dissolved solids (TDS) resulting from enhanced mineral weathering due to acids produced during biodegradation. In this study, we evaluated the above model by investigating the vertical distribution of bulk conductivity, TDS, and specific conductance in groundwater. The results showed higher TDS at contaminated locations consistent with the above model. Further, steep vertical gradients in bulk conductivity and TDS suggest vertical and spatial heterogeneity at the site. We observed that at fluid conductivities <40 mS/m, bulk conductivity was inversely related to fluid conductivity, but at fluid conductivities >40 mS/m, bulk conductivity increased with increasing fluid conductivity. However, at fluid conductivities >80 mS/m, bulk conductivities increased without a corresponding increase in fluid conductivity, resulting in a poor correlation between bulk conductivity and fluid conductivity for the contaminated samples. This suggests that electrolytic conductivity was not completely responsible for the observed variability in bulk conductivity. We suggest two possible reasons for the inverse relationship at low fluid conductivity and poor positive correlation at high fluid conductivity: (1) geochemical heterogeneity due to biological processes not captured at a scale comparable to the bulk conductivity measurement and (2) variability in the surface conductivity, consistent with a simple petrophysical model that suggests higher surface conductivity for contaminated sediments. We conclude that biodegradation processes can impact both electrolytic and surface conduction properties of contaminated sediments and these two factors can account for the higher bulk conductivities observed in sediments impacted by hydrocarbon.     

Sediment movement rates and processes on cinder cones in the maritime Subantarctic (Marion Island)

Sediment transport in the scoria areas of Marion Island is primarily the result of needle‐ice‐induced frost creep associated with diurnal soil frost cycles. Clasts move most rapidly in ?ne textured areas (532 mm a^?1; SD 382), more slowly in stony areas (161 mm a^?1; SD 179), and most slowly in blocky areas (26 mm a^?1; SD 23). Movement rates increase with increasing frost susceptibility of sediments, slope angle and altitude. The heave of dowels indicates that frost heave is active in all the scoria areas examined. The depth of effective frost heave increases with increasing altitude, with frost heave being restricted to the upper 100 mm of the soil in low altitude areas (<200 m). The heave of 150 mm dowels at the higher altitude sites provides evidence for segregation ice formation at depths greater than those associated with needle ice and diurnal soil frost cycles. Vertical movement pro?les show a concave downslope pro?le, with sediment movement rates being most rapid at the soil surface and decreasing rapidly with depth. This pro?le shape is typical of areas dominated by diurnal freeze–thaw cycles and needle ice. The capture of sediments moving downslope in troughs and the sampling of material lifted by needle ice, suggest that sediment transport by needle ice under present conditions is extremely effective. Observations suggest that although both ?ne material and clasts are transported downslope, some preferential transport of clasts occurs. Experiment results and observations of soil frost processes suggest that frost creep associated with needle ice activity is the dominant slope process in the scoria areas of Marion Island. Other slope processes such as slopewash and debris ?ows appear to play a relatively minor and localized role in sediment transport. It is suggested that needle ice activity is likely to be the dominant geomorphic agent in other areas of the Subantarctic with similar climatic characteristics to Marion Island. Copyright © 2004 John Wiley & Sons, Ltd.     

Another look at anisotropy in geostatistics

A thorough geostatistical data analysis includes a careful study of how the data's second-order variation, as characterized by the semivariogram, depends on the relative orientation of data locations. If the semivariogram depends on only the (Euclidean) distance between locations, then the semivariogram is isotropic; otherwise, it is anisotropic. In this article, I take another look at the modeling of anisotropy in geostatistics. A new, more specific classification of types of anisotropy is proposed. More importantly, some heretofore inadequately understood implications of the dependence of various semivariogram attributes on direction are discussed, and the wisdom of some current practices for modeling the direction-dependence of these attributes is questioned.     

Food habits of two larval flies (Dolichopodidae: Diptera) in two gulf coast oligohaline tidal marshes

Food habits of two species of dolichopodid fly larvae, from two Gulf Coast oligohaline tidal marshes, were analyzed from monthly collections taken between June 1979 and May 1980. Larvae ofPelastoneurus abbreviatus Loew andThinophilus frontalis Van Duzee, taken from aJuncus roemerianus Scheele dominated marsh, fed predominantly on oligochaetes and nematodes.Pelastoneurus abbreviatus, collected in a nearbySpartina cynosuroides (L.) Roth marsh, also fed on oligochaetes but consumed more polychaetes than nematodes. By being predators and prey in turn, these larvae serve in the transfer of energy between benthic, aquatic, and terrestrial components of the marsh, system.     

Computationally efficient restricted maximum likelihood estimation of generalized covariance functions

Computational aspects of the estimation of generalized covariance functions by the method of restricted maximum likelihood (REML) are considered in detail. In general, REML estimation is computationally intensive, but significant computational savings are available in important special cases. The approach taken here restricts attention to data whose spatial configuration is a regular lattice, but makes no restrictions on the number of parameters involved in the generalized covariance nor (with the exception of one result) on the nature of the generalized covariance function's dependence on those parameters. Thus, this approach complements the recent work of L. G. Barendregt (1987), who considered computational aspects of REML estimation in the context of arbitrary spatial data configurations, but restricted attention to generalized covariances which are linear functions of only two parameters.