Time-temperature-transformation (TTT) analysis of cation disordering in omphacite

The kinetics of cation disordering in a natural ordered (P2/n) omphacite have been followed at P=18 and 30 kb, T= 750–1,260° C, for times of between 1.5 min and 16 days in a piston-cylinder apparatus. Time-temperature-transformation (TTT) analysis of the experimental data, using the presence or absence of the 11¯1 reflection in single crystal X-ray precession photographs to indicate the extent of reaction, yields an equilibrium order/disorder temperature (T _ord) of 865±10° C, an activation enthalpy (1 bar) of 71±6 kcal mole^–1 and an activation volume of 9±4 cm³ mole^–1 (plus and minus figures represent the precision of a best fit between experimental data and TTT theory rather than absolute errors). The activation volume is consistent with a vacancy mechanism of cation diffusion. H₂O, added in the form of oxalic acid, appears to speed the process up slightly. The overall transformation mechanism is continuous, involving neither the nucleation of a disordered phase nor a change in antiphase-domain distribution. This is consistent with both first- and non-first-order character for the C2/cP2/n transformation, though a range of ordered states below T _ord is indicated by the weakening of h+k=odd reflections. A simple extrapolation of the disordering rates to geological conditions leads to the first estimate of how long disordered omphacites would take to order in nature, ranging from less than one year at T800° C to more than 10⁷ years at T<350° C.     

Polycyclic aromatic hydrocarbon (PAH)-phase associations in Washington coastal sediment

Polycyclic aromatic (PAH) and aliphatic hydrocarbon compositions, organic carbon, nitrogen and lignin contents were determined in whole, unfractionated sediment from the Washington continental shelf and in discrete sediment fractions separated by particle size and density. At least 20 to 25% of perylene and PAH derived from pyrolytic processes and 50% of the retene measured in whole sediment are contained within organic C- and lignin-rich panicles of density ≤ 1.9 g/cc. These particles, which include primarily vascular plant remains and bits of charcoal, comprise less than 1% of the total sediment weight. In contrast, a series of methylated phenanthrene homologs, possibly of fossil origin, are concentrated in some component of the more dense, lithic matrix of the sediment. Equilibrium models of PAH sorption/desorption from aqueous phase onto small particles of high surface area do not appear applicable to the behavior of the major PAH types identified in this aquatic environment.     

Identification of buried sinkholes using refraction tomography at Ft. Campbell Army Airfield,Kentucky

Karst aquifers are highly susceptible to contamination, with numerous points of entry for contaminants through recharge features such as sinkholes, swallow holes and solutionally enlarged fractures. These recharge features may be filled or obscured at the surface, requiring the use of geophysical or remote sensing techniques for their identification. This study uses seismic refraction data collected at the Ft. Campbell Army Airfield (CAAF), Kentucky, USA, to test the hypothesis that refraction tomography is a useful tool for imaging bedrock depressions beneath thick overburden (greater than 20 m of unconsolidated sediment). Southeast of the main taxiway of CAAF seismic velocity tomograms imaged a bedrock low, possibly a closed depression, at a depth of 25 m that had been earlier identified through delay-time analysis of the same refraction data. Tomography suggests the bedrock low is about 250-m wide by 10-m deep at its widest point. High rates of contaminant vapor extraction over the western extension of this feature suggest a high concentration of contaminants above, and within, this filled bedrock low, the base of which may contain solutionally enlarged fractures (i.e. karst conduits) that could funnel these contaminants to the upper or lower bedrock aquifers. This study thus demonstrates the viability of seismic refraction tomography as a tool for identification of filled sinkholes and bedrock depressions in karst areas.     

The potential impact of herbivores on the susceptibility of the marsh plantSagittaria lancifolia to saltwater intrusion in coastal wetlands

The objective of this study was to experimentally evaluate the effects of simulated herbivory on the ability of a freshwater marsh plant to recover from temporary saltwater intrusion such as can be caused by tropical storms. Sods containingSagittaria lancifolia, a dominant plant in interior coastal marshes, were manipulated in the field so as to subject plants to a pulse of 15‰ salt water for a duration of 1 wk. In addition to the exposure to salt water, some plants were also subjected to both short-term and long-term flooding treatments of 20 cm, and to simulated herbivory (clipping). Following exposure to salt water, plants were allowed to recover over the winter and were harvested the next June. Neither simulated herbivory, nor salinity, nor flooding caused any long-term effect either singly or in pairwise combinations. However, when plants were subjected to herbivory, salt water, and flooding simultaneously, reduced growth and plant death occurred. These results suggest that high levels of grazing by herbivores may increase the susceptibility of coastal marsh plants to damage from saltwater intrusion. *** DIRECT SUPPORT *** A01BY073 00002     

Outlying plasmasphere structure detected by whistlers

Whistlers recorded at Eights ($\text{L ? 4}$) and Byrd ($\text{f ? 7}$), Antarctica have been used to study large-scale structure in equatorial plasma density at geocentric distances $\text{?3–6}\text{R}{}_{\mathrm{E}}$. The observations were made during conditions of magnetic quieting following moderate disturbance. The structures were detected by a “scanning” process involving relative motion, at about one tenth of the Earth's angular velocity or greater, between the observed density features and the observing whistler station or stations. Three case studies are described, from 26 March 1965, 11 May 1965 and 29 August 1966. The cases support satellite results by showing outlying high density regions at $\text{?4–6}\text{R}{}_{\mathrm{E}}$ that are separated from the main plasmasphere by trough-like depressions ranging in width from $\text{?0.2}$ to 1 R_E. The structures evidently endured for periods of 12 hr or more. In the cases of deepest quieting their slow east-west motions with respect to the Earth are probably of dynamo origin. The cases observed during deep quieting (11 May 1965 and 29 August 1966) suggest the approximate rotation with the Earth of structure formed during previous moderate disturbance activity in the dusk sector. The third case, from 26 March 1965, may represent a structure formed near local midnight. The reported structures appear to be closely related to the bulge phenomenon. The present work supports other experimental and theoretical evidence that the dusk sector is one of major importance in the generation of outlying density structure. It is inferred that irregularities of the type reported here regularly develop near 4–5 R_E during moderate substorm activity. This research suggests that at least a major class of the density structures that develop near 4 R_E are tail-like in nature, joined to the main body of the plasmasphere. The apparent disagreement with Chappell's results from OGO 5, which are interpreted as showing regions of “detached” plasma beyond 5 R_E, may be related to the pronounced spatial structure of electric fields observed in high-latitude ionospheric regions that are conjugate to the magnetospheric regions in which the OGO-5 observations were made.     

Partitioning of manganese,iron, copper,zinc, lead,cobalt, and nickel in black coatings on stream boulders in the vicinity of the Magruder mine,Lincoln Co., Georgia

Sequential digestions of Fe-Mn oxide coated boulders collected upstream and downstream from the Magruder mine, Lincoln Co., Georgia, indicate probable partitioning relationships for Zn, Cu, Pb, Co, and Ni with respect to Mn and Fe. Initial digestion with 0.1M hydroxylamine hydrochloride (Hxl) in 0.01M HNO₃ selectively dissolyes Mn oxides, whereas subsequent digestion with 1:4 HCl dissolves remaining Fe oxides.The results indicate that partitioning is not constant, but varies systematically with respect to the location of metal-rich waters derived from sulfide mineralization. Upstream from the mineralized zone Zn and Ni are distinctly partitioned to the Fe oxide component and Co and Cu are partitioned to the Mn oxide component. Immediately downstream from the mineralized zone, Mn oxides become relatively more enriched in Zn, whereas Fe oxides are relatively more enriched in Cu, Co, and Ni. Analytical precision for Pb is poor, but available data suggests it is more closely associated with Fe oxides.For routine geochemical surveys utilizing coated surfaces, a one-step digestion method is probably adequate. Parameters useful for detecting sulfide mineralization are metal concentrations normalized to surface area or various ratios (e.g. Zn/(Mn + Fe), Cu/Mn, Pb/Fe). Ratios can be obtained much faster, and at lower analytical costs than conventional analysis of stream sediment.     

Comparison of heat and bromide as ground water tracers near streams

Heat and bromide were compared as tracers for examining stream/ground water exchanges along the middle reaches of the Santa Clara River, California, during a 10-hour surface water sodium bromide injection test. Three cross sections that comprise six shallow (<1 m) piezometers were installed at the upper, middle, and lower sections of a 17 km long study reach, to monitor temperatures and bromide concentrations in the shallow ground water beneath the stream. A heat and ground water transport simulation model and a closely related solute and ground water transport simulation model were matched up for comparison of simulated and observed temperatures and bromide concentrations in the streambed. Vertical, one-dimensional simulations of sediment temperature were fitted to observed temperature results, to yield apparent streambed hydraulic conductivities in each cross section. The temperature-based hydraulic conductivities were assigned to a solute and ground water transport model to predict sediment bromide concentrations, during the sodium bromide injection test. Vertical, one-dimensional simulations of bromide concentrations in the sediments yielded a good match to the observed bromide concentrations, without adjustment of any model parameters except solute dispersivities. This indicates that, for the spatial and temporal scales examined on the Santa Clara River, the use of heat and bromide as tracers provide comparable information with respect to apparent hydraulic conductivities and fluxes for sediments near streams. In other settings, caution should be used due to differences in the nature of conservative (bromide) versus nonconservative (heat) tracers, particularly when preferential flowpaths are present.     

Metal accumulation in surface salt marsh sediments of the Bay of Fundy,Canada

We measured the amount of arsenic, chromium, copper, lead, nickel, vanadium, and zinc accumulated over a five-year period from 1997 to 2002 in surface sediments of seven salt marshes along the New Brunswick coast of the Bay of Fundy, Canada. Study sites extended from outer to inner Bay, spanning a gradient in tidal range (6–12 m) and mean sediment deposition rate (0.27–1.76 cm yr⁻¹). In each study site, metal concentrations were measured in low and high marsh areas. Concentrations of chromium, nickel, and zinc appear to be within their natural range, while arsenic, lead, and vanadium are enriched in some sites. Calculated sediment metal loadings rates showed variability among marsh sites that closely followed sediment deposition patterns, suggesting sediment deposition rate is the driving factor of short-term metal accumulation in Fundy marshes. The value of salt marshes as a sink for metals may be enhanced by high sedimentation rates.     

Organo-sulfur compounds in sediments of the Puget Sound basin

Sediment samples from a variety of different environments were analyzed for organo-sulfur compounds (OSC) to provide the first characterization of the amounts and types of these compounds in sediments of the greater Puget Sound basin. A gas Chromatograph equipped with a sulfur specific flame photometric detector was used to quantify individual OSC. Compositions of OSC mixtures were essentially constant throughout the study area. Dibenzothiophene (DBT), its alkylated homologs, and an unknown compound were the predominant OSC in most samples. Concentrations of total OSC and DBT ranged from 4 to 60 and 0.4 to 2 μg/g organic carbon, respectively. The flux of OSC to the sediments at a station in central Puget Sound west of Seattle was approximately 140 ng/cm²/yr. The profile of total OSC concentration with depth showed three organic sulfur compounds that are apparently created in situ in the vicinity of where hydrogen sulfide production begins. The concentrations of the aromatic OSC were relatively constant with depth. Although several anthropogenic sources of OSC were identified, there was no evidence that OSC from these sources were accumulating in the sediments. The major source of the aromatic OSC in the sediments is apparently atmospheric input from natural sources such as forest fires.     

The early diagenesis of aliphatic hydrocarbons and organic matter in sedimentary particulates from Dabob Bay,Washington

Aliphatic hydrocarbon compositions were quantitatively characterized in plankton, sediment trap-collected particulate materials and sediments from Dabob Bay using high resolution glass capillary gas chromatography. The average net accumulation of individual hydrocarbons measured in a 1-yr series of sediment traps was compared with the net accumulation of corresponding compounds measured in three depth intervals of ²¹⁰Pb-dated bottom sediments. Systematic and rapid decreases in the net accumulation of individual hydrocarbons were observed from the sediment traps to the sediments. Most pronounced decreases were measured for planktonically derived hydrocarbon constituents (e.g. pristane and two unsaturated compounds) which are rapidly remineralized at or near the sediment-water interface. Consequently, the amount of each compound measured in deposited sediments is not necessarily a quantitative indication of its initial flux to the sediments. The n-alkanes (C_25,27,29,31). characteristic of terrestrial plant waxes, are the predominant hydrocarbons measured by 4–6 cm depth in these sediments and show reasonably constant net accumulation below this interval.Significant diagenetic alteration of the bulk organic matter contained in the average sediment trap particulate material is also noted through comparison with bottom sediments on the basis of organic C/N and δ¹³C measurements. Organic matter elementally similar to marine plankton is preferentially remineralized upon deposition of the sedimentary particulates. The residual organic matter remaining and buried in the bottom sediments closely resembles terrestrial organic matter.