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The fugacity and fugacity coefficient of H 2 O at the liquid-vapor equilibrium, the fugacity and the Gibbs free energy of formation of H 2 O at 1 atm (1.01325 bars) total pressure have been calculated from published data on the physical and thermodynamic properties of H 2 O and are presented at ten-degree intervals from 0° to 350°C.
The dissolution of Iceland spar in CO 2 -saturated solutions at 25°C and 1 atm total pressure has been followed by measurement of pH as a function of time. Surface concentrations of reactant and product species have been calculated from bulk fluid data using mass transport theory and a model that accounts for homogeneous reactions in the bulk fluid. The surface concentrations are found to be close to bulk solution values. This indicates that calcite dissolution under the experimental conditions is controlled by the kinetics of surface reaction. The rate of calcite dissolution follows an empirical second order relation with respect to calcium and hydrogen ion from near the initial condition (pH 3.91) to approximately pH 5.9. Beyond pH 5.9 the rate of surface reaction is greatly reduced and higher reaction orders are observed. Calculations show that the rate of calcite dissolution in natural environments may be influenced by both transport and surface-reaction processes. In the absence of inhibition, relatively short times should be sufficient to establish equilibrium.
Exudates from conifer trees, presumably consisting largely of volatile materials, were sampled at 19 subalpine localitites in Colorado and Idaho where anomalous amounts of several metals were determined in vegetation and mull during previous geochemical testing. The trees sampled were lodgepole pine ( Pinus contorta ), Engelmann spruce ( Picea engelmannii ) and Douglas fir ( Pseudotsuga menziesii ). The condensed exudates were passed through No. 40 Whatman filters, and through 5-micron, 0.45-micron, and 0.05-micron average-pore-diameter membrane filters, evaporated to dryness, and each residue was ashed and analyzed by a semiquantitative spectrographic method. The ashed residues of the exudates contain lithium, beryllium, boron, sodium, magnesium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, arsenic, strontium, yttrium, zirconium, molybdenum, silver, lead, bismuth, cadmium, tin, antimony, barium, and lanthanum. The presence of these elements suggests that volatile exudates from vegetation are a medium for the transport of elements in the biogeochemical cycle in subalpine environments. Thus, air sampling and analysis of aerosols derived from volatile exudates may be a useful tool in geochemical exploration.
Surface water contamination by chemical pollutants increasingly threatens water quality around the world. Among the many contaminants found in surface water, there is growing concern regarding endocrine disrupting chemicals, based on their ability to interfere with some aspect of hormone action in exposed organisms, including humans. This study assessed water quality at several sites across Missouri (near wastewater treatment plants and airborne release sites of bisphenol A) based on hormone receptor activation potencies and chemical concentrationspresent in the surface water. We hypothesized that bisphenol A and ethinylestradiol would be greater in water near permitted airborne release sites and wastewater treatment plant inputs, respectively, and that these two compounds would be responsible for the majority of activities in receptor-based assays conducted with water collected near these sites. Concentrations of bisphenol A and ethinylestradiol were compared to observed receptor activities using authentic standards to assess contribution to total activities, and quantitation of a comprehensive set of wastewater compounds was performed to better characterize each site. Bisphenol A concentrations were found to be elevated in surface water near permitted airborne release sites, raising questions that airborne releases of BPA may influence nearby surface water contamination and may represent a previously underestimated source to the environment and potential for human exposure. Estrogen and androgen receptor activities of surface water samples were predictive of wastewater input, although the lower sensitivity of the ethinylestradiol ELISA relative to the very high sensitivity of the bioassay approaches did not allow a direct comparison. Wastewater-influenced sites also had elevated anti-estrogenic and anti-androgenic equivalence, while sites without wastewater discharges exhibited no antagonist activities.
Laser desorption ionization (LDI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to analyze shale oils. Previous work showed that LDI is a sensitive ionization technique for assessing aromatic nitrogen compounds, and oils generated from Green River Formation oil shales are well-documented as being rich in nitrogen. The data presented here demonstrate that LDI is effective in ionizing high-double-bond-equivalent (DBE) compounds and, therefore, is a suitable method for characterizing compounds with condensed structures. Additionally, LDI generates radical cations and protonated ions concurrently, the distribution of which depends upon the molecular structures and elemental compositions, and the basicity of compounds is closely related to the generation of protonated ions. This study demonstrates that LDI FT-ICR MS is an effective ionization technique for use in the study of shale oils at the molecular level. To the best of our knowledge, this is the first time that LDI FT-ICR MS has been applied to shale oils.
No abstract available.
Between July 2000 and August 2001 forty-three air samples were collected in the northern Caribbean: Twenty-six in the US Virgin Islands, and 17 samples aboard ship during two 1-week cruises. Samples were collected during African dust events and non-dust conditions and screened for the presence of culturable bacteria and fungi. A total of 3,652 liters of air were collected during non-dust conditions, with 19 bacteria and 28 fungi being recovered. During dust conditions a total of 2,369 liters of air were screened resulting in the recovery of 171 bacteria and 76 fungi. A statistically significant difference was found between the two data sets. These results support previous African dust research and further demonstrate that dust particles can serve as a vessel for the global dispersion of bacteria and fungi. Dustborne microorganisms may play a significant role in the ecology and health of downwind ecosystems.
A study was undertaken to investigate differences between laboratory and field pH measurements for precipitation samples collected from 135 weekly precipitation-monitoring sites in the National Trends Network from 12/30/1986 to 12/28/1999. Differences in pH between field and laboratory measurements occurred for 96% of samples collected during this time period. Differences between the two measurements were evaluated for precipitation samples collected before and after January 1994, when modifications to sample-handling protocol and elimination of the contaminating bucket o-ring used in sample shipment occurred. Median hydrogen-ion and pH differences between field and laboratory measurements declined from 3.9 ??eq L-1 or 0.10 pH units before the 1994 protocol change to 1.4 ??eq L-1 or 0.04 pH units after the 1994 protocol change. Hydrogen-ion differences between field and laboratory measurements had a high correlation with the sample pH determined in the field. The largest pH differences between the two measurements occurred for high-pH samples (>5.6), typical of precipitation collected in Western United States; however low- pH samples (<5.0) displayed the highest variability in hydrogen-ion differences between field and laboratory analyses. Properly screened field pH measurements are a useful alternative to laboratory pH values for trend analysis, particularly before 1994 when laboratory pH values were influenced by sample-collection equipment.
Microbes (bacteria, fungi, algae, and viruses) are the most successful types of life on Earth because of their ability to adapt to new environments, reproduce quickly, and disperse globally. Dispersal occurs through a number of vectors, such as migrating animals or the hydrological cycle, but transport by wind may be the most common way microbes spread. General awareness of airborne microbes predates the science of microbiology. People took advantage of wild airborne yeasts to cultivate lighter, more desirable bread as far back as ancient Egypt by simply leaving a mixture of grain and liquids near an open window. In 1862, Louis Pasteur's quest to disprove spontaneous generation resulted in the discovery that microbes were actually single-celled, living creatures, prevalent in the environment and easily killed with heat (pasteurization). His rudimentary experiments determined that any nutrient medium left open to the air would eventually teem with microbial life because of free-floating, colonizing cells. The same can happen in a kitchen: Opportunistic fungal and bacterial cells cause food items exposed to the air to eventually spoil.
A hydrothermally grown synthetic quartz crystal with 370±60 ppm hydroxyl impurity was cut into right rectangular prisms in eight crystallographic orientations. We compressed the prisms under constant axial force corresponding to a uniaxial stress of 140.0±0.5 MPa, and temperatures of 510° and 750°C. All but one of the samples sustained permanent axial strains of 2–3%. We established the operating slip systems from specimen shape change, slip bands and dislocation etch pits on polished surfaces, crystallographic orientation changes, stress optical features in thin sections, and transmission electron microscopy. The observed creep behavior and plasticity divided the samples into three groups: (1) Crystals compressed at 45° to [0001] and [ ] and those compressed ⊥( ) and ⊥( ) deformed principally by slip parallel to [0001]. Creep rates were relatively high and were not strongly sensitive to test temperature. Dislocation arrays approximately parallel to ( ) are common. Dislocation loops are elongate parallel to [0001], indicating that the edge segments were more mobile than the screw segments. (2) The second group of samples were loaded normal to [0001] in three orientations: ⊥( ), ⊥( ), and at 45° to ( ). These samples deformed primarily by { } 〈a〉 slip with some evidence for secondary slip on the other systems. They were more creep resistant than the first group and displayed a much higher sensitivity of creep rate to test temperature. Dislocation loops are very elongate parallel to [0001], indicating that the screw dislocation segments were much more mobile than the edge segments. (3) A sample compressed parallel to [0001] at 750°C crept at a barely detectable rate (∼10 s) and no optical scale slip features were observed. These results confirm our earlier work on one orientation each from groups 1 and 2, which indicated a strong creep anisotropy for this same crystal. This creep anisotropy parallels a remarkably similar anisotropy in the diffusivity of impurities in quartz, suggesting a causal relationship between impurity diffusion and creep associated with hydrolytic weakening. Appendix Tables A1‐A5 are available with entire article on microfiche. Order from American Geophysical Union, 2000 Florida Avenue, N.W., Washington, DC 20009. Document B84‐004; $2.50. Payment must accompany order.
Landscape drying associated with permafrost thaw is expected to enhance microbial methane oxidation in arctic soils. Here we show that ice-rich, Yedoma permafrost deposits, comprising a disproportionately large fraction of pan-arctic soil carbon, present an alternate trajectory. Field and laboratory observations indicate that talik (perennially thawed soils in permafrost) development in unsaturated Yedoma uplands leads to unexpectedly large methane emissions (35–78 mg m −2 d −1 summer, 150–180 mg m −2 d −1 winter). Upland Yedoma talik emissions were nearly three times higher annually than northern-wetland emissions on an areal basis. Approximately 70% emissions occurred in winter, when surface-soil freezing abated methanotrophy, enhancing methane escape from the talik. Remote sensing and numerical modeling indicate the potential for widespread upland talik formation across the pan-arctic Yedoma domain during the 21 st and 22 nd centuries. Contrary to current climate model predictions, these findings imply a positive and much larger permafrost-methane-climate feedback for upland Yedoma.
Gaseous elemental mercury (GEM), particulate mercury (PHg) and reactive gaseous mercury (RGM) were measured every other hour at a rural location in south central Wisconsin (Devil's Lake State Park, WI, USA) between April 2003 and March 2004, and at a predominantly downwind urban site in southeastern Wisconsin (Milwaukee, WI, USA) between June 2004 and May 2005. Annual averages of GEM, PHg, and RGM at the urban site were statistically higher than those measured at the rural site. Pollution roses of GEM and reactive mercury (RM; sum of PHg and RGM) at the rural and urban sites revealed the influences of point source emissions in surrounding counties that were consistent with the US EPA 1999 National Emission Inventory and the 2003-2005 US EPA Toxics Release Inventory. Source-receptor relationships at both sites were studied by quantifying the impacts of point sources on mercury concentrations. Time series of GEM, PHg, and RGM concentrations were sorted into two categories; time periods dominated by impacts from point sources, and time periods dominated by mercury from non-point sources. The analysis revealed average point source contributions to GEM, PHg, and RGM concentration measurements to be significant over the year long studies. At the rural site, contributions to annual average concentrations were: GEM (2%; 0.04 ng m-3); and, RM (48%; 5.7 pg m-3). At the urban site, contributions to annual average concentrations were: GEM (33%; 0.81 ng m-3); and, RM (64%; 13.8 pg m-3). ?? The Royal Society of Chemistry.
Root growth and physiological responses to elevated CO 2 were investigated for three important Mojave Desert grasses: the C 3 perennial Achnatherum hymenoides , the C 4 perennial Pleuraphis rigida and the C 3 annual Bromus madritensis ssp. rubens . Seeds of each species were grown at ambient (360 μl l −1 ) or elevated (1000 μl l −1 ) CO 2 in a glasshouse and harvested at three phenological stages: vegetative, anthesis and seed fill. Because P. rigida did not flower during the course of this study, harvests for this species represent three vegetative stages. Primary productivity was increased in both C 3 grasses in response to elevated CO 2 (40 and 19% for A. hymenoides and B. rubens , respectively), but root biomass increased only in the C 3 perennial grass. Neither above-ground nor below-ground biomass of the C 4 perennial grass was significantly affected by the CO 2 treatment. Elevated CO 2 did not significantly affect root surface area for any species. Total plant nitrogen was also not statistically different between CO 2 treatments for any species, indicating no enhanced uptake of N under elevated CO 2 . Physiological uptake capacities for NO 3 and NH 4 were not affected by the CO 2 treatment during the second harvest; measurements were not made for the first harvest. However, at the third harvest uptake capacity was significantly decreased in response to elevated CO 2 for at least one N form in each species. NO 3 uptake rates were lower in A. hymenoides and P. rigida , and NH 4 uptake rates were lower in B. rubens at elevated CO 2 . Nitrogen uptake on a whole root-system basis (NO 3 +NH 4 uptake capacity × root biomass) was influenced positively by elevated CO 2 only for A. hymenoides after anthesis. These results suggest that elevated CO 2 may result in a competitive advantage for A. hymenoides relative to species that do not increase root-system N uptake capacity. Root respiration measurements normalized to 20 °C were not significantly affected by the CO 2 treatment. However, specific root respiration was significantly correlated with either root C∶N ratio or root water content when all data per species were included within a simple regression model. The results of this study provide little evidence for up-regulation of root physiology in response to elevated CO 2 and indicate that root biomass responses to CO 2 are species-specific.
Two Amerindian demographic shifts are attributed to climate change in the northwest plains of North America: at ???11,000 calendar years before present (yr BP), Amerindian culture apparently split into foothills-mountains vs. plains biomes; and from 8,000-5,000 yr BP, scarce archaeological sites on the open plains suggest emigration during xeric "Altithermal" conditions. We reconstructed paleoclimates from stable isotopes in prehistoric bison bone and relations between weather and fractions of C4 plants in forage. Further, we developed a climate-change model that synthesized stable isotope, existing qualitative evidence (e.g., palynological, erosional), and global climate mechanisms affecting this midlatitude region. Our isotope data indicate significant warming from ???12,400 to 11,900 yr BP, supporting climate-driven cultural separation. However, isotope evidence of apparently wet, warm conditions at 7,300 yr BP refutes emigration to avoid xeric conditions. Scarcity of archaeological sites is best explained by rapid climate fluctuations after catastrophic draining of the Laurentide Lakes, which disrupted North Atlantic Deep Water production and subsequently altered monsoonal inputs to the open plains.
The solubilities in the system CaSO 4 - NaCl -H 2 O, at 1 atm pressure and 35° , 50° , and 70°C, have been determined by approaching the solubility curves from both the undersaturation and supersaturation sides. The experimental runs are of long duration, as much as 3 months; these rates should be commensurate with those of the appropriate geological processes, and so the results should be directly applicable to the interpretation of evaporite deposits.
10.1111/j.1752-1688.1997.tb04104.x
Experiments at 700°C and 800 bars total pressure demonstrate positive deviations from ideality for mixtures of hydrogen and H 2 O gases. The deviations are greater than predicted with Stockmayer's method. The composition of the mixture and the fugacity of hydrogen are controlled by diffusing hydrogen through metallic membranes. The results give the fugacities of both H 2 O and oxygen.