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.     

Evaluation of toxicity in tributaries of the Mersey estuary using the isopod Asellus aquaticus (L.)

Increasing numbers of industrial, agricultural and natural chemicals are present in sewage effluent and are known to elicit toxic effects in laboratory exposures, but little is known of their combined sub-lethal effect in the field. In this study, a combination of esterase activity and ventilation rate assays was performed to determine the neurological and physiological function of the freshwater crustacean Asellus aquaticus (L.) at sites above and below a sewage treatment works (STW). Cholinesterase and carboxylesterase activities were significantly inhibited (n=8, P<0.05) and ventilation rates increased (n=8, P=0.0001) in A. aquaticus at STW sites compared to those from reference sites, indicating a decrease in neurological and physiological function. The ecological relevance of these findings for the population dynamics of the organisms in the field is discussed.     

Thermodynamic characterization of the partitioning of iron between soluble and colloidal species in the Atlantic Ocean

Recent electrochemical measurements have shown that iron (Fe) speciation in seawater is dominated by complexation with strong organic ligands throughout the water column and have provided important thermodynamic information about these compounds. Independent work has shown that iron exists in both soluble and colloidal fractions in the Atlantic Ocean. Here we have combined these approaches in samples collected from a variety of regimes within the Atlantic Ocean. We measured the partitioning of Fe between soluble (< 0.02 μm) and colloidal (0.02 to 0.4 μm) size classes and characterized the concentrations and conditional stability constants of Fe ligands within these size classes. Results suggest that equilibrium partitioning of Fe between soluble and colloidal ligands is partially responsible for the distribution of Fe between soluble and colloidal size classes. However, a significant fraction of the colloidal Fe was inert to ligand exchange as soluble Fe concentrations were generally lower than values predicted by a simple equilibrium partitioning model.In surface waters, strong ligands with conditional stability constants of 10¹³ relative to total inorganic Fe appeared to dominate speciation in both the soluble and colloidal fractions. In deep waters these ligands were absent, and instead we found ligands with stability constants 12–15 fold smaller that were predominantly in the soluble pool. Nevertheless, significant levels of colloidal Fe were found in these samples, which we inferred must be inert to coordination exchange.     

Thermodynamic data from redox reactions at high temperatures. IV. Calibration of the Re-ReO2 oxygen buffer from EMF and NiO+Ni-Pd redox sensor measurements

The chemical potential of oxygen defined by the equilibrium:

Reservoir timescales for anthropogenic CO2 in the atmosphere

Non-steady state timescales are complicated and their application to specific geophysical systems requires a common theoretical foundation. We first extend reservoir theory by quantifying the difference between turnover time and transit time (or residence time) for time-dependent systems under any mixing conditions. We explicitly demonstrate the errors which result from assuming these timescales are equal, which is only true at steady state. We also derive a new response function which allows the calculation of age distributions and timescales for well-mixed reservoirs away from steady state, and differentiate between timescales based on gross and net fluxes. These theoretical results are particularly important to tracer-calibrated "box models" currently used to study the carbon cycle, which usually approximate reservoirs as well-mixed. We then apply the results to the important case of anthropogenic CO2 in the atmosphere, since timescales describing its behavior are commonly used but ambiguously defined. All relevant timescales, including lifetime, transit time, and adjustment time, are precisely defined and calculated from data and models. Apparent discrepancies between the current, empirically determined turnover time of 30-60 years and longer model-derived estimates of expected lifetime and adjustment time are explained within this theoretical framework. We also discuss the results in light of policy issues related to global warming, in particular since any comparisons of the "lifetimes" of different greenhouse gases (CO2, CH4, N2O, CFC's etc.) must use a consistent definition to be meaningful.     

Thermodynamic data from redox reactions at high temperatures. II. The MnO-0Mn3O4 oxygen buffer,and implications for the thermodynamic properties of MnO and Mn3O4

The \(\mu _{O_2 } \) defined by the reaction 6 MnO+O₂ =2 Mn₃O₄ has been determined from 917 to 1,433 K using electrochemical cells (with calcia-stabilized zirconta, CSZ) of the type: Steady emfs were achieved rapidly at all temperatures on both increasing and decreasing temperature, indicating that the MnO-Mn₃O₄ oxygen buffer equilibrates relatively easily. It therefore makes a useful alternative choice in experimental petrology to Fe₂O₃-Fe₃O₄ for buffering oxygen potentials at oxidized values. The results are (in J/mol, temperature in K, reference pressure 1 bar); \(\mu _{O_2 } \) (±200)=-563,241+1,761.758T-220.490T inT+0.101819T ² with an uncertainty of ±200 J/mol. Third law analysis of these data, including a correction for the deviations in stoichiometry of MnO, impliesS _298.15 for Mn₃O₄ of 166.6 J/K · mol, which is 2.5 J/K · mol higher than the calorimetric determination of Robie and Hemingway (1985). The low value of the calorimetric entropy may be due to incomplete ordering of the magnetic spins. The third law value of Δ _r H _298.15 ⁰ is-450.09 kJ/mol, which is significantly different from the calorimetric value of-457.5±3.4 kJ/mol, calculated from Δ _f H _298.15 ⁰ of MnO and Mn₃O₄, implying a small error in one or both of these latter.