Journal of Geophysical Research Atmospheres

The Mars Environmental Compatibility Assessment (MECA) instrument was designed, built, and flight qualified for the now canceled MSP (Mars Surveyor Program) '01 Lander. The MECA package consisted of a microscope, electrometer, material patch plates, and a wet chemistry laboratory (WCL). The primary goal of MECA was to analyze the Martian soil (regolith) for possible hazards to future astronauts and to provide a better understanding of Martian regolith geochemistry. The purpose of the WCL was to analyze for a range of soluble ionic chemical species and electrochemical parameters. The heart of the WCL was a sensor array of electrochemically based ion-selective electrodes (ISE). After 20 months storage at -23 degrees C and subsequent extended freeze/thawing cycles, WCL sensors were evaluated to determine both their physical durability and analytical responses. A fractional factorial calibration of the sensors was used to obtain slope, intercept, and all necessary selectivity coefficients simultaneously for selected ISEs. This calibration was used to model five cation and three anion sensors. These data were subsequently used to determine concentrations of several ions in two soil leachate simulants (based on terrestrial seawater and hypothesized Mars brine) and four actual soil samples. The WCL results were compared to simulant and soil samples using ion chromatography and inductively coupled plasma optical emission spectroscopy. The results showed that flight qualification and prolonged low-temperature storage conditions had minimal effects on the sensors. In addition, the analytical optimization method provided quantitative and qualitative data that could be used to accurately identify the chemical composition of the simulants and soils. The WCL has the ability to provide data that can be used to "read" the chemical, geological, and climatic history of Mars, as well as the potential habitability of its regolith.

We use a Monte Carlo model to simulate impact histories of possible Titans, Callistos, and Ganymedes. Comets create or erode satellite atmospheres, depending on their mass and velocity distributions: faster and bigger comets remove atmophiles; slower or smaller comets supply them. Mass distributions and the minimum total mass of comets passing through the Saturn system were derived from the crater records of Rhea and Iapetus. These were then scaled to give a minimum impact history for Titan. From this cometary population, of 1000 initially airless Titans, 16% acquired atmospheres larger than Titan's present atmosphere (9 x 10(21) g), and more than half accumulated atmospheres larger than 10(21) g. In contrasts to the work of Zahnle et al. (1992), we find that, in most trials, Callisto acquires comet-based atmospheres. Atmospheres acquired by Callisto and, especially, Ganymede are sensitive to assumptions regarding energy partitioning into the ejecta plume. If we assume that only the normal velocity component heats the plume, the majority of Ganymedes and half of the Callistos accreted atmospheres smaller than 10(20) g. If all the impactor's velocity heats the plume, Callisto's most likely atmosphere is 10(17) g and Ganymede's is negligible. The true cometary flux was most likely larger than that derived from crater records, which raises the probability that Titan, Ganymede, and Callisto acquired substantial atmospheres. However, other loss processes (e.g., sputtering by ions swept up by the planetary magnetic field, solar UV photolysis of hydrocarbons) are potentially capable of eliminating small atmospheres over the age of the solar system. The dark material on Callisto's surface may be a remnant of an earlier, now vanished atmosphere.

A 7 % gradient in the delta 13C of suspended particulate organic matter (POM) was observed in samples taken during two transects across the Drake Passage during March 1986. This POM delta 13C transition from -23.2 % at 53.3 degrees S to values as low as -30.3 % at > 62 degrees S does not track previously reported abrupt changes in water chemistry and plankton species composition associated with the Polar Front Zone that resides at approximately 58 degrees S in this region. Also, the north-south isotopic trend is not accompanied by significant changes in POM carbon or nitrogen concentrations, or in POM C/N. Differences in plankton standing crop or biochemistry (e.g., lipid content) therefore do not appear responsible for the isotopic trends observed. The latitudinal change in POM delta 13C is, however, highly correlated with water temperature and with the calculated concentration of CO2 (aq) at equilibrium with atmospheric CO2. These observations are consistent with the hypothesis that [CO2 (aq)] significantly influences POM delta 13C in ocean surface waters.

Using the California Institute of Technology/Jet Propulsion Laboratory two-dimensional transport model, with transport coefficients taken from Yang and Tung (1989), we study the time evolution of excess carbon 14 in the stratosphere and the troposphere from October, 1963 to December, 1966. The model provides a satisfactory simulation of the observed data. Due to the impulsive nature of its source, initial distributions of excess carbon 14 exhibit large spatial gradients. This permits important constraints on the range of transport coefficients in the lower stratosphere to be derived. The standard model uses the circulation and eddy diffusivity of the year 1980. Large deviations (by factor of 2) from this standard transport are ruled out by our model. A self-consistently derived Kyy which is small (approximately 10(9) cm2 s-1) in tropical regions, but is larger (approximately 10(10) cm2 s-1) at higher latitudes is preferred. A Kzz as large as 1 x 10(4) cm2 s-1 would be inconsistent with the data. Excess carbon 14 is removed from the atmosphere with surface deposition velocities vS = 3 x 10(-3) cm s-1 and vN = 5 x 10(-3) cm s-1 in the southern and northern hemispheres, respectively. The last result is contrary to the current understanding that the oceans are the dominant sink for excess 14C.

The role of cyanoacetylene (HC3N) in the atmospheric photochemistry of Titan and its relevance to polymer formation are discussed. Investigation of the relative light absorption of HC3N, acetylene (C2H2), and diacetylene (C4H2) revealed that HC3N is an important absorber of UV light in the 205- to 225-nanometer wavelength region in Titan's polar regions. Laboratory studies established that photolysis of C2H2 initiates the polymerization of HC3N even though the HC3N is not absorbing the UV light. Quantum yield measurements establish that HC3N is 2-5 times as reactive as C2H2 for polymer formation. Photolysis of HC3N with 185-nanometer light in the presence of N2, H2, Ar, or CF4 results in a decrease in the yield of 1,3,5-tricyanobenzene (1,3,5-tcb), while photolysis in the presence of CH4, C2H6, or n-C4H10 results in an increase in 1,3,5-tcb. The rate of loss of HC3N is increased by all gases except H2, where it is unchanged. It was not possible to detect 1,3,5-tcb as a photoproduct when the partial pressure of HC3N was decreased to 1 torr. Photolysis of HC3N with 254-nanometer light in the presence of H2 or N2 results in the formation of 1,2,4-tcb, while photolysis in the presence of CH4, C2H6, or n-C4H10 results in the formation of increasing amounts of 1,3,5-tcb. Mechanisms for the formation of polymers are presented.

Referenced to calender year 1981.0 and assuming a sinusoidal seasonal cycle superimposed on a linear total column increase with time, HF and HCl increase rates of (10.9±1.1)% yr-1 and (5.1±0.7)% yr-1 and total columns of (3.17±0.11) × 1014 and (1.92±0.06) × 1015 molecules cm-2 (2 sigma) are derived, respectively; the corresponding best fit mean exponential increase rates are equal to (7.6±0.6)% yr-1 and (4.2±0.5)% yr-1 (2 sigma). Over the 13-year observing period, the HF and HCl total columns increased by factors of 3.2 and 1.8, respectively. Based on HF and HCl total columns deduced from measurements on the same day, the HF/HCl total columns ratio increased from 0.14 in May 1977 to 0.23 in June 1990. -from Authors

A new wavelength-dependent model of the single-scattering properties of the Martian dust is presented. The model encompasses the solar wavelengths (0.3 to 4.3 micrometers at 0.02 micrometer resolution) and does not assume a particular mineralogical composition of the particles. We use the particle size distribution, shape, and single-scattering properties at Viking Lander wavelengths presented by Pollack et al. [1995]. We expand the wavelength range of the aerosol model by assuming that the atmospheric dust complex index of refraction is the same as that of dust particles in the bright surface geologic units. The new wavelength-dependent model is compared to observations taken by the Viking Orbiter Infrared Thermal Mapper solar channel instrument during two dust storms. The model accurately matches afternoon observations and some morning observations. Some of the early morning observations are much brighter than the model results. The increased reflectance can be ascribed to the formation of a water ice shell around the dust particles, thus creating the water ice clouds which Colburn et al. [1989], among others, have predicted.

A one-dimensional photochemical model has been used to estimate the flux of dissolved hydrogen peroxide (H2O2) and of other soluble species in rainwater as a function of atmospheric oxygen level. H2O2 should have replaced O2 as the dominant oxidant in rainwater at oxygen levels below 10(-3)-10(-2) times the present atmospheric level (PAL). The exact value of pO2 at which H2O2 becomes more important than O2 depends on the abundance of trace gases such as CO, CH4, and NO. H2O2 was probably an important oxidant even in an O2-free atmosphere, provided that CO2 levels were significant higher than today's. In model atmospheres containing free O2 the concentration of photochemically produced oxidants generally exceeds that of photochemically produced reductants. The oxidizing power of rainwater is therefore greater than that due to dissolved molecular O2 alone. The difference is small at present but becomes important at O2 levels less than 10(-3) PAL. At O2 levels between 10(-4) and 10(-5) PAL the oxidizing power of rainwater is almost independent of pO2. Precambrian soils in which a part or all of the Fe2+ in their source rocks has been oxidized to Fe3+ could therefore have developed in the presence of an atmosphere with very low values of pO2. On the other hand, the upper limit for pO2 during early and mid-Precambrian time suggested by the incomplete oxidation of FeO in soils developed on basaltic rocks is affected only slightly by the presence of photochemical products in rainwater.

Extensive testing of the advective scheme, proposed by Prather (1986), has been carried out in support of the California Institute of Technology-Jet Propulsion Laboratory two-dimensional model of the middle atmosphere. We generalize the original scheme to include higher-order moments. In addition, we show how well the scheme works in the presence of chemistry as well as eddy diffusion. Six types of numerical experiments including simple clock motion and pure advection in two dimensions have been investigated in detail. By comparison with analytic solutions it is shown that the new algorithm can faithfully preserve concentration profiles, has essentially no numerical diffusion, and is superior to a typical fourth-order finite difference scheme.

The presence of a stratospheric haze layer may produce increases in both the actinic flux and the irradiance below this layer. Such haze layers result from the injection of aerosol-forming material into the stratosphere by volcanic eruptions. Simple heuristic arguments show that the increase in flux below the haze layer, relative to a clear sky case, is a consequence of "photon trapping." We explore the magnitude of these flux perturbations, as a function of aerosol properties and illumination conditions, with a new radiative transfer model that can accurately compute fluxes in an inhomogenous atmosphere with nonconservative scatterers having arbitrary phase function. One calculated consequence of the El Chichon volcanic eruption is an increase in the midday surface actinic flux at 20 degrees N latitude, summer, by as much as 45% at 2900 angstroms. This increase in flux in the UV-B wavelength range was caused entirely by aerosol scattering, without any reduction in the overhead ozone column.

Correlative aerosol measurements taken at a limited number of altitudes during coordinated field experiments are used to test the validity of particulate extinction coefficients derived from limb path solar radiance measurements taken by the Stratospheric Aerosol and Gas Experiment (SAGE) II Sun photometer. In particular, results are presented from correlative measurement missions that were conducted during January 1985, August 1985, and July 1986. Correlative sensors included impactors, laser spectrometers, and filter samplers aboard an U-2-airplane, an upward pointing lidar aboard a P-3 airplane, and balloon-borne optical particle counters (dustsondes). The main body of this paper focuses on the July 29, 1986, validation experiment, which minimized the many difficulties (e.g., spatial and temporal inhomogeneities, imperfect coincidences) that can complicate the validation process. On this day, correlative aerosol measurements taken at an altitude of 20.5 km agreed with each other within their respective uncertainties, and particulate extinction values calculated at SAGE II wavelengths from these measurements validated corresponding SAGE II values. Additional validation efforts on days when measurement and logistical conditions were much less favorable for validation are discussed in an appendix.

This paper describes an investigation of the comprehensive aerosol correlative measurement experiments conducted between November 1984 and July 1986 for satellite measurement program of the Stratospheric Aerosol and Gas Experiment (SAGE II). The correlative sensors involved in the experiments consist of the NASA Ames Research Center impactor/laser probe, the University of Wyoming dustsonde, and the NASA Langley Research Center airborne 14-inch (36 cm) lidar system. The approach of the analysis is to compare the primary aerosol quantities measured by the ground-based instruments with the calculated ones based on the aerosol size distributions retrieved from the SAGE II aerosol extinction measurements. The analysis shows that the aerosol size distributions derived from the SAGE II observations agree qualitatively with the in situ measurements made by the impactor/laser probe. The SAGE II-derived vertical distributions of the ratio N0.15/N0.25 (where Nr is the cumulative aerosol concentration for particle radii greater than r, in micrometers) and the aerosol backscatter profiles at 0.532- and 0.6943-micrometer lidar wavelengths are shown to agree with the dustsonde and the 14-inch (36-cm) lidar observations, with the differences being within the respective uncertainties of the SAGE II and the other instruments.

Optical constants n and k are measured for thin hydrocarbon films produced from charged particles (RF plasma) irradiation of (1) 100% CH4; (2) 7% CH4, 93% H2; (3) 0.5% CH4, 99.5% H2; (4) 0.0002% CH4, 99.3% H2 (with impurities); and (5) 3 to 25% CH4, 25% He, remainder H2--all at submillibar pressures. In all experiments, yellow to deep brown-red solid products are synthesized which are hypothesized to be, at least in part, the unidentified visible and near-UV chromophores in the stratospheres of Uranus and Neptune. Results for experiments 2, 3, and 4 are in good mutual accord, but are significantly different from experiments 1 and 5. He in the precursor gases affects the product composition. Typical solid products for experiments 5 show, at 0.55 micrometer wavelength, n = 1.60 +/- 0.05, 3 x 10(-2) > or = k > or = 3 x 10(-3), and [C/H] approximately equal to 0.7. These results are, for n and k respectively, consistent with and in excellent agreement with those derived from high phase angle Voyager 2 photometry of Uranus (Pollack et al., this issue). Aerosols produced directly from the atmosphere by precipitating magnetospheric charged particles may be competitive with those produced by UV and charged particle irradiation of simple hydrocarbon condensates. The optical and chemical properties of aerosols in the Uranian and Neptunian atmospheres may evolve toward higher values of n and k and higher carbon content as the particles sediment through changing radiation and thermal environments.

In this paper we consider design of instruments for collection of aerosols during entry in Titan's atmosphere. Major constraints on designs are small sample collection time, low aerosol column density, and the need to collect 1-10 micrograms of aerosol for gas chromatographic analysis. Thus it is important to maximize aerosol collection through collector design, which includes consideration of various types of collectors and maximizing the collection efficiency of a given type of collector. Sampling systems discussed include inertial impactors, filters, electrostatic devices, and multistage instruments. Aerosol sampling is reviewed in the context of high-altitude (200-70 km) and low-altitude (60-30 km) regions of Titan's atmosphere.

During the next decade or so, NASA, in conjunction with the European Space Agency, plans to send a spacecraft to the Saturnian system so that local studies of Saturn and its satellite, Titan, can be made. In order to study the atmosphere of Titan, analysis of both aerosols and gases will have to be made. To accomplish this, gas chromatographic instrumentation for the collection and analysis of organic gases and aerosols in Titan's atmosphere is being developed. The aerosols will be collected and then subjected to pyrolysis-gas chromatography. Results using a simple pyrolysis-GC system and tholin, made by subjecting a nominal Titan mixture (96.8% N2, 3% CH4, 0.2% H2) to laser-supported shocks, show that many compounds, including hydrocarbons and simple nitriles, can be identified by this technique. Atmospheric gases will be collected using large volume (>10 cm3) sample loops and then analyzed by gas chromatography. Large volume samples are required because the ambient pressures, where the probe instruments are first deployed, will be low (<10 mbar). Preliminary studies using a 20 cm3 sampling system and a very sensitive meta-stable ionization detector show that hydrocarbon components at the 10 ppb level can be detected. Work will continue to improve GC sensitivity, minimize analysis time, and develop interfaces with suitable sample collectors for analysis of atmospheres by future spacecraft.

We examine the consequences of the eruption of the El Chichon volcano on the Earth's stratospheric chemistry. The results of a one-dimensional radiative transfer model show that the total radiation increased by 8% within the aerosol layer longward of 3000 Å. Consequently, there are changes in the photolysis rates obtained with a one-dimensional photochemical model: for example, O2 photodissociation rate constants decrease by 10%, while O3 photodissociation rate constants increase by a comparable amount. The combined radiative and thermal perturbations on the concentrations of O, O(1D), OH, HO2, H2O2, NO, NO2, NO3, N2O5, HNO3, HO2NO2, Cl, ClO, ClO2, HOCl, ClNO3, and HCl are computed and presented in detail. However, these changes as calculated are insufficient to explain the observations of significant decreases in NO and NO2 and increases in HCl. -from Authors

Several theories have been proposed to explain the development of harmful algal blooms (HABs) produced by the toxic dinoflagellate Karenia brevis on the West Florida Shelf. However, because the early stages of HAB development are usually not detected, these theories have been so far very difficult to verify. In this paper we employ simulated Lagrangian coherent structures (LCSs) to trace potential early locations of the development of a HAB in late 2004 before it was transported to a region where it could be detected by satellite imagery. The LCSs, which are extracted from surface ocean currents produced by a data-assimilative HYCOM (HYbrid-Coordinate Ocean Model) simulation, constitute material fluid barriers that demarcate potential pathways for HAB evolution. Using a simplified population dynamics model we infer the factors that could possibly lead to the development of the HAB in question. The population dynamics model determines nitrogen in two components, nutrients and phytoplankton, which are assumed to be passively advected by surface ocean currents produced by the above HYCOM simulation. Two nutrient sources are inferred for the HAB whose evolution is found to be strongly tied to the simulated LCSs. These nutrient sources are found to be located nearshore and possibly due to land runoff.

A simple analytic model for the catastrophic disruption and deceleration of impactors in a thick atmosphere is used to (1) reproduce observed Venusian cratering statistics and (2) generate radar-dark disks by the impact of atmospheric shock waves with the surface. When used as input to Monte Carlo simulations of Venusian cratering, the model nicely reproduces the observed low diameter cutoff. Venusian craters are found to be more consistent with an asteroidal rather than a cometary source. The radar-dark "shadows" of the title are surface features, usually circular, that have been attributed to airbursting impactors. A typical craterless airburst is the equivalent of a approximately 10(6) megaton explosion. The airburst is treated as a massive, extended explosion using a thin-shell, isobaric cavity approximation. The strong atmospheric shock waves excited by the airbust are then coupled to surface rock using the usual impedance matching conditions. Peak shock pressures experienced by surface rock typically exceed 0.2 GPa for distances 15-30 km from ground zero (the place on the surface immediately beneath the site of the airburst), and 1 GPa for 10-20 km. These high shock pressures are felt to considerable depth, often more than a kilometer. Beneath the airburst the shock could reduce surface rocks to fine rubble, while at greater distance the weaker shock would leave fields of broken blocks, perhaps in part accounting for radar-bright halos that often surround the dark shadows.

High-temperature models for origin of the carbonates in Martian meteorite ALH84001 are implausible. The impact metasomatism model, invoking reaction between CO2 rich fluid and the host orthopyroxenite, requires conversion of olivine into orthopyroxene, yet olivine in ALH84001 shows no depletion in carbonate-rich areas; or else conversion of orthopyroxene into silica, which should have yielded a higher silica/carbonate ratio. The impact melt model implies that the fracture-linked carbonates, as products of melt injection, should appear as continuous planar veins, but in many areas they do not. Both vapor deposition and impact melting seem inconsistent with the zoned poikilotopic texture of many large carbonates. The popular hydrothermal model is inconsistent with the virtual absence of secondary hydrated silicates in ALH84001. Prior brecciation should have facilitated alteration. Hydrothermal fluids would be warm, and rate of hydration of mafic silicates obeys an Arrhenius law, at least up to approximately 100 degrees C. Most important, hydrothermal episodes tend to last for many years. Many areas of the ancient Martian crust show evidence for massive flooding. I propose that the carbonates formed as evaporite deposits from floodwaters that percolated through the fractures of ALH84001, but only briefly, as evaporation and groundwater flow caused the water table to quickly recede beneath the level of this rock during the later stages of the flood episode. The setting might have been a layer of megaregolith beneath a surface catchment of pooled floodwater, analogous to a playa lake. Carbonate precipitation would occur in response to evaporative concentration of the water. To explain the scarcity of sulfates in ALH84001, the water table must be assumed to recede quickly relative to the rate of evaporation. During the period when ALH84001 was above the water table, evaporation would have slowed, as the evaporation front passed beneath the surface of the debris layer, and possibly earlier, if the shrinking pool of surface water developed a porous sulfate crust. Alternatively, ALH84001 may have developed as a Martian form of calcrete, i.e., the evaporating flood(s) may have been entirely below ground as it (they) passed slowly through ALH84001. The greatest advantage of the flood evaporite model is that it exposes ALH84001 to carbonate precipitation without prolonged exposure to aqueous alteration. The model also seems consistent with the heavy and extremely heterogeneous oxygen isotopic compositions of the carbonates. However, this hypothesis seems no more than marginally consistent with the suggestion of McKay et al. [1996] that the carbonates are biogenic.

A review of the mineralogical, isotopic, and chemical properties of the carbonates and associated submicrometer iron oxides and sulfides in Martian meteorite ALH84001 provides minimal evidence for microbial activity. Some magnetites resemble those formed by magnetotactic microorganisms but cubic crystals <50 nm in size and elongated grains <25 nm long are too small to be single-domain magnets and are probably abiogenic. Magnetites with shapes that are clearly unique to magnetotactic bacteria appear to be absent in ALH84001. Magnetosomes have not been reported in plutonic rocks and are unlikely to have been transported in fluids through fractures and uniformly deposited where abiogenic magnetite was forming epitaxially on carbonate. Submicrometer sulfides and magnetites probably formed during shock heating. Carbonates have correlated variations in Ca, Mg, and 18O/16O, magnetite-rich rims, and they appear to be embedded in pyroxene and plagiociase glass. Carbonates with these features have not been identified in carbonaceous chondrites and terrestrial rocks, suggesting that the ALH84001 carbonates have a unique origin. Carbonates and hydrated minerals in ALH84001, like secondary phases in other Martian meteorites, have O and H isotopic ratios favoring formation from fluids that exchanged with the Martian atmosphere. I propose that carbonates originally formed in ALH84001 from aqueous fluids and were subsequently shock heated and vaporized. The original carbonates were probably dolomite-magnesite-siderite assemblages that formed in pores at interstitial sites with minor sulfate, chloride, and phyllosilicates. These phases, like many other volatile-rich phases in Martian meteorites, may have formed as evaporate deposits from intermittent floods.

Spectral and other physicochemical properties were determined for a suite of submicron powders of hematite (alpha-Fe2O3), maghemite (gamma-Fe2O3), magnetite (Fe3O4), goethite (alpha-FeOOH), and lepidocrocite (gamma-FeOOH). The spectral reflectivity measurements were made between 0.35 and 2.20 micrograms over the temperature interval between about -110 degrees and 20 degrees C. Other physicochemical properties determined were mean particle diameter, particle shape, chemical composition, crystallographic phase, magnetic properties, and Mossbauer properties. Only the magnetite powders have significant departures from the stoichiometric phase; they are actually cation-deficient magnetites having down to about 18.0 wt % FeO as compared with 31.0 wt % FeO for stoichiometric magnetite. A structured absorption edge due to crystal field transitions and extending from weak absorption in the near-IR to intense absorption in the near-UV is characteristic of the ferric oxides and oxyhydroxides and is responsible for their intense color. Particularly for hematite, the number and position of the spectral features are consistent with significant splitting of the degenerate cubic levels by noncubic components of the crystal field. The position of the crystal-field band at lowest energy, assigned to the envelope of the components of the split cubic 4T1 level, is near 0.86, 0.91, 0.92, and 0.98 microgram at room temperature for hematite, goethite, maghemite, and lepidocrocite, respectively. Comparison with Mossbauer data suggests covalent character increases sequentially through the aforementioned series. The positions of the spectra features are relatively independent of temperature down to about -110 degrees C. The maximum shifts observed were on the order of about 0.02 microgram shortward for the ferric oxyhydroxides. Variations in the magnitude of the reflectivity of the hematite powders as a function of mean particle diameter are consistent with scattering theory. The absorption strength of the crystal-field bands increases with increasing mean particle diameter over the range 0.1-0.8 micrometer; visually this corresponds to a change in color from orange to deep purple. The position of the split cubic 4T1 band shifts longward by about 0.02 micrometer with decreasing mean particle diameter over the same range; this trend is consistent with wavelength-dependent scattering. The cation-deficient magnetite powders are very strong absorbers throughout the near-UV, visible and near-IR; their spectral properties are independent of temperature between about -110 and 20 degrees C.

The effects of many environmental stressors such as UV radiation are mediated by dissolved organic matter (DOM) properties. Therefore, determining the factors shaping spatial and temporal patterns is particularly essential in the most susceptible, low dissolved organic carbon (DOC) lakes. We analyzed spatiotemporal variations in dissolved organic carbon concentration and dissolved organic matter optical properties (absorption and fluorescence) in 11 transparent lakes located above tree line in the Sierra Nevada Mountains (Spain), and we assessed potential external (evaporation and atmospheric deposition) and internal (bacterial abundance, bacterial production, chlorophyll a, and catchment vegetation) drivers of DOM patterns. At spatial and temporal scales, bacteria were related to chromophoric DOM (CDOM). At the temporal scale, water soluble organic carbon (WSOC) in dust deposition and evaporation were found to have a significant influence on DOC and CDOM in two Sierra Nevada lakes studied during the ice-free periods of 2000-2002. DOC concentrations and absorption coefficients at 320 nm were strongly correlated over the spatial scale (n = 11, R(2) = 0.86; p < 0.01), but inconsistently correlated over time, indicating seasonal and interannual variability in external factors and a differential response of DOC concentration and CDOM to these factors. At the continental scale, higher mean DOC concentrations and more CDOM in lakes of the Sierra Nevada than in lakes of the Pyrenees and Alps may be due to a combination of more extreme evaporation, and greater atmospheric dust deposition.

Determining the mineralogy of the Martian surface material provides information about the past and present environments on Mars which are an integral aspect of whether or not Mars was suitable for the origin of life. Mineral identification on Mars will most likely be achieved through visible-infrared remote sensing in combination with other analyses on landed missions. Therefore, understanding the visible and infrared spectral properties of terrestrial samples formed via processes similar to those thought to have occurred on Mars is essential to this effort and will facilitate site selection for future exobiology missions to Mars. Visible to infrared reflectance spectra are presented here for the fine-grained fractions of altered tephra/lava from the Haleakala summit basin on Maui, the Tarawera volcanic complex on the northern island of New Zealand, and the Greek Santorini island group. These samples exhibit a range of chemical and mineralogical compositions, where the primary minerals typically include plagioclase, pyroxene, hematite, and magnetite. The kind and abundance of weathering products varied substantially for these three sites due, in part, to the climate and weathering environment. The moist environments at Santorini and Tarawera are more consistent with postulated past environments on Mars, while the dry climate at the top of Haleakala is more consistent with the current Martian environment. Weathering of these tephra is evaluated by assessing changes in the leachable and immobile elements, and through detection of phyllosilicates and iron oxide/oxyhydroxide minerals. Identifying regions on Mars where phyllosilicates and many kinds of iron oxides/oxyhydroxides are present would imply the presence of water during alteration of the surface material. Tephra samples altered in the vicinity of cinder cones and steam vents contain higher abundances of phyllosilicates, iron oxides, and sulfates and may be interesting sites for exobiology.

Recent models of chaotic variation in the Martian obliquity suggest that CO2 could be released during times of high obliquity and then recaptured in the polar caps as ice or clathrate during times of lower obliquity (Jakosky, et al., 1995). A natural implication of clathrate trapping is that other species in the Martian atmosphere, including noble gases, must incorporate in the water ice structure as well, in varying amounts according to the size and polarizability of the molecules as well as their atmospheric abundances. For nominal estimates of cap volume and amount of incorporated CO2 , we find that the current atmospheric inventory of noble gases is not representative of the bulk inventory in the Martian surface-atmosphere system. In particular, xenon and krypton are underrepresented in the present atmosphere. Models of source regions for Martian volatiles, which are constrained by noble gas abundances, must be modified to take these fractionation effects into account if indeed evidence for large amounts of polar clathrates is found.

Light absorption and reflectance by smectite clays containing various adsorbed ions were measured in the UV, VIS, and NIR ranges and compared to Martian dust and surface soil spectra. Structural iron in the octahedral sheet of smectites is responsible for a characteristic absorption feature in the UV at 240-260 nm, resulting from an O2 --> Fe3+ charge transfer that is similar to one observed in the Martian spectrum. Adsorbed iron affects, via crystal field absorptions, the reflectance of montmorillonite in the VIS and NIR (to 1.3 micrometers), causing stronger absorption and higher opacity in the wavelength range 0.4-0.6 micrometer, without developing any specific pronounced absorption feature. In both general appearance and presence of, or lack of, spectral features, the iron-montmorillonite reflectance spectra in the VIS and NIR are similar to the Martian spectra. At present, however, spectral similarity cannot be used as the sole criterion for constraining Martian mineralogy since several other minerals, other than Fe-smectites, show sufficient similitude to the Martian spectra; other properties have to be explored and combined to obtain a definitive identification.

The immediate task facing exopaleontology is to define a strategy to explore Mars for a fossil record during the decade-long exploration program that lies ahead. Consideration of the quality of paleontological information preserved under different geological conditions is important if we are to develop a strategy with broad applicability. The preservation of microbial fossils is strongly influenced by the physical, chemical, and biological factors of the environment which, acting together, determine the types of information that will be captured and retained in the rock record. In detrital sedimentary systems, preservation is favored by rapid burial in fine-grained, clay-rich sediments. In chemical sedimentary systems, preservation is enhanced by rapid entombment in fine-grained chemical precipitates. For long-term preservation, host rocks must be composed of stable minerals that are resistant to chemical weathering and that form an impermeable matrix and closed chemical system to protect biosignatures from alteration during subsequent diagenesis or metamorphism. In this context, host rocks composed of highly ordered, chemically stable mineral phases, like silica (e.g., cherts) or phosphate (e.g., phosphorites), are especially favored. Such lithologies tend to have very long crustal residence times and, along with carbonates and shales, are the most common host rocks for the Precambrian microfossil record on Earth. Although we make the defensible assumption that Mars was more like the Earth early in its history, clearly, the geological and historical differences between the two planets are many. Such differences must be carefully considered when adapting an Earth-based strategy to Mars.

A portion of the secular change of the geomagnetic field leads to a drift of the trapped belt South Atlantic Anomaly (SAA). If this drift is not taken into account, models of the trapped particle population give erroneous predictions of particle fluxes. The dose rates measured on two manned spacecrafts, Skylab (50 degrees inclination x 438 km orbit) and Mir orbital station (51.65 degrees inclination x 400 km orbit), were used to determine the drift rate of the SAA. The longitude and latitude drift rates of the SAA as a whole, between 1973 and 1995, were estimated to be 0.28 +/- 0.03 degrees W per year, and 0.08 +/- 0.03 degrees N per year, respectively. These measurements are consistent with determinations made using the AP8 models for radiation trapped belts and are in excellent agreement with drift rates observed for the geomagnetic field.

Ozone column amounts obtained by the total ozone mapping spectrometer (TOMS) in the southern polar region are analyzed during late austral winter and spring (days 240-300) for 1980-1991 using area-mapping techniques and area-weighted vortex averages. The vortex here is defined using the -50 PVU (1 PVU = 1.0 x 10(-6) K kg-1 m2 s-1) contour on the 500 K isentropic surface. The principal results are: (1) there is a distinct change after 1985 in the vortex-averaged column ozone depletion rate during September and October, the period of maximum ozone loss, and (2) the vortex-averaged column ozone in late August (day 240) has dropped by 70 Dobson units (DU) in a decade due to the loss in the dark and the dilution effect. The mean ozone depletion rate in the vortex between day 240 and the day of minimum vortex-averaged ozone is about 1 DU d-1 at the beginning of the decade, increasing to about 1.8 DU d-1 by 1985, and then apparently saturating thereafter. The vortex-average column ozone during September and October has declined at the rate of 11.3 DU yr-1 (3.8%) from 1980 to 1987 (90 DU over 8 years) and at a smaller rate of 2 DU yr-1 (0.9%) from 1987 to 1991 (10 DU over 5 years, excluding the anomalous year 1988). We interpret the year-to-year trend in the ozone depletion rate during the earlier part of the decade as due to the rise of anthropogenic chlorine in the atmosphere. The slower trend at the end of the decade indicates saturation of ozone depletion in the vortex interior, in that chlorine amounts in the mid-1980s were already sufficiently high to deplete most of the ozone in air within the isolated regions of the lower-stratospheric polar vortex. In subsequent years, increases in stratospheric chlorine may have enhanced wintertime chemical loss of ozone in the south polar vortex even before major losses during the Antarctic spring.

We report results from 10 years of ice thickness measurements at perennially ice-covered Lake Hoare in southern Victoria Land, Antarctica. The ice cover of this lake had been thinning steadily at a rate exceeding 20 cm yr-1 during the last decade but seems to have recently stabilized at a thickness of 3.3 m. Data concerning lake level and degree-days above freezing are presented to show the relationship between peak summer temperatures and the volume of glacier-derived meltwater entering Lake Hoare each summer. From these latter data we infer that peak summer temperatures have been above 0 degrees C for a progressively longer period of time each year since 1972. We also consider possible explanations for the thinning of the lake ice. The thickness of the ice cover is determined by the balance between freezing during the winter and ablation that occurs all year but maximizes in summer. We suggest that the term most likely responsible for the change in the ice cover thickness at Lake Hoare is the extent of summer melting, consistent with the rising lake levels.

The possibility for abiotic synthesis of condensed hydrocarbons in cooling/diluting terrestrial volcanic gases has been evaluated on the basis of the consideration of metastable chemical equilibria involving gaseous CO, CO2, H2 and H2O. The stabilities of n-alkanes and polycyclic aromatic hydrocarbons (PAHS) have been evaluated for several typical volcanic gas compositions under various conditions for cooling/diluting of quenched volcanic gas. The modeling shows that n-alkanes and PAHs have a thermodynamic potential to form metastably from H2 and CO below approximately 250 degrees C within the stability field of graphite. Despite the predominance of CO2 in volcanic gases, synthesis of hydrocarbons from CO2 and H2 is less favored energetically than from CO and H2. Both low temperature and a high H/C atomic ratio in volcanic gas generally favor stability of hydrocarbons with higher H/C ratios. PAHs are thermodynamically stable at temperatures approximately 10 degrees -50 degrees C higher than large n-alkanes; however, at lower temperatures, PAHs and n-alkanes have similar stabilities and are likely to form metastable mixtures. Both the energetic drive to form hydrocarbons and possible temperatures of formation increase as the oxidation state (fO2) of the volcanic gases decreases and as the cooling/dilution ratios of volcanic gases increase. Synthesis of hydrocarbons is energetically more likely in cooling trapped gases than in ashcloud eruptive columns. Mechanisms for hydrocarbon formation may include Fischer-Tropsch-type synthesis catalyzed by magnetite from solid volcanic products. On the early Earth, Mars, and Jupiter's satellite Europa, several factors would have provided more favorable conditions for hydrocarbon synthesis in volcanic gases than under current terrestrial conditions and might have contributed to the production of organic compounds required for the emergence of life.

A comprehensive one-dimensional photochemical model extending from the middle atmosphere (50 km) to the exobase (432 km) has been used to study the escape of hydrogen and deuterium from the Earth's atmosphere. The model incorporates recent advances in chemical kinetics as well as atmospheric observations by satellites, especially the Atmosphere Explorer C satellite. The results suggest: (1) the escape fluxes of both H and D are limited by the upward transport of total hydrogen and total deuterium at the homopause (this result is known as Hunten's limiting flux theorem); (2) about one fourth of total hydrogen escape is thermal, the rest being nonthermal; (3) escape of D is nonthermal; and (4) charge exchange and polar wind are important mechanisms for the nonthermal escape of H and D, but other nonthermal mechanisms may be required. The efficiency to escape from the terrestrial atmosphere for D is 0.74 of the efficiency for H. If the difference between the D/H ratio measured in deep-sea tholeiite glass and that of standard sea water, delta D = -77%, were caused by the escape of H and D, we estimate that as much water as the equivalent of 36% of the present ocean might have been lost in the past.

The photochemistry of 32 neutral and 21 ion species in Triton's atmosphere is considered. Parent species N2, CH4, and CO (with a mixing ratio of 3 x 10(-4) in our basic model) sublime from the ice with rates of 40, 208, and 0.3 g/cm2/b.y., respectively. Chemistry below 50 km is driven mostly by photolysis of methane by the solar and interstellar medium Lyman-alpha photons, producing hydrocarbons C2H4, C2H6, and C2H2 which form haze particles with precipitation rates of 135, 28, and 1.3 g/cm2/b.y., respectively. Some processes are discussed which increase the production of HCN (by an order of magnitude to a value of 29 g/cm2/b.y.) and involve indirect photolysis of N2 by neutrals. Reanalysis of the measured methane profiles gives an eddy diffusion coefficient K = 4 x 10(3) cm2/s above the tropopause and a more accurate methane number density near the surface, (3.1 +/- 0.8) x 10(11) cm-3. Chemistry above 200 km is driven by the solar EUV radiation (lambda < 1000 angstroms) and by precipitation of magnetospheric electrons with a total energy input of 10(8) W (based on thermal balance calculations). The most abundant photochemical species are N, H2, H, O, and C. They escape with the total rates of 7.7 x 10(24) s-1, 4.5 x 10(25) s-1, 2.4 x 10(25) s-1, 4.4 x 10(22) s-1, and 1.1 x 10(24) s-1, respectively. Atomic species are transported to a region of 50-200 km and drive the chemistry there. Ionospheric chemistry explains the formation of an E region at 150-240 km with HCO+ as a major ion, and of an F region above 240 km with a peak at 320 km and C+ as a major ion. The ionosphere above 500 km consists of almost equal densities of C+ and N+ ions. The model profiles agree with the measured atomic nitrogen and electron density profiles. A number of other models with varying rate coefficients of some reactions, differing properties of the haze particles (chemically passive or active), etc., were developed. These models show that there are four basic unknown values which have strong impacts on the composition and structure of the atmosphere and ionosphere. These values and their plausible ranges are the CO mixing ratio fco = 10(-4)-10(-3), the magnetospheric electron energy input (1 +/- 0.5) x 10(8) W, the rate coefficient of charge-exchange reaction N2(+) + C k = 10(-11)-10(-10) cm3/s, and the ion escape velocity Vi approximately equal to 150 cm/s.

The Galileo probe mass spectrometer determined the composition of the Jovian atmosphere for species with masses between 2 and 150 amu from 0.5 to 21.1 bars. This paper presents the results of analysis of some of the constituents detected: H2, He, Ne, Ar, Kr, Xe, CH4, NH3, H2O, H2S, C2 and C3 nonmethane hydrocarbons, and possibly PH3 and Cl. 4He/H2 in the Jovian atmosphere was measured to be 0.157 +/- 0.030. 13C/C12 was found to be 0.0108 +/- 0.0005, and D/H and 3He/4He were measured. Ne was depleted, < or = 0.13 times solar, Ar < or = 1.7 solar, Kr < or = 5 solar, and Xe < or = 5 solar. CH4 has a constant mixing ratio of (2.1 +/- 0.4) x 10(-3) (12C, 2.9 solar), where the mixing ratio is relative to H2. Upper limits to the H2O mixing ratio rose from 8 x 10(-7) at pressures <3.8 bars to (5.6 +/- 2.5) x 10(-5) (16O, 0.033 +/- 0.015 solar) at 11.7 bars and, provisionally, about an order of magnitude larger at 18.7 bars. The mixing ratio of H2S was <10(-6) at pressures less than 3.8 bars but rose from about 0.7 x 10(-5) at 8.7 bars to about 7.7 x 10(-5) (32S, 2.5 solar) above 15 bars. Only very large upper limits to the NH3 mixing ratio have been set at present. If PH3 and Cl were present, their mixing ratios also increased with pressure. Species were detected at mass peaks appropriate for C2 and C3 hydrocarbons. It is not yet clear which of these were atmospheric constituents and which were instrumentally generated. These measurements imply (1) fractionation of 4He, (2) a local, altitude-dependent depletion of condensables, probably because the probe entered the descending arm of a circulation cell, (3) that icy planetesimals made significant contributions to the volatile inventory, and (4) a moderate decrease in D/H but no detectable change in (D + 3He)/H in this part of the galaxy during the past 4.6 Gyr.

Earth appears to have been warm during its early history despite the faintness of the young Sun. Greenhouse warming by gaseous CO2 and H2O by itself is in conflict with constraints on atmospheric CO2 levels derived from paleosols for early Earth. Here we explore whether greenhouse warming by methane could have been important. We find that a CH4 mixing ratio of 10(-4) (100 ppmv) or more in Earth's early atmosphere would provide agreement with the paleosol data from 2.8 Ga. Such a CH4 concentration could have been readily maintained by methanogenic bacteria, which are thought to have been an important component of the biota at that time. Elimination of the methane component of the greenhouse by oxidation of the atmosphere at about 2.3-2.4 Ga could have triggered the Earth's first widespread glaciation.

The role photochemical reactions in the early Earth's atmosphere played in the prebiotic synthesis of simple organic molecules was examined. We have extended an earlier calculation of formaldehyde production rates to more reduced carbon species, such as methanol, methane, and acetaldehyde. We have simulated the experimental results of Bar-Nun and Chang (1983) as an acid in the construction of our photochemical scheme and as a way of validating our model. Our results indicate that some fraction of CO2 and H2 present in the primitive atmosphere could have been converted to simple organic molecules. The exact amount is dependent on the partial pressure of CO2 and H2 in the atmosphere and on what assumptions are made concerning the shape of the absorption spectra of CO2 and H2O. In particular, the results are most sensitive to the presence or absence of absorption at wavelengths longward of 2000 angstroms. We also find that small quantities of CH4 could have been present in the prebiotic Earth's atmosphere as the result of the photoreduction of CO.

Atmospheric heavy ozone is enriched in the isotopes 18O and 17O. The magnitude of this enhancement, of the order of 100%, is very large compared with that commonly known in atmospheric chemistry and geochemistry. The heavy oxygen atom in heavy ozone is therefore useful as a tracer of chemical species and pathways that involve ozone or its derived products. As a test of the isotopic exchange reactions, we successfully carry out a series of numerical experiments to simulate the results of the laboratory experiments performed by Wen and Thiemens [1993] on ozone and CO2. A small discrepancy between the experimental and the model values for 17O exchange is also revealed. The results are used to compute the magnitude of isotopic exchange between ozone and carbon dioxide via the excited atom O(1D) in the middle atmosphere. The model for 18O is in good agreement with the observed values.

Less than 15 min are required for the determination of delta 13CPDB with a precision of 0.2% (1 sigma, single measurement) in 5-mL samples of air containing CH4 at natural levels (1.7 ppm). An analytical system including a sample-introduction unit incorporating a preparative gas chromatograph (GC) column for separation of CH4 from N2, O2, and Ar is described. The 15-min procedure includes time for operation of that system, high-resolution chromatographic separation of the CH4, on-line combustion and purification of the products, and isotopic calibration. Analyses of standards demonstrate that systematic errors are absent and that there is no dependence of observed values of delta on sample size. For samples containing 100 ppm or more CH4, preconcentration is not required and the analysis time is less than 5 min. The system utilizes a commercially available, high-sensitivity isotope-ratio mass spectrometer. For optimal conditions of sample handling and combustion, performance of the system is within a factor of 2 of the shot-noise limit. The potential exists therefore for analysis of samples as small as 15 pmol CH4 with a standard deviation of <1%.

We present a satellite observation of the spectrum of gamma radiation from the Earth's atmosphere in the energy interval from 300 keV to 8.5 MeV. The data were accumulated by the gamma ray spectrometer on the Solar Maximum Mission over 3 1/2 years, from 1980 to 1983. The excellent statistical accuracy of the data allows 20 atmospheric line features to be identified. The features are superimposed on a continuum background which is modeled using a power law with index -1.16. Many of these features contain a blend of more than one nuclear line. All of these lines (with the exception of the 511-keV annihilation line) are Doppler broadened. Line energies and intensities are consistent with production by secondary neutrons interacting with atmospheric 14N and 16O. Although we find no evidence for other production mechanisms, we cannot rule out significant contributions from direct excitation or spallation by primary cosmic ray protons. The relative intensities of the observed line features are in fair agreement with theoretical models; however, existing models are limited by the availability of neutron cross sections, especially at high energies. The intensity and spectrum of photons at energies below the 511-keV line, in excess of a power law continuum, can be explained by Compton scattering of the annihilation line photons in traversing an average of approximately 21 g cm-2 of atmosphere.

Voyager 2 found that the Uranian magnetosphere has a substantial flux of energetic charged particles, which becomes rich in higher energies at low magnetospheric L near the orbit of Miranda. The electrons precipitate to produce aurorae, which have been observed in the ultraviolet. The more energetic component of the precipitating electrons can initiate radiation chemistry in the methane-poor stratosphere, near 0.1 mbar where the CH4 mole fraction XCH4 approximately equal to 10(-5). We present laboratory results for cold plasma (glow) discharge in continuous flow H2-He-CH4 atmospheres with mol fractions XCH4 = 10(-2) to 10(-3) and total pressure p = 60 to 0.6 mbar. The yields of simple hydrocarbons in these experiments and an estimate of precipitating electron flux consistent with the Voyager ultraviolet spectroscopy results indicate the globally averaged auroral processing rate of CH4 to higher hydrocarbons approximately equal to 3 x 10(6) C cm-2 s-1, comparable to the globally averaged photochemical production rate. The local rate approximately 2 x 10(8) C cm-2 s-1 in the auroral zones (approximately 20 degrees in diameter) at 15 degrees S and 45 degrees N latitude greatly exceeds the photochemical rate. Even at very low XCH4 approximately equal to 10(-3) the yield (summed over all products) G > approximately 10(-2) C/100 eV and the average slope alpha = <log10¿eta sigma [C eta Hx]/(eta - 1) sigma [C eta - 1 Hx]¿> > approximately -0.4, where the summation is over all product molecules of a given carbon number eta and the square brackets denote abundance. The yield therefore decreases slowly with molecular complexity: hydrocarbons through C7Hx should be present in auroral zones at abundances > approximately 10(-2) of the simplest C2 hydrocarbons. Saturated hydrocarbons (C2H6, C3H8, C4H10, etc.) are mostly shielded from photodissociation by C2H2 and will therefore persist at the sunlit, as well as the currently dark, magnetic polar regions.

Sulfide samples obtained from the U.S. Geological Survey's DSRV Alvin dives on the southern Juan de Fuca Ridge closely resemble those from the same area described by Koski et al. (1984). Major minerals include sphalerite, wurtzite, pyrite, marcasite, isocubanite, anhydrite, and chalcopyrite. Equilibrium, if attained at all, during deposition of most sulfides was a transient event over a few tens of micrometers at most and was perturbed by rapid temperature and compositional changes of the circulating fluid. Two new minerals were found: one, a hydrated Zn, Fe hydroxy-chlorosulfate, and the other, a (Mn, Mg, Fe) hydroxide or hydroxy-hydrate. Both were formed at relatively low temperatures. Lizardite, starkeyite, and anatase were found for the first time in such an environment. Sulfide geothermometry involving the system Cu-Fe-S indicates a vent temperature of <328 degrees C for one sample. Fluid inclusion studies on crystals from the same vicinity of the same sample give pressure-corrected homogenization temperatures of 268 degrees and 285 degrees C. Ice-melting temperatures on inclusions from the same sample are about -2.8 degrees C, indicating that the equivalent salinity of the trapped fluid is about 50% greater than that of seawater. Volatile concentrations from vesicle-free basalt glass from the vent field are about 0.013 wt% CO2 and 0.16 wt% H2O, CO2 contents in these samples yield an entrapment depth of 2200 m of seawater, which is the depth from which the samples were collected.

Lava flows comprise three-phase mixtures of melt, crystals, and bubbles. While existing one-phase treatments allow melt phase viscosity to be assessed on the basis of composition, water content, and/or temperature, two-phase treatments constrain the effects of crystallinity or vesicularity on mixture viscosity. However, three-phase treatments, allowing for the effects of coexisting crystallinity and vesicularity, are not well understood. We investigate existing one- and two-phase treatments using lava flow case studies from Mauna Loa (Hawaii) and Mount Etna (Italy) and compare these with a three-phase treatment that has not been applied previously to basaltic mixtures. At Etna, melt viscosities of 425 ± 30 Pa s are expected for well-degassed (0.1 w. % H(2)O), and 135 ± 10 Pa s for less well-degassed (0.4 wt % H(2)O), melt at 1080°C. Application of a three-phase model yields mixture viscosities (45% crystals, 25-35% vesicles) in the range 5600-12,500 Pa s. This compares with a measured value for Etnean lava of 9400 ± 1500 Pa s. At Mauna Loa, the three-phase treatment provides a fit with the full range of field measured viscosities, giving three-phase mixture viscosities, upon eruption, of 110-140 Pa s (5% crystals, no bubble effect due to sheared vesicles) to 850-1400 Pa s (25-30% crystals, 40-60% spherical vesicles). The ability of the three-phase treatment to characterize the full range of melt-crystal-bubble mixture viscosities in both settings indicates the potential of this method in characterizing basaltic lava mixture viscosity.

The potential biomass that could have existed on Mars is constrained by the total amount of energy available to construct it. From an inventory of the available geochemical sources of energy, we estimate that from the time of the onset of the visible geologic record 4 b.y. ago to the present, as much as 20 g cm-2 of biota could have been created. This is the same amount that could have been constructed on the early Earth in only 100 million years. This indicates that there likely was sufficient energy available to support an origin of life on Mars but not sufficient energy to create a ubiquitous and lush biosphere. Similar calculations for Europa suggest that even less would have been available there.

If hydrothermal Systems existed on Mars, hydration of crustal rocks may have had the potential to affect the water budget of the planet. We have conducted geochemical model calculations to investigate the relative roles of host rock composition, temperature, water-to-rock ratio, and initial fluid oxygen fugacity on the mineralogy of hydrothermal alteration assemblages, as well as the effectiveness of alteration to store water in the crust as hydrous minerals. In order to place calculations for Mars in perspective, models of hydrothermal alteration of three genetically related Icelandic volcanics (a basalt, andesite, and rhyolite) are presented, together with results for compositions based on SNC meteorite samples (Shergotty and Chassigny). Temperatures from 150 degrees C to 250 degrees C, water-to-rock ratios from 0.1 to 1000, and two initial fluid oxygen fugacities are considered in the models. Model results for water-to-rock ratios less than 10 are emphasized because they are likely to be more applicable to Mars. In accord with studies of low-grade alteration of terrestrial rocks, we find that the major controls on hydrous mineral production are host rock composition and temperature. Over the range of conditions considered, the alteration of Shergotty shows the greatest potential for storing water as hydrous minerals, and the alteration of Icelandic rhyolite has the lowest potential.

This paper delineates the role of physical and biological processes contributing to hypoxia, dissolved oxygen (DO) < 1.4 mL/L, over the continental shelf of Washington State in the northern portion of the California Current System (CCS). In the historical record (1950-1986) during the summer upwelling season, hypoxia is more prevalent and severe off Washington than further south off northern Oregon. Recent data (2003-2005) show that hypoxia over the Washington shelf occurred at levels previously observed in the historical data. 2006 was an exception, with hypoxia covering ~5000 km(2) of the Washington continental shelf and DO concentrations below 0.5 mL/L at the inner shelf, lower than any known previous observations at that location. In the four years studied, upwelling of low DO water and changes in source water contribute to interannual variability, but cannot account for seasonal decreases below hypoxic concentrations. Deficits of DO along salinity surfaces, indicating biochemical consumption of DO, vary significantly between surveys, accounting for additional decreases of 0.5-2.5 mL/L by late summer. DO consumption is associated with denitrification, an indicator of biochemical sediment processes. Mass balances of DO and nitrate show that biochemical processes in the water column and sediments each contribute ~50% to the total consumption of DO in near-bottom water. At shorter than seasonal time scales on the inner shelf, along-shelf advection of hypoxic patches and cross-shelf advection of seasonal gradients are both shown to be important, changing DO concentrations by 1.5 mL/L or more over five days.

Proposed evolutionary histories of solar luminosity, atmospheric carbon dioxide amounts, Earth rotation rate, and continent formation have been used to generate a time evolution of Earth's surface temperature. While speculative because of uncertainties in the input parameters, such a study does help to prioritize the areas of most concern to paleoclimatic research while illustrating the relationships and mutual dependencies. The mean temperature averages about 5 K higher than today over most of geologic time; the overall variation is less than 15 K. The evolution of Earth's rotation rate makes a significant contribution to the surface temperature distribution as late as 0.5 b.y. ago. While there is little change in equatorial temperatures, polar temperatures decrease, being some 15 K lower 3.5 b.y. ago than with present day rotation. The effect of continent growth on albedo is of secondary importance.

We study the interactions between the geochemical cycles of carbon and long-term changes in climate. Climate change is studied with a simple, zonally averaged energy balance climate model that includes the greenhouse effect of carbon dioxide explicitly. The geochemical model balances the rate of consumption of carbon dioxide in silicate weathering against its release by volcanic and metamorphic processes. The silicate weathering rate is expressed locally as a function of temperature, carbon dioxide partial pressure, and runoff. The global weathering rate is calculated by integrating these quantities over the land area as a function of latitude. Carbon dioxide feedback stabilizes the climate system against a reduction in solar luminosity and may contribute to the preservation of equable climate on the early Earth, when solar luminosity was low. The system responds to reduced land area by increasing carbon dioxide partial pressure and warming the globe. Our model makes it possible to study the response of the system to changing latitudinal distribution of the continents. A concentration of land area at high latitudes leads to high carbon dioxide partial pressures and high global average temperature because weathering of high-latitude continents is slow. Conversely, concentration of the continents at low latitudes yields a cold globe and ice at low latitudes, a situation that appears to be representative of the late Precambrian glacial episode. This model is stable against ice albedo catastrophe even when the ice line occurs at low latitudes. In this it differs from energy balance models that lack the coupling to the geochemical cycle of carbon.

Newly discovered fluid inclusions in thin sections of Bjurbole chondrules, shergottite EETA79001, lunar meteorite ALHA81005, and Apollo 16 glasses possess physical properties similar to those fluid inclusions found in thin sections of five stony meteorites recently described by Warner et al. (1983). The distribution and physical properties of these new fluid inclusions indicate they may be artifacts of thin section preparation; we suggest that saw coolant was sucked into vacuum vesicles in glasses and minerals through submicroscopic fractures produced during sawing. The similarities between these fluid inclusions and fluid inclusions previously described by Warner et al. (1983) lead us to conclude that many of the fluid inclusions reported earlier may be artifacts. Consequently, the origin of any fluid inclusions observed in thin sections of extraterrestrial materials must be interpreted with caution. The most probable true extraterrestrial fluid inclusions are those that have been observed in grains prepared without exposure to liquids of any kind.

Integrating the potential for climate change impacts into policy and planning decisions requires quantification of the emergence of sub-regional climate changes that could occur in response to transient changes in global radiative forcing. Here we report results from a high-resolution, century-scale, ensemble simulation of climate in the United States, forced by atmospheric constituent concentrations from the Special Report on Emissions Scenarios (SRES) A1B scenario. We find that 21(st) century summer warming permanently emerges beyond the baseline decadal-scale variability prior to 2020 over most areas of the continental U.S. Permanent emergence beyond the baseline annual-scale variability shows much greater spatial heterogeneity, with emergence occurring prior to 2030 over areas of the southwestern U.S., but not prior to the end of the 21(st) century over much of the southcentral and southeastern U.S. The pattern of emergence of robust summer warming contrasts with the pattern of summer warming magnitude, which is greatest over the central U.S. and smallest over the western U.S. In addition to stronger warming, the central U.S. also exhibits stronger coupling of changes in surface air temperature, precipitation, and moisture and energy fluxes, along with changes in atmospheric circulation towards increased anticylonic anomalies in the mid-troposphere and a poleward shift in the mid-latitude jet aloft. However, as a fraction of the baseline variability, the transient warming over the central U.S. is smaller than the warming over the southwestern or northeastern U.S., delaying the emergence of the warming signal over the central U.S. Our comparisons with observations and the Coupled Model Intercomparison Project Phase 3 (CMIP3) ensemble of global climate model experiments suggest that near-term global warming is likely to cause robust sub-regional-scale warming over areas that exhibit relatively little baseline variability. In contrast, where there is greater variability in the baseline climate dynamics, there can be greater variability in the response to elevated greenhouse forcing, decreasing the robustness of the transient warming signal.

The results of laboratory experiments simulating the irradiation of hydrocarbon-H2O or hydrocarbon-H2O/NH3 clathrates by charged particles in the outer solar system are reported. Ices produced by condensing and boiling liquid CH4 on an H2O frost surface at 100 K or by cocondensing frosts from gaseous mixtures were exposed to coronal-discharge electron irradiation at 77 K, and the spectral properties of the irradiated surfaces were determined. Significant darkening of the initially white ices was observed at doses of 1 Gerg/sq cm, corresponding to 8-500 yrs of irradiation by Uranian magnetospheric electrons on the surfaces of the principal Uranian satellites, or to total destruction of CH4 in the upper 1 mm of the satellite surfaces after 0.05-3.0 Myr. It is estimated that 10 m or more of icy satellite or comet surfaces would be radiation-hardened to a CH4-free ice-tholin mixture over 4 Gyr.

A comprehensive analysis of volatiles in the Chicxulub impact strongly supports the hypothesis that impact-generated sulfate aerosols caused over a decade of global cooling, acid rain, and disruption of ocean circulation, which contributed to the mass extinction at the Cretaceous/Tertiary (K/T) boundary. The crater size, meteoritic content of the K/T boundary clay, and impact models indicate that the Chicxulub crater was formed by a short period comet or an asteroid impact that released 0.7-3.4 x 10(31) ergs of energy. Impact models and experiments combined with estimates of volatiles in the projectile and target rocks predict that over 200 gigatons (Gt) each of SO2 and water vapor, and over 500 Gt of CO2, were globally distributed in the stratosphere by the impact. Additional volatiles may have been produced on a global or regional scale that formed sulfate aerosols rapidly in cooler parts of the vapor plume, causing an early, intense pulse of sulfuric acid rain. Estimates of the conversion rate of stratospheric SO2 and water vapor to sulfate aerosol, based on volcanic production of sulfate aerosols, coupled with calculations of diffusion, coagulation, and sedimentation, demonstrate that the 200 Gt stratospheric SO2 and water vapor reservoir would produce sulfate aerosols for 12 years. These sulfate aerosols caused a second pulse of acid rain that was global. Radiative transfer modeling of the aerosol clouds demonstrates (1) that if the initial rapid pulse of sulfate aerosols was global, photosynthesis may have been shut down for 6 months and (2) that for the second prolonged aerosol cloud, solar transmission dropped 80% by the end of first year and remained 50% below normal for 9 years. As a result, global average surface temperatures probably dropped between 5 degrees and 31 degrees K, suggesting that global near-freezing conditions may have been reached. Impact-generated CO2 caused less than 1 degree K greenhouse warming and therefore was insignificant compare to the sulfate cooling. The magnitude of sulfate cooling depends largely upon the rate of ocean mixing as surface waters cool, sink, and are replaced by upwelling of deep ocean water. This upwelling apparently drastically altered ocean stratification and circulation, which may explain the global collapse of the delta 13C gradient between surface and deep ocean waters at the K/T boundary.