Water isotopic ratios from a continuously melted ice core sample

A new technique for on-line high resolution isotopic analysis of liquid water, tailored for ice core studies is presented. We built an interface between a Wavelength Scanned Cavity Ring Down Spectrometer (WS-CRDS) purchased from Picarro Inc. and a Continuous Flow Analysis (CFA) system. The system offers the possibility to perform simultaneuous water isotopic analysis of δ18O and δD on a continuous stream of liquid water as generated from a continuously melted ice rod. Injection of sub μl amounts of liquid water is achieved by pumping sample through a fused silica capillary and instantaneously vaporizing it with 100% efficiency in a~home made oven at a temperature of 170 °C. A calibration procedure allows for proper reporting of the data on the VSMOW–SLAP scale. We apply the necessary corrections based on the assessed performance of the system regarding instrumental drifts and dependance on the water concentration in the optical cavity. The melt rates are monitored in order to assign a depth scale to the measured isotopic profiles. Application of spectral methods yields the combined uncertainty of the system at below 0.1‰ and 0.5‰ for δ18O and δD, respectively. This performance is comparable to that achieved with mass spectrometry. Dispersion of the sample in the transfer lines limits the temporal resolution of the technique. In this work we investigate and assess these dispersion effects. By using an optimal filtering method we show how the measured profiles can be corrected for the smoothing effects resulting from the sample dispersion. Considering the significant advantages the technique offers, i.e. simultaneuous measurement of δ18O and δD, potentially in combination with chemical components that are traditionally measured on CFA systems, notable reduction on analysis time and power consumption, we consider it as an alternative to traditional isotope ratio mass spectrometry with the possibility to be deployed for field ice core studies. We present data acquired in the field during the 2010 season as part of the NEEM deep ice core drilling project in North Greenland.

Influence of microphysical schemes on atmospheric water in the Weather Research and Forecasting model

This study examines how different microphysical parameterization schemes influence orographically induced precipitation and the distributions of hydrometeors and water vapour for midlatitude summer conditions in the Weather Research and Forecasting (WRF) model. A high-resolution two-dimensional idealized simulation is used to assess the differences between the schemes in which a moist air flow is interacting with a bell-shaped 2 km high mountain. Periodic lateral boundary conditions are chosen to recirculate atmospheric water in the domain. It is found that the 13 selected microphysical schemes conserve the water in the model domain. The gain or loss of water is less than 0.81% over a simulation time interval of 61 days. The differences of the microphysical schemes in terms of the distributions of water vapour, hydrometeors and accumulated precipitation are presented and discussed. The Kessler scheme, the only scheme without ice-phase processes, shows final values of cloud liquid water 14 times greater than the other schemes. The differences among the other schemes are not as extreme, but still they differ up to 79% in water vapour, up to 10 times in hydrometeors and up to 64% in accumulated precipitation at the end of the simulation. The microphysical schemes also differ in the surface evaporation rate. The WRF single-moment 3-class scheme has the highest surface evaporation rate compensated by the highest precipitation rate. The different distributions of hydrometeors and water vapour of the microphysical schemes induce differences up to 49 W m−2 in the downwelling shortwave radiation and up to 33 W m−2 in the downwelling longwave radiation.

Spectroscopy and detectability of liquid brines on mars

Recent geomorphological observations as well as chemical and thermodynamic studies demonstrate that liquid water should be stable today on the Martian surface at some times of the day. In Martian conditions, brines would be particularly more stable than pure water because salts can depress the freezing point and lower the evaporation rate of water. Despite this evidence, no clear spectral signature of liquid has been observed so far by the hyperspectral imaging spectrometers OMEGA and CRISM. However, past spectral analysis lacks a good characterization of brines׳ spectral signatures. This study thus aims to determine how liquid brines can be detected on Mars by spectroscopy. In this way, laboratory experiments were performed for reproducing hydration and dehydration cycles of various brines while measuring their spectral signatures. The resulting spectra first reveal a very similar spectral evolution for the various brine types and pure water, with the main difference observed at the end of the dehydration with the crystallization of various hydrated minerals from brines. The main characteristic of this spectral behavior is an important decoupling between the evolution of albedo and hydration bands depths. During most of the wetting/drying processes, spectra usually display a low albedo associated with shallow water absorption band depths. Strong water absorption band depth and high albedo are respectively only observed when the surface is very wet and when the surface is very dry. These experiments can thus explain why the currently active Martian features attributed to the action of a liquid are only associated with low albedo and very weak spectral signatures. Hydration experiments also reveal that deliquescence occurs easily even at low temperature and moderate soil water vapor pressure and could thus cause seasonal darkening on Mars. These experiments demonstrate that the absence of water absorptions in CRISM in the middle afternoon does not rule out water activity and suggest future spectral investigations to identify water on the Martian surface.

Atmospheric water parameters measured by a ground-based microwave radiometer and compared with the WRF model

The microwave radiometer TROWARA measures integrated water vapour (IWV) and integrated cloud liquid water (ILW) at Bern since 1994 with a time resolution of 7 s. In this study, we compare TROWARA measurements with a simulation of summer 2012 in Switzerland performed with the Weather Research and Forecasting (WRF) model. It is found that the WRF model agrees very well with TROWARA’s IWV variations with a mean bias of only 0.7 mm. The ILW distribution of the WRF model, although similar in shape to TROWARA’s distribution, overestimates the fraction of clear sky periods (83% compared to 60%).

MiniCASCC - A battery driven fog collector for ecosystem research

We developed a small version of the Caltech active strand cloud water collector (CASCC) for biogeochemical investigations in ecological applications. The device is battery powered and thus allows operation at locations where mains power is not available. The collector is designed for sampling periods of up to one week, depending on fog frequency. Our new device is equipped with standard sensors for air temperature, relative humidity, wind, and horizontal visibility for fog detection with a low-cost optical sensor. In mountain areas and during times when clouds are thin the installation of the visibility sensor became a key issue, which limits the potential to estimate liquid water content of the sampled fog. Field tests with 5 devices at three different sites in the Swiss Alps (Niesen) and the Jura Mountains (Lägeren, Switzerland) during two extended summer seasons in 2006 and 2007 showed that in almost all cases it was possible to obtain sample volumes which were large enough for the examination of basic inorganic chemistry of the collected cloud water. Collection rates varied typically from 12 to 30 mL h− 1. The fog droplet cutoff diameter is ≈ 6 μm, which is low enough to include all droplet sizes that are relevant for the liquid water content of typical fog types in the collected samples. From theoretical assumptions of the collection efficiency and theoretical droplet spectra it is possible to estimate the liquid water content of the sampled fog or cloud. Our new fog collector can be constructed and operated at relatively low costs. In combination with chemical and isotopic analyses of the sampled water, this allows to quantify nutrient and pollutant fluxes as is typically needed in ecosystem biogeochemistry studies.

Photometric properties of Mars soils analogs

We have measured the bidirectional reflectance of analogs of dry, wet, and frozen Martian soils over a wide range of phase angles in the visible spectral range. All samples were produced from two geologic samples: the standard JSC Mars-1 soil simulant and Hawaiian basaltic sand. In a first step, experiments were conducted with the dry samples to investigate the effects of surface texture. Comparisons with results independently obtained by different teams with similar samples showed a satisfying reproducibility of the photometric measurements as well as a noticeable influence of surface textures resulting from different sample preparation procedures. In a second step, water was introduced to produce wet and frozen samples and their photometry investigated. Optical microscope images of the samples provided information about their microtexture. Liquid water, even in relatively low amount, resulted in the disappearance of the backscattering peak and the appearance of a forward-scattering peak whose intensity increases with the amount of water. Specular reflections only appeared when water was present in an amount large enough to allow water to form a film at the surface of the sample. Icy samples showed a wide variability of photometric properties depending on the physical properties of the water ice. We discuss the implications of these measurements in terms of the expected photometric behavior of the Martian surface, from equatorial to circum-polar regions. In particular, we propose some simple photometric criteria to improve the identification of wet and/or icy soils from multiple observations under different geometries.

Recurring slope lineae in equatorial regions of Mars

The presence of liquid water is a requirement of habitability on a planet. Possible indicators of liquid surface water on Mars include intermittent flow-like features observed on sloping terrains. These recurring slope lineae are narrow, dark markings on steep slopes that appear and incrementally lengthen during warm seasons on low-albedo surfaces. The lineae fade in cooler seasons and recur over multiple Mars years. Recurring slope lineae were initially reported to appear and lengthen at mid-latitudes in the late southern spring and summer and are more common on equator-facing slopes where and when the peak surface temperatures are higher. Here we report extensive activity of recurring slope lineae in equatorial regions of Mars, particularly in the deep canyons of Valles Marineris, from analysis of data acquired by the Mars Reconnaissance Orbiter. We observe the lineae to be most active in seasons when the slopes often face the sun. Expected peak temperatures suggest that activity may not depend solely on temperature. Although the origin of the recurring slope lineae remains an open question, our observations are consistent with intermittent flow of briny water. Such an origin suggests surprisingly abundant liquid water in some near-surface equatorial regions of Mars.

Morphological ripening of fluid inclusions and coupled zone-refining in quartz crystals revealed by cathodoluminescence imaging: Implications for CL-petrography, fluid inclusion analysis and trace-element geothermometry

Cathodoluminescence (CL) studies have previously shown that some secondary fluid inclusions in luminescent quartz are surrounded by dark, non-luminescent patches, resulting from fracture-sealing by late, trace-element-poor quartz. This finding has led to the tacit generalization that all dark CL patches indicate influx of low temperature, late-stage fluids. In this study we have examined natural and synthetic hydrothermal quartz crystals using CL imaging supplemented by in-situ elemental analysis. The results lead us to propose that all natural, liquid-water-bearing inclusions in quartz, whether trapped on former crystal growth surfaces (i.e., of primary origin) or in healed fractures (i.e., of pseudosecondary or secondary origin), are surrounded by three-dimensional, non-luminescent patches. Cross-cutting relations show that the patches form after entrapment of the fluid inclusions and therefore they are not diagnostic of the timing of fluid entrapment. Instead, the dark patches reveal the mechanism by which fluid inclusions spontaneously approach morphological equilibrium and purify their host quartz over geological time. Fluid inclusions that contain solvent water perpetually dissolve and reprecipitate their walls, gradually adopting low-energy euhedral and equant shapes. Defects in the host quartz constitute solubility gradients that drive physical migration of the inclusions over distances of tens of μm (commonly) up to several mm (rarely). Inclusions thus sequester from their walls any trace elements (e.g., Li, Al, Na, Ti) present in excess of equilibrium concentrations, thereby chemically purifying their host crystals in a process analogous to industrial zone refining. Non-luminescent patches of quartz are left in their wake. Fluid inclusions that contain no liquid water as solvent (e.g., inclusions of low-density H2O vapor or other non-aqueous volatiles) do not undergo this process and therefore do not migrate, do not modify their shapes with time, and are not associated with dark-CL zone-refined patches. This new understanding has implications for the interpretation of solids within fluid inclusions (e.g., Ti- and Al-minerals) and for the elemental analysis of hydrothermal and metamorphic quartz and its fluid inclusions by microbeam methods such as LA-ICPMS and SIMS. As Ti is a common trace element in quartz, its sequestration by fluid inclusions and its depletion in zone-refined patches impacts on applications of the Ti-in-quartz geothermometer.

Effect of Nontronite Smectite Clay on the Chemical Evolution of Several Organic Molecules under Simulated Martian Surface Ultraviolet Radiation Conditions

Most of the phyllosilicates detected at the surface of Mars today are probably remnants of ancient environments that sustained long-term bodies of liquid water at the surface or subsurface and were possibly favorable for the emergence of life. Consequently, phyllosilicates have become the main mineral target in the search for organics on Mars. But are phyllosilicates efficient at preserving organic molecules under current environmental conditions at the surface of Mars? We monitored the qualitative and quantitative evolutions of glycine, urea, and adenine in interaction with the Fe3+-smectite clay nontronite, one of the most abundant phyllosilicates present at the surface of Mars, under simulated martian surface ultraviolet light (190-400 nm), mean temperature (218 +/- 2 K), and pressure (6 +/- 1 mbar) in a laboratory simulation setup. We tested organic-rich samples that were representative of the evaporation of a small, warm pond of liquid water containing a high concentration of organics. For each molecule, we observed how the nontronite influences its quantum efficiency of photodecomposition and the nature of its solid evolution products. The results reveal a pronounced photoprotective effect of nontronite on the evolution of glycine and adenine; their efficiencies of photodecomposition were reduced by a factor of 5 when mixed at a concentration of 2.6x10(-2) mol of molecules per gram of nontronite. Moreover, when the amount of nontronite in the sample of glycine was increased by a factor of 2, the gain of photoprotection was multiplied by a factor of 5. This indicates that the photoprotection provided by the nontronite is not a purely mechanical shielding effect but is also due to stabilizing interactions. No new evolution product was firmly identified, but the results obtained with urea suggest a particular reactivity in the presence of nontronite, leading to an increase of its dissociation rate. Key Words: Martian surface-Organic chemistry-Photochemistry-Astrochemistry-Nontronite-Phyllosilicates. Astrobiology 15, 221-237.

A Maximum Radius for Habitable Planets

We compute the maximum radius a planet can have in order to fulfill two constraints that are likely necessary conditions for habitability: 1- surface temperature and pressure compatible with the existence of liquid water, and 2- no ice layer at the bottom of a putative global ocean, that would prevent the operation of the geologic carbon cycle to operate. We demonstrate that, above a given radius, these two constraints cannot be met: in the Super-Earth mass range (1-12 M-earth), the overall maximum that a planet can have varies between 1.8 and 2.3 R-earth. This radius is reduced when considering planets with higher Fe/Si ratios, and taking into account irradiation effects on the structure of the gas envelope.

Geological and hydrological histories of the Argyre province, Mars

The geologic history of the multi-ringed Argyre impact basin and surroundings has been reconstructed on the basis of geologic mapping and relative-age dating of rock materials and structures. The impact formed a primary basin, rim materials, and a complex basement structural fabric including faults and valleys that are radial and concentric about the primary basin, as well as structurally-controlled local basins. Since its formation, the basin has been a regional catchment for volatiles and sedimentary materials as well as a dominant influence on the flow of surface ice, debris flows, and groundwater through and over its basement structures. The basin is interpreted to have been occupied by lakes, including a possible Mediterranean-sized sea that formed in the aftermath of the Argyre impact event The hypothesized lakes froze and diminished through time, though liquid water may have remained beneath the ice cover and sedimentation may have continued for some time. At its deepest, the main Argyre lake may have taken more than a hundred thousand years to freeze to the bottom even absent any heat source besides the Sun, but with impact-induced hydrothermal heat, geothermal heat flow due to long-lived radioactivities in early martian history, and concentration of solutes in sub-ice brine, liquid water may have persisted beneath thick ice for many millions of years. Existence of an ice-covered sea perhaps was long enough for life to originate and evolve with gradually colder and more hypersaline conditions. The Argyre rock materials, diverse in origin and emplacement mechanisms, have been modified by impact, magmatic, eolian, fluvial, lacustrine, glacial, periglacial, alluvial, colluvial, and tectonic processes. Post-impact adjustment of part of the impact-generated basement structural fabric such as concentric faults is apparent. Distinct basin-stratigraphic units are interpreted to be linked to large-scale geologic activity far from the basin, including growth of the Tharsis magmatic-tectonic complex and the growth into southern middle latitudes of south polar ice sheets. Along with the migration of surface and sub-surface volatiles towards the central part of the primaiy basin, the substantial difference in elevation with respect to the surrounding highlands and Tharsis and the Thaumasia highlands result in the trapping of atmospheric volatiles within the basin in the form of fog and regional or local precipitation, even today. In addition, the impact event caused long-term (millions of years) hydrothermal activity, as well as deep-seated basement structures that have tapped the internal heat of Mars, as conduits, for far greater time, possibly even today. This possibility is raised by the observation of putative open-system pingos and nearby gullies that occur in linear depressions with accompanying systems of faults and fractures. Long-term water and heat energy enrichment, complemented by the interaction of the nutrient-enriched primordial crustal and mantle materials favorable to life excavated to the surface and near-surface environs through the Argyre impact event, has not only resulted in distinct geomorphology, but also makes the Argyre basin a potential site of exceptional astrobiological significance. (C) 2015 Elsevier Inc. All rights reserved.