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Chemistry of manganese precipitation in Pinal Creek, Arizona, USA: A laboratory study

Groundwater underlying the valley of Pinal Creek downstream from Globe, Arizona, has been contaminated by low-pH metal-enriched wastewater from copper mining and ore processing at Miami, Arizona. At present, the acidity and most of the dissolved metal content, except for Mn, of the wastewater is removed by reactions with carbonate and other solids in the alluvial aquifer before the neutralized contaminated water enters the creek channel and becomes surface flow. Where flow in the creek is perennial, Mn-bearing precipitates are formed in the stream bed and in some places in the subsurface. As an aid to understanding the processes involved and explaining the mineralogy of the precipitates, closely controlled laboratory redox titration experiments were performed on samples of surface flow and groundwater taken near the head of perennial flow in the creek. The high content of dissolved Ca, Mg, Mn and COP 2 species in the neutralized contaminated groundwater caused precipitation of some of the Mn as kutnahorite, (Mn, Mg)Ca(CO 3 ) 2 , when the experimental system was held between pH 8.5 and 9.0 while CO 2 -free air was bubbled into the solution. Hausmannite and manganite also were precipitated, in somewhat lower amounts. When the concentrations of dissolved CO 2 species in the groundwater sample were decreased before the experiment was started, the Mn precipitated was predominantly in the oxides hausmannite and manganite. In some of the experimental titrations clinoenstatite, (MgSiO 3 ), was precipitated. After titrations were stopped the solutions and precipitates were allowed to stand, with limited access to the atmosphere, for several months. During this aging period the degree of oxidation of the precipitated Mn increased and in one precipitate from an experimental solution the Ca + Mn 4+ oxides todorokite and takanelite were identified. These oxides also have been identified in streambed precipitates. Some of these precipitates also gave X-ray diffraction reflections for kutnahorite. Thermodynamic feasibilities of eight potential chemical reactions forming solid phases of interest were evaluated by calculating their respective reaction affinities attained during titration and aging. The results are in general agreement with the indications for the presence of these species given by X-ray and electron diffraction. The presence of carbonates in precipitated encrustations formed from groundwater below the land surface and their occurrence in manganese oxide crusts that precipitate from the creek water, also are predicted by these results.

Geochimica et Cosmochimica Acta↗

Television experiment for Mariner Mars 1971

The Television Experiment objectives are to provide imaging data which will complement previously gathered data and extend our knowledge of Mars. The two types of investigations will be fixed-feature (for mapping) and variable-feature (for surface and atmospheric changes). Two cameras with a factor-of-ten difference in resolution will be used on each spacecraft for medium- and high-resolution imagery. Mapping of 70% of the planet's surface will be provided by medium-resolution imagery. Spot coverage of about 5% of the surface will be possible with the high-resolution imagery. The experiment's 5 Principal Investigators and 21 Co-Investigators are organized into a team. Scientific disciplines and technical task groups have been formed to provide the formulation of experiment requirements for mission planning and instrument development. It is expected that the team concept will continue through the operational and reporting phases of the Mariner Mars 1971 Project.

Icarus↗

Imaging experiment: The Viking Mars orbiter

The general objectives of the Imaging Experiment on the Viking Orbiter are to aid the selection of Viking Lander sites, to map and monitor the chosen sites during lander operations, to aid in the selection of future landing sites, and to extend our knowledge of the planet. The imaging system consists of two identical vidicon cameras each attached to a 1026 mm T/8 telescope giving approximately 1° square field of view. From an altitude of 1500 km the picture elements will be approximately 24m apart. The vidicon is coupled with an image intensifier which provides increased sensitivity and permits electronic shuttering and image motion compensation. A vidicon readout time of 2.24 sec enables pictures to be taken in rapid sequence for contiguous coverage at high resolution. The camera differs from those previously flown to Mars by providing contiguous coverage at high resolution on a single orbital pass, by having sufficient sensitivity to use narrow band color filters at maximum resolution, and by having response in the ultraviolet. These capabilities will be utelized to supplement lander observations and to extend our knowledge particularly of volcanic, erosional, and atmospheric phenomena on Mars.

Icarus↗

Imaging experiment: The Viking Lander

The Viking Lander Imaging System will consist of two identical facsimile cameras. Each camera has a high-resolution mode with an instantaneous field of view of 0.04°, and survey and color modes with instantaneous fields of view of 0.12°. Cameras are positioned one meter apart to provide stereoscopic coverage of the near-field. The Imaging Experiment will provide important information about the morphology, composition, and origin of the Martian surface and atmospheric features. In addition, lander pictures will provide supporting information for other experiments in biology, organic chemistry, meteorology, and physical properties.

Icarus↗

Inorganic chemical investigation by x-ray fluorescence analysis: The Viking Mars Lander

The inorganic chemical investigation added in August 1972 to the Viking Lander scientific package will utilize an energy-dispersive X-ray fluorescence spectrometer in which four sealed, gas-filled proportional counters will detect X-rays emitted from samples of the Martian surface materials irradiated by X-rays from radioisotope sources ( 55 Fe and 109 Cd). The output of the proportional counters will be subjected to pulse-height analysis by an on-board step-scanning single-channel analyzer with adjustable counting periods. The data will be returned to Earth, via the Viking Orbiter relay system, and the spectra constructed, calibrated, and interpreted here. The instrument is inside the Lander body, and samples are to be delivered to it by the Viking Lander Surface Sampler. Calibration standards are an integral part of the instrument. The results of the investigation will characterize the surface materials of Mars as to elemental composition with accuracies ranging from a few tens of parts per million (at the trace-element level) to a few percent (for major elements) depending on the element in question. Elements of atomic number 11 or less are determined only as a group, though useful estimates of their individual abundances maybe achieved by indirect means. The expected radiation environment will not seriously hamper the measurements. Based on the results, inferences can be drawn regarding (1) the surface mineralogy and lithology; (2) the nature of weathering processes, past and present, and the question of equilibrium between the atmosphere and the surface; and (3) the extent and type of differentiation that the planet has undergone. The Inorganic Chemical Investigation supports and is supported by most other Viking Science investigations.

Icarus↗

Possible fossil H2O liquid-ice interfaces in the Martian crust

Throughout the northern equatorial region of Mars, extensive areas have been uniformly stripped, roughly to a constant depth. These terrains vary widely in their relative ages. A model is described here to explain this phenomenon as reflecting the vertical distribution of H 2 O liquid and ice in the crust. Under present conditions the Martian equatorial regions are stratified in terms of the stability of water ice and liquid water. This arises because the temperature of the upper 1 or 2 km is below the melting point of ice and liquid is stable only at greater depth. It is suggested here that during planetary outgassing earlier in Martian history H 2 O was injected into the upper few kilometers of the crust by subsurface and surface volcanic eruption and lateral migration of the liquid and vapor. As a result, a discontinuity in the physical state of materials developed in the Martian crust coincident with the depth of H 2 O liquid-ice phase boundary. Material above the boundary remained pristine; material below underwent diagenetic alteration and cementation. Subsequently, sections of the ice-laden zone were erosionally stripped by processes including eolian deflation, gravitational slump and collapse, and fluvial transport due to geothermal heating and melting of the ice. The youngest plains which display this uniform stripping may provide a minimum stratigraphic age for the major period of outgassing of the planet. Viking results suggest that the total amount of H 2 O outgassed is less than half that required to fill the ice layer, hence any residual liquid eventually found itself in the upper permafrost zone or stored in the polar regions. Erosion stopped at the old liquid-ice interface due to increased resistance of subjacent material and/or because melting of ice was required to mobilize the debris. Water ice may remain in uneroded regions, the overburden of debris preventing its escape to the atmosphere. Numerous morphological examples shown in Viking and Mariner 9 images suggest interaction of impact, volcanic, and gravitational processes with the ice-laden layer. Finally, volcanic eruptions into ice produces a highly oxidized friable amorphous rock, palagonite. Based on spectral reflectance properties, these materials may provide the best analog to Martian surface materials. They are easily eroded, providing vast amounts of eolian debris, and have been suggested (Toulmin et al. , 1977) as possible source rocks for the materials observed at the Viking landing sites.

Icarus↗

Mars and Earth: Comparison of cold-climate features

On Earth, glacial and periglacial features are common in areas of cold climate. On Mars, the temperature of the present-day surface is appropriate for permafrost, and the presence of water is suspected from data relating to the outgassing of the planet, from remote-sensing measurements over the polar caps and elsewhere on the Martian surface, and from recognition of fluvial morphological features such as channels. These observations and the possibility that ice could be in equilibrium with the atmosphere in the high latitudes north and south of ±40° latitude suggest that glacial and periglacial features should exist on the planet. Morphological studies based mainly on Viking pictures indicate many features that can be attributed to the action of ice. Among these features are extensive talus aprons; debris avalanches; flows that resemble glaciers or rock glaciers; ridges that look like moraines; various types of patterned ground, scalloped scarps, and chaotically collapsed terrain that could be attributed to thermokarst processes; and landforms that may reflect the interaction of volcanism and ice.

Icarus↗

Mars: A water-rich planet?

Mars had outgassed at least 0.5 to 1 km of water, 10 to 20 bar of CO 2 , and 0.1 to 0.3 bar of N 2 . The volatiles that have been retained are mostly in the cratered uplands. Terrain softening, fretted channels, debris flows, and closed depressions indicate that at least the upper 2 km of the cratered uplands at high latitudes (>30°) contain ice in amounts that exceed the porosity, estimated to be 10–20%. Theoretical studies, and lack of these features in the cratered uplands at low latitudes, suggest that the upper 1 km of the uplands at low latitudes is ice poor. However, valley networks indicate that water was present near the surface early in the planet's history, although in amounts smaller than at high latitudes. The entire upper 1 km, planetwide is estimated to have contained 75–125 m of water at the end of heavy bombardment. The largest sink for water is the megaregolith below 1 km. Episodic eruption of water from the deep megaregolith cut many of the large outflow channels. From the volume of water needed to cut the circum-Chryse channels, and assuming uniform planetwide distribution of water, the deep megaregolith is estimated to have contained at least 350 m of water at the end of heavy bombardment, thereby giving a total minimum inventory of 424–475 m planetwide. Most of the water lost from the low-latitude uplands by diffusion and in cutting the valley networks is now believed to be in the polar layered terrains. Most of the water involved in cutting the outflow channels is in the low-lying northern plains where a variety of features that have been attributed to ground ice is present. A large fraction of the planet's surface has been overplated with water-poor volcanics, of which we have samples in the SNC meteorites. The younger volcanics have reacted extensively with the old volatile-rich basement. Some of the CO 2 and N 2 outgassed was lost during heavy bombardment by impact erosion of the atmosphere and other processes. The remaining was fixed carbonates and folded deep into the megaregolith during heavy bombardment.

Icarus↗

Global color and albedo variations on Io

Three multispectral mosaics of Io have been produced from Voyager imaging data: a global mosaic from each of the Voyager 1 and Voyager 2 data sets and a high-resolution mosaic of the region surrounding the volcano Ra Patera. The mosaics are maps of normal albedo and color in accurate geometric map formats. Io's photometric behavior, mapped with a two-image technique, is spatially variable, especially in the bright white areas. The disk-integrated color and albedo of the satellite have been remarkably constant over recent decades, despite the volcanic activity and the many differences between Voyager 1 and 2 images (acquired just 4 months apart). This constancy is most likely due to the consistent occurrence of large Pele-type plumes with relatively dark, red deposits in the region from long 240 to 360°. A transient brightening southeast of Pele during the Voyager 1 encounter was probably due to real changes in surface and/or atmospheric materials, rather than to photometric behavior. The intrinsic spectral variability of Io, as seen in a series of two-dimensional histograms of the multispectral mosaics, consists of continuous variation among three major spectral end members. The data were mapped into five spectral units to compare them with laboratory measurements of candidate surface materials and to show the planimetric distributions. Unit 1 is best fit by the spectral reflectance of ordinary elemental sulfur, and it is closely associated with the Peletype plume deposits. Unit 2 is strongly confined to the polar caps above about latitude ±50°, but its composition is unknown. Unit 5 is probably SO 2 with relatively minor contamination; it is concentrated in the equatorial region and near the long-lived Prometheus-type plumes. Units 3 and 4 are gradational between units 1 and 5. In addition to SO 2 and elemental sulfur, other plausible components of the surface are polysulfur oxides, FeCl 2 , Na 2 S, and NaHS.

Icarus↗

The global distribution, abundance, and stability of SO2 on Io

Sulfur dioxide distribution and abundances, bolometric hemispheric albedos, and passive surface temperatures on Io are modeled and mapped globally from Voyager multispectral mosaics, Earth-based spectra, and photometric descriptions. Photometric models indicate global average values for regolith porosity of 75-95% and macroscopic roughness with a mean slope angle of ~30??. Abundances of SO2 suggested by observations at uv-visible wavelengths and at 4.08 ??m are partially reconciled by intimate-mixing models; 30-50% SO2 coverage of the integral disk is indicated. Three major spectral end members, with continuous mixing, are recognized from the Voyager multispectral mosaics; one of these end members is identified as SO2. Intimate-mixing models with the three spectal end members are used to produce abundance maps for the optical surface; ~30% of Io's total optical surface consists of SO2. The SO2 is concentrated in the bright equatorial band and is relatively deficient in the region of Pele-type volcanic reuptions (long 240??-360??) and the polar regions. Temperatures are computed to vary over a 40??K range, at the same illumination angle, according to variations in surface bolometric hemispheric albedo. The brightest (and locally coldest) areas correspond to areas rich in SO2 and are concentrated in an equatorial band (??30?? lat), but many small cold patches occur elsewhere. These cold patches have radiative equilibrium temperatures ???120??K at the subsolar point, resulting in SO2 saturation vapor pressures ???10-8 bar. Midlatitude areas and the region of Pele-type plume eruptions are generally warmer (due to lower albedos). These results for surface temperatures and SO2 abundances and distribution support the regional coldtrapping model for the surface and atmospheric SO2 presented by F.P. Fanale, W.B. Banerdt, L.S. Elson, T.V. Johnson, and R.W. Zurek (1982, In Satellites of Jupiter (D. Morrison, Ed.), pp. 756-781, Univ. of Arizona Press, Tucson), although the region of Pele-type volcanic eruptions may be better characterized by the regolith condtrapping/volcanic-venting model of D.L. Matson and D.B. Nash (1983, J. Geophys. Res. 88, 4771-4783). The bright equatorial band is especially effective at slowing the formation of polar caps of SO2, both by reducing the sublimation rate near the subsolar point and by coldtrapping the SO2 in the equatorial region, so that competing processes of sputtering and volcanic resurfacing may prevent the formation of polar SO2 caps.

Icarus↗

Earth and Mars: Water inventories as clues to accretional histories

The Earth has 2.7 km of water on its surface. Its mantle contains at least 150 ppm water, and probably significantly more depending on the amount of undepleted mantle and subducted crustal water that is present. Geologic evidence suggests that a few hundred meters of water are close to the Martian surface, but evidence from SNC meteorites indicates that the Martian mantle is very dry, containing no more than about 35 ppm water. Part of the difference in water content of the mantles of the two planets is attributed to plate tectonics. However, the Earth's mantle appears to contain at least several times the water content of the Martian mantle, even accounting for plate tectonics. We attribute the difference to two possible causes. The first possibility is that melting of the Earth's surface during accretion, as a result of the development of a steam atmosphere, allowed impact-devolatized water at the surface to dissolve into the Earth's interior. In contrast, because of Mars' smaller size and greater distance from the Sun, the Martian surface may not have melted, so that the devolatilized water could not dissolve into the surface. A second and preferred possibility is that Mars, like the Earth, acquired a late volatile rich veneer, but it did not get folded into the interior as with the Earth, but instead remained as a water-rich veneer. The perception of Mars as having a wet surface, but a dry interior, is consistent with what we know of the geologic history of Mars, which can be viewed as the progressive intrusion and overplating of a water-rich crust by dry, mantle-derived volcanic rocks.

Icarus↗

Irradiation of fish fillets: Relation of vapor phase reactions to storage quality

Fish fillets irradiated under air, nitrogen, oxygen, or carbon dioxide atmospheres developed rancidlike flavors when they were stored at refrigerated temperatures. Packing and irradiating under vacuum or helium prevented development of off-flavors during storage. Significant quantities of nitrate and oxidizing substances were formed when oxygen, nitrogen, or air were present in the vapor or liquid phases contained in a Pyrex glass model system exposed to ionizing radiation supplied by a 60 Co source. It was demonstrated that the delayed flavor changes that occur in stored fish fillets result from the reaction of vapor phase radiolysis products and the fish tissue substrates.

International Journal of Applied Radiation and Iso↗

Mixing models and ionic geothermometers applied to warm (up to 60°C) springs: Jordan Rift Valley, Israel

Mixing models and evaluation of SiO 2 contents of warm-water manifestations in the Jordan—Dead Sea Rift Valley indicate that these waters are fed by aquifers with estimated temperatures of up to 68°C. These calculations and Na/K ratios, concentrations of Na, K and Ca, concentrations of atmospheric Ne, Ar, Kr and Xe; and concentrations of the stable hydrogen and oxygen isotopes all indicate below-boiling temperatures. No indications are available for the existence of above-boiling geothermal systems in the Jordan Rift Valley. Slightly higher than observed temperatures are concluded for a deep component at the springs of Hammat Gader (67°C), Gofra (68°C), the Russian Garden (40°C), and the Yesha well (53–65°C). These temperatures may encourage further developments for spas and bathing installations and, to a limited extent, for space heating, but are not favorable for geothermal power generation.

Journal of Hydrology↗

Reconnaissance estimates of natural recharge to desert basins in Nevada, U.S.A., by using chloride-balance calculations

A chloride-balance method for estimating average natural recharge to groundwater basins in the Basin and Range Province of the western United States may be a useful alternative or complement to current techniques. The chloride-balance method, as presented in this paper, equates chloride in recharge water and runoff to chloride deposited in mountainous recharge-source areas by precipitation and dry fallout. Given estimates of annual precipitation on these source areas and chloride concentrations of bulk precipitation and recharge water, the rate of recharge can be estimated providing that: (1) no other major sources of chloride exist; (2) direct runoff to discharge areas in the basin is small or can otherwise be taken in account in the balance; and (3) the recharge sources for the basin are correctly delineated. The estimates are sensitive to the estimated rate of input of chloride from the atmosphere; this is the greatest data need for future applications of the method. Preliminary applications of the method to sixteen basins in Nevada, including Las Vegas Valley, indicate that the method can be a useful tool for hydrologists and resource managers. Correlation coefficients between recharge efficiencies for the basins - estimated on the basis of recharge estimates that use the chloride-balance method and two other currently used techniques - range from 0.54 to 0.95, depending on assumptions about where the method may be applied.

Nevada↗

Diffusion and consumption of methane in an unsaturated zone in north-central Illinois, U.S.A.

The distribution of CH 4 in unsaturated glacial and eolian deposits adjacent to buried low-level radioactive waste was measured, and movement of the gas from the waste source was simulated using a two-dimensional finite-difference model for gas diffusion in the unsaturated zone. Mean P CH 4 was greatest (1.56 Pa) in a pebbly-sand deposit 11.6 m below the land surface and 12 m from the waste, and generally decreased with increased horizontal distance from the waste. Mean P CH 4 was least (0.07 Pa) at depth of 1.8 m below land surface, regardless of distance from the waste. P CH 4 at the land surface averaged 0.17 Pa. Depth versus P CH 4 profiles suggest consumption of both waste-produced and atmospheric CH 4 in the upper unsaturated zone, presumably by methanotrophic microorganisms. Numerical simulations of methane movement support the consumption observation; inclusion of a term in the model for consumption of CH 4 in the upper 2 m of the unsaturated zone resulted in simulated P CH 4 within 30% of mean P CH 4 at eleven of thirteen sampling locations. A similar fit of the data was obtained for only four locations when consumption was not considered.

Illinois↗

Detectability of the effects of a hypothetical temperature increase on the Thornthwaite moisture index

Climatic changes that result from increasing concentrations of atmospheric carbon dioxide may affect the availability of water for vegetation, groundwater recharge, runoff, and human consumption. Most studies of the effects of climatic change on water resources focus on changes in mean characteristics of hydrologic variables and do not consider the effects of these changes amid natural climatic variability. In this study, the Thornthwaite moisture index, an index of the supply of water in an area (precipitation) relative to the climatic demand for water (potential evapotranspiration), was used to examine the effects of a hypothetical increase in air temperature on moisture conditions in the United States. The effects of a gradual increase in air temperature at the rate of 4°C per 100 years, with no accompanying change in precipitation, was used to induce a change in Thornthwaite moisture index values for the United States in order to: (i) determine the relation between natural variability in climate and the time needed for significant trends in the moisture index to occur in response to hypothetical warming; (ii) identify the characteristics of areas (e.g. wet/cool, hot/dry etc.) that are most likely to be the first to experience significant changes in the moisture index given the hypothetical temperature increase. The increased temperature resulted in increased potential evapotranspiration and a decrease in the moisture index across the United States. Decreases in the moisture index were greatest in cool/wet regions and least in hot/dry regions. The time required to detect significant trends in the moisture index was a function of both the magnitude of change in the moisture index and the natural year-to-year variability of the moisture index. In general, when the ratio of the magnitude of change in the moisture index to the magnitude of variability was large, the time required to detect significant trends was short. This ratio was largest in cool/wet regions resulting in the shortest detection times.

Journal of Hydrology↗

A comparison of short-term measurements of lake evaporation using eddy correlation and energy budget methods

Concurrent short-term measurements of evaporation from a shallow lake, using eddy correlation and energy budget methods, indicate that sensible and latent heat flux between lake and atmosphere, and energy storage in the lake, may vary considerably across the lake. Measuring net radiation with a net radiometer on the lake appeared to be more accurate than measuring incoming radiation nearby and modeling outgoing radiation. Short-term agreement between the two evaporation measurements was obtained by using an energy storage term that was weighted to account for the area-of-influence of the eddy correlation sensors. Relatively short bursts of evaporation were indicated by the eddy correlation sensors shortly after midnight on two of three occasions.

Oklahoma↗

Seasonal cycles of dissolved constituents in streamwater in two forested catchments in the mid-Atlantic region of the eastern U.S.A.

Streamwater discharge and chemistry of two small catchments on Catoctin Mountain in north-central Maryland have been monitored since 1982. Repetitive seasonal cycles in stream-water chemistry have been observed each year, along with seasonal cycles in the volume of stream discharge and in groundwater levels. The hypothesis that the observed streamwater chemical cycles are related to seasonal changes in the hydrological flow paths that contribute to streamflow is examined using a combination of data on groundwater levels, shallow and deep groundwater chemistry, streamwater discharge, streamwater chemistry, soil-water chemistry, and estimates of water residence times. The concentrations of constituents derived from rock weathering, particularly bicarbonate and silica, increase in streamwater during the summer when the water table is below the regolith-bedrock interface and stream discharge consists primarily of deep groundwater from the fractured-bedrock aquifer. Conversely, the concentrations in streamwater of atmospherically derived components, particularly sulfate, increase in winter when the water table is above the regolith-bedrock interface and stream discharge consists primarily of shallow groundwater from the regolith. Tritium and chlorofluorocarbon (CFC) measurements suggest that the groundwater in these systems is young, with a residence time of less than several years. The results of this study have implications for the design of large-scale water-quality monitoring programs.

Maryland↗