Mobility of arsenic and vanadium in waterlogged calcareous soils due to addition of zeolite and manganese oxide amendments

Addition of manganese(IV) oxides (MnO2) and zeolite can affect the mobility of As and V in soils due to geochemical changes that have not been studied well in calcareous, flooded soils. This study evaluated the mobility of As and V in flooded soils surface-amended with MnO2 or zeolite. A simulated summer flooding study was conducted for 8 weeks using intact soil columns from four calcareous soils. Redox potential was measured in soils, whereas pH, major cations, and As and V concentrations were measured biweekly in pore water and floodwater. Aqueous As and V species were modeled at 0, 4, and 8 weeks after flooding (WAF) using Visual MINTEQ modeling software with input parameters of redox potential, temperature, pH, total alkalinity, and concentrations of major cations and anions. Aqueous As concentrations were below the critical thresholds (<100 μg L−1), whereas aqueous V concentrations exceeded the threshold for sensitive aquatic species (2–80 μg L−1). MnO2-amended soils were reduced to sub-oxic levels, whereas zeolite-amended and unamended soils were reduced to anoxic levels by 8 WAF. MnO2 decreased As and V mobilities, whereas zeolite had no effect on As but increased V mobility, compared to unamended soils. Arsenic mobility increased under anoxic conditions, and V mobility increased under oxic and alkaline pH conditions. Conversion of As(V) to As(III) and V(V) to V(IV) was regulated by MnO2 in flooded soils. MnO2 can be used as an amendment in immobilizing As and V, whereas the use of zeolite in flooded calcareous soils should be done cautiously."This research was financially supported by Environment and Climate Change Canada through Lake Winnipeg Basin Program, University of Winnipeg Major Grant and Canadian Queen Elizabeth II Diamond Jubilee Scholarships: Advanced Scholars program."https://acsess.onlinelibrary.wiley.com/doi/10.1002/jeq2.2045

Natural Analogue Constraints on Europa's Non-ice surface Material

Non-icy material on the surface of Jupiter’s moon Europa is hypothesised to have originated from its subsurface ocean, and thus provide a record of ocean composition and habitability. The nature of this material is debated, but observations suggest that it comprises hydrated sulfate and chloride salts. Analogue spectroscopic studies have previously focused on single phase salts under controlled laboratory conditions. We investigated natural salts from perennially cold (<0 °C) hypersaline springs, and characterised their reflectance properties at 100 K, 253 K and 293 K. Despite similar major ion chemistry, these springs form mineralogically diverse deposits, which when measured at 100 K closely match reflectance spectra from Europa. In the most sulfate-rich samples, we find spectral features predicted from laboratory salts are obscured. Our data are consistent with sulfate-dominated europan non-icy material, and further, show that the emplacement of endogenic sulfates on Europa’s surface would not preclude a chloride-dominated ocean

Biosignature detection by Mars rover equivalent instruments in samples from the CanMars Mars Sample Return Analogue Deployment

The University of Winnipeg's HOSERLab was established with funding from the Canada Foundation for Innovation, the Manitoba Research Innovations Fund and the Canadian Space Agency, whose support is gratefully acknowledged. This study was supported with grants from the Canadian Space Agency through their FAST program, NSERC, and UWinnipeg.This work details the laboratory analysis of a suite of 10 samples collected from an inverted fluvial channel near Hanksville, Utah, USA as a part of the CanMars Mars Sample Return Analogue Deployment (MSRAD). The samples were acquired along the rover traverse for detailed off-site analysis to evaluate the TOC and astrobiological significance of the samples selected based on site observations, and to address one of the science goals of the CanMars mission: to evaluate the ability of different analytical techniques being employed by the Mars2020 mission to detect and characterize any present biosignatures. Analytical techniques analogous to those on the ExoMars, MSL and the MER rovers were also applied to the samples. The total organic carbon content of the samples was <0.02% for all but 4 samples, and organic biosignatures were detected in multiple samples by UV–Vis–NIR reflectance spectroscopy and Raman spectroscopy (532 nm, time-resolved, and UV), which was the most effective of the techniques. The total carbon content of the samples is < 0.3 wt% for all but one calcite rich sample, and organic C was not detectable by FTIR. Carotene and chlorophyll were detected in two samples which also contained gypsum and mineral phases of astrobiological importance for paleoenvironment/habitability and biomarker preservation (clays, gypsum, calcite) were detected and characterized by multiple techniques, of which passive reflectance was most effective. The sample selected in the field (S2) as having the highest potential for TOC did not have the highest TOC values, however, when considering the sample mineralogy in conjunction with the detection of organic carbon, it is the most astrobiologically relevant. These results highlight importance of applying multiple techniques for sample characterization and provide insights into their strengths and limitations.PostprintPeer reviewe

Spectral reflectance (0.35-2.5 mu m) properties of garnets: Implications for remote sensing detection and characterization

The utility of spectral reflectance for identification of the main end-member garnets: almandine (Fe32+Al2Si3O12), andradite (Ca3Fe23+Si3O12), grossuiar (Ca3Al2Si3O12), pyrope (Mg3Al2Si3O12), spessartine (Mn32+Al2Si3O12), and uvarovite (Ca3Cr23+Si3O12) was studied using a suite of 60 garnet samples. Compositional and structural data for the samples, along with previous studies, were used to elucidate the mechanisms that control their spectral reflectance properties. Various cation substitutions result in different spectral properties that can be determine the presence of various optically-active cations and help differentiate between garnet types. It was found that different wavelength regions are sensitive to different compositional and structural properties of garnets. Crystal-field absorptions involving Fe2+ and/or Fe3+ are responsible for the majority of spectral features in the garnet minerals examined here. There can also be spectral features associated with other cations and mechanisms, such as Fe2+-Fe3+ and Fe2+-Ti4+ intervalence charge transfers. The visible wavelength region is useful for identifying the presence of various cations, in particular, Fe (and its oxidation state), Ti4+, Mn2+, and Cr3+. In the case of andradite, spessartine and uvarovite, the visible region absorption bands are characteristic of these garnets in the sense that they are associated with the major cation that distinguishes each: Fe-[6](3+) for andradite, Mn-[8](2+) for spessartine, and Cr-[6](3+) for uvarovite. For grossuiar, the presence of small amounts of Fe3+ leads to absorption bands near 0.370 and 0.435 mu m. These bands are also seen in pyrope-almandine spectra, which also commonly have additional absorption bands, due to the presence of Fe2+. The common presence of Fe2+ in the dodecahedral site of natural garnets gives rise to three Fe2+ spin-allowed absorption bands in the 1.3,1.7, and 2.3 mu m regions, providing a strong spectral fingerprint for all Fe2+-bearing garnets studied here. Garnets containing Mn2+ have additional visible (similar to 0.41 mu m ) spectral features due to Mn-[8](2+). Garnets containing Cr3+, exhibits two strong absorption bands near similar to 0.7 mu m due to spin-forbidden Cr-[6](3+) transitions, as well as Cr-[6](3+) spin-allowed features near 0.4-0.41 mu m and 0.56-0.62 mu m, and( [6])Cr(3+) spin-allowed transitions between 0.41 and 0.68 mu m. Common silicate garnet spectra, in summary, are distinct from many other rock-forming silicates and can be spectrally distinct from one garnet species to another. Iron dominates the spectral properties of garnets, and the crystallographic site and oxidation state of the iron both affect garnet reflectance spectra

Mineralogical Criteria for the Parent Asteroid of the “Carbonaceous” Achondrite NWA 6704

The unique achondrite meteorite Northwest Africa (NWA) 6704 and its paired samples are fragments of an unknown parent asteroid that experienced large-scale igneous melting early in our solar system's history. The geochemistry and mineralogy of NWA 6704 show that its parent asteroid has affinities with carbonaceous chondrites and that the precursor materials were relatively oxidized. While large-scale melting has affected the meteorite, there is no evidence for equilibration with a metallic melt. NWA 6704 paired meteorites therefore provide insights into the evolution of planetesimals and bodies that accreted from source materials, possibly in the ice-rich outer solar system. Currently, we lack an understanding of the distribution of potential parent asteroids of the NWA 6704 meteorites. We have undertaken a detailed multiwavelength (0.35-25 mu m) spectroscopic and geochemical investigation of NWA 6704 to provide constraints on the potential parent asteroids of these enigmatic meteorites. In comparison with asteroid spectra, NWA 6704 is similar to the S(VI) subtypes of the S-asteroid complex. By using the Bus-DeMeo Taxonomic Classifier, we determine that NWA 6704 has affinities toward V-type (Vesta type) asteroids. We have determined that the parent asteroid of NWA 6704 would be a V-type asteroid that is not dynamically linked to Vesta and also fall in the S(VI) subtype of the Band I center versus Band area ratio diagram. A search in the literature for potential parent bodies yielded one asteroid, (34698) 2001 OD22, as a possible candidate.This item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]

Effects of viewing geometry, aggregation state, and particle size on reflectance spectra of the Murchison CM2 chondrite deconvolved to Dawn FC band passes

Several current and soon-to-launch missions will investigate ‘dark’ asteroids, whose spectra have few weak or no distinct spectral features. Some carbonaceous chondrites, particularly the CI and CM groups, are reasonable material analogues for many dark asteroid surfaces. In addition to compositional variations, many non-compositional effects, including viewing geometry, surface particle size and particle sorting, can influence reflectance spectra, potentially complicating mineralogical interpretation of such data from remote surfaces. We have carried out an investigation of the effects of phase angle, particle size, aggregation state, and intra-sample heterogeneity on the reflectance spectra (0.4–1.0 μm) of the Murchison CM2 carbonaceous chondrite, deconvolved to Dawn Framing Camera (FC) band passes. This study was motivated by the desire to derive information about the surface of Ceres from Dawn FC data. Key spectral parameters derived from the FC multispectral data include various two-band reflectance ratios as well as three-band ratios that have been derived for mineralogical analysis. Phase angle effects include increased visible slope with increasing phase angle, a trend that may reverse at very high phase angles. Fine-grained particles exert a strong influence on spectral properties relative to their volumetric proportion. Grain size variation effects include a decrease in spectral contrast and increased visible spectral slope with decreasing grain size. Intra-sample heterogeneity, while spectrally detectable, is of relatively limited magnitude

Spectral reflectance "deconstruction" of the Murchison CM2 carbonaceous chondrite and implications for spectroscopic investigations of dark asteroids

International audienceCarbonaceous chondrites (CCs) are important materials for understanding the early evolution of the solar system and delivery of volatiles and organic material to the early Earth. Presumed CC-like asteroids are also the targets of two current sample return missions: OSIRIS-REx to asteroid Bennu and Hayabusa-2 to asteroid Ryugu, and the Dawn orbital mission at asteroid Ceres. To improve our ability to identify and characterize CM2 CC-type parent bodies, we have examined how factors such as particle size, particle packing, and viewing geometry affect reflectance spectra of the Murchison CM2 CC. The derived relationships have implications for disc-resolved examinations of dark asteroids and sampleability. It has been found that reflectance spectra of slabs are more blue-sloped (reflectance decreasing toward longer wavelengths as measured by the 1.8/0.6 μm reflectance ratio), and generally darker, than powdered sample spectra. Decreasing the maximum grain size of a powdered sample results in progressively brighter and more red-sloped spectra. Decreasing the average grain size of a powdered sample results in a decrease in diagnostic absorption band depths, and redder and brighter spectra. Decreasing porosity of powders and variations in surface texture result in spectral changes that may be different as a function of viewing geometry. Increasing thickness of loose dust on a denser powdered substrate leads to a decrease in absorption band depths. Changes in viewing geometry lead to different changes in spectral metrics depending on whether the spectra are acquired in backscatter or forward-scatter geometries. In backscattered geometry, increasing phase angle leads to an initial increase and then decrease in spectral slope, and a general decrease in visible region reflectance and absorption band depths, and frequent decreases in absorption band minima positions. In forward scattering geometry, increasing phase angle leads to small non-systematic changes in spectral slope, and general decreases in visible region reflectance, and absorption band depths. The highest albedos and larger band depths are generally seen in the lowest phase angle backscattering geometry spectra. The reddest spectra are generally seen in the lowest phase angle backscatter geometry spectra. For the same phase angle, spectra acquired in forward scatter geometry are generally redder and darker and have shallower absorption bands than those acquired in backscatter geometry. Overall, backscatter geometry-acquired spectra are flatter, brighter, and have deeper 0.7 μm region absorption band depths than forward scatter geometry-acquired spectra. It was also found that the 0.7, 0.9, and 1.1 μm absorption bands in Murchison spectra, which are attributable to various Fe electronic processes, are ubiquitous and can be used to recognize CM2 chondrites regardless of the physical properties of the meteorite and viewing geometry