Other
Scientific paper
Dec 2008
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2008agufm.p43b1403k&link_type=abstract
American Geophysical Union, Fall Meeting 2008, abstract #P43B-1403
Other
3255 Spectral Analysis (3205, 3280), 6225 Mars
Scientific paper
A Mössbauer doublet assigned to ferric sulfate (Fe3D2) was identified in Paso Robles, Mars, spectra by Morris et al. (2006), who noted that its parameters are not diagnostic of any specific mineral because a number of different sulfates with varying parageneses might be responsible for this doublet. Work by Lane et al. (2008) used a multi-instrument approach based on Fe3+ sulfate spectra acquired with VNIR and midinfrared reflectance, mid-infrared emission and Mössbauer spectrometers to narrow down the possible ferric sulfate phases present at Paso Robles to ferricopiapite possibly mixed with other ferric sulfates such as butlerite, parabutlerite, fibroferrite, or metahomanite. Thus, we explore here the crystal-chemical rationale behind these interpretations of the Mössbauer results, using similarities and difference among mineral structures to explore which phases might have similar coordination polyhedra around the Fe atoms in sulfates. Work by Hawthorne et al. (2000) organizes the sulfate minerals into groups with analogous crystal structures. Mössbauer doublets assigned to ferric sulfates ubiquitously have isomer shifts (IS) of 0.40-53 mm/s so that IS is non-diagnostic. However, quadrupole splitting of doublets in these mineral groups has a wide range (0-1.4 mm/s) and the variation can be systematically correlated with different structure types. Members of the hydration series Fe2(SO4)3 · n H2O, which includes quenstedtite, coquimbite, paracoquimbite, kornelite, and lausenite have Mössbauer spectra that closely resemble singlets because of their near-zero QS. These minerals share structures involving finite clusters of sulfate tetrahedral and Fe octahedral or chains of depolymerized clusters, and all mineral species with these structures share similar Mössbauer parameters. At the other extreme, ferric sulfates with structures based on infinite sheets (hydrotalcite, alunite, jarosite), tend to have large electric field gradients at the nucleus of the Fe3+ cation, resulting in larger QS values (1-1.4 mm/s). Between these extremes of QS are two populations of structures based on finite clusters of polyhedra with QS = 0.36-0.80 mm/s (coquimbite, römerite, halotrichite, rozenite) and infinite chains with QS = 0.70-0.97 mm/s (chalcanthite, butlerite, fibroferrite, metahomanite). Our fits to the Paso Robles sol 429A data show two ferric doublets, both with IS = 0.42-0.43 mm/s but with differing QS = 0.36 and 0.93 mm/s; these parameters rule out mineral structures that have spectra with very high or very low QS. Ferric sulfates with structures composed of finite clusters and infinite chains thus provide the closest matches to the Paso Robles Mössbauer doublets, as well as spectra of other bright soils. Further constraints provided by other types of spectroscopy are then needed to determine which species within these structure groups are present. As additional sulfate structures are characterized, it will be possible to better understand the interrelationships among sulfate crystal structures and their spectral characteristics may provide additional constraints on mineral identification from ferric materials of all types. Morris et al. (2006) JGR, 111, doi: 10.1029/2005JE002584. Lane et al. (2008) Amer. Mineral., 93, 738-739. Hawthorne et al. (2000) Revs. Mineral., 40, 1-112.
Bishop Janice L.
Darby Dyar M.
Knutson J.
Lane Melissa D.
Sklute Elizabeth C.
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