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Variations in the Fe mineralogy of bright Martian soil

Bright regions on Mars are interpreted as 'soil' derived by chemical alteration of crustal rocks, whose main pigmentary component is ferric oxide or oxyhydroxide. The mineralogy and mineralogic variability of ferric iron are important evidence for the evolution of Martian soil: mineralogy of ferric phases is sensitive to chemical conditions in their genetic environments, and the spatial distributions of different ferric phases would record a history of both chemical environments and physical mixing. Reflectance spectroscopic studies provide several types of evidence that discriminate possible pigmentary phases, including the position of a crystal field absorption near 0.9 microns and position and strengths of absorptions in the UV-visible wavelength region. Recent telescopic spectra and laboratory measurements of Mars soil analogs suggest that spectral features of bright soil can be explained based on a single pigmentary phase, hematite (alpha-Fe2O3), occurring in both 'nanophase' and more crystalline forms. Here we report on a systematic investigation of Martian bright regions using ISM imaging spectrometer data, in which we examined spatial variations in the position and shape of the approximately 0.9 microns absorption. We found both local and regional heterogeneities that indicate differences in Fe mineralogy. These results demonstrate that bright soils do not represent a single lithology that has been homogenized by eolian mixing, and suggest that weathering of soils in different geologic settings has followed different physical and chemical pathways.

Murchie, Scott↗

Moessbauer mineralogy of calcined Murchison meteorite

The three Antarctic meteorites B7904, Y82162, and Y86720 are unusual because they have characteristics in common with both CI and CM groups and because they apparently underwent thermal alteration after hydrous alteration on their parent body. They are also spectrally similar (visible and near-IR) to C, G, B, and F asteroids, which may imply that the surface materials on those asteroids may have undergone thermal alteration. Based on the reflectance spectra of samples of Murchison (CM2 carbonaceous chondrite) that were thermally altered in the laboratory (cryopumped and initial 10(exp -5) atm H2), Hiroi et al. concluded that putative thermal alteration occurred at temperatures of 600 to 1000 C. Similar experiments have been done on Murchison and reported mineralogical changes based on data from transmission electron diffraction microscopy, electron diffraction, and analytical electron microscopy. We report here the Mossbauer mineralogy of the same samples of thermally-altered Murchison. Mossbauer mineralogy gives the molar distribution of Fe among its oxidation states and iron-bearing mineralogies.

Morris, Richard V.↗

Moessbauer Mineralogy on the Moon: The Lunar Regolith

A first-order requirement for spacecraft missions that land on solid planetary objects is instrumentation for mineralogical analyses. For purposes of providing diagnostic information about naturally-occurring materials, the element iron is particularly important because it is abundant and multivalent. Knowledge of the oxidation state of iron and its distribution among iron-bearing mineralogies tightly constrains the types of materials present and provides information about formation and modification (weathering) processes. Because Moessbauer spectroscopy is sensitive to both the valence of iron and its local chemical environment, the technique is unique in providing information about both the relative abundance of iron-bearing phases and oxidation state of the iron. The Moessbauer mineralogy of lunar regolith samples (primarily soils from the Apollo 16 and 17 missions to the Moon) were measured in the laboratory to demonstrate the strength of the technique for in situ mineralogical exploration of the Moon. The regolith samples were modeled as mixtures of five iron-bearing phases: olivine, pyroxene, glass, ilmenite, and metal. Based on differences in relative proportions of iron associated with these phases, volcanic ash regolith can be distinguished from impact-derived regolith, impact-derived soils of different geologic affinity (e.g., highlands, maria) can be distinguished on the basis of their constituent minerals, and soil maturity can be estimated. The total resonant absorption area of the Moessbauer spectrum can be used to estimate total FeO concentrations.

Morris, Richard V.↗

Martian Global Surface Mineralogy from the Thermal Emission Spectrometer: Surface Emissivity, Mineral Map, and Spectral Endmember Data Products

One of the primary goals of the Thermal Emission Spectrometer experiment on the Mars Global Surveyor is to determine the mineralogy of the Martian surface. This information has been used to place constraints on the range of igneous processes present. The extent of water related processes on Mars has been significantly constrained by the TES experiment. The mineralogy of the Martian dust has also been refined using TES data. These mineralogical results have made a significant contribution towards determining the development of Mars, complimenting other datasets and existing information. Mineralogical determination requires the isolation of surface emissivity from the measured radiance and a variety of techniques have been developed for this purpose. Additionally, deconvolution techniques have been developed and extensively tested to separate the individual mineral contributions to the surface emissivity. These methods and techniques have produced a variety of data products that are currently available through http://tes.asu.edu/

J L Bandfield↗

Iron Mineralogy and Aqueous Alteration on Mars from the MER Moessbauer Spectrometers

The twin Mars Exploration Rovers Spirit (Gusev crater) and Opportunity (Meridiani Planum) used MIMOS II Moessbauer spectrometers to analyze martian surface materials in the first application of extraterrestrial Moessbauer spectroscopy. The instruments acquired spectra that identified the speciation of Fe according to oxidation state, coordination state, and mineralogical composition and provided quantitative information about the distribution of Fe among oxidation states, coordination states, and Fe-bearing phases. A total of 12 unique Fe-bearing phases were identified: Fe(2+) in olivine, pyroxene, and ilmenite; Fe(2+) and Fe(3+) in magnetite and chromite; Fe(3+) in nanophase ferric oxide (npOx), hematite, goethite, jarosite, an unassigned Fe3+ sulfate, and an unassigned Fe(3+) phase associated with jarosite; and Fe(0) in kamacite. Weakly altered basalts at Gusev crater (SO3 = 2.5 +/- 1.4 wt.% and Fe(3+)/Fe(sub T) = 0.24 +/- 0.11) are widespread on the Gusev plains and occur in less abundance on West Spur and Husband Hill in the Columbia Hills. Altered low-S rocks (SO3 = 5.2 +/- 2.0 wt.% and Fe(3+)/Fe(sub T) = 0.63 +/- 0.18) are the most common type of rock in the Columbia Hills. Ilm-bearing, weakly altered basalts were detected only in the Columbia Hills, as was the only occurrence of chromite in an altered low-S rock named Assemblee. Altered high-S rocks (SO3 > 14.2 wt.% and Fe(3+)/Fe(sub T) = 0.83 +/- 0.05) are the outcrop rocks of the ubiquitous Burns formation at Meridiani Planum. Two Fe(0)-bearing rocks at Meridiani Planum (Barberton and Heat Shield Rock) are meteorites. Laguna Class soil is weakly altered (SO3 = 6 +/- 2 wt.% and Fe(3+)/Fe(sub T) = 0.29 +/- 0.08) and widely distributed at both Gusev crater and Meridiani Planum, implying efficient global mixing processes or a global distribution of precursor rocks with comparable Fe mineralogical compositions. Paso Robles Class soil is heavily altered (SO3 approx. 31 wt.% and Fe(3+)/Fe(sub T) = 0.83 +/- 0.05), is relatively uncommon, and occurs as subsurface deposits in the Columbia Hills. Berry Class soil is also heavily altered (SO3 = 5 +/- 1 wt.% and Fe(3+)/Fe(sub T) = 0.60 +/- 0.13) and occurs at Meridiani Planum as lag deposits, at the crests of aeolian bedforms, and as isolated pockets on outcrop surfaces. Magnetite is identified as the strongly magnetic component in martian soil. Jarosite (in the Burns outcrop at Meridiani Planum) and goethite (in Clovis Class rocks at Gusev crater) are mineralogical markers for aqueous processes because they contain the hydroxide anion (OH(-)) as an essential part of their structure. Each yields approx.10 wt.% H2O upon dehydroxylation. The presence of Fe sulfates on opposite sides of Mars is evidence that aqueous processes under acid sulfate conditions are or were common. Except for Independence Class rocks in the Columbia Hills, the overall Fe mineralogical compositions and similar basaltic bulk chemical compositions (calculated with respect to S = Cl = 0) of the population of altered rocks analyzed by MER imply isochemical alteration of basaltic precursors at low water-to-rock ratios.

Morris, Richard V.↗

Comparison of the Mineralogy of Comet Wild 2 Coma Grains to Other Astromaterials

We propose that Kuiper Belt samples (in this case comet coma grains from the Jupiter family comet Wild 2) are recognizably different from the bulk of materials in outer belt asteroids, because of their different formation positions and times in the early solar system. We believe this despite similarities found between some Wild 2 grains and components of carbonaceous chondrites (i.e. some CAI and chondrules). Kuiper Belt samples must preserve measurable mineralogical and compositional evidence of formation at unique positions and times in the early solar nebula, and these formational differences must have imparted recognizable special characteristics. We hypothesize that these characteristics include: (1) Unique major element compositional ranges of common astromaterial minerals, especially olivine and pyroxene; (2) Unique minor element compositions of major silicate phases, especially olivine and low-Ca pyroxene; (3) Degree and effects of radiation processing -- including amorphous rims, metal coatings, and Glass with Embedded Metal and Sulfides (GEMS); (4) Presence of abundant presolar silicate grains as recognized by anomalous oxygen in silicates; (5) Oxidation state of the mineral assemblage. We are working our way through all available Wild 2 samples, selecting 1-2 non-consecutive viable TEM grids from each possible extracted Wild 2 grain. We especially prefer TEM grids from grains for which complete mineralogical details have not been published (which is to say the majority of the extracted grains). We are performing a basic mineralogic survey by E-beam techniques, to establish the essential features of the extracted Wild 2 grains. We are making a particular effort to carefully and accurately measure minor elements of olivine and pyroxene, as these minerals are widespread in astromaterials, and comparisons of their compositions will serve to place the Wild 2 silicates in contact with asteroids, meteorites and chondritic interplanetary dust particles processing. We are also making a special effort to search for mineralogical products of aqueous alteration, since their presence would reveal that Wild 2 was once internally heated, a result with dramatic implications for models of early solar system primitive bodies. Thus far carbonates are the only potential evidence for aqueous alteration for Wild 2.

Frank, David↗

Coordinated Mineralogical and Isotopic Analysis of a Cosmic Symplectite Identified in a Stardust Terminal Particle

Comet Wild-2 samples returned by the Stardust spacecraft contain a chemically diverse mixture of material, underscoring the complex nature of comets. Studies of entire Stardust aerogel tracks afford the opportunity to examine the fine-grained particle fragments distributed along the length of the track as well as the terminal particles. Previous TEM characterization of a terminal particle (TP) in track #147 revealed a symplectically intergrown iron sulfide and oxide assemblage. Mineralogically similar assemblages, known as cosmic symplectites (COS, formerly termed "new-PCP"), have only been identified in the primitive carbonaceous chondrite Acfer 094. Meteoritic COS have isotopically heavy O compositions (delta (sup 17), O-18 = 180per mille) that point to interactions with early solar system primordial water. In this study we report mineralogical and O isotopic measurements of the Wild-2 COS assemblage. Experimental: Track #147 is a "bulbous"-type track (4600 microns long) containing 7 terminal particles. The TPs were removed from the track, embedded in epoxy, and ultramicrotomed. A JEOL 2500SE 200 keV field-emission scanning-transmission electron microscope was used to obtain quantitative elemental maps and detailed mineralogical characterization. Following TEM analysis, two thin sections of TP4 (12 microns) were analyzed for O isotopes by raster ion imaging with the JSC NanoSIMS 50L. All three O isotopes were measured simultaneously using electron multipliers. San Carlos olivine grains were used as isotopic standards. Results and Discussion: The COS in the Wild-2 track #147 TP4 sample consists of symplectically intergrown pentlandite and nanocrystalline maghemite which coexists with high-Ca pyroxene with Na and Cr (kosmochlor component). This kosmochlor component could have a nebular origin and be precursors to type II chondrules in ordinary chondrites. Yet pentlandite is not a stable phase in the nebula. The COS in Acfer 094 also consists of pentlandite, but contains magnetite [4] rather than the more oxidized maghemite observed in the Wild-2 COS. The Acfer 094 COS display heavy O isotopic compositions that are the result of sulfidization and oxidation of Fe, Ni-metal grains and sulfides by O-17- and O-18-rich water in the solar nebula or possibly on the parent body. The O isotopic composition of the Wild-2 COS, however, is indistinguishable from terrestrial, indicating it was not altered by the same primordial aqueous reservoir as the Acfer 094 COS. The alteration could have occurred on the parent body by isotopically equilibrated ice. The mineralogy and petrography of Wild-2 samples suggests an incomplete or nascent hydration process. In future work we will analyze S isotopes in the track #147 TP4 COS and search for additional COS in Stardust samples.

Nguyen, A. N.↗

Mineralogy of Fluvio-Lacustrine Sediments Investigated by Curiosity During the Prime Mission: Implications for Diagenesis

The Mars Science Laboratory rover Curiosity investigated sedimentary rocks that were deposited in a diversity of fluvio-lacustrine settings. The entire science payload was employed to characterize the mineralogy and chemistry of the Sheepbed mudstone at Yellowknife Bay and the Windjana sandstone at the Kimberley. Data from the CheMin instrument, a transmission Xray diffractometer, were used to determine the quantitative mineralogy of both samples. The Sheepbed mudstone contains detrital basaltic minerals, calcium sulfates, iron oxides or hydroxides, iron sulfides, trioctahedral smectite, and amorphous material. The mineral assemblage and chemical data from APXS suggest that the trioctahedral smectite and magnetite formed authigenically as a result of alteration of olivine. The apparent lack of higher-grade phyllosilicates (e.g., illite and chlorite) and the presence of anhydrite indicate diagenesis at ~50- 80 ºC. The mineralogy of the Windjana sandstone is different than the Sheepbed mudstone. Windjana contains significant abundances of K-feldspar, low- and high-Ca pyroxenes, magnetite, phyllosilicates, and amorphous material. At least two distinct phyllosilicate phases exist: a 10 Å phase and a component that is expanded with a peak at ~11.8 Å. The identity of the expanded phase is currently unknown, but could be a smectite with interlayer H2O, and the 10 Å phase could be illite or collapsed smectite. Further work is necessary to characterize the phyllosilicates, but the presence of illite could suggest that Windjana experienced burial diagenesis. Candidates for the cementing agents include fine-grained phyllosilicates, Fe-oxides, and/or amorphous material. Interpretations of CheMin data from the Windjana sandstone are ongoing at the time of writing, but we will present an estimate of the composition of the amorphous material from mass balance calculations using the APXS bulk chemistry and quantitative mineralogy from CheMin.

Rampe, Elizabeth B.↗

Mineralogical, Spectral, and Compositional Changes During Heating of Hydrous Carbonaceous Chondrites

Hydrous carbonaceous chondrites experienced hydration and subsequent dehydration by heating, which resulted in a variety of mineralogical and spectral features [e. g., 1-6]. The degree of heating is classified according to heating stage (HS) II to IV based on mineralogy of phyllosilicates [2], because they change, with elevating temperature, to poorly crystal-line phases and subsequently to aggregates of small secondary anhydrous silicates of mainly olivine. Heating of hydrous carbonaceous chondrites also causes spectral changes and volatile loss [3-6]. Experimental heating of Murchison CM chondrite showed flattening of whole visible-near infrared spectra, especially weakening of the 3μm band strength [1, 4, 7]. In order to understand mineralogical, spectral, and compositional changes during heating of hydrous carbonaceous chondrites, we have carried out systematic investigation of mineralogy, reflectance spectra, and volatile composition of hydrated and dehydrated carbonaceous chondrites as well as experimentally-heated hydrous carbonaceous chondrites. In addition, we investigated reflectance spectra of tochilinite that is a major phase of CM chondrites and has a low dehydration temperature (~250degC).

Nakamura, T.↗

Correlated Amino Acid and Mineralogical Analyses of Milligram and Submilligram Samples of Carbonaceous Chondrite Lonewolf Nunataks 94101

Amino acids, the building blocks of proteins, have been found to be indigenous in the eight carbonaceous chondrite groups. The abundances, structural, enantiomeric and isotopic compositions of amino acids differ significantly among meteorites of different groups and petrologic types. These results suggest parent-body conditions (thermal or aqueous alteration), mineralogy, and the preservation of amino acids are linked. Previously, elucidating specific relationships between amino acids and mineralogy was not possible because the samples analyzed for amino acids were much larger than the scale at which petrologic heterogeneity is observed (sub mm-scale differences corresponding to sub-mg samples); for example, Pizzarello and coworkers measured amino acid abundances and performed X-ray diffraction (XRD) on several samples of the Murchison meteorite, but these analyses were performed on bulk samples that were 500 mg or larger. Advances in the sensitivity of amino acid measurements by liquid chromatography with fluorescence detection/time-of-flight mass spectrometry (LC-FD/TOF-MS), and application of techniques such as high resolution X-ray diffraction (HR-XRD) and scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS) for mineralogical characterizations have now enabled coordinated analyses on the scale at which mineral heterogeneity is observed. In this work, we have analyzed samples of the Lonewolf Nunataks (LON) 94101 CM2 carbonaceous chondrite. We are investigating the link(s) between parent body processes, mineralogical context, and amino acid compositions in meteorites on bulk samples (approx. 20mg) and mineral separates (< or = 3mg) from several of spatial locations within our allocated samples. Preliminary results of these analyses are presented here.

LONEWOLF NUNATAKS 94101↗

Mineralogy and Geochemistry of Sedimentary Rocks and Eolian Sediments in Gale Crater, Mars: A Review After Six Earth Years of Exploration with Curiosity

The Mars Science Laboratory Curiosity rover arrived at Mars in August 2012 with a primary goal of characterizing the habitability of ancient and modern environments. Curiosity was sent to Gale crater to study a sequence of ∼3.5 Ga old sedimentary rocks that, based on orbital visible and near- to short-wave infrared reflectance spectra, contain secondary minerals that suggest deposition and/or alteration in liquid water. The sedimentary sequence in the lower slopes of Mount Sharp in Gale crater preserves a dramatic shift on early Mars from a relatively warm and wet climate to a cold and dry climate, based on a transition from smectite-bearing strata to sulfate-bearing strata. The rover is equipped with instruments to examine the sedimentology and identify compositional changes in the stratigraphy. The Chemistry and Mineralogy (CheMin) instrument is one of two internal laboratories on Curiosity and includes a transmission X-ray diffractometer (XRD) and X-ray fluorescence (XRF) spectrometer. CheMin measures loose sediment samples scooped from the surface and drilled rock powders, and the XRD provides quantitative mineralogy to a detection limit of ∼1 wt.% for crystalline phases. Curiosity has traversed>20 km since landing and has primarily been exploring an ancient lake environment fed by streams and groundwater. Of the 19 drilled rock samples analyzed by CheMin as of sol 2300 (January 2019), 15 are from fluvio-lacustrine deposits that comprise the Bradbury and Murray formations. Most of these samples were drilled from units that did not have a clear mineralogical signature from orbit. Results from CheMin demonstrate an astounding diversity in the mineralogy of these rocks that signifies geochemical variations in source rocks, transportation mechanisms, and depositional and diagenetic fluids. Most detrital igneous minerals are basaltic, but the discovery in a few samples of abundant silicate minerals that usually crystallize from evolved magmas on Earth remains enigmatic. Trioctahedral smectite and magnetite at the base of the section may have formed from low-salinity pore waters with a circumneutral pH in lake sediments. A transition to dioctahedral smectite, hematite, and Ca-sulfate going up section suggests a change to more saline and oxidative aqueous conditions in the lake waters themselves and/or in diagenetic fluids. Perhaps one of the biggest mysteries revealed by CheMin is the high abundance of X-ray amorphous materials (15–73 wt.%) in all samples drilled or scooped to date. CheMin has analyzed three modern eolian sands, which have helped constrain sediment transport and mineral segregation across the active Bagnold Dune Field. Ancient eolian sandstones drilled from the Stimson formation differ from modern eolian sands in that they contain abundant magnetite but no olivine, suggesting that diagenetic processes led to the alteration of olivine to release Fe(II) and precipitate magnetite. Fracture-associated halos in the Stimson and the Murray formations are evidence for complex aqueous processes long after the streams and lakes vanished from Gale crater. The sedimentology and composition of the rocks analyzed by Curiosity demonstrate that habitable environments persisted intermittently on the surface or in the subsurface of Gale crater for perhaps more than a billion years.

E.B. Rampe↗

Recent Mineralogical Discoveries in Gale Crater, Mars from the CheMin XRD Instrument

Curiosity landed in Gale crater in August 2012 and has traversed ~27 km through sedimentary rocks that comprise the lower slopes of a ~5 km-high mound, informally known as Mount Sharp, to investigate depositional/diagenetic environments and potential habitability. Orbital visible/short-wave infrared spectra revealed some strata on lower Mount Sharp contain mineral assemblages that are indicative of water-rock interactions (1-3), with sulfate-bearing units overlying phyllosilicate-bearing units. This mineralogical succession may mark the beginning of the transition from a relatively wet/warm to a very dry/cold Mars (e.g., 1, 4). Curiosity began studying the strata that show mineralogical signatures from orbit in 2018, with the investigation of Vera Rubin ridge. Here, we describe the mineralogical diversity in these strata using X-ray diffraction data collected by the CheMin instrument. We report on the mineral assemblages from the hematite-rich Vera Rubin ridge, the smectite-rich Glen Torridon region, and the transition from the smectite-bearing rocks to the sulfate-bearing unit. We will present hypotheses explaining the changes in mineralogy throughout the strata, including changes in depositional environment, diagenetic reactions with saline groundwater, and groundwater-lake water interactions (e.g., 5-7).

V. M. Tu↗

Iron precipitation under controlled oxygen flow: Mineralogical implications for BIF precursors in the Archean ocean

Banded iron formation (BIF) deposition in the Archean ocean is thought to have been initiated by the oxidation of dissolved iron into ferric primary precursor phases that descended through the water column and were deposited on the seafloor. Effective interpretation of the trace element and isotopic composition of BIFs in the geologic record requires an understanding of the identity and longevity of those precursor phases. Temporal and spatial variation in oxidant concentration and ocean chemistry may have driven precursor mineralogy. Furthermore, precursor phases may undergo transitions during descent and burial. This experimental study follows the evolution of iron mineralogy, speciation, and redox state during the precipitation of iron under variable oxygen fluxes and in fluids containing different iron-complexing anions (chloride, sulfate, and phosphate). Additionally, suspensions collected after incomplete oxidation were anoxically aged to simulate changes to precursor mineralogy during descent below the seawater redoxcline. Results from X-ray diffraction, sequential dissolution, colorimetric determination of Fe redox state, and Fe K-edge X-ray absorption fine structure spectroscopy showed that under all experimental conditions, intermediate precipitates collected before complete iron uptake contained mineralized ferrous iron. Purely ferric mineral assemblages were not observed until iron was removed from solution. In low-oxygen experiments, intermediate precipitates contained phases with stoichiometric Fe 2+ , including magnetite, vivianite, and green rust (GR). Chloride green rust (GR1) had more ferric iron than sulfate green rust (GR2) and more readily transitioned to magnetite via disproportionation. GR2 was stable over a broader range of iron uptake; magnetite appeared mainly as an additional oxidation product in sulfate solution. In high oxygen experiments, mineralized ferrous iron occurred in amorphous phases or as a non-stoichiometric component in ferric oxides; final ferric assemblages were less crystalline than in low-oxygen equivalents. Low concentrations of phosphate increased the total iron oxidation rate, but also increased the ferrous content of intermediate precipitates. The incorporation of phosphate stabilized GR2 and facilitated GR2 precipitation over a larger range of iron uptake. In higher concentrations of phosphate, vivianite and poorly crystalline ferric hydroxides formed in place of GR. Here, these findings suggest that over a range of possible ocean chemistries, mixed-valence phases may have been short lived but relevant precursors to BIF. Additionally, anionic chemistry and oxidant concentration are shown to influence the crystallinity and chemical resistivity of final ferric assemblages, affecting their reactivity during later anoxic burial.

58 GEOSCIENCES↗

Spatial variability of aerosol iron mineralogy and oxidation states over the Arctic Ocean

The mineralogy and oxidation state of aerosol iron (Fe) play important roles in controlling aerosol Fe solubility and consequent bioavailability in seawater. In this study, the spatial variability of Fe mineralogy and oxidation states in aerosols collected during the US GEOTRACES Western Arctic cruise (GN01) were determined using synchrotronbased X-ray absorption near edge structure (XANES) spectroscopy. Both Fe(II) minerals (biotite, ilmenite) and Fe (III) minerals (ferrihydrite, hematite, Fe(III) phosphate) were found in these samples. However, aerosol Fe mineralogy and solubility observed during this cruise varied spatially and can be grouped into three clusters based on the air masses that affected aerosols collected in different regions: (1) biotite-enriched particles (87 % biotite, 13 % hematite) with the air masses passing over Alaska, showing relatively low Fe solubility (4.0 +/- 1.7 %); (2) ferrihydrite-enriched particles (82 % ferrihydrite, 18 % ilmenite) collected in the remote Arctic air, showing relatively high Fe solubility (9.6 +/- 3.3 %); (3) the fresh dust derived from North America and Siberia, primarily dominated by hematite (41 % hematite, 25 % Fe(III) phosphate, 20 % biotite, 13 % ferrihydrite), showing relatively low Fe solubility (5.1 +/- 3.5). A significant positive correlation was found between Fe oxidation state and Fe fractional solubility, suggesting that long-range transport could modify iron (hydr) oxide such as ferrihydrite through atmospheric processing, influencing aerosol Fe solubility and consequently Fe bioavailability in the remote Arctic Ocean.

54 ENVIRONMENTAL SCIENCES↗

How Does the Use of Different Soil Mineralogical Atlases Impact Soluble Iron Deposition Estimates?

Atmospheric deposition is the primary input of soluble iron (Fe) in remote regions of the open ocean. Fe constitutes a fundamental micro-nutrient for marine biota, affecting biogeochemical cycles and ultimately carbon uptake. Fe is emitted to the atmosphere primarily from dust sources. Fe solubility at emission is origin-dependent, being mostly insoluble when associated with dust minerals. Earth System Models (ESMs) commonly assume that dust aerosols have a globally uniform composition, neglecting known regional variations in soil mineralogy. This work assesses the implications of soil composition uncertainties on the bio-available Fe delivery to the ocean by using a state-of-the-art ESM with a detailed atmospheric Fe cycle (EC-Earth3-Iron). We run two 1-year simulations considering two different Soil Mineralogy Atlases (SMAs). Our results reveal a non-negligible impact of soil mineralogy uncertainties on soluble Fe estimates. By only changing the source of information for the soil composition and updating the Fe content in minerals, we find differences of 31.5% in mineral Fe emissions and 26.7% in soluble Fe deposition budgets.

soluble iron↗

Reply to “A Comment on ‘an Evolutionary System of Mineralogy: Proposal for A Classification of Planetary Materials Based on Natural Kind Clustering’”

I welcome the “Comment” from Hatert et al. (2021) related to the proposal for an “Evolutionary system of mineralogy” (Hazen 2019) and thank them for their historically informed, conceptually nuanced, and consistently constructive contribution. They offer corrections related to two facets of my paper that seemed unfairly to criticize aspects of the International Mineralogical Association’s Commission on New Minerals, Nomenclature and Classification (IMA-CNMNC) protocols for classifying minerals. First, they note an unfortunate inferred ambivalence with respect to the relationship between the IMA system and the new evolutionary system. If I was once ambivalent, that view has changed. Having spent the past two years in an ongoing effort to develop this new historical approach, I am struck every day by the power of the IMA-CNMNC system of species classification and nomenclature, which is fundamental and indispensable to the science of mineralogy. As Hatert et al. suggest, any new approach to organizing natural solids, including one focused on planetary evolution, must rest on the foundation provided by the IMA-CNMNC and its many volunteers who selflessly bring order to the mineral kingdom. In the best scenario, the evolutionary system may one day emerge as one of several useful approaches that complement and amplify but in no way replace this core IMA-CNMNC foundation, as clearly stated in the abstract of Hazen (2019). Second, Hatert et al. (2021) offer corrections regarding the IMA-CNMNC approach to classification, in particular a mischaracterization of the formal process to incorporate amorphous phases, poorly crystalline materials, and loosely defined “mineraloids.” I am grateful for the clarifications, as well as the implication that IMA protocols may facilitate the embrace of additional such phases in the future. Finally, I welcome the chance to explore further the emerging concept of “natural kinds” as applied to the mineral kingdom. Here, our thoughts differ. I suggest that minerals, considered in their information-rich, idiosyncratic, paragenetic contexts (in contrast to IMA-CNMNC species), have the potential to represent quintessential examples of “natural kinds.” Furthermore, when viewed in their evolutionary context, minerals offer an intriguing opportunity to expand the concept of “historical natural kinds” beyond its present limited and, at times, controversial use in biology, into the realm of the co-evolving geosphere and biosphere.

Philosophy of mineralogy↗

Lithological controls on soil geochemistry and clay mineralogy across Spodosols in the coastal temperate rainforest of southeast Alaska

The interaction of similar soil forming factors with different parent materials determines soil chemical weathering, influencing soil processes and properties. In the coastal temperate rainforests of southeast Alaska, Spodosols is the dominant soil order in well-drained parent materials regardless of the lithology. Yet, the role of lithology on chemical weathering, base cation depletion, and mineral transformation during pedogenesis remains elusive. Here, we established a lithosequence comprised of soils derived from tonalite, phyllite, slate, and metavolcanic rocks to test the hypothesis that despite the soils in southeast Alaska presenting similar taxonomy and morphology, the influence of lithology in chemical weathering intensity and mineralogy can be detected. We evaluated physicochemical properties, clay mineralogy, Fe-Al oxides, chemical weathering, and elemental mass balance on eleven Spodosols sampled along the lithosequence. We also propose a new weathering index, the Weathering Index for Spodosols (WISP), suitable to evaluate the weathering degree of soils with Al mobility and base-rich parent materials. This index fills a gap in traditional weathering indices that uses Al as an immobile element and/or does not evaluate the leaching of main base cations. We found the pedons across the lithosequence expressed similar physicochemical properties, with predominantly thick profiles, presenting andic properties, relatively thick spodic horizons, and thin E horizons. Podzolization imposed similar mineral transformation trends, mainly dissolution of chlorite, mica alteration to interstratified mica-vermiculite, and formation of smectite in E horizons. Kaolinite was detected in the soils from all lithologies, but only in trace amounts in phyllite soils. Fe oxides depth distribution was similar but with a higher concentration in the slate (44.5 ± 4.2 g/kg), followed by metavolcanic (31.6 ± 4.0 g/kg), phyllite (27.9 ± 3.8 g/kg), and tonalite soils (19.9 ± 5.7 g/kg) and predominantly as organometallic complexes (extracted by Na-pyrophosphate). The stronger weathering of chlorite and mica in the E horizons was reflected in larger losses of Mg and K, while Ca and Na were more depleted in the spodic horizons, suggesting plagioclase weathering. Slate soils were the most depleted in base cations, followed by phyllite, tonalite, and metavolcanic soils. The more depleted status of slate soils was supported by the higher WISP values (WISP = 62), followed by phyllite (WISP = 55), tonalite (WISP = 53), and metavolcanic soils (WISP = 45). Our results demonstrated that lithology controlled elemental depletion intensities, Fe oxide concentrations, and partially the clay fraction mineralogy in addition to podzolization acting as a dominant pedogenic process across all sites. These findings advance our understanding of the role of lithology on soil mineralogy/geochemistry that impacts critical soil functions, such as the soil carbon cycle, elemental fluxes, organo-mineral interactions, and solid-solution reactions.

54 ENVIRONMENTAL SCIENCES↗

Quantifying fish otolith mineralogy for trace-element chemistry studies

Otoliths are frequently used to infer environmental conditions or fish life history events based on trace-element concentrations. However, otoliths can be comprised of any one or combination of the three most common polymorphs of calcium carbonate - aragonite, calcite, and vaterite - which can affect the ecological interpretation of otolith trace-element results. Previous studies have reported heterogeneous calcium carbonate compositions between left and right otoliths but did not provide quantitative assessments of polymorph abundances. In this study, neutron diffraction and Raman spectroscopy were used to identify and quantify mineralogical compositions of Chinook salmon Oncorhynchus tshawytscha otolith pairs. We found mineralogical compositions frequently differed between otoliths in a pair and accurate calcium carbonate polymorph identification was rarely possible by visual inspection alone. The prevalence of multiple polymorphs in otoliths is not well-understood, and future research should focus on identifying otolith compositions and investigate how variations in mineralogy affect trace-element incorporation and potentially bias environmental interpretations.

60 APPLIED LIFE SCIENCES↗