The Fe/S ratio of pyrrhotite group sulfides in chondrites: An indicator of oxidation and implications for return samples from asteroids Ryugu and Bennu.

Determining compositional trends among individual minerals is key to understanding the thermodynamic conditions under which they formed and altered, and is also essential to maximizing the scientific value of small extraterrestrial samples, including returned samples and meteorites. Here we report the chemical compositions of Fe-sulfides, focusing on the pyrrhotite-group sulfides, which are ubiquitous in chondrites and are sensitive indicators of formation and alteration conditions in the protoplanetary disk and in small Solar System bodies. Our data show that while there are trends with the at.% Fe/S ratio of pyrrhotite with thermal and aqueous alteration in some meteorite groups, there is a universal trend between the Fe/S ratio and degree of oxidation. Relatively reducing conditions led to the formation of troilite during: (1) chondrule formation in the protoplanetary disk (i.e., pristine chondrites) and (2) parent body thermal alteration (i.e., LL4 to LL6, CR1, CM, and CY chondrites). Oxidizing and sulfidizing conditions led to the formation of Fe-depleted pyrrhotite with low Fe/S ratios during: (1) aqueous alteration (i.e., CM and CI chondrites), and (2) thermal alteration (i.e., CK and R chondrites). The presence of troilite in highly aqueously altered carbonaceous chondrites (e.g., CY, CR1, and some CM chondrites) indicates they were heated after aqueous alteration. The presence of troilite, Fe-depleted pyrrhotite, or pyrite in a chondrite can provide an estimate of the oxygen and sulfur fugacities at which it was formed or altered. The data reported here can be used to estimate the oxygen fugacity of formation and potentially the aqueous and/or thermal histories of sulfides in extraterrestrial samples, including those returned by the Hayabusa2 mission and due to be returned by the OSIRIS-REx mission in the near future.

Ecosystem-bedrock interaction changes nutrient compartmentalization during early oxidative weathering.

Ecosystem-bedrock interactions power the biogeochemical cycles of Earth's shallow crust, supporting life, stimulating substrate transformation, and spurring evolutionary innovation. While oxidative processes have dominated half of terrestrial history, the relative contribution of the biosphere and its chemical fingerprints on Earth's developing regolith are still poorly constrained. Here, we report results from a two-year incipient weathering experiment. We found that the mass release and compartmentalization of major elements during weathering of granite, rhyolite, schist and basalt was rock-specific and regulated by ecosystem components. A tight interplay between physiological needs of different biota, mineral dissolution rates, and substrate nutrient availability resulted in intricate elemental distribution patterns. Biota accelerated CO2 mineralization over abiotic controls as ecosystem complexity increased, and significantly modified the stoichiometry of mobilized elements. Microbial and fungal components inhibited element leaching (23.4% and 7%), while plants increased leaching and biomass retention by 63.4%. All biota left comparable biosignatures in the dissolved weathering products. Nevertheless, the magnitude and allocation of weathered fractions under abiotic and biotic treatments provide quantitative evidence for the role of major biosphere components in the evolution of upper continental crust, presenting critical information for large-scale biogeochemical models and for the search for stable in situ biosignatures beyond Earth.

Ecosystem Composition Controls the Fate of Rare Earth Elements during Incipient Soil Genesis.

The rare earth elements (REE) are increasingly important in a variety of science and economic fields, including (bio)geosciences, paleoecology, astrobiology, and mining. However, REE distribution in early rock-microbe-plant systems has remained elusive. We tested the hypothesis that REE mass-partitioning during incipient weathering of basalt, rhyolite, granite and schist depends on the activity of microbes, vascular plants (Buffalo grass), and arbuscular mycorrhiza. Pore-water element abundances revealed a rapid transition from abiotic to biotic signatures of weathering, the latter associated with smaller aqueous loss and larger plant uptake. Abiotic dissolution was 39% of total denudation in plant-microbes-mycorrhiza treatment. Microbes incremented denudation, particularly in rhyolite, and this resulted in decreased bioavailable solid pools in this rock. Total mobilization (aqueous + uptake) was ten times greater in planted compared to abiotic treatments, REE masses in plant generally exceeding those in water. Larger plants increased bioavailable solid pools, consistent with enhanced soil genesis. Mycorrhiza generally had a positive effect on total mobilization. The main mechanism behind incipient REE weathering was carbonation enhanced by biotic respiration, the denudation patterns being largely dictated by mineralogy. A consistent biotic signature was observed in La:phosphate and mobilization: solid pool ratios, and in the pattern of denudation and uptake.

Redetermination of metarossite, CaV5+2O6·2H2O.

The crystal structure of metarossite, ideally CaV2O6·2H2O [chemical name: calcium divanadium(V) hexa-oxide dihydrate], was first determined using precession photographs, with fixed isotropic displacement parameters and without locating the positions of the H atoms, leading to a reliability factor R = 0.11 [Kelsey & Barnes (1960 ▸). Can. Mineral.6, 448-466]. This communication reports a structure redetermination of this mineral on the basis of single-crystal X-ray diffraction data of a natural sample from the Blue Cap mine, San Juan County, Utah, USA (R1 = 0.036). Our study not only confirms the structural topology reported in the previous study, but also makes possible the refinement of all non-H atoms with anisotropic displacement parameters and all H atoms located. The metarossite structure is characterized by chains of edge-sharing [CaO8] polyhedra parallel to [100] that are themselves connected by chains of alternating [VO5] trigonal bipyramids parallel to [010]. The two H2O mol-ecules are bonded to Ca. Analysis of the displacement parameters show that the [VO5] chains librate around [010]. In addition, we measured the Raman spectrum of metarossite and compared it with IR and Raman data previously reported. Moreover, heating of metarossite led to a loss of water, which results in a transformation to the brannerite-type structure, CaV2O6, implying a possible dehydration pathway for the compounds M2+V2O6·xH2O, with M = Cu, Cd, Mg or Mn, and x = 2 or 4.

Petrography, stable isotope compositions, microRaman spectroscopy, and presolar components of Roberts Massif 04133: A reduced CV3 carbonaceous chondrite.

Here, we report the mineralogy, petrography, C-N-O-stable isotope compositions, degree of disorder of organic matter, and abundances of presolar components of the chondrite Roberts Massif (RBT) 04133 using a coordinated, multitechnique approach. The results of this study are inconsistent with its initial classification as a Renazzo-like carbonaceous chondrite, and strongly support RBT 04133 being a brecciated, reduced petrologic type >3.3 Vigarano-like carbonaceous (CV) chondrite. RBT 04133 shows no evidence for aqueous alteration. However, it is mildly thermally altered (up to approximately 440 °C); which is apparent in its whole-rock C and N isotopic compositions, the degree of disorder of C in insoluble organic matter, low presolar grain abundances, minor element compositions of Fe,Ni metal, chromite compositions and morphologies, and the presence of unequilibrated silicates. Sulfides within type I chondrules from RBT 04133 appear to be pre-accretionary (i.e., did not form via aqueous alteration), providing further evidence that some sulfide minerals formed prior to accretion of the CV chondrite parent body. The thin section studied contains two reduced CV3 lithologies, one of which appears to be more thermally metamorphosed, indicating that RBT 04133, like several other CV chondrites, is a breccia and thus experienced impact processing. Linear foliation of chondrules was not observed implying that RBT 04133 did not experience high velocity impacts that could lead to extensive thermal metamorphism. Presolar silicates are still present in RBT 04133, although presolar SiC grain abundances are very low, indicating that the progressive destruction or modification of presolar SiC grains begins before presolar silicate grains are completely unidentifiable.

Lanthanite-(Nd), Nd2(CO3)3·8H2O.

Lanthanite-(Nd), ideally Nd2(CO3)3·8H2O [dineodymium(III) tricarbonate octa-hydrate], is a member of the lanthanite mineral group characterized by the general formula REE2(CO3)3·8H2O, where REE is a 10-coordinated rare earth element. Based on single-crystal X-ray diffraction of a natural sample from Mitsukoshi, Hizen-cho, Karatsu City, Saga Prefecture, Japan, this study presents the first structure determination of lanthanite-(Nd). Its structure is very similar to that of other members of the lanthanite group. It is composed of infinite sheets made up of corner- and edge-sharing of two NdO10-polyhedra (both with site symmetry ..2) and two carbonate triangles (site symmetries ..2 and 1) parallel to the ab plane, and stacked perpendicular to c. These layers are linked to one another only through hydrogen bonding involving the water mol-ecules.

Pirquitasite, Ag(2)ZnSnS(4).

Pirquitasite, ideally Ag(2)ZnSnS(4) (disilver zinc tin tetra-sulfide), exhibits tetra-gonal symmetry and is a member of the stannite group that has the general formula A(2)BCX(4), with A = Ag, Cu; B = Zn, Cd, Fe, Cu, Hg; C = Sn, Ge, Sb, As; and X = S, Se. In this study, single-crystal X-ray diffraction data are used to determine the structure of pirquitasite from a twinned crystal from the type locality, the Pirquitas deposit, Jujuy Province, Argentina, with anisotropic displacement parameters for all atoms, and a measured composition of (Ag(1.87)Cu(0.13))(Zn(0.61)Fe(0.36)Cd(0.03))SnS(4). One Ag atom is located on Wyckoff site Wyckoff 2a (symmetry -4..), the other Ag atom is statistically disordered with minor amounts of Cu and is located on 2c (-4..), the (Zn, Fe, Cd) site on 2d (-4..), Sn on 2b (-4..), and S on general site 8g. This is the first determination of the crystal structure of pirquitasite, and our data indicate that the space group of pirquitasite is I-4, rather than I-42m as previously suggested. The structure was refined under consideration of twinning by inversion [twin ratio of the components 0.91 (6):0.09 (6)].

Agardite-(Y), Cu(2+) 6Y(AsO4)3(OH)6·3H2O.

Agardite-(Y), with a refined formula of Cu(2+) 5.70(Y0.69Ca0.31)[(As0.83P0.17)O4]3(OH)6·3H2O [ideally Cu(2+) 6Y(AsO4)3(OH)6·3H2O, hexa-copper(II) yttrium tris-(arsenate) hexa-hydroxide trihydrate], belongs to the mixite mineral group which is characterized by the general formula Cu(2+) 6 A(TO4)3(OH)6·3H2O, where nine-coordinated cations in the A-site include rare earth elements along with Al, Ca, Pb, or Bi, and the T-site contains P or As. This study presents the first structure determination of agardite-(Y). It is based on the single-crystal X-ray diffraction of a natural sample from Jote West mine, Pampa Larga Mining District, Copiapo, Chile. The general structural feature of agardite-(Y) is characterized by infinite chains of edge-sharing CuO5 square pyramids (site symmetry 1) extending down the c axis, connected in the ab plane by edge-sharing YO9 polyhedra (site symmetry -6..) and corner-sharing AsO4 tetra-hedra (site symmetry m..). Hy-droxyl groups occupy each corner of the CuO5-square pyramids not shared by a neighboring As or Y atom. Each YO9 polyhedron is surrounded by three tubular channels. The walls of the channels, parallel to the c axis, are six-membered hexa-gonal rings comprised of CuO5 and AsO4 polyhedra in a 2:1 ratio, and contain free mol-ecules of lattice water.

Nioboaeschynite-(Ce), Ce(NbTi)O(6).

Nioboaeschynite-(Ce), ideally Ce(NbTi)O(6) [cerium(III) niobium(V) titanium(IV) hexa-oxide; refined formula of the natural sample is Ca(0.25)Ce(0.79)(Nb(1.14)Ti(0.86))O(6)], belongs to the aeschynite mineral group which is characterized by the general formula AB(2)(O,OH)(6), where eight-coordinated A is a rare earth element, Ca, Th or Fe, and six-coordinated B is Ti, Nb, Ta or W. The general structural feature of nioboaeschynite-(Ce) resembles that of the other members of the aeschynite group. It is characterized by edge-sharing dimers of [(Nb,Ti)O(6)] octa-hedra which share corners to form a three-dimensional framework, with the A sites located in channels parallel to the b axis. The average A-O and B-O bond lengths in nioboaeschynite-(Ce) are 2.471 and 1.993 Å, respectively. Moreover, another eight-coordinated site, designated as the C site, is also located in the channels and is partially occupied by A-type cations. Additionally, the refinement revealed a splitting of the A site, with Ca displaced slightly from Ce (0.266 Šapart), presumably resulting from the crystal-chemical differences between the Ce(3+) and Ca(2+) cations.