Band 108, Heft 10

Halogens and other volatiles are widely recycled into the deep mantle by subduction and are key components to metasomatize the sub-continental lithospheric mantle (SCLM). Lamprophyres are well known to be rich in volatiles and are important for understanding the halogen characteristics of the metasomatized SCLM and/or the mobilization of halogens during the ascent of such volatile-rich, low-degree partial melts. The North China Craton (NCC) hosts lamprophyre dikes coeval with extensive thinning of the eastern NCC in the Mesozoic and generated from lithosphere metasomatized by multiple-stage subduction components. Here we report bulk-rock heavy halogens (Cl, Br, and I) of 16 lamprophyres from the eastern NCC. The bulk-rock halogen concentrations are overall very low (Cl = 58–170 μg/g, Br = 285–559 ng/g, and I <5 ng/g), comparable with depleted Mid-Ocean ridge basalts (N-MORBs). Volatile-rich minerals (e.g., amphibole and biotite) are abundant (20–30 vol%) in these lamprophyres, however, electron probe microanalyses (EPMA) data indicate that amphiboles are mainly rich in OH and F but display very low Cl concentrations (0.01–0.04 wt%). The bulk rock and amphibole data consistently indicate low abundances of heavy halogens in the lamprophyres, which is dificult to reconcile with the remarkable enrichment of fluid-mobile large ion lithophile elements such as Ba, Rb, and K. Based on low Cl/Nb and Br/Nb but high Ba/Nb and K/Nb ratios, the low halogen concentrations likely resulted from extensive volatile loss (>90%) during melt ascent. The low Cl concentrations in early-stage amphiboles (Mg# 60–64) further indicate that such loss would have occurred before amphibole crystallization at a depth of ~15 km. We thus propose that crystallization of early olivines and pyroxenes and reaction with surrounding mantle rocks likely induced volatile saturation and exsolution, leading to strong partitioning of the halogens into the exsolved aqueous volatile phases and thus the extensive loss of halogens from the rising melt. These results reveal that significant volatile loss of halogens not only occurs during surficial low-pressure eruption but also at much deeper levels in the crust, as also identified for some kimberlites. Consequently, it would be dificult to constrain the primitive halogen components of the mantle sources via lamprophyres or similar magmas.

Ba-, Ti-, and Cl-rich micas associated with other Ba- and/or Cl-rich minerals in the rock matrix or in garnet and clinopyroxene hosted multiphase solid inclusions (MSI) are observed in mantle-derived garnet pyroxenites. The micas show extremely high variability in chemical composition ranging between Ba-rich phlogopite, chloroferrokinoshitalite, and oxykinoshitalite. Elemental covariation trends in mineral chemical data reveal the principal substitution mechanisms responsible for the observed chemical variability. The substitution Ba 2+ Al 3+ ↔ K 1+ Si 4+ associated with either OH 1– ↔ Cl 1– or Ti 4+ 2O 2– ↔ Mg 2+ 2OH 1 links phlogopite to chloroferrokinoshitalite and oxykinoshitalite, respectively, whereas the substitution Ti 4+ 2O 2– ↔ Fe 2+ 2Cl 1– links chloroferrokinoshitalite to oxykinoshitalite. The preferred incorporation of Cl in Fe-rich mica and of Ti+O in Mg-rich mica indicates that XFe (Fe tot /Fe tot +Mg) exerts an important control on mica composition. The positive correlation of XFe with Cl led to the formation of possibly the most Cl-rich mica so far described classified as chloroferrokinoshitalite (XFe 0.88 , Ba 0.95 K 0.03 Fe 2.68 Mg 0.37 Al 1.91 Si 2.01 Cl 1.98 ) with 10.98 wt% Cl. Substantial substitution of OH – by Cl – and O 2– in mica, and the presence of Cl-apatite, a rare Cl-rich phosphate goryainovite, and carbonates together with Cl-rich micas indicate high-Cl and -CO 2 activity and low-H 2 O activity in metasomatizing fluids or melts that may be classified as Ba-Cl-rich silicocarbonatitic. The coexistence of two micas with distinct compositions close to chloroferrokinoshitalite (XFe 0.57–0.77 , K ~0.1 Ba 0.6–0.8 Mg 0.7–1.3 Fe 1.7–2.3 Ti 0.0–0.1 Si 2.2–2.3 Al 1.5–1.7 Cl 1.2–1.8 ) and oxykinoshitalite (XFe 0.19–0.20 , K ~0.3 Ba ~0.5 Mg 2.0–2.1 Fe ~0.5 Ti 0.2–0.4 Si 2.4–2.6 Al ~1.8 Cl ~0.3 ) suggests that a miscibility gap exists between these two compositions. The exotic mineral assemblage was formed by interaction with metasomatizing fluids or melts whose origin cannot be defined with certainty. They may be derived from crustal or mantle lithologies or from the host garnet pyroxenites. The textural position of the MSI in garnet and their characteristic mineral assemblages indicate that they have been introduced into the garnet crystals under post-peak conditions, possibly during decompression. With this research we document substitution mechanisms in Ba-, Ti-, and Cl-rich micas and shed light on the behavior and composition of fluids or melts at the upper mantle/lower crust interface.

Fluid-mediated calcium metasomatism is often associated with strong silica mobility and the presence of chlorides in solution. To help quantify mass transfer at lower crustal and upper mantle conditions, we measured quartz solubility in H 2 O-CaCl 2 solutions at 0.6–1.4 GPa, 600–900 °C, and salt concentrations to 50 mol%. Solubility was determined by weight loss of single-crystals using hydrothermal piston-cylinder methods. All experiments were conducted at salinity lower than salt saturation. Quartz solubility declines exponentially with added CaCl 2 at all conditions investigated, with no evidence for complexing between silica and Ca. The decline in solubility is similar to that in H 2 O-CO 2 but substantially greater than that in H 2 O-NaCl at the same pressure and temperature. At each temperature, quartz solubility at low salinity ( X CaCl 2 < 0.1) depends strongly on pressure, whereas at higher X CaCl 2 it is nearly pressure independent. This behavior is consistent with a transition from an aqueous solvent to a molten salt near X CaCl 2 ~0.1. The solubility data were used to develop a thermodynamic model of H 2 O-CaCl 2 fluids. Assuming ideal molten-salt behavior and utilizing previous models for polymerization of hydrous silica, we derived values for the activity of H 2 O ( a H2O ), and for the CaCl 2 dissociation factor (α), which may vary from 0 (fully associated) to 2 (fully dissociated). The model accurately reproduces our data along with those of previous work and implies that, at conditions of this study, CaCl 2 is largely associated (<0.2) at H 2 O density <0.85 g/cm 3 . Dissociation rises isothermally with increasing density, reaching ~1.4 at 600 °C, 1.4 GPa. The variation in silica molality with a H2O in H 2 O-CaCl 2 is nearly identical to that in H 2 O-CO 2 solutions at 800 °C and 1.0 GPa, consistent with the absence of Ca-silicate complexing. The results suggest that the ionization state of the salt solution is an important determinant of a H2O , and that H 2 O-CaCl 2 fluids exhibit nearly ideal molecular mixing over a wider range of conditions than implied by previous modeling. The new data help interpret natural examples of large-scale Ca-metasomatism in a wide range of lower crustal and upper mantle settings.

Boron nitride (BN) is a commonly used pressure-transmitting material in experimental petrology. It is often considered to be as inert as MgO or Al 2 O 3 , and its redox potential is seldomly discussed. It is generally implied that, when used as a capsule sleeve, BN may impose relatively reduced conditions, similar to the effect of the fayalite-magnetite-quartz (FMQ) buffer. However, sediment melting experiments performed at 1050 °C and 3 GPa with BN as the capsule sleeve, produced a hydrous rhyolitic melt with dissolved H 2 S and CH 4 (Li et al. 2021). The resulting f O2 estimate is significantly more reduced than that for the magnetite-wüstite (MW)-buffered experiment where H 2 S and CH 4 were undetected (Li et al. 2021), possibly to the extent of the quartz-iron-fayalite (QIF) buffered conditions produced when BN is used as a capsule or crucible (Wendlandt et al. 1982). To establish an explanation for such a discrepancy, we have conducted further investigation to better constrain the f O2 imposed by BN, when used as a capsule sleeve. Here we report results on analyses of Fe content in Au capsules, a comparative experiment using a QIF buffer and an experiment with an Fe-(Mg,Fe) O sensor for direct analysis of f O2 . The calibration of the equilibrium between FeO in melt and Fe in the Au capsule, from Ratajeski and Sisson (1999) appears to be inadequate in constraining f O2 for our experiments. However, we were able to obtain Fe diffusion coefficients in Au from the Fe diffusion profiles observed in the capsule of the Fe-(Mg,Fe)O sensor experiment, and both the inner and outer capsules of the MW-buffered experiment, with resulting values of 1 × 10 –13 m 2 /s, 3 × 10 –14 m 2 /s, and 5 × 10 –14 m 2 /s, respectively. The QIF-buffered and Fe-(Mg,Fe)O sensor experiments provide several lines of evidence supporting the observation that BN imposes QIF-like redox conditions. First, the Fe-(Mg,Fe)O sensor returned an f O2 value of QIF. Second, the “apparent” partition coefficients between FeO content in melt and Fe in the Au capsules are similar between the BN experiment and the QIF-buffered experiment. Third, we observe CH 4 and H 2 O peaks with similar intensities in the Raman spectra of melts from these two experiments, suggesting similar H 2 and thus O 2 fugacity. As our experiments were performed on a cubic press with the experimental assembly encased in a pyrophyllite cube, we interpret that the significantly reduced conditions imposed by BN are likely due to high H 2 O activity maintained by dehydration of pyrophyllite, which can be explained using the reaction 2BN + 3H 2 O = B 2 O 3 + N 2 + 3H 2 . Lower H 2 O activity will reduce or inhibit the oxidation of BN and its f O2 buffering ability. If heat-treated, BN acts as a highly efficient H 2 barrier, as shown by Truckenbrodt et al. (1997). Through our efforts to determine the f O2 imposed by using BN as a capsule sleeve in our experimental assembly, we are able to demonstrate the reducing ability of BN as an assembly component and, furthermore, shed light on the process by which BN imposes such reduced f O2 . We hereby present what we have learned during the course of this investigation in the hope that the effect of BN on f O2 control is both recognized and further exploited in future experimental studies.

Speciation and transport properties of supercritical fluids is critical for understanding their behavior in the Earth’s interior. Here, we report a systematic first principles molecular dynamics simulation study of the structure, speciation, self-difusivity ( D ), and viscosity (η) of SiO 2 melt, NaAlSi 3 O 8 melt, SiO 2 -H 2 O and NaAlSi 3 O 8 -H 2 O fluids at 2000–3500 K with 0–70 wt% H 2 O. Our calculations show that as the water content increases, the proportion of Q 0 species (Q n species, where n is the number of bridging oxygens in an individual Si/Al-O polyhedra) increases while Q 4 decreases. The proportions of Q 1 , Q 2 , and Q 3 species first increase and then decrease with increasing water content. The diffusivity sequence for the supercritical SiO 2 -H 2 O fluids is D H > D O > D Si , and for the supercritical NaAlSi 3 O 8 -H 2 O fluids, on the whole, is D Na ≈ D H > D O > D Al ≈ D Si . The viscosities of the two systems decrease drastically at the beginning of the increase in water content, and then decrease slowly. We demonstrate that the exponential decrease in the viscosity of polymerized silicate melt with increasing water content is due to a sharp decrease in the proportion of Q 4 species and increase in Si-O-H. The typical structural feature of supercritical fluid is that it contains a large amount of easy-to-flow partially polymerized or depolymerized protonated silicate units, which leads to a low viscosity while being enriched in silicate. This feature provides supercritical fluids the potential to transport elements that are hard to migrate in aqueous fluids or hydrous silicate melts, such as high field strength elements.

Clay-mineral evolution in supergene environments is commonly a complex process subject to hydrologic influences on clay-mineral transformations, yet these influences remain insufficiently investigated to date. A quaternary red soil profile with evident redoximorphic features in subtropical monsoonal China was investigated with a focus on processes of secondary clay-mineral transformation. Evidence provided by soil physical and chemical descriptions, clay-mineral analysis, spectroscopic characterization, extractions of pedogenic Al and Fe species, and geochemical compositions reveals a complex relationship of clay minerals and iron phases to pedogenic weathering conditions as a function of depth in the studied soil profile. The soil profile can be divided into a homogenous horizon (HH; 0–2.0 m), a redoximorphic horizon (RH; 2.0–6.0 m), and a basal layer (BL; 6.0–7.2 m), and these three horizons are dominated by various intermediate clay phases. The HH is characterized by moderately acidic conditions (mean pH = 5.2) and low total organic content (TOC; TOC ≤2.1 g kg –1 ). More importantly, compared with the lower horizons, the HH contains significantly more active acid-forming cations, as reflected by a greater abundance of Al phases and higher aluminum saturation levels. We infer that the occurrence of hydroxy-interlayered vermiculite (HIV) in the HH is tightly coupled with the nature of the soil acidic pools, which include both H + ions (i.e., pH) and active acid-forming cations (e.g., Al 3+ and Fe 3+ ). The reaction pathway from primary minerals to final weathering products appears to be highly sensitive to dynamic hydrological processes. HIV is favored in generally oxic, well-drained soil systems with adequate acidic cations to maintain acidic weathering. When soils are more waterlogged and the aqueous solution is dominated by base cations, primary minerals tend to transform to smectite group minerals. Therefore, discrete smectite, interstratified illite-smectite (I-S), and interstratified kaolinite-smectite (K-S) were observed only in the RH and BL. We present a novel framework that links clay-mineral transformation pathways to soil hydrological disturbances, providing new insights into understanding the kinetics of water-mineral interactions in natural soil systems.

Electron backscatter diffraction (EBSD) investigation of strain mainly uses polycrystalline samples to study fabric development. We extend the use of EBSD for the analysis of large single mineral grains by measuring the apparent surficial subdomain boundary density per unit area, reported here as unit segment length (USL). We apply this USL technique to examine and quantify the plastic deformation recorded by naturally shocked olivine in the low to moderately shocked ureilite meteorite Northwest Africa 2221 and the highly shocked martian dunitic cumulate meteorite Northwest Africa 2737, by assessing the types of subdomain boundaries and the increase of subdomain misorientation with increasing shock metamorphism. We further compare USL results for the shocked olivine in the meteorites with those for the terrestrial deformation of Hawaiian olivine. USL of olivine increases with shock level, and USL from shocked olivine is significantly greater than that of terrestrially deformed olivine. USL is a promising tool for the quantification of plastic deformation in large single crystals from shock as well as terrestrial deformation. The results derived from USL measurements along with local EBSD maps are complementary with quantitative 2D X-ray difraction analysis of crystal deformation and disruption, leading to a more comprehensive understanding of characteristic shock deformation recorded by large single crystals.

The origin of Libyan Desert Glass (LDG) found in the western parts of Egypt close to the Libyan border is debated in planetary science. Two major theories of its formation are currently competing: (1) melting by airburst and (2) formation by impact-related melting. While mineralogical and textural evidence for a high-temperature event responsible for the LDG formation is abundant and convincing, minerals and textures indicating high shock pressure have been scarce. This paper provides a nanostructural study of the LDG, showing new evidence of its high-pressure and high-temperature origin. We mainly focused on the investigation of Zr-bearing and phosphate aggregates enclosed within LDG. Micro- and nanostructural evidence obtained with transmission electron microscopy (TEM) are spherical inclusions of cubic, tetragonal, and orthorhombic ( Pnma or OII) zirconia after zircon, which indicate high-pressure, high-temperature decomposition of zircon and possibly, melting of ZrO 2 . Inclusions of amorphous silica and amorphous Al-phosphate with berlinite composition (AlPO 4 ) within mosaic whitlockite and monazite aggregates point at decomposition and melting of phosphates, which formed an emulsion with SiO 2 melt. The estimated temperature of the LDG melts was above 2750 °C, approaching the point of SiO 2 boiling. The variety of textures with different degrees of quenching immediately next to each other suggests an extreme thermal gradient that existed in LDG through radiation cooling. Additionally, the presence of quenched orthorhombic OII ZrO 2 provides direct evidence of high-pressure (>13.5 GPa) conditions, confirming theory 2, the hypervelocity impact origin of the LDG.

The first-row transition element (FRTE) and high field strength element (HFSE) systematics are powerful tools for tracking the source and evolution of mantle-derived magmas. Clinopyroxene is generally considered a key fractionating mineral controlling the partitioning of trace elements between melt and residual solid during mantle melting. Although partitioning of FRTE and HFSE between clinopyroxene and basaltic melts has been well-studied, experimental constraints on their partitioning behavior in the presence of siliceous, aluminous, and alkali-rich melts are still lacking. Here we present clinopyroxene-silicic melt (67–69 wt% SiO 2 ) partitioning experiments at 1 bar pressure and 1070–1100 °C for Co, Mn, Ni, Cu, Zn, Fe, Sc, Cr, V, Ti, Zr, Hf, Nb, and Ta. Run products consist of diopsidic clinopyroxene coexisting with various melt compositions with non-bridging oxygen to tetrahedral cation ratio (NBO/T) ranging from 0.10 to 0.22. Using our new partition coeficients ( D s) and combined with literature data, we assess some of the effects of crystal chemistry and the melt composition on the partitioning of FRTE and HFSE in this simple system. We show that partitioning of FRTE varies from mildly incompatible (e.g., D = ~0.1−1 for V, Cu, and Zn) to highly compatible (e.g., D > 10 for Cr and Ni), with the highest compatibilities observed for Ni ( D Ni = 13−34). The partitioning of HFSE varies from highly incompatible ( D = 0.01−0.08) for Nb and Ta to mildly incompatible ( D = 0.18−0.82) for Zr, Hf, and Ti. Our measured clinopyroxenemelt D s are consistent with the theoretical predictions of the lattice strain model. D s data for most tri-, tetra-, and pentavalent elements tend to increase with increasing tetrahedrally coordinated Al content, in agreement with those anticipated from crystal-chemical considerations. In contrast to iv Al concentrations, the clinopyroxene Na concentration has very little efect on trace element partitioning due to its low concentrations in clinopyroxene at relatively low-pressure conditions. These data further support a significant control of melt composition/structure on partitioning for highly polymerized melts. In general, measured D s roughly increase to diferent extents with increasing polymerization of the melt (i.e., lower NBO/T or higher ASI). For our equilibrium melt compositions, D s for several FRTE, such as Co and Ni, correlate well with the melt molar Mg 2+ /(M + + M 2+ ), whereas D s for HFSE vary as a function of the melt alkali concentration. These well-defined trends support the role of melt NBO species (e.g., Mg 2+ ) or complexing ligands (e.g., Na + and K + ) in controlling the partitioning of these elements. Overall, our new D s data demonstrate that even very small changes in melt major-element compositions can greatly afect element partitioning in strongly polymerized silicic systems. These findings have important implications relevant to petrogenetic studies of the interaction between silicic melt and peridotite that occurs at shallow mantle conditions in various tectonic settings.

Microbially induced formation and transformation of clay minerals are known to be ubiquitous in nature. This work investigated the smectite-to-kaolinite transformation by Bacillus mucilaginosus , a kind of silicate-weathering bacterium. Results showed that the microbe-smectite system doubled protein production compared with the abiotic controls and enhanced dissolved 1.6% of total Si and 0.9% of total Al from smectite after the 25 days experiment. The formation of kaolinite was verified through its distinguished d (001) -spacing of 0.710 nm revealed by synchrotron radiation X-ray difrac-tion (SR-XRD) and high-resolution transmission electron microscope (HR-TEM). HR-TEM analysis indicated some mixed layers of smectite and kaolinite appeared in the form of a super-lattice structure. Moreover, the compositional and morphological changes of the solids suggested the emergence of kaolinite was associated with the formation of amorphous SiO 2 and fragmented clay particles with lower Si/Al ratio and exposed crystal edge. Based on the detection of –C=O species on the smectite surface and the decrease of pH from 8.5 to 6.5, we inferred the organic ligands secreted by Bacillus mucilaginosus complexed with cations, especially for Si, which stripped the tetrahedral sheets and promoted the kaolinization of smectite. To our knowledge, this is the first report of microbially induced smectite-to-kaolinite transformation under ambient conditions in a highly-efficient way. This work could shed light on a novel pathway of microbe-promoted weathering of smectite to kaolinite at the Earth surface conditions. Such a robust and eficient transformation from expansive smectite to non-expansive clays as kaolinite may be of great potential in enhancing oil recovery in reservoirs.

Hydroxylation of wadsleyite, β-(Mg,Fe) 2 SiO 4 , is associated with divalent cation defects and well known to afect its physical properties. However, an atomic-scale understanding of the defect structure and hydrogen bonding at high pressures is needed to interpret the influence of water on the behavior of wadsleyite in the mantle transition zone. We have determined the pressure evolution of the wadsleyite crystal symmetry and structure, including all O∙∙∙O interatomic distances, up to 32 GPa using single-crystal X-ray difraction on two well-characterized, Fe-bearing (Fo 90 ) samples containing 0.25(4) and 2.0(2) wt% H 2 O. Both compositions undergo a pressure-dependent monoclinic distortion from orthorhombic symmetry above 9 GPa, with the less hydrous sample showing a larger increase in distortion at increased pressures due to the diference in compressibility of the split M3 site in the monoclinic setting arising from preferred vacancy ordering at the M3B site. Although hydrogen positions cannot be modeled from the X-ray difraction data, the pressure evolution of the longer O1∙∙∙O4 distance in the structure characterizes the primary hydrogen bond length. We observe the hydrogen-bonded O1∙∙∙O4 distance shorten gradually from 3.080(1) Å at ambient pressure to about 2.90(1) Å at 25 GPa, being still much longer than is defined as strong hydrogen bonding (2.5–2.7 Å). Above 25 GPa and up to the maximum pressure of the experiment at 32.5 GPa, the hydrogen-bonded O1∙∙∙O4 distance decreases no further, despite the fact that previous spectroscopic studies have shown that the primary O-H stretching frequencies continuously drop into the regime of strong hydrogen bonding (<3200 cm –1 ) above ~15 GPa. We propose that the primary O1-H∙∙∙O4 hydrogen bond in wadsleyite becomes highly nonlinear at high pressures based on its deviation from frequency-distance correlations for linear hydrogen bonds. One possible explanation is that the hydrogen position shifts from being nearly on the long O1-O4 edge of the M3 site to a position more above O1 along the c -axis.

Diverse fluid sources and complex fluid flow paths in skarn systems appear to be well documented. Nevertheless, in situ microanalysis of oxygen isotopes by secondary ion microprobe (SIMS) in skarn minerals can provide further high spatial resolution information on this complexity and the formation of skarns and associated ore deposits. In this study, we investigated the Haobugao skarn Zn-Fe-Sn deposit (0.36 M tonnes Zn) in the southern Great Xing’an Range, northeast (NE) China, and the associated Early Cretaceous Wulanba biotite granite. Based on drill hole logging, four early skarn phases are recognized: proximal red-brown garnet-hedenbergite exoskarn, central green garnet exoskarn, light brown garnet-diopside exoskarn, and distal pyroxene skarn. Oxygen isotope analyses of garnet, pyroxene, and other minerals from skarn, oxide, and quartz-sulfide stages were carried out using SIMS to determine the origin and evolution of the skarn-forming hydrothermal system. Garnet from exoskarn has a much wider range in δ 18 O VSMOW , between –8.1 and +6.0‰, than other stages and minerals. The estimated δ 18 O values of fluids in equilibrium with the Haobugao skarn vary widely from –5.1‰ to +8.9‰, suggesting that the skarn formed via episodic flux of magmatic fluid and meteoric water. Low δ 18 O values of cassiterite and quartz from quartz-sulfide stage rocks are +1.2 to +3.6‰, and +5.7 to +5.9‰, respectively, indicating significant contributions of meteoric water during deposition of Pb-Zn sulphides. Therefore, meteoric fluids were periodically present throughout most of the stages of skarn formation at Haobugao.

Crocobelonite, CaFe 23+ (PO 4 ) 2 O, is a new natural oxyphosphate discovered in the pyrometamorphic complexes of the Hatrurim Formation in Israel and Jordan. Crocobelonite-bearing assemblages contain a series of anhydrous Fe-Ni phosphates, hematite, diopside, anorthite, and phosphides—barringerite Fe 2 P, transjordanite Ni 2 P, murashkoite FeP, halamishite Ni 5 P 4 , and negevite NiP 2 . Crocobelonite forms submillimeter-sized aggregates of prismatic to acicular crystals of saffron-red to pinkish-red color. There are two polymorphic modifications of the mineral whose structures are interrelated by the unit-cell twinning. Crocobelonite-2 O is orthorhombic, Pnma , a = 14.2757(1), b = 6.3832(1), c = 7.3169(1) Å, V 666.76(1) Å 3 , Z = 4. This polymorphic modification is isotypic with synthetic oxy-phosphates A   V 2 3 + P O 4 2 O $A \mathrm{~V}_{2}^{3+}\left(\mathrm{PO}_{4}\right)_{2} \mathrm{O}$where A = Ca, Sr, Cd. The crystal structure has been refined to R B = 0.71% based on powder XRD data, using the Rietveld method and the input structural model obtained from the single-crystal study. Chemical composition (electron microprobe, wt%) is: CaO 16.03, MgO 0.56, Fe 2 O 3 43.37, Al 2 O 3 0.33, SiO 2 0.32, P 2 O 5 39.45, Total 100.06. The empirical formula based on O = 9 apfu is C a 1.02 F e 1.94 3 + M g 0.05 A l 0.02 2.01 P 1.98 S i 0.02 2.00 O 9.00 $\mathrm{Ca}_{1.02}\left(\mathrm{Fe}_{1.94}^{3+} \mathrm{Mg}_{0.05} \mathrm{Al}_{0.02}\right)_{2.01}\left(\mathrm{P}_{1.98} \mathrm{Si}_{0.02}\right)_{2.00} \mathrm{O}_{9.00}$ with $D_{\text {calc }}=3.555 \mathrm{~g} / \mathrm{cm}^{3}.$The strongest lines of powder XRD pattern [ d (Å)( I )( hkl )] are: 6.54(16)(200), 5.12(26)(201), 3.549(100)(102), 3.200(50) (401), 2.912(19)(220), 2.869(40)(411), 2.662(21)(501). Crocobelonite- 1 M is monoclinic, P 2 1/m , a = 7.2447(2), b = 6.3832(1), c = 7.3993(2) Å, β = 106.401(2)°, V = 328.252(14) Å 3 , Z = 2. This polymorphic modification does not have direct structural analogs. Its crystal structure has been solved and refined based on the single-crystal data to R 1 = 1.81%. Chemical composition is: CaO 15.56, MgO 0.16, NiO 0.78, Fe 2 O 3 41.28, Al 2 O 3 0.45, V 2 O 3 0.42, Cr 2 O 3 0.23, TiO 2 0.79, P 2 O 5 39.94, Total 99.61, corresponding to the empirical formula ( O = 9 a p f u ) C a 0.99 F e 1.85 3 + N i 0.04 T i 0.04 A l 0.03   V 0.02 3 + C r 0.01 M g 0.01 2.00 P 2.01 O 9.00 $(\mathrm{O}=9 \mathrm{apfu}) \mathrm{Ca}_{0.99}\left(\mathrm{Fe}_{1.85}^{3+} \mathrm{Ni}_{0.04} \mathrm{Ti}_{0.04} \mathrm{Al}_{0.03} \mathrm{~V}_{0.02}^{3+} \mathrm{Cr}_{0.01} \mathrm{Mg}_{0.01}\right)_{2.00} \mathrm{P}_{2.01} \mathrm{O}_{9.00}$with D calc = 3.604 g/cm 3 . The strongest lines of powder XRD pattern [ d (Å)( I )( hkl )] are 6.98(17)(100), 4.40(22)(101), 3.547(100)(201), 3.485(21)(200), 3.195(50)(020), 2.855(38)(102), 2.389(33)(122). Crocobelonite represents a novel type of phosphate mineral formed by oxidation of phosphide minerals at temperatures higher than 1000 °C and near-atmospheric pressure (pyrolytic oxidation).

Tetrahedrite-(Ni) (IMA2021-031), ideally Cu 6 (Cu 4 Ni 2 )Sb 4 S 13 , is the first natural Ni-member of tetrahedrite group mineral found in Luobusa chromite deposit, Tibet, China. The new species occurs as anhedral grains 2 to 20 μm in size, associated with gersdorffite, vaesite, and chalcostibite, which are disseminated in a matrix of dolomite, magnesite, quartz, Cr-rich mica, and Cr-bearing clinochlore. Tetrahedrite-(Ni) is black in color with a reddish-black streak and metallic luster. It is brittle with uneven fractures and has a calculated density of 5.073 g·cm –3 . The mean values of 9 electron micro-probe analyses (wt%) are Cu 39.83, Ni 5.67, Fe 1.45, Sb 21.69, As 5.45, S 25.39, total 99.48, and the empirical formula calculated on the basis of cation = 16 apfu is M (2) Cu 6.00 M (1) [Cu 4.03 (Ni 1.55 Fe 0.42 ) Σ1.97 ] Σ6.00 X (3) (Sb 2.85 As 1.16 ) Σ4.01 S 12.67 . Tetrahedrite-(Ni) is cubic, with space group I 43 m , a = 10.3478(4) Å, V = 1108.00(14) Å 3 , and Z = 2. Its crystal structure has been solved by X-ray single-crystal diffraction on the basis of 188 independent reflections, with a final R 1 = 0.0327. Tetrahedrite-(Ni) is isostructural with tetrahedrite group minerals. It represents the first natural tetrahedrite-group mineral with a Ni-dominated charge-compensating constituent. Tetrahedrite-(Ni) may be the product of late-serpentinization at moderately high-temperature conditions around 350 °C. In this case, tetrahedrite-(Ni) and its mineral paragenesis record an entire geological process of nickel enrichment, migration, activation, precipitation, and alteration from deep mantle to shallow crust.

This issue of New Mineral Names summarizes new species that contain toxic heavy metals and rare earth elements with a partial focus on new minerals found in China. All these new minerals have potential uses for environmental and technological applications, and their origins reflect historical mining or cultural significance. Here we look at fluorbritholite-(Nd), napoliite, scenicite, evseeite, haitaite-(La), dongchuanite, liguowuite, and gysinite-(La).