Reconstructing the late-accretion history of the Moon.

The importance of highly siderophile elements (HSEs; namely, gold, iridium, osmium, palladium, platinum, rhenium, rhodium and ruthenium) in tracking the late accretion stages of planetary formation has long been recognized. However, the precise nature of the Moon's accretional history remains enigmatic. There is a substantial mismatch in the HSE budgets of the Earth and the Moon, with the Earth seeming to have accreted disproportionally more HSEs than the Moon1. Several scenarios have been proposed to explain this conundrum, including the delivery of HSEs to the Earth by a few big impactors1, the accretion of pebble-sized objects on dynamically cold orbits that enhanced the Earth's gravitational focusing factor2, and the 'sawtooth' impact model, with its much reduced impact flux before about 4.10 billion years ago3. However, most of these models assume a high impactor-retention ratio (the fraction of impactor mass retained on the target) for the Moon. Here we perform a series of impact simulations to quantify the impactor-retention ratio, followed by a Monte Carlo procedure considering a monotonically decaying impact flux4, to compute the impactor mass accreted into the lunar crust and mantle over their histories. We find that the average impactor-retention ratio for the Moon's entire impact history is about three times lower than previously estimated1,3. Our results indicate that, to match the HSE budgets of the lunar crust and mantle5,6, the retention of HSEs should have started 4.35 billion years ago, when most of the lunar magma ocean was solidified7,8. Mass accreted before this time must have lost its HSEs to the lunar core, presumably during lunar mantle crystallization9. The combination of a low impactor-retention ratio and a late retention of HSEs in the lunar mantle provides a realistic explanation for the apparent deficit of the Moon's late-accreted mass relative to that of the Earth.

Chondrules reveal large-scale outward transport of inner Solar System materials in the protoplanetary disk.

Dynamic models of the protoplanetary disk indicate there should be large-scale material transport in and out of the inner Solar System, but direct evidence for such transport is scarce. Here we show that the ε50Ti-ε54Cr-Δ17O systematics of large individual chondrules, which typically formed 2 to 3 My after the formation of the first solids in the Solar System, indicate certain meteorites (CV and CK chondrites) that formed in the outer Solar System accreted an assortment of both inner and outer Solar System materials, as well as material previously unidentified through the analysis of bulk meteorites. Mixing with primordial refractory components reveals a "missing reservoir" that bridges the gap between inner and outer Solar System materials. We also observe chondrules with positive ε50Ti and ε54Cr plot with a constant offset below the primitive chondrule mineral line (PCM), indicating that they are on the slope ∼1.0 in the oxygen three-isotope diagram. In contrast, chondrules with negative ε50Ti and ε54Cr increasingly deviate above from PCM line with increasing δ18O, suggesting that they are on a mixing trend with an ordinary chondrite-like isotope reservoir. Furthermore, the Δ17O-Mg# systematics of these chondrules indicate they formed in environments characterized by distinct abundances of dust and H2O ice. We posit that large-scale outward transport of nominally inner Solar System materials most likely occurred along the midplane associated with a viscously evolving disk and that CV and CK chondrules formed in local regions of enhanced gas pressure and dust density created by the formation of Jupiter.

The impact and recovery of asteroid 2018 LA.

The June 2, 2018, impact of asteroid 2018 LA over Botswana is only the second asteroid detected in space prior to impacting over land. Here, we report on the successful recovery of meteorites. Additional astrometric data refine the approach orbit and define the spin period and shape of the asteroid. Video observations of the fireball constrain the asteroid's position in its orbit and were used to triangulate the location of the fireball's main flare over the Central Kalahari Game Reserve. 23 meteorites were recovered. A consortium study of eight of these classifies Motopi Pan as a HED polymict breccia derived from howardite, cumulate and basaltic eucrite, and diogenite lithologies. Before impact, 2018 LA was a solid rock of ~156 cm diameter with high bulk density ~2.85 g/cm3, a relatively low albedo pv ~ 0.25, no significant opposition effect on the asteroid brightness, and an impact kinetic energy of ~0.2 kt. The orbit of 2018 LA is consistent with an origin at Vesta (or its Vestoids) and delivery into an Earth-impacting orbit via the v6 resonance. The impact that ejected 2018 LA in an orbit towards Earth occurred 22.8 ± 3.8 Ma ago. Zircons record a concordant U-Pb age of 4563 ± 11 Ma and a consistent 207Pb/206Pb age of 4563 ± 6 Ma. A much younger Pb-Pb phosphate resetting age of 4234 ± 41 Ma was found. From this impact chronology, we discuss what is the possible source crater of Motopi Pan and the age of Vesta's Veneneia impact basin.

The fall, recovery, classification, and initial characterization of the Hamburg, Michigan H4 chondrite.

The Hamburg meteorite fell on January 16, 2018, near Hamburg, Michigan, after a fireball event widely observed in the U.S. Midwest and in Ontario, Canada. Several fragments fell onto frozen surfaces of lakes and, thanks to weather radar data, were recovered days after the fall. The studied rock fragments show no or little signs of terrestrial weathering. Here, we present the initial results from an international consortium study to describe the fall, characterize the meteorite, and probe the collision history of Hamburg. About 1 kg of recovered meteorites was initially reported. Petrology, mineral chemistry, trace element and organic chemistry, and O and Cr isotopic compositions are characteristic of H4 chondrites. Cosmic ray exposure ages based on cosmogenic 3He, 21Ne, and 38Ar are ~12 Ma, and roughly agree with each other. Noble gas data as well as the cosmogenic 10Be concentration point to a small 40-60 cm diameter meteoroid. An 40Ar-39Ar age of 4532 ± 24 Ma indicates no major impact event occurring later in its evolutionary history, consistent with data of other H4 chondrites. Microanalyses of phosphates with LA-ICPMS give an average Pb-Pb age of 4549 ± 36 Ma. This is in good agreement with the average SIMS Pb-Pb phosphate age of 4535.3 ± 9.5 Ma and U-Pb Concordia age of 4535 ± 10 Ma. The weighted average age of 4541.6 ± 9.5 Ma reflects the metamorphic phosphate crystallization age after parent body formation in the early solar system.

Previously unknown class of metalorganic compounds revealed in meteorites.

The rich diversity and complexity of organic matter found in meteorites is rapidly expanding our knowledge and understanding of extreme environments from which the early solar system emerged and evolved. Here, we report the discovery of a hitherto unknown chemical class, dihydroxymagnesium carboxylates [(OH)2MgO2CR]-, in meteoritic soluble organic matter. High collision energies, which are required for fragmentation, suggest substantial thermal stability of these Mg-metalorganics (CHOMg compounds). This was corroborated by their higher abundance in thermally processed meteorites. CHOMg compounds were found to be present in a set of 61 meteorites of diverse petrological classes. The appearance of this CHOMg chemical class extends the previously investigated, diverse set of CHNOS molecules. A connection between the evolution of organic compounds and minerals is made, as Mg released from minerals gets trapped into organic compounds. These CHOMg metalorganic compounds and their relation to thermal processing in meteorites might shed new light on our understanding of carbon speciation at a molecular level in meteorite parent bodies.

Branching Ratio Measurements of the Predissociation of 12C16O by Time-Slice Velocity-Map Ion Imaging in the Energy Region from 106 250 to 107 800 cm-1.

Photodissociation of CO is a fundamental chemical mechanism for mass-independent oxygen isotope fractionation in the early Solar System. Branching ratios of photodissociation channels for individual bands quantitatively yield the trapping efficiencies of atomic oxygen resulting into oxides. We measured the branching ratios for the spin-forbidden and spin-allowed photodissociation channels of 12C16O in the vacuum ultraviolet (VUV) photon energy region from 106 250 to 107 800 cm-1 using the VUV laser time-slice velocity-map imaging photoion technique. The excitations to four 1Π bands and three 1Σ+ bands of 12C16O were identified and investigated. The branching ratios for the product channels C(3P) + O(3P), C(1D) + O(3P), and C(3P) + O(1D) of these predissociative states strongly depend on the electronic and vibrational states of CO being excited. By plotting the branching ratio of the spin-forbidden dissociation channels versus the excitation energy from 102 500 to 110 500 cm-1 that has been measured so far, the global pattern of the 1Π-3Π interaction that plays a key role in the predissociation of CO is revealed and discussed.

Rapid effects of terrestrial alteration on highly siderophile elements in the Sutter's Mill meteorite.

The 187Re-187Os isotopic systematics of many bulk chondrites plot well beyond analytical uncertainties of a primordial isochron. Limited variations in 187Os/188Os, coupled with large variations in Re/Os ratios among chondrites, suggest that this apparently open-system behavior is a result of the comparatively recent gain or loss of Re and/or Os. In order to assess whether or not rapid alteration in the terrestrial environment could be responsible for open-system behavior in chondrites, four pieces of the Sutter's Mill meteorite were examined for Os isotopic systematics and abundances of highly siderophile elements. Pieces SM1 and SM2 were collected prior to a rain event, within 2 days of the fall. Pieces SM51 and SM53 were collected after a rain event. There are significant but minor relative and absolute variations in the abundances of the highly siderophile elements, as well as 187Os/188Os among the four pieces. Rhenium-Os isotopic data for SM1 and SM2 plot within analytical uncertainties of a primordial isochron, while powders made from SM51 and SM53 do not. These results suggest that interactions with rain caused some redistribution of Re, and to a lesser extent Os, within small pieces of the meteorite. Thus, Re-Os isotopic systematics of

Rotationally resolved state-to-state photoionization and the photoelectron study of vanadium monocarbide and its cations (VC/VC(+)).

By employing two-color visible (VIS)-ultraviolet (UV) laser photoionization and pulsed field ionization-photoelectron (PFI-PE) techniques, we have obtained highly rotationally resolved photoelectron spectra for vanadium monocarbide cations (VC(+)). The state-to-state VIS-UV-PFI-PE spectra thus obtained allow unambiguous assignments for the photoionization rotational transitions, resulting in a highly precise value for the adiabatic ionization energy (IE) of vanadium monocarbide (VC), IE(VC) = 57512.0 ± 0.8 cm(-1) (7.13058 ± 0.00010 eV), which is defined as the energy of the VC(+)(X(3)Δ1; v(+) = 0; J(+) = 1) ← VC(X(2)Δ3/2; v'' = 0; J'' = 3/2) photoionization transition. The spectroscopic constants for VC(+)(X(3)Δ1) determined in the present study include the harmonic vibrational frequency ωe(+) = 896.4 ± 0.8 cm(-1), the anharmonicity constant ωe(+)xe(+) = 5.7 ± 0.8 cm(-1), the rotational constants Be(+) = 0.6338 ± 0.0025 cm(-1) and αe(+) = 0.0033 ± 0.0007 cm(-1), the equilibrium bond length re(+) = 1.6549 ± 0.0003 Å, and the spin-orbit coupling constant A = 75.2 ± 0.8 cm(-1) for VC(+)(X(3)Δ1,2,3). These highly precise energetic and spectroscopic data are used to benchmark state-of-the-art CCSDTQ/CBS calculations. In general, good agreement is found between the theoretical predictions and experimental results. The theoretical calculations yield the values, IE(VC) = 7.126 eV; the 0 K bond dissociation energies: D0(V-C) = 4.023 eV and D0(V(+)-C) = 3.663 eV; and heats of formation: ΔH°(f0)(VC) = 835.2, ΔH°(f298)(VC) = 840.4, ΔH°(f0)(VC(+)) = 1522.8, and ΔH°(f298)(VC(+)) = 1528.0 kJ mol(-1).

Carbon and other light element contents in the Earth's core based on first-principles molecular dynamics.

Carbon (C) is one of the candidate light elements proposed to account for the density deficit of the Earth's core. In addition, C significantly affects siderophile and chalcophile element partitioning between metal and silicate and thus the distribution of these elements in the Earth's core and mantle. Derivation of the accretion and core-mantle segregation history of the Earth requires, therefore, an accurate knowledge of the C abundance in the Earth's core. Previous estimates of the C content of the core differ by a factor of ∼20 due to differences in assumptions and methods, and because the metal-silicate partition coefficient of C was previously unknown. Here we use two-phase first-principles molecular dynamics to derive this partition coefficient of C between liquid iron and silicate melt. We calculate a value of 9 ± 3 at 3,200 K and 40 GPa. Using this partition coefficient and the most recent estimates of bulk Earth or mantle C contents, we infer that the Earth's core contains 0.1-0.7 wt% of C. Carbon thus plays a moderate role in the density deficit of the core and in the distribution of siderophile and chalcophile elements during core-mantle segregation processes. The partition coefficients of nitrogen (N), hydrogen, helium, phosphorus, magnesium, oxygen, and silicon are also inferred and found to be in close agreement with experiments and other geochemical constraints. Contents of these elements in the core derived from applying these partition coefficients match those derived by using the cosmochemical volatility curve and geochemical mass balance arguments. N is an exception, indicating its retention in a mantle phase instead of in the core.

Rotationally resolved state-to-state photoionization and photoelectron study of titanium carbide and its cation (TiC/TiC⁺).

Titanium carbide and its cation (TiC/TiC(+)) have been investigated by the two-color visible (VIS)-ultraviolet (UV) resonance-enhanced photoionization and pulsed field ionization-photoelectron (PFI-PE) methods. Two visible excitation bands for neutral TiC are observed at 16,446 and 16,930 cm(-1). Based on rotational analyses, these bands are assigned as the respective TiC((3)Π1) ← TiC(X(3)Σ(+)) and TiC((3)Σ(+)) ← TiC(X(3)Σ(+)) transition bands. This assignment supports that the electronic configuration and term symmetry for the neutral TiC ground state are …7σ(2)8σ(1)9σ(1)3π(4) (X(3)Σ(+)). The rotational constant and the corresponding bond distance of TiC(X(3)Σ(+); v″ = 0) are determined to be B0″ = 0.6112(10) cm(-1) and r0″ = 1.695(2) Å, respectively. The rotational analyses of the VIS-UV-PFI-PE spectra for the TiC(+)(X; v(+) = 0 and 1) vibrational bands show that the electronic configuration and term symmetry for the ionic TiC(+) ground state are …7σ(2)8σ(1)3π(4) (X(2)Σ(+)) with the v(+) = 0 → 1 vibrational spacing of 870.0(8) cm(-1) and the rotational constants of B(e)(+) = 0.6322(28) cm(-1), and α(e)(+) = 0.0085(28) cm(-1). The latter rotational constants yield the equilibrium bond distance of r(e)(+) = 1.667(4) Å for TiC(+)(X(2)Σ(+)). The cleanly rotationally resolved VIS-UV-PFI-PE spectra have also provided a highly precise value of 53 200.2(8) cm(-1) [6.5960(1) eV] for the adiabatic ionization energy (IE) of TiC. This IE(TiC) value along with the known IE(Ti) has made possible the determination of the difference between the 0 K bond dissociation energy (D0) of TiC(+)(X(2)Σ(+)) and that of TiC(X(3)Σ(+)) to be D0(Ti(+)-C) - D0(Ti-C) = 0.2322(2) eV. Similar to previous experimental observations, the present state-to-state PFI-PE study of the photoionization transitions, TiC(+)(X(2)Σ(+); v(+) = 0 and 1, N(+)) ← TiC((3)Π1; v', J'), reveals a strong decreasing trend for the photoionization cross section as |ΔN(+)| = |N(+) - J'| is increased. The maximum |ΔN(+)| change of 7 observed here is also consistent with the previous experimental results for the 3d transition-metal carbides, oxides, and nitrides. However, the VIS-UV-PFI-PE spectra for TiC(+)(X(2)Σ(+); v(+) = 0 and 1, N(+)) are found to display only the negative ΔN(+) (N(+)-J'≤ 0) transitions, indicating that the cross sections for the formation of positive ΔN(+) (N(+)-J' > 0) transitions by both the channel coupling mechanism and direct photoionization are negligibly small.

Precise determination of the lutetium isotopic composition in rocks and minerals using multicollector ICPMS.

Evidence of (176)Hf excess in select meteorites older than 4556Ma was suggested to be caused by excitation of long-lived natural radionuclide (176)Lu to its short-lived isomer (176m)Lu, due to an irradiation event during accretion in the early solar system. A result of this process would be a deficit in (176)Lu in irradiated samples by between 1‰ and 7‰. Previous measurements of the Lu isotope ratio in rock samples have not been of sufficient precision to resolve such a phenomenon. We present a new analytical technique designed to measure the (176)Lu/(175)Lu isotope ratio in rock samples to a precision of ~0.1‰ using a multicollector inductively coupled mass spectrometer (MC-ICPMS). To account for mass bias we normalized all unknowns to Ames Lu. To correct for any drift and instability associated with mass bias, all standards and samples are doped with W metal and normalized to the nominal W isotopic composition. Any instability in the mass bias is then corrected by characterizing the relationship between the fractionation factor of Lu and W, which is calculated at the start of every analytical session. After correction for isobaric interferences, in particular (176)Yb, we were able to measure (176)Lu/(175)Lu ratios in samples to a precision of ~0.1‰. However, these terrestrial standards were fractionated from Ames Lu by an average of 1.22 ± 0.09‰. This offset in (176)Lu/(175)Lu is probably caused by isotopic fractionation of Lu during industrial processing of the Ames Lu standard. To allow more straightforward data comparison we propose the use of NIST3130a as a bracketing standard in future studies. Relative to NIST3130a, the terrestrial standards have a final weighted mean δ(176)Lu value of 0.11 ± 0.09‰. All samples have uncertainties of better than 0.11‰; hence, our technique is fully capable of resolving any differences in δ(176)Lu of greater than 1‰.

Branching ratio measurements for vacuum ultraviolet photodissociation of 12C16O.

The branching ratios for the spin-forbidden photodissociation channels of (12)C(16)O in the vacuum ultraviolet (VUV) photon energy region from 102,500 (12.709 eV) to 106,300 cm(-1) (13.180 eV) have been investigated using the VUV laser time-slice velocity-map imaging photoion technique. The excitations to three (1)Σ(+) and six (1)Π Rydberg-type states, including the progression of W(3sσ) (1)Π(v' = 0, 1, and 2) vibrational levels of CO, have been identified and investigated. The branching ratios for the product channels C((3)P) + O((3)P), C((1)D) + O((3)P), and C((3)P) + O((1)D) of these predissociative states are found to depend on the electronic, vibrational, and rotational states of CO being excited. Rotation and e/f-symmetry dependences of the branching ratios into the spin-forbidden channels have been confirmed for several of the (1)Π states, which can be explained using the heterogeneous interaction with the repulsive D'(1)Σ(+) state. The percentage of the photodissociation into the spin-forbidden channels is found to increase with increasing the rotational quantum number for the K(4pσ) (1)Σ(+) (v' = 0) state. This has been rationalized using a (1)Σ(+) to (1)Π to (3)Π coupling scheme, where the final (3)Π state is a repulsive valence state correlating to the spin-forbidden channel.

Coupled 182W-142Nd constraint for early Earth differentiation.

Recent high precision (142)Nd isotope measurements showed that global silicate differentiation may have occurred as early as 30-75 Myr after the Solar System formation [Bennett V, et al. (2007) Science 318:1907-1910]. This time scale is almost contemporaneous with Earth's core formation at approximately 30 Myr [Yin Q, et al. (2002) Nature 418:949-952]. The (182)Hf-(182)W system provides a powerful complement to the (142)Nd results for early silicate differentiation, because both core formation and silicate differentiation fractionate Hf from W. Here we show that eleven terrestrial samples from diverse tectonic settings, including five early Archean samples from Isua, Greenland, of which three have been previously shown with (142)Nd anomalies, all have a homogeneous W isotopic composition, which is approximately 2epsilon-unit more radiogenic than the chondritic value. By using a 3-stage model calculation that describes the isotopic evolution in chondritic reservoir and core segregation, as well as silicate differentiation, we show that the W isotopic composition of terrestrial samples provides the most stringent time constraint for early core formation (27.5-38 Myr) followed by early terrestrial silicate differentiation (38-75 Myr) that is consistent with the terrestrial (142)Nd anomalies.

I/Pu reveals Earth mainly accreted from volatile-poor differentiated planetesimals.

The observation that mid-ocean ridge basalts had ~3× higher iodine/plutonium ratios (inferred from xenon isotopes) compared to ocean island basalts holds critical insights into Earth's accretion. Understanding whether this difference stems from core formation alone or heterogeneous accretion is, however, hindered by the unknown geochemical behavior of plutonium during core formation. Here, we use first-principles molecular dynamics to quantify the metal-silicate partition coefficients of iodine and plutonium during core formation and find that both iodine and plutonium partly partition into metal liquid. Using multistage core formation modeling, we show that core formation alone is unlikely to explain the iodine/plutonium difference between mantle reservoirs. Instead, our results reveal a heterogeneous accretion history, whereby predominant accretion of volatile-poor differentiated planetesimals was followed by a secondary phase of accretion of volatile-rich undifferentiated meteorites. This implies that Earth inherited part of its volatiles, including its water, from late accretion of chondrites, with a notable carbonaceous chondrite contribution.

Igneous meteorites suggest Aluminium-26 heterogeneity in the early Solar Nebula.

The short-lived radionuclide aluminium-26 (26Al) isotope is a major heat source for early planetary melting. The aluminium-26 - magnesium-26 (26Al-26Mg) decay system also serves as a high-resolution relative chronometer. In both cases, however, it is critical to establish whether 26Al was homogeneously or heterogeneously distributed throughout the solar nebula. Here we report a precise lead-207 - lead-206 (207Pb-206Pb) isotopic age of 4565.56 ± 0.12 million years (Ma) for the andesitic achondrite Erg Chech 002. Our analysis, in conjunction with published 26Al-26Mg data, reveals that the initial 26Al/27Al in the source material of this achondrite was notably higher than in various other well-preserved and precisely dated achondrites. Here we demonstrate that the current data clearly indicate spatial heterogeneity of 26Al by a factor of 3-4 in the precursor molecular cloud or the protoplanetary disk of the Solar System, likely associated with the late infall of stellar materials with freshly synthesized radionuclides.

Geochemistry: does U-Pb date Earth's core formation?

Constraining the timing of the formation of Earth's core, which defines the birth of our planet, is essential for understanding the early evolution of Earth-like planets. Wood and Halliday and Halliday discuss the apparent discrepancy between the U-Pb (60-80 Myr) and Hf-W clocks (30 Myr) in determining the timescale of Earth's accretion and core formation. We find that the information the authors present is at times contradictory (for example, compare Fig. 1 in ref. 1 with Fig. 1 in ref. 2) and confusing and could suggest that the U-Pb clock constrains core formation better than the Hf-W system. Here we point out the limitations of the U-Pb system and show that the U-Pb age cannot be used to argue for protracted accretion and/or core formation (>50 Myr) because this clock only records the processes that occurred during the last 1% of Earth's accretion and core formation in the Wood and Halliday mechanism.

Branching ratio measurements of the predissociation of 12C16O by time-slice velocity-map ion imaging in the energy region from 108,000 to 110,500 cm(-1).

Direct branching ratio measurements of the three lowest dissociation channels of (12)C(16)O that produce C((3)P) + O((3)P), C((1)D) + O((3)P), and C((3)P) + O((1)D) are reported in the vacuum ultraviolet region from 108,000 cm(-1) (92.59 nm) to 110,500 cm(-1) (90.50 nm) using the time-slice velocity-map ion imaging and nonlinear resonant four-wave mixing techniques. Rotationally, resolved carbon ion yield spectra for both (1)Σ(+) and (1)Π bands of CO in this region have been obtained. Our measurements using this technique show that the branching ratio in this energy region, especially the relative percentages of the two spin-forbidden channels, is strongly dependent on the particular electronic and vibrational energy levels of CO that are excited.

The Mg isotopic systematics of granitoids in continental arcs and implications for the role of chemical weathering in crust formation.

Continental crust is too Si-rich and Mg-poor to derive directly from mantle melting, which generates basaltic rather than felsic magmas. Converting basalt to more felsic compositions requires a second step involving Mg loss, which is thought to be dominated by internal igneous differentiation. However, igneous differentiation alone may not be able to generate granites, the most silicic endmember making up the upper continental crust. Here, we show that granites from the eastern Peninsular Ranges Batholith (PRB) in southern California are isotopically heavy in Mg compared with PRB granodiorites and canonical mantle. Specifically, Mg isotopes correlate positively with Si content and O, Sr, and Pb isotopes and negatively with Mg content. The elevated Sr and Pb isotopes require that a component in the source of the granitic magmas to be ancient preexisting crust making up the prebatholithic crustal basement, but the accompanying O and Mg isotope fractionations suggest that this prebatholithic crust preserved a signature of low-temperature alteration. The protolith of this basement rock may have been the residue of chemical weathering, which progressively leached Mg from the residue, leaving the remaining Mg highly fractionated in terms of its isotopic signature. Our observations indicate that ancient continental crust preserves the isotopic signature of compositional modification by chemical weathering.

An Acid-Based Method for Highly Effective Baddeleyite Separation from Gram-Sized Mafic Rocks.

Dating mafic igneous rocks (silica-undersaturated) is difficult for the lack of suitable minerals such as zircons (ZrSiO4) commonly found in the sialic rocks such as granites. In this regard, baddeleyite (ZrO2) has been long recognized as the most important mineral to serve as a geochronometer for dating silica-undersaturated igneous rocks. However, separating baddeleyite is difficult due to its small grain size, typical tabular morphology, and low abundance in samples. The standard water-based separation technique requires kilogram-sized samples and usually has a very low recovery rate. In this study, a new separation method based on the different solubilities of the minerals within HF + HCl + HNO3 reagents was developed to achieve a high recovery of baddeleyite. With ∼19 g of diabase powder, the new method recovers 150-160 baddeleyite grains of 10-100 µm length and 4-50 µm width, an order of magnitude improvement over the water-based separation method, which typically recovers 11-12 similarly sized baddeleyite grains out of the ∼19 g sample. Subsequent secondary ion mass spectrometry U-Pb analyses demonstrate that the baddeleyite grains recovered by the new separation method keep the U-Pb system closed, indicating no Pb loss during acid treatment. Thus, this new method enables the most efficient baddeleyite recovery from gram-sized rocks and is anticipated to greatly contribute to the geochronological study of silica-unsaturated mafic rocks.

Visual, spectral, and microchemical quantification of crystalline anomalies in otoliths of wild and cultured delta smelt.

Developmental abnormalities in otoliths can impact growth and survival in teleost fishes. Here, we quantified the frequency and severity of developmental anomalies in otoliths of delta smelt (Hypomesus transpacificus), a critically endangered estuarine fish that is endemic to the San Francisco Estuary. Left-right asymmetry and anomalous crystalline polymorphs (i.e., vaterite) were quantified and compared between wild and cultured populations using digital image analysis. Visual estimates of vaterite were validated using X-ray diffraction, Raman spectroscopy, laser ablation ICPMS, and electron probe microanalysis. Results indicated that cultured delta smelt were 80 times more likely to contain a vateritic otolith and 18 times more likely to contain relatively large (≥ 15%) amounts of vaterite. Similarly, cultured fish exhibited 30% greater asymmetry than wild fish. These results indicate that cultured delta smelt exhibit a significantly higher frequency of vestibular abnormalities which are known to reduce fitness and survival. Such hatchery effects on otolith development could have important implications for captive culture practices and the supplementation of wild fish populations with cultured individuals.