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Day, JMD, Taylor LA, Floss C, Patchen AD, Schnare DW, Pearson DG.  2006.  Comparative petrology, geochemistry, and petrogenesis of evolved, low-Ti lunar mare basalt meteorites from the LaPaz Icefield, Antarctica. Geochimica Et Cosmochimica Acta. 70:1581-1600.   10.1016/j.gca.2005.11.015   AbstractWebsite

New data is presented for five evolved, low-Ti lunar mare basalt meteorites from the LaPaz Icefield, Antarctica, LAP 02205, LAP 02224, LAP 02226, LAP 02436, and LAP 03632. These basalts have nearly identical mineralogies, textures, and geochemical compositions, and are therefore considered to be paired. The LaPaz basalts contain olivine (Fo(64-2)) and pyroxene (Fs(32)Wo(8)En(60) to Fs(84-86)Wo(15)En(2-0)) crystals that record extreme chemical fractionation to Fe-enrichment at the rims, and evidence for silicate liquid immiscibility and incompatible element enrichment in the mesostasis. The basalts also contain FeNi metals with unusually high Co and Ni contents, similar to some Apollo 12 basalts, and a single-phase network of melt veins and fusion crusts. The fusion crust has similar chemical characteristics to the whole rock for the LaPaz basalts, whereas the melt veins represent localized melting of the basalt and have an endogenous origin. The crystallization conditions and evolved nature of the LaPaz basalts are consistent with fractionation of olivine and chromite from a parental liquid similar in composition to some olivine-phyric Apollo 12 and Apollo 15 basalts or lunar low-Ti pyroclastic glasses. However, the young reported ages for the LaPaz mare basalts (similar to 2.9 Ga) and their relative incompatible element enrichment compared to Apollo mare basalts and pyroclastic glasses indicate they cannot be directly related. Instead, the LaPaz mare basalts may represent fractionated melts from a magmatic system fed by similar degrees of partial melting of a mantle source similar to that of the low-Ti Apollo mare basalts or pyroclastic glasses, but which possessed greater incompatible element enrichment. Despite textural differences, the LaPaz basalts and mare basalt meteorite NWA 032 have similar ages and compositions and may originate from the same magmatic system on the Moon. (c) 2005 Elsevier Inc. All rights reserved.

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Sarbadhikari, AB, Goodrich CA, Liu Y, Day JMD, Taylor LA.  2011.  Evidence for heterogeneous enriched shergottite mantle sources in Mars from olivine-hosted melt inclusions in Larkman Nunatak 06319. Geochimica Et Cosmochimica Acta. 75:6803-6820.   10.1016/j.gca.2011.09.001   AbstractWebsite

Larkman Nunatak (LAR) 06319 is an olivine-phyric shergottite whose olivine crystals contain abundant crystallized melt inclusions. In this study, three types of melt inclusion were distinguished, based on their occurrence and the composition of their olivine host: Type-I inclusions occur in phenocryst cores (Fo(77-73)); Type-II inclusions occur in phenocryst mantles (Fo(71-66)); Type-III inclusions occur in phenocryst rims (Fo(61-51)) and within groundmass olivine. The sizes of the melt inclusions decrease significantly from Type-I (similar to 150-250 mu m diameter) to Type-II (similar to 100 mu m diameter) to Type-III (similar to 25-75 mu m diameter). Present bulk compositions (PBC) of the crystallized melt inclusions were calculated for each of the three melt inclusion types based on average modal abundances and analyzed compositions of constituent phases. Primary trapped liquid compositions were then reconstructed by addition of olivine and adjustment of the Fe/Mg ratio to equilibrium with the host olivine (to account for crystallization of wall olivine and the effects of Fe/Mg re-equilibration). The present bulk composition of Type-I inclusions (PBC1) plots on a tie-line that passes through olivine and the LAR 06319 whole-rock composition. The parent magma composition can be reconstructed by addition of 29 mol% olivine to PBC1, and adjustment of Fe/Mg for equilibrium with olivine of Fo(77) composition. The resulting parent magma composition has a predicted crystallization sequence that is consistent with that determined from petrographic observations, and differs significantly from the whole-rock only in an accumulated olivine component (similar to 10 wt%). This is consistent with a calculation indicating that similar to 10 wt% agnesian (Fo(77-73)) olivine must be subtracted from the whole-rock to yield a melt in equilibrium with Fo(77). Thus, two independent estimates indicate that LAR 06319 contains similar to 10 wt% cumulate olivine. The rare earth element (REE) patterns of Type-I melt inclusions are similar to that of the LAR 06319 whole-rock. The REE patterns of Type-II and Type-III melt inclusions are also broadly parallel to that of the whole-rock, but at higher absolute abundances. These results are consistent with an LAR 06319 parent magma that crystallized as a closed-system, with its incompatible-element enrichment being inherited from its mantle source region. However, fractional crystallization of the reconstructed LAR 06319 parent magma cannot reproduce the major and trace element characteristics of all enriched basaltic shergottites, indicating local-to-large scale major-and trace-element variations in the mantle source of enriched shergottites. Therefore, LAR 06319 cannot be parental to the enriched basaltic shergottites. (C) 2011 Elsevier Ltd. All rights reserved.

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Filiberto, J, Chin E, Day JMD, Franchi IA, Greenwood RC, Gross J, Penniston-Dorland SC, Schwenzer SP, Treiman AH.  2012.  Geochemistry of intermediate olivine-phyric shergottite northwest Africa 6234, with similarities to basaltic shergottite northwest Africa 480 and olivine-phyric shergottite northwest Africa 2990. Meteoritics and Planetary Science. 47(8):1256-1273.   10.1111/j.1945-5100.2012.01382.x   Abstract

The newly found meteorite Northwest Africa 6234 (NWA 6234) is an olivine (ol)-phyric shergottite that is thought, based on texture and mineralogy, to be paired with Martian shergottite meteorites NWA 2990, 5960, and 6710. We report bulk-rock major- and trace-element abundances (including Li), abundances of highly siderophile elements, Re-Os isotope systematics, oxygen isotope ratios, and the lithium isotope ratio for NWA 6234. NWA 6234 is classified as a Martian shergottite, based on its oxygen isotope ratios, bulk composition, and bulk element abundance ratios, Fe/Mn, Al/Ti, and Na/Al. The Li concentration and δ7Li value of NWA 6234 are similar to that of basaltic shergottites Zagami and Shergotty. The rare earth element (REE) pattern for NWA 6234 shows a depletion in the light REE (La-Nd) compared with the heavy REE (Sm-Lu), but not as extreme as the known “depleted” shergottites. Thus, NWA 6234 is suggested to belong to a new category of shergottite that is geochemically “intermediate” in incompatible elements. The only other basaltic or ol-phyric shergottite with a similar “intermediate” character is the basaltic shergottite NWA 480. Rhenium-osmium isotope systematics are consistent with this intermediate character, assuming a crystallization age of 180 Ma. We conclude that NWA 6234 represents an intermediate compositional group between enriched and depleted shergottites and offers new insights into the nature of mantle differentiation and mixing among mantle reservoirs in Mars.

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Stronik, NA, Trumbull RB, Krienitz M-S, Niedermann S, Romer RL, Harris C, Day JMD.  2017.  Helium isotope evidence for a deep-seated mantle plume involved in South Atlantic breakup. Geology. 45(9):827-830.   10.1130/G39151.1   Abstract

Earth history has been punctuated by episodes of short-lived (<10 m.y.), high-volume (>106 km3) magmatism. The origin of these events and their manifestations as large igneous provinces (LIPs) with associated continental flood basalts do not fit in the current plate-tectonic paradigm. Upper-mantle processes have been invoked for some LIPs, whereas the origin of others appears to be related to plumes rising from the deep mantle. The Paraná-Etendeka LIP has remained enigmatic and highly contested in terms of plume versus upper-mantle models. Here, we provide evidence for a plume origin based on new isotopic (He, O, Sr, Nd, Pb) and trace-element data from olivine-rich dikes from Namibia. The composition of the dikes can be explained by mixing at shallow depths between a plume source with high 3He/4He (>26 RA) and ambient asthenospheric mantle, before ascent through the thinning lithosphere.

Gannoun, A, Burton KW, Day JMD, Harvey J, Schiano P, Parkinson I.  2016.  Highly Siderophile Element and Os Isotope Systematics of Volcanic Rocks at Divergent and Convergent Plate Boundaries and in Intraplate Settings. Reviews in Mineralogy and Geochemistry. 81:651-724.   10.2138/rmg.2016.81.11   Abstract

Terrestrial magmatism is dominated by basaltic compositions. This definition encompasses mid-ocean ridge basalts (MORB), which account for more than eighty percent of Earth’s volcanic products and which are formed at divergent oceanic plate margins, as well as intraplate volcanic rocks such as ocean island basalts (OIB), continental flood basalts (CFB) and continental rift-related basalts, and highly magnesian ultramafic volcanic rocks that dominantly occur in Archean terranes, termed komatiites. All of these broadly basaltic rocks are considered to form by partial melting of the upper mantle, followed by extraction from their source regions and emplacement at the Earth’s surface. For these reasons, basalts can be used to examine the nature and extent of partial melting in the mantle, the compositions of mantle sources, and the interactions between the crust and mantle. Because much of Earth’s mantle is inaccessible, basalts offer some of the best ‘proxies’ for examining mantle composition, mantle convection and crust–mantle interactions. By contrast, at arcs, volcanism is dominated by andesitic rock compositions. While some arcs do have basaltic and picritic magmatism, these magma types are rare in convergent plate margin settings and reflect the complex fractional crystallization and often associated concomitant assimilation processes occurring in arcs. Despite the limited occurrence of high MgO magmas in arc volcanic rocks, magmas from this tectonic setting are also important for elucidating the behavior of the HSE from creation of basaltic compositions at mid-ocean ridges to the subduction of this crust beneath arcs at convergent plate margins.

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Day, JMD, O'Driscoll B, Strachan RA, Daly JS, Walker RJ.  2017.  Identification of mantle peridotite as a possible Iapetan ophiolite sliver in south Shetland, Scottish Caledonides. Journal of the Geological Society. 174(1):88-92.   http://dx.doi.org/10.1144/jgs2016-074   Abstract

The Neoproterozoic Dunrossness Spilite Subgroup of south Shetland, Scotland, has been interpreted as a series of komatiitic and mafic lava flows formed in a marginal basin in response to Laurentian continental margin rifting. We show that ultramafic rocks previously identified as komatiites are depleted mantle peridotites that experienced seafloor hydrothermal alteration. The presence of positive Bouguer gravity and aeromagnetic anomalies extending from the Dunrossness Spilite Subgroup northward to the Shetland Ophiolite Complex suggests instead that these rocks may form part of an extensive ophiolite sliver, obducted during Iapetus Ocean closure in a forearc setting.

Inglis, EC, Moynier F, Creech J, Deng Z, Day JMD, Teng F-Z, Bizzarro M, Jackson M, Savage P.  2019.  Isotopic fractionation of zirconium during magmatic differentiation and the stable isotope composition of the silicate Earth. Geochimica et Cosmochimica Acta. 250:311-323.   10.1016/j.gca.2019.02.010   Abstract

High-precision double-spike Zr stable isotope measurements (expressed as δ94/90ZrIPGP-Zr, the permil deviation of the 94Zr/90Zr ratio from the IPGP-Zr standard) are presented for a range of ocean island basalts (OIB) and mid-ocean ridge basalts (MORB) to examine mass-dependent isotopic variations of zirconium in Earth. Ocean island basalt samples, spanning a range of radiogenic isotopic flavours (HIMU, EM) show a limited range in δ94/90ZrIPGP-Zr (0.046 ± 0.037‰; 2sd, n = 13). Similarly, MORB samples with chondrite-normalized La/Sm of >0.7 show a limited range in δ94/90ZrIPGP-Zr (0.053 ± 0.040‰; 2sd, n = 8). In contrast, basaltic lavas from mantle sources that have undergone significant melt depletion, such as depleted normal MORB (N-MORB) show resolvable variations in δ94/90ZrIPGP-Zr, from −0.045 ± 0.018 to 0.074 ± 0.023‰. Highly evolved igneous differentiates (>65 wt% SiO2) from Hekla volcano in Iceland are isotopically heavier than less evolved igneous rocks, up to 0.53‰. These results suggest that both mantle melt depletion and extreme magmatic differentiation leads to resolvable mass-dependent Zr isotope fractionation. We find that this isotopic fractionation is most likely driven by incorporation of light isotopes of Zr within the 8-fold coordinated sites of zircons, driving residual melts, with a lower coordination chemistry, towards heavier values. Using a Rayleigh fractionation model, we suggest a αzircon-melt of 0.9995 based on the whole rock δ94/90ZrIPGP-Zr values of the samples from Hekla volcano (Iceland). Zirconium isotopic fractionation during melt-depletion of the mantle is less well-constrained, but may result from incongruent melting and incorporation of isotopically light Zr in the 8-fold coordinated M2 site of orthopyroxene. Based on these observations lavas originating from the effect of melt extraction from a depleted mantle source (N-MORB) or that underwent zircon saturation (SiO2 > 65 wt%) are removed from the dataset to give an estimate of the primitive mantle Zr isotope composition of 0.048 ± 0.032‰; 2sd, n = 48. These data show that major controls on Zr fractionation in the Earth result from partial melt extraction in the mantle and by zircon fractionation in differentiated melts. Conversely, fertile mantle is homogenous with respect to Zr isotopes. Zirconium mass-dependent fractionation effects can therefore be used to trace large-scale mantle melt depletion events and the effects of felsic crust formation.

Franz, HB, Kim ST, Farquhar J, Day JMD, Economos RC, McKeegan KD, Schmitt AK, Irving AJ, Hoek J, Dottin J.  2014.  Isotopic links between atmospheric chemistry and the deep sulphur cycle on Mars. Nature. 508:364-+.   10.1038/nature13175   AbstractWebsite

The geochemistry of Martian meteorites provides a wealth of information about the solid planet and the surface and atmospheric processes that occurred on Mars. The degree to which Martian magmas may have assimilated crustal material, thus altering the geochemical signatures acquired from their mantle sources, is unclear(1). This issue features prominently in efforts to understand whether the source of light rare-earth elements in enriched shergottites lies in crustal material incorporated into melts(1,2) or in mixing between enriched and depleted mantle reservoirs(3). Sulphur isotope systematics offer insight into some aspects of crustal assimilation. The presence of igneous sulphides in Martian meteorites with sulphur isotope signatures indicative of mass-independent fractionation suggests the assimilation of sulphur both during passage of magmas through the crust of Mars and at sites of emplacement. Here we report isotopic analyses of 40 Martian meteorites that represent more than half of the distinct known Martian meteorites, including 30 shergottites (28 plus 2 pairs, where pairs are separate fragments of a single meteorite), 8 nakhlites (5 plus 3 pairs), Allan Hills 84001 and Chassigny. Our data provide strong evidence that assimilation of sulphur into Martian magmas was a common occurrence throughout much of the planet's history. The signature of mass-independent fractionation observed also indicates that the atmospheric imprint of photochemical processing preserved in Martian meteoritic sulphide and sulphate is distinct from that observed in terrestrial analogues, suggesting fundamental differences between the dominant sulphur chemistry in the atmosphere of Mars and that in the atmosphere of Earth(4).

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Schnare, DW, Day JMD, Norman MD, Liu Y, Taylor LA.  2008.  A laser-ablation ICP-MS study of Apollo 15 low-titanium olivine-normative and quartz-normative mare basalts. Geochimica Et Cosmochimica Acta. 72:2556-2572.   10.1016/j.gca.2008.02.021   AbstractWebsite

Apollo 15 low-Ti mare basalts have traditionally been subdivided into olivine- and quartz-normative basalt types, based on their different SiO(2), FeO, and TiO(2) whole-rock compositions. Previous studies have reconciled this compositional diversity by considering the olivine- and quartz-normative basalts as originating from different lunar mantle source regions. To provide new information on the compositions of Apollo 15 low-Ti mare basalt parental magmas, we report a study of major and trace-element compositions of whole rocks, pyroxenes, and other phases in the olivine-normative basalts 15016 and 15555 and quartz-normative basalts 15475 and 15499. Results show similar rare-earth-element patterns in pyroxenes from all four basalts. The estimated equilibrium parental-melt compositions from the trace-element compositions of pyroxenes are similar for 15016, 15555 and 15499. Additionally, an independent set of trace-element distribution coefficients has been determined from measured pyroxene and mesostasis compositions in sample 15499. These data suggest that fractional crystallization may be a viable alternative to compositional differences in the mantle source to explain the similar to 25% difference in whole-rock TiO(2), and corresponding differences in SiO(2) and FeO between the Apollo 15 olivine- and quartz-normative basalts. In this model, the older (similar to 3.35 Ga) quartz-normative basalts, with lower TiO(2) experienced olivine, chromite, and Cr-ulvospinel fractionation at 'crustal levels' in magma chambers or dikes, followed by limited near-surface mineral fractionation, within the lava flows. In contrast, the younger (similar to 3.25 Ga) olivine-normative basalts experienced only limited magmatic differentiation at 'crustal-levels', but extensive near-surface mineral fractionation to produce their evolved mineral compositions. A two-stage mineral-fractionation model is consistent with textural and mineralogical observations, as well as the mineral trace-element constraints developed by this study. (C) 2008 Elsevier Ltd. All rights reserved.

Day, JMD, Moynier F, Shearer CK.  2017.  Late-stage magmatic outgassing from a volatile-depleted Moon. Proceedings of the National Academy of Sciences. 114(35):9547-9551.   10.1073/pnas.1708236114   AbstractWebsite

The abundance of volatile elements and compounds, such as zinc, potassium, chlorine, and water, provide key evidence for how Earth and the Moon formed and evolved. Currently, evidence exists for a Moon depleted in volatile elements, as well as reservoirs within the Moon with volatile abundances like Earth’s depleted upper mantle. Volatile depletion is consistent with catastrophic formation, such as a giant impact, whereas a Moon with Earth-like volatile abundances suggests preservation of these volatiles, or addition through late accretion. We show, using the “Rusty Rock” impact melt breccia, 66095, that volatile enrichment on the lunar surface occurred through vapor condensation. Isotopically light Zn (δ66Zn = −13.7‰), heavy Cl (δ37Cl = +15‰), and high U/Pb supports the origin of condensates from a volatile-poor internal source formed during thermomagmatic evolution of the Moon, with long-term depletion in incompatible Cl and Pb, and lesser depletion of more-compatible Zn. Leaching experiments on mare basalt 14053 demonstrate that isotopically light Zn condensates also occur on some mare basalts after their crystallization, confirming a volatile-depleted lunar interior source with homogeneous δ66Zn ≈ +1.4‰. Our results show that much of the lunar interior must be significantly depleted in volatile elements and compounds and that volatile-rich rocks on the lunar surface formed through vapor condensation. Volatiles detected by remote sensing on the surface of the Moon likely have a partially condensate origin from its interior.

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Korhonen, FJ, Saito S, Brown M, Siddoway CS, Day JMD.  2010.  Multiple Generations of Granite in the Fosdick Mountains, Marie Byrd Land, West Antarctica: Implications for Polyphase Intracrustal Differentiation in a Continental Margin Setting. Journal of Petrology. 51:627-670.   10.1093/petrology/egp093   AbstractWebsite

Production of granite in the middle to lower crust and emplacement into the middle to upper crust at convergent plate margins is the dominant mechanism of crustal differentiation. The Fosdick Mountains of West Antarctica host migmatitic paragneisses and orthogneisses corresponding to the middle to lower crust and granites emplaced as dikes, sills and small plutons, which record processes of intracrustal differentiation along the East Gondwana margin. U-Pb chronology on magmatic zircon from granites reveals emplacement at c. 358-336 Ma and c. 115-98 Ma, consistent with a polyphase tectonic evolution of the region during Devonian-Carboniferous continental arc activity and Cretaceous continental rifting. The gneisses and granites exposed in the Fosdick migmatite-granite complex were derived from Early Paleozoic quartzose turbidites of the Swanson Formation and Ford Granodiorite suite calc-alkaline plutonic rocks, both of which are widely distributed outside the Fosdick Mountains and have affinity with rock elsewhere in East Gondwana. Granites of both Carboniferous and Cretaceous age have distinct chemical signatures that reflect different melting reactions and accessory phase behavior in contrasting sources. Based on whole-rock major and trace element geochemistry and Sr-Nd isotope compositions, Carboniferous granites with low Rb/Sr are interpreted to be products of melting of the Ford Granodiorite suite. Extant mineral equilibria modeling indicates that the Ford Granodiorite suite compositions produce melt volumes > 10 vol. % at temperatures above biotite stability, involving the breakdown of hornblende + plagioclase, consistent with the high CaO and Na(2)O contents in the low Rb/Sr granites. The Carboniferous low Rb/Sr granites show a sequence from near-melt compositions to compositions with increasing amounts of early crystallized biotite and plagioclase and evidence for apatite dissolution in the source. Carboniferous granites derived from the Swanson Formation are scarce, suggesting that the significant quantities of melt produced from the now residual paragneisses were emplaced at shallower crustal levels than are now exposed. The Cretaceous granites are divided into two distinct groups. An older group of granites (c. 115-110 Ma) has compositions consistent with a dominant Ford Granodiorite source, and characteristics that indicate that they may be less evolved equivalents of the regionally exposed Byrd Coast Granite suite at higher crustal levels. The younger group of granites (c. 109-102 Ma) has distinct light rare earth element depleted signatures. The chemical and isotopic data suggest that these granites were derived from partial melting of both fertile and residual Swanson Formation and had low water contents, indicating that the source rocks may have been dehydrated prior to anatexis as the Byrd Coast Granite suite magmas were transferring through and accumulating at higher crustal levels. The Cretaceous granites derived from the Swanson Formation make up a prominent horizontally sheeted leucogranite complex. The accumulation of these melts probably facilitated melt-induced weakening of the crust during a well-documented transition from regional shortening to regional extension, the formation of a detachment structure, and rapid exhumation of the Fosdick migmatite-granite complex. These multiple episodes of melting along the East Gondwana margin resulted in initial stabilization of the continental crust in the Carboniferous and further intracrustal differentiation in the Cretaceous.

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Liu, Y, Spicuzza MJ, Craddock PR, Day JMD, Valley JW, Dauphas N, Taylor LA.  2010.  Oxygen and iron isotope constraints on near-surface fractionation effects and the composition of lunar mare basalt source regions. Geochimica Et Cosmochimica Acta. 74:6249-6262.   10.1016/j.gca.2010.08.008   AbstractWebsite

Oxygen and iron isotope analyses of low-Ti and high-Ti mare basalts are presented to constrain their petrogenesis and to assess stable isotope variations within lunar mantle sources. An internally-consistent dataset of oxygen isotope compositions of mare basalts encompasses five types of low-Ti basalts from the Apollo 12 and 15 missions and eight types of high-Ti basalts from the Apollo 11 and 17 missions. High-precision whole-rock delta(18)O values (referenced to VSMOW) of low-Ti and high-Ti basalts correlate with major-element compositions (Mg#, TiO(2), Al(2)O(3)). The observed oxygen isotope variations within low-Ti and high-Ti basalts are consistent with crystal fractionation and match the results of mass-balance models assuming equilibrium crystallization. Whole-rock delta(56)Fe values (referenced to IRMM-014) of high-Ti and low-Ti basalts range from 0.134 parts per thousand to 0.217 parts per thousand. and 0.038 parts per thousand, to 0.104 parts per thousand, respectively. Iron isotope compositions of both low-Ti and high-Ti basalts do not correlate with indices of crystal fractionation, possibly owing to small mineral-melt iron fractionation factors anticipated under lunar reducing conditions. The delta(18)O and delta(56)Fe values of low-Ti and the least differentiated high-Ti mare basalts are negatively correlated, which reflects their different mantle source characteristics (e.g., the presence or absence of ilmenite). The average delta(56)Fe values of low-Ti basalts (0.073 +/- 0.018 parts per thousand), n = 8) and high-Ti basalts (0.191 +/- 0.020 parts per thousand, n = 7) may directly record that of their parent mantle sources. Oxygen isotope compositions of mantle sources of low-Ti and high-Ti basalts are calculated using existing models of lunar magma ocean crystallization and mixing, the estimated equilibrium mantle olivine delta(18)O value, and equilibrium oxygen-fractionation between olivine and other mineral phases. The differences between the calculated whole-rock delta(18)O values for source regions, 5.57 parts per thousand for low-Ti and 5.30 parts per thousand for high-Ti mare basalt mantle source regions, are solely a function of the assumed source mineralogy. The oxygen and iron isotope compositions of lunar upper mantle can be approximated using these mantle source values. The delta(18)O and delta(56)Fe values of the lunar upper mantle are estimated to be 5.5 +/- 0.27. (2 sigma) and 0.085 +/- 0.040 parts per thousand (2 sigma), respectively. The oxygen isotope composition of lunar upper mantle is identical to the current estimate of Earth's upper mantle (5.5 0.2 parts per thousand), and the iron isotope composition of the lunar upper mantle overlaps within uncertainty of estimates for the terrestrial upper mantle (0.044 +/- 0.030 parts per thousand.). (C) 2010 Elsevier Ltd. All rights reserved.

Spicuzza, MJ, Day JMD, Taylor LA, Valley JW.  2007.  Oxygen isotope constraints on the origin and differentiation of the Moon. Earth and Planetary Science Letters. 253:254-265.   10.1016/j.epsl.2006.10.030   AbstractWebsite

We report new high-precision laser fluorination three-isotope oxygen data for lunar materials. Terrestrial silicates with a range of delta O-18 values (-0.5 to 22.9 parts per thousand) were analyzed to independently determine the slope of the terrestrial fractionation line (TFL; lambda = 0.5259 +/- 0.0008; 95% confidence level). This new TFL determination allows direct comparison of lunar oxygen isotope systematics with those of Earth. Values of Delta O-17 for Apollo 12, 15, and 17 basalts and Luna 24 soil samples average 0.01 parts per thousand and are indistinguishable from the TFL. The delta O-18 values of high- and low-Ti lunar basalts are distinct. Average whole-rock delta O-18 values for low-Ti lunar basalts from the Apollo 12 (5.72 +/- 0.06 parts per thousand) and Apollo 15 landing sites (5.65 +/- 0.12 parts per thousand) are identical within error and are markedly higher than Apollo 17 high-Ti basalts (5.46 +/- 0.11 parts per thousand). Evolved low-Ti LaPaz mare-basalt meteorite delta O-18 values (5.67 +/- 0.05 parts per thousand) are in close agreement with more primitive low-Ti Apollo 12 and 15 mare basalts. Modeling of lunar mare-basalt source composition indicates that the high- and low-Ti mare-basalt mantle reservoirs were in oxygen isotope equilibrium and that variations in delta O-18 do not result from fractional crystallization. Instead, these differences are consistent with mineralogically heterogeneous mantle sources for mare basalts, and with lunar magma ocean differentiation models that result in a thick feldspathic crust, an olivine-pyroxene-rich mantle, and late-stage ilmenite-rich zones that were convectively mixed into deeper portions of the lunar mantle. Higher average delta O-18 (WR) values of low-Ti basalts compared to terrestrial mid ocean ridge basalts (Delta=0.18 parts per thousand) suggest a possible oxygen isotopic difference between the terrestrial and lunar mantles. However, calculations of the delta O-18 of lunar mantle olivine in this study are only 0.05 parts per thousand higher than terrestrial mantle olivine. These observations may have important implications for understanding the formation of the Earth-Moon system. (c) 2006 Elsevier B.V. All rights reserved.

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Sarbadhikari, AB, Day JMD, Liu Y, Rumble D, Taylor LA.  2009.  Petrogenesis of olivine-phyric shergottite Larkman Nunatak 06319: Implications for enriched components in martian basalts. Geochimica Et Cosmochimica Acta. 73:2190-2214.   10.1016/j.gca.2009.01.012   AbstractWebsite

We report on the petrography and geochemistry of the newly discovered olivine-phyric shergottite Larkman Nunatak (LAR) 06319. The meteorite is porphyritic, consisting of megacrysts of olivine (<= 2.5 mm in length, F(O77-52)) and prismatic zoned pyroxene crystals with Wo(3)En(71) in the cores to Wo(8-30)En(23-45) at the rims. The groundmass is composed of finer grained olivine (<0.25 mm, Fo(62-46)), Fe-rich augite and pigeonite, maskelynite and minor quantities of chromite, ulvospinel, magnetite, ilmenite, phosphates, sulfides and glass. Oxygen fugacity estimates, derived from the olivine-pyroxene-spinel geo-barometer, indicate that LAR 06319 formed under more oxidizing conditions (QFM -1.7) than for depleted shergottites. The whole-rock composition of LAR 06319 is also enriched in incompatible trace elements relative to depleted shergottites, with a trace-element pattern that is nearly identical to that of olivine-phyric shergottite NWA 1068. The oxygen isotope composition of LAR 06319 (Delta(17)O = 0.29 +/- 0.03) confirms its martian origin. Olivine megacrysts in LAR 06319 are phenocrystic, with the most Mg-rich megacryst olivine being close to equilibrium with the bulk rock. A notable feature of LAR 06319 is that its olivine megacryst grains contain abundant melt inclusions hosted within the forsterite cores. These early-trapped melt inclusions have similar trace element abundances and patterns to that of the whole-rock, providing powerful evidence for closed-system magmatic behavior for LAR 06319. Calculation of the parental melt trace element composition indicates a whole-rock composition for LAR 06319 that was controlled by pigeonite and augite during the earliest stages of crystallization and by apatite in the latest stages. Crystal size distribution and spatial distribution pattern analyses of olivine indicate at least two different crystal populations. This is most simply interpreted as crystallization of megacryst olivine in magma conduits, followed by eruption and subsequent crystallization of groundmass olivine. LAR 06319 shows close affinity in mineral and whole-rock chemistry to olivine-phyric shergottite, NWA 1068 and the basaltic shergottite NWA 4468. The remarkable features of these meteorites are that they have relatively similar quantities of mafic minerals compared with olivine-phyric shergottites (e.g., Y-980459, Dho 019), but flat and elevated rare earth element patterns more consistent with the LREE-enriched basaltic shergottites (e.g., Shergotty, Los Angeles). This relationship can be interpreted as arising from partial melting of an enriched mantle source and subsequent crystal-liquid fractionation to form the enriched olivine-phyric and basaltic shergottites, or by assimilation of incompatible-element enriched martian crust. The similarity in the composition of early-trapped melt inclusions and the whole-rock for LAR 06319 indicates that any crustal assimilation must have occurred prior to crystallization of megacryst olivine, restricting such processes to the deeper portions of the crust. Thus, we favor LAR06319 forming from partial melting of an "enriched" and oxidized mantle reservoir, with fractional crystallization of the parent melt upon leaving the mantle. (c) 2009 Elsevier Ltd. All rights reserved.

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Sato, KN, Andersson AJ, Day JMD, Taylor JRA, Frank MB, Jung JY, McKittrick J, Levin LA.  2018.  Response of sea urchin fitness traits to environmental gradients across the Southern California oxygen minimum zone. Frontiers in Marine Science. 5   10.3389/fmars.2018.00258   AbstractWebsite

Marine calcifiers are considered to be among the most vulnerable taxa to climate-forced environmental changes occurring on continental margins with effects hypothesized to occur on microstructural, biomechanical, and geochemical properties of carbonate structures. Natural gradients in temperature, salinity, oxygen, and pH on an upwelling margin combined with the broad depth distribution (100-1,100 m) of the pink fragile sea urchin, Strongylocentrotus (formerly Allocentrotus) fragilis, along the southern California shelf and slope provide an ideal system to evaluate potential effects of multiple climate variables on carbonate structures in situ. We measured, for the first time, trait variability across four distinct depth zones using natural gradients as analogues for species-specific implications of oxygen minimum zone (OMZ) expansion, deoxygenation and ocean acidification. Although S. fragilis may likely be tolerant of future oxygen and pH decreases predicted during the twenty-first century, we determine from adults collected across multiple depth zones that urchin size and potential reproductive fitness (gonad index) are drastically reduced in the OMZ core (450-900 m) compared to adjacent zones. Increases in porosity and mean pore size coupled with decreases in mechanical nanohardness and stiffness of the calcitic endoskeleton in individuals collected from lower pH(Total) (7.57-7.59) and lower dissolved oxygen (13-42 mu mol kg(-1)) environments suggest that S. fragilis may be potentially vulnerable to crushing predators if these conditions become more widespread in the future. In addition, elemental composition indicates that S. fragilis has a skeleton composed of the low Mg-calcite mineral phase of calcium carbonate (mean Mg/Ca = 0.02 mol mol(-1)), with Mg/Ca values measured in the lower end of values reported for sea urchins known to date. Together these findings suggest that ongoing declines in oxygen and pH will likely affect the ecology and fitness of a dominant echinoid on the California margin.

Riches, AJV, Day JMD, Walker RJ, Simonetti A, Liu Y, Neal CR, Taylor LA.  2012.  Rhenium–osmium isotope and highly-siderophile-element abundance systematics of angrite meteorites. Earth and Planetary Science Letters. 353:208-218.   10.1016/j.epsl.2012.08.006   Abstract

Coupled 187Os/188Os compositions and highly-siderophile-element (HSE: Os, Ir, Ru, Pt, Pd, and Re) abundance data are reported for eight angrite achondrite meteorites that include quenched- and slowly-cooled textural types. These data are combined with new major- and trace-element concentrations determined for bulk-rock powder fractions and constituent mineral phases, to assess angrite petrogenesis. Angrite meteorites span a wide-range of HSE abundances from <0.005 ppb Os (e.g., Northwest Africa [NWA] 1296; Angra dos Reis) to >100 ppb Os (NWA 4931). Chondritic to supra-chondritic 187Os/188Os (0.1201–0.2127) measured for Angra dos Reis and quenched-angrites correspond to inter- and intra-sample heterogeneities in Re/Os and HSE abundances. Quenched-angrites have chondritic-relative rare-earth-element (REE) abundances at 10–15×CI-chondrite, and their Os-isotope and HSE abundance variations represent mixtures of pristine uncontaminated crustal materials that experienced addition (<0.8%) of exogenous chondritic materials during or after crystallization. Slowly-cooled angrites (NWA 4590 and NWA 4801) have fractionated REE-patterns, chondritic to sub-chondritic 187Os/188Os (0.1056–0.1195), as well as low-Re/Os (0.03–0.13), Pd/Os (0.071–0.946), and relatively low-Pt/Os (0.792–2.640). Sub-chondritic 187Os/188Os compositions in NWA 4590 and NWA 4801 are unusual amongst planetary basalts, and their HSE and REE characteristics may be linked to melting of mantle sources that witnessed prior basaltic melt depletion. Angrite HSE-Yb systematics suggest that the HSE behaved moderately-incompatibly during angrite magma crystallization, implying the presence of metal in the crystallizing assemblage.

The new HSE abundance and 187Os/188Os compositions indicate that the silicate mantle of the angrite parent body(ies) (APB) had HSE abundances in chondritic-relative proportions but at variable abundances at the time of angrite crystallization. The HSE systematics of angrites are consistent with protracted post-core formation accretion of materials with chondritic-relative abundances of HSE to the APB, and these accreted materials were rapidly, yet inefficiently, mixed into angrite magma source regions early in Solar System history.

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Pringle, EA, Moynier F, Savage PS, Jackson MG, Moriera M, Day JMD.  2016.  Silicon isotopes reveal recycled altered oceanic crust in the mantle sources of Ocean Island Basalts. Geochimica et Cosmochimica Acta. 189:282-295.   10.1016/j.gca.2016.06.008   Abstract

The study of silicon (Si) isotopes in Ocean Island Basalts (OIB) has the potential to discern between different models for the origins of geochemical heterogeneities in the mantle. Relatively large (several per mil per atomic mass unit) Si isotope fractionation occurs in low-temperature environments during biochemical and geochemical precipitation of dissolved Si, where the precipitate is preferentially enriched in the lighter isotopes relative to the dissolved Si. In contrast, only a limited range (tenths of a per mil) of Si isotope fractionation has been observed from high-temperature igneous processes. Therefore, Si isotopes may be useful as tracers for the presence of crustal material within OIB mantle source regions that experienced relatively low-temperature surface processes in a manner similar to other stable isotope systems, such as oxygen.

Characterizing the isotopic composition of the mantle is also of central importance to the use of the Si isotope system as a basis for comparisons with other planetary bodies (e.g., Moon, Mars, asteroids). Here we present the first comprehensive suite of high-precision Si isotope data obtained by MC-ICP-MS for a diverse suite of OIB. Samples originate from ocean islands in the Pacific, Atlantic, and Indian Ocean basins and include representative endmembers for the EM-1, EM-2, and HIMU mantle components. On average, d30Si values for OIB (0.32 ± 0.09‰, 2 sd) are in general agreement with previous estimates for the d30Si value of Bulk Silicate Earth (0.29 ± 0.07‰, 2 sd; Savage et al., 2014). Nonetheless, some small systematic variations are present; specifically, most HIMU-type (Mangaia; Cape Verde; La Palma, Canary Islands) and Iceland OIB are enriched in the lighter isotopes of Si (d30Si values lower than MORB), consistent with recycled altered oceanic crust and lithospheric mantle in their mantle sources.

Riches, AJV, Liu Y, Day JMD, Spetsius ZV, Taylor LA.  2010.  Subducted oceanic crust as diamond hosts revealed by garnets of mantle xenoliths from Nyurbinskaya, Siberia. Lithos. 120:368-378.   10.1016/j.lithos.2010.09.006   AbstractWebsite

The similar to 380 Ma Nyurbinskaya kimberlite pipe Yakutia Siberia sampled a highly-diamondiferous and unusual mantle xenolith population dominated by eclogites New in-situ major- and trace-element data for garnets previously analyzed for oxygen isotope compositions show that Group A eclogitic garnets have Mg# >68 and are LREE-depleted Group B and Group C eclogitic garnets cover a range of Mg# and are each divided into two types based on their trace-element characteristics Type B1 and Cl eclogitic garnets are dominant and are LREE-depleted Less common Type B2 and C2 garnets generally have Mg# >60 and convex-upward REE profiles Harzburgitic garnets are a minor component of the Nyurbinskaya xenolith suite and have high Mg# (similar to 84) high Cr contents (similar to 11 wt% Cr(2)O(3)) and sinusoidal REE-patterns Group A Type B1 and Cl eclogitic garnets define a broad negative correlation between Mg# and Yb abundances consistent with a shallow origin as basaltic and gabbroic portions of oceanic crust Harzburgitic Type B2 and C2 eclogitic garnets have trace-element characteristics indicative of interaction with a C-O-H-N-S-rich fluid in lithospheric environments These results provide clear evidence for the presence of subducted crustal materials in the Siberian mantle lithosphere and support models of craton formation by subduction zone stacking (C) 2010 Elsevier BV All rights reserved

Peters, BJ, Shahar A, Carlson RW, Day JMD, Mock TD.  2019.  A sulfide perspective on iron isotope fractionation during ocean island basalt petrogenesis. Geochimica et Cosmochimica Acta. 245:59-78.   https://doi.org/10.1016/j.gca.2018.10.015   Abstract

Iron isotopic compositions are demonstrably powerful tracers of foundational planetary processes, including crust and core formation. In many volcanic environments, however, geochemical vestiges of these processes are obscured by the effects of magmatic differentiation on Fe isotopic compositions. Recent decades have witnessed continued refinement of observational and experimental approaches to Fe isotope fractionation during silicate differentiation. In contrast, the influence of sulfide fractionation on Fe isotopic compositions in terrestrial environments is known only from theoretical approaches and limited experimental data for relatively siliceous magmatic systems. One reason for this may be that sulfide fractionation is difficult to definitively trace using traditional major and minor element variation patterns. We utilize well-characterized lavas and cumulate xenoliths from Piton de la Fournaise and Piton des Neiges, Réunion Island, that have previously been examined for their highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re) contents to investigate the effect of sulfide fractionation on Fe isotopes. The Fe isotopic compositions of the basalts range from δ56Fe values of 0.04 to 0.15‰ (average: 0.10‰) and the compositions of the cumulate xenoliths range from δ56Fe values of -0.07 to 0.08‰ (average: 0‰). In the absence of metal, HSE preferentially partition into sulfide phases, making them important tracers of sulfide segregation during magmatic differentiation. We find that commonly-observed co-variations between Fe isotopic compositions and major element oxide abundances are relatively underdeveloped for Réunion lavas. The correlation between Fe isotopic composition and MgO, for example, has a similar statistical significance to the correlation between Fe isotopic composition and Pd/Ir ratios, suggesting an important role of sulfides during Fe isotopic fractionation. After accounting for sulfide segregation, we determine that the parental magma Fe isotopic composition calculated for Piton de la Fournaise would be overestimated by 0.04‰ (within propagated error, 0.01-0.06‰) when considering silicate differentiation alone. An analogous calculation for Kilauea Iki basalts, for which there is available Fe isotopic and HSE data, yields a somewhat smaller difference of 0.02‰ (0-0.03‰). These differences may partially explain Fe isotopic compositions in other settings that could not previously be reconciled with a dominantly peridotitic and/or chondritic mantle source. This discovery may warrant discussion of the apparent decoupling between Fe and radiogenic isotopes in ocean island basalts, where the latter shows significant global variations and the former may show little or none. Our work highlights the need for additional constraints on the behavior of Fe isotopes during crustal recycling processes and reinforces the notion that consideration must be given to the effect of magmatic differentiation on Fe isotopic compositions.

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Day, JMD, Waters CL, Schaefer BF, Walker RJ, Turner S.  2016.  Use of Hydrofluoric Acid Desilicification in the Determination of Highly Siderophile Element Abundances and Re-Pt-Os Isotope Systematics in Mafic-Ultramafic Rocks. Geostandards and Geoanalytical Research. 40(1):49-65.   DOI: 10.1111/j.1751-908X.2015.00367.x   Abstract

Properly combining highly siderophile element (HSE: Re,Pd, Pt, Ru, Ir, Os) abundance data, obtained by isotope dilution, with corresponding 187Os/188Os and 186Os/188Os measurements of rocks requires efficient digestion of finely-ground powders and complete spike-sample equilibration. Yet, because of the nature of commonly used methods for separating Os from a rock matrix, hydrofluoric acid (HF) is typically not used in such digestions. Consequently, some silicates are not completely dissolved, and HSE residing within these silicates may not be fully accessed. Consistent with this, some recent studies of basaltic reference materials (RMs) have concluded that an HF-desilicification procedure is required to fully access the HSE (Ishikawa et al. (2014)Chemical Geology, 384, 27–46; Li et al. (2015) Geostandards and Geoanalytical Research, 39, 17–30). Highly siderophile element abundance and Os isotope studies of intraplate basalts typically target samples with a range of MgO contents (< 8to> 18% m/m, or as mass fractions, < 8 to> 18 g per 100 g), in contrast to the lower MgO mass fractions (< 10 g per 100 g) of basalt and diabase RMs (i.e., BIR-1, BHVO-2, TDB-1). To investigate the effect of HF-desilicification on intraplate basalts, experiments were performed on finely ground Azores basalts (8.1–17 g per 100 g MgO) using a‘standard acid digestion’ (2:1 mixture of concentrated HNO3 and HCl), and a standard acid digestion, followed by HF-desilicification. No systematic trends in HSE abundances were observed between data obtained by standard acid digestion and HF-desilicification. Desilicifi-cation procedures using HF do not improve liberation ofthe HSE from Azores basalts, or some RMs (e.g., WPR-1).We conclude that HF-desilicification procedures are useful for obtaining total HSE contents of some young lavas, but this type of procedure is not recommended for studies where Re-Pt-Os chronological information is desired. The collateral effect of a standard acid digestion to liberate Os, followed by HF-desilicification to obtain Re and Pt abundances in samples, is that the measured Re/Os and Pt/Os may not correspond with measured 187Os/188Os or 186Os/188Os.

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Cabral, RA, Jackson MG, Koga KT, Rose-Koga EF, Hauri EH, Whitehouse MJ, Price AA, Day JMD, Shimizu N, Kelley KA.  2014.  Volatile cycling of H2O, CO2, F, and Cl in the HIMU mantle: A new window provided by melt inclusions from oceanic hot spot lavas at Mangaia, Cook Islands. Geochemistry, Geophysics, Geosystems. 15(11):4445-4467.   10.1002/2014GC005473   Abstract

Mangaia hosts the most radiogenic Pb-isotopic compositions observed in ocean island basalts and represents the HIMU (high m5238U/204Pb) mantle end-member, thought to result from recycled oceanic crust. Complete geochemical characterization of the HIMU mantle end-member has been inhibited due to a lack of deep submarine glass samples from HIMU localities. We homogenized olivine-hosted melt inclusions separated from Mangaia lavas and the resulting glassy inclusions made possible the first volatile abundances to be obtained from the HIMU mantle end-member. We also report major and trace element abundances and Pb-isotopic ratios on the inclusions, which have HIMU isotopic fingerprints. We evaluate the samples for processes that could modify the volatile and trace element abundances postmantle melting, including diffusive Fe and H2O loss, degassing, and assimilation. H2O/Ce ratios vary from 119 to 245 in the most pristine Mangaia inclusions; excluding an inclusion that shows evidence for assimilation, the primary magmatic H2O/Ce ratios vary up to 200, and are consistent with significant dehydration of oceanic crust during subduction and long-term storage in the mantle. CO2 concentrations range up to 2346 ppm CO2 in the inclusions. Relatively high CO2 in the inclusions, combined with previous observations of carbonate blebs in other Mangaia melt inclusions, highlight the importance of CO2 for the generation of the HIMU mantle. F/Nd ratios in the inclusions (3069; 2r standard deviation) are higher than the canonical ratio observed in oceanic lavas, and Cl/K ratios (0.07960.028) fall in the range of pristine mantle (0.02–0.08).

Day, JMD, Sossi PA, Shearer CK, Moynier F.  2019.  Volatile distributions in and on the Moon revealed by Cu and Fe isotopes in the ‘Rusty Rock’ 66095. Geochimica et Cosmochimica Acta. 266:131-143.   10.1016/j.gca.2019.02.036   Abstract

The Apollo 16 ‘Rusty Rock’ impact melt breccia 66095 is a volatile-rich sample, with the volatiles inherited through vapor condensation from an internal lunar source formed during thermo-magmatic evolution of the Moon. We report Cu and Fe isotope data for 66095 and find that bulk-rocks, residues and acid leaches span a relatively limited range of compositions (3.0 ±1.3 wt.% FeO [range = 2.0-4.8 wt.%], 5.4 ±3.1 ppm Cu [range = 3-12 ppm], average δ56Fe of 0.15 ± 0.05‰ [weighted mean = 0.16‰] and δ65Cu of 0.72 ± 0.14‰ [weighted mean = 0.78‰]). In contrast to the extreme enrichment of light isotopes of Zn and heavy isotopes of Cl in 66095, δ65Cu and δ56Fe in the sample lie within the previously reported range for lunar mare basalts (0.92 ± 0.16‰ and 0.12 ± 0.02‰, respectively). The lack of extreme isotopic fractionation for Cu and Fe isotopes reflects compositions inherent to 66095, with condensation of a cooling gas from impact-generated fumarolic activity at temperatures too low to lead to the condensation of Cu and Fe, but higher than required to condense Zn. Together with thermodynamic models, these constraints suggest that the gas condensed within 66095 between 700 and 900 °C (assuming a pressure of 10-6 and an fO2 of IW-2). That the Cu and Fe isotopic compositions of sample 66095 are within the range of mare basalts removes the need for an exotic, volatile-enriched source. The enrichment in Tl, Br, Cd, Sn, Zn, Pb, Rb, Cs, Ga, B, Cl, Li relative to Bi, Se, Te, Ge, Cu, Ag, Sb, Mn, P, Cr and Fe in the ‘Rusty Rock’ is consistent with volcanic outgassing models and indicates that 66095 likely formed distal from the original source of the gas. The volatile-rich character of 66095 is consistent with impact-generated fumarolic activity in the region of the Cayley Plains, demonstrating that volatile-rich rocks can occur on the lunar surface from outgassing of a volatile-poor lunar interior. The ‘Rusty Rock’ indicates that the lunar interior is significantly depleted in volatile elements and compounds and that volatile-rich lunar surface rocks likely formed through vapor condensation. Remote sensing studies have detected volatiles on the lunar surface, attributing them dominantly to solar wind. Based on the ‘Rusty Rock’, some of these surface volatiles may also originate from the Moon’s interior.