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Control of structure at the atomic level can precisely and effectively tune catalytic properties of materials, enabling enhancement in both activity and durability. We synthesized a highly active and durable class of electrocatalysts by exploiting the structural evolution of platinum-nickel (Pt-Ni) bimetallic nanocrystals. The starting material, crystalline PtNi3 polyhedra, transforms in solution by interior erosion into Pt3Ni nanoframes with surfaces that offer three-dimensional molecular accessibility. The edges of the Pt-rich PtNi3 polyhedra are maintained in the final Pt3Ni nanoframes. Both the interior and exterior catalytic surfaces of this open-framework structure are composed of the nanosegregated Pt-skin structure, which exhibits enhanced oxygen reduction reaction (ORR) activity. The Pt3Ni nanoframe catalysts achieved a factor of 36 enhancement in mass activity and a factor of 22 enhancement in specific activity, respectively, for this reaction (relative to state-of-the-art platinum-carbon catalysts) during prolonged exposure to reaction conditions.

The abundance and distribution of water within Mars through time plays a fundamental role in constraining its geological evolution and habitability. The isotopic composition of Martian hydrogen provides insights into the interplay between different water reservoirs on Mars. However, D/H (deuterium/hydrogen) ratios of Martian rocks and of the Martian atmosphere span a wide range of values. This has complicated identification of distinct water reservoirs in and on Mars within the confines of existing models that assume an isotopically homogenous mantle. Here we present D/H data collected by secondary ion mass spectrometry for two Martian meteorites. These data indicate that the Martian crust has been characterized by a constant D/H ratio over the last 3.9 billion years. The crust represents a reservoir with a D/H ratio that is intermediate between at least two isotopically distinct primordial water reservoirs within the Martian mantle, sampled by partial melts from geochemically depleted and enriched mantle sources. From mixing calculations, we find that a subset of depleted Martian basalts are consistent with isotopically light hydrogen (low D/H) in their mantle source, whereas enriched shergottites sampled a mantle source containing heavy hydrogen (high D/H). We propose that the Martian mantle is chemically heterogeneous with multiple water reservoirs, indicating poor mixing within the mantle after accretion, differentiation, and its subsequent thermochemical evolution.Mars’s mantle is chemically heterogeneous and contains multiple primordial water reservoirs, according to an analysis of the hydrogen isotopic composition of minerals in Martian meteorites.

Absolute ages for planetary surfaces are often inferred by crater densities and only indirectly constrained by the ages of meteorites. We show that the <5 million-year-old and 55-km-wide Mojave Crater on Mars is the ejection source for the meteorites classified as shergottites. Shergottites and this crater are linked by their coinciding meteorite ejection ages and the crater formation age and by mineralogical constraints. Because Mojave formed on 4.3 billion–year-old terrain, the original crystallization ages of shergottites are old, as inferred by Pb-Pb isotope ratios, and the much-quoted shergottite ages of <600 million years are due to resetting. Thus, the cratering-based age determination method for Mars is now calibrated in situ, and it shifts the absolute age of the oldest terrains on Mars backward by 200 million years.

The only martian rock samples on Earth are meteorites ejected from the surface of Mars by asteroid impacts. The locations and geological contexts of the launch sites are currently unknown. Determining the impact locations is essential to unravel the relations between the evolution of the martian interior and its surface. Here we adapt a Crater Detection Algorithm that compile a database of 90 million impact craters, allowing to determine the potential launch position of these meteorites through the observation of secondary crater fields. We show that Tooting and 09-000015 craters, both located in the Tharsis volcanic province, are the most likely source of the depleted shergottites ejected 1.1 million year ago. This implies that a major thermal anomaly deeply rooted in the mantle under Tharsis was active over most of the geological history of the planet, and has sampled a depleted mantle, that has retained until recently geochemical signatures of Mars’ early history. The ejection sites of the martian meteorites are still unknown. Here, the authors build a database of 90 million craters and show that Tharsis region is the most likely source of depleted shergottites ejected 1.1 Ma ago, thus confirming that some portions of the mantle were recently anomalously hot.

Direct analysis of the composition of Mars is possible through delivery of meteorites to Earth. Martian meteorites include ∼165 to 2400 Ma shergottites, originating from depleted to enriched mantle sources, and ∼1340 Ma nakhlites and chassignites, formed by low degree partial melting of a depleted mantle source. To date, no unified model has been proposed to explain the petrogenesis of these distinct rock types, despite their importance for understanding the formation and evolution of Mars. Here we report a coherent geochemical dataset for shergottites, nakhlites and chassignites revealing fundamental differences in sources. Shergottites have lower Nb/Y at a given Zr/Y than nakhlites or chassignites, a relationship nearly identical to terrestrial Hawaiian main shield and rejuvenated volcanism. Nakhlite and chassignite compositions are consistent with melting of hydrated and metasomatized depleted mantle lithosphere, whereas shergottite melts originate from deep mantle sources. Generation of martian magmas can be explained by temporally distinct melting episodes within and below dynamically supported and variably metasomatized lithosphere, by long-lived, static mantle plumes. A unified model for the formation of martian rock types is required to understand Mars’s formation and evolution. Here the authors show that nakhlite and chassignite meteorites originate from melting of metasomatized depleted mantle lithosphere, whereas shergottite melts originate from deep plume sources.

We report data on the martian meteorite Northwest Africa (NWA) 7034, which shares some petrologic and geochemical characteristics with known martian meteorites of the SNC (i.e., shergottite, nakhlite, and chassignite) group, but also has some unique characteristics that would exclude it from that group. NWA 7034 is a geochemically enriched crustal rock compositionally similar to basalts and average martian crust measured by recent Rover and Orbiter missions. It formed 2.089 ± 0.081 billion years ago, during the early Amazonian epoch in Mars' geologic history. NWA 7034 has an order of magnitude more indigenous water than most SNC meteorites, with up to 6000 parts per million extraterrestrial H2O released during stepped heating. It also has bulk oxygen isotope values of Δ 17 O = 0.58 ± 0.05 per mil and a heat-released water oxygen isotope average value of Δ 17 O = 0.330 ± 0.011 per mil, suggesting the existence of multiple oxygen reservoirs on Mars.

Martian meteorite ALH84001 (ALH) is the oldest known igneous rock from Mars and has been used to constrain its early history. Lutetium-hafnium (Lu-Hf) isotope data for ALH indicate an igneous age of 4.091 ± 0.030 billion years, nearly coeval with an interval of heavy bombardment and cessation of the martian core dynamo and magnetic field. The calculated Lu/Hf and Sm/Nd (samarium/neodymium) ratios of the ALH parental magma source indicate that it must have undergone extensive igneous processing associated with the crystallization of a deep magma ocean. This same mantle source region also produced the shergottite magmas (dated 150 to 570 million years ago), possibly indicating uniform igneous processes in Mars for nearly 4 billion years.

Most extraterrestrial samples feature the two accessory Ca-phosphates (apatite-group minerals and merrillite), which are important carrier phases of the rare earth elements (REE). The trace-element concentrations (REE, Sc, Ti, V, Cr, Mn, Co, As, Rb, Sr, Y, Zr, Nb, Ba, Hf, Ta, Pb, Th, and U) of selected grains were analyzed by LA-ICP-MS and/or SIMS (REE only). This systematic investigation includes 99 apatite and 149 merrillite analyses from meteorites deriving from various asteroidal bodies including 1 carbonaceous chondrite, 8 ordinary chondrites, 3 acapulcoites, 1 winonaite, 2 eucrites, 5 shergottites, 1 ureilitic trachyandesite, 2 mesosiderites, and 1 silicate-bearing IAB iron meteorite.Although Ca-phosphates predominantly form in metamorphic and/or metasomatic reactions, some are of igneous origin. As late-stage phases that often incorporate the vast majority of their host's bulk REE budget, the investigated Ca-phosphates have REE enrichments of up to two orders of magnitude compared to the host rock's bulk concentrations. Within a single sample, each phosphate species displays a uniform REE-pattern, and variations are mainly restricted to their enrichment, therefore indicating similar formation conditions. Exceptions are brecciated samples, i.e., the Adzhi-Bogdo (LL3-6) ordinary chondrite. Despite this uniformity within single samples, distinct meteorite groups do not necessarily have unique REE-patterns. Four basic shapes dominate the REE patterns of meteoritic Ca-phosphates: (1) flat patterns, smoothly decreasing from La-Lu with prominent negative Eu anomalies (acapulcoites, eucrites, apatite from the winonaite and the ureilitic trachyandesite, merrillite from ordinary chondrites); (2) unfractionated patterns, with only minor or no anomalies (mesosiderites, enriched shergottites, IAB-iron meteorite); (3) LREE-enriched patterns, with either positive or slightly negative Eu anomalies (chondritic apatite); and (4) strongly LREE-depleted patterns, with negative Eu anomalies (depleted shergottites). The patterns do not correlate with the grade of metamorphism (petrologic type), specific adjacent mineral assemblages or with Ca-phosphate grain size. Neither the proportions of different REE, nor particular REE patterns themselves are universally correlated to a specific formation mechanism yet Eu (i.e., magnitude of the Eu anomaly) is a sensitive indicator to evaluate the timing of plagioclase and phosphate crystallization. Based on our data, U and Th abundances in apatite increase (almost linearly) with the grade of metamorphism, as well as with the differentiation of their host rock.

Tissint (Morocco) is the fifth martian meteorite collected after it was witnessed falling to Earth. Our integrated mineralogical, petrological, and geochemical study shows that it is a depleted picritic shergottite similar to EETA79001A. Highly magnesian olivine and abundant glass containing martian atmosphere are present in Tissint. Refractory trace element, sulfur, and fluorine data for the matrix and glass veins in the meteorite indicate the presence of a martian surface component. Thus, the influence of in situ martian weathering can be unambiguously distinguished from terrestrial contamination in this meteorite. Martian weathering features in Tissint are compatible with the results of spacecraft observations of Mars. Tissint has a cosmic-ray exposure age of 0.7 ± 0.3 million years, consistent with those of many other shergottites, notably EETA79001, suggesting that they were ejected from Mars during the same event.

The composition of Mars' crust records the planet's integrated geologic history and provides clues to its differentiation. Spacecraft and meteorite data now provide a global view of the chemistry of the igneous crust that can be used to assess this history. Surface rocks on Mars are dominantly tholeiitic basalts formed by extensive partial melting and are not highly weathered. Siliceous or calc-alkaline rocks produced by melting and/or fractional crystallization of hydrated, recycled mantle sources, and silica-poor rocks produced by limited melting of alkali-rich mantle sources, are uncommon or absent. Spacecraft data suggest that martian meteorites are not representative of older, more voluminous crust and prompt questions about their use in defining diagnostic geochemical characteristics and in constraining mantle compositional models for Mars.