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We present compositional data for 358 lithic fragments (2–4-mm size range) and 15 soils (

Geochemical data for a comprehensive suite of over 700 samples of massif anorthosite and associated rocks from the Adirondack Mountains, New York, exhibit a ubiquitous mixed tholeiitic and calc-alkaline signature indicating a complex petrogenesis. The origin and relationship of massif anorthosite to associated rocks has been a major petrological problem despite decades of study. The Adirondack Mountains is one of the best areas to study these rocks because it contains one of the world9s most abundant occurrences of massif anorthosite and associated rocks forming bedrock over thousands of square kilometers. The suite of rocks analyzed includes both anorthosite suite rocks, consisting of anorthosites, leucogabbros, gabbros, oxide apatite gabbronorites (OAGNs), and oxide gabbronorites (OGNs) (defined in text), and mangerite suite rocks consisting of jotunites, monzodiorites, mangerites, and charnockites. Representative major-element compositions were determined largely by X-ray fluorescence (XRF) analysis for 352 massif anorthosites and associated rocks and a variety of trace elements were determined by XRF, instrumental neutron activation analysis (INAA), and inductively coupled plasma mass spectroscopy (ICP-MS) for 296 massif anorthosites and associated rocks. All rock types show a mixture of tholeiitic and calc-alkaline compositional characteristics with major elements exhibiting a strong iron enrichment tholeiitic trend and trace elements showing a depletion of Nb and Ta characteristic of calc-alkaline rocks. Prior to this study the geochemistry of these rocks in the Adirondacks has been only poorly characterized from scattered local studies. The anorthosite suite of rocks exhibits two distinct compositional trends. Massif anorthosites, leucogabbros, gabbros, OAGNs, OGNs, along with jotunites, separate into two distinct compositional trends on P 2 O 5 -MgO and TiO 2 -MgO diagrams, whereas monzodiorites, mangerites, and charnockites have only one compositional trend. Two trends in anorthosites are caused by two varieties of anorthosite: one type with a characteristic mineralogy dominated by plagioclase plus pyroxene and another type dominated by plagioclase plus oxide minerals and apatite. Mafic enclaves at some localities near the margins of anorthosite masses contain gabbro, OGN, and OAGN in close spatial association, suggesting they represent crystallization from the same or similar parental magmas at different stages of evolution.

The Raman spectra of a large number of natural feldspar-group minerals were obtained to determine what compositional and structural information can be inferred solely from their Raman spectra. The feldspar minerals selected cover a wide range of Na, K, and Ca proportions, crystal structures and degrees of cation disorder. The samples include both homogeneous feldspar phases and a few with visible intergrowths. From the positions of the strongest Raman peak in the spectrum, four structural types of feldspars can be readily identified: orthoclase (and microcline), albite, high-temperature plagioclase, and anorthite. Using a Raman spectral database of feldspar minerals established during this study and an autonomous spectral search-and-match routine, up to seven different types of feldspar can be unambiguously determined. Three additional feldspar types can be further resolved by careful visual inspection of the Raman spectra. We conclude that ten types of feldspars can be classified according to their structure, crystallinity, and chemical composition solely on the basis of their Raman spectra. Unlike olivine, pyroxene and some Fe-oxides, the Raman peak positions of the feldspars cannot be used to extract quantitative information regarding the cation composition of the feldspar phases. We also define the necessary specifications of a field Raman spectrometer capable of characterizing feldspar minerals during planetary surface exploration.

The regolith of the Apollo 16 lunar landing site is composed mainly of feldspathic lithologies but mafic lithologies are also present. A large proportion of the mafic material occurs as glass. We determined the major element composition of 280 mafic glasses (>10 wt% FeO) from six different Apollo 16 soil samples. A small proportion (∼5%) of the glasses are of volcanic origin with picritic compositions. Most, however, are of impact origin. Approximately half of the mafic impact glasses are of basaltic composition and half are of noritic composition with high concentrations of incompatible elements. A small fraction have compositions consistent with impact mixtures of mare material and material of the feldspathic highlands. On the basis of major-element chemistry, we identified six mafic glass groups: VLT picritic glass, low-Ti basaltic glass, high-Ti basaltic glass, high-Al basaltic glass, KREEPy glass, and basaltic-andesite glass. These glass groups encompass ∼60% of the total mafic glasses studied. Trace-element analyses by secondary ion mass spectroscopy for representative examples of each glass group (31 total analyses) support the major-element classifications and groupings. The lack of basaltic glass in Apollo 16 ancient regolith breccias, which provide snapshots of the Apollo 16 soil just after the infall of Imbrium ejecta, leads us to infer that most (if not all) of the basaltic glass was emplaced as ejecta from small- or moderate-sized impacts into the maria surrounding the Apollo 16 site after the Imbrium impact. The high-Ti basaltic glasses likely represent a new type of basalt from Mare Tranquillitatis, whereas the low-Ti and high-Al basaltic glasses possibly represent the composition of the basalts in Mare Nectaris. Both the low-Ti and high-Al basaltic glasses are enriched in light-REEs, which hints at the presence of a KREEP-bearing source region beneath Mare Nectaris. The basaltic andesite glasses have compositions that are siliceous, ferroan, alkali-rich, and moderately titaniferous; they are unlike any previously recognized lunar lithology or glass group. Their likely provenance is within the Procellarum KREEP Terrane, but they are not found within the Apollo 16 ancient regolith breccias and therefore were likely deposited at the Apollo 16 site post-Imbrium. The basaltic-andesite glasses are the most ferroan variety of KREEP yet discovered.

The dominant feature of the olivine Raman spectrum is a doublet that occurs in the spectral region of 815–825 cm � 1 (DB1) and 838– 857 cm � 1 (DB2). These features arise from coupled symmetric and asymmetric stretching vibrational modes of the constituent SiO4 tetrahedra. The frequencies of both peaks show monotonic shifts following cation substitution between forsterite and fayalite. We present a calibration for extracting olivine Fo contents (Fo = Mg/(Mg + Fe) molar ratio; Fo0–100) from the peak positions of this doublet, permitting estimates of chemical composition from Raman spectra (acquired in the laboratory or field) as well as providing information on crystal structure (distinction of polymorphs). Eight samples spanning the compositional range from forsterite to fayalite were used to develop the calibration equations for the DB1 and DB2 peaks individually and together. The data indicate that the DB1 peak is more reliable for calculating the compositions of Fe-rich olivine but that the DB2 peak is better for magnesian compositions. The two-peak calibration overcomes the limitations of the single-peak calibrations and is capable of calculating olivine compositions to within ±10 Fo units.

We present the petrography and geochemistry of five 2-4 mm basalt fragments from the Apollo 16 regolith. These fragments are 1) a high-Ti vitrophyric basalt compositionally similar to Apollo 17 high-Ti mare basalts, 2) a very high-Ti vitrophyric basalt compositionally similar to Apollos 12 and 14 red-black pyroclastic glass, 3) a coarsely crystalline high-Al basalt compositionally similar to group 5 Apollo 14 high-Al mare basalts, 4) a very low-Ti (VLT) crystalline basalt compositionally similar to Luna 24 VLT basalts, and 5) a VLT basaltic glass fragment compositionally similar to Apollo 17 VLT basalts. High-Ti basalt has been reported previously at the Apollo 16 site; the other basalt types have not been reported previously. As there are no known cryptomaria or pyroclastic deposits in the highlands near the Apollo 16 site (ruling out a local origin), and scant evidence for basaltic material in the Apollo 16 ancient regolith breccias or Apollo 16 soils collected near North Ray Crater (ruling out a basin ejecta origin), we infer that the basaltic material in the Apollo 16 regolith originated in maria near the Apollo 16 site and was transported laterally to the site by small- to medium-sized post-basin impacts. On the basis of TiO2 concentrations derived from the Clementine UVVIS data, Mare Tranquillitatis (300 km north) is the most likely source for the high-Ti basaltic material at the Apollo 16 site (craters Ross, Arago, Dionysius, Maskelyne, Moltke, Sosigenes, Schmidt), Mare Nectaris/Sinus Asperitatis (220 km east) is the most likely source for the low-Ti and VLT basaltic material (craters Theophilus, Madler, Torricelli), and a large regional pyroclastic deposit near Mare Vaporum (600 km northwest) is the most likely source region for pyroclastic material (although no source craters are apparent in the region).

We report on the bulk composition and petrography of four new basaltic meteorites found in AntarcticaLAP (LaPaz Icefield) 02205, LAP 02224, LAP 02226, and LAP 02436--and compare the LAP meteorites to other lunar mare basalts. The LAP meteorites are coarse-grained (up to 1.5 mm), subophitic low-Ti basalts composed predominantly of pyroxene and plagioclase, with minor amounts of olivine, ilmenite, and a groundmass dominated by fayalite and cristobalite. All of our observations and results support the hypothesis that the LAP stones are mutually paired with each other. In detail, the geochemistry of LAP is unlike those of any previously studied lunar basalt except lunar meteorite NWA (Northwest Africa) 032. The similarities between LAP and NWA 032 are so strong that the two meteorites are almost certainly source crater paired and could be two different samples of a single basalt flow. Petrogenetic modeling suggests that the parent melt of LAP (and NWA 032) is generally similar to Apollo 15 low-Ti, yellow picritic glass beads, and that the source region for LAP comes from a similar region of the lunar mantle as previously analyzed lunar basalts.

The cover shows part of the Larry's Lookout panorama, seen from the Mars Exploration Rover (MER) Spirit during its drive up Husband Hill: the summit is about 200 metres from the rover. Six papers this week report in detail on the MER mission. An Analysis compares predictions used to select a landing site with the conditions actually encountered. This ‘ground truth’ will be invaluable for interpreting future remote-sensing data. Surface chemistry suggests that the upper layer of soil may contain 1% meteoritic material. MER provides a unique glimpse of solar transits of the moons Phobos and Deimos. Rover Opportunity examined wind-related processes, and spectroscopy indicates a dry origin for atmospheric dust. Features from within the Gusev crater give more information on the role of liquid water in Mars's past. An accompanying News and Views puts the MER data in context. Gusev crater was selected as the landing site for the Spirit rover because of the possibility that it once held a lake. Thus one of the rover's tasks was to search for evidence of lake sediments1. However, the plains at the landing site were found to be covered by a regolith composed of olivine-rich basaltic rock and windblown ‘global’ dust2. The analyses of three rock interiors exposed by the rock abrasion tool showed that they are similar to one another, consistent with having originated from a common lava flow3,4,5,6,7,8. Here we report the investigation of soils, rock coatings and rock interiors by the Spirit rover from sol (martian day) 1 to sol 156, from its landing site to the base of the Columbia hills. The physical and chemical characteristics of the materials analysed provide evidence for limited but unequivocal interaction between water and the volcanic rocks of the Gusev plains. This evidence includes the softness of rock interiors that contain anomalously high concentrations of sulphur, chlorine and bromine relative to terrestrial basalts and martian meteorites9; sulphur, chlorine and ferric iron enrichments in multilayer coatings on the light-toned rock Mazatzal; high bromine concentration in filled vugs and veins within the plains basalts; positive correlations between magnesium, sulphur and other salt components in trench soils; and decoupling of sulphur, chlorine and bromine concentrations in trench soils compared to Gusev surface soils, indicating chemical mobility and separation.

The Mars Exploration Rover Opportunity has investigated the landing site in Eagle crater and the nearby plains within Meridiani Planum. The soils consist of fine-grained basaltic sand and a surface lag of hematite-rich spherules, spherule fragments, and other granules. Wind ripples are common. Underlying the thin soil layer, and exposed within small impact craters and troughs, are flat-lying sedimentary rocks. These rocks are finely laminated, are rich in sulfur, and contain abundant sulfate salts. Small-scale cross-lamination in some locations provides evidence for deposition in flowing liquid water. We interpret the rocks to be a mixture of chemical and siliciclastic sediments formed by episodic inundation by shallow surface water, followed by evaporation, exposure, and desiccation. Hematite-rich spherules are embedded in the rock and eroding from them. We interpret these spherules to be concretions formed by postdepositional diagenesis, again involving liquid water.

The Spirit landing site in Gusev Crater on Mars contains dark, fine-grained, vesicular rocks interpreted as lavas. Pancam and Mini–Thermal Emission Spectrometer (Mini-TES) spectra suggest that all of these rocks are similar but have variable coatings and dust mantles. Magnified images of brushed and abraded rock surfaces show alteration rinds and veins. Rock interiors contain ≤25% megacrysts. Chemical analyses of rocks by the Alpha Particle X-ray Spectrometer are consistent with picritic basalts, containing normative olivine, pyroxenes, plagioclase, and accessory FeTi oxides. Mössbauer, Pancam, and Mini-TES spectra confirm the presence of olivine, magnetite, and probably pyroxene. These basalts extend the known range of rock compositions composing the martian crust.

Using the Raman point-count procedure that we anticipate using in planetary surface exploration, we have identified and characterized the major, minor and trace mineral phases in rock chips of a Martian meteorite, EETA 79001. Raman spectra are shown for pyroxene, olivine, maskelynite (shocked, isotropized feldspar), chromite, magnetite, ilmenite, ulvospinel, pyroxferroite, merrillite, apatite, anatase, an Fe sulfide, calcite and hematite. Raman spectra provide information on compositional variations of pyroxene, olivine and FeTiCr oxides and modal proportions of the rock. The maskelynite-free mineral mode obtained on rough rock surfaces is consistent with modes obtained by optical microscopy on a thin section of lithology A of this meteorite. Compositions and variations in compositions of major silicate minerals (pyroxene and olivine) on the basis of Raman peak positions are consistent with those obtained in previous studies by electron probe microanalysis. The variations in composition of the silicate minerals represent different stages of crystallization during the formation of this rock near the Martian surface. Copyright © 2004 John Wiley & Sons, Ltd.

Raman spectral features of chromite, ulvospinel, magnetite, ilmenite, hematite, and some of their solid solutions are presented. Although most Fe-Ti-Cr-oxides produce relatively weak Raman signals compared to oxyanionic minerals, sufficient information can be extracted from their spectra to identify the end-member mineral phases as well as some information about compositional variations in solid solutions. Correlations between Raman spectral features and mineral chemistry are used to interpret the Raman data of Fe-Ti-Cr oxides found during Raman point-count measurements on rock chips of Martian meteorite EETA79001, as an analog to Mars on-surface planetary investigations. In general, ulvospinel, magnetite, and chromite end-members are readily distinguished by their Raman spectral patterns, as are ilmenite and hematite. In the low signal-to-noise (S/N) spectra generally obtained from the Raman point-count procedure, the position and shape of the strongest peak of Fe-Ti-Cr oxides in the region 660–680 cm−1 (A1g mode) is the most useful for discriminating Fe3+-Ti-Cr-Al substitutions in the magnetite-ulvospinel, ulvospinel-chromite, and chromite-spinel series, but minor peaks in the range 300–600 cm−1 also assist in discrimination. These spectral features are useful for investigating the variability among Fe-Ti-Cr-Al oxide solid solutions in natural samples. In EETA79001, a Martian basaltic meteorite, most of the oxide grains (as measured with the electron microprobe) are ulvospinel, chromian ulvospinel, and chromite, but ilmenite, titanian chromite, and titanomagnetite are also observed. The Fe-Ti-Cr-oxides identified by Raman point-count include end-member ilmenite, low-Al chromite-spinel solid solutions, ulvospinel-magnetite solid solutions, and more complex chromite-spinel-ulvospinel-magnetite solid solutions; the latter exhibit a wide range of main peak positions and broadened peak widths that may reflect structural disorder as well One Raman spectrum suggests end-member magnetite, and one spectrum from a different rock chip appears to be that of non-terrestrial hematite, reflecting local oxidizing alteration, which has not been observed previously in this meteorite. These results show that analyses done in an automated mode on the surface of an unprepared Martian rock sample can provide useful constraints on the Fe-Ti-Cr oxide mineralogy present and on compositional variations within those minerals, including an indication of oxygen fugacity.

We present new compositional data for six feldspathic lunar meteorites, two from cold deserts (Yamato 791197 and 82192) and four from hot deserts (Dhofar 025, Northwest Africa 482, and Dar al Gani 262 and 400). The concentrations of FeO (or Al2O3) and Th (or any other incompatible element) together provide first-order compositional information about lunar polymict samples (breccias and regoliths) and regions of the lunar surface observed from orbit. Concentrations of both elements on the lunar surface have been determined from data acquired by orbiting spacecraft, although the derived concentrations have large uncertainties and some systematic errors compared to sample data. Within the uncertainties and errors in the concentrations derived from orbital data, the distribution of FeO and Th concentrations among lunar meteorites, which represent ∼18 source regions on the lunar surface, is consistent with that of 18 random samples from the surface. Approximately 11 of the lunar meteorites are low-FeO and low-Th breccias, consistent with large regions of the lunar surface, particularly the northern farside highlands. Almost all regoliths from Apollo sites, on the other hand, have larger concentrations of both elements because they contain Fe-rich volcanic lithologies from the nearside maria and Th-rich lithologies from the high-Th anomaly in the northwestern nearside. The feldspathic lunar meteorites thus offer our best estimate of the composition of the surface of the feldspathic highlands, and we provide such an estimate based on the eight most well-characterized feldspathic lunar meteorites. The variable but high (on average) Mg/Fe ratio of the feldspathic lunar meteorites compared to ferroan anorthosites confirms a hypothesis that much of the plagioclase at the surface of the feldspathic highlands is associated with high-Mg/Fe feldspathic rocks such as magnesian granulitic breccia, not ferroan anorthosite. Geochemically, the high-Mg/Fe breccias appear to be unrelated to the mafic magnesian-suite rocks of the Apollo collection. Models for the formation of the upper lunar crust as a simple flotation cumulate composed mainly of ferroan anorthosite do not account for the complexity of the crust as inferred from the feldspathic lunar meteorites.

We have developed a quantitative model for predicting characteristics of ejecta deposits that result from basin-sized cratering events. This model is based on impact crater scaling equations (Housen, Schmitt, and Holsapple 1983; Holsapple 1993) and the concept of ballistic sedimentation (Oberbeck 1975), and takes into account the size distribution of the individual fragments ejected from the primary crater. Using the model, we can estimate, for an area centered at the chosen location of interest, the average distribution of thicknesses of basin ejecta deposits within the area and the fraction of primary ejecta contained within the deposits. Model estimates of ejecta deposit thicknesses are calibrated using those of the Orientale Basin (Moore, Hodges, and Scott 1974) and of the Ries Basin (Horz, Ostertag, and Rainey 1983). Observed densities of secondary craters surrounding the Imbrium and Orientale Basins are much lower than the modeled densities. Similarly, crater counts for part of the northern half of the Copernicus secondary cratering field are much lower than the model predicts, and variation in crater densities with distance from Copernicus is less than expected. These results suggest that mutual obliteration erases essentially all secondary craters associated with the debris surge that arises from the impacting primary fragments during ballistic sedimentation; if so, a process other than ballistic sedimentation is needed to produce observable secondary craters. Regardless, our ejecta deposit model can be useful for suggesting provenances of sampled lunar materials, providing information complementary to photogeological and remote sensing interpretations, and as a tool for planning rover traverses (e.g., Haskin et al. 1995, 2002).

Mineralogy, major element compositions of minerals, and elemental and oxygen isotopic compositions of the whole rock attest to a lunar origin of the meteorite Northwest Africa 032 (NWA 032), an unbrecciated basalt found in October 1999. The rock consists predominantly of olivine, pyroxene and chromite phenocrysts, set in a crystalline groundmass of feldspar, pyroxene, ilmenite, troilite and trace metal. Whole-rock shock veins comprise a minor, but ubiquitous portion of the rock. Undulatory to mosaic extinction in olivine and pyroxene phenocrysts and micro-faults in groundmass and phenocrysts also are attributed to shock. Several geochemical signatures taken together indicate unambiguously that NWA 032 originated from the Moon. The most diagnostic criteria include whole-rock oxygen isotopic composition and ratios of Fe:Mn in the whole rock, olivine, and pyroxene. A lunar origin is documented further by the presence of Fe-metal, troilite, and ilmenite; zoning to extremely Fe-rich compositions in pyroxene; the ferrous oxidation state of all Fe in pyroxene; and the rare-earth element pattern with a well-defined negative europium anomaly. This rock is similar in major element chemistry to basalts from Apollo 12 and 15, but is enriched in light rare-earth elements and has an unusually high Th/Sm ratio. Some Apollo 14 basalts yield a closer match to NWA 032 in rare-earth element patterns, but have higher concentrations of Al2O3. Ar-Ar step release results are complex, but yield a whole-rock age of ca. 2.8 Ga, suggesting that NWA 032 was extruded at 2.8 Ga or earlier. This rock may be the youngest sample of mare basalt collected to date. Noble gas concentrations combined with previously collected radionuclide data indicate that the meteorite exposure history is distinct from currently recognized lunar meteorites. In short, the geochemical and petrographic features of NWA 032 are not matched by Apollo or Luna samples, nor by previously identified lunar meteorites, indicating that it originates from a previously unsampled mare deposit. Detailed assessment of petrographic features, olivine zoning, and thermodynamic modelling indicate a relatively simple cooling and crystallization history for NWA 032. Chromite-spinel, olivine, and pyroxene crystallized as phenocrysts while the magma cooled no faster than 2 °C/hr based on the polyhedral morphology of olivine. Comparison of olivine size with crystal growth rates and preserved Fe-Mg diffusion profiles in olivine phenocrysts suggest that olivine was immersed in the melt for no more than 40 days. Plumose textures in groundmass pyroxene, feldspar, and ilmenite, and Fe-rich rims on the phenocrysts formed during rapid crystallization (cooling rates ~ 20 to 60 °C/hr) after eruption.

This study reports the use of Raman spectral features to characterize the structural and compositional characteristics of different types of pyroxene from rocks as might be carried out using a portable field spectrometer or by planetary on-surface exploration. Samples studied include lunar rocks, martian meteorites, and terrestrial rocks. The major structural types of quadrilateral pyroxene can be identified using their Raman spectral pattern and peak positions. Values of Mg/(Mg + Fe + Ca) of pyroxene in the (Mg, Fe, Ca) quadrilateral can be determined within an accuracy of ± 0.1. The precision for Ca/(Mg + Fe + Ca) values derived from Raman data is about the same, except that corrections must be made for very low-Ca and very high-Ca samples. Pyroxenes from basalts can be distinguished from those in plutonic equivalents from the distribution of their Mg ′ [Mg/(Mg + Fe)] and Wo values, and this can be readily done using point-counting Raman measurements on unprepared rock samples. The correlation of Raman peak positions and spectral pattern provides criteria to distinguish pyroxenes with high proportions of non-quadrilateral components from (Mg, Fe, Ca) quadrilateral pyroxenes.

Major features of the Moon's Procellarum KREEP Terrane include subdued relief and extensive resurfacing with mare basalt, consistent with high concentrations of Th and other heat-producing elements at depth. We relate the chemistry of sampled materials to the geomorphology, Th surface concentrations determined by the Lunar Prospector (2° pixels), and FeO and TiO2 concentrations derived from Clementine ultraviolet-visible spectral data. On the basis of geologic maps, each pixel was classified as mare, terra, or mixed. Near the periphery of the terrane, terra pixel compositions are relatively feldspathic; in the interior they mainly represent Imbrium basin rim or ejecta deposits and are mainly incompatible trace element rich norites and presumably represent materials from a thick section (tens of kilometers) of the pre-Imbrium crust of the terrane excavated by the Imbrium event. (Although Imbrium ejecta are the principal source of surface terra materials, the Imbrium event did not create the Th-rich Procellarum KREEP Terrane.) Broad, continuous expanses of mare pixels are observed, with little interruption from protruding terra or terra-penetrating craters. The mare-basalt-dominated regoliths of these areas have a wide range of TiO2 concentrations ( 18%), leading to the conclusion that the high Th concentrations are in the mare basalts and are not present in the regoliths as terra-derived materials. Volcanic glasses and impact glasses of mare basalt composition collected from the Procellarum KREEP Terrane support this conclusion.

On-surface identification of minerals on Mars is likely to depend mainly on observations of rocks and soils as found, without access to fresh surfaces or other sample preparation. Both the original mineralogy of rocks and their alteration mineralogy will be important. To determine the capability of Raman spectroscopy to provide good mineralogical characterization of an altered igneous rock such as might be encountered on Mars, we have analyzed the heavily weathered, exterior surface of a cobble of Keweenawan basalt and compared the results with those from a roughly cut, unpolished interior surface, using a Raman point-counting method. Despite ubiquitous hematite, a strong Raman scatterer, and despite considerable alteration, original igneous plagioclase and pyroxene were identified and their approximate proportions determined from point-counting traverses on the original surface of the rock. Saponite, an alteration product, was easily identified on the freshly cut surface but could only occasionally be identified on the weathered surface, where saponite-rich areas were highly photoluminescent. Amygdular fill gave strong spectra of calcite and thomsonite (a zeolite). Tiny, sparse crustose lichen gave clear spectra of their waxy organic coating. On the basis of the surface Raman spectra alone, the rock could be identified as a mafic rock, probably basaltic, that was hydrothermally altered in an oxidizing environment at a temperature between ∼250 and ∼350°C.

To demonstrate the ability of Raman spectroscopy to determine the mineralogical character of a rock that originated on Mars, we analyzed a small slab of “normal Zagami” by point analyses and multipoint scans using laboratory spectrometers. Spectra of clinopyroxenes were dominant; their compositions were estimated from a calibration of Raman peak positions with Mg/(Mg+Fe) based on lunar pyroxenes of known composition, and these agree with compositions obtained by electron microprobe. A few spectra of orthopyroxene were observed. The broad spectrum of maskelynite was observed, but not that of plagioclase feldspar. Spectra of minor phosphates, magnetite, and pyrrhotite were obtained, as were spectra of an organic contaminant and of hematite, both apparently introduced during sample handling prior to Raman analysis. The modal analysis based on the multipoint scans agrees well with published values. If the spectra had been obtained on the surface of Mars by Raman spectroscopic analysis as a stand-alone method and no other information about the sample was available (and by ignoring the spurious hematite and organic material), we could rule out sedimentary and plutonic rock types and conclude that the sample was a pyroxene-phyric basalt.

— Mafic, Th-rich impact-melt breccias, most of which are identified with the composition known as low-K Fra Mauro (LKFM), are the most common rock type in the nonmare regoliths of the Apollo lunar landing sites. The origin of mafic impact-melt breccias bears on many lunar problems: the nature of the late meteoroid bombardment (cataclysm); the spatial distribution of KREEP, both near the surface and at depth; the ages of the major basins; and the composition of the early crust of the nearside lunar highlands. Thus, it is crucial that the origin of mafic impact-melt breccias be accurately understood. Because of both intra- and intersite differences in compositions of mafic impact-melt breccia samples, apparent differences in crystallization age, and differences in siderophile-element ratios, previous studies have argued that either (1) most mafic impact-melt breccias are the products of several large craters local to the site at which they were found but that some are of basin origin or that (2) they are all from the Imbrium (Apollos 14 and 15), Nectaris (Apollo 16), and Serenitatis (Apollo 17) basins. Here, we reconsider the hypothesis that virtually all of the Th-rich, mafic impact-melt breccias from the Apollo missions are products of the Imbrium impact. Ejecta deposit modeling based on modern crater scaling indicates that the Imbrium event produced ejecta deposits that average hundreds of meters thick or more at all Apollo highland sites, which is thicker than some previous estimates. Substantial amounts of Imbrium ejecta should have been sampled at every Apollo highland site. We suggest that the mafic impact-melt breccias may be the principal form of those ejecta. The Imbrium projectile impacted into Th-rich material that we regard as part of a unique, mafic, lunar geochemical province we call the High-Th Oval Region. Based on the surface distribution of Th, only basins within the High-Th Oval Region excavated Th-rich material; the Th concentrations of the highlands as observed by the Apollo orbiting γ-ray experiments are consistent with the estimates from ejecta modeling. Of the younger basin-forming impacts, only Imbrium was large enough to produce the copious amount of melt required by the ubiquitous presence of mafic impact-melt breccias in the Apollo-sampled regolith. The High-Th Oval Region still may have been molten or hot at shallow depths ∼4 Ga ago when the Imbrium projectile struck. We reason that compositional heterogeneity of ejected melt breccia is to be expected under these circumstances. We argue that siderophile-element “fingerprints” of mafic impact-melt breccias are not inconsistent with production of all common types by a single projectile. We suggest that the narrow range of ages of 3.7–4.0 Ga for all successfully dated mafic impact-melt breccias may reflect a single event whose age is difficult to measure precisely, rather than a number of discrete impact events closely spaced in time, such that reported age variations among mafic impact-melt breccias reflect the ability to measure 40Ar/39Ar ages with greater precision than the accuracy with which measured portions of mafic impact-melt breccias have recorded the time of their formation.

Raman spectroscopy has the potential to provide definitive identification and detailed characterization of the minerals that comprise rocks and soils on planetary surfaces. We have designed a probe head for Raman spectroscopy that is suitable for use on a spectrometer deployed by a rover or a lander on the surface of a planet such as Mars, the Moon, or an asteroid. The probe head is lightweight, low power, rugged, and simple. It is based on a tiny distributed feedback diode laser and volume holographic components. A protective shell surrounds the probe head and serves as a mechanical stop for the mechanical arm of a planetary rover or lander during placement of the probe head onto the surface of a rock or soil. Pressing the shell against the rough surface of a target rock or soil also places the sampling objective of the probe head in rough focus, and the probe head is designed to be tolerant of focusing errors of ∼5 mm. A breadboard version of the probe head gave spectra of high quality on clean crystals of diamond, sulfur, calcite, quartz, and olivine. The results are qualitatively comparable to those obtained by using a conventional micro-Raman spectrometer on fine-grained travertine and on difficult specimens of basaltic lavas and impactites whose original mineralogy had been altered by reaction with water and air.

Late in the Moon's heavy bombardment period, the impact that formed the Imbrium Basin excavated and melted a tremendous volume of material that was subsequently distributed over most of the Moon's surface. The Apollo orbiting γ ray experiments [Metzger et al., 1977] show that the Imbrium projectile struck in a Th-rich area, called the High-Th Oval Region here and regarded as a unique lunar geochemical province. Imbrium primary ejecta were thus probably rich in Th. It is shown here using ejecta deposit modeling that the distribution of Th in the highlands surface along the ground tracks of the γ ray spectrometers is consistent with the distribution expected for Imbrium ejecta deposits. Deep basins other than Imbrium appear to have excavated regions of lower crust that were mafic and Fe-bearing but not Th-rich. The possibility that the surface Th distribution arises mainly from Imbrium ejecta has implications for the nature of the Moon's igneous differentiation and the nature of the proposed “cataclysm” or late bombardment with large meteoroids.

On Holsnoy, an island off the coast of Western Norway, an anorthositic complex metamorphosed to granulite facies was partially overprinted by a later eclogite facies metamorphism. Eclogite facies rocks (containing omphacite, garnet, kyanite and hydrous phases such as mica and zoisite) occur in shear zones of various scales and adjacent to veins. Previous studies of shear zones on Holsnoy reported evidence for substantial element mobility (Jamtveit et al., 1990; Mattey et al., 1994). In this work, we compare chemical compositions of granulite and its undeformed eclogitized equivalent adjacent to veins in locations where a single band of granulite can be traced and sampled as it approaches the vein. This tracing is crucial because the pre-granulite rocks cover a substantial compositional range, indicative of a petrologically variable protolith consisting of anorthosite, gabbro and jotunite. We analysed multiple core samples collected across nine separate granulite-eclogite transition zones located at veins in anorthositic, jotunitic and gabbroic protoliths for major and trace elements. For each transition, no compositional difference between the average granulite and average eclogite composition was found at the 90% confidence level except for LOI (loss on ignition), which was consistently significantly higher in the eclogite samples. Although not significant at the 90% confidence level for any single traverse, the average eclogite concentrations of SiO2 , Na2O, Cs, As and Br exceed the average granulite concentrations for eight or all nine of the traverses. For most traverses, statistical analysis of the data limits any gain of SiO2 in the eclogites to no more than a few relative per cent. Other than the introduction of volatile substances, presumably an H2O-rich fluid, eclogitization associated with vein formation was essentially isochemical.

Rocks from several outcrops of low-grade Littleton Formation and laterally equivalent Carrabassett Formation were analyzed for major elements and Zr. Compositional variations well outside of analytical uncertainties were observed, in order of increasing magnitude, for the following: 10-gram subsamples from a 2-kg hand sample of visually homogeneous slate; 100-gram samples taken 10 meters apart in the same outcrop; 10-g subsamples from a visually homogeneous quartzite; samples of relict turbidite beds in the same outcrop; and single 100-g samples from seven outcrops. We regard these variations as inherited from the sedimentary protolith with little if any alteration over distance scales of centimeters or greater. All could be modeled successfully as mixtures mainly of clay, quartz, and chlorite-mica, although the compositions of the clay and the chloritemica components had to be adjusted for different sets of samples, within reasonable bounds for sedimentary-diagenetic minerals. Compositional variations and trends in 2-kg samples of higher-grade Littleton rocks are essentially the same as for the low-grade samples. For example, SiO2 and Zr correlate positively, as expected for sedimentary sorting of quartz and zircon from clay, but not for selective metamorphic mobilization of silica. Also found was centimeter-scale separation of K2O from Al2O3 and strong covariation of Zn with Al2O3 in ~10-g subsamples of a staurolite schist, compositional evidence of element transport over distances of a few centimeters. Because the protolith includes at least two major, Al2O3-bearing components in variable proportions, element ratios to Al2O3 can vary such that variation in metamorphic rocks need not be a sensitive indicator of element mobility relative to Al2O3 even if Al is immobile. The population of low-grade rocks encompasses a broad compositional range. Thus, it is not feasible to obtain a sample average with a small standard deviation. It would also be difficult to demonstrate conclusively whether a set of samples was representative of its metamorphic grade, or whether rocks of all metamorphic grades developed from the same combination of protolith compositions and physical characteristics.

Through analysis by instrumental neutron activation (INAA) of 789 individual lithic fragments from the 2 mm-4 mm grain-size fractions of five Apollo 17 soil samples (72443, 72503, 73243, 76283, and 76503) and petrographic examination of a subset, we have determined the diversity and proportions of rock types recorded within soils from the highland massifs. The distribution of rock types at the site, as recorded by lithic fragments in the soils, is an alternative to the distribution inferred from the limited number of large rock samples. The compositions and proportions of 2 mm-4 mm fragments provide a bridge between compositions of less than 1 mm fines and types and proportions of rocks observed in large collected breccias and their clasts. The 2 mm-4 mm fraction of soil from South Massif, represented by an unbiased set of lithic fragments from station-2 samples 72443 and 72503, consists of 71% noritic impact-melt breccia, 7% Incompatible-Trace-Element-(ITE)-poor highland rock types (mainly granulitic breccias), 19% agglutinates and regolith breccias, 1% high-Ti mare basalt, and 2% others (very-low-Ti (VLT) basalt, monzogabbro breccia, and metal). In contrast, the 2 mm - 4 mm fraction of a soil from the North Massif, represented by an unbiased set of lithic fragments from station-6 sample 76503, has a greater proportion of ITE-poor highland rock types and mare-basalt fragments: it consists of 29% ITE-poor highland rock types (mainly granulitic breccias and troctolitic anorthosite), 25% impact-melt breccia, 13% high-Ti mare basalt, 31 % agglutinates and regolith breccias, 1% orange glass and related breccia, and 1% others. Based on a comparison of mass- weighted mean compositions of the lithic fragments with compositions of soil fines from all Apollo 17 highland stations, differences between the station-2 and station-6 samples are representative of differences between available samples from the two massifs. From the distribution of different rock types and their compositions, we conclude the following: (1) North-Massif and South-Massif soil samples differ significantly in types and proportions of ITE-poor highland components and ITE-rich impact-melt-breccia components. These differences reflect crudely layered massifs and known local geology. The greater percentage of impact-melt breccia in the South- Massif light-mantle soil stems from derivation of the light mantle from the top of the massif, which apparently is richer in noritic impact-melt breccia than are lower parts of the massifs. (2) At station 2, the 2 mm-4 mm grain-size fraction is enriched in impact-melt breccias compared to the less than 1 mm fraction, suggesting that the

In a study of metamorphosed pelites of the Devonian-aged Littleton Formation, New Hampshire, Shaw (1954) found little evidence for large scale compositional change other than devolatilization. Because his data are still used for such studies, we have reanalyzed his original samples using more precise methods and for additional elements to provide a more useful data set. Since Shaw’s study, remapping in New Hampshire has shown that 21 samples from the original set of 67 appear to be from underlying Silurian formations. The new data for the remaining 46 Littleton samples show statistically unambiguous differences between sample sets in average concentration ratios to Al2O3 or TiO2 for several elements (on a loss-on-ignition-free basis). The data do not, however, show systematic compositional differences as a function of metamorphic grade. Variations in element concentrations within sample sets of low, medium, and high metamorphic grade are as large or larger than differences in average concentrations between pairs of sample sets. This renders the method of comparing average compositions intrinsically insensitive even to substantial compositional change during metamorphism. We find no compelling evidence in support of metamorphic gain or loss of the elements we studied, but taken at face value, the statistical uncertainties would allow considerable gain or loss of most elements during metamorphism of Littleton pelites. Further detailed sampling would be required to determine whether the samples of each metamorphic grade are representative and to interpret the compositional variations and differences accurately in terms of metamorphic element mobility on the one hand and inheritance from the heterogeneous sedimentary protolith on the other.

The impact that produced North Ray Crater, Apollo 16 landing site, exhumed rocks that include relatively mafic members of the lunar ferroan anorthositic suite. Bulk and mineral compositions indicate that a majority of 2-4 mm lithic fragments from sample 67513, including impact breccias and monomict igneous rocks, are related to a common noritic-anorthosite precursor. Compositions and geochemical trends of these lithic fragments and of related samples collected along the rim of North Ray Crater suggest that these rocks derived from a single igneous body. This body developed as an orthocumulate from a mixture of cumulus plagioclase and mafic intercumulus melt, after the plagioclase had separated from any cogenetic mafic minerals and had become concentrated into a crystal mush (approximately 70 wt% plagioclase, 30 wt% intercumulus melt). We present a model for the crystallization of the igneous system wherein "system" is defined as cumulus plagioclase and intercumulus melt. The initial accumulation of plagioclase is analogous to the formation of thick anorthosites of the terrestrial Stillwater Complex; however, a second stage of formation is indicated, involving migration of the cumulus-plagioclase-intercumulus-melt system to a higher crustal level, analogous to the emplacement of terrestrial massif anorthosites. Compositional variations of the lithic fragments from sample 67513 are consistent with dominantly equilibrium crystallization of intercumulus melt. The highly calcic nature of orthocumulus pyroxene and plagioclase suggests some reaction between the intercumulus melt and cumulus plagioclase, perhaps facilitated by some recrystallization of cumulus plagioclase. Bulk compositions and mineral assemblages of individual rock fragments also require that most of the mafic minerals fortned in close contact with cumulus plagioclase, not as separate layers. The distribution of compositions (and by inference, modes) has a narrow peak at anorthosite and a broader, larger peak at noritic anoilhosite. Characteristics of the samples and their geochemical trends imply an origin in a system that was large relative to the (unknown) size of the impact that produced the breccias of ferroan noritic-anorthosite composition that were excavated later by the formation of North Ray Crater, and they appear to be consistent with an origin of the suite within a perched plagioclase cumulate. If the Moon's crust formed by accumulation of plagioclase in a magma ocean, ferroan noritic anothosite, formed as an orthocumulate, is an alternative to extensive adcumulus formation of ferroan anorthosite (greater than 90 vol% plagiclase). This provides a relatively mafic ferroan anorthositic component (approximately 15 vol% mafics), which is required by mass-balance models of compositions of polymict lunar-crustal materials. The inferred bulk composition of the system of cumulus plagioclase and intercumulus melt is similar to that of ferroan regolith breccia MacAlpine Hills 88104/5, a lunar-highland meteorite, and may represent a common and widespread component of the Moon's early highland crust.

Variations in activity coefficients for oxides in silicate melts are complex functions of silicate melt composition. For example, the activity coefficient (y) for NiO shows a minimum when plotted against a parameter reflecting the degree of polymerization (or basicity or fraction of bridging oxygens) (e.g., Pretorius and Muan, 1992). In this paper, we propose that this complexity occurs in part because NiO is not an actual species in silicate melts. Variations in y can be better understood and predicted if the activity of NiO is treated as the product of activities of Ni2+ and 02− ions. Using voltammetric methods, we have measured independent activity coefficients for Ni2+ and O- for compositions between diopsidic and anorthitic melt and have found that variations in these values are more easily understood in terms of the melt composition and structure and permit qualitative variations in γNiOo (activity coefficient of NiO relative to the free energy of formation reported in Robie and Waldbaum, 1968) to be predicted in compositions other than those studied. We suggest that a similar consideration of ionic behavior might improve our understanding of activity coefficients for other oxides in silicate melts as well. In addition, we report diffusion rates for Ni and free energies for the reaction Ni2+ + 02- ⇌ Ni0 + 1202, for melt compositions along the compositional joins CaMgSi206-CaAl2Si208 and CaMgSi206-MgAl2Si 2O8.

Compositions, including REEs determined by ion microprobe, of apatite and whitlockite in lunar rock assemblages rich in incompatible trace elements, are presented. Concentrations of REEs in lunar whitlockites are high, ranging from about 1.2 to 2.1 REEs (lanthanides + Y) per 56 oxygens. This slightly exceeds the level of two REE atoms per 56 oxygens at which the dominant substitution theoretically becomes saturated. This saturation effect leads to whitlockite REE(3+) D values at typical lunar whitlockite REE concentrations which are 30-40 percent lower than the D values at low concentrations. The halogen-to-phosphorous ratio in lunar melts is a key factor determining the REE distribution with crystalline assemblages. As long as P and REE concentrations of melts are in KREEP-like proportions, one or both of the phosphates will saturate in melts at similar REE concentrations.

We have characterized a comprehensive suite of individual green-glass beads from Apollo 15 soil to determine interelement behavior and to constrain petrogenetic relationships. We analyzed 365 particles for trace elements by instrumental neutron activation analysis and analyzed 52 of them, selected to cover the compositional ranges observed for trace elements, for major elements by electron microprobe analysis. We confirm the observation of Delano (1979) that the beads comprise discrete compositional groups, although two of the groups he defined are further split on the basis of trace-element compositions. Each of the resulting seven groups has distinct average rare-earth abundances. The coherence between major- and trace-element data was masked in previous studies by imprecision, correlated error, and nonrepresentative sampling of the different groups. Most of the compositional characteristics of the green glasses can be explained by a model for batch equilibrium melting of a nearly homogeneous, ultramafic source region, when the complicating effects of high pressure and low oxygen fugacity are taken into account. The previously puzzling behavior of Ni and Co as apparently incompatible elements may arise from partial reduction of those elements to the zero oxidation state, resulting in low mineral/melt partition coefficients. The model also offers explanations for why the green glasses form boomerang-shaped trends on many two-element variation diagrams and why certain compositions (Groups A and D) are more abundant than glasses with other compositions.

The equilibrium concentrations of Ni between silicate melt and Pt were determined experimentally as a function of oxygen fugacity. The results demonstrate that metallic species derived in linear sweep voltammetry experiments in silicate melts are diffusing into Pt electrodes and not into the melt, as was concluded by previoius studies. This requires reinterpretation of previous linear sweep voltammetry results and recalculation and correction of reported reduction potentials. This paper reports these corrected reduction potentials. Also reported are the activity coefficients for Ni in synthetic basalt and diopsidic melts and for Co in diopsidic melt.

Twenty about 100-mg random fragments of the Bruderheim chondrite were analyzed by INAA to determine extents of heterogeneity and to check earlier results that gave anomalous LREE concentrations. Considerable compositional heterogeneity was observed in both concentrations (maximum/minimum of 1.7 for Ir, 1.8 for Na, 6.8 for La, 7.4 for Co) and concentration ratios (greater than 3 x for Ni/Co and La/Eu). Compositions could be modeled quantitatively in terms of end-member components of constant composition representing the minerals olivine + orthopyroxene, clinopyroxene, plagioclase, kamacite, taenite, troilite, chromite, and phosphate. The model yields the proportions of minerals in each sample as well as the meteorite as a whole; accurate determination of the end members depends on high intrasample precision for many elements. No evidence of compositional heterogeneity of end members for trace elements was found. It is shown that these analyses, which used only about 2 grams of the meteorite, are equivalent in accuracy to a single sample of several tens of grams, and that knowledge of the extent of heterogeneity is essential to knowing the quality of sampling as well as for comparing results from one analysis with another and of one meteorite with another.

Results are presented on determinations of reduction potentials and their temperature dependence of selected ions in diopsidic melt, by using linear sweep voltammetry. Diffusion coefficients were measured for cations of Eu, Mn, Cr, and In. Enthalpies and entropies of reduction were determined for the cations V(V), Cr(3+), Mn(2+), Mn(3+), Fe(2+), Cu(2+), Mo(VI), Sn(IV), and Eu(3+). Reduction potentials were used to study the structural state of cations in the melt.

[1] On its traverse to Columbia Hills, the Mars Exploration Rover Spirit investigated an outcrop designated “Wooly Patch” that exhibited morphological, mineralogical, and geochemical characteristics at the extreme ends of ranges observed among rocks studied at West Spur, a westward projecting salient near the foot of the Columbia Hills, Gusev crater. The major-element composition and Fe-mineralogy, as determined by the Alpha-Particle X-ray Spectrometer and Mossbauer Spectrometer, are inconsistent with any reasonable assemblage of basaltic minerals in that there is an excess of Si and Al. The combined data are best explained by the presence of 14–17% phyllosilicate minerals. Phyllosilicates that account for the composition and cation ratios include members of the kaolinite, serpentine, chlorite, and septechlorite groups. The potential existence of kaolinite-type Al-rich phyllosilicates within the Wooly Patch outcrop suggests a mildly acidic environment (pH 4–6) in the past and an open hydrologic system with good drainage conditions in the environment where these rocks were altered.

Excavating into the shallow Martian subsurface has the potential to expose stratigraphic layers and mature regolith, which may hold a record of more ancient aqueous interactions than those expected under current Martian surface conditions. During the Spirit rover's exploration of Gusev crater, rover wheels were used to dig three trenches into the subsurface regolith down to 6-11 cm depth: Road Cut, the Big Hole, and The Boroughs. A high oxidation state of Fe and high concentrations of Mg, S, Cl, and Br were found in the subsurface regolith within the two trenches on the plains, between the Bonneville crater and the foot of Columbia Hills. Data analyses on the basis of geochemistry and mineralogy observations suggest the deposition of sulfate minerals within the subsurface regolith, mainly Mg-sulfates accompanied by minor Ca-sulfates and perhaps Fe-sulfates. An increase of Fe2O3, an excess of SiO2, and a minor decrease in the olivine proportion relative to surface materials are also inferred. Three hypotheses are proposed to explain the geochemical trends observed in trenches: (1) multiple episodes of acidic fluid infiltration, accompanied by in situ interaction with igneous minerals and salt deposition; (2) an open hydrologic system characterized by ion transportation in the fluid, subsequent evaporation of the fluid, and salt deposition; and (3) emplacement and mixing of impact ejecta of variable composition. While all three may have plausibly contributed to the current state of the subsurface regolith, the geochemical data are most consistent with ion transportation by fluids and salt deposition as a result of open-system hydrologic behavior. Although sulfates make up >20 wt.% of the regolith in the wall of The Boroughs trench, a higher hydrated sulfate than kieserite within The Boroughs or a greater abundance of sulfates elsewhere than is seen in The Boroughs wall regolith would be needed to hold the structural water indicated by the water-equivalent hydrogen concentration observed by the Gamma-Ray Spectrometer on Odyssey in the Gusev region. Copyright 2006 by the American Geophysical Union.

Spirit landed on the floor of Gusev Crater and conducted initial operations on soil covered, rock-strewn cratered plains underlain by olivine-bearing basalts. Plains surface rocks are covered by wind-blown dust and show evidence for surface enrichment of soluble species as vein and void-filling materials and coatings. The surface enrichment is the result of a minor amount of transport and deposition by aqueous processes. Layered granular deposits were discovered in the Columbia Hills, with outcrops that tend to dip conformably with the topography. The granular rocks are interpreted to be volcanic ash and/or impact ejecta deposits that have been modified by aqueous fluids during and/or after emplacement. Soils consist of basaltic deposits that are weakly cohesive, relatively poorly sorted, and covered by a veneer of wind blown dust. The soils have been homogenized by wind transport over at least the several kilometer length scale traversed by the rover. Mobilization of soluble species has occurred within at least two soil deposits examined. The presence of mono-layers of coarse sand on wind-blown bedforms, together with even spacing of granule-sized surface clasts, suggest that some of the soil surfaces encountered by Spirit have not been modified by wind for some time. On the other hand, dust deposits on the surface and rover deck have changed during the course of the mission. Detection of dust devils, monitoring of the dust opacity and lower boundary layer, and coordinated experiments with orbiters provided new insights into atmosphere-surface dynamics.

The mineralogical and elemental compositions of the martian soil are indicators of chemical and physical weathering processes. Using data from the Mars Exploration Rovers, we show that bright dust deposits on opposite sides of the planet are part of a global unit and not dominated by the composition of local rocks. Dark soil deposits at both sites have similar basaltic mineralogies, and could reflect either a global component or the general similarity in the compositions of the rocks from which they were derived. Increased levels of bromine are consistent with mobilization of soluble salts by thin films of liquid water, but the presence of olivine in analysed soil samples indicates that the extent of aqueous alteration of soils has been limited. Nickel abundances are enhanced at the immediate surface and indicate that the upper few millimetres of soil could contain up to one per cent meteoritic material.

The Mars Exploration Rover Spirit and its Athena science payload have been used to investigate a landing site in Gusev crater. Gusev is hypothesized to be the site of a former lake, but no clear evidence for lacustrine sedimentation has been found to date. Instead, the dominant lithology is basalt, and the dominant geologic processes are impact events and eolian transport. Many rocks exhibit coatings and other characteristics that may be evidence for minor aqueous alteration. Any lacustrine sediments that may exist at this location within Gusev apparently have been buried by lavas that have undergone subsequent impact disruption.

[1] Raman spectroscopy is a powerful tool for mineral characterization and for detection of water and organic and inorganic forms of carbon. The Mars microbeam Raman spectrometer (MMRS) is designed for close-up analysis of rocks and soils in planetary surface exploration. The MMRS consists of a probe (in a flight unit to be deployed by a robotic arm) and a spectrograph, laser source, and electronics (in a flight unit to reside on a rover or lander). The Raman probe has a scanning optical bench that enables a 1-cm linear traverse across a target rock or soil, both on target materials as encountered and on fresh surfaces of rocks exposed by abrasion or coring. From these spectra, one can identify major, minor, and trace minerals, obtain their approximate relative proportions, and determine chemical features (e.g., Mg/Fe ratio) and rock textural features (e.g., mineral clusters, amygdular fill, and veins). One can also detect and identify organic species, graphitic carbon, and water-bearing phases. Extensive performance tests have been done on a brassboard model of the MMRS using a variety of geological materials (minerals, rocks, Martian meteorites, etc.). These tests show that a Raman spectrometer can be built that is suitably miniaturized, sufficiently robust, and low enough in power usage to serve as an on-surface planetary instrument, yet the spectrometer can retain high detection sensitivity and yield near laboratory quality spectra over a broad wavelength range. These features are essential to provide definitive mineralogy in a planetary exploration.

International audience; In light of global remotely sensed data, the igneous crust of the Moon can no longer be viewed as a simple, globally stratified cumulus structure, composed of a flotation upper crust of anorthosite underlain by progressively more mafic rocks and a residual‐melt (KREEP) sandwich horizon near the base of the lower crust. Instead, global geochemical information derived from Clementine multispectral data and Lunar Prospector gamma‐ray data reveals at least three distinct provinces whose geochemistry and petrologic history make them geologically unique: (1) the Procellarum KREEP Terrane (PKT), (2) the Feldspathic High‐lands Terrane (FHT), and (3) the South Pole‐Aitken Terrane (SPAT). The PKT is a mafic province, coincident with the largely resurfaced area in the Procellarum‐Imbrium region whose petrogenesis relates to the early differentiation of the Moon. Here, some 40% of the Th in the Moon's crust is concentrated into a region that constitutes only about 10% of the crustal volume. This concentration of Th (average ∼5 ppm), and by implication the other heat producing elements, U and K, led to a fundamentally different thermal and igneous evolution within this region compared to other parts of the lunar crust. Lower‐crustal materials within the PKT likely interacted with underlying mantle materials to produce hybrid magmatism, leading to the magnesian suite of lunar rocks and possibly KREEP basalt. Although rare in the Apollo sample collection, widespread mare volcanic rocks having substantial Th enrichment are indicated by the remote data and may reflect further interaction between enriched crustal residues and mantle sources. The FHT is characterized by a central anorthositic region that constitutes the remnant of an anorthositic craton resulting from early lunar differentiation. Basin impacts into this region do not excavate significantly more mafic material, suggesting a thickness of tens of kilometers of anorthositic crust. The feldspathic lunar meteorites may represent samples from the anorthositic central region of the FHT. Ejecta from deep‐penetrating basin impacts outside of the central anorthositic region, however, indicate an increasingly mafic composition with depth. The SPAT, a mafic anomaly of great magnitude, may include material of the upper mantle as well as lower crust; thus it is designated a separate terrane. Whether the SPA basin impact simply uncovered lower crust such as we infer for the FHT remains to be determined.

Concentrations of 33 elements were determined in relatively unaltered, matrix-rich samples of impact breccia at approximately 3-m-depth intervals in the M-1 core from the Manson impact structure, Iowa. In addition, 46 matrix-rich samples from visibly altered regions of the M-7, M-8, and M-10 cores were studied, along with 42 small clasts from all four cores. Major element compositions were determined for a subset of impact breccias from the M-1 core, including matrix-rich impact-melt breccia. Major- and trace-element compositions were also determined for a suite of likely target rocks. In the M-1 core, different breccia units identified from lithologic examination of cores are compositionally distinct. There is a sharp compositional discontinuity at the boundary between the Keweenawan-shale-clast breccia and the underlying unit of impact-melt breccia (IMB) for most elements, suggesting minimal physical mixing between the two units during emplacement. Samples from the 40-m-thick IMB (M-1) are all similar to each other in composition, although there are slight increases in concentration with depth for those elements that have high concentrations in the underlying fragmental-matrix suevite breccia (SB) (e.g., Na, Ca, Fe, Sc), presumably as a result of greater clast proportions at the bottom margin of the unit of impact-melt breccia. The high degree of compositional similarity we observe in the impact-melt breccias supports the interpretation that the matrix of this unit represents impact melt. That our analyses show such compositional similarity results in part from our technique for sampling these breccias: for each sample we analyzed a few small fragments (total mass: approximately 200 mg) selected to be relatively free of large clasts and visible signs of alteration instead of subsamples of powders prepared from a large mass of breccia. The mean composition of the matrix-rich part of impact-melt breccia from the M-1 core can be modeled as a mixture of approximately 35% shale and siltstone (Proterozoic "Red Clastics"), 23% granite, 40% hornblende-biotite gneiss, and a small component (less than 2%) of mafic-dike rocks.

Nature 436, 49–54 (2005) Reference 34 should have read: “34. Goetz, W. et al. Indication of drier periods on Mars from the chemistry and mineralogy of atmospheric dust. Nature doi:10.1038/nature03807 (this issue).” The HTML version has been corrected online.

We test the effectiveness of using an alpha backscatter, alpha-proton, X ray spectrometer on a remotely operated rover to analyze soils and provide geologically useful information about the Moon during a simulated mission to a hypothetical site resembling the Apollo 17 landing site. On the mission, 100 soil samples are “analyzed” for major elements at moderate analytical precision (e.g., typical relative sample standard deviation from counting statistics: Si [11%], Al [18%], Fe [6%], Mg [20%], Ca [5%]). Simulated compositions of soils are generated by combining compositions of components representing the major lithologies occurring at the site in known proportions. Simulated analyses are generated by degrading the simulated compositions according to the expected analytical precision of the analyzer. Compositions obtained from the simulated analyses are modeled by least squares mass balance as mixtures of the components, and the relative proportions of those components as predicted by the model are compared with the actual proportions used to generate the simulated composition. Boundary conditions of the modeling exercise are that all important lithologic components of the regolith are known and are represented by model components, and that the compositions of these components are well known. The effect of having the capability of determining one incompatible element at moderate precision (25%) is compared with the effect of the lack of this capability. We discuss likely limitations and ambiguities that would be encountered, but conclude that much of our knowledge about the Apollo 17 site (based on the return samples) regarding the distribution and relative abundances of lithologies in the regolith could be obtained. This success requires, however, that at least one incompatible element be determined.

The sharp, nonoverlapping Raman bands for plagioclase, pyroxene, and olivine would be advantageous for on-surface, active mineralogical analysis of lunar materials. A robust, light-weight, low-power, rover-based Raman spectrometer with a laser exciting source, entirely transmission-mode holographic optics, and a charge-coupled device (CCD) detector could fit within a less than 20 cm cube. A sensor head on the end of an optical fiber bundle that carried the laser beam and returned the scattered radiation could be placed against surfaces at any desired angle by a deployment mechanism; otherwise, the instrument would need no moving parts. A modem micro-Raman spectrometer with its beam broadened (to expand the spot to 50-micrometer diameter) and set for low resolution (7/cm in the 100-1400/cm region relative to 514.5-nm excitation), was used to simulate the spectra anticipated from a rover instrument. We present spectra for lunar mineral grains, less than 1 mm soil fines, breccia fragments, and glasses. From frequencies of olivine peaks, we derived sufficiently precise forsterite contents to correlate the analyzed grains to known rock types and we obtained appropriate forsterite contents from weak signals above background in soil fines and breccias. Peak positions of pyroxenes were sufficiently well determined to distinguish among orthorhombic, monoclinic, and triclinic (pyroxenoid) structures; additional information can be obtained from pyroxene spectra, but requires further laboratory calibration. Plagioclase provided sharp peaks in soil fines and most breccias even when the glass content was high.

New trace element analyses of 25 basalt samples from a vertical traverse in an 11 m thick flow of Icelandic tholeiite show compositional differences which exceed analytical uncertainties and are random with respect to height. These variations suggest a short-range segregation model in which the amounts of phenocrysts, groundmass materials, and residual liquid vary randomly in different samples of the flow; a least-squares method is applied to determine if these variations reflect different proportions of crystallizing phases and residual liquid. Monte Carlo computations indicate that short-range segregation results in inhomogeneity of a magnitude of interflow compositional differences; this causes incoherence in elements with different geochemical behaviors while preserving coherence in elements of similar behavior.

Trace-element concentrations in separated minerals and rock fragments from a coarsely crushed and sieved sample of medium-grained lunar basalt are determined by high-precision instrumental neutron activation analysis for three main purposes. These are: (1) to test a previously proposed model for describing trace-element behavior during solidification of a silicate liquid under conditions of a closed system; (2) to compare trace-element concentrations among different size fractions of a comminuted basalt; and (3) to investigate small-scale heterogeneity within a single medium-grained basalt. It is found that an excellent mass balance for the whole rock is attained in terms of the trace-element concentrations of the component minerals and mesostasis, that the mixing model describing this mass balance yields a superior modal analysis for the whole rock, and that different size fractions of the coarsely crushed basalt vary in mineral composition. The closed-system model is shown to account properly for the average behavior of the trace elements during solidification of the basalt, and values of distribution coefficients are obtained for incompatible elements in that rock.

Results are reported for a study of the behavior of Ni(2+), Co(2+), and Zn(2+) in molten diopside, determined by cyclic voltametry, as a first step in adapting electrochemical methods for use in experimental geochemistry. The techniques used are described, the theory is briefly discussed, and it is demonstrated that Ni(2+), Co(2+), and Zn(2+) can be reduced, then reoxidized in an uncomplicated case of reversible charge transfer at the Pt electrode. This implies that the neutral metal atoms remain undissolved in the melt. The kinetics of the reduction process, the effects of concentration, the standard reduction potentials, and the diffusion coefficients are discussed in detail. The observations are consistent with the mechanism of Ni(2+) diffusion by transport from site to site. As the proportion of SiO2 in the melt increases, a higher activation energy is required for Ni(2+) to move, and the rate of diffusion is lowered.