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The NASA/ESA Mars Sample Return (MSR) Campaign seeks to establish whether life on Mars existed where and when environmental conditions allowed. Laboratory measurements on the returned samples are useful if what is measured is evidence of phenomena on Mars rather than of the effects of sterilization conditions. This report establishes that there are categories of measurements that can be fruitful despite sample sterilization and other categories that cannot. Sterilization kills living microorganisms and inactivates complex biological structures by breaking chemical bonds. Sterilization has similar effects on chemical bonds in non-biological compounds, including abiotic or pre-biotic reduced carbon compounds, hydrous minerals, and hydrous amorphous solids. We considered the sterilization effects of applying dry heat under two specific temperature-time regimes and the effects of γ-irradiation. Many measurements of volatile-rich materials are sterilization sensitive—they will be compromised by either dehydration or radiolysis upon sterilization. Dry-heat sterilization and γ-irradiation differ somewhat in their effects but affect the same chemical elements. Sterilization-sensitive measurements include the abundances and oxidation-reduction (redox) states of redox-sensitive elements, and isotope abundances and ratios of most of them. All organic molecules, and most minerals and naturally occurring amorphous materials that formed under habitable conditions, contain at least one redox-sensitive element. Thus, sterilization-sensitive evidence about ancient life on Mars and its relationship to its ancient environment will be severely compromised if the samples collected by Mars 2020 rover Perseverance cannot be analyzed in an unsterilized condition. To ensure that sterilization-sensitive measurements can be made even on samples deemed unsafe for unsterilized release from containment, contingency instruments in addition to those required for curation, time-sensitive science, and the Sample Safety Assessment Protocol would need to be added to the Sample Receiving Facility (SRF). Targeted investigations using analogs of MSR Campaign-relevant returned-sample types should be undertaken to fill knowledge gaps about sterilization effects on important scientific measurements, especially if the sterilization regimens eventually chosen are different from those considered in this report. Executive Summary: A high priority of the planned NASA/ESA Mars Sample Return Campaign is to establish whether life on Mars exists or existed where and when allowed by paleoenvironmental conditions. To answer these questions from analyses of the returned samples would require measurement of many different properties and characteristics by multiple and diverse instruments. Planetary Protection requirements may determine that unsterilized subsamples cannot be safely released to non-Biosafety Level-4 (BSL-4) terrestrial laboratories. Consequently, it is necessary to determine what, if any, are the negative effects that sterilization might have on sample integrity, specifically the fidelity of the subsample properties that are to be measured. Sample properties that do not survive sterilization intact should be measured on unsterilized subsamples, and the Sample Receiving Facility (SRF) should support such measurements. This report considers the effects that sterilization of subsamples might have on the science goals of the MSR Campaign. It assesses how the consequences of sterilization affect the scientific usefulness of the subsamples and hence our ability to conduct high-quality science investigations. We consider the sterilization effects of (a) the application of dry heat under two temperature-time regimes (180°C for 3 hours; 250°C for 30 min) and (b) γ-irradiation (1 MGy), as provided to us by the NASA and ESA Planetary Protection Officers (PPOs). Measurements of many properties of volatile-rich materials are sterilization sensitive—they would be compromised by application of either sterilization mode to the subsample. Such materials include organic molecules, hydrous minerals (crystalline solids), and hydrous amorphous (non-crystalline) solids. Either proposed sterilization method would modify the abundances, isotopes, or oxidation-reduction (redox) states of the six most abundant chemical elements in biological molecules (i.e., carbon, hydrogen, nitrogen, oxygen, phosphorus, and sulphur, CHNOPS), and of other key redox-sensitive elements that include iron (Fe), other first-row transition elements (FRTE), and cerium (Ce). As a result of these modifications, such evidence of Mars' life, paleoenvironmental history, potential habitability, and potential biosignatures would be corrupted or destroyed. Modifications of the abundances of some noble gases in samples heated during sterilization would also reset scientifically important radioisotope geochronometers and atmospheric-evolution measurements. Sterilization is designed to render terminally inactive (kill) all living microorganisms and inactivate complex biological structures (including bacterial spores, viruses, and prions). Sterilization processes do so by breaking certain pre-sterilization chemical bonds (including strong C-C, C-O, C-N, and C-H bonds of predominantly covalent character, as well as weaker hydrogen and van der Waals bonds) and forming different bonds and compounds, disabling the biological function of the pre-sterilization chemical compound. The group finds the following: No sterilization process could destroy the viability of cells whilst still retaining molecular structures completely intact. This applies not only to the organic molecules of living organisms, but also to most organic molecular biosignatures of former life (molecular fossils). As a matter of biological principle, any sterilization process would result in the loss of biological and paleobiological information, because this is the mechanism by which sterilization is achieved. Thus, almost all life science investigations would be compromised by sterilizing the subsample by either mode. Sterilization by dry heat at the proposed temperatures would lead to changes in many of the minerals and amorphous solids that are most significant for the study of paleoenvironments, habitability, potential biosignatures, and the geologic context of life-science observations. Gamma-(γ-)irradiation at even sub-MGy doses induces radiolysis of water. The radiolysis products (e.g., free radicals) react with redox-sensitive chemical species of interest for the study of paleoenvironments, habitability, and potential biosignatures, thereby adversely affecting measurements of those species. Heat sterilization and radiation also have a negative effect on CHNOPS and redox-sensitive elements. MSPG2 was unable to identify with confidence any measurement of abundances or oxidation-reduction states of CHNOPS elements, other redox-sensitive elements (e.g., Fe and other FRTE; Ce), or their isotopes that would be affected by only one, but not both, of the considered sterilization methods. Measurements of many attributes of volatile-rich subsamples are sterilization sensitive to both heat and γ-irradiation. Such a measurement is not useful to Mars science if what remains in the subsample is evidence of sterilization conditions and effects instead of evidence of conditions on Mars. Most measurements relating to the detection of evidence for extant or extinct life are sterilization sensitive. Many measurements other than those for life-science seek to retrieve Mars' paleoenvironmental information from the abundances or oxidation-reduction states of CHNOPS elements, other redox-sensitive elements, or their isotopes (and some noble gases) in returned samples. Such measurements inform scientific interpretations of (paleo)atmosphere composition and evolution, (paleo)surface water origin and chemical evolution, potential (paleo)habitability, (paleo)groundwater-porewater solute chemistry, origin and evolution, potential biosignature preservation, metabolic element or isotope fractionation, and the geologic, geochronological, and geomorphic context of life-sciences observations. Most such measurements are also sterilization sensitive. The sterilization-sensitive attributes cannot be meaningfully measured in any such subsample that has been sterilized by heat or γ-irradiation. Unless such subsamples are deemed biohazard-safe for release to external laboratories in unsterilized form, all such measurements must be made on unsterilized samples in biocontainment. An SRF should have the capability to carry out scientific investigations that are sterilization-sensitive to both PPO-provided sterilization methods (Figure SE1). The following findings have been recognized in the Report. Full explanations of the background, scope, and justification precede the presentation of each Finding in the Section identified for that Finding. One or more Findings follow our assessment of previous work on the effects of each provided sterilization method on each of three broad categories of measurement types—biosignatures of extant or ancient life, geological evidence of paleoenvironmental conditions, and gases. Findings are designated Major if they explicitly refer to both PPO-provided sterilization methods or have specific implications for the functionalities that need to be supported within an SRF. FINDING SS-1: More than half of the measurements described by iMOST for investigation into the presence of (mostly molecular) biosignatures (iMOST Objectives 2.1, 2.2 and 2.3) in returned martian samples are sterilization-sensitive and therefore cannot be performed with acceptable analytical precision or sensitivity on subsamples sterilized either by heat or by γ-irradiation at the sterilization parameters supplied to MSPG2. That proportion rises to 86% of the measurements specific to the investigation of extant or recent life (iMOST Objective 2.3) (see Section 2.5). This Finding supersedes Finding #4 of the MSPG Science in Containment report (MSPG, 2019). FINDING SS-2: Almost three quarters (115 out of 160; 72%) of the measurements described by iMOST for science investigations not associated with Objective 2 but associated with Objectives concerning geological phenomena that include past interactions with the hydrosphere (Objectives 1 and 3) and the atmosphere (Objective 4) are sterilization-tolerant and therefore can (generally) be performed with acceptable analytical precision or sensitivity on subsamples sterilized either by heat or by γ-irradiation at the sterilization parameters supplied to MSPG2 (see Section 2.5). This Finding supports Finding #6 of the MSPG Science in Containment report (MSPG, 2019).MSPG2 endorses the previously proposed strategy of conducting as many measurements as possible outside the SRF where the option exists. FINDING SS-3: Suggested strategies for investigating the potential for extant life in returned martian samples lie in understanding biosignatures and, more importantly, the presence of nucleic acid structures (DNA/RNA) and possible agnostic functionally similar information-bearing polymers. A crucial observation is that exposure of microorganisms to temperatures associated with sterilization above those typical of a habitable surface or subsurface environment results in a loss of biological information. If extant life is a target for subsample analysis, sterilization of material via dry heat would likely compromise any such analysis (see Section 3.2). FINDING SS-4: Suggested strategies for investigating the potential for extant life in returned martian samples lie in understanding biosignatures, including the presence of nucleic acid structures (DNA/RNA) and possible agnostic functionally similar information-bearing polymers. A crucial observation is that exposure of microorganisms to γ-radiation results in a loss of biological information through molecular damage and/or destruction. If extant life is a target for subsample analysis, sterilization of material via γ-radiation would likely compromise any such analysis (see Section 3.3). FINDING SS-5: Suggested strategies for investigating biomolecules in returned martian samples lie in detection of a variety of complex molecules, including peptides, proteins, DNA (deoxyribonucleic acid) and RNA (ribonucleic acid), as well as compounds associated with cell membranes such as lipids, sterols, and fatty acids and their geologically stable reaction products (hopanes, steranes, etc.) and possible agnostic functionally similar information-bearing polymers. Exposure to temperatures above MSR Campaign-Level Requirements for sample temperature, up to and including sterilization temperatures, results in a loss of biological information. If the presence of biosignatures is a target for subsample analysis, sterilization of material via dry heat would likely compromise any such analysis (see Section 4.2). FINDING SS-6: Suggested strategies for investigating biomolecules in returned martian samples lie in detection of a variety of complex molecules, including peptides, proteins, DNA (deoxyribonucleic acid) and RNA (ribonucleic acid), and compounds associated with cell membranes such as lipids, sterols and fatty acids and their geologically stable reaction products (hopanes, steranes, etc.) and possible agnostic functionally similar information-bearing polymers. Exposure to radiation results in a loss of biological information. If the presence of biosignatures is a target for subsample analysis, sterilization of material via γ-irradiation would likely compromise any such analysis (see Section 4.3). FIG. SE1. A key SRF strategy is that the SRF is designed to initially accommodate only the measurements and analyses that cannot reasonably be made outside of biocontainment, including those required for initial sample characterization, Sample Safety Assessment Protocol (SSAP) tests, and time-sensitive science. Two scenarios are shown for sterilization-sensitive measurements that are contingent upon SSAP determination that sample is safe for unsterilized release (green YES path to uncontained outside laboratories) or unsafe for unsterilized release (red NO path to uncontained outside laboratories for sterilization tolerant science PLUS contained contingency laboratories enabling sterilization sensitive MSR Campaign measurements on unsterilized samples that cannot be deemed safe for release from containment). From Carrier et al. (2022). MAJOR FINDING SS-7: The use of heat or γ-irradiation sterilization should be avoided for subsamples intended to be used for organic biosignature investigations (for extinct or extant life). Studies of organic molecules from extinct or extant life (either indigenous or contaminants, viable or dead cells) or even some organic molecules derived from abiotic chemistry cannot credibly be done on subsamples that have been sterilized by any means. The concentrations of amino acids and other reduced organic biosignatures in the returned martian samples may also be so low that additional heat and/or γ-irradiation sterilization would reduce their concentrations to undetectable levels. It is a very high priority that these experiments be done on unsterilized subsamples inside containment (see Section 4.4). FINDING SS-8: Solvent extraction and acid hydrolysis at ∼100°C of unsterilized martian samples will inactivate any biopolymers in the extract and would not require additional heat or radiation treatment for the subsamples to be rendered sterile. Hydrolyzed extracts should be safe for analysis of soluble free organic molecules outside containment and may provide useful information about their origin for biohazard assessments; this type of approach, if approved, is strongly preferred and endorsed (see Section 4.4). FINDING SS-9: Minerals and amorphous materials formed by low temperature processes on Mars are highly sensitive to thermal alteration, which leads to irreversible changes in composition and/or structure when heated. Exposure to temperatures above MSR Campaign-Level Requirements for sample temperature, up to and including sterilization temperatures, has the potential to alter them from their as-received state. Sterilization by dry heat at the proposed sterilization temperatures would lead to changes in many of the minerals that are most significant for the study of paleoenvironments, habitability, and potential biosignatures or biosignature hosts. It is crucial that the returned samples are not heated to temperatures above which mineral transitions occur (see Section 5.3). FINDING SS-10: Crystal structure, major and non-volatile minor element abundances, and stoichiometric compositions of minerals are unaffected by γ-irradiation of up to 0.3–1 MGy, but crystal structures are completely destroyed at 130 MGy. Measurements of these specific properties cannot be acquired from subsamples γ-irradiated at the notional 1 MGy dose—they are sterilization-sensitive (see Section 5.4). FINDING SS-11: Sterilization by γ-irradiation (even at sub-MGy doses) results in significant changes to the redox state of elements bound within a mineral lattice. Redox-sensitive elements include Fe and other first-row transition elements (FRTE) as well as C, H, N, O, P and S. Almost all minerals and naturally occurring amorphous materials that formed under habitable conditions, including the ambient paleotemperatures of Mars' surface or shallow subsurface, contain at least one of these redox-sensitive elements. Therefore, measurements and investigations of the listed properties of such geological materials are sterilization sensitive and should not be performed on γ-irradiated subsamples (see Section 5.4). FINDING SS-12: A significant fraction of investigations that focus on high-temperature magmatic and impact-related processes, their chronology, and the chronology of Mars' geophysical evolution are sterilization-tolerant. While there may be a few analyses involved in such investigations that could be affected to some degree by heat sterilization, most of these analyses would not be affected by sterilization involving γ-irradiation (see Section 5.6). MAJOR FINDING SS-13: Scientific investigations of materials containing hydrous or otherwise volatile-rich minerals and/or X-ray amorphous materials that formed or were naturally modified at low (Mars surface-/near-surface) temperature are sterilization-sensitive in that they would be compromised by changes in the abundances, redox states, and isotopes of CHNOPS and other volatiles (e.g., noble gases for chronometry), FRTE, and Ce, and cannot be performed on subsamples that have been sterilized by either dry heat or γ-irradiation (see Section 5.7). MAJOR FINDING SS-14: It would be far preferable to work on sterilized gas samples outside of containment, if the technical issues can all be worked out, than to build and operate a large gas chemistry laboratory inside containment. Depending on their reactivity (or inertness), gases extracted from sample tubes could be sterilized by dry heat or γ-irradiation and analyzed outside containment. Alternatively, gas samples could be filtered through an inert grid and the filtered gas analyzed outside containment (see Section 6.5). MAJOR FINDING SS-15: It is fundamental to the campaign-level science objectives of the Mars Sample Return Campaign that the SRF support characterization of samples returned from Mars that contain organic matter and/or minerals formed under habitable conditions that include the ambient paleotemperatures of Mars' surface or subsurface (<∼200°C)—such as most clays, sulfates, and carbonates—in laboratories on Earth in their as-received-at-the-SRF condition (see Section 7.1). MAJOR FINDING SS-16: The search for any category of potential biosignature would be adversely affected by either of the proposed sterilization methods (see Section 7.1). MAJOR FINDING SS-17: Carbon, hydrogen, nitrogen, oxygen, sulfur, phosphorus, and other volatiles would be released from a subsample during the sterilization step. The heat and γ-ray sterilization chambers should be able to monitor weight loss from the subsample during sterilization. Any gases produced in the sample headspace and sterilization chamber during sterilization should be captured and contained for future analyses of the chemical and stable isotopic compositions of the evolved elements and compounds for all sterilized subsamples to characterize and document fully any sterilization-induced alteration and thereby recover some important information that would otherwise be lost (see Section 7.2). This report shows that most of the sterilization-sensitive iMOST measurement types are among either the iMOST objectives for life detection and life characterization (half or more of the measurements for life-science sub-objectives are critically sterilization sensitive) or the iMOST objectives for inferring paleoenvironments, habitability, preservation of potential biosignatures, and the geologic context of life-science observations (nearly half of the measurements for sub-objectives involving geological environments, habitability, potential biosignature preservation, and gases/volatiles are critically sterilization sensitive) (Table 2; see Beaty et al.,2019 for the full lists of iMOST objectives, goals, investigations, and sample measurement types). Sterilization-sensitive science about ancient life on Mars and its relationship to its ancient environment will be severely impaired or lost if the samples collected by Perseverance cannot be analyzed in an unsterilized condition. Summary: ○ The SRF should have the capability to carry out or otherwise support scientific investigations that are sensitive to both PPO-provided sterilization methods. ○ Measurements of most life-sciences and habitability-related (paleoenvironmental) phenomena are sensitive to both PPO-provided sterilization modes. (Major Finding SS-7, SS-15, SS-16 and Finding SS-1, SS-3, SS-4, SS-5, SS-6, SS-9, SS-11, SS-13) If subsamples for sterilization-sensitive measurement cannot be deemed safe for release, then additional contingency analytical capabilities are needed in the SRF to complete MSR Campaign measurements of sterilization-sensitive sample properties on unsterilized samples in containment (Figure SE1, below). ○ Measurements of high-temperature (low-volatile) phenomena are tolerant of both PPO-provided sterilization modes (Finding SS-12). Subsamples for such measurements may be sterilized and released to laboratories outside containment without compromising the scientific value of the measurements. ○ Capturing, transporting, and analyzing gases is important and will require careful design of apparatus. Doing so for volatiles present as headspace gases and a dedicated atmosphere sample will enable important atmospheric science (Major Finding SS-14). Similarly, capturing and analyzing gases evolved during subsample sterilization (i.e., gas from the sterilization chamber) would compensate for some sterilization-induced loss of science data from volatile-rich solid (geological) subsamples (Finding SS-14, SS-17; other options incl. SS-8). [ABSTRACT FROM AUTHOR]

The target bodies of C‐complex asteroid sample return missions are carbonaceous chondrite‐like near‐Earth asteroids (NEAs), chosen for the abundance and scientific importance of their organic compounds and "hydrous" (including hydroxylated) minerals, such as serpentine‐group phyllosilicates. Science objectives include returning samples of pristine carbonaceous regolith from asteroids for study of the nature, history, and distribution of its constituent minerals, organic material, and other volatiles. Heating after the natural aqueous alteration that formed the abundant phyllosilicates in CM and similar carbonaceous chondrites dehydroxylated them and altered or decomposed other volumetrically minor constituents (e.g., carbonates, sulfides, organic molecules; Tonui et al. 2003, 2014). We propose a peak‐temperature thermometer based on dehydroxylation as measured by analytical totals from electron probe microanalysis (EPMA) of matrices in a number of heated and aqueously altered (but not further heated) CM chondrites. Some CM lithologies in Maribo and Sutter's Mill do not exhibit the matrix dehydroxylation expected for surface temperatures expected from insolation of meteoroids with their known orbital perihelia. This suggests that insolated‐heated meteoroid surfaces were lost by ablation during passage through Earth's atmosphere, and that insolation‐heated material is more likely to be encountered among returned asteroid regolith samples than in meteorites. More generally, several published lines of evidence suggest that episodic heating of some CM material, most likely by impacts, continued intermittently and locally up to billions of years after assembly and early heating of ancestral CM chondrite bodies. Mission spectroscopic measures of hydration can be used to estimate the extent of dehydroxylation, and the new dehydroxylation thermometer can be used directly to select fragments of returned samples most likely to contain less thermally altered inventories of primitive organic molecules. [ABSTRACT FROM AUTHOR]

Several nakhlites (clinopyroxenite meteorites from Mars) contain olivine phenocrysts with corrosion features identical in size, shape and distribution to the smaller etch-pits of well-characterized weathered terrestrial olivine. Miller Range (MIL) 03346 is an Antarctic nakhlite find, recovered after long exposure to Antarctic conditions. The distribution of discrete olivine etch-pits almost exclusively within a few hundred microns of allocation MIL 03346,171’s documentably exposed surface suggests that they formed by terrestrial weathering in Antarctica. The small size of olivine etch-pits in MIL 03346,171 relative to commonly much larger etch-pits in even incipiently weathered terrestrial examples suggests that the duration of its exposure to weathering conditions was short, or the weathering conditions to which it was exposed did not favor olivine corrosion (in the form of etch-pit formation), or both. Time-scales for the formation of etch-pits, estimated from experimentally determined dissolution rates of olivine over a range of pHs, are comparable to the measured terrestrial age of the meteorite and short relative to the time available for possible similar corrosion on Mars. Etch-pits of the observed size on MIL 03346 olivine phenocrysts would be relatively easy to form supraglacially under brief episodic acidic Antarctic conditions, but the terrestrial age of MIL 03346 is long enough that its olivine might have been weathered to the observed state by englacial films of alkaline Antarctic water. The paucity of similar etch-pits in olivine from the interior of MIL 03346 suggests that olivine in this Mars meteorite was exposed to even less aqueous alteration after iddingsitization during its 1.3 billion years on Mars than its exterior was subjected to during its Pleistocene–Holocene exposure to Antarctic weathering conditions. [ABSTRACT FROM AUTHOR]

Nakhlites, clinopyroxenite meteorites from Mars, share common crystallization and ejection ages, suggesting that they might have been ejected from the same place on Mars by the same ejection event (impact) and are different samples of the same thick volcanic flow unit or shallow sill. Mean modal abundances and abundance ranges of pyroxene, olivine, and mesostasis vary widely among different thin-sections of an individual nakhlite. Lithologic heterogeneity is the main factor contributing to the observed modal-abundance variations measured in thin-sections prepared from different fragments of the same stone. Two groups of nakhlites are distinguished from one another by which major constituent varies the least and the abundance of that constituent. The group consisting of Nakhla, Lafayette, Governador Valadares, and the Yamato nakhlite pairing group is characterized by low modal mesostasis and pyroxene-olivine covariance, whereas the group consisting of the Miller Range nakhlite pairing group and Northwest Africa 5790 is characterized by low modal olivine and pyroxene-mesostasis covariance. These two groups sample the slowest-cooled interior portion and the chilled margin, respectively, of the nakhlite emplacement body as presently understood, and appear to be also related to recently proposed nakhlite groups independently established using compositional rather than petrographic observations. Phenocryst modal abundances vary with inferred depth in the nakhlite igneous body in a manner consistent with solidification of the nakhlite stack from dynamically sorted phenocryst-rich magmatic crystal-liquid mush. [ABSTRACT FROM AUTHOR]

Isovolumetric replacement of euhedral and anhedral olivine by serpentine produced both centripetal and meshwork textures in the CM2 chondrites ALH 81002 and Nogoya. The compositions of these textural varieties of serpentine are uniform within narrow limits within each previously studied meteorite, independent of the composition of olivine being replaced, and different between the two meteorites. In QUE 93005 (CM2), coarse olivines of widely varying compositions (Fo <76–99 ) are replaced in a texturally similar manner by compositionally uniform serpentine (Mg 0.73±0.05 Fe 0.27±0.05 ) 3 Si 2 O 5 (OH) 4 . The narrow compositional range of serpentine replacing coarse olivine indicates that the aqueous solution from which the serpentine formed was compositionally uniform on scales at least as large as the meteorite (∼2.5 cm in longest dimension). Isovolumetric textures and compositional observations constrain elemental redistribution from coarse olivine to serpentine and to surrounding phases during serpentinization. Regardless of olivine’s composition, isovolumetric replacement of coarse olivines by serpentine of the observed composition released more Mg and Si from olivine than was required to form the serpentine. Excess Mg and Si released by olivine destruction and not retained in serpentine were exported from the replaced volume. Olivines with different Fa/Fo proportions contributed different amounts of Fe and Mg to the serpentine. Ferroan olivines released more Fe than required to form the serpentines replacing them, so some of the Fe released from ferroan olivine was exported from the replaced volumes. Forsteritic olivines released less Fe than required to form the serpentines replacing them, so some Fe was imported into the replaced volumes augmenting the small amount of Fe released from forsteritic olivine. In QUE 93005 Fo 83.8 is the threshold composition between Fe-exporting and Fe-importing behavior in individual olivine–serpentine pairs, which released exactly the amount of Fe required to form serpentine of the observed uniform composition. Compositions of serpentines isovolumetrically replacing olivines, and threshold olivine compositions, in QUE 93005 differ from the corresponding values in Nogoya. Solvent and solute species diffused through the serpentine between the olivine–serpentine interface and the aqueous solution outside the isovolumetrically replaced volume. In QUE 93005, some of the Fe released from ferroan olivine in excess of the amount required to form serpentine reacted with S sourced from outside the pseudomorphs to form Fe-sulfide decorating the margins of the pseudomorphs of serpentine after fayalitic olivine. Such Fe-sulfide-decorated outlines after fayalitic olivine do not occur in ALH 81002 or Nogoya, indicating different Fe and S mass transfer regimes in different CM2 chondrites. Mg, Fe, Si, and S in the aqueous solution, including the excess Mg and Si exported from all serpentine pseudomorphs after olivine of any composition, were available to be incorporated into other phases spatially separate from the pseudomorphs after olivine, including regularly interstratified serpentine–tochilinite. Serpentines that replaced coarse olivines in QUE 93005 and ALH 81002 are less magnesian than those in Nogoya, indicating that the Nogoya aqueous-alteration environment was more evolved toward Mg-rich solutions. This easily located and characterized phase assemblage may be potentially useful for characterizing clasts of varying degrees of alteration in brecciated and heterogeneous CM chondrites, and future returned samples from mineralogically similar asteroids. [ABSTRACT FROM AUTHOR]

- The Hayabusa mission recently returned the first samples from an ordinary chondrite (OC) parent body. Olivine, low-Ca pyroxene, and kamacite compositions fall within the known ranges of minerals from LL4 to LL6 chondrites. Hayabusa samples are being processed and stored in a pure N2 atmosphere. However, during recovery, prior to receiving, and during preliminary examination, some Hayabusa samples were briefly exposed to terrestrial atmosphere. Some of the minerals already identified in the Hayabusa samples (olivine, sulfides) are known to be among the most vulnerable to weathering reactions in moist, oxidizing terrestrial environments. Oxidation of Fe in metal, sulfides, and ferrous silicates is ubiquitous in naturally weathered OC finds, in samples of falls subjected to even a few decades of weathering before recovery, and in OC falls recovered and curated promptly after recovery. All prerecovery oxidation, hydrolysis, hydration, and product-forming phenomena documented to affect OC finds have been documented to continue in OC samples in curatorial and laboratory settings, producing mineralogical and textural effects at scales easily discernable by electron microscopy, on timescales of decades. Hayabusa samples will be exposed to similar terrestrial conditions at times throughout sample processing, allocation, and examination. Maximizing the science yield from these important samples requires thorough understanding of how LL chondrite minerals like those in the Hayabusa samples react with terrestrial moisture and oxidants in support of proper planning for maintaining Hayabusa sample integrity after allocation, and for proper anticipation of the effects of inevitable exposure to Earth's atmosphere during storage and examination in terrestrial analytical laboratories. [ABSTRACT FROM AUTHOR]

Abstract: Coarse (chondrule and isolated) olivine in some CM chondrites is replaced by serpentine in both centripetal and meshwork replacement textures. Locally preserved textures formed by partial replacement of coarse olivine by serpentine in the carbonaceous chondrite Nogoya (CM2) establish unique associations between each individual mass of serpentine and the specific olivine from which that serpentine formed. Electron probe microanalyses show that the composition of serpentine replacing coarse olivine is uniform throughout all analyzed volumes of Nogoya, and is independent of the composition of the olivine being replaced. If, as previously proposed, late-stage alteration fluids were Mg-rich because Fe-source minerals were depleted in earlier stages, then the uniform Mg-rich composition of the serpentine replacing large silicate grains during advanced stages of alteration may indicate diffusional homogenization of the aqueous solutions over progressively larger spatial scales, enabled by long timescales and previously proposed stagnant or slow-moving fluids. The range of olivine compositions replaced in Nogoya is even larger than previously reported from ALH 81002 (CM2). This militates against hypotheses of strong primary-mineral control on the compositions of alteration products, at least at advanced stages of alteration. The serpentine formed by olivine replacement in Nogoya is more magnesian than the counterpart serpentine replacing all anhydrous primary silicates in ALH 81002. This intermeteorite heterogeneity of replacement-serpentine composition between ALH 81002 and Nogoya indicates that the aqueous solutions in which the olivine-serpentine replacement reactions occurred were of different compositions in the two different CM parent-body volumes sampled by ALH 81002 and Nogoya. The more magnesian character of serpentines in Nogoya than in ALH 81002 indicates that the Nogoya aqueous-alteration environment was even more highly evolved toward Mg-rich solutions than the environment indicated by the composition of the serpentine in ALH 81002. Persistence of primary-silicate remnants within centripetal and meshwork serpentine indicates that either the aqueous alteration episodes in the parent-body volumes represented by individual meteorites were too short to allow complete replacement of olivine by serpentine, or one or more reactants (most likely water) were completely consumed before the coarse primary silicate was completely replaced. Seemingly incompatible arguments for and against primary-mineral control of serpentine composition during CM chondrite alteration may be reconciled by considering the different grain sizes and reaction timescales that likely existed in different textural settings. [Copyright &y& Elsevier]

- To constrain the effects of capture modification processes, the size distribution of nanoscale refractory Fe-Ni-S inclusions ('droplets') was measured in five allocations extracted from throughout the depth of Stardust Track 35. The Fe/S ratio has been previously shown to increase significantly with penetration depth in this track, suggesting increasing capture-related modification along the track. Astronomical image analysis tools were employed to measure the sizes of more than 8000 droplets from TEM images, and completeness simulations were used to correct the distribution for detection bias as a function of radius. The size distribution characteristics are found to be similar within independent regions of individual allocations, demonstrating uniformity within grains. The size distribution of the Fe-Ni-S droplets in each allocation is dominated by a mode near 11 nm, but is coarse-skewed and leptokurtic with a mean of ∼17 nm and a standard deviation of ∼9 nm. The size distribution characteristics do not vary systematically with penetration depth, despite the strong trend in bulk Fe/S ratio. This suggests that the capture modification process is not primarily responsible for producing the morphology of these nanoscale droplets. The Stardust Track 35 droplet size distribution indicates slightly smaller sizes, but otherwise resembles those in carbonaceous chondrite Acfer 094, and chondritic porous interplanetary dust particles that escaped nebular annealing of sulfides. The size distribution of metal-sulfide beads in Stardust's quenched melted-grain emulsions appears to be inherited from the size distribution of unmelted sulfide mineral grains in comet-dust particles of chondritic character. [ABSTRACT FROM AUTHOR]

- Weathering of meteorites at the scale of the entire Antarctic Search for Meteorites program population is studied by analyzing the recent version of the online Antarctic meteorite classification database that includes information about 15,263 meteorites. This paper updates, supplements, and expands on the last Antarctic meteorite weathering census by , Meteoritics 23:151-159). On average 5% of all Antarctic meteorites are indicated as evaporite bearing in the Antarctic Meteorite Database. Evaporite formation depends on compositional group. Evaporites are much more common on C chondrites than on ordinary chondrites, supporting previous findings. Ordinary chondrites of petrologic type 3 more often have evaporites on their surface than meteorites of other petrologic types. Contrary to previous findings, there is no apparent relation between evaporite formation and meteorite rustiness. Some meteorite-bearing fields influence the frequency of evaporite-mineral formation on meteorites. The influence of location is apparently related to differences in environmental conditions, most probably microclimate or/and hydrologic conditions. There is no relation between abundance of evaporite-bearing meteorites and distance from the sea. Evaporite formation varies with year of collection; however, it was not possible to distinguish whether this is related to annual changes in environment or an artifact of sample categorization or curation. [ABSTRACT FROM AUTHOR]

Abstract: Naturally weathered olivine occurring as phenocrysts in Hawai’ian volcanic rocks from several volcanic centers and regolith/outcrop settings, and as tectonized olivines from several metadunite bodies in the southern Appalachian Blue Ridge, are all similarly corroded by natural weathering. Conical (funnel-shaped) etch pits occur as individual pits, base-to-base pairs of cone-shaped pits, or en echelon arrays. Etch-pit shapes and orientations in the smallest etch-pit arrays visible in conventional scanning electron microscopy resemble even smaller features previously reported from transmission electron microscope investigations of olivine weathering. Etch pits occur in samples with chemical and/or mineralogical evidence of weathering, and/or are associated with, or proximal or directly connected to, fractures or exposed outcrop surface, and therefore are formed by weathering and not inherited from pre-weathering aqueous alteration (e.g., serpentinization, iddingsitization) of these parent rocks. Many etch pits are devoid of weathering products. Natural weathering of olivine is surface-reaction-limited. Similarity of corrosion forms from naturally weathered olivine from multiple igneous and metamorphic parent-rock bodies suggests that olivine weathers in the same manner regardless of its specific crystallization/recrystallization history, eruption/weathering/exposure ages of the olivine’s host rock, and the local regolith history. [Copyright &y& Elsevier]

Natural weathering of hornblende from the Tallulah Falls Formation (Georgia, U.S.A.) takes place under thoroughly leached, oxidizing conditions. At the earliest stage of weathering, corrosion of hornblende forms denticulated terminations, with only minimal porosity apparent within the partially pseudomorphic kaolin-group weathering product or between it and the reactant mineral. Isovolumetric replacement of hornblende by kaolin-group clay or precursor products implies inheritance of parent-mineral silica tetrahedra by the weathering products and largely immobile behavior of Si during early weathering. Aluminum, normally considered immobile or minimally mobile during weathering, must be imported into early-stage weathering products. More advanced weathering of hornblende forms denticulated terminations, separated from the earlier-formed products by a large, continuous peripheral void; porosity is much more conspicuous at this stage. Late-stage ferruginous products precipitate from Fe mobilized in solution. Dissolved Fe to form the late-stage goethite can be entirely derived from the parent hornblende, requiring only short transport distances for aqueous Fe between the source parent mineral and the location of product precipitation. Textural and volumetric relationships between naturally weathered hornblende and its partially pseudomorphic weathering products suggest structurally controlled immobility of much parent-mineral Si and considerable mobilization of Al at early stages of weathering, but at more advanced stages of weathering the textural and volumetric relationships are consistent with immobility of Al and Fe and leaching of substantial Si and all base cations. [ABSTRACT FROM AUTHOR]

Abstract: Solute-based geochemical mass balance methods are commonly used in small-watershed studies to estimate rates of a variety of geochemical processes at the Earth’s surface, including primary-mineral weathering and soil formation, and the quantitative contribution of these elemental transfer processes to cation budgets, nutrient cycling, and landscape susceptibility to acid deposition. Weathering rates of individual minerals in watershed mass-balance studies are determined by solving a system of simultaneous linear geochemical mass-balance equations with constant (stoichiometric) coefficients. These equations relate the measured net fluxes to the (known) stoichiometries and (unknown) rates of weathering reactions for multiple minerals in the weathering profiles. Solving the system of equations requires petrologic, mineralogic, hydrologic, botanical, and aqueous geochemical data. The number of mineral-weathering rates that can be determined is limited by the number of elements for which solute mass-balance equations can be written. In addition to calculating mineral weathering rates, elemental transfer into or out of the biomass may also be calculated. Elemental uptake by aggrading forest vegetation can act as an intrawatershed sink for at least some mineral-derived cations, producing mineral weathering rates higher than would be estimated from solute fluxes alone; similarly, element release from decaying forest biomass can result in higher solute fluxes than are produced by weathering alone. The mathematics of, significant contributions from, role of biomass in, and recent advances in, watershed geochemical mass-balance methods are discussed using examples from the Appalachian headwaters watersheds of the Coweeta Hydrologic Laboratory in the southern Blue Ridge Physiographic Province of North Carolina, USA. [Copyright &y& Elsevier]

Rates of clay formation in three watersheds located at the Coweeta Hydrologic Laboratory, western North Carolina, have been determined from solute flux-based mass balance methods. A system of mass balance equations with enough equations and unknowns to allow calculation of secondarymineral formation rates as well as the more commonly determined primary-mineral dissolution rates was achieved by including rare earth elements (REE) in the mass balance. Rates of clay-mineral formation determined by mass balance methods have been used to calculate the time needed for a 5% (50 g kg-1) change in relative clay abundance in the saprolite at Coweeta; this corresponds to the "response time" of the clay mineral to, for example, a change in climate. The 5% change in relative clay abundance is the smallest change that can generally be detected using X-ray diffraction (XRD). Response times range from tens of thousands to hundreds of thousands of years. Extrapolating the Coweeta clay formation rates to other southern Appalachian regoliths, the time required to form measured clay abundances ("production times") in eastern Blue Ridge and Inner Piedmont regolith have been calculated. The production times of clay-mineral assemblages range from 2 k.y. to 2 m.y., with mean values ranging from 50 k.y. to 1 m.y. The results of this study are consistent with the arguments of Thiry (2000) that the best resolution of the paleoclimatic record in marine clay-rich sediments and mudrocks is ∼1 or 2 m.y. [ABSTRACT FROM AUTHOR]

Allanite and epidote occur in the parent rocks of weathered regolith at the Coweeta Hydrologic Laboratory in North Carolina and exhibit different responses to weathering. Petrographically, epidote and allanite are identical at Coweeta, and only with additional analytical techniques (e.g., EDS or LA-ICP-MS) can the two be distinguished. Allanite is more abundant in unweathered bedrock but weathers readily below the weathering front. In contrast, the much less abundant epidote persists into the solum with only minimal evidence of weathering. The rapid dissolution of allanite is likely influenced by its metamict nature. Both epidote and allanite at Coweeta dissolve by interface-controlled dissolution kinetics, evidenced by etch pits on grain surfaces. Etch pits appear to be either large "negative crystals," or small, shallow, and elongated. The incipient stage of allanite weathering is characterized by Al mobility and Fe precipitation as goethite. During the initial stage of allanite weathering, carbonate precipitates, but with progressive weathering the carbonate is dissolved. Based on electron microprobe analyses and point-count data of the Ca-bearing phases in the Coweeta bedrock, accessory (<1%) allanite contains a minimum of approximately 25% of the total bedrock Ca by volume, whereas garnet and plagioclase contain 5% and 70%, respectively. Although allanite and epidote are Ca-hosts, only allanite is present in significant quantities, and is weathering sufficiently rapidly, to serve as an important source of Ca in pore and stream waters at Coweeta. Allanite weathering should, therefore, be evaluated in weathering studies of crystalline silicate bedrock, especially where other lines of evidence indicate the need to invoke additional Ca sources. [ABSTRACT FROM AUTHOR]

Chemical weathering indices are commonly used for characterizing weathering profiles by incorporating bulk major element oxide chemistry into a single metric for each sample. Generally, on homogeneous parent rocks, weathering indices change systematically with depth. However, the weathering of heterogeneous metamorphic rocks confounds the relationship between weathering index and depth. In this paper, we evaluate previously defined chemical weathering indices for their suitability in characterizing weathering profiles developed on felsic, heterogeneous, metasedimentary bedrock from Coweeta Hydrologic Laboratory, North Carolina, USA.Among the weathering indices evaluated here, the Weathering Index of Parker (WIP) is the most appropriate for application to weathering profiles on heterogeneous (and homogeneous) parent rock. Because the WIP includes only the highly mobile alkali and alkaline earth elements in its formulation, it yields values that differ greatly from those of the parent rock. In addition, the WIP allows for aluminum mobility, unlike other weathering indices. These characteristics combine to make the Weathering Index of Parker the most applicable index for studying the weathering of heterogeneous metasedimentary rocks. However, the WIP should be applied judiciously, as alkali and alkaline earth metals may be readily depleted during weathering.In addition to reflecting weathering, the Chemical Index of Alteration (CIA), Chemical Index of Weathering (CIW), Plagioclase Index of Alteration (PIA) and Vogt''s Residual Index (V) may be sensitive to subtle geochemical changes such as hydrothermal alteration along a fault and/or alteration at the water table. Weathering indices that include iron in their calculations were not included in this study, because they do not distinguish between ferric and ferrous iron. The oxidation state and distribution of iron in a weathering profile is influenced by the proportion of oxidation states in the pre-weathered metamorphic rock and interaction with groundwater during weathering. [Copyright &y& Elsevier]

Trace element mobility has been studied in spheroidally weathered corestone–shell complexes developed on Late Tertiary and Quaternary volcanic rocks. The parent materials are basalts and andesites related to (1) a subduction zone (Tecuamburro and Moyuta Volcanoes, Guatemala) and (2) a hot spot (Hawaiian Islands of Oahu, Maui and Hawai''i). The initial major element compositions are largely preserved in the corestones; each corestone sample shows major element abundances characteristic of the different magmatic processes through which the lavas were generated. However, the changes in trace element compositions due to weathering show similar patterns in the corestone–shell complexes independent of the tectonic setting and age.Element mobility within the different corestone–shell complex was determined using an isovolumetric reference frame. In this method, bulk density is chosen as an independent measure of the extent of weathering. Based on volumetric concentrations, the notion of element immobility cannot be applied to all the corestone–shell complexes. Elements commonly assumed to be immobile (e.g., Zr, Ti, and Al) vary in volumetric concentration for some corestone–shell complex. Despite petrographic evidence of only minor weathering, two corestones (Oahu and Tecuamburro) have become enriched in REE3+ relative to other lava flows from the same volcanoes, and display negative Ce anomalies. The exfoliated shells from these complexes tend to have lower concentrations of REE3+, and have positive Ce anomalies. The fractionation of Ce from the other rare earth elements (REE) is inferred to be a manifestation of changes in the valence state of Ce from trivalent to tetravalent under oxidizing conditions. In settings where the development of corestone–shell complex is advanced, an acidic solution can mobilize trivalent REE, leach them out of more extensively weathered materials, and transport them to less acidic portions of the regolith undergoing incipient weathering. The precipitation of the REE3+ in the rinds and centers of the corestones are likely due to increases of the pH of the weathering solution. Systematic weathering-induced REE behavior (enrichment of most REE, with lesser Ce enrichment resulting in a negative Ce anomaly) can be discerned even in corestone samples that exhibit major element abundances and petrographic features otherwise similar to unweathered basalts and andesites. [Copyright &y& Elsevier]

Examines bond strength and relative weathering rates of orthosilicates. Components of natural orthosilicates; Comparison between the bonding rate of the silicates; Function of reactant-product molar-volume ratios in the formation protective surface layers; Correlation of protective layer formation with the weathering rates of common orthosilicates.

Studies the factors affecting the formation of a protective surface layer during silicate-mineral weathering. Silicate weathering; Behavior of elements normally considered immobile; Volume ratio of product to reactant.

Reports on the Arrhenius activation energy of feldspar weathering from natural systems. Weathering rates for minerals as determined by geochemical mass balance; Approximations in the calculations; Stream water samples; Feedback on long-term greenhouse warming.

Imbricate wedge marks (facets) on garnets in sandstones of the Cambrian Munising Formation of northern Michigan are associated with mouldic secondary porosity developed at the expense of garnet. Mouldic pores surrounding faceted garnets indicate that garnets in these sandstones have been affected by intrastratal dissolution (retreat of the mineral surface from its original boundaries) rather than by grain enlargement, which would be expected if garnet overgrowths had formed. The association of garnet facets with textural evidence of garnet dissolution proves that garnet facets form by intrastratal dissolution. These results confirm similar findings in other recent studies, and extend the geographic and stratigraphic range or proven occurrences of facet formation by intrastratal dissolution. [ABSTRACT FROM AUTHOR]

Examines the crystallographic control of the natural weathering of staurolite. Crystallographic and crystal-chemical control of staurolite etching; Evidence for formation of protective surface layers; Staurolite weathering relative to other silicate minerals.

Abstract: Microdenticles (with lengths in the micron-submicron range rather than tens of microns) are developed on the lateral surfaces of larger “classic” denticles on naturally weathered hornblende from weathered amphibolite of the Carroll Knob Complex in western North Carolina. Microdenticles share the shape and orientation of the larger more typical denticles, producing arrays of microdenticles that give the larger host denticle the appearance of a surface covered with imbricate pointed or rounded scales. The arrays of imbricate microdenticles are formed by low-temperature aqueous alteration during weathering of the Carroll Knob Complex hornblende; they are later-stage corrosion forms on already-corroded surfaces of hornblende that show larger-scale evidence of typical weathering. In the Carroll Knob occurrence, hornblende microdenticles are associated with dilute weathering solutions, suggesting possible control by extreme undersaturation of solutions with respect to hornblende. [Copyright &y& Elsevier]

An introduction is presented in which the editor discusses the crystallography on planet Mars.

The document titled "Thresholds of Temperature and Time for Mars Sample Return: Final Report of the Mars Sample Return Temperature-Time Tiger Team" provides valuable information on the potential risks and effects of exposing Mars Sample Return (MSR) samples to specific temperature ranges. The report was conducted by a team of scientists from various disciplines to assess the impact of temperature on the integrity and scientific value of the samples. It discusses the potential reactions and processes that may occur when samples collected from Mars are heated, including the release of volatiles, chemical reactions, and effects on inorganic and organic materials. The document also emphasizes the importance of preserving hydrated minerals and the potential impact of temperature changes on the scientific analysis and interpretation of the samples. Additionally, it discusses the potential risks and challenges associated with the MSR mission, including the presence of terrestrial contaminants and the assessment of potential Martian life in the samples. Overall, this document provides valuable insights for library patrons conducting research on Mars Sample Return and the impact of temperature on sample preservation and scientific analysis. [Extracted from the article]

Various approaches have been used to estimate when and how long liquid water was present at the surface of Mars. The olivine dissolution-lifetime application suggested by Stopar et al. (2006) and Olsen and Rimstidt (2007) is here adapted and tested at the scale of individual etch-pits using published data from an experimental system in which the volume of mineral removed and the duration of the mineral removal episode are known. Different assumptions about the specific geometry of etch-pits on olivine result in surface-area estimates that vary by less than a factor of two from the simple hemispherical pit used in the calculations. Given that other sources of uncertainty in mass-time relationships of silicate-mineral dissolution during natural weathering can be up to four orders of magnitude, the effects of differing geometric assumptions about the shapes and surface areas of the etch-pits are negligible. Using compiled experimentally determined forsterite dissolution rates and the imaged etch-pit sizes from experiments recovers the duration of the experiment that produced the imaged etch-pits to within less than a factor of two. This suggests that extensively etched olivine surfaces imply a dominance of the etch-pit walls over the bulk surface between the etch-pits during olivine corrosion. The approach adopted here recovers the timescales of experimental etch-pit production on olivine at STP and extreme undersaturation of the solution with respect to olivine in experiments where pH is known. Continued progress in understanding the fundamentals of olivine dissolution kinetics will narrow the ranges of uncertainty in mineral-lifetime estimates at Mars' surface in support of constraining the compositions and duration of potentially habitable aqueous solutions on Mars [ABSTRACT FROM AUTHOR]

A letter to the editor is presented regarding National Aeronautics and Space Administration (NASA)'s Mars Science Laboratory or Curiosity imager which aims to see silt-sized grains on Mars.

Abstract: Many etch-pits on olivine grains occur as a pair of cone-shaped pits sharing a base, which consequently appear as diamond-shaped etch-pits in cross-section. Quantitative image analysis of back-scattered electron images establishes empirical dimensions of olivine etch-pits in naturally weathered samples from Hawaii and North Carolina. Images of naturally etched olivine were acquired from polished thin-sections by scanning electron microscopy. An average cone-radius-to-height ratio (r:h) of 1.78 was determined for diamond-shaped cross-sections of etch-pits occurring in naturally weathered olivine grains, largely consistent with previous qualitative results. Olivine etch-pit shape as represented by r:h varies from slightly more than half the average value to slightly more than twice the average. Etch-pit shape does not appear to vary systematically with etch-pit size. [Copyright &y& Elsevier]

Gypsum, a mineral that requires water to form, is common on the surface of Mars. Most of it originated before 3.5 Gyr when the Red Planet was more humid than now. However, occurrences of gypsum dune deposits around the North Polar Residual Cap (NPRC) seem to be surprisingly young: late Amazonian in age. This shows that liquid water was present on Mars even at times when surface conditions were as cold and dry as the present-day. A recently proposed mechanism for gypsum formation involves weathering of dust within ice (e.g., Niles, P.B., Michalski, J. [2009]. Nat. Geosci. 2, 215–220.). However, none of the previous studies have determined if this process is possible under current martian conditions. Here, we use numerical modelling of heat transfer to show that during the warmest days of the summer, solar irradiation may be sufficient to melt pure water ice located below a layer of dark dust particles (albedo ⩽ 0.13) lying on the steepest sections of the equator-facing slopes of the spiral troughs within martian NPRC. During the times of high irradiance at the north pole (every 51 ka; caused by variation of orbital and rotational parameters of Mars e.g., Laskar, J. et al. [2002]. Nature 419, 375–377.) this process could have taken place over larger parts of the spiral troughs. The existence of small amounts of liquid water close to the surface, even under current martian conditions, fulfils one of the main requirements necessary to explain the formation of the extensive gypsum deposits around the NPRC. It also changes our understanding of the degree of current geological activity on Mars and has important implications for estimating the astrobiological potential of Mars. [ABSTRACT FROM AUTHOR]

Samples returned from Mars would be placed under quarantine at a Sample Receiving Facility (SRF) until they are considered safe to release to other laboratories for further study. The process of determining whether samples are safe for release, which may involve detailed analysis and/or sterilization, is expected to take several months. However, the process of breaking the sample tube seal and extracting the headspace gas will perturb local equilibrium conditions between gas and rock and set in motion irreversible processes that proceed as a function of time. Unless these time-sensitive processes are understood, planned for, and/or monitored during the quarantine period, scientific information expected from further analysis may be lost forever. At least four processes underpin the time-sensitivity of Mars returned sample science: (1) degradation of organic material of potential biological origin, (2) modification of sample headspace gas composition, (3) mineral-volatile exchange, and (4) oxidation/reduction of redox-sensitive materials. Available constraints on the timescales associated with these processes supports the conclusion that an SRF must have the capability to characterize attributes such as sample tube headspace gas composition, organic material of potential biological origin, as well as volatiles and their solid-phase hosts. Because most time-sensitive investigations are also sensitive to sterilization, these must be completed inside the SRF and on timescales of several months or less. To that end, we detail recommendations for how sample preparation and analysis could complete these investigations as efficiently as possible within an SRF. Finally, because constraints on characteristic timescales that define time-sensitivity for some processes are uncertain, future work should focus on: (1) quantifying the timescales of volatile exchange for core material physically and mineralogically similar to samples expected to be returned from Mars, and (2) identifying and developing stabilization or temporary storage strategies that mitigate volatile exchange until analysis can be completed. Executive Summary: Any samples returned from Mars would be placed under quarantine at a Sample Receiving Facility (SRF) until it can be determined that they are safe to release to other laboratories for further study. The process of determining whether samples are safe for release, which may involve detailed analysis and/or sterilization, is expected to take several months. However, the process of breaking the sample tube seal and extracting the headspace gas would perturb local equilibrium conditions between gas and rock and set in motion irreversible processes that proceed as a function of time. Unless these processes are understood, planned for, and/or monitored during the quarantine period, scientific information expected from further analysis may be lost forever. Specialist members of the Mars Sample Return Planning Group Phase 2 (MSPG-2), referred to here as the Time-Sensitive Focus Group, have identified four processes that underpin the time-sensitivity of Mars returned sample science: (1) degradation of organic material of potential biological origin, (2) modification of sample headspace gas composition, (3) mineral-volatile exchange, and (4) oxidation/reduction of redox-sensitive materials (Figure 2). Consideration of the timescales and the degree to which these processes jeopardize scientific investigations of returned samples supports the conclusion that an SRF must have the capability to characterize: (1) sample tube headspace gas composition, (2) organic material of potential biological origin, (3) volatiles bound to or within minerals, and (4) minerals or other solids that host volatiles (Table 4). Most of the investigations classified as time-sensitive in this report are also sensitive to sterilization by either heat treatment and/or gamma irradiation (Velbel et al., 2022). Therefore, these investigations must be completed inside biocontainment and on timescales that minimize the irrecoverable loss of scientific information (i.e., several months or less; Section 5). To that end, the Time-Sensitive Focus Group has outlined a number of specific recommendations for sample preparation and instrumentation in order to complete these investigations as efficiently as possible within an SRF (Table 5). Constraints on the characteristic timescales that define time-sensitivity for different processes can range from relatively coarse to uncertain (Section 4). Thus, future work should focus on: (1) quantifying the timescales of volatile exchange for variably lithified core material physically and mineralogically similar to samples expected to be returned from Mars, and (2) identifying and developing stabilization strategies or temporary storage strategies that mitigate volatile exchange until analysis can be completed. List of Findings: FINDING T-1: Aqueous phases, and oxidants liberated by exposure of the sample to aqueous phases, mediate and accelerate the degradation of critically important but sensitive organic compounds such as DNA. FINDING T-2: Warming samples increases reaction rates and destroys compounds making biological studies much more time-sensitive. MAJOR FINDING T-3: Given the potential for rapid degradation of biomolecules, (especially in the presence of aqueous phases and/or reactive O-containing compounds) Sample Safety Assessment Protocol (SSAP) and parallel biological analysis are time sensitive and must be carried out as soon as possible. FINDING T-4: If molecules or whole cells from either extant or extinct organisms have persisted under present-day martian conditions in the samples, then it follows that preserving sample aliquots under those same conditions (i.e., 6 mbar total pressure in a dominantly CO2 atmosphere and at an average temperature of -80°C) in a small isolation chamber is likely to allow for their continued persistence. FINDING T-5: Volatile compounds (e.g., HCN and formaldehyde) have been lost from Solar System materials stored under standard curation conditions. FINDING T-6: Reactive O-containing species have been identified in situ at the martian surface and so may be present in rock or regolith samples returned from Mars. These species rapidly degrade organic molecules and react more rapidly as temperature and humidity increase. FINDING T-7: Because the sample tubes would not be closed with perfect seals and because, after arrival on Earth, there will be a large pressure gradient across that seal such that the probability of contamination of the tube interiors by terrestrial gases increases with time, the as-received sample tubes are considered a poor choice for long-term gas sample storage. This is an important element of time sensitivity. MAJOR FINDING T-8: To determine how volatiles may have been exchanged with headspace gas during transit to Earth, the composition of martian atmosphere (in a separately sealed reservoir and/or extracted from the witness tubes), sample headspace gas composition, temperature/time history of the samples, and mineral composition (including mineral-bound volatiles) must all be quantified. When the sample tube seal is breached, mineral-bound volatile loss to the curation atmosphere jeopardizes robust determination of volatile exchange history between mineral and headspace. FINDING T-9: Previous experiments with mineral powders show that sulfate minerals are susceptible to H2O loss over timescales of hours to days. In addition to volatile loss, these processes are accompanied by mineralogical transformation. Thus, investigations targeting these minerals should be considered time-sensitive. FINDING T-10: Sulfate minerals may be stabilized by storage under fixed relative-humidity conditions, but only if the identity of the sulfate phase(s) is known a priori. In addition, other methods such as freezing may also stabilize these minerals against volatile loss. FINDING T-11: Hydrous perchlorate salts are likely to undergo phase transitions and volatile exchange with ambient surroundings in hours to days under temperature and relative humidity ranges typical of laboratory environments. However, the exact timescale over which these processes occur is likely a function of grain size, lithification, and/or cementation. FINDING T-12: Nanocrystalline or X-ray amorphous materials are typically stabilized by high proportions of surface adsorbed H2O. Because this surface adsorbed H2O is weakly bound compared to bulk materials, nanocrystalline materials are likely to undergo irreversible ripening reactions in response to volatile loss, which in turn results in decreases in specific surface area and increases in crystallinity. These reactions are expected to occur over the timescale of weeks to months under curation conditions. Therefore, the crystallinity and specific surface area of nanocrystalline materials should be characterized and monitored within a few months of opening the sample tubes. These are considered time-sensitive measurements that must be made as soon as possible. FINDING T-13: Volcanic and impact glasses, as well as opal-CT, are metastable in air and susceptible to alteration and volatile exchange with other solid phases and ambient headspace. However, available constraints indicate that these reactions are expected to proceed slowly under typical laboratory conditions (i.e., several years) and so analyses targeting these materials are not considered time sensitive. FINDING T-14: Surface adsorbed and interlayer-bound H2O in clay minerals is susceptible to exchange with ambient surroundings at timescales of hours to days, although the timescale may be modified depending on the degree of lithification or cementation. Even though structural properties of clay minerals remain unaffected during this process (with the exception of the interlayer spacing), investigations targeting H2O or other volatiles bound on or within clay minerals should be considered time sensitive upon opening the sample tube. FINDING T-15: Hydrated Mg-carbonates are susceptible to volatile loss and recrystallization and transformation over timespans of months or longer, though this timescale may be modified by the degree of lithification and cementation. Investigations targeting hydrated carbonate minerals (either the volatiles they host or their bulk mineralogical properties) should be considered time sensitive upon opening the sample tube. MAJOR FINDING T-16: Current understanding of mineral-volatile exchange rates and processes is largely derived from monomineralic experiments and systems with high surface area; lithified sedimentary rocks (accounting for some, but not all, of the samples in the cache) will behave differently in this regard and are likely to be associated with longer time constants controlled in part by grain boundary diffusion. Although insufficient information is available to quantify this at the present time, the timescale of mineral-volatile exchange in lithified samples is likely to overlap with the sample processing and curation workflow (i.e., 1-10 months; Table 4). This underscores the need to prioritize measurements targeting mineral-hosted volatiles within biocontainment. FINDING T-17: The liberation of reactive O-species through sample treatment or processing involving H2O (e.g., rinsing, solvent extraction, particle size separation in aqueous solution, or other chemical extraction or preparation protocols) is likely to result in oxidation of some component of redox-sensitive materials in a matter of hours. The presence of reactive O-species should be examined before sample processing steps that seek to preserve or target redox-sensitive minerals. Electron paramagnetic resonance spectroscopy (EPR) is one example of an effective analytical method capable of detecting and characterizing the presence of reactive O-species. FINDING T-18: Environments that maintain anoxia under inert gas containing <<1 ppm O2 are likely to stabilize redox-sensitive minerals over timescales of several years. MAJOR FINDING T-19: MSR investigations targeting organic macromolecular or cellular material, mineral-bound volatile compounds, redox sensitive minerals, and/or hydrous carbonate minerals can become compromised at the timescale of weeks (after opening the sample tube), and scientific information may be completely lost within a time timescale of a few months. Because current considerations indicate that completion of SSAP, sample sterilization, and distribution to investigator laboratories cannot be completed in this time, these investigations must be completed within the Sample Receiving Facility as soon as possible. [ABSTRACT FROM AUTHOR]

Abstract: Nakhlite Miller Range (MIL) 03346 contains many secondary phases resulting from aqueous processes, including formation of poorly crystalline iddingsite-like veins in olivine, the precipitation of Ca-sulfates and Fe,K-sulfates from evaporating fluids, alteration of titanomagnetite to secondary Fe-oxides, and the dissolution of magmatic Ca-phosphates and residual glass in the mesostasis. A surprising variety of alteration products occur in association with olivine in MIL 03346, including: patches of incipiently-altered olivine, large Si-enriched olivine-hosted veins (up to 10μm across) some of which are complex in morphology and are composed of several phases, small Fe,S(±K)-rich veinlets that crosscut the Si-enriched veins, Ca-sulfates filling cracks in olivine, and secondary Ca-phosphates. Elemental abundances and distributions in these alteration products are consistent with the mobilization of elements from readily dissolved phases in the mesostasis such as phosphates and residual glass. Under favorable weathering conditions, these phases dissolve more readily than pyroxenes, plagioclase, and even olivine at low pH. The occurrence (crosscut and devolatilized by the fusion crust) and composition of Si-enriched alteration veins in olivine are consistent with their formation on Mars. Si-enriched, poorly crystalline alteration products and secondary Ca-sulfates commonly occur in nakhlites, but the habit and composition of these alteration products differ between meteorites. Elemental distributions in these secondary phases suggest at least two episodes of alteration have affected MIL 03346, and subtle differences in secondary minerals and chemistry indicate that each nakhlite experienced its own unique alteration history either on Mars, Earth, or both. The variable Al content and range of morphologies of the olivine-hosted Si-enriched veins suggest variable alteration conditions consistent with a water-limited regime. If the secondary phases in MIL 03346 can be shown to have formed on Mars, their chemistry will provide important clues to the aqueous environments and processes at the time of their formation. However, elevated S and REEs, Ce anomalies, and association of secondary minerals with post-impact cracks and voids indicate that terrestrial weathering has significantly affected MIL 03346. This work highlights the difficulty in distinguishing pre-terrestrial aqueous alteration from later chemical weathering of susceptible mineral phases even in meteorites with limited terrestrial modification. [Copyright &y& Elsevier]

Abstract: The Dry Valleys of Antarctica are an excellent analog of the environment at the surface of Mars. Soil formation histories involving slow processes of sublimation and migration of water-soluble ions in polar desert environments are characteristic of both Mars and the Dry Valleys. At the present time, the environment in the Dry Valleys is probably the most similar to that in the mid-latitudes on Mars although similar conditions may be found in areas of the polar regions during their respective Mars summers. It is thought that Mars is currently in an interglacial period, and that subsurface water ice is sublimating poleward. Because the Mars sublimation zones seem to be the most similar to the Antarctic Dry Valleys, the Dry Valleys-type Mars climate is migrating towards the poles. Mars has likely undergone drastic obliquity changes, which means that the Dry Valleys analog to Mars may be valid for large parts of Mars, including the polar regions, at different times in geologic history. Dry Valleys soils contain traces of silicate alteration products and secondary salts much like those found in Mars meteorites. A martian origin for some of the meteorite secondary phases has been verified previously; it can be based on the presence of shock effects and other features which could not have formed after the rocks were ejected from Mars, or demonstrable modification of a feature by the passage of the meteorite through Earth''s atmosphere (proving the feature to be pre-terrestrial). The martian weathering products provide critical information for deciphering the near-surface history of Mars. Definite martian secondary phases include Ca-carbonate, Ca-sulfate, and Mg-sulfate. These salts are also found in soils from the Dry Valleys of Antarctica. Results of earlier Wright Valley work are consistent with what is now known about Mars based on meteorite and orbital data. Results from recent and current Mars missions support this inference. Aqueous processes are active even in permanently frozen Antarctic Dry Valleys soils, and similar processes are probably also occurring on Mars today, especially at the mid-latitudes. Both weathering products and life in Dry Valleys soils are distributed heterogeneously. Such variations should be taken into account in future studies of martian soils and also in the search for possible life on Mars. [Copyright &y& Elsevier]

Weathering can be used as a highly effective relative age indicator. One such application involves etching of hornblende grains in soils. Etching increases with time (duration) and decreases with depth in soils and surficial sediments. Other variables, related to intensity of weathering and soil formation, are generally held as constant as possible so as to only minimally influence the time–etching relationship. Our study focuses on one of the variables usually held constant—climate—by examining hornblende etching and quartz/feldspar ratios in soils of similar age but varying degrees of development due to climatic factors. We examined the assumption that the degree of etching varies as a function of soil development, even in soils of similar age. The Spodosols we studied form a climate-mediated development sequence on a 13,000-yr-old outwash plain in Michigan. Their pedogenic development was compared to weathering-related data from the same soils. In general, soils data paralleled weathering data. Hornblende etching was most pronounced in the A and E horizons, and decreased rapidly with depth. Quartz/feldspar ratios showed similar but more variable trends. In the two most weakly developed soils, the Q/F ratio was nearly constant with depth, implying that this ratio may not be as effective a measure as are etching data for minimally weathered soils. Our data indicate that hornblende etching should not be used as a stand-alone relative age indicator, especially in young soils and in contexts where the degree of pedogenic variability on the geomorphic surface is large. [Copyright &y& Elsevier]

Cosmic ray exposure (CRE) ages of CM chondrites have been found to have multiple peaks (as many as four), in stark contrast to other groups of chondrites (Nishiizumi and Caffee 2012; Herzog and Caffee 2014). In this study, we sought correlations between the CRE ages and petrography of CM chondrites, and we conclude that the degree of aqueous alteration does appear to vary with the CRE ages—the CMs displaying the most aqueous alteration all have relatively short exposure ages. However, some CMs with low degrees of alteration also have short exposure ages—thus, this apparent correlation is not exclusive. We also found a definite inverse relation between the number of distinctive lithologies in a CM and its exposure age, which could indicate different responses of homogeneous and heterogeneous meteoroids to the space environment between their onset of exposure (exhumation and ejection from the parent body) and arrival at Earth. Breccias have more internal surfaces of lithologic discontinuity, possibly resulting in weaker meteoroids that disintegrate more readily than their more homogeneous counterparts. Our results suggest that CM chondrite regoliths consist of numerous genomict lithologies in a breccia with millimeter‐ to decimeter‐scale clasts, with varying degree of heating/metamorphism. [ABSTRACT FROM AUTHOR]

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

The bulk of the comet 81P/Wild 2 (hereafter Wild 2) samples returned to Earth by the Stardust spacecraft appear to be weakly constructed mixtures of nanometer-scale grains, with occasional much larger (over 1 micrometer) ferromagnesian silicates, Fe-Ni sulfides, Fe-Ni metal, and accessory phases. The very wide range of olivine and low-Ca pyroxene compositions in comet Wild 2 requires a wide range of formation conditions, probably reflecting very different formation locations in the protoplanetary disk. The restricted compositional ranges of Fe-Ni sulfides, the wide range for silicates, and the absence of hydrous phases indicate that comet Wild 2 experienced little or no aqueous alteration. Less abundant Wild 2 materials include a refractory particle, whose presence appears to require radial transport in the early protoplanetary disk. [ABSTRACT FROM AUTHOR]