Soluble organic compounds in the Tagish Lake meteorite

The C2 ungrouped Tagish Lake meteorite preserves a range of lithologies, reflecting variable degrees of parent‐body aqueous alteration. Here, we report on soluble organic compounds, including aliphatic and aromatic hydrocarbons, monocarboxylic acids, and amino acids, found within specimens representative of the range of aqueous alteration. We find that differences in soluble organic compounds among the lithologies may be explained by oxidative, fluid‐assisted alteration, primarily involving the derivation of soluble organic compounds from macromolecular material. In contrast, amino acids probably evolved from precursor molecules, albeit in parallel with other soluble organic compounds. Our results demonstrate the role of parent‐body alteration in the modification of organic matter and generation of prebiotic compounds in the early solar system, and have implications for interpretation of the complement of soluble organic compounds in carbonaceous chondrites.     

Estimated optical constants of the Tagish Lake meteorite

Abstract— The visible, near‐infrared, and mid‐infrared (0.3–25 μm) real and imaginary indices of refraction are derived from reflectance measurements of the Tagish Lake meteorite. These are compared to some real and imaginary indices of refraction of the individual minerals composing the Tagish Lake meteorite. From this comparison, it is clear that the imaginary indices of several individual minerals contribute to the estimated imaginary index of this meteorite.     

Magnetic study of magnetite in the Tagish Lake meteorite

Abstract— The saturation magnetization, saturation remanent magnetization, the coercive, and remanent coercive force were determined at room and liquid nitrogen temperatures for three pieces of the Tagish Lake meteorite. The results are compared to similar data for four other chondrites (Allende, Murray, Orgueil, and Murchison). The data suggests that the Tagish Lake meteorite is magnetically homogeneous, and is not as magnetically hard as the comparison chondrites. The magnetization measurements indicate that it contains about 10–11% multi‐domain magnetite. Magnetic susceptibility measurements on all the samples from 77 K to room temperature showed a Verwey transition for all the samples which contain a significant amount of multi‐domain magnetite. The coercive force data further indicate that the magnetite in Tagish Lake is multi‐domain and that the grain size is small and approximately 4–9 μm.     

The fall and recovery of the Tagish Lake meteorite

Abstract— The Tagish Lake C2 (ungrouped) carbonaceous chondrite fall of January 18, 2000, delivered ?10 kg of one of the most primitive and physically weak meteorites yet studied. In this paper, we report the detailed circumstances of the fall and the recovery of all documented Tagish Lake fragments from a strewnfield at least 16 km long and 3 to 4 km wide. Nearly 1 kg of “pristine” meteorites were collected one week after the fall before new snow covered the strewnfield; the majority of the recovered mass was collected during the spring melt. Ground eyewitnesses and a variety of instrument‐recorded observations of the Tagish Lake fireball provide a refined estimate of the fireball trajectory. From its calculated orbit and its similarity to the remotely sensed properties of the D‐ and P‐class asteroids, the Tagish Lake carbonaceous chondrite apparently represents these outer belt asteroids. The cosmogenic nuclide results and modeled production indicate a prefall radius of 2.1–2.4 m (corresponding to 60–90 tons) consistent with the observed fireball energy release. The bulk oxygen‐isotope compositions plot just below the terrestrial fractionation line (TFL), following a trend similar to the CM meteorite mixing line. The bulk density of the Tagish Lake material (1.64 ± 0.02 g/cm³) is the same, within uncertainty, as the total bulk densities of several C‐class and especially D‐ and P‐class asteroids. The high microporosity of Tagish Lake samples (?40%) provides an obvious candidate material for the composition of low bulk density primitive asteroids.     

Cold curation of pristine astromaterials: Insights from the Tagish Lake meteorite

The curation and handling of volatile‐bearing astromaterials is of prime importance in current and future plans for sample return missions to targets containing organic compounds, ices, or other volatile components. We report on the specific curation constraints required for the preservation of the Tagish Lake meteorite, a C2 ungrouped chondrite that contains significant concentrations of organic matter, including compounds of prebiotic interest or volatile in character, and which was recovered from a frozen lake surface a few days after its fall. Here, we review the circumstances of the meteorite's handling, its complement of intrinsic and contaminant organic compounds, and an unusual reaction between some of the specimens and the Al foil in which they were enclosed. From our results, we derive the requirements for curation of the meteorite, and describe a specialized facility that enables its curation and handling. The Subzero Facility for Curation of Astromaterials consists of a purified Ar glove box enclosed within a freezer chamber, and enables investigations relevant to curation of samples at or below ?10 °C. We provide several recommendations based on insights obtained from the commissioning and initial use of the facility that are relevant to collection of freshly fallen meteorites, curation of volatile‐bearing meteorites and other astromaterials, and planning and implementation of curation plans for future sample return missions to volatile‐bearing targets.     

Unusual nonterrestrial l‐proteinogenic amino acid excesses in the Tagish Lake meteorite

Abstract– The distribution and isotopic and enantiomeric compositions of amino acids found in three distinct fragments of the Tagish Lake C2‐type carbonaceous chondrite were investigated via liquid chromatography with fluorescence detection and time‐of‐flight mass spectrometry and gas chromatography isotope ratio mass spectrometry. Large l ‐enantiomeric excesses (l _ee ～ 43–59%) of the α‐hydrogen aspartic and glutamic amino acids were measured in Tagish Lake, whereas alanine, another α‐hydrogen protein amino acid, was found to be nearly racemic (d ≈ l ) using both techniques. Carbon isotope measurements of d ‐ and l ‐aspartic acid and d ‐ and l ‐alanine in Tagish Lake fall well outside of the terrestrial range and indicate that the measured aspartic acid enantioenrichment is indigenous to the meteorite. Alternate explanations for the l ‐excesses of aspartic acid such as interference from other compounds present in the sample, analytical biases, or terrestrial amino acid contamination were investigated and rejected. These results can be explained by differences in the solid–solution phase behavior of aspartic acid, which can form conglomerate enantiopure solids during crystallization, and alanine, which can only form racemic crystals. Amplification of a small initial l ‐enantiomer excess during aqueous alteration on the meteorite parent body could have led to the large l ‐enrichments observed for aspartic acid and other conglomerate amino acids in Tagish Lake. The detection of nonterrestrial l ‐proteinogenic amino acid excesses in the Tagish Lake meteorite provides support for the hypothesis that significant enantiomeric enrichments for some amino acids could form by abiotic processes prior to the emergence of life.     

Molecular and isotopic analyses of Tagish Lake alkyl dicarboxylic acids

Abstract— The Tagish Lake meteorite soluble organic suite has a general composition that differs from those of both CI and CM chondrites. These differences suggest that distinct processes may have been involved in the formation of different groups of organics in meteorites. Tagish Lake alkyl dicarboxylic acids have a varied, abundant distribution and are, with carboxylated pyridines, the only compounds to have an occurrence comparable to that of the Murchison meteorite. This study has undertaken their molecular and isotopic characterization, with the aim to understand their origin and to gain insights into the evolutionary history of the meteorite parent body. Tagish Lake alkyl dicarboxylic acids are present as a homologous series of saturated and unsaturated species with three‐ through ten‐carbon atom chain length. Linear saturated acids are predominant and show decreasing amounts with increasing chain length. A total of 44 of these compounds were detected with the most abundant, succinic acid, present at ?40 nmol/g meteorite. Overall the molecular distribution of Tagish Lake dicarboxylic acids shows a remarkable compound‐to‐compound correspondence with those observed in the Murchison and Murray meteorites. In both Tagish Lake and Murchison, the imides of the more abundant dicarboxylic acids were also observed. The hydrogen and carbon isotopic compositions of individual Tagish Lake dicarboxylic acids were determined and compared to those of the corresponding acids in the Murchison meteorite. All δD and δ¹³C values for Tagish Lake acids are positive and show a substantial isotopic enrichment. δD values vary from, approximately, +1120%_o for succinic acid to +1530%_o for methyl glutaric acid. δ¹³C values ranged from +12.6%_o for methyl glutaric acid to +22.9%_o for glutaric acid, with adipic acid having a significantly lower value (+5.5%_o). Murchison dicarboxylic acid showed similar isotopic values: their δ5¹³C values were generally higher by an average 17% and δD values were lower for succinic and glutaric acids, possibly due to contamination. The molecular and isotopic data collected for these compounds restrict their possible origin to processes, either interstellar or of very cold nebular regions, that produced significant isotopic enrichments. Saturated or partially unsaturated nitriles and dinitriles appear to be good precursor candidates as their hydrolysis, upon water exposure, would produce dicarboxylic acids and other carboxylated species found in Tagish Lake. This evolutionary course could possibly include pre‐accretionary processes.     

Water abundance in the Tagish Lake meteorite from TGA and IR spectroscopy: Evaluation of aqueous alteration

Here, we evaluate the extent of aqueous alteration among five pristine specimens of the ungrouped Tagish Lake carbonaceous chondrite (TL5b, TL11h, TL11i, TL4, and TL10a) using thermogravimetric analysis (TGA) and infrared (IR) transmission spectroscopy. Both TGA and IR spectroscopy have proven to be reliable methods for determining the extent of aqueous alteration among different carbonaceous chondrites, in particular the CM chondrites (e.g., Garenne et al. 2014), with which Tagish Lake shares some affinities. Using these two methods, our goal is to incorporate TL4 and TL10a into the known alteration sequence of TL5b < TL11h < TL11i (Herd et al. 2011; Blinova et al. 2014a). This study highlights the compositional variability of the Tagish Lake specimens, which we ascribe to its brecciated nature. Our TGA and IR spectroscopy results are congruent with the reported alteration sequence, allowing us to introduce the TL4 and TL10a specimens in the following order: TL4 < TL5b ≤ TL10a < TL 11h < TL11i. Notably, these two specimens appear to be similar to the least altered lithologies previously reported, and the alteration of Tagish Lake is similar to that experienced by lesser altered members of the CM chondrites (>CM1.6). Based on these findings, Tagish Lake could be considered a 1.6–2.0 ungrouped carbonaceous chondrite. Visible and near‐IR reflectance measurements of Tagish Lake were also acquired in this study to revisit the Tagish Lake parent body connection. While other studies have paired Tagish Lake with D‐ and T‐type asteroid parent bodies, the reflectance spectra acquired in this study are variable among the different Tagish Lake specimens in relation to their alteration sequences; results match with spectra characteristic of C‐, X‐, Xc‐, and D‐type asteroids. The heterogeneity of Tagish Lake coupled with its low albedo makes the parent body connection a challenge.     

Diradicaloids in the insoluble organic matter from the Tagish Lake meteorite: Comparison with the Orgueil and Murchison meteorites

Abstract— The radicals in the insoluble organic matter (IOM) from the Tagish Lake meteorite were studied by electron paramagnetic resonance and compared to those existing in the Orgueil and Murchison meteorites. As in the Orgueil and Murchison meteorites, the radicals in the Tagish Lake meteorite are heterogeneously distributed and comprise a substantial amount (?42%) of species with a thermally accessible triplet state and with the same singlet‐triplet gap, ΔE ?0.1 eV, as in the Orgueil and Murchison meteorites. These species were identified as diradicaloid moieties. The existence of similar diradicaloid moieties in three different carbonaceous chondrites but not in terrestrial IOM strongly suggests that these moieties could be “fingerprints” of the extraterrestrial origin of meteoritic IOM and markers of its synthetic pathway before its inclusion into a parent body.     

New insights into the heterogeneity of the Tagish Lake meteorite: Soluble organic compositions of variously altered specimens

The Tagish Lake carbonaceous chondrite exhibits a unique compositional heterogeneity that may be attributed to varying degrees of aqueous alteration within the parent body asteroid. Previous analyses of soluble organic compounds from four Tagish Lake meteorite specimens (TL5b, TL11h, TL11i, TL11v) identified distinct distributions and isotopic compositions that appeared to be linked to their degree of parent body processing (Herd et al. 2011; Glavin et al. 2012; Hilts et al. 2014). In the present study, we build upon these initial observations and evaluate the molecular distribution of amino acids, aldehydes and ketones, monocarboxylic acids, and aliphatic and aromatic hydrocarbons, including compound‐specific δ¹³C compositions, for three additional Tagish Lake specimens: TL1, TL4, and TL10a. TL1 contains relatively high abundances of soluble organics and appears to be a moderately altered specimen, similar to the previously analyzed TL5b and TL11h lithologies. In contrast, specimens TL4 and TL10a both contain relatively low abundances of all of the soluble organic compound classes measured, similar to TL11i and TL11v. The organic‐depleted composition of TL4 appears to have resulted from a relatively low degree of parent body aqueous alteration. In the case of TL10a, some unusual properties (e.g., the lack of detection of intrinsic monocarboxylic acids and aliphatic and aromatic hydrocarbons) suggest that it has experienced extensive alteration and/or a distinct organic‐depleted alteration history. Collectively, these varying compositions provide valuable new insights into the relationships between asteroidal aqueous alteration and the synthesis and preservation of soluble organic compounds.     

Heating experiments of the Tagish Lake meteorite: Investigation of the effects of short‐term heating on chondritic organics

We present in this study the effects of short‐term heating on organics in the Tagish Lake meteorite and how the difference in the heating conditions can modify the organic matter (OM) in a way that complicates the interpretation of a parent body's heating extent with common cosmothermometers. The kinetics of short‐term heating and its influence on the organic structure are not well understood, and any study of OM is further complicated by the complex alteration processes of the thermally metamorphosed carbonaceous chondrites—potential analogues of the target asteroid Ryugu of the Hayabusa2 mission—which had experienced posthydration, short‐duration local heating. In an attempt to understand the effects of short‐term heating on chondritic OM, we investigated the change in the OM contents of the experimentally heated Tagish Lake meteorite samples using Raman spectroscopy, scanning transmission X‐ray microscopy utilizing X‐ray absorption near edge structure spectroscopy, and ultraperformance liquid chromatography fluorescence detection and quadrupole time of flight hybrid mass spectrometry. Our experiment suggests that graphitization of OM did not take place despite the samples being heated to 900 °C for 96 h, as the OM maturity trend was influenced by the heating conditions, kinetics, and the nature of the OM precursor, such as the presence of abundant oxygenated moieties. Although both the intensity of the 1s?σ* exciton cannot be used to accurately interpret the peak metamorphic temperature of the experimentally heated Tagish Lake sample, the Raman graphite band widths of the heated products significantly differ from that of chondritic OM modified by long‐term internal heating.     

Associations of organic matter with minerals in Tagish Lake meteorite via high spatial resolution synchrotron‐based FTIR microspectroscopy

We have investigated spatial and spectral associations between mineral species and organic matter in the Tagish Lake meteorite. Synchrotron‐based infrared microspectroscopy allowed us to spatially locate specific organic and inorganic compounds within multiple Tagish Lake grains with high spatial resolution. Generated two‐dimensional infrared maps present strong spatial association between aliphatic C‐H and OH in phyllosilicates in Tagish Lake grains. These observations indicate possible roles of phyllosilicates for the formation, evolution, and preservation of organic matter. Infared spectra of all studied Tagish Lake grains show a strong carbonate band, which also shows a weak but positive correlation with organic matter in some grains. However, intergrain correlation was not observed between carbonates and organics, which is likely due to the difference of carbonate occurrence, e.g., presence of larger grains or intergrowth of carbonates on phyllosilicates. Possible scenarios further explaining the observed associations of organics with phyllosilicates and carbonates are presented.     

Fragmentation model analysis of the observed atmospheric trajectory of the Tagish Lake fireball

Abstract— A recently published meteoroid fragmentation model (FM) was applied to observational data on the Tagish Lake meteoric fireball. An initial mass of 56,000 kg, derived from seismic and infrasound data by Brown et al. (2002), proved to be consistent with a very low value of intrinsic ablation coefficient of 0.0009 s² km^?2. The average residual of the best fit to the observed light curve was ±0.10 stellar magnitude. The apparent ablation coefficient varied from 0.0009 to 1.52 s² km^?2 with an average value of 0.054 s² km^?2 (determined by the gross fragmentation [GF] model). The FM found 33 individual fragmentation events during the penetration of the 56,000 kg initial mass of the Tagish Lake meteoroid through the atmosphere, with five of the events fragmenting more than 10% of the instantaneous mass of the main body. The largest event fragmented 88% of the mass of the main body at a height of 34.4 km. The velocity of the main body mass of 2660 kg at a height of 29.2 km (the last observed light) was 13.1 km/s. Strong fragmentation at heights lower than 29.2 km is very probable. The extreme fragmentation process of the Tagish Lake meteoroid puts its classification well outside the IIIB type in the direction of less cohesive bodies. The light curve could not be explained at all by making use of only the apparent ablation coefficient and apparent luminous efficiency.     

Mineralogy of Tagish Lake: An ungrouped type 2 carbonaceous chondrite

Abstract— In this paper we describe the recovery, handling and preliminary mineralogical investigation of the Tagish Lake meteorite. Tagish Lake is a type 2 carbonaceous chondrite which bears similarities to CI1 and CM chondrite groups, but is distinct from both. Abundant phyllosilicates as well as chondrules (however sparse) and common olivine grains in the matrix preclude any other classification. The bulk density of Tagish Lake (1.67 g/cc) is far lower than CI or CM chondrites (2.2‐2.3 and 2.6‐2.9 g/cc, respectively), or any other meteorite for that matter. We have identified two lithologies: a dominant carbonate‐poor lithology and a less‐abundant carbonate‐rich lithology. The meteorite is a breccia at all scales. We have noted similarities between Tagish Lake and some clasts within the enigmatic meteorite Kaidun; possibly there are genetic relationships here worth exploring. In the paper we describe a clast of CM1 material within Tagish Lake which is very similar to a major lithology in Kaidun.     

Petrography and mineral chemistry of the anhydrous component of the Tagish Lake carbonaceous chondrite

Abstract— Most studies of Tagish Lake have considered features that were either strongly affected by or formed during the extensive hydrous alteration experienced by this meteorite. This has led to some ambiguity as to whether Tagish Lake should be classified a CI, a CM, or something else. Unlike previous workers, we have focused upon the primary, anhydrous component of Tagish Lake, recovered through freeze‐thaw disaggregation and density separation and located by thin section mapping. We found many features in common with CMs that are not observed in CIs. In addition to the presence of chondrules and refractory forsterite (which distinguish Tagish Lake from the CIs), we found hibonite‐bearing refractory inclusions, spinel‐rich inclusions, forsterite aggregates, Cr‐, Al‐rich spinel, and accretionary mantles on many clasts, which clearly establishes a strong link between Tagish Lake and the CM chondrites. The compositions of isolated olivine crystals in Tagish Lake are also like those found in CMs. We conclude that the anhydrous inclusion population of Tagish Lake was, originally, very much like that of the known CM chondrites and that the inclusions in Tagish Lake are heavily altered, more so than even those in Mighei, which are more heavily altered than those in Murchison.     

Comparison of the trace element composition of Tagish Lake with other primitive carbonaceous chondrites

Abstract— A meteorite fall on 2000 January 18 was detected by U.S. Defense Department satellites which established its pre‐impact orbit. Fresh samples were collected from frozen Tagish Lake in British Columbia a week later and some properties of these samples reveal it to be a unique meteorite. We characterized Tagish Lake and 8 other samples using inductively‐coupled plasma mass spectrometry and radiochemical neutron activation analysis: data for 47 elements reveal that each of 9 carbonaceous chondrites of different type exhibit the Orgueil‐normalized plateaus expected for members of such types. Trends evident in Tagish Lake differ from all other carbonaceous chondrites, including CI and CM. Samples of Tagish Lake collected later show similar patterns affected by weathering.     

An entry model for the Tagish Lake fireball using seismic,satellite and infrasound records

Abstract— We present instrumental observations of the Tagish Lake fireball and interpret the observed characteristics in the context of two different models of ablation. From these models we estimate the pre‐atmospheric mass of the Tagish Lake meteoroid to be ?56 tonnes and its porosity to be between 37 and 58%, with the lowest part of this range most probable. These models further suggest that some 1300 kg of gram‐sized or larger Tagish Lake material survived ablation to reach the Earth's surface, representing an ablation loss of 97% for the fireball. Satellite recordings of the Tagish Lake fireball indicate that 1.1 times 10¹² J of optical energy were emitted by the fireball during the last 4 s of its flight. The fraction of the total kinetic energy converted to light in the satellite pass band is found to be 16%. Infrasonic observations of the airwave associated with the fireball establish a total energy for the event of 1.66 ± 0.70 kT TNT equivalent energy. The fraction of this total energy converted to acoustic signal energy is found to be between 0.10 and 0.23%. Examination of the seismic recordings of the airwave from Tagish Lake have established that the acoustic energy near the sub‐terminal point is converted to seismic body waves in the upper‐most portion of the Earth's crust. The acoustic energy to seismic energy coupling efficiency is found to be near 10^?6 for the Tagish Lake fireball. The resulting energy estimate is near 1.7 kT, corresponding to a meteoroid 4 m in diameter. The seismic record indicates extensive, nearly continuous fragmentation of the body over the height intervals from 50 to 32 km. Seismic and infrasound energy estimates are in close agreement with the pre‐atmospheric mass of 56 tonnes established from the modeling. The observed flight characteristics of the Tagish Lake fireball indicate that the bulk compressive strength of the pre‐atmospheric Tagish Lake meteoroid was near 0.25 MPa, while the material compressive strength (most appropriate to the recovered meteorites) was closer to 0.7 MPa. These are much lower than values found for fireballs of ordinary chondritic composition. The behavior of the Tagish Lake fireball suggests that it represents the lowest end of the strength spectrum of carbonaceous chondrites or the high end of cometary meteoroids. The bulk density and porosity results for the Tagish Lake meteoroid suggest that the low bulk densities measured for some small primitive bodies in the solar system may reflect physical structure dominated by microporosity rather than macroporosity and rubble‐pile assemblages.     

Fine‐grained dust rims in the Tagish Lake carbonaceous chondrite: Evidence for parent body alteration

Abstract— The Tagish Lake carbonaceous chondrite consists of heavily aqueously altered chondrules, CAIs, and larger mineral fragments in a fine‐grained, phyllosilicate‐dominated matrix. The vast majority of the coarse‐grained components in this meteorite are surrounded by continuous, 1.5 to >200 μm wide, fine‐grained, accretionary rims, which are well known from meteorites belonging to petrological types 2 and 3 and whose origin and modification is still a matter of debate. Texturally, the fine‐grained rims in Tagish Lake are very similar throughout the entire meteorite and independent of the nature of the enclosed object. They typically display sharp boundaries to the core object and more gradational contacts to the meteorite matrix. Compared to the matrix, the rims are much more finegrained and characterized by a significantly lower porosity. The rims consist of an unequilibrated assemblage of phyllosilicates, Fe,Ni sulfides, magnetites, low‐Ca pyroxenes, and forsteritic olivines, and are, except for a much lower abundance of carbonates, very similar to the Tagish Lake matrix. Electron microprobe and synchrotron X‐ray microprobe analyses show that matrix and rims are also very similar in composition and that the rims differ significantly from matrix and bulk meteorite only by being depleted in Ca. X‐ray elemental mapping and mineralogical observations indicate that Ca was lost during aqueous alteration from the enclosed objects and preferentially crystallized as carbonates in the porous matrix. The analyses also show that Ca is strongly fractionated from Al in the rims, whereas there is no fractionation of the Ti/Al‐ratios. Our data suggest that the fine‐grained rims in Tagish Lake initially formed by accretion in the solar nebula and were subsequently modified by in situ alteration on the parent body. This pervasive alteration removed any potential evidence for pre‐accretionary alteration but did not change the overall texture of the Tagish Lake meteorite.