Curation protocol of Phobos sample returned by Martian Moons eXploration

Japan Aerospace Exploration Agency's Martian Moons eXploration (MMX) mission will launch a spacecraft in 2024 to return samples from Phobos in 2029. Curatorial work for the returned Phobos samples is critical for the sample allocation without degrading the sample integrity and subsequent sample analysis that will provide new constraints on the origin of Phobos and the evolution of the circum-Mars environment. The Sample Analysis Working Team of the MMX is designing the sample curation protocol. The curation protocol consists of three phases: (1) quick analysis (extraction and mass spectrometry for gases), (2) pre-basic characterization (bulk-scale observation), and (3) basic characterization (grain-by-grain observation and allocation of the sample aliquots). Nondestructive analyses within the clean chamber (e.g., visible and near-infrared spectral imaging) and outside the chamber (e.g., gas mass spectrometry) are incorporated into the curation flow in coordination with the MMX mission instrument teams for ground-truthing the remote-sensing data sets. The MMX curation/sample analysis flow enables the seamless integration between the sample and remote-sensing data sets to maximize the scientific value of the collected Phobos samples.     

Hf-W mineral isochron for Ca,Al-rich inclusions: Age of the solar system and the timing of core formation in planetesimals

Application of ¹⁸²Hf-¹⁸²W chronometry to constrain the duration of early solar system processes requires the precise knowledge of the initial Hf and W isotope compositions of the solar system. To determine these values, we investigated the Hf-W isotopic systematics of bulk samples and mineral separates from several Ca,Al-rich inclusions (CAIs) from the CV3 chondrites Allende and NWA 2364. Most of the investigated CAIs have relative proportions of ¹⁸³W, ¹⁸⁴W, and ¹⁸⁶W that are indistinguishable from those of bulk chondrites and the terrestrial standard. In contrast, one of the investigated Allende CAIs has a lower ¹⁸⁴W/¹⁸³W ratio, most likely reflecting an overabundance of r-process relative to s-process isotopes of W. All other bulk CAIs have similar ¹⁸⁰Hf/¹⁸⁴W and ¹⁸²W/¹⁸⁴W ratios that are elevated relative to average carbonaceous chondrites, probably reflecting Hf-W fractionation in the solar nebula within the first ∼3 Myr. The limited spread in ¹⁸⁰Hf/¹⁸⁴W ratios among the bulk CAIs precludes determination of a CAI whole-rock isochron but the fassaites have high ¹⁸⁰Hf/¹⁸⁴W and radiogenic ¹⁸²W/¹⁸⁴W ratios up to ∼14 ε units higher than the bulk rock. This makes it possible to obtain precise internal Hf-W isochrons for CAIs. There is evidence of disturbed Hf-W systematics in one of the CAIs but all other investigated CAIs show no detectable effects of parent body processes such as alteration and thermal metamorphism. Except for two fractions from one Allende CAI, all fractions from the investigated CAIs plot on a single well-defined isochron, which defines the initial ε¹⁸²W = −3.28 ± 0.12 and ¹⁸²Hf/¹⁸⁰Hf = (9.72 ± 0.44) × 10⁻⁵ at the time of CAI formation. The initial ¹⁸²Hf/¹⁸⁰Hf and ²⁶Al/²⁷Al ratios of the angrites D’Orbigny and Sahara 99555 are consistent with the decay from initial abundances of ¹⁸²Hf and ²⁶Al as measured in CAIs, suggesting that these two nuclides were homogeneously distributed throughout the solar system. However, the uncertainties on the initial ¹⁸²Hf/¹⁸⁰Hf and ²⁶Al/²⁷Al ratios are too large to exclude that some ²⁶Al in CAIs was produced locally by particle irradiation close to an early active Sun. The initial ¹⁸²Hf/¹⁸⁰Hf of CAIs corresponds to an absolute age of 4568.3 ± 0.7 Ma, which may be defined as the age of the solar system. This age is 0.5-2 Myr older than the most precise ²⁰⁷Pb-²⁰⁶Pb age of Efremovka CAI 60, which does not seem to date CAI formation. Tungsten model ages for magmatic iron meteorites, calculated relative to the newly and more precisely defined initial ε¹⁸²W of CAIs, indicate that core formation in their parent bodies occurred in less than ∼1 Myr after CAI formation. This confirms earlier conclusions that the accretion of the parent bodies of magmatic iron meteorites predated chondrule formation and that their differentiation was triggered by heating from decay of abundant ²⁶Al. A more precise dating of core formation in iron meteorite parent bodies requires precise quantification of cosmic-ray effects on W isotopes but this has not been established yet.     

Drivers of interannual and intra‐annual variability of dissolved organic carbon concentration in the River Thames between 1884 and 2013

The world's longest record of river water quality (River Thames—130 years) provides a unique opportunity to understand fluvial dissolved organic carbon (DOC) concentrations dynamics. Understanding riverine DOC variability through long‐term studies is crucial to capture patterns and drivers influencing sources of DOC at scales relevant for decision making. The Thames basin (United Kingdom) has undergone massive land‐use change, as well as increased urbanisation and population during the period considered. We aimed to investigate the drivers of intra‐annual to interannual DOC variability, assess the variability due to natural and anthropogenic factors, and understand the causes for the increased DOC variability over the period. Two approaches were used to achieve these aims. The first method was singular spectrum analysis, which was used to reconstruct the major oscillatory modes of DOC, hydroclimatic variables, and atmospheric circulation patterns and to visualise the interaction between these variables. The second approach used was generalised additive modelling, which was used to investigate other non‐natural drivers of DOC variability. Our study shows that DOC variability increased by 80% over the data period, with the greatest increase occurring from the beginning of World War II onwards. The primary driver of the increase in DOC variability was the increase in the average value of fluvial DOC over the period of record, which was itself linked to the increase in basin population and diffuse DOC sources to the river due to land‐use and land‐management changes. Seasonal DOC variability was linked to streamflow and temperature. Our study allows to identify drivers of fluvial intra‐annual and interannual DOC variability and therefore empowers actions to reduce high DOC concentrations.     

Late Cretaceous extension overprinting a steep belt in the Northern Calcareous Alps (Schesaplana, R?tikon, Switzerland and Austria)

The Triassic to Cretaceous sediment succession of the Lechtal Nappe in the western part of the Northern Calcareous Alps (NCA) has been deformed into large-scale folds and crosscut by thrust and extensional faults during Late Cretaceous (Eoalpine) and Tertiary orogenic processes. The following sequence of deformation is developed from overprinting relations in the field: (D1) NW-vergent folds related to thrusting; (D2) N–S shortening leading to east–west-trending folds and to the formation of a steep belt (Arlberg Steep Zone) along the southern border of the NCA; (D3) E–W to NE–SW extension and vertical shortening, leading to low-angle normal faulting and recumbent “collapse folds” like the Wildberg Syncline. D1 and D2 are Cretaceous in age and predate the Eocene emplacement of the Austroalpine on the Penninic Nappes along the Austroalpine basal thrust; the same is probably true for D3. Finally, the basal thrust was deformed by folds related to out-of-sequence thrusting. These results suggest that the NCA were at least partly in a state of extension during the sedimentation of the Gosau Group in the Late Cretaceous.     

Complexation of aqueous elements by DOC in a clay aquitard

The extent of partitioning of several elements (Cu, Mn, Mo, Ni, Sr, U, and Zn) on dissolved organic carbon (DOC) was investigated in pore water samples collected from a clay-rich aquitard. High DOC concentrations in the aquitard, ranging from 21 to 143 mg C/L, and natural aqueous metal concentrations higher than in most ground water environments facilitated complexation studies at this site. Analyses were conducted using on-line coupling of asymmetrical flow field-flow fractionation with ultraviolet, total organic carbon, and inductively coupled plasma-mass spectrometry detectors. Of the elements investigated, only U and Zn were complexed with all DOC samples, ranging from 2.2 to 60 microg U/g DOC (0.4% to 3% of the total U in the pore water) and 0.04 to 0.5 microg Zn/g DOC (0.1% to 0.9% of the total Zn in the pore water), respectively. Laboratory experiments conducted over a range in pH (1.3 to 9.7) and geochemical modeling supported the measured complexation of U and Zn on the DOC. The in situ association constant, K(d), for U decreased with depth from 76 mL/g C for pore water samples at 2.2 m below ground (BG) to 24 mL/g C at 9.7 m BG. The decrease was attributed to a decrease in aromaticity of the DOC with depth. Zn K(d)constants ranged from 2 to 12 mL/g C and exhibited no trend with depth. Results of the current study suggest minor masses of U and Zn (less than or equal to 4% of total) complex with this DOC under in situ pH conditions. Our data suggest that competitive complexation by other ligands may limit the importance of DOC-facilitated transport of the elements studied in water of similar chemical composition.