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Tandem LA-ICP-MS & LIBS; A New Micro-Analytical Technique for the Measurement of Every Element in the Periodic Table

Laser Ablation ICP-MS (LA-ICP-MS) has been widely accepted as a microanalytical technique for in-situ trace (ppb) elemental analysis on the micron scale in a variety of geologic materials. LA-ICP-MS (single or multi-collector) provides both elemental and isotopic measurements critical for a wide range of geological research by generating a fine grained aerosol (nm scale) during the laser ablation event and delivering that aerosol to the ICP ion source of the mass spectrometer via an inert carrier gas. LA-ICP-MS, however, suffers from limitations in analyzing high ionization potential elements as well as elements subject to atmospheric and argon based interferences. LA-ICP-MS also has limitations in analyzing major elements due to detector saturation. An alternative laser ablation technique, Laser Induced Breakdown Spectroscopy (LIBS), employs an optical spectrometer integrated into the laser ablation system that analyzes the laser induced plasma at the sample surface across the entire optical spectrum for emission lines of every element in the periodic table. Elements that are difficult or impossible to measure with LA-ICP-MS are now possible to analyze with LIBS down to low ppm levels with CCD and/or ICCD detection. We introduce a new laser based technique, “Tandem LA-LIBS”, that combines LA for ICP-MS and LIBS into one integrated laser ablation system. This system has the effect of expanding the elemental coverage and the dynamic range of the laser ablation experiment as measurements from ppb to % level matrix elements can now be analyzed in a single ablation experiment. We present both femtosecond and nanosecond Tandem LA-LIBS quantitative and qualitative data on wide range of geological materials for those elements that are difficult or impossible by traditional LA-ICP-MS techniques such as F, H, O, N, C, S, halogens, etc. We also demonstrate that the simultaneous measurement of trace, minor and major elements are now possible in a single laser ablation experiment with Tandem LA-LIBS technology.

LA-ICP-MS↗

Upper limits to trace constituents in Jupiter's atmosphere from an analysis of its 5 micrometer spectrum

A high-resolution spectrum of Jupiter at 5 micrometers recorded at the Kuiper Airborne Observatory is used to determine upper limits to the column density of 19 molecules. The upper limits to the mixing ratios of SiH4, H2S, HCN, and simple hydrocarbons are discussed with respect to current models of Jupiter's atmosphere. These upper limits are compared to expectations based upon the solar abundance of the elements. This analysis permits upper limit measurements (SiH4), or actual detections (GeH4) of molecules with mixing ratios with hydrogen as low as 10 to the minus 9th power. In future observations at 5 micrometers the sensitivity of remote spectroscopic analyses should permit the study of constituents with mixing ratios as low as 10 to the minus 10th power, which would include the hydrides of such elements as Sn and As as well as numerous organic molecules.

Treffers, R. R.↗

Chemiresistor sensor based on ion-imprinted polymer (IIP)-functionalized rGO for Cd(II) ions in water

This study reports the design and development of a novel chemiresistor (CR) sensor using ion imprinted polymer (IIP)-functionalized reduced graphene oxide (rGO) [IIP/rGO-CR] for cadmium ions (Cd(II)) determination in water. The sensor consisted of a CR transducer made of rGO channel bridging source and drain electrodes prepared by self-assembly and thermal reduction of graphene oxide (GO) on Au interdigitated electrodes chip fabricated on Si/SiO 2 substrate. The IIP was then grafted on rGO using surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization with polyethylenimine (PEI) and methylacrylic acid (MAA) as dual functional monomers and Cd(II) ions as template through UV light-initiated copolymerization. The IIP functionalized on rGO acted as an effective recognition element that modulated the resistance of rGO-CR upon binding of Cd(II), enabling Cd(II) detection at ppb level in aqueous solutions. The prepared IIP/rGO-CR sensor worked effectively in the linear range of 2~200ppb and achieved a limit of detection (LOD) of 0.83 ppb, which is lower than the World Health Organization guidelines of 3ppb for drinking water quality. The developed sensor of IIP/rGO-CR showed a high selectivity against a variety of trace and heavy metal ions found in water and good stability for up to 60 days when stored at room temperature for Cd(II) determination in water. Further, the sensor was successfully applied to analyzing Cd(II) spiked in tap, lake and river waters with a 94.5%–113.5% recovery, demonstrating a high degree of accuracy even in complex water samples. Finally, our results illustrated that the CR sensor of IIP functionalized rGO provides a potential platform for sensitive, robust and low-cost environmental analysis of Cd(II) in water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Aqueous Rare Earth Element Patterns and Concentration in Thermal Brines Associated With Oil and Gas Production

This study is part of a joint effort by the University of Wyoming (UW) School of Energy Resources (SER), the UW Engineering Department, Idaho National Laboratories (INL), and the United States Geological Survey (USGS) to describe rare earth element concentrations in oil and gas produced waters and in coal-fired power station ash ponds. In this work we present rare earth element (REE) and trace metal behavior in produced water from four Wyoming oil and gas fields and surface ash pond water from two coal-fired power stations. The concentration of REEs in oil and gas produced waters is largely unknown. For example, of the 150,000 entries in the USGS National Produced Waters Geochemical Database less than 5 include data for REEs. Part of the reason for this scarcity is the analytical challenge of measuring REEs in high salinity, hydrocarbon-bearing waters. The industry standard for water analysis struggles to detect REEs in natural waters under ideal conditions. The detection of REEs in oil and gas field samples becomes all but impossible with the background noise and interferences caused by high concentrations of non-REE ions and residual hydrocarbons. The INL team members have overcome many of these challenges (e.g. McLing, 2014), and continue to develop their methods. Using the methods of the INL team members we measured REEs in high salinity oil and gas produced waters. Our results show that REEs exist as a dissolved species in all waters measured for this project, typically within the parts per trillion range. The samples may be grouped into two broad categories analytically, and these categories match their genesis: Wyoming oil and gas brines contain elevated levels of Europium, and Wyoming industrial pond waters show elevation in heavy REEs (HREEs). While broadly true, important variations exist within both groups. In the same field Europium can vary by more than an order of magnitude, and likewise HREEs in industrial ponds at the same site can vary by more than an order of magnitude. Future work will investigate the reasons for these variations.

01 COAL, LIGNITE, AND PEAT↗

Improved sample utilization in thermal ionization mass spectrometry isotope ratio measurements: refined development of porous ion emitters for nuclear forensic applications

The precise and accurate determination of isotopic composition in nuclear forensic samples is vital for assessing origin, intended use and process history. Thermal ionization mass spectrometry (TIMS) is widely accepted as the gold standard for high performance isotopic measurements and has long served as the workhorse in the isotopic ratio determination of nuclear materials. Nuclear forensic and safeguard specialists have relied heavily on such methods for both routine and atypical e orts. Despite widespread use, TIMS methods for the assay of actinide systems continue to be hindered by poor ionization e ciency, often less than tenths of a percent; the majority of a sample is not measured. This represents a growing challenge in addressing nextgeneration nuclear detection needs by limiting the ability to analyze ultratrace quantities of high priority elements that could potentially provide critical nuclear forensic signatures. Porous ion emitter (PIE) thermal ion sources were developed in response to the growing need for new TIMS ion source strategies for improved ionization e ciency, PIEs have proven to be simple to implement, straightforward approach to boosting ion yield. This work serves to expand the use of PIE techniques for the analysis of trace quantities of plutonium and americium. PIEs exhibited superior plutonium and americium ion yields when compared to direct lament loading and the resin bead technique, one of the most e cient methods for actinide analysis, at similar mass loading levels. Initial attempts at altering PIE composition for the analysis of plutonium proved to enhance sample utilization even further. Preliminary investigations of the instrumental fractionation behavior of plutonium and uranium analyzed via PIE methods were conducted. Data collected during these initial trial indicate that PIEs fractionate in a consistent, reproducible manner; a necessity for high precision isotope ratio measurements. Ultimately, PIEs methods were applied for the age determination of various uranium isotopic standards. PIEs did not exhibit signi cant advantages for the determination of model ages when compared to traditional laments; however, this trial was able to provide valuable insight for guiding future investigations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spectroscopic, orbital, and physical properties of the binary Feige 24 and detection of transient He II absorption in the system

We have obtained new high-dispersion optical spectroscopy at Kitt Peak National Observatory (KPNO) and new International Ultraviolet Explorer (IUE) spectroscopy of the white dwarf+red dwarf binary system Feige 24. The optical range shows a composite DA+dM spectrum, together with H I Balmer and He I emission. The orbital phase dependence of the emission shows that it results from extreme ultraviolet (EUV) light reprocessing in the red dwarf upper atmosphere. The systems close enough and hot enough to show this reprocessing signature only recently emerged from common-envelope evolution. The ultraviolet spectrum exclusively emanates from the white dwarf and shows numerous heavy element absorption lines. We measured accurate radial velocities of the red dwarf component motion, traced by both optical absorption and emission lines, and new radial velocities of the white dwarf, traced by ultraviolet Fe V lines. Combining these measurements, we refined the orbital parameters presented by Vennes et al. (1991), and we confirmed that the white dwarf gravitational redshift is exceptionally small with 9 +/- 2 km/s. From this we deduced that the interior is either pure helium or carbon with a thick hydrogen layer, and we derived, for the combined interior compositions, a white dwarf mass and radius of M(sub WD) = 0.44-050 solar mass and R(sub WD) = 0.028-0.036 solar radius. We suggest that Feige 24 could be a typical case of close binary evolution leading to the formation of a low-mass helium white dwarf. The mass of the red dwarf and the inclination of the system naturally follow: M(sub dM) = 0.26-0.33 solar mass, i greater than or equal to 75 deg. High-dispersion H-alpha line profiles are asymmetrical, strongly enhanced toward the blue, suggesting a moving atmosphere possibly linked to a mass loss rate of 10(exp -10) solar mass/yr. The IUE spectra taken when the system is near inferior conjunction show strong He II 1640 A absorption. The profile is highly variable in width and intensity. Because it is correlated with the passage of the white dwarf at inferior conjunction, the absorption may occur in some foreground plasma emanated by the red dwarf and accumulating near a Lagrangian point or, alternatively, it may originate in an accretion spot on the white dwarf surface coaligned with the major orbital axis. Either way, the He II detection may imply substantial mass loss from the red dwarf with a corollary reclassification of Feige 24 as a mixed He/H DAO white dwarf resulting from accretion of secondary mass-loss material. Feige 24 is the prototype of a class of young, EUV-emitting, binary systems comprising a late main sequence secondary and a hot H-rich white dwarf; the class is characterized by optical and ultraviolet photospheric He II absorption, circumstellar C IV lambda (1550) absorption, and by the presence of EUV-induced, phase-dependent Balmer fluorescence. These young systems present the best opportunity to constrain theory of common-envelope evolution.

Vennes, Stephane↗

Total metals, carbon, nitrogen & anion concentration data; Slate River & East River floodplains, Crested Butte, CO; May 2022-October 2022

This data package includes processed and undiluted measurements for metal, total carbon, total nitrogen, and anion concentrations from pore water (groundwater) and surface water samples from the Slate River and East River floodplains of Crested Butte, CO, focus field sites for the SLAC Floodplain Hydro-Biogeochemistry SFA. The data was generated as part of the work targeting the overarching research question for the SLAC SFA: How do ubiquitous subsurface interfaces mediate molecular-scale biogeochemical processes and groundwater quality in floodplains and watersheds? Samples were collected between May and October of 2022. These measurements were all recorded at the Arizona Laboratory for Emerging Contaminants (ALEC) at the University of Arizona located in Tucson, AZ. Groundwater samples were extracted from a network of installed rhizon (Rhizosphere Research Products, part no. 19.60.21F, 0.6 micrometer mesh size) and piezometer wells within the river floodplain. All water samples were shaded from sun exposure during extraction from the subsurface and preserved at 4C until measured at ALEC.Analysis by ICP-MS (metals):Measurements for total metals were made on the Agilent 7700x ICP-MS (for total metals) – Agilent Technologies, Santa Clara, CA. The analytical QA/QC protocol was adapted from US EPA Method 200.8 for analysis by ICP-MS. Calibration standards were prepared from multi-element stock solutions (SPEX Certiprep, Metuchen, NJ). Calibration curves include at least 7 points with correlation coefficients > 0.995. The QC protocol includes a continuing calibration blank (CCB), a continuing calibration verification (CCV) solution and at least one quality control sample (QCS) to be analyzed just after calibration and again after every 12 samples and at the completion of the run. The QCS solutions are from an independent source, such as NIST SRM 1643e - Trace elements in water, or QCS solutions from High Purity Standards (Charleston, SC). Acceptable QC responses must be between 90 and 110% of the certified value. Lastly, a suitable internal standard (usually Rh, In, Ga or Ge) is added using on-line addition into the sample line and mixing tee.Analysis by Shimadzu TOC-L (TOC/TN):The TOC-L system is a combustion technique where liquid samples are injected and combusted into CO2 for carbon detection by non-dispersive infrared (NDIR) and NO for detection by chemiluminescence. A calibration curve using five standard solutions between 0.1 and 7 ppm for carbon and 0.05 and 3.5 ppm for nitrogen is made for each type of measurement with a linearity >0.99. All samples, standards, and QC’s are prepared in 24mL scintillation vials that have been baked for 4hrs at 475 Cº and made using RO water (18.2mΩ). QC’s include a calibration blank check (CCB), continuing calibration check (CCC), and a certified reference material check (CRM). All QC’s are within ±10% error and are run before and after each batch of samples. Samples are diluted and rerun if any measurement concentrations are above the highest standard.Analysis by Ion Chromatography (Anions):The instrument used is the Thermo Scientific Dionex ICS-6000 using AS+AG22 column set for anion analysis with sodium carbonate eluent. A calibration curve using five standard solutions between 5 and 250 umol/L is made with a linearity >0.99. Standards and QC’s are prepared in 15mL polypropylene conical tubes, pipetted along with the samples into 1.5mL polypropylene vials. Dilutions are made using RO water (18.2mΩ). QC’s include a calibration blank check (CCB), continuing calibration check (CCC), and a certified reference material check (CRM). All QC’s are within ±10% error and are run before and after each batch of samples. Samples are diluted and rerun if any measurement concentrations are above the highest standard.All files are in csv format.

54 ENVIRONMENTAL SCIENCES↗

Design of a Thermal Precipitator for the Characterization of Smoke Particles from Common Spacecraft Materials

A thermal precipitator (TP) was designed to collect smoke aerosol particles for microscopic analysis in fire characterization research. Information on particle morphology, size and agglomerate structure obtained from these tests supplements additional aerosol data collected. Modeling of the thermal precipitator throughout the design process was performed with the COMSOL Multiphysics finite element software package, including the Eulerian flow field and thermal gradients in the fluid. The COMSOL Particle Tracing Module was subsequently used to determine particle deposition. Modeling provided optimized design parameters such as geometry, flow rate and temperatures. The thermal precipitator was built and testing verified the performance of the first iteration of the device. The thermal precipitator was successfully operated and provided quality particle samples for microscopic analysis, which furthered the body of knowledge on smoke particulates. This information is a key element of smoke characterization and will be useful for future spacecraft fire detection research.

Smoke↗

Lunar and Planetary Science XXXVI, Part 17

The following topics were discussed: A Model for the Formation of Paterae on Io; LIBS-based Detection of As, Br, C, Cl, P, and S in the VUV Spectral Region in a Mars Atmosphere; Mass Independent Sulfur in Achondrites: Possible Evidence of Photochemistry in the Solar Nebula; Grain Size-dependent Viscosity and Oceans in Icy Satellites; Claritas Paleolake Studied from the MEX HRSC Data; Mars Express HRSC Colors of White Rock, Arabia, Mars; Lava and Flows of the Arcadia Region of Mars; Isotopic Composition of Lunar Soils and the Early Differentiation of the Moon; Trace Element Analysis of Lunar Soils by ICP-MS; Highly Siderophile Elements and Osmium Isotope Systematics in Ureilites: Are the Carbonaceous Veins Primary Components?; Evaporative Evolution of Martian Brines Based on Halogens in Nakhlites and MER Samples; Io from High-Resolution Galileo PPR Data Taken Simultaneously with SSI or NIMS Observations; Loki, Io: Groundbased Observations and a Model for Periodic Overturn; Deconstructing a Few Myths in the Interpretation of Satellite-Altitude Crustal Magnetic Field: Examples from Mars Global Surveyor; Semi-Autonomous Rover Operations: A Mars Technology Program Demonstration; Rotational Studies of Asteroids with Small Telescopes; Mineralogy and Temperature-induced Spectral Investigations of A-type Asteroids 246 Asporina and 446 Aeternitas; and Thermal History Calculations Versus Full Convection Models: Application to the Thermal Evolution of Mercury. Recent Solar-Proton Fluxes

Source record↗

Trace elements in chondritic stratospheric particles - Zinc depletion as a possible indicator of atmospheric entry heating

Major-element abundances in 11 C, C?, and TCA cosmic dust particles have been measured using SEM and TEM energy dispersive X-ray (EDX) systems. The Fe/Ni ratio, when coupled with major element abundances, appears to be a useful discriminator of cosmic particles. Three particles classified as C?, but having Fe/Ni peak height ratios similar to those measured on the powdered Allende meteorite sample in their HSC EDX spectra, exhibit chondritic minor-/trace-element abundance patterns, suggesting they are extraterrestrial. The one particle classified as C-type, but without detectable Ni in its JSC EDX spectrum, exhibits an apparently nonchondritic minor-/trace-element abundance pattern. A class of particles that are chondritic except for large depletions in the volatile elements Zn and S has been identified. It is likely that these particles condensed with a C1 abundance pattern and that Zn and S were removed by some subsequent process.

Flynn, G. J.↗

Long-term Accumulation, Depth Distribution, and Speciation of Silver Nanoparticles in Biosolids-Amended Soils

Biosolids, when applied to soil, can be a source of metals and metal nanoparticles. One of the metals that forms nanoparticles is silver (Ag), which is commonly used in elemental (Ag(0)) form as an engineered nanomaterial in industrial or consumer products. The objective of this study was to quantify and characterize the accumulation and transport of Ag in a natural soil that has received agronomically-recommended rates of biosolids as fertilizer for the past 23 years (1994{2017). Total Ag concentrations were measured in biosolids and soil samples collected from 0 to 10 cm between 1996 and 2017. In addition, the depth distribution of Ag in the soil down to 60-cm depth was measured in 2017. Electron microscopy, in combination with X-ray spectroscopy, and X-ray absorption spectroscopy were used to identify the elemental association and oxidation state of the Ag in the samples. The Ag concentrations in the biosolids-amended soil increased steadily from 1996 until 2007, after which the concentrations leveled off at about 1.25 mg Ag kg-1 soil. This corresponded with a decrease of Ag concentrations in the biosolids over time. The majority of the Ag (82%) was confined to the top 10 cm of the soil, small amounts (14%) were detected in 10 to 20-cm depth, and trace amounts (4%) in 30 to 40-cm depth. The Ag in the biosolids and soil was identified as Ag-containing nanoparticles with a diameter of 10 to 12 nm. Ag was associated with S suggest that these 19 nanoparticles are Ag2S. This could be corroborated in biosolids with X-ray absorption spectroscopy (XANES); however, the Ag concentrations in the soil samples were too low to allow identification with XANES. Biosolids, when applied at agronomic rates in dryland cropping systems, represent an economically viable source of crop nutrients. In our study, long-term application of biosolids did not increase the concentration of total Ag in soil above a maximum of 1.5 mg Ag kg-1, and the Ag is present in the sulfide form. This concentration is below ecotoxicity limits for Ag2S in soil.

Taylor, Stephen E.↗

Progress in Uranium Chemistry: Driving Advances in Front-End Nuclear Fuel Cycle Forensics

The front-end of the nuclear fuel cycle encompasses several chemical and physical processes used to acquire and prepare uranium for use in a nuclear reactor. These same processes can also be used for weapons or nefarious purposes, necessitating the need for technical means to help detect, investigate, and prevent the nefarious use of nuclear material and nuclear fuel cycle technology. Over the past decade, a significant research effort has investigated uranium compounds associated with the front-end of the nuclear fuel cycle, including uranium ore concentrates (UOCs), UF 4 , UF 6 , and UO 2 F 2 . These efforts have furthered uranium chemistry with an aim to expand and improve the field of nuclear forensics. Focus has been given to the morphology of various uranium compounds, trace elemental and chemical impurities in process samples of uranium compounds, the degradation of uranium compounds, particularly under environmental conditions, and the development of improved or new techniques for analysis of uranium compounds. Overall, this research effort has identified relevant chemical and physical characteristics of uranium compounds that can be used to help discern the origin, process history, and postproduction history for a sample of uranium material. This effort has also identified analytical techniques that could be brought to bear for nuclear forensics purposes. Continued research into these uranium compounds should yield additional relevant chemical and physical characteristics and analytical approaches to further advance front-end nuclear fuel cycle forensics capabilities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of LOCA Scenarios in the NIST Research Reactor Before and After Fuel Conversion

An analysis has been done of hypothetical loss-of-coolant-accidents (LOCAs) in the research reactor (NBSR) at the National Institute of Standards and Technology (NIST). The purpose of the analysis is to determine if the peak clad temperature remains below the Safety Limit, which is the blister temperature for the fuel. The configuration of the NBSR considered in the analysis is that projected for the future when changes will be made so that shutdown pumps do not operate when a LOCA signal is detected. The analysis was done for the present core with high-enriched uranium (HEU) fuel and with the proposed low-enriched uranium (LEU) fuel that would be used when the NBSR is converted from one to the other. The analysis consists of two parts. The first examines how the water would drain from the primary system following a break and the possibility for the loss of coolant from within the fuel element flow channels. This work is performed using the TRACE system thermal-hydraulic code. The second looks at the fuel clad temperature as a function of time given that the water may have drained from many of the flow channels and the water in the vessel is in a quasi-equilibrium state. The temperature behavior is investigated using the three-dimensional heat conduction code HEATING7.3. The results in all scenarios considered for both HEU and LEU fuel show that the peak clad temperature remains below the blister temperature.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Elemental composition of airborne particulates and source identification - An extensive one year survey

Concentrations of 60 chemical elements in the airborne particulate matter were measured at 16 sites in Cleveland, OH over a 1 year period during 1971 and 1972 (45 to 50 sampling days). Analytical methods used included instrumental neutron activation, emission spectroscopy, and combustion techniques. Uncertainties in the concentrations associated with the sampling procedures, the analytical methods, the use of several analytical facilities, and samples with concentrations below the detection limits are evaluated in detail. The data are discussed in relation to other studies and source origins. The trace constituent concentrations as a function of wind direction are used to suggest a practical method for air pollution source identification.

King, R. B.↗

On the Hunt for Detectable Biosignatures in Jezero Crater: What to Look for and Where

Introduction: The Perseverance rover, which is currently exploring Jezero crater on Mars, is equipped with seven instruments that allow for observation of textures, minerals, color, structure, and chemistry of rocks and sediments in order to search for signs of ancient life, understand the geologic history of the crater, and identify candidates for sample return (Farley et al. 2020). The first of these aims includes the direct detection of potential biosignatures, including textures, organic molecules, minerals, and elemental chemistries that are of biogenic origin (Mustard et al. 2013). The presence of these biosignatures will be constrained by the habitability of the local region, the preservation potential of the host rocks, and the sensitivity of the instrument suite, and their biogenicity will be investigated after return to Earth as part of the Mars Sample Return campaign. Here, we examine key targets on the three planned campaigns, potential biosignatures that may be present, and the capabilities of key rover instruments. High Potential Biosignature Sites in Jezero: To date, measurements have been made on multiple sites that both contain minerals known in terrestrial settings to preserve biosignatures and likely were habitable settings (Williford et al. 2021). Two examples include the fine-grained rocks at the base of the delta fan and the NW inner margin of the crater. Fine-grained Rocks at Base of Delta Fan. Fine-grained, clay-bearing rocks may have been deposited as muddy lake sediments that could have hosted life and preserved biosignatures settling out of the water column. The report of organic molecules by the Curiosity rover in the Sheepbed mudstone and Murray formation has highlighted this site in particular. Potential biosignatures in mudstones, especially those rich in silica (McMahon et al. 2018), microbialites and complex organics. NW Inner Margin of Crater. This unit, located along the inner margin of the crater, contains strong carbonate signatures and may have been the littoral zone of a lake (Horgan et al. 2020). The potential biosignatures here include microfossils, microbialites, biominerals, and complex organics. Detectability of Biosignatures by the Mars 2020 Instrument Suite: The Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument comprises a Deep UV spectrometer, context imager, and color camera to generate spatially resolved chemical maps (Bhartia et al. 2020). It is sensitive to trace organics as well as a range of minerals and can detect native fluorescence from aromatic organics; the WATSON and ACI cameras can be used to observe morphologies such as stromatolitic laminations or filaments ranging from the tens of micron to millimeter scale. SHERLOC can detect organics that may be present in either of the high potential biosignature targets, as well as detect carbonates in the latter. However, the presence of high amounts of iron, such as in iron-rich clays, would cause attenuation of spectral response through UV absorption. The Planetary Instrument for X-ray Lithochemistry (PIXL) comprises an X-ray fluorescence spectrometer and camera that can scan rock surfaces to generate elemental maps (Allwood et al. 2020). PIXL can detect chemical biosignatures such as spatial variations of elemental abundances that may have resulted from biological activity. PIXL would be particularly useful in detecting fine textures and elemental chemistries in either high potential biosignature target, but cannot directly detect minerals such as carbonate. The SuperCam instrument performs three types of spectroscopy, color imaging, and acoustic recording to remotely examine elemental composition, minerals, organics, and textures (Maurice et al. 2021). Using laser induced breakdown spectroscopy and time resolved luminescence spectroscopy, SuperCam can detect major elemental building blocks of organics (i.e., C, H, N, O, P, S) and conjugated organic structures, respectively, which may be found in either site. While in other contexts, luminescence is a useful tool for biosignature identification, luminescence generated by the 532 nm laser may obscure the Raman signal. Conclusion: The three instruments discussed can be used collaboratively to establish the presence of potential biosignatures in samples. These high-priority samples may then be returned to Earth for detailed laboratory analysis.

S. Sharma↗

The Hubble Space Telescope quasar absorption line key project. 6: Properties of the metal-rich systems

We present an analysis of the properties of a sample of 18 metal-rich, low-redshift z(sub abs) much less than z(sub em) absorbers seen in low- and medium-resolution spectra obtained for the Quasar Absorption Line Key Project with the Hubble Space Telescope Faint Object Spectrograph (HST/FOS). For most of the C IV and Lyman-limit systems, observations in the optical wavelength range of the expected associated Mg II absorption are available. As at high redshift (z approximately 2), there are two subclasses of absorbers which are characterized by the presence or absence of MG II absorption. However, some low-redshift Mg II and Fe absorptions originate from regions optically thin to UV ionizing photons and thus, at low redshift, the low-ionization systems do not always trace high opacities, as is the case at high redshift. This implies that the mean ionization state of metal-rich, optically thin absorbing clouds falls with decreasing redshift, which is consistent with the hypothesis that the gas is photoionized by the metagalactic UV background radiation field. Two main constraints are derived from the analysis of the Lyman-limit sample, assuming photoionization models are valid. First, a low opacity to ionizing photons (tau(sub LL) approximately less than 1), as observed for several Mg II-Fe II systems at z approximately 0.5, sets limits on the ionization level of hydrogen, thus on the total hydrogen column density and the heavy element abundances, (Z/H) approximately -0.5 to -0.3. Second, the dimensions of individual Mg II clouds are smaller than at high redshift by a factor 3-10. At z approximately greater than 0.6, the O VI absorption doublet is detected in four of the five z(sub abs) much less than z(sub em) systems for which the O VI wavelength range has been observed, whereas the associated N V doublet is detected in only two cases. This suggests that the presence of a high-ionization O VI phase is a general property of z approximately 0.6-1 absorption systems, as is also probably the case at high redshift. These O VI absorbers can be ionized by the UV metagalactic field if their density is low, nH approximately less than 3 x 10(exp -4)/cc. The O VI phase would then be a homogeneous region of large extent, r approximately greater than 50 kpc. A detailed photoionization model of the z(sub abs) = 0.791 absorber toward PKS 2145+06 confirms the properties derived from the Mg II, C IV, O VI, and Lyman-limit samples. The galaxy causing this extensive metal-line absorption system has been identified, and its possible contribution to the UV ionizing flux does not substantially modify the value of the derived parameters. The heavy element abundances are about half the solar values. The O VI region has a density about 20 times lower than the Mg II clouds and a size of approximately 70 kpc. Alternatively, the high-ionization phase could be collisionally ionized and trace gas associated with a possible group of galaxies at the absorber redshift.

Bergeron, Jacqueline↗

River thorium concentrations can record bedrock fracture processes including some triggered by distant seismic events

Fractures are integral to the hydrology and geochemistry of watersheds, but our understanding of fracture dynamics is very limited because of the challenge of monitoring the subsurface. Here we provide evidence that long-term, high-frequency measurements of the river concentration of the ultra-trace element thorium (Th) can provide a signature of bedrock fracture processes spanning neighboring watersheds in Colorado. River Th concentrations show abrupt (subdaily) excursions and biexponential decay with approximately 1-day and 1-week time constants, concentration patterns that are distinct from all other solutes except beryllium and arsenic. The patterns are uncorrelated with daily precipitation records or seasonal trends in atmospheric deposition. Groundwater Th analyses are consistent with bedrock release and dilution upon mixing with river water. Most Th excursions have no seismic signatures that are detectable 50 km from the site, suggesting the Th concentrations can reveal aseismic fracture or fault events. We find, however, a weak statistical correlation between Th and seismic motion caused by distant earthquakes, possibly the first chemical signature of dynamic earthquake triggering, a phenomenon previously identified only through geophysical methods.

58 GEOSCIENCES↗

Inorganic chemical investigation by X-ray fluorescence analysis - The Viking Mars Lander

The inorganic chemical investigation experiment added in August 1972 to the Viking Lander scientific package uses an energy-dispersive X-ray fluorescence spectrometer in which four sealed, gas-filled proportional counters detect X-rays emitted from samples of the Martian surface materials irradiated by X-rays from radioisotope sources (Fe-55 and Cd-109). The instrument is inside the Lander body, and samples are to be delivered to it by the Viking Lander Surface Sampler. Instrument design is described along with details of the data processing and analysis procedures. The results of the investigation will characterize the surface materials of Mars as to elemental composition with accuracies ranging from a few tens of parts per million (at the trace-element level) to a few per cent (for major elements) depending on the element in question.

Toulmin, P., III↗