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Allophane on Mars: Significance for Chemical Weathering and Soil Development

It has been suggested that allophane or related poorly crystalline aluminosilicates are present on Mars, and that they comprise the high-silica phase detected by the Thermal Emission Spectrometer (TES) in Surface Type 2 materials (Michalski et al., 2005). Using new laboratory spectra of allophanic materials, we (Rampe et al., this meeting) have detected allophane on the Martian surface via spectral modeling of TES data. We find that ST2 materials in the Northern Plains are consistent with a significant amount of high-silica allophane-like materials. In addition, we find that allophane may be present in some areas of ancient highlands (TES surface type 1), but spectra of those regions are more consistent with aluminous allophane. The presence of allophane and its chemical variability have important implications for chemical weathering and soil development on Mars. Allophane-like materials are amorphous or poorly crystalline hydrous aluminosilicates formed from chemical weathering of glasses, feldspars, and other silicates (cf. Parfitt, 2009). True allophane is a combination of SiO2, Al2O3 and H2O where Al:Si ranges from ~0.5-2. Aluminosilicate gels are amorphous and chemically similar to allophane but can have higher SiO2 contents. The presence of allophane indicates low-temperature chemical weathering and provides constraints on alteration conditions, limiting pH to circum-neutral (~4.5-8). Our model results indicate that weathering occurred in the relatively young northern plains of Mars. The high-silica allophane-like material present there implies little silica mobility through the soil column, which suggests that weathering involved small amounts of liquid water, consistent with our previous models of weathering in ice-rich soils (Kraft et al., 2007). The aluminous allophane indicated by our spectral models to be present in the highlands suggest that those regions experienced greater amounts of SiO2 leaching and weathering in those soils may have involved much larger amounts of water. The presence of allophane-like materials suggests that these weathering regimes were not influenced by the acidic weathering that appears to have affected other areas of Mars and has been proposed as a planetwide alteration process (Hurowitz and McLennan, 2007). Soil development in basaltic material (typically tephra) on Earth usually leads to formation of andosols. Although we do not suggest a one-to-one analogy between dark basaltic Martian soils and andosols, there may be important similarities, as andosols are typified by significant production of allophane as well as poorly crystalline Fe-hydroxides. The detection of allophane on Mars suggests a positive utility of an andosol model for Martian soils, particularly when coupled with the ubiquitous presence of Feoxide materials on Mars. An andosol model of soil formation is mineralogically consistent with palagonite models for the formation of Martian dust (cf. Banin et al., 1992; Morris et al., 2001), which suggests a possible genetic relationship of dust and bright soils to the broader soil layer of Mars.

Kraft, M. D.↗

A Data-driven Phytotechnology Framework for Identification and Remediation of Leached-Metals-Contaminated Soil Near Coal Ash Impoundments

This project developed and evaluated advanced remote sensing and machine learning approaches to identify, monitor, and address environmental contamination associated with coal combustion residual (CCR) impoundments and landfills at coal-fired power plants. In Phase I, historical and multi-temporal Sentinel-2 satellite imagery, groundwater monitoring data, and environmental variables were integrated to detect vegetation stress potentially caused by toxic metal leaching from coal ash disposal sites. Multiple vegetation and biophysical indices were analyzed to determine their effectiveness in identifying abnormal vegetation growth patterns linked to contamination. Results from case studies conducted at coal ash–impacted power plant sites in North Carolina and Virginia demonstrated that satellite-based vegetation monitoring can serve as an effective early indicator of environmental stress associated with metals such as arsenic, cadmium, cobalt, lead, lithium, radium, and thallium.

01 COAL, LIGNITE, AND PEAT↗

Size-Controlled Nanoparticles Embedded in a Mesoporous Architecture Leading to Efficient and Selective Hydrogenolysis of Polyolefins

A catalytic architecture, comprising a mesoporous silica shell surrounding platinum nanoparticles (NPs) supported on a solid silica sphere (mSiO2/Pt-X/SiO2; X is the mean NP diameter), catalyzes hydrogenolysis of melt-phase polyethylene (PE) into a narrow C23-centered distribution of hydrocarbons in high yield using very low Pt loadings (~10 -5 g Pt/g PE). During catalysis, a polymer chain enters a pore and contacts a Pt NP where the C–C bond cleavage occurs and then the smaller fragment exits the pore. mSiO 2 /Pt/SiO 2 resists sintering or leaching of Pt and provides high yields of liquids; however, many structural and chemical effects on catalysis are not yet resolved. Here, we report the effects of Pt NP size on activity and selectivity in PE hydrogenolysis. Time-dependent conversion and yields and a lumped kinetics model based on the competitive adsorption of long vs short chains reveal that the activity of catalytic material is highest with the smallest NPs, consistent with a structure-sensitive reaction. Remarkably, the three mSiO 2 /Pt-X/SiO 2 catalysts give equivalent selectivity. We propose that mesoscale pores in the catalytic architecture template the C 23 -centered distribution, whereas the active Pt sites influence the carbon–carbon bond cleavage rate. This conclusion provides a framework for catalyst design by separating the C–C bond cleavage activity at catalytic sites from selectivity for chain lengths of the products influenced by the structure of the catalytic architecture. The increased activity, selectivity, efficiency, and lifetime obtained using this architecture highlight the benefits of localized and confined environments for isolated catalytic particles under condensed-phase reaction conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lead Isotopes in Olivine-Phyric Shergottite Tissint: Implications for the Geochemical Evolution of the Shergottite Source Mantle

Geochemically-depleted shergottites are basaltic rocks derived from a martian mantle source reservoir. Geochemical evolution of the martian mantle has been investigated mainly based on the Rb-Sr, Sm-Nd, and Lu-Hf isotope systematics of the shergottites [1]. Although potentially informative, U-Th- Pb isotope systematics have been limited because of difficulties in interpreting the analyses of depleted meteorite samples that are more susceptible to the effects of near-surface processes and terrestrial contamination. This study conducts a 5-step sequential acid leaching experiment of the first witnessed fall of the geochemically-depleted olivinephyric shergottite Tissint to minimize the effect of low temperature distrubence. Trace element analyses of the Tissint acid residue (mostly pyroxene) indicate that Pb isotope compositions of the residue do not contain either a martian surface or terrestrial component, but represent the Tissint magma source [2]. The residue has relatively unradiogenic initial Pb isotopic compositions (e.g., 206Pb/204Pb = 10.8136) that fall within the Pb isotope space of other geochemically-depleted shergottites. An initial μ-value (238U/204Pb = 1.5) of Tissint at the time of crystallization (472 Ma [3]) is similar to a time-integrated mu- value (1.72 at 472 Ma) of the Tissint source mantle calculated based on the two-stage mantle evolution model [1]. On the other hand, the other geochemically-depleted shergottites (e.g., QUE 94201 [4]) have initial μ-values of their parental magmas distinctly lower than those of their modeled source mantle. These results suggest that only Tissint potentially reflects the geochemical signature of the shergottite mantle source that originated from cumulates of the martian magma ocean

Moriwaki, R.↗

Olivine Dissolution and Formation of Secondary phases in Ultramafic Soils

Introduction: Olivine has been proposed as an indicator for the duration of water-rock interaction within Martian rocks and sediments [1-3]. The use of olivine as a mineralogical indicator for past aqueous alteration on Mars requires interpretation of a complex combination of factors including pH, temperature, and composition [5,6]. Here, we examine the persistence of natural olivine within terrestrial ultramafic soils (Fe/Mg-rich, Al-poor) developing under different climatic conditions and the incipient dissolution of emplaced forsterite (Fo) and fayalite (Fa) surfaces to investigate environmental effects on incipient olivine dissolution, olivine persistence in soils, and formation of secondary phases. Methods: Field Sites. We examined olivine weathering and secondary material formation in ultramafic soils at 6 sites in the Klamath Mountains (KM) of northern California with a mean annual temperature of ~12.8℃ and precipitation of ~55.7-95.4 cm/year [7], and soil pH of ~6.5-7.3; 4 sites in the Tablelands (TB) of Newfoundland, Canada with a mean annual temperature of <3.9℃ and precipitation of ~120.0 cm/year [8], and soil pH of ~7.7; and at 3 sites at Pickhandle Gulch (PG), Nevada with a mean annual temperature of ~14.4℃ and precipitation of ~14.1 cm/year [7], and soil pH of ~8.5. Sampling sites span an age range of ~12.1-50+ kya in the Klamath Mountains [9,10] and ~13-30 kya in the Tablelands [11]. Pickhandle Gulch sites are undated. Parent Material and Soil Analyses. Polished thin sections of bulk soil prepared by Wagner Petrographic, Inc were carbon-coated and analyzed on a JEOL 2100 SEM in back-scattered electron mode in the EMIL lab at UNLV and at the 13-ID-E synchrotron beamline at Argonne National Laboratory using µXRF, µXRD, and XAS. Soil and parent material samples were powdered in a Fritsch pulverisette and analyzed by XRD and soil by VNIR. Soil preparation is further described in [12]. Disk Preparation, Burial, and Collection. Fo disks were cut from a column prepared via hot-pressing and Fa disks by sintering synthetic fayalite powder, see [13] for detail. Disks were polished to a 0.25-micron level with diamond grit. Disks were buried in 3 KM soils, 4 TB soils, and 3 PG soils, collected after exactly 365 days, and washed gently with 100% reagent grade ethanol to remove potential adhered soil material. Weathered disks and soil samples were stored in a -20℃ freezer until analysis. Unaltered control disks prepared identically to the buried disks were stored at -20℃ for the duration of the experiment. Disk Analyses. One Fo and Fa disk from each climate zone was analyzed on a variable pressure Zeiss Supra 40VP SEM at Northern Arizona University. A separate Fo and Fa disk from each climate zone was analyzed by XPS using a Physical Electronics VersaProbe II at the Penn State Univ. Materials Characterization Lab after a Na-dodecyl sulfate wash and ozonation to remove carbon contamination as in [14]. VNIR measurements were conducted at Johnson Space Center using an ASD FieldSpec3 under ambient lab conditions on a separate Fo and Fa disk from each climate zone. One separate Fo and Fa control sample was analyzed for each technique for comparison with weathered samples. XPS uncertainty was determined from 5 repeat measurements on controls. Results: Bedrock and Soil Results Olivine is present in the parent material in the KM and TB. Olivine is found in ~12.1 ka KM soils but is absent from all older soils, while persisting into the oldest (>20 ka) TB soil (Figure 1). In both locations, olivine is found as cores surrounded by a serpentine rind (Figure 2). VNIR spectra from the analyzed soils possess strong OH-associated spectral features at ~2.33 µm indicating the presence of Mg-rich phyllosilicates as well as ferric-oxide features at ~0.92 µm in the KM (Figure 3). Primary crystalline silicate grains mostly incorporate Fe2+, while poorly crystalline weathering rinds are best fit by ferric oxide XAS standards (Figure 4). µXRF also shows that Fe and Ni concentrate in weathering rinds and Cr remains within interior silicate grains (Figure 4). Buried Sample Results All Fo surfaces exhibited formation of dissolution features including shallow pitting not observed on controls. Dissolution features were most visually widespread on the KM disk (Figure 5). Leaching of Mg from KM and TB Fo disks was evident from <1.6 Mg/Si ratios measured by XPS (Figure 6). Fe-rich precipitates in SEM (Figure 5) and Fe presence in XPS scans (Figure 6) indicate Fe deposition onto KM and TB Fo disk surfaces. The appearance of a spectral feature at 0.55 µm in the VNIR spectra from the TB Fo suggests this Fe is ferric (Figure 7). The PG Fo appears least altered, with minimal formation of dissolution features in SEM (Figure 5), a Mg/Si ratio inconsistent with leaching (~2) (Figure 6), and VNIR spectra almost identical to the control sample. Analysis of Fa surfaces is ongoing. The higher temperatures and more acidic pH in the KM soils likely drive the faster dissolution of the Fo disks described above. While the TB soils experience greater precipitation than in the KM, the cooler temperatures and more basic soil pH facilitate observable but more limited alteration. The dry climate and basic soil pH at PG lead to minimal dissolution of the PG disk surfaces.

A D Feldman↗

Space motion sickness medications: interference with biomedical parameters

The possibility that drugs administered to Skylab 3 (SL-3) and 4 (SL-4) crewmen for space motion sickness may have interfered with their biomedical evaluation in space was investigated. Healthy volunteers received combinations of Scopolamine/Dexedrine for four days in regimens similar to those used in these missions. Urine samples, heart rate, body temperature, mood and performance were analyzed for drug-related changes. Twenty-four hour urine samples were analyzed by the same procedures as those used to analyze the flight samples. Hormone concentrations determined included cortisol, epinephrine, norepinephrine, aldosterone and antidiuretic hormone (ADH). In addition, volume, specific gravity, osmolarity, sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), chloride (Cl), inorganic phosphate, uric acid and creatinine were measured. Performance was not affected by the Scopolamine/Dexedrine. The drug combination increased daily mean heart rate (HR) significantly in all the subjects and daily mean rectal temperature (RT) in some of the subjects. A 2-4 hr phase shift in the HR circadian rhythm was also observed which indicates that internal circadian synchrony was disturbed by the drugs. Psychological and subjective evaluation indicated that the subjects could usually identify which days they were given the drugs by an increase in tension and anxiety, decreased patience, restlessness, decreased appetite, difficulty in sleeping and feelings of increased heart rate and body temperature. Urinary electrolytes were not changed significantly by the drug, but marked and significant changes occurred in urine volume and hormone excretion patterns. Scopolamine/Dexedrine caused consistent elevations in urinary cortisol and epinephrine and a transient elevation in ADH. Norepinephrine excretion was decreased, but there was no significant change in aldosterone excretion or in 24 hr urine volume. A comparison of these findings with the first four days of inflight data from the SL-3 and SL-4 missions leads to the conclusion that the dramatic increases in aldosterone excretion during the first three days of spaceflight probably can be directly attributed to weightlessness, whereas the antimotion sickness medication could have substantially contributed to the early increased excretion of epinephrine and cortisol during these missions.

manned↗

Zeolitic Imidazole Framework Decorated Substrates for Lead Removal From Water

Lead contamination in water supplies necessitates efficient and mechanistically understood removal strategies. Zeolitic imidazole frameworks (ZIFs) are promising adsorbents; however, ZIF-67 (Co-based) is more susceptible to hydrolysis than its zinc analogue ZIF-8, raising questions about stability during metal uptake. In this study, we systematically compare ZIF-8 and ZIF-67 under controlled pH conditions and evaluate how substrate anchoring influences hydrolytic stability and Pb 2+ adsorption behavior. By integrating adsorption capacity measurements, kinetic analysis, metal-node leaching data, and structural characterization, we distinguish ion exchange from framework degradation and clarify the temporal interplay between adsorption and hydrolysis. Although ZIF-67 exhibits greater hydrolytic sensitivity, coordination with phosphoryl-bearing Mucor hiemalis membranes significantly reduces Co 2+ leaching and enhances structural retention. Under the optimized conditions (pH 5), ZIF-67@Mucor achieves a maximum Pb 2+ adsorption capacity of 867 mg g −1 . These findings demonstrate that substrate-dependent stabilization enables controlled exploitation of ZIF reactivity for aqueous metal remediation.

Adsorption↗

Pathways of nitrogen loss following land clearing in a humid tropical forest

Tropical deforestation generally leads to large losses of carbon and nitrogen. The Premontane Wet Forest Life Zone is subject to the highest rate of deforestation in Central America, and carbon and nutrient losses in from these fertile soils is very rapid and extreme. Losses of 2000 to 3000 kgN/ha have been reported. Losses of this magnitude could be extremely significant on a regional or global scale if even a small proportion of this nitrogen is lost as nitrous oxide to the atmosphere or through leaching of nitrate to rivers. This study seeks to measure the rates and regulation of nitrogen transformations, and the pathways of nitrogen losses following land clearing and burning at a site in the Premontane Wet Forest Life Zone near Turrialba, Costa Rica.

Matson, Pamela↗

Space physiology and medicine (2nd edition)

The fundamental biomedical issues involved in manned space flight are examined in review chapters contributed by leading U.S. experts. Sections are devoted to the history of manned space flight, the space environment, space-flight systems and procedures, physiological adaptation to space flight, health maintenance of space crewmembers, and medical problems of space flight. Extensive diagrams, drawings, graphs, photographs, and tables of numerical data are provided.

Nicogossian, Arnauld E.↗

Phosphate‐functionalized Zirconium Metal–Organic Frameworks for Enhancing Lithium–Sulfur Battery Cycling

Abstract Lithium–sulfur batteries are promising candidates for next‐generation energy storage devices due to their outstanding theoretical energy density. However, they suffer from low sulfur utilization and poor cyclability, greatly limiting their practical implementation. Herein, we adopted a phosphate‐functionalized zirconium metal–organic framework (Zr‐MOF) as a sulfur host. With their porous structure, remarkable electrochemical stability, and synthetic versatility, Zr‐MOFs present great potential in preventing soluble polysulfides from leaching. Phosphate groups were introduced to the framework post‐synthetically since they have shown a strong affinity towards lithium polysulfides and an ability to facilitate Li ion transport. The successful incorporation of phosphate in MOF‐808 was demonstrated by a series of techniques including infrared spectroscopy, solid‐state nuclear magnetic resonance spectroscopy, and X‐ray pair distribution function analysis. When employed in batteries, phosphate‐functionalized Zr‐MOF (MOF‐808‐PO4) exhibits significantly enhanced sulfur utilization and ion diffusion compared to the parent framework, leading to higher capacity and rate capability. The improved capacity retention and inhibited self‐discharge rate also demonstrate effective polysulfide encapsulation utilizing MOF‐808‐PO4. Furthermore, we explored their potential towards high‐density batteries by examining the cycling performance at various sulfur loadings. Our approach to correlate structure with function using hybrid inorganic–organic materials offers new chemical design strategies for advancing battery materials.

Liu, Bingqian↗

Intergranular precipitation-enhanced wetting and phase transformation in an Al0.4CoCrFeNi high-entropy alloy exposed to lead-bismuth eutectic

We report after exposure to oxygen-poor (10 -13 –10 -14 wt%) liquid lead-bismuth eutectic (LBE) at 500 °C for 500 h, LBE penetrates more than one order of magnitude deeper in an FCC Al 0.4 CoCrFeNi high-entropy alloy (HEA) decorated with a network of BCC (Ni, Al)-rich intergranular (IG) precipitates than in a single-phase, FCC Al 0.3 CoCrFeNi HEA without the IG precipitate network. This deterioration of corrosion resistance is attributed to the energetic nature of the BCC/FCC interphase boundaries (IBs) and resultant IB wetting. The LBE ingress film selectively leaches nickel located at those low-indexed crystalline planes, resulting in phase transformation from FCC to BCC structure.

36 MATERIALS SCIENCE↗

Metabolism and biochemistry in hypogravity

The headward shift of body fluid and increase in stress-related hormones that occur in hypogravity bring about a number of changes in metabolism and biochemistry of the human body. Such alterations may have important effects on health during flight and during a recovery period after return to earth. Body fluid and electrolytes are lost, and blood levels of several hormones that control metabolism are altered during space flight. Increased serum calcium may lead to an increased risk of renal stone formation during flight, and altered drug metabolism could influence the efficacy of therapeutic agents. Orthostatic intolerance and an increased risk of fracturing weakened bones are concerns at landing. It is important to understand biochemistry and metabolism in hypogravity so that clinically important developments can be anticipated and prevented or ameliorated.

Leach, Carolyn S.↗

Formation and Detriments of Residual Alkaline Compounds on High-Nickel Layered Oxide Cathodes

High-nickel layered oxides LiNi x M 1-x O 2 (x ≥ 0.9) have emerged as promising cathode materials for automotive batteries due to their high energy density and lower cost. However, the formation and accumulation of surface alkaline compounds during storage hinder their mass production and commercialization. Here, in this study, a validated chemical method is employed to deconvolute and quantify the evolution of each residual lithium compound in four representative cathodes during ambient-air storage, viz., LiNiO 2 (LNO), LiNi 0.95 Co 0.05 O 2 (NC), LiNi 0.95 Mn 0.05 O 2 (NM), and LiNi 0.95 Al 0.05 O 2 (NA). Furthermore, the activation energy of the reaction between water and the cathode is determined by measuring the leached LiOH concentration at various temperatures. While residual lithium and time-of-flight secondary-ion mass spectrometry measurements collectively reveal that the air stability overall follows the trend of NM > NA ≈ NC > LNO, the aged NM exhibits the highest charge-transfer resistance and the worst electrochemical performance among the cathodes. In situ, X-ray diffraction and scanning transmission electron microscopy unveil that the aged NM is plagued by a large area of resistive spinel-like M 3–x Li x O 4 phases, leading to aggravated particle reaction heterogeneity. Finally, a one-step recalcination method is demonstrated effective in fully restoring the degraded cathodes. This work provides insights into overcoming air sensitivity issues of high-Ni cathodes.

(S)TEM↗

Increasing the Lifetime of Epoxy Components with Antioxidant Stabilizers

Epoxy thermoset resins are ubiquitous materials with extensive applications where they are used as encapsulants, composites, and adhesives/staking compounds used to secure sensitive components. Epoxy resins are inherently sensitive to thermo-oxidative aging, especially at elevated temperatures, which changes the bulk properties of the material and can lead to component failure for example by cracking due to embrittlement or by adhesion failure between the epoxy and filler material in a composite. This project investigated the effects of three commercial antioxidants (Irganox ® 1010 (I-102), butylated hydroxytoluene (BHT), or Chisorb ® 770 (HALS)) at two different loadings (2.5 and 5 wt%) on the mechanical and chemical aging of a model epoxy system (EPON TM 828 / Jeffamine ® T-403) under ambient conditions, 65, 95, and 110 °C. Additionally, synthetic routes towards an antioxidant capable of being covalently bound to the resin so as to prevent leaching were explored with one such molecule being successfully synthesized and purified. One commercial antioxidant (Irganox ® 1010) was found to reduce the degree of thermo-oxidatively induced damage in the system.

36 MATERIALS SCIENCE↗

Comparative analysis of new crystal and plastic scintillators for fast and thermal neutron detection

This paper considers scintillation and physical properties of efficient organic scintillators tested as single crystals and as components of plastics with pulse shape discrimination (PSD). For the first time, single crystals of 9,9-dimethyl-2-phenyl-9H-fluorene (PhF) were grown for studies of the basic scintillation properties of this new compound. Comparison to classical organic crystals, like anthracene, trans-stilbene, and p-terphenyl, and to more recently introduced organic glass showed that the new crystal belongs to a group of the most efficient scintillators, with light output exceeding that of trans-stilbene and PSD comparable to that of p-terphenyl. Furthermore, additional studies were conducted to evaluate scintillation performance and physical properties, like hardness and dye leaching, of plastic scintillators prepared with PhF, organic glass, and liquid diisopropylnaphthalene (DIPN) that were considered as examples for potential replacement of PPO (2,5-diphenyloxazole) in current commercial PSD plastic scintillators. Comparison of the highest performing plastic scintillators prepared with these dyes shows that PhF formulations produced a record light output (LO) increase of 69 % relative to EJ-200. Similar improvements obtained with 6 Li-loaded formulations showed that future development of PSD plastics should not be limited to use of PPO but must involve the search and exploration of new efficient dyes that may lead to discovery of much brighter organic scintillators with improved physical properties required for fast and thermal neutron detection, fast neutron spectroscopy, and antineutrino detection applications.

9,9-dimethyl-2-phenyl-9H-fluorene↗

Saltstone Third Quarter Calendar Year 2021 (3QCY21) Toxicity Characteristic Leading Procedure (TCLP) Results

The aqueous waste from Tank 50 (salt solution) is sampled quarterly for transfers to the Saltstone Production Facility (SPF). Salt solution is treated at SPF and disposed of in the Saltstone Disposal Facility (SDF). Per request of customer, X-TTR-Z-00023, Revision 0, two SDF waste form (saltstone) samples were prepared in the Savannah River National Laboratory (SRNL) from the Tank 50 Waste Acceptance Criteria (WAC) sample and Z-Area premix material for the third quarter of calendar year 2021(3QCY21). One sample contained a Full Premix which included 10:45:45 (by weight) of cement, slag and fly ash. The second sample contained 60:40 (by weight) of slag and fly ash only referred to as the “Cement-Free grout sample”. Results from this technical report support Task 2: ‘Grout Leaching Analyses’ of the Task Technical Request (TTR) prepared by Savannah River Remediation (SRR). After at least 28 days cured, a sample of each of the SDF waste forms was collected and shipped to a certified laboratory for analysis using the Toxicity Characteristic Leaching Procedure (TCLP). The 3QCY21 saltstone (Full Premix) and the Cement-Free grout samples met the South Carolina (SC) Code of Regulations for Hazardous Waste Management Regulations (HWMR) 61-79.261.24 and 61-79-268.48 requirements for a non-hazardous waste form with respect to Resource Conservation and Recovery Act (RCRA) metals and Underlying Hazardous Constituents (UHCs), and also met the SPF WAC that was in effect at the time of the tank sampling.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Water acidification aggravates lithium-induced toxicity represented by energy supply, oxidative stress, and cell fate in Daphnia magna neonates

Lithium is extensively utilized in industrial energy production, particularly in lithium-ion batteries, and in pharmaceuticals for the treating clinical mood disorders. Consequently, lithium is frequently detected in various environmental matrices. It has been reported to cause a range of toxic effects on aquatic organisms including oxidative stress, neurological disorders, and reproductive suppression. Water acidification is a global issue with numerous negative impacts on aquatic organisms. It can alter the physio-chemical properties and bioavailability of metal ions. The acidic leaching process during lithium battery treatment and global water acidification both suggest that lithium contamination often occurs in acidic environments. In the present study, Daphnia magna neonates were exposed to four treatments (control, lithium alone, low pH, and combined) to investigate whether an acidic environment exacerbates the toxic effects of lithium on aquatic organisms and to explore potential toxic action mechanisms. The results indicated that low pH posed a significant threat to the growth and reproduction of D. magna. When exposed to both lithium and low pH, there was increased lithium accumulation and an energy trade-off response, leading to increased energy allocation to reproduction and reduced energy for growth. Lithium exposure stimulated D. magna activity, while low pH inhibited it, suggesting that an imbalance in energy consumption and supply. Combined exposure to lithium and low pH resulted in severe oxidative stress due to mitochondrial dysfunction, under-utilization of energy substances, and increased ionic homeostasis disturbances. Consequently, the exposed organism altered apoptosis and autophagy processes to maintain homeostasis. In conclusion, the present study demonstrated that lithium and water acidification posed a population-level threat to D. magna, and their combined exposure significantly largely exacerbated the toxic effects.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

Shergottite Lead Isotope Signature in Chassigny and the Nakhlites

The nakhlites/chassignites and the shergottites represent two differing suites of basaltic martian meteorites. The shergottites have ages less than or equal to 0.6 Ga and a large range of initial Sr-/Sr-86 and epsilon (Nd-143) ratios. Conversely, the nakhlites and chassignites cluster at 1.3-1.4 Ga and have a limited range of initial Sr-87/Sr-86 and epsilon (Nd-143). More importantly, the shergottites have epsilon (W-182) less than 1, whereas the nakhlites and chassignites have epsilon (W-182) approximately 3. This latter observation precludes the extraction of both meteorite groups from a single source region. However, recent Pb isotopic analyses indicate that there may have been interaction between shergottite and nakhlite/chassignite Pb reservoirs.Pb Analyses of Chassigny: Two different studies haveinvestigated 207Pb/204Pb vs. 206Pb/204Pb in Chassigny: (i)TIMS bulk-rock analyses of successive leaches and theirresidue [3]; and (ii) SIMS analysis of individual minerals[4]. The bulk-rock analyses fall along a regression of SIMSplagioclase analyses that define an errorchron that is olderthan the Solar System (4.61±0.1 Ga); i.e., these define amixing line between Chassigny’s principal Pb isotopic components(Fig. 1). Augites and olivines in Chassingy (notshown) also fall along or near the plagioclase regression [4].This agreement indicates that the whole-rock leachateslikely measure indigenous, martian Pb, not terrestrial contamination[5]. SIMS analyses of K-spars and sulfides definea separate, sub-parallel trend having higher 207Pb/206Pbvalues ([4]; Fig. 1). The good agreement between the bulkrockanalyses and the SIMS analyses of plagioclases alsoindicates that the Pb in the K-spars and sulfides cannot be amajor component of Chassigny.The depleted reservoir sampled by Chassigny plagioclaseis not the same as the solar system initial (PAT) andrequires a multi-stage origin. Here we show a two-stagemodel (Fig. 1) with a 238U/204Pb (μ) of 0.5 for 4.5-2.4 Gaand a μ of 7 for 2.4-1.4 Ga. This is not a unique model butdoes produce a Pb composition that falls on the plagioclaseregression at 1.4 Ga, the approximate igneous age of Chassigny [1]. It should be noted that low-μ single-stage modelsare not capable of producing sufficiently radiogenic 206Pb/204Pb at 1.4 Ga.Relation to Shergottites: The Chassigny K-spars and sulfides fall along a second mixing line defined by leachesand residues of depleted and intermediate shergottites [6]. This mixing line falls above the plagioclase regression.Therefore, we also interpret the radiogenic component of this mixing line to represent indigenous martian Pb. It ispossible that the depleted and intermediate shergottites and the Chassigny plagioclases sample radiogenic Pb from thethe same source, i.e., the mixing lines may intersect at high 206Pb/204Pb.Both K-spar and sulfide are late-stage phases. At the time of their crystallization, the Chassigny system appearsto have remained open to a depleted shergottite Pb reservoir. The depleted component of the shergottite mixing linecan be generated by a single-stage evolution from PAT (4.5 to 1.4 Ga) in a reservoir having a μ ~2. A similar modelfor the most depleted shergottites is also possible: μ = 1.5 for 4.5 to 0.3 Ga.Nakhlites: Nakhlite analyses plot between the shergottite and Chassigny plagioclase regressions [3]. So again,members of the nakhlite/chassignite suite show affinities to shergottite Pb.

Jones, J. H.↗