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At least 73 records · Page 4

Probing Neodymium Isotopic Variations in the Inner Solar System

One of the key problems in planetary science is the identification of the building blocks of Earth, and whether they exist within our current collection of meteorites. Stable mass independent isotopic anomalies, usually nucleosynthetic in origin, are a key tool in fingerprinting material coming from different accretionary regions within the protoplanetary disk. For a number of isotopic systems such as O, Ni, Ti and Cr, enstatite chondrites (EC) appear to be the strongest candidates for Earth's building blocks, despite their low Mg/Si ratios relative to the bulk Earth. It has been proposed that Earth, the Moon-forming impactor and enstatite chondrites all were originally sourced from the same reservoir in the protoplanetary disk, but subsequently experienced divergent chemical evolution pathways. This was recently challenged by who used the correlation between Mo and Nd isotopes in bulk meteorites to argue that such a reservoir does not exist as the isotopic composition of enstatite chondrites is resolvable from Earth. However, in detail the Nd isotopic ratios of EC ((142)Nd/(144)Nd, (148)Nd/(144)Nd, (150)Nd/(144)Nd) show considerable variability, and overlap significantly with the isotopic composition of both the bulk Earth and ordinary chondrites (OC). previously identified Nd isotopic variability in EC, linking it to the degree of equilibration the meteorite had experienced, however they only focused on collecting high precision (142)Nd/(144)Nd, which also has contributions from the decay of the short-lived Sm-146 nuclide (t(sub 1/2) ~103 Myr), making identification of nucleosynthetic anomalies less clear. While the study of reports all the Nd isotopic ratios measured at high precision, only equilibrated EC were analyzed. Therefore, with the currently published data it is unclear to what extent thermal equilibration in the EC is responsible for the variation observed in the stable Nd isotopic ratios, and whether the EC reservoir can be resolved from Earth. In order to better understand the genetic relationship between enstatite chondrites and the Earth we are carrying out a more systematic study including both equilibrated and unequilibrated enstatite chondrites, focusing on high precision analysis of all the stable Nd isotopic ratios.

SOLAR SYSTEM↗

Low 13 C- 13 C abundances in abiotic ethane

Distinguishing biotic compounds from abiotic ones is important in resource geology, biogeochemistry, and the search for life in the universe. Stable isotopes have traditionally been used to discriminate the origins of organic materials, with particular focus on hydrocarbons. However, despite extensive efforts, unequivocal distinction of abiotic hydrocarbons remains challenging. Recent development of clumped-isotope analysis provides more robust information because it is independent of the stable isotopic composition of the starting material. Here, we report data from a 13 C- 13 C clumped-isotope analysis of ethane and demonstrate that the abiotically-synthesized ethane shows distinctively low 13 C- 13 C abundances compared to thermogenic ethane. A collision frequency model predicts the observed low 13 C- 13 C abundances (anti-clumping) in ethane produced from methyl radical recombination. In contrast, thermogenic ethane presumably exhibits near stochastic 13 C- 13 C distribution inherited from the biological precursor, which undergoes C-C bond cleavage/recombination during metabolism. Further, we find an exceptionally high 13 C- 13 C signature in ethane remaining after microbial oxidation. In summary, the approach distinguishes between thermogenic, microbially altered, and abiotic hydrocarbons. The 13 C- 13 C signature can provide an important step forward for discrimination of the origin of organic molecules on Earth and in extra-terrestrial environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Carbonates in ALH 84001 Record the Evolution of the Martian Atmosphere Through Multiple Formation Events

Current Martian conditions restrict the presence of liquid water due to low temperatures (approx 210K), a thin atmosphere (approx 7mb), and intense UV radiation. However, past conditions on Mars may have been different with the possibility that the ancient Martian climate was warm and wet with a dense CO2 atmosphere. The cycling of carbon on Mars through atmospheric CO2 and carbonate minerals is critical for deciphering its climate history. In particular stable isotopes contained in carbonates can provide information of their origin and formation environment as well as possibly hinting at the composition of global reservoirs such as atmospheric CO2. Martian meteorite ALH 84001 contains widely studied carbonate rosettes that have been dated to approx. 3.9 Ga and have been used to interpret climatic conditions present at that time. However, there is mount-ing evidence for multiple episodes of carbonate formation in ALH 84001 with potentially distinct isotopic compositions. This study seeks to tease out these different carbonate assemblages using stepped phosphoric acid dissolution and analysis of carbon and triple oxygen stable isotopes. In addition, we report SIMS analyses of the delta O-18 several petrographically unusual carbonate phases in the meteorite.

Shaheen, R.↗

Microbiome processing of organic nitrogen input supports growth and cyanotoxin production of Microcystis aeruginosa cultures

Abstract Nutrient-induced blooms of the globally abundant freshwater toxic cyanobacterium Microcystis cause worldwide public and ecosystem health concerns. The response of Microcystis growth and toxin production to new and recycled nitrogen (N) inputs and the impact of heterotrophic bacteria in the Microcystis phycosphere on these processes are not well understood. Here, using microbiome transplant experiments, cyanotoxin analysis, and nanometer-scale stable isotope probing to measure N incorporation and exchange at single cell resolution, we monitored the growth, cyanotoxin production, and microbiome community structure of several Microcystis strains grown on amino acids or proteins as the sole N source. We demonstrate that the type of organic N available shaped the microbial community associated with Microcystis, and external organic N input led to decreased bacterial colonization of Microcystis colonies. Our data also suggest that certain Microcystis strains could directly uptake amino acids, but with lower rates than heterotrophic bacteria. Toxin analysis showed that biomass-specific microcystin production was not impacted by N source (i.e. nitrate, amino acids, or protein) but rather by total N availability. Single-cell isotope incorporation revealed that some bacterial communities competed with Microcystis for organic N, but other communities promoted increased N uptake by Microcystis, likely through ammonification or organic N modification. Our laboratory culture data suggest that organic N input could support Microcystis blooms and toxin production in nature, and Microcystis-associated microbial communities likely play critical roles in this process by influencing cyanobacterial succession through either decreasing (via competition) or increasing (via biotransformation) N availability, especially under inorganic N scarcity.

54 ENVIRONMENTAL SCIENCES↗

Endogenous Production and Vibrational Analysis of Heavy-Isotope-Labeled Peptides from Cyanobacteria

Stable isotope labeling is an extremely useful tool for characterizing the structure, tracing the metabolism, and imaging the distribution of natural products in living organisms using mass-sensitive measurement techniques. In this study, a cyanobacterium was cultured in 15 N/ 13 C-enriched media to endogenously produce labeled, bioactive oligopeptides. The extent of heavy isotope incorporation in these peptides was determined with LC–MS, while the overall extent of heavy isotope incorporation in whole cells was studied with nanoSIMS and AFM-IR. Up to 98 % heavy isotope incorporation was observed in labeled cells. Three of the most abundant peptides, microcystin-LR (MCLR), cyanopeptolin-A (CYPA), and aerucyclamide-A (ACAA), were isolated and further studied with Raman and FTIR spectroscopies and DFT calculations. This revealed several IR and Raman active vibrations associated with functional groups not common in ribosomal peptides, like diene, ester, thiazole, thiazoline, and oxazoline groups, which could be suitable for future vibrational imaging studies. More broadly, this study outlines a simple and relatively inexpensive method for producing heavy-labeled natural products. Finally, manipulating the bacterial culture conditions by the addition of specific types and amounts of heavy-labeled nutrients provides an efficient means of producing heavy-labeled natural products for mass-sensitive imaging studies.

60 APPLIED LIFE SCIENCES↗

Stable water isotope behavior during the last glacial maximum: A general circulation model analysis

Global water isotope geochemisty during the last glacial maximum (LGM) is simulated with an 8 deg x 10 deg atmospheric general circulation model (GCM). The simulation results suggest that the spatial delta O-18/temperature relationships observed for the present day and LGM climates are very similar. Furthermore, the temporal delta O-18/temperature relationship is similar to the present-day spatial relationship in regions for which the LGM/present-day temperature change is significant. This helps justify the standard practice of applying the latter to the interpretation of paleodata, despite the possible influence of other factors, such as changes in the evaportive sources of precipitation or in the seasonality of precipitation. The model suggests, for example, that temperature shifts inferred from ice core data may differ from the true shifts by only about 30%.

Jouzel, Jean↗

Challenges in correlating oxygen stable isotope ratios of hydrates on uranium ore concentrates to process waters

Exchange of oxygen stable isotopes (δ 18 O values) between precipitation waters and uranium oxides is governed by thermodynamics or kinetics. It has been assumed that meteoric waters can be related to precipitation waters in uranium ore concentrates and their calcination and reduced uranium oxide products. With this assumption, the δ 18 O values of uranium materials could provide forensic signatures that identify the production history and geolocation of nuclear materials. To further exploit the potential of δ 18 O values in nuclear material analysis, this study examines the oxygen stable isotope exchange in two UOCs, magnesium diuranate (MDU) and sodium diuranate (SDU). MDU and SDU were synthesized from solutions of uranyl nitrate hexahydrate using precipitation waters with unique oxygen isotope compositions. The structures of the MDU and SDU were analyzed using powder X-ray diffraction (p-XRD) and thermal mass loss curves, while the δ 18 O values of waters generated during thermal decomposition were analyzed using a thermogravimetric analyzer coupled to an isotope ratio infrared spectrometer (TGA-IRIS). By p-XRD, the MDU was uniform and amorphous across all syntheses with residual crystalline material incorporated as a minor component. Combined with the TGA results, all of the MDU is likely amorphous MgU 2 O 7 ·3H 2 O with MgO impurities present throughout. In contrast, the SDU synthesis resulted in multiple phases with many samples exhibiting crystalline phases including a combination of Na(UO 2 ) 4 O 2 (OH) 5 ·5H 2 O and Na 2 (UO2) 6 O 4 (OH) 6 ·8H 2 O with a Na 2 U 2 O 7 minor phase. A small fraction of the SDU samples were amorphous with no crystalline XRD peaks observed. Mass loss curves of the SDU samples revealed that the amorphous samples contained inclusions of similar crystalline phases compared to the crystalline materials. The uniformity of the MDU samples enabled highly reproducible measurements of δ 18 O values of the water vapor yielded for two dehydration events at 170 °C and 500 °C. In contrast, the multiphase composition of the SDU samples resulted in poor reproducibility in δ 18 O values. In conclusion, neither system revealed any correlation between the δ 18 O values of precipitation water, and the waters released during dehydration of the UOCs.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Correlative SIP-FISH-Raman-SEM-NanoSIMS links identity, morphology, biochemistry, and physiology of environmental microbes

Microscopic and spectroscopic techniques are commonly applied to study microbial cells but are typically used on separate samples, resulting in population-level datasets that are integrated across different cells with little spatial resolution. To address this shortcoming, we developed a workflow that correlates several microscopic and spectroscopic techniques to generate an in depth analysis of individual cells. By combining stable isotope probing (SIP), fluorescence in situ hybridization (FISH), scanning electron microscopy (SEM), confocal Raman microspectroscopy (Raman), and nano-scale secondary ion mass spectrometry (NanoSIMS), we illustrate how individual cells can be thoroughly interrogated to obtain information about their taxonomic identity, structure, physiology, and metabolic activity. Analysis of an artificial community demonstrated that our correlative approach was able to resolve the activity of single cells using heavy water SIP in conjunction with Raman and/or NanoSIMS and establish their taxonomy and morphology using FISH and SEM. We then applied this workflow to a sample of yet uncultured multicellular magnetotactic bacteria. In addition to establishing their identity and activity, backscatter electron microscopy (BSE), NanoSIMS, and energy-dispersive X-ray spectroscopy (EDS) were employed to characterize the magnetosomes within the cells. By integrating these techniques, we demonstrate a cohesive approach to thoroughly study environmental microbes at single cell resolution.

Schaible, George↗

Stable isotope laser spectroscopy

Recent advances in semiconductor laser technology have produced a reliable lightweight device ideally suited for a spacecraft high resolution molecular spectrometer. Lead-salt tunable diode lasers (TDL) emit in several spectral modes, each with a very narrow linewidth of -0.0003/cm. This spectral resolution is much narrower than typical Doppler broadened molecular linewidths in the mid-IR range. Thus it is possible to detect individual rotational lines within the vibrational band and measure their intensity, which can be used to determine gas concentration. The narrow spectral lines of any impurity gas tend to lie between the narrow lines of the gas of interest. This represents a major advantage over the accepted gas chromatograph mass spectrometer (GCMS) technique for measuring gas concentrations and isotope ratios. The careful and extensive gas purification procedures required to remove impurities for reliable GCMS measurements will not be required for an IR laser gas analysis. The infrared laser gas analysis technique is being developed to measure stable isotopic ratios of gases such as CO2, CH4, N2O, and NH3. This will eventually lead to development of instruments capable of in situ istopic measurements on planets such as Mars. The carbon (C-12, C-13) isotope ratio is indicative of the type of carbon fixation mechanisms (e.g., photosynthesis, respiration) in operation on a planet, while the nitrogen (N-14, N-15) isotope ratio can probably be used to date nitrogen-bearing Martian samples. The absorbance ratio of two adjacent lines of CO2 in the 2300/cm (4.3 micron) region of the spectrum was measured. The precision of the measurement is presently better than 1 percent and significant improvement is anticipated as rapid sweep-integration techniques and computer controlled data acquistion capabilities are incorporated.

Becker, J. F.↗

Selective and Stable In-Promoted Fe Catalyst for Syngas Conversion to Light Olefins

A selective and stable alumina-supported In-promoted Fe catalyst (10 mol % In based on Fe) was discovered for converting syngas (2:1 H 2 /CO ratio) to olefins with high selectivity (45% with CO 2 included) and a remarkable stability (72 h run) at a CO conversion of 10% at 400 °C and 5 bar. The X-ray photoelectron spectroscopy results indicated that incorporating In into Fe catalysts changed the chemical bonding state of Fe and Fe/In composition near the surface layers, which affected the catalytic reactivity. Steady-state isotopic transient kinetic analysis showed that more stable CHx fragments are present on the catalyst surface when incorporating In into Fe, which can promote C–C coupling reaction toward olefins. Our study demonstrates that introducing In into Fe catalysts on Al 2 O 3 support can lower CO activation abilities. It has more impacts on lowering hydrogenation activity, which permits more C–C couplings and like of “ene” hydrogenation. Furthermore, weakening CO adsorption both in terms of sites and strength encouraged CO toward hydrocarbons rather than CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Compound-Specific Isotopic Analysis of Meteoritic Amino Acids as a Tool for Evaluating Potential Formation Pathways

Measurements of stable hydrogen, carbon, and nitrogen isotopic ratios (delta D, delta C-13, delta N-15) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may point towards the most likely of these proposed pathways. The technique of gas chromatography coupled with mass spectrometry and isotope ratio mass spectrometry provides compound-specific structural and isotopic information from a single splitless injection, enhancing the amount of information gained from small amounts of precious samples such as carbonaceous chondrites. We have applied this technique to measure the compound-specific C, N, and H isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites. We are using these measurements to evaluate predictions of expected isotopic enrichments from potential formation pathways and environments, leading to a better understanding of the origin of these compounds.

Elsila, Jamie E.↗

The formation of weathering products on the LEW 85320 ordinary chondrite - Evidence from carbon and oxygen stable isotope compositions and implications for carbonates in SNC meteorites

Isotopic analysis of nesquehonite recovered from the surface of the LEW 85320 H5 ordinary chondrite shows that the delta C-13 and delta O-18 values of the two generations of bicarbonate (Antarctic and Texas) are different: delta C-13 = + 7.9 per mil and + 4.2 per mil; delta O-18 = + 17.9 per mil and + 12.1 per mil, respectively. Carbon isotopic compositions are consistent with equilibrium formation from atmospheric carbon dioxide at - 2 + or - 4 C (Antarctic) and + 16 + or - 4 C (Texas). Oxygen isotopic data imply that the water required for nesquehonite precipitation was derived from atmospheric water vapor or glacial meltwater which had locally exchanged with silicates, either in the meteorite or in underlying bedrock. Although carbonates with similar delta C-13 values have been identified in the SNC meteorites EETA 79001 and Nakhla, petrographic and temperature constraints argue against their simply being terrestrial weathering products.

Grady, Monica M.↗

Use of Stable Mercury Isotopes to Assess Mercury and Methylmercury Transformation and Transport across Critical Interfaces from the Molecular to the Watershed Scale (Final Report)

This project titled “Use of Stable Mercury Isotopes to Assess Mercury and Methylmercury Transformation and Transport across Critical Interfaces from the Molecular to the Watershed Scale” represents a collaborative effort between the University of Michigan (Jason Demers, PI) and Oak Ridge National Laboratory (Scott Brooks, co-I). Much has been learned about mercury (Hg) cycling in stream ecosystems, and East Fork Poplar Creek (EFPC) in particular, through decades of previous research. Nevertheless, some of the most fundamental questions regarding the sources of bioavailable Hg and its transformation to toxic methylmercury (MeHg) have remained unanswered. These fundamental questions include: (1) what are the sources and biogeochemical processes that lead to the input of dissolved Hg to stream water across critical subsurface interfaces within stream ecosystems, and EFPC in particular? and (2) what are the sources and biogeochemical processes that control the production and fate of bioaccumulative MeHg within stream ecosystems, and in EFPC in particular? To address these fundamental questions, our project aimed to couple laboratory experiments and field observations, both utilizing natural abundance Hg stable isotope techniques, to identify the processes responsible for generating mobile, bioavailable dissolved Hg from recalcitrant legacy sources within critical subsurface zones (e.g., streambed hyporheic zone, riparian floodplain subsurface). We used the isotopic signature of this bioavailable dissolved Hg to track its mobilization across these critical interfaces in order to link diffuse subsurface sources of dissolved Hg with increases in surface water dissolved Hg flux measured at the watershed scale. Additionally, our research aimed to determine the isotopic composition of MeHg within these same critical subsurface zones. We directly assessed the isotopic composition of MeHg within biota in order to gain insight into which subsurface sources of inorganic Hg and toxic MeHg are available for bioaccumulation within the EFPC ecosystem. Net fluxes of dissolved Hg along the flow path of EFPC were shown to vary spatially and temporally. In the Upper EFPC, within the Y12 boundary, stream water flux of dissolved Hg consistently decreased between the outfall and the downstream boundary of Y12 (57% ± 29%, 1SD). Within the Upper EFPC, an assessment of Hg isotopic composition suggested that losses were strongly reaction-driven, although isotopic diagnostics did not conform to any known processes. Downstream of Y12, in the upper reach of the Lower EFPC, dissolved Hg fluxes tended to increase during the dormant season (net gain of 11-120%), and decrease during the growing season (net loss of 23% +/- 18%, 1SD). In the downstream-most reach of Lower EFPC, dissolved Hg fluxes increased by 12-108% in 9 out of 10 monthly assessments. Overall, diffuse fluxes from the non-Y12 watershed accounted for 34% (+/- 17%, 1SD) of all dissolved Hg exported during base flow. Within Lower EFPC, an assessment of Hg isotopic composition was consistent with the contribution of diffuse Hg inputs from high-concentration hotspots within riparian floodplains and streambed hyporheic pore water. To investigate remobilization of recalcitrant Hg from legacy sediment sources, we developed procedures that coupled isotopic analysis with sequential extractions of streambed sediment. We found that the proportion of weakly-bound Hg within EFPC streambed sediment was relatively small, but could still account for a large proportion of the annual flux of dissolved Hg from EFPC. These sequential extractions also showed that this weakly-bound Hg fraction could be replenished from the much larger fraction of recalcitrant Hg in sediment. The isotopic composition of these weakly-bound and remobilized recalcitrant Hg fractions within the sediment was consistent with high-concentration dissolved Hg hotspots within hyporheic pore water. Thus, this research provided novel evidence that legacy mercury sources within streambed sediment could provide an ongoing contribution of dissolved Hg to surface waters. Finally, we developed new methods for the direct determination of the MeHg isotopic composition of organisms, which allowed a more direct evaluation of inorganic Hg and MeHg sources accumulating in the food web. We found that fish and aquatic invertebrates in both EFPC and a regional background site obtained inorganic Hg and MeHg from multiple isotopically distinct sources, including sediment, suspended particulates, and periphyton. Photodemethylation was found to be an important reaction influencing MeHg dynamics at both sites. However, the balance of microbial methylation and demethylation processes differed between the two streams, with fractionation resulting from methylation and demethylation processes being relatively in balance within the regional background site, whereas microbial methylation appeared to be dominant over microbial demethylation within the EFPC ecosystem. Broadly, the application of Hg isotopic analysis in this study led to numerous novel insights regarding the biogeochemical cycling of Hg in stream ecosystems. This research project promoted the development of two new approaches, including the coupling of sequential extractions with Hg isotopic analysis to assess remobilization of recalcitrant Hg within sediments, and a new method for the isotopic analysis of MeHg isolated from environmental samples. Both of these efforts represent advances in capacity for the field of mercury isotopic analysis and environmental assessment. Overall, this study demonstrates that the application of Hg stable isotope techniques continues to provide new insights into the biogeochemical cycling of Hg in complex aquatic environments, both within the EFPC and beyond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Calcium fluoride as a dominating matrix for quantitative analysis by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS): A feasibility study

Here, calcium fluoride formed by the reaction between ammonium bifluoride and calcium chloride was investigated as a dominating matrix for quantitative analysis by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Transformation from a solid sample to the calcium fluoride-based matrix permitted quantitative analysis based on calibration standards made from elemental standards. A low abundance stable calcium isotope, i.e. 44 Ca + , was monitored as the internal standard for quantitative analysis by LA-ICP-MS. Correlation coefficient factors for multiple elements were obtained with values over 0.999. The results for multiple elements in a certified reference material of soil (NIST SRM 2710a) agreed with the certified values in the range of expanded uncertainty, indicating the present method was valid for quantitation of elements in solid samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Geochemical Changes in Response to CO 2 Injection in a CO 2 -EOR Complex in Northern Michigan

The overall purpose of the geochemical monitoring program under Midwestern Regional Carbon Sequestration Partnership (MRCSP) is to use stable and radiogenic isotope geochemistry in concert with analysis of general geochemical parameters of fluids and gases and analysis of core samples to determine geochemical processes occurring in the reef structure because of CO 2 injection..

54 ENVIRONMENTAL SCIENCES↗

Geochemical Changes in Response to CO 2 Injection in a CO 2 -EOR Complex in Northern Michigan (Volume II.1)

The Midwest Regional Carbon Sequestration Partnership (MRCSP) was founded in 2003 as part of the U.S. Department of Energy’s (DOE’s) Regional Carbon Sequestration Partnership initiative. Since its founding, MRCSP has made significant strides toward making CCUS a viable option for states in the region. The public/private consortium, funded through the DOE Regional Carbon Sequestration Initiative, brings together nearly 40 industry partners and 10 states. Battelle, as the project lead, oversees research, development and operations and coordinates activities among the partners. The incremental, phased approach has built a valuable knowledge base for the industry and paved the way for commercial-scale adoption of CCUS technologies. From 2008 to 2020, MRCSP Phase III focused on the development of large-scale injection projects. This report is part of a series of reports prepared under the Midwestern Regional Carbon Sequestration Partnership (MRCSP) Phase III (Development Phase). These reports summarize and detail the findings of the work conducted under the Phase III project. The report describes the geochemical monitoring program under MRCSP to use stable and radiogenic isotope geochemistry in concert with analysis of general geochemical parameters of fluids and gases and analysis of core samples to determine geochemical processes occurring in the reef structure because of CO 2 injection. Specifically, brine and gas samples were collected and analyzed to determine changes occurring between reefs prior to and following CO 2 injection. The analytical results for general geochemical parameters were modeled with chemical equilibrium models to determine if the injection of CO 2 resulted in the mineral dissolution or precipitation. Finally, core samples were collected and analyzed to determine if there was evidence of dissolution features or mineral precipitation.

01 COAL, LIGNITE, AND PEAT↗

Trace element and isotope geochemistry of Cretaceous-Tertiary boundary sediments: identification of extra-terrestrial and volcanic components

Trace element and stable isotope analyses were performed on a series of sediment samples crossing the Cretaceous-Tertiary (K-T) boundary from critical sections at Aumaya and Sopelano, Spain. The aim is to possibly distinguish extraterrestrial vs. volcanic or authigenic concentration of platinum group and other elements in K-T boundary transitional sediments. These sediments also have been shown to contain evidence for step-wise extinction of several groups of marine invertebrates, associated with negative oxygen and carbon isotope excursions occurring during the last million years of the Cretaceous. These isotope excursions have been interpreted to indicate major changes in ocean thermal regime, circulation, and ecosystems that may be related to multiple events during latest Cretaceous time. Results to date on the petrographic and geochemical analyses of the Late Cretaceous and Early Paleocene sediments indicate that diagenesis has obviously affected the trace element geochemistry and stable isotope compositions at Zumaya. Mineralogical and geochemical analysis of K-T boundary sediments at Zumaya suggest that a substantial fraction of anomalous trace elements in the boundary marl are present in specific mineral phases. Platinum and nickel grains perhaps represent the first direct evidence of siderophile-rich minerals at the boundary. The presence of spinels and Ni-rich particles as inclusions in aluminosilicate spherules from Zumaya suggests an original, non-diagenetic origin for the spherules. Similar spherules from southern Spain (Caravaca), show a strong marine authigenic overprint. This research represents a new approach in trying to directly identify the sedimentary mineral components that are responsible for the trace element concentrations associated with the K-T boundary.

Margolis, S. V.↗

Micrometeorite pre-solar diamonds from Greenland cryoconite?

An acid-resistant residue prepared from Greenland cryoconite has been investigated to determine whether the micrometeorite component within the cryoconite contains pre-solar material analogous to that found in primitive chondritic meteorites. The residue has been analyzed for carbon content and stable isotopic comparison, by electron probe micro-analysis (EPMA) for major element chemistry and then by a combination of X-ray diffraction (XRD) and transmission electron microscopy (TEM) to elucidate the structure of any constituent mineral phases. The cryoconite sample, which was collected ca. 25 km inland of the ice margin at the latitude of Sondre Stromfjord on the west coast of Greenland, was processed following procedures used on bulk meteorite samples for the isolation of pre-solar dust components.

Yates, P. D.↗