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At least 757 records · Page 42
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

The Principal Hugoniot of Iron-Bearing Olivine to 1465 GPa

Shock compression experiments on natural compositions are imperative to accurately model planetary accretion and the interior dynamics of planets. Combining shock compression experiments from the Sandia Z Machine and the OMEGA EP laser facility with density functional theory-based molecular dynamics calculations, we report the first pressure-density-temperature (P-ρ-T) relationship of natural iron (Fe)-bearing olivine ((Mg 0.91 Fe 0.09 ) 2 SiO 4 ) on the principal Hugoniot between 166 and 1,465 GPa. Additionally, we report the first reflectivities of natural olivine liquid in this pressure range. Compared to the magnesium-endmember forsterite (Mg 2 SiO 4 ), the presence of Fe in typical mantle abundance (~9 wt% FeO) alters the U S -u P relation of olivine. Furthermore, the shock temperature and reflectivity of olivine are indistinguishable from forsterite where experimental conditions overlap. Both forsterite and olivine increase in reflectivity (and hence optical conductivity) with increasing temperature, with a maximum reflectivity of ~31% at shock velocities greater than 22 km/s (~800 GPa).

58 GEOSCIENCES↗
DOE OSTI2022

Proteomic Analysis of Methanococcus voltae Grown in the Presence of Mineral and Nonmineral Sources of Iron and Sulfur

Iron sulfur (Fe-S) proteins are essential and ubiquitous across all domains of life, yet the mechanisms underpinning assimilation of iron (Fe) and sulfur (S) and biogenesis of Fe-S clusters are poorly understood. This is particularly true for anaerobic methanogenic archaea, which are known to employ more Fe-S proteins than other prokaryotes. Here, we utilized a deep proteomics analysis of Methanococcus voltae A3 cultured in the presence of either synthetic pyrite (FeS 2 ) or aqueous forms of ferrous iron and sulfide to elucidate physiological responses to growth on mineral or nonmineral sources of Fe and S. The liquid chromatography-mass spectrometry (LCMS) shotgun proteomics analysis included 77% of the predicted proteome. Through a comparative analysis of intra- and extracellular proteomes, candidate proteins associated with FeS 2 reductive dissolution, Fe and S acquisition, and the subsequent transport, trafficking, and storage of Fe and S were identified. The proteomic response shows a large and balanced change, suggesting that M. voltae makes physiological adjustments involving a range of biochemical processes based on the available nutrient source. Among the proteins differentially regulated were members of core methanogenesis, oxidoreductases, membrane proteins putatively involved in transport, Fe-S binding ferredoxin and radical S-adenosylmethionine proteins, ribosomal proteins, and intracellular proteins involved in Fe-S cluster assembly and storage. This work improves our understanding of ancient biogeochemical processes and can support efforts in biomining of minerals. Clusters of iron and sulfur are key components of the active sites of enzymes that facilitate microbial conversion of light or electrical energy into chemical bonds. The proteins responsible for transporting iron and sulfur into cells and assembling these elements into metal clusters are not well understood. Using a microorganism that has an unusually high demand for iron and sulfur, we conducted a global investigation of cellular proteins and how they change based on the mineral forms of iron and sulfur. Understanding this process will answer questions about life on early earth and has application in biomining and sustainable sources of energy.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Metagenomic analysis reveals global-scale patterns of ocean nutrient limitation

Genomes reveal nutrient stress patterns Within the surface ocean, nitrogen, iron, and phosphorous can all be limiting nutrients for phytoplankton depending on location. Ustick et al. used the prevalence of Prochlorococcus genes involved in nutrient acquisition to develop maps of inferred nutrient stress across the global ocean (see the Perspective by Coleman). They found broad patterns of limitation consistent with an Earth system model and nutrient addition experiments. Leveraging metagenomic data in this manner is an appealing approach that will help to expand our understanding of the biogeochemistry in the vast open ocean. Science , this issue p. 287 ; see also p. 239

Science & Technology - Other Topics↗
DOE OSTI2021

Exploring a quantum-information-relevant magnonic material: Ultralow damping at low temperature in the organic ferrimagnet V[TCNE]x

Quantum information science and engineering require novel low-loss magnetic materials for magnon-based quantum-coherent operations. The search for low-loss magnetic materials, traditionally driven by applications in microwave electronics near room temperature, has gained additional constraints from the need to operate at cryogenic temperatures for many applications in quantum information science and technology. Whereas yttrium iron garnet (YIG) has been the material of choice for decades, the emergence of molecule-based materials with robust magnetism and ultra-low damping has opened new avenues for exploration. Specifically, thin films of vanadium tetracyanoethylene (V[TCNE]x) can be patterned into the multiple, connected structures needed for hybrid quantum elements and have shown room-temperature Gilbert damping (α = 4 × 10−5) that rivals the intrinsic (bulk) damping otherwise seen only in highly polished YIG spheres (far more challenging to integrate into arrays). Here, the authors present a comprehensive and systematic study of the low-temperature magnetization dynamics for V[TCNE]x thin films, with implications for their application in quantum systems. These studies reveal a temperature-driven, strain-dependent magnetic anisotropy that compensates the thin-film shape anisotropy and the recovery of a magnetic resonance linewidth at 5 K that is comparable to room-temperature values (roughly 2 G at 9.4 GHz). The authors can account for these variations of the V[TCNE]x linewidth within the context of scattering from very dilute paramagnetic impurities and anticipate additional linewidth narrowing as the temperature is further reduced.

Yusuf, H. (ORCID:0000000194627928)↗
NASA NTRS1999

Massive Chromite in the Brenham Pallasite and the Fractionation of Cr During the Crystallization of Asteroidal Cores

Large (greater than or equal to 2 mm) chromite grains are present in IIIAB iron meteorites and in the main-group a pallasites (PMG), closely related to high-Au IIIAB irons, Pallasites seem to have formed by the intrusion of a highly evolved metallic magma from a IIIAB-like core into fragmented olivine of the overlying dunite mantle. High Cr contents are commonly encountered during the analyses of metallic samples of high-Au IIIAB irons and main-group pallasites, an indication that Cr contents were high in the intruding liquid and that Cr behaved as an incompatible element during the crystallization of the IIIAB magma, contrary to expectations based on the negative IIIAB Cr-Ni and Cr-Au trends among low-Au IIIAB irons. In a region about 10 cm across in the Brenham main-group pallasite massive chromite fills the interstices between olivine grains, the site normally occupied by metal in Brenham and other pallasites. The massive chromite may have formed as a late cumulus phase; because Fe-Ni was also crystallizing, its absence in the chromite-rich region suggests a separation associated with differences in liquid buoyancy. The coexisting chromite and olivine are zoned; in the olivine FeO is highest in pallasitic (olivine-metal) regions, lowest in rims adjacent to chromite, and intermediate in the cores of these olivines. Chromite shows the opposite zoning, with the highest FeO contents at grain edges adjacent to olivine. The observed gradients are those expected to form by Fe-Mg exchange between olivine and chromite during slow cooling at subsolidus temperatures. Compared to normal Brenham, contents of phosphoran olivine and phosphates are higher in the chromitic pallasitic region. We also report data for large-to-massive chromites present in PMG Molong and in high-Au IIIAB Bear Creek that, like Brenham, formed from a highly evolved magma. The Bear Creek chromite has a much lower Mg content than that in the pallasites, implying that, in the PMG, the Mg was extracted from the olivine during high-temperature reaction with the precipitating chromite. There are other circumstantial arguments indicating that Cr was incompatible in the metal during the crystallization of the IIIAB magma, with the concentration in die residual magma rising from an initial value of about 300 micrograms/g to a value around 700 micrograms/g when Bear Creek and Brenham were formed. We consider possible explanations for these negative Cr-Au and Cr-Ni trends and find the most probable one to be that they reflect sampling artefacts resulting from analysts avoiding visible chromite (and the commonly associated phase FeS) when choosing metal samples.

Wasson, John T.↗
NASA NTRS1985

Impact wear of iron rich superalloys

The impact-sliding wear resistance of chill cast and aligned eutectic Fe-base superalloys against M42 and 17-4 PH steel counterface materials is examined. The aligned material tests were run with carbide fibers perpendicular to the counterface contact surface and the characterization focused on fracture processes as observed in the subsurface microstructure of the worn materials. Metallographic analyses were performed on specimens exposed to various numbers of repetitive impact load cycles, and for comparison, two other aligned composites were tested with the same fiber orientation under identical test conditions against hardened M42 tool steel. A strong improvement was found in wear resistance of an aligned eutectic structure as compared to the corresponding randomized chill cast structure. Experiments with the softer 17-4 counterface were characterized by transfer onto the Fe-base superalloy, and the cracks formed were oriented transverse to the relative sliding direction and occurred in a periodic fashion. Observations in subsurface regions of the worn materials indicated crack intergranularity with an occasional transgranular fracture of the M7C3 carbide phase.

Wayne, S. F.↗
DOE OSTI2022

Temperature-Dependent Reaction Pathways in FeS 2 : Reversibility and the Electrochemical Formation of Fe 3 S 4

The present study has used a variety of characterization techniques to determine the products and reaction pathways involved in the rechargeable Li–FeS 2 system. We revisit both the initial lithiation and subsequent cycling of FeS 2 employing an ionic liquid electrolyte to investigate the intermediate and final charge products formed under varying thermal conditions (room temperature to 100 °C). The detection of Li 2 S and hexagonal FeS as the intermediate phases in the initial lithiation and the electrochemical formation of greigite, Fe 3 S 4 , as a charge product in the rechargeable reaction differ significantly from previous reports. The conditions for Fe 3 S 4 formation are shown to be dependent on both the temperature (~60 °C) and the availability of sulfur to drive a FeS to Fe 3 S 4 transformation. Upon further cycling, Fe 3 S 4 transforms to a lower sulfur content iron sulfide phase, a process which coincides with the loss of sulfur based on the new reaction pathways established in this work. The connection between sulfur loss, capacity fade, and charge product composition highlights the critical need to retain sulfur in the active material upon cycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Organic preservation of vase‐shaped microfossils from the late Tonian Chuar Group, Grand Canyon, Arizona, USA

Abstract Vase‐shaped microfossils (VSMs) are found globally in middle Neoproterozoic (800–730 Ma) marine strata and represent the earliest evidence for testate (shell‐forming) amoebozoans. VSM tests are hypothesized to have been originally organic in life but are most commonly preserved as secondary mineralized casts and molds. A few reports, however, suggest possible organic preservation. Here, we test the hypothesis that VSMs from shales of the lower Walcott Member of the Chuar Group, Grand Canyon, Arizona, contain original organic material, as reported by B. Bloeser in her pioneering studies of Chuar VSMs. We identified VSMs from two thin section samples of Walcott Member black shales in transmitted light microscopy and used scanning electron microscopy to image VSMs. Carbonaceous material is found within the internal cavity of all VSM tests from both samples and is interpreted as bitumen mobilized from Walcott shales likely during the Cretaceous. Energy dispersive X‐ray spectroscopy (EDS) and wavelength dispersive X‐ray spectroscopy (WDS) reveal that VSM test walls contain mostly carbon, iron, and sulfur, while silica is present only in the surrounding matrix. Raman spectroscopy was used to compare the thermal maturity of carbonaceous material within the samples and indicated the presence of pyrite and jarosite within fossil material. X‐ray absorption spectroscopy revealed the presence of reduced organic sulfur species within the carbonaceous test walls, the carbonaceous material found within test cavities, and in the sedimentary matrix, suggesting that organic matter sulfurization occurred within the Walcott shales. Our suite of spectroscopic analyses reveals that Walcott VSM test walls are organic and sometimes secondarily pyritized (with the pyrite variably oxidized to jarosite). Both preservation modes can occur at a millimeter spatial scale within sample material, and at times even within a single specimen. We propose that sulfurization within the Walcott Shales promoted organic preservation, and furthermore, the ratio of iron to labile VSM organic material controlled the extent of pyrite replacement. Based on our evidence, we conclude that the VSMs are preserved with original organic test material, and speculate that organic VSMs may often go unrecognized, given their light‐colored, translucent appearance in transmitted light.

58 GEOSCIENCES↗
DOE OSTI2020

High-sensitivity in vivo contrast for ultra-low field magnetic resonance imaging using superparamagnetic iron oxide nanoparticles

Magnetic resonance imaging (MRI) scanners operating at ultra-low magnetic fields (ULF; <10 mT) are uniquely positioned to reduce the cost and expand the clinical accessibility of MRI. A fundamental challenge for ULF MRI is obtaining high-contrast images without compromising acquisition sensitivity to the point that scan times become clinically unacceptable. Here, we demonstrate that the high magnetization of superparamagnetic iron oxide nanoparticles (SPIONs) at ULF makes possible relaxivity- and susceptibility-based effects unachievable with conventional contrast agents (CAs). We leverage these effects to acquire high-contrast images of SPIONs in a rat model with ULF MRI using short scan times. This work overcomes a key limitation of ULF MRI by enabling in vivo imaging of biocompatible CAs. These results open a new clinical translation pathway for ULF MRI and have broader implications for disease detection with low-field portable MRI scanners.

42 ENGINEERING↗
DOE OSTI2023

Trace Metal Uptake and Mercury Methylation by Sediments from a Stream in Tennessee

The formation and transport of methylmercury (MeHg), a neurotoxin, in aquatic environments is a global concern for human health as MeHg can bioaccumulate and biomagnify to high concentrations in aquatic food webs. MeHg is formed by conversion from inorganic mercury through microbial mediated methylation. Sulfate-reducing bacteria have been identified as the primary organisms responsible for MeHg production. Pure-culture studies suggest that low availability of cobalt and copper may inhibit mercury methylation, but whether such limitations occur in the environment is unclear. To explore the possible interaction between trace metal availability and mercury methylation, sediments from the East Fork Poplar Creek in Oak Ridge, Tennessee were sampled and then incubated in the presence and absence of added dissolved cobalt and copper. Three types of data are provided in this package. The first reports the uptake of dissolved cobalt and copper by these stream sediments on short time scales (24 hours) in the form of final dissolved and adsorbed concentrations. The second data component consists of a time series of dissolved concentrations and pH values for stream sediments incubated with artificial stream water containing different addition levels of dissolved cobalt or copper. The dissolved concentrations reported include total iron, manganese, sulfur, phosphorus, nickel, zinc and cobalt, dissolved concentrations of sulfate and orthophosphate, and the amount of cobalt or copper adsorbed by the sediment. The third data component reports data at 0 and 72 hours of incubation time for stream sediments to which cobalt was added. These data include concentrations of methylmercury with isotope labeling to enable determination of methylation and demethylation rates as well as dissolved concentrations of sulfate, phosphate, chloride, iron, cobalt, and organic carbon. All data are provided in text-based CSV format with header sections indicating the data contained in each file and the corresponding units. Note that "u" is used in place of Greek lower-case mu to indicate the micro prefix on units. A Table of Contents file (Data_package_TableofContents.txt) provides an index for the data contained in the individual files.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1967

The Cu-Fe system

Temperature and concentration effects on electric resistance determined in Cu-Fe base alloys

ELECTRIC RESISTANCE↗
NASA NTRS1972

NASA-EPA automotive thermal reactor technology program

The status of the NASA-EPA automotive thermal reactor technology program is summarized. This program is concerned primarily with materials evaluation, reactor design, and combustion kinetics. From engine dynamometer tests of candidate metals and coatings, two ferritic iron alloys (GE 1541 and Armco 18-SR) and a nickel-base alloy (Inconel 601) offer promise for reactor use. None of the coatings evaluated warrant further consideration. Development studies on a ceramic thermal reactor appear promising based on initial vehicle road tests. A chemical kinetic study has shown that gas temperatures of at least 900 K to 1000 K are required for the effective cleanup of carbon monoxide and hydrocarbons, but that higher temperatures require shorter combustion times and thus may permit smaller reactors.

Blankenship, C. P.↗
NASA NTRS1995

Determination of stores pointing error due to wing flexibility under flight load

The in-flight elastic wing twist of a fighter-type aircraft was studied to provide for an improved on-board real-time computed prediction of pointing variations of three wing store stations. This is an important capability to correct sensor pod alignment variation or to establish initial conditions of iron bombs or smart weapons prior to release. The original algorithm was based upon coarse measurements. The electro-optical Flight Deflection Measurement System measured the deformed wing shape in flight under maneuver loads to provide a higher resolution database from which an improved twist prediction algorithm could be developed. The FDMS produced excellent repeatable data. In addition, a NASTRAN finite-element analysis was performed to provide additional elastic deformation data. The FDMS data combined with the NASTRAN analysis indicated that an improved prediction algorithm could be derived by using a different set of aircraft parameters, namely normal acceleration, stores configuration, Mach number, and gross weight.

Lokos, William A.↗
NASA NTRS2009

The Evolution and Development of the Lunar Regolith and Implications for Lunar Surface Operations and Construction

The lunar regolith consists of about 90% submillimeter particles traditionally termed lunar soil. The remainder consists of larger particles ranging up to boulder size rocks. At the lower size end, soil particles in the 10s of nanometer sizes are present in all soil samples. Lunar regolith overlies bedrock which consists of either lava flows in mare regions or impact-produced megaregolith in highland regions. Lunar regolith has been produced over billions of years by a combination of breaking and communition of bedrock by meteorite bombardment coupled with a variety of complex space weathering processes including solar wind implantation, solar flare and cosmic ray bombardment with attendant radiation damage, melting, vaporization, and vapor condensation driven by impact, and gardening and turnover of the resultant soil. Lunar regolith is poorly sorted compared to most terrestrial soils, and has interesting engineering properties including strong grain adhesion, over-compacted soil density, an abundance of agglutinates with sharp corners, and a variety of properties related to soil maturity. The NASA program has supported a variety of engineering test research projects, the production of bricks by solar or microwave sintering, the production of concrete, the in situ sintering and glazing of regolith by microwave, and the extraction of useful resources such as oxygen, hydrogen, iron, aluminum, silicon and other products. Future requirements for a lunar surface base or outpost will include construction of protective berms, construction of paved roadways, construction of shelters, movement and emplacement of regolith for radiation shielding and thermal control, and extraction of useful products. One early need is for light weight but powerful digging, trenching, and regolith-moving equipment.

McKay, David↗
NASA NTRS2017

Results of Simulated Galactic Cosmic Radiation (GCR) and Solar Particle Events (SPE) on Spectra Restraint Fabric

Spectra or similar Ultra-high-molecular-weight polyethylene (UHMWPE) fabric is the likely choice for future structural space suit restraint materials due to its high strength-to-weight ratio, abrasion resistance, and dimensional stability. During long duration space missions, space suits will be subjected to significant amounts of high-energy radiation from several different sources. To insure that pressure garment designs properly account for effects of radiation, it is important to characterize the mechanical changes to structural materials after they have been irradiated. White Sands Test Facility (WSFTF) collaborated with the Crew and Thermal Systems Division at the Johnson Space Center (JSC) to irradiate and test various space suit materials by examining their tensile properties through blunt probe puncture testing and single fiber tensile testing after the materials had been dosed at various levels of simulated GCR and SPE Iron and Proton beams at Brookhaven National Laboratories. The dosages were chosen based on a simulation developed by the Structural Engineering Division at JSC for the expected radiation dosages seen by space suit softgoods seen on a Mars reference mission. Spectra fabric tested in the effort saw equivalent dosages at 2x, 10x, and 20x the predicted dose as well as a simulated 50 year exposure to examine the range of effects on the material and examine whether any degradation due to GCR would be present if the suit softgoods were stored in deep space for a long period of time. This paper presents the results of this work and outlines the impact on space suit pressure garment design for long duration deep space missions.

Peters, Benjamin↗
DOE OSTI2021

Electrochemically induced metal- vs. ligand-based redox changes in mackinawite: identification of a Fe 3+ - and polysulfide-containing intermediate

Under anaerobic conditions, ferrous iron reacts with sulfide producing FeS, which can then undergo a temperature, redox potential, and pH dependent maturation process resulting in the formation of oxidized mineral phases, such as greigite or pyrite. A greater understanding of this maturation process holds promise for the development of iron-sulfide catalysts, which are known to promote diverse chemical reactions, such as H + , CO 2 and NO 3 - reduction processes. Hampering the full realization of the catalytic potential of FeS, however, is an incomplete knowledge of the molecular and redox processess ocurring between mineral and nanoparticulate phases. Here, we investigated the chemical properties of iron-sulfide by cyclic voltammetry, Raman and X-ray absorption spectroscopic techniques. Tracing oxidative maturation pathways by varying electrode potential, nanoparticulate n(Fe 2+ S 2- ) (s) was found to oxidize to a Fe 3+ containing FeS phase at -0.5 V vs. Ag/AgCl (pH = 7). In a subsequent oxidation, polysulfides are proposed to give a material that is composed of Fe 2+ , Fe 3+ , S 2- and polysulfide (S n 2- ) species, with its composition described as Fe 2+ 1-3x Fe 3+ 2x S 2- 1-y (S n 2- ) y . Thermodynamic properties of model compounds calculated by density functional theory indicate that ligand oxidation occurs in conjunction with structural rearrangements, whereas metal oxidation may occur prior to structural rearrangement. These findings together point to the existence of a metastable FeS phase located at the junction of a metal-based oxidation path between FeS and greigite (Fe 2+ Fe 3+ 2 S 2- 4 ) and a ligand-based oxidation path between FeS and pyrite (Fe 2+ (S 2 ) 2- ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2013

Preparation of a Bimetal Using Mechanical Alloying for Environmental or Industrial Use

Following the 1976 Toxic Substances Control Act ban on their manufacture, PCBs remain an environmental threat. PCBs are known to bio-accumulate and concentrate in fatty tissues. Further complications arise from the potential for contamination of commercial mixtures with other more toxic chlorinated compounds such as polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Until recently, only one option was available for the treatment of PCB-contaminated materials: incineration. This may prove to be more detrimental to the environment than the PCBs themselves due to the potential for formation of PCDDs. Metals have been used for the past ten years for the remediation of halogenated solvents and other contaminants in the environment; however, zero-valent metals alone do not possess the activity required to dehalogenate PCBs. Palladium has been shown to act as an excellent catalyst for the dechlorination of PCBs with active metals. This invention is a method for the production of a palladium/magnesium bimetal capable of dechlorinating PCBs using mechanical milling/mechanical alloying. Other base metals and catalysts may also be alloyed together (e.g., nickel or zinc) to create a similarly functioning catalyst system. Several bimetal catalyst systems currently can be used for processes such as hydrogen peroxide synthesis, oxidation of ethane, selective oxidation, hydrogenation, and production of syngas for further conversion to clean fuels. The processes for making these bimetal catalysts often involve vapor deposition. This technology provides an alternative to vapor deposition that may provide equally active catalysts. A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts. Preferably, the hydrogenation catalyst is a bimetallic particle formed from a zero-valent iron or zero-valent magnesium particle coated with palladium that is impregnated onto a high-surface-area graphite support. The zero-valent metal particles should be microscale or nanoscale zero-valent magnesium or zero-valent iron particles. Other zero-valent metal particles and combinations may be used. Additionally, the base material may be selected from a variety of minerals including, but not limited to, alumina and zeolites. The catalytic metal is preferably selected from the group consisting of noble metals and transition metals, preferably palladium. The mechanical milling process includes milling the base material with a catalytic metal impregnated into a high-surface-area support to form the hydrogenation catalyst. In a preferred mechanical milling process, a zero-valent metal particle is provided as the base material, preferably having a particle size of less than about 10 microns, preferably 0.1 to 10 microns or smaller, prior to milling. The catalytic metal is supported on a conductive carbon support structure prior to milling. For example, palladium may be impregnated on a graphite support. Other support structures such as semiconductive metal oxides may also be used.

Quinn, Jacqueline↗
DOE OSTI2023

Environmental impact of solution pH on the formation and migration of iron colloids in deep subsurface energy systems

Deep subsurface stimulation processes often promote fluid-rock interactions that can lead to the formation of small colloidal particles that are suspected to migrate through the rock matrix, partially or fully clog pores and microfractures, and promote the mobilization of contaminants. Thus, the goal of this work is to understand the geochemical changes of the host rock in response to reservoir stimulation that promote the formation and migration of colloids. Two different carbonate-rich shales were exposed to different solution pHs (pH = 2 and 7). In this study, iron and other mineral transformations at the shale-fluid interface were first characterized by synchrotron-based XRF mapping. Then, colloids that were able to migrate from the shale into the bulk fluid were characterized by synchrotron-based extended X-ray absorption structure (EXAFS), scanning electron microscopy (SEM), and single-particle inductively coupled plasma time-of-flight mass spectrometry (sp-icpTOF-MS). When exposed to the pH = 2 solution, extensive mineral dissolution and secondary precipitation was observed; iron-(oxyhydr)oxide colloids colocated with silicates were observed by SEM at the fluid-shale interfaces, and the mobilization of chromium and nickel with these iron colloids into the bulk fluid was detected by sp-icpTOF-MS. Iron EXAFS spectra of the solution at the shale-fluid interface suggests the rapid (within minutes) formation of ferrihydrite-like nanoparticles. Thus, we demonstrate that the pH neutralization promotes the mobilization of existing silicate minerals and the rapid formation of new iron colloids. These Fe colloids have the potential to migrate through the shale matrix and mobilize other heavy metals (such as Cr and Ni, in this study) and impacting groundwater quality, as well produced waters from these hydraulic fracturing operations.

54 ENVIRONMENTAL SCIENCES↗