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122 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Pan-Arctic seasonal cycles and long-term trends of aerosol properties from 10 observatories

Even though the Arctic is remote, aerosol properties observed there are strongly influenced by anthropogenic emissions from outside the Arctic. This is particularly true for the so-called Arctic haze season (January through April). In summer (June through September), when atmospheric transport patterns change, and precipitation is more frequent, local Arctic sources, i.e., natural sources of aerosols and precursors, play an important role. Over the last few decades, significant reductions in anthropogenic emissions have taken place. At the same time a large body of literature shows evidence that the Arctic is undergoing fundamental environmental changes due to climate forcing, leading to enhanced emissions by natural processes that may impact aerosol properties. In this study, we analyze 9 aerosol chemical species and 4 particle optical properties from 10 Arctic observatories (Alert, Kevo, Pallas, Summit, Thule, Tiksi, Barrow/Utgiavik, Villum, and Gruvebadet and Zeppelin Observatory – both at Ny-Ålesund Research Station) to understand changes in anthropogenic and natural aerosol contributions. Variables include equivalent black carbon, particulate sulfate, nitrate, ammonium, methanesulfonic acid, sodium, iron, calcium and potassium, as well as scattering and absorption coefficients, single scattering albedo and scattering Ångström exponent. First, annual cycles are investigated, which despite anthropogenic emission reductions still show the Arctic haze phenomenon. Second, long-term trends are studied using the Mann–Kendall Theil–Sen slope method. We find in total 41 significant trends over full station records, i.e., spanning more than a decade, compared to 26 significant decadal trends. The majority of significantly declining trends is from anthropogenic tracers and occurred during the haze period, driven by emission changes between 1990 and 2000. For the summer period, no uniform picture of trends has emerged. Twenty-six percent of trends, i.e., 19 out of 73, are significant, and of those 5 are positive and 14 are negative. Negative trends include not only anthropogenic tracers such as equivalent black carbon at Kevo, but also natural indicators such as methanesulfonic acid and non-sea-salt calcium at Alert. Positive trends are observed for sulfate at Gruvebadet. No clear evidence of a significant change in the natural aerosol contribution can be observed yet. However, testing the sensitivity of the Mann–Kendall Theil–Sen method, we find that monotonic changes of around 5 % yr –1 in an aerosol property are needed to detect a significant trend within one decade. This highlights that long-term efforts well beyond a decade are needed to capture smaller changes. It is particularly important to understand the ongoing natural changes in the Arctic, where interannual variability can be high, such as with forest fire emissions and their influence on the aerosol population. To investigate the climate-change-induced influence on the aerosol population and the resulting climate feedback, long-term observations of tracers more specific to natural sources are needed, as well as of particle microphysical properties such as size distributions, which can be used to identify changes in particle populations which are not well captured by mass-oriented methods such as bulk chemical composition.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

The Solar System calcium isotopic composition inferred from Ryugu samples

The Hayabusa2 spacecraft has returned samples from the Cb-type asteroid (162173) Ryugu to Earth. Previous petrological and chemical analyses support a close link between Ryugu and CI chondrites that are presumed to be chemically the most primitive meteorites with a solar-like composition. However, Ryugu samples are highly enriched in Ca compared to typical CI chondrites. To identify the cause of this discrepancy, here we report stable Ca isotopic data (expressed as δ 44/40 Ca SRM915a ) for returned Ryugu samples collected from two sites. We found that samples from both sites have similar δ 44/40 Ca SRM915a (0.58 ± 0.03 ‰ and 0.55 ± 0.08 ‰, 2 s.d.) that fall within the range defined by CIs. This isotopic similarity suggests that the Ca budget of CIs and Ryugu samples is dominated by carbonates, and the variably higher Ca contents in Ryugu samples are due to the abundant carbonates. Precipitation of carbonates on Ryugu likely coincided with a major episode of aqueous activity dated to have occurred ~5 Myr after Solar System formation. Based on the pristine Ryugu samples, the average δ 44/40 Ca SRM915a of the Solar System is defined to be 0.57 ± 0.04 ‰ (2 s.d.).

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1991

Coastal lithofacies and biofacies associated with syndepositional dolomitization and silicification (Draken Formation, Upper Riphean, Svalbard)

The Draken Formation (120-250 m) of northeast Spitsbergen (Svalbard) forms part of a thick Upper Proterozoic carbonate platform succession. It consists predominantly of intraformational dolomitic conglomerates, with excellent textural preservation. Six main lithofacies were recognized in the field: quartz sandstones, stromatolitic mats, conglomerates with silicified intraclasts, dolostone conglomerates with desiccated mudrocks, oolitic/pisolitic grainstones and fenestral dolostones. A series of five main gradational biofacies were recognized from silicified (and rare calcified) microfossils. Biofacies 1 represents low-energy subtidal benthos (erect filaments) and plankton (acritarchs and vase-shaped microfossils) whereas biofacies 2 to 5 are microbial mat assemblages (with filamentous mat-builders, and associated dwellers and washed-in plankton) ranging from basal intertidal to high intertidal/supratidal. Colour values (a measure of the lightness of the colour shade) of sawn rock samples were quantified using a Munsell chart, and exhibit a pronounced variation (means of major groups varying from 4.0 to 5.95) across the spectrum of subtidal to supratidal sediments as inferred from other criteria. The lightening in progressively more exposed sediments is related to lowering of organic carbon contents, probably mainly by oxidation. Six types of early cement have been recognized. Calcite microspar (type 1) is common as a subtidal cement in many Proterozoic formations, whereas types 2 (subtidal isopachous fringes), 3 (subtidal hardground dolomicrite) and 4 (intertidal meniscus dolomicrite) are very similar to Phanerozoic examples except for their dolomitic mineralogy. Types 5 and 6 are complex and variable dolomite growths associated with expansion and replacive phenomena. They characterize the fenestral lithofacies and compare with modern supratidal cements. Consideration of diagenetic fabrics and truncation textures of intraclasts indicates that leaching, dolomitization, silicification were all significant syndepositional processes altering the original metastable carbonates. The data set provides evidence for a spectrum of peritidal environments including ooid shoals, protected subtidal, tidal sandflats and protected carbonate mudflats. Different sections show a preponderance of particular facies. The coastal lithofacies continuum was completely dolomitized, unlike offshore to ooid shoal facies of adjacent formations. Dolomitization thus bears a relationship to depositional bathymetry. Although hydrodynamics clearly have a role, the potential importance of whiting precipitation in raising Mg/Ca in marginal marine environments is also stressed.

Non-NASA Center↗
DOE OSTI2021

Dynamic Barriers to Crystallization of Calcium Barium Carbonates

Metastable carbonates play important roles in geochemistry, biomineralization and serve as model systems for nonclassical theories of nucleation and growth. Balcite (Ca 0.5 Ba 0.5 CO 3 ) is a remarkable carbonate phase that is isostructural with a high-temperature modification of calcite (CaCO 3 ), yet can be synthesized at ambient conditions. Here, we investigate crystallization pathways in the Ba-Ca-CO 3 -H 2 O system, with a focus on the transformation of amorphous calcium barium carbonate (ACBC) to balcite and subsequent decomposition into the equilibrium calcite (CaCO3) and witherite (BaCO 3 ) phases. Density functional theory calculations show that balcite is an unstable solid solution (Ca 1-x BaxCO 3 , R 3¯ m) in the range 0.17 < x < 0.5, but is accessible through the amorphous ACBC precursor for x ≲ 0.5, and predict its decomposition into calcite and witherite. We confirm this pathway experimentally but found demixing to proceed slowly and remain incomplete even after 9 months. Nucleation kinetics of balcite from ACBC was assessed using a microfluidic assay, where increasing barium content led to a surprising increase in the balcite nucleation rate, despite decreasing thermodynamic driving force. We attribute crystallization rates that dramatically accelerate with time to changes in interfacial structure and composition during coarsening of the amorphous precipitate. By carefully quantifying the thermodynamic and kinetic contributions in the multistep crystallization of a metastable carbonate, we produce insights that allow us to better interpret the formation and persistence of metastable minerals in natural and synthetic environments.

36 MATERIALS SCIENCE↗
NASA NTRS1990

Carbonate deposition during the late Proterozoic Era: an example from Spitsbergen

Carbonate sediments reflect the physico-chemical and biological circumstances of their formation; thus, features of limestones and dolomites may provide insights into both environmental and evolutionary change through geological time. The Upper Proterozoic (approx 800-700 Ma) Akademikerbreen Group, Spitsbergen, comprises 2000 m of carbonates, with only minor intercalations of quartz arenite and shale. Although Proterozoic carbonates are often seen as predominantly dolomitic, the Akademikerbreen Group is about 45 percent limestone. Stromatolites are conspicuous in outcrop but constitute only 25 percent of the total section. Micrites and coarser intraclastic carbonates derived mainly from micritric precursors comprise 60 percent of the group, while oolites make up the remaining 15 percent. Distinctive sedimentary features of the group include giant (up to 16 mm) ooids, very early diagenetic calcite nodules and cements, micrites containing subaqueous shrinkage cracks filled with equant microspar cement, and strong 13C enrichment in both carbonates and co-occurring organic matter. The principal features of Akademikerbreen carbonates are widely distributed in coeval successions. However, these rocks appear to differ from older limestones and dolomites in their relative abundance of grainstones and, perhaps, micrites, as well as their paucity of tufa-like laminates and columnar or coniform stromatolites that preserve petrographic evidence of in situ precipitation as a dominant means of carbonate accretion. Upper Proterozoic carbonates also differ from Paleozoic accumulations, but the transition is not abrupt. Most changes accompanying the Proterozoic/Phanerozoic transition can be interpreted in terms of the consequences rather than the causes of metazoan and metaphyte evolution, including the evolution of biomineralization. Carbonate sedimentology reinforces data from other sources which indicate the last 200 to 300 Ma of the Proterozoic Eon was a distinctive interval of Earth history.

NASA Discipline Number 52-30↗
DOE OSTI2025

CarbStor: Development, Analysis and Modification of Carbon Storing Model Soil Communities

Soil microbial communities carry out a number of key processes including plant growth promotion, bioremediation and cycling of nutrients. Carbon cycling is among the most important of these nutrients that are metabolized and processed by the soil microbial community. Many of the carbon inputs are converted to alternative organic forms of carbon that can be used by plants or act as biomass for microbial growth. However, inorganic forms of carbon can also be produced by soil microbial communities including calcium carbonate (CaCO 3 ). Production of calcium carbonate is beneficial for the ecosystem in several ways: it can stabilize soils and improve soil health, especially denser soils with high clay content, it can act as a method of bioremediation, it can serve as an alternative carbon source for plants and it can be a way to store carbon in soil in a stable, inorganic manner for the long term. While the chemistry surrounding individual species carrying out this process is well known what is lacking is an understanding of how species interact in a community to drive carbonate production. As all microbial species in soil exist in a community setting gaining this knowledge is critical to our predicting and controlling this microbial phenotype to greatly improve soil health. The CarbStor project is focused on developing, analyzing and modifying defined microbial soil consortia that express phenotypes at both the species and community level to convert carbon into recalcitrant stable sources such as precipitated carbonate or microbial necromass. To take full advantage of the soil community for this process we will need to fill several key knowledge gaps (KG), three of which are the focus of CarbStor. KG1: Whether and to what degree microbial communities can be developed that produce precipitated carbon via microbial metabolism. KG2: What interspecies interactions drive the individual member phenotypes in defined communities that lead to carbon precipitation. KG3: How can these interactions be modified to enhance carbon sequestration beyond what native communities are capable of. We hypothesize that in a carbon sequestering community only a subset of species will express phenotypes related to carbon storage processes. We also hypothesize that these phenotypes are expressed as a result of interactions with other species in the community that are not involved in carbon storage processes and that these interactions can be harnessed to enhance community carbon sequestration.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Linking water quality, fouling layer composition, and performance of reverse osmosis membranes

Fouling of polyamide membranes during reverse osmosis (RO) is a major challenge for adopting membrane technologies to treat highly contaminated waters, especially those containing organic foulants (e.g., natural organic matter (NOM), polysaccharides) and dominant cations (e.g., sodium, magnesium, calcium). Here, this work combines bench-scale membrane fouling experiments with detailed characterization of feedwater chemistry and fouling layer composition/morphology to reveal fundamental mechanisms of (in)organic fouling during RO. Divalent cations are shown to promote fouling by hydrophobic NOM containing aromatic and carboxyl groups, while NOM fouling in the presence of a monovalent cation, sodium, occurs by smaller fulvic acids containing larger fractions of carboxyl groups and other oxygen-rich moieties. Calcium-carboxyl bridging occurs in solution and near the membrane surface to induce NOM aggregation on nanometer length scales. In complex waters containing foulant mixtures, co-fouling by calcium-carboxyl bridging and CaCO 3 precipitation influence membrane performance at longer timeframes. However, the flux decline observed for the co-fouling mechanism was less significant than the sum of its parts, suggesting both synergistic and antagonistic fouling mechanisms should be considered in membrane design/operation. These results encourage the design of pretreatment processes to reduce concentrations of multivalent ions and hydrophobic NOM in RO feedwaters, and of membrane materials to limit attachment/deposition of aggregates to/on polyamide surfaces.

42 ENGINEERING↗
DOE OSTI2024

Preparation and Characterization of Materials for Low- to Intermediate-Temperature CO2 Adsorption

Global carbon dioxide emissions are rising and the use of fossil fuels in several sectors are the leading causes. As global population and economies continue to grow significantly, the most practical method of lowering such emissions is to capture CO2. Although other technologies are more developed, adsorption is very promising and has attracted much attention. To ensure this technology’s success, it is essential to have suitable CO2 adsorbent materials. In this work, several new hydrotalcites (HTs) with different initial concentrations of ion precursors were prepared for the first time by the co-precipitation method—it was possible to verify that the ion concentrations influence the characteristics of the materials. The prepared HTs were characterized by thermogravimetric analysis (TG), X-Ray diffraction (XRD), surface area measurements and temperature-programmed desorption of CO2 (TPD-CO2) to relate their CO2 capture capacity to their physicochemical properties; the CO2 adsorption equilibrium isotherms were determined at 35 and 300 °C for the prepared samples, as well as for some commercial materials: magnesium oxide, calcium oxide, aluminium oxide and Zeolite 13X. After determining which materials present the best CO2 adsorption capacity, these were submitted to adsorption-desorption cycles to study their stability. The main objective of the work was to prepare and study different CO2 adsorbents for processes that are carried out at low and intermediate temperatures. From the experimental results, it was possible to conclude that the Zeolite 13X showed the best capacity at 35 °C, 3.38 mmol·g−1 (@ pCO2 = 1 bar), and a prepared calcined HT (c-HT2) was the best at 300 °C, 0.97 mmol·g−1 (@ pCO2 = 1 bar). Moreover, it seems there is an optimum initial concentration of the ions’ solutions for the tested HTs, which depends on the final application—c-HT1 showed a better capacity at 35 °C and c-HT2 at 300 °C. From the adsorption-desorption cycles—performed at 35 and 300 °C with the best materials using a magnetic suspension microbalance at 1 bar of CO2 partial pressure —, a working cyclic capacity of 2.69 mmol∙g−1 was achieved by the Zeolite at 35 °C; in turn, c-HT2 showed a working cyclic capacity of 0.79 mmol∙g−1 at 300 °C.

Figueiredo, Anabela↗
NASA NTRS1990

Carbonate petrography, kerogen distribution, and carbon and oxygen isotope variations in an early Proterozoic transition from limestone to iron-formation deposition, Transvaal Supergroup, South Africa

The transition zone comprises Campbellrand microbialaminated (replacing "cryptalgalaminate") limestone and shale, with minor dolomite, conformably overlain by the Kuruman Iron Formation of which the basal part is characterized by siderite-rich microbanded iron-formation with minor magnetite and some hematite-containing units. The iron-formation contains subordinate intraclastic and microbialaminated siderite mesobands and was deposited in deeper water than the limestones. The sequence is virtually unaltered with diagenetic mineral assemblages reflecting a temperature interval of about 110 degrees to 170 degrees C and pressures of 2 kbars. Carbonate minerals in the different rock types are represented by primary micritic precipitates (now recrystallized to microsparite), early precompactional sparry cements and concretions, deep burial limpid euhedral sparites, and spar cements precipitated from metamorphic fluids in close contact with diabase sills. Paragenetic pathways of the carbonate minerals are broadly similar in all lithofacies with kerogen intimately associated with them. Kerogen occurs as pigmentation in carbonate crystals, as reworked organic detritus in clastic-textured carbonate units, and as segregations of kerogen pigment around late diagenetic carbonate crystals. Locally kerogen may also be replaced by carbonate spar. Carbon isotope compositions of the carbonate minerals and kerogen are dependent on their mode of occurrence and on the composition of the dominant carbonate species in a specific lithofacies. Integration of sedimentary, petrographic, geochemical, and isotopic results makes it possible to distinguish between depositional, early diagenetic, deep burial, and metamorphic effects on the isotopic compositions of the carbonate minerals and the kerogen in the sequence. Major conclusions are that deep burial thermal decarboxylation led to 13C depletion in euhedral ferroan sparites and 13C enrichment in kerogen (organic carbon). Metamorphic sparites are most depleted in 13C. Carbonates in oxide-rich iron-formations are more depleted in 13C than those in siderite-rich iron-formation whereas the kerogens in oxide banded iron-formations (BIF) are more enriched. This implies that the siderite-rich iron-formations were not derived from oxide-rich iron-formation through reduction of ferric iron by organic matter. Organic matter oxidation by ferric iron did, however, decrease the abundance of kerogen in oxide-rich iron-formation and led to the formation of isotopically very light sparry carbonates. Siderite and calcmicrosparite both represent recrystallized primary micritic precipitates but differ in their 13C composition, with the siderites depleted in 13C by 4.6 per mil on average relative to calcmicrosparite. This means that the siderites were precipitated from water with dissolved inorganic carbon depleted in 13C by about 9 per mil relative to that from which the limestones precipitated. This implies an ocean system stratified with regard to total carbonate, with the deeper water, from which siderite-rich iron-formation formed, depleted in 13C. Iron-formations were deposited in areas of very low organic matter supply. Depletion of 13C may, therefore, derive not from degradation of organic matter but from hydrothermal activity, a conclusion which is supported by 18O composition of the carbonate minerals and trace element and rare earth element (REE) compositions of the iron-formations.

NASA Discipline Number 52-30↗
DOE OSTI2020

Application of electrodialysis pretreatment to enhance boron removal and reduce fouling during desalination by nanofiltration/reverse osmosis

we report membranes have emerged as promising technologies for treatment of non-traditional waters, but fouling and poor rejection of small, neutral solutes (e.g., boric acid) impede their further implementation for water purification. Boron rejection is increased by raising the pH to convert boric acid to borate ion, but this change often leads to calcite supersaturation. This study investigated the use of a hybrid electrodialysis-nanofiltration/reverse osmosis (ED-NF/RO) system to reduce fouling from calcite precipitation and calcium-polysaccharide sorption to NF/RO membranes. Also, the study examined the potential of the hybrid process to increase permeate flux and boron rejection during NF/RO of synthetic saline water. ED pretreatment reduced calcite oversaturation and reduced flux decline during NF/RO. Low alginate concentrations (25 mg/L) limited NF/RO fouling, but high concentrations (100 mg/L) appeared to promote calcite scaling. ED pretreatment reduced the osmotic pressure of the NF/RO feed water, enabling lower operating pressures or greater permeate water fluxes. Boron rejection during NF/RO increased with ED pretreatment, probably due to stronger electrostatic repulsion and an increase in the fraction of total boron present as B(OH)4- following ED. This hybrid ED-NF/RO system shows promise as a novel approach to enhancing the performance of current membrane systems for treating complex feed waters.

alginate↗
DOE OSTI2024

Real-Time Atomic-Scale Structural Analysis Resolves the Amorphous to Crystalline CaCO 3 Mechanism Controversy

Amorphous calcium carbonate (ACC) occurs as a precursor to geological and biogenic calcium carbonate (CaCO 3 ), yet its transformation pathways and reaction mechanisms remain inconsistent and controversial. In this study, we investigated the transformation of ACC to calcite under both solution and dry conditions, in the presence and absence of impurity ions, utilizing operando time-resolved synchrotron X-ray diffraction (TRXRD) and reactive transport modeling. Results demonstrate that TRXRD techniques allow us to differentiate dissolution-reprecipitation versus solid-state transformation mechanisms for amorphous to crystalline phase transitions. Specifically, we observe that in environments with abundant water, ACC transforms to calcite through a dissolution-reprecipitation mechanism. This features an activation energy of 63 ± 2 kJ/mol and unit cell volume contraction during calcite crystal growth. Conversely, under water-limited conditions, ACC to calcite transformation proceeds via a solid-state transformation mechanism, with an activation energy of 210 ± 2 kJ/mol, three times greater than the dissolution-reprecipitation route, and a unit cell expansion during crystalline calcite growth. Further, to illustrate the magnitude of these effects, the rates of calcite growth were similar during dissolution-reprecipitation at 3 °C [0.00207(35) s –1 ] and solid-state transformation at 280 °C [0.00134(11) s –1 ]. Moreover, the incorporation of an impurity, strontium, significantly retards the rate of calcite growth while expanding its unit cell but whose incorporation is history dependent. Reactive transport modeling of the dissolution–precipitation kinetics suggests that ACC must be dissolving as compact aggregates. These various transformation mechanisms drive diverse geological and biological carbonate formations, impacting their use as paleoenvironmental markers and functional materials synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1997

Whiting events: biogenic origin due to the photosynthetic activity of cyanobacterial picoplankton

An annual whiting event occurs each year in late May to early June in Fayetteville Green Lake, New York. The initiation of this event correlates with exponential growth of the Synechococcus population within the lake. Synechococcus is the dominant (by approximately 4 orders of magnitude) autotrophic organism owing to the oligotrophic condition of the lake. The delta 13C values of the dissolved inorganic C range seasonally from -9.5% in winter to -6.2% in summer due to photosynthetic activity. Calcite precipitates principally in the microenvironment surrounding Synechococcus because of a photosynthetically driven alkalization process and the availability of the cells as nucleation sites. This calcite has a heavier delta 13C value (>4%) than does the dissolved inorganic C of the lake water owing to the cells' preferential uptake of 12C. A conceptual model suggests that photosynthetic activity and cell surface chemistry, together with the substantial surface area that arises from the great abundance of micron-sized cells, allow Synechococcus to dominate the annual whiting events in Fayetteville Green Lake.

NASA Center ARC↗
NASA NTRS2014

Nutritional Status Assessment (SMO 016E)

The Nutritional Status Assessment Supplemental Medical Objective was initiated to expand nominal clinical nutrition testing of ISS astronauts, and to gain a better understanding of the time course of changes in nutritional status during flight. The primary activity of this effort was collecting blood and urine samples during flight for analysis after return to Earth. Samples were subjected to a battery of tests. The resulting data provide a comprehensive survey of how nutritional status and related systems are affected by 4-6 months of space flight. Analysis of these data has yielded many findings to date, including: Vision. Documented evidence that biochemical markers involved in one-carbon metabolism were altered in crewmembers who experienced vision-related issues during and after flight (1). Iron, Oxidative Stress, and Bone. In-flight data document a clear association of increased iron stores, markers of oxidative damage to DNA, and bone loss (2). Exercise. Documented that well-nourished crewmembers performing heavy resistance exercise returned from ISS with bone mineral densities unchanged from preflight (3). Furthermore, the response of bone to space flight and exercise countermeasures was the same in men and women (4). Body Mass. Crewmembers lose 2-5% of their body mass in the first month of flight, and maintain the lower body mass during flight (5). Additionally, the two devices to measure body mass on orbit, the SLAMMD and BMMD, provide similar results (5). Cytokines. Findings indicated that a pattern of persistent physiological adaptations occurs during space flight that includes shifts in immune and hormonal regulation (6). Fish/Bone. Documented a relationship between fish intake and bone loss in astronauts (that is, those who ate more fish lost less bone) (7). Vitamin K. Documented that in generally well-fed and otherwise healthy individuals, vitamin K status and bone vitamin K-dependent proteins are unaffected by space flight (and bed rest) (8). Testosterone. Documented that blood concentrations of testosterone were unchanged during flight, but a transient decline occurred after landing (9). Calcium. Nutrition SMO data contributed to the ISS Program by helping understand how and why the Urine Processor Assembly clogged with calcium sulfate precipitate (10). Sample Processing. Ground-based analytical testing results have also been published (11).

Smith, S. M.↗
DOE OSTI2023

Physical, Chemical, and Mineralogical Characterizations of MSWI Ash Product and Recommendations for Downstream Processing

The primary objectives of this project are to (1) systematically characterize MSWI ash, and (2) based on characterization findings, design preliminary flowsheets for downstream processing. To achieve these objectives, a total of ten tasks were completed, including sample collection, physical separation tests, liberation tests, synthetic MSWI ash preparation, elemental composition analysis, sequential chemical extraction, mineralogical characterization, pozzolanic activity characterization, thermal stability characterization, processing flowsheet design, TEA and T2M, and project performance reporting. Many useful findings and conclusions were obtained from the exhaustive efforts of this project from several different aspects, including: a) Valuable Metals in MSWI Ash: MSWI ash contains a diverse array of valuable metals. Based on potential recoverable values, the most valuable metals present in MSWI ash include Fe, Ti, Mn, Cu, Zn, V, Co, Ni, Sr, Sn, Ag, Mo, and Sc. Some of these metals have been identified as critical minerals by DOE and DOI, suggesting that MSWI is a promising feedstock for critical mineral recovery. Noticeable graphical and seasonable variations in the valuable metal content of MSWI ash were observed. Nevertheless, it was challenging to discern any clear, definitive patterns for conclusions from those observations. Compared with bottom ash, fly ash contains more volatile metals, such as Zn and Sn, but less nonvolatile metals, such as Fe, Mn, Cu, Zn, Co, and Ni. Mineralogical analyses showed that MSWI ash contains a substantial amount of calcium minerals, such as portlandite, lime, gypsum, and calcite. In addition, it was found that different types of valuable metals often exist in the same particles. b) Physical Separation of MSWI Ash: Both dry sieving and wet sieving were performed on MSWI ash. A notable disparity in the size distribution of the same material was observed when using the two different sieving methods. The disparity is due to the agglomeration of small particles. For the valuable metals investigated, no significant enrichment in a specific size fraction was observed, suggesting that it is challenging to preconcentrate the valuable metals through size fractionation. Due to the presence of ferromagnetic materials, such as Fe, most of the materials reported to the magnetic products obtained by dry magnetic separation. However, the enrichment effect is minimal due to the existence of particle agglomerates. Density separation at a cut-off density of 2.7 SG or higher led to noticeable enrichment of selected valuable metals, particularly Ti. The unburned carbon present in MSWI ash was effectively removed by flotation using diesel as the collector. A novel reagent scheme, Na2S plus cationic collectors, that can efficiently beneficiate nonferrous metals plus Co was developed. c) Liberation Tests: The particle size of MSWI ash was effectively reduced by grinding, and as a result, the encapsulated valuable metal particles (if any) were liberated to a certain degree. However, particle size reductions did not noticeably enhance the beneficiation performance using the physical separation methods, primarily due to the inefficiency of these methods in processing fine particles and/or a possibility that insufficient liberation is not a limiting factor for achieving satisfactory physical separation performance. Valuable metals were classified into water leachable, ion-exchangeable, acid soluble, reducible, oxidable, and insoluble forms. It was found that the distributions in the different categories, i.e., the occurrence modes of the valuable metals, were not affected by the particle size. d) Leaching Characteristics of Metals from MSWI Ash: Most of the valuable metals were extracted from the fly ash samples when using 1 M HCl or HNO3 as the lixiviant. The leaching reaction is a very fast process, which can reach equilibrium within the first 5 min. The releasing of Co, Ni and Ag are sensitive to leaching temperature, a higher recovery value could be obtained when using relatively higher leaching temperatures. The leachability of the valuable metals present in MSWI bottom ash is relatively lower than that of fly ash. Leaching recoveries increased with elevations in the acid concentration. Relatively high leaching recoveries were obtained for REEs, Mn, Co, Ni, Cu, and Zn using 1 M HCl or HNO3 as the lixiviant. Elevations in the reaction temperature noticeably increased the leachability of the valuable metals, whereas the leachability was barely influenced by oxidizing and reducing agents. Similar to fly ash, leaching valuable metals from bottom ash is a rapid process, with most of the leaching reaction completed within the first 5 minutes. e) Combusted iPhones: The original structure of iPhones was remained after treating at 400 ºC and 600 ºC, while after being treated at 800℃, the screen bent, and the back cover of iPhone melted. Increasing the combustion temperature to 1000℃, the screen scattered, and most of the components turned into ashes. Combustion enhanced the leachability of REEs, while the leachability of the other valuable metals, except for Zn, was barely affected. Most of the REEs present in the original iPhones occurred as oxidizable forms. With elevations in the combustion temperature up to 600 ºC, the oxidizable REEs were transformed to acid soluble forms. However, further elevations in temperature resulted in decreases in the acid soluble fraction and corresponding increases in the reducible and oxidizable forms. Additionally, combustion temperature also significantly altered the occurrence modes of other metals present in the iPhones. f) Synthetic MSWI Ash: It was found that in the absence of hydrogen peroxide, all the elements except for Si were leached to certain degrees. It is noteworthy that approximately 80% of Zn was leached with 1.2 M HCl. When hydrogen peroxide was added to the reaction system, noticeable increases in the leaching recovery of Fe, Mn, Co, Ni, and Cu were observed. The leaching recovery of Al and Si was barely affected by adding hydrogen peroxide. These results suggested that the majority of Zn in the synthetic MSWI ash existed as metal oxide, a portion of Fe, Mn, Co, Ni, and Cu existed as metal oxide, and Al and Si are associated with glasses which are difficult to leach. Additionally, the remaining Fe, Mn, Co, Ni, and Cu in the metallic form were efficiently oxidized in the presence of hydrogen peroxide. g) Pozzolanic Activity and Thermal Stability of MSWI Ash: MSWI fly ash has higher pozzolanic activity compared to the bottom ash sample, which indicates that the fly ash sample consumed more portlandite because of its smaller particle size as reactivity fundamentally relates to reaction surface area. However, after the recovery of valuable elements, the pozzolanic activity of both the valuable elements fraction and the less valuable elements-rich products decreased significantly, which means that the valuable elements recovery lowers the Ca(OH)2 consumption, thus leading to the low activity of SCM. h) Flowsheet Design for Metal Recovery from MSWI Ash: Based on the results of the comprehensive physical separation and acid leaching tests, circuits that enable the beneficiation of the valuable metals were developed. In these circuits, the valuable metals are recovered into nonferrous, ferrous, and other valuable metal concentrates, which are processed separately in the acid leaching step. The subsequent separation and purification steps are simplified due to the physical beneficiation step. In addition, the overall recovery cost is reduced since physical beneficiation is much cheaper compared with chemical processing. Using different technologies, such as selective precipitation and solvent extraction, a comprehensive hydrometallurgical circuit was designed, and compounds of Cu, Zn, Mn, Co, and Ni with a purity close to or even higher than 95% were successfully generated.

36 MATERIALS SCIENCE↗