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This work is a first-order study to assess the suitability of an organic acid lixiviant to extract rare earth elements (REE) from coal preparation fines refuse sourced from a Pennsylvania mine with a total REE of ~ 300 ppm. The extraction of REE using an organic acid, in this case 0.1 M citric acid and 0.5 M trisodium citrate solution, is compared against 0.5 M (NH4)2SO4, 1 M HCl, 1.2 M H2SO4, and 0.5 M ethylenediaminetetraacetic acid (EDTA). Ashing the coal waste material prior to leaching tests with the citrate solution nominally improved REE extraction. Buffered citrate solution recovered 7% of the total REE in the as-received Isabella Fines as compared to 11% in ashed samples, whereas (NH4)2SO4 extracted 5–6%, respectively. EDTA recovered up to 33% of the total REE, most likely due to the higher coordination chelate bond. Mineral acids, however, outperformed the organic acids on ashed material (16–52% REE recovery), suggesting that organic acids may not be a suitable competitive option for REE extraction from these types of feedstocks.

Geologic CO2 storage (GCS) is a method to mitigate the adverse impact of global climate change. Potential leakage of CO2 from fractured cement at the wellbore poses a risk to the feasibility of GCS. Foamed cement is widely applied in deepwater wells where fragile geologic formations cannot support the weight of conventional cement. Thus, it is critical to know whether fractures in foamed cement self-seal in a similar manner as conventional cement systems. This study is the first to investigate the changes in physical and chemical attributes of foamed cement under dynamic flow conditions using CO2-saturated water. Self-sealing of fractures in the cement was observed at a solution flow rate of 0.1 mL/min and a pressure of 6.9 MPa. The formation of CaCO3 precipitates in pore spaces and fractures led to a decrease in permeability by 1 order of magnitude. The extents of self-sealing in foamed cement samples, specifically the 20 and 30% air volume formulations, were similar to that of conventional cements. We attribute this to the greater alteration depth in the foamed cement, which compensated for the reduced availability of Portlandite and higher initial porosity. The results can be used to evaluate the risk of leakage associated with foamed cement.

The search for a reliable U.S. domestic source of rare earth elements (REE) is necessary to support the demand of advanced energy applications (e.g., catalysts, electronics, magnets). Sedimentary deposits may be sources for selectively recovering REE and critical metals&mdash, specifically the interbedded seat rock, or underclay, that underlies or forms the floor of a coal seam. This material is often a major component of coal waste fines and refuse and thus readily available. This study examines several Appalachian Basin underclays associated with actively mined coal seams as potential feedstocks for the REE. Multimodal microanalytical electron microscopy (SEM, FIB-SEM, EMPA) synchrotron-based &micro, XRF, and image processing techniques are coupled with detailed elemental and mineral data to classify the 2D and 3D petrophysical properties of the materials. The REE contents of Appalachian Basin underclays were measured from 235&ndash, 399 ppm and predominantly observed as discrete REE-bearing minerals such as monazite and xenotime on the order of 10&ndash, 100 &micro, m in size. These REE-bearing minerals typically accounted for less than 1% of the scanned areas and volumes under SEM and FIB-SEM analysis, with the exception of regions enriched in crandallite. Synchrotron-based &micro, XRF elemental maps further identified several REE deposition environments in different underclays, including micro-scale (10&ndash, m) light REEs co-localizing with Ca and P, micro-scale heavy REEs with Fe, and large-scale light REEs (&gt, 200 &micro, m) co-localizing with Sr, Ba, Ca and P.

Multimodal microanalytical characterization techniques are applied to identify and quantify rare earth element (REE) and REE + Y (REY) bearing mineral phases in coal utilization byproducts (CUB) from various coal-fired power plants. The characterization work provides quantitative assessments of REE in coal and CUB as obtained from 2- and 3D imaging, elemental mapping, volumetric estimates, and advanced high-resolution pixel classification. REY-bearing phosphate minerals rhabdophane (Ce,La)(PO4·H2O), monazite (Ce,La,Nd,Th)(PO4,SiO4), xenotime (YPO4,SiO4), and apatite (Ca5(PO4)3(F,Cl,OH), as well as REE-enriched calcium oxide were identified via electron microscopy and microprobe analysis. The minerals generally occurred as 1–20 μm-long crystals in the rock and ash samples. The most notable finding was that REEs are present as monomineralic grains dispersed within the ash, as well as fused to or encapsulated by amorphous aluminosilicate glass particles, also referred to as slag. It is indicative that conventional coal combustion processes sequester REE-bearing mineral phases such as rhabdophane, monazite, and zircon from the coal feed into aluminosilicate glass phases. The advanced microscopy and image analysis techniques applied in this study make it possible to deduce the average density of ash particles and quantify REE phases encapsulated in glass. Consequently, these REE phases may be targeted and recovered via density separation. These findings advance resource recovery techniques and commercial REE separation technologies for coal and combustion byproducts.

Reference standard NIST SRM 1633b and FA 345, a fly ash sample from an eastern U.S. coal power plant, were analyzed to determine and quantify the mineralogical association of rare earth elements (REE). These analyses were completed using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and a scanning electron microscope, equipped with an energy-dispersive X-ray spectrometer (SEM-EDS). Internal standardization was avoided by quantifying elemental concentrations by normalizing to 100% oxides. Mineral grains containing elevated REE concentrations were found in diverse chemical environments, but were most commonly found in regions where Al and Si were predominant. Dividing the spot analyses into time segments yielded plots that showed the REE content changing over time as individual mineral grains were being ablated. SEM-EDS images of FA 345 confirmed the trends that were found in the LA-ICP-MS results. Small grains of apatite, monazite, or zircon were frequently observed as free mineral grains or embedded in amorphous aluminosilicate glass and were not associated with ferrous particles. This finding is consistent with previous reports that magnetic enrichment may be an effective way of concentrating non-magnetic REE phases. Furthermore, aggressive mechanical and chemical-based separation schemes will be required to separate and recover REE from aluminosilicate glass.

Active layer detachments (ALDs) are permafrost disturbances associated with climate change and increased seasonal warming. Such perturbations result from thawing of the upper permafrost and downslope movement of the overlying thawed material, including the active layer. ALDs have the potential to impact soil microbial community composition and function in arctic soil ecosystems. Here we report an initial investigation of an ALD located at Cape Bounty on Melville Island in the Canadian High Arctic. We examined soil nutrient content as well as microbial community structure using denaturing gradient gel electrophoresis and sequencing. Soil from the disturbed site showed changes in microbial communities with strikingly different fungal community composition compared to soils from an adjacent undisturbed site. These community changes were correlated with enhanced levels of dissolved organic carbon, microbial carbon, total dissolved nitrogen, and microbial nitrogen. The Nitrososphaerales—an order of am...

Rare earth elements (REE) are necessary for advanced technological and energy applications. To support the emerging need, it is necessary to identify new domestic sources of REE and technologies to separate and recover saleable REE product in a safe and economical manner. Underclay rock associated with Central Appalachian coal seams and prevalent in coal utilization waste products is an alternative source of REE to hard rock ores that are mainly composed of highly refractory REE-bearing minerals. This study utilizes a suite of analytical techniques and benchtop leaching tests to characterize the properties and leachability of the coal seam underclays sampled. Laboratory bench-top and flow-through reactor leaching experiments were conducted on underclay rock powders to produce a pregnant leach solution (PLS) that has relatively low concentrations of gangue elements Al, Si, Fe, and Th and is amenable to further processing steps to recover and produce purified REE product. The leaching method described here uses a chelating agent, the citrate anion, to solubilize elements that are adsorbed, or weakly bonded to the surface of clay minerals or other mineral solid phases in the rock. The citrate PLS produced from leaching specific underclay powders contains relatively higher concentrations of REE and lower concentrations of gangue elements compared to PLS produced from sequential digestion using ammonium sulfate and mineral acids. Citrate solution leaching of underclay produces a PLS with lower concentrations of gangue elements and higher concentrations of REE than achieved with hydrochloric acid or sulfuric acid. The results provide a preliminary assessment of the types of REE-bearing minerals and potential leachability of coal seam underclays from the Central Appalachian basin.

Pressurised slurries of fine-grained sediment expelled from the base of the active layer have been observed in recent years in the High Arctic. Such mud ejections, however, are poorly understood in terms of how exactly climate and landscape factors determine when and where they occur. Mud ejections at the Cape Bounty Arctic Watershed Observatory, Melville Island, Nunavut, were systematically mapped in 2012 and 2013, and this was combined with observations of mud ejection activity and climatic measurements carried out since 2003. The mud ejections occur late in the melt season during warm years and closely following major rainfall events. High-resolution satellite imagery demonstrates that mud ejections are associated with polar semi-desert vegetative settings, flat or low-sloping terrain and south-facing slopes. The localised occurrence of mud ejections appears to be related to differential soil moisture retention. Copyright © 2015 John Wiley & Sons, Ltd.

Two ∼4 m vertical sequences of basal ice were collected from tunnels dug into the northern lateral margin of Taylor Glacier, McMurdo Dry Valleys, Antarctica. In both cases the basal sequences exhibit two contrasting ice facies groups; clean (debris-free) and banded dispersed (debris-rich). Debris-rich ices exhibit elevated CO2 and depleted O2 concentrations compared to the clean facies. Bacterial cell numbers, respiration rates, and nutrient concentrations are highest in debris-rich layers. Together, our geochemical and biological data indicate that microbial heterotrophic respiration is likely occurring in situ within the basal ice matrix at ambient temperatures near −15°C. This implies that the basal ice zone of polar glaciers and larger ice sheets is a viable subglacial microbial habitat and active biome of significant volume that has not previously been considered.

[1] A 30 day time course laboratory weathering experiment was conducted using rock samples collected from the West Fork of the Gallatin River watershed (WFW) in southwestern Montana, USA. The goal of these experiments was to quantify the amount of labile nitrogen in rock samples collected from the watershed and determine if chemical weathering is a source of dissolved nitrogen in stream water. Several rock samples investigated produced nitrate in significantly higher concentrations than the silica bead control (p

Biological ice nucleators (IN) function as catalysts for freezing at relatively warm temperatures (warmer than −10 °C). We examined the concentration (per volume of liquid) and nature of IN in precipitation collected from Montana and Louisiana, the Alps and Pyrenees (France), Ross Island (Antarctica), and Yukon (Canada). The temperature of detectable ice-nucleating activity for more than half of the samples was ≥ −5 °C based on immersion freezing testing. Digestion of the samples with lysozyme (i.e., to hydrolyze bacterial cell walls) led to reductions in the frequency of freezing (0–100%); heat treatment greatly reduced (95% average) or completely eliminated ice nucleation at the measured conditions in every sample. These behaviors were consistent with the activity being bacterial and/or proteinaceous in origin. Statistical analysis revealed seasonal similarities between warm-temperature ice-nucleating activities in snow samples collected over 7 months in Montana. Multiple regression was used to construct models with biogeochemical data [major ions, total organic carbon (TOC), particle, and cell concentration] that were accurate in predicting the concentration of microbial cells and biological IN in precipitation based on the concentration of TOC, Ca 2+ , and NH 4 + , or TOC, cells, Ca 2+ , NH 4 + , K + , PO 4 3− , SO 4 2− , Cl − , and HCO 3 − . Our results indicate that biological IN are ubiquitous in precipitation and that for some geographic locations the activity and concentration of these particles is related to the season and precipitation chemistry. Thus, our research suggests that biological IN are widespread in the atmosphere and may affect meteorological processes that lead to precipitation.