Pollution and health-risk assessments of Cr-contaminated soils from a tannery waste lagoon, Hebei, north China: With emphasis on Cr speciation.

In this paper, heavy metals (i.e., V, Cr, Co, Cu, Zn, Cd, Pb, and Sb) in soils from a tannery waste lagoon, Hebei, north China were investigated. Element concentrates were determined by a portable X-ray fluorescence in situ and an inductively coupled plasma mass spectrometry in the lab. Two sets of indexes, including geological accumulation index, contamination factor, and pollution load index, and hazard quotient and total carcinogenic risk were adopted to evaluate the pollution and health-risk of heavy metals. A scanning electron microscopy in conjunction with an energy dispersive X-ray spectroscopy and an X-ray photoelectron spectroscopy was used to observe chromium occurrence and speciation. With an average of 6493.11 mg/kg, chromium contents in the lagoon soils reached up to 12971.19 mg/kg, 211-times higher than the threshold of Chinese soils (61.00 mg/kg). Elevated Cr contents resulted in significantly high pollution and noncarcinogenic and carcinogenic risks in the studied area. Chromium in most soils occurred predominately as Cr3+ (60-74%), and to a lesser extent, Cr6+. The mechanism responsible for decreasing Cr6+ percentages in soils with increasing depth was summarized: Cr6+ favors aqueous environment; soil moisture decreased with increasing depth; in soils especially in the lower portion, Cr6+ was reduced by Fe0 and Fe2, transforming into Cr3+ and Fe3+. In addition, the alkaline condition promoted Cr3+ to precipitate, resulting more Cr3+ absorbing in soils. The intimate association of Cr and Fe in soils (i.e., Cr mainly occurred in Fe oxides and dolomite) further confirmed our assumptions. A combined application of microorganism (e.g., Aeromonas hydrophila) and biochar (prepared from maize stalk or peanut shells) were recommended to alleviate Cr pollution in the soils.

Combustion conditions and feed coals regulating the Fe- and Ti-containing nanoparticles in various coal fly ash.

Quantitative characteristics and sizes of nanoparticles (NPs) in coal fly ash (CFA) produced in coal-fired power plants as a function of coal type and plant design will help reveal the NP emission likelihood and their environmental implications. However, little is known about how combustion conditions and types of coal regulate the NP abundance in CFAs. In this study, based on single particle (SP)-ICP-MS technology, particle number concentrations (PNCs) and sizes of Fe- and Ti-containing NPs in CFAs were determined for samples collected from power plants of different designs and burning different types of coal. The PNCs of Fe- and Ti-containing NPs in all CFAs measured were in the range of 1.3 × 107 - 3.4 × 108 and 6.8 × 106 - 2.2 × 108 particles/mg, with the average particle sizes of 111 nm and 87 nm, respectively. The highest Fe-NP PNCs likely relate to the highest contents of Fe and pyrite in the feed coal. In addition, high TOC in CFAs are associated with metal-containing NPs, resulting in elevated abundances of these NPs with relatively large sizes. Moreover, elevated PNCs of NPs were found in CFAs produced by coal-fired power plants burning low-rank coals and with small installed capacity (especially those under 100-MW units). Compared to cyclone filters, ESPs and FFs with higher removal efficiency typically retain more Fe-/Ti- containing NPs with smaller sizes. Based on a structural equation (SE) model, raw coal properties (coal rank and Fe/Ti content), boiler types, and efficiency of particulate emission control devices likely indirectly affect PNCs of Fe- and Ti-containing NPs by influencing TOC contents and their corresponding metal concentrations of CFAs. This study provides the first analytic and comprehensive information concerning the direct and indirect regulating factors on NPs in various CFAs.

Rapid removal of PFOA and PFOS via modified industrial solid waste: Mechanisms and influences of water matrices.

Emerging perfluoroalkyl and polyfluoroalkyl substances contaminate waters at trace concentrations, thus rapid and selective adsorbents are pivotal to mitigate the consequent energy-intensive and time-consuming issues in remediation. In this study, coal combustion residuals-fly ash was modified (FA-SCA) to overcome the universal trade-off between high adsorption capacity and fast kinetics. FA-SCA presented rapid adsorption (teq = 2 min) of PFOX (perfluorooctanoic acid and perfluorooctanesulfonic acid, collectively), where the dynamic adsorption capacity (qdyn = qm/teq) was 2-3 orders of magnitude higher than that of benchmark activated carbons and anion-exchange resins. Investigated by advanced characterization and kinetic models, the fast kinetics and superior qdyn are attributed to (1) elevated external diffusion driven by the submicron particle size; (2) enhanced intraparticle diffusion caused by the developed mesoporous structure (Vmeso/Vmicro = 8.1); (3) numerous quaternary ammonium anion-exchange sites (840 µmol/g), and (4) appropriate adsorption affinity (0.031 L/µmol for PFOS, and 0.023 L/µmol for PFOA). Since the adsorption was proven to be a synergistic process of electrostatic and hydrophobic interactions, effective adsorption ([PFOX]ini = 1.21 µM, concentration levels of highly-contaminant-sites) was obtained at conventional natural water chemistries. High selectivity (>85.4% removal) was also achieved with organic/inorganic competitors, especially compounds with partly similar molecular structures to PFOX. In addition, >90% PFOX was removed consistently during five cycles in mild regeneration conditions (pH 12 and 50 °C). Overall, FA-SCA showed no leaching issues of toxic metals and exhibits great potential in both single-adsorption processes and treatment train systems.

Soils and spoils: mineralogy and geochemistry of mining and processing wastes from lead and zinc mining at the Gratz Mine, Owen County, Kentucky.

Purpose: Mineralogical and geochemical features of mining and processing wastes collected in Owen County, part of the Central Kentucky Lead-Zinc district, were investigated. The Gratz mine, abandoned in the 1940s, is on a dairy farm. Aside from discerning the nature of mining refuse at the site, the investigation was part of the University of Kentucky College of Pharmacy's mission to explore unusual environments in the search for unique microbiological communities. Materials and methods: Four samples of a soil-plus-spoils mix were collected from spoil piles and two samples, the sluice and coarse samples, were closely associated with the site of the ore processing. Optical petrology (polarized reflected-light, oil-immersion optics at a final magnification of 500 ×), X-ray diffraction, X-ray fluorescence, inductively coupled plasma mass spectrometry, field emission scanning electron microscopy (FE-SEM), and high-resolution transmission electron microscope (HR-TEM) with selected area electron diffraction (SAED) and/or microbeam diffraction (MBD), scanning transmission electron microscopy (STEM), and energy-dispersive X-ray spectrometer (EDS) analyses were employed to characterize the samples. Results and discussion: Calcite is the main mineral in most samples, followed by near equal amounts of quartz and dolomite. Sphalerite and galena are the principal sulfides and barite is the dominant sulfate. Geochemistry of major elements reflected the mineralogy, whereas trace elements showed different groupings between the minerals. Scandium, Cu, Ga, Ge, Cd, and Sb were found predominantly associated with Zn and Pb and sulfide minerals; Bi, Hf, In, Sn, and Zr with heavy mineral fraction; while the remaining trace elements, including the rare earths, were mostly distributed among other present phases, i.e., oxyhalides, oxides, silicates, and carbonaceous material. The data were used to illustrate the processes and conditions that control the sulfide-mineral oxidation and its potential for the environmental release of associated reaction products. Conclusions: The wastes represent a potential source of environmentally disruptive concentrations of Zn, Pb, and other sulfide-associated elements. The high share of carbonates suggests near-neutral conditions in deposited wastes, restricting sulfide weathering and further limiting the oxidant activity of Fe. The low-Fe content and its predominant presence in highly resistant hematite also constrain sulfide weathering. Consequently, the spoils have a low potential for generation of acidity and release of heavy metal(loid)s in the surrounding environment.

Metal-Containing Nanoparticles in Low-Rank Coal-Derived Fly Ash from China: Characterization and Implications toward Human Lung Toxicity.

Characterization of nanoparticles (NPs) in coal fly ashes (CFAs) is critical for better understanding the potential health-related risks resulting from coal combustion. Based on single-particle (SP)-inductively coupled plasma mass spectrometry (ICP-MS) coupled with transmission electron microscopy techniques, this study is the first to determine the concentrations and sizes of metal-containing NPs in low-rank coal-derived fly ashes. Despite only comprising a minor component of the studied CFAs by mass, NPs were the dominant fraction by particle number. Fe- and Ti-containing NPs were identified as the dominant NPs with their particle number concentration ranging from 2.5 × 107 to 2.5 × 108 particles/mg. In addition, the differences of Fe-/Ti-containing NPs in various CFAs were regulated by the coalification degree of feed coals and combustion conditions of all of the low-rank CFAs tested. In the cases where these NPs in CFAs become airborne and are inhaled, they can be taken up in pulmonary interstitial fluids. This study shows that in Gamble's solution (a lung fluid simulant), 51-87% of Fe and 63-89% of Ti (ratio of the mass of Fe-/Ti-containing NPs to the total mass of Fe/Ti) exist in the NP form and remain suspended in pulmonary fluid simulants. These NPs are bioavailable and may induce lung tissue damage.

The key roles of Fe-bearing minerals on arsenic capture and speciation transformation during high-As bituminous coal combustion: Experimental and theoretical investigations.

The conversion of As vapor released from coal combustion to less hazardous solids is an important process to alleviate As pollution especially for high-As coal burning, but the roles of key ash components are still in debate. Here, we used multiple analytical methods across the micro to bulk scale and density functional theory to provide quantitative information on As speciation in fly ash and clarify the roles of ash components on As retention. Fly ash samples derived from the high-As bituminous coal-fired power plants showed a chemical composition of typical Class F fly ash. In-situ electron probe microanalysis (EPMA) was for the first time used to quantify and distinguish the inter-particle As distribution difference within coal fly ash. The spatial distribution of As was consistent with Fe, O, and sometimes with Ca. Grain-scale distribution of As in coal fly ash was quantified and As concentrations in single ash particles followed the order of Fe-oxides > aluminosilicates > unburned carbon > quartz. Sequential extraction and Wagner chemical plot of As confirmed that Fe minerals rather than Al-/Ca-bearing minerals played a vital role in capturing and oxidizing As3+ into solid phase (As5+). Magnetite content in fly ash well-correlated with the increase ratio of As before and after magnetic separation, suggesting magnetite enhanced As enrichment in fly ash. Density functional theory (DFT) indicated that the bridges O sites of octahedral structure on Fe3O4 (111) surface were likely strong active sites for As2O3 adsorption. This study highlights the importance of magnetite on As transformation during bituminous or high-rank coal combustion in power plants and has great implications for developing effective techniques for As removal.

Portable dehumidifiers as an original matrix for the study of inhalable nanoparticles in school.

Good air quality is documented as a significant factor of social justice. The human health hazards associated with air pollution are not distributed equally across cities; the most vulnerable people are more exposed to ambient air as they commute to work and wait for buses or trains at the stations. Aerosols play important roles in atmosphere quality and the climate; their oxidation at the nanoscale level may possibly increase the reactivity and toxicity of atmospheric particulates. Indoor school environments are characterized by high concentrations of different airborne particulate and gaseous pollutants. The documentation of nanoparticles (NPs), ultra-fine particles (UFPs), and micron-size particle species present in indoor primary schools are an important aspect in the recognition of their influence in respirational difficulties and decreased cognitive progress in children. This work utilizes the study of condensed water, sampled with portable dehumidifiers (PD), to describe NPs and UFPs in the vapor stage of enclosed zones. The acquired extracts were analyzed by advanced electron microscopy techniques. A total of 392 NPs and 251 UFPs were examined in a set of 22 samples acquired in moderately limited or inadequately ventilated indoor areas from several schools. Noting that NPs-related disorders happen at particular places of respirational structure, identification of site-specific NPs accumulation should be anticipated in direction to better verify the corresponding human health outcomes resulting from respirable NPs.

Mercury stable isotope fractionation during gaseous elemental mercury adsorption onto coal fly ash particles: Experimental and field observations.

Mercury (Hg) stable isotopes have a great potential to track coal combustion Hg emissions, but mass-dependent fractionation (MDF) during Hg adsorption onto fly ash particles could significantly alter isotope signatures of emitted Hg species. The detailed processes causing this MDF, however, are not well understood. Here, we simulated how isotopes fractionate during gaseous Hg0 adsorption onto fly ash at different times and temperatures. Kinetic MDF that preferably transfers light Hg isotopes to fly ash dominated Hg0 adsorption processes. The magnitude of MDF during Hg0 adsorption was invariable in the time-series experiment but increased significantly with increasing temperature in the temperature-series experiment. The external mass transfer and chemisorption are suggested to be the controlling processes for isotopic fractionation. Relative to diffusion-driven Hg0 adsorption, chemisorption is suggested to be a more important Hg0 adsorption step causing MDF, especially at high temperatures. The chemisorption involves Hg redox change from Hg0 to HgII and is likely enhanced with increasing temperature (50-180 °C). The proposed kinetic MDF model reveals that MDF in modern coal-fired power plants is likely driven by temperature-induced redox processes during Hg0 adsorption, and has great implications for developing MDF models in coal-fired boilers and tracing coal combustion Hg emissions.

Structure Determination, Functional Characterization, and Biosynthetic Implications of Nybomycin Metabolites from a Mining Reclamation Site-Associated Streptomyces.

We report the isolation and characterization of three new nybomycins (nybomycins B-D, 1-3) and six known compounds (nybomycin, 4; deoxynyboquinone, 5; α-rubromycin, 6; ß-rubromycin, 7; γ-rubromycin, 8; and [2α(1E,3E),4ß]-2-(1,3-pentadienyl)-4-piperidinol, 9) from the Rock Creek (McCreary County, KY) underground coal mine acid reclamation site isolate Streptomyces sp. AD-3-6. Nybomycin D (3) and deoxynyboquinone (5) displayed moderate (3) to potent (5) cancer cell line cytotoxicity and displayed weak to moderate anti-Gram-(+) bacterial activity, whereas rubromycins 6-8 displayed little to no cancer cell line cytotoxicity but moderate to potent anti-Gram-(+) bacterial and antifungal activity. Assessment of the impact of 3 or 5 cancer cell line treatment on 4E-BP1 phosphorylation, a predictive marker of ROS-mediated control of cap-dependent translation, also revealed deoxynyboquinone (5)-mediated downstream inhibition of 4E-BP1p. Evaluation of 1-9 in a recently established axolotl embryo tail regeneration assay also highlighted the prototypical telomerase inhibitor γ-rubromycin (8) as a new inhibitor of tail regeneration. Cumulatively, this work highlights an alternative nybomycin production strain, a small set of new nybomycin metabolites, and previously unknown functions of rubromycins (antifungal activity and inhibition of tail regeneration) and also provides a basis for revision of the previously proposed nybomycin biosynthetic pathway.

Selective Recovery of Rare Earth Elements from Coal Fly Ash Leachates Using Liquid Membrane Processes.

Coal combustion residues and other geological waste materials have been proposed as a resource for rare earth elements (REEs, herein defined as the 14 stable lanthanides, yttrium, and scandium). The extraction of REEs from residues often generate acidified leachates that require highly selective separation methods to recover the REEs from other major soluble ions in the leachates. Here, we studied two liquid membrane processes (liquid emulsion membranes, LEM, and supported liquid membranes, SLM) and compared them to standard solvent extraction techniques for selective recovery and concentration of REEs from a leachate of coal fly ash. All separation methods involved an organic solution of di(2-ethylhexyl)phosphoric acid dissolved in kerosene or mineral oil and an acid strippant solution of 5 M nitric acid for the liquid-based separations. The LEM configuration, which separated REEs by immersing an acid-in-oil emulsion in the ash leachate, resulted in similar recovery percentages of individual REEs as the conventional solvent extraction approach. The recovery of REEs in the SLM configuration, which involved the impregnation of the solvent in a hydrophobic membrane, was slower than the LEM process. However, the SLM process was notably more selective for the heavy (and higher value) REEs, while the conventional extraction and LEM processes were more selective for the light REEs. A flux-based model of the extraction processes suggested that recovery rates were limited by REE affinity for the solvent chelator in the SLM, while the rates of REEs separation via LEM were limited by diffusive mass transfer across the liquid membrane. Altogether, these results help to identify specific steps in the recovery process that future work should target in the development of scalable liquid membrane separations for REE recovery.

Environmental evaluation and nano-mineralogical study of fresh and unsaturated weathered coal fly ashes.

Coal combustion and the disposal of combustion wastes emit enormous quantities of nano-sized particles that pose significant health concerns on exposure, particularly in unindustrialized countries. Samples of fresh and weathered class F fly ash were analysed through various techniques including X-ray fluorescence (XRF), X-ray diffraction (XRD), focused ion beam scanning electron microscopy (FIB-SEM), field-emission gun scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM) coupled with energy dispersive x-ray spectroscopy (EDS), and Raman Spectroscopy. The imaging techniques showed that the fresh and weathered coal fly ash nanoparticles (CFA-NPs) are mostly spherical shaped. The crystalline phases detected were quartz, mullite, ettringite, calcite, maghemite, hematite, gypsum, magnetite, clay residues, and sulphides. The most abundant crystalline phases were quartz mixed with Al-Fe-Si-K-Ti-O-amorphous phases whereas mullite was detected in several amorphous phases of Al, Fe, Ca, Si, O, K, Mg, Mn, and P. The analyses revealed that CFA-NPs are 5-500 nm in diameter and encapsulate several potentially hazardous elements (PHEs). The carbon species were detected as 5-50 nm carbon nanoballs of graphitic layers and massive fullerenes. Lastly, the aspects of health risks related to exposure to some detected ambient nanoparticles are also discussed.

Differences in bulk and microscale yttrium speciation in coal combustion fly ash.

Coal combustion ash is a promising alternative source of rare earth elements (REE; herein defined as the 14 stable lanthanides, yttrium, and scandium). Efforts to extract REE from coal ash will depend heavily on the location and speciation of these elements in the ash. This study sought to identify the major chemical forms of yttrium (Y), as a representative REE in coal fly ash samples selected from major coal sources in the United States. Y speciation was evaluated using both bulk scale analyses (sequential extractions, Y K-edge X-ray absorption near-edge spectroscopy - XANES) and complementary analyses at the micron scale (micro-focus X-ray fluorescence and micro-XANES). Sequential selective extractions revealed that the REE were primarily in the residual (unextracted fraction) of coal fly ash samples. Extraction patterns for yttrium resembled those of the lanthanides, indicating that these elements were collectively dispersed throughout the aluminosilicate glass in fly ash. Bulk XANES analysis indicated that Y coordination states resembled a combination of Y-oxides, Y-carbonate, and Y-doped glass, regardless of ash origin. However, in the microprobe analysis, we observed "hotspots" of Y (∼10-50 µm) in some samples that included different Y forms (e.g., Y-phosphate) not observed in bulk measurements. Overall, this study demonstrated that yttrium (and potentially other REEs) are entrained in the glass phase of fly ash and that microscale investigations of individual high-REE regions in fly ash samples do not necessarily capture the dominant speciation.

Emission and transformation behavior of minerals and hazardous trace elements (HTEs) during coal combustion in a circulating fluidized bed boiler.

Emission of hazardous trace elements (HTEs) from energy production is receiving much attention due to concerns about the toxicity to the ecosystem and human health. This study presented new field measurement data on the HTEs partitioning behavior and size-segregated elemental compositions of gaseous particular matter (PM) generated from a commercial circulating fluidized bed (CFB) power plant. Mineralogical and morphological characteristics of combustion ash and PM2.5 (particle diameter less than 2.5 µm) were determined by X-ray diffractometer (XRD) and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS). Functional groups alteration during CFB combustion was characterized by Fourier transform infrared spectroscopy (FTIR). The presence of aliphatic hydrogen at 2910 cm-1 and 2847 cm-1 in the PM2.5 suggested that the aliphatic carbon-rich volatiles were absorbed on the fine particles with large surface area. Fine fly ash (PM2.5) occurred as irregular glass particles or/and as unburned carbon. The typical irregular particles were mainly composed of Al-Si-Ca or Al-Si-Fe phases. The enrichment behavior of HTEs was determined for the airborne size-segregated particular matter. Elemental occurrences, combustion temperature, unburnt carbon, and limestone additives during CFB combustion were critical in the transformation behavior of HTEs. The total potentially mobile pollutants that exit the CFB power plant every year were estimated as follows: 0.22 tons of Cr, 0.12 tons of Co, 0.73 tons of Ni, 0.04 tons of As, 0.07 tons of Se, 3.95 kg of Cd, and 3.34 kg of Sb.

Ranking Coal Ash Materials for Their Potential to Leach Arsenic and Selenium: Relative Importance of Ash Chemistry and Site Biogeochemistry.

The chemical composition of coal ash is highly heterogeneous and dependent on the origin of the source coal, combustion parameters, and type and configuration of air pollution control devices. This heterogeneity results in uncertainty in the evaluation of leaching potential of contaminants from coal ash. The goal of this work was to identify whether a single leaching protocol could roughly group high-leaching potential coal ash from low-leaching potential coal ash, with respect to arsenic (As) and selenium (Se). We used four different leaching tests, including the Toxicity Characteristic Leaching Protocol (TCLP), natural pH, aerobic sediment microcosms, and anaerobic sediment microcosms on 10 different coal ash materials, including fly ash, lime-treated ash, and flue gas desulfurization materials. Leaching tests showed promise in categorizing high and low-leaching potential ash materials, indicating that a single point test could act as a first screening measure to identify high-risk ash materials. However, the amount of contaminant leached varied widely across tests, reflecting the importance of ambient conditions (pH, redox state) on leaching. These results demonstrate that on-site geochemical conditions play a critical role in As and Se mobilization from coal ash, underscoring the need to develop a situation-based risk assessment framework for contamination by coal ash pollutants.

Determination of Chemical Speciation of Arsenic and Selenium in High-As Coal Combustion Ash by X-ray Photoelectron Spectroscopy: Examples from a Kentucky Stoker Ash.

Knowledge of the chemical speciation of arsenic and selenium in coal fly ash is essential in the evaluation of the environmental behavior of fly ash disposed in a landfill in a natural environment. In this study, a series of high-As coal fly ash from stoker boilers were collected to determine the chemical forms of arsenic and selenium. The ash surface chemical characteristics and the speciation of arsenic and selenium were characterized by X-ray photoelectron spectroscopy and X-ray-induced Auger electron spectroscopy. The results indicate that the surface enrichment ratio for selenium (63.3-309.5) is higher than that of arsenic (1.2-21.2). The Wagner chemical-state plot of arsenic indicates that As is mainly present as As(V) bonded to oxygen ligands, that is, the [AsO4]3- anion; Se is found predominantly as elemental Se (62.0-83.3%), followed by selenite (16.7-38%). The extreme enrichment of both arsenic and selenium arsenic is controlled by iron oxides in the coal fly ash.

Ultrafine Mineral Associations in Superhigh-Organic-Sulfur Kentucky Coals.

Two high-organic-sulfur Kentucky coals, the eastern Kentucky River Gem coal and the western Kentucky Davis coal, are examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), both including elemental analysis by energy-dispersive spectroscopy (EDS). From the SEM-EDS analysis, it is observed that the western Kentucky coal had areas with Pb and Cd in addition to the expected Fe and S and the eastern Kentucky coal had individual Fe-S-rich areas with La and Ni and with Si, Al, Cr, Ni, and Ti. TEM and selected area electron diffraction (SAED) analyses demonstrate that anglesite with a rim of Pb-bearing amorphous Fe-oxide occurs in the western Kentucky coal. Melanterite, an Fe-sulfate, with minor Al, Si, and K EDS peaks, suggests that clay minerals may be in close association with the sulfate, is also detected in the coal. A polycrystalline metal in the eastern Kentucky sample with a composition similar to stainless steel is adjacent to an Al-rich shard. Euhedral pyrite grains surrounded by kaolinite and gibbsite are detected. Overall, it is noted that element associations should not be assumed to be organic just because minerals cannot be seen with optical microscopy or with standard bulk analytical techniques, such as X-ray diffraction (XRD).

Discovery and ramifications of incidental Magnéli phase generation and release from industrial coal-burning.

Coal, as one of the most economic and abundant energy sources, remains the leading fuel for producing electricity worldwide. Yet, burning coal produces more global warming CO2 relative to all other fossil fuels, and it is a major contributor to atmospheric particulate matter known to have a deleterious respiratory and cardiovascular impact in humans, especially in China and India. Here we have discovered that burning coal also produces large quantities of otherwise rare Magnéli phases (Ti x O2x-1 with 4 ≤ x ≤ 9) from TiO2 minerals naturally present in coal. This provides a new tracer for tracking solid-state emissions worldwide from industrial coal-burning. In its first toxicity testing, we have also shown that nanoscale Magnéli phases have potential toxicity pathways that are not photoactive like TiO2 phases, but instead seem to be biologically active without photostimulation. In the future, these phases should be thoroughly tested for their toxicity in the human lung.Solid-state emissions from coal burning remain an environmental concern. Here, the authors have found that TiO2 minerals present in coal are converted into titanium suboxides during burning, and initial biotoxicity screening suggests that further testing is needed to look into human lung consequences.

Bi- and Tetracyclic Spirotetronates from the Coal Mine Fire Isolate Streptomyces sp. LC-6-2.

The structures of 12 new "enantiomeric"-like abyssomicin metabolites (abyssomicins M-X) from Streptomyces sp. LC-6-2 are reported. Of this set, the abyssomicin W (11) contains an unprecedented 8/6/6/6 tetracyclic core, while the bicyclic abyssomicin X (12) represents the first reported naturally occurring linear spirotetronate. Metabolite structures were determined based on spectroscopic data and X-ray crystallography, and Streptomyces sp. LC-6-2 genome sequencing also revealed the corresponding putative biosynthetic gene cluster.

Mccrearamycins A-D, Geldanamycin-Derived Cyclopentenone Macrolactams from an Eastern Kentucky Abandoned Coal Mine Microbe.

Four cyclopentenone-containing ansamycin polyketides (mccrearamycins A-D), and six new geldanamycins (Gdms B-G, including new linear and mycothiol conjugates), were characterized as metabolites of Streptomyces sp. AD-23-14 isolated from the Rock Creek underground coal mine acid drainage site. Biomimetic chemical conversion studies using both simple synthetic models and Gdm D confirmed that the mccrearamycin cyclopentenone derives from benzilic acid rearrangement of 19-hydroxy Gdm, and thereby provides a new synthetic derivatization strategy and implicates a potential unique biocatalyst in mccrearamycin cyclopentenone formation. In addition to standard Hsp90α binding and cell line cytotoxicity assays, this study also highlights the first assessment of Hsp90α modulators in a new axolotl embryo tail regeneration (ETR) assay as a potential new whole animal assay for Hsp90 modulator discovery.

Spoxazomicin D and Oxachelin C, Potent Neuroprotective Carboxamides from the Appalachian Coal Fire-Associated Isolate Streptomyces sp. RM-14-6.

The isolation and structure elucidation of six new bacterial metabolites [spoxazomicin D (2), oxachelins B and C (4, 5), and carboxamides 6-8] and 11 previously reported bacterial metabolites (1, 3, 9-12a, and 14-18) from Streptomyces sp. RM-14-6 is reported. Structures were elucidated on the basis of comprehensive 1D and 2D NMR and mass spectrometry data analysis, along with direct comparison to synthetic standards for 2, 11, and 12a,b. Complete 2D NMR assignments for the known metabolites lenoremycin (9) and lenoremycin sodium salt (10) were also provided for the first time. Comparative analysis also provided the basis for structural revision of several previously reported putative aziridine-containing compounds [exemplified by madurastatins A1, B1, C1 (also known as MBJ-0034), and MBJ-0035] as phenol-dihydrooxazoles. Bioactivity analysis [including antibacterial, antifungal, cancer cell line cytotoxicity, unfolded protein response (UPR) modulation, and EtOH damage neuroprotection] revealed 2 and 5 as potent neuroprotectives and lenoremycin (9) and its sodium salt (10) as potent UPR modulators, highlighting new functions for phenol-oxazolines/salicylates and polyether pharmacophores.