Olivine Dissolution in Simulated Lung and Gastric Fluid as an Analog to the Behavior of Lunar Particulate Matter Inside the Human Respiratory and Gastrointestinal Systems.

With the Artemis III mission scheduled to land humans on the Moon in 2025, work must be done to understand the hazards lunar dust inhalation would pose to humans. In this study, San Carlos olivine was used as an analog of lunar olivine, a common component of lunar dust. Olivine was dissolved in a flow-through apparatus in both simulated lung fluid and 0.1 M HCl (simulated gastric fluid) over a period of approximately 2 weeks at physiological temperature, 37°C. Effluent samples were collected periodically and analyzed for pH, iron, silicon, and magnesium ion concentrations. The dissolution rate data derived from our measurements allow us to estimate that an inhaled 1.0 µm diameter olivine particle would take approximately 24 years to dissolve in the human lungs and approximately 3 weeks to dissolve in gastric fluid. Results revealed that inhaled olivine particles may generate the toxic chemical, hydroxyl radical, for up to 5-6 days in lung fluid. Olivine dissolved in 0.1 M HCl for 2 weeks transformed to an amorphous silica-rich solid plus the ferric iron oxy-hydroxide ferrihydrite. Olivine dissolved in simulated lung fluid shows no detectable change in composition or crystallinity. Equilibrium thermodynamic models indicate that olivine in the human lungs can precipitate secondary minerals with fibrous crystal structures that have the potential to induce detrimental health effects similar to asbestos exposure. Our work indicates that inhaled lunar dust containing olivine can settle in the human lungs for years and could induce long-term potential health effects like that of silicosis.

The Role of Iraqi Dust in Inducing Lung Injury in United States Soldiers-An Interdisciplinary Study.

United States soldiers are returning from the Greater Middle East with respiratory illnesses ranging from new onset asthma to constrictive bronchiolitis. The etiology of the diseases is unknown. A study was conducted to determine the possible role of local mineral dust in the development of abnormal respiratory illnesses in soldiers during and after deployment in Iraq. A dust sample obtained in proximity to a burn pit in Camp Victory, Iraq, (CVD) was characterized both chemically and mineralogically. For comparison, a dust sample from Fort Irwin, California, (FID) was also collected. The ability of the dust samples to generate reactive oxygen species (ROS) was quantified, as well as their ability to generate an inflammatory stress response (ISR) in human lung epithelial cells. Both samples are comprised of common silicate and carbonate minerals and contain heavy metals with concentration ranges expected for mineral dust. The ISR generated by each sample was within the range of inert material with the minimal stress generated associated with the carbonate phases. The findings based on this one sample suggest that the origin of the disease is not driven by the particles ability to generate ROS. However it is likely that particle overload, and associated complications, or endotoxin contribute extensively to pathogenesis.

Effect of Phospholipid on Pyrite Oxidation and Microbial Communities under Simulated Acid Mine Drainage (AMD) Conditions.

The effect of phospholipid on the biogeochemistry of pyrite oxidation, which leads to acid mine drainage (AMD) chemistry in the environment, was investigated. Metagenomic analyses were carried out to understand how the microbial community structure, which developed during the oxidation of pyrite-containing coal mining overburden/waste rock (OWR), was affected by the presence of adsorbed phospholipid. Using columns packed with OWR (with and without lipid adsorption), the release of sulfate (SO4(2-)) and soluble iron (FeTot) was investigated. Exposure of lipid-free OWR to flowing pH-neutral water resulted in an acidic effluent with a pH range of 2-4.5 over a 3-year period. The average concentration of FeTot and SO4(2-) in the effluent was ≥20 and ≥30 mg/L, respectively. In contrast, in packed-column experiments where OWR was first treated with phospholipid, the effluent pH remained at ∼6.5 and the average concentrations of FeTot and SO4(2-) were ≤2 and l.6 mg/L, respectively. 16S rDNA metagenomic pyrosequencing analysis of the microbial communities associated with OWR samples revealed the development of AMD-like communities dominated by acidophilic sulfide-oxidizing bacteria on untreated OWR samples, but not on refuse pretreated with phospholipid.

The effect of pyrite on Escherichia coli in water: proof-of-concept for the elimination of waterborne bacteria by reactive minerals.

We present proof-of-concept results for the elimination of waterborne bacteria by reactive minerals. We exposed Escherichia coli MG1655 suspended in water to the reactive mineral pyrite (FeS2) at room temperature and ambient light. This slurry eliminates 99.9% of bacteria in fewer than 4 hours. We also exposed Escherichia coli to pyrite leachate (supernatant liquid from slurry after 24 hours), which eliminates 99.99% of bacteria over the same time-scale. Unlike SOlar water DISinfection (SODIS), our results do not depend on the presence of ultraviolet (UV) light. We confirmed this by testing proposed SODIS additive and known photo-catalyst anatase (TiO2) for antibacterial properties and found that, in contrast to pyrite, it does not eliminate E. coli under our experimental conditions. Previous investigations of naturally antibiotic minerals have focused on the medical applications of antibiotic clays, and thus have not been conducted under experimental conditions resembling those found in water purification. In our examination of the relevant literature, we have not found previously reported evidence for the use of reactive minerals in water sanitization. The results from this proof-of-concept experiment may have important implications for future directions in household water purification research.

Metal-sulfide mineral ores, Fenton chemistry and disease--particle induced inflammatory stress response in lung cells.

The inhalation of mineral particulates and other earth materials, such as coal, can initiate or enhance disease in humans. Workers in occupations with high particulate exposure, such as mining, are particularly at risk. The ability of a material to generate an inflammatory stress response (ISR), a measure of particle toxicity, is a useful tool in evaluating said exposure risk. ISR is defined as the upregulation of cellular reactive oxygen species (ROS) normalized to cell viability. This study compares the ISR of A549 human lung epithelial cells after exposure to well-characterized common metal-sulfide ore mineral separates. The evaluation of the deleterious nature of ore minerals is based on a range of particle loadings (serial dilutions of 0.002m(2)/mL stock) and exposure periods (beginning at 30min and measured systematically for up to 24h). There is a wide range in ISR values generated by the ore minerals. The ISR values produced by the sphalerite samples are within the range of inert materials. Arsenopyrite generated a small ISR that was largely driven by cell death. Galena showed a similar, but more pronounced response. Copper-bearing ore minerals generated the greatest ISR, both by upregulating cellular ROS and generating substantial and sustained cell death. Chalcopyrite and bornite, both containing ferrous iron, generated the greatest ISR overall. Particles containing Fenton metals as major constituents produce the highest ISR, while other heavy metals mainly generate cell death. This study highlights the importance of evaluating the chemistry, oxidation states and structure of a material when assessing risk management.

Reduction of nitrite and nitrate on nano-dimensioned FeS.

The reaction of nitrite (NO2(-)) and nitrate (NO3(-)) on nanometer-sized FeS particles was investigated in alkaline (initial pH = 10.3) solutions at reaction temperatures of 22, 70, and 120 °C using in situ attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and fluorescence spectroscopy that allowed an analysis of adsorbate complexation on the FeS and reaction product in the aqueous phase, respectively. ATR-FTIR showed that NO was a surface-bound intermediate on FeS during its exposure to NO2(-) at all three reaction temperatures. Ammonia/ammonium (NH3/NH4(+)) product was also produced when FeS was exposed to NO2(-) at the 70 °C and 120 °C reaction temperatures. Activation of NO3(-) to form surface-bound NO was experimentally observed to occur at 120 °C on FeS, but not at the lower reaction temperatures. Furthermore, NH3/NH4(+) product in the aqueous phase was only present during the reaction of FeS with NO3(-) at the highest temperature used in this study.

Inflammatory stress response in A549 cells as a result of exposure to coal: evidence for the role of pyrite in coal workers' pneumoconiosis pathogenesis.

UNLABELLED: On the basis of a recent epidemiological study it is hypothesized that pyrite content in coal is an important factor in coal workers' pneumoconiosis (CWP) pathogenesis. While the role of pyrite in pathogenesis remains to be resolved, the ability of the mineral to generate reactive oxygen species (ROS) through various mechanisms is likely a contributing factor. The aim of this study was to elucidate the importance of the pyrite content of coal in generating an inflammatory stress response (ISR), which is defined as the upregulation of ROS normalized by cell viability. The ISR of A549 human lung epithelial cells in the presence of natural coal samples with variable pyrite contents was measured. Normalized to surface area, five particle loadings for each coal reference standard were analyzed systematically for a total of 24 h. The ISR generated by coals containing 0.00, 0.01, and 0.49 wt.% pyritic sulfur is comparable to,though less than, the ISR generated by inert glass beads (299% of the control). The coals containing 0.52 and 1.15 wt.% pyritic sulfur generated the greatest ISR (798% and 1426% of the control, respectively). CONCLUSIONS: While ISR does not increase proportionally to pyrite content in coal, the two coals with the highest pyritic sulfur and available iron contents generate the greatest ISR. Therefore, the present study indicates that coals with elevated pyrite contents are likely to induce a significant health burden by stimulating inflammation within the lungs, and may contribute to the development of CWP.

Reduction of nitrite and nitrate to ammonium on pyrite.

An important constraint on the formation of the building blocks of life in the Hadean is the availability of small, activated compounds such as ammonia (NH(3)) relative to its inert dinitrogen source. Iron-sulfur particles and/or mineral surfaces have been implicated to provide the catalytic active sites for the reduction of dinitrogen. Here we provide a combined kinetic, spectroscopic, and computational modeling study for an alternative source of ammonia from water soluble nitrogen oxide ions. The adsorption of aqueous nitrite (NO(2)(-)) and nitrate (NO(3)(-)) on pyrite (FeS(2)) and subsequent reduction chemistry to ammonia was investigated at 22°C, 70°C, and 120°C. Batch geochemical and in situ Attenuated Total Reflection - Fourier Transform Infrared (ATR-FTIR) spectroscopy experiments were used to determine the reduction kinetics to NH(3) and to elucidate the identity of the surface complexes, respectively, during the reaction chemistry of NO(2)(-) and NO(3)(-). Density functional theory (DFT) calculations aided the interpretation of the vibrational data for a representative set of surface species. Under the experimental conditions used in this study, we detected the adsorption of nitric oxide (NO) intermediate on the pyrite surface. NH(3) production from NO(2)(-) occurred at 70 and 120°C and from NO(3)(-) occurred only at 120°C.

Pyrite-driven reactive oxygen species formation in simulated lung fluid: implications for coal workers' pneumoconiosis.

The origin of coal worker's pneumoconiosis (CWP) has been long debated. A recent epidemiological study shows a correlation between what is essentially the concentration of pyrite within coal and the prevalence of CWP in miners. Hydrogen peroxide and hydroxyl radical, both reactive oxygen species (ROS), form as byproducts of pyrite oxidative dissolution in air-saturated water. Motivated by the possible importance of ROS in the pathogenesis of CWP, we conducted an experimental study to evaluate if ROS form as byproducts in the oxidative dissolution of pyrite in simulated lung fluid (SLF) under biologically applicable conditions and to determine the persistence of pyrite in SLF. While the rate of pyrite oxidative dissolution in SLF is suppressed by 51% when compared to that in air-saturated water, the initial amount of hydrogen peroxide formed as a byproduct in SLF is nearly doubled. Hydroxyl radical is also formed in the experiments with SLF, but at lower concentrations than in the experiments with water. The formation of these ROS indicates that the reaction mechanism for pyrite oxidative dissolution in SLF is no different from that in water. The elevated hydrogen peroxide concentration in SLF suggests that the decomposition, via the Fenton mechanism to hydroxyl radical or with Fe(III) to form water and molecular oxygen, is initially inhibited by the presence of SLF components. On the basis of the oxidative dissolution rate of pyrite measured in this paper, it is calculated that a respirable two micron pyrite particle will take over 3 years to dissolve completely.