Heterogeneous Photocatalysis of Amoxicillin under Natural Conditions and High-Intensity Light: Fate, Transformation, and Mineralogical Impacts

The β-Lactam antibiotic amoxicillin is among the most widely used antibiotics in human and veterinary medicine. Consequently, amoxicillin is abundant in natural waters and can undergo diverse abiotic reactions to form degradation compounds under environmental conditions. Yet, little is known about these decay pathways and mineralogical impacts on environmental amoxicillin degradation. The current study focuses on understanding the mineralogical influences of amoxicillin degradation under ecological conditions. We studied the role of anatase and kaolinite on amoxicillin degradation under irradiated and non-irradiated conditions. Anatase increases amoxicillin degradation by 4.5-fold in the presence of light compared to just being exposed to sunlight. Interestingly, anatase also showed a higher degradation rate under dark than light controls. Conversely, kaolinite diminishes the amoxicillin degradation under irradiation. The formation of degradation compounds was mineralogy-controlled, while no mineralization was observed. Further, we irradiated amoxicillin with a high-intensity light to evaluate its removal from wastewater. The formation of varying amoxicillin degradation products with high-intensity light will limit its removal from wastewater. Our study emphasizes that the mineralogical impact on amoxicillin degradation is diverse, and the role of anatase is significant. Consequently, the increased addition of manufactured titanium nanoparticles to the environment can further enhance these effects

Atmospheric Processing and Iron Mobilization of Ilmenite: Iron-Containing Ternary Oxide in Mineral Dust Aerosol

Over the last several decades, iron has been identified as a limiting nutrient in about half of the world’s oceans. Its most significant source is identified as deposited iron-containing mineral dust that has been processed during atmospheric transportation. The current work focuses on chemical and photochemical processing of iron-containing mineral dust particles in the presence of nitric acid, and an organic pollutant dimethyl sulfide under atmospherically relevant conditions. More importantly, ilmenite (FeTiO₃) is evaluated as a proxy for the iron-containing mineral dust. The presence of titanium in its lattice structure provides higher complexity to mimic mineral dust, yet it is simple enough to study reaction pathways and mechanisms. Here, spectroscopic methods are combined with dissolution measurements to investigate atmospheric processing of iron in mineral dust, with specific focus on particle mineralogy, particle size, and their environmental conditions (i.e., pH and solar flux). Our results indicate that the presence of titanium elemental composition enhances iron dissolution from mineral dust, at least by 2-fold comparison with its nontitanium-containing counterparts. The extent of iron dissolution and speciation is further influenced by the above factors. Thus, our work highlights these important, yet unconsidered, factors in the atmospheric processing of iron-containing mineral dust aerosol

Heterogeneous Uptake and Adsorption of Gas-Phase Formic Acid on Oxide and Clay Particle Surfaces: The Roles of Surface Hydroxyl Groups and Adsorbed Water in Formic Acid Adsorption and the Impact of Formic Acid Adsorption on Water Uptake

Organic acids in the atmosphere are ubiquitous and are often correlated with mineral dust aerosol. Heterogeneous chemistry and the uptake of organic acids on mineral dust particles can potentially alter the properties of the particle. In this study, heterogeneous uptake and reaction of formic acid, HCOOH, the most abundant carboxylic acid present in the atmosphere, on oxide and clays of the most abundant elements, Si and Al, present in the Earth’s crust are investigated under dry and humid conditions. In particular, quantitative adsorption measurements using a Quartz Crystal Microbalance (QCM) coupled with spectroscopic studies using Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR) spectroscopy are combined to allow for both quantification of the amount of uptake and identification of distinct adsorbed species formed on silica, alumina, and kaolinite particle surfaces at 298 K. These oxides and clay particles show significant differences in the extent and speciation of adsorbed HCOOH due to inherent differences in surface −OH group reactivity. Adsorbed water, controlled by relative humidity, can increase the irreversible uptake of formic acid. Interestingly, the resulting layer of adsorbed formate on the particle surface decreases the particle hydrophilicity thereby decreasing the amount of water taken up by the surface as measured by QCM. Atmospheric implications of this study are discussed

Heterogeneous Atmospheric Chemistry of Lead Oxide Particles with Nitrogen Dioxide Increases Lead Solubility: Environmental and Health Implications

Heterogeneous chemistry of nitrogen dioxide with lead-containing particles is investigated to better understand lead metal mobilization in the environment. In particular, PbO particles, a model lead-containing compound due to its widespread presence as a component of lead paint and as naturally occurring minerals, massicot, and litharge, are exposed to nitrogen dioxide at different relative humidity. X-ray photoelectron spectroscopy (XPS) shows that upon exposure to nitrogen dioxide the surface of PbO particles reacts to form adsorbed nitrates and lead nitrate thin films with the extent of nitrate formation relative humidity dependent. NO₂-exposed PbO particles are found to have an increase in the amount of lead that dissolves in aqueous suspensions at circumneutral pH compared to particles not exposed. These results point to the potential importance and impact that heterogeneous chemistry with trace atmospheric gases can have on increasing solubility and therefore the mobilization of heavy metals, such as lead, in the environment. This study also shows that surface intermediates that form, such as adsorbed lead nitrates, can yield higher concentrations of lead in water systems. These water systems can include drinking water, groundwater, estuaries, and lakes

Surface Chemistry of α-FeOOH Nanorods and Microrods with Gas-Phase Nitric Acid and Water Vapor: Insights into the Role of Particle Size, Surface Structure, and Surface Hydroxyl Groups in the Adsorption and Reactivity of α-FeOOH with Atmospheric Gases

In this study, heterogeneous interactions of H₂O and HNO₃ on goethite, α-FeOOH, a component of mineral dust aerosol, are investigated with simultaneous QCM measurements and ATR-FTIR spectroscopy. Laboratory synthesized α-FeOOH of varying sizes (microrods and nanorods) when exposed to gas phase H₂O and HNO₃ results in the uptake of these gases. This combined approach of QCM measurements and ATR-FTIR spectroscopy allows for both quantification of the amount of uptake and spectroscopic data that provides information on speciation of adsorbed products. The results show that, in the case of H₂O, both microrods and nanorods take up water and that the total amounts of water, when normalized to surface area, are similar. However, for HNO₃ uptake, the saturation coverage of total and irreversibly bound HNO₃ on microrods was observed to be higher than that on nanorods, a size effect which is attributed to surface structural changes that occur as a function of particle size. Furthermore, an investigation of the behavior of nitric acid reacted with α-FeOOH in aqueous media was carried out such as to better understand the effects of atmospheric processing upon dispersal within the hydrosphere

Fate, Transformation, and Toxicological Impacts of Pharmaceutical and Personal Care Products in Surface Waters

With the growth of the human population, a greater quantity of pharmaceutical and personal care products (PPCPs) have been released into the environment. Although research has addressed the levels and the impact of PPCPs in the environment, the fate of these compounds in surface waters is neither well known nor characterized. In the environment, PPCPs can undergo various transformations that are critically dependent on environmental factors such as solar radiation and the presence of soil particles. Given that the degradation products of PPCPs are poorly characterized, these “secondary residues” can be a significant environmental health hazard due to their drastically different toxicologic effects when compared with the parent compounds. To better understand the fate of PPCPs, we studied the degradation of selected PPCPs, including ibuprofen and clofibric acid, in aqueous solutions that contained kaolinite clay and were irradiated with a solar simulator. The most abundant degradation products were identified and assessed for their toxicologic impact on selected microorganisms. The degraded mixtures showed lower toxicity than the starting compounds; however, as these degradation products are capable of further transformation and interaction with other PPCPs in natural waters, our work highlights the importance of additionally characterizing the PPCP degradation products

Surface Photochemistry of Adsorbed Nitrate: The Role of Adsorbed Water in the Formation of Reduced Nitrogen Species on α‑Fe₂O₃ Particle Surfaces

The surface photochemistry of nitrate, formed from nitric acid adsorption, on hematite (α-Fe₂O₃) particle surfaces under different environmental conditions is investigated using X-ray photoelectron spectroscopy (XPS). Following exposure of α-Fe₂O₃ particle surfaces to gas-phase nitric acid, a peak in the N1s region is seen at 407.4 eV; this binding energy is indicative of adsorbed nitrate. Upon broadband irradiation with light (λ > 300 nm), the nitrate peak decreases in intensity as a result of a decrease in adsorbed nitrate on the surface. Concomitant with this decrease in the nitrate coverage, there is the appearance of two lower binding energy peaks in the N1s region at 401.7 and 400.3 eV, due to reduced nitrogen species. The formation as well as the stability of these reduced nitrogen species, identified as NO^– and N^–, are further investigated as a function of water vapor pressure. Additionally, irradiation of adsorbed nitrate on α-Fe₂O₃ generates three nitrogen gas-phase products including NO₂, NO, and N₂O. As shown here, different environmental conditions of water vapor pressure and the presence of molecular oxygen greatly influence the relative photoproduct distribution from nitrate surface photochemistry. The atmospheric implications of these results are discussed

Characterization and Toxicity Analysis of Lab-Created Respirable Coal Mine Dust from the Appalachians and Rocky Mountains Regions

Coal mine workers are continuously exposed to respirable coal mine dust (RCMD) in workplaces, causing severe lung diseases. RCMD characteristics and their relations with dust toxicity need further research to understand the adverse exposure effects to RCMD. The geographic clustering of coal workers’ pneumoconiosis (CWP) suggests that RCMD in the Appalachian region may exhibit more toxicity than other geographic regions such as the Rocky Mountains. This study investigates the RCMD characteristics and toxicity based on geographic location. Dissolution experiments in simulated lung fluids (SLFs) and in vitro responses were conducted to determine the toxicity level of samples collected from five mines in the Rocky Mountains and Appalachian regions. Dust characteristics were investigated using Fourier-transform infrared spectroscopy, scanning electron microscopy, the BET method, total microwave digestion, X-ray diffraction, and X-ray photoelectron spectroscopy. Inductively coupled plasma mass spectrometry was conducted to determine the concentration of metals dissolved in the SLFs. Finer particle sizes and higher mineral and elemental contents were found in samples from the Appalachian regions. Si, Al, Fe, Cu, Sr, and Pb were found in dissolution experiments, but no trends were found indicating higher dissolutions in the Appalachian region. In vitro studies indicated a proinflammatory response in epithelial and macrophage cells, suggesting their possible participation in pneumoconiosis and lung diseases development

Characterization and Toxicity Analysis of Lab-Created Respirable Coal Mine Dust from the Appalachians and Rocky Mountains Regions

Coal mine workers are continuously exposed to respirable coal mine dust (RCMD) in workplaces, causing severe lung diseases. RCMD characteristics and their relations with dust toxicity need further research to understand the adverse exposure effects to RCMD. The geographic clustering of coal workers’ pneumoconiosis (CWP) suggests that RCMD in the Appalachian region may exhibit more toxicity than other geographic regions such as the Rocky Mountains. This study investigates the RCMD characteristics and toxicity based on geographic location. Dissolution experiments in simulated lung fluids (SLFs) and in vitro responses were conducted to determine the toxicity level of samples collected from five mines in the Rocky Mountains and Appalachian regions. Dust characteristics were investigated using Fourier-transform infrared spectroscopy, scanning electron microscopy, the BET method, total microwave digestion, X-ray diffraction, and X-ray photoelectron spectroscopy. Inductively coupled plasma mass spectrometry was conducted to determine the concentration of metals dissolved in the SLFs. Finer particle sizes and higher mineral and elemental contents were found in samples from the Appalachian regions. Si, Al, Fe, Cu, Sr, and Pb were found in dissolution experiments, but no trends were found indicating higher dissolutions in the Appalachian region. In vitro studies indicated a proinflammatory response in epithelial and macrophage cells, suggesting their possible participation in pneumoconiosis and lung diseases development