Environmentally persistent free radicals mediated removal of Cr(VI) from highly saline water by corn straw biochars

Heavy metal ions coexisting with salts in the contaminant water are difficult to remove due to the interference of salts. Herein, biochars were pyrolyzed by corn straw at different temperatures, aiming to remove Cr(VI) in the presence of salts. Results show that biochars had surprisingly selective adsorption of Cr(VI). X-ray photoelectron and X-ray absorption near edge spectra revealed that Cr(VI) was reduced to Cr(III). All the adsorption was conducted at pH~7, which differed from the previous studies that Cr(VI) could only be reduced at pH 2~4. Environmental persistent free radicals (EPFRs) on biochars were found to play the role in reducing Cr(VI) in neutral solutions, which was confirmed by electron spin resonance and free radical quenching. The biochar with EPFRs reveals a highly selective removal of Cr(VI), which has implications for the remediation of contaminated water. This work provides a new insight into biochar’s properties and potential environmental applications

Non Linear Contracting and Endogenous Buyer Power between Manufacturers and Retailers: Empirical Evidence on Food Retailing in France

We present the first empirical estimation of a structural model taking into account explicitly the endogenous buyer power of downstream players facing two part tariffs contracts offered by the upstream level. We consider vertical contracts between manufacturers and retailers where resale price maintenance may be used with two part tariffs and allow retailers to have some endogenous buyer power from the horizontal competition of manufacturers. Our contribution allows to recover price-cost margins at the upstream and downstream levels in these different structural models using the industry structure and estimates of demand parameters. We apply it to the market of bottled water in France, estimating a mixed logit demand model on individual level data. Empirical evidence shows that two part tari¤s contracts are used with no resale price maintenance and that the buyer power of supermarket chains is endogenous to the structure of manufacturers competition

Quantitative aspects of the interfacial catalytic oxidation of Dithiothreitol by dissolved oxygen in the presence of carbon nanoparticles

The catalytic nature of particulate matter is often advocated to explain its ability to generate reactive oxygen species, but quantitative data are lacking. We have performed molecular characterization of three different carbonaceous nanoparticles (NP) by 1. identifying and quantifying their surface functional groups based on probe gas-particle titration; 2. studying the kinetics of dissolved oxygen consumption in the presence of suspended NP's and dithiothreitol (DTT). We show that these NP's can reversibly change their oxidation state between oxidized and reduced functional groups present on the NP surface. By comparing the amount of O2 consumed and the number of strongly reducing sites on the NP, its average turnover ranged from 35 to 600 depending on the type of NP. The observed quadratic rate law for O2 disappearance points to a Langmuir-Hinshelwood surface-based reaction mechanism possibly involving semiquinone radical. In the proposed model, the strongly reducing surface site is assumed to be a polycyclic aromatic hydroquinone whose oxidation to the corresponding conjugated quinone is rate-limiting in the catalytic chain reaction. The presence and strength of the reducing surface functional groups are important for explaining the catalytic activity of NP in the presence of oxygen and a reducing agent like DTT

Environmentally persistent free radicals: Methods for combustion generation, whole-body inhalation and assessing cardiopulmonary consequences

Particulate matter (PM) containing environmentally persistent free radicals (EPFRs) results from the incomplete combustion of organic wastes which chemisorb to transition metals. This process generates a particle-pollutant complex that continuously redox cycles to produce reactive oxygen species. EPFRs are well characterized, but their cardiopulmonary effects remain unknown. This publication provides a detailed approach to evaluating these effects and demonstrates the impact that EPFRs have on the lungs and vasculature. Combustion-derived EPFRs were generated (EPFR lo: 2.1e−16 radical/g, EPFR hi: 5.5e−17 radical/g), characterized, and verified as representative of those found in urban areas. Dry particle aerosolization and whole-body inhalation were established for rodent exposures. To verify that these particles and exposures recapitulate findings relevant to known PM-induced cardiopulmonary effects, male C57BL6 mice were exposed to filtered air, ∼280 μg/m3 EPFR lo or EPFR hi for 4 h/d for 5 consecutive days. Compared to filtered air, pulmonary resistance was increased in mice exposed to EPFR hi. Mice exposed to EPFR hi also exhibited increased plasma endothelin-1 (44.6 vs 30.6 pg/mL) and reduced nitric oxide (137 nM vs 236 nM), suggesting vascular dysfunction. Assessment of vascular response demonstrated an impairment in endothelium-dependent vasorelaxation, with maximum relaxation decreased from 80% to 62% in filtered air vs EPFR hi exposed mice. Gene expression analysis highlighted fold changes in aryl hydrocarbon receptor (AhR) and antioxidant response genes including increases in lung Cyp1a1 (8.7 fold), Cyp1b1 (9 fold), Aldh3a1 (1.7 fold) and Nqo1 (2.4 fold) and Gclc (1.3 fold), and in aortic Cyp1a1 (5.3 fold) in mice exposed to EPFR hi vs filtered air. We then determined that lung AT2 cells were the predominate locus for AhR activation. Together, these data suggest the lung and vasculature as particular targets for the health impacts of EPFRs and demonstrate the importance of additional studies investigating the cardiopulmonary effects of EPFRs

Environmentally Persistent Free Radicals: Insights on a New Class of Pollutants

© 2018 American Chemical Society. Environmentally persistent free radicals, EPFRs, exist in significant concentration in atmospheric particulate matter (PM). EPFRs are primarily emitted from combustion and thermal processing of organic materials, in which the organic combustion byproducts interact with transition metal-containing particles to form a free radical-particle pollutant. While the existence of persistent free radicals in combustion has been known for over half-a-century, only recently that their presence in environmental matrices and health effects have started significant research, but still in its infancy. Most of the experimental studies conducted to understand the origin and nature of EPFRs have focused primarily on nanoparticles that are supported on a larger micrometer-sized particle that mimics incidental nanoparticles formed during combustion. Less is known on the extent by which EPFRs may form on engineered nanomaterials (ENMs) during combustion or thermal treatment. In this critical and timely review, we summarize important findings on EPFRs and discuss their potential to form on pristine ENMs as a new research direction. ENMs may form EPFRs that may differ in type and concentration compared to nanoparticles that are supported on larger particles. The lack of basic data and fundamental knowledge about the interaction of combustion byproducts with ENMs under high-temperature and oxidative conditions present an unknown environmental and health burden. Studying the extent of ENMs on catalyzing EPFRs is important to address the hazards of atmospheric PM fully from these emerging environmental contaminants

Exposure to combustion generated environmentally persistent free radicals enhances severity of influenza virus infection

© 2014 Lee et al. Background: Exposures to elevated levels of particulate matter (PM) enhance severity of influenza virus infection in infants. The biological mechanism responsible for this phenomenon is unknown. The recent identification of environmentally persistent free radicals (EPFRs) associated with PM from a variety of combustion sources suggests its role in the enhancement of influenza disease severity. Methods: Neonatal mice (\u3c seven days of age) were exposed to DCB230 (combustion derived PM with a chemisorbed EPFR), DCB50 (non-EPFR PM sample), or air for 30 minutes/day for seven consecutive days. Four days post-exposure, neonates were infected with influenza intranasally at 1.25 TCID50/neonate. Neonates were assessed for morbidity (% weight gain, peak pulmonary viral load, and viral clearance) and percent survival. Lungs were isolated and assessed for oxidative stress (8-isoprostanes and glutathione levels), adaptive immune response to influenza, and regulatory T cells (Tregs). The role of the EPFR was also assessed by use of transgenic mice expressing human superoxide dismutase 2. Results: Neonates exposed to EPFRs had significantly enhanced morbidity and decreased survival following influenza infection. Increased oxidative stress was also observed in EPFR exposed neonates. This correlated with increased pulmonary Tregs and dampened protective T cell responses to influenza infection. Reduction of EPFR-induced oxidative stress attenuated these effects. Conclusions: Neonatal exposure to EPFR containing PM resulted in pulmonary oxidative stress and enhanced influenza disease severity. EPFR-induced oxidative stress resulted in increased presence of Tregs in the lungs and subsequent suppression of adaptive immune response to influenza

Detection and characterization of environmentally persistent free radicals (EPFRs) in soils and sediments from superfund sites

Environmentally persistent free radicals (EPFRs) from combustion-generated PM have been demonstrated to form via reactions of molecular precursors with redox-active transition metals at 150-500C thermal reactions in a few seconds reaction times. While ambient temperatures are much lower, soils/sediments contain similar transition metals, and reaction times of contaminants in soils/sediments are years, rather than seconds. This questions whether EPFRs could be formed at ambient temperatures in soils/sediments from Superfund sites that are contaminated with hazardous materials. Superfund soils contaminated with PCP from Georgia and Montana, and sediments contaminated with PAHs from Washington. Using EPR spectroscopy, EPFR concentrations and structural assignments were determined. Contaminated soils/sediments were ~30x, ~12x, ~2x higher than the background at the Georgia, Montana, and Washington sites, respectively. Conventional humic substances extraction procedures revealed ~90% of the EPFRs originated from clays/minerals/humins fraction. Similarity of EPR signals in the Georgia and Montana PCP contaminated soils were observed (g = 2.00300 and ΔHp-p = 6.0 G), whereas, signals in the Washington sediments were similar to other PAH contaminated soils (g = 2.00270 and ΔHp-p = 9.0G). Several methods of analyses (Total Carbon Content, GC-MS, ICP-AES, Vapor and gas/liquid phase dosing) confirm pentachlorophenoxyl EPFR. Chemisorption and electron transfer from PCP or PAHs to transition metals and other electron sinks in soil are indicated for EPFRs formation. Low temperature thermal treatment of PCP contaminated soil in an open type heating system indicated the formation of a more oxygen-centered structure of the pentachlorophenoxyl radical or new, similar radicals. Both type of heating system, open and closed, demonstrated an EPFR concentrations that peaked at ~10 x 10E+18 spins/g of soil at ~75-100C, with lifetimes of 2 – 24 days at room temperature in ambient air indicating persistency in the environment. Discovery of EPFRs formed in PCP contaminated soils indicates that EPFRs are not only confined to combustion-generated particles. Studies on EPFR similar to pentachlorophenoxyl cause cardiopulmonary dysfunctions via induction of oxidative stress. The existence of potentially toxic EPFRs questions the long held belief that sorption of an organic pollutant to a soil matrix is a method of mitigating its environmental impact

A Scalable Field Study Protocol and Rationale for Passive Ambient Air Sampling: A Spatial Phytosampling for Leaf Data Collection

© 2017 American Chemical Society. Stable, bioreactive, radicals known as environmentally persistent free radicals (EPFRs) have been found to exist on the surface of airborne PM2.5. These EPFRs have been found to form during many combustion processes, are present in vehicular exhaust, and persist in the environment for weeks and biological systems for up to 12 h. To measure EPFRs in PM samples, high volume samplers are required and measurements are less representative of community exposure; therefore, we developed a novel spatial phytosampling methodology to study the spatial patterns of EPFR concentrations using plants. Leaf samples for laboratory PM analysis were collected from 188 randomly drawn sampling sites within a 500-m buffer zone of pollution sources across a sampling grid measuring 32.9 × 28.4 km in Memphis, Tennessee. PM was isolated from the intact leaves and size fractionated, and EPFRs on PM quantified by electron paramagnetic resonance spectroscopy. The radical concentration was found to positively correlate with the EPFR g-value, thus indicating cumulative content of oxygen centered radicals in PM with higher EPFR load. Our spatial phytosampling approach reveals spatial variations and potential hotspots risk due to EPFR exposure across Memphis and provides valuable insights for identifying exposure and demographic differences for health studies

Phytosampling of Ambient Air Particulate Matter (PM) -New Method of PM-Associated Pollution Characterization

Ambient air particulate matter (PM) has been documented to be a contributor to a lot of pollution-related health effects. Due to the common anthropogenic origin, PM could be an effective vehicle to carry and deliver many toxic materials, including environmentally persistent free radicals (EPFRs) and polycyclic aromatic hydrocarbons (PAHs) into the human body, thus significantly raise the health risk of PM exposure. Studies of ambient air PM potentially bear artifacts stemming from the collection methods. We investigated the effects of collection methods on the ambient air PM composition and developed a static collection method relying on the particle entrapment by the plant’s leaf through electrostatic interactions and surface trichomes (“phytosampling”). This method allows for easy particle recovery from the matrix, collection under natural environmental conditions, and enables a dense collection network to represent spatial pollutants distribution more accurately. The experimental results show that the new “phytosampling” method is an effective method to collect PM from ambient air. And the PM retrieving process does not compromise the leaf integrity. On phytosampling collected PM, we detected relatively more potassium and calcium, the larger contribution of oxygen-centered EPFRs, different decay behavior, more consistent PAHs distribution between PM sizes, and less toxicological effects in cell viability test compared to the standard sampling method PM samples. These results indicate that the phytosampling method could prevent some unpredictable changes during PM collection, and collected PM will be more representative as the PM that the general public is exposed to. However, phytosampling cannot evaluate the absolute PM concentration in the air, so it serves as an excellent supplementary tool to work in conjunction with the standard PM collection method. This method has been successfully applied to field studies