Environmentally Persistent Free Radicals: Linking Air Pollution and Poor Respiratory Health?
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ABSTRACT:
SUBMITTER: Sly PD
PROVIDER: S-EPMC7330507 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:A chemical spin trap, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), in conjunction with electron paramagnetic resonance (EPR) spectroscopy was employed to measure the production of hydroxyl radical (·OH) in aqueous suspensions of 5% Cu(II)O/silica (3.9% Cu) particles containing environmentally persistent free radicals (EPFRs) of 2-monochlorophenol (2-MCP). The results indicate: (1) a significant differences in accumulated DMPO-OH adducts between EPFR containing particles and non-EPFR control samples, (2) a strong correlation between the concentration of DMPO-OH adducts and EPFRs per gram of particles, and (3) a slow, constant growth of DMPO-OH concentration over a period of days in solution containing 50 μg/mL EPFRs particles + DMPO (150 mM) + reagent balanced by 200 μL phosphate buffered (pH = 7.4) saline. However, failure to form secondary radicals using standard scavengers, such as ethanol, dimethylsulfoxide, sodium formate, and sodium azide, suggests free hydroxyl radicals may not have been generated in solution. This suggests surface-bound, rather than free, hydroxyl radicals were generated by a surface catalyzed-redox cycle involving both the EPFRs and Cu(II)O. Toxicological studies clearly indicate these bound free radicals promote various types of cardiovascular and pulmonary disease normally attributed to unbound free radicals; however, the exact chemical mechanism deserves further study in light of the implication of formation of bound, rather than free, hydroxyl radicals.
| S-EPMC3236504 | biostudies-literature
Project description:For the first time, an expansive study into the concentration and extended decay behavior of environmentally persistent free radicals in PM2.5 was performed. Results from this study revealed three types of radical decay-a fast decay, slow decay, and no decay-following one of four decay patterns: a relatively fast decay exhibiting a 1/e lifetime of 1-21 days accompanied by a slow decay with a 1/e lifetime of 21-5028 days (47% of samples); a single slow decay including a 1/e lifetime of 4-2083 days (24% of samples); no decay (18% of samples); and a relatively fast decay displaying an average 1/e lifetime of 0.25-21 days followed by no decay (11% of samples). Phenol correlated well with the initial radical concentration and fast decay rate. Other correlations for common atmospheric pollutants (ozone, NOx, SO2, etc.) as well as meteorological conditions suggested photochemical processes impact the initial radical concentration and fast decay rate. The radical signal in PM2.5 was remarkably similar to semiquinones in cigarette smoke. Accordingly, radicals inhaled from PM2.5 were related to the radicals inhaled from smoking cigarettes, expressed as the number of equivalent cigarettes smoked. This calculated to 0.4-0.9 cigarettes per day for nonextreme air quality in the United States.
| S-EPMC4309365 | biostudies-literature
Project description:Additional experimental evidence is presented for in vitro generation of hydroxyl radicals because of redox cycling of environmentally persistent free radicals (EPFRs) produced after adsorption of 2-monochlorophenol at 230 °C (2-MCP-230) on copper oxide supported by silica, 5% Cu(II)O/silica (3.9% Cu). A chemical spin trapping agent, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), in conjunction with electron paramagnetic resonance (EPR) spectroscopy was employed. Experiments in spiked O(17) water have shown that ?15% of hydroxyl radicals formed as a result of redox cycling. This amount of hydroxyl radicals arises from an exogenous Fenton reaction and may stay either partially trapped on the surface of particulate matter (physisorbed or chemisorbed) or transferred into solution as free OH. Computational work confirms the highly stable nature of the DMPO-OH adduct, as an intermediate produced by interaction of DMPO with physisorbed/chemisorbed OH (at the interface of solid catalyst/solution). All reaction pathways have been supported by ab initio calculations.
| S-EPMC4140529 | biostudies-literature
Project description:Environmentally persistent free radicals (EPFRs) are a kind of hazardous substance that exist stably in the atmosphere for a long time. EPFRs combined with fine particulate matter (PM2.5) can enter the human respiratory tract through respiration, causing oxidative stress and DNA damage, and they are also closely related to lung cancer. In this study, the inhalation risk for EPFRs in PM2.5 and factors influencing this risk were assessed using the equivalent number of cigarette tar EPFRs. The daily inhalation exposure for EPFRs in PM2.5 was estimated to be equivalent to 0.66-8.40 cigarette tar EPFRs per day. The concentration level and species characteristics were investigated using electron paramagnetic resonance spectroscopy. The concentration of EPFRs in the study ranged from 1.353-4.653 × 1013 spins/g, and the types of EPFRs were mainly oxygen- or carbon-centered semiquinone-type radicals. Our study showed that there is a strong correlation between the concentrations of EPFRs and conventional pollutants, except for sulfur dioxide. The major factors influencing EPFR concentration in the atmosphere were temperature and wind speed; the higher the temperature and wind speed, the lower the concentration of EPFRs. The findings of this study provide an important basis for further research on the formation mechanism and health effects of EPFRs.
| S-EPMC9321939 | biostudies-literature
Project description:Hydroxyl radicals were generated from an aqueous suspension of ambient PM2.5 and detected utilizing 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a spin trap coupled with electron paramagnetic resonance (EPR) spectroscopy. Results from this study suggested the importance of environmentally persistent free radicals (EPFRs) in PM2.5 to generate significant levels of ·OH without the addition of H2O2. Particles for which the EPFRs were allowed to decay over time induced less hydroxyl radical. Additionally, higher particle concentrations produced more hydroxyl radical. Some samples did not alter hydroxyl radical generation when the solution was purged by air. This is ascribed to internal, rather than external surface associated EPFRs.
| S-EPMC4308723 | biostudies-literature
Project description:Environmentally persistent free radicals (EPFRs), a group of emerging pollutants, have significantly longer lifetimes than typical free radicals. EPFRs form by the adsorption of organic precursors on a transition metal oxide (TMO) surface involving electron charge transfer between the organic and TMO. In this paper, dihalogenated benzenes were incorporated to study the role of electronegativity in the electron transfer process to obtain a fundamental knowledge of EPFR formation mechanism on ZnO. Upon chemisorption on ZnO nanoparticles at 250 °C, electron paramagnetic resonance (EPR) confirms the formation of oxygen adjacent carbon-centered organic free radicals with concentrations between 1016 and 1017 spins/g. The radical concentrations show a trend of 1,2-dibromobenzene (DBB) > 1,2-dichlorobenzene (DCB) > 1,2-difluorobenzene (DFB) illustrating the role of electronegativity on the amount of radical formation. X-ray absorption spectroscopy (XAS) confirms the reduction of the Zn2+ metal center, contrasting previous experimental evidence of an oxidative mechanism for ZnO single crystal EPFR formation. The extent of Zn reduction for the different organics (DBB > DCB > DFB) also correlates to their polarity. DFT calculations provide theoretical evidence of ZnO surface reduction and exhibit a similar trend of degree of reduction for different organics, further building on the experimental findings. The lifetimes of the EPFRs formed confirm a noteworthy persistency.
| S-EPMC10983065 | biostudies-literature
Project description:Environmentally persistent free radicals (EPFRs) have been shown to form on the surfaces of various types of transition metal-containing particulate matter (PM), and it has been demonstrated they are capable of initiating adverse health impacts. Following sonification and solvent extraction for chemical analysis, they are partially converted to molecular species. Alcoholic solvents extracted the EPFRs with near 100% efficiency, while nonpolar hydrocarbon solvents exhibited <20% efficiency and dichloromethane exhibited 20-55% efficiency. The extracted radicals reacted in solution to form multiple molecular reaction products including catechol, hydroquinone, phenol, chlorinated phenols, dibenzo-p-dioxin, and dibenzofuran. This suggests that EPFRs in environmental samples are indistinguishable from molecular pollutants and are subject to misidentification as molecular adsorbates when traditional extraction and chemical analysis methods are employed. On the basis of these findings, the origin of the toxicity of particulate matter contaminated with toxic organic compounds should be considered for re-evaluation to include the possibility that EPFRs may be a significant contributor, and the impact of some molecular pollutants may have been overestimated.
| S-EPMC4315178 | biostudies-literature
Project description:Exposure to airborne particles is associated with increased cardiovascular morbidity and mortality. During the combustion of chlorine-containing hazardous materials and fuels, chlorinated hydrocarbons chemisorb to the surface of transition metal-oxide-containing particles, reduce the metal, and form an organic free radical. These radical-particle systems can survive in the environment for days and are called environmentally persistent free radicals (EPFRs). This study determined whether EPFRs could decrease left ventricular function before and after ischemia and reperfusion (I/R) in vivo. Male Brown-Norway rats were dosed (8 mg/kg, intratracheal) 24 h prior to testing with particles containing the EPFR of 1, 2-dichlorobenzene (DCB230). DCB230 treatment decreased systolic and diastolic function. DCB230 also produced pulmonary and cardiac inflammation. After ischemia, systolic, but not diastolic function was significantly decreased in DCB230-treated rats. Ventricular function was not affected by I/R in control rats. There was greater oxidative stress in the heart and increased 8-isoprostane (biomarker of oxidative stress) in the plasma of treated vs. control rats after I/R. These data demonstrate for the first time that DCB230 can produce inflammation and significantly decrease cardiac function at baseline and after I/R in vivo. Furthermore, these data suggest that EPFRs may be a risk factor for cardiac toxicity in healthy individuals and individuals with ischemic heart disease. Potential mechanisms involving cytokines/chemokines and/or oxidative stress are discussed.
| S-EPMC3152960 | biostudies-literature
Project description:The impact of COVID-19 control on air quality have been prevalent for the past two years, however few studies have explored the toxicity of atmospheric particulate matter during the epidemic control. Therefore, this research highlights the characteristics and sources of oxidative potential (OP) and the new health risk substances environmentally persistent free radicals (EPFRs) in comparison to city lockdown (CLD) with early days of 2019-2020. Daily particulate matter (PM2.5) samples were collected from January 14 to February 3, 2020, with the same period during 2019 in Xi'an city. The results indicated that the average concentration of PM2.5 decreased by 48% during CLD. Concentrations of other air pollutants and components, such as PM10, NO2, SO2, WSIs, OC and EC were also decreased by 22%, 19%, 2%, 17%, 6%, and 4% respectively during the CLD, compared to the same period in 2019. Whereas only O3 increased by 30% during CLD. The concentrations of EPFRs in PM2.5 was considerably lower than in 2019, which decreased by 12% during CLD. However, the OP level was increased slightly during CLD. Moreover, both EPFRs/PM and DTTv/PM did not decrease or even increase significantly, manifesting that the toxicity of particulate matter has not been reduced by more gains during the CLD. Based on PMF analysis, during the epidemic period, the contribution of traffic emission is significantly reduced, while EPFRs and DTTv increased, which consist of significant O3 and secondary aerosols. This research leads to able future research on human health effect of EPFRs and oxidative potential and can be also used to formulate the majors to control EPFRs and OP emissions, suggest the need for further studies on the secondary processing of EPFRs and OP during the lockdown period in Xi'an. .The COVID-19 lockdown had a significant impact on both social and economic aspects. The city lockdown, however, had a positive impact on the environment and improved air quality, however, no significant health benefits were observed in Xi'an, China.
| S-EPMC9558116 | biostudies-literature
Project description:Environmentally persistent free radicals (EPFRs) have attracted increasing research interest in recent years. Herein, the generation of EPFRs during the hydrothermal carbonization of sewage sludge (SS) was studied. First, the surface morphology, functional groups, constituent elements and free radicals were characterized for a holistic description of the raw SS and the selected hydrochar obtained from hydrothermal carbonization of SS (SHC). Then, the impact of hydrothermal temperature, residence time and initial pH on the formation of EPFRs was explored in detail through the investigation of g-factors and intensities of EPFRs identified in SHC. The results have shown that the formation of EPFRs was affected by the factors mentioned above, in which the impact of temperature is the greatest. Two types of EPFRs were spotted in the hydrochar, oxygen-centered (O-centered) and carbon-centered (C-centered) EPFRs, which were caught in 120-150 °C and 260-280 °C, respectively. Moreover, the intensities of Electron Paramagnetic Resonance (EPR) signals enhanced with increasing hydrothermal temperature. Whereas, residence time and initial pH only affected the amount of EPFRs in a manner. Additionally, the half-life of the O-centered EPFRs and the C-centered EPFRs was determined as long as 160.45 days and 401.10 days, respectively, indicating that EPFRs are stable in a long time.
| S-EPMC6863856 | biostudies-literature