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Generation of hydroxyl radicals from ambient fine particles in a surrogate lung fluid solution.

ABSTRACT: While it has been hypothesized that the adverse health effects associated with ambient particulate matter (PM) are due to production of hydroxyl radical (*OH), few studies have quantified *OH production from PM. Here we report the amounts of *OH produced from ambient fine particles (PM2.5) collected in northern California and extracted in a cell-free surrogate lung fluid (SLF). On average, the extracted particles produced 470 nmol *OH mg(-1)-PM2.5 during our 15-month collection period. There was a clear seasonal pattern in the efficiency with which particles generated *OH, with highest production during spring and summer and lowest during winter. In addition, nighttime PM was typically more efficient than daytime PM at generating *OH. Transition metals played the dominant role in *OH production: on average (+/-sigma), the addition of desferoxamine (a chelator that prevents metals from forming *OH) to the SLF removed (90 +/- 5) % of *OH generation. Furthermore, based on the concentrations of Fe in the PM2.5 SLF extracts, and the measured yield of *OH as a function of Fe concentration, dissolved iron can account for the majority of *OH produced in most of our PM2.5 extracts.

SUBMITTER: Vidrio E

PROVIDER: S-EPMC2649737 | biostudies-literature | 2009 Feb

REPOSITORIES: biostudies-literature

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Generation of hydroxyl radicals from ambient fine particles in a surrogate lung fluid solution.

Vidrio Edgar E Phuah Chin H CH Dillner Ann M AM Anastasio Cort C

Environmental science & technology 20090201 3

While it has been hypothesized that the adverse health effects associated with ambient particulate matter (PM) are due to production of hydroxyl radical (*OH), few studies have quantified *OH production from PM. Here we report the amounts of *OH produced from ambient fine particles (PM2.5) collected in northern California and extracted in a cell-free surrogate lung fluid (SLF). On average, the extracted particles produced 470 nmol *OH mg(-1)-PM2.5 during our 15-month collection period. There was ...[more]

PMID: 19245037

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Project description:Inhalation of ambient particulate matter causes morbidity and mortality in humans. One hypothesized mechanism of toxicity is the particle-induced formation of reactive oxygen species (ROS) - including the highly damaging hydroxyl radical ((·)OH) - followed by inflammation and a variety of diseases. While past studies have found correlations between ROS formation and a variety of metals, there are no quantitative measurements of (·)OH formation from transition metals at concentrations relevant to 24-hour ambient particulate exposure. This research reports specific and quantitative measurements of (·)OH formation from 10 individual transition metals (and several mixtures) in a cell-free surrogate lung fluid (SLF) with four antioxidants: ascorbate, citrate, glutathione, and uric acid. We find that Fe and Cu can produce (·)OH under all antioxidant conditions as long as ascorbate is present and that mixtures of the two metals synergistically increase (·)OH production. Manganese and vanadium can also produce (·)OH under some conditions, but given that their ambient levels are typically very low, these metals are not likely to chemically produce significant levels of (·)OH in the lung fluid. Cobalt, chromium, nickel, zinc, lead, and cadmium do not produce (·)OH under any of our experimental conditions. The antioxidant composition of our SLF significantly affects (·)OH production from Fe and Cu: ascorbate is required for (·)OH formation, citrate increases (·)OH production from Fe, and both citrate and glutathione suppress (·)OH production from Cu. MINTEQ ligand speciation modeling indicates that citrate and glutathione affect (·)OH production by changing metal speciation, altering the reactivity of the metals. In the most realistic SLF (i.e., with all four antioxidants), Fe generates approximately six times more (·)OH than does the equivalent amount of Cu. Since levels of soluble Fe in PM are typically higher than those of Cu, our results suggest that Fe dominates the chemical generation of (·)OH from deposited particles in the lungs.

Project description:In this study, steady-state and time-resolved radiolysis methods were used to determine the primary reaction pathways and kinetic parameters for the reactions of hydroxyl radical with microcystin-LR (MC-LR). The fundamental kinetic data is critical for the accurate evaluation of hydroxyl-radical based technologies for the destruction of this problematic class of cyanotoxins. The bimolecular rate constant for the reaction of hydroxyl radical with MC-LR is 2.3 (+/-0.1) x 10(10) M(-1)s(-1) based on time-resolved competition kinetics with SCN-at low conversions using pulsed radiolysis experiments. The reaction of hydroxyl radical with MC-LR can occur via a number of competing reaction pathways, including addition to the benzene ring and diene and abstraction of aliphatic hydrogen atoms. LC-MS analyses indicate the major products from the reaction of hydroxyl radicals with MC-LR involve addition of hydroxyl radical to the benzene ring and diene moieties of the Adda side chain. Transient absorption spectroscopy monitored between 260-500 nm, following pulsed hydroxyl radical generation, indicate the formation of a transient species with absorption maxima at 270 and 310 nm. The absorption maxima and lifetime of the transient species are characteristic of hydroxycyclohexadienyl radicals resulting from the addition of hydroxyl radical to the benzene ring. The rate constant for the formation of hydroxycyclohexadienyl radical is 1.0 (+/-0.1) x 10(10) M(-1)s(-1) accounting for approximately 40% of the primary reaction pathways. Representative rate constants and partitioning of hydroxyl radical reactions were assessed based on the reactivities of surrogate substrates and individual amino acids. Summation of the individual reactivities of hydroxyl radical at the different reactive sites (amino acids) leads to a rate constant of 2.1 x 10(10) M(-1) s(-1) in good agreementwith the rate constant determined in our studies. The relative magnitude of the rate constants for the reactions of hydroxyl radical with the individual amino acids and appropriate surrogates, suggest 60-70% reactions of hydroxyl radical occur at the benzene and diene functional groups of the Adda moiety.

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Generation of hydroxyl radicals from ambient fine particles in a surrogate lung fluid solution.

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Generation of hydroxyl radicals from ambient fine particles in a surrogate lung fluid solution.

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