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Impacts of Antioxidants on Hydroxyl Radical Production from Individual and Mixed Transition Metals in a Surrogate Lung Fluid.

ABSTRACT: 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.

SUBMITTER: Charrier JG

PROVIDER: S-EPMC3223868 | biostudies-literature | 2011 Nov

REPOSITORIES: biostudies-literature

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Impacts of Antioxidants on Hydroxyl Radical Production from Individual and Mixed Transition Metals in a Surrogate Lung Fluid.

Charrier Jessica G JG Anastasio Cort C

Atmospheric environment (Oxford, England : 1994) 20111101 40

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 ...[more]

PMID: 22125412

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Project description:BackgroundSome heavy metals can be harmful to human health in elevated doses such as zinc (Zn) and magnesium (Mg), while others such as lead (Pb), cadmium (Cd), mercury (Hg), and copper (Cu) have harmful consequences to health even in small doses. Heavy metals and additives are incorporated into crude oil to enhance performance.3,4,5 Crude oil is well known to contain heavy metals like Cu, Cd, Ni and Pb.3,6,7.ObjectiveThe current study aimed to assess levels of heavy metals and the impact of these metals on antioxidant levels and physiological variables in the serum of oil refinery workers in Iraq.MethodsHeavy metals such as Pb, Cd, Hg, Zn, Cu and Mg were assessed in the serum of a sample of refinery workers (N=40) and a control group (N=20) using atomic absorption spectrometry (AAS). Additionally, levels of malondialdehyde (MDA), δ-aminolaevulinic acid dehydratase (ALAD) and total antioxidant capacity (TAC), and physiological variables such as blood urea, serum creatinine, glutamate-oxaloacetic transaminase (GOT), glutamate-pyruvic transaminase (GPT), and gamma-glutamyl transferase (GGT) were measured to assess impact of these heavy metals.ResultsMercury, Cd, and Pb were significantly elevated in the refinery worker group in comparison with the control group, while the levels of Zn, Cu, and Mg were significantly lower in the refinery worker group compared to the control group. There was a significant difference between the control group and the worker group for most of the antioxidants and functional variables. Total antioxidant capacity (TAC), δ-aminolevulinic acid dehydratase (ALAD), and malondialdehyde (MDA) were significantly lower in the worker group while blood urea, serum creatinine, glutamate pyruvate transaminase (GPT), and gamma-glutamyl transferase (GGT) showed a significant elevation in the workers' group. Glutamic oxaloacetic transaminase (GOT) showed no significant difference between the control group and the worker group.ConclusionsRefinery workers are at increased risk of having higher serum levels of Pb, Cd, and Hg compared to controls which can lead to an increase in oxidative stress, decrease in TAC, and decrease in the essential trace elements Zn, Cu and Mg.Participant consentObtained.Ethics approvalThis study was approved by the ethics committee within the Nineveh Health Department, Mosul, Iraq.Competing interestsThe authors declare no competing financial interests.

Project description:Understanding the mechanism of hydrazine oxidation reaction by OH radical along with the rate constants of all possible pathways leads to explain the fate of hydrazine in the atmosphere. In this article, the comprehensive mechanisms and kinetics of the hydrazine plus hydroxyl radical reaction have been investigated theoretically at different temperatures and pressures. To achieve the main goals, a series of high levels of quantum chemical calculations have been widely implemented in reliable channels of the H-abstraction, SN2, and addition/elimination reactions. The energy profile of all pathways accompanied by the molecular properties of the involved stationary points has been characterized at the MP2, M06-2X, and CCSD(T)/CBS levels. To estimate accurate barrier energies of the H-abstraction channels, large numbers of the CCSD (T) calculations in conjunction with various augmented basis sets have been implemented. The direct dynamic calculations have been carried out using the validated M06-2X/maug-cc-pVTZ level, and also by the CCSD(T) (energies) + MP2 (partition functions) level. The pressure-dependent rate constants of the barrierless pathways have been investigated by the strong collision approach. Therefore, the main behaviors of the N2H4 + OH reaction have been explored according to the influences of temperature and pressure on the computed rate coefficients within the well-behaved theoretical frameworks of the TST, VTST, and RRKM theories. It has been found that the H-abstraction mechanism (to form N2H3) is dominant relative to the SN2 reaction and OH-addition to the N center of N2H4 moiety (to form H2NOH + NH2). The computed high pressure limit rate constant of the main reaction pathway, k(298.15) = 7.31 × 10-11 cm3 molecule-1 s-1, has an excellent agreement with the experimental value (k (298.15) = (6.50 ± 1.3) × 10-11 cm3 molecule-1 s-1) recommended by Vaghjiani. Also, the atmospheric lifetime of hydrazine degradation by OH radicals has been demonstrated to be 32.80 to 1161.11 h at the altitudes of 0-50 km. Finally, the disagreement in the calculated rate constants between the previous theoretical study and experimental results has been rectified.

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Impacts of Antioxidants on Hydroxyl Radical Production from Individual and Mixed Transition Metals in a Surrogate Lung Fluid.

Publications

Impacts of Antioxidants on Hydroxyl Radical Production from Individual and Mixed Transition Metals in a Surrogate Lung Fluid.

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