PM-induced oxidative potential: Two years measurements and source apportionment, on a seasonal basis, in Athens, Greece

Author(s):  
Despina Paraskevopoulou ◽  
George Grivas ◽  
Aikaterini Bougiatioti ◽  
Iasonas Stavroulas ◽  
Maria Tsagkaraki ◽  
...  

<p>PM-induced oxidative stress has been proposed as a primary mechanism in cardiovascular and respiratory diseases, as well as premature death. Consequently, a variety of in vitro and in vivo assays have been developed in order to estimate the oxidative potential of ambient PM (Particulate matter), including the acellular assay of DTT (dithiothreitol), which is used in the present study. Athens, Greece is representative of air masses arriving over Eastern Mediterranean, highlighting the effect of long-range aerosol transportation and intense local emissions, such as wood burning for domestic heating purposes during the coldest period of the year. </p><p>Most studies of aerosol oxidative potential (OP) cover a short period of time, while in this study the OP was measured during two years (2016-2018), in parallel with other PM chemical components, in order to identify the sources of aerosol OP. Fine aerosol fraction (PM<sub>2.5</sub>, diameter < 2.5 μm) was collected, using quartz fibre filters and low-volume samplers, in the centre of Athens city.</p><p>An innovative semi-automated system was used for the determination of PM water soluble oxidative potential, following the approach of Fang et al. (2015). Concurrent estimation of inorganic and organic aerosol components’ concentrations was accomplished through Ion chromatography, Aerosol Chemical Speciation Monitor, Aethalometer and OC/EC analyser. Additionally, the samples were further analyzed by Inductively coupled plasma mass spectrometry for major and trace water-soluble metal concentrations. Principal component analysis and Positive Matrix Factorization are applied to identify the sources of fine aerosol at the studied site in Athens, and determine the contribution of each source to aerosol OP, on a seasonal basis</p><p>As expected, OP presented higher values during wintertime, when wood burning appeared to be the dominant source of aerosol. These results agree with previous studies, indicating that the combustion is the major source of water-soluble OP, both as primary and secondary emission (Paraskevopulou et al. 2019). Whereas during summer, the current study reveals, for the first time, the significant impact of water-soluble metals in aerosol toxicity during the warmest period of the year, over the studied area. The aforementioned combination of various PM chemical parameters leads to a scarce identification of various aerosol OP sources on a temporal basis, in the area of Eastern Mediterranean.</p>

2020 ◽  
Vol 20 (9) ◽  
pp. 5197-5210 ◽  
Author(s):  
Dong Gao ◽  
Krystal J. Godri Pollitt ◽  
James A. Mulholland ◽  
Armistead G. Russell ◽  
Rodney J. Weber

Abstract. The capability of ambient particles to generate in vivo reactive oxygen species (ROS), called oxidative potential (OP), is a potential metric for evaluating the health effects of particulate matter (PM) and is supported by several recent epidemiological investigations. Studies using various types of OP assays differ in their sensitivities to varying PM chemical components. In this study, we systematically compared two health-relevant acellular OP assays that track the depletion of antioxidants or reductant surrogates: (i) the synthetic respiratory-tract lining fluid (RTLF) assay that tracks the depletion of ascorbic acid (AA) and glutathione (GSH) and (ii) the dithiothreitol (DTT) assay that tracks the depletion of DTT. Yearlong daily samples were collected at an urban site in Atlanta, GA (Jefferson Street), during 2017, and both DTT and RTLF assays were performed to measure the OP of water-soluble PM2.5 components. PM2.5 mass and major chemical components, including metals, ions, and organic and elemental carbon were also analyzed. Correlation analysis found that OP as measured by the DTT and AA depletion (OPDTT and OPAA, respectively) were correlated with both organics and some water-soluble metal species, whereas that from the GSH depletion (OPGSH) was exclusively sensitive to water-soluble Cu. These OP assays were moderately correlated with each other due to the common contribution from metal ions. OPDTT and OPAA were moderately correlated with PM2.5 mass with Pearson's r=0.55 and 0.56, respectively, whereas OPGSH exhibited a lower correlation (r=0.24). There was little seasonal variation in the OP levels for all assays due to the weak seasonality of OP-associated species. Multivariate linear regression models were developed to predict OP measures from the particle composition data. Variability in OPDTT and OPAA were not only attributed to the concentrations of metal ions (mainly Fe and Cu) and organic compounds but also to antagonistic metal–organic and metal–metal interactions. OPGSH was sensitive to the change in water-soluble Cu and brown carbon (BrC), a proxy for ambient humic-like substances.


2020 ◽  
Author(s):  
Sara DAronco ◽  
Chiara Giorio ◽  
Federica Chiara ◽  
Roberta Seraglia ◽  
Valerio Di Marco ◽  
...  

<p>Aerosol particle components can mix and interact with oxidants and organic compounds present in the atmosphere. How these chemical components interact and how the interactions affect the Earth’s climate, particle toxicity and human health is largely unknown. In the case of trace metals, the main focus so far has been the determination of the total amount while much less attention has been directed towards the metal speciation. Aqueous phase processing of aerosol can lead to substantial modifications of aerosol chemical and physical properties [1] by promoting the formation of metal-organic ligand complexes in atmospheric aqueous phases, like fog/cloud droplets and deliquescent aerosol. Such process can increase the solubility of metals, therefore their bioavailability [2], and affect their capability to generate reactive oxygen species.</p><p>We investigated the formation of metal-organic ligand complexes, especially those involving small dicarboxylic acids, in urban aerosol collected in the city centre of Padua (Italy), in the Po Valley. We assessed the effects of metal-ligand complexes formation on the solubility and solubilisation kinetic of metals from the particles to aqueous solutions simulating fog/cloud water. We found that solubilisation kinetics of many metals depended on the chemical form in which they were present in the aerosol and they were influenced by the environmental conditions during the campaign. Changes in oxidative potential (OP) and cytotoxicity of particles due to the formation of metal-ligand complexes were investigated by performing acellular and cellular in vitro tests, respectively. Preliminary results showed that metals and their complexed forms are both characterized by different OP and cellular toxicity.</p><p> </p><p>References</p><p>[1] Decesari, S., Sowlat, M. H., Hasheminassab, S., Sandrini, S., Gilardoni, S., Facchini, M. C., Fuzzi, S., and Sioutas, C. Atmos. Chem. Phys., <strong>17</strong>, 7721‑7731 (2017).</p><p>[2] Okochi, H., and Brimblecombe, P. Sci. World J., <strong>2</strong>, 767–786(2002).</p>


2014 ◽  
Vol 7 (7) ◽  
pp. 7245-7279 ◽  
Author(s):  
T. Fang ◽  
V. Verma ◽  
H. Guo ◽  
L. E. King ◽  
E. S. Edgerton ◽  
...  

Abstract. A variety of methods are used to measure the capability of particulate matter (PM) to catalytically generate reactive oxygen species (ROS) in vivo, also defined as the aerosol oxidative potential. A widely used measure of aerosol oxidative potential is the dithiothreitol (DTT) assay, which monitors the depletion of DTT (a surrogate for cellular antioxidants) as catalyzed by the redox-active species in PM. However, a major constraint in the routine use of the DTT assay for integrating it with the large-scale health studies is its labor-intensive and time-consuming protocol. To specifically address this concern, we have developed a semi-automated system for quantifying the oxidative potential of aerosol liquid extracts using the DTT assay. The system, capable of unattended analysis at one sample per hour, has a high analytical precision (Coefficient of Variation of 12% for standards, 4% for ambient samples), and reasonably low limit of detection (0.31 nmol min−1). Comparison of the automated approach with the manual method conducted on ambient samples yielded good agreement (slope = 1.08 ± 0.12, r2 = 0.92, N = 9). The system was utilized for the Southeastern Center for Air Pollution and Epidemiology (SCAPE) to generate an extensive data set on DTT activity of ambient particles collected from contrasting environments (urban, road-side, and rural) in the southeastern US. We find that water-soluble PM2.5 DTT activity on a per air volume basis was spatially uniform and often well correlated with PM2.5 mass (r = 0.49 to 0.88), suggesting regional sources contributing to the PM oxidative potential in southeast US. However, the greater heterogeneity in the intrinsic DTT activity (per PM mass basis) across seasons indicates variability in the DTT activity associated with aerosols from sources that vary with season. Although developed for the DTT assay, the instrument can also be used to determine oxidative potential with other acellular assays.


Atmosphere ◽  
2019 ◽  
Vol 10 (10) ◽  
pp. 626 ◽  
Author(s):  
Pietrogrande ◽  
Russo ◽  
Zagatti

This work is an overview of the oxidative potential (OP) values up to date measured in Italy, with the aim to provide a picture of the spatial and seasonal variability of OP in the various geographical areas across Italy. The summarized works used the common acellular assays-based dithiothreitol (OPDTT), ascorbic acid (OPAA), glutathione (OPGSH), and 2',7'-dichlorodfluorescein (OPDCFH) assays. The paper describes the association of OP responses with PM chemical composition, the sensitivity of various acellular OP assays to PM components and emission sources, and PM size distribution of the measured OP values. Our synthesis indicates that crustal and transition metals (e.g., Fe, Ni, Cu, Cr, Mn, Zn, and V), secondary ions and carbonaceous components (elemental carbon, EC, organic carbon, OC and water soluble carbon, WSOC) show significant correlations with OP across different urban and rural areas and size ranges. These chemical species are mainly associated with various PM sources, including residual/fuel oil combustion, traffic emissions, and secondary organic aerosol formation. Although the OP assays are sensitive to the same redox-active species, they differ in the association with PM chemical components. The DDT assay is mainly sensitive to the organic compounds that are mostly accumulated in the fine PM fraction, i.e., tracers of burning sources, and redox active organics associated with other markers of photochemical aging. In contrast, OPAA and OPGSH were mostly responsive to metals, mainly those related to non-exhaust traffic emissions (Cu, Zn, Cr, Fe, Ni, Mn, Sn, Cd, Pb), that are mainly accumulated in the coarse PM. Among the investigated sites, our synthesis shows larger OP values in Trentino region and the Po Valley, that may be explained by the high density of anthropogenic sources, and the orographic and meteorological characteristics, that favor the pollutants accumulation and aerosol photo-oxidative aging.


2015 ◽  
Vol 8 (1) ◽  
pp. 471-482 ◽  
Author(s):  
T. Fang ◽  
V. Verma ◽  
H. Guo ◽  
L. E. King ◽  
E. S. Edgerton ◽  
...  

Abstract. A variety of methods are used to measure the capability of particulate matter (PM) to catalytically generate reactive oxygen species (ROS) in vivo, also defined as the aerosol oxidative potential. A widely used measure of aerosol oxidative potential is the dithiothreitol (DTT) assay, which monitors the depletion of DTT (a surrogate for cellular antioxidants) as catalyzed by the redox-active species in PM. However, a major constraint in the routine use of the DTT assay for integrating it with large-scale health studies is its labor-intensive and time-consuming protocol. To specifically address this concern, we have developed a semi-automated system for quantifying the oxidative potential of aerosol liquid extracts using the DTT assay. The system, capable of unattended analysis at one sample per hour, has a high analytical precision (coefficient of variation of 15% for positive control, 4% for ambient samples) and reasonably low limit of detection (0.31 nmol min−1). Comparison of the automated approach with the manual method conducted on ambient samples yielded good agreement (slope = 1.08 ± 0.12, r2 = 0.92, N = 9). The system was utilized for the Southeastern Center for Air Pollution & Epidemiology (SCAPE) to generate an extensive data set on DTT activity of ambient particles collected from contrasting environments (urban, roadside, and rural) in the southeastern US. We find that water-soluble PM2.5 DTT activity on a per-air-volume basis was spatially uniform and often well correlated with PM2.5 mass (r = 0.49 to 0.88), suggesting regional sources contributing to the PM oxidative potential in the southeastern US. The correlation may also suggest a mechanistic explanation (oxidative stress) for observed PM2.5 mass-health associations. The heterogeneity in the intrinsic DTT activity (per-PM-mass basis) across seasons indicates variability in the DTT activity associated with aerosols from sources that vary with season. Although developed for the DTT assay, the instrument can also be used to determine oxidative potential with other acellular assays.


Author(s):  
Jasmina Brboric ◽  
Aleksandra Klisic ◽  
Jelena Kotur-Stevuljevic ◽  
Giovanna Delogu ◽  
Darinka Gjorgieva Ackova ◽  
...  

IntroductionPhenols are a large family of natural and synthetic compounds with known antioxidant activity. The aim of this study was to preform an in vitro screening of natural and natural-like phenol monomers and their C2-symetric dimers (hydroxylated biphenyls) in order to identify those representatives which pharmacophores have the strongest antioxidant and the lowest prooxidant activity.Material and methodsAntioxidative properties of 36 compounds (monomers and their C2-symmetric dimers) were evaluated in vitro. Different (red/ox) assays were used to measure their total oxidative potential (TOP), their total antioxidative capacity (TAC), the pro-oxidative-antioxidant balance (PAB) and total SH-group content (SHG) in a biologically relevant environment. The Pro-oxidative Score, Antioxidative Score and the Oxy Score were also calculated. Trolox, a water soluble analogue of α-tocopherol was used as a positive control.ResultsIn an assay consisting of pooled human serum 6 of the 36 compounds indicated significant antioxidant activity (compounds 6, 7, 12, 13, 26, and 27) whereas 4 indicated extremely weak antioxidant activity (compounds 2, 29, 30, and 31). Within the 36 compounds comprising of zingerone, dehydrozingerone, aurone, chalcone, magnolol derivatives, in both monomeric and dimeric forms, the 2 compounds that indicated the highest antioxidant activity were dehydrozingerone derivatives (compounds 6 and 12). Trolox’s activity was found between the strong and weak antioxidant compounds analysed in our study.ConclusionsIn this study selected dehydrozingerones were identified as good candidates for in-depth testing of their biological behaviour and for possible precursors for the synthesis of novel polyphenolic molecules with potential therapeutic applications.


2019 ◽  
Author(s):  
Dong Gao ◽  
Krystal J. Pollitt ◽  
James A. Mulholland ◽  
Armistead G. Russell ◽  
Rodney J. Weber

Abstract. The capability of ambient particles to generate in vivo reactive oxygen species (ROS), called the oxidative potential (OP), is a potential metric for relating particulate matter (PM) to health effects and is supported by several recent epidemiological investigations. However, studies using various types of OP assays differ in their sensitivities to varying PM chemical components. In this study, we systematically compared two health-relevant acellular OP assays that track the depletion of antioxidants or reductant surrogates: the synthetic respiratory tract lining fluid (RTLF) assay that tracks the depletion of ascorbic acid (AA) and glutathione (GSH), and the dithiothreitol (DTT) assay that tracks the depletion of DTT. Year-long daily samples were collected at an urban site (Jefferson Street) in Atlanta during 2017 and both DTT and RTLF assays were applied to measure the OP of water-soluble PM2.5 components. PM2.5 mass and major chemical components, including metals, ions, and organic and elemental carbon were also analyzed. Correlation analysis found that OP as measured by the DTT and AA depletion (OPDTT and OPAA, respectively) were correlated with both organics and some water-soluble metal species, whereas that from the GSH depletion (OPGSH) was exclusively sensitive to water-soluble Cu. These OP assays were moderately correlated with each other due to the common contribution from metal ions. OPDTT and OPAA were moderately correlated with PM2.5 mass, with Pearson’s r = 0.55 and 0.56, respectively, whereas OPGSH had a significantly lower correlation (r = 0.24). There was little seasonal variation in the OP levels for all assays due to the weak seasonality of OP-associated species. Multivariate linear regression models were developed to predict OP measures from the particle composition data. The models indicated that the variabilities in OPDTT and OPAA were attributed to not only the concentrations of metal ions (mainly Fe and Cu) and organic compounds, but also antagonistic metal–organic and metal–metal interactions. OPGSH was sensitive to the change in water-soluble Cu and brown carbon (BrC), a proxy for ambient humic-like substances.


2015 ◽  
Vol 15 (21) ◽  
pp. 30609-30644 ◽  
Author(s):  
T. Fang ◽  
V. Verma ◽  
J. T. Bates ◽  
J. Abrams ◽  
M. Klein ◽  
...  

Abstract. The ability of certain components of particulate matter to induce oxidative stress through catalytic generation of reactive oxygen species (ROS) in vivo may be one mechanism accounting for observed linkages between ambient aerosols and adverse health outcomes. A variety of assays have been used to measure this so-called aerosol oxidative potential. We developed a semi-automated system to quantify oxidative potential of filter aqueous extracts utilizing the dithiothreitol (DTT) assay and have recently developed a similar semi-automated system using the ascorbic acid (AA) assay. Approximately 500 PM2.5 filter samples collected in contrasting locations in the southeastern US were analyzed using both assays. We found that water-soluble DTT activity on a per air volume basis was more spatially uniform than water-soluble AA activity. DTT activity was higher in winter than in summer/fall, whereas AA activity was higher in summer/fall compared to winter, with highest levels near highly trafficked highways. DTT activity was correlated with organic and metal species, whereas AA activity was correlated with water-soluble metals (especially water-soluble Cu, r=0.70–0.91 at most sites). Source apportionment models, Positive Matrix Factorization (PMF) and a Chemical Mass Balance Method with ensemble-averaged source impact profiles (CMB-E), suggest a strong contribution from secondary processes (e.g., organic aerosol oxidation or metal mobilization by formation of an aqueous particle with secondary acids) and traffic emissions to both DTT and AA activities in urban Atlanta. Biomass burning was a large source for DTT activity, but insignificant for AA. DTT activity was well correlated with PM2.5 mass (r=0.49–0.86 across sites/seasons), while AA activity did not co-vary strongly with mass. A linear model was developed to estimate DTT and AA activities for the central Atlanta Jefferson Street site, based on the CMB-E sources that are statistically significant with positive coefficients. The model was used to estimate oxidative potential at this site over the period 1998–2009. Time-series epidemiological analyses were conducted to assess daily emergency department (ED) visits data for the five-county Atlanta metropolitan area based on the estimated 10 year backcast oxidative potential. Results suggest that estimated DTT activity was associated with ED visits for both asthma/wheeze and congestive heart failure, while AA activity was not linked to any health outcomes. The findings point to the importance of both organic components and transition metals from biomass burning and mobile sources to adverse health outcomes in this region.


2016 ◽  
Vol 16 (6) ◽  
pp. 3865-3879 ◽  
Author(s):  
Ting Fang ◽  
Vishal Verma ◽  
Josephine T. Bates ◽  
Joseph Abrams ◽  
Mitchel Klein ◽  
...  

Abstract. The ability of certain components of particulate matter to induce oxidative stress through the generation of reactive oxygen species (ROS) in vivo may be one mechanism accounting for observed linkages between ambient aerosols and adverse health outcomes. A variety of assays have been used to measure this so-called aerosol oxidative potential. We developed a semi-automated system to quantify oxidative potential of filter aqueous extracts utilizing the dithiothreitol (DTT) assay and report here the development of a similar semi-automated system for the ascorbic acid (AA) assay. Approximately 500 PM2.5 filter samples collected in contrasting locations in the southeastern US were analyzed for a host of aerosol species, along with AA and DTT activities. We present a detailed contrast in findings from these two assays. Water-soluble AA activity was higher in summer and fall than in winter, with highest levels near heavily trafficked highways, whereas DTT activity was higher in winter compared to summer and fall and more spatially homogeneous. AA activity was nearly exclusively correlated with water-soluble Cu (r  =  0.70–0.94 at most sites), whereas DTT activity was correlated with organic and metal species. Source apportionment models, positive matrix factorization (PMF) and a chemical mass balance method with ensemble-averaged source impact profiles (CMB-E), suggest a strong contribution from traffic emissions and secondary processes (e.g., organic aerosol oxidation or metals mobilization by secondary acids) to both AA and DTT activities in urban Atlanta. In contrast, biomass burning was a large source for DTT activity, but insignificant for AA. AA activity was not correlated with PM2.5 mass, while DTT activity co-varied strongly with mass (r  =  0.49–0.86 across sites and seasons). Various linear models were developed to estimate AA and DTT activities for the central Atlanta Jefferson Street site, based on the CMB-E sources. The models were then used to estimate daily oxidative potential at this site over the 1998–2009 period. Time series epidemiological analyses were conducted to assess daily emergency department (ED) visits data for the five-county Atlanta metropolitan area based on the estimated 10-year backcast oxidative potential. Estimated AA activity was not statistically associated with any tested health outcome, while DTT activity was associated with ED visits for both asthma or wheeze and congestive heart failure. The findings point to the importance of both organic components and transition metals from biomass burning and mobile sources to adverse health outcomes in this region.


2018 ◽  
Vol 4 (4) ◽  
pp. 523-531
Author(s):  
Hina Mumtaz ◽  
Muhammad Asim Farooq ◽  
Zainab Batool ◽  
Anam Ahsan ◽  
Ashikujaman Syed

The main purpose of development pharmaceutical dosage form is to find out the in vivo and in vitro behavior of dosage form. This challenge is overcome by implementation of in-vivo and in-vitro correlation. Application of this technique is economical and time saving in dosage form development. It shortens the period of development dosage form as well as improves product quality. IVIVC reduce the experimental study on human because IVIVC involves the in vivo relevant media utilization in vitro specifications. The key goal of IVIVC is to serve as alternate for in vivo bioavailability studies and serve as justification for bio waivers. IVIVC follows the specifications and relevant quality control parameters that lead to improvement in pharmaceutical dosage form development in short period of time. Recently in-vivo in-vitro correlation (IVIVC) has found application to predict the pharmacokinetic behaviour of pharmaceutical preparations. It has emerged as a reliable tool to find the mode of absorption of several dosage forms. It is used to correlate the in-vitro dissolution with in vivo pharmacokinetic profile. IVIVC made use to predict the bioavailability of the drug of particular dosage form. IVIVC is satisfactory for the therapeutic release profile specifications of the formulation. IVIVC model has capability to predict plasma drug concentration from in vitro dissolution media.


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