scholarly journals A method for measuring total aerosol oxidative potential (OP) with the dithiothreitol (DTT) assay and comparisons between an urban and roadside site of water-soluble and total OP

2017 ◽  
Vol 10 (8) ◽  
pp. 2821-2835 ◽  
Author(s):  
Dong Gao ◽  
Ting Fang ◽  
Vishal Verma ◽  
Linghan Zeng ◽  
Rodney J. Weber

Abstract. An automated analytical system was developed for measuring the oxidative potential (OP) with the dithiothreitol (DTT) assay of filter extracts that include both water-soluble and water-insoluble (solid) aerosol species. Three approaches for measuring total oxidative potential were compared. These include using methanol as the solvent with (1) and without (2) filtering the extract, followed by removing the solvent and reconstituting with water, and (3) extraction in pure water and performing the OP analysis in the extraction vial with the filter. The water extraction method (the third approach, with filter remaining in the vial) generally yielded the highest DTT responses with better precision (coefficient of variation of 1–5 %) and was correlated with a greater number of other aerosol components. Because no organic solvents were used, which must be mostly eliminated prior to DTT analysis, it was easiest to automate by modifying an automated analytical system for measuring water-soluble OP developed by Fang et al. (2015). Therefore, the third method was applied to the field study for the determination of total OP. Daily 23 h filter samples were collected simultaneously at a roadside (RS) and a representative urban (Georgia Tech, GT) site for two 1-month study periods, and both water-soluble (OPWS-DTT) and total (OPTotal-DTT) OP were measured. Using PM2. 5 (aerodynamic diameter  <  2.5 µm) high-volume samplers with quartz filters, the OPWS-DTT-to-OPTotal-DTT ratio at the urban site was 65 % with a correlation coefficient (r) of 0.71 (N  =  35; p value  <  0.01), compared to a ratio of 62 % and r = 0. 56 (N  =  31; p value  <  0.01) at the roadside site. The same DTT analyses were performed, and similar results were found using particle composition monitors (flow rate of 16.7 L min−1) with Teflon filters. Comparison of measurements between sites showed only slightly higher levels of both OPWS-DTT and OPTotal-DTT at the RS site, indicating both OPWS-DTT and OPTotal-DTT were largely spatially homogeneous. These results are consistent with roadway emissions as sources of DTT-quantified PM2. 5 OP and indicate that both soluble and insoluble aerosol components contributing to OP are largely secondary.

2017 ◽  
Author(s):  
Dong Gao ◽  
Ting Fang ◽  
Vishal Verma ◽  
Linghan Zeng ◽  
Rodney Weber

Abstract. An automated analytical system was developed for measuring the oxidative potential (OP) with the dithiothreitol (DTT) assay of filter extracts that include both water-soluble and water-insoluble (solid) aerosol species. Three approaches for measuring total oxidative potential were compared. These include using methanol as the solvent with (1) and without (2) filtering the extract, followed by removing the solvent and reconstituting with water, and (3) extraction in pure water and performing the OP analysis in the extraction vial with the filter. The water extraction method (the third approach, with filter remaining in the vial) generally yielded highest DTT responses with better precision (coefficient of variation of 1–5 %), and was correlated with a greater number of other aerosol components. Because no organic solvents were used, which must be mostly eliminated prior to DTT analysis, it was the easiest to automate by modifying an automated analytical system for measuring water-soluble OP developed by Fang et al. (2015). Daily 23h filter samples were collected simultaneously at a roadside (RS) and a representative urban (GT) site for two one-month study periods, and both water-soluble (OPWS-DTT) and total (OPTotal-DTT) OP were measured. Using PM2.5 (aerodynamic diameter


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.


2011 ◽  
Vol 4 (10) ◽  
pp. 2073-2086 ◽  
Author(s):  
E. Bahlmann ◽  
I. Weinberg ◽  
R. Seifert ◽  
C. Tubbesing ◽  
W. Michaelis

Abstract. The isotopic composition of volatile organic compounds (VOCs) can provide valuable information on their sources and fate not deducible from mixing ratios alone. In particular the reported carbon stable isotope ratios of chloromethane and bromomethane from different sources cover a δ13C-range of almost 100‰ making isotope ratios a very promising tool for studying the biogeochemistry of these compounds. So far, the determination of the isotopic composition of C1 and C2 halocarbons others than chloromethane is hampered by their low mixing ratios. In order to determine the carbon isotopic composition of C1 and C2 halocarbons with mixing ratios as low as 1 pptv (i) a field suitable cryogenic high volume sampling system and (ii) a chromatographic set up for processing these samples have been developed and validated. The sampling system was tested at two different sampling sites, an urban and a coastal location in Northern Germany. The average δ13C-values for bromomethane at the urban site were −42.9 ± 1.1‰ and agreed well with previously published results. But at the coastal site bromomethane was substantially enriched in 13C by almost 10‰. Less pronounced differences were observed for chlorodifluoromethane, 1,1,1-trichloroethane and chloromethane. We suggest that these differences are related to the turnover of these compounds in ocean surface waters. Furthermore we report first carbon isotope ratios for iodomethane (−40.4‰ to −79.8‰), bromoform (−13.8‰ to 22.9‰), and other halocarbons.


2001 ◽  
Vol 68 (4) ◽  
pp. 675-688 ◽  
Author(s):  
ERWAN ENGEL ◽  
CHANTAL SEPTIER ◽  
NADINE LECONTE ◽  
CHRISTIAN SALLES ◽  
JEAN-LUC LE QUERE

The taste-active compounds of a Camembert cheese selected for its intense bitterness defect were investigated. The water-soluble fraction (WSE) was extracted with pure water and fractionated by successive tangential ultrafiltrations and nanofiltration. The physicochemical assessment of these fractions led to the construction of a model WSE which was compared by sensory evaluation to the crude water-soluble extract, using a panel of 16 trained tasters. As no significant difference was perceived, this model WSE was then used directly or mixed with other cheese components for omission tests. Among the main taste characteristics of the WSE (salty, sour, umami and bitter), bitterness was found to be due to small peptides whose mass distribution was obtained by RPHPLC-MS (400–3000 Da) and whose taste properties are discussed.


2018 ◽  
Author(s):  
Joseph V. Puthussery ◽  
Chen Zhang ◽  
Vishal Verma

Abstract. We developed an online instrument for measuring the oxidative potential (OP) of ambient particulate matter (PM) using dithiothreitol (DTT) assay. The instrument uses a mist chamber (MC) to continuously collect the ambient PM2.5 in water, followed by its DTT activity determination using an automated syringe pump system. The instrument was deployed at an urban site in the University of Illinois campus, and its field performance was evaluated by comparing the results with the offline DTT activity measurements of simultaneously collected PM-laden filters. The online DTT activity measurements correlated well with the offline measurements but were higher than both methanol (slope = 0.86, R2 = 0.93) and Milli-Q water (slope = 0.52, R2 = 0.86) extracts of the PM filters, indicating a better efficiency of MC for collecting the water-insoluble fraction of PM. The hourly measurements of ambient PM2.5 OP were obtained by running the online instrument intermittently for 50 days with minimal manual assistance. The daytime DTT activity levels were generally higher than at night. However, a four-fold increase in the hourly averaged activity was observed on the night of July 04 (Independence Day fireworks display). Diurnal profile of the hourly averaged OP during weekdays showed a bimodal trend, with a sharp peak in the morning (around 7:00 AM), followed by a broader afternoon peak, which plateaus around 2:00 PM, and starts subsiding at night (around 7:00 PM). To investigate the association of the diurnal profile of DTT activity with the emission sources at the site, we collected time-segregated composite PM filter samples in four different time periods of the day [morning (7:00 AM–10:00 AM), afternoon (10:00 AM–3:00 PM), evening (3:00 PM–7:00 PM) and night (7:00 PM–7:00 AM)] and determined the diurnal variations in the redox active components [i.e. water soluble Cu, Fe, Mn, organic carbon, elemental carbon and water soluble organic carbon]. Based on this comparison, we attributed the daytime OP of ambient PM2.5 to the water-soluble Cu from both exhaust and non-exhaust emissions, whereas secondary particles formed by the photochemical transformation of primary emissions appear to enhance the OP of PM during the afternoon and evening period.


2018 ◽  
Vol 11 (10) ◽  
pp. 5767-5780 ◽  
Author(s):  
Joseph V. Puthussery ◽  
Chen Zhang ◽  
Vishal Verma

Abstract. We developed an online instrument for measuring the oxidative potential (OP) of ambient particulate matter (PM) using the dithiothreitol (DTT) assay. The instrument uses a mist chamber (MC) to continuously collect the ambient PM2.5 in water, and then determines its DTT activity using an automated syringe pump system. The instrument was deployed at an urban site in the University of Illinois campus, and its field performance was evaluated by comparing the results with the offline DTT activity measurements of simultaneously collected PM-laden filters. The online DTT activity measurements correlated well with the offline measurements but were higher than both methanol (slope =1.08, R2=0.93) and Milli-Q water (slope =1.86, R2=0.86) extracts of the PM filters, indicating a better efficiency of the MC for collecting the water-insoluble fraction of PM. The hourly measurements of ambient PM2.5 OP were obtained by running the online instrument intermittently for 50 days with minimal manual assistance. The daytime DTT activity levels were generally higher than at night. However, a 4-fold increase in the hourly averaged activity was observed on the night of 4 July (Independence Day fireworks display). The diurnal profile of the hourly averaged OP during weekdays showed a bimodal trend, with a sharp peak in the morning (around 07:00 LT), followed by a broader afternoon peak which plateaus around 14:00 LT and starts subsiding at night (around 19:00 LT). To investigate the association of the diurnal profile of DTT activity with the emission sources at the site, we collected time-segregated composite PM filter samples in four different time periods of the day (morning, 07:00–10:00 LT; afternoon, 10:00–15:00 LT; evening, 15:00–19:00 LT; and night, 19:00–07:00 LT) and determined the diurnal variations in the redox active components (i.e., water-soluble Cu, Fe, Mn, organic carbon, elemental carbon, and water-soluble organic carbon). Based on this comparison, we attributed the daytime OP of ambient PM2.5 to the vehicular (both exhaust and non-exhaust) emissions and resuspended dust, whereas secondary photochemical transformation of primary emissions appear to enhance the OP of PM during the afternoon and evening period.


2011 ◽  
Vol 4 (2) ◽  
pp. 2161-2188 ◽  
Author(s):  
E. Bahlmann ◽  
I. Weinberg ◽  
R. Seifert ◽  
C. Tubbesing ◽  
W. Michaelis

Abstract. The isotopic composition of volatile organic compounds (VOCs) can provide valuable information on their sources and fate not deducible from mixing ratios alone. In particular the reported carbon stable isotope ratios of chloromethane and bromomethane from different sources cover a δ13C-range of almost 100‰ making isotope ratios a very promising tool for studying the biogeochemistry of these compounds. So far, the determination of the isotopic composition of C1 and C2 halocarbons others than chloromethane is hampered by their low mixing ratios. In order to determine the carbon isotopic composition of C1 and C2 halocarbons with mixing ratios as low as 1 pptv (i) a field suitable cryogenic high volume sampling system and (ii) a chromatographic set up for processing these samples have been developed and validated. The sampling system was tested at two different sampling sites, an urban and a coastal location in Northern Germany. The average δ13C-values for bromomethane at the urban site were −42.9±1.1‰ and agreed well with previously published results. But at the coastal site bromomethane was substantially enriched in 13C by almost 10‰. Less pronounced differences were observed for chlorodifluoromethane, 1,1,1-trichloroethane and chloromethane. We suggest that these differences are related to the turnover of these compounds in ocean surface waters. Furthermore we report first carbon isotope ratios for iodomethane (−53.6‰), bromoform (−13.5‰) and other halocarbons.


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.


2000 ◽  
Vol 39 (05) ◽  
pp. 121-126 ◽  
Author(s):  
R. Werz ◽  
P. Reuland

Summary Aim of the study was to find out wether there is a common stop of growth of mandibular bone, so that no individual determination of the optimal time for surgery in patients with asymmetric mandibular bone growth is needed. As there are no epiphyseal plates in the mandibular bone, stop of growth cannot be determined on X-ray films. Methods: Bone scans of 731 patients [687 patients (324 male, 363 female) under 39 y for exact determination of end of growth and 44 (21 male, 23 female) patients over 40 y for evaluation of nongrowth dependant differences in tracer uptake] were reviewed for the study. All the patients were examined 3 hours after injection of 99mTc-DPD. Tracer uptake was measured by region of interest technique in different points of the mandibular bone and in several epiphyseal plates of extremities. Results: Tracer uptake in different epiphyseal plates of the extremities shows strong variation with age and good correlation with reported data of bone growth and closure of the epiphyseal plates. The relative maximum of bone activity is smaller in mandibular bone than in epiphyseal plates, which show well defined peaks, ending at 15-18 years in females and at 18-21 years in males. In contrast, mandibular bone shows no well defined end of growing but a gradually reduction of bone activity which remains higher than bone activity in epiphyseal plates over several years. Conclusion: No well defined end of growth of mandibular bone exists. The optimal age for surgery of asymmetric mandibular bone growth is not before the middle of the third decade of life, bone scans performed earlier for determination of bone growth can be omitted. Bone scans performed at the middle of the third decade of life help to optimize the time of surgical intervention.


2019 ◽  
Vol 7 (1) ◽  
pp. 9-20
Author(s):  
Inna Yeung

Choice of profession is a social phenomenon that every person has to face in life. Numerous studies convince us that not only the well-being of a person depends on the chosen work, but also his attitude to himself and life in general, therefore, the right and timely professional choice is very important. Research about factors of career self-determination of students of higher education institutions in Ukraine shows that self-determination is an important factor in the socialization of young person, and the factors that determine students' career choices become an actual problem of nowadays. The present study involved full-time and part-time students of Institute of Philology and Mass Communications of Open International University of Human Development "Ukraine" in order to examine the factors of career self-determination of students of higher education institutions (N=189). Diagnostic factors of career self-determination of students studying in the third and fourth year were carried out using the author's questionnaire. Processing of obtained data was carried out using the Excel 2010 program; factorial and comparative analysis were applied. Results of the study showed that initial stage of career self-determination falls down on the third and fourth studying year at the university, when an image of future career and career orientations begin to form. At the same time, the content of career self-determination in this period is contradictory and uncertain, therefore, the implementation of pedagogical support of this process among students is effective.


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