Review of PM Oxidative Potential Measured with Acellular Assays in Urban and Rural Sites across Italy
Abstract
:1. Introduction
2. Methodology
2.1. PM Sampling and Filter Extraction
2.2. Quantification of PM Oxidative Potential Using Acellular Assays
2.2.1. DTT Assay
2.2.2. AA and GSH Assays
2.2.3. DCFH Assay
2.3. Analytical Methodologies for Chemical Characterization
3. Results and Discussion
3.1. Study Overview
3.2. Association of Oxidative Potential with PM Chemical Composition
- -
- Metals. The major PM components, such as alkali (Na, K) and hearth metals (Ca, Mg, Ba, Al) can be originated from resuspension of road dust, road abrasion, and soil dust emissions. Trace elements are several transition metals (i.e., Fe Cu, Zn, Pb, Cr, Ni, Mn, Sn, Cd) associated with non-tail pipe traffic emissions, mainly related to brake and tire wear [11,25,39,41,42,43,44]. Finally, K and Rb can be considered as tracers of the biomass burning [23,26].
- -
- Carbonaceous components. They include elemental, EC, organic, OC, and water soluble organic carbon, WSOC. OC may be discriminated between primary (POC) and secondary organic species (SOC), based on the quantification of individual compounds, as tracers of specific sources, i.e., sugars, levoglucosan—widely used tracer of biomass burning [22,31,37,43]; n-alkane and PAHs—tracers of tail pipe traffic emissions [20]; carboxylic acids and quinones—markers of photochemical formation of SOA [45,46,47,48,49,50,51,52].
- -
3.2.1. Association with Metals
3.2.2. Association with Organic Species
3.2.3. Intercorrelation among Species
3.3. Comparison among Different Acellular Assays
3.3.1. Sensitivity of Different Acellular Assays
3.3.2. Correlation between OP Responses from Different Acellular Assays
3.3.3. PM Size Distribution of OP Responses
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- Similar OPDTTV values were measured in Lecce for PM2.5 and PM10 fractions (close to 0.20 ± 0.04 nmol min−1 m−3), while the intrinsic OPDTTm value was larger for PM2.5 than for PM10 [24];
- ■
- An average ratio of 0.86 (±0.10 standard deviation) was found between OPDTTV of PM2.5 and PM10 particles in an independent study in Lecce, with the differences between the two fractions maximized for Saharan dust events and minimized for high carbon content samples [27];
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- By investigating OP distribution of size-segregated PM samples collected in Rome and Ferrara, Simonetti found that OPDTTV, as well as OPDCFHV responses, shows a size distribution profile characterized by of a broad maximum in the 0.32–1.8 μm PM, that is similar to that of the markers of BB emissions [25];
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- In a study concerning PM3, PM3–7, and PM>7 in 17 sites in Europe, including Milan, Shafer found that OPDTTV is dominated by the PM3 fraction, since it represents 76% of total OP activity, with the PM3-7 contributing on average 17% and PM>7 7%. Accordingly, PM3 fraction showed a higher intrinsic OPDTTm in comparison with the larger particles. No chemical components were found associated with DTT activity (Spearman r > 0.7) in the PM3 size cut, while tracers of biomass burning—K and Rb—and of non-tailpipe vehicle emission—Fe, Sn, Cu, Sb, and Ba—exhibited good correlations with OPDTTV in the PM3–7 size fraction [16].
3.4. Spatial Variability of OP in Different Areas across Italy
3.4.1. OP Responses of PM10 Particles
3.4.2. OP Responses of PM2.5 Particles
4. Conclusions
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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PM Fraction | Ref. | Location | Sampling Period | Sampling Duration | OP Assay | Chemical Characterization |
---|---|---|---|---|---|---|
TSP | [28] | Milan | January, June, October 2013 | 24 h | DTT, DCFH | EC, OC, inorganic ions, metals, trace organic compounds |
PM10 | [23] | Trento | April–May 2016 | 24 h | DTT, AA | WSTC, ions, metals, sugars |
[34] | Lecce | December 2014–October 2015 | 24 h | DTT, AA | metals, ions, EC, OC, POC, LW carboxylic acids | |
[29] | Milan | Winter 2009 | 24 h | DTT (cit-c) | OC, metals, quinones | |
PM10 and PM2.5 | [24] | Lecce | December 2014–October 2015 | 24 h | DTT, AA | metals, ions, EC, OC, POC, LW carboxylic acids |
[27] | Lecce | Fall/Winter 2013–2016 | 24 h | DTT | OC, EC, POC, SOC, TC | |
[35] | Milan | December 2009–November 2010 | 24 h | DCFH | OC, EC, WSOC, ions, metals, levoglucosan, PAHs, hopanes, alkanes | |
PM2.5 | [18] | Bologna | February–July 2013 | 24 h | DTT, AA | metals, EC, OC |
[30] | Bologna | mar 2018 | 24 h | AA | metals, EC, OC | |
[20] | Rome | January 2010–January 2011 | 24h | DTT | OC, EC, PAH, hopanes | |
[21] | Rome | January–February 2017 | 24 h | DCFH | OC, EC, BC, WSOC, water soluble BrC, metals, levoglucosan, PAH | |
[19] | Turin | February 2010–January 2011 | 24 h | AA, GSH | metals, NO2 | |
[17,32] | Milan, Florence | Summer/Winter 2012–2013 | 24 h | AA, GSH | OC, EC, ions, metals | |
[31] | Turin, Pavia | June–December 2000 | 24 h | AA, GSH | metals | |
PM3–PM3–7–PM7 | [16] | Milan | April–July 20 | 3–4 days | DTT, DCFH | metals, ions |
9 PM fractions 0.18–18 μm | [25] | Ferrara, Rome | February–March 2017 | 24 h | DTT, AA, DCFH | ions, metals |
50 µm dust | [26,33] | specific sources | - | - | DTT, AA, DCFH | OC, EC, WSOC, ions, metals |
PM Fraction | Ref. | Correlation | Assay | Chemical Species | |
---|---|---|---|---|---|
TSP | [28] | Milan | Spearman p < 0.01 | DTT | Solar Radiation |
DCFH | TSP mass, OC, TC, SO42−, NO3−, NH4+, Ca, Mn, Co, Zn, As | ||||
PM10 | [23] | Trento | Pearson p < 0.01 | DTT | SO42−, NH4+, NO3−, Cl−, Ca, Mg, K, Mn, Cu, Rb, and Zn, Fe, Ni, Pb, Sr, V, WSOC, sugars, levoglucosan |
AA | SO42−, NH4+, NO3−, Cl−, Ca, Mg, K, Mn, Cu, Rb and Zn, Fe, Ni, Pb, Sr, V, WSOC, sugars | ||||
[34] | Lecce | Pearson p < 0.01 | DTT | AW: K+, Ca2+, Ba, Cd, Ce, Cr, Cu, Fe, Mn, OC, EC, POC | |
SS: NO3−, NH4+, Cu, OC, EC, POC, LW carboxylic acids | |||||
AA | AW: K+, Ca2+, Ba, Ce, Cr, Cu, Fe, Mn, OC, EC, POC | ||||
SS: NH4+, nss-K+, nss-Mg2+, nss-Ca2+, nss-SO42−, Cu, Mn, P, Pb, LW carboxylic acids | |||||
PM10 and PM2.5 | [24] | Lecce | Pearson p < 0.01 | DTT | AW: K+, NO3−, Ba, Cd, Cu, Fe, Mn, P, V, OC, EC, carboxylic acids |
SS: NO3−, SO42−, OC, EC, TC, POC | |||||
AA | AW: NO3−, Ba, Cd, Cu, Fe, Mn, P, V, OC, EC | ||||
SS: NO3−, SO42−, OC, EC, TC, POC | |||||
PM2.5 | [27] | Lecce | Pearson p < 0.05 | DTT | OC, EC |
[35] | Milan | Spearman p < 0.05 | DCFH | Ni, Cr, Cu, OC | |
[18] | Bologna | Pearson p < 0.01 | DTT | Mn, Fe, Cu, Cr, Zn, OC, EC | |
AA | Mn, Cu, OC, EC | ||||
[30] | Bologna | Pearson p < 0.01 | AA | Mn, Fe, Cu, Cr, Zn, OC, EC | |
[20] | Rome | linear regression | DTT | OC, EC Levoglucosan, ∑PAHs | |
[21] | Rome | linear regression | DCFH | equivalent Black Carbon, ∑PAHs | |
[19] | Turin | Pearson p < 0.05 | AA | PM2.5 mass, NO2, Cu, Fe | |
GSH | NO2, Cu, Fe | ||||
[17] | Milan, Florence | Spearman p < 0.01 | AA | Indoor: Cu, Mo, OC | |
Outdoor: Fe, Cu, Cr, Ni, Cd, Sn, Sb, K+ | |||||
GSH | Indoor: Cu, Mo, OC | ||||
Outdoor: Cu, Sn, OC | |||||
[31] | Turin, Pavia | Pearson | AA | Fe, Cu, Zn | |
GSH | Cu, Al | ||||
PM3, PM3–7, PM7 | [16] | Milan | Spearman r > 0.70 | DTT | <3 µm: - |
3–7 µm: Fe, Sn, Cu, Sb, Ba | |||||
>7 µm: As, Al, Ti, Sr, Li |
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Pietrogrande, M.C.; Russo, M.; Zagatti, E. Review of PM Oxidative Potential Measured with Acellular Assays in Urban and Rural Sites across Italy. Atmosphere 2019, 10, 626. https://doi.org/10.3390/atmos10100626
Pietrogrande MC, Russo M, Zagatti E. Review of PM Oxidative Potential Measured with Acellular Assays in Urban and Rural Sites across Italy. Atmosphere. 2019; 10(10):626. https://doi.org/10.3390/atmos10100626
Chicago/Turabian StylePietrogrande, Maria Chiara, Mara Russo, and Elisa Zagatti. 2019. "Review of PM Oxidative Potential Measured with Acellular Assays in Urban and Rural Sites across Italy" Atmosphere 10, no. 10: 626. https://doi.org/10.3390/atmos10100626