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Levels of POPs in airbone PM10 and PM2.5: preliminary results.

Authors:

Abstract

Airborne particulate matter (PM) comprises a complex mixt. of inorg. and org. substances with a wide range of sizes. Among these PM, the larger ones (ca. > 30 μm) have mainly their origin on re-suspended soils and dusts from roads and industries, remaining in the air for a short period of time. Smaller particles remain suspended for larger periods of time and have primarily an anthropogenic origin, due to combustions and also to secondary sources, like e.g. re-condensation of org. vapors and gas-phase reactions. The smaller the particle size, the easiest they can penetrate in the respiratory system. For these reasons, the European Union has set a limits of PM10 (particulate matter < 10 μm) in order to avoid human health risks. However, this regulation will be soon replaced by PM2.5 (particulate matter < 2.5 μm) because of their harmful potential. This work presents a preliminary study of several classes persistent org. pollutants (POPs) in both PM10 and PM2.5 collected from an urban area. The
LEVELS OF POPs IN AIRBONE PM10 AND PM2.5: PRELIMINARY RESULTS
Quintana JB
1
, Fernández-Villarrenaga V
2
, López-Mahía P
1,3*
, Muniategui Lorenzo S
3
, Prada Rodríguez D
1,3
1
IUMA - University Institute of Environment, University of A Coruña, Pazo da Lóngora, Liáns, 15179 Oleiros (A
Coruña), Spain.
2
Scientific Research Support Services, University of A Coruña, Edificio SCI, Campus de Elviña s/n, 15071 A
Coruña, Spain.
3
Department of Analytical Chemistry, Faculty of Sciences, University of A Coruña, Campus A Zapateira 15071 A
Coruña, Spain.
* E-mail: purmahia@udc.es
Introduction
Airborne particulate matter (PM) comprises a complex mixture of inorganic and organic substances and also a broad
range of sizes. Among these PM, the larger ones (ca. > 30 µm) have mainly their origin on re-suspended soils and
dusts from roads and industries, remaining in the air for a short period of time. On the other hand, smaller particles
remain suspended for larger periods of time and have primarily an anthropogenic origin, due to combustions and also
to secondary sources, like e.g. re-condensation of organic vapours and gas-phase reactions. Moreover, the smaller the
particle size, the easiest they can penetrate in the respiratory system. For these reasons, the actual European Union
legislation
1
has established limit values for PM10 (particulate matter < 10 µm) in order to avoid human health risks.
However, this regulation will be soon replaced by PM2.5
2
(particulate matter < 2.5 µm) because of their harmful
potential.
Thus, this work presents a preliminary study of several classes persistent organic pollutants (POPs) in both PM10
and PM2.5 collected from an urban area, aiming to identify them and their relative concentrations in both kinds of
samples and to study the implications of this regulation change. This work will be further extended as a part of a
project that aims to characterise airborne PM from urban, industrial and rural environments in a long term study.
Materials and Methods
Parallel 24 h samples of PM2.5 and PM10 were collected on an urban area in the city of A Coruña (Galicia, NW
Spain, Fig. 1) influenced by a main traffic road (ca. 20 000 vehicles / day) with some potential contribution from
petroleum, metallurgy industries and a coal power plant located at ca. 5-15 km. Collection was made though quartz
fibre filters (UNE-EN 12341) with a sampling flow of 2.3 and 68 m
3
/h for both PM10 and PM2.5, respectively (Fig.
1). Field filter blanks were also collected.
Figure 1. Sampling point location and PM samplers. A Coruña, 43º22’04’’N & 08º25’08’’W.
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Total Organic Carbon (TOC) was determined by elemental analysis with a Flash EA 1112 (Carlo Erba, Milan, Italy).
Polycyclic Aromatic Hydrocarbons (PAHs) were analysed by microwave assisted extraction and liquid
chromatography-fluorescence detection as described elsewhere
3
. Polychlorodibenzodioxins/polychlorodibenzofurans
(PCDD/Fs) and polychlorinated biphenyls (PCBs) were determined by isotope dilution gas chromatography-high
resolution mass spectrometry (GC-HRMS) after Soxhlet extraction and a fractionation on a Power Prep FMS system
based on a previously published method for PCDD/Fs only
4
. In brief, this fractionation was adapted to the
determination of ‘dioxin-like PCBs’ and was done over disposable columns: multilayer silica columns, basic alumina
columns and PX-21 carbon columns. Two extracts were recovered, the first containing the mono-ortho PCB and the
second containing the non-ortho PCBs and the PCDDs/Fs. This first extract was also employed for the GC-HRMS
quantification of polybromodiphenylethers (PBDEs) by the external standard procedure and the identification of
chlorinated phenols (CPs) and polychloronaphthalenes (PCNs).
Results and Discussion
The total concentration of four POP classes (PAHs, PCDD/Fs, ‘dioxin-like PCBs’ and PBDEs) that were quantified
in this study is presented in Fig. 2. The first thing that may be observed from that figure is that the concentration of
PM10 is above the EU daily limit
1
of 50 µg/m
3
, that may be surpassed a maximum of seven times per year. It must
be kept on mind however, that Fig. 2 corresponds to a single sampling day and also that the location of the sampling
point may be regarded as a hot spot in very close to a main traffic road and it does not represent human exposure.
Also, Fig. 2 (left) shows that the concentration of most POPs is higher in PM2.5 than PM10, with the exception of
PAHs. This ratio increases by looking at the PM mass related concentration (Fig. 2 right), pointing out that POPs
may be preferentially associated to lower size particles, due to their different original sources and to their higher
specific surface area. Obviously, this hypothesis needs to be confirmed by a long term study.
0
50
100
150
200
PM (µg/m3)
TOC (µg/m3)
PAHs
(ng/m3)
I-TEQ
PCDD/Fs
(fg/m3)
I-TEQ PCBs
(fg/m3)
PBDEs
(pg/m3)
PM10
PM2.5
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
PAHs
(µg/mg)
I-TEQ
PCDD/Fs
(pg/mg)
I-TEQ PCBs
(pg/mg)
PBDEs
(ng/mg)
PM10
PM2.5
4.6
Figure 2. Total concentration of the different POPs in PM, related to sampled volume (left) and to mass of PM
(right).
A closer look at the different POPs is depicted in Fig. 3. Again, this figure shows a relatively high concentrations of
PAHs is and, in particular, the concentration of benzo(a)pyrene (BaP) would surpass the EU average annual limit
5
of
1 ng/m
3
, which may be due to the sampling location and needs is being studied in a long term basis. Regarding the
distribution of PAHs in PM10 and PM2.5, no significant differences can be observed, either in the profile or
concentration of the different compounds. On the other hand, PCDD/Fs and ‘dioxin-like’ PCBs, although both PM10
and PM2.5 show a similar profile, indicating a same source, but being at higher levels in the PM2.5 fraction. In the
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case of PBDEs, two trends are observed, for PBDE-47, PBDE-100 and PBD-99 the concentration is higher in the
lower particle size fraction, while for PBDE-209 there is not significant difference. This may represent a different
origin, as the first three PBDEs are representative of the Penta-BDE mix, whereas PBDE-209 is constitutes ca. 98 %
of the Deca-BDE.
0
2
4
6
8
10
12
14
16
Phe
Anth
Ft
Pyr
BaA
Chry
BbFt
BkFt
BaP
DBahA
BghiP
IP
Conc. (ng/m3)
PM10
PM2.5
0
100
200
300
400
500
2378-TCDD
12378-PeCDD
123478-HxCDD
123678-HxCDD
123789-HxCDD
1234678-HpCDD
OCDD
2378-TCDF
12378-PeCDF
23478-PeCDF
123478-HxCDF
123678-HxCDF
234678-HxCDF
123789-HxCDF
1234678-HpCDF
1234789-HpCDF
OCDF
Conc. (fg/m3)
PM10
PM2.5
1260
0
100
200
300
400
500
600
PCB81
PCB77
PCB123
PCB118
PCB114
PCB105
PCB126
PCB167
PCB156
PCB157
PCB169
PCB189
Conc. (fg/m3)
PM10
PM2.5
1018
0
2
4
6
8
10
12
14
16
PBDE-47
PBDE-100
PBDE-99
PBDE-209
Conc. (pg/m3)
PM10
PM2.5
Figure 3. Concentration of different POPs in PM10 and PM2.5.
A further screening for other POP classes was carried out by analyzing the first extract fraction by GC-HRMS. It
revealed the presence of several CPs (data not shown) and some PCNs (Fig. 4) in both PM samples, which were not
yet quantified due to the lack of standards in the laboratory. Nevertheless, they could be tentatively identified by
monitoring three exact m/z values for each compound and their relative abundance, and comparing their relative
retention time with literature values.
Thus, it can be concluded from these preliminary set of experiments that several classes of POPs can be found both
in PM10 and PM2.5, but their concentration in both fractions can be rather different. This contrasts e.g. with the
observations of Martínez et al.
6
from the concentrations of PCDD/Fs in PM10 and total suspended particles, where
not significant difference is observed. Obviously this preliminary results need to be confirmed by a long term study
that is being done at the moment and considers not only urban samples, but also industrial and rural ones.
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Figure 4. GC-HRMS chromatogram and tentative identification of three PCNs in PM10 and PM2.5 samples.
Acknowledgments
This work was financially supported by ‘Ministerio de Educación y Ciencia’ (Project no. REN2003-08603-C04-01).
We are indebt to the University’s Scientific Research Support Services (SAI) for sample analysis. JBQ
acknowledges ‘Xunta de Galicia’ for his contract sponsorship though the ‘Isidro Parga Pondal’ program.
References
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6. Martínez K, Abad E, Gustems L, Manich A, Gómez R, Guinart X, Hernández I, Rivera J. Atmos. Environ. 2006,
46: 576.
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... Inhalation exposures at the industrial site was lower than those calculated in China (6760 pg day À1 ; Chen et al., 2006), in France (1293 pg day À1 ; Castro-Jim enez et al., 2011), in Italy (427 and 720 pg day À1 for the cold and warm season, respectively; Cincinelli et al., 2014) and in Turkey (767 pg day À1 ; Cetin and Odabasi, 2008). Inhalation exposures at the traffic-background site were in the same range with those calculated in United Kingdom (120 pg day À1 ; Harrad et al., 2004), in Austria (163 pg day À1 ; Gans et al., 2007), in Greece (173 pg day À1 , Mandalakis et al., 2009), in Spain (177 pg day À1 ; Quintana et al., 2006) and in Japan (176 pg day À1 ; Takigami et al., 2009) and lower than with those calculated in Italy (Cincinelli et al., 2014) and Turkey (Cetin and Odabasi, 2008). Inhalation exposures at the urban-background site were in the same range with those calculated for a suburban site in United States (66.7 pg day À1 ; Strandberg et al., 2001) and for a remote site in Baltic sea (57.3 pg day À1 ; Ter and lower than those calculated in suburbs site of Heraklion, Greece (100 pg day À1 , Mandalakis et al., 2009) and in Kuwait (93 and 173 pg day À1 for the cold and warm season respectively; Gevao et al., 2013). ...
... pg/kg/day and 0.6e1.1 pg/kg/day, respectively. The inhalation exposure to P PBDEs calculated in this study were much below than those estimated in United Kingdom (120 pg/kg/day), Austria (163 pg/kg/day), Greece (173 pg/kg/day), Spain (177 pg/kg/day) and Japan (176 pg/kg/day) (Harrad et al., 2004;Quintana et al., 2006;Gans et al., 2007;Mandalakis et al., 2009;Takigami et al., 2009). The estimated exposure of BDE-47,- 99,-153, and À209 in this study are compared with oral reference dose (RfD) of respective compounds given by USEPA (Table 2). ...
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... In addition, it is the 70 major factor determining the atmospheric behavior of aerosols and thereby controls 71 the removal mechanisms, the residence time and the transport potential of particle- 72 bound contaminants. In contrast to other organic pollutants, studies regarding the 73 particle-size distribution of PBDEs are exceptionally limited indicating a distinct 74 enrichment in the finest particle fractions (Particles less than 2.5 micrometers in 75 diameter (PM 2.5 ) in Quintana et al., 2006; PM 2.5 in Deng et al., 2007; <0.57 μm in 76 Mandalakis et al., 2009). ...
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  • López Mahía
  • Muniategui Lorenzo
  • López Moure
  • Piñeiro Iglesias
  • Prada Rodríguez
López Mahía P, Muniategui Lorenzo S, López Moure M, Piñeiro Iglesias M, Prada Rodríguez D. Environ. Sci. Pollut. Res. 2003, 10:98.
  • K Martínez
  • E Abad
  • L Gustems
  • A Manich
  • R Gómez
  • X Guinart
  • I Hernández
  • J Rivera
Martínez K, Abad E, Gustems L, Manich A, Gómez R, Guinart X, Hernández I, Rivera J. Atmos. Environ. 2006, 46: 576.
  • Fernández Martínez
  • López Vilariño
  • López Mahía
  • Muniategui Lorenzo
  • Prada Rodríguez
  • D Abad
  • E Rivera
Fernández Martínez G, López Vilariño JM, López Mahía P, Muniategui Lorenzo S, Prada Rodríguez D, Abad E, Rivera J. Chemosphere 2004, 57:67.
Council Directive 1999/30/EC
Council Directive 1999/30/EC. Official J. Eur. Communities 1999, L163: 41.
Commission Decision 2004/470/EC
Commission Decision 2004/470/EC. Official J. Eur. Communities 2004, L160: 51.
Directive 2004/107/EC
Directive 2004/107/EC. Official J. Eur. Communities 2004, L23: 3.