Elsevier

Atmospheric Environment

Volume 36, Issue 19, July 2002, Pages 3113-3125
Atmospheric Environment

Source apportionment analysis of atmospheric particulates in an industrialised urban site in southwestern Spain

https://doi.org/10.1016/S1352-2310(02)00257-1Get rights and content

Abstract

A detailed physical and chemical characterisation of total suspended particles (TSP) in the highly industrialised city of Huelva (southwestern Spain) was carried out. The results evidenced a coarse grain-size prevalence (PM10 accounting for only 40% of TSP mass, 37 and 91 μg/m3, respectively). PM10 levels are in the usual range for urban background sites in Spain. The crustal, anthropogenic and marine components accounted for a mean of a 40%, 24% and 5% of bulk TSP, respectively. As expected from the industrial activities, relatively high PO43− and As levels for an urban site were detected. In addition to the crustal and marine components, source apportionment analysis revealed three additional emission sources influencing the levels and composition of TSP: (a) a petrochemical source, (b) a mixed metallurgical-phosphate source, (c) and an unknown source (Sb and NO3).

Due to the high local emissions, the mean TSP anthropogenic contribution (mostly PM10) obtained for all possible air mass transport scenarios reached 18–29 μg/m3. The 2010 annual EU PM10 limit value (20 μg/m3) would be exceeded by the anthropogenic load recorded for all the air mass transport scenarios, with the exception of the North Atlantic transport (only 15% of the sampling days). Under African air mass transport scenarios (20% of sampling days), the TSP crustal contribution reached near three times the local crustal contribution. It must be pointed out that this crustal input should diminish when sampling PM10 due to the dominant coarse size distribution of this type of particles.

Introduction

In the light of studies on the health impact of particulate matter (PM) (Schwartz et al., 1996; Dockery and Pope, 1996; Donaldson and MaCnee, 1999) the European Commission has included PM10 (PM<10 μm) limit values in the new air quality directive (European Commission, 1999). This directive also considers the possibility of including PM2.5 (PM<2.5 μm) standards in the 2003 evaluation.

Given that PM is emitted into the atmosphere by a number of anthropogenic and natural sources, the physical and chemical patterns may vary considerably. Both natural and anthropogenic emissions supply primary (direct emission of PM) and secondary (formed from gaseous precursors) PM. On a global scale (IPCC, 1996), PM emissions reach 3400 million tonnes/year. Anthropogenic sources account for only 10% of total PM emissions, whereas the natural primary PM emissions reach 85% (2900 million tonnes/year). These figures may change drastically on a local scale in highly industrialised areas such as the Huelva estuary, where large industrial emissions are mixed with urban and natural (local soil re-suspension and Saharan dust inputs) emissions.

The source apportionment analysis has been widely used to quantify the contribution of different sources to the ambient PM levels (Eldering and Cass, 1996; Kleeman and Cass, 1998; Henry et al., 1984; Gertler et al., 1995; Chow et al., 1996; Harrison et al (1997a), Harrison et al (1997b); Pio et al., 1998). Receptor modelling techniques are based on the evaluation of data acquired at receptor sites, and most of them do not require previously identified emission sources (Henry et al., 1984). These types of models have played a key role in the evaluation of PM sources with respect to national air quality standards in certain countries. In the United States, the Chemical Mass Balance Model (Gertler et al., 1995; Chow et al., 1996) has been widely used, whereas in Europe receptor modelling techniques have been mainly based on methods that do not require chemical profiles from source emissions (Harrison et al (1997a), Harrison et al (1997b); Pio et al., 1998).

The present study focuses on the detailed physical and chemical characterisation of total suspended particles (TSP) in the city of Huelva in order to identify the major emission sources having a significant influence on the levels and composition of TSP, using receptor modelling techniques. As described below, Huelva may be influenced by the particulate emissions from a complex multi-emission sources area, and a detailed geochemical study has been carried out to detect the major contributions to the bulk TSP. Furthermore, the levels and grain-size distribution of a variety of particulate species was investigated to determine if major anthropogenic pollutants are concentrated in the TSP, PM10 or PM2.5 fractions. The size resolved sampling of TSP allowed also to investigate the degree of neutralisation of the acidic species.

TSP instead of PM10 sampling was preferred in the current study, carried out from July 1999 to December 2000, to characterise all the PM size ranges. A further study in progress, started on January 2001, focused on the PM10 and PM2.5 source apportionment analysis.

Section snippets

The study area

The city of Huelva (round 160,000 inhabitants) is located in the southwestern end of the Andalusia autonomous region (Spain). The city spreads out over a flat area in the southern end of the “V” shaped confluence between the Odiel and Tinto rivers (Fig. 1). This area has a relatively dry Atlantic-Iberian climate with very dry summers (around 520 mm/year and 35 mm as a mean for June–September period). The NW, SW and NE winds predominate with frequencies from 22% to 28% (Fig. 1), due to the

Methodology

Stage 1: The 1996–1999 time series of daily PM10 levels recorded at 4 stations, located in the city of Huelva (M. Lois, Pozo Dulce, La Orden, La Rábida, see Fig. 1), belonging to the air quality monitoring network from the Andalusia Autonomous Government (AQMNAG), were evaluated in terms of: (a) comparison with the current limit values of the forthcoming EU environmental standards, and (b) identification of possible seasonal patterns. The PM10 measurements at the AQMNAGs stations are carried

Results and discussion

Stage 1: 1996–1999 PM10 time series. Table 1 summarises the mean annual PM10 levels recorded at the M. Lois, Pozo Dulce, La Orden, La Rábida monitoring stations. These values are also compared with the forthcoming EU limit values for 2010. The annual PM10 levels would exceed the forthcoming EU limit value (50 and 20 μg PM10/m3 for 2005 and 2010, respectively) over all the period 1996–1999. The highest PM10 levels were recorded in 1996–1997 when up to 60 μg PM10/m3 were recorded as a mean annual

Conclusions

The major goal of this study was the identification of the different atmospheric emission sources that have a significant influence on the concentrations of atmospheric particulates in the highly industrialised area of Huelva, in southwestern Spain. A detailed chemical characterisation of TSP allowed to identify the five major natural and anthropogenic sources accounting for 82% of the variance. In addition to the crustal and marine sources, the following differentiated anthropogenic sources

Acknowledgements

This study has been supported by the Comisión Interministerial de Ciencia y Tecnologı́a (AMB98-1044 and Acción Especial AMB99-1778-E). The authors wish to thank the Department of the Environment from La Junta de Andalucı́a for supplying the 1996–2000 PM10 time series and meteorological data and for their collaboration in this study, and to NASA/Goddard Space Flight Center, Laboratory for Atmospheres, Greenbelt, Maryland, (USA), the Atmospheric Modelling and Weather Forecasting Group from the

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