Journal of Environmental Management 91 (2009) 133141

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Journal of Environmental Management

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Determination of direct and fugitive PM emissions in a Mediterranean harbour by means of classic and novel tracer methods
Natalia Moreno a, *, Mar Viana a, Marco Pandol a, Andres Alastuey a, Xavier Querol a, Servando Chinchon b, Juan Francisco Pinto c, Federico Torres d, Juan Manuel Dez d, Jose Saez d
a

Department of Geosciences, IDAEA-CSIC, Jordi Girona 18-26, 08034 Barcelona, Spain Architectural Constructions Department, University of Alicante, Carretera San Vicente del Raspeig s/n, 03690 San Vicente del Raspeig, Alicante, Spain SIR S.A., Avda. de la Industria, 3, 28760 Tres Cantos, Madrid, Spain d Valencia Port Authority, Avda Muelle del Turia s/no, 46024 Valencia, Spain
b c

a r t i c l e i n f o
Article history: Received 8 October 2008 Received in revised form 6 July 2009 Accepted 22 July 2009 Available online 29 August 2009 Keywords: Particulate matter Enlargement works Phenolphthalein PCA CMB Petroleum coke Clinker Harbour Solid in bulk Air quality

a b s t r a c t
Remodelling works are frequent in harbour areas, given that they must adapt to rapidly changing market requirements. Depending on their nature (construction, demolition, etc.), these works may be carried out during long periods of time and thus exert a signicant impact on the air quality at the harbours and their surroundings. The air quality at the Valencia harbour was studied during an enlargement project. Four sampling stations aimed to cover the major dust-emitting activities in the harbour. In addition, a sampling campaign was carried out to collect dust materials at their emission sources (e.g., loading and unloading of clinker and petroleum coke, as well as the enlargement works). Differences obtained between PM levels at the monitoring sites were correlated with the distance between sampling stations and enlargement works and/or harbour operations, as well as with the preferential wind direction. In all cases, the days with the highest PM_10 levels were linked to wind directions coinciding with the location of the enlargement works or the clinker and petroleum coke stocks. Classic source apportionment methodologies (PCA and CMB) were applied to the data, but their interpretation was complex due to the similar chemical signatures of PM originating from direct and fugitive emissions from stocked materials (e.g., clinker), and the enlargement works. To overcome this difculty, a novel non-statistical approach was used to obtain quantitative estimations of the contributions from sources (petroleum coke and clinker), based on the correlation between specic PM components (e.g., carbonaceous species) and source tracers (e.g., V). Finally, a qualitative test using phenolphthalein was devised to identify the presence of clinker on the lters, which provided positive results. This novel tracer approach is thus recommended for harbour authorities. 2009 Elsevier Ltd. All rights reserved.

1. Introduction The growing concern about air quality in harbours is a result of the high impact of harbour operations and ship emissions on human health and environment (Arimoto, 2001; Pope and Dockery, 2006). Epidemiological studies have demonstrated that the harmful effects of atmospheric particles in harbours may be originated by the handling of dusty materials (Gupta et al., 2002; Lucialli et al., 2007; Gomez-Olles et al., 2007) Asthma outbreaks caused by unloading of soybeans in harbour areas have been widely documented in Spain (Anto et al., 1989; Hernando et al., 1989; Navarro et al., 1993; Ballester et al., 1999), Italy (Cocco et al., 1995) and the US (White et al.,

* Corresponding author. Tel.: 34 93409 5410; fax: 34 93411 0012. E-mail address: nmoreno@ija.csic.es (N. Moreno). 0301-4797/$ see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.jenvman.2009.07.009

1997). However, maritime employees may also be exposed to a variety of other products carried as cargo or to chemicals used in the maintenance of ships, producing occupational asthma in maritime environment (Lucas et al., 2006). On the other hand, marine transport emissions are also a signicant source of air pollution with local, national and global environmental effects (Corbett and Fischbeck, 1997; Huebert, 1999; Isakson et al., 2001; Sinha et al., 2003; Corbett, 2003; Cooper, 2003; Saxe and Larsen, 2004; Wang et al., 2008). Ships are major sources of emissions of sulphur dioxide (SO2) and nitrogen oxides (NOx), and also primary particulate matter (PM). Corbett et al. (2007) estimated global and regional mortalities by applying ambient PM increases due to ships indicating that shipping-related PM emissions are responsible for approximately 60,000 cardiopulmonary and lung cancer deaths annually, with most deaths occurring near coastlines in Europe, East Asia, and South Asia. Under current regulation and with the expected growth

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in shipping activity, they have estimated that annual mortalities could increase by 40% by 2012. It should be noted that high trafc density (mainly trucks and trains in some cases) is another signicant source of PM in harbour areas. In addition, maritime ports are generally located in the vicinity of urban areas and petrochemical and energy intensive industries, whose emissions tend to present a high degree of mixture with harbour emissions. In this work, the air quality in the harbour of Valencia (E Spain) was evaluated. In addition to studying the levels and composition of PM 10, source apportionment analyses were carried out with the aim to evaluate the impact on PM levels of fugitive sources such as clinker and petroleum coke stocks, as well as of enlargement works in the harbour. Remodelling works are frequent in harbour areas, given that they must adapt to rapidly changing market requirements. However, the quantication of the contribution to PM 10 levels of such works is generally complex, due to the similarities between the chemical signatures of the dust generated by different sources (e.g., enlargement works and loading, unloading and transport operations). This is a common problem in harbour areas across Europe. This study aims to provide useful tools to clearly separate PM sources. Three techniques were applied: a factor analytical tool, namely Principal Component Analysis (PCA, Thurston and Spengler, 1985), the Chemical Mass Balance (CMB, Watson et al., 1997) model, and an experimental approach based on colorimetry by means of phenolphthalein, which permits to identify the presence of clinker on the lters. PCA was rst applied to individuate the number of the possible contributing sources and their main markers, and then CMB model was used to quantify the contribution of the sources. The harbour of Valencia is Spains leading Mediterranean port in terms of commercial trafc (basically containerised cargo),

particularly because of its dynamic area of inuence and an extensive network connecting it to major ports around the world. It is located in line with the eastwest maritime corridor crossing the Suez Canal and the Strait of Gibraltar, positioning it as the rst and last stopover for all major regular shipping lines connecting America, the Mediterranean basin and the Far East (Fig. 1). It is managed by the Valencia Port Authority. In addition to usual harbour emissions (stocking and handling of dusty materials, truck and vessel trafc, dust re-suspension by wind and trucks, etc.), and enlargement works, PM levels during the sampling period were possibly affected by the 32nd Americas cup (the most prestigious regatta and match race in the sport of sailing) mainly as a consequence of the large number of visitors. As for the city of Valencia, it is a medium-sized city with 810.064 inhabitants in the metropolitan area and an approximate extension of 130 km2. The main PM sources in the area are vehicle trafc and secondary aerosols. Agricultural emissions (mostly rice and orange trees) are expected to have an impact on PM levels, even though no studies are available on this issue in the literature. The inuence of industry is rather scarce, and mostly linked to power generation. 2. Experimental 2.1. Sampling PM 10 sampling was carried out between 23rd May and 6th July 2007 at four air quality monitoring stations (E1E4) in the Valencia harbour. A total of 132 lters (33 per station, Schleicher & Schuell, QF 20) were collected by MCV high-volume samplers with PM 10 inlets. The sampling duration was 24 h for each lter, with nominal start time at 9:00 a.m. Fig. 1 shows the map of the study area, including the monitoring sites and the North dock, where clinker

E1
clinker & petcoke stocks

E2 Enlargement works E3

E4

Fig. 1. Harbour of Valencia location (left) and map of harbour of Valencia showing the location of sampling stations (E1, E2, E3 and E4), dust material stocks (clinker and petroleum coke) and locations of enlargement works.

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and petroleum coke stocks were located, and the location of the enlargement works (in white colour). The location of the four sampling stations was selected depending on their distance from the considered fugitive sources. E1 and E2 stations were placed in the proximity of the clinker and petroleum coke stocks with possible inuence of fugitive emissions from works and road trafc, while E3 and E4 stations were placed in harbour background/sub-urban areas with possible inuence of fugitive emission from harbour activities and road trafc. Approximate distances from clinker and petroleum coke stocks to the following stations were: (a) E1: 847 m, (b) E2: 653 m (c) E3: 1850 and (d) E4: 1800 m. Likewise the distance between E1 and E2 is 1080 m, between E2 and E3 is 1108 m and between E3 and E4 of 2708 m. In addition, a sampling campaign was carried out to collect dust materials emitted during loading and unloading operations, e.g., dust from clinker and petroleum coke stocks, as well as dusty material from enlargement works, and harbour dust. These dust materials were chemically, physically and mineralogically characterised with the procedures described in the following section. Wind direction and velocity data were supplied by the harbour authorities. 2.2. Analyses PM 10 concentrations were determined by gravimetry. Chemical analyses were carried out following the methodology described by Querol et al. (1996, 2001), which includes: acid digestion of one section of the lter and analysis of major and trace elements by ICP-MS and ICP-AES; leaching of one section and analysis by IC and FIA colorimetry; and CHNS elemental analysis for total carbon concentrations. For most elements, relative analytical errors were 5%, with the exception of P and K for which a 10% error was determined. Indirect determinations from Querol et al. (2001) were carried out for SiO2 (SiO2 Al2O3 2), CO2 (CO2 Ca 60/40) 3 3 and Cnon mineral contents (Cnm CtotalCCcarbonates). Chemical analyses for deposited dust material were carried out using the methodology described in Querol et al. (1997), and the grain size distribution of the deposited fraction was determined by means of a laser light scattering-based particle size (Malvern MASTERSIZER/E). The mineralogy and morphology of deposited dusty materials was analysed by X-ray diffraction (DRX, using a SIEMENS D501 powder diffractometer) and a scanning electron microscope (SEMEDX, JEOL6400), respectively. The presence of clinker on the lters was identied using a colorimetry test based on the addition of phenolphthalein. In ambient air, the reaction of clinker with relative humidity generates portlandite (Ca(OH)2) as by-product, which produces an alkaline pH of 12.5. With the addition of minor amounts of phenolphthalein (23 drops), lter samples containing portlandite will change to show a marked roseviolet colour due to the highly basic pH, and thus indicate the presence of clinker. Conversely, the presence of other mineral particulates containing calcium in the form of calcite or dolomite (both with pH <9) will not result in a change of colour after the addition of phenolphthalein. Therefore, we tested this procedure as a qualitative and straightforward method to identify the presence of clinker in the samples. It must be stressed, however, that it does not provide a quantitative determination of the mass of clinker on the lters. The colour change on clinker-containing lters is immediate and highly evident after the addition of phenolphthalein, whereas no reaction is observed (no change in colour or any other characteristics) on lters with no clinker contribution. Due to the fact that it is a qualitative method, it is not possible to provide detection limits for this approach.

2.3. Source contribution Source contribution was evaluated by means of receptor modelling techniques. These are well established and widely used techniques for source identication and apportionment (Hopke, 1991 Watson and Chow, 2005). The conceptual basis of the most commonly used receptor models, including strengths and weaknesses, has been reviewed over the past years by a number of authors (see Bruinen de Bruin et al., 2006; Viana et al., 2008) and is therefore not reported here. In the present study PCA (Thurston and Spengler, 1985) and CMB (Watson et al., 1997; Schauer et al., 2006) were applied to ambient PM measurements. PCA is a multivariate analytical tool used to determine the major components within a dataset, and it was applied in order to individuate the possible contributing source types by looking at the characteristic marker elements within each retrieved factor. The source contribution estimates were then obtained by CMB, which used both the chemical speciation of ambient PM and the chemical proles of the sampled sources as input. 3. Results 3.1. Characterisation of dusty bulk materials Table 1 summarises the chemical composition of the dusty materials with potential impact on ambient PM levels, originated from harbour operations, stocks and/or works. As a result of this characterisation, specic tracers for these materials were identied: a) Clinker: The mineralogical phases identied by XRD were in major proportion tri-/di-calcium silicate (main clinker phase), with minor proportions of portlandite Ca(OH)2, which is produced by means of the hydration of calcium silicates due to the humidity of the harbour and the high surface area of this material. Chemically, clinker was constituted mainly by CaO (63%) and minor proportions of SiO2 (21%), Al2O3 (5%) and Fe2O3 (3%), with relatively high contents of Sr (920 mg/kg), Ba (140 mg/kg) and Zr (62 mg/kg). Similar results were reported by Moreno et al. (2007). b) Petroleum coke was mainly composed by amorphous carbon material of graphitic nature with a high background of DRX between 20 and 30 of 2q. Chemically, major tracers of this material are organic matter (w81% Ctotal was determined by Moreno et al., 2007), relatively high concentrations of SO3 (w7%), V and Ni (1900 and 360 mg/kg, respectively). Grain size distribution analyses demonstrated that this material presented the coarsest grain size distribution (with less than 20% <450 mm) with respect to the rest of dust materials collected (with median of 35100 mm). c) Harbour dust (HD, sampled in the proximity of E1), was constituted by typical crystalline phases from soils, such as quartz and calcite, with the following chemical composition: 32% by CaO, 27% constituted by SiO2, and 25% of LOI, which is formed mainly by organic matter and other crustal elements, such as Al, Mg and Fe. The concentrations of Zn, Ba, Pb, Cu and Sb (with values of 168, 165, 38, 37 and 3 mg/kg, respectively) identied in this material may be attributed to the emissions of the road trafc in the harbour (Sternbeck et al., 2002; Moreno et al., 2007). d) Enlargement works dust sampled in the surroundings of E2, this sample showed crystalline phases calcite (CaCO3), quartz (SiO2), microcline (KAlSiO3O8), muscovite and dolomite (CaMg(CO3)2). Its chemical composition is characterised by high contents of crustal components such as SiO2 (32%), CaO

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Table 1 Chemical composition of deposited dusty materials sampled in the harbour of Valencia. LOI: loss on ignition. HD: harbour dust. EW: enlargement works. % Moisture LOI SiO2 Al2O3 CaO Na2O K2O MgO TiO2 SO3 P2O5 Fe2O3 Clinker 0.4 2.9 21.4 4.5 63 0.1 0.7 2.4 0.2 0.5 <0.05 2.9 Petroleum coke 0.4 91.2 1.5 <0.01 0.1 0.014 <0.01 <0.01 <0.01 7 <0.01 0.03 HD 0.9 24.5 26.5 2.8 32.4 0.5 0.8 2.2 0.1 0.6 0.1 1.4 EW 1.9 21.2 31.7 5.3 26.9 0.3 1.4 4 0.2 0.2 0.1 1.8 mg/kg As Ba Be Bi Cd Ce Co Cr Cs Cu Dy Er Eu Ga Gd Ge Hf Hg Ho La Li Lu Mn Mo Clinker 25.9 140 1.1 0.9 0.8 29.6 7.4 42.5 3.9 32.7 2.1 1.1 <0.1 6.5 3.2 1.3 1.8 <0.01 <0.1 13.6 25.4 <0.1 617.7 2.3 Petroleum coke 2.2 2 <0.1 <0.1 <0.1 <0.1 1.7 1.8 <0.1 4 <0.1 <0.1 <0.1 0.8 <0.1 <0.1 <0.1 0.08 <0.1 <0.1 <0.1 <0.1 1.3 6.9 HD 27.7 165.4 <0.1 1.5 0.8 18.8 3.8 18 2 37.4 1.1 <0.1 <0.1 3.8 2 <0.1 0.9 0.02 <0.1 8.6 12.1 <0.1 240.3 3 EW 14.6 226.6 1.2 <0.1 0.1 36.1 4.8 23.4 4.4 20.4 1.9 0.9 <0.1 7.3 3.7 0.4 1.6 0.1 <0.1 15.6 26.2 <0.1 228.1 6.2 mg/kg Nb Nd Ni Pb Pr Rb Sb Sc Se Sm Sn Sr Ta Tb Th Tl Tm U V W Y Yb Zn Zr Clinker 4.6 13.6 34.7 28.7 3.2 29.7 1.2 3.7 5.1 2.7 1.2 923.2 <0.1 <0.1 5.3 <0.1 <0.1 2.2 37.7 4.7 12.5 1.3 75.2 61.8 Petroleum coke <0.1 <0.1 363 9.8 <0.1 <0.1 <0.1 <0.1 2.3 <0.1 <0.1 2.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 1876.1 <0.1 <0.1 <0.1 16.9 0.3 HD 4 8.9 24.8 38.1 2.1 27.9 2.4 <0.1 1.6 1.8 4.2 290.6 0.8 <0.1 3.4 <0.1 <0.1 1.6 91.1 2 6.2 <0.1 167.8 27.4 EW 2.7 16.9 13.2 25.9 3.9 57 1.3 2.6 2.4 3.4 2.2 284.9 <0.1 <0.1 6.7 <0.1 <0.1 3 32.9 <0.1 9.6 1 70 48.8

(27%), Al2O3 (5%), MgO (4%), and Fe2O3 (2%), coupled with a fraction of organic components of 21%. Elements linked to truck trafc emissions (227 mgBa/Kg, 57 mgRb/kg, 70 mgZn/kg and 26 mgPb/kg) were also identied in this source (Sternbeck et al., 2002; Moreno et al., 2007).

3.2. PM 10 levels Fig. 2 shows the daily PM 10 mean for each station during the sampling period. E1 registered the highest PM 10 levels with a daily mean of 142 mgPM 10/m3, ranging from 57 to 331 mgPM 10/m3. Mean daily PM 10 levels at E2 station were 106 mgPM 10/m3(from 32 to 224 mgPM 10/m3). E3 and E4 registered lower daily PM 10 mean levels than E1 and E2, with 52 mgPM 10/m3 for E3 and 49 mgPM 10/m3 for E4. It is important to take into account that these PM 10 levels must not be compared with PM 10 limit values from air quality directives due to the proximity to the emission sources of the sampling stations and the different period of the sampling (an annual period for the directive). The correlation between PM 10 levels and wind velocity and direction have demonstrated that peak PM episodes coincided with days with prevailing WSW direction at E1, and with SE winds at E2. These wind directions correspond with the location of clinker and petroleum coke stocks in the harbour, and thus evidence the signicant impact of fugitive emissions from these stocks on PM levels (maximum on peak events 80190 mgPM 10/m3, Fig. 2). 3.3. Chemical characterisation of PM 10 Approximately 50% of the samples from sites E1 and E2 (closest to the clinker and petroleum coke stocks) and E4 (representing the lowest PM levels), corresponding at the rst period of sampling, were selected for chemical analysis (Table 2 and Fig. 3). Samples collected at E3 were not analysed due to the high similarity of this site with E4. The representativity of the selected samples was ensured by comparison of their mean PM levels with those registered during the entire sampling period.

Fig. 3 illustrates the average concentration determined for different PM components in the three stations, compared with usual concentration ranges obtained at urban sites in Spain (Querol et al., 2004). It should be taken into account that this evaluation is meant only as a reference, and that the concentrations must not be directly compared due to the proximity to the emission sources at the Valencia harbour. The major components have been grouped as follows: (a) crustal components (CO2 SiO2 Al2O3 Ca 3 KMg Fe) (b) marine aerosols (Na Cl) (c) OM EC: organic mater (determined applying 1.6 factor to organic carbon, Turpin et al., 2000) elemental carbon, and (d) SIC, secondary inorganic components (SO2 NO NH). 4 3 4 The daily mean crustal concentration for every station (80 mg/m3, 55% of PM 10 at E1; 40 mg/m3, 41% of PM 10 at E2; 16 mg/m3, 34% of PM 10 at E4) showed clear differences between the high concentrations determined at E1 and E2 with respect to E4. E2 and mainly E1, showed higher daily crustal means than usual urban background ranges in Spain, whereas E4 was within the range (Fig. 3, top). These differences were mainly attributed to a major contribution of crustal material at E1 and E2 due to their proximity to the clinker stocks and the enlargement works. The highest marine aerosol concentrations were recorded at the E1 site, followed by E2 and E4, (8, 5 and 3 mg/m3, respectively). The daily average concentration recorded at E1 (8 mg/m3) is higher than the usual values registered at coastal urban sites in Eastern Spain (Querol et al., 2004), probably due to the location of the monitoring site directly above the breakwater. The mean daily OM EC concentrations (23, 27 and 14 mg/m3, for E1, E2 and E4 respectively) were out of the usual urban range in urban sites in Spain (Fig. 3, top,), especially in the cases of E1 and E2. Such high OM EC levels are the result of the close proximity to the petroleum coke stocks in the harbour. The correlation between V (petroleum coke tracer) and OM EC in E1 was calculated, and the results showed that the relation between both components was [coke](mg/m3) [V](ng/m3)/1.95(ng/mg), with a high correlation (R2 0.94). This result is very similar to the correlation extracted from petroleum coke characterisation, where [coke](Kg) [V](g)/ 1.90(g/kg) (Table 1). Based on these results, it was concluded that the petroleum coke concentration in the analysed lters may be

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Rosa
Valencia 3 Silo (32) jueves, 31 de mayo de 2007
GEONICA

Rosa
Valencia 3 Silo (32) lunes, 4 de junio de 2007
GEONICA

350 300 E1 E2 E3 E4

PM-10 (g/m3)

250 200 150 100 50 0 23/05/2007 25/05/2007 27/05/2007 29/05/2007 31/05/2007 02/06/2007 04/06/2007 06/06/2007 08/06/2007 10/06/2007 12/06/2007 14/06/2007 16/06/2007 18/06/2007 20/06/2007 22/06/2007 24/06/2007 26/06/2007 28/06/2007 30/06/2007 02/07/2007 04/07/2007

Fig. 2. PM 10 concentrations in the 4 stations at the harbour of Valencia (bottom). Examples of wind direction favouring the transport from clinker and pet-coke from stocks to E1 (left) and E2 (right).

derived from V concentration in each lter, as will be described in the following section. The daily mean SIC concentrations were very similar in the three stations (13, 13 and 11 mg/m3, for E1, E2 and E4 respectively), owing to the predominantly regional-scale origin of these compounds. Even at a harbour area where the contribution of shipping emissions to SO2 could be expected to be large, these results evidence 4 the similarity in SIC levels at all sites. In addition, SIC levels were also similar to the usual ranges at urban sites in Spain. In relative

Table 2 Mean concentration and standard deviation for major (mgm3) and trace elements (ngm3) in PM 10 for analysed lters from E1, E2 and E4 for the period 23/05/2007 21/06/2007. # samples PM 10 E1 20 146 21 15 23 26 10 5 35 1.4 3 1.4 2 8 5 5 0.3 85 st dv E1 71 15 12 17 19 6 3 25 0.8 1 1 1 3 3 2 0.1 12 E2 22 99 20 18 27 12 6 3 16 0.8 2 1 1 7 5 3 0.5 88 st dv E2 47 12 11 16 8 3 1 11 0.4 1 1 1 3 3 2 0.2 9 E4 21 47 10 9 14 4 3 1 6 0.5 2 0.4 0.7 6 4 1.2 0.6 95 st dv E4 12 3 3 5 2 1.0 0.5 2 0.1 1 0.2 0.2 2 3 2 0.3 7

terms, however, their contribution is very different at the 3 stations (9, 12 and 23 % of PM 10 for E1, E2 and E4, respectively). Concerning trace element concentrations, the comparison with the levels measured in urban stations in Spain (Fig. 3, bottom) concluded that signicantly high concentrations of Ti, Mn, V, Sr, Cr, Ni, Mo, Rb, As, Li and light rare earth elements (LREE) were determined in the harbour. As described above (Table 1), these elements are tracers of petroleum coke (V, Ni, and in minor proportion Mo) and clinker and/or enlargement works (Ti, Mn, Sr, Cr, Rb, As, Li, and LREE). The high levels recorded at the harbour result from both fugitive emissions of these materials (mainly stocking, handling operations and dispersion by wind) and from re-suspension of deposited materials due to trafc within the harbour. With respect to elements with European limit (Pb) and target (As, Cd, Ni) values, it is noteworthy that none of the elements exceeded EU regulations at any of the monitoring sites in the harbour. 3.4. Source apportionment Source apportionment was performed on a mean and daily basis for the 3 stations described above (E1, E2, E4). Preliminary source identication was carried out by means of PCA, followed by CMB for source contribution estimates. In addition, a novel tracer methodology developed during this study was also applied to the dataset, with the aim to separate the contribution of clinker from crustal materials, and that of petroleum coke from OM EC. Consequently, three different and complementary methodologies were applied, allowing us to obtain a detailed picture of PM sources and their contributions in the Valencia harbour. Because of the relatively limited number of samples available for each monitoring site, PCA was run on one single dataset consisting

Ctotal CNM OM EC CO 3 SiO2 Al2O3 Ca K Na Mg Fe SO2 4 NO 3 Cl NH 4 % Deter

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1000,0 Urban ranges in Spain E1 100,0 E2 E4

g/m3

10,0

1,0

0,1 Crustal
1000,00 Urban ranges in Spain 100,00 E1 E2 E4

Marine

OM+EC

SIC

10,00

ng/m3
1,00 0,10 0,01 Zn Ti Cu Ba PbMn V Sr Zr Sb Cr Ni M oSn RbAs Ce Se Bi Li Cd La NdCo Hf Y U Tl Th Sc Pr Cs Sn
Fig. 3. Usual concentration ranges obtained at urban sites in Spain (shaded grey, Querol et al., 2004) and average daily concentrations obtained in the Valencia harbour. Major components expressed in mg/m3 (top) and trace elements in ng/m3 (bottom).

of the data from the three separate sites. Therefore, a total of 63 samples and 34 variables were analysed. The ratio samples to variables is somewhat lower than usually considered as optimal in the literature (ratio 3:1, Thurston & Spengler, 1985), but the analysis was carried out taking this limitation into account. Throughout all runs (with a varying number of input variables), PCA consistently identied 5 separate sources (principal components, Table 3): soil and dusty materials stocked on the docks (crustal material, Cr, Rb, As, among others), road dust (traced by Cu, Sn, Sb, Pb), a mixture of marine aerosol and secondary nitrate (Na, Cl, NO), secondary 3 sulphate with traces of V and Ni (NH, Ni, V, SO2) and an 4 4 unidentied source traced by Mo, Zn and Cd (with a minor contribution to the variance). Sources such as clinker or petroleum coke were not detected, and therefore are assumed to be included as mixed sources in the reported principal components. Thus, this analysis evidenced the inability of PCA to clearly separate sources in this study, owing to the limited number of samples available as well as to the similarities in their chemical signatures (e.g., clinker, soil and dusty materials). The CMB8 receptor model was then used to estimate the source contributions to PM 10 in E1, E2 and E4. The chemical proles of the collected bulk samples, namely petroleum coke, clinker, enlargement works and harbour dust, were included in the CMB together with the ambient PM 10 data, and the analysis was performed for each station and for each day of measurement. Previous study from Moreno et al. (2007) showed a clear relationship between the PM 10 fraction and the bulk material composition of the collected sample types with similar chemical proles. Twenty-four chemical

species were used within the present analysis. Species not directly emitted from the aforementioned sources such as Na, Cl, NO, SO2 3 4 were also included within the model, in the form of a sea-salt aerosol prole based on the bulk composition of sea water (U.S. EPA SPECIATE, 2006) and pure secondary aerosol source proles, i.e. ammonium sulphate, ammonium bisulphate, ammonium nitrate, sodium nitrate, and sulphuric acid (Chow et al., 1992). The chemical proles of these secondary sources were calculated based on the stoichiometric ratios of the corresponding species while the sum of the retrieved contributions was used to estimate the overall contribution from secondary aerosols to the ambient PM 10 mass (SIC in Fig. 4). The most appropriate combination of sources was determined by detecting non-linearly independent sources. In this study, the harbour dust source was found collinear with the clinker and enlargement works dust sources and not considered in the calculation. The collinearity was observed mainly because the harbour dust source is a mixture of elements directly emitted from clinker, enlargement works dust and coke and deposited on the ground. Moreover, as already evidenced, the PCA model identied a road dust/trafc factor traced by Cu, Sn and Sb, markers for brake pad wear (Schauer et al., 2006). Because of the lack of an experimental trafc source prole to use within the CMB, the aforementioned vehicle-wear markers were not introduced in the model. Each model result was then evaluated by using the regression statistics parameters accompanying each CMB output (see Watson et al., 1997 for details). The sources, which contributions are shown in Fig. 4, were the main sources of PM in the harbour explaining about 8590% of PM 10 mass depending on the

N. Moreno et al. / Journal of Environmental Management 91 (2009) 133141 Table 3 Factor loadings and explained variance for the 5 factors identied by PCA analysis. Factor loadings >0.70 are highlighted in bold. Soil & dusty materials Ctotal Al2O3 Ca K Na Mg Fe SO2 4 NO 3 Cl NH 4 V Cr Co Ni Cu Zn Ga As Se Rb Sr Zr Mo Cd Sn Sb Cs Ba La Pb Bi Th U Expl.Var 0.74 0.94 0.97 0.95 0.19 0.73 0.96 0.52 0.05 0.29 0.30 0.61 0.92 0.88 0.61 0.14 0.12 0.94 0.98 0.95 0.98 0.98 0.74 0.23 0.40 0.09 0.04 0.97 0.78 0.96 0.25 0.79 0.94 0.85 58% Road dust 0.09 0.03 0.08 0.06 0.04 0.07 0.07 0.23 0.08 0.01 0.14 0.02 0.01 0.13 0.07 0.92 0.07 0.06 0.07 0.07 0.07 0.06 0.22 0.20 0.04 0.86 0.87 0.07 0.14 0.07 0.64 0.21 0.07 0.11 9% Marine aerosol 0.06 0.18 0.10 0.23 0.91 0.46 0.13 0.59 0.83 0.78 0.04 0.06 0.17 0.00 0.01 0.06 0.11 0.09 0.07 0.21 0.07 0.04 0.24 0.11 0.36 0.08 0.01 0.08 0.14 0.05 0.12 0.16 0.12 0.07 8% Secondary sulphate 0.30 0.02 0.01 0.04 0.22 0.12 0.01 0.43 0.32 0.42 0.79 0.64 0.02 0.10 0.67 0.01 0.09 0.01 0.05 0.01 0.01 0.03 0.16 0.04 0.14 0.05 0.11 0.01 0.01 0.04 0.15 0.11 0.00 0.06 5% Mo/Zn/Cd 0.37 0.16 0.07 0.08 0.02 0.31 0.13 0.13 0.04 0.00 0.07 0.27 0.02 0.24 0.25 0.02 0.67 0.21 0.07 0.06 0.06 0.10 0.25 0.70 0.37 0.31 0.07 0.00 0.44 0.19 0.20 0.07 0.26 0.45 4%

139

measurement site. The non-simulated PM 10 mass, namely other in Fig. 4, includes potential contributions from other sources not used within the CMB such as mainly road dust/trafc (as evidenced by PCA analysis) and to a lesser extent shipping. A sensitivity test was performed in order to understand if the lack within the CMB of fuel oil sources such as shipping (emitting V) and of a vehicular source (emitting mainly carbonaceous aerosols) inuenced the results, given their similarities in the ngerprints mainly with
Clinker 160 140 120 100
16 11 7 18 17 13 8 18 14 9 11 4 21 23 13 5 19 8 10 2 6 11 11 6 11 3 11 15 1

petroleum coke. The MPIN matrix from the CMB (Table 4) showed that OM EC was low or null in inuence for the experimental local sources considered in the present work (Kim and Henry, 1999). Thus, the performed sensitivity test revealed that the contribution of the petroleum coke source (for which the highest OM EC MPIN number was observed) varied only between 0.3% and 1.7% in the three stations when OM EC was not used as tting species within the CMB. Moreover, different fuel oil sources (U.S. EPA SPECIATE) were introduced within the model and in all cases the fuel oil source contributions were close to zero with a very low statistical signicance (Tstat < 1). Thus meaning that the CMB recognized petroleum coke as the main source of ambient V. However, we want to stress that the CMB model, even if with some approximations, was used as a tool to estimate the contributions from major sources and to evaluate the major differences with the novel method proposed in the present manuscript. On average the three measurement stations were inuenced by the harbour activities, such as loading, unloading and transport of dusty materials (clinker and coke), and by the enlargement works, even if the effect of these sources decreased strongly from E1 to E4 (Fig. 4). The sum of the contributions from clinker, coke and the enlargement works dust added up to 77, 75, and 60% of the ambient PM 10 mass in E1, E2 and E4 respectively. In E1 clinker was the main source of PM with a contribution of 77 8 mg/m3 (ranging from 7 to 210 mg/m3) reduced to about 23 5 mg/m3 (ranging from 4 to 130 mg/m3) in E2 and 11 3 mg/m3 (ranging from 0 to 26 mg/m3) in E4. As a consequence of the proximity between E2 station and the works area in the harbour, the impact of the enlargement works was higher in E2 (32 4 mg/m3) even if it was still signicant in E1 (17 5 mg/m3) and E4 (11 2 mg/m3). The analysis showed that in all stations clinker and enlargement works dust explained the measured levels of all the typical crustal elements such as Al, Ca, Fe, K, Mg, Mn, and Sr (Table 4) for which levels considerably above the urban range were measured (especially in E1 and E2 stations, Fig. 3). Petroleum coke, which contribution was estimated in 18 2 mg/m3 (ranging from 6 to 78 mg/m3) in E1, 21 2 mg/m3 (ranging from 5 to 43 mg/m3) in E2 and 6 1 mg/m3 (ranging from 1 to 13 mg/m3) in E4, was found as the major source of V, Ni and OM EC, coinciding with the results obtained from the chemical characterisation of PM sources (see above). It is important to
Table 4 Mean MPIN absolute numbers calculated in the three stations with standard deviation. E1, E2, E4 MPIN abs. MPIN abs. numbers MPIN abs. MPIN abs. numbers clinker petroleum coque numbers works numbers marine OM EC Al Ca K Na Mg Fe Cl Li Ti V Mn Co Ni As Rb Sr Y Cs Ba Th U 0.10 0.05 0.30 0.09 0.94 0.05 0.37 0.10 0.08 0.04 0.70 0.06 0.27 0.11 0.17 0.01 0.02 0.01 0.04 0.03 0.00 0.01 0.60 0.17 0.05 0.04 0.11 0.06 0.13 0.07 0.15 0.05 0.90 0.06 0.01 0.01 0.00 0.01 0.05 0.09 0.01 0.00 0.00 0.01 0.35 0.02 0.03 0.02 0.03 0.01 0.02 0.01 0.00 0.01 0.04 0.02 0.02 0.02 0.01 0.00 0.00 0.01 0.01 0.01 0.98 0.01 0.02 0.01 0.00 0.01 0.46 0.06 0.00 0.01 0.01 0.01 0.02 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.09 0.05 0.60 0.07 0.38 0.04 0.48 0.12 0.11 0.07 0.99 0.00 0.04 0.07 0.23 0.01 0.06 0.02 0.13 0.02 0.01 0.01 0.29 0.09 0.00 0.01 0.07 0.04 0.03 0.03 0.19 0.07 0.49 0.04 0.01 0.00 0.01 0.00 0.07 0.13 0.02 0.01 0.01 0.01 0.02 0.01 0.14 0.03 0.01 0.01 0.01 0.00 0.55 0.29 0.11 0.02 0.04 0.01 0.97 0.02 0.01 0.01 0.03 0.01 0.00 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.04 0.03 0.04 0.01 0.00 0.01 0.00 0.01 0.01 0.02 0.00 0.01 0.00 0.00

Enlarg.works E1
27

petroleum coke E2

Marine

SIC E4

other.

g/m3

80 60 40 20

77

66

32 27 23 13

0 CMB NSA CMB NSA

CMB

NSA

Fig. 4. Comparison of source contribution estimates for E1, E2 and E4 stations by means CMB and non-statistical approach.

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consider that the petroleum coke contribution could be slightly overestimated due to the fact that a shipping emission prole was not included in the CMB analysis, which would contribute to V levels. The results of the OM EC apportionment showed that in all stations about 67 mg/m3 of OM EC were unaccounted for by the sources used within the CMB model. Consequently, other sources not considered within the CMB model such as mainly local trafc must contribute to the unaccounted OM EC levels, given that petroleum coke explained about 16, 20 and 7 mg/m3 of OM EC in E1, E2 and E4 respectively. The contribution from the marine source was the highest in E1 (7 1 mg/m3) this station being the nearest one to the sea, while the lowest marine contribution was estimated in E4 with about 2.0 0.2 mg/m3. The overall contribution of the considered secondary source proles was quite similar in all the stations (11.0 0.5, 11.0 0.4 and 10 0.2 mg/m3 in E1, E2 and E4 respectively) being the levels of secondary sulphate and nitrate comparable in E1, E2 and E4. These levels coincide with those obtained by means of the chemical characterisation of the aerosols (described in Section 3.3), with 1113 mg/m3 of secondary inorganic compounds at all the monitoring sites. The same good comparability was obtained for the marine aerosol, accounting for 1.6 7.0 mg/m3 of PM 10 according to CMB and for 1.28 mg/m3 according to the chemical speciation (Table 2). As a nal step of the source apportionment analysis, two nonstatistical approaches were attempted to estimate the contributions from petroleum coke and clinker to ambient PM levels. These tests were performed with the aim to evaluate their performance as simple but efcient alternative tools to estimate source contributions without the help of receptor modelling techniques. In the case of petroleum coke, its concentration on the lters was calculated based on V concentrations, with the following ratio: [petroleum coke] (Kg) [V] (g)/1.9 (g/kg) (Table 1). As a result, petroleum coke reached concentrations ranging from 26 to 78 mg/m3 in E1, and from 20 to 36 mg/m3 for predominant SE wind direction favouring the transport of petroleum coke from stock to E2. For both stations the results were in good agreement with the CMB analysis. It is important to point out that on the days for which this calculation was performed, the predominant wind direction favoured the transport of petroleum coke dust material and from ships emissions to the respective stations. In the case of clinker, its presence on lter substrates was detected using the colorimetry-based approach using phenolphthalein. As a result of the application of this test, the presence of clinker was identied in a signicant number of samples, therefore allowing us to evidence that clinker is an important contributor to PM levels in the study area. The number of samples containing clinker was 14 at E1, 4 at E2 and 1 at E3, highlighting the larger inuence of this PM source at E1. It is important to point out that the days for which the presence of clinker was detected showed a predominant wind direction favouring its transport towards the monitoring stations. In addition, it must be taken into account that the presence of clinker as detected by this colorimetry-based approach should be considered as a minimum. Due to the qualitative nature of this approach, and to the highly complex mixture of particulates on the lters, it was not possible to determine experimentally the lowest clinker concentrations detectable by this method. Therefore, all samples which showed positive results with the phenolphthalein test (a change in colour) are certain to contain clinker, whereas those samples with negative results may potentially contain low clinker concentrations, which remain undetected by this test. As a result, by applying this methodology it is not possible to obtain false positives, and its only limitation is that it could slightly underestimate clinker contributions. In order to assess the quality of these results (QA/QC), two samples were selected for analysis by SEMEDX and DRX analyses:

one of them positive in the phenolphthalein test (sample 29/05/07 from E1), and one negative in this test (sample 12/06/07 in E4). SEMEDX and DRX analyses conrmed that, for sample 29/05/07, the main particles had a similar morphology and a major phase of calcium silicate typically present in clinker. Conversely, the 12/06/07 sample showed irregular particles of Ca and Si, which were also detected in lower proportions, and DRX analysis did not detect typical phases of clinker. As a result of these quality assurance tests, the validity of the methodology was conrmed. Taking into consideration the qualitative nature of this test, an attempt was made to quantify the contribution of clinker as a PM source in the study area. To this end, the days for which the presence of clinker was not detected were selected, and the mean background Ca concentration was calculated. This Ca concentration was obtained from the relationship E1E4 and E2E4 for the days without clinker contributions. These ratios were then extrapolated for the remaining sampling days, and Ca from clinker was determined as the difference between total Ca and background Ca. Finally, the contribution from clinker was obtained by applying the ratio [clinker](mg/m3) [Ca] (mg/m3) 1.4/0.63 (see the clinker characterisation section above). As a result, clinker daily contributions ranged from 14 to 174 mg/m3 at E1, from 4 to 100 mg/m3 at E2, and were 16 mg/m3 at E4 (detected only for one sample28/05/ 2008). As stated above, it is necessary to stress the qualitative nature of the phenolphthalein test and the fact that these results should be taken as an estimation of the lower end of the contributions of the clinker source, which may be slightly underestimated by this approach. The comparison between the results from the CMB model and the non-statistical approaches show that similar clinker and petroleum coke contributions to E1, E2, and E4 PM mass were obtained. However, the contribution estimates were only slightly underestimated by the non-statistical approaches (Fig. 4). Despite the conceptual differences between the two methodologies, the clinker and petroleum coke contribution ranges from the two methods were similar for all stations, thus reinforcing the robustness of the retrieved source contributions. Moreover, the decreasing trend of clinker and petroleum coke contributions from E1 to E4 was clearly detected by both methods.

4. Conclusions The impact of direct and fugitive emissions on PM 10 levels in a Mediterranean harbour (Valencia, Spain) was evaluated in this study. Special attention was dedicated to the identication and quantication of sources such as enlargement works carried out at the harbour at the time of sampling, and the handling and stocking of clinker and petroleum coke materials. The main conclusions extracted from this work may be summarised as follows: - Fugitive emissions from stocks located on the docks (clinker, petroleum coke) exert a major inuence on PM 10 levels in the harbour, which increased by 80190 mg/m3 on a daily mean level during peak episodes. On average, the contribution from such emissions to PM 10 was signicant, accounting for 23 53% of the PM 10 mass in the case of clinker, and from 12 to 21% of PM 10 in the case of petroleum coke. Thus, stocked materials on docks represent major sources of PM in harbour areas, and dedicated measures should be undertaken by harbour authorities to minimise their impact on air quality. - The emissions from the enlargement works in the harbour accounted for 1232% of the PM 10 mass, and thus constituted another of the major PM sources. Given the relatively high frequency of such works in harbour areas, it would be advisable

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that specic measures should also be undertaken to limit the emission of atmospheric particulates. - A qualitative test based on colorimetry by phenolphthalein was applied as an easy and not costly qualitative technique to determine the presence of clinker on lter samples. The efciency of this test was proved in this study. Its main limitation is that it could underestimate clinker contributions, and thus results should be considered as minimum values. - The contribution from petroleum coke emissions by means of a non-statistical approach was evaluated, based on the correlation between petroleum coke and V concentrations on the lters. The results obtained were comparable to those provided by CMB. Acknowledgements This work was partially funded by the Spanish Ministries of the Environment and Education and Science (Secretara de Estado de Universidades e Investigacion), as well as by the Ministry of the Environment by means the project CALIOPE (Ref.: 441-2006-312.1). The authors gratefully acknowledge the Harbour of Valencia. References
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