STUDY OF DISTRIBUTION AND SOURCES OF ... - Semantic Scholar

ANNALS OF “DUNAREA DE JOS” UNIVERSITY OF GALATI – FASCICLE II █████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████

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ANNALS OF “DUNAREA DE JOS” UNIVERSITY OF GALATI MATHEMATICS, PHYSICS, THEORETICAL MECHANICS FASCICLE II, YEAR IV (XXXV) 2012

STUDY OF DISTRIBUTION AND SOURCES OF POLYCYCLIC AROMATIC HYDROCARBONS (PAHs) IN TOPSOILS FROM SE ROMANIA USING MULTIVARIATE STATISTICAL ANALYSIS Antoaneta Ene1, Thomas Spanos2 1

„Dunarea de Jos” University of Galati, Faculty of Sciences and Environment, Department of Chemistry, Physics and Environment, Physics Division, 47 Domneasca St., 800008 Galati, Romania, E-mail: [email protected] 2 Kavala Institute of Technology, Department of Sciences, St. Lukas, 654 04 Kavala, Greece

Abstract Multivariate statistical methods such as Cluster Analysis (CA) and Principal Component Analysis (PCA) were used for the study of distribution and sources of 16 polycyclic aromatic hydrocarbons (PAHs) in topsoils from seventeen locations in SE Romania, including industrial, agricultural and natural soils. The investigated dataset consists of concentrations of individual PAHs listed by the US Environmental Protection Agency (EPA) and the European Community as priority pollutants – naphthalene (NAP), acenaphthylene (ACY), acenaphthene (ACE), fluorene (FLU), phenanthrene (PHE), anthracene (ANT), fluoranthene (FLN), pyrene (PYR), chrysene (CHR), benz[a]anthracene (BaA), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP), dibenzo[a,h]anthracene (DahA), benzo[g,h,i]perylene (BghiP) and indeno[1,2,3-cd]pyrene (InP) - and the total concentration of PAHs (TPAHs) in Romanian surface soils, which have been previously determined by GC-MS technique. Clustering of the variables highlights that NAP is the only variable which differs drastically from all others. It may mean that this parameter comes from a different source of pollution as compared to the other variables. The rest of variables form a homogeneous cluster with the exception of FLU and ACE, but they should not be excluded from the group of the other chemicals, since they fall into significance level of clustering (33.3% of squared Euclidian distance Dmax). The slight difference between FLU and ACE on one hand, and the rest of PAHs, on the other hand, could be due to different sources of emission, different absorption on the soil surface, soil properties etc. Clustering of cases (sampling sites) also points out the similarity between all sampling sites. The only drastic exception is a cattle farm site (Galati County), being very different from the other 16 sites, as mentioned by the input data - the most polluted site with the highest concentrations of organics. The source of PAHs in this location could be the systematic incineration of agricultural residues and the using of vehicles for various farm practices or generators. Using PCA - factor loadings, only one latent factor was identified, explaining almost 90% of the total variance. It means that one major source of pollution (combustion) is available in the region of study, being the source of all chemicals except for NAP, as indicated also by cluster analysis. The fact that NAP is not related to the other chemicals (even it shows a negative correlation to the others) speaks for the possible existence of another pollution source specific to NAP. Keywords: PAHs, multivariate statistical methods, soil pollution, SE Romania

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1. INTRODUCTION Polycyclic aromatic hydrocarbons (PAHs) represent important groups of pollutants that have caused increasing worldwide concern as toxic environmental contaminants [1-4] and 16 PAHs were listed by the United States Environmental Protection Agency (US EPA) and the European Community as priority pollutants [2; 5]. The sources of PAH contaminants in soils are complex, being of both pyrogenic (burning of fuels and wastes, industrial emissions, domestic heating, traffic exhausts, etc.) and petrogenic (petroleum) origin. The presence of PAHs in soil can affect the quality of food, groundwater, microorganisms activity, plant growth etc. and the determination of their sources is a very important task for environmental scientists [6-9]. PAH loading in the soils is strongly affected by proximity to sources and the likelihood of atmospheric deposition [10]. Once deposited on surface soils, PAHs often persist for many years and affect soil quality, accumulate in plants and enter food chains [11]. Human exposure to PAHs is mainly caused by consumption of contaminated food with products of animal origin or plant products [12,13]. Assessment at trace level of these widespread priority hazardous substances [14] with continuous releases in environment, resulting in essentially persistent exposure of biota [1], has become a topic of global relevance and could be accomplished using very high sensitivity techniques, such as gas chromatography-mass spectrometry (GC–MS) [5]. The main objective of this paper is to employ multivariate statistical methods such as Cluster Analysis (CA) and Principal Component Analysis (PCA) [15] in order to determine the sources and distribution of PAHs in soils in the vicinity of Iron and Steel Integrated Works (ISIW) at Galati, Romania, which is one of the most important metallurgical complexes in the South-East of Europe, and in some agricultural and natural protected areas in the SE region of Romania [5].

2. METHODS The concentrations of US-EPA 16 PAHs - naphthalene (NAP), acenaphthylene (ACY), acenaphthene (ACE), fluorene (FLU), phenanthrene (PHE), anthracene (ANT), fluoranthene (FNL), pyrene (PYR), chrysene (CHR), benz[a]anthracene (BaA), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP), dibenzo[a,h]anthracene (DahA), benzo[g,h,i]perylene (BghiP) and indeno[1,2,3-cd]pyrene (InP) - in the soil samples were determined by GC-MS technique and reported in [5]. Soil samples were collected in April 2009 at 17 different points, labeled C1–C17, located in Braila, Galati and Constanta counties in SE Romania, an important region in the Lower Danube and Black Sea basin. Information regarding the studied area (the GPS coordinates and some characteristics of the investigated sites), was described in detail by Ene et al. (2012) [5]. Nine sampling points were chosen in the industrial area of the iron–steel plant of Galati, at three rural sites from Braila County (Vadeni, sites C1–C3), three rural (Sendreni, C4 and C5; Mihail Kogalniceanu–Smardan, C7), two suburban (Movileni–Sendreni, C6 and Smardan, C8) and one in an urban site (Galati town, Tiglina I district, C9) from Galati County. Other points were located in rural sites, as following: a forested area at Adam–Draguseni (C10), a cattle farm in the Prut River basin at Foltesti (C11) and wetland sites from Lower Prut Meadow natural reserve (Vadeni–Cavadinesti, C12 and C13; Rogojeni–Suceveni, C14; Oancea, C15; and Vladesti, C16) in Galati County, near the border with the Republic of Moldova, and also from Bugeac–Ostrov in Constanta County (C17), near the border with Bulgaria. With the exception of C6, which is the closest point to the iron–steel complex (coking and sinter plant and blast furnaces), all the rural sites are agricultural/pasture lands, located near cultivated areas or domestic gardens. The sites C3 and C6 are in the proximity of a heavy traffic European road, C2 near railway and C7, C8, C11, C14–C16 near local roads. Cluster Analysis (CA) and Principal Component Analysis (PCA) were applied for statistical analysis, using STATISTICA software.

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ANNALS OF “DUNAREA DE D JOS” UNIVERSITY OF GALATI – FASCICLE II █████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████ █████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████

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3. RESULTS AND DISCUSSION DISCU Using the analytical data reported in [5], in i Fig. 1 we present the distribution of the levels of of: Lower Molecular Weight (LMW) PAHs - NAP,ACY,ACE,FLU, PHE, ANT;; Higher Molecular Weight (HMW) PAHs - FLN, PYR, PYR CHR, BaA, BbF, BkF, BaP, DahA, BghiP,InP and the sum of 16 US-EPA PAHs as Total PAHs (TPAHs). Fig. 2 presents the site distribution of the seven seven carcinogenic (7–CAR) PAHs (CHR,, BaA, BbF, BkF, BaP, DahA, and InP) InP [8, 16-19] . For multivariate statistical assessment of environmental data, the concentration of 0.001 mg/kg was used in the case of not detected concentrations and ACY was not included in the analysis due to the fact that this compound was not detected in any soil sample. Clustering of the variables (15 compounds and TPAHs), TPAHs) illustrated in Fig.3, put in evidence that NAP is the only variable which differs drastically from all others. It m may ay mean that this parameter comes from a different source of pollution as compared to the other variables. The rest of variables form a homogeneous cluster and even FLU and ACE, showing a higher level of linkage, should not be excluded from the group of thee other chemicals, since they fall into significance level of clustering on 33.3% of squared Euclidian distance Dmax. The slight difference between FLU and ACE on one hand, and the rest of PAHs, on the other, could be due to different sources of emission, different absorption on the soil surface, soil properties, etc. Clustering of cases (17 sampling sites), sites) presented in Fig. 4, also highlights the similarity between all sampling sites. The only drastic exception is site C 11 (cattle farm, Galati County), being very different from the other 16 sites, as it could be seen from the distributions from Figs.1 and 2 built using input data, being the most polluted site with the highest concentrations of organics. The source of PAHs Hs in this location could be the systematic incineration of agricultural residues residues, which is a common practice in rural areas, and the using of vehicles for various farm practices or generators [5]. Using PCA - factor loadings (Table 1), only one latent factor tor was identified, explaining almost 90% of the total variance. It means that one major source of pollution (combustion) is available in the region of study, being the source of all chemicals except for NAP, as indicated also by cluster analysis. The fact that NAP is not related to the other chemicals (it even shows a negative correlation to the others) speaks for the possible existence of another pollution source specific to NAP.

Fig. 1. Site distribution of PAHs in SE Romanian soils: Lower Molecular Weight (LMW) PAHs NAP,ACY,ACE,FLU, PHE, ANT; Higher Molecular Weight (HMW) PAHs - FLN,, PYR, CHR, BaA, BbF, BkF, BaP, DahA, BghiP,InP; BghiP,InP TPAHs-sum sum of 16 US EPA priority PAHs. 17

ANNALS OF “DUNAREA DE D JOS” UNIVERSITY OF GALATI – FASCICLE II █████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████ █████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████████

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Fig. 2. Site distribution of seven carcinogenic (7-CAR) PAHs (CHR, CHR, BaA, BbF, BkF, BaP, DahA, and InP ) in SE Romanian soils.

Fig. 3. Cluster luster analysis of 16 variables (15 15 PAH compounds and TPAHs)

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Fig. 4. Cluster analysis of 17 cases (sites) Table 1. Factor loadings Factor

PAH

0.15124

NAP

-0.75068

ACE

-0.78949

FLU

-0.98359

PHE

-0.96157

ANT

-0.99808

FLN

-0.99782

PYR

-0.99718

CHR

-0.99790

BaA

-0.99724

BbF

-0.99728

BkF

-0.99649

BaP

-0.99604

BghiP

-0.99588

DahA

-0.99770

InP

-0.99787

TPAHs

0.87755

Expl. var.

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4. CONCLUSIONS Multivariate statistical methods such as Cluster Analysis (CA) and Principal Component Analysis (PCA) were used for the study of distribution and sources of 16 priority polycyclic aromatic hydrocarbons (PAHs) in topsoils from seventeen locations in SE Romania, including sites placed in the vicinity of Galati iron and steel plant and Lower Prut Meadow nature reserve in Galati County. PCA - factor loadings indicate that one major source of pollution (combustion) is available in the region of study, being the source of all chemicals except for NAP, as indicated also by cluster analysis. The fact that NAP is not related to the other chemicals (it even shows a negative correlation to the others) highlights the possible existence of another pollution source specific to NAP. Further studies will be carried out in the region for the establishing of PAH distribution pattern in industrial, agricultural and natural soils.

ACKNOWLEDGEMENT Assoc. Prof. dr. Antoaneta Ene acknowledges the financial support of Lifelong Learning Programme - Erasmus at „Dunarea de Jos” University of Galati, Romania, Contracts Nos. 25 STA/2011 and 27 STT/2012.

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