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Heavy metals in albanian coastalsedimentsPaola Rivaro , Carmela Ianni , Serena Massolo , Nicoletta Ruggieri& Roberto Frachea Sezione di Chimica Analitica ed Ambientale – Dipartimentodi Chimica e Chimica Industriale – Università di Genova , viaDodecaneso, 31 – 16146 Genova, ItalyPublished online: 07 Aug 2006.

To cite this article: Paola Rivaro , Carmela Ianni , Serena Massolo , Nicoletta Ruggieri & RobertoFrache (2004) Heavy metals in albanian coastal sediments, Toxicological & EnvironmentalChemistry, 86:2, 87-99, DOI: 10.1080/02772240410001688260

To link to this article: http://dx.doi.org/10.1080/02772240410001688260

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Toxicol. and Environ. Chem., 2004, Vol. 86, No. 2, pp. 87–99

HEAVY METALS IN ALBANIAN

COASTAL SEDIMENTS

PAOLA RIVARO*, CARMELA IANNI, SERENA MASSOLO,NICOLETTA RUGGIERI and ROBERTO FRACHE

Sezione di Chimica Analitica ed Ambientale – Dipartimento di Chimica e Chimica Industriale –Universita di Genova, via Dodecaneso, 31 – 16146 Genova, Italy

(Received 17 April 2002; Revised 11 December 2002; In final form 12 February 2004)

Heavy metals (Fe, Mn, Cr, Ni, Cu, Cd, Pb, Sn) concentration has been determined on 39 coastal sedimentsamples collected in Albania. The relationship between the heavy metals content and the grain size hasbeen considered. All metals, except Cu and Cd, resulted accumulated in the finest fraction, which constitutedup to 95% of most of the considered sediments. A good correlation has been found for Ni, Cr, Fe, Zn, Cu inthe entire area, indicating a common origin for these metals in the analyzed sediments. Concentration valuesfall in the range reported for Dinaric chain derived sediments, revealing, generally, a natural origin of themetal contents. Though in some selected areas such as the Drin and the Skumbin Bay, an antropogenicinput of Cr, Fe, Ni and Cu can be observed, as the result of discharging of mines and smelter activities.

Keywords: Adriatic Sea; Albania; Sediments; Heavy metals; Grain size

INTRODUCTION

Determination of heavy metals concentration in sediments has become a commonmeans of assessing the extent of anthropogenic input impact on a certain area [1].However, chemical analyses alone can lead to an overestimation of the anthropogeniccontribution of a particular heavy metal. Therefore, it is necessary to take in to accountthe petrography and the origin of sediments [2].

The Adriatic Sea is an oblong land locked basin, bordered on the western side by theApennines and on the eastern side by the Dynaric chain [3]. For many years it has beenregarded as a heavily polluted sea because of its morphology and dynamics [4].However the knowledge regarding heavy metal distribution in the coastal area sedi-ments presents differences between Italian and Albanian coast. In fact many recentpapers refer to heavy metals distribution in sediments collected along the Italiancoasts [4–7], while few publications concern the eastern Adriatic coast, all regarding

*Corresponding Author. Fax: þ39 010 3536190. E-mail: rivaro@chimica.unige.it

ISSN 0277-2248 print: ISSN 1029-0486 online/04/020087-13 � 2004 Taylor & Francis Ltd

DOI: 10.1080/02772240410001688260

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mainly Yugoslavia sediments [1,8]. No papers were found on heavy metals distributionin sediments of Albania.

Albania coastline is 476 km long washed by the Adriatic and Ionian Seas. Adriaticshore is mainly sandy, whereas Ionian is almost total rocky alternated with pebble orhard sandy shores. The coastal Adriatic line represents a big potential natural resource,because of the presence of 8 lagoon ecosystems, most subject to intensive fishery and/orshellfish exploitation [9]. Several Albanian rivers flow into the Adriatic Sea; the biggestand the most important are Drini, Mati, Ishmi, Shkumbini, Vjosa. Moreover there arenumerous small spring and temporary rain and snow torrents. It has been estimatedthat on the Albanian coast, large quantities of waters with more than 50� 106 t ofsuspended solids per year enter the south-eastern Adriatic [10].

Albanian rivers provide a sufficient sediment supply to overcome redistribution bywaves; the sediment dispersal pattern is transversally directed toward the deeper partof the basin [3]. The hydrographic basins of the rivers show a prevalence of serpentinesoils and the country is characterized by a high density of mines and metal smelters.In fact, Albania ranks third in the world nickel mineral deposits and first in chromitedeposits [11].

Lateritic deposits of nickel–silicate and iron–nickel containing Cr and Co are locatedin three main regions, i.e. Kukes in the north, Librazhd-Progradec and Korce in thesouth-east. Also volcanogenic massive sulphide copper deposits are found in northAlbania, an area where serpentine soils are also well represented [12]. The miningindustry has probably discharged in the past years large amounts of solid matter inthe rivers, which flow into the Adriatic Sea. Marine sediments are characterized byan epidote and chromite association supplied by material transported by the Skumbi,Semeni and Vjosa rivers and they are distributed along a belt facing the Slavian–Albanese coast [3].

This article refers to an evaluation of the concentration levels and distribution ofheavy metals in the sediments to assess possible anthropogenic inputs in this area.In particular, we will discuss the contents of Fe, Mn, Cr, Ni, Cu, Cd, Pb, Sn, also inrelation to the grain size and the geological characteristics of the area.

METHODS

Sampling

Sediments were collected during 2000–2001 oceanographic cruises in 39 stations alongtransects perpendicular to the Albanian coast line, as shown in Fig. 1. Geographicalposition and depth of the stations are reported in Table I. The samples were collectedusing a stainless steel grab and sampled from the center of the grab to avoid contam-ination by the metallic parts. After draining off the excess water, they were placed inpolyethylene containers and stored at �20�C until analysis.

Analytical Procedures

An amount of the sediments was separated in two size fractions with a sieve of 63 mmmesh size; both the fractions and the reminder sediments were dried at 40�C in oven,homogenized at 320 rpm for 15min with an automatic agate grinder and stored at

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room temperature. The total metal contents was determined in the two size fractionsand in not-sieved sediments (total sediment). 0.2 g of the samples were treated inmicrowave teflon vessels with 4mL of aqua regia (HCl/HNO3, 3 : 1) and heated in amicrowave oven (CEM MDS 2000) with the following program: 5min at 250Wpower, 5min at 320W power and 10min at 380W. The digests were filtered throughSchleicher-Schull blue-band filters (i.e. 2 mm pore size), made up to 20mL with deio-nized water, transferred in polyethylene containers and stored at 4�C until analysis.

All the reagents employed were of Suprapur grade (Merck Eurolab, Italy).The determination of Sn, Zn, Cu, Fe, Mn, Cr, Pb was carried out with an Inductively

Coupled Plasma Atomic Emission Spectrometer (ICP/AES) Jobin Yvon JY 24. Cd wasdetermined by Electrothermal Atomization Atomic Absorption Spectroscopy (ETA/AAS) (Varian Spectra A300 Spectrometer with Zeeman effect backgroundcorrection and autosampler Varian model 96). In Table II the analytical wavelengthsused for metals determination are summarized.

The accuracy of the procedure was tested using a certified reference material (marinesediment reference material PACS-2 of National Research Council – Canada). Blankanalysis were carried out, showing negligible contamination.

FIGURE 1 Map of sampling stations.

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TABLE I Co-ordinates and depths of sediment sampling stations

Station Latitude (N) Longitude (W) Depth (m)

4 41� 37.010 19� 20.670 505 41� 42.942 19� 22.107 466 41� 48.575 19� 22.896 277 41� 48.881 19� 30.808 368 41� 45.019 19� 31.452 338B 41� 45.019 19� 31.452 339 41� 41.050 19� 32.320 2210 41� 38.245 19� 32.443 1511 41� 38.770 19� 26.187 2912 41� 37.824 19� 12.993 8513 41� 38.040 18� 54.100 18216 41� 30.000 19� 19.000 5817 41� 29.953 19� 23.515 1818 41� 22.493 19� 21.109 3919 41� 18.055 19� 22.359 3723 41� 07.991 19� 05.179 8824 41� 07.974 19� 14.607 8025 41� 08.062 19� 23.628 2626 41� 02.586 19� 24.007 2127 41� 02.313 19� 13.289 2329 40�57.994 19�12.328 8030 40� 51.857 19� 22.160 20032 40� 53.320 19� 20.662 9533 40� 51.261 19� 20.039 8234 40� 53.176 19� 12.131 8737 40� 47.497 19� 18.401 2138 40� 43.030 19� 18.250 1439 40� 42.909 19� 11.667 3342 40� 38.843 19� 16.226 11643 40� 36.011 19� 16.660 39045 40� 29.127 19� 09.953 44446 40� 31.368 19� 14.219 87947 40� 33.155 19� 18.307 56048 40� 27.743 19� 14.762 22748B 40� 29.011 19� 20.169 22749 40� 21.979 19� 18.501 9250 40�20.609 19�12.365 1552 40� 13.542 19� 23.402 9052B 40� 13.542 19� 23.402 9053 40� 05.758 19� 33.860 17054 40� 03.173 19� 21.694 25058 39� 59.014 18� 56.121 910

TABLE II Analytical wavelengths used for the metal determination

Element Wavelength (nm)

Sn 189.989Zn 213.856Pb 220.353Ni 231.604Fe 259.940Cr 267.716Mn 293.930Cu 324.754Cd 228.8

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RESULTS

In Tables III–V the results of metal concentrations found in not-sieved (total) sedi-ments, in <63 mm and >63 mm fractions, respectively, are reported. Total sedimentconcentration values fall in the same range as those found in other coastal area ofMediterranean Sea and Adriatic Sea [4,5,13]. Mean concentrations of Cd, Cu, Zn, Pbare comparable with data reported for Yugoslavian coastal area, while Ni, Cr and Mnresult higher [8,14].

As it can be seen from Table III, Zn, Fe, Ni, Cu, Sn showed the highest concentra-tions in sediments sampled in stations 9 and 10 in front of Drin and Mat mouths, whilelowest values were found in stations 49 and 58 (sampled in the center of Otrantochannel). Spatial distribution of some representative metals in not-sieved sediments,are shown in Fig. 2. All metals have a common trend, showing a decreasing concentra-tion gradient from the coast toward the open sea. It is clear that freshwater inputs areable to influence the distribution of both major elements, such as Fe, and trace elementsin the surface sediments of the Albanian coast. Metal distribution in some casespresents a more homogeneous trend, as found for Fe and Ni, while in others, itshows relative maxima corresponding to Drin and Skumbin mouth (case of Cr) or toDrin mouth (case of Cu, Zn, Mn and Cd).

Rivers are a less important input for Pb. In fact, this metal shows an oppositecoastal – open sea concentration gradient and presents relative concentration minimain correspondence of the river mouths. It is well known that atmospheric fall-out is amajor source of Pb for the marine environment. Enrichment by anthropogenic leadwas observed in the Drin Bay, near Lehze, one of the most important Albanian towns.

The correlation coefficient matrix (p 1%) between the heavy metals contents isreported in Table VI. As it can be seen, Ni, Cr, Cu, Zn and Fe are positively andhighly correlated in the entire area, indicating a common origin. Mn has a low correla-tion with the other elements indicating a different source. Cd presents no correlationwith other studied metals.

The Principal Component Analysis (PCA) statistical method was employed for thisstudy. In Fig. 3 the biplot of PCA, that concerns a matrix in which the 39 sampleshave been considered as objects and metal concentrations as variables, is reported.Two significant components were identified explaining 49 and 17% of the totalvariance. Two groups of objects can be distinguished: in the center of the plot thereare the stations sampled in the northern and middle Albanian coast, characterized byhigher contents of all metals. From this main group of objects, a pool of stations(50, 52–54, 58–60 and 62) is separated, presenting higher Mn, and to a lesser extent,Pb concentrations. This result can be ascribed to a different geological origin ofthese sediment samples: in fact, they resulted richer in carbonate rocks respect to allthe others [15] and it is well known that Mn and Pb have a considerable affinity forcarbonates.

In Fig. 4 the distribution of pelite fraction (<63 mm) percentage in the studied area isreported. Most of the sediments have very high pelite content (>95%), whereas the con-tribution of the coarser grains was significant only in stations 13, 23, 38, 49, 58 with apercentage of 22, 72, 39, 62, 35% respectively.

The homogeneous granulometric composition in most of the coastal stations may beexplained by the relatively weak energy of water mass in the sampling area, whichresults in the settling down of the particles without further resuspension. Moreover

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TABLE III Heavy metals total contents (mg/g, except Fe in mg/g) in total sediments. Data represent the mean±standard deviation of three replicates

Stations Zn Pb Ni Fe Cr Mn Cu Sn Cd

4 107±1 47.5±2.2 327±2 44.4±0.1 183±1 670±6 44.8±1.1 22.2±2.1 0.208±0.0045 102±1 74.3±1.3 294±3 45.2±0.5 202±2 639±2 35.1±0.9 25.2±0.4 0.117±0.0067 118±1 58.7±0.2 314±1 53.5±0.6 201±2 897±1 63.4±1.1 31.5±0.9 0.155±0.0078 97.7±1.3 42.8±1.1 302±3 43.0±1.0 170±2 683±1 60.8±0.9 16.7±1.6 0.109±0.0029 121±1 58.6±1.6 418±6 57.9±0.2 215±2 808±10 130±2 35.3±2.5 0.128±0.01110 128±1 61.9±0.7 396±1 59.3±0.2 224±4 928±4 147±1 16.0±0.8 0.199±0.00911 101±1 46.0±0.8 277±1 44.3±0.2 180±3 594±6 42.6±0.8 22.7±0.8 0.175±0.00912 98.8±1.2 49.3±0.4 279±4 44.0±0.6 174±2 681±13 37.3±0.7 24.9±0.2 0.127±0.00613 75.8±0.9 45.6±1.0 195±1 34.6±0.1 142±1 700±2 26.3±0.3 17.4±0.8 0.069±0.00316 101±2 48.2±0.7 299±3 45.8±0.9 215±2 658±1 36.4±0.1 23.9±0.2 0.162±0.00617 85.7±0.6 36.9±1.7 279±3 37.0±0.5 178±1 560±1 32.4±0.2 8.77±0.5 0.135±0.00619 94.5±0.1 49.4±0.8 363±5 42.8±0.5 214±1 672±3 34.6±0.1 13.5±1.5 0.135±0.00623 48.2±0.2 32.2±0.6 306±4 32.8±0.5 196±3 701±3 14.9±0.2 11.3±0.2 0.141±0.00724 102±5 59.5±0.9 355±2 44.8±1.0 223±2 649±7 39.5±0.1 16.6±0.8 0.126±0.00625 86.8±0.1 48.7±0.4 384±1 41.8±0.2 224±2 682±5 33.8±0.3 11.3±2.2 0.068±0.00326 93.6±0.5 47.1±1.3 398±3 47.4±0.7 253±3 658±1 38.6±0.2 18.6±0.6 0.172±0.00527 87.8±0.8 48.4±0.1 299±1 40.5±0.1 181±2 652±6 35.7±0.1 23.3±1.2 0.180±0.00929 94.4±0.3 51.7±1.1 361±5 47.8±0.1 238±1 777±4 48.8±0.1 – 0.102±0.02430 73.0±0.6 36.5±0.9 321±1 38.0±0.4 204±1 665±5 30.5±0.1 16.7±1.9 0.124±0.06232 86.9±0.4 38.0±0.2 346±2 42.3±0.2 213±4 668±7 38.8±0.7 23.3±1.8 0.158±0.00633 83.5±2.2 36.3±1.5 354±2 41.4±0.7 227±3 720±10 34.9±0.1 14.6±0.5 0.144±0.00634 96.6±0.1 54.5±0.7 346±5 46.6±0.5 221±2 732±1 43.3±0.2 27.3±0.3 0.191±0.01037 79.7±0.4 41.8±0.7 346±1 43.1±0.1 222±4 795±25 44.7±0.5 – 0.055±0.02038 61.6±1.6 26.0±0.5 272±3 31.6±0.3 163±1 619±8 25.2±0.8 12.6±0.6 0.116±0.00539 99.0±0.6 54.8±0.5 331±0.8 45.8±0.2 249±3 750±12 42.0±0.1 22.2±0.2 0.194±0.00342 87.5±2.5 39.9±0.2 359±2 40.3±0.1 193±5 772±27 40.1±0.4 20.5±0.9 0.156±0.00743 89.0±0.7 39.3±0.7 325±1 41.9±1.3 189±2 673±3 38.6±0.8 22.3±0.2 0.224±0.01145 98.4±0.9 65.0±0.7 292±1 40.1±0.2 200±1 1072±7 37.5±0.3 16.2±0.1 0.132±0.00846 93.1±0.3 46.9±0.9 306±3 42.1±0.5 188±2 641±1 36.5±0.5 24.5±0.2 0.269±0.00447 83.1±0.2 44.9±0.5 329±2 38.3±0.2 200±5 641±5 35.9±0.4 11.8±0.9 0.122±0.00948 95.6±0.4 50.7±0.2 303±1 42.6±0.2 224±1 700±7 36.5±0.4 20.5±0.4 0.158±0.01148 BIS 89.3±0.7 45.9±1.1 349±3 40.0±0.4 211±8 686±3 38.8±0.1 27.5±0.6 0.177±0.01249 39.4±0.5 22.0±0.1 107±1 17.4±0.2 53.1±0.6 361±5 14.7±0.1 12.1±0.4 0.753±0.00750 77.8±0.6 41.5±0.7 207±3 36.0±0.3 146±2 1824±42 40.6±0.1 – 0.117±0.04652 77.4±0.2 66.4±0.2 185±1 32.5±0.4 121±1 874±5 29.0±0.1 23.1±1.6 0.139±0.00853 77.3±0.3 72.2±1.0 165±1 32.7±0.1 119±2 958±14 27.1±0.1 24.0±0.6 0.143±0.00754 78.5±0.4 69.4±0.8 146±1 31.4±0.2 103±1 1568±7 33.7±0.1 24.1±0.9 0.143±0.01158 60.1±0.9 36.7±0.3 67.2±1.3 23.4±0.8 53.2±1.0 1042±22 22.8±0.1 20.0±1.2 0.131±0.001

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TABLE IV Heavy metals total contents (mg/g, except Fe in mg/g) in <63mm fraction. Data represent the mean±standard deviation of three replicates

Station Zn Pb Ni Fe Cr Mn Cu Sn Cd

4 103±2 53.0±1.8 339±1 46.0±0.7 202±4 656±8 44.2±0.9 38.5±1.6 0.281±0.0105 95.5±0.1 46.7±0.7 306±6 41.4±0.3 186±1 661±3 39.4±0.9 36.6±2.7 0.219±0.0116 102±2 51.7±1.8 301±1 45.5±0.1 186±5 833±10 54.2±0.4 31.5±1.4 0.230±0.0117 134±1 80.8±0.3 416±4 52.0±0.8 201±6 892±9 74.1±0.9 95.8±2.2 0.406±0.0208 132±12 57.0±0.7 351±1 52.3±1.4 209±6 847±1 77.9±0.3 41.9±1.2 0.590±0.0299 125±1 59.1±1.7 414±3 58.9±0.1 227±5 843±15 139±1.2 51.9±1.4 0.381±0.01910 128±2 80.0±3.9 415±20 63.5±0.8 247±4 915±16 147±1 25.0±1.8 0.288±0.01411 119±1 56.7±0.7 364±2 43.8±0.8 174±3 613±14 50.6±0.4 63.5±0.5 0.216±0.01112 122±0.2 68.0±0.1 393±3 47.3±0.1 189±2 721±26 47.2±0.3 78.5±1.1 0.566±0.02813 90±2 56.9±1.6 227±1 40.5±0.3 183±2 801±9 31.0±0.1 26.2±1.0 0.155±0.00716 96.9±0.1 49.3±1.1 304±1 44.2±0.7 185±2 636±3 38.3±0.1 24.7±0.1 0.203±0.01017 79.2±1.9 56.9±0.5 259±1 37.1±0.6 171±2 551±2 25.7±0.2 20.0±0.8 0.199±0.01018 92.7±1.1 46.6±2.3 337±2 42.0±0.4 209±7 712±9 35.9±0.1 46.3±2.4 0.288±0.01419 91.0±0.1 65.4±2.6 347±1 43.8±0.1 222±2 653±7 30.4±0.1 22.2±2.7 0.225±0.01123 109±1 59.2±0.7 322±1 45.4±0.5 240±1 814±3 35.3±0.1 20.9±0.4 0.179±0.00924 102±1 71.6±1.5 333±10 47.1±0.1 230±4 647±2 36.7±0.3 23.0±3.3 0.224±0.01125 81.6±0.8 58.6±0.7 359±7 41.6±0.4 224±1 639±1 30.0±0.1 20.9±0.4 0.260±0.01526 82.0±0.8 39.9±0.8 358±1 43.3±0.9 206±2 611±6 37.1±0.2 17.6±1.1 0.151±0.00727 102±1 70.2±1.6 341±5 45.8±0.3 220±1 659±19 34.4±0.6 22.3±0.4 0.184±0.00930 78.0±3.3 53.8±1.7 329±7 39.0±0.3 199±5 644±5 28.2±0.2 18.7±1.8 0.167±0.00832 96.1±0.4 49.0±1.9 462±1.1 42.3±0.5 209±4 665±5 44.6±0.1 62.2±0.1 0.286±0.01833 79.2±1.6 41.4±0.8 350±3 42.9±0.3 210±2 741±4 37.1±0.3 19.0±0.5 0.151±0.01034 100±3 73.9±2.1 358±1 46.5±0.6 245±4 733±7 37.5±0.9 22.9±0.7 0.219±0.01538 90.7±1.9 46.2±0.2 408±4 40.0±0.3 194±2 651±7 39.7±0.4 57.4±0.5 0.165±0.01139 92.3±0.5 51.0±0.6 328±7 44.2±0.4 207±2 686±5 42.9±0.2 23.8±0.9 0.216±0.00842 83.4±0.8 39.1±0.2 344±5 38.8±0.4 200±1 734±13 40.6±0.8 36.6±0.8 0.270±0.02043 102±1 47.8±1.1 412±3 42.2±0.6 192±3 671±2 46.4±0.2 59.0±1.2 0.309±0.02245 93.4±0.7 69.2±0.9 288±1 41.7±0.7 194±2 974±18 35.6±0.5 21.5±1.7 0.290±0.02046 111±4 68.9±0.3 412±1 43.5±0.1 206±6 655±2 43.7±0.5 90.1±0.4 0.265±0.01847 84.8±0.3 61.8±1.3 316±5 39.7±0.1 220±3 656±4 33.1±0.6 20.2±1.4 0.187±0.01448 90.8±0.9 53.4±2.3 306±1 42.4±1.1 204±2 701±4 38.5±0.4 25.0±1.0 0.262±0.01848 BIS 92.9±1.4 45.6±1. 7 350±1 40.2±1.0 211±2 684±10 38.8±0.3 33.5±1.1 0.278±0.02049 106±1 58.4±0.3 331±3 37.7±0.4 163±3 593±4 35.6±0.1 70.2±1.6 0.646±0.04552 76.2±0.2 40.8±0.8 178±1 30.2±0.4 110±1 1235±1 31.9±0.3 25.6±0.8 0.284±0.01853 90.7±0.2 51.7±1.0 176±2 31.0±0.2 106±2 2344±14 35.9±1.0 34.0±1.2 0.369±0.02554 82.3±1.7 55.3±1.1 165±1 31.3±0.3 106±2 1301±1 40.1±1.2 37.7±1.2 0.725±0.05058 78.8±1.1 59.4±0.17 97.7±2.2 31.3±0.3 81.4±0.1 1322±24 31.6±0.4 48.0±1.3 0.506±0.035

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TABLE V Heavy metals total contents (mg/g, except Fe in mg/g) in >63mm fraction. Data represent the mean� standard deviation of three replicates

Station Zn Pb Ni Fe Cr Mn Cu Sn Cd

4 69.3±0.6 63.3±0.02 183±1 26.5±0.1 134±4 638±8 64.4±1.8 28.1±0.6 –5 48.2±0.9 2.5±0.01 171±2 19.7±0.4 189±3 678±3 59.2±0.3 – –6 26±0.6 25.7±1.3 144±1 17.9±0.2 103±1 753±17 57.3±0.2 3.05±0.4 1.75±0.057 41.7±0.5 9.52±0.28 158±2 20.4±0.2 70.3±0.9 931±3 47.6±0.4 11.1±0.3 –8 66.1±0.6 50.7±2.3 224±4 28.5±0.3 166±3 924±13 70.4±0.7 33.5±0.5 1.18±0.109 111±1 56.8±0.8 391±7 42.9±0.3 231±5 681±6 336±1.2 41.9±1.2 2.22±0.1110 135±1 51.2±0.3 443±3 52.0±0.1 212±3 729±1 246±3 26.8±1.6 1.03±0.0511 54.2±1.6 29.3±1.5 160±4 22.9±0.8 78.6±0.4 416±10 54.5±0.6 19.5±0.1 2.18±0.1112 26.5±0.3 27.4±0.3 77.9±0.7 11.0±0.5 27.3±0.7 738±2 30.8±0.7 8.34±0.22 –13 23.0±0.2 26.7±0.1 74.4±0.1 14.3±0.2 48.3±0.5 691±1 10.5±0.2 6.91±1.05 1.29±0.0616 60.6±0.8 46.9±0.1 134±1 21.5±0.4 97.3±0.1 479±6 83.0±0.2 11.5±0.1 2.74±0.1417 54.6±0.1 24.0±1.2 193±2 27.5±0.1 95.8±0.7 504±3 35.4±0.2 5.44±0.30 1.21±0.0618 47.6±0.5 17.0±0.8 145±3 20.9±0.2 90.8±0.4 446±1 29.2±0.2 2.40±0.30 0.84±0.0419 81.0±0.1 49.4±1.4 327±1 38.1±0.2 167±4 676±1 118±1 18.1±0.5 0.79±0.0423 21.2±0.1 19.0±0.1 293±2 26.8±0.1 185±2 702±14 5.23±0.12 7.42±0.56 0.65±0.0524 20.9±0.2 44.3±0.2 90.8±1.4 11.8±0.2 77.0±0.9 582±3 9.22±0.4 17.6±1.4 1.12±0.0625 58.2±0.1 32.5±0.5 400±1 34.7±0.4 182±4 614±2 32.4±0.2 12.3±0.2 1.27±0.0626 42.1±0.6 18.8±1.7 323±2 25.0±0.4 166±1 501±6 34.5±0.6 4.1±0.1 0.42±0.0227 13.8±0.2 8.35±1.3 98.7±1.1 14.2±0.5 53.9±3.3 416±4 6.31±0.1 – 0.64±0.0330 43.6±1.2 26.6±0.1 328±4 28.3±0.6 145±5 649±3 19.3±0.1 9.90±0.07 0.63±0.0332 63.5±0.6 39.6±0.4 424±9 33.5±0.4 235±1 523±4 93.2±1.4 13.2±0.3 1.20±0.0333 65.9±0.6 30.6±0.1 361±8 33.8±0.1 250±3 662±1 40.3±0.8 11.4±0.2 1.99±0.1034 34.1±0.1 25.9±2.5 96.2±7.1 9.00±0.7 101±1 363±5 27.2±0.5 16.4±0.7 4.14±0.3338 37.6±0.6 13.5±0.5 249±2 22.1±0.4 135±1 560±8 13.7±0.2 5.69±0.12 0.63±0.0239 48.6±0.5 37.1±2.2 86.7±1.2 11.3±0.1 71.5±0.7 518±3 56.5±0.2 8.7±0.2 –42 48±1 24.2±0.1 301±2 25.8±0.1 202±1 598±1 35.5±0.3 8.94±0.71 1.32±0.0643 53.7±0.9 31.2±0.2 260±1 25.0±0.4 146±2 571±7 87.3±0.8 10.0±0.5 4.08±0.2145 34.0±1.4 53.9±0.6 72.1±2.5 16.2±0.3 54.4±0.1 575±1 13.2±0.1 19.7±0.2 4.38±0.2346 17.3±0.2 19.3±0.2 53.0±0.1 6.35±0.30 10.3±0.3 347±6 21.2±0.2 2.05±0.17 –47 34.7±0.1 25.0±0.1 243±2 23.5±0.2 164±2 578±1 21.2±0.1 12.6±0.3 1.12±0.0648 25.9±0.3 29.8±0.7 73.0±1.0 9.80±0.76 56.9±0.3 466±1 30.6±0.5 6.07±0.58 5.03±0.3448 BIS 60.8±2.2 35.2±1.6 283±2 30.1±0.5 174±2 493±8 50.0±0.1 13.0±0.4 1.40±0.0449 9.64±0.33 10.2±0.8 31.6±0.7 6.45±0.55 – 284±2 5.14±0.09 – 1.26±0.0752 14.9±0.2 17.0±0.2 21.2±0.6 4.70±0.1 4.10±0.1 403±3 11.0±0.1 7.27±0.56 5.09±0.2753 23.0±0.2 22.9±1.1 35.4±0.8 6.59±0.1 22.4±0.3 831±4 13.5±0.2 8.12±0.32 5.71±0.3254 60.7±0.1 29.7±2.9 59.0±0.5 21.9±0.1 40.0±0.3 653±11 39.5±0.1 14.9±1.02 4.82±0.2158 21.3±0.1 6.3±0.7 15.3±0.1 9.96±0.3 15.6±1.3 568±3 7.06±0.1 – 0.82±0.01

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as it can be seen from the graph (Fig. 4), stations characterized by lowest pelite percen-tage are situated more toward offshore respect to the others, or are not interested byriver inputs, as for example, station 49.

As regards to the effect of the particle size on the distribution of metals in the sedi-ments, in Fig. 5 the distributions of Cr, Ni and Cu, in <63 and >63 mm fractionsrespectively, are reported.

FIGURE 2 Spatial distribution of Fe, Ni, Cr, Cu, Mn, Pb in total sediments. Metal concentrations areexpressed in mg/g, except for Fe (mg/g).

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Generally, the pelitic fraction contained a larger amount of all the studied metals,except for Cu and Cd. As it can be seen, distribution of metals in general overlapsthe trend showed by the pelite distribution, because of the high contribution of thisfraction to the sediments. As previously reported, the lowest metal content wasfound in stations 49 and 58, which have higher coarse grain content. On the other

FIGURE 3 Biplot of principal component analysis (PCA).

TABLE VI Correlation matrix between metal concentrations in sediments

Cr Cu Fe Mn Ni Pb Sn Zn Cd

Cr 0.43 0.85 0.02 0.97 0.27 0.34 0.59 �0.08Cu 0.43 0.74 0.20 0.52 0.37 0.32 0.71 �0.03Fe 0.85 0.74 0.13 0.84 0.52 0.43 0.89 �0.14Mn 0.02 0.20 0.13 �0.03 0.41 0.01 0.16 �0.20Ni 0.97 0.52 0.84 �0.03 0.19 0.37 0.57 �0.03Pb 0.27 0.37 0.52 0.41 0.19 0.41 0.68 �0.18Sn 0.34 0.32 0.43 0.01 0.37 0.41 0.42 0.22Zn 0.59 0.71 0.89 0.16 0.57 0.68 0.42 �0.18Cd �0.08 �0.03 �0.14 �0.20 �0.03 �0.18 0.22 �0.18

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hand, Cu exhibited the highest values in the >63 mm fraction, particularly at Drin rivermouth. Data concerning the mineralogical composition of the sediments of Drin Bayreveal a significant percentage of organogenic material [15,16], which can influencethe enrichment of Cu, because of its high affinity for organic material. This behaviorhas been already reported for this metal [8].

Cd presents higher values in coarse fraction respect to the fine one, particularly instations 52, 53, 54. As previously said, these sediment samples resulted rich in carbonaterocks. Several authors reported that increased concentrations of cadmium in sedimentsobserved in different areas of the Adriatic Sea were related to an increasing percentageof carbonate fraction [8,17]. Our results seem to confirm this trend.

High Cd concentrations were also found in Drin Bay sediments, rich in organogenicmaterial. Because of its nutrient type behavior, Cd presents a certain affinity for organicsubstances, which can justify the high values found [14].

The enrichment of Ni and other elements specific for basic eruptive rocks is foundeverywhere in the Dinaric chain area [14]. The high concentration values of Cr andNi found in sediments collected in front of river mouths can be explained by takingin to account the geological composition of the hydrographic basins of Albania. Infact, rivers flow in serpentine and ultrabasic soils that generate an enrichment of

FIGURE 4 Distribution of pelite fraction (<63 mm) percentage in the studied area.

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nickel and chromium in sediment, especially at the mouth and along the coast. Thesame feature was observed in previous studies concerning the distribution of Cr andNi in Ligurian Sea sediments, which present the same geological characteristics asAlbanian sediments [17–19]. Moreover, also the contribution of mining industry dis-charges to Cu, Ni and Cr distribution in estuarine areas has to be considered.

FIGURE 5 Distributions of Cr, Ni and Cu, in <63 and >63 mm fractions. Metal concentrations areexpressed in mg/g.

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In particular, in Elbasan region, where river Skumbin flows, in the past years,smelters have been estimated to process 35 000 t ferrochrome and the majority of the1.0Mt of iron–nickel ores mined from Librazhd-Progradec district [20]. Munelle andGiejan, which are two of the more important copper deposits in Albania, are part ofthe hydrographic basin of the Drin river. The effects of the discharging can be clearlyobserved from the distribution of metals reported in Fig. 5.

CONCLUSIONS

The distribution of the studied metals in coastal sediments of Albania showed the influ-ence of river inputs. All metals, apart from Cu and Cd, resulted mainly associated tothe pelitic fraction, which contributed for more than 95% to the grain size of coastalsediments.

These two metals are probably associated with coarser organic debris, and in the caseof Cd even with carbonates. Concentration values fall in the range reported for Dinaricchain sediments, revealing an essentially natural origin of most of the metals studied.Moreover, in some selected areas, such as the Drin and the Skumbinit Bay, an antro-pogenic input of Cr, Fe, Ni and Cu can be observed, as a result of discharging of minesand smelter activities.

Acknowledgments

This research is part of a two-year multidisciplinary research project entitled ‘‘InterregII Italia-Albania’’ financially supported by Regione Puglia and National Interuniver-sity Consortium for Marine Sciences (CoNISMa).

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