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Heavy Metal Signature and Environmental Assessment of Nearshore Sediments: Port of Koper (Northern Adriatic Sea)

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Heavy Metal Signature and Environmental Assessment of Nearshore Sediments: Port of Koper (Northern Adriatic Sea) geosciences Article Heavy Metal Signature and Environmental Assessment of Nearshore Sediments: Port of Koper (Northern Adriatic Sea) Nastja Rogan Šmuc 1,*, Matej Dolenec 1, Sabina Kramar 2 and Ana Mladenovi´c 2 1 Department of Geology, Faculty of Natural Sciences and Engineering, University of Ljubljana, Aškerˇceva12, 1000 Ljubljana, Slovenia; [email protected] 2 Slovenian National Civil Engineering Institute, Dimiˇceva12, 1000 Ljubljana, Slovenia; [email protected] (S.K.); [email protected] (A.M.) * Correspondence: [email protected]; Tel.: +386-1-777-2731 Received: 30 August 2018; Accepted: 23 October 2018; Published: 31 October 2018 Abstract: Heavy metal abundance and potential environmental risks are reported for surface sediments (n = 21) from the Port of Koper area, Republic of Slovenia. The enrichment factor (EF) indicates minor enrichment in arsenic (As), cadmium (Cd), copper (Cu), molybdenum (Mo), lead (Pb), antimony (Sb), and zinc (Zn), moderately to severely enriched with nickel (Ni). The trace metal chemistries, in the context of sediment quality guidelines (SQG), imply adverse threshold effect concentrations (TEC) and probable effect concentrations (PEC), for Ni only. Sediment sequential leaching experiments demonstrated that the majority of heavy metals were of natural lithogenic origin and low bioavailability. The heavy metals’ potential for “Risk Assessment Code” values exhibited no or low anthropogenic environmental burden, with the exception of Mo. Keywords: port sediments; heavy metals; chemical speciation; risk assessment; Northern Adriatic Sea 1. Introduction Coastal environments are often environmentally burdened by port and traffic infrastructure, large industrial areas, urban settlements, and tourism activities. Thus, the flux of various anthropogenic contaminants, especially heavy metals, are discharged and accumulated into marine coastal ecosystems [1–5]. Heavy metals are among the most persistent pollutants in the aquatic ecosystem, and they are not nullified from water by self-purification [6]. Sediments are a significant repository for heavy metals present in the upper water column and, in addition, they act as a secondary source. Due to a series of physical and biochemical processes (e.g., diagenetic, bioturbation, and resuspension processes, currents and waves, dredging, and shipping activities) the remobilisation of heavy metals occurs at the sediment water interface, affecting overlying water, aquatic organisms, and threatening human health [7–9]. The appearance and loading of heavy metals in vulnerable marine environments originates from both anthropogenic and natural processes, e.g., geological background [10–12]. A precise designation of anthropogenically/geogenically derived heavy metals is of importance in the evaluation and prevention of the pollution burden, and in planning the appropriate remedial action. Further on, the mobility potential and bioavailability of heavy metals in the surrounding environments is heavily dependent on their specific chemical forms and type of bindings. The geochemical characteristics of sediment from the Gulf of Trieste (North Adriatic Sea, Italy) have been studied in detail by several groups [13–23] over a significant period of time. Few studies, however, have been conducted on the adjacent Adriatic sediments of the Koper Bay, especially from the Port of Koper [22–24]. Thus, precisely defined anthropogenic/geogenic character, heavy metal mobility Geosciences 2018, 8, 398; doi:10.3390/geosciences8110398 www.mdpi.com/journal/geosciences Geosciences 2018, 8, x FOR PEER REVIEW 2 of 18 Geosciences 2018, 8, 398 2 of 18 the Port of Koper [22–24]. Thus, precisely defined anthropogenic/geogenic character, heavy metal mobility potential, the application of sediment quality guidelines (SQG), and eligible statistical potential,analyses in the Koper application Bay sediments, of sediment was undertaken quality guidelines for the first (SQG), time. and eligible statistical analyses in KoperKoper/Capodistria Bay sediments, was is a undertaken small coastal for city the located first time. in Slovenia´s Mediterranean region. Due to its geographicKoper/Capodistria location, it is is ainfluenced small coastal by various city located anthropogenic in Slovenia ´contaminations Mediterranean sources region. from Due an to itsinternational geographic port—the location, Port it is of influenced Koper, an by industrial various anthropogeniczone with a chemical contamination factory, sourcesagriculture, from and an internationalviticulture developed port—the in Portthe hinterland of Koper, anof the industrial city. The zone port with is one a chemicalof the biggest factory, and agriculture, most important and viticultureports in the developed Northern inAdriatic the hinterland Sea and, of thus, the city. represents The port a ismajor one ofcontaminant the biggest source and most to sediments important portsfoundin in thethe NorthernKoper Bay. Adriatic Additionally, Sea and, in thus,the framework represents of a the major Global contaminant Environmental source Facility to sediments (GEF) foundproject, in sediments the Koper from Bay. the Additionally, Koper Bay have in the already framework been ofmarked the Global as a contamination Environmental “hot Facility spot”. (GEF) Due project,to massive sediments cargo and from intense the Koper port activities, Bay have we already have also been included, marked asin aour contamination study estimating “hot heavy spot”. Duemetals’ to massiveanthropogenic cargo and impact, intense Mo, port Au, activities, and Sb. Mo we havecan be also introduced included, into in our the study environment estimating through heavy metals’its presence anthropogenic in steel, catalysts, impact, Mo,dyes, Au, lubricants; and Sb.Mo (2) canraw be Au introduced gold represents into the an environment urgent material through for itsjewellers; presence and in (3) steel, Sb is catalysts, type-metal dyes, alloy lubricants; (with Pb to (2) prevent raw Au corrosion); gold represents we can anfind urgent it also material in electrical for jewellers;applications, and semiconductors, (3) Sb is type-metal flameproof alloy (with pigments, Pb to prevent and glass corrosion); [25]. we can find it also in electrical applications,In this context, semiconductors, the main objectives flameproof of the pigments, present and study glass were [25 as]. follows: (1) to determine detailed mineralogicalIn this context, and elemental the main content objectives in the of the surface present sediments study were of the as Port follows: of Koper (1) to area; determine (2) to estimate detailed mineralogicalthe degree and and distribution elemental contentof heavy in themetal surface contamination sediments ofin thethePort sediments of Koper using area; contamination (2) to estimate theindices, degree sediment and distribution quality guidelines of heavy (SQGs) metal and contamination various methods in the sedimentsof statistical using analysis; contamination and (3) to indices,define the sediment possible quality natural guidelinesand/or anthropogenic (SQGs) and sources various and methods pathways of statistical of heavy analysis;metals, as and deduced (3) to definefrom a thesequential possible extraction natural and/or procedure. anthropogenic sources and pathways of heavy metals, as deduced from a sequential extraction procedure. 2. Materials and Methods 2. Materials and Methods 2.1. Geographical and Geological Setting of the Study Area 2.1. Geographical and Geological Setting of the Study Area The Port of Koper was established in 1957, and lies in a semi-enclosed basin in the shallowest part Theof the Port Adriatic of Koper Sea waswith established a maximum in depth 1957, andof approximately lies in a semi-enclosed 24 m (Figure basin 1). in It theis the shallowest deepest partindentation of the Adriatic into the SeaEuropean with a continent, maximum providing depth of approximatelyan accessible Mediterranean 24 m (Figure1 port). It iswith the a deepest railway indentationtrack and road into links the European for intermodal continent, and providingcombined antransport. accessible The Mediterranean Port of Koper port is a withmultipurpose a railway trackport with and roadinternational links for trade intermodal connections. and combined The current transport. annual The maritime Port of throughput Koper is a multipurpose is over 15 million port withtonnes. international trade connections. The current annual maritime throughput is over 15 million tonnes. Figure 1. Geographical map of the study area. Geosciences 2018, 8, 398 3 of 18 Geosciences 2018, 8, x FOR PEER REVIEW 3 of 18 The Bay of Koper and its hinterland structurally belong to to the the Adriatic-Apulian Adriatic-Apulian foreland foreland [26,27]. [26,27]. In thethe Mesozoic,Mesozoic, thethe areaarea belongedbelonged toto thethe DinaricDinaric CarbonateCarbonate Platform,Platform, mainlymainly withwith shallow-watershallow-water carbonate sedimentation while,while, inin the Kenozoic, the area became part of the advancing foreland basin with flyschflysch sedimentationsedimentation [[28].28]. In the Quaternary, the investigated area was an environmentenvironment with fluvialfluvial sedimentationsedimentation up up until until 8000 8000 years years ago, ago, when when the mainthe main sea transgressionsea transgression occurred occurred [24,29 ].[24,29]. From thatFrom time that onward, time onward, the bay the has bay been has characterised been characterised by a sedimentation by a sedimentation of mainly
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