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Impact of a Coastal Ferronickel Metallurgy on the Marine Ecosystem: the Case of Larymna Bay

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Impact of a Coastal Ferronickel Metallurgy on the Marine Ecosystem: the Case of Larymna Bay NATIONAL AND KAPODISTRIAN UNIVERSITY OF ATHENS SCHOOL OF SCIENCES POST GRADUATE COURSE IN OCEANOGRAPHY AND MARINE ENVIRONMENTAL MANAGEMENT Ph. D. THESIS Impact of a coastal ferronickel metallurgy on the marine ecosystem: The case of Larymna Bay LEILA BORDBAR MARINE BIOLOGIST ATHENS FEBRUARY 2017 Ph. D. THESIS Impact of a coastal ferronickel metallurgy on the marine ecosystem. The case of Larymna bay LEILA BORDBAR Α.Μ.: 052 SUPERVISOR: Emmanuel Dassenakis, Professor, Department of Chemistry, National and Kapodistrian University of Athens SUPERVISORY COMMITEE: Emmanuel Dassenakis, Professor NKUA Persefoni Megalofonou, Associate Professor, Dept. of Biology, NKUA Vasiliki- Angeliki Catsiki, Research Director, HCMR EXAMINING COMMITEE Emmanuel Dassenakis, Professor, Dept of Chemistry, NKUA Persefoni Megalofonou, Associate Professor, Dept. of Biology, NKUA Dr. Angeliki-Vasiliki Catsiki, Research Director, HCMR Serafeim Poulos, Professor, Dept of Geology and Geoenvironment, NKUA Evangelia Krasakopoulo, Associate Professor, Dept. of Marine Sciences, University of Aegean Dr. Eleni Kaberi, Researcher, HCMR Dr. Nomiki Simboura, Research Director, HCMR DATE OF EXAMINATION 03/02/2017 ABSTRACT Larymna Bay in N. Evoikos hosts a leading mining and metallurgical company of Greece which is among the biggest of this type in Europe. Apart from the raw materials produced from domestic ores, large quantities of ferronickel by- product are also produced. The slag has been dumped in N. Evoikos in a government authorized area since 1969. This study was carried out accordingly to previous research and monitoring campaigns in this area to investigate the long term impact of the dumped slag to the marine environment including the deposition area and the coastline. For these purposes two suits of samples were collected in this area; one from the deposition area which is defined as offshore and one from the coastline, assigned as inshore (near shore area) where the smelting plant is located. Surface sediment, surface and bottom water (1 m above the sediment), along with three crustacean species (Munida rugosa, Liocarcinus depurator and Nephrops norvegicus) were collected from the slag dumping area and a reference station (Offshore area) for three years from 2009 to 2011. From the coastline (Inshore area), water samples were collected and two species of gastropods (Phorcus turbinatus and Patella caerulea) were handpicked from seven stations along the shore for four seasons representing a possibly contaminated area. In addition gastropods samples were also collected from two other stations far from the smelting plant possibly representing reference conditions. For biomarker analysis, crustacean samples (Munida rugosa) from the offshore area, gastropod samples (Ph.turbinatus) and one fish species (Sparus aurata) from the inshore area were taken. Ni, Cr, Fe, Mn, Al, Zn, Cu and Hg measured in the surface sediment samples. All the mentioned metals expect for Al and Hg were determined in the seawater samples, in the three different tissues of crustaceans (gill, muscle and exoskeleton) and in the soft tissue of gastropods. In terms of biomarkers; AChE (acetylcholinesterase), CAT (Catalase) and GST (glutathione-s-transferase) were analyzed in the muscle, hepatopancreas (M.rugosa), liver (fish), eye and gill of biota samples. The results showed high concentrations of Ni, Fe, Cr and Mn in seawaters and sediment samples from both the contaminated and reference areas. The concentrations of Cu and Zn which are mostly attributed to other anthropogenic sources of pollution are also relatively high in seawater samples. The Enrichment factors (EF) and Geo- Index (Igeo) calculated from bibliographic data of a deep core sample from the area 1 and the average shale showed that area is heavily impacted from the metals related to the smelting plant and in particular Cr. The concentrations of two metals, Ni and Cr, in the sediment are higher than the US EPA criteria and could definitely cause adverse biological effects. However, the dissolved concentrations of these metals in the sea water were lower than the chronic and acute toxicity concentrations of USEPA standards. Quite high concentrations of all metals were detected in the gill tissue of all the crustacean samples from both areas. Besides, the higher concentrations of metals found in female specimens are mostly attributed to the physiological needs of females during the reproduction cycle and their specific strategy of food uptake during ovigerous cycle. The concentration of all metals in the soft tissues of all the crustacean species from the off shore area except for Mn are lower than the international standards proposed by FAO, 1993, WHO,1998 and USDA, 2009. High concentrations of all metals related to the smelting plant were also detected in the gastropod samples. The results show that Patella is a good indicator for Mn and Phorcus seems to better accumulate Fe, Ni and Zn. The clear inhibition of AChE activities in the samples from the contaminated area in comparison to those from the reference area showed that this enzyme responds well to metal pollution. GST showed obvious increased activities in the liver of S.aurata samples from the contaminated area. However no significant differences were found in the activities of GST and CAT in M. rugosa and Ph. turbinatus. Finally, the long term slag discharging in this area has highly impacted not only the sediments, but has also caused elevated concentrations of metals bioaccumulated by marine organisms. Due to the severe impact of the smelting plant to the marine organisms based on the findings from this study and the previous researches carried out in this area, it is suggested that regular monitoring of this area is implemented, focusing mostly to edible marine organisms. Furthermore, the assessment of possible impacts of the smelting plant on human health should be seriously taken into consideration, planned and executed. SUBJECT AREA: BIOGEOCHEMICAL OCEANOGRAPHY KEYWORDS: heavy metals, bioaccumulation, crustaceans, gastropods, biomarkers 2 Περίληψη ΢ηνλ Β. Δπβνηθό θόιπν, ζηε Λάξπκλα, βξίζθεηαη κηα από ηηο ζεκαληηθόηεξεο εμνξπθηηθέο θαη κεηαιινπξγηθέο βηνκεραλίεο ηεο Διιάδα (ΛΑΡΚΟ) θαη κηα απν ηηο κεγαιύηξεο ηνπ είδνπο ηεο ζηελ Δπξώπε. ΢ην εξγνζηάζην απηό νξπθηή πξώηε ύιε από νξπρεία ηεο Έπβνηαο θαη ηεο Β. Διιάδαο πθίζηαηαη επεμεξγαζία θαη παξάγεηαη ζηδεξνληθέιην πξνο εμαγσγή. Δπηπιένλ όκσο παξάγνληαη θαη πνιύ κεγάιεο πνζόηεηεο παξαπξντόληνο (ζθνπξηά). Η ζθνπξηά απνξξίπηεηαη ζηε ζάιαζζα από ην 1969 ζε θαζνξηζκέλε από ηελ πνιηηεία πεξηνρή. Η παξνύζα κειέηε πξαγκαηνπνηήζεθε αθνινπζώληαο θνληηλή (παξόκνηα;) κεζνδνινγία κε παιηόηεξεο κειέηεο θαη πξνγξάκκαηα παξαθνινύζεζεο ηεο ξύπαλζεο ζηελ ζπγθεθξηκέλε πεξηνρή. ΢θνπόο ηεο εξγαζίαο ήηαλ λα δηεξεπλήζεη ηε καθξνρξόληα επίδξαζε ηεο απνξξηπηόκελε ζθνπξηάο ζην ζαιάζζην πεξηβάιινλ, ηόζν αθξηβώο ζηελ πεξηνρή απόζεζεο όζν θαη ζηελ αθηνγξακκή. Πξνθεηκέλνπ λα επηηεπρζεί ν ζθνπόο ηεο εξγαζίαο ζπιιέρζεζαλ δείγκαηα ηόζν από ηελ πεξηνρή απόζεζεο (αλνηρηά) όζν θαη από ηελ αθηνγξακκή (παξάθηηα) όπνπ βξίζθεηαη θαη ην εξγνζηάζην. Από ηελ αλνηρηή ζαιάζζηα πεξηνρή (ζεκεία απόζεζεο θαη από έλα ζηαζκό αλαθνξάο) ιήθζεζαλ δείγκαηα επηθαλεηαθνύ ηδήκαηνο, ζαιαζζηλνύ λεξνύ από ηελ επηθάλεηα θαη ηνλ ππζκέλα (1 κ πάλσ από ην ίδεκα) θαζώο θαη δείγκαηα νξγαληζκώλ από ηξία είδε θαξθηλνεηδώλ (Munida rugosa, Liocarcinus depurator and Nephrops norvegicus) γηα ηξία έηε (2009 έσο 2011). Από ηελ παξάθηηα πεξηνρή ζπιιέρζεθαλ δείγκαηα λεξνύ θαη νξγαληζκώλ (γαζηεξόπνδα Phorcus turbinatus θαη Patella caerulea) ζε ηέζζεξηο επνρηαθέο δεηγκαηνιεςίεο από 7 ζηαζκνύο θνληά ζην εξγνζηάζην πνπ αληηπξνζσπεύνπλ ζπλζήθεο πςειήο ξύπαλζεο θαη δύν ζηαζκνύο αξθεηά καθξηά πνπ αληηπξνζσπεύνπλ ζπλζήθεο αλαθνξάο. Γηα ηηο αλαιύζεηο βηνδεηθηώλ επηιέρζεθαλ δείγκαηα Munida rugosa από ηελ αλνηρηή ζαιάζζηα πεξηνρή θαη δείγκαηα Ph.turbinatus από ηελ παξάθηηα θαζώο θαη έλα είδνο ςαξηνύ από θνληηλή ηρζπνθαιιηέξγεηα (Sparus aurata). ΢ηα επηθαλεηαθά ηδήκαηα κεηξήζεθαλ ηα κέηαιια Ni, Cr, Fe, Mn, Al, Zn, Cu θαη Hg. Δπίζεο όια απηά ηα κέηαιια εθηόο ηνπ Al θαη Hg πξνζδηνξίζηεθαλ ζηα δείγκαηα ζαιαζζηλνύ λεξνύ, ζε ηξείο δηαθνξεηηθνύο ηζηνύο ησλ θαξθηλνεηδώλ (βξάγρηα, κπο θαη εμσζθειεηόο) θαη ζην καιαθό ηζηό ησλ γαζηεξόπνδσλ. Ωο πξνο ηνπο βηνδείθηεο, πξνζδηνξίζηεθαλ νη AChE (αθεηπινρνιηλεζηεξάζε), CAT (Καηαιάζε) and GST (κεηαθνξάζε ηεο γινπηαζεηόλεο) ζην κπ θαη ην επαηνπάγθξεαο ηνπ (M.rugosa) θαζώο θαη ζε δείγκαηα από ζπθώηη, κάηηα θαη βξάγρηα ησλ ςαξηώλ. 3 Σα απνηειέζκαηα έδεημαλ αξθεηά πςειέο ζπγθεληξώζεηο Ni, Fe, Cr θαη Mn ζην ζαιαζηζηλό λεξό θαη ηα ηδήκαηα ηόζν από ηε ξππαζκέλε πεξηνρή όζν θαη από ηηο πεξηνρέο αλαθνξάο. Οη ζπγθεληξώζεηο Cu θαη Zn, είλαη επίζεο ζρεηηθά πςειέο ζην ζαιαζζηλό λεξό θαη απνδίδνληαη ζε άιιεο αλζξσπνγελείο δξαζηεξηόηεηεο. Οη ζπληειεζηέο εκπινπηηζκνύ (EF) θαη Geo-Index (Igeo) ζηα ηδήκαηα πνπ ππνινγίζηεθαλ από βηβιηνγξαθηθά δεδνκέλα από παιηό δείγκα ππξήλα ηεο πεξηνρήο (ζε πάλσ από 50 cm βάζνο) θαη από ηηο πεξηεθηηθόηεηεο ηνπ κέζνπ θινηνύ έδεημαλ όηη ε πεξηνρή είλαη ηδηαίηεξα επηβαξπκέλε κε κέηαιια πνπ έρνπλ ζρέζε κε ηε κεηαιινπξγηθή δξαζηεξηόηεηα θαη ηδηαίηεξα κε Cr. Οη ζπγθεληξώζεηο ηνπ Ni θαη Cr ζην ίδεκα είλαη πςειόηεξεο από ηα αλώηεξα θξηηήξηα πνηόηεηαο ηεο US EPA θαη άξα κπνξνύλ κε βεβαηόηεηα λα πξνθαιέζνπλ επηβιαβείο βηνινγηθέο επηπηώζεηο ζε νξγαληζκνύο. Πάλησο νη ζπγθεληξώζεηο ησλ κεηάιισλ απηώλ ζην ζαιαζζηλό λεξό είλαη ρακειόηεξεο από ηα όξηα ρξόληαο θαη νμείαο ηνμηθόηεηαο ηεο USEPA. Μεηξήζεθαλ αξθεηά πςειέο ζπγθεληξώζεηο όισλ ησλ κεηάιισλ ζηα βξάγρηα ησλ θαξθηλνεηδώλ
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