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Assessment of Groundwater Contamination by Hexavalent Chromium and Its Remediation at Avlida Area, Central Greece*

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Assessment of Groundwater Contamination by Hexavalent Chromium and Its Remediation at Avlida Area, Central Greece* Project 35 :17 2/14/11 9:00 PM Page 175 Hellenic Journal of Geosciences, vol. 45, 175 Assessment of groundwater contamination by hexavalent chromium and its remediation at Avlida area, Central Greece* Antonia Moraki Faculty of Geology & Geoenvironment, University of Athens, Panepistimiopolis, Ano Ilissia, Athens 15784 ABSTRACT: Trivalent chromium [Cr(III)] is an essential trace element involved in stimulation of enzymes, peripheral action of insulin and lipid metabolism. In contrast, hexavalent chromium [Cr(VI)] is toxic, carcinogenic and teratogenic, since Cr(VI) can enter the body when people breathe air, eat food, or drink water. In the present study, which is part of my M.Sc. Thesis, some analytical data concerning the contamination of the ground - water at the area of Avlida are given, as well as the results of the remediation testing, aiming to the assessment of the contamination in groundwater at that area, and propose ways for the water remediation. There is a wide variability in Cr concentration in groundwater from domestic, irrigation and municipal wells, ranging from 13 to 160 µg L-1 and a heterogeneous distribution, although sampling locations are close to each other spatially. Relatively, high concentrations of Na and B, Li, As and Se in groundwater and a high positive correlation between the latter elements and Na reflect sea water intrusion into the Avlida aquifer. The remedi - ation testing using high-Si and relatively low pH fly ash from Megalopolis confirmed that this material is very efficient for uptaking Cr (VI) from water. Also, the present study demonstrated the ability of EDC-M to directly reduce Cr(VI), suggesting that it may provide a significant contribution for in situ remediation of water and soil contaminated by Cr(VI). Key words: Groundwater contamination, hexavalent chromium, Avlida, Greece. ΠΕΡΙΛΗΨΗ : Το τρισθενές χρώµιο [Cr(III)] είναι ένα ιχνοστοιχείο απαραίτητο για την δράση των ενζύµων και τον µεταβολισµό της γλυκόζης και των λιπιδίων. Αντίθετα, το εξασθενές χρώµιο [Cr(VI)] είναι τοξικό, καρκινογόνο και δηµιουργεί τερατογενέσεις, διότι το Cr(VI) µπορεί να εισχωρήσει στον ανθρώπινο οργανισµό µε τον αέρα, την τροφή ή το νερό. Στην παρούσα µελέτη, η οποία αποτελεί µέρος της ∆ιπλωµατικής Εργασίας Ειδίκευσης, δίνονται αρκετά αναλυτικά δεδοµένα σχετικά µε την αποτίµηση του βαθµού ρύπανσης στον υδροφόρο ορίζοντα της περιοχής της Αυλίδας, καθώς επίσης τα αποτελέσµατα από δοκιµές χρησιµοποιώντας ιπταµένη τέφρα και το οργανικό υλικό EDC-M για την αποµάκρυνση του Cr(VI) από το νερό, ώστε να προταθούν τρόποι για την αποκατάσταση του υδροφόρου ορίζοντα. Τα αποτελέσµατα έδειξαν ότι υπάρχει µεγάλη διακύµανση στην συγκέντρωση του χρωµίου στο νερό από γεωτρήσεις του ∆ήµου, ύδρευσης και άρδευσης που κυµαίνονται από 13 έως 160 ppb, και µία ανοµοιογενής κατανοµή παρ’ όλο που µπορεί να βρίσκονται σε γειτονικά σηµεία της περιοχής. Οι σχετικά µεγάλες συγκεντρώσεις Na, B, Li, As και Se που προσδιορίστηκαν στον υδροφόρο ορίζοντα της Αυλίδας, και η καλή θετική σχέση µεταξύ των τελευταίων στοιχείων µε το νάτριο υποδηλώνουν διείσδυση θαλασσινού νερού στον υδροφόρο ορίζοντα. Οι δοκιµές µε ιπτάµενη τέφρα από την Μεγαλόπολη, η οποία χαρακτηρίζεται από σχετικά µεγάλη περιεκτικότητα πυριτίου και χαµηλό pH επιβεβαίωσαν την πολύ αποτελεσµατική της δράση στην αποµάκρυνση του Cr (VI) από το νερό. Επίσης, οι δοκιµές µε το EDC-M έδειξαν ότι επετεύχθη η αναγωγή του Cr(VI) στο νερό, σε µικρό χρονικό διάστηµα, και ότι θα µπορούσε να χρησιµοποιηθεί για in situ δοκιµές στο νερό και το έδαφος που έχουν ρυπανθεί από Cr(VI). Λέξεις κλειδιά: υδροφόρος ορίζοντας, ρύπανση, εξασθενές χρώµιο, αποκατάσταση, Αυλίδα, Ελλάδα. INTRODUCTION the manufacture of alloys, corrosion inhibitory paints, wood preservatives, mordants and fixatives for dyes and tanning, Heavy metal impact on the ecosystems is dependent on their photographic sen-sitizers and pigment for rubber and ceram - concentration and speciation. The various chemical and bio - ics, and as anticorrosive in cooking systems and boilers ( COT - logical changes that chromium undergoes in the environment MAN et al ., 2004). Ηigh concentrations of chromium are depend on the conditions that govern its speciation and other toxic, carcinogenic and teratogenic. Cr(VI) can enter the activities. The solubility and adsorption by soil and sediments body when people breathe air, eat food, or drink water. depend on the form of chromium species. Within the ranges Cr(VI) is also found in house dust and soil. Certain Cr(VI) of redox potentials and pH commonly found in soils, compounds have been found to be carcinogenic in humans, chromium exists predominantly as oxyanions of Cr(III) and in particular into the lung and that it is dependent on high ex - Cr(VI). Chromium is an essential trace element involved in posures ( ASMATULLAH et al. , 1998). Hexavalen chromium stimulation of enzymes, peripheral action of insulin, lipid me - compounds are emitted into the air, water, and soil by a num - tabolism and possibly in the stabilization of nucleic acids ber of different industri al activities , for instance during metal (ANDERSON et al ., 1983; ANDERSON , 1998; VINCENT , 2000). finishing processes. In the air, chromium compounds are Trivalent chromium [Cr (III )] occurs naturally in rocks, soil, present mainly as fine dust particles that eventually settle plants, animals, and volcanic emissions. Chromium is used in over the land and water. The U.S. Environmental Protection * Αποτίµηση της ρύπανσης του υδροφόρου ορίζοντα στην περιοχή της Αυλίδας , Κεντρική Ελλάδα , από εξασθενές χρώµιο και η αποκατάστασή του Project 35 :17 2/14/11 9:00 PM Page 176 176 Antonia Moraki Fig. 1. Sketch map showing the sampling locations. Agency (USEPA) regulates chromium releases into the en - formations comprise continental sediments consisting of con - vironment. Directive 98/83/EC has established a maximum glomerates with small intercalations of marl, marl limestone, permissible limit of 50 mg / l or ppb for total chromium in metaclastic schist, sandstone, clays and flysch. The lowest drinking water, likewise the World Health Organization. parts of the basin consist of alternations of yellow lake marls The crucial environmental problem in the Assopos basin, and marl limestones hosting thin black lignite horizons ( PA- due to intense industrial activity in the area since 1969 is well PANIKOLAOU et al ., 1988; CHATOUPIS & F OUNTOULIS , 2004). known since 2007. The detected hexavalent chromium This sequence is dominant in the region of Oropos- reaches levels of more than 150 µg/L in dinking water - over Sykamino-Chalkoutsi-Avlona-Avlida, although there is vari - 3 times the European Union’s 50- µg/L limit for total ation of the thickness of both conglomerates and the lake to chromium in a groundwater monitoring well. Research on shallow sea fine-grained sediments. Although peridotites, as Cr(VI) in the Assopos basin (covering an area of approxi - dismembered parts of ophiolite complexes are rare through - mately 700 km 2) and central Euboea is ongoing at the Uni - out the Assopos basin the presence of chromite and other Cr- versity of Athens, Department of Geology and Geoenvironment bearing minerals may be present. (MEGREMI , 2010; VASILATOS et al ., 2008, 2010; ECONOMOU - The Vathi-Faros aquifer at the area of Avlida is located ELIOPOULOS et al, 2010). Also, more efforts are being made within continental sediments consisting of conglomerates by the above research team, either itself, or in cooperation with small intercalations of marl, marly limestone, meta - with other researchers for experimenting in some low cost clastic schist, sandstone, clays and flysch ( GIANOULOPOULOS , remediation techniques ( ITSKOS et al ., 2010 a, b, KOUKOUZAS 2008). The ground water samples were representative of do - et al ., 2010). mestic, irrigation and municipal wells (of a depth ranging be - In the present study some analytical data concerning the tween 150 and 200 meters) of the Avlida area (Fig. 1). contamination of the groundwater at the area of Avlida are presented, as well as the results of remediation testing aim - MATERIALS AND METHODS ing atc the assessment of the groundwater and soil contami - nation , the determination of Cr-hosts, at the Avlida area, as a Groundwater and soil s amples were collected from the Avl - contribution to the effective influence of industry versus nat - ida area (Fig. 1) during November 2008. Ground water sam - ural process, and the ways for water remediation. ples were representative of domestic, irrigation and municipal wells of this area. The physicochemical parameters GEOLOGICAL CHARACTERISTICS of the water samples (pH, Eh, CND, TDS) were measured OF THE STUDY AREA using a portable Consort 561 Multiparameter Analyzer. The hexavalent chromium was determined colorimetrically The Neogene Assopos basin, is mainly composed of more within 24h following the 1,5-diphenylcarbohydrazide than 400 meters thick Tertiary and Quaternary sediments, method, using a HACH DR/4000 spectrophotometer (Amer - covering an area of approximately 700 km 2. The uppermost ican Public Health Association et al., 1989). The estimated Project 35 :17 2/14/11 9:00 PM Page 177 Hellenic Journal of Geosciences, vol. 45, 175-184 177 detection limit of the method was determined at 4 µg L-1. phase mineral analysis from polished blocks. Microprobe The analyses of total chromium were performed using analyses and SEM imaging were carried out at the University GFAAS (Perkin Elmer 1100B). Concentrations of Al, B, Ba, of Athens, Department of Geology
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