Ingineria Mediului i Antreprenoriatul Dezvoltrii Durabile Vol. 2, Nr.

1 (2013)

RESEARCH ON THE MIGRATION OF Cu, Zn AND Mn IN A POLLUTED SITE CERCETRI PRIVIND MIGRAREA Cu, Zn I Mn NTR-UN SIT POLUAT
Cosmina Simona BBU*, Valer MICLE, Adrian Florin POTRA, Andreea COSTE (BN)
Technical University of Cluj-Napoca, Faculty of Materials and Environmental Engineering, Department Environmental Engineering and Sustainable Development Entrepreneurship, 103-105 Muncii Ave, Cluj-Napoca, Romania

Abstract: This paper presents a study on the behavior of heavy metals in soil of Zlatna, a historically polluted area due to existing plants. The soil samples subjected to analysis were taken according to STAS 7184/1-75, from the place where the slag warehouse of former copper ore plant S.C Ampelum Zlatna S.A was located. Chemical analyzes performed have revealed values exceeding intervention limit of 45 and 3 times for Cu and respectively Zn. According to these data it is highlighted excessive soil pollution with those heavy metals, the necessity of a remedial method being essential. Keywords: contaminated soil, heavy metals, pollution, Zlatna

Rezumat: Aceast lucrare prezint un studiu efectuat asupra comportamentului metalelor grele din solul oraului Zlatna, zon istoric poluat datorit uzinelor existente. Probele de sol supuse analizelor s-au prelevat conform STAS 7184/1-75, din locul unde a fost amplasat depozitul de zgur a fostei uzine de minereu de cupru S.C Ampelum Zlatna S.A. Analizele chimice efectuate au evideniat depiri ale valorilor de intervenie de 45 i de 3 ori pentru Cu i respectiv Zn. Conform acestor date este pus n eviden poluarea excesiv a solului cu aceste metale grele, necesitatea aplicrii unei metode de remediere fiind esenial. Cuvinte cheie: sol contaminat ,metale grele , poluare, Zlatna.

1. Introduction Soil contamination with heavy metals is a worldwide problem that affects a large number of sites. Accumulation of metals in soils is an important issue because of the adverse effects they can have on the food quality, soil health and the environment. In response to these negative effects, a variety of technologies are under development for the remediation of soils affected by heavy metal contamination [1]. Multiple contaminated soils usually require more than one treatment option so that all contaminants present in the soil are effectively eliminated. A typical case is the simultaneous presence of heavy metal cations and anionic metalloids that cannot be treated with the same techniques due to their different chemical characteristics. For example, Zn cations can generally be removed from the ground, using either acid or chelating reagents, as has been demonstrated in several studies [2].

1. Introducere Contaminarea solului cu metale grele este o problem la nivel mondial, care afecteaz un numr mare de situri. Acumularea metalelor n sol este o chestiune important datorit efectelor adverse pe care acestea le pot avea n calitatea alimentar, sntatea solului i a mediului. Ca rspuns la aceste efecte negative, sunt n curs de dezvoltare o varietate de tehnologii de remediere a solurilor afectate de contaminarea cu metale grele [1]. Solurile contaminate multiplu necesit de obicei mai mult de o opiune de tratament, astfel nct toi contaminanii prezeni n sol s fie eficient eliminai. Un caz tipic este prezena simultan a cationilor de metale grele i metaloizilor anionici, care nu pot fi tratai cu aceleai tehnici datorit caracteristicile lor chimice diferite. De exemplu cationii de Zn, pot fi, n general, eliminai din sol, utiliznd fie acizi, fie reactivi de chelatare, aa cum s-a demonstrat n mai multe studii [2].

*Corresponding author / Autor de coresponden: Phone: +40 / 264 401725; Fax: +40 264 / 415054 e-mail: babut.simona@yahoo.com; Cosmina.Babut@imadd.utcluj.ro

Environmental Engineering and Sustainable Development Entrepreneurship Vol. 2, No. 1 (2013)

Soil organic matter and its chemical reaction (pH) are part of the factors that control the immobilization (sorption) and influence the mobility of heavy metals [3]. Pollutants imbued in soil suffer phenomena of: transport, transformation, transfer or accumulation and fixation. These phenomena contribute to spreading and distribution of elements in the soil and they change the chemical structure of soil [3]. The present work has as a primary objective the determination of the concentration of studied heavy metals (Cu, Zn and Mn) in the polluted soil, and then establishing the chemical elements that shows values that exceed the limits of intervention (according to Order no. 756/1997) for less sensitive used soils [4]. 2. Material and method Soil samples were taken in 2011, according to STAS 7184/1-75, from a single point and four depths: 0-15 cm, 15-30 cm, 30-45 cm and 45-60 cm. Figure 1 shows the location of the slag former warehouse of copper plant Zlatna, which has ceased its activity about 10 years ago [5].

Materia organic din sol i reacia chimic a acestuia (valoarea pH-ului) fac parte din factorii care controleaz imobilizarea (sorbia) i influeneaz mobilitatea metalelor grele [3]. Poluanii ptruni n sol sufer fenomene de: transport, transformare, transfer sau de acumulare i fixare. Aceste fenomene contribuie la rspndirea i distribuia elementelor n sol i la modificarea structurii chimice a acestuia [3]. Lucrarea de fa are ca i un prim obiectiv determinarea concentraiei metalelor grele studiate (Cu, Zn i Mn) din solul poluat, iar mai apoi stabilirea elementelor chimice care prezint valori ce depesc limitele de intervenie (conform Ordinului nr. 756/1997) pentru solurile cu folosin mai puin sensibile [4]. 2. Material i metod Probele de sol au fost prelevate n anul 2011, conform STAS 7184/1-75, dintr-un singur punct, pe patru adncimi: 0-15 cm, 15-30 cm, 30-45 cm i 45-60 cm. Figura 1 prezint locul unde se afl fostul depozit de zgur a uzinei de cupru Zlatna, care i -a ncetat activitatea cu aproximativ 10 ani n urm [5].

Figure 1. Slag former warehouse of the copper plant Zlatna.

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Ingineria Mediului i Antreprenoriatul Dezvoltri i Durabile Vol. 2, Nr. 1 (2013)

Soil profile from sampling point (figure 2) shows in the first two depths i.e.: 0-15 cm and 15-30 cm a yellowish color, instead in the last two depths the color becomes reddish. The soil heavy metals content depends on the material parent which these soils were formed. After primary mineral alteration due to different climatic conditions various pedogenetic processes occurred, leading to the migration and accumulation of heavy metals in soil. The main soil types in this region belong to: districambisoils, luvisoils, preluvisoils, eutricambosoils, erodosoils and regosoils [6].

Profilul solului din punctul de prelevare (figura 2) prezint pe primele dou adncimi i anume 0-15 cm respectiv 15-30 cm o culoare glbuie, n schimb pe ultimele dou adncimi culoarea devine roiatic. Coninutul de metale grele din sol depinde de tipul materialelor parentale pe care s-au format solurile respective. Dup alterarea mineralelor primare datorit diferitelor condiii climatice, s-au manifestat variate procese pedogenetice, care au determinat migrarea sau acumularea metalelor grele n sol. Principalele tipuri de sol din aceast regiune aparin districambisolurilor, luvosolurilor, preluvosolurilor, eutricambosolurilor, erodosolurilor, i regosolurilor [6].

Figure 2. Soil profile from sampling point.

Analyses for the total content of heavy metals were conducted at the Research Institute for Analytical Instrumentation, ICIA Cluj Napoca, using soil extraction of microelements soluble in aqua regia. The used method was the Atomic Emission Spectrometry Inductively Coupled Plasma (ICP-AES), with the SpectroFlame Spectrometer FMD 07. The method for pH determination is made in aqueous suspension obtained from 20 g of soil and 50 ml of distilled water (ratio soil: water is 1:2.5 w/v), according to STAS 7184/13-88. The samples are stirred for 2 hours on a shaker, then allowed to settle for an hour before taking measurements with a pH-meter (pH MEGA AGRAR 2000) [7]. 3. Results and discussions 3.1. pH variation in the soil Figure 3 shows the pH variation of soil samples. It is noted that with the sampling at a higher depth of soil, the pH changes from alkaline to slightly acid, reaching a value of 6 for a sampling interval of 45 to 60 cm.

Analizele pentru determinarea coninutului total de metale grele au fost efectuate la Institutul de Cercetri pentru Instrumentaie Analitic, ICIA ClujNapoca, utiliznd extracia din sol a microelementelor solubile n ap regal. Metoda utilizat a fost spectrometria de emisie atomic n plasm cuplat inductiv (ICP -AES), cu spectrometrul SpectroFlame FMD 07. Metoda pentru determinarea pH-ului se face n suspensia apoas obinut din 20 g de sol i 50 ml de ap distilat (raportul sol:ap este de 1:2,5 mas/volum), conform STAS 7184/13-88. Probele sunt puse la agitare timp de 2 ore pe un agitator, apoi se las s se decanteze pentru o or nainte de a se efectua msurtorile cu ajutorul pHmetrului (pH MEGA AGRAR 2000) [7]. 3. Rezultate i discuii 3.1. Variaia pH-ului n sol n figura 3 este prezentat variaia pH-ului probelor de sol. Se observ c o dat cu prelevarea de la o adncime mai mare a solului, pH-ul se modific de la bazic la uor acid, ajungnd pn la o valoare sub 6 pe intervalul de prelevare 45-60 cm.

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Environmental Engineering and Sustainable Development Entrepreneurship Vol. 2, No. 1 (2013)

8 6
pH

4 2

0 0-15 15-30 30-45 45-60

3.2. Variation of the metals concentration in soil Table 1 shows the values of the heavy metals concentration in soil samples investigated. There is an increase of values in the depth for copper and zinc. Manganese concentration shows relatively constant values on all sampling depths.
Table 1. Variation of Cu, Zn and Mn concentration in soil samples.

3.2. Variaia concetraiei metalelor n sol n tabelul 1 sunt prezentate valorile concentraiei metalelor grele studiate n probele de sol. Se observ o cretere n adncime a valorilor pentru cupru i zinc. Concentraia manganului prezint valori relativ constante pe toate adncimile de prelevare.

Depth [cm] Metal [mg/kg]

0-15

15-30

30-45

45-60

12970 3967 451,7

15080 4297 480,5

17580 4663 472,2

22760 4885 451,9

When copper reaches the soil, it is attached to organic matter and minerals. Due to the negative influence on some microorganisms, soil activity is affected and the organic matter decomposition is slowing down [8]. In collected soil samples, copper concentration varies according to depth (figure 4), exceeding the intervention limits considered for less sensitive soils (500 mg/kg) approximately 45 times at the sampling depth of 45-60 cm.

Cnd cuprul ajunge n sol se ataeaz materiei organice i mineralelor. Datorit influenei negative pe care o are asupra unor microorganisme, activitatea din sol este afectat, iar descompunerea materiei organice este ncetinit [8]. n probele de sol prelevate, concentraia cuprului variaz n funcie de adncime (figura 4), depind limitele de intervenie considerate pentru soluri mai puin sensibile (500 mg/kg) de aproximativ 45 de ori pe adncimea de prelevare 45-60 cm.

Figure 4. Variation of copper concentration on depth.

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The mobility of zinc in the soil depends on the solubility forms in which the element can be found, on the properties such as cation exchange capacity, pH, redox potential and on the chemical species present in the soil [9]. The concentration of zinc in the soil from the former slag warehouse of plant Zlatna has values exceeding the normal values of metal existence in the soil (100 mg/kg). Taking into account the fact that the pH decreases with the sampling depth, it can be said that the concentration of zinc is inversely proportional to the pH, increasing in depth as can be seen in figure 5.

Mobilitatea zincului n sol depinde de solubilitatea formelor n care se ntlnete elementul, de proprieti precum: capacitatea de schimb cationic, pH-ul, potenialul redox i de speciile chimice prezente n sol [9]. Concentraia zincului n solul de la fostul depozit de zgur al uzinei Zlatna, are valori ce depesc valorile normale de existen a metalului n sol (100 mg/kg). innd cont de faptul c valoarea pH-ului scade o dat cu adncimea de prelevare, se poate afirma c concentraia zincului este invers proporional cu pH, crescnd n adncime aa cum se poate observa n figura 5.

Figure 5. Variation of zinc concentration on depth.

Total manganese content in soils from Romania ranges between 200 and 1700 mg/kg, being higher in clay soils and lower in the sandy ones [10]. Manganese is the only metal of the three ones studied that shows values falling below the normal value of existence into the soil (Figure 6). On all four levels of sampling, the concentrations of this chemical element are approximately similar.

Coninutul n mangan total al solurilor din Romnia variaz ntre 200 i 1700 mg/kg, fiind mai mare n solurile argiloase i mai sczut n cele nisipoase [10]. Manganul este singurul metal dintre cele trei studiate, ce prezint valori ce se ncadreaz sub valoarea normal de existen n sol (figura 6). Pe toate cele patru niveluri de prelevare acest element chimic prezint concentraii aproximativ similare.

Figure 6. Variation of manganese concentration on depth.

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4. Conclusions Analysis performed for the determination of the studied heavy metals concentration on these soil samples, show alarming exceeded intervention values of 45 and 3 times and the alert values of 91 and 7 times for copper and respectively zinc at the last sampling depths. Therefore results a trend of copper and zinc to migrate in depth, while instead the manganese values remain approximately constant, falling below the accepted normal values for less sensitive used soils. The results of this study highlight the increased pollution with Cu and Zn in the soil from the former slag warehouse of Ampelum plant, and as a result the application of remediation complex technologies that do not affect negatively the physico-chemical properties of the soil is necessary. 5. Acknowledgment This paper was supported by the project "Improvement of the doctoral studies quality in engineering science for development of the knowledge based society-QDOC contract no. POSDRU/107/1.5/S/78534, project co-funded by the European Social Fund through the Sectorial Operational Program Human Resources 2007-2013. References
[1.] [2.] [3.]

4. Concluzii Analizele efectuate pe aceste probe de sol n vederea determinrii concentraiei metalelor grele studiate, evideniaz o depire alarmant pe ultimele adncimi de prelevare a pragului de intervenie de 45 i 3 ori i a celui de alert de 91 si 7 ori pentru cupru i respectiv zinc. Rezult deci o tendin a cuprului i a zincului de a migra n adncime, n schimb ce valorile manganului rmn aproximativ constante ncadrndu-se sub valorile normale acceptate pentru solurile cu folosin mai puin sensibile. Rezultatele n urma acestui studiu pun n eviden poluarea accentuat cu Cu i Zn a solului din zona fostului depozit de zgur a uzinei Ampelum, i ca urmare este necesar aplicarea unor tehnologii complexe de depoluare care s nu influeneze negativ proprietile fizico-chimice ale solului. 5. Mulumiri Aceast lucrare a beneficiat de suport financiar prin proiectul "Creterea calitii studiilor doctorale n tiine inginereti pentru sprijinirea dezvoltrii societii bazate pe cunoatere - QDOC", contract: POSDRU/107/1.5/S/78534, proiect cofinanat din Fondul Social European prin Programul Operaional Sectorial Dezvoltarea Resurselor Umane 2007-2013.

[4.] [5.] [6.]

[7.] [8.] [9.] [10.]

Gray, C.W. et al, Field evaluation of in situ remediation of a heavy metal contaminated soil using lime and redmud, Environmental Pollution, 2006, No. 142, 530-539. Vaxevanidou, Katerina et al, Removal of heavy metals and arsenic from contaminated soils using bioremediation and chelant extraction techniques, Chemosphere, 2008, No. 70, 13291337. Pavel, V. L., Teza de doctorat, Studii privind comportarea metalelor grele n sol i a unor alternative de remediere (Studies regarding the behavior of heavy metals in soil and some remedial alternatives), Universitatea Tehnic Gheorghe Asachi din Iai, Scoala Doctoral a Facultii de Inginerie Chimic i Protecia Mediului, Iai, 2012. ***, ORDIN nr. 756/1997 al MAPPM, 1997. Pentru aprobarea Reglementrii privind evaluarea polurii mediului (Approving the Regulation on the Assessment of Environmental Pollution). ***, STAS 7184/1-75 privind Recoltarea probelor de sol pentru studii pedologice si agrochimice (Soil sampling for pedological and agrochemical studies). Cercetri privind poluarea cu metale grele ca efect al activitilor industriale (Research on heavy metal pollution as a result of industrial activities) - Rezumat Teza Doctorat, On line at: http://www.usamv.ro/fisiere/file/documente-de-invatamant/Manea%20Alexandrina/3_Rezumat_rom.pdf. ***, STAS 7184/13-88 privind Masurarea pH-ului solului (Measurement of soil pH). ***, Environmental effects of copper, On line at:http://www.lenntech.com/periodic/elements/cu.htm#Environmental%20effects%20of%20copper. ***, Zinc, Potential for human exposure, 156. On line at: http://www.atsdr.cdc.gov/toxprofiles/tp60-c6.pdf. Determinarea coninutului n unele metale grele a solurilor din judeul Timi (The determination of the content of some heavy metals in soils in Timi County), On line at: http://www.scribd.com/doc/59218367/Metalele-Grele-Din-Sol.

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