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Dr. K.I. Nikolaou Organization of the Master Plan & Environmental Protection of Thessaloniki (OMPEPT) 54636 Thessaloniki, Greece Abstracted/ indexed in: Biology & Environmental Sciences, BIOSIS, C.A.B. International, Cambridge Scientific Abstracts, Chemical Abstracts, Current Awareness, Current Contents/ Agri- culture, CSA Civil Engineering Abstracts, CSA Mechanical & Transportation Engineering, IBIDS database, Information Ven-

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tures, NISC, Research Alert, Science Citation Index (SCI), SciSearch, Selected Water Resources Abstracts CONTENTS

ORIGINAL PAPERS

EFFECTS OF ACUTE TRICHLOROACETIC ACID TREATMENT ON THE 256 IN-VIVO ACTIVITY OF GLUCOSE 6-PHOSPHATE DEHYDROGENASE AND CARBONIC ANHYDRASE IN VARIOUS TISSUES OF RATS I. Celik and H. Demir

EXPOSURE TO HIGH LEVELS OF BENZENE AND RISK OF CANCER 259 A. Gioda, J.A. Sales, P.M.S. Cavalcanti, M.F. Maia, L.F.P.G. Maia, F.R. Aquino Neto

CHARACTERIZATION OF DIFFERENT COAL FLY ASHES FOR THEIR APPLICATION 263 IN THE SYNTHESIS OF ZEOLITE X AS CATION EXCHANGER FOR SOIL REMEDIATION R. Terzano, M. Spagnuolo, L. Medici, F. Tateo and P. Ruggiero

RAPID ASSESSMENT OF RIVER WATER QUALITY 268 IN TURKEY USING BENTHIC MACROINVERTEBRATES S. Uyanik, G. Yilmaz, M.I. Yesilnacar, M. Aslan and O. Demir

PUBLIC ATTITUDES TOWARDS THE RESTORATION 273 AND MANAGEMENT OF LAKE VELA (CENTRAL PORTUGAL) R. Pereira, A..M.V.M. Soares, R. Ribeiro and F. Gonçalves

ORGANIC POLLUTANTS IN STREAM SEDIMENTS 282 OF KUPA RIVER DRAINAGE BASIN S. Frančišković-Bilinsk, H. Bilinski and S. Širac

STUDY ON FLUORESCENCE EMISSION AND SYNCHRONOUS-SCAN 291 FLUORESCENCE SPECTRA OF Nitzschia hantzschiana SOLUTION WITH FE(III) X. Liu, N. Deng, S. Tao, F. Wu, T. Fang and Jiantong Liu

REMOVAL OF HEAVY METAL IONS FROM AQUEOUS SOLUTIONS 296 IN FIXED BEDS BY USING HORSE CHESTNUT AND OAK VALONIA A. Murathan

INVESTIGATION OF WATER QUALITY OF THE WORLD’S LARGEST 300 IRRIGATION TUNNEL SYSTEM, THE SANLIURFA TUNNELS IN TURKEY M.I. Yesilnacar and S. Uyanik

LEACHABILITY OF POLLUTANTS FROM 307 SOLID RESIDUES OF A HAZARDOUS WASTE INCINERATOR A. Karademir, M. Bakoglu and E. Durmusoglu

REMOVAL OF SOME INORGANIC COMPOUNDS FROM PAPER 315 MILL EFFLUENTS BY THE ELECTROCOAGULATION METHOD

914 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

M. Uğurlu

ORIGINAL PAPERS

UV DISINFECTION: RADIATION AND WASTEWATER 322 QUALITY PARAMETERS AS OPERATIONAL INDICATORS E. Alonso, A. Santos and P. Riesco

SPECIES COMPOSITION OF THE TINTINNIDS FOUND IN THE 327 NERITIC WATER OF BOZCAADA ISLAND, AEGEAN SEA, TURKEY N. Balkıs and A. Wasik

PRESS RELEASES 334

INDEX 336

255 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

EFFECTS OF ACUTE TRICHLOROACETIC ACID TREATMENT ON THE IN-VIVO ACTIVITY OF GLUCOSE 6- PHOSPHATE DEHYDROGENASE AND CARBONIC ANHYDRASE IN VARIOUS TISSUES OF RATS

Ismail Celik1 and Halit Demir2

1Yuzuncu Yil University, Faculty of Arts and Sciences, Department of Biology, Van-Turkey 2Yuzuncu Yil University, Faculty of Arts and Sciences, Department of Chemistry, Van-Turkey

SUMMARY

This study was carried out to investigate possible tri- Due to the indiscriminate use of pesticides in agricul- chloroacetic acid (TCA) effects on the activity of glucose ture, there has been an immense disruption of the ecologi- 6-phosphate dehydrogenase (G6PD) and carbonic anhy- cal balance causing damage to non-target organism in- drase (CA) in muscle and liver tissues of rats under labor- cluding vertebrates. Among the pesticides, TCA has been atory conditions. Five Sprague-Dawley albino rats were used as selective herbicide and common weed killer in used for experiments, and 200 mg TCA/kg body weight Turkey. But the effects of TCA have not abundantly evi- was administered intraperitoneally. Tissue G6PD and CA denced up to date. Public health programs in many devel- activities in muscle and liver of rats were determined six oping countries including Turkey also utilize this chemi- hours after treatment. According to the results, the TCA cal as pesticide to control disease-transmitting organisms. treatment caused significant decrease in muscle and liver The various effects of TCA on vertebrates have already G6PD, but no significant difference in liver CA level was been investigated in several studies [12-17], but reports observed, in comparison to control rats. Therefore, it is concerning vertebrates are both very limited and conflicting conceivable that TCA is a toxicant like other pesticides, each other. It is reported that TCA causes change in bio- and is primarily interacting with liver and muscle tissue chemical parameters of male rats, following a 7-days drink- cells. ing water exposure [12]. Poon et al. [13] have investigated

gross and microscopic examinations, serum chemistry,

hematology, biochemical analysis; neurogenic amine analy-

KEYWORDS: Trichloroacetic acid, carbonic anhydrase, glu- sis and serum TCA analysis at the end of a TCA- cose6-phosphate dehydrogenase, rats. treatment period. Mather et al. [14] suggest that TCA and DCA (dichloroacetic acid) produce substantial systemic

organ toxicity to liver and kidney during a 90-days sub-

chronic exposure. Acharya et al. [15] show that interaction

of TBA (tertiary butyl alcohol) +TCA brought about altera-

tions in biochemical parameters, which may play a pivotal INTRODUCTION role in toxic responses on long-term exposure results. Bryant et al. [16] observed that monochloroacetic acid Pollution by residues of pesticides is of major envi- (MCAA), a derivative of TCA, caused the increase of ronmental concern, due to their extensive use in agricul- blood ALT and AST. ture and public health programs. There is abundant evi- dence that many pesticides act as acute toxins by inhibit- This study was aimed to determine any possible toxic ing enzymes. In addition, these chemicals via the food effects of commonly used TCA on rat liver and muscle CA, - chain may initiate harmful physiological mechanisms. In which catalyzes the reversible hydration of CO2 to HCO3 general, enzyme activity was strongly reduced by heavy and H+ [17], and G6PD, which is the key enzyme that in metal cations, and less strongly by organic ones [1]. On vivo catalyzes the first step of the hexose monophosphate the other hand, many chemicals, even at relatively low pathway [18]. For this aim, TCA was injected intraperito- dosages, disturb the metabolism of biota by altering nor- neal to rats, because the effects of chemicals represent a mal enzyme activity [2-11]. well-characterized in vivo toxicity model system.

256 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

MATERIALS AND METHODS U-test was employed to determine the differences between the means of the treated and non-treated control Materials. NADP, glucose 6-phosphate, MgCl2 and rats. The significance level was considered to be p = 0, 05 protein assay reagents were purchased from Sigma Chem. for all tests. Co (USA). Sodium carbonate, sodium bicarbonate, p- nitrophenyl acetate, NaCl, acetone, and TCA were from E. Merck. RESULTS

Animals. Male rats (Sprague-Dawley albino), eight TCA treatment of rats produced changes in the levels weeks old and weighing 150-200 g, were provided by the of liver and tissue enzyme (Table 1). 200 mg/kg TCA was animal house in the Medical School of Yuzuncu Yil Univer- injected intra-peritoneally to the rats. According to the sity, and housed in 2 groups, each group containing 5 rats. results, the treatment of TCA caused a significant de- All animals were fed with a wheat-soybean-meal-based crease in muscle and liver G6PD, which decreased signif- diet and water ad libitum in stainless cages, and received icantly after six hours. No significant differences in the human care according to the criteria outlined in the levels of CA in liver were observed when compared to ‘Guide for the Care and Use of Laboratory Animals’ that of the control rats. prepared by the National Academy of Science and published by the National Institutes of Health [19]. The ani- TABLE 1 - G6PD and CA levels in liver and mals were housed at 20±2 °C and under daily light/dark muscle tissues of rats after a 6-h treatment with TCA. CONTROL (n=5) TCA (n=5) after 6 h cycles. ENZYMES X ± SD X ± SD * Treatment of Rats. This investigation was performed Muscle CA (U/g tissue) 117.38±1.88 42.08±1.44 Muscle G6PD (U/ g tissue 1.35±0.38 1.25±0.47* with male rats and 200 mg/kg TCA was injected intra- Liver CA (U/g tissue) 55.83±4.37 48.07±1.44 peritoneally. The control rats were treated only with phys- Liver G6PD (U/ g tissue) 1.42±0.587 1.32±0.11* iological saline. * p<0.05

At the end of the treatment, the rats were anesthetized with diethyl ether and sacrificed, to obtaine the tissue DISCUSSION samples. The tissues were dissected and put in Petri dish- es. After the tissues were washed with physiological saline (0.9% NaCl), the samples were taken and kept at-87 The first aim of this study was to investigate whether °C until analysis. TCA could affect liver and muscle enzymes (CA and G6PD). The data collected in this study were all from one Preparation of the homogenate. 10 g of fresh rat liver and time-points of the experiment. As shown in Table 1, the muscle tissues were cut with a knife. Then excess blood, treatment with TCA caused significant decreases in mus- foreign tissues and membranes were removed from the cle and liver G6PD, especially after six hours. No signifi- samples. The cleaned-up tissues were suspended in 100 ml cant differences in the levels of CA in liver tissues were of 5 mM phosphate buffer (pH 7.4) containing 458 mM observed in comparison to control rats. saccharine, and homogenized using a mixer at top speed So far, no study examining the effect of TCA in vivo for 3 min and an ultrasonic homogenizer for 40 min. Af- on tissues` enzymes activities has been made. Therefore, terwards, the homogenate was centrifuged at 14100 rpm we could not have the chance to compare our results with (21000xg) for 60 min, and the supernatant was removed. previous ones. However, Tek [20] has investigated the This process was repeated three times, and temperature was inhibition of CA by TCA in vitro. They found that TCA maintained at 4 °C during the homogenization process. can inhibit CA non-competitively, which agrees with our results. In addition, because of the high variability in Enzyme Activity Determination. The homogenates were analyzing enzyme-chemical interactions in vitro and in used for the determination of liver and muscle G6PD and vivo, which is due to inconsistent factors, such as treat- CA total activity. CA was determined by using the hydra- ment time and manner, purity and species tissue differ- tase method [18], and G6DP activity was measured by the ences etc., it is difficult to compare data from different Beutler’s method (G6PD activity was determined at 37 °C laboratories for toxicological effects. and 340 nm in the presence of 1 M Tris-HCl, 5 mM EDTA (pH=8), 0.1 M MgCl2, 2 mM NADP, water and 6 mM The present study indicates that TCA possesses toxic G6P) [19]. effects. This is evidenced by decreased G6PD and CA levels in liver and muscle tissues after TCA treatment. Analysis of Data. The data were expressed as mean ± Besides, TCA exerted different effects on rat liver and standard deviation (SD) values. For statistical analysis the muscle functions, causing G6PD and CA decreases. It is SPSS/PC+ package (SPSS/PC+, Chicago, IL, USA) was also postulated that damage in liver and muscle indicator used for all parameters, and means and SDs were calcu- enzymes might offer a marker of choice for monitoring lated according to standard methods. The Mann-Whitney biotoxicity of acting compounds, such as TCA. However,

257 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

it is conceivable that toxic TCA primarily interacts with the [11] R.M. Hochster, M. Kate, and J.H. Quastel (1972) Metabolic liver and muscle tissue cells like other pesticides. Further inhibitors. Vols 3,4. New York: Academic press: 72-89 studies are required to correlate the in vivo damage to liver [12] R. Poon, B. Nadeau and I. Chu (2000) Biochemical effects of and muscle G6PD and CA. chloral hydrate on male rats following 7-day drinking water exposure. J Appl Toxicol. 20(6): 455-61.

[13] R. Poon, J. Nakai, A. Yagminas, F. Benoit, D. Moir, I. Chu. CONCLUSION and V.E. Valli (2002) Subchronic toxicity of chloral hydrate on rats: a drinking water study. J Appl Toxicol., 22(4): 227-36. Today it is impossible to prohibit all the kinds of [14] G.G. Mather, J.H. Exon and L.D. Koller (1990) Subchronic chemicals, which are used to prevent crop losses. But the 90 day toxicity of dichloroacetic and trichloroacetic acid in use of these pesticides should be decreased by further rats.Toxicology, 64(1):71-80. improving the resistance of plant species against diseases and harmful agents. This still existing gap brought the [15] S. Acharya, K. Mehta, S. Rodrigues, J. Pereira, S. Krishnan researchers to investigate the toxic potential of TCA used and C.V. Rao (1995) Administration of subtoxic doses of t- as pesticide. butyl alcohol and trichloroacetic acid to male Wistar rats to study the interactive toxicity. Toxicol Lett., 80(1-3):97-104.

[16] B.J. Bryant, M.P. Jokinen, S.L. Eustis, M.B. Thompson and K.M. Abdo (1992) Toxicity of monocholoroacetic acid ad- REFERENCES ministered by gavage to F344 rats and B6C3F1 mice for up to 13 weeks. Toxicology, 72: 77-87. [1] S.M. Waliszevski, V.T. Pardio Sedus and K.N. Waliszevski, (1996) Detection of some organocholrine pesticides in cow’s [17] T.H. Maren (1960) A simplified micromethod for the deter- milk. Food Additives and contaminants, 13(2): 231-235. mination of carbonic anhydrase and 1+5 inhibitors. J. Phar- mac. Exp. Ther. 160: 26. [2] O. Arslan, R. Sekeroglu., I. Celik and M. Tarakcı (1997) The inhibition effects of some pesticides on the activity of five se- [18] E. Beutler (1971) Red cell metabolism manual of biochemi- rum enzymes in vitro. J. Environ. Sci. Health, A 32(2): 361- cal methods. Academic Press., London, p.68. 365. [19] World Medical Association Declaration of Helsinki. 52nd [3] I. Celik, H. Camas, O. Arslan, E. Yegin and O.I Kufrevioglu WMA General Assembly, Edinburgh, Scotland, (2000). (1996a). The effects of some pesticides on the activity of liver and erythrocyte enzymes in vitro. J. Environ. Sci. Health, [20] V. Tek (1993). Değişik orijinli karbonik anhidraz izoenzim- A 31(7): 1645-1649. leri üzerinde bazı çevre kirleticilerinin ve kafeinin etkileri ve kinetik özelliklerinin araştırılması. Atatürk Üniv. Fen bilim- [4] I. Celik, H. Camas, O. Arslan, and O.I. Kufrevioglu (1996b) leri enstitüsü kimya anabilimdalı Doktora tezi. Erzurum. The effects of some pesticides on human and bovine erythrocyte carbonic anhydrase enzyme activities in vitro. J. Envi- ron. Sci. Health, A 31(10): 2651-2657.

[5] I. Celik and M. Kara (1997) The effects of plant growth regulators on activity of eight serum enzymes in vitro. J. Envi- ron. Sci. Health, A 32(6): 1755-1961.

[6] I. Celik, V. Turkoglu and H. Camas (1997) In vitro activation Received: March 02, 2004 human and bovine erythrocyte carbonic anhydrase isoen- Revised: September 02, 2004; October 20, 2004 zymes by some plant growth regulators. Bio-Science Re- Accepted: November 10, 2004 search Bulletin., 13(2): 99-104.

[7] M. Kara and I. Celik (1997) The effects of some fungicides CORRESPONDING AUTHOR on activity of eight serum enzymes in vitro. J. Environ. Sci. Health, A 32(5): 1377-1382. Ismail Celik [8] R. Sekeroglu, I. Celik and O. Arslan (1997) The influence of Yuzuncu Yil University some pesticides on activity of seven serum enzymes in vitro. Faculty of Arts and Sciences J. Environ. Sci. Health, A 32(7): 1975-1980. Department of Biology 65080 Van-TURKEY [9] V. Turkoglu, H. Camas and I. Celik (1999). In vitro inhibition Acetylcholinesterase purificated from bovine serum by Phone: ++90 432 2251084/2278 some commercial pesticides. Bulletin of Pure and Applied Sciences, 18(1): 31-35. Fax: ++90 432 2251114 e-mail: [email protected] [10] E.D. Mary (1990) Subacute toxicity of trichloroacetic acid in male female rats. Toxicology, 63: 63-72. FEB/ Vol 14/ No 4/ 2005 – pages 256 - 258

258 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

EXPOSURE TO HIGH LEVELS OF BENZENE AND RISK OF CANCER

Adriana Gioda1,2, José A. Sales3, Paulina M.S. Cavalcanti3, Marilza F. Maia3, Luiz F.P.G. Maia4 and Francisco R. Aquino Neto1

1 LADETEC, Instituto de Química, Centro de Tecnologia, Bloco A, Sala 607, Ilha do Fundão, Universidade Federal do Rio de Janeiro, 21949-900 Rio de Janeiro-RJ, Brasil 2 Departamento de Química, UNIVILLE, Joinville-SC, Brasil 3 DIAAR/FEEMA-Governo do Estado do Rio de Janeiro, Rio de Janeiro - RJ, Brasil 4 Departamento de Meteorologia, IGEO-CCMN, Universidade Federal do Rio de Janeiro, Rio de Janeiro-RJ, Brasil

SUMMARY

The city of Volta Redonda has as main source of in- On the other hand, this municipal district is placed in a dustrial activity, the largest steel facility in Brazil. Its strategic area - halfway between São Paulo and Rio de coke production is claimed to be a major source of ben- Janeiro. Thus, there is a high air pollution potential due to zene in the city. Two campaigns coordinated by FEEMA vehicles` motor exhaust from heavy traffic. Many other (Rio de Janeiro State Environmental Protection Agency) factories were established in the area, contributing to the were carried out to determine the benzene levels. In the complex array of possible air pollution sources. FEEMA, first campaign (1995/96) extremely high values of ben- the Rio de Janeiro State Environmental Protection Agency, zene (highest 1,644 µg/m3) were found presenting a mean decided to monitor the air quality in several stationary of 70 µg/m3. In the 1999 evaluation, these values dropped sampling sites in the city, aiming to follow the implemen- to 104 µg/m3 and 23 µg/m3, respectively. However, the tation of pollution control measures in industries, espe- measured benzene concentrations are still above the inter- cially CSN. Two campaigns were carried out in 95/96 and national recommendations. The high benzene levels can 1999, and amongst other compounds, benzene was sam- be correlated with the high cancer rates found in that city. pled and analyzed [2]. Sampling sites were chosen after These results show that the facility`s environmental pro- careful evaluation of wind regime, location of possible cedures have to be further evaluated and the monitoring pollution sources, and the major-affected residential areas program has to be continued to serve as a guidance for the in downstream plume direction. final solution of this problem.

MATERIALS AND METHODS

KEYWORDS: Monitored area air pollution, benzene, cancer risk, steel industry, Volta Redonda. Volta Redonda is located in Rio de Janeiro State, Brazil. The municipal district of Volta Redonda is placed at the margins of the Paraíba do Sul river, between the Mantiqueira and Mar mountain ranges between the paral- INTRODUCTION lels 22 22' 11" and 22 38' of south latitude, and the merid- ians 44o 09'25" and 44o 20' of west longitude [1]. The city of Volta Redonda has grown surrounding the biggest steel producing facility in Brazil (4.6 x 106 metric The benzene monitoring was performed at 5 stations, tons/year). The current population is 250,000 inhabitants which are strategic places within the municipal district. and the city accounts for the state’s principal economy The choice of the sampling points was based on the repre- wealth [1]. The environmental problems are basically relat- sentativeness of the area and in the surroundings on the ed to air pollution in that city, derived from type and main pollution sources, considering the predominant wind location of the industrial activities in its area. The main directions. Using these criteria, four sampling points were source of organic pollutants is benzene in the monitored selected from leeward side: FEEMA (FE), Belmonte (BE), area and formed in the production of coke at National Retiro (RE), and Centro de Pesquisas stations (CP), and Steel Company (Companhia Siderúrgica Nacional, CSN). one point to the windward side, Aeroclube (AE) (back-

259 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

ground). In the first evaluation (Dec/95-May/96) all sites were less than 10%. The dectection limit of the method were equipped to measure the concentrations of benzene. was 1 µg m-3. Benzene sampling in the first evaluation In the second evaluation (Apr-May/99), only at FE and (Dec/95-May/96) was realized continuously, during seven RE benzene was measured. days every month, corresponding to 42 sampling days. In the second campaign it was collected every two days, in a Benzene analysis total of 11 days. In both evaluations, two samples were Air samples were collected in adsorbent tubes (Supelco collected within 12 hours. ORBO 100, batch 6719, Bellefonte, PA, EUA), which contained two sections of activated charcoal. Solvent de- sorption method with carbon disulfide (Tedia, Fairifield, RESULTS AND DISCUSSION OH, USA) was used. 2 µL of samples were injected into a capillary column (CARBOWAX 20 M - HP-20M; 25 m x Table 1 presents the results of benzene levels obtained 0.2 mm, film thickness 0.2 µm), installed in a Hewlett- in the municipal district of Volta Redonda during both Packard 5890 GC, Series II with flame ionization detector evaluations. In the first one (Dec/95-May/96), the average (FID). Split mode 1:100 was used. The temperature of the concentration for benzene was 70 µg m-3 and in the second column oven was maintained initially at 30 °C for 12 min, one (Apr-May/99) 23 µg m-3, being approximately four then increased at 25 °C per min to 180 °C. Benzene stock times lower than in the first one. Benzene in Volta Redon- solutions were prepared from high purity standards ob- da and different cities of the world are also presented in tained commercially (Riedel, Germany). The samples were Table 1. The average benzene concentrations in cities of injected in duplicate, and blanks and standard solutions in South America have been reported to be 5-24 µg m-3, for triplicate. Standard deviations between sample injections European, North-American and Oceanian cities, < 5 µg m-3,

TABLE 1 - Average concentrations of benzene (ranges in parentheses) during the sampling periods (Dec/95-May/96 and Apr-May/99) in Volta Redonda city and other regions of the world.

Site Benzene Source References (µg m-3) South America 1, 3, 4, 8 Brazil (RJ) (nd-11) Traffic Brazil (SP) (5-30) Traffic Brazil (POA) 25 Traffic Chile (7-40) Traffic Venezuela (3-44) Traffic North America 1, 4, 5 USA (1-16) Industry USA 6 Traffic USA 1.5 Rural area Europe 1, 4, 9, 10, 11 Germany (10-30) Cokery Germany (1-15) Industry Germany (1-3) Traffic Denmark (3-5) Traffic Asia 3, 4, 12, 13 India (576-918) Industry India (11-28,555) Industry Thailand (3.4-35) Traffic Phillipines (nd-47) Traffic Volta Redonda 1995-96 1999 FEEMA 83 20 (3-705) (11-104) Belmonte 52 * (3-340) Retiro 93 26 Industry This study (nd-1,644) (nd-90) Aeroclube 58 * (nd-430) Centro Pesquisas/Conforto 65 * (nd-1,451) Average 70 23 (*) = not analyzed; nd = not detected

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and Asian ones, 7-31 µg m-3 (except Calcuta 28,555 µg m-3) CONCLUSIONS [3, 4]. Benzene levels of Volta Redonda, recorded in the first evaluation (Dec/95-May/96), were among the highest Benzene concentrations (mean 70 µg m-3) of the first in cities worldwide. In the second campaign they de- evaluation (Dec/95-May/96) could be reduced by 70% in creased and remained within the levels normally found in the second one (mean 23 µg m-3), but values were still too the cities of Latin America and Brazil. high. T/B ratios observed were lower than 0.5, indicating that industrial activity is the predominant pollution source Benzene does not have recommended limits according in Volta Redonda. According to meteorological infor- to Brazilian legislation. This compound is a special case in mation, gas emissions during coke production and raw presenting health risk, even in low concentrations. There- benzene storage at CSN are probably the main pollution fore, it does not have a standard value, but a reference effects. These elevated benzene concentrations are capa- concentration. WHO [5] considered that the excess life- ble to influence population health in Volta Redonda direct- time risk of leukemia at an air concentration of 1 µg m-3 is -6 ly. This risk is confirmed by lofty benzenism index (688 6 x 10 , i. e., six extra-cases of leukemia in a million registered cases from 1984 to 1999). people exposed during their life. FEEMA adopts as reference the limits suggested by the German Governmental Agency [6], 2.5 µg m-3, and WHO [5], 1.0 µg m-3. In both cases, the benzene values of Volta Redonda exceeded ACKNOWLEDGEMENTS both reference concentrations. FAPERJ, CNPq, CAPES and FUJB for research In Volta Redonda benzene concentrations ranged grants. from 52 to 93 µg m-3 in the first evaluation (Dec/95- -3 May/96), and from 20 to 26 µg m in the second one (Apr-May/99). The maximum concentrations found were -3 -3 1,644 µg m at Retiro (1995/96) and 104 µg m at FEEMA REFERENCES (1999). These average concentrations may correspond to 120-558 extra-cases of leukemia in a population of a [1] FEEMA, Rio de Janeiro State Environmental Engineering million exposed citizens. Considering Volta Redonda Foundation (1999) Air Quality in Volta Redonda, Report of population around 250,000 inhabitants, this would mean results obtained in monitoring evaluation of 96 and 99, 78-140 extra-cases and 30-40 extra-cases in the first and FEEMA/GTZ (document in Portuguese). second evaluation, respectively. Considering the maxi- -3 [2] A. Gioda, J.A. Sales, P.M.S. Cavalcanti, M.F. Maia, L.F.P.G. mum benzene values obtained, 1,664 and 104 µg m , this Maia and F.R. Aquino Neto (2000) BTX as makers for pollu- could possibly cause 156-2,500 extra-cases of leukemia. tion sourcing in Volta Redonda. In: Proceedings Air Pollu- These estimates of extra-cases of leukemia may be real, tion VIII, 593-600. since the Secretary of Health from Volta Redonda [7] registered 688 cases of benzenism from 1984 to 1999. The [3] M. B. Fernandes, L.S.R. Brickus, J.C. Moreira and J.N. Car- doso (2002) Atmospheric BTX and polyaromatic hydrocar- actual number is probably higher, because several sympto- bons in Rio de Janeiro, Brazil. Chemosphere 47, 417-425. matic cases are not recognized by the Brazilian Health Integrated System yet. [4] I.L. Gee and C.J. Sollars (1998) Ambient air levels of volatile organic compounds in Latin American and Asian cities. The high levels of benzene indicate the necessity to Chemosphere 36, 2497-2506. discover the emission sources. Based on wind directions and T/B ratio it was possible to identify the pollutant [5] WHO, World Health Organization (2000) Air Quality Guide- source. T/B average ratio in the first evaluation (Dec/95- lines. 2nd Edition, Regional Office for Europe. Also available in: http://www.euro.who.int/air/Activities, accessed in May/96) was 0.4 and in the second one about 0.18. When August 2003. T/B ratio is less than 0.5, it corresponds predominantly to industrial sources [4], thus underlining that, during both [6] EC, European Communities (1996) Council directive evaluations, benzene is basically due to industrial emis- 96/62/EC of 27 September 1996, Ambient air quality assess- sions. According to meteorological information, the pre- ment and management, Official Journal of the European Communities, L 296/55, 21 November 1996. dominant wind direction in the region is east to west, varying from northeast to southeast. During both cam- [7] SSVR-RJ, Health Secretary of Volta Redonda (1999) Report paigns, the maximum benzene concentration was obtained about benzenism cases in Volta Redonda Municipality, at the north and southeast sections of the studied area, in Health integrated system (document in Portuguese). Retiro and FEEMA. Wind direction correlation with aromatic hydrocarbon levels permitted to establish the loca- [8] E. Grosjean, A.R. Reinhold and D. Grosjean (1998) Ambient tion of the pollution source: the coke producing facility at level of gas pollutants in Porto Alegre, Brazil. Atmos. Envi- ron. 32, 3371-3379. CSN. The reduction in the benzene levels in the second campaign is due to new technologies implemented by [9] D. Gladtke (1998) Air pollution in the Rhine-Ruhr-area. Tox- CSN, especially its coke producing facility. ic. Lett. 96, 97, 277-283.

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[10] P. Schneider, I. Gebefugi, K. Richter, G. Wolke, J. Schnelle, H.E. Wichmann, and J. Heinrich (2001) Indoor and outdoor BTX levels in German cities. Sci. Total Environ. 267, 41-51.

[11] H. Skov, A. B. Hansen, G. Lorenzen, H.V. Andersen, P. Lofstrom and C.S. Christensen (2001) Benzene exposure and the effect of traffic pollution in Copenhagen, Denmark. At- mos. Environ. 35, 2463-2471

[12] G. Chattopadhyay, S. Chatterjee and D. Chakraborti (1996) Determination of benzene, toluene and xylene in ambient air inside three major steel plant airsheds surrounding residential areas. Environ. Technol. 17, 477-488.

[13] G. Samanta, G. Chattopadhyay, B.K. Mandal, T. R. Chow- dhury, C.R. Chanda, P. Banerjee, D. Lodh, D. Das and D. Chakraborti (1998) Air pollution in Calcutta during winter – a three-year study. Curr. Sci. 75, 123-138.

Received: June 02, 2004 Accepted: August 23, 2004

CORRESPONDING AUTHOR

Adriana Gioda LADETEC Instituto de Química Centro de Tecnologia Bloco A, Sala 607 Ilha do Fundão Universidade Federal do Rio de Janeiro 21949-900 Rio de Janeiro-RJ – BRASIL

e-mail: [email protected]

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CHARACTERIZATION OF DIFFERENT COAL FLY ASHES FOR THEIR APPLICATION IN THE SYNTHESIS OF ZEOLITE X AS CATION EXCHANGER FOR SOIL REMEDIATION

Roberto Terzano1, Matteo Spagnuolo1, Luca Medici2, Fabio Tateo3 and Pacifico Ruggiero1

1 Dipartimento di Biologia e Chimica Agroforestale ed Ambientale, Università degli Studi di Bari, Bari, Italy 2 I.M.A.A. - Istituto di Metodologie per l’Analisi Ambientale - C.N.R., Tito Scalo (PZ), Italy 3 I.G.G. – Istituto di Geoscienze e Georisorse – C.N.R., Padova, Italy

SUMMARY INTRODUCTION

Four different coal fly ashes have been characterized Coal fly ash is the most abundant coal combustion for their potential application in the synthesis of Zeolite X by-product and, even if a large proportion of it is used in for its use as cation exchanger for the remediation of concrete and cement manufacturing, novel potential ap- heavy metal-polluted soils. plications have been developed or are in progress of development [1, 2]. Their chemical composition, with particular attention to the concentration of trace elements potentially toxic for For the purpose of transforming this waste material the environment, has been determined by total dissolution into final products possessing a higher added-value, coal and ICP-OES analysis. The relative amount of Zeolite X fly ash is widely employed in the synthesis of high cation synthesized after 4 days of incubation at 60 °C starting exchange capacity (CEC) zeolites [3, 4]. from fly ash and the possible synthesis of other minerals has been investigated by means of X-ray diffraction. Among their several applications, zeolites can be successfully used as cation exchangers to reduce the mobility The fly ashes have been evaluated by their morpholo- of toxic metals in polluted soils [5]. In particular, Zeolite gy (SEM analysis), granulometry (laser granulometry) X (zeolite belonging to the Faujasite series) has shown and loss on ignition (L.O.I.). Moreover, the fraction of itself to be highly effective, even for the removal of cati- + potentially toxic elements, such as As, Cd, Cr, Cu, Pb and ons of big dimension like Cs [6]. Zn, which can be released in solution during the synthetic process, has been quantified. When using coal fly ash for this particular application, it is necessary to fully characterize the starting mate- Among the coal fly ash varieties analyzed, one result- rials in order to find out the more suitable properties they ed to possess suitable properties for the synthesis of envi- should have not only for a successful conversion into the ronmentally applicable Zeolite X, since it showed higher expected zeolite, but also to avoid that this product itself yield, no by-products, lower mean particle size (useful for becomes a source of environmental pollution. a quicker dissolution of the ash), and very low concentrations of potentially toxic elements. Finally, this coal fly In particular, an important limitation for the applica- ash has been fully characterized with regards to its chemi- tion of the zeolitic material synthesized from fly ash is the cal composition (major and minor constituents) by total possible occurrence of potentially hazardous leachable dissolution and ICP-OES analysis, but also X-ray fluores- elements when direct conversion products are used [1]. cence of its fused powder. Therefore, its characterization is an essential prelimi-

nary step before its transformation to be used for many

industrial, agricultural and environmental applications [7].

KEYWORDS: In this work, four different coal fly ashes have been Fly ash; Zeolite X; soil remediation; trace metals. characterized for their application in the synthesis of Zeolite X. In order to select the coal fly ash more suitable for this synthesis, several parameters have been investi-

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gated and compared taking into account the yield of the TABLE 3 - Comparison between FA2 chemical composition synthetic process and the potential threat of some toxic fly determined by XRF and total acidic dissolution followed by ICP-OES analysis (n =n =3). ash elements to the environment. 1 2

XRF (% dry weight) ICP-OES (% dry weight) * SiO2 48 ± 7 48 ± 7 Al2O3 26 ± 5 25 ± 4 MATERIALS AND METHODS Fe2O3 6.0 ± 0.2 5.4 ± 0.4 TiO2 1.3 ± 0.1 1.2 ± 0.2 Coal fly ash MnO 0.11 ± 0.02 0.08 ± 0.04 Four coal fly ash samples (FA1, FA2, FA3 and FA4), CaO 8.7 ± 1.5 8.1 ± 0.7 K2O 1.0 ± 0.7 0.6 ± 0.2 resulting from the combustion of four different coal mate- MgO 2.8 ± 1.1 2.8 ± 0.9 rials, were obtained from ENEL thermoelectric power * = determined by XRF, not analyzable with ICP-OES methodology plant of Cerano (Brindisi, Italy). described in this study

The concentrations of potentially harmful trace ele- Scanning electron microscopy (SEM, LEO Stereos- ments, such as As, Cd, Cr, Cu, Pb, and Zn, were determined can 440) was used to characterize the morphology of the using inductively coupled plasma optical emission spectro- fly ashes consisting mainly of hollow spherical particles photometry (ICP-OES) (Thermo Jarrel Ash, Trace Scan) (Figure 1). X-ray diffraction analysis (XRD, Rigaku D- after the total acid dissolution treatment of the samples Max micro-diffractometer) showed the presence of quartz, (Table 1), generally employed for soil samples [8] and mullite and ematite as the main crystalline phases of these based on the sample digestion by using mixtures of high coal fly ashes. purity strong acids, such as HClO4, HNO3, HCl and HF.

TABLE 1 - Trace element contents, mean particle size and L.O.I. of the four different coal fly ash samples (n=3).

FA1 FA2 FA3 FA4 As (µg/g) 42 ± 3 21 ± 1 17.0 ± 0.9 131 ± 7 Cd (µg/g) 5.0 ± 0.6 0.9 ± 0.1 7.3 ± 0.8 9.6 ± 0.9 Cr (µg/g) 98 ± 7 51 ± 4 86 ± 9 117 ± 8 Cu (µg/g) 105 ± 11 2.1 ± 0.2 71 ± 5 101 ± 7 Pb (µg/g) 64 ± 5 42 ± 3 109 ± 9 91 ± 7 Zn (µg/g) 138 ± 11 136 ± 12 394 ± 24 181 ± 13 Mean particle 44 19 21 24 size (µm) L.O.I. 4.2 5.6 6.9 7.6 (% dry weight)

The employed method of analysis was validated using a BCR coal fly ash (CRM 038) as reference material (Table 2, FIGURE 1 number of replicates n=3, significance level α=0.05, t-test). Scanning electron microscopy (SEM) of coal fly ash FA2.

TABLE 2 - Comparison between trace element composition of a certi- Average particle size (Table 1) was determined using fied coal fly ash reference material (BCR - CRM 038) and that ana- a laser granulometer (Malvern Mastersizer/E) [9]. Loss on lyzed by using the methodology described in this study (n=3). ignition (L.O.I.) was calculated as the lost in weight Certified value (µg/g) Determined value (µg/g) measured from 110 °C to 750 °C (ASTM C 311 method). As 48.0 ± 2.3 51 ± 2 Cd 4.6 ± 0.3 5.1 ± 0.5 Zeolite X synthesis Cr 192 ± 10 188 ± 5 Zeolite X was synthesized starting from the four coal Cu 176 ± 9 180 ± 10 fly ashes investigated following the method of Chang and Pb 262 ± 11 254 ± 5 Zn 581 ± 29 552 ± 38 Shih [6], in the presence of NaOH or after a fusion pre- treatment with NaOH. FA2 was also characterized for its major chemical con- During the fusion process, coal fly ash was mixed stituents by means of X-ray fluorescence (XRF) (Philips with NaOH powder (5:6 w/w). The obtained mixture was spectrometer PW2400; powders fused with lithium tetra- heated for 1 hour at 550 °C in a muffle furnace. Zeolite borate at a 1:10 w/w ratio and quantitative determination synthesis was carried out by pouring 8.8 g of the ground obtained against about 30 international geologic standards) fused powder into a polypropylene bottle, followed by the and ICP-OES analysis after acidic sample dissolution. The addition of 43 ml of deionized water. The mixture was results obtained using these two techniques were not signif- stirred for 1 day at room temperature and atmospheric icantly different (Table 3, n1=n2=3, α=0.05). pressure. After this step, the mixture was incubated with-

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out stirring in an electrical oven at 60 °C and atmospheric dissolution step, as a consequence of the fusion process [1, pressure for 4 days. 10]. The low dimension of the fly ash particles can be a Parallel experiments were conducted without any fu- favourable property to enhance its dissolution rate during sion pre-treatment: 4.0 g of coal fly ash was mixed with the preliminary fusion step or, if fusion is not used, during 4.4 g of NaOH powder (5:6 w/w) and 43 ml of deionized the synthetic process itself. The higher the amount of water. The mixture was stirred and incubated as reported dissolved species (especially Si and Al), the higher the above for the fused samples. yield of products as can be inferred when looking at the After 4 days of incubation, the solid phases were col- amount of Zeolite X synthesized from FA2. In fact, FA2 lected by centrifugation (20,600 × g), washed two times showed the lower mean particle size among the coal fly with deionized water and dried at 80 °C for 12 hours. ash samples analyzed (Table 1). XRD patterns were collected using a Rigaku D-max Rapid In Table 4 the different zeolitic phases, identified af- micro-diffractometer operating at 40 kV and 30 mA with ter the 4-days incubation of the four coal fly ashes at 60 °C CuKα radiation and flat graphite monochromator. The rela- both with or without fusion pre-treatment, are listed. tive amount of Zeolite X synthesized was studied by X-ray diffraction using BaTiO3 as an internal standard [6]. TABLE 4 - Zeolitic phases identified after the The supernatants obtained after centrifugation were incubation of coal fly ash at 60°C for 4 days. collected and analyzed for As, Cd, Cr, Cu, Pb and Zn by No fusion pre-treatment After fusion pre-treatment ICP-OES. FA1 Zeolite X Zeolite X FA2 Zeolite X Zeolite X RESULTS AND DISCUSSION Zeolite X FA3 Zeolite X Zeolite P The relative amounts of Zeolite X (referred to the max- Zeolite X imum amount of synthesized Zeolite X observed), obtained FA4 Zeolite X Zeolite P Zeolite A after 4 days of incubation at 60 °C from the different coal fly ashes using or not the fusion process before the synthet- Without fusion, Zeolite X was the only zeolitic phase ic step, are shown in Figure 2. It can be clearly seen that synthesized, while after fusion treatment other zeolitic FA2 shows the highest yield of Zeolite X synthesis in phases (Zeolite A and Zeolite P) were synthesized from both fused and not fused samples. FA3 and FA4. Figure 3 displays the XRD pattern of the product ob-

after fusion tained after 4 days of incubation at 60 °C for the fused no fusion 1.0 FA2 sample, and clearly demonstrates that Zeolite X is the only crystalline product of reaction. 0.8

0.6 ≈ 14.44

0.4 Zeolite X (relative amount) (relative Zeolite X 0.2

0.0 FA1 FA2 FA3 FA4

≈ 2.91 FIGURE 2 ≈ 3.81 ≈ 3.34 ≈ 5.75 ≈ 8.85 Relative amount of Zeolite X (referred to the maximum ≈ 7.56 ≈ 3.05 ≈ 2.80 ≈ 4.43

amount of observed synthesized Zeolite X) obtained ≈ 2.68 ≈ 4.82 ≈ 4.24

from coal fly ash after 4 days of incubation at 60 °C. ≈ 2.40 ≈ 2.11 ≈ 2.20 ≈ 2.04 ≈ 2.00

When FA1, FA2 and FA3 are considered, the adoption Cu 2Θ° of the preliminary fusion process led to a yield of Zeolite X about 40% higher than that obtained without the fusion 10 20 30 40 step. Only FA4 showed a much higher increase of Zeolite FIGURE 3 X (about 110%) after the fusion treatment. This behaviour Characteristic XRD pattern of Zeolite X obtained after could be related to higher relative concentrations of re- 4-days incubation of the fused coal fly ash FA2 at 60 °C. sistant alumino-silicate phases, such as quartz and mullite, in FA4, which may become more available during the Zeolite X has a very large pore size (7.4 Å), a higher specific area and high CEC (500 meq/100 g), when com-

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pared to Zeolite P (another zeolite which can be easily FIGURE 4 synthesized from coal fly ash, in particular at higher tem- Percentage of trace elements released into the reaction solution after 4-days incubation of the fused coal fly ash at 60 °C. peratures). Among the zeolites obtainable from coal fly ash, only Zeolite A possesses properties similar to that of According to these findings, prior to application of Zeolite X, except for a smaller pore size (4.2 Å) [10]. the zeolitized coal fly ash to soil, the reaction solution Therefore, it evidenced a lower CEC for big dimensioned should be removed to lower the level of potentially toxic cations like Cs+ [4]. elements present in the starting fly ash. FA2 not only drives zeolite synthesis towards higher Thus, the zeolitic materials synthesized from FA2 yield of Zeolite X without other competitive phases, but could even be up to the ecological criteria of the law also it possesses a lower amount of environmentally toxic 2001/688/EC of the European Community concerning the elements (As, Cd, Cr, Cu, Pb, and Zn; Table 1). limitations for the maximum allowable contents of As, Cd, Cr, Zn, Cu, and Pb in soil improvers [12]. However, the total amount of potentially toxic ele- Generally, it has been verified that in most cases, ments in coal fly ash is not the most relevant aspect to take when the reaction solution is removed prior to use, the care of. What is more important, is the fraction of the ele- content of toxic leachable elements in the zeolitic products ments remaining in the products synthesized from fly ash obtained from coal fly ash is low enough to compete with and could be released into the environment as a conse- the benefits of the heavy metal cation uptake processes [1]. quence of aging processes in soil. Moreover, FA2 was completely characterized by During synthesis, especially of fused coal fly ash sam- XRF and total acidic dissolution followed by ICP-OES ples, a fraction of their elements are released into the reac- analysis concerning its major chemical constituents (Ta- tion solution (Figure 4). Cu, Pb, and Zn are only slightly ble 3). This was required, since this coal fly ash variety solubilized, whereas Cd is to be found in higher amounts was employed in other studies about zeolite synthesis (20%) for FA1 and FA2. from pre-treated coal fly ashes in presence of soil as a tool Completely different is the behaviour shown by As, for soil remediation [13]. which is almost completely released from FA2, while 50% is mobilized from FA1 and FA3 and about 20% from FA4. Similarly, about 90% of Cr is released in solu- CONCLUSIONS tions from FA1 and FA3, but only about 30% from FA4 and 5% from FA2. Among the different coal fly ashes analyzed, FA2 possessed the best properties for synthesis of environmen- The higher solubilities of As and Cr could be explained tally applicable Zeolite X. In fact, FA2 gave the highest by their easy anionic mobilization as arsenite and/ or arse- yield of Zeolite X (with and without fusion pre-treatment) nate and chromate at the high alkaline pH (ca. pH 13) of and contained no detectable crystalline by-products. The zeolite synthesis. highest yield of Zeolite X could be partly due to its lower mean particle size, an important characteristic to boost The different behaviour observed among the studied Zeolite X synthesis. coal fly ash samples could be related to the different mobility of As and Cr fractions. In particular, the higher Moreover, FA2 showed a lower overall concentration solubility noticed for As in FA2 and for Cr in FA1 and of elements (As, Cd, Cr, Cu, Pb, Zn) potentially toxic for FA3, could be due to higher amounts of mobile As(V) or the environment. It has been shown that almost all As and Cr(VI) forms [11]. parts of the other elements could be lost in the reaction solution, and the final zeolitic product could possess an even lower amount of toxic elements compared to the

100 FA1 initial coal fly ash. FA2 FA3 The characterization approach described in this work 80 FA4 may contribute to draw a more general scheme for coal fly ash characterization to be employed in the synthesis of

60 zeolitic materials for environmental applications.

40 REFERENCES % of% released element

20 [1] Querol, X., Moreno, N., Umana, J.C., Alastuey, A., Hernan- dez, E., Lopez-Soler, A. And Plana, F. (2002) Synthesis of 0 zeolites from coal fly ash: an overview. International Journal As Cd Cr Cu Pb Zn of Coal Geology 50, 413-423.

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[2] Chahbane, N., Souabi, S., Almardhy, H., Schramm, K.-W., Lenoir, D., Hustert, K. And Kettrup, A. (2003) Removal of organic matter from textile wastewater using power station coal fly ash. Fresenius Environmental Bulletin 12 (1), 56-61.

[3] Singer, A. And Berkgaut, V. (1995) Cation exchange properties of hydrothermally treated coal fly ash. Evironmental Sci- ence and Technology 29, 1748-1753.

[4] Shih, W.H. And Chang, H.L. (1996) Conversion of fly ash into zeolites for ion-exchange applications. Materials Letters 28, 263-268.

[5] Lin, C.F., Lo, S.-S., Lin, H.-Y. And Lee, Y. (1998). Stabili- zation of cadmium contaminated soils using synthesized zeolite. Journal of Hazardous Materials 60, 217–226.

[6] Chang, H.C. And Shih, W.H. (1998) A general method for the conversion of fly ash into zeolites as ion exchangers for cesium. Industrial and Engineering Chemical Research 37, 71-78.

[7] Mohapatra, R. And Rao, J.R. (2001) Some aspects of characterisation, utilisation and environmental effects of fly ash. Journal of Chemical Technology and Biotechnology 76, 9-26.

[8] Soltanpour, P.N. (1996) Inductively coupled plasma emission spectrometry and inductively coupled plasma-mass spectrometry. In: Methods of soil analysis. Part 3: Chemical Methods. SSSA Book Series: 5 (Editor: Sparks, D.L.) SSSA, Madison, Wisconsin, USA, 91-139.

[9] Summa, V. (2000) Analisi granulometrica dei sedimenti. In: A.I.P.E.A. - Incontri Scientifici. Volume II (Editor: Fiore, S.) Istituto di Ricerca sulle Argille – C.N.R., Tito Scalo (PZ), Italy, 19-29.

[10] Chang, H.L. And Shih, W.H. (2000) Synthesis of zeolite A and X from fly ashes and their ion-exchange behaviour with cobalt ions. Industrial and Engineering Chemical Research 39, 4185-4191.

[11] Huggins, F.E. And Huffman, G.P. (2004) Quantifying hazardous species in particulate matter derived from fossil-fuel combustion. Environmental Science and Technology 38, 1836-1842.

[12] European Commission Decision 688 (2001) establishing ecological criteria for the award of the Community eco-label to soil improvers and growing media. Official Journal of the European Communities, L 242/17-L 242/22.

[13] Terzano, R., Spagnuolo, M., Medici, L., Tateo, F. And Rug- giero, P. (2005) Zeolite synthesis from pre-treated coal fly Received: July 16, 2004 ash in presence of soil as a tool for soil remediation. Applied Accepted: August 25, 2004 Clay Science 29 (2), 99-110.

CORRESPONDING AUTHOR

Roberto Terzano Dipartimento di Biologia e Chimica Agroforestale ed Ambientale Facoltà di Agraria Università degli Studi di Bari Via Amendola 165/A 70126 Bari - ITALY

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Phone +39 080 5442847 Fax +39 080 5442850 e-mail: [email protected]

FEB/ Vol 14/ No 4/ 2005 – pages 263 - 267

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RAPID ASSESSMENT OF RIVER WATER QUALITY IN TURKEY USING BENTHIC MACROINVERTEBRATES

Sinan Uyanik, Guzel Yilmaz, M. Irfan Yesilnacar, Mustafa Aslan and Ozlem Demir

Harran University, Environmental Engineering Department, Osmanbey Campus, Şanlıurfa, Turkey

SUMMARY

A study of the relationship between benthic macro- In an ideal situation, the quality of running water invertebrates and water quality parameters, such as bio- should be assessed by the use of physical, chemical and chemical oxygen demand (BOD), chemical oxygen de- biological parameters in order to provide a complete spec- mand (COD) and dissolved oxygen (DO), in a river in trum of information for appropriate water management. Turkey was carried out in order to assess the ecological However, such a study needs much more time and ex- impact of polluted water discharge into rivers. Five sam- penses than that of the biological parameters, which, as it pling stations were selected on the river; three of them is widely accepted, can give reliably all the information upstream of an industrial and domestic wastewater dis- needed [2]. Biological assessments show the cumulative charge and two of them downstream. Seven samplings of effects of physical, chemical and biological stresses in the water and benthic fauna were carried out at the stations whole water system. fortnightly between March 2004 and June 2004. The kick sampling method was used in collecting benthic macro- Macro-invertebrates live in lakes, rivers, lagoons and invertebrates. The Biological Monitoring Working Party wetlands. These biological creatures help to show the whole (BMWP), Trent Biotic Index (TBI), and Chandler Score status of ecology. Therefore, the observation of their were used to quantify the conditions of the biota at the changes as a biological assessment in a water body gives study sites. The results of water quality parameter tests and direct indications of water quality. Besides being an im- the scores obtained from the indices showed similar re- portant link in the food chain, macro-invertebrates can sponses for pollution. Statistical analysis of the data showed also serve as an indicator of water quality. Some stream- a trend toward gradual pollution in the water, and a peak bottom macro-invertebrates cannot survive in polluted was observed after domestic wastewater discharge. Hence, water, while others can survive or even thrive in polluted the results of the study support the hypothesis that the use of water. A healthy ecosystem supports diversity of organ- macro-invertebrates as indicator in a water body is an ideal isms, so in a healthy stream, the stream-bottom community methodology for the assessment of the water quality. will include a variety of pollution-sensitive macro-invertebrates. Conversely, an unhealthy stream will support only a few types of non-sensitive macro-invertebrates. Aquatic

KEYWORDS: Water quality assessment, macro-invertebrates, macro-invertebrates provide information about the quality biological assessment, sediment. of a stream over long periods of time. The use of benthic macro-invertebrates as biological indicators has been widely applied in river quality assessment, because these organisms are affected by changes in the natural variables of INTRODUCTION rivers, such as width, depth, type of substratum, water velocity and physico-chemical variables, which are provoked Assessing the conditions of an ecosystem before and by both natural and human activities [3]. after effluent discharges is a procedure that has been recommended for the USA, Australia and South Africa, and It may be difficult to identify stream pollution with was followed by a number of researchers [1]. The reason water analysis parameters, such as pH and dissolved oxy- is that only biological techniques can demonstrate the in- gen, which can only provide information for the time of tegrity of the ecosystem. An accurate assessment of water sampling. Even the presence of fish may not provide pollution is not possible by carrying out only chemical information about a pollution problem because fish can analyses. It is, therefore, essential to employ a biological move away to avoid polluted water and then return when assessment of water quality to assist and complete the conditions were improved. However, most aquatic macro- chemical analyses. invertebrates cannot move to avoid pollution. A macroin-

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vertebrate sample may provide information about pollu- (Global Flow Probe- FP 101). Substratum was visually tion that is not present at the time of sample collection. categorized as fine material (generally <2 mm diameter) Water chemistry and aquatic habitat assessment values or coarse material (generally >2 mm diameter). were compared and evaluated for sampling points. Five sampling sites were chosen at the river. The lo- The absence of studies of this type in Turkey should cations of the sites are shown in Figure 1. At each study be seen as a lack, and assessment of water quality using site, field procedures included information about the habi- macro-invertebrates should be performed. The goal of this tat’s physical structure, flow regime, and sampling of 1 L study is the investigation of the use of macro-invertebrates of water for water quality analyses and that of sediments for applicability in the assessment of water quality in for biological study for an integrated assessment. Turkish rivers, presenting firstly a general account of the water quality and benthic macro-invertebrate species com- Water Quality position and diversity within a selected river, and second- DO, pH, and temperature were measured on the sites ly, giving a comparative account of the same ecological by WTW Multiline P4. COD, BOD and turbidity of water characteristics upstream and downstream of the discharge samples were measured at the laboratory. All water quali- with a view to identify significant changes attributable to ty analyses followed the American Public Health Associa- the discharge. tion guidelines [4].

Benthic Macroinvertebrates MATERIAL AND METHODS The three-minute kick sampling method was used in Study Site and Habitat collecting benthic macro-invertebrates. A D-frame net The study was conducted in Egri River, located near with a 300 µm mesh bag and a square frame net with a Atatürk Dam in the Southeast part of Turkey (N 37o46, E 500 µm mesh bag were used for this technique. Field elu- 38o14). It is 32 km long and has an annual average flow triation of the sample is required to reduce the sample vol- rate of 1.24 m3/s. Water from the river upstream is used ume. Then macro-invertebrates were separated from sedi- for human consumption in the city of Adıyaman, directly ments at the laboratory by visual examination and stere- after disinfection. It is gradually polluted, at first by agri- omicroscopy (MOTIC), and identified to the lowest practi- cultural activity around the watershed and later by indus- cal level, usually species, and the American Public Health trial and domestic wastewater discharge. Industrial Association guidelines were used for identification [4]. wastewater comes from small-scaled dairy productions. The Enumerations of the species were carried out. The scores annual average flow for this industrial wastewater is 0.1 were then calculated according to selected biotic indices, m3/h and the average COD is 520 mg/l. Domestic i.e. BMWP, TBI and Chandler Score [1, 5 and 6]. wastewater comes from a housing estate yielding a flow of 0.03 m3/s and an average COD of 240 mg/l. Statistical Analyses of Data Statistical analyses of water quality parameters and Habitat variables (depth, flow and substratum) were benthic macro-invertebrate data were performed. One- measured at the sampling sites. Flow velocity and depth way analysis of variances (ANOVA) was used to test for were measured at 50 cm increments along cross-stream differences between the sites and any two items of data. transects and used to determine total discharge and depth Data analysis was performed by the Minitab (Release profiles. Water velocity was measured with a flow meter 13.20) computer program.

FIGURE 1 Location of the sampling sites.

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RESULTS AND DISCUSSION 8 7 Water Quality 6 The pH values were approximately the same at all sta- 5 tions (Figure 2). Although sampling point 5 showed slightly acidic pH, there were no significant differences between 4 the sites (P=0.11). 3 2

9 12 1

8 Biochemical Oxygen Demand, mg/l 0 10 1 2 3 4 5 7 BOD 0,3 0,4 0,5 6,9 1,2 6 8 Sampling Points 5

pH 6 4 FIGURE 4 3 4 COD values at each sampling site. 2 2 Dissolved Oxygen,mg/l 1 Figures 3 and 4 show the average BOD and COD 0 0 values at the sampling sites. Statistical differences be- 1 2 3 4 5 tween the sampling sites with regard to BOD and COD pH 8 8,4 8,5 8,5 6,8 results are tabulated in Table 1, indicating that sampling Dissolved Oxygen 9,4 9,2 10,3 8,3 10 Sampling Points point 4 is significantly different from sampling points 1 and 2. It also shows that the river gradually recovers from FIGURE 2 the pollution after 1 km (the distance between sampling pH and Dissolved Oxygen (DO) values at each sampling site. points 4 and 5).

The average concentration of DO was lowest (8.3 mg/l) Benthic Macroinvertebrates after 50 m of discharge (sampling point 4), and it ranged Thirty-four taxa comprising 5734 species were col- between 9.2-10.3 mg/l at the other stations (Figure 2). lected in this study. Table 2 shows the abundance and diversity of the species at each sampling point. Hydracarina, diving beetle, damselfly, Crustacea (Pre- 8 carida), and Megaloptera (Sialidae) species were seen only 7 at the sampling points before the discharges. This is ex- 6 pected due to the fact that they are classified as pollution- 5 intolerant organisms. Similarly, as a clean-water benthos, an 4 Ephemeroptera mayfly was dominant at sampling points 1, 3 2 and 3. On the other hand, Oligocheata segmented worms, Hirudinea leeches, and midges are known to be the highly 2 pollution-tolerant organisms, and were abundant at sam- 1 pling points 4 and 5 as expected. Biochemical Oxygen Demand, mg/l 0 1 2 3 4 5 The highest number of macro-invertebrates was ob- BOD 0,3 0,4 0,5 6,9 1,2 served at sampling point 3. This is due to the fact that food Sampling Points availability is the most important factor governing the

FIGURE 3 abundance of benthos. If there is not any physical or or- BOD values at each sampling site. ganic stress in the environment, macro-invertebrates thrive.

TABLE 1 - Statistical differences (P*) between the sampling sites.

Difference Difference Difference Difference Sampling Points Significance (P) Significance(P) Sampling Points Significance (P) Significance(P) for BOD values for COD values for BOD values for COD values 1 and 2 0,412 0,818 2 and 4 0,028 0,031 1 and 3 0,298 0,149 2 and 5 0,318 0,042 1 and 4 0,024 0,039 3 and 4 0,101 0,172 1 and 5 0,209 0,058 3 and 5 0,738 0,382 2 and 3 0,365 0,099 4 and 5 0,057 0,483

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TABLE 2 - The overall composition and distribution of macro-invertebrates in the Egri River sampling stations.

Macroinvertebrates Sampling Points 1 2 3 4 5 Ephemeroptera mayflies Potamandidae 23 33 17 10 5 Hepatagenidae 99 216 151 8 50 Caenidae 12 19 50 - 43 B.Rhodani 13 172 23 1 17 B.Muticus 10 65 4 - 12 Odanata Dragonflies Aeshnidae 10 11 6 - 1 Gomphididae 3 3 4 Corduliidae 7 8 11 1 13 Diptera true flies Tabanidae 45 71 18 11 Limoniinae 12 102 - 1 1 Doliphocpodidae 4 10 - - - Epididae 4 1 1 1 Thamaulidae 200 51 - - - Diamesinae 162 294 292 181 504 Trichoptera uncased caddis Hydropsychidae 31 54 19 - 8 Psycomiidae 12 32 - - 12 Coleoptera adult beetles Hydrophilidae 2 1 8 - - Dytiscidae - - - - - Oligocheata-segmented worms Gordius - - 4 9 - Aquaticus - - - - - Lumbricillus - - 66 1 9 Limnodrillus 20 9 566 385 280 Hellobdella - - - - - Tubifex - - 3 - - Eisseniella - - 1 7 - Hemiclepsis - - - - - Stylaria - - 5 101 1 Hirudinea leeches 1 1 9 45 3 Midgefly 40 3 6 199 206 Hydracarina 18 19 50 - - Diving Beetle 76 31 27 1 - Damselfly 6 5 2 - - Crustacea Precarida 1 1 1 - - Megaloptera Sialidae 1 - 1 - - Total 808 1215 1579 966 1166

TABLE 3 - Score of sampling points according to BMWP, Chandler, and Trent Biotic Index.

Scores Sampling Points BMWP Trent Chandler 1 61 13 572 2 76 14 657 3 49 12 451 4 22 2 209 5 48 3 407

Table 3 shows the scores versus sampling points ob- indication of the water quality. As can be seen in Table 3, tained from the biotic indices. As can be seen, similar the highest score was obtained at sampling point 2. The results were obtained from all, indicating that although the water quality of this sampling point is slightly better than biotic indices give different scores, they all give a similar that of point 1.

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At the sampling sites without deterioration, mayflies [4] American Public Health Association (APHA) (1985) Stand- th and Diptera were dominant. On the other hand, Oligoe- ard Methods for Examination of Water and Wastewater, 16 . Edition, Greenberg A.E., Trussell R.R. and Clisceri L.S. chaeta, midges and leeches became dominant after the (eds.), Washington, DC. discharge. [5] Hawkes, H. A (1997) Origin and Development of the Biolog- ical Monitoring Working Party Score System. Water Re- CONCLUSION search 32 (3), 964-968.

[6] Hewitt, G (1991) River Quality Investigations, Part 1. Some Water quality, the physical environment of occupa- Diversity and Biotic Indices. Journal of Biological Education tion and food availability are the important factors gov- 25 (1), 44-53. erning the abundance and distribution of benthos. The highest number of macro-invertebrates in this study was observed at sampling point 3. This point was slightly polluted (i.e. organic matter was present) and there was not any organic stress (i.e., it was before the point of industrial wastewater discharge). The lowest number of species was seen at sampling point 1. This was because the water has high quality (i.e. organic matter is limited).

Statistical analyses of the data suggest that the sampling points fit the following interpretation. Sampling points 1 and 2 have clean water, whereas sampling point 3 has a borderline between natural water quality and some deterioration due to agricultural activities. Sampling point 4 has major deterioration due to discharge, and sampling point 5 has only some deterioration. Recovering could be observed after the bad conditions at sampling point 4.

According to the results, both the physico-chemical water quality and biological sediment quality show similar results. Hence, the results of the study supported the hypothesis that the use of macro-invertebrates as an indicator in a water body is an ideal method for the assessment of water quality.

ACKNOWLEDGEMENT

Special thanks to the Scientific and Technical Re- search Council of Turkey (TUBITAK) for funding this study.

Received: July 26, 2004 Revised: October 14, 2004 REFERENCES Accepted: December 11, 2004

[1] Dickens C. W. S, and Graham P. M (1998) Biomonitoring for Effective Management of Wastewater Discharges and the CORRESPONDING AUTHOR Health of the River Environment. Aquatic Ecosystem Health and Management 1 (2), 199-217. Sinan Uyanik Harran University [2] Iliopoulou-Georgudaki J., Kantzaris V., Katharios P., Kaspiris P., Georgiadis Th. and Montesantou B. (2003) An Dept. of Environmental Engineering Application of Different Bioindicators for Assessing Water Osmanbey Campus Quality: A Case Study in the rivers Alfeios and Pineios (Pel- 63000 Sanliurfa - TURKEY oponnisos, Greece). Ecological Indicators 2 (4), 345-360. Phone: +90 414 3440020 [3] Kantzaris V., Iliopoulou- Georgudaki J., Katharios P. and Kaspiris P. (2002) A Comparison of Several Biotic Indices e-mail: [email protected] Used for Water Quality Assessment at the Greek Rivers. Fresenius Environmental Bulletin 11 (11), 1000 – 1007

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PUBLIC ATTITUDES TOWARDS THE RESTORATION AND MANAGEMENT OF LAKE VELA (CENTRAL PORTUGAL)

Ruth Pereira1,2, Amadeu M.V.M. Soares 1, Rui Ribeiro3 and Fernando Gonçalves1

1 Departamento de Biologia da Universidade de Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro, Portugal. 2 Instituto Piaget, Campus Académico de Viseu, Estrada do Alto do Gaio, Lordosa. 3510-651 Viseu, Portugal. 3 Instituto do Ambiente e Vida, Departamento de Zoologia da Universidade de Coimbra, Largo Marquês de Pombal , 3004-547 Coimbra, Portugal

SUMMARY

Lake Vela local inhabitants' and visitors' environmen- involvement in environmental resources management, tal attitudes and opinions about ecological conditions of mainly at the local and regional levels [1-4]. the area and future management strategies to be implemented were investigated. The facilities required and the Many forms of public involvement are available for proposal to promote tourism activities, to enhance eco- collecting information that could be used in the develop- nomic development, have revealed public illiteracy about ment of local conservation plans. These include local ecosystems functioning and carrying capacity. This lack advisory committees, friends groups, questionnaire sur- of scientific knowledge was recognized by a great per- veys and periodic information meetings, some of which centage of individuals (61%, n=175), who mentioned have been successfully used in natural areas` planning [2, environmental education programs as one of the main 5-10]. Oral questionnaires were considered to be one of activities to be developed in the area. To spend some the most cost-effective and efficient methods, since much hours in a calm and healthy environment (67.6%, n=194), information could be gathered with lower economical and to share some moments with friends (58.2%, n=167), temporal costs [11]. Local inhabitants are an important picnics (49.5, n=49.5%), and wildlife observation (46.7%, source of information about environmental conditions, the n=134) were the main motives cited by respondents to main anthropogenic activities developed, their own eco- visit Lake Vela. These activities do not need to be re- nomic and social needs, and their expectations about local stricted in the management of the area, but only directed natural resources [5, 12, 13]. This information will be of for specific areas and carefully monitored, since they are extreme importance in the definition of management passive activities that yield few significant impacts. The strategies that try to combine the restoration and man- study also proposed some social benefits that could be agement of local natural resources with the provision of integrated in the management of the area, in order to in- economic, recreational and educational opportunities [5]. crease the quality of visitors` experiences and, hence, to get public compliance and involvement in the preserva- The present study was conducted as part of the for- tion of that natural resources. mulation of a management plan for Lake Vela (Central Portugal), a freshwater body severely impacted by human

activities [14]. The main purpose was to gather infor-

mation about the types of activities carried out by local KEYWORDS: freshwater lakes, management, facilities, public attitudes, questionnaires. inhabitants and visitors and their socio-economic expectations as well as their opinions about the conditions of the lake and some of the restoration and preservation measures that were planned. INTRODUCTION

Currently, it is largely recognized that patterns of MATERIAL AND METHODS natural resources use are unacceptable, and the principles of environmental sustainability need to be followed. There- Study site fore, following the formulation of the Local Agenda 21 Lake Vela, a coastal freshwater lake with a surface and national legislation in force (e.g. Portuguese National area of 70 ha and a maximum depth of 2 m, is located in Strategy for Nature and Biodiversity Conservation) great Central Portugal, near Figueira da Foz. On its west is a efforts are being made by all the countries to promote public Pinus sp.-wooded area, and on its east margin agricultural

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fields are present. Corn and grazing fields also proliferate tain information about demographic variables like gender, on its catchment area. This lake belongs to a system age, residence, educational level and occupation, was formed by three other small lakes, in which water levels followed by twelve questions. Four questions were en- fluctuate significantly with weather conditions and drain- closed, in which respondents could choose different op- age for human and agricultural consumption [15]. tions or include other aspects not taken under consideration during the questionnaire design. As for the other Lake Vela is an important regional natural resource eight, six were in true-false format or were questions with classified by the European Community program CORINE a graduated scale, and two were open questions. Based on 85/338/CEE, 27 June, that attracts many tourists, especial- previous knowledge of the social and cultural level of the ly those seeking an alternative to the beach and a refuge population, acquired during several years of scientific from nearby urban areas. This lake is also an important research in the area, the questionnaire was carefully de- habitat for wildlife, especially migratory birds, which signed according to survey research methodology [28-30]. have been disturbed by the intense recreational pressure. The questionnaire was presented by direct interviews to More recently, in order to protect a valuable freshwater the local population and Lake Vela visitors during the resource of European interest and its biodiversity, the lake summer. This was considered to be the best method, since was included within a national site from the Natura 2000 the interviewer could immediately clarify any question Network (PTCON0055) established by the Directive that might have been misunderstood [31]. The interview- nº92/43/CEE of Council, of 21 of May [16]. ers received precise information about their role and the main objectives of the questionnaire. Agricultural practices and cattle breeding on Lake Vela margins have been responsible for soil saturation Statistical analysis with manure, fertilizers and other chemicals. The conse- The questions were coded for statistical analysis, after quent leaching of high loads of nutrients and organic the questionnaire’s presentation. The category of "no matter to the lake was responsible for the high concentra- answer/no opinion" was also defined in all the questions tions of nitrogen and phosphorus compounds recorded in to include non-responded questions. Those cases may be Lake Vela, mainly in autumn and winter months 17-19 . [ ] important and should not be ignored in questionnaire During the summer months the increase in temperature analysis, because they do not necessarily mean that the usually causes the reduction of dissolved oxygen concen- individual has no opinion. By contrast, the question could trations, which, together with high levels of pH, may have focus on a sensitive issue and the inquired could have been responsible for the release of phosphorus com- preferred to be neutral 30 . pounds from the sediments to the water column and the [ ] decrease in N:P ratio recorded in Lake Vela, which fa- Contingency tables were constructed and multiple voured the dominance of the phytoplankton community choice questions were analysed using Chi-square test to by cyanobacteria 20-23 . The blooms of cyanobacteria, [ ] measure independence between groups, for each of the mainly Microcystis aeruginosa, observed during the five pre-defined socio-economic variables. When groups summer and autumn months, became increasingly fre- were not independent, Cramers V was reported [32, 33]. quent 18 , and had a negative influence on the ecologi- [ ] cal, aesthetic and recreational values of the lake. Since data was not normally distributed, Mann With- ney and Kruskall-Wallis analyses were performed for true- Another sign of the severe eutrophication process was false format questions and questions with a graduated scale. the high macrophyte biomass productivity rate recorded Whenever significant differences were found, Dunn’s mul- in the east margin, mainly attributed to emergent species tiple comparison test was performed [33]. [24]. This observation has confirmed the nutrient inflows from surrounding agricultural fields. Machás [24] also found low frequencies and relative abundance for submerged macrophytes. Those species are an important RESULTS component of a healthy shallow lake and their disappear- ance is a common occurrence during the eutrophication A total of 287 interviews were carried out. The de- process [25-27]. In summary, Lake Vela is a turbid lake, mographic results are presented in Table 1. The majority threatened by eutrophication and is also facing the prolif- of respondents (78.7%, n=226) lived less than 10 km from eration of exotic fish species [18]. the lake. Their educational level can be considered to be low and it differed significantly according to age (H=34.875, d.f.=5, p<0.001). The two younger groups Questionnaire design and implementation were significantly different (p>0.05) from the two older The questionnaire covered four issues: i) personal da- ones, which had the same educational level. This is a ta; ii) attitudes towards the environment; iii) knowledge of consequence of the fact that a great percentage of the the area; and iv) attitudes towards new management strat- older individuals only attended the first level of basic egies to be implemented. The first item, designed to ob- school (Table 2).

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TABLE 1 - Respondents distribution by sex, age, residence location, educational level and occupation (n=287).

Total (n) Percentages (%) Sex Female 116 40.4 Male 171 59.6 Age Less or equal to18 years old 59 20.6 19-25 52 18.1 26-35 60 20.9 36-45 44 15.3 46-65 54 18.8 More than 65 18 6.3 Residence location Less or equal to 10 km 226 78.7 More than 10 km 61 21.3 Educational level 1st level of basic school 74 25.8 2nd level of basic school 30 10.5 Secondary school 111 38.7 University 40 13.9 Didn't study/no answer 32 11.1 Occupation Student 79 27.5 Public functionary worker 29 10.1 Market/industry 77 26.8 Farmer 14 4.9 Housewife 22 7.7 Retired 10 3.5 Others 40 13.9 Unemployed/ Didn't answer 16 5.6

TABLE 2 Respondents distribution by age and educational level (n=287).

≤ 18 19-25 26-35 36-45 46-65 > 65 Educational level N % N % N % N % N % N % 1st level of basic school 2 3.4 4 7.7 8 13.3 18 40.9 27 50 15 83.3 2nd level of basic school 4 6.8 4 7.7 12 20 6 13.6 4 7.4 0 0 Secondary school 46 78 29 55.8 18 30 10 22.7 7 13 1 5.6 University 0 0 13 25 14 23.3 7 15.9 6 11.1 0 0 Didn't study/no answer 7 11.9 2 3.8 8 13.3 3 6.8 10 18.5 2 11.1 N = number

Attitudes towards the environment farmers gave little or no importance to the maintenance of When asked about environmental conservation im- good environmental conditions. However, those results portance and their contribution for it, 92.3% (n=265) of should be carefully interpreted, since this group was rep- the respondents said they considered it to be a very im- resented by only 4.9% (n=14) of the respondents and portant issue and 92% (n=264) stated that they contribut- more research should focus on the attitudes of this group. ed to a better environment. On the first question, differ- Educational level groups also had significantly different ences in opinion were found among occupational groups answers (H=75.353, d.f.=4; p=<0.001). Respondents who (H= 24.331, d.f.=7, p<=0.001). Dunn's multiple compari- had not attended school were significantly different son test could not distinguish which groups were differ- (p<0.05) from the other groups, and they were represent- ent. Compared to the other groups, a greater percentage of ed by a higher percentage of individuals that did not con-

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tribute, in any way, to a better environment. Somewhat that required specific information and a personal envi- surprising was the fact that no differences were found ronmental ethic (Figure 1). Regarding the other groups, a between individuals with basic school studies and those great percentage of individuals that had attended universi- with university degrees (Q=7.845, p>0.05). Taking into ty (62.5%) stated that they separated glass and paper for consideration that 43.2% (n=42) of the respondents from recycling. The actions cited in our study were also signifi- the former group were more than 45 years old, two possi- cantly related to residence location (χ2=18.909, d.f.=7, bilities could explain those results: (1) older individuals are p=0.008, V=1.0). A greater percentage of individuals, that highly sensitized for local environmental problems, and resided more than 10 km from Lake Vela, stated that they direct their actions to minimize harmful impacts of their separated trash for recycling (60.6%, n=37) and were activities; (2) or, at least, they think they are doing that. concerned with buying only CFC-free sprays (49.2%, Significantly different answers were also found among n=30). occupational groups (H=40.117, d.f.=7, p<0.001).

To pour the garbage out in appropriate facilities and TABLE 3 - Forms through which respondents use to contribute to preserve the environment (n=287). to be careful when lighting a fire, as well as doing it in the proper place, were environmental practices of the great Total (n) % majority of the respondents (Table 3). Those actions A. Pay attention to the kind of deter- 89 31.0 were associated with gender (χ2=15.585, d.f.=7, p=0.029, gents used 2 B. Pour out the garbage in appropriate V=0.99) and educational level (χ =60.467, d.f.=28, p<0.001, 266 92.7 V=0.61). Regarding gender, chi-square was recalculated facilities C. Send paper and glass bottles for 91 31.7 after removing option A (see Table 3) from contingency recycling 2 table (χ =3.740, d.f.=6, p=0.712, V=0.516). Women seemed D. Use only CFC free sprays 96 33.4 to be more concerned with the kind of chemical products E. Teach the children to respect nature 125 43.6 they bought, and in using them as little as possible. A F. Make fire only in appropriate places 196 68.3 G. Use the less quantity of chemical great percentage of women (37.9%, n=44) also separated 133 46.3 litter and sent it for recycling. products as possible H. Others 22 7.7

It is interesting to note that respondents with university degrees were the main participants in ecological actions

1st lev. Basic Sch. 2nd lev. Basic Sch. Second. Sch. Univ. 100 Didn't study/no answer

90 80 aaa 70

60 50

Respondents (%) Respondents 20

0 A B C D E F G Others

Actions practiced for environmental preservation

FIGURE 1 - Percentage of ecological actions performed by respondents according to their educational level (A - Pay attention to the kind of detergents used; B - Pour out the garbage in appropriate facilities; C - Send paper and glass bottles for recycling; D - Use only CFC-free sprays; E - Teach the children to respect nature; F - Make fire only in appropriate places; G - Use the less quantity of chemical products as possible).

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Knowledge about the area and TABLE 4 - Motives to visit Lake Vela (n=287). attitudes towards its management The great majority of individuals (96.2%, n= 276) Total (n) % A. Spend some hours in a calm and had previous knowledge about the area due to the proxim- 194 67.6 ity of their residences (78.7%, n=226), or because they healthy environment had agricultural fields in Lake Vela catchment’s area B. Enjoy some moments with friends 167 58.2 C. Picnics 142 49.5 (9.6%, n=27). Only 3.1% (n=9) stated that it was their D. Recreational fishing 82 28.6 first time at Lake Vela. E. Swimming 94 32.8 F. Wildlife observation 134 46.7 The individuals were asked to specify (through multi- G. Photographing 97 33.8 ple-choice answers) their motives to visit Lake Vela and its H. Others 21 7.3 surrounding area. The need to spend some hours in a healthy and calm environment, to share some pleasant In the assessment of the degree of satisfaction, when moments with friends, and picnics were the main motives considering the environmental conditions of the area, it that led respondents to visit the lake (Table 4). The motives was recorded that 39.0% (n=112) and 46% (n=132) of the cited were strongly related with gender (χ2=25.876, d.f.=7, respondents were little or not satisfied with the degree of p<=0.001, V=1) and less with the educational level deterioration of Lake Vela and its surrounding area. Sig- (χ2=117.262, d.f.=32, p=<0.001, V=0.52). A higher per- nificant differences were found between gender groups centage of men visited the lake to engage in recreational (U=4.023, d.f.=1, p=0.045). Regarding gender, a greater fishing (39.8%, n=68), while women were comparatively percentage of men stated not to be satisfied with the con- more interested in photographing the landscape and its ditions of Lake Vela natural features. As well, a great wildlife (40.5%, n=47). Concerning educational level, majority of respondents (88.2%, n=253) agreed with the individuals with university studies tended to visit the lake necessity to formulate, design and implement new man- mainly to observe wildlife (85%, n=40) (Figure 2). Sport agement strategies in the area. No significant differences activities and walking or strolling were some of the addi- (p>0.05) were found among groups with respect to each tional activities mentioned by the people interviewed. of the five socio-economic variables.

1st level Basic Sch. 2nd level Basic Sch. Second. Sch. Univ. Didn't study/ No answer 90

70 aaa 60

50 40

(%) Respondents 20

0 A B C D E F G H

Motives to visit Vela lake FIGURE 2 - Percentage of motives to visit Vela lake cited by respondents according their educational level (A - Spend some hours in a calm and healthy environment; B - Enjoy some moments with friends; C - Picnics; D - Recreational fishing; E - Swimming; F - Wildlife observation; G - Photographing; H -Others).

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90 Female 80 Male

aaa 60

50 40 30 20 Respondents (%) Respondents 10 0

Games No Others Fis hing Popular Camping Research Scientific

Educ ati on Intervention Improvement Envi r onme ntal Quality Water

FIGURE 3 - Activities that the respondents would like to see developed in Vela lake according to gender.

A boat, a bar and a car parking area were the main fa- TABLE 5 cilities and services that respondents identified as lacking Infrastructures and facilities that inquires considered to be necessary in Vela lake area to improve the quality of their visits (n=287). in the Lake Vela area, and mentioned them as a way to improve the quality of their visits (Table 5). The facilities Total (n) % cited were not related with gender, age, educational level, A. Bar 163 56.8 residence, or professional activity. B. W. C. 225 78.4 C. Parking area 126 43.9 When asked about the main activities they would like D. Boats 162 56.4 E. Nature guide 91 31.7 to see developed in Lake Vela area, the rehabilitation of F. Tourism office 80 27.9 water quality, environmental education programs and rec- G. Bus 39 13.6 reational fishing (56.4%, n=162) were the most frequently H. Bicycles 113 39.4 mentioned by respondents. A significantly high percentage I. Others 54 18.8 of men (67.8%, n=116) preferred the development of recreational fishing, while women preferred environmental According to the respondents, Lake Vela may be used education activities (71.6%, n=83) (χ2=19.20, d.f.=7, to promote economic development in the local area, p=0.008) (Figure 3). through the promotion and development of tourism activities (42%, n=103), and 20% (n=34) added that new infra- The participants were also asked about closing the structure and facilities (e.g. hotels, camping, golf camp) Lake Vela shores to car and motorcycle traffic. The ma- should be created in the area. No statistically significant jority (52.6%, n=151) agreed with this proposal. Statisti- differences in opinion were found between the different cally significant differences were found in the eight occu- groups defined for each of the variables. pational groups (χ2=14.937, d.f. =7; p=0.037). However, Dunn's multiple comparison test was not able to distinguish which groups were different. 48.1% (n=50 in 104) DISCUSSION of the justifications given by respondents with a favourable opinion was that prohibiting traffic circulation in the Usually, the human society looks to ecosystems mainly area would be the best management practice to prevent as sources of economical and social benefits, without being pollution, whereas maintaining the right to drive cars and concerned with potential harmful impacts that can result motorcycles up to the shores was the main justification from the extraction of those benefits [34, 35]. Once more, presented by respondents with a non-favourable opinion this utilitarian point of view was observed in Lake Vela (46.4%, n=26 in 56). local inhabitants and visitors. Notwithstanding, the great

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percentage of respondents considered the maintenance of managers may be the explanation for vandalism recorded environmental quality as a very important issue. The de- in the area. mand for facilities and infrastructure to promote tourism in the area has revealed the lack of awareness of relation- It is widely recognized that the public has increasing ship between human activities and environmental degra- preferences for outdoor recreation activities in natural dation. Consequently, we believe that the concern with areas [31]. Outdoor recreation could produce impacts on the lake’s environmental health, demonstrated by a great biodiversity, as severe as that resultant from logging and percentage of respondents who mentioned the improve- livestock grazing [44]. However, the type of activities ment of water quality as a priority action, results only from carried out in Lake Vela, namely wildlife observation and the value of the lake as a potential economic and social picnics, were passive ones. Those activities, in addition to resource. In fact, although Roe [36] argued that the public recreational fishing, could be compatible with resources is really interested in ecosystems where they reside, Holl preservation, and with the maintenance of the quality of et al. [37] recorded that public with lower educational visitors' experiences, whether they were directed to spe- level was more concerned with the improvement of eco- cific areas or with simultaneous implementation of strate- nomic conditions than with environmental problems. gies to prevent crowding. The provision of a parking area Therefore, if public participation in the management of in addition to prohibition of cars from that area and limit- Lake Vela is to be profitable and long-term effectiveness ing the number of wood tables and benches could be some of restoration strategies guaranteed, formal and non- of those strategies. The recent findings of some authors formal education programs should be planned. According [45, 46] note that crowding seemed to be an acceptable to Heinen [38], education programs without social and impact for different national park visitors, but it should be economic benefits are not likely to work, but they are of prevented in Lake Vela. Because of its small area, the high importance as precursors of restoration efforts. In ecological carrying capacity of the lake is likely to be this study, 61% (n=175) of Lake Vela local inhabitants quickly overcome. and visitors required educational programs, which was a good indication about the predictable effectiveness of According to Jussof and Majid [47], the offer of some these programs, because the public was the first to recog- social and economic benefits is a key factor in promoting nize their lack of knowledge about environmental issues. public participation in the development of local conserva- A great percentage of managers interviewed by Manning tion plans, and in complying with conservation actions. et al. [39] preferred visitors educational programs as a However, one of the main reasons for the failure of envi- highly effective management strategy. ronmental restoration programs, results from the fact that benefits yielded are not received by those who incur the Non-formal environmental education programs could costs [48]. Therefore, the knowledge of socio-economic improve the understanding of the complexity of ecosys- expectations of local inhabitants and Lake Vela visitors tem functioning, the carrying capacity of resource sys- will allow the consideration of some of them in the man- tems, the impacts of human activities on ecosystem integ- agement of the area, if they were compatible with the rity and beauty, and the expected time lag between the goals defined. Although, economic issues are frequently implementation of management strategies and the occur- mentioned by neighbourhood inhabitants of natural areas rence of observable outcomes [40, 41]. And it could also [2], it is important to make people perceive that conserva- demonstrate other possible benefits that conservation can tion programs also involve costs, such as restricted access bring to local communities. Previous studies carried out to some areas, and the cessation of some activities. More- on Donãna National Park have demonstrated the im- over, it is important to acknowledge non-economic social portance of active local participation in environmental benefits derived from the environment, such as aesthetics, programs to improve landscape perception and apprecia- spiritual benefits, education and recreation. The lack of tion [42]. In fact, people that interact directly with the environmental knowledge to take this reality seriously landscape usually develop ecological aesthetics` sense compromises the future of ecosystems. and enhance understanding and appreciation of ecosystem management activities [43]. The existent Lake Vela environmental education centre could be used for temporary exhibitions and meetings (with resources managers) in ACKNOWLEDGEMENTS order to provide information to the public, especially local inhabitants, about ongoing restoration activities. Addi- The authors are very grateful to Pedro Raposo, M.J. tionally, informative signboards could be put in manage- Ferreira, I. Lopes and other colleagues who helped in the ment areas, and interpretative nature trails could be used field work. Special thanks are due to local residents and to explain management decisions implemented. Accord- visitors who participated in the research and to S. Penha ing to Gobster [43], such facilities are useful tools to for the English revision. This study was partially support- communicate with the public, which is of extreme im- ed by a grant to R. Pereira, from Fundação para a Ciência portance in this area, since we believe that a misunder- e a Tecnologia (Portugal). standing about some actions and rules already defined by

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[13] Lawrence, R.L. and Daniels, S.E. (1996). Public involvement [27] Abe, T., Lawson, T., Weyers, J.D.B. and Codd, G.A. (1996). in natural resource decision-making: goals, methodology, and Mycroscystin-LR inhibits photosynthesis of Phaseolus vul- evaluation. Papers in Forest Policy 3, 3-49. garis primary leaves: implications for current spray irrigation practice. New Phytol. 133, 651-658. [14] Pereira, R. (1997). Plano de Ordenamento e Gestão das La- goas das Braças e da Vela (Centro Litoral). M. Sc. thesis. [28] Oppenheim, A.N. (1966). Questionnaire design and attitude Faculdade de Ciências e Tecnologia da Universidade de measurement. 1st Ed. Basic Books Inc. Publishers, New Coimbra, Coimbra, Portugal. York, USA, 1-298.

[15] Anonymous (1994). Lagoas de Quiaios: estudos e planos de [29] Banks, J.A. and Clegg Jr, A.A. (1973). Teaching strategies utilização. Relatório final. Instituto do Ambiente e Vida, for the social studies. Inquiry, valuing and decision-making. Universidade de Coimbra, Coimbra,Portugal. Addison-Wesley Publishing Company, Inc. Menlo Park, Cal- ifornia, USA. [16] CM – Conselho De Ministros (2000). Resolução do Conselho de Ministros nº 76/2000. Diário da República, Série I-B, 153, [30] Ghiglione, R. and Matalon, B. (1995). O inquérito. Teoria e 2933-2945. prática. Celta Editora, Oeiras, Portugal.

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[31] Gülez, S. (1996). Relationship between recreation demand and some natural landscape elements in Turkey: a case study. Environ. Manage. 20(1), 113-122.

[32] Calder, J. (1996). Statistical Techniques. In: Data Collection and Analysis. (R. Sapsford and V. Jupp Eds.) Sage Publica- tions, London, UK, 225-262.

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[34] Cairns Jr., J. (1995). Ecosocietal Restoration. Re-establishing humanity's relationship with natural systems. Environment 37 (5), 30-33.

[35] Spash, C.L. (1997). Ethics and the environmental attitudes with implications for economic valuation. J. Environ. Man- age. 50, 403-416.

[36] Roe, E. (1996). Why ecosystem management can't work without social science: an example from California northern spotted owl controversy. Environ. Manage. 20(5), 667-674. [37] Holl, K.D, Gretchen, C.D. and Ehrlich, P.R. (1996). Knowledge and perceptions in Costa Rica regarding environment, population and biodiversity issues. Conserv. Biol. 9(6), 1548-1558.

[38] Heinen, J.T. (1996). Human behaviour, incentives and protected area management. Conserv. Biol. 10(2), 681-684.

[39] Manning, R.E., Ballinger, N.L., Marion, J. and Roggenbuck, J. (1996). Recreation management in natural areas: problems, status and trends. Nat. Area J. 16, 142-146.

[40] Jacobson, S.K. and Marynowski, S.B. (1996). Public attitudes and knowledge about ecosystem management on department of Defense Land in Florida. Conserv. Biol. 11 (3), 770-781.

[41] Diduck, A. (1999). Critical education in resource and environmental management: learning and empowerment for sus- tainable future. J. Environ. Manage. 57, 85-97.

[42] Múgica, M. and De Lucio, J.V. (1996). The role of on-site experience on landscape preferences. A case study at Doñana National Park (Spain). J. Environ. Manage. 47, 229-239.

[43] Gobster, P.H. (1995). Aldo's Leopold Ecological aesthetic. Integrating aesthetic and biodiversity values. J. Forest. 93(2), 6-10. Received: July 28, 2004 Accepted: October 25, 2004 [44] Knight, R.L. (1996). Aldo Leopold, The land ethic, and ecosystem management. J. Wildl. Manage. 60(3), 471-474.

[45] Floyd, M.F., Jang, H. and Noe, F.P. (1997). The relationship CORRESPONDING AUTHOR between environmental concern and acceptability of environmental impacts among visitors to two U.S. National park Ruth Pereira settings. J. Environ. Manage. 51, 391-412. Departamento de Biologia [46] Noe, F.P., Hammitt, W.E. and Bixler, R.D. (1997). Park user Universidade de Aveiro perceptions of resource use and impacts under varied situations Campus Universitário de Santiago in three national parks. J. Environ. Manage. 49, 323-336. 3810- 193 Aveiro - PORTUGAL

[47] Jusoff, K. and Majid, N.M. (1995). Integrating needs of local Phone: +351234370200 (ext. 22712) community to conserve forest biodiversity in the State of Ke- lantan. J. Environ. Manage. 45, 143-161. Fax: +351234370777 e-mail: [email protected] [48] Dixon, J.A. and Sherman, P.B. (1991). Economic of protected areas. Ambio 20(2), 68-74. FEB/ Vol 14/ No 4/ 2005 – pages 273 – 281

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ORGANIC POLLUTANTS IN STREAM SEDIMENTS OF KUPA RIVER DRAINAGE BASIN

Stanislav Frančišković-Bilinski1*, Halka Bilinski1 and Siniša Širac2

1Institute “Ruđer Bošković”, POB 180, 10002 Zagreb, Croatia 2Hrvatske Vode, Ulica grada Vukovara 220, 10000 Zagreb, Croatia

SUMMARY

This paper presents the first results of distribution of or- state of pollution. Also, some parts of drainage basin are ganic pollutants in 44 sediment samples (fraction <63 µm) National Parks, so that it is very important to investigate of Kupa River drainage basin, which is a significant water the quality of water and sediments. resource for Croatia, Slovenia and BiH (Bosnia and Her- In this work, 5 organic pollutants (PCBs, lindane iso- zegovina). The investigated region aimed to be used as a mers, phenolic index, total oils and mineral oils) were model for future studies, necessary to meet Decision No. studied in Kupa River drainage basin. PCBs (polychlorin- 2455/2001/EC. Some parts of the drainage basin are na- ated biphenyls) are the most harmful of all of them [1]. tional parks (Risnjak and Plitvice Lakes). Also, a great part They have the general chemical formula C H Cl , in was affected by war 1991-1995 and is still under mines, 12 10-n n which n = 1-10. There are 209 congeners of PCBs (chemi- what makes it difficult to sample. cals with the same basic structure), where biphenyl struc- Sediments have shown a good record of pollution. ture has atoms of chlorine changed with atoms of hydro- Concentrations of total polychlorinated biphenyls (PCBs) gen in various degrees. From them, about 100 congeners were found above toxic levels (>0.02 ppm) for 7 sediment are present in different technical mixtures of PCBs, which samples. Total phenols were determined above 0.65 ppm were commercially produced in big amounts until the end for 23 sediment samples, which was characterized as heavi- of the 1970-decade [2]. PCBs were mostly used in electric ly polluted sites. Mineral oils above 100 ppm were found equipments, as transformers and capacitors, in hydraulic in 13 sediment samples, which are, therefore, moderately fluids, etc [2]. It is one of the most toxic organic pollu- polluted. Total lindane isomers in all sediments were tants, due to their low degradation rate. PCBs stay in below the detection limit of 0.0004 ppm, and, therefore, environment and animals, and bioaccumulate in food far below the toxic level of 0.0009 ppm. chain and present a risk for human health and environ- Results have shown unexpectedly that the western part ment [3]. PCBs, but also other organic pollutants, are of Kupa River drainage basin, with karst aquifers of high being transported by streams and rivers over big distances risk located in the boarder area of Croatia and Slovenia, has and are often precipitated in areas, where they have never sediments, which were more polluted with organic con- been produced [4]. taminants from those affected by the war in the middle The state of organic contamination of the Kupa River and eastern part of the basin. Further studies of sediments ecosystem is not known yet. Generally, a limited number and protection of karst aquifers in this region is suggested. of studies concerning organic contamination has been performed. Picer and Holoubek [5] and Picer et al. [6]

have investigated PCBs in karstic environment of Slove-

KEYWORDS: PCBs, phenols, total oils, mineral oils, lindane, nia and Croatia. In the last 20 years in Slovenia and Croa- stream sediments, Kupa River drainage basin, Croatia, Slovenia, tia were two serious incidents, in which significant amounts Bosnia and Herzegovina. of PCB were introduced into the bioecological cycle of karstic environment.

The first incident was at the beginning of the 1970- INTRODUCTION ties, because of inadequate PCB disposal from the capaci- tor factory “Iskra” in Semič, Bela Krajina, Slovenia. This Kupa River drainage basin is a very poorly investigated pollution was discovered in 1983, during research of area in terms of geochemistry and organic pollution. As water samples of the small Krupa River, as potential drink- Kupa River is rich in water resources significant for both ing water source for Bela Krajina region in Slovenia. The Croatia and Slovenia, it is very important to investigate its pollution spread to Lahinja River and then to Kupa River

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and continued about 200 km downstream. It is estimated MATERIALS AND METHODS that 1962-1985 about 3-6 t of PCBs were emitted into the atmosphere, and a similar amount was lost during differ- The study area of the Kupa River drainage basin, to- ent technological processes. Also, 65-75 t were inade- gether with a location map for Slovenia, Croatia and Bos- quately disposed, mostly into karstic holes in the vicinity nia and Herzegovina is presented in Figure 1. Kupa River of the factory. In 1986 was a big remediation of the area, itself is 296 km long, from its source under Risnjak and 30-50 t of PCB waste were collected. In the same Mountain in Gorski Kotar to its inflow to Sava River in time, it was assumed that 30-40 t of PCB waste still exist Sisak. The drainage basin covers 10.052 km2. Most of its in the karstic area of Bela Krajina, Slovenia [5]. For com- part is situated in Croatia, and minor parts are in Slovenia parison, in the whole UK environment their amount was and in Bosnia and Herzegovina. It is very asymmetric: north estimated to be 400 t [7]. from Kupa it is narrow (approximate width is < 20 km), while southwards it stretches up to 80 km from Kupa River The second incident occurred during the war in Croatia flow. The main tributaries flowing from south are Kupica, (1991-1995), when unknown amounts of PCBs were re- Dobra, Mrežnica, Korana, Glina and Petrinjčica, whereas leased into the environment by destruction of many trans- those flowing from north are Čabranka, Lahinja and former stations, and from explosives and their side prod- Kupčina rivers. ucts. By non-controlled burning of PCB and other organo- halogens, polyhalogenated dibenzofurans and dibezodiox- The hydrogeological characteristics of Kupa River ins are formed, which makes the area of war activities drainage basin are as follows: From Slovenia to Bosnia even more dangerous. In Croatia there are several loca- there is a 120 km long series of anticline structures with tions, at which is suspected on pollution as result of war Jurassic dolomites in the core, which represent the total activities. One of them is located in Kupa River drainage barrier and force the groundwaters to flow northward and basin, because in Delnice a 5/10 kV transformer station spring from the series of 12 permanent springs with mini- 3 was bombed. However, the soil samples have not shown mal flows of 0.1-1.0 m /s. Those springs form the streams significant pollution. There could be also many more sites Ogulinska Dobra, Zagorska Mrežnica, Dretulja, Lička in war-affected areas, where minor pollution could be Jasenica and, occasionally, Lake Begovac. These springs present, as described in a recent study “Inventory of poly- sink when they pass dolomite bedrock, and groundwater chlorinated biphenyls (PCBs) in the Republic of Croatia, again springs at new lower series of 12 strong permanent Summary” [8]. sources, which form permanent rivers: Kupa, Čabranka, Dobra, Mrežnica, Korana, their tributaries, and Plitvice Besides PCBs, phenols are one of the main organic pol- Lakes National Park. In such a way there are formed two lutants in sediments. According to Omuro Lupetti et al. [9], large karstic hydrogeological “stairs”. The line of lower the presence of phenols in aquatic environment indicates springs represents also the boarder between high-karstic anthropogenic pollution, whose main sources are colors, and fluvio-karstic sub-regions and it extends far away in petroleum, cellulose, paper industry, pesticides` produc- the drainage basin of Krka River in Slovenia. tion and their use. Phenols are very toxic for humans, and they damage blood, liver and kidneys [10]. As several Sampling in Kupa River drainage basin was performed during three summer months of 2003, between 4th June and different phenols can be present in aquatic environments, th their monitoring can be performed by total phenols` de- 29 August. In Figure 1 the sketch-map of the investigated termination. area is presented, with the numbers of 44 sampling stations, in which organic pollutants have been analyzed. The aim of the present work The summer of 2003 was extremely dry and warm, so The aim of the work was to present a model pollution water levels of most streams and rivers were low, which study of the chosen Kupa River drainage basin, and to was a very suitable time for sampling. Sampling was com- determine the concentrations of organic pollutants in plicated by the fact that a big part of Kupa River drainage stream sediments. The preliminary results can give a clear basin was affected by war, and also mined. Therefore, the picture about the current state of the water resources of Croatian center for de-mining in Sisak was consulted be- interest for Croatia, Slovenia and Bosnia and Herzegovina. fore all field trips, and planned locations of some samples The growing importance of this research is to prove the were modified, according to the mine situation in the field. quality of water, because according to Biondić et al. [11] Surface sediments in contact with running water were col- karst aquifers of the western part of Kupa River drainage lected manually, using an acrylic glass tube, 20 cm long basin are of high risk. There are zones of major traffic and of 6 cm diameter. It was looked out that the sampling corridors, oil pipelines, railways, wood industry, saw and locations were representative, to exclude contamination of flower mills. Middle and eastern parts of the basin were sediment by sliding down of the material from the affected by the war activities 1991-1995, what is assumed riverbanks. At each sampling site 3-5 kg of sediment was to contribute to pollution. collected, so that it would be possible to obtain enough fractions < 63 µm, on which all analyses were performed. We aim to define the regions of further necessary re- Samples were dried in open air, in the shadow, at the air- search and protection. temperature of about 30-35 ºC, and then dry-sieved using

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three standard sieves of diameter 63, 500 and 2000 µm following conditions: Start position: 2θ 4.01; End posi- (Fritsch, Germany). The 500 and 2000 µm mesh sieves tion: 2θ 62.99; Generator settings: 40 kV, 40 mA. The were used to eliminate coarse grains, and that with 63 µm mineral phases were identified using the program X-pert. was used for obtaining the fraction f < 63 µm (silt + clay), Analysis of total PCBs and lindane was performed in on which all analyses were performed. an authorized institution, according to German standard To obtain the mineralogical composition of sedi- method DIN 38 414-20, based on extraction and gas ments, semi-quantitative mineralogical analysis was per- chromatography. The detection limit was 0.005 ppm formed, as described by Boldrin et al. [12]. A diffract (mg/kg of dry weight) for PCBs and 0.0004 ppm (mg/kg meter Philips 3040/60, X-pert MPD was used, with the of dry weight for lindane, as described by Šmit et al. [13].

FIGURE 1 - A sketch-map of Kupa River drainage basin with 44 sampling stations (above) and location map for Slovenia, Croatia and Bosnia-Herzegovina with the position of Kupa River drainage basin (below).

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Analysis of total and mineral oils was performed in mined in Dobra at Vrbovsko. Higher concentrations of an authorized institution, according to German standard phenols were measured in Kupa at Severin na Kupi and in method DIN 38 409-18. As medium for extraction of oils, Lahinja at Primostek, Slovenia (3-4.5 ppm), and 4.5-5 ppm 1,1,2–trichlorotrifluorethane (freone-113) was used. For are found in Dobra river at Ogulin and Donje Stative. The quantitative determination with infrared spectroscopy, the highest concentration of total phenols (9.7 ppm) was -1 characteristic adsorption of CH3-group (υ=2968 cm ), measured in Dobra at Trošmarija. -1 CH2-group (υ=2924 cm ) and CH-aromate group (υ= -1 In the eastern part of Kupa River drainage basin, the 3030 cm ) was used. This extraction mean does not cause concentrations of total oils are <200 ppm. In this part are disturbances during determination of the oils. only two localities (Kupa at Lijevo Sredičko and Glina at Analysis of total phenols was carried out in an au- Glina), where the concentrations were <100 ppm. Con- thorized institution, according to the German standard centrations of 200-250 ppm were determined in Kupa at method DIN 38409-16. Phenol index (in µg/L) is deter- Severin, Muljevac at Brihovo and Mrežnica at Mala mined spectrophotometrically at 510 nm, after distillation Švarča. Concentrations of 250-300 ppm were observed in and with adding the reagent 4-AAP (4-aminoantipirine) in Kupa at Žaga, Dobra at Trošmarija and Donje Stative, alkaline solution. Phenol detection limit in sediment was Kupa at Levkušje-Zorkovac, Kupčina at Donja Kupčina 0.1 ppm (mg/kg of dry weight). and Kladušnica at Barake-Velika Kladuša (Bosnia and Herzegovina). Concentrations of 300-350 ppm were in Kupa at Hrvatsko, Dobra at Lipa and at Jarče Polje, and RESULTS high concentrations (350-400 ppm) of total oils were measured in Kupa at Brod na Kupi and Karlovac, in Determination of organic pollutants Kupica at Brod na Kupi, Lahinja at Primostek (Slovenia) and in Dobra at Ogulin. The highest concentrations of Table 1 is presenting sample numbers and description total oils in the whole Kupa River drainage basin were of sampling locations, together with the concentrations of found in Čabranka (432.0 ppm) at Osilnica, Slovenia and organic pollutants determined. Each group of organic in Dobra River (504.4 ppm) at Vrbovsko. pollutants is described separately. The lowest concentrations of mineral oils (<80 ppm) From the distribution of total PCBs in sediments it is were found in the eastern part of Kupa River drainage obvious that, in the middle and most of the eastern part of basin, where only at two localities (Glina at Glina and Kupa River drainage basin, PCBs have concentration levels Glinica at Glinica, Bosnia and Herzegovina) concentra- below the detection limit. Low concentrations (0.005- tions of <50 ppm were measured. 80-100 ppm were de- 0.010 ppm) are present in sediments of Čabranka at Osilnica termined in Kupa at Žaga and Severin na Kupi, in (Slovenia), Kupa at Severin, Ozalj, Levkušje-Zorkovac and Muljevac at Brihovo, Dobra at Donje Stative and in Glina at Lijevo Sredičko. Concentrations of 0.010-0.020 ppm at Gejkovac, whereas 100-120 ppm of mineral oils were were determined in Kupa at Žaga and at Letovanić. Concen- obtained in Kupa at Hrvatsko, in Lahinja at Primostek trations of 0.020-0.025 ppm were measured in Trepča River (Slovenia), Kupa at Levkušje-Zorkovac, Dobra at Jarče at Trepča, and 0.025-0.030 ppm were obtained in Dobra at Polje and Mrežnica at Mala Švarča. Rather high concen- Trošmarija and Petrinjčica at Petrinja. High concentrations trations of 120-140 ppm were measured in Kupa at Brod of 0.055-0.065 ppm were found in Lahinja at Primostek na Kupi and in Kladušnica at Barake-Velika Kladuša (Slovenia), while the highest concentrations in the whole (Bosnia and Herzegovina), and 140-160 ppm in Kupica at Kupa River drainage basin were measured in Kupa at Brod na Kupi. High concentrations of mineral oils (160- Hrvatsko in National Park Risnjak, upstream from Čabranka 180 ppm) were determined in Čabranka at Osilnica (Slo- River inflow (0.066 ppm), and in Kupa at Brod na Kupi venia), Dobra at Vrbovsko, and in Kupa at Karlovac. The (0.072 ppm), at the boarder of Croatia and Slovenia. highest concentration of mineral oils in the whole Kupa Total lindane isomers were not detected in any of the River drainage basin was measured in Dobra at Ogulin 44 sediments, namely, they were below the detection limit. (185.9 ppm), before the sinking hole.

Concentrations of total phenols are the lowest in the Mineralogical composition eastern part of Kupa River drainage basin, where amounts Mineralogical composition was determined in each of <0.3 ppm prevail. Concentrations of 0.3-0.7 ppm were sediment sample semi-quantitatively, and the details will found in Kupa River at Žaga and in Dobra before its inflow be presented elsewhere. The results in this work are pre- in Kupa. Concentrations of 0.7-1 ppm were determined in sented only for samples with the highest concentrations of Budačka Rijeka at Donji Budački and Mutnica at Pjanići pollutants. (Bosnia and Herzegovina). Increased levels of total phenols (1-2 ppm) were obtained in Kupica at Brod na Kupi, In sample 52, which has the highest content of PCBs, Čabranka at Osilnica (Slovenia), Kupa at Brod na Kupi and silica (33-1161) was found as predominant mineral, >30%; at Čabranka inflow, Kupa at Jurovo, Ozalj, Karlovac, Leto- and calcite (05-0586), dolomite (11-0078) and muscovite vanić and Petrinja, Dobra at Jarče Polje, and in Korana at (07-0032) were less abundant, 10-30%; and clinochlore Belajske Poljice. Concentrations of 2-3 ppm were deter- ferroan (07-0076) and albite (09-0466) were trace minerals.

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TABLE 1 - Sampling locations and results of analysis of organic pollutants in sediments (f<63 µm) from Kupa drainage basin.

Smpl. Geographic height Total Total phenols Total oils Mineral oils Lindane Sampling site River flows into No. coordinates (m) PCBs (ppm) (ppm) (ppm) (ppm) (ppm) 45º38’51” N 1 Primostek (SLO) Lahinja Kupa 136 0.059 3.250 363.2 118.3

Danube 90 0.043 1.717 171.4 98.9

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In sample 46, which has the highest amount of phenols, tants. The adsorption mechanism is complex, particularly the predominant minerals (>30%) were quartz (46-1045), for hydrophobic substances, and needs further research. calcite (24-0027) and dolomite ferroan (34-0517). Less abundant (10-30%) was albite (41-1480), and phlogopite (16-0344) was only trace mineral. DISCUSSION In sample 48, which has the biggest amount of total To illustrate distribution of organic pollutants in the oils and also a very high one for mineral oils, the predomi- two most-polluted rivers, Kupa and Dobra, concentrations nant minerals (>30%) were silica (33-1161) and dolomite are presented as histograms along the flow direction (km) ferroan (34-0517). Numbers in parenthesis are of JCPDF in Figure 2. Sediment quality will be discussed in view of (Powder Diffraction File) cards. the available sediment quality criteria and guidelines for These minerals alone, with hydrophilic surfaces do not the protection of aquatic life, issued by the University of seem to be good adsorbents for the studied organic pollu- Waterloo, Canada [14].

Kupa: PCB (ppm) Dobra: PCB (ppm) 0,08 0,03 0,025 0,06 0,02 0,04 0,015 0,01

PCB (ppm) 0,02 PCB (ppm) 0,005 0 0 0 23 59 127 155 174 213 262 286 0 22 42 56 75 82 92 102 103 km from the source km from the source

Kupa: total phenols (ppm) Dobra: total phenols (ppm) 3,5 12 3 10 2,5 2 8 1,5 6 1 4 0,5 2 (ppm) phenols tot. 0 tot. phenols (ppm) phenols tot. 0 0 23 59 127 155 174 213 262 286 0 22 42 56 75 82 92 102 103 km from the source km from the source

Kupa: total oils (ppm) Dobra: total oils (ppm) 400 600 500 300 400 200 300 100 200 total oils (ppm) oils total

total oils (ppm) oils total 100 0 0 0 23 59 127 155 174 213 262 286 0 22 42 56 75 82 92 102 103 km from the source km from the source

Kupa: mineral oils (ppm) Dobra: mineral oils (ppm) 200 120 100 150 80 100 60 50 40 20 (ppm) oils mineral

0 (ppm) oils mineral 0 0 23 59 127 155 174 213 262 286 0 22 42 56 75 82 92 102 103 km from the source km from the source

FIGURE 2 - Histograms showing downstream distribution of organic pollutants in Kupa River (left) and in Dobra River (right).

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State and origin of PCBs from Dobra River at Trošmarija (9.7 ppm). The high phenol PCBs are the most harmful of all organic pollutants, concentration at this site resulted from Gojak hydro-power which were determined in this work. Their concentrations plant. The next two most-polluted samples were measured were measured above detection limit of 0.005 ppm in also in Dobra River: one at Ogulin (4.9 ppm) and at Donje 36% of the analyzed samples. According to American Stative (4.5 ppm). Furthermore, a high concentration of standards, toxic level threshold for PCBs in sediments is phenols was determined in Dobra at Vrbovsko (2.1 ppm). 0.02 ppm [14]. Concentrations above this level were meas- From this can be concluded that Dobra is the most-polluted ured in 16% of the samples. Increased levels of PCBs in river with phenols in the whole Kupa River drainage basin. Lahinja River (Slovenia) are resulting from wastes of In the upper part of its course, the pollution originated from Iskra capacitors factory in Semič, Bela Krajina (Slove- the industry in Vrbovsko, and especially from wagon wash nia), which have polluted Krupa, Lahinja and Kupa rivers of the Croatian Railways located in Moravice, upstream before 1985, when the factory was closed [5]. PCBs, from Vrbovsko, where washed tank wagons are used for the found in levels below toxic threshold at Ozalj and Lev- transport of chemicals. Wastewaters, originating from these kušje-Zorkovac, further downstream Kupa River after sites, are discharged directly into Dobra River without any inflow of Lahinja, also originated from Iskra factory in treatment. Increased concentrations of phenols in the upper Semič, and partly from hydro-power plant in Ozalj. Rather course of Kupa River, the same as PCBs, came there from high concentrations of PCBs in sediments from Trepča at underground flows of settlements in Gorski Kotar. The Trepča, Petrinjčica at Petrinja, and Sava at Lukavec Posav- high concentration of phenols in Lahinja River, Slovenia ski are results of war activities in this region, from de- (3.1 ppm) was caused by the pollution from the capacitors stroyed transformer stations or oils from numerous de- factory Iskra in Semič. stroyed tanks. PCBs in samples of sediment from Dobra The highest peak of total phenols in Dobra coincided River at Trošmarija have their origin from the nearby hy- with the highest peak of PCBs. dro-power plant Gojak, located upstream. Surprisingly, the two highest concentrations of PCBs in the whole Kupa State and origin of mineral oils River drainage basin were found in samples from the upper No quality criteria for mineral oils in sediments and most part of Kupa River, one of them located in Risnjak soils are available. Aesthetic or phytotoxicity considera- National Park. In this area, upstream from Hrvatsko to tions were typically the basis for the development of Kupa source, there were no settlements, roads, nor indus- standards, while little or no consideration was given to the try. Also, there were no direct war activities. So, the only human health risks associated with the contaminant levels. explanation is that the pollution has come to Kupa River by Numerical criteria for maximum concentrations range from groundwaters from the broader area, as it is a typically 1,000 to 20,000 ppm for oil and grease [16]. For mineral karstic area, and ground-waters are flowing fast from rather oils used criteria [17] are the following: unpolluted sedi- big distances. Looking for possible pollution sources, the ments contain <100 ppm of mineral oils, moderately pol- sinking river Velika Voda at the outskirt of National Park luted contain 100-1000 ppm, while heavily polluted sedi- Risnjak was observed. According to Biondić et al. [11], ments contain >1000 ppm of mineral oils. When in sedi- karst aquifers are of high risk and should be protected. ments concentration of mineral oils exceed 5000 ppm, a recovery of the area is necessary. In Kupa River drainage Pollution with PCBs should not be ignored, because it basin there were no heavily polluted sediments. Mineral was present above the toxic levels in the region used for oils, determined in concentrations > 100 ppm, which corre- tourism, sport and fishing, at the Croatian-Slovenian bor- spond to moderately polluted sediments, were found in der. According to findings of Gevao et al. [15] the sedi- 30% of the samples analyzed. The highest concentration of ment-water flux is upward for PCBs, indicating that the mineral oils was in Sava at Strelečko (242 ppm), due to sediments may be acting as a secondary source for PCBs. upstream pollution from Zagreb industry. In Kupa River Also, Wolska et al. [4] reported that transport of PCBs in drainage basin, the highest concentration of mineral oils the river takes place both with the aqueous phase and the was found in the upper coarse of Dobra River: at Ogulin suspended matter. (186 ppm) and at Vrbovsko (177 ppm). Mineral oil pollution in Vrbovsko is due to upstream wagon wash of the State and origin of total phenols Croatian Railways in Moravice. In Ogulin, in addition to Concentrations of total phenols were found above de- this pollution source, mineral oils come partly from the tection limit (0.1 ppm) in 64% of analyzed samples. Ac- water mill in Puškarić Selo, below which was sampled. In cording to American standards [14] as unpolluted are this mill the owners used waste mineral oils for lubricat- considered sediments with <0.42 ppm, as moderately ing the mill wheel, and entering into water and sediment. polluted those with 0.42-0.65 ppm, and heavily polluted In Kupa River near its source (National Park Risnjak), that with >0.65 ppm of total phenols. Only three samples mineral oils came via an underground way from a sinking in the whole Kupa River drainage basin were found to be tributary, Velika Voda, along which numerous mills are unpolluted, while all the other samples were moderately situated. The high mineral oil levels in Kupica River to heavily polluted. The most-polluted sediment sample originate from tributary Delnički Potok, bringing with phenols in the whole Kupa River drainage basin was wastewaters from Delnice. Pollution in Dobra River at

290 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

Jarče Polje could come either from the nearby road and its REFERENCES upstream bridge, or from the mill near the sampling point. [1] Brunström, B., Andersson, L., Nikoladidis, E. and Dencker, L. (1990). Non-ortho- and mono-ortho-chlorine-substituted polyb- iphenyls – Embryotoxicity and inhibition of lymphoid devel- CONCLUSIONS opment. Chemosphere 20, 1125-1128.

[2] URL 1: http://www.deh.gov.au/industry/ chemicals/ scheduled- The following conclusions could be drawn: waste/pcbs/plan/index.html - Stream sediments showed stable records of occa- [3] Ohsaki, Y., Matsueda, T. and Kurokawa, Y. (1997). Distribu- sional and special pollution and are suggested to tion of polychlorinated dibenzo-p-dioxins, polychlorinated be used in future monitoring of water quality; dibenzofurans and non-ortho coplanar polychlorinated biphenyls in river and offshore sediments. Environmental Pol- - Analysis of organic pollutants in sediments has lution 96(1), 79-88. clearly shown that the western part of Kupa River drainage basin is more affected than its war-exposed [4] Wolska, L., Galer, K. and Namieśnik, J. (2003). Transport and speciation of PAHs and PCBs in a river ecosystem. middle and eastern parts; Journal of Environmental Studies 12(1), 105-110.

- At several locations, particularly in the upper flow [5] Picer, M. and Holoubek, I. (2003). PCBs in the karstic envi- of Kupa (at Croatian-Slovenian border) and Dobra, ronment of Slovenia and Croatia as consequence of their acci- concentrations of PCBs, total phenols and mineral dental release. Fresenius Environmental Bulletin 12(2), 86-93. oils were above the toxic levels; [6] Picer, M., Perkov, S. and Picer, N. (1995). Contamination of - The karst aquifers of high risk, described by Biondić Bela Krajina, Slovenia with polychlorinated byphenyls. 1. Levels of some high molecular chlorinated hydrocarbons in et al. [11], seem to be partly polluted. They should the water and fish of the Kupa River in Croatia. Water, Air & be further studied including stream sediments, and Soil Pollution 82(3-4), 559-581. possibly protected by joint efforts of Croatia and Slovenia. [7] Harrad, S.J., Sewart, A.P., Alcock, R., Boumphrey, R., Bur- nett, V., Duartedavidson, R., Halsall, C., Sanders, G., Water- - Results are aimed to be a small contribution from house, K., Wild, S.R. and Jones, K.C. (1994). Polychlorinat- South Europe to the recent global contamination ed biphenyls (PCBs) in the British environment – sinks, sources and temporal trends. Environmental Pollution 85(2), study of Breivik et al. [18]. 131-146.

[8] Inventory of polychlorinated biphenyls (PCBs) in the Repub- lic of Croatia, Summary (2003). APO Ltd., Environmental services, Savska cesta 41/IV, 10000 Zagreb, Croatia, Sep- ACKNOWLEDGEMENTS tember 2003, p.1-19.

This research was performed within the project [9] Omuro Lupetti, K., Rocha, F.R.P. and Fatibello-Filho, O. 0098041, financed by the Ministry of Science Education (2004). An improved flow system for phenols determination and Sport of Republic of Croatia and by a bilateral project exploiting multicommutation and long pathlength spectro- photometry. Talanta 62, 463-467. between Croatia and Slovenia. The analyses of organic pollutants, performed in an authorized laboratory – Za- [10] URL 2: http://www.epa.gov greb public health institute, by Z. Šmit and V. Soukup, were financed by Croatian Waters. [11] Biondić, B., Biondić, R. and Kapelj, S. (2003). Protection of the karst aquifers in the river Kupa catchment area and sus- tainable development. RMZ-Materials and Geoenvironment This paper is a part of the corresponding author’s 50(1), 33-36. Ph.D. thesis, submitted in November 2004 to the Depart- ment of Geology, Faculty of Science, University of Za- [12] Boldrin, A., Juračić, M., Menegazzo Vitturi, L., Rabitti, S. greb, Croatia (supervisors L. Palinkaš and E. Prohić). The and Rampazzo, G. (1992). Sedimentation of river-borne ma- supervisors are thanked for their suggestion to study or- terial in a shallow shelf sea: Adiga River, Adriatic Sea. Ma- rine Geology 103, 473-485. ganic pollutants in addition to geochemical and mineralogical investigations of the region. [13] Šmit, Z., Drevenkar, V. and Kordić-Šmit, M. (1987). Poly- chlorinated biphenyls in the Kupa River, Croatia, Yugosla- via. Chemosphere 16, 2351-2358.

[14] URL 3: http://wvlc.uwaterloo.ca/biology/447/modules/module1/ sedaquat1.html

[15] Gevao, B., Hamilton-Taylor, J. and Jones, K.C. (2000). To- wards a complete mass balance and model for PCBs and PAHs in a small rural lake, Cumbria UK. Limnology & Oceanography 45(4), 881-894.

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[16] URL 4: http://www.nature.nps.gov/hazardssafety/toxic/oil& FEB/ Vol 14/ No 4/ 2005 – pages 282 - 290 grea.pdf

[17] Soukup, Vesna, Zagreb public health institute, (Croatia) (2004), private communication.

[18] Breivik, K., Sweetman, A., Pacyna, J.M. and Jones, K.C. (2002). Towards a global historical emission inventory for selected PCB congeners – a mass balance approach 1. Global production and consumption. Science of the Total Environ- ment 290(1-3), 181-198.

Received: August 03, 2004 Revised: November 24, 2004 Accepted: December 23, 2004

CORRESPONDING AUTHOR

Stanislav Frančišković-Bilinski Institute “Ruđer Bošković” POB 180 10002 Zagreb - CROATIA

e-mail: [email protected]

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STUDY ON FLUORESCENCE EMISSION AND SYNCHRONOUS-SCAN FLUORESCENCE SPECTRA OF Nitzschia hantzschiana SOLUTION WITH FE(Ⅲ)

Xianli Liu1,2,3, Nansheng Deng2, Shu Tao1, Feng Wu2, Tao Fang4 and Jiantong Liu4

1 College of Environmental Sciences, Peking University, Beijing 100871, P.R. China 2Department of Environmental Science, Wuhan University, Wuhan 430072, P. R. China 3 Huangshi College of Technology, Huangshi 435003, P. R. China 4 Institute of Hydrobiology, Chinese Academy of Sciences, Wuhan 430072, P. R. China

SUMMARY

The characterization of the algal Nitzschia hantzschi- Few efforts have been made to characterize the com- ana solution with (or without) Fe(III) was carried out plex of metal ions and algae. Fe(III) is a very important using fluorescence emission and synchronous-scan spec- metal ion for algae and in waters [3-6]. Piana et al. [7] troscopy. An emission peak (excited at 440 nm) was ob- investigated the binding site interactions of humic sub- served at 675 nm for Nitzschia hantzschiana solution. The stances with various metals ions using synchronous-scan effective characterization method used was synchronous- spectroscopy and the quenching effects of Fe(III). Fluo- scan fluorescence spectroscopy (SFS). A wavelength dif- rescence quenching of anthropogenic fulvic acids by ference (△λ) of 90 nm was maintained between excitation Fe(III) was studied by da Silva et al. [8]. and emission wavelengths. The peak was observed at about So far, no study has been published on the characteri- 236ex nm (326em nm) for synchronous fluorescence spec- zation of algae-Fe(III) complexes in aqueous solution with troscopy. Fe(III) was an effective quencher. The relation- fluorescence spectrometer. ship between I0/I (quenching efficiency) and c (concentration of Fe (III) added) was a linear correlation for the algal Synchronous fluorescence spectroscopy (SFS) is a solution with Fe(III). Effects of pH on synchronous-scan method wherein simultaneous scan of both the excitation fluorescence intensity were evident. and emission spectra is carried out at a constant offset value or difference between the emission and excitation wavelengths, △λ (△λ=λem－λex). SFS has been used for characterization and identification of natural organic matter KEYWORDS: Fluorescence spectroscopy, synchronous-scan, from various origins [9-13], and was also used for charac- quenching, algae, Nitzschia hantzschiana, Fe(III). terization in our work.

Our objective was to present and analyze the fluorescence emission and synchronous-scan fluorescence spectra of fresh water algae (Nitzschia hantzschiana) solutions INTRODUCTION with (or without) Fe(III).

Fluorescence has been a tool for the study of organic matter for a long time. Stephan et al. [1] reported about MATERIALS AND METHODS results of detailed fluorescence excitation (λex=230 nm) and emission (λem=330 nm) analyses of marine algae and Chemicals: HCl, FeCl3·6H2O, CaCl2·2H2O, H3BO3, bacteria. The fluorescence was compared with signals from CaSO4·H2O, Ca(H2PO4)2·2H2O, CuSO4·5H2O, K2HPO4, metabolites of aromatic amino acids and proteins of known KH2PO4, KCl, MgSO4·7H2O, MnSO4·4H2O, composition. Hilton et al. [2] have studied the in vivo MnCl2·4H2O, MoO3, NaOH, NaCl, Na2CO3, NaHCO3, fluorescence spectra of freshwater algae and the conse- Na2MoO4·2H2O, NaNO3, Na2SiO3·9H2O, (NH4)2SO4, quences for their automatic identification. Although work ZnSO4·7H2O, ferric citrate, and ascorbic acid were ana- on the fluorescent properties of algae has been carried out lytic grade. Double-distilled water was used in experi- on both marine and freshwater species, its extension to ments. algal characterization has been applied mainly to marine phytoplankton.

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Algae: Nitzschia hantzschiana algae were used in the intensity, while synchronously scanning at both the excita- experiments, which were obtained from Wuhan Hydrobiol- tion and emission wavelengths. The wavelength difference ogy Institute of the Chinese Academy of Sciences (Wuhan, of 90 nm was maintained between excitation and emission P.R. China). The algae were grown in culture medium at wavelengths. We have examined the wavelength difference 25 ºC using a 24-hours light cycle. The culturing box was (△λ) (over the range of 0-200 nm). The peaks of fluores- equipped with daylight lamps, light intensity: 2000 lx. cence emission resulted from algae, and scattering light -1 △ The culture medium consisted of 120 mg L NaNO3, could be separated effectively using λ=90 nm, which is -1 -1 -1 70 mg L MgSO4·7H2O, 40 mg L K2HPO4, 80 mg L the optimized offset. The fluorescence emission spectra and -1 -1 KH2PO4, 20 mg L CaCl2·2H2O, 10 mg L NaCl, 100 mg synchronous-scan fluorescence spectra of algal solutions -1 -1 -1 L Na2SiO3·9H2O, 2 mg L MnSO4·4H2O, 5 mg L with (or without) Fe(III) were corrected with performing -1 -1 ferric citrate, 2.86 mg L H3BO3, 1.81 mg L the arithmetic operation of subtracting the spectrum (back- -1 -1 MnCl2·4H2O, 0.22 mg L ZnSO4·7H2O, 0.079 mg L ground spectrum) of double-distilled water from them. The -1 CuSO4·5H2O, 0.039 mg L Na2MoO4·2H2O, and 20 ml fluorescence intensity defined in the present study is essen- L-1 soil extract. tially a unitless entity.

The algae were cultured in axenic medium. When the algae were growing in a logarithmic growth phase and RESULT AND DISCUSSION their density was high (normally 12-14 days), they were taken for use in the experiments after being washed. Emission spectra at excitation wavelength of 440 nm Prior to fluorescence spectrometer analysis, to re- and 3D fluorescence spectra: As shown in Figure 1(a), a move colloidal ferric hydroxide particles that might have weak emission was observed at 675 nm for Nitzschia been adsorbed on the algal cells, a modified version of the hantzschiana solution, which was mainly caused by chlo- procedure [14] was used in experiments. This procedure rophyll. This is similar to spectra of other algae reported involved washing the cells by gentle agitation for 30 min in a previous study [17]. It should be noticed that there was with 0.01M aqueous ascorbic acid adjusted to pH 3.0. a weak peak caused by scattering light at about 665 nm Then the algae were washed with double-distilled water (Figure 1(b)). thrice, to obtain the resulting algal suspension in this way. The cell-counting was carried out and the density of algae (cells L-1) was calculated. Thus, the algae were prepared for their next use. Different concentrations of algae were gained through diluting the washed algae with double- distilled water. These experiments were carried out at room temperature (25±2 °C).

Fluorescence measurements: The aqueous solution of algae with (or without) Fe(III), added with FeCl3, were mixed thoroughly. The concentration of algae and Fe(III) 8 -1 in aqueous solutions ranged from 2×10 cells L to 2.0×109 cells L-1 and from 10 µM to 60 µM, respectively, (a) and pH ranged from 3.0 to 7.0. After dark adaption for at least 60 min [15, 16], room temperature fluorescence spectra were recorded sufficiently quickly, so that settlement was not important. Fluorescence spectra were obtained from the algal sus- pensions using a fluorescence spectrophotometer (F-4500, Hitachi, Japan). A 1-cm2 fluorescence quartz cell was used to hold the samples. The emission spectra at excitation (EX) wavelength of 440 nm were studied. Most algae showed an emission peak at EX 440 nm, which was caused by chlorophyll [17]. The fluorescence emission (EM) measurement types used were (b) wavelength scan and 3D-scan (Emission scan mode: EX -1 FIGURE 1 - Fluorescence emission spectra at excitation and EM slit: 2.5-10 nm, Scan speed: 240 nm min (or wavelength 440 nm (Excitation and emission slits: 10 nm. -1 2400 nm min ), PMT Voltage: 700V, Response: 8.0 s). (a) Nitzschia hantzschiana, pH = 6.5; (b) 0.001M Ba(OH)2). Synchronous-scan fluorescence spectra measurements were carried out. Synchronous-scan spectra were recorded It was verified by the fluorescence measurements of by using two monochromators recording the fluorescence 0.001M Ba(OH)2 that it was an almost ideal scattering

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and non-fluorescent material in our experiments. As far as bility of the sites on algal cells, but also the fluorophore we have been able to ascertain, there is no published study and quenchers were in close physical association with mentioning the weak peak at EM 665 nm. each other. Total fluorescence spectra (fluorescence contour spectra) were obtained. A typical spectrum of the full scan is shown in Figure 2. The obtained spectra matched the results reported by Hilton [2]. Similar total fluorescence spectra were observed for the algal solution with Fe(III). Evident differences between these total fluorescence spectra mentioned above was not observed. In the meanwhile, a similar total fluorescence spectrum was observed for 0.001 M Ba(OH)2.

(a)

400

300

200

100 Fluorescence intensity Fluorescence 0 0 5 10 15 20 25

8 Concentration of N.hantzschiana (10 cells/L) (b) FIGURE 3 - Effect of Nitzschia hantzschiana concentration on FIGURE 2 - Total fluorescence spectrum (fluorescence con- synchronous-scan fluorescence intensity (I). △λ = 90nm, EX tour spectrum) over the full wavelength range for 5×108 cells slit: 5 nm, EM slit: 10 nm, scanning speed = 240 nm min-1, pH L-1 Nitzschia hantzschiana solution. EX (EM) slit: 2.5 nm, 6.5. A: 2×108 cells L-1; B: 5×108 cells L-1; C: 8×108 cells L-1; D: scan speed: 2400 nm min-1, pH 6.5. 1.0×109 cells L-1; E: 2.0×109 cells L-1.

Synchronous-scan fluorescence spectra measurements: As shown in Figure 3, a peak was observed at about EX 236 nm/EM 326 nm for synchronous fluorescence spectroscopy. This peak resulted from the organic substance on algal surface [1]. No peak resulted from scattering light and Fe(III) within the range of EM 300-350 nm. The higher algal concentration, the greater synchronous-scan fluorescence intensity at EM 326 nm (see Fig- ure 3). As shown in Figure 4, it indicates the obvious effect of the presence of the quencher Fe(III) on the fluorescence emission intensity. Figure 4(A) represents the emission spectrum of Nitzschia hantzschiana solution in the absence of Fe(III), whereas the spectra in Fig. 4B-4F show the fluorescence emission of the Nitzschia hantzschiana solution in the presence of increasing concentrations of the quencher Fe(III). From Figure 4, it was obvious that Fe(III) was an effective quencher. The interaction between the quencher FIGURE 4 - Effect of Fe (III) concentration on synchronous-scan 8 -1 and the algae was based upon compatibility and availa- fluorescence intensity of 5×10 cells L Nitzschia hantzschiana

295 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

solution with Fe(III). △λ = 90 nm, EX slit: 5 nm, EM slit: 10 nm, 1×109 cells L-1 Nitzschia 0.723 0.891 1.000 scanning speed = 240 nm min-1, pH 6.5. A: without Fe(III), B: hantzschiana + 10 µM Fe(III) 5×108 cells L-1 Nitzschia with 10µM Fe(III), C: with 20µM Fe(III), D: with 30µM Fe(III), 0.878 0.979 0.998 E: with 40µM Fe(III), F: with 60µM Fe(III). hantzschiana + 10 µM Fe(III) Determination of Stern-Volmer Quencher Constant: As Evident effects were observed for the samples I and II. shown in Figure 5, the higher the Fe(III) concentration, At acidic pH (e.g. pH 3.0), the quenching efficiency was the greater the quenching efficiency (I0/I). obvious. The fluorescence intensity of the samples at pH 3.0 was lower than that at pHs 4.0-7.0 (see Table 1). 6 At pH 3.0, Fe(III) was only slightly hydrolyzed. But at pHs 6.0 and 7.0, the effective hydrolysis of Fe(III) resulted in the decrease of the quantity of Fe(III)-binding 4 on algal cells, so that this effect made the quenching efficiency decrease. Experimental results indicated that the

I pH effect was more evident at higher Fe(III) concentra- / 0

I tions in algal solutions compared to lower ones (see Ta- 2 ble 1). IpH3/IpH7 values of the above-mentioned samples were 0.723 and 0.878, respectively. In our experiments, the effect of hydrolysis of Fe(III) 0 on fluorescence quenching was dominant. On the other 0 2 4 6 hand, other effects could also exist. For example, when Fe(III) concentration (10 -5 M) pH was ≥ 7, the algae were deprotonated resulting in a more overall negative surface charge, to which more cati- FIGURE 5 - Effects of Fe (III) concentration on I0/I for onic species could bind. Some of the functional groups 5×108 cells L-1 Nitzschia hantzschiana solution with Fe(III). were protonated at acidic pH, giving a lower total charge on the surface of algal cells and, therefore, leading to poor To study the relationship between I0/I (I0 and I are the association between Fe(III) and algae. fluorescence intensities of the algal solution in the absence and presence of the quencher species, respectively) Similar experiments were repeated for Chlorella vul- and c(Fe(III) concentration (M), kinetics` analyses were garis or Anabaena cylindrica solutions with (without) carried out. According to the result of calculation (linear Fe(III). Similar fluorescence quenching caused by Fe(III) regression), the r (correlation coefficient) value was was observed too. Further studies on the characterization 0.99189. When the sampling number (n) is 6, the critical of algae-Fe(III) systems need to be carried out. correlation coefficient r was 0.97406 (a = 0.001; r> r ). c c So, the results indicated that the relationship between I0/I and c was a linear correlation. The pseudo-zero order equa- CONCLUSION 4 tion is I0/I = 1+ 6.277×10 c. This linear correlation match- Fluorescence emission spectra (excited at wavelength es the Stern-Volmer equation (I0/I = 1 + Ksv [Q]). The Stern-Volmer equation related any decrease in fluorescence of 440 nm) and fluorescence contour spectra of Nitzschia intensity that occurs due to the addition of a quenching hantzschiana solution with (or without) Fe(III) were studied. A weak emission peak was observed at 675 nm for species. Ksv is the Stern-Volmer constant. A plot of I0/I against the quencher (Fe(III)) concentration [Q] can be Nitzschia hantzschiana solution. Synchronous fluorescence spectroscopy (SFS) was found to be an effective used to obtain the Ksv value for a particular quencher (here, 4 -1 method. The wavelength difference (△λ) of 90 nm was Ksv = 6.277×10 M ). maintained between excitation and emission wavelengths. pH Effect on synchronous-scan fluorescence intensity: A peak was observed at about EX 236 nm (EM 326 nm). The experiments to study the pH effect on the synchro- The higher the algal concentration, the greater fluores- nous-scan fluorescence intensity of algal solutions with cence intensity. It was obvious that Fe(III) was clearly an 8 -1 Fe(III) were carried out. The samples were I (5×10 cells L effective quencher. The relationship between I0/I (quench- Nitzschia hantzschiana + 10 µM Fe(III)) and II (1.0× ing efficiency) and c was a linear correlation. Effects of 9 -1 10 cells L Nitzschia hantzschiana + 10 µM Fe(III)). Also pH on synchronous-scan fluorescence intensity in algal control experiments were carried out. The synchronous- solutions with Fe(III) were evident, especially at higher scan fluorescence spectra of samples at different pH (e.g. concentrations, compared to lower concentrations of algal pH 3-7) were obtained. IpH 3/IpH 7 and IpH 6/IpH 7 were calcu- solution with Fe(III). lated according to the fluorescence intensities at the EM wavelength of 326 nm (EX wavelength of 236 nm).

TABLE 1 - pH Effect on synchronous-scan fluorescence intensity (I).

Samples IpH3/IpH7 IpH4/IpH7 IpH6/IpH7

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ACKNOWLEDGEMENTS [13] Ritchelita, P.G., Aloysius, U.B., Kazuaki, I., Tetsuo, M., Eiji, S. and Mitsumasa, O. (1998) Detection of domestic wastes in Kurose river using synchronous fluorescence spectroscopy. This work was supported by the National Natural Sci- Wat. Res., 32, 2232-2239. ence Foundation of P.R. China (No.20177017), the Nation- al 973 Project of P.R. China (No.2002CB412304), and [14] Zepp, R.G. and Schlotzhauer, P.F. (1983) Influence of algae Wuhan Environmental Protection Bureau, P.R. China. on photolysis rates of chemicals in water. Environ. Sci. Tech- REFERENCES nol., 17, 462-468.

[15] Thompson, J.A. (1997) Cellular fluorescence capacity as an [1] Stephan, D., Lobbes, J.M., Rainer, R. and Jurgen, R. (1998) endpoint in algal toxicity testing. Chemosphere, 35, 2027- Ultraviolet fluorescence excitation and emission spectrosco- 2037. py of marine algae and bacteria. Marine Chemistry, 62, 137– 156. [16] Heaney, I. (1978) Some observations on the use of the in– vivo fluorescence technique to determine chlorophyll a in [2] Hilton, J., Rigg, E.,and Jaworski G. (1989) In vivo algae fluo- natural populations and cultures of freshwater phytoplankton. rescence, spectral change due to light intensity changes and Freshwater Biology, 8, 115-126. the automatic characterization of algae. Freshwater biology, 21, 375-382. [17] Philipp, M., Russell, C. and Niels, N. (1997) A simple in vitro fluorescence method for biomass measurements in algal [3] Liu, X.L., Wu, F. and Deng, N.S. (2004) Photoproduction of growth inhibition tests. Wat. Res., 31, 2525-2531. hydroxyl radicals in aqueous solution with algae under high- pressure mercury lamp. Environmental Science & Technolo- gy, 38(1), 296-299.

[4] Liu, X.L., Wu, F., Liao, Z.H, Li, S.X. and Deng, N.S. (2004) Photodegradation of 17α-ethynylestradiol in aqueous solution with Nitzschia hantzschiana or Chlorella vulgaris and Fe3+. Wuhan University Journal of Nature Sciences, 9(1), 109-114.

[5] Liu, X.L., Wu, F. and Deng, N.S. (2003) Photodegradation of 17α-ethynylestradiol in aqueous solution exposed to high- pressure mercury lamp (250W). Environ. Pollut., 126, 393- 398.

[6] Liu, X.L., Liu, B., Wu, F. and Deng, N.S. (2003) Photodeg- radation of 17α-ethynylestradiol in aqueous solution with Anabaena cylindrica under UV light. Fresenius Environ. Bull., 12, 690-694.

[7] Piana, M.J. and Zahir, K.O.(2000) Investigation of metal ions binding of humic substances using fluorescence emission and synchronous-scan spectroscopy. J. Environ Sci. Health, B35, 87-102.

[8] Da Silva, J.C.G.E., Machado, A.A.S.C., Oliveira, C.J.S. and Pinto, M.S.S.D.S.(1998) Fluorescence quenching of anthro- 2+ pogenic fulvic acids by Cu(II), Fe(III) and UO2 . Talanta, 45, 1155-1165.

[9] Miano, T.M. and Senesi, N. (1992) Synchronous excitation fluorescence spectroscopy applied to soil humic substances chemistry. Sci. Total Environ., 117-118, 41-51.

[10] Senesi, N., Miano, T.M., Provenzano, M.R. and Brunett, G. (1991) Characterization, differentiation, and classification of

humic substances by fluorescence spectroscopy. Soil Sci., 152, 259-271.

[11] De Souza, S.M.M., Donard, O.F.X., Lamotte, M.B.C. and Ewald, M. (1994) Fluorescence spectroscopy of coastal and marine waters. Mar. Chem., 47, 127-144. Received: August 25, 2004 Accepted: October 14,2004 [12] Coble, P.G. (1996) Characterization of marine and terrestrial DOM in seawater using excitation-emission matrix spectroscopy. Mar. Chem., 51, 325-346.

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CORRESPONDING AUTHOR

Jiantong Liu Institute of Hydrobiology Chinese Academy of Sciences Wuhan 430072, Hubei - P.R. CHINA

e-mail: [email protected]

FEB/ Vol 14/ No 4/ 2005 – pages 291 – 295

298 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

REMOVAL OF HEAVY METAL IONS FROM AQUEOUS SOLUTIONS IN FIXED BEDS BY USING HORSE CHESTNUT AND OAK VALONIA

Atilla Murathan

Gazi University, Chemical Engineering Department, 06570 Maltepe, Ankara, Turkey

SUMMARY

The most common methods for the treatment of water soil layer in the zone [1]. Copper and strontium could be containing heavy metals include precipitation and adsorp- adsorbed by a novel carbon material manufactured from tion. Recently coagulation, ion exchange and ion ex- pecan shells. As a result, a maximum of 95 mg Cu2+ and change combined with precipitation gain importance for 180 mg Sr2+ are adsorbed per g carbon at pH 3.6 and 8.5, the recovery of heavy metals. respectively [2, 3]. Total dissolved beryllium, cadmium,

2+ 2+ 2+ 2+ chromium, copper, iron, magnesium, manganese, mercu- In this study, the removal of Sr , Cd , Zn and Cu ry, nickel, selenium, strontium, vanadium and zinc were from aqueous solutions were investigated. Horse chestnut measured in the drinking water of 101 households, and 21 (Aesculus Hippocastanum) and oak valonia (Quercus samples of retail bottled waters purchased in Riyadh, petraea) were used as adsorbents. Solutions, prepared by Saudi Arabia to ascertain the water quality for human dissolving pure strontium, cadmium, zinc and copper salts consumption [4]. Decaying leaves have been proven to be in distilled water, were used as water samples. Water capable of partially removing heavy metals from polluted samples were taken from the bottom of the fixed bed for water, and several factors affecting the removal process 2 2+ 2+ 2+ Sr , Cd , Zn and Cu analysis. have been studied by various researchers [5-9]. Salvinia and Spirodela have been used for the removal of lead As a result of this study, it was seen that oak valonia from its synthetic solution by Stivastav et al. [10]. Mura- was a more effective adsorbent than horse chestnut for 2+ 2+ 2+ 2+ than et al [11] studied adsorption of copper from water onto Sr , Cd , Zn and Cu ions. various solid surfaces. In another study removal of stronti-

um from water onto sepiolite by adsorption was described

by Murathan et al. [12]. Yücekutlu [13] studied adsorption

KEYWORDS: Adsorption, strontium, cadmium, zinc, copper, fixed of zinc ions from water onto various adsorbents in fixed bed, horse chestnut, oak valonia. beds. The study into the sorption of three divalent metal ions, namely cadmium, copper and zinc, onto peat in single component, binary and ternary systems was made by McKay and Porter [14]. The Langmuir, Freundlich and INTRODUCTION Redlich-Peterson equilibrium isotherms for each metal ion in each system have been determined and correlated. Among the technologies used for heavy metal control, The Langmuir isotherms have been found to have the such as precipitation and ion exchange, the adsorption highest regression correlation coefficients. The adsorption seems to be an attractive method, especially when low process of four metals in solution (Pb, Cu, Zn, Cd) to Chlo- cost materials can be used as sorbents. Many studies have rella vulgaris has been described and compared to a previ- been performed on adsorption of heavy metals in waters. ous study of Pascucci [15], using three metals (Pb, Cu, Zn) The distribution of Chernobyl-derived radionuclides in in solution. As a result of this study, it has been found that river and lake water bodies at 6–40 km distance from the the binding capacity of Chlorella vulgaris to four elements Chernobyl Nuclear Power Plant was studied. Current simultaneously increases with time and mass of algae up to levels of radionuclides (Cesium-137, Strontium-90, Plu- a temperature of about 20,0 °C. The effectiveness of peat in tonium, Americium and Curium isotopes) in water bodies adsorbing copper, nickel and zinc from wastewater has and their relation to the ground contamination are pre- been studied by Viraraghavan and Dronamraju, [16]. Batch sented. The investigation of the radionuclide composition kinetic and isotherm studies have been carried out to of aqueous and ground contamination revealed that radio- determine the effects of contact time, pH, initial concen- nuclides on suspended solids (particulate form) originate tration of the adsorbate, and temperature on adsorption. In mainly from the erosion of the contaminated surface another study, the effectiveness of fly ash in adsorbing

299 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

copper, nickel and zinc has been studied by conducting both kinetic and isotherm experiments (Viraraghavan and Dronamraju [17]). The effects of contact time, pH, initial concentration of the adsorbate and temperature on the adsorption process were studied as above, and fly ash was found to be an effective adsorbent. Randal et al. [18] studied the removal of heavy metals by using the bark of the trees, especially alder as adsorbent. They suggested that heavy metals are captured by bark substrates by means of exchanging H+ ions from phenolic groups within the tannins as bearing compounds. Jain et al. [19] have tried Azolla pinnata R. Br. and Lemna minor L. as adsorbents for the removal of lead and zinc from wastewaters. The obtained experimental results showed that these two plants adsorb zinc and lead very effectively.

MATERIALS AND METHODS FIGURE 1 - Schematic diagram of the experimental set-up. 1. Packed column, 2. Liquid inlet, 3. Liquid outlet, 4. Liq- Horse chestnut and oak valonia were separately used as uid rotameter, 5. Valve, 6. Peristaltic pump, 7 Liquid tank, packing materials under the same operating conditions. 8. Water inlet, 9. Water outlet Stock solutions of Sr2+, Cd2+, Zn2+ and Cu2+ ions were prepared from their nitrate salts in double-distilled water. All chemicals used were of analytical reagent grade. A RESULTS AND DISCUSSION pyrex-glass column was used as packed bed with spherical glass beads. Packing materials were placed to the middle It can be seen from Figs. 2-5, although both oak valo- part of the bed, and, before starting each experiment, dis- nia and horse chestnut are good adsorbents for the remov- tilled water was passed through the bed. In all experiments, al of strontium, cadmium, zinc and copper from aqueous the liquids` flow rate was measured by a rotameter and kept solutions, oak valonia is the more effective adsorbent constant. The temperature was maintained constant by compared to horse chestnut. means of thermostated water flowing through the jacked surrounding the column. Strontium, cadmium, zinc and 0,5 copper solutions were fed to the top of the packed column Oak valonia Horse chestnut by using a peristaltic pump. Samples were taken from the 0,4 bottom of the column and then heavy metal analyses were done. The strontium, cadmium, zinc and copper amounts 0,3 /g Adsorbent /g adsorbed were calculated by the concentrations of the solu- 2+ 0,2

tion at inlet and outlet of the column. In each case, the Zn mg samples from the effluent were collected at short intervals 0,1 and tested for Sr2+, Cd2+, Zn2+ and Cu2+ using a Varian 300 0,0 flame atomic absorption spectrometer. 0 10 20 30 40 50 60 70 t, min

The apparatus used in the experiments is schematically FIGURE 2 shown in Figure 1. The operating conditions are summa- Zinc adsorption on oak valonia and horse chestnut. rized in Table 1.

0,6 TABLE 1 Oak valonia Horse chestnut The operating conditions of the experimental set-up. 0,5

Column diameter, cm 5,5 0,4

Column length, cm 40 0,3 /g Adsorbent /g Column cross section, cm2 23,76 2+ 0,2 Packing size, mm 5 Cd mg Height of bed, cm 20,0 0,1

Liquid flow rate, L/s 0,075 0,0 0 20 40 60 80 100 Concentration, mg / l Water 5,.00 t, min Temperature, oC 25,0 FIGURE 3 Packing type Horse chestnut, Oak valonia Cadmium adsorption on oak valonia and horse chestnut.

300 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

0,5 [3] Murathan-Selek A. (2004) Removal of strontium, aluminium, Oak valonia manganese and iron ions from aqueous solutions in packed Horse chestnut beds, Fresen Environ. Bull., 13(6), 1-4. 0,4

[4] Al-Saleh. I and Al-Doush I. (1998) Survey of trace elements 0,3 in household and bottled drinking water samples collected in

/g Adsorbent /g Riyadh, Saudi Arabia. The Sci. Tot. Env., 216, 181-192. 2+ 0,2

mg Sr mg [5] Ringqvist L, Holmgren A and Öborn I, (2002) Poorly humid- 0,1 ified peat as an adsorbent for metals in wastewater, Wat. Res., 36: 2394-2404 0,0 0 10 20 30 40 50 60 70 t, min [6] Murathan Selek A. and Yıldırım E. (2003) Co-treatability of some industrial and domestic wastewaters by the activated- FIGURE 4 sludge method, Energy Education Science and Technology, Strontium adsorption on oak valonia and horse chestnut. 11(1): 33-43.

Oak valonia and horse chestnut contain tannins in [7] Alicilar A and Özer D (2001) Removal of chromium pollution in waters by adsorption on natural sepiolite in packed high ratio [20, 21]. Tannins have high binding capacities beds, Fresen Environ. Bull., 10(8), 679-683. for heavy metals and are abundantly found in the nature [22-24]. Tannins are divided into two main categories, the [8] Laçin, O., Ekmekyapar, A. and Gül, R.(1999) Removal of +2 hydrolyzed and condensed tannins, also to be found in Iron from Solutions Containing Fe by Different Adsorbents, Energy, Education, Science and Technology, 3(2), 99-108. oak valonia and horse chestnut [25, 26]. Oak valonia tannins are mainly hydrolyzed ones, whereas those of horse [9] Benli S. (2003) The Removal of copper(II), lead(II) and chestnut are mainly condensed. Therefore, oak valonia is zınc(II) from the waters by the adsorption in packed columns. the better adsorbent. M.Sc. Thesis, Gazi Üniversity Institute of Science and Tech- nology, Ankara, Turkey.

0,7 [10] Stivastav, R.K, Gupta SK, Nigam KDP, Vasudevan P., Oak valonia (1994) Use of aquatic plants for the removal of heavy metals 0,6 Horse chestnut from wastewater, . Int.J.Env.Stud., 45(1), 43-50. 0,5

0,4 [11] Murathan, A., Alıcılar A. and Murathan A (1998) Removal of copper from water in packed beds, I. International Workshop /g Adsorbent /g

2+ 0,3 on Enviromental Quality and Environmental Engineering in Middle East Region, Konya, Turkey, Konya, Turkey, 652-

mg Cu mg 0,2 663. 0,1

0,0 [12] Murathan A., Alıcılar A. and Murathan A. (1998) The re- 0 10 20 30 40 50 60 70 moval of strontium pollution in packed columns on beige se- t, min piolite by adsorption, III National Chem. Eng. Congress, Ata- türk University, Erzurum, Turkey, 240-244. FIGURE 5 Copper adsorption on oak valonia and horse chestnut. [13] Yücekutlu AY (1999) Adsorption of zinc in wastewater by using packed columns, M.Sc. Thesis, Gazi University, Insti- tute of Science and Terchnolgy, Ankara, Turkey,. CONCLUSIONS [14] McKay G and Porter FJ ( 1999) Equilibrium parameters for From the present study, the following conclusion is the sorption of copper, cadmium and zinc ions onto peat, Journal of Chemical Technology and Biotechnology, 69(3): obtained: Oak valonia is an effective low-cost adsorbent for 309-320. the removal of strontium, cadmium, zinc and copper ions from aqueous solutions, whereas horse chestnut can also be [15] Pascucci PR. (1993) Simultaneous multielement study of used, but is less effective. binding of metal in solution by an algal biomass, Cholorella Vulgaris. Analitycal Letters, 26(3): 445-455. [16] Viraraghavan T and Dronamraju MM. (1993) Use of fly ash in the removal of copper, nickel and zinc from wastewater. REFERENCES Water Pollution Research Journal of Canada, 28 (2): 369- 384. [1] Matsunaga T, Ueno T, Amano H, Tkatchenko Y, Kovalyov A, Watanabe M. and Onuma Y. (1998) Characteristics of Cherno- [17] Viraraghavan T and Dronamraju MM. (1993) Removal of byl-derived radionuclides in particulate form in surface waters copper, nickel and zinc from wastewater by adsorption using in the exclusion zone around the Chernobyl Nuclear Power peat, Journal of Environmental Science and Health, Part A: Plant. Journal of Contaminant Hydrology, 35: 101-113. Environmental,Science and Engineering, 28 (6): 1261-1276.

[2] Shawabkeh R.A., Rockstraw DA and Bhada, RK (2002) [18] Randall JM, Bermann RL, Garet V and Waiss AC. (1974) Copper and strontium adsorption by a novel carbon material Use of bark to remove heavy metal ions from waste solu- manufactured from pecan shells, Carbon, (2002) 40, 781-786. tions. Forest Production Journal, 24(8) : 80-84.

301 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

[19] Jain, S.K., Vasudevan, P. and Jha, N.K.(1988) Azolla Pinnata R.Br. and Lemna Minor L. for removal of lead and zinc from polluted water, Water Res, 24 (2) 363-373.

[20] Huş S, (1969) Orman mahsulleri kimyası, İ.Ü. Orman Fak. Yayınları, İstanbul,.

[21] Kandemir A and Beyazoglu AO. (2002) The medical and economic plants of the Köse Mountains (Gümüşhane), SDÜ, Fen Bilimleri Enstitüsü Dergisi, 6(3) 148-157.

[22] Koçyiğit H (1999) The removal of cadmium pollution from water in packed beds by adsorption, M. Sc., Thesis, Gazi University, Institute of Science and Technology, Ankara, Turkey.

[23] Hıdıroğlu NB. (2003) Removal of nickel ions from wastewater by adsorption, M. Sc. Gazi Üniversity Institute of Science and Technology, Ankara, Turkey.

[24] Murathan A., Yücekutlu AY and Murathan A. (2001) Re- moval of zinc ions from aqueous solutions in packed columns 2001 First International Chemical Engineering Con- ference, University of Jordan, Amman, 198-203.

[25] Laks P.E. (1989) An overview of condensed tannin structure, (RW Hemingway and JJ Karchesy, Eds.) Chemistry and significance of Condensed tannins, Plenum Press, New York 131-136.

[26] Haslam E. (1966) Chemistry of vegetable tannins, Academic Press, London.

Received: August 13, 2004 Accepted: October 25, 2004

CORRESPONDING AUTHOR

Atilla Murathan Gazi University Chemical Engineering Department 06570 Maltepe, Ankara - TURKEY

Phone: ++90 312-2317400-2518 Fax: ++90 312-2308434 e-mail: [email protected]

FEB/ Vol 14/ No 4/ 2005 – pages 296 - 299

302 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

INVESTIGATION OF WATER QUALITY OF THE WORLD’S LARGEST IRRIGATION TUNNEL SYSTEM, THE SANLIURFA TUNNELS IN TURKEY

M. Irfan Yesilnacar and Sinan Uyanik

Harran University, Environmental Engineering Department, Osmanbey Campus, 63000 Sanliurfa, Turkey

SUMMARY

In this study, the quality of the water supplied from The project called the Southeastern Anatolia Project in- Atatürk Dam Lake, which is the largest fresh water re- cludes 22 dams, 19 hydroelectric power plants, two 26.4 km source of Turkey and Middle East Region, by means of long irrigation tunnels (7.62 m in diameter - the largest in Sanliurfa Tunnels was investigated. The water qualities the world), thousands of miles of irrigation canals to irri- were evaluated according to the Turkish Water Pollution gate ca. 1 800 000 ha of land, roads, airports etc., and co- Control Regulations, Turkish Water Intended for Human vers an area of 74 000 km2, ca. one-tenth of the country [1- Consumption (TS 266), and WHO (1993). Water samples 2]. were analyzed monthly for some water quality parameters (e.g. temperature, pH, Cl, SO4, NH3-N, NO2-N, NO3-N, The supplied water is conveyed to the Sanliurfa - TDS (Total Dissolved Solids), color, and Na) from 2000 Harran Plain through an open channel, which provides the to 2003. irrigation of 476,000 hectares of land (358,000 hectares of land by gravity, 118,000 hectares of land by pumping). As a result of the study; the water of Atatürk Dam for human consumption from the view of physical and inor- Construction of the tunnels started in 1977. Both tun- ganic properties is generally a high-quality one. The nels have been used for water conveyance since 17 May, amount of coliform bacteria is an important problem for 1997. the waters. It has an increasing trend because of wastewater discharges and must be controlled from the The purpose of constructing the Sanliurfa tunnels, in view of bacteriological pollution. In general, the quality addition to irrigation, was to supply water for the urban of the water fulfills the irrigation standards, and irriga- center of Sanliurfa with a drinking water treatment plant tional water quality class is determined to be C2 – S1. For on the left abutment of the main outlet line (Figure 2), irrigation purposes, the high-quality water must be used which was built in 2004 and has a capacity of 300,000 m3/ carefully, when taking into consideration the salinization day. At the same time, a 2x26 MW hydroelectric plant problem. was under construction at approx. the 5-km point of the Sanliurfa-Mardin road on Sanliurfa’s main canal, making

use of a 50-m difference in elevation. Thus, the Sanliurfa KEYWORDS: tunnel system will secure other benefits in addition to GAP project, Sanliurfa Tunnels, water quality. irrigation, such as the supply of drinking and usage water, and the generation of energy.

The purpose of this study is to classify these water re- INTRODUCTION sources used for irrigation, drinking and other purposes, according to the Turkish Water Pollution Control Regula- The Sanliurfa tunnels are the largest irrigation tunnels tions, and to compare this according to TS 266 and WHO in the world. Located in the Southeastern Anatolia Region (1993) [3-5]. Furthermore, evaluations will be made ac- in Turkey, they are the centerpiece of a project called the cording to the USA Salinity Diagram and the Wilcox Southeastern Anatolia Project (GAP: Turkish initials) Diagram in order to determine the irrigation quality of (Figure 1). There is no doubt that Sanliurfa tunnels` sys- these waters. The data obtained in this study will be of use tem is one of the GAP key structures, because of its both in evaluating the performance of the Sanliurfa drink- length and the amount of water carried by the tunnels.

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ing water treatment plant and in managing the quality of the water conveyed to Harran Plain.

304 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

FIGURE 1 Location map of the study area.

FIGURE 2 Location of Sanliurfa drinking-water treatment plant and the sampling point on the general layout of the tunnels.

MATERIALS AND METHODS Water quality was evaluated according to the Turkish Water Pollution Control Regulations published in the Offi- In this study, water samples were taken monthly from cial Gazette of 4 September, 1998, no. 19919. In addition, the exit mouth of the Sanliurfa tunnel over a period of four comparisons were made according to Turkish Water In- years (2000-2003). Since there was no abnormal deviation tended for Human Consumption and the Guidelines for in the monthly values, the averaged monthly value for the Drinking-Water Quality. Irrigation water quality was eval- entire 4-years period was used. Standard methods were uated in accordance with the USA Salinity Diagram and used for data analysis given in Table 1. the Wilcox Diagram.

TABLE 1 Hydrochemical analysis results of the water samples.

Months (a) 3 4 5 6 7 8 9 10 Water quality classes TS 266 WHO (1993) Physical and inorganic chemical parameters Parameters Unit I II III IV Max. o Temperature C 14.00 20.00 22.00 22.00 26.00 26.00 26.00 23.00 25 25 25 > 30 25 — pH 7.62 8.30 8.30 8.30 8.30 8.30 8.16 8.30 6.5-8.5 6.5-8.5 6.0-9.0 <6.0-9.0> 6.5-9.2 6.5-9.5 Cl mg/l 24.74 27.10 25.70 25.90 26.80 25.90 25.80 27.00 25 200 400 >400 600 250

SO4 mg/l 40.55 35.50 36.85 35.70 34.40 34.70 36.40 36.40 200 200 400 >400 250 max.250

NH3-N mg/l 0.48 0.28 0.30 0.29 0.33 0.24 0.20 0.29 0.2 1 2 >2 0.5 0.2

NO2-N mg/l 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.002 0.01 0.05 >0.05 0.1 —

NO3-N mg/l 2.32 2.23 3.52 3.50 3.45 3.60 3.00 3.26 5 10 20 >20 50 (b) 50 TDS mg/l 239.00 238.00 243.00 242.00 246.50 231.00 228.00 234.00 500 1500 5000 >5000 1500 — Colour Pt-Co 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5 50 300 >300 20 15 Na mg/l 15.20 12.80 13.50 14.20 12.70 12.40 14.50 14.00 125 125 250 >250 175 200 Organic parameters Organic carbon mg/l 1.60 1.55 1.65 1.55 1.64 1.36 1.35 1.33 5 8 12 >12 — — Inorganic pollution parameters F μg/l 0.97 0.72 0.86 0.56 0.86 0.67 0.47 0.62 1000 1500 2000 >2000 4000-1500 1500 Fe μg/l 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 300 1000 5000 >5000 200 300 Bacteriologic parameters T.Coliform EMS/100 ml 180.00 53.30 52.50 125.00 82.50 150.00 150.00 183.00 100 20000 100000 >100000 1< 0.01 F.Coliform EMS/100 ml 12.00 10.00 11.00 46.00 38.70 20.00 73.30 16.60 10 200 2000 >2000 1< 0 (a) The samples were not taken in J anuary, February, November and December. Because, these months are out of irrigation season. (b) Also, max. nitrate level is 50 mg/l according to the R egulations of P rotection of Waters against Nitrate P ollution from Agricultural Activities [6].

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(a) The samples were not taken in January, February, November and December, because these months are out of irrigation season. (b) Also, max. nitrate level is 50 mg/l according to the Regulations of Protection against Nitrate Pollution from Agricultural Activities [6]. RESULTS (1993). The average hardness of the samples was calculated to be 18-19, according to French hardness. With such val- The Quality of Surface Water and Drinking Water ues, these waters are classified as “slightly hard.” Accord- Quality classification of surface and drinking water ing to Turkish Water Pollution Control Regulations, the was performed according to the guidelines and standards bacteriological parameters “fecal coliform” and “total coli- indicated above. As shown in Table 1, according to the form” belong to the category “Class II: Slightly Polluted Turkish Water Pollution Control Regulations, it was de- Water,” which is defined as water that may be used for the termined that the following physical and inorganic pa- following purposes: rameters were in “Class I: High-Quality Water”: tempera- • Drinking-water supply with advanced or appropri- ture, pH, Cl, SO4, NH3-N, NO2-N, NO3-N, TDS, color, ate treatment, and Na. It was also determined that the parameters organic matter and inorganic pollution belong to Class I. • Recreation purposes, • Non-trout fish farming, According to the Turkish Water Pollution Control Regulations, “Class I: High-Quality Water” is defined as • All purposes other than those specified for Class I. water that may be used for the following purposes: The bacteriological above-mentioned parameters Drinking-water supply with disinfection alone, • were determined to be above the maximum levels indicat- • Recreational purposes (including those that require ed in TS 266 and WHO (1993). The values were particu- bodily contact with water, such as swimming), larly high during the hot months (July, August and Sep- • Trout breeding, tember), the reason being the increase in wastewaters` volume discharged into the dam lake and that of the re- • Animal breeding and farming needs, sultant microbial pollution through the effect of tempera- • Other purposes. ture.

Similarly, the above parameters were observed to be The main settlement centers within the catchment area below the maximum values indicated by TS 266 and WHO of Atatürk Dam Lake include Adıyaman Province and the districts of Kahta, Samsat, Bozova, and Hilvan (Figure 3).

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FIGURE 3 Main settlements in the catchment area of Atatürk Dam.

140 140

120 120

100 100 (x10) 3 80 80

60 60

40 40

Irrigated area, ha (x1000) 20 20 Amount of water, hm 0 0 1995 1996 1997 1998 1999 2000 2001 2002 2003

Irrig a ted a rea 31,29 38,71 54,36 78,28 98,38 114,9 121,6 120,7 123,2 Amount of water 28,3 34,5 55,9 116,9 129,1 120,7 100,8 104,9 119,8 Years

FIGURE 4 Distribution of water amounts carried to the Harran Plain and irrigated areas according to the years 1995-2003.

Since there are no wastewater treatment plants in any Samples taken from the lake water in the vicinity of of these areas, the waters are discharged into the reservoir the axis of Atatürk Dam were subjected to a similar clas- without any treatment. sification, and it was observed that coliform bacteria levels here were also remarkedly high during the hot months. With regard to eutrophication, it was determined that total

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nitrogen and phosphorus levels have displayed an upward FIGURE 5 trend since 1996 [7]. Nowadays, it is well-known that Wilcox diagram of the waters. some part of the Lake of Keban Dam, the previously A number of methods are recommended for the de- constructed dam of the same project, has a high trophic termination of the chemical properties of irrigation water. level because of extensive agricultural activities and use The most common of these is the use of diagrams prepared of fertilizers around the lake [8]. according to %Na, SAR, and EC. On the Wilcox diagram prepared according to EC-%Na values, the waters fell into The Quality of Irrigation Water the classification "Very Good to Good" (Figure 5). Thus, these waters can easily be used for irrigation. As seen in Irrigation on the Harran Plain was firstly initiated at Table 2, the EC was 321-400, and this value falls within the end of 1994. The amount of water used to irrigate the the range C2 (250-750 micromhos (µS)/cm). plain and the distribution of the irrigated regions according to the years are shown in Figure 4. TABLE 2 It is clear from this figure that there has been a de- Characteristics of the waters with regard to irrigation. crease in the overall amount of water since 2000, despite Class an increase of irrigation area. The reason for this is the EC USA La- Years %Na SAR Wilcox transition from the former flooding method to modern (mikromhos/cm) boratory Diagram irrigation methods (trickle, subsurface irrigation, etc.) in Diagram 2000. As can also be seen from Fig. 4, the total area irri- Very good 2000 321 13.7 0.43 C2 – S1 gated since 2003 represents only 26% of the total area to good Very good 2001 372 13.6 0.44 C – S intended with the operation of the Sanliurfa tunnels. to good 2 1 Very good Excessive amounts of dissolved ions in irrigation wa- 2002 437 13.4 0.43 C – S to good 2 1 ter affect plants and agricultural soil physically and chem- Very good 2003 400 12.6 0.39 C – S ically, thus reducing the productivity. The physical effects to good 2 1 of these ions are to lower the osmotic pressure in the plant structural cells, thus preventing water from reaching the branches and leaves. The chemical effects disrupt plant metabolism. It is the quantity of certain ions, such as sodium and boron, rather than the total salt concentration that affects plant development [9-10].

FIGURE 6 USA laboratory diagram of the waters.

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In other words, waters of moderate salinity can irrigate [7] Yazgan, M.S, Armagan, B. and Yeşilnacar, M. İ. (2001) Sea- all plants in soils of medium drainage with no excessive sonal Variations of the Water Quality of Ataturk Dam Lake, International Conference on Water Resources and Environ- salinity hazards. With regard to general sodium hazard, mental Impact Assessments, Turkish Water Foundations, 11- SAR was 0.39-0.44, placing it in the S1 category, or low- 13 July 2001, İstanbul, pp. 27-35. sodium water, which can be used in nearly all soils without sodium hazard. Transferred to the USA Na diagram, these [8] Topkaya, B. (1994) Multi-purpose use of Keban Dam Lake values lie within the C2-S1 region (Figure 6), which means and the environmental problems, Proceedings of the Protec- tion of Water and Soil Sources of Turkey, Vol. 3, pp. 1243- that they can be used for all types of irrigation. 1255.

[9] Kızılkaya, T. (1988) Irrigation and Drainage, DSI printing of- CONCLUSION fice, Second edition, 390p, Ankara, Turkey.

In this study, water used for irrigation was classified [10] Şahinci, A. (1991) Geochemistry of Natural Waters, Reform as "Class I: High-Quality Water", according to the Turk- printing office, 548p, Izmir, Turkey. ish Water Pollution Control Regulations. Similarly, the above parameters were found to be below the maximum values specified by TS 266 and WHO (1993). The bacteriological parameters, fecal and total coliforms, were found to be above the maximum limits, according to Class II: Low Pollution, and TS 266 and WHO (1993). The values were observed to be particularly high during the hot months, as a result of the effect of temperature on the microbial pollution caused by wastewater discharged into the dam lake.

In the classification of the water with regard to its usage for irrigation, it was found to be in the "Very Good to Good" class on the Wilcox diagram, and the C2-S1 regions on the USA Salinity diagram. Thus, these waters were found to be suitable for all types of irrigation. Consequently, the data obtained in this study pertain- ing to water quality may be used in evaluating the performance of the Sanliurfa drinking water treatment plant and the management of water used for irrigation in Harran Plain.

REFERENCES

[1] Kolars, J.F. and Mitchell, W.A. (1991) The Euphrates River and the Southeast Anatolia Development Project, Southern Illinois University Press, USA, 297p.

[2] Yesilnacar, M.I. (2003) Grouting applications in the San- liurfa tunnels of GAP, Turkey, Tunneling and Underground Space Technology incorporating Trenchless Technology Re- search, Vol. 18/4, pp. 321-330.

[3] Anonymous (1988) The Turkish Water Pollution Control Regulations, The Turkish Official Gazette of 4 September 1998, no. 19919, Ankara, Turkey.

[4] TSE (Turkish Standards Institute) (1997) Turkish Water In- Received: September 08, 2004 tended for Human Consumption, TS 266, Ankara, Turkey. Accepted: September 29, 2004

[5] WHO (World Health Organization) (1993) The Guidelines for Drinking-Water Quality, Second edition, WHO, Geneva. CORRESPONDING AUTHOR [6] Anonymous (2004) The Regulations of Protection of Waters against Nitrate Pollution from Agricultural Activities, The M. Irfan Yesilnacar Turkish Official Gazette of 18 February 2004, no. 25377, Harran University Ankara, Turkey. Environmental Engineering Department

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Osmanbey Campus 63000 Sanliurfa - TURKEY

e-mail: [email protected]

FEB/ Vol 14/ No 4/ 2005 – pages 300 – 306

LEACHABILITY OF POLLUTANTS FROM SOLID RESIDUES OF A HAZARDOUS WASTE INCINERATOR

Aykan Karademir, Mithat Bakoglu and Ertan Durmusoglu

University of Kocaeli, Department of Environmental Engineering, 41040 İzmit, Kocaeli, Turkey

SUMMARY by treatment of the downstream flue gas in a scrubber. These solid residues are, in general, heterogeneous mate- Leachability of pollutants including heavy metals, to- rials resulting from complex processes occurring during tal organic carbon (TOC) and halogens from solid resi- the incineration and the raw gas treatment. Bottom ashes, dues of a hazardous waste incinerator was evaluated. or slag, include the ash residues dropping into the ash Leaching tests were applied to the solid residue samples chamber from the end of the kiln. The ash residue consists (bottom ash, fly ash, filter cake and gypsum) taken in nine trial burns at different times, and results were evaluated in relation to the waste composition and from the toxicity primarily of coarse non-combustible materials and un- point of view. Origins of the pollutants and their distribu- burned organic matter collected at the outlet of the com- tion between the types of wastes were also studied. The bustion chamber in a quenching/cooling tank. The siftings results showed that the bottom ash contains soluble organ- include relatively fine materials passing through the grate ics at high levels due to cold points and pyrolytic condi- and being collected at the bottom of the combustion tions that could occur locally in the kiln causing for- chamber. The fly ashes from the electrostatic precipitator mation of products of incomplete combustion. The fly (ESP) contain original fuel materials that have been me- ashes were characterized by high metal concentrations in chanically transferred into the flue gas as well as conden- leachates, while those of the filter cake and the gypsum sate species found on the surfaces of the fly ash particles, wastes had high sulfate concentrations. More than half of which result from the condensation of volatile species the Cd input was detected in the leachates, especially in the during the cooling phase of the flue gas inside the boiler. fly ash, showing its affinity to form soluble compounds. The filter cakes (or wet scrubber residues) contain salts from the neutralization of acid gases, mercury-bearing compounds, and other volatile-rich metal compounds depending on the particle slip of the filter. Fly ashes are potentially the most polluting byproducts of combustion KEYWORDS: Leaching tests, heavy metals, incinerator residues, due to the high furnace temperatures and the high volatility bottom ash, fly ash. of transition elements and heavy metals, such as arsenic, cadmium, chromium, mercury, nickel, lead and zinc. Addi- tionally, many organic compounds that are products of incomplete combustion could be found in these wastes. Release of such pollutants during storage can pollute water INTRODUCTION sources and endanger living organisms. From the toxicity point of view, the fly ash is the most harmful component The main concerns for waste incineration are the emis- because of having highly leachable heavy metals. Accord- sion of toxic flue gas to the atmosphere and the release of ing to the existing legislation of most countries, the slag harmful substances from the incineration residues. These may be directly disposed in landfills without solidification/ residues include bottom ashes and the solid residues result- stabilization or any other treatments [1-5]. ing from the treatment of flue gas i.e., fly ashes collected from electro-filtration of flue gas and filter cakes produced

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In this study, solid residues are obtained from Izmit Samples from solid wastes were taken according to Hazardous and Clinical Waste Incinerator (IZAYDAS). TS 12090 and ICS 13.03.10, while those of liquid wastes The solid residues of the plant are landfilled in the haz- (special liquid wastes, waste oils, etc.) were taken accord- ardous waste landfill site at a distance of 750 m from the ing to TS-ISO 5667-5–10 for determination of waste com- incinerator. The issues on the disposal of hazardous wastes position. Since the solid wastes fed by bunker were com- to landfills are regulated by Turkish Hazardous Wastes posed heterogeneously, they are mixed in a bunker for 24 h Control Act (TAKY) [6]. In compliance with the Europe- to form a representative mixture as the sample before slic- an Directive on landfilling of wastes (2003/33/EC) [7], ing it thoroughly. Metal analyses were made by inductively TAKY classifies these wastes into three groups according coupled plasma atomic emission spectroscopy (ICP/AES) to the laboratory leaching test, namely, inert wastes, non- (Spectra) after an acidic digestion, and expressed on weight hazardous wastes and hazardous wastes, stipulating that the basis (weight of metal to total dry weight of sample). For wastes whose leachates have pollutant concentrations higher solid wastes, 3 g of samples taken from the amounts of 2 kg than the values for hazardous wastes have to be treated from dried and grounded waste samples were digested before disposal. This study presents a leachability evalua- with 50 ml of HNO3:HCl mixture at 3:1 by volume for 3 h tion of pollutants from solid residues of IZAYDAS. before ICP/AES analysis. The same procedure was applied Therefore, leaching tests were applied to the solid residue to 2 l aliquots of the liquid waste samples. Chloride con- samples i.e., bottom ash, fly ash, filter cake and gypsum, tents were analyzed by ion chromatography, whereas haz- taken in nine trial burns at different times. ardous organic compounds were analyzed by gas chromatography/mass spectrometry (GC/MSD) (HP 6890 GC 5973 N MSD) after a 24-h hexane-extraction. EXPERIMENTAL Samples of bottom ash, fly ash, filter cake and gyp- Incinerator Residuals sum were also taken according to TS 12090 and ICS 13.03.10. For each group, a sample of 100 g was taken, The detailed information on the plant and its flow put into 1 L distilled water, shaked with 180 rpm for 24 h, scheme were given in Bakoglu et al. [3]. The incinerator and then filtered before leaching tests. Although different has a two-stage combustion system consisting of a rotary leaching tests have been developed for different purposes kiln with combustion temperatures between 950-1050 oC [8], the single bath extraction (equilibrium test) is usually and retention times between 2-2.5 h for solids, and a ver- suggested by the regulations in order to classify wastes as tical shaft with a retention time of 2 s at 1150-1250 oC as hazardous or non-hazardous, based on the pollutant con- a post-combustion chamber. Air pollution control system centrations in the leachate and/or bioassays [2]. Both the consists of an ESP, and a two-stage venturi scrubber. In European Community and Turkish Regulations have estab- the first stage of the venture scrubber HCl, HF and heavy lished an equilibrium test for the characterization of haz- metals together with fine particulate matter escaping from ardous wastes in solubility terms after evaluation of the ESP are removed by a two-stage pulverization washing. chemical composition or biotoxicity of the liquid phase In the second stage, flue gas contacts with the lime solu- [7, 8]. The leaching test given in TAKY [6] corresponds tion to remove SO , organic gases and any remaining 2 to “Compliance test for leaching of granular waste mate- pollutants. The wastewaters from the scrubbers are treated rials and sludges - part 2 (EN 12457/2)”, which includes by coagulation-flocculation-sedimentation processes. batch extraction of samples at a liquid/solid ratio of 10 Solid samples of four different incinerator residues (L/S = 10 L/kg) for 24 h. were used in leaching tests: bottom ash, fly ash, filter cake Heavy metals in leachates were analyzed by ICP/AES and gypsum wastes. The bottom ash is the mixture of slag as mentioned above. Total organic carbon (TOC) and ad- of the rotary kiln and bottom ashes of the vertical furnace. sorbable organic halogens (AOXs) were determined using Since the incineration of most wastes takes place in the a TOC-Analyzer and an AOX-Analyzer, respectively. rotary kiln, almost all of the bottom ash is comprised of Chloride, phenols, ammonium, cyanide, sulfate and nitrite the kiln slag. Bottom ash is taken to an ash-quenching concentrations were determined spectrophotometrically, chamber to contact with water for 10 min, and then trans- while fluoride was analyzed with an ion analyzer. ferred to the landfill site. The fly ash consists of the particles both accumulated in boiler and collected by the ESP.

The filter cakes are produced by the physico-chemical RESULTS AND DISCUSSION treatment of the wastewaters from both scrubbers. The gypsum samples were taken from the precipitates in bot- Waste Composition tom of the lime scrubber, formed by the reaction of lime In the incinerator, wastes are fed to the rotary kiln with water and SO2. In a normal operation, they move with wastewater to the treatment plant and join to filter through five different inlets. Most of the solid wastes are cake, but they were sampled separately in trial burns. fed in barrels from a feeding bunker and include certain industrial solid wastes and clinical wastes. The liquid Experimental Methods wastes are classified into three parts based on their characteristics, such as calorific value, pollutant content, vis-

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cosity etc., and fed separately as combustible liquids with high calorific value and low water content aqueous liquids and special liquids. The special liquids are viscous industrial wastes with high pollutant content. A general summary of the waste properties and their amounts according to the feeding types in the tests is given in Table 1. The results observed in nine trial burns showed that the waste amounts and compositions have not changed significantly in the plant. The ratios of the amounts of waste types relative to each other are kept constant, based on a pre-determined combustion menu. Therefore, the average values given in Table 1 could be accepted as representa- tives for the wastes incinerated in the plant. The organic compounds given in Table 1 are the only ones detected by

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TABLE 1 - Average waste properties in nine tests.

Bunker Barrels Combustible liquids Aqueous liquids Special liquids Amount (kg/d) 51400 9500 12300 11200 6340 Calorific value (kJ/kg) 12100 1000 25600 1000 7580 Viscosity (cP) - - 324 196 550 Density (g/cm3) - - 0.95 0.98 1.46 Water (%) 32.5 17.6 - - - Chlorine (%) 0.86 0.20 0.92 0.19 62.8 Metals (%, w/w) (x 10-3) Cd 0.301 0.041 0.049 0.053 0.036 Tl 0.302 0.011 0.003 0.009 0.003 Hg 0.001 n.d. 0.011 0.065 0.013 Sb n.d. n.d. 0.020 n.d. 0.014 As 0.078 0.140 0.656 0.072 0.234 Pb 167 0.339 0.391 0.178 0.104 Cr 27.8 0.687 0.438 0.201 0.395 Co 0.009 0.011 0.010 0.006 0.005 Cu 85.1 7.52 3.41 3.33 0.451 Mn 59.3 0.183 0.109 0.018 0.046 Ni 82.7 4.91 1.37 1.72 0.159 V 1.57 0.359 0.127 0.464 0.015 Sn 9.79 0.422 0.365 0.024 0.018 Zn 1150 3.87 2.33 9.76 0.505 Organic compounds (%, w/w) Acetonitrile n.d. n.d. n.d. n.d. 2.07 Trichloro ethylene n.d. n.d. n.d. 0.065 58.4 Benzene 0.041 n.d. 0.010 0.039 0.237 Toluene 0.713 n.d. 1.06 0.004 0.712 Xylene 0.500 0.015 1.24 1.13 0.192 Ethyl benzene 0.376 0.007 1.86 0.008 0.131 1,3,5-trimethyl benzene 0.189 0.020 0.321 0.003 0.192 Chloroform n.d. n.d. n.d. n.d. 0.001 Tetrachloro ethylene n.d. n.d. 0.009 n.d. 2.02 Chloro benzene n.d. n.d. 0.020 n.d. n.d. Total Organic Carbon 34.6 17.5 54.7 3.56 23.6 n.d.= not detected (detection limits are between 1-5x10-6 (%) for metals, and 1x10-4 (%) for the organic compounds).

GC/MS analysis, out of many other volatile and semi- in understanding the behavior of pollutants in the highly volatile compounds included in US EPA Methods 601, heterogeneous environment of the rotary kiln. 602 and 624, which were determined as undetectable. Figure 1 shows that most of the pollutants originate The forms of waste pollutants play a significant role from the solid bunker wastes. Especially the metals con- in the subsequent fate of them in incineration process, stituting more than 99 % of the total metal input were especially that of heterogeneous wastes. For example, found in bunker at about 99 % level. Among the other incineration of solid wastes causes some difficulties, such metals, Cd, Tl, V, and to a certain extent, Co (with ca. 70 % as poor mixing, local differences in temperature and rea- of solid waste origin) showed similar distribution, while gent concentrations, and requirement of long residence Hg, Sb and As had higher liquid waste percentages. On times for a complete combustion. Since penetration of the other hand, almost all the chlorine input comes from outside temperature into the furthest point inside the solid special industrial liquids, or namely, trichloroethylene (i.e., the center) could last longer than the theoretical wastes. Since about 70 % of the total organic content of time, the pollutants in the solids tend to be retained in the wastes originates from the solid bunker-fed wastes bottom ash, even when the physical and chemical condi- and barrels, the presence of some organics, i.e., the prod- tions are suitable for volatilization. Therefore a better ucts of incomplete combustion, may be expected in the identification of the sources of pollutants could be helpful bottom ashes of the rotary kiln.

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B unker Barrel Com. Liq. Aqu. L iq. Spec. Liq. 100%

80%

60%

40%

20%

0% Cd Hg As P b, C u, Cl Non-C l Cl- TOC C r, Mn, organics organics Ni, S n, Zn

FIGURE 1 - Contribution of waste types to the total pollutant input.

Leaching Tests tions were obtained in the leachates from bottom ashes. The results of leaching tests applied to the bottom ash, The GC/MS analyses were performed for 15 chlorinated fly ash, filter cake and gypsum are presented in Table 2. As organics (included in Method ISO 10301), 8 pesticides shown in Table 2, nearly all the residues have leachate and 12 PCBs (included in Method USEPA 608/8080B) in concentrations higher than the limit values. This indicates leachates, however they were determined to be undetecta- -4 that these wastes should be treated before landfilling, for ble (detection limit of 1x10 mg/L). The compounds iden- example, by solidification/stabilization. Very high TOC tified by GC/MS database (confidence 90 % or higher) in levels and relatively high phenol and chloride concentra- these tests are given in Table 3.

TABLE 2 - Average results of leaching tests.

Bottom ash Fly ash Filter cake Gypsum Limit valuea Amount (kg/d) 29570 2370 3812 1123 - pH 9.17 6.51 8.39 8.39 4-13 TOC (mg/l) 2530.74 47.90 4.77 21.73 200 AOX (mg7l)) 1.56 0.26 1.08 0.27 3.0 Phenols (mg/l) 5.89 0.05 0.003 0.01 100 Ammonium (mg/l) 6.40 6.31 0.82 2.13 1000 Cyanide (mg/l) 0.12 0.38 0.09 0.10 1.0 Sulfate (mg/l) 193 1017 1230 1812 1000 Nitrite (mg/l) 7.11 14.11 1.4 1.0 30 Halogens (mg/l) Chloride 23.13 1.09 15.28 2.78 6000 Fluoride 1.51 2.30 1.80 2.38 50 Metals (mg/l)ba Cd n.d. 4.4502 0.0183 0.0006 0.5 Pb 0.0184 1.3441 0.0086 0.0197 2.0 Cr 0.067 0.0398 0.0089 0.0060 0.5 Cu 0.2628 48.6531 0.2256 0.0088 10 Ni 0.2823 16.1868 0.025 0.0089 2.0 Zn 0.1508 1041.189 0.0196 0.1020 10 a Upper limits of TAKY (1995) for the “hazardous wastes” that could be landfilled to the special sites without any treatment. b Other metals were not detected in the leachates (detection limits were between 1-4x10-3 mg/l). Additionally, 15 chlorinated organics (included in Method ISO 10301), 8 pesticides and 12 PCBs (included in Method USEPA 608/8080B) were found to be undetectable in GC/MS analyses (detection limit of 1x10-4 mg/l).

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TABLE 3 - The organic compounds identified in the leachates of incinerator residues.

Compound Bottom Ash Fly Ash Filter Cake Gypsum

1,2-Benzene dicarboxyclic acid (C8H6O4) X X X X Benzene (C6H6) X X X X Ethyl hexanol (C18H18O) X Benzothiazole (C7H5NS) X Acetamide (C2H5NO) X X Phenols (C14H14O, C14H22O) X X Decane (C10H22) Undecane (C11H24) X Dodecene (C12H24) X Tridecane (C13H28) X Pentadecane (C15H32) X Heptadecane (C17H36) X Octadecane (C18H38) X X X X Nonadecane (C19H40) X X X X Eicosane (C20H42) X X X X Heneicosane (C21H44) X X Docosane (C22H46) X X X X Tricosane (C23H48) X X X Tetracosane (C24H50) X Pentacosane (C25H52) X X X X Hexacosane (C26H54) X X X Heptacosane (C27H56) X X X Octacosane (C28H58) X X Nonacosane (C29H60) X X Traicontane (C30H62) X 2-Heptadecanone (C17H34O) X 2-Pentadecanone (C15H30O) X Hexadecanoic acid (C16H32O2) X X X Octadecanoic acid (C18H36O2) X Nonahexacontanoic acid (C69H138O2) X Epoxyheptachlor (C10H5Cl7O) X

The organic contents of the leachates were mainly in water [10]. High pH values and relatively high carbo- composed of 1,2-benzene dicarboxyclic acid (phthalic cyclic acid and phenol concentrations in leachates support acid) and benzene, which were responsible for about 70 % this statement, although there could be other complex reac- and 20 % of the total peak area in the GC/MS chromato- tions between organic compounds and metals, halogens grams, respectively; while the other organic compounds etc. to form soluble salts. were found in trace quantities. High TOC concentrations Chloride concentrations in the leachates from the bot- in the bottom ash resulted from the products of incom- tom ash were also high with regard to that of other resi- plete combustion. Since boiling points of the organics dues. Due to the low metal concentrations, it could be increase with the increase of number of carbons, the pres- assumed that the chloride content of the bottom ash re- ence of organic compounds with less than six carbon atoms sults mainly from the salts of alkali metals, such as Na, K, is not expected in the bottom ash. On the other hand, Mg, Ca etc. The presence of other elements (H, Na, Mg, solubility of organic compounds decreases as the number K, Ca, Ba, Al, Si, Fe, etc.) with affinity to chlorine has of carbons increases. One possible explanation of these also an effect, by decreasing the Cl available for for- high TOC concentrations is that the temperatures could mation of volatile metal chlorides [11-13]. Moreover, it is locally be below 300 oC in some areas of the very hetero- reported that about 80 % of the chlorine is converted to geneous environment of the rotary kiln. This is in agree- gaseous HCl, and between 10 to 15 % is bound in chlo- ment with the study of Ferrari et al. [9] showing that or- rides [14]. In the literature, the presence of alkali chlo- ganic compounds might not reach the critical temperature rides, such as NaCl, KCl, MgCl , and CaOHCl, in resi- on the furnace grate necessary for thermal decomposition. 2 dues from incinerators are also reported [4, 13, 15]. The dominances of 1,2-benzene dicarboxyclic acid and benzene with six carbons in the leachates are in agree- Fly ash had leachate concentrations of Cd, Cu, Ni and ment with this suggestion. Furthermore, some organics Zn, which are 4 to 10 times higher than the limit values. The including carbocyclic acids and phenols could be dissolved behavior of Cd is important, since it showed high leachabil- in aqueous NaOH solutions, while they are slightly soluble ity, although Cd content of the waste is very low as com-

315 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

pared to the other metals. The behavior of Cd observed in pounds in the treatment plant, most of them are discharged trial burns agreed with the studies of Wang et al. [13], who by the effluent, unlike gypsum, which is precipitated and reported that about 80 % of Cd was partitioned to fly ash retained in the filter cake. The gypsum wastes were taken at molar ratios of Cl/metal higher than 100 (major species from the precipitates at the bottom of the lime scrubber. of Cd in fly ash at these ratios was CdCl2), and that 27 % Since they are formed by the reaction of the lime with of fly ash Cd was leached. The concentration of Pb in the water and SO2, high sulfate concentrations were observed fly ash leachate was much higher as compared to other in their leachates. TOC concentrations in the leachates of leachates, confirming the study of Bakoglu et al. [3] report- the gypsum resulted from the removal of organic com- ing high Pb content of fly ash in IZAYDAS. However, the pounds in the lime scrubber. Heavy metal concentrations in fraction of Pb leached was very low (about 0.4 % of total the leachates of the gypsum wastes and the filter cakes Pb input), in contrast to Cu, Ni and Zn (between 2 to 4 %). were very low or lower than the detection limits. Taking into account that sulfate concentrations were high (unlike chlorides) and comparable to those of filter cake Finally, mass balance studies were performed to observe the leachability of the pollutants in the incinerator. and gypsum wastes, which were directly related to SO2 removal by CaO, it could be assumed that metal sulfates For metals, these studies indicated that, in average, 59 % are dominant in fly ash, besides the significant amounts of of Cd input to the rotary kiln was detected in leachates, while this percentage did not exceed 4 % for the other CaSO4 as shown by many studies [1, 4, 16, 17]. This metals. Furthermore, the amount of Cd leached showed a could explain the low leachability of Pb, since PbSO4 is less soluble than the sulfates of Cu, Ni and Zn. These good correlation with Cd input (see Figure 2). Leachabil- results are similar to that given by Idris and Saed [18] for ity ratios of the metals were in the rank of Cd>Zn>Cu> fly ash of a hospital waste incinerator, while they are Ni>Cr>As>Pb, except other metals not detected in the much higher than the concentrations of TCLP leachates of leachates. More than 80 % of the heavy metals leached the fly ash from incinerators (except for Cr) given by come from fly ash leachates, except for Cr (87 % of Cr Wang et al. [13] and Youcai et al. [19], indicating the leached was found in the bottom ash leachates). On the effects of waste composition. other hand, 3 % of TOC input to the incinerator was measured in the leachates, and more than 99 % of it could Filter cakes are produced by the treatment of the be observed in bottom ash leachates, like other organic- wastewaters from both the venturi and lime scrubbers. based pollutants e.g., phenols and AOX. They showed high sulfate concentrations in leaching tests, resulting from high wastewater sulfate content. Chloride Some metals, such as Hg, Tl, Co, and V, found below concentrations in wastewaters were also relatively high, the detection limits in leachates, were detected in scrubber but those in the leachates were comparatively low (be- wastewaters. As compared to their inputs, the amounts of tween 8-21 mg/l), in spite of the addition of FeCl3 (be- Tl, Co and V removed by scrubber wastewaters were very tween 15-25 kg per day) as coagulant. Since there is no low (0.4, 3 and 0.05 %, respectively). However, Hg amount precipitation mechanism to remove chlorinated com- corresponded to 44 % of Hg input in average. Since Hg is

0,35

0,3 R2 = 0,8616 0,25

0,2

0,15

Cd-leached(kg) 0,1

0,05

0 0 0,05 0,1 0,15 0,2 0,25 0,3 0,35 0,4 0,45 0,5 Cd-input (kg)

FIGURE 2 - Graph of Cd input vs. Cd leached.

316 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

the most volatile metal and its compounds could remain ACKNOWLEDGEMENTS in gas phase, even at low temperatures, it may not under- go the processes causing most of the metals to be ad- The authors thank to IZAYDAS for their collabora- sorbed on the particles (nucleation-condensation process- tion in sampling, analyses and evaluation of the results, es during the flue gas cooling). Results showed that and for their close interest and efforts during the perfor- scrubbers in IZAYDAS removed almost half of the Hg mance tests. Special thanks to Prof. Dr. Savaş Ayberk for input. Taking into account that Hg concentration in the his support of this work and useful discussions. final (emitted) flue gas was never found to be above the detection limits in many tests performed during its operation, it could be assumed that the rest is retained in the bottom or fly ash. In the treatment plant, TMT 15 (trimer- REFERENCES captotriazine) is used (6-9 kg per day) to fix Hg by form- ing organic sulfides. [1] Forestier L. and Libourel, G. (1998) Characterization of flue gas residues from municipal solid waste combustors, Envi- ron. Sci. Technol. 32, 2250-2256.

CONCLUSIONS [2] Ibanez, R., Andres, A., Viguri, J. R., Ortiz, I. and Irabien, J.A. (2000) Characterisation and management of incinerator wastes, a) In solid waste incinerators, bottom ash may con- Journal of Hazardous Materials A79, 215-227. tain soluble organics at high levels due to the difficulties in the combustion of solids. Although the [3] Bakoglu, M., Karademir A. and Ayberk S. (2003) Partitioning characteristics of targeted heavy metals in IZAYDAS hazard- temperatures inside the kiln are suitable for com- ous waste incinerator, Journal of Hazardous Materials B99, plete combustion, cold points and pyrolytic condi- 89-105. tions could occur locally and may cause the formation of products of incomplete combustion. [4] Bodenan, F. and Deniard P. (2003) Characterization of flue gas cleaning residues from European solid waste incinerators: b) Although bottom ash is rarely classified as hazard- assessment of various Ca-based sorbent processes, Chemo- sphere 51, 335-347. ous, and is disposed without further treatment in landfills, the results showed that it may contain [5] Sabbas, T., Polettini, A., Pomi, R., Astrup, T., Hjelmar, O., high TOC levels in leachates, and, therefore, re- Mostbauer, P., Cappai, G., Magel, G., Salhofer, S., Speiser, quires additional treatment before landfilling. C., Heuss-Assbichler, S., Klein, R. and Lechner, P. (2003) Management of municipal solid waste incineration residues, Waste Management 23, 61-88. c) Fly ash collected by electrostatic precipitators was classified as a hazardous waste due to its high con- [6] TAKY (1995) Turkish Hazardous Waste Control Act, Offi- tent of soluble metals including Cd, Pb, Zn, Cu cial Paper No:22387. and Ni in leachates. The sulfate concentrations in leachates were also high due to the soluble metal [7] EC (2003) European Community, Council Decision of 19 sulfates. Filter cake and gypsum wastes also had December 2002 establishing a criteria and procedures for the high sulfate concentrations in their leachates, due acceptance of waste at landfills pursuant to Article 16 of and Annex II to Directive 1999/31/EC, Official Journal of the Eu- to the reaction of lime with water and SO2 in lime ropean Communities L 11/27-49, 16.1.2003. scrubbers. [8] Lagrega, M. D., Buckingham, P. L. and Evans, J. C. (1994) d) More than 50 % of Cd input was detected in Hazardous Waste Management, McGraw-Hill International leachates (especially in fly ash leachates), showing Editions, Civil Engineering Series, Mc-Graw Hill, Inc. Princeton Road, S-1 Highstown, NJ. (ISBN: 0-07-113454-9). its affinity to form soluble compounds. On the other hand, about half of the Hg input was found in [9] Ferrari, S., Belevi, H. and Baccini, P. (2002) Chemical speci- scrubber wastewaters indicating its volatility and ation of carbon in municipal solid waste incinerator residues, the importance of wet scrubbers to remove it. The- Waste Management 22, 303-314. se two metals should be carefully controlled in the plant due to their toxicity. [10] Solomons, G. and Frhyle, C. (2000) Organic Chemistry, Sev- enth Ed., John Wiley & Sons, Inc. ISBN: 975-8431-87-0. e) Leaching tests are generally performed in weak [11] Trouvé, G., Kauffmann, A. and Delfosse, L. (1998) Compar- acidic solutions, since solubility of metals increases ative thermodynamic and experimental study of some heavy in acidic conditions. However, the solubility of or- metal behaviors during automotive shredder residues incin- ganic compounds decreases with increasing pHs eration, Waste Management 18, 301–307. and vice versa. Therefore, the presence of organic compounds should also be taken into account in [12] Wey, M.-Y., Yu, L.-J. and Jou, S.-I. (1998) The influence of heavy metals on the formation of organics and HCl during the design of leaching tests, especially for the bot- incineration of PVC-containing waste, Journal of Hazardous tom ashes of solid waste incinerators. Materials 60, 259–270.

317 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

[13] Wang, K.S., Chiang, K.Y., Tsai, C.C., Sun, C.J., Tsai, C.C. and Lin, K.L. (2001) The effects of FeCl3 on the distribution of heavy metals Cd, Cu, Cr and Zn in a simulated multimetal incineration system, Environment International 26, 257–263.

[14] Wichmann, H., Sprenger, R., Wobst, M. and Bahadir, M. (2000) Combustion induced transport of heavy metals in the gas phase—a review, Fresenius Environ. Bull. 9, 72–125.

[15] Kersch, C., Pereto Ortiz, S., Woerlee, G. F. and Witkamp, G. J. (2004) Leachability of metals from fly ash: leaching tests

before and after extraction with supercritical CO2 and ex- tractants, Hydrometallurgy 72, 119-127.

[16] Nagib, S. and Inoue K. (2000) Recovery of lead and zinc from fly ash generated from municipal incineration plants by means of acid andror alkaline leaching, Hydrometallurgy 56, 269-292.

[17] Huang, W.-J. and Chu, S.-C. (2003) A study on the cement- like properties of municipal waste incineration ashes, Cement and Concrete Research 33, 1795-1799.

[18] Idris, A. and Saed, K. (2002) Characteristics of slag produced from incinerated hospital waste, Journal of Hazardous Mate- rials B93, 201–208.

[19] Youcai, Z., Lijie, S. and Guojian, L. (2002) Chemical stabilization of MSW incinerator fly ashes, Journal of Hazardous Materials B95, 47-63.

Received: September 22, 2004 Accepted: November 03, 2004

CORRESPONDING AUTHOR

Aykan Karademir

University of Kocaeli

Department of Environmental Engineering

41650 İzmit/ Kocaeli - TURKEY

Phone: ++90 335 55 59

Fax: ++90 335 55 59

e-mail: [email protected]

FEB/ Vol 14/ No 4/ 2005 – pages 307 - 314

318 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

REMOVAL OF SOME INORGANIC COMPOUNDS FROM PAPER MILL EFFLUENTS BY THE ELECTROCOAGULATION METHOD

Mehmet Uğurlu

Department of Chemistry, Faculty of Science and Arts, Muğla University, Muğla 48000, Turkey

SUMMARY

The purpose of this study is to perform the experi- Electrocoagulation is a process consisting of creating mental investigation of paper mill effluent treatment using a flock of metallic hydroxides, within the effluent could the electrocoagulation method. Removal of ammonium, be cleaned by electro-dissolution of soluble anodes. Com- phosphate, nitrite and nitrate from paper mill effluents pared with traditional flocculation and coagulation, elec- was examined by different current intensity, electrodes tro-coagulation has, in theory, the advantage of removing (Al and Fe), and electrolysis time. The experimental re- the smallest colloidal particles. These smallest charged sults show that the removal efficiency depends on the particles have a greater probability of being coagulated electrolysis time, the types of electrodes and the applied because of the electric field setting them in motion. It has current. From the experiments carried out at 12 V and at a also the advantage of producing a relatively low amount current intensity of 77.13 mA it was found that two minutes of sludge [7]. Secondary pollution may be caused by are sufficient for the removal of the pollutants (except for chemical substances added at high concentrations, when nitrate) using either electrodes. Biochemical Oxygen De- chemical coagulation is applied to treat dyeing mand (BOD) and Chemical Oxygen Demand (COD) re- wastewaters. Excessively added coagulants can be avoid- moval, however, required longer electrolysis times. ed by electro-coagulation, due to the generation of the coagulants by electro-oxidation of a sacrificial anode. The main characteristics of electro-coagulation are simple

KEYWORDS: Paper mill effluent, electrocoagulation, ammonium, equipment and easy operation, brief reactive retention phosphate, nitrite, nitrate. period, decreased or negligible equipment for adding chemicals and decreased amounts of sludge. Therefore, electro-coagulation has been widely used to treat waters

INTRODUCTION containing food and protein wastes, oil wastes, synthetic detergent effluent mine wastes and heavy metal– containing solutions. This method can also be used to Industrial, agricultural and domestic wastes, due to remove phosphate, and for defluorization of water to treat the rapid development in technology and urbanization, are potable water [3, 5]. However, it has never before been distributed to several receivers, but generally to the near- attempted to use it for paper mill effluents. est water sources, such as rivers, lakes, and seas. Control of wastewater pollution has great importance for both Characteristics of Pulp and Paper Mill Effluents kinds of organisms, those who live in water or benefit The pulp and paper industry is the sixth largest pol- from water. Wastewaters are usually purified by conven- luter (after oil, cement, leather, textile and steel indus- tional methods, such as biological oxidation, adsorption, tries) discharging a variety of gaseous, liquid and solid flotation, coagulation, UV photo-decomposition, and wastes into the environment. It is the pollution of water electrochemistry [1]. bodies, however, which is of major concern because large The electrochemical technologies have attracted a volumes of wastewater are generated per metric ton of great deal of attention because of their versatility, which paper produced, depending upon the nature of the raw makes the treatment of liquids, gases and solids possible, material, finished product and the extent of water reuse. and their environmental compatibility [2]. In recent years, Since the pulp produced corresponds to only approxi- electrocoagulation has been successfully tested to treat mately 40-50% of the original weight of the wood, the various industrial wastewaters [3-10]. All the applications effluents are heavily loaded with organic matter. These of electrochemical treatment for the purification of effluents cause considerable damage to receiving waters if wastewater have been of special interest and have attract- discharged untreated, since they have high biochemical ed the attention of some researchers [11]. oxygen demand (BOD) and chemical oxygen demand

319 © by PSP Volume 14 – No 4. 2005 Fresenius Environmental Bulletin

(COD), and are rich in phenolic compounds, chlorinated phate, nitrite and nitrate were measured spectrophotomet- compounds, suspended solids, fatty acids, tannins, lignin, rically before and after electrolysis. At the end of elec- and its derivatives [12]. trolysis, the treated solutions were filtered, and then the concentrations of the compounds were measured by the Several physical and chemical processes for colour standard method [17]. and some inorganic ions` removal in paper mill effluents have been extensively studied, including rapid filtration through soil, ultra-filtration, ion-exchange chromatography, lime precipitation and modified bleaching sequences, such as peroxide addition during extraction, the replacement of chlorine by hypo-chlorite, sorption on hypo- and alum- sludge, activated carbon, and on allophonic compounds etc. [13- 16]. Moreover, the problem remains unsolved.

The purpose of the study is to perform the experimental investigation of paper mill effluents` treatment using the electrochemical method. Removal of ammonium, phosphate, nitrite, nitrate, BOD, and COD from paper mill effluents was investigated by different current intensity, electrodes (Al and Fe), and electrolyse time.

MATERIALS AND METHODS

Experimental Method FIGURE 1 - Experimental apparatus. The paper mill effluents utilized for this study were taken from a modern bleached Kraft mill located in West- 1. D.C Power Supply, 2. Digital Ammeter ern Turkey. Its wastewater (4500 m3/h) is discharged into 3. Digital Voltmeter, 4. Anode, 5. Cathode, Gökova gulf (Muğla, Turkey) by deep-discharging after 6. Magnetic bar, 7. Magnetic Stirring Controller being collected in sedimentation pools and aerated for about a week. Wastewater samples used in this study were taken from aerated logons right before the sea-discharging RESULTS AND DISCUSSION process. The effluent characteristics are given in Table 1. The Effect of Treatment Time

TABLE 1 The effect of electrolysis time on the removal of Characteristics of bleach Kraft mill effluents. phosphates from wastewater is shown in Fig. 2 for both Parameter Value Al and Fe electrodes. As can be seen, an increase in phos- Color Brown phate removal was observed for both electrodes with pH (average) 7,50 increasing time for the first two min, but then phosphate Compounds (mg/L) removal remains constant. It was found that the phosphate -3 PO 4 0,18 removal rate by Fe electrode (95%) was higher than that - NO2 0,21 by Al electrode (70%) (Fig. 2). - NO3 0,18 + NH4 9,88 100 COD 426.15 BOD 25.54 80

Experimental Set-up and Measurements In these experiments, iron and aluminum plates (4.0 cm 60 x 4.0cm x 0.1cm) were used as electrodes. They were cleaned with a 15% HCl solution prior to use. The dis- 40 tance between anode and cathode was 2.0 cm. The exper- Electrode imental apparatus is given in Fig. 1. Phosphate removal, % 20 Al Homogenization was carried out by using a magnetic 0 Fe stirrer. A Topward Dual-Tracking DC 6303D was used as 0 2 4 6 8 power supply. Cell current was measured using a Keithley 2010 multimetre. For each electrode type, the experiments Time (Min.) were conducted as a function of electrolysis time and FIGURE 2 - Phosphate removal as a function of electro- current intensity. The concentrations of ammonium, phos- lyse time (potential:12 V, current intensity: 77.13 mA).

Ammonium removal rates as a function of electroly- 100 sis time by both Al and Fe electrodes are shown in Fig 3.

Similar to phosphate removal, ammonium removal also 80 rapidly increases during the first two min of electrolysis. After 7.5 min, approximately 80% of ammonium was removed by Al and Fe electrodes. 60

40 100

Nitrate removal (%) Electrode 20 80 Al

0 Fe 60 0 2 4 6 8

Time (Min.) 40 FIGURE 5 - Nitrate removal as a function of Electrode time (potential: 12V, current intensity: 77.13 mA).

Ammonium removal (%) 20 Al The mechanism of the electrochemical process in 0 Fe aqueous systems is quite complex [2]. Oxidation of the 0 2 4 6 8 electrochemical process occurs, respectively, at the anode Time (Min.) and cathode of the Fe and Al electrodes according to [18].

FIGURE 3 - Ammonium removal as a function of 2+ - time (potential: 12V, current intensity: 77.13 mA). Anode: 4Fe ↔ 4Fe + 8e (1) 2+ + 4Fe + 10H2O + O2 ↔ 4Fe(OH)3 + 8H (2) + - Fig. 4 shows the nitrite removal as a function of elec- Cathode: 8H + 8e ↔ 4H2 (3) trolyses time for both Al and Fe electrodes. About 80% of With sufficient current intensity and time, organic nitrite was effectively removed by both types of elec- and inorganic molecules in wastewaters are reduced at the trodes at the end of 2 min, and, thereafter, a plateau was cathode to small molecules. Some of the small molecules reached. The Al electrode appears to remove nitrite faster and the suspended solids are captured by Fe(OH) and than the Fe one. After 7.5 min, nitrite removal percent- 3 Al(OH) , which are removed by sedimentation or by H ages were identical for both electrodes. 3 2 flotation [20]. We assume that negatively charged nitrite, phosphate and nitrate ions were adsorbed by Fe(OH) and 100 3 Al(OH)3 during electrolysis.

80 As it can be seen from the Figs. 2-5, the removal is higher with increasing electrolyse time, when the Al electrode is used. This makes us think that large-scaled mon- 60 omeric hydrolysis products, such as [Al(OH)]+2 and [Al(OH)2]+4, occur faster and neutralisation is influenced 40 by electrostatic forces. It is also thought that increasing

Nitrite removal (%) Electrode electrolysis time improves the efficiency of removal by 20 inducing faster aggregation of these hydrolysis products. Al During electrochemical treatment, when a potential is 0 Fe applied between a soluble anode (made from Fe or Al) 0 2 4 6 8 and the cathode, ferrous/or aluminum ions are generated Time (Min.) at the anode and hydroxyl ions at the cathode. It is known that the hydrolysis products of Al3+ and Fe3+ are responsi- FIGURE 4 - Nitrite removal as a function of time (potential: 12 V, current intensity: 77.13 mA). ble for effects observed during particle aggregations, and polymerisations as depicted in the following formula will usually take place: the possible combination of various Nitrate removal as a function of electrolyse time is hydrolysis products is endless and one or more of them given in Fig. 5. When the Fe-electrode is used, it was may be responsible for the observed action of aluminum found that removal is increasing slowly with time, thus or iron [19]. requiring a longer electrolysis time. At the end of 7.5 min 2+ 4+ almost all nitrate (95%) was removed from the solutions. H2O OH O H O Me OH (H O) Me Me(H O) When Al electrode is used, nitrate removal increases up to 2 2 2 2 4 2 4 + 2 H2O O 6 min, and then reaches a plateau. H2O OH2

Then, nitrite, nitrate, phosphate and ammonium are Sheng et al. [8] stated that 8-10 min is deemed neces- removed by sorption onto the highly dispersed ferric-/or sary to achieve good colour and COD reduction in textile aluminum-hydroxide micro flocks. wastewater. As a consequence, in the present study a considerable colour reduction was observed in wastewater BOD and COD removal for Al and Fe electrodes are during a 5-min time span. This also indicates that grubs investigated at the same conditions. The BOD removal caused colour, and contamination is reduced considerably efficiency as a function of time is seen in Fig. 6. Initially, at the electrolysis cell (about 50%). Increasing amounts of BOD removal for Al and Fe electrodes are identical for BOD and COD removal supported these results. We as- the first 2 min. However, with increasing time the rate of sumed that the organic compounds in paper mill effluents removal obtained with Al is higher than that obtained do not turn into colourless organic molecules at the end of with Fe. Then, the percentage of removal for Al electrode electro-coagulation experiments, but they are removed appears to become constant after 5 min (70%), but the from the solution via adsorption, sedimentation and float- percentage of removal for the Fe-electrode continues to ation. increase with time. The Effect of Current Intensity 100 The phosphate, ammonium, nitrite, nitrate, COD and BOD removal rates in the paper mill effluent were ob- 80 served within a 5-min time period at different current intensities. Previously, the current intensity has been 60 shown to influence the treatment efficiency of the electrochemical process for different wastewaters [8]. The effect 40 of current intensity on the phosphate removal is given in Fig. 8. BOD removal % Electrode 20 Al 100 0 Fe 0 2 4 6 8 80

Time (Min.)

FIGURE 6 - BOD removal as a function of time 60 (potential: 12 V, current intensity: 77.13 mA). 40 Fig 7 shows COD removal as a function of time. COD Electrode removal by the Al-electrode appears to be much higher Phosphate removal (%) 20 than that of the Fe-electrode during the first 4 min. Alt- Al hough COD removal by Al electrode appears to reach a 0 Fe plateau after 2 min, it starts increasing again around 5 min 0 20 40 60 80 and continues to increase up to 7.5 min, where it reaches Current intensity (mA) about 70%. COD removal for the Fe electrode was constant after 5 min (50%). FIGURE 8 - Effect of current intensity on phosphate removal (time: 5 min). 80 As can be seen in Fig. 8, the phosphate removal for both types of electrodes increased with increasing current 60 intensity. When Fe electrode was used, the percentage of phosphate removal was much higher than that with the Al electrode. However, while the phosphate removal for the 40 Fe-electrode was constant at around 30 mA, that of the Al-electrode was constant between 30-50 mA. At values COD removal % 20 Electrode higher than 50 mA, phosphate removal increased with Al increasing current intensity (75%).

0 Fe The effect of current ammonium removal by both Al 0 2 4 6 8 and Fe electrodes was found to be approximately the Time (Min.) same. However, initially the ammonium removal for the

FIGURE 7 - COD removal as a function of time Al electrode is much higher than that of the Fe electrode (potential:12 V, current intensity: 77.13 mA). (Fig. 9).

70 80

50 60

30 40

20 Electrode Nitrate removal (%) Ammonium removal (%) 20 Electrode 10 Al Al 0 Fe 0 20 40 60 80 0 Fe 0 20 40 60 80 Current intensity (mA) Current intensity (mA) FIGURE 9 - Effect of current intensity on ammonium removal (time: 5 min). FIGURE 11 Effect of current intensity on nitrate removal (time: 5 min). The nitrite removal for both electrodes increased with current intensity for both electrodes (Fig. 10). It remained BOD and COD removals from the paper mill effluent nearly constant between current 30-55 mA. But then it as a function of current intensity were measured within a started to increase. The nitrite removal obtained with the 5-min time period. With sufficient power supply, the Fe electrode was higher than that with Al at current inten- organic compounds are reduced to smaller molecules at sities higher than about 25mA. the cathode. Some of these small organic molecules and the suspended solids are captured by Fe(OH)3 or Al(OH)3, 100 which is removed by sedimentation or by H2 flotation [4, 23]. In fact, during the present experiments small amounts 80 of sludge were scraped off from the top and the bottom of the electrolytic cell, evidencing both sedimentation and flotation action. 60 For both Al and Fe electrodes, BOD removal in- 40 creased with the current intensity (Fig. 12). While BOD removal reaches a plateau (40%) for Fe at about 40 mA, it Nitrite removal (%) Electrode continuous to increase for the Al electrode (70%). For all 20 Al current intensities, BOD removal by the Al electrode is much higher than that of the Fe electrode. 0 Fe

0 20 40 60 80 70 Current intensity (mA) 60 FIGURE 10 Effect of current intensity on nitrite removal (time: 5 min). 50

The percentage of nitrate removal as a function of 40 current intensity for both electrodes is shown in Fig. 11. With increasing current intensity, the nitrate removal in- 30 creased rapidly. It was also observed that the nitrate remov- BOD removal % 20 Electrode al at a current intensity of 75 mA for the Fe-electrode was much higher than that of the Al electrode. 10 Al 0 Fe In previous investigations the current intensity was 0 20 40 60 80 found to influence the treatment efficiency of the electrochemical process [1, 4, 8, 19]. In all these studies it was Current intensity (mA) shown that the inorganic compound removal efficiency FIGURE 12 from wastewater was increased significantly with the Effect of current intensity on BOD removal (time: 5 min). applied current intensity. These enhancement effects are attributed to the increase in the driving force of the elec- At low current intensities both electrodes show simi- trode reaction, in addition to the increase in current, with lar behavior for COD removal. The results are given in increasing voltage. This is because potential is the major Fig. 13. Approximately at 70mA, the same efficiency of driving force for the respective phenomena of interest in removal (50%) is obtained by both electrodes. It is also electrochemical reactors [21]. reported in a similar study that when organic pollutants in

effluents are treated with electrochemical methods, COD through a decrease in intra-resistance of the solution and and colour removal increase with increasing current in- an associated increase at the transfer sped up of organics tensity [23]. and in organic species to the electrodes.

60 Kinetic of removal The rate constant for removal of COD, BOD, ammo- 50 nium, phosphate, nitrite and nitrate from the paper mill effluents by electro-coagulation may be obtained by as- 40 suming a first-order reaction as follows:

30 [C]t In = −kt (4) 20 COD removal % C Electrode [ ]0

10 Al The slope of the plot of log Ct/C0 versus time gives -1 0 Fe the value of the rate constant k, min . Here, C0 is the 0 20 40 60 80 initial concentration in mg per litre, and Ct is the concentration value in mg per litre at time t. The above equation Current intensity (mA) may be of the type y = mx, and a line plot of ln Ct/Co FIGURE 13 versus t indicates the validity of the first-order reaction of Effect of current intensity on COD removal (time: 5 min). the electro-coagulation process (Table 2). Table 2 provides the rate constant (k), respective the r2 values, and In the experiments carried out at different current in- energy consumption for COD, BOD, ammonium, phos- tensities, the removal rates being high can be explained phate, nitrite and nitrate removal.

TABLE 2 – Summary of the kinetic and other properties of the paper mill effluents by the electrocoagulation methods (potential: 12.0 V and current intensity: 77.13mA).

Kinetics Energy consumption Final concentration Initial concentration Rate constant kWh/kg of kWh/m3 of Compounds (mg/L) r2 (mg/L) k’ (Min-1) compound compound Fe Al Fe Al Fe Al Fe Al Fe Al COD 426.12 198.04 206.31 0.085 0.118 0.99 0.81 0.6 0.5 0.136 0.105 BOD 25.53 15.31 6.38 0.119 0.159 0.80 0.91 11 5.1 0.113 0.091 Ammonium 9.88 1.97 1.78 0.146 0.109 0.99 0.96 15 14 0.119 0.113 Phosphate 0.17 0.01 0.05 0.297 0.043 0.97 0.94 723 964 0.116 0.115 Nitrite 0. 21 0.04 0.03 0.092 0.094 0.67 0.74 680 642 0.115 0.114 Nitrate 0.18 0.05 0.06 0.034 0.149 0.64 0.96 889 960 0.115 0.113

CONCLUSIONS In an era when phenomena of environment attract a great attention, the electrochemical methods can be said The efficiency of electrochemical methods for the re- to be a promising cleaning and purifying technology of moval of phosphate, ammonium, nitrate, BOD and COD wastewaters from the paper industry. removal are examined in this study. From the experiments carried out at 12 V and a current intensity of 77.13 mA it can be said that for both electrodes the removal of these pollutants, except for nitrate, can be sufficiently achieved REFERENCES within two min. However, it was also found that BOD and COD removal required a little bit more time. When the [1] Gürses, A., Yalçın, M. and Doğar, Ç. (2002) Electrocoagula- effects of current intensity on removal were examined, an tion of some reactive dyes: a statistical investigation of some electrochemical variables. Waste Management. 22, 491-499. increase of removal efficiency was generally observed with increasing current intensity, as it was expected. It was [2] Panizzo, M., Bocca, C. and Cerisola, G. (2000) Electrochem- found that 40-80 mA is sufficient on a large scale for the ical treatment of wastewater containing polyaromatic organic removal of the above-mentioned pollutants. pollutants. Wat. Res. 34(9):2601-2605.

[3] Do, J.S. and Chen, M.L. (1994) Decolourisations of dye- [19] Öğütveren, Ü.B. and Koparal, S. (1994) Colour removal from containing solutions by electrocoagulation. J.App. Electro- textile effluents by Electrochemical Destruction. J. Environ. chem. 24,785-790. Sci Health. A29 (1), 1-16.

[4] Lin, S.H., Shyu, C.T. and Sun, M.C. (1998) Saline [20] Johnson, P.N. and Amirtharajah, A. (1983) Ferric chloride wastewater treatment by electrochemical method. Wat.Res. and alum as single and dual coagulants. AWWA. 5,232-239 32,1059-1066 [21] Xiong, Y. and Karlsson, H.T. (2002) An experimental inves- [5] Vik, E.A., Carlson, D.A., Eikum A.S. and Gjessing, E.T. tigation of chemical oxygen demand removal from the (1984) Electrocoagulation of potable water. Wat. Res. wastewater containing oxalic acid using three-phase three- 18,1355-1360. dimensional electrode reactor”, Advances in Environmental Research. 7, 139-145. [6] Lin, S.H. and Peng, C.F. (1996) Continuous treatment of textile wastewater by combined coagulation, electrochemical [22] Vlyssides, A.G., Papaioannou, D., Loizidoy, M., Karlis, A.A. oxidation and activated sludge. Wat.Res. 30, 587-592. and Zarpas, A.A. (2000) Testing an electrochemical method for treatment of textile dye wastewater. Waste Management. [7] Pouet, M.F. and Grasmick, A. (1995) Urban wastewater 20, 569-574. treatment by electrocoagulation and flotation. Wat. Sci.Tech. 31,275-283. [23] Uğurlu, M. (2001) The treatment of paper industry wastewaters by adsorption and electrochemical methods. [8] Lin, S.H. and Peng, C.F. (1994) Treatment of textile Doctoral thesis. Atatürk University, K.K. Education faculty, wastewater by electrochemical method. Wat.Res. 28,277- Erzurum. Turkey. 282.

[9] Tsai, C.T., Lin, S.T., Shue, Y.C. and Su, P.L. (1997) Elec- trolysis of soluble organic matter in leachate from landfills. Wat.Res. 31, 3073-3081.

[10] Naumczyk,, L. and Szpgrkowiez, F. (1996) Electrochemical Treatment of Textile Wastewaters. Wat. Sci. Texh. 34(11),17-24.

[11] Koparal, A.S. and Öğütveren, Ü.B. (2002) Removal of nitrate from water by electro reduction and electrocoagulation. J. Haz. Mat. B 89, 83-94.

[12] Muna, Ali, T.R. (2001) Aquatic toxicity from pulp and paper mill effluents: a review. Advances in Environmental Re- search. 5, 175-196.

[13] Clark, T., Bruce, M. and Anderson, S. (1994) Decolourisa- tion of extraction stage bleach plant effluent by combined hypochlorite oxidation and anaerobic treatment. Water Sci. Tech. 29(5-6), 421-432.

[14] Frostell, B., Boman, B., Ek, M., Palvall, B., Berglund, M. and Linstrom, A. (1994) Influence of bleaching conditions and membrane filtration on pilot scale biological treatment of Kraft mill bleach effluent. Water Sci. Tech. 29(5-6), 163-176.

[15] Streat, M., Patrick, J.W. and Camporro-Perez, M.J. (1995) Sorption of phenol and chlorophenol from water using con- ventional and novel activated carbons. Water Sci. Res., 29: 467-472.

[16] Diez, M.C., Mora, M.L. and Videla, S. (1999) Adsorption of Received: September 27, 2004 phenolic compounds and colour from bleached Kraft mill ef- Accepted: October 21, 2004 fluent allophonic compounds. Water Res., 33(1): 125-130.

[17] APHA (1995) Standard Methods for the examination of water and wastewater. CORRESPONDING AUTHOR

[18] Pykhteev, O. Yu., Efimov, A.A. and Moskvin, L.N. (1999). Mehmet Uğurlu Hydrolysis of iron (III) aqua complexes, Russian Journal of Department of Chemistry Applied Chemistry. 72 (1), 9-20. Faculty of Science & Arts Muğla University 48000 Muğla -TURKEY

FEB/ Vol 14/ No 4/ 2005 – pages 315 – 321 e-mail:[email protected]

UV DISINFECTION: RADIATION AND WASTEWATER QUALITY PARAMETERS AS OPERATIONAL INDICATORS

Esteban Alonso1, Antonio Santos2 and Pascual Riesco3 prc 2.4.02 17:15 Gelöscht: of disinfection efficiency 1Department of Analytical Chemistry, Faculty of Chemistry, University of Seville, 41012, Seville, Spain 2Centre for the New Water Technologies (CENTA), Isla de la Cartuja, 41092, Seville, Spain 3Department of Fluid Mechanics, University of Seville, 41092, Seville, Spain.

SUMMARY resistant microorganisms, such as viruses, bacterial and fungal spores, and cysts of protozoa [4, 5]. Several parameters, such as total suspended solids, chemical oxygen demand, and parameters related to the plant operation (intensity of radiation of the lamps and Ultraviolet light acts like a microbiocide agent by alter- transmittance) have been used as operational indicators of ing the genetic material (DNA and RNA) and affecting its the disinfection efficiency of a secondary effluent from a reproductive capacity. The wavelengths achieving highest wastewater treatment plant using UV radiation at 253.7 nm. disinfection rates range from 250 to 270 nm, and that most The results obtained were statistically analysed to establish the correlations between the quality parameters of the commonly used is 253.7 nm [6-10]. When applying UV- disinfection, the quality of the water to be treated is an influent and the operational conditions of the lamps, un- important factor on account of the screening effect resulting der standard conditions of the influx water. A significant from suspended solids and other substances, such as float- (P<0.001) relationship was found between lamp radiation intensity and the radiation obtained by the microorganisms. ing oils and fats, coloured compounds or metals (Fe, Mn). Such substances have a modifying effect on the radiation intensity received by the microorganisms [11, 12]. The radiation emitted by the ultraviolet lamps is not KEYWORDS: Ultraviolet disinfection, wastewater, tertiary treatment, pilot plant, pathogenic organisms removal. fully transmitted to the microorganisms. Therefore, an estimation of the net radiation impinging on these is essential to calculate the inactivation rates achieved and to opti- mize the UV-treatment plants [13]. In the present study, a statistical analysis was carried out between the radiation INTRODUCTION intensity received by the microorganisms and important wastewater parameters (total suspended solids (TSS) and Human exposure to wastewater released to the envi- chemical oxygen demand (COD)). ronment, combined with the presence of certain types of health–hazardous microorganisms in the effluents, have resulted in a growing demand for tertiary treatments in- MATERIAL AND METHODS cluding disinfection. The mostly used common disinfection process is the The experiments were carried out over a two-months chlorination. However, the presence of ammoniacal nitro- period. A 315K-PTP Trojan pilot plant was used, consist- gen and organic substances derived from the chlorination ing of a rectangular-section stainless steel channel in which favours the formation of chloramines and trihalomethanes, twelve lamps, separated into two groups of six lamps in whose harmful effects for the reuse of the treated water series, were submerged. The installations were designed for 3 -1 are well-known [1-3]. Disinfection by UV radiation is a a maximum flow rate of 20 m h , with wastewater flowing clean and safe alternative without toxic effects achieving in from the effluent of a wastewater treatment plant target disinfection levels within a shorter treatment time, (WWTP: activated sludge) operating as a part of the inte- and a lower-cost one compared to chemical techniques, gral sanitation system of Seville, Spain (WWTP North I). such as ozonization. Disinfection with intensive UV ra- JonMMx 2000 12.3.02 11:25 diation is very effective in the inactivation of chlorine- Gelöscht: (other)

The whole experimental process was carried out in a of the plant are given in Table 1. Analytical determina- continuous operation mode. Samples were collected at tions were carried out for TSS, COD, and fecal and total both the water inlet and outlet. The operational conditions coliforms (membrane filter technique). Standard analytical TABLE 1 - Operational conditions of the plant. JonMMx 2000 12.3.02 12:28 Gelöscht: . Flow rate Dose Intensity Reaction time Transmittance (m3 h-1) (mW·s cm-2) (Mw cm-2) (s) (%) 9.5 78.7 – 311.7 2.09 - 6.03 18.0 77.3 – 80.2 2.8 235.2 – 738.5 2.5 – 8.3 122.83 45.4 – 79.9 8 108.4 – 311.4 3.76 – 7.27 42.84 65.7 – 84.9 15 49.8 – 166.1 2.85 – 7.27 22.85 55.3 - 85

methods were applied to all the wastewater analyses [14]. the two parameters under observation (100% elimination The intensity of the radiation received by the microorgan- of total and fecal coliforms). isms was estimated by means of a direct measurement of Figure 1 shows the values of emitted UV-intensity the absorbance of wastewater at 253.7 nm (wavelength of (mW cm-2) and the associated transmittance (%) for the radiation lamps). samples taken at the plant inlet, as well as two quality The radiation intensity received by the microorgan- parameters, TSS (mg l-1) and COD (mg l-1). As expected, isms was directly read from the experimental set-up. The high TSS values in the influent water are associated with resulting data were compared with an empirical curve low transmittance values (see samples 17, 25 and 29). The provided by the commercial firm for standard influent COD curve roughly follows the same pattern as the TSS water (SPSS Trojan method, 1997; see Fig. 2). curve, thus showing that most oxygen-demanding substances are present in suspended form. This is a typical Correlation analyses were carried out by means of the feature of urban wastewater, where most of the pollution Statsoft Statistics for Windows software. is organic. Some exceptions (samples 12 and 13) point to

the presence of soluble oxygen-demanding compounds.

RESULTS AND DISCUSSION A statistical analysis provides further confirmation of such trends. A multivariate statistical analysis consisting During the two-months experimental period, a se- of correlation analysis between variables [15] was carried quence of influent samples, numbered from 1 to 62, were out. As a result, a correlation matrix with the parameters subjected to UV-radiation. The intensity emitted ranged concerned was developed and the matrix indices illustrate from 2.09 to 7.27 mW cm-2. In all samples, a complete the association between the parameters under study (Ta- elimination of the microbial flora was reported in terms of ble 2).

300

250

200

150

100

0 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45 47 49 51 53 55 57 59 61

Sample number

Intensity (mW cm-2) Transmittance (%) COD (mg l-1) TSS (mg l-1)

FIGURE 1- Values of emitted UV-intensity (mW/cm2), associated transmittance (%) and influent quality parameters, total suspended solids (TSS, mg/L) and chemical oxygen demand (COD, mg/L), for the complete sample collection. TABLE 2 - Correlation matrix of the parameters intensity of radiation, transmittance, total suspended solids, and chemical oxygen demand.

Variables Intensity of radiation Transmittance T.S.S. C.O.D. Intensity of radiation 1.00 0.90 -0.72 -0.68 Transmittance 1.00 -0.82 -0.78 T.S.S. 1.00 0.72 C.O.D. 1.00

9 20

8 18 Intensityradiation UV of (mW.cm-2);

7 16 14 6

12 TROJAN 5 10 4 8

3 6 2 4 · cm-2)of UV (mW radiation Intensity 1 2

0 0 40 45 50 55 60 65 70 75 80 85 90 Transmittance (%)

FIGURE 2 - Emitted UV-radiation vs. transmittance: direct readings (dots) compared with reference curve proposed by TROJAN (dashed line) for a standard wastewater influent.

A relationship between the emitted radiation intensity the WWTP to which the experimental set-up was con- and transmission is to be expected because the average nected. influents do not show substantial departures from the standard empirical curve provided by the manufacturer. In Correlations between transmission and TSS are also any case, the optimal correlation indices obtained confirm significant, but reflect an opposite trend. This is only to be the suitability of the approach followed. Figure 2 shows expected, since the presence of suspended solids in the empirical curve (corresponding to an average-quality wastewater screens and scatters UV penetration through influent) as a dashed line, together with a dotted cloud for the liquid. As a result, the microorganisms do not receive direct measurements. A consistent pattern is observed, the full intensity of the radiation initially applied. although lower transmission is attained in our experiment (as compared to the ideal Trojan reference) for the same The fact that similar correlations are also reported for emitted radiation. This fact may be explained as a conse- COD values is due to the predominance of organic waste quence of the systematically high TSS effluent values of in the solids. Figures 3 and 4 show a graphical representa- tion of the relationships between the transmission and the

values of TSS and COD. The correlation is relatively tions given as an approximation of the link between these small, thus suggesting that TSS is not the only factor parameters can be used to monitor the quality evolution of influencing transmission. It can certainly be expected that the influent through a direct lamp reading, and thus, to the aggregation mode (size and shape) of the suspended furnish a simple control means for the operation of the substances is also determinant. However, the linear equa- process.

40 TSS (mg l-1) TSS (mg

38 43 48 53 58 63 68 73 78 83 88 y = -1,1185x + 98,688 Transmittance (%) R2 = 0,6783

FIGURE 3 - Transmittance of UV radiation vs. total suspended solids.

180

160

140

120

100

COD (mgCOD l-1) 60 40

0 38 43 48 53 58 63 68 73 78 83 88 y = -2,4411x + 239,02 Transmittance (%) R2 = 0,6015

FIGURE 4 - Transmittance of UV radiation vs. COD.

CONCLUSIONS modelling of medium pressure UV systems. Water Research 34(16): 4007-4013. The estimation of UV-radiation intensity received by [11] Whitby, G.E., Palmateer, (1993). G. The effect of UV trans- the microorganisms in the disinfection of wastewater is an mission, suspended solids and photoreactivation on microor- essential parameter to reach the desired inactivation rate. ganisms in wastewater treated with UV-light. Water Science UV-transmission is inversely correlated with TSS content, and Technology 27: 379-386. and, in most urban wastewaters, an indirect correlation is also reported for COD. Individual wastewater quality, [12] Tchobanoglous, G., Loge, F., Darby, J., Devries, M. (1996). however, gives rise to unexpected disinfection outputs. UV design: comparison of probabilistic and deterministic design approaches. Water Science and Technology 33(10-11): 251-260. The influence of characteristic indicators of water quality on disinfection performance should deserve further [13] Linden, K.G. and Darby, J.L. (1998). Ultraviolet disinfection prc 2.4.02 17:25 investigation. However, provided that the wastewater to of marginal effluents: determining ultraviolet absorbance and Gelöscht: the most be treated remains within standard quality bounds, a sim- subsequent estimation of ultraviolet intensity. Water Envi- ronmental Research 70(2): 214-223. ple correlation can be applied to infer water quality from UV-readings and inversely. This correlation may prove to [14] APHA (1994). Standard Methods for the examination of wa- be a helpful control means for the monitoring of disinfec- ter and wastewater. 19th edn. Amer. Publ. Health Assoc., tion efficiency. Amer. Water Works Assoc., Water Poll. Control Fed. Wash- ington D.C.

[15] Hopke, P.K. (1983). An introduction to multivariate analysis of environmental data in Analytical Aspects of Environmen- REFERENCES tal Chemistry, Natusch, D.F.S. and Hopke, P.K. 219-262, J. Wiley & Sons, Inc., New York. [1] E.P.A. (U.S. Environmental Protection Agency) (1999). Wastewater Technology Fact Sheet: Chlorine disinfection. EPA/832/F99/062.

[2] Monarca, S., Feretti, D., Collivignarelli, C., Guzzella, L., Zerbini, I., Bertanza, G., Pedrazzani, R. (2000) The influence of different disinfectants on mutagenicity and toxicity of urban wastewater. Water Research: 34(17), 4261-4269.

[3] Collivignarelli, C., Bertanza, G., Pedrazzani, R. (2000) A comparison among different wastewater disinfection systems: experimental results. Environmental Technology 21(1): 1-16.

[4] E.P.A. (U.S. Environmental Protection Agency) (1999). Wastewater Technology Fact Sheet: Ultraviolet disinfection. EPA/832/F99/064.

[5] Ho, Chu-Fei, H., Pitt, P., Chiu, C., Jolis, D. (1998). Evalua- tion of UV disinfection systems for large-scale secondary effluent. Water Environmental Research 70(6): 1142-1150.

[6] Darby, J.L., Snider, K.E., Tchobanoglous, G. (1993). Ultra- violet disinfection for wastewater reclamation and reuse subject to restrictive standards. Water Environment Research 65: 169-180.

[7] Failly, J. (1994). Disinfection of wastewater by ultraviolet radiation. L´eau, l´industrie, les nuisances 176: 58-60.

[8] Baron, J.; Corre, S.; Denis, P.; Dufaut, J.C.; Patris, T.; Prin- gent, J.P. (1994). The UV disinfection of treatment plant effluents. A survey in Brest area. Techniques Sciences Méthodes, Génie Urbain Génie Rural 5: 263-267.

[9] Gschlossl, T. (1995). UV-Disinfection of treated wastewater. Possible effects on surface waters. Water Science and Tech- nology 29: 255-266.

[10] Giese, N. and Darby, J. (2000). Sensitivity of microorgan- Received: November 03, 2004 isms to different wavelengths of UV light: implications on Accepted: January 24, 2005

41011 Seville - SPAIN

CORRESPONDING AUTHOR Phone: +34-954-55-2858 Fax: +34-954-55-7168 Esteban Alonso e-mail: [email protected] Department of Analytical Chemistry Faculty of Chemistry FEB/ Vol 14/ No 4/ 2005 – pages 322 – 326 University of Seville C/ Virgen de África, 7 SPECIES COMPOSITION OF THE TINTINNIDS FOUND IN THE NE- RITIC WATER OF BOZCAADA ISLAND, AEGEAN SEA, TURKEY

Neslihan Balkıs1 and Anna Wasik2

1Istanbul University, Faculty of Science, Department of Biology, 34118 Vezneciler/Istanbul, Turkey. 2Department of Cell Biology, Nencki Institute of Experimental Biology, 3 Pasteur str., 02-093 Warszawa, Poland

SUMMARY ecosystem’s primary production [3], due to their high metabolic and reproduction rate [4, 5]. This study on the species composition of tintinnids Ciliates belonging to the suborder Tintinnina are to be was carried out from 2000 to 2001 in surface water of the found in different environments and climatic zones, and, Aegean Sea near Bozcaada Island, Turkey. The samples according to Pierce and Turner categories [6], all genera were collected with horizontal tows from the subsurface might be divided into 6 groups on the basis of their bio- (0.5 m) with a 55 µm plankton net at four stations. A total of geographic distribution. Irrespective, however, of their 36 tintinnid species were identified according to their lorica location 90% of tintinnids are found in the upper part of shape as the usual important criterion, and four of which the water column [1]. [Codonella galea Haeckel, Eutintinnus tubulosus (Osten- feld) Kofoid and Campbell, Parundella aculeata (Jörgen- sen) Kofoid and Campbell, and Protorhabdonella curta The protoplast of these free swimming ciliates is pro- (Cleve) Jörgensen] were new for Turkish coastal waters. tected by the lorica. Its shape and size was previously Two genera, Favella and Eutintinnus, dominated in terms of treated as the only criterion for tintinnids classification. species number. Eutintinnus lusus-undae and Rhabdonella Although the lorica is till now used for systematic status spiralis were the most common species found during the determination of genera and species, it should not be for- sampling periods. Primary hydrographic conditions, such as gotten that tintinnids loricae present a high level of poly- salinity (32.2-37.8 practical salinity units), temperature morphism [7, 8], and protoplast morphology and ultrastruc- (13.7-23 °C) and dissolved oxygen (7.47-9.67 mg L-1) were ture, as well as oral ciliature organization, should be taken recorded on each sampling occasion. into account as a final criterion [i.e., 9, 10].

Ciliates in Turkish coastal waters of the Aegean Sea KEY WORDS: were previously reported by Koray and Özel [11] and Tintinnids, new records, Bozcaada Island. Koray et al. [12]. The species composition found near Bozcaada Island is generally in agreement with those for

Turkish seas, however, four species were not mentioned INTRODUCTION in the first catalogue. The aim of this study was to report about the biodiversity of tintinnids` community and new The suborder Tintinnina comprises ciliates, one of the record species in the waters near Bozcaada Island, an area most abundant group among protozooplankton. They are never examined before with respect to tintinnids presence. an important component of marine food web being a When comparing the results from both areas, Codonella linking element between producers and higher level con- galea Haeckel, Eutintinnus tubulosus (Ostenfeld) Kofoid sumers [1, 2]. It ought to be underlined that they have a and Campbell, Parundella aculeata (Jörgensen) Kofoid high grazing capacity and can consume up to 60% of an and Campbell, and Protorhabdonella curta (Cleve) Jörgen- sen were found in Turkish coastal waters for the first time.

FIGURE 1 - Research stations in Bozcaada Island. under an inverted phase contrast microscope equipped with MATERIAL AND METHODS a microphotosystem (magnification 400X). All tintinnid species were identified according to their lorica shape as 2 Bozcaada Island (42 km area) is located between lon- the usual important criterion. gitudes 25°57ʹ48ʺE-26°05ʹ00ʺE and latitudes 39°47ʹ18ʺN- 39°50ʹ54ʺ in the Northeast Aegean Sea. The northern Measurements of salinity (psu), temperature (°C) and -1 surface waters in the Aegean Sea are under effects of the dissolved oxygen (mg L ) were performed at each sam- Black Sea waters, characterized as brackish. The salinity pling point. The Mohr-Knudsen method [14] was used for of these waters is 26-35 practical salinity units (psu), and measuring the salinity values, and the Winkler method the deep water mass of the Aegean Sea extends from a [15] for dissolved oxygen (DO). Spearman rank order depth of approximately 300 m down to the bottom with a correlation was used to correlate the species number of 38.8 psu value [13]. Samples for species identification tintinnids and hydrographical parameters. The Sorensen were collected within seven months between May 2000 similarity matrix [16] was calculated in order to group the and December 2001 from waters surrounding this island, sampling stations and months according to the species using horizontal tows from the subsurface (0.5 m) with a involved. 55 µm plankton net at four stations (Fig. 1). Material was fixed with neutral 4% formaldehyde solution and observed RESULTS

Hydrobiological data During the course of this study, water temperature went through a seasonal cycle characterized by a minimum of 13.7 °C (February) and a maximum of 23.0 °C (August) (Fig. 2). Salinity values ranged from 32.2 psu (August) to 37.8 psu (December). And that of dissolved oxygen varied between 7.47 mg L-1 (February) and 9.67 mg L-1 (Novem- ber). According to Spearman rank order correlation, salinity is negatively correlated to temperature (rs = -0.76, p< 0.05) and to dissolved oxygen (rs = -0.42, p<0.05). Any correlation could not be determined between the species number of tintinnids and the hydrographical parameters.

16 40 14 35 12 30 10 25 8 20 6 15 4 10 Hydrographical parameters

Speciesnumber of tintinnids 2 5 0 0 2 3 4 2 3 4 2 3 4 2 3 4 2 3 4 2 3 4 2 3 4 Feb.1 Sep.1 May.1 Aug.1 Nov.1 June1 Dec.1 Months and Stations

Tintinnids Dissolved oxygen Temperature Salinity

FIGURE 2 - Variations of species number of tintinnids according to sampling months, temperature (°C), salinity (psu) and dissolved oxygen (mg L-1) in surface water (0.5 m). TABLE 1 Tintinnid species found in the neritic waters of Bozcaada Island (*new records).

Species May 2000 Aug. 2000 Nov. 2000 Feb. 2001 June 2001 Sep. 2001 Dec. 2001 st.1 st.2 st.3 st.4 st.1 st.2 st.3 st.4 st.1 st.2 st.3 st.4 st.1 st.2 st.3 st.4 st.1 st.2 st.3 st.4 st.1 st.2 st.3 st.4 st.1 st.2 st.3 st.4 Tintinnids Amphorides amphora (Clap.and Lach.) Strand + + + + + + + + + + Amphorides quadrilineata (Clap. and Lach.) Strand + + + + Codonella amphorella Biedermann + Codonella aspera Kofoid and Campbell + + + + + + * Codonella galea Haeckel + + Codonellopsis orthoceras (Haeckel) Jörgensen + + + + + + Codonellopsis schabi (Brandt) Kofoid and Camp- + + bell Dadayiella ganymedes (Entz) Kofoid and Campbell + + Dictyocysta mitra Haeckel + + + + Epiplocylis undella (Ostenfeld and Schmidt) + + + + + Jörgensen Eutintinnus apertus Kofoid and Campbell + + + + + + + + + + + + Eutintinnus fraknoi (Daday) Kofoid and Campbell + + + + + + + + + Eutintinnus lusus-undae (Entz) Kofoid and Camp- + + + + + + + + + + + + + + + + + + + + bell Eutintinnus macilentus (Jörg.) Kofoid and Camp- + bell * Eutintinnus tubulosus (Ost.) Kofoid and Campbell + Favella azorica (Cleve) Jörgensen + + + + + + + + Favella campanula (Schmidt) Kofoid and Campbell + +

Favella ehrenbergi (Clap. and + + + + Lach.) Jörgensen Favella serrata (Möbius) + + + + + + + + Jörgensen Favella markusovszkyi (Daday) + Jörgensen Helicostomella subulata + + (Ehrenberg) Jörgensen * Parundella aculeata (Jörg.) + Kofoid and Campbell

Parundella lohmanni (Jörg.) + + + Kofoid and Campbell Parundella longa Jörgensen + Proplectella claparedei (Entz) + + + + + Kofoid and Campbell *Protorhabdonella curta + (Cleve) Jörgensen Protorhabdonella simplex + + + + (Cleve) Jörgensen Rhabdonella spiralis (Fol) + + + + + + + + + + + + + + + + + + + Brandt Salpingella acuminata (Clap. + + + + + and Lach.) Jörgensen Salpingella decurtata Jörgen- + + + + sen Steenstrupiella steenstrupii (Clap. and Lach.) Kof. and + + + + + + + + + + + + Camp. Tintinnopsis cylindrica Daday + + Tintinnopsis radix (Imhof) + + + + + Brandt Undella hyalina Daday + + + + + + + + + + + + + + Xystonella lohmanni (Brandt) + + + Brandt Xystonella treforti (Daday) + + + + Laackmann

Tintinnid composition Undella hyalina (f = 85.71%), Amphorides amphora and A total of 36 tintinnid species belonging to 18 genera Eutintinnus apertus (f = 71.43%). Codonella amphorella, were identified (Table 1). Four of them [Codonella galea Eutintinnus macilentus, E. tubulosus, Favella Haeckel, Eutintinnus tubulosus (Ostenfeld) Kofoid and markusovszkyi, Helicostomella subulata, Parundella Campbell, Parundella aculeata (Jörgensen) Kofoid and aculeata, P. longa and Protorhabdonella curta were ob- Campbell and Protorhabdonella curta (Cleve) Jörgensen] served to be the rare species (f = 14.29%). In addition, (Figs. 3 a-d) were recorded in the Turkish coastal waters according to the stations, the most common species were for the first time. E. lusus-undae (f = 71.43%), R. spiralis (f = 67.86%), U. hyalina (f = 50%), E. apertus, S. steenstrupii (f = Regarding the species number, the genera Eutintinnus 42.86%), A. amphora (f = 35.71%) and E. fraknoi (f = and Favella, with five species, are the most significant, 32.14%). followed by Codonella and Parundella (three species). The most frequent species found throughout the whole The highest species numbers were recorded in Novem- sampling period were Eutintinnus lusus-undae, ber (24 species) and February (18 species), whereas August Rhabdonella spiralis (f = 100%), Steenstrupiella steen- was the month with the fewest species (11 species). strupii,

FIGURE 3 - a) Codonella galea, b) Eutintinnus tubulosus, c) Parundella aculeata, d) Protorhabdonella curta (scale bar: 20 µm).

30 dix, Undella hyalina and Xystonella treforti, was noticed in both months. The second group was composed of two 40 subgroups, and the first one included September, Decem- ber and June. Within this subgroup, September and De- cember linked together with a similarity of 59%. Eight 50 tintinnid species, Dictyocysta mitra, Epiplocylis undella,

% Eutintinnus apertus, E. lusus-undae, Protorhabdonella 60 simplex, Rhabdonella spiralis, Steenstrupiella steenstrupii

Similarity and Undella hyalina, were then observed. June joined this

70 subgroup with a relatively less similarity and the second subgroup included May and August with 60% similarity. Amphorides amphora, Eutintinnus fraknoi, Favella serra- 80 ta, Rhabdonella spiralis and Salpingella decurtata were present at that time. 90 The highest similarity among the stations appeared to be between stations 3 and 4 (78%) (Fig. 4b) with 20 asso-

Dec. ciated species noticed at both. The lowest similarity June Sep. 100 Feb. Nov. May Aug. among the stations was found between stations 1 and 2 (a) (57%) with only 12 associated species.

DISCUSSION

Ciliates are of great importance in protozoan popula- 60 tions of marine ecosystems. Their biogeograpic distribution, place in the food web, as well as the interrelations between them and other groups of organisms were examined by many authors [i.e. 17-19]. In the Turkish seas, 90 ciliate species upto now were identified [20]. Free living and lori- 70 cated tintinnids are known to be an important component of the planktonic ciliated community. Öztürk [21] reported on 17, whereas Türkoğlu and Koray [22] on 18 tintinnid species in the Turkish territorial waters of the Black Sea.

Similarity% Balkıs [23] determined 14 species in the Sea of Marmara, 80 and Koray and Özel [11] and Koray et al. [12] observed 43 and 25 tintinnid species from İzmir and Gökova Bay of the Aegean Sea, respectively. Pitta and Ginnakourou [24] reported about 82 ciliate species and mentioned that spe- 90 cies richness was higher in the South Aegean (70 species) than in the North (50 species), and tintinnids represented 18% of the total species number in the North Aegean Sea. So far, a total of 174 tintinnid species has been identified from the Mediterranean Sea [25]. Pitta et al. [26] 100 determined 55 species along the west-east transect in this 3 4 1 2 (b) sea. Balech [27] detected 60 , Travers and Travers [28] 82, while Gόmez and Gorsky [29] only 19 species from FIGURE 4 - Dendrograms constructed from Sorensen similarity the Western Mediterranean Sea. In addition, El-Maghraby matrix between a) sampling months and b) sampling stations. and Halim [30] found 17 species, Kimor and Wood [31] 10 species, and Polat et al. [32] 48 species from the East- Cluster analysis (Figs. 4 a and b), made to combine ern Mediterranean Sea. the months and stations according to the species they involve, showed two distinct groups (Fig. 4a). The first It was interesting to examine tintinnids` appearance group included November and February with 62% simi- in waters near Bozcaada Island, a region never studied larity. The presence of 13 tintinnid species, Amphorides before from that viewpoint. According to Pierce and amphora, Codonella aspera, C. galea, Codonellopsis or- Turner [6], 19 genera were found in this region belonging thoceras, Eutintinnus lusus-undae, Parundella lohmanni, to the cosmopolitan, neritic and warm-water ones. Codo- Proplectella claparedei, Rhabdonella spiralis, Salpingella nella galea, Eutintinnus tubulosus, Parundella aculeata acuminata, Steenstrupiella steenstrupii, Tintinnopsis ra- and Protorhabdonella curta are known as cosmopolitan

and were found for the first time in Turkish coastal wa- [4] Verity, P. G. (1985) Grazing, respiration, excretion and ters. growth rates of tintinnids. Limnol. Oceanogr. 30: 1268-1282. The North Aegean Sea is considered to be more pro- [5] Verity, P. G. (1986) Grazing of phototrophic nanoplankton ductive than the South Aegean Sea, with higher nutrient by microzooplankton in Narragansett Bay. Mar. Ecol. Prog. Ser. 29: 105-115. input, influenced by the colder and less saline Black Sea waters passing through the Dardanelles straits and receiv- [6] Pierce, R. W. and Turner, J. T. (1993) Global biogeography ing the outflow of several rivers discharging along the of marine tintinnids. Mar. Ecol. Prog. Ser. 94: 11-26. northern coast [24, 33]. In the area examined, a negative correlation between salinity and temperature was deter- [7] Laval-Peuto, M. and Brownlee, D. C. (1986) Identification and systematics of the Tintinnina (Ciliophora): evaluation mined. However, it is known that salinity usually increas- and suggestions for improvement. Ann. Inst. Oceanogr. 62: es with temperature, but in hot August (mean temp. 22.6 69-84. °C) salinity was very low (mean 33.0 psu) due to the large amounts of brackish water input from the Black Sea. Such [8] Wasik, A. and Mikołajczyk, E. (1994a) Annual cycle of tin- effects are observed in higher degrees during the late tinnids in the Admiralty Bay with an emphasis on seasonal variability in Cymatocylis affinis/convallaria lorica morphol- spring and summer, when compared to the winter values ogy. J. Plankton Res. 16: 1-8. [33, 34]. The influence of the Black Sea waters in Aegean Sea is especially noticed in August [13, 35]. In February, [9] Wasik, A. and Mikołajczyk, E. (1992) The morphology and June, November and December, the values of salinity ultrastructure of the Antarctic Ciliate, Cymatocylis convallar- ranged between 36.0 and 37.5 psu (Fig. 2). This may be ia (Tintinnina). Acta Protozool. 31: 233-239. the effect of vertical mixing of saline waters originating [10] Wasik, A. and Mikołajczyk, E. (1994b) Infraciliature of Cy- from the Mediterranean. matocylis affinis/convallaria (Tintinnina). Acta Protozool. 33: 79-85. This is the first report concerning tintinnids` community composition in Bozcaada Island. Thirty-six different [11] Koray, T. and Özel İ. (1983). İzmir Körfezi planktonunda species could be identified, and 4 of them, previously saptanan Tintinnoinea türleri. I. Ulusal deniz ve tatlısu reported in the Mediterranean basin, were determined to araştırmaları kongresi tebliğleri. 15-17 Ekim 1981, İzmir. be new for Turkish coastal waters. Thus, our research E.U. Faculty of Sci., Ser. B (I): 220-244. contributed not only to the recognition of biological di- [12] Koray, T., Benli, H. A. and Sever, T. M. (1994) Gökova Körfe- versity of the Turkish seas, but also allowed to find spe- zi (Ege Denizi)’nin fitoplankton ve protozooplankton türleri cies new for this almost untouched region. If the sampling üzerine bir araştırma. E. U. Su Urünleri Der. 42-43-44: 9-16. had been carried out using a smaller mesh size, more tintinnid species might have been detected. By determin- [13] Yüce, H. (1995) Northern Aegean water masses. Estuarine, Coastal and Shelf Science 41: 325-343. ing the distribution of the species according to seasons, the study has further attempted to find out the relationship [14] Ivanoff, A. (1972) Introduction al’océanographie. Tome I. between other organisms, and ecological factors will be Librairie Vuibert, Paris, 208 pp. explored in future studies. [15] Winkler, L. W. (1888) The determination of dissolved oxygen in water. Berlin. Deut. Chem. Ges. 21: 2843-2855. [16] Sorensen, T. (1948) A method of establishing groups of equal ACKNOWLEDGEMENTS amplitude in plant sociology based on similar species content and its application to analyses of vegetation on Danish com- This work was supported by the Research Fund of Is- mons. Biologiske Skrifte 5: 1-34. tanbul University, project numbers 1595/30042001 and [17] Garrison, D. L. (1991) An overview of the abundance and BYP-234/15072003. role of protozooplankton in Antarctic waters. J. Mar. Syst. 2: 317-331.

[18] Finlay, B. J. (1998) The global diversity of protozoa and other small species. Int. J. Parasitol. 28: 29-48. REFERENCES [19] Sherr, E. B. and Sherr, B. F. (2002) Significance of predation [1] Middlebrook, K., Emerson, C. W. , Roff, J. C. and Lynn, D. H. by protests in aquatic microbial food webs. Antonie van (1987) Distribution and abundance of tintinnids in the Quoddy Leuwenhoek 81: 293-308. Region of the Bay of Fundy. Can. J. Zool. 65: 594-601. [20] Koray, T., Gökpınar, Ş., Yurga, L., Türkoğlu, M. and Polat, S. [2] Pierce, R. W. and Turner, J. T. (1992) Ecology of planktonic (7th Apr. 1999) Microplankton species of Turkish seas. ciliates in marine food webs. Rev. aquat. Sci. 6: 139-181. (2003). [3] Sherr, E. B., Sherr, B. F. and Paffenhofer, G. A. (1986) Phagotrophic protozoa as food for metazoans: a “missing” [21] Öztürk, B. (1999) Black Sea biological diversity, Turkey. trophic link in marine pelagic food webs? Mar. Microb. Food Black Sea environmental series, 9, United Nations Publica- Webs 1: 61-80. tions, New York, 144 pp.

[22] Türkoğlu, M. and Koray, T. (2000) Ecological and geograph- ical distributions of the planktonic protista in the southern parts of the Black Sea (neritic waters of Sinop Peninsula, Tü- rkiye). E.Ü. Su Ürünleri Dergisi 17: 161-178.

[23] Balkıs, N. (2004) Tintinnids (Protozoa: Ciliophora) of the Büyükçekmece Bay in the Sea of Marmara. Sci. Mar. 68: 33-44.

[24] Pitta, P. and Giannakourou, A. (2000) Planktonic ciliates in the oligotrophic Eastern Mediterranean: vertical, spatial distribution and mixotrophy. Mar. Ecol. Prog. Ser. 194: 269-282.

[25] Trégouboff, G. and Rose, M. (1957) Manuel de planctonolo- gie Méditerranéenne, I, II. Centre National de la Recherche Scientifique, Paris, 587 pp.

[26] Pitta, P., Giannakourou, A. and Christaki U. (2001) Plankton- ic ciliates in the oligotrophic Mediterranean Sea: longitudinal trends of standing stocks, distributions and analysis of food vacuole contents. Aquat. Microb. Ecol. 24: 297-311.

[27] Balech, E. (1959) Tintinnoinea del Mediterraneo. Trabajos del intitudo Espanol de oceanografia, 28, Madrid.

[28] Travers, A. and Travers, M. (1975) Catalogue du microplankton du golfe de Marseille. Int. Rev. Ges. Hydrobiol. 60: 251- 276.

[29] Gόmez, F. and Gorsky G. (2003) Annual microplankton cycles in Villefranche Bay, Ligurian Sea, NW Mediterranean. J. Plankton Res. 25: 323-339.

[30] El-Maghraby, A. M. and Halim, Y. (1965) A quantitative and qualitative study of the plankton of Alexandria waters. Hy- drobiologia 2: 221-238.

[31] Kimor, B. and Wood, E. J. F. (1975) A plankton study in the Eastern Mediterranean Sea. Mar. Biol. 29: 321-333.

[32] Polat, S., Toklu, B. and Piner, M. P. (2001) Babadıllimanı Koyu (Silifke-İçel) tintinnid (Ciliata) türleri. XI. Ulusal Su Ürünleri Sempozyumu, 04-06 Eylül, 2001, Hatay: 504-512. [33] Poulos, S. E., Drakopoulos, P. G. and Collins, M. B. (1997) Seasonal variability in sea surface oceanographic conditions in the Aegean Sea (Eastern Mediterranean): an overview. J. Mar. Syst. 13: 225-244.

[34] Özsoy, E., Oğuz, T., Latif, M. A. and Ünlüata, Ü. (1986) Oceanography of Turkish Straits. First Annual Report, Vol. I: Physical Oceanography of the Turkish Straits. METU Insti- Received: November 18, 2004 tute of Marine Science, Erdemli, 223 pp. Accepted: January 24, 2005

[35] Yüce, H. (1987) Ege Denizi yüzey suyu sıcaklık, tuzluluk, çözünmüş oksijen değişim özellikleri. Bülten 3: 105-115. CORRESPONDING AUTHORS

Neslihan Balkıs

Istanbul University

Faculty of Science

Department of Biology

34118 Vezneciler/Istanbul - TURKEY

e-mail: [email protected]

FEB/ Vol 14/ No 4/ 2005 – pages 327 - 333

SECOTOX WORLD CONGRESS AND RECETOX Prof. Dr. John Giesy CONFERENCE “ECOTOX 2005 – Advances and Prof. Dr. Colin Janssen Trends in Ecotoxicology” PFOS Workshop 4th WORKSHOP “Environmental chemistry and ecotoxicology of perfluorinated substances” Prof. Dr. John Giesy Dr. Pim de Voogt September 5 - 8, 2005, Brno, Czech Republic

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Keynote Speakers SCIENTIFIC ORGANISING COMMITTEE

ECOTOX 2005 ECOTOX 2005 Dr. Christian Blaise • Ivan Holoubek, RECETOX - TOCOEN & Associ- Prof. Dr. Peter Callow ates, Czech Republic (Chair)

• Colin Janssen, University of Ghent, Belgium (Chair) • Karel Bláha, Ministry of Environment, Czech Re- public • Christian Blaise, Centre Saint-Laurent, Montreal, Canada • Kevin C. Jones, Lancaster University, UK • Antonius Kettrup, Technical University, München, Germany • Harun Parlar, Technical University, München, Ger- many • Paul Vasseur, University Metz, France • Karl-Werner Schramm, IOC GSF Neuherberg, Ger- many

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SUBJECT INDEX

A N adsorption 296 new records 327 air pollution 259 nitrate 315 algae 291 nitrite 315 ammonium 315 Nitzschia hantzschiana 291

B O benzene 259 oak valonia 296 biological assessment 268 Bosnia and Herzegovina 282 P bottom ash 307 paper mill effluent 315 Bozcaada Island 327 pathogenic organisms removal 322 PCBs 282 C phenols 282 cadmium 296 phosphate 315 cancer risk 259 pilot plant 322 carbonic anhydrase 256 public attitudes 273 copper 296 Croatia 282 Q quenching 291 E questionnaires 273

electrocoagulation 315 R

F rats 256

facilities 273 S Fe(III) 291 Sanliurfa Tunnels 300 fixed bed 296 sediment 268 Fluorescence spectroscopy 291 Slovenia 282 fly ash 263 soil remediation 263 fly ash 307 steel industry 259 freshwater lakes 273 stream sediments 282 strontium 296 G synchronous-scan 291 GAP project 300 glucose6-phosphate dehydrogenase 256 T tertiary treatment 322 H Tintinnids 327 heavy metals 307 total oils 282 horse chestnut 296 trace metals 263 trichloroacetic acid 256 I U incinerator residues 307 ultraviolet disinfection 322

K V Kupa River drainage basin 282 Volta Redonda 259

L W leaching tests 307 wastewater 322 lindane 282 water quality 300 water quality assessment 268 M macro-invertebrates 268 Z management 273 zeolite X 263 mineral oils 282 zinc 296

AUTHOR INDEX

A T Alonso, Esteban 322 Tao, Shu 291 Aquino Neto, Francisco R. 259 Tateo, Fabio 263 Aslan, Mustafa 268 Terzano, Roberto 263

B U Bakoglu, Mithat 307 Uğurlu, Mehmet 315 Balkıs, Neslihan 327 Uyanik, Sinan 268 Bilinski, Halka 282 Uyanik, Sinan 300

C W Cavalcanti, Paulina M.S. 259 Wasik, Anna 327 Celik, Ismail 256 Wu, Feng 291

D Y Demir, Halit 256 Yesilnacar, M. Irfan 268 Demir, Ozlem 268 Yesilnacar, M. Irfan 300 Deng, Nansheng 291 Yilmaz, Guzel 268 Durmusoglu, Ertan 307

F author-index

Fang, Tao 291 Frančišković-Bilinski, Stanislav 282

G Gioda, Adriana 259 Gonçalves, Fernando 273

K Karademir, Aykan 307

L Liu, Jiantong 291 Liu, Xianli 291

M Maia, Luiz F.P.G. 259 Maia, Marilza F. 259 Medici, Luca 263 Murathan, Atilla 296

P Pereira, Ruth 273

R Ribeiro, Rui 273 Riesco, Pascual 322 Ruggiero, Pacifico 263

S Sales, José A. 259 Santos, Antonio 322 Širac, Siniša 282 Soares, Amadeu M.V.M. 273 Spagnuolo, Matteo 263

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