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STUDIA UNIVERSITATIS BABEŞ-BOLYAI, PHYSICA, SPECIAL ISSUE, 2003 CHARACTERISATION OF ORGANIC POLLUTANTS DETECTED IN SOMES RIVER BY GC/MS Z. Moldovan(1) and J. M. Bayona(2) (1) National Institute of Research and Development of Isotopic and Molecular Technology, 3400 Cluj-Napoca, P.O.B. 700, Romania, e-mail: [email protected] (2) Instituto de Investigaciones Quimicas y Ambientales de Barcelona, c/J. Girona 18-26, Spain INTRODUCTION The directives of the European Community indicates that all wastewater in the territories of the European Union have to be properly collected and subjected to biological treatment before being discharged in rivers waters. However in Romania the majority of wastewater, from high populated cities and industrial complex zones, is still discharged into surface waters without proper treatment. In respect to this, one of priority tasks is to determine the environmental distribution of organic pollutants in the surface waters The present paper purpose is the mass spectrometric characterization of organic pollutants to evaluate the Structure of contaminant in the Somes-Tisa basin, from Transylvania (Romania) region and 2) study of photo-degradation processes of some types of pollutants on TiO2 aerogels. In studied area it is some potential sources of pollution as: -On the river Somes long of 250 km are as residents around of 800 000 people resulting an important quantity of synthetic compounds from domestic activity. -In this area it is industrial activity as pharmaceutical, food, pulp and paper production as well as metallurgical production known as main sources of organic contaminants. EXPERIMENTAL a) Sample Preparation Sample collection: The 500 ml surface water (river water) from 1m under surface were collected and were stored at 50C for maximum 5 days. For every sample 200 ml was acidified with 2N HCl to pH 2. Cartridge condition: Oasis 60mg cartridge (Waters) was conditioned with 6 ml dichloromethane, 6 ml acetonitrile and 6 ml of HPLC water. Sample elution/1/: Samples were percolated through the cartridge at a flow of 6ml/min. The cartridge were rinsed with 1ml HPLC water (at a flow of 3ml/min) and dried by vacuum for 50 min. The elution was carried out with 2.5 ml of acetonitrile-diclormethane (1:1) and 3.2 ml of dichlormetane. After elution the extract was transferred to vials and the excess of solvent was evaporated under a stream of nitrogen and than dissolved in iso-octane. The IS diphenilamine of 2 ppb were added at initial sample. Z. MOLDOVAN AND J. M. BAYONA b) Instrumentation. The GC/MS analyses were performed using a Fisons MD 800 mass spectrometer operated in the EI mode to 70 eV. The source temperature was 2300C and emission current 300 A. A HP-5MS (30x0.25mm) with 0.25m film thickness) containing 5% phenyl methyl siloxane was programmed from 900C(1min) to 1200C at 30C/min, from 1200C to 2000C at 3.50C/min and than to 3150C at 50C/min (keeping this temperature for 11 min.) RESULTS AND DISCUSSION The following families of compounds were detected: 1) Steroidal compounds (13 compounds) of type 5-stanols C27 (coprostanol) C28 (campestanol) and C29 (stigmastanol) with base peak to m/z 215 are shown in the Fig.1. Theirs precursors, 5-stenols as C27 (cholesterol), C28 (campesterol) and C29 (Sitosterol) are shown by ion chromatogram to m/z 213. They have a high chemical stability and are used as molecular biomarkers/2/ of human activity. The ratio of 5-colestanol (coprostanol) to 5-Stigmastanol is a precise indicator of fecal imput/3/. In our samples the ratio was 4.2 resulting that they originating main from omnivore fecal mater (human+porcine). Fig. 1. Identification of compound from t=47.053(Cholesterol) 2) Phthalate acid esters (PAEs) esters widely used in different industrial activities. Their main application are as plasticizers for PVC resins, adhesives and cellulose film coating /4/. Analytical data about presence and levels of PAEs in surface water can be used to identification of contamination sources. POLLUTANTS DETECTED IN SOMES RIVER BY GC/MS Fig. 2. Identification of the compound t=33.314 (Benzyl Butyl Phthalate) Fig 3. Identification of the compound from t=34.131(Octadecanamide) Their profile can be obtained by selected ion at m/z 149 (5 compounds). The high abundance of Di-2-ethylhexyl phthalate (DEHP) is to be mentioned. Z. MOLDOVAN AND J. M. BAYONA 3) A family of 8 polyetoxylate compounds is shown. Thy have diagnostic ions m/z 89, 133, 177 (generally) and m/z=M-113 (specific). The probable structure and denomination is presented. The identification was made based on comparison of obtained MS with library MS. 4) An important class of compounds is identified as antioxidants (14 compounds). They are compounds with high-branched chains/5/. Their probable structure is also presented. 5) A number of 3 compounds were identified as long chain amides in the range C18-C22. The relative high abundance of unsaturated C22 amide, probable 17docosenoicamide is to be mentioned. 6) A number of 9 pharmaceutical compounds were detected. They originated from municipal wastewater. These compounds could lead to ground water and soil and consequently accelerate the development of resistance in many disease organisms. Some mass spectra of compounds identified as pharmaceuticals are shown. The caffeine is originating from coffee drink or as pharmaceutics used as stimulant. The cocaine metabolite is present in smaller abundance and probable is originated from the consume of cocaine as a prohibit drug. Triclosan is a pharmaceutic used as antimichotic. The compound N-(2,3)-dihydro-1,5-dimethyl-3oxo-2-Phenyl-1H Pyrazol-4-yl) Acetamide is an analgesic and anti-inflammatory product. Apazone (Azapropazone) is a pharmaceutics from Pyrazole class used for the treatment of Rheumatism inflammatory and Rheumatism articulate. Pentoxifylline is a xantine derivative used as a hemorrheologic agent/6/. The Ethanoic acid, Bis(cyclohexylidenehydrazide) is a compound of type Cuprizone used in Brain Pathology/7/. Fig. 4. Identification of the compound from t=20.991 (Caffeine) POLLUTANTS DETECTED IN SOMES RIVER BY GC/MS 7) A number of 5 compounds were identified as long chain fatty acids in the range C12-C18. Relative high abundance can be seen for the acid C16 and C18. 8) Some natural products as Decanedioic acid dibutylester, Squalene and Vitamin E Acetate were also detected in relative high concentration (Squalene 3.395) 9) The alkyl esters of phosphoric acid were identified in concentration of 1.067ug/l (Phosphoric acid tri-iso-butyl ester) and 0.107 ug/l (Phosphoric acid trin-butyl ester). REFERENCES 1) Silvia Lacorte, Ingrid Guiffard, D. Fraisse and Damia Barcelo, Anal. Chem., 72, (2000) 1430-1440 2/) Cristina Maldonado, J. Dachs and J. M. Bayona, Environ. Sci. Technol. 33 (1999) 3290 3) R. P. Eveson and P. H. Bethell, Archaeological Chemistry, ACS Symposium Series, 1996, 157-172. 4) M. Guidoti, G. Macilenti and C. Cremisini, Environmental International, 23 (1997) 337 5) Z. Moldovan, and J. M. Bayona, Rapid Comm. Mass Spectrom. 14, (2000) 379-389 6) Patricia McCloskey, Medications, Springhouse Corporation, II Series, Springhouse, Pennsylvania 1994 7) G. K. Matsushima and P. Morell, Brain Pathology 11, (2001). 107-116