Download IDENTIFICATION OF ORGANIC POLLUTANTS IN SOMES RIVER

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 0.25m 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).
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