Danuta Bodzek

Determination of polycyclic aromatic compounds and heavy metals in sludges from biological sewage treatment plants

The procedure of the analysis of polycyclic aromatic hydrocarbons (PAHs) and their derivatives in the sludges from biological sewage treatment plants has been worked out. The analysis included isolation of organic matter from sludges, separation of the extract into fractions of similar chemical character, qualitative-quantitative analysis of individual PAHs and their nitrogenated and oxygenated derivatives. Liquid-solid chromatography, solid-phase extraction and semipreparative band thin-layer chromatography techniques were used for the separation. Capillary gas chromatography-mass spectrometry analysis of the separated fractions enabled identification of more than 21 PAHs, including hydrocarbons which contained 2-6 aromatic rings as well as their alkyl derivatives, 10 oxygen derivatives, 9 nitroarenes, aminoarenes and over 20 azaarenes and carbazoles. Using the capillary gas chromatography-flame ionization detection technique the content of 17 dominant PAHs was determined. The content of heavy metals was determined in investigated sludges with the use of atomic absorption spectrometry. The concentrations of the respective metals could be ranked in the order Cd < Co < Ni < Pb < Cr < or = Cu < Mn < Zn < Fe. The sludges were analysed for the first time in Poland in view of their possible utilisation in agriculture and in cultivating dumps of coal mine wastes, taking into consideration the contents of toxic organic pollutants and heavy metals.

Clean-up procedures for the analysis of heterocyclic aromatic amines (aminoazaarenes) from heat-treated meat samples

The purpose of the study was to determine optimum conditions for the isolation and quantitation of five most biologically active aminoazaarenes [2-amino-3-methylimidazo[4,5-f]quinoline (IQ), 2-amino3,4-dimethylimidazo[4,5-f]quinoline (MeIQ), 2-amino-3,8-dimethyl-imidazo[4,5-f]quinoxaline (MeIQx), 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx), 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP)]. Some multistep procedures based on ultrasonic extraction, Soxhlet extraction, liquid-liquid extraction and solid-phase extraction (SPE) were tested in order to choose the optimum isolation conditions for aminoazaarenes from fried meat samples spiked with known amounts of standards. According to the tested methods the qualitative-quantitative analysis was performed on the unspiked sample of pork roasted in typical household conditions. The qualitative-quantitative analysis of the aminoazaarenes was performed by a HPLC method. A HPLC Hewlett-Packard HP 1090 liquid chromatograph equipped with a UV diode array detector (DAD) was used. Chemically bonded HPLC columns C8 and TSK-gel ODS 80-T(M) were used under gradient elution conditions. A two-component mixture containing triethylamine-phosphate buffer (pH 3.2 and 3.3) and acetonitrile was used as a mobile phase. The results of the studies showed that a solid-phase extraction procedure using diatomaceous earth (Extrelut, 20 ml), propylsulphonic acid (PRS, 500 mg) and octadecylsilane (C18, 500 mg) columns was the quickest and simplest one. Recoveries of the aminoazaarenes, spiked and isolated from meat samples by the chosen SPE procedure, were as follows: IQ 85%, MeIQ 50%, MeIQx 46%, 4,8-DiMeIQx 62%, PhIP 50%.

Comparison of Polycyclic Aromatic Compounds and Heavy Metals Contents in Sewage Sludges from Industrialized and Non-Industrialized Region

The total contents of PAHs, organic polar fractions and 14 major hydrocarbons containing 3–6 aromatic rings as well as heavy metal contents were determined in sewage sludges from highly industrialized (Upper Silesia), agricultural and recreational regions of Poland. Sludges from the industrial region showed markedly increased concentrations of all the organic micropollutants and 2–10 times higher levels of the following heavy metals: Pb, Cd, Cr, Cu, Fe, Zn, Ni, Mn and Co. The levels, however, did not exceed the Polish as well as European Economic Community limit values, which renders all the sludges applicable to land and some of them suitable for utilization on agricultural soils.

Occurence of PAHs in Various Elements of Environment in Zabrze (Upper Silesia, Poland)

The Polycyclic Aromatic Hydrocarbons (PAHs) pollution state of the chosen town (Zabrze) of Upper Silesia, the most industrialised region in Poland, was presented. Zabrze is a town of medium size, having population twenty times bigger than a medium town polulation in Poland. In this study we determined the qualitative and quantitative composition of PAHs fraction separated from the following elements of environment: suspended dust, drinking water, soil and sewage sludge. The following analytical techniques were used: Soxhlet Extraction, Solid Phase Extraction, Gas Chromatography-Mass Spectrometry, Capillary Gas Chromatography and High Performance Liquid Chromatography. The results confirmed the significant state of examined region pollution. They stated the exceed of contents B(a)P in suspended dust. The soils in that place were heavily polluted with PAHs, about 4000 µg · kg-1 for the sum of PAHs. The total contents of PAHs in sewage sludge of Zabrze did not exceed the analogous contents published for West European sewage sludge treatment plants and the level of determined PAHs in drinking water did not show any claims.

The analysis of PAHs nitrogen derivatives in the sewage sludges of upper Silesia, Poland

The dimethylformamide extracts from sewage sludges from a chosen sewage — treatment plant in highly industrialized region of Poland were investigated. Using the column chromatography with Al2O3 and silicic acid as the stationary phases, the fraction of azaarenes has been separated. GC-MS analysis of azaarenes fraction made it possible to identify 10 azaarenes and several of their alkyl derivatives, which dominate in the organic matter extracted from sewage sludges. The silicic acid column chromatography in connection with the reduction of nitroarenes and derivatization with pentafluoropropionic acid anhydride yielded an enriched nitrofraction. Nitroarenes present in this fraction as amide derivatives were also analysed by GGMS method. There was found presence of 3 nitroarenes and their methyl derivatives.

Application of planar chromatography to the analysis of polycyclic aromatic hydrocarbons and their derivatives in environmental samples

The main aspects of using planar chromatography to isolate and identify polycyclic aromatic hydrocarbons (PAHs) and their derivatives in environmental samples are described. Several carbonyl, nitro polycyclic aromatic compounds, azaarenes, and polar PAHs, which are very dangerous for human health, were identified. These results have been confirmed by gas chromatography coupled with mass spectrometry. Progress in the application of these techniques using different stationary and mobile phases, as well as in the modernization of chromatographic chambers, are presented.

Concentration of Polycyclic Aromatic Hydrocarbons and Base Cations in the Air and Drinking Water of the Silesian Rehabilitation Centre, Poland

Investigations were carried out to assess air and potable waterpollution with selected highly bioactive organic compounds,including polycyclic aromatic hydrocarbons (PAHs), in theenvironment of the Silesian Rehabilitation Centre, Repty Śląskie, Poland. The results were compared with those forother towns of the region.Solid phase extraction (SPE) and capillary gas chromatography(CGC) with flame ionization detector (FID) and mass spectrometer(MS) were used for a qualitative-quantitative analysis. Moreover, water concentration of calcium, magnesium ions andnitrite ions were measured by spectrophotometric methods. Thequality of the Centre environment air and water found to besatisfactory and better than that in the other sampling sites which were studied for all the parameters.

Determination of 7-ketocholesterol and 7-hydroxycholesterol in meat samples by TLC with densitometric detection

Concentrations of two oxycholesterols: 7-ketocholesterol and 7- hydroxycholesterol in meat samples (raw and cooked) were determined by TLC with densitometric detection. To obtain the oxycholesterols fraction, a multistage clean-up procedure based on liquid extraction and solid-phase extraction (SPE) was performed on silica gel and Florisil columns. The oxycholesterol fractions isolated from meat samples were separated by TLC on silica gel in an horizontal chamber. Quantitation was performed densitometrically directly after the TLC separation for 7-ketocholesterol and after Liebermann—Burchard reaction for 7-hydroxycholesterol. The presence of oxycholesterols determined by TLC was confirmed by GC—MS analysis of oxysterols derivatized to trimethylsilyl ethers. The investigations showed that the 7-ketocholesterol and 7-hydroxycholesterol content of the meat eaten most often in Poland ranged from approximately 40 ng g−1 to 3.5 µg g−1 of the sample.

Densitometric thin-layer chromatography of polycyclic aromatic sulfur compounds

Thin-layer chromatography has been used to separate a mixture of sulfur polynuclear aromatic hydrocarbons (S-PAH), heterocyclic compounds with mutagenic and carcinogenic properties. S-PAH were oxidized to give the sulfone derivatives and then S-PAH standards, their oxidized forms, and PAH were applied to silica gel and RP-18 plates and developed in a horizontal chamber with different mobile phases. After chromatography the plates were observed in UV light at λ = 254 nm and scanned densitometrically at the same wavelength. RF values were determined for the compounds.