Hydrology in Mountainous Regions. I - Hydrological Measurements; the Water Cycle (Proceedings of two Lausanne Symposia, August 1990). IAHS Publ. no. 193,1990. Polycyclic aromatic hydrocarbons as pollutants of the aquatic environment in the Sudety Mts, southwestern Poland T.BABELEK & J. GROCHMALICKA-MIKOLAJCZYK Department of Inorganic and Analytical Chemistry,Medical Academy, Grunwaldzka 6, 60-780, Poland ABSTRACT Results of determination of the natural background concentration of PAH in aquatic environment of Sudety Mts. (South - West Poland) are presented. Generally, 78 underground and 11 surface water sources in Sudety Mts. were selected for PAH analysis. In a period from 1983 to 1989 235 underground and 46 surface waters from this region were analysed. Fourteen compounds of the polycyclic aromatic group have been found in the analysed waters. Different chemical composition of the analysed waters from different sources have been noted. The highest concentration of PAH, according to the WHO standards, in underground waters does not exceed the total allowed amount of these compounds in drinking water. The determined natural background of six PAH in underground waters of Sudety Mts. is 60-160 ng/dm. The mean value for the same compounds in surface waters is 366 ng/dm. The high level of PAH in surface waters and occasionally also in underground waters can result from the activity of industry localised in this region. INTRODUCTION Polycyclic aromatic hydrocarbons (PAH) are present in the environment from both natural and anthropogenic sources. As a group, they are widely distributed in the environment, having been detected in sediments, soils, air and various water sources. Some PAH, including benzo(a)pyrene - B(a)P, indeno(l,2,3-c,d)pyrene - IP and benzo(b)fluoranthene - B(b)F were shown cancerogenic both to animals and to man (Neff, 1979). The level of PAH in surface water is influenced by industrial discharges. These compounds tend to accumulate in the aqueous environment. Investigational works on PAH in waters (Borneff & Kunte, 1969) have mainly been confined to six compounds (including B(a)P) which are relatively easily detected and can serve as indicators for the whole group. Previous European and international standards for drinking water proposed a limit of 200 ng/dm for the sum of six named indicator PAH in drinking water (WHO, 1971). The concentration of the indicator PAH in different types of water were typically 10-50 ng/dm in underground waters, 50-250 ng/dm in relatively unpolluted river waters and higher in polluted rivers and effluents. WHO in 1984 (WHO, 1984) based on the application of the linear
T. Bqbelek & J. Grochmalicka-Mikoïajczyk 424 multistage extrapolation model to the available toxicological data for B(a)P and taking account of the fact that this substance is associated in water with other PAH of known carcinogenity, a limit value at 10 ng/dm for this compound was fixed. Grochmalicka et all (1979) showed the appearance of six PAH in selected drinking waters in Poland. Studies by Babelek and Cieékowski (1989) showed the necessity of analysis water samples from Southwestern Poland for their PAH content. Results of the analysis of PAH content in the underground waters in the Sudety region were some of the first, and therefore there were difficulties in interpreting them. The level of the natural background impurities was still unknown in the underground waters of that region. That was the reason why the studies were performed in the Sudety region. Basing on this results it was possible to determine the natural background concentration of PAH in underground waters of South - Western Poland. EXPERIMENTAL PART In a period from 1983 to 1989 235 underground and 46 surface waters samples from Sudety Mts. were analysed. Generally 78 underground and 11 surface water sources from this region were selected for PAH analysis (Fig.l). FIGURE 1. LOCATION SKEETCH OF ^ ANALYSED UNDERGROUND AND < SURFACE WATERS IN SUDETY MTS. 1. I;;;:;::::! CRISTALIC ROCKS (EFFUSIVE ROCKS O ^ SEDIMENTARY ROCKS MAIN SAMPLING POINTS 3. UNDERGROUND WATERS 4. a SURFACE WATERS FIG. 1
425 Pofycyclic aromatic hydrocarbons as pollutants Analysis of water samples consists of three stages: (a) extraction with nyclohexane as a solvent and two dimensional thin-layer chromatographic separation (b) qualitative analysis; spectrofluorometry at 77 K (c) quantitative analysis; spectrofluorometry at room temperature. The content of six representative PAH was determined (Table 1). TABLE 1 PAH identified in underground and surface waters in the Sudety Mts. Number Name of compound Abbreviation 1 2 3* 4 5* 6* 7 8* 9 10 11* 12* 13 14 Anthracene Benzo(a)anthracene Benzo(b)fluoranthene Benzo(j)fluoranthene Benzo(k)fluoranthene Benz o ( a ) pyr ene Benzo(e)pyrene Benzo(g,h,i)perylene Coronene Dibenzo(a,h)anthracene Fluoranthene Indeno(l,2,3-c,d)pyrene Perylene Pyrene An B(a)A B(b)F B(j)F B(k)F B(a)P B(e)P B(g,h,i)P COR Db(a,h)A FL IP Per Pyr * Compound included in WHO Standards for Drinking Water (1971) RESULTS AND DISCUSSION Qualitative analysis of water samples after chromatographic separation revealed the presence of 14 compounds of the PAH group as shown in table 1. All of these compounds were present both in sources of analysed underground and surface waters. Different chemical composition of the analysed underground and surface waters from different sources have been noted. The growth of the number of identified compounds from 1983 to 1989 can suggest the progressive contamination of waters by the egzogenous hydrocarbons.the smallest number of the identified polycyclic compounds in one source was 5. Two hydrocarbons i.e. anthracene and benzo(a)pyrene were found in all analysed waters, but benzo(k)fluoranthene, benzo(g,h,i)perylene and indeno(l,2,3-c,d)pyrene were detected periodically. Benzo(e)pyrene, perylene, pyrene and coronene belong to compounds which were present in the smallest number of analysed sources. The presence of B(a)P (the most cancerogenic compound of the PAH group) in all analysed kinds of waters was very important.
T. Bqbelek & J. Grochmalicka-Mikofajczyk 426 TABLE 2 Content of 6 representative PAH and B(a)P in underground and surface waters in the Sudety Mts. Analysed water Number of analysed sources Number of samples The Sum of 6 PAH min/max X ng/dm a min/max B(a)P X a Undergroud waters 78 235 52/444 162 79 1/22 8 4 Surface waters 11 46 96/1172 366 143 5/80 24 16 Table 2 shows the mean contents of B(a)P and the sum of 6 representative PAH determined in water samples from the period 1983 to 1989. The mean content of the analysed compounds was very high. The highest concentration of PAH was determined in surface waters. 30- n- ~ a b to- 20-10' r f Th-HI n. r ]fl 1 -l n n 100 15 20 25 CONCENTRATION [ng/dm 3 ] FIG. 2 Frequency distribution of B(a)P and 6 PAH content in underground waters in the Sudety Mts,. a - sum of 6 PAH b - B(a)P According to WHO standards the total admissible amount of six typical hydrocarbons in drinking water is 200 ng/dm and the concentration of B(a)P is allowed to be up to 10 hg/dm. The results
427 Pofycyclic aromatic hydrocarbons as pollutants of PAH determination in the underground waters in most cases do not exceed the mentioned values. However, there were sources in which the quantities of PAH were higher than the upper limit value. The mean content of the sum of PAH in underground waters was 162 ng/dm and B(a)E 8 ng/dm. The same data for surface waters were 366 and 24 ng/dm. On figure 2 the frequences of B(a)P and the sum of 6 PAH content in analysed underground waters are presented. Figure 3 shows the cumulative curves of the distribution of B(a)P and 6 PAH determined in/ the underground waters from Sudety region. Basing on these curves it was possible to determined the natural background of six representative PAH (60-160 ng/dm ) and B(a)P (3-8 ng/dm ) in underground waters from this region. 250 200 u. 150 o SUM OF SIX PAH B(a)P 50 300 15 20 25 CONCENTRATION [ng/dm 3 ] FIG. 3 Cumulative curves of the distribution of B(a)P and 6 PAH determination in underground waters in- the Sudety Mts. The high level of PAH in surface waters and also in underground waters in the Sudety Mts. can be connected with the activity of industry which is localized in this region. Results presented above showed the necessity of analysis of underground waters for their PAH content. PAH can serve as a sensitive indicators of underground water pollution. REFERENCES Babelek, T., Cieékowski, W. (1989) Polycyclic aromatic hydrocarbons as an indicator of contamination of medicinal waters in the spas in the Sudetes mountains of South - Western Poland. Environ. Geol. Water Sci. 14 (2), 93-97.
T. Bqbelek&J. Grochmalicka-Mikoïajczyk 428 Borneff, J. & Kunte, H. (1969) Kanzerogene Substanzen in Wasser und Boden. XXVI. Routinhiethode zur bestimmung von polyzyclischen Aromaten im Wasser. Arch.Hyg. 153 (3), 220-229. Grochmalicka-Mikoîajczyk, J., Ochocka, J.R. & Lulek, J. (1979) Polycyclic aromatic hydrocarbons (PAH) in the municipal waters in the towns above 100.000 of population. Problemy Higieny 8, 125-136. Neff, J.M. (1979) Polycyclic aromatic hydrocarbons in the aquatic environment. Sources, fates and biological effects. Applied Science Publishers, England. World Health Organisation. (1971) International Standards for Drinking Water Quality, Geneva. World Health Organisation. (1984) Guidelines for Drinking Water Quality, Geneva.