Pharmaceuticals and Care Products in the Environment - American

Chapter 6

Phenazone Analgesics in Soil and Groundwater below a Municipal Solid Waste Landfill 1

2

Marijan Ahel and Ivana Jeličić 1

Center for Marine and Environmental Research, Ruđer Bošković Institute, Bijenička 54, HR-10000 Zagreb, Croatia Faculty of Food Technology and Biotechnology, University of Zagreb, Pierottijeva 6, HR-10000 Zagreb, Croatia

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Analgesics of the phenazone type, including propyphenazone, aminopyrine, and antipyrine, were determined in solid waste and leachate from the main landfill of the city of Zagreb, Croatia, as well as in soil and groundwater below the landfill. All structural identifications and quantitative analyses were performed using high-resolution gas chromatography/mass spectrometry. The analyses of solid waste revealed that propyphenazone and aminopyrine were among the most abundant specific anthropogenic compounds in the landfill, while antipyrine was detected only in trace concentrations. Since the landfill does not include any protective barrier, heavily contaminated landfill leachate plume penetrates rapidly into the underlying soil, which is composed of highly permeable alluvial sediments, and eventually reaches groundwater aquifer. A s a consequence, propyphenazone and aminopyrine were determined in high concentrations (up to 67μg/L) in groundwater below the landfill. However, aminopyrine seems to be strongly attenuated in the aquifer section near the landfill, while propyphenazone showed a rather high persistence and mobility in the leachate plume.

100

© 2001 American Chemical Society

In Pharmaceuticals and Care Products in the Environment; Daughton, C., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2001.

101 In the last few years, the number of reports in the literature expressing concern about possible environmental effects of various pharmaceutical chemicals is rapidly increasing (see ref. / for review). A wide variety of these highly biochemically active chemicals, including lipid regulating agents, antiphlogistics, betablockers, /? symphatomimetics, psychiatric drugs, antiepileptic drugs, synthetic estrogens, and antibiotics, is used in human and veterinary medicine and subsequently released into the environment (1,2,3). The percentage of manufactured pharmaceuticals that are eventually excreted into the aquatic environment is dependent on their pharmacokinetics and therefore is very specific for individual drugs. The direct input of pharmaceuticals into the environment, such as wastewater discharge from manufacturing units and disposal of unused medications, can also be significant, especially at some hotspots. Antiphlogistic drugs (analgesics-antipyretics) belong to the most popular pharmaceutical chemicals. Several reports indicated recently that analgesic compounds are rather common constituents of municipal wastewaters (2-5). Analgesics of the phenazone type were detected in most of the examined German municipal sewage effluents and rivers with the median concentration values of 0.16 and 0.024 μg/L, respectively (3). Heberer et al. (6) indicated a possible impact of sewage effluents, containing propyphenazone and antipyrine, on groundwater from wells situated downstream of sewage treatment plants. The concentrations of phenazone analgesics in sewage effluents and groundwater were of the same order of magnitude, suggesting their efficient infiltration into groundwater. Another important route of input of the pharmaceutical chemicals into groundwater is the release from landfills. Since many of the disposal sites are open dumps without protective barriers and leachate collection systems (7), the infiltration of heavily contaminated leachates could seriously jeopardize the quality of groundwater near landfills (8, 9). Landfill leachates were shown to contain complex assemblages of various contaminants (10) but until recently pharmaceutical chemicals have been neglected as possibly important groundwater contaminants (9, 10). However, studies by Eckel et al. (77) and Holm et al. (72) indicate that pharmaceutical chemicals, including analgesics, are among the most prominent anthropogenic constituents in landfill-leachate polluted groundwater. The aim of this study was to deterarine the impact of phenazone analgesics (Fig. 1) from the municipal solid waste landfill of the city of Zagreb (Jakusevec landfill), Croatia, on underlying soil and groundwater below and near the landfill.


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Materials and Methods Field site This study was conducted on the main landfill of the city of Zagreb (Jakusevec landfill), Croatia (Fig. 2), which has been operated since 1965 and covers an


102

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C H 3

CH


ANTIPYRINE

CH

3

3

PROPYPHENAZONE

CH

H C—Ν 3

\

CH

3

3

3

AMINOPYRINE

Figure 1. Chemical structures ofphenazone analgesics

2

area of 800,000 m . The landfill contains presently about 5-7 million tons of solid waste (13). The waste is mostly of domestic origin, but significant contributions of commercial and industrial waste were also detected (14). Until 1997, the whole landfill, which is now under reconstruction, was operated as an open dump and posed a major risk to groundwater resources situated downstream (15, 16). The prevailing direction of groundwater flow is parallel with the Sava River bed (toward southeast). The waste has been disposed directly onto highly permeable alluvial sediments, while the permanently saturated zone of the aquifer is situated only 2 to 4 m below the landfill bottom. Consequently, the penetration of landfill leachates into the groundwater is very fast and efficient, resulting in a large leachate plume, which can be detected at distances longer than 1.5 km (16). This study was carried out in the southeastern part of the landfill, which consisted of two different sectors depicted as A and Β in Figure 2. The height of filling in sector A was highly variable, ranging from 0-1 m (boreholes JRP-2, JRP-3, JRP-6) to 9-12 m (boreholes JRP-4, JRP-5, JRP-7 and JRP-9). Its average age at the moment of sampling was

(min)

Figure 3. SIM-GC/MS chromatogram of a landfill leachate sample collected at the edge of the landfill of the city of Zagreb; 1 - deuterated phenanthrene (internal standard), 2 - antipyrine, 3 - aminopyrine, 4 - propyphenazone. The amount of phenazone compounds in the southeastern part of the landfill was estimated assuming that each core was representative of the zone situated around the given borehole and taking into account the thickness of the solid waste layer in each zone (Table I). Since the total area of the southeastern part of the landfill (sectors A and B) was 155,000 m , the area associated with each of 17 boreholes was 9000 m . The estimate shows that this part of the landfill contains about 800 kg of propyphenazone and 3 kg of aminopyrine. Propyphenazone and aminopyrine are relatively polar compounds, which reveal high solubility in water (19) and moderate log Ko values of 2.32 (12) and 0.80 (20), respectively. A s a consequence, both compounds could be easily remobilized from the solid waste by infiltrating leachates. The distribution of propyphenazone and aminopyrine in landfill leachate samples collected at different locations around the southeastern part of the landfill are presented in Figure 5. A l l leachates contained combined phenazone analgesics with total concentrations ranging from 4.3 to 67 μg/L. Most of the leachate samples were collected after strong rain events and are therefore more dilute compared with those leachates that are formed by a slower percolation of infiltrating water during the drier periods. Propyphenazone was the clearly predominant individual compound in all landfill leachates (3.7-60 μg/L), while the concentration of aminopyrine was lower (0.06-16 μg/L). However, the relative 2

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0.8 Downloaded by UNIV OF ARIZONA on July 28, 2012 | http://pubs.acs.org Publication Date: July 30, 2001 | doi: 10.1021/bk-2001-0791.ch006

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Borehole Figure 4. Distribution ofphenazone analgesics in solid waste from the main landfill of the city of Zagreb. PRO - propyphenazone; AM- aminopyrine. contribution of aminopyrine was somewhat higher than in the solid waste. This is probably a consequence of a comparatively higher solubility of aminopyrine in the aqueous phase. Moreover, leachate integrates the contaminants over a larger area than the solid core, and its composition may be more representative of an average situation. The water balance for the southeastern part of the landfill predicts that highly reducing leachate infiltrates into the aquifer at an average rate of about 100 m per day (21). Taking an average concentration of 25 μg/L of propyphenazone and 3 μg/L of aminopyrine (Fig. 5), the total amount of phenazone analgesics released from this part of the landfill is estimated to be about 1 kg/year. Considering that the landfill contains about 800 kg of phenazone analgesics (Table I), it further suggests that the amount present should be sufficient to maintain their high levels in groundwater for more than 100 years. 3


108 Table I. Estimation of the total amounts of phenazone analgesics in solid waste disposed of in the sectors A and Β (Fig. 2) of the southeastern part of the Jakusevec landfill (PRO=propyphenazone; AM=aminopyrine). Borehole

Waste thickness (m)

Amount* (kg)

AM


PRO JRP1 JRP2 JRP3 JRP4 JRP5 JRP6 JRP7 JRP8 JRP9 JRP10 JRP11 JRP12 JRP13 JRP 14 JRP15 JRP16 JRP17 Total

1.7 0 0 10 9 0.6 10 4 12 2.1 2.0 1.6 0 0.6 1.2 1.5 1.2

-

0.054 0 0 0.203 0.269 0.057 0.608 0.243 0.691 0.291 0.098 0.069 0 0.035 0.057 0.067 0.091 2.83

0.56 0 0 5.60 3.69 0.13 15.7 3.38 28.08 408 308 1.54 0 0.18 14.9 1.66 0.180 791.72

a

Ratio

PRO/AM 10.4

-

27.6 13.7 2.3 25.7 13.9 40.6 1407 3143 22.3

5.0 266 24.8 2.0

-

2

2

The total area of the sectors A and Β = 155 000 m (area/borehole = 9000 m ); average density of the analyzed waste = 2.5 g/cm . 3

The analyses of soil from the layer situated immediately below the landfill bottom (0-1 m) showed that phenazone analgesics were present in all samples in detectable concentrations with minima of 3 ng/g found in the boreholes JRP-13 and JRP-17 (Fig. 6). This can be explained by the fact that borehole JRP-13 was situated at the edge of the landfill and had no visible layer of solid waste, while solid waste from borehole JRP-17 contained very low concentration (0.012 mg/kg) of phenazone analgesics. The concentration of propyphenazone in soil was much lower than that in solid waste and varied in a wide range from 0.003 to 2.9 mg/kg. The spatial distribution reflected the general situation in the overlying waste, showing a maximum at the borehole JRP-10. Aminopyrine was also detected in the majority of the analyzed samples, but its concentration was low and varied in a relative narrow range of 0.003 to 0.007 mg/kg.



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Figure 5. Distribution ofphenazone analgesics in leachate samples collected on the main landfill of the city of Zagreb. PRO - propyphenazone; ΛΜaminopyrine. Taking into account the concentration of phenazone analgesics in soils at different locations of the landfill, it was estimated that their total amount sorbed in a 1-m soil layer below the landfill equals about 60 kg. This is only about 10% of the amount present in the landfill (Table I). Still, considering that the release of phenazone analgesics into the aquifer by infiltrating leachates at a rate of 1 kg/year resulted in a significant contamination of underlying groundwater, the phenazone pool in the polluted soils below the landfill must be considered significant. Therefore, it was recommended that remediation of the Jakusevec landfill should include not only removal of solid waste, but also the excavation of at least 1 m of contaminated soils below the landfill. The analyses of groundwater samples collected from the piezometers within (JRP 9-10, JP1) and near (JM 7-12, JP18) the landfill (Fig. 2) in 1995 and 1996 revealed that phenazone analgesics were present in significant concentrations (Fig. 7 and Fig. 8). Propyphenazone was the prevailing compound in most of the analyzed samples, which clearly reflected its predominance in the landfill leachate. The concentration of propyphenazone in piezometers situated within the landfill was found typically in the range of 5-50 μg/L, which is the same order of magnitude as in the collected leachates. The concentration of aminopyrine varied widely from

Pharmaceuticals and Care Products in the Environment - American

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