1. Sewage sludge – nutrient-rich fertilizer or hazardous waste? Kohtla-Järve 27th April, 2010 Lembit Nei and Egge Haiba Tallinn University of Technology Merike Lillenberg Estonian University of Life Sciences Karin Kipper and Koit Herodes Tartu University

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4. Introduction (1) The amount of sewage sludge increases all over the world Sewage sludge compost may be used as a fertilizer. Heavy metals, E. coil and helmints’ eggs are of concern. Sludge contains traces of several pharmaceuticals, including antibiotics Maximum residue limit for pharmaceuticals in manure is 100 μg/kg and 10 or 1 μg/kg in soil.

5. Introduction (2) The accumulation of pharmaceuticals into plants depends on many factors and mainly on their soil concentrations No limits have been set for drugs in plant products at present Even small amounts of antibiotics in everyday food may generate resistant bacteria, provoke allergy and affect the liver

8. Antibiotics in sewage sludge (1) Traces of tetracyclines (TCs), fluoroquinolones (FQs) and sulfonamides (SAs) were analyzed from sewage sludge and its compost from two Estonian wastewater treatment plants Pressurized liquid extraction followed by solid phase extraction and LC-MS analysis method for simultaneous determination of 7 antibiotics in sludge were developed and validated

9. Antibiotics in sewage sludge (2) Sludge from two sewage treatment plants of Estonian largest cities, Tallinn and Tartu μg/L

10. Samples FQs and SAs traces and their uptake by lettuce from soil mixed with aqueous solution of pharmaceuticals were analyzed Lettuce samples after 40 days.

11. Antibiotics in plants (1) Chromatograms of the analysed antibiotics in lettuce root. Sulfadimethoxine Sulfamethoxazole Norfloxacin

12. Antibiotics in plants (2) Ciprofloxacin Ofloxacin

13. Antibiotics in plants (3) Antibiotics content in dry lettuce (μg/kg) Sample c (soil) [mg/kg] SMX SDM NOR CIP OFL Roots1078302050498383454 Leaves10446175n.d. 107 Roots140047n.d.535339 Leaves1n.d. 7 Roots0,541124215561612121 Leaves0,5n.d. 1313 Roots0,110358n.d.79n.d. Leaves0,1n.d.

14. Antibiotics in plants (4) Sulfamethoxazole concentrations in lettuce samples

15. Publications Lillenberg, M.; Yurchenko, S.; Kipper, K.; Herodes, K.; Pihl, V.; Lõhmus, R.; Ivask, M.; Kuu, A. ; Kutti, S.; Litvin, S. V.; Nei, L. (2010). Presence of fluoroquinolones and sulfonamides in urban sewage sludge and their degradation as a result of composting. International Journal of Environmental Science and Technology, 7(2), 307 - 312. Lillenberg, M.; Herodes, K.; Kipper, K.; Nei, L. (2010). Plant Uptake of some Pharmaceuticals from Fertilized Soils. Proceedings of 2009 International Conference on Environmental Science and Technology, 5p [in press] Lillenberg, M.; Herodes, K.; Kipper, K; Nei, L. (2010). Fluoroquinolones and sulfonamides in sewage sludge and its compost. In: Abstract book: SETAC Europe 19th Annual Meeting, Seville:, 2010. [in press] Lillenberg, M.; Yurchenko, S.; Kipper, K.; Herodes, K..; Pihl, V.; Sepp, K.; Lõhmus, R.; Nei, L. (2009). Simultaneous determination of fluoroquinolones, sulfonamides and tetracyclines in sewage sludge by pressurized liquid extraction and liquid chromatography electrospray ionization-mass spectrometry. Journal of Chromatography A, 1216, 5949 - 5954. Nei, L.; Kruusma, J.; Ivask, M.; Kuu, A. (2009). Novel approaches to heavy metals bioindication in soils contaminated by oil shale wastes. Oil Shale, 26(3), 424 - 431. Kipper, Karin; Lillenberg, Merike; Yurchenko, Sergei; Herodes, Koit; Pihl, Viljar; Sepp, Kalev; Lõhmus, Rünno; Nei, Lembit (2009). Determination of antibiotic residues in sewage sludge by pressurized liquid extraction and LC-ESI-MS. In: Book of Abstracts: 5th Conference by Nordic Separation Sciense Society, 26.-29. Aug., 2009, Tallinn, Estonia., 2009, 102. Nei, Lembit; Lillenberg, Merike (2009). Reoveesettest valmistatud komposti peab hoolega kontrollima.. Keskkonnatehnika, 7, 12 - 13. Lillenberg, Merike; Yurchenko, Sergei; Kipper, Karin; Herodes, Koit; Nei, Lembit (2008). Degradation of antibiotic residues during sewage sludge composting. In: Abstract Book: SETAC North America 29th Annual Meeting, Tampa., 2008, 197. Lillenberg, M.; Herodes, K.; Yurchenko, S.; Kipper, K; Sepp, K.; Nei, L. (2008). Antibiotic residues in some fertilizers. In: Abstract Book: SETAC Europe 18th Annual Meeting, Warsaw., 2008, 79 - 80.

16. Conclusion Method for determination of antibiotic residues in plants was developed Uptake of ciprofloxacin, norfloxacin, ofloxacin, sulfadimethoxine and sulfamethoxazole was demonstrated in lettuce Detected levels of the studied pharmaceuticals in leaves were relatively low if compared to soil concentrations Concentrations in lettuce roots were 4 to 18 times higher than in leaves Further studies are needed to determine the uptake of pharmaceuticals by various crop plants

17. Acknowledgements Present work was funded:  Estonian Environmental Investment Centre  Estonian Science Foundation (grant no 7127)  Estonian research target project SF 0180058s07

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