Occurrence and Fate of Organochlorinated Pesticides and PAH in Agricultural Soils from the Ebro River Basin

  • Alain Hildebrandt
  • Sílvia Lacorte
  • Damià Barceló
Article

Abstract

This study was aimed to assess the presence and fate of 22 organochlorinated pesticides (OCHs) and their degradation products and 16 Environmental Protection Agency-priority polycyclic aromatic hydrocarbons (PAHs) in soils of the Ebro River basin (NE Spain) during a 3-year period. The study site is characterized by a long and active agricultural history where pesticides have largely been used. Soils were extracted using pressurized liquid extraction followed by gas chromatography–mass spectrometry. This procedure was optimized in terms of multiresidue analysis and effective cleanup and proved to have excellent analytical performance (recoveries ranging between 71% and 133%, standard deviation <14%, and a method detection limit from 0.19 to 7.38 μg/kg). Soils form the Ebro basin showed a prevalence of 4,4′-DDT and 4,4′-DDE, found in 53% and 88% of the soil samples between 0.13 and 58.17 μg/kg-dw (dry weight), respectively, indicating a slight decreasing trend of DDT within time. PAHs were detected in all soil samples at concentrations up to 465 μg/kg-dw, and the phenanthrene/anthracene (<10) and fluoranthene/pyrene (>1) ratios indicated combustion processes as the main source attributing to the burning of weeds and vegetable wastes after harvesting. No traces of any of the OCHs and PAHs were detected in groundwater, indicating that leaching for agricultural fields is not an important process of transport for these compounds. Overall, we propose the need to perform a monitoring program to evaluate the temporal tendencies and potential impact of pesticides and PAH in soils.

References

  1. Aislabie JM, Richards NK, Boul HL (1997) Microbial degradation of DDT and its residues a review. NZ J Agric Res 40(2):269–282Google Scholar
  2. Baird WM, Hooven LA, Mahadevan B (2005) Carcinogenic polycyclic aromatic hydrocarbon-DNA adducts and mechanism of action. Environ Mol Mutagen 45(2–3):106–114CrossRefGoogle Scholar
  3. Barcelo D, Hennion MC (1995) On-line sample handling strategies for the trace-level determination of pesticides and their degradation products in environmental waters. Anal Chim Acta 318(1):1–41CrossRefGoogle Scholar
  4. Benlahcen KT, Chaoui A, Budzinski H, Bellocq J, Garrigues P (1997) Distribution and sources of polycyclic aromatic hydrocarbons in some Mediterranean coastal sediments. Marine Pollut Bull 34(5):298–305CrossRefGoogle Scholar
  5. Bidleman TF et al (2006) Emission of legacy chlorinated pesticides from agricultural and orchard soils in British Columbia, Canada. Environ Toxicol Chem 25(6):1448–1457CrossRefGoogle Scholar
  6. Bucheli TD, Blum F, Desaules A, Gustafsson O (2004) Polycyclic aromatic hydrocarbons, black carbon, and molecular markers in soils of Switzerland. Chemosphere 56(11):1061–1076CrossRefGoogle Scholar
  7. Colombo JC, Pelletler E, Brochu C, Khalil M, Catoggio JA (1989) Determination of hydrocarbon sources using n-alkane and polyaromatic hydrocarbon distribution indexes Case study: Rio de La Plata estuary, Argentina. ES T Contents 23(7):888–894Google Scholar
  8. Chung MK, Hu R, Cheung KC, Wong MH (2007) Pollutants in Hong Kong soils: polycyclic aromatic hydrocarbons. Chemosphere 67(3):464–473CrossRefGoogle Scholar
  9. Environmental Protection Agency (1990) Code of Federal Regulations. Available from http://www.access.gpo.gov/nara/cfr/waisidx_06/40cfr180_06.html
  10. European Commission (1986) Council Directive 86/362/EEC. Offic J Eur Communities L221:37–42Google Scholar
  11. European Commission (1990) Council Directive 90/642/EEC. Offic J Eur Communities L350:71–79Google Scholar
  12. European Commission (2001) Decision No 2455/2001/EC. Offic J Eur Communities L331:1–5Google Scholar
  13. Falandysz J, Brudnowska B, Kawano M, Wakimoto T (2001) Polychlorinated biphenyls and organochlorine pesticides in soils from the southern part of Poland. Arch Environ Contam Toxicol 40(2):173–178CrossRefGoogle Scholar
  14. Fernández P, Grimalt JO (2003) On the global distribution of persistent organic pollutants. Chimia 57(9):514–521CrossRefGoogle Scholar
  15. Ferrer I, Barcelo D (1999) Validation of new solid-phase extraction materials for the selective enrichment of organic contaminants from environmental samples. Trends Anal Chem 18(3):180–192CrossRefGoogle Scholar
  16. Flury M (1996) Experimental evidence of transport of pesticides through field soils: a review. J Environ Qual 25(1):25–45CrossRefGoogle Scholar
  17. Food and Agriculture Organization of the United Nations (2008) Codex Alimentarius FAO/WHO food standards. Available from http://www.codexalimentarius.net/mrls/pestdes/jsp/pest_q-e.jsp
  18. Gaw SK, Wilkins AL, Kim ND, Palmer GT, Robinson P (2006) Trace element and ΣDDT concentrations in horticultural soils from the Tasman, Waikato and Auckland regions of New Zealand. Sci Total Environ 355(1–3):31–47Google Scholar
  19. Gong ZM et al (2004) Level and distribution of DDT in surface soils from Tianjin, China. Chemosphere 54(8):1247–1253CrossRefGoogle Scholar
  20. Gustafson DI (1989) Groundwater ubiquity score: a simple method for assessing pesticide leachability. Environ Toxicol Chem 8:339–357CrossRefGoogle Scholar
  21. Hernández LM, Fernández MA, González MJ (1992) Organochlorine pollutants in water, soils, and earthworms in the Guadalquivir River, Spain. Bull Environ Contam Toxicol 49:192–198CrossRefGoogle Scholar
  22. Hildebrandt A, Lacorte S, Barcelo D (2007) Assessment of priority pesticides, degradation products, and pesticide adjuvants in groundwaters and top soils from agricultural areas of the Ebro river basin. Anal Bioanal Chem 387(4):1459–1468CrossRefGoogle Scholar
  23. Hussen A, Westbom R, Megersa N, Mathiasson L, Bjorklund E (2007) Selective pressurized liquid extraction for multi-residue analysis of organochlorine pesticides in soil. J Chromatogr A 1152(1–2):247–253CrossRefGoogle Scholar
  24. Katagi T (2002) Abiotic hydrolysis of pesticides in the aquatic environment. Rev Environ Contam Toxicol 175:79–261Google Scholar
  25. Leung AM, McDonough DM, West CD (1998) Determination of endosulfans in soil/sediment samples from Point Mugu, Oxnard, CA using capillary gas chromatography/mass selective detection (GC/MSD). Environ Monit Assess 50(1):85–94CrossRefGoogle Scholar
  26. Maliszewska-Kordybach B (1996) Polycyclic aromatic hydrocarbons in agricultural soils in Poland: preliminary proposals for criteria to evaluate the level of soil contamination. Appl Geochem 11(1–2):121–127CrossRefGoogle Scholar
  27. Mansour M, Feicht EA, Behechti A, Scheunert I (1997) Experimental approaches to studying the photostability of selected pesticides in water and soil. Chemosphere 35(1–2):39–50CrossRefGoogle Scholar
  28. Martens D, Maguhn J, Spitzauer P, Kettrup A (1997) Occurrence and distribution of polycyclic aromatic hydrocarbons (PAHs) in an agricultural ecosystem. Fresenius’ J Anal Chem 359(7):546–554CrossRefGoogle Scholar
  29. Martínez E, Gros M, Lacorte S, Barceló D (2004) Simplified procedures for the analysis of polycyclic aromatic hydrocarbons in water, sediments and mussels. J Chromatogr A 1047:181–188Google Scholar
  30. McCarthy L (2007) 2006 Was Earth’s fifth warmest year. National Aeronautics and Space Administration. Available from http://www.nasa.gov/centers/goddard/news/topstory/2006/2006_warm.html
  31. Nam JJ, Song BH, Eom KC, Lee SH, Smith A (2003) Distribution of polycyclic aromatic hydrocarbons in agricultural soils in South Korea. Chemosphere 50(10):1281–1289CrossRefGoogle Scholar
  32. Ramos L, Kristenson EM, Brinkman UAT (2002) Current use of pressurised liquid extraction and subcritical water extraction in environmental analysis. J Chromatogr A 975(1):3–29CrossRefGoogle Scholar
  33. Ripley BD, Ritcey GM, Harris CR, Denomme MA, Lissemore LI (2003) Comparative persistence of pesticides on selected cultivars of specialty vegetables. J Agric Food Chem 51(5):1328–1335CrossRefGoogle Scholar
  34. Tadeo JL, Castro J, Sánchez-Brunete C (2004) Multiresidue determination in soil of pesticides used in tomato crops by sonication-assisted extraction in small columns and gas chromatography. Int J Environ Anal Chem 84(1–3):29–37CrossRefGoogle Scholar
  35. Thapar S, Bhushan R, Mathur RP (1995) Degradation of organophosphorus and carbamate pesticides in soils: HPLC determination. Biomed Chromatogr 9(1):18–22CrossRefGoogle Scholar
  36. Vieira EDR, Torres JPM, Malm O (2001) DDT environmental persistence from its use in a vector control program: a case study. Environ Res 86(2):174–182CrossRefGoogle Scholar
  37. Wan MT, Kuo JN, Pasternak J (2005) Residues of endosulfan and other selected organochlorine pesticides in farm areas of the Lower Fraser Valley, British Columbia, Canada. J Environ Qual 34(4):1186–1193CrossRefGoogle Scholar
  38. Wang Z et al (2007) Distribution and sources of polycyclic aromatic hydrocarbons from urban to rural soils: a case study in Dalian, China. Chemosphere 68(5):965–971CrossRefGoogle Scholar
  39. Young D, Ozretich R, Lee Ii H, Echols S, Frazier J (2001) Persistence of DDT residues and dieldrin off a pesticide processing plant in San Francisco Bay, California. ACS Sympos Ser 772:204–217CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2008

Authors and Affiliations

  • Alain Hildebrandt
    • 1
  • Sílvia Lacorte
    • 1
  • Damià Barceló
    • 1
  1. 1.Department of Environmental ChemistryIIQAB – CSICBarcelonaSpain

Personalised recommendations