Copper and Zinc Fractionation in Apple Orchard Soil in the Village of Bukevje (Croatia) Using the Revised Four-Step BCR Extraction Procedure

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The aim of this study was to establish the fractionation of copper and zinc in a small apple orchard using the revised (four-step) Bureau Communautaire de Reference (BCR) sequential extraction procedure and assess their potential mobility in soil. Soil samples were collected at the depth of 10 cm to 25 cm, sixteen from the orchard and five control samples from a meadow located some 200 m away from the orchard. As the distribution of trace-element concentrations in the control samples was normal, they were used for comparison as background levels. We also determined soil mineralogical composition, carbonate content, soil pH, cation exchange capacity, and soil organic matter. The extraction yields of Cu and Zn from the control soil were lower than from the orchard soil (25 % vs. 34 % and 47 % vs. 52 %, respectively), which pointed to natural processes behind metal bonding in the control soil and greater influence of man-made activities in the orchard soil. Compared to control, the orchard soil had significantly higher concentrations of total Cu (P=0.0009), possibly due to the application of Cu-based fungicides. This assumption was further supported by greater speciation variability of Cu than of zinc, which points to different origins of the two, Cu from pesticides and Zn from the parent bedrock. Copper levels significantly better (P=0.01) correlated with the oxidisable fraction of the orchard soil than of control soil. Residual and organically bound copper and zinc constituted the most important fractions in the studied soils. However, the use of Cu-based fungicides in the apple orchard did not impose environmental and health risk from Cu exposure.

1. Merry RH, Tiller KG, Alston AM. Accumulation of copper, lead and arsenic in some australian orchard soils. Aust J Soil Res 1983;21:549-61. doi: 10.1071/SR9830549

2. Romić M, Romić D. Heavy metals distribution in agricultural topsoils in urban area. Environ Geol 2003;43:795-05. doi: 10.1007/s00254-002-0694-9

3. Xiaorong W, Mingde H, Mingan S. Copper fertilizer effects on copper distribution and vertical transport in soils. Geoderma 2007;138:213-20. doi: 10.1016/j. geoderma.2006.11.012

4. Adriano DC. Trace Elements in Terrestrial Environments. Biogeochemistry, Bioavailability, and Risks of Metals. New York: Springer Verlag; 2001.

5. Merrington G, Rogers SL, Van Zwieten L. The potential impact of long-term copper fungicide usage on soil microbial biomass and microbial activity in an avocado orchard. Aust J Soil Res 2002;40:749-59. doi: 10.1071/SR01084

6. Vogeler I, Vachey A, Deurer M, Bolan N. Impact of plants on the microbial activity in soils with high and low levels of copper. Eur J Soil Biol 2008;44:92-100. doi: 10.1016/j. ejsobi.2007.12.001

7. Wang Q-Y, Zhou D-M, Cang L. Microbial and enzyme properties of apple orchard soil as affected by long-term application of copper fungicide. Soil Biol Biochem 2009;41:1504-9. doi: 10.1016/j.soilbio.2009.04.010

8. Komarek M, Čadkova E, Chrastny V, Bordas F, Bollinger J-C. Contamination of vineyard soils with fungicides: A review of environmental and toxicological aspects. Environ Int 2010;36:138-51. doi: 10.1016/j.envint.2009.10.005

9. Oreščanin V, Katunar A, Kutle A, Valković V. Heavy metals in soil, grape, and wine. J Trace Microprobe Tech 2003;21:171-80.

10. Pietrzak U, McPhail DC. Copper accumulation, distribution and fractionation in vineyard soils of Victoria, Australia. Geoderma 2004;122:151-66. doi: 10.1016/j. geoderma.2004.01.005

11. Moćko A, Wacławek W. Three-step extraction procedure for determination of heavy metals availability to vegetables. Anal Bioanal Chem 2004;380:813-7. PMID: 15517201

12. Menzies NW, Donn MJ, Kopittke PM. Evaluation of extractants for estimation of the phytoavailable trace metals in soils. Environ Pollut 2007;145:121-30. doi: 10.1016/j. envpol.2006.03.021

13. Nogueirol RC, Alleoni LRF, Nachtigall GR, Wellington de Melo G. Sequential extraction and availability of copper in Cu fungicide-amended vineyard soils from Southern Brazil. J Hazard Mater 2010;181:931-7. doi: 10.1016/j. jhazmat.2010.05.102

14. Fan J, He Z, Ma LQ, Stoffella PJ. Accumulation and availability of copper in citrus grove soils as affected by fungicide application. J Soil Sediment 2011;11:639-48. doi: 10.1007/s11368-011-0349-0

15. Quevauviller Ph. SM&T activities in support of standardisation of operationally-defi ned extraction procedures for soil and sediment analysis. In: Quevauviller Ph, editor. Methodologies in soil and sediment fractionation studies. Cambridge: The Royal Society of Chemistry; 2002. p. 1-9.

16. Rao CRM, Sahuquillo A, Lopez-Sanchez JF. A review of the different methods applied in environmental geochemistry for single and sequential extraction of trace elements in soils and related metarials. Water Air Soil Pollut 2008;189:291-33. doi: 10.1007/s11270-007-9564-0

17. Bacon JR, Davidson cm. Is there a future for sequential chemical extraction? Analyst 2008;133:25-46. doi: 10.1039/ b711896a

18. Rauret G, Lopez-Sanchez JF, Sahuquillo A, Rubio R, Davidson C, Ure A, Quevauviller Ph. Improvement of the BCR three step sequential extraction procedure prior to certifi cation of new sediment and soil reference materials. J Environ Monitor 1999;1:57-61. doi: 10.1039/A807854H

19. Lopez-Sanchez JF, Sahuquillo A, Rauret G, Lachica M, Barahona E, Gomez A, Ure AM, Muntau H, Quevauviller Ph. Extraction procedures for soil analysis. In: Quevauviller Ph, editor. Methodologies in soil and sediment fractionation studies. Cambridge: The Royal Society of Chemistry; 2002. p. 28-65.

20. Šikić K, Basch O, Šimunić A. Osnovna geološka karta SFRJ, 1:100000. Tumač za list Zagreb [Basic geological map of Yugoslavia, 1:100000. Geology of Zagreb Sheet, in Croatian] Beograd: Savezni geološki zavod Beograd i Institut za geološka istraživanja Zagreb; 1979.

21. Pavlović G, Prohić E, Tibljaš D. Statistical assessment of geochemical pattern in overbank sediments of the river Sava, Croatia. Environ Geol 2004;46:132-43. doi: 10.1007/s00254-004-1019-y

22. Van Olphen H, Fripiat JJ. Data Handbook for Clay Materials and Other Non-Metallic Minerals. Oxford: Pergamon Press; 1979.

23. Zeiner M, Juranović Cindrić I, Lovrenčić Mikelić I, Medunić G, Kampić Š, Tomašić N, Stingeder G. The determination of the extractability of selected elements from agricultural soil. Environ Monit Assess 2013;185:223-9. doi:10.1007/ s10661-012-2546-8.

24. Oreščanin V, Lovrenčić Mikelić I, Mikelić L, Lulić S. Applicability of MiniPal 4 compact EDXRF spectrometer for soil and sediment analysis. X-Ray Spectrom 2008;37:508-11. doi: 10.1002/xrs.1079

25. Helling B, Reinecke SA, Reinecke AJ. Effects of the fungicide copper oxychloride on the growth and reproduction of Eisenia fetida (Oligochaeta). Ecotoxicol Environ Saf 2000;46:108-16. PMID: 10806001

26. Roussos PA, Gasparatos D. Apple tree growth and overall fruit quality under organic and conventional orchard management. Scientia Horticulturae 2009;123:247-52. doi: 10.1016/j.scienta.2009.09.011

27. Matschullat J, Ottenstein R, Reimann C. Geochemical background - can we calculate it? Environ Geol 2000;39:990-1000. doi: 10.1007/s002549900084

28. Salomons W, Forstner U. Metals in the Hydrocycle. Berlin- Heidelberg: Springer-Verlag; 1984.

29. Pravilnik o zaštiti poljoprivrednog zemljišta od onečišćenja [Regulations on the protection of cultivated land from contamination, in Croatian]. Narodne novine 032/2010.

30. Halamić J, Galović L, Šparica M. Heavy metal (As, Cd, Cu, Hg, Pb and Zn) distribution in topsoil developed on alluvial sediments of the Drava and Sava Rivers in NW Croatia. Geol Croat 2003;56:215-32.

31. Abollino O, Giacomino A, Malandrino M, Mentasti E, Aceto M, Barberis R. Assessment of metal availability in a contaminated soil by sequential extraction. Water Air Soil Pollut 2006;137:315-38. doi: 10.1007/s11270-005-9006-9

32. Arias M, Lopez E, Soto B. Copper distribution and fractionation in aggregate fractions from vineyard soils: comparison with zinc. Agrochimica 2005;49:60-9.

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