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TECHNICAL REPORTS

Heavy Metals in the Environment

Spatiotemporal Evolution of Soil pH and Zinc after the Aznalcóllar Mine Spill

^a CIFA "Las Torres-Tomejil", I.F.A.P.A. -C.I.C.E. (Junta de Andalucía), Ctra. Sevilla-Cazalla, km 12,2, 41200 Alcalá del Río, Sevilla, Spain
^b CIFA "Alameda del Obispo", I.F.A.P.A.-C.I.C.E. (Junta de Andalucía), 14080 Córdoba, Spain;
^c Dep. of Agronomy, University of Córdoba,Avda. Menéndez Pidal, s/n, 14080 Córdoba, Spain

^* Corresponding author (karl.vanderlinden.ext{at}juntadeandalucia.es)

Received for publication October 18, 2004. The residual pollution after the Aznalcóllar (southwestern Spain) pyrite mine spill is still a threat due to the continuing oxidation of sulfuric minerals. The objective of this paper was to analyze the combined effect of pyrite oxidation, sugar beet foam applications, and meteorological conditions on the spatiotemporal evolution of the pH and EDTA-extractable Zn concentration, using non co-located data from 11 sampling dates between June 1999 and March 2002. Median pH values ranged from 4.4 at the beginning of the monitoring period to 7.6 at the end, although values near 2.5 were observed throughout the entire period, despite of two sugar beet foam (SBF) applications. Zinc distributions were positively skewed and median concentrations ranged from 17 to 94 mg kg^–1. The inverse relationship between pH and Zn became weaker toward the end of the monitoring period as a consequence of the precipitation and posterior dissolution of newly formed minerals from the reaction products of the pyrite oxidation. Normal score maps showed that after the SBF applications only 0.5% of the monitored area was below the pH = 4 threshold, while on other dates up to one-third of the area remained below this value. The better performance of the second SBF application could be explained in terms of pyrite oxidation pathways and environmental conditions. From this analysis, with data obtained under uncontrolled field conditions, it is concluded that SBF should be applied before or during the wet and cold season to alleviate acidification, caused by the oxidation of pyrite or other sulfuric minerals.

Abbreviations: MAE, mean absolute error • ME, mean error • ns, normal score • SBF, sugar beet foam