The use of trees for biomonitoring of mercury (Hg) and other atmospheric pollutants is of increasing importance today. Leaves from different species have been the most widely used plant organ for this purpose, but only pine bark, and not leaves, was used to monitor Hg pollution. In Almadén (South Central Spain), the largest cinnabar (HgS) deposits in the world have been mined for over 2000 years to obtain metallic Hg and this activity has caused the widespread dispersion of this toxic element in the local environment. A strip of pine trees, 2750 m in length, adjacent and to the South of the mining town has been studied in order to evaluate pine tree needles as monitors for Hg contamination in this heavily polluted area. The study involved the collection of pine tree leaves from several discrete sites along the strip, as well as samples from other nearby locations, together with soil samples and monitoring of atmospheric Hg in the area during both the day and night. Leaves and soils were analyzed for total Hg concentration by means of atomic absorption spectrometry; the leachable fraction of soil Hg was also analyzed by the CV-AFS technique. The results indicate that soils from the investigated area were not directly affected by mining related pollution, with low total Hg levels (3-280 mg kg-1) found in comparison with the nearby Almadén metallurgical precinct and very low leachable Hg contents (0.27-59.65 mg kg-1) were found. Moreover, pine tree needles have a low uptake capacity, with lower THg levels (0.03-6.68 mg kg-1) when compared to those of olive trees in Almadén. However, pine needles do show significant variability with regard to the distance from the source. Gaseous Hg exhibits a similar pattern, with higher levels close to the source, especially during night time (225 ng m-3). A multiple linear regression analysis (MLRA) revealed that gaseous Hg in the nocturnal period is the prime factor that influences the amount of Hg uptake by pine tree needles. This finding makes pine needles a promising candidate to biomonitor gaseous Hg on a local or regional scale worldwide. Almadén pine tree needles have been exposed to a number of different Hg sources, including the primary one, namely the old mine dump, and secondary sources such as polluted roads or illegal urban residual waste. The secondary sources cause some minor discrepancies in the model established by the MRLA. The biomonitoring capacity of pine needles needs to be evaluated in areas far from the source. The process involved in gaseous Hg uptake by pine needles appears more likely to involve sorption in the external part of the needle than uptake through stomas, thus making this process strongly dependent on high atmospheric Hg concentrations.
Keywords: Almadén; Mercury; Pine tree leaves; Plant uptake; Total gaseous mercury.