Geochemistry and water dynamics: II. Trace metals and Pb–Sr isotopes as tracers of water movements and erosion processes

A dynamic scheme for water movements over a flood in a small watershed was proposed in a previous paper [Ben Othman, D., Luck, J.M., Tournoud, M.G., 1997. Geochemistry and water dynamics: application to short-time scale flood phenomena in a small Mediterranean catchment: I. Alkalis, alkali-earths and Sr isotopes. Chem. Geol. [140] 9–28] based on major, alkali–alkali earth trace elements and Sr isotopes. In the present paper, metal contents and Pb isotope data are reported for the same samples, and compared to natural and anthropogenic local sources analysed for this purpose. Water treatment plants have stable but show relatively large variations, presumably related to yet unidentified (industrial?) Pb sources. Some Cu–Zn-rich chemicals used extensively on vineyards have unradiogenic around 17.7. Local rains sampled over two years show roughly similar low values. Pb from rocks is variable and more radiogenic (≈18.8–22.8). Except for the first hours, trace element concentrations in the dissolved load are similar to or slightly higher than those observed over the year, and similar to other moderately anthropogenic areas [Shiller, A.M., Boyle, E.A., 1987. Variability of dissolved trace metals in the Mississippi river. Geochim. Cosmochim. Acta [51] 3273–3277] for [Pb] (0.05–0.45 nM), [Zn] (10–75 nM) and [Cd] (0.03–0.18 nM). Dissolved [U] and [Co] show simple variations correlated to carbonate, related to local natural sources. Most trace elements in the particulate load are strongly correlated. Lead isotopes in the dissolved and particulate loads show ranges over the flood, again similar to those observed over the year (≈17.9–18.3), implying the same sources. The very good alignments observed in and vs. diagrams, especially for the particulate, are interpreted as mixing phenomena. Generally Pb isotopic signature of the dissolved load is less radiogenic than the particulate, indicating differences in sources or proportions and absence of isotopic equilibration with respect to the time of transfer. Pb isotopes shift regularly with time away from the road runoff endmember towards more radiogenic values. The strong negative correlation between Pb isotopes in the particulate load and Sr isotopes in the dissolved load, observed for the first time in a small watershed, probably reflects the local coupling between mechanical and chemical erosion, respectively.