Assessment of mixing between shallow and thermal waters using geochemical and environmental isotope tracers (N Portugal): a review and reinterpretation

Caldas de Moledo thermal (27–46 °C) spring and borehole waters issue in the region of the famous Port Wine vineyards, in the Douro River valley (Northern Portugal). The most abundant lithotypes are lower Cambrian metasedimentary rocks, Variscan granitoids and aplite-pegmatitic veins. The thermal waters are characterised by pH ≈ 9.0, TDS ranging from 200 to 350 mg/L, and belong to the HCO₃–Na facies indicating that the reservoir rock should be mainly granite. Since the local Spa is strongly dependent on water quality, the effects of mixing between local shallow cold groundwaters and deep thermal waters have been properly investigated. In the SO₄ ²⁻ (mg/L) versus δ¹⁸O (‰ vs. V-SMOW) diagram we can observe that some of the thermal springs show evidences of mixing (higher SO₄ ²⁻ concentrations) with local meteoric waters infiltrated at lower altitude sites (enriched δ¹⁸O signatures), showing the “altitude effect” in the isotopic composition of the recharge waters. Similar trends can be found in the K⁺, NO₃ ⁻, Ca²⁺ and Na⁺ (mg/L) versus δ¹⁸O (‰ vs. V-SMOW) diagrams. It should be stated that SO₄ ²⁻, K⁺ and Ca²⁺ are present in the fertilizers and fungicides used in the vineyards in the northern part of the country. Up to now, the thermal waters from boreholes used in the local Spa do not show evidences of mixing with shallow groundwaters contaminated with agrochemicals. The results obtained so far indicate that in the near future, special attention should be put on the possible occurrence of diffuse agricultural contamination (related to the Port Wine vineyards) in the thermal spring waters.