Exploring the long-term response of undisturbed Mediterranean catchments to changes in atmospheric inputs through time series analysis

• Mediterranean montane catchments respond quickly to atmospheric changes.
• Short water residence times are related to topography and seasonality.
• Despite high N loads, the forests strongly retain this nutrient.

The aim of this study was to gain insights on the potential hydrological and biogeochemical mechanisms controlling the response of two nested Mediterranean catchments to long-term changes in atmospheric inorganic nitrogen and sulphate deposition. One catchment was steep and fully forested (TM9, 5.9 ha) and the other one had gentler slopes and heathlands in the upper part while side slopes were steep and forested (TM0, 205 ha). Both catchments were highly responsive to the 45% decline in sulphate concentration measured in atmospheric deposition during the 1980s and 1990s, with stream concentrations decreasing by 1.4 to 3.4 μeq L− 1 y− 1. Long-term changes in inorganic nitrogen in both, atmospheric deposition and stream water were small compared to sulphate. The quick response to changes in atmospheric inputs could be explained by the small residence time of water (4–5 months) in these catchments (inferred from chloride time series variance analysis), which was attributed to steep slopes and the role of macropore flow bypassing the soil matrix during wet periods. The estimated residence time for sulphate (1.5–3 months) was substantially lower than for chloride suggesting unaccounted sources of sulphate (i.e., dry deposition, or depletion of soil adsorbed sulphate). In both catchments, inorganic nitrogen concentration in stream water was strongly damped compared to precipitation and its residence time was of the order of decades, indicating that this essential nutrient was strongly retained in these catchments. Inorganic nitrogen concentration tended to be higher at TM0 than at TM9 which was attributed to the presence of nitrogen fixing species in the heathlands. Our results indicate that these Mediterranean catchments react rapidly to environmental changes, which make them especially vulnerable to changes in atmospheric deposition.