Changes in atmospheric deposition and streamwater chemistry over 25 years in undisturbed catchments in a Mediterranean mountain environment.

Surface water chemistry has changed in response to reduced atmospheric deposition of sulphur and acidity in many regions of Europe and North America. Most of these studies come from acidic or low-alkalinity surface waters under high acidic deposition. Mediterranean climates offer a different biogeochemical context, characterised by streamwaters of higher alkalinity and low acid inputs. In this paper, we use surveys of streamwater chemistry conducted in 1981-1984 and again in 2007 in the Montseny natural park (NE Spain) to test whether streamwaters of these well-buffered catchments respond to changes in atmospheric deposition, which has declined for S during the last decades in NE Spain while remaining about stable for nitrogen. The 23 sampled streams drained heathland, beech forests and evergreen oak forests in relatively undisturbed small catchments underlain by silicate bedrock. Bulk deposition of sulphate at Montseny decreased by 54% while nitrate bulk deposition increased (non-significantly) by 30% in this period. Total N deposition is estimated in the range 15-30 kg N ha(-1) y(-1) for NE Spain. This is well above threshold values (e.g. 10 kg N ha(-1) y(-1)) reported as starting nitrogen saturation symptoms in forest ecosystems in Europe. Baseflow sulphate concentrations decreased on average by 47 μeq L(-1) or 29% of early 1980s concentrations. Baseflow mean nitrate concentrations increased significantly but only from 5.5 to 8.9 μeq L(-1). Thus, despite decades of high N deposition, these ecosystems appear to be still far from N saturation. Baseflow alkalinity and base cation concentrations increased substantially, probably a combined result of decreased S deposition, enhanced silicate weathering under current higher temperatures, reduced plant cation uptake as vegetation matures, and slightly drier conditions in the survey of 2007. Overall, these well-buffered catchments have shown sizable changes in baseflow chemistry in response to changed atmospheric deposition and other environmental changes.