A 125 year record of fluvial calcium flux from a temperate catchment: Interplay of climate, land-use change and atmospheric deposition

This paper analyses the world's longest fluvial record of water hardness and calcium (Ca) concentration. We used records of permanent and temporary hardness and river flow for the UK's River Thames (catchment area 9998 km(2)) to estimate annual Ca flux from the river since 1883. The Thames catchment has a mix of agricultural and urban land use; it is dominated by mineral soils with groundwater contributing around 60% of river flow. Since the late 1800s, the catchment has undergone widespread urbanisation and climate warming, but has also been subjected to large-scale land-use change, especially during World War II and agricultural intensification in the 1960s. Here, we use a range of time series methods to explore the relative importance of these drivers in determining catchment-scale biogeochemical response. Ca concentrations in the Thames rose to a peak in the late 1980s (106 mg Ca/l).

The flux of Ca peaked in 1916 at 385 ktonnes Ca/yr; the minimum was in 1888 at 34 ktonnes Ca/yr. For both the annual average Ca concentration and the annual flux of Ca, there were significant increases with time; a significant positive memory effect relative to the previous year; and significant correlation with annual water yield. No significant correlation was found with either temperature or land use, but sulphate deposition was found to be significant. It was also possible, for a shorter time series, to show a significant relationship with inorganic nitrogen inputs into the catchment. We suggest that ionic inputs did not acidify the mineral soils of the catchment but did cause the leaching of metals, so we conclude that the decline in river Ca concentrations is caused by the decline in both S and N inputs. (C) 2012 Elsevier B.V. All rights reserved.