Changes in soil chemistry accompanying acidification over more than 100 years under woodland and grass at Rothamsted Experimental Station, UK

Summary We have examined the effect that acid deposition and other sources of acidity have had over the last 110–140 years on soil under woodland (Broadbalk and Geescroft Wildernesses) and grassland (Park Grass) comprising some of the Classical Experiments at Rothamsted Experimental Station. Changes in soil chemistry have been followed by analysing some of the unique archive of stored samples for pH, water‐soluble and exchangeable base cations, aluminium, iron and manganese, exchangeable acidity, cation exchange capacity (CEC) and soluble anions. Proton balances and historical data show the importance of acid deposition to acidification and concomitant changes in the chemistry of the soil. The pH of the surface soil of Geescroft Wilderness has fallen from 6.2 to 3.8 since 1883. The decrease in the pH of the unlimed, unfertilized plot on Park Grass was less over a similar period (from pH 5.2 to 4.2), illustrating the significant effect of the woodland canopy on the interception of acidifying pollutants. The effect of increasing acidity on the soil chemistry of Geescroft Wilderness is seen in its decreasing base saturation and CEC, with base cations moving down the soil profile. Clay minerals are being irreversibly weathered, and Mn and Al progressively mobilized, so that today Al occupies 70% of the exchange complex in the surface soil. Even with present reductions in sulphur deposition critical loads for sulphur, nitrogen and acidity are still exceeded. Such semi‐natural ecosystems are unsustainable under the current climate of pollution.