The effects of acidification on the soil chemistry and plant availability of the metals Pb, Cd, Zn, Cu, Mn and Ni in new and archived soil and plant samples taken from the >100-year-old experiments on natural woodland regeneration (Geescroft and Broadbalk Wildernesses) and a hay meadow (Park Grass) at Rothamsted Experimental Station are examined. We measured a significant input of metals from atmospheric deposition, enhanced under woodland by 33% (Ni) to 259% (Zn); Pb deposition was greatly influenced by vehicle emissions and the introduction of Pb in petrol. The build up of metals by long-term deposition was influenced by acidification, mobilization and leaching, but leaching, generally, only occurred in soils at pH<4. Mn and Cd were most sensitive to soil acidity with effective mobilization occurring at pH 6.0–5.5 (0.01 M CaCl2), followed by Zn, Ni and Cu at pH 5.5–5.0. Pb was not mobilized until pH<4.5. Acidification to pH 4 mobilized 60–90% of total soil Cd but this was adsorbed onto ion exchange surfaces and/or complexed with soil organic matter. This buffering effect of ion exchange surfaces and organic matter in soils down to pH 4 was generally reflected by all the metals investigated. For grassland the maximum accumulation of metals in herbage generally corresponded to a soil pH of 4.0. For woodland the concentration of Pb, Mn and Cd in oak saplings (Quercus robur) was 3-, 4- and 6-fold larger at pH 4 than at pH 7. Mature Oak trees contained 10 times more Mn, 4 times more Ni and 3 times more Cd in their leaves at pH 4 than at pH 7. At pH values <4.0 on grassland the metal content in herbage declined. Only for Mn and Zn did this reflect a decline in the plant available soil content attributed to long-term acid weathering and leaching. The chief cause was a long-term decline in plant species richness and the increased dominance of two acid-tolerant, metal-excluder species
