Many plants are exposed to prolonged episodes of anthropogenic acid pr
ecipitation with pH values of 4 or less, but there is little evidence
of widespread direct damage to the plant cells. Acids appear to permea
te leaf cuticle via charged pores, which act as a fixed buffer that de
lays but does not stop acid movement. We investigated the effect of ca
tions on the movement of protons through astomatous isolated leaf cuti
cles of pear (Pyrus communis L.) and rough lemon (Citrus limon [L.] Bu
rm. fils cv Ponderosa). Chloride salt solutions of Na, K, Ca, Cd, Mg,
Gd, or Y in a diffusion apparatus were applied to the morphological in
ner surface of the cuticle, while the outer surface faced a large volu
me of pH 3 or 4 sulfuric acid. Effective permeability was calculated f
rom the change in the pH of the inner solution as measured with a pH m
icroelectrode. Monovalent cations caused either no change (pear) or pr
omotion (rough lemon) of proton movement. Divalent cations reduced pro
ton movement in a concentration-dependent manner (both species), where
as trivalent cations (rough lemon only) caused the effective permeabil
ity to decrease to near zero. Inhibition by 10 mm CaCl2 was reversed w
ith water. The effects of these cations on the permeability of cuticle
s to protons was used to elucidate mechanisms by which cations can pro
tect leaves from acid precipitation in nature.