Abstract

SummaryNegative correlations between soil pH and cation exchange capacity (CEC) or base saturation in soils of the northeastern USA and Scandinavia have raised questions regarding the nature of cation exchange in acid forest soils. Using data from three small‐catchment studies and an extensive regional survey of soils in the northeastern USA, I examined relationships among total carbon, effective CEC (CECe), soil pHs (in 0.01 m CaCl2) and base saturation. Organic matter is the predominant source of soil surface charge in these coarse‐grained, glacially derived soils. Correlation coefficients (r) between total carbon and CECe ranged from 0.43 to 0.74 in organic horizons and from 0.46 to 0.83 in mineral horizons. In all cases, the intercepts of functional relations between CECe and total C were near zero. In O horizons, the CECe per unit mass of organic carbon (CECe:C) was positively correlated with pHs in three of the four data sets, consistent with the weak‐acid behaviour of the organic matter. However, CECe:C was negatively correlated with pHs in mineral soils in two data sets, and uncorrelated in the other two. The CECe in mineral soils represents the portion of total CEC not occupied by organically bound Al. The negative correlations between CECe:C and pHs can therefore be explained by increased Al binding at higher pHs. Aluminium behaves like a base cation in these soils. When Al was considered a base cation, the relation between base saturation and pHs could be effectively modelled by the extended Henderson–Hasselbalch equation. When modelled without Al as a base cation, however, there were no consistent relationships between pHs and base saturation across sites or soil horizons. Because of the non‐acidic behaviour of Al, it is difficult to predict the effect of ongoing reductions in acid deposition on the base status of soils in the northeastern USA.

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