Deriving soil critical limits for Cu, Zn, Cd, and Pb: a method based on free ion concentrations.

We present a method to calculate critical limits of cationic heavy metals accounting for variations in soil chemistry. We assume the free metal ion concentration (Mfree) to be the most appropriate indicator of toxicity, combined with a protective effect of soil cations (e.g., H+, Ca2+). Because soil metal cations tend to covary with pH, the concentration of Mfree exerting a given level of toxic effect (Mfree,toxic) can be expressed as a function of pH alone. We use linear regression equations to derive Mfree,toxic in toxicity experiments from soil pH, organic matter content, and endpoint soil metal. Chronic toxicity data from the literature, for plants, invertebrates, microbial processes, and fungi are interpreted in terms of an average log Mfree,toxic together with distributions of species sensitivity. This leads to critical limit functions to protect 95% of species, of the form log Mfree,CRIT = (pH + gamma. Appreciable effects of soil pH upon log Mfree,CRIT are found, with alpha = -1.21 (Cu), -0.34 (Zn), -0.43 (Cd), and -0.83 (Pb). Critical limit functions in terms of the geochemically active soil metal (Msoil,CRIT), that pool of metal which controls the free ion concentration, have also been derived, with soil pH and organic matter content as variables. The pH effect on Msoil,CRIT is relatively small, with slopes of 0.05 (Cu), 0.19 (Zn), 0.16 (Cd), and 0.20 (Pb), since the effect of pH on Mfree,CRIT is countered by the variation of Mfree with pH.