Metal speciation in rivers affected by enhanced soil erosion and acidity

Dissolved (<1. kDa), colloidal (1. kDa-0.45. μm) and particulate (>0.45. μm) size fractions of 30 elements were determined for four rivers (Sirppujoki, Laajoki, Mynäjoki and Paimionjoki), including 12 low-order inflow streams, largely affected by soil erosion and acidity in SW Finland. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these rivers. Total metal concentrations were relatively high but most of the elements occurred mainly in a colloidal or particulate form and even elements expected to be very soluble occurred to a large extent in colloidal form. According to geochemical modelling these patterns could be explained by in-stream metal complexation/adsorption only to a limited extent. Instead there were strong indications that the high metal concentrations and dominant solid fractions were largely caused by erosion of metal bearing phyllosilicates. A strong influence of acid sulphate (AS) soils, known to exist in the catchment, could be clearly distinguished in Sirppujoki river as it had very high concentrations of dissolved metals, while in the two nearby rivers (Laajoki and Mynäjoki) the influence of AS soils was largely masked by eroded phyllosilicates. In Paimionjoki river the colloidal and particulate fractions dominated very strongly, indicating that total metal concentrations are almost solely controlled by erosion of phyllosilicates. Consequently, rivers draining clay plains sensitive to erosion, like those in SW Finland, have generally high " background" metal concentrations due to erosion of relatively non-toxic colloidal/particulate phyllosilicates. Thus, relying on only semi-dissolved (<0.45. μm) concentrations obtained in routine monitoring and/or speciation modelling can lead to a great overestimation of the water toxicity in this environment.