Macroporosity affects water movement and pore water sampling in peat soils

The measurement of chemical concentration profiles in pore water is a starting point for the analysis of biogeochemical processes in waterlogged peat soils. Concentration patterns may be obscured when macroporosity causes preferential flow in column experiments and when pore water is retrieved from the peat by suction. To investigate the magnitude of such effects, we used LiBr as a tracer in peat columns at outflow rates of 0, 2-3, and 8 nun d(-1). The results were compared with modeled advective-diffusive migration rates. Twenty to fifty percent of the tracer was recovered from depths at which the tracer would have been absent if preferential flow had not occurred. At the high flow rate, the preferential flow was stronger, and the retrieved pore-water was probably in disequilibrium with the matrix. When pore water was retrieved by suction, linear concentration gradients decreased by about 30% through the recovery of water from different depths, and the quality of fitted linear gradients decreased from R-2 = 0.99 to R-2 = 0.82. When flow rates are low (<3 mm d(-1)) and pore water concentration values from samplers are aggregated or regressed, the obtained concentration profiles seem to represent the vertical distribution of chemical species reasonably well. The use and interpretation of pore water profiles in peat soils is problematic if flow rates are higher and if vertical gradients are based on individual or few data points that have been obtained by suction samplers.