The terrestrial export of dissolved organic matter (DOM) is associated with climate, vegetation and land use, and thus is under the influence of climatic variability and human interference with terrestrial ecosystems, their soils and hydrological cycles. The present study provides an assessment of spatial variation of DOM concentrations and export, and interactions between DOM, catchment characteristics, land use and climatic factors in boreal catchments. The influence of catchment characteristics, land use and climatic drivers on the concentrations and export of total organic carbon (TOC), total organic nitrogen (TON) and dissolved organic phosphorus (DOP) was estimated using stream water quality, forest inventory and climatic data from 42 Finnish pristine forested headwater catchments, and water quality monitoring, GIS land use, forest inventory and climatic data from the 36 main Finnish rivers (and their sub-catchments) flowing to the Baltic Sea. Moreover, the export of DOM in relation to land use along a European climatic gradient was studied using river water quality and land use data from four European areas. Additionally, the role of organic and minerogenic acidity in controlling pH levels in Finnish rivers and pristine streams was studied by measuring organic anion, sulphate (SO4) and base cation (Ca, Mg, K and Na) concentrations. In all study catchments, TOC was a major fraction of DOM, with much lower proportions of TON and DOP. Moreover, most of TOC and TON was in a dissolved form. The correlation between TOC and TON concentrations was strong and TOC concentrations explained 78% of the variation in TON concentrations in pristine headwater streams. In a subgroup of 20 headwater catchments with similar climatic conditions and low N deposition in eastern Finland, the proportion of peatlands in the catchment and the proportion of Norway spruce (Picea abies Karsten) of the tree stand had the strongest correlation with the TOC and TON concentrations and export. In Finnish river basins, TOC export increased with the increasing proportion of peatland in the catchment, whereas TON export increased with increasing extent of agricultural land. The highest DOP concentrations and export were recorded in river basins with a high extent of agricultural land and urban areas, reflecting the influence of human impact on DOP loads. However, the most important predictor for TOC, TON and DOP export in Finnish rivers was the proportion of upstream lakes in the catchment. The higher the upstream lake percentage, the lower the export, indicating organic matter retention in lakes. Molar TOC:TON ratio decreased from headwater catchments covered by forests and peatlands to the large river basins with mixed land use, emphasising the effect of the land use gradient on the stoichiometry of rivers. This study also demonstrated that the land use of the catchments is related to both organic and minerogenic acidity in rivers and pristine headwater streams. Organic anion dominated in rivers and streams situated in northern Finland, reflecting the higher extent of peatlands in these areas, whereas SO4 dominated in southern Finland and on western coastal areas, where the extent of fertile areas, agricultural land, urban areas, acid sulphate soils, and sulphate deposition is highest. High TOC concentrations decreased pH values in the stream and river water, whereas no correlation between SO4 concentrations and pH was observed. This underlines the importance of organic acids in controlling pH levels in Finnish pristine headwater streams and main rivers. High SO4 concentrations were associated with high base cation concentrations and fertile areas, which buffered the effects of SO4 on pH.

Agricultute as a contributor to water pollution in Southwestern Finland.

Gypsum (CaSO4∙2H2O) amendment is a promising way of decreasing the phosphorus loading of arable lands, and thus preventing aquatic eutrophication. However, in freshwaters with low sulfate concentrations, gypsum-released sulfate may pose a threat to the biota. To assess such risks, we performed a series of sulfate toxicity tests in the laboratory and conducted field surveys. These field surveys were associated with a large-scale pilot exercise involving spreading gypsum on agricultural fields covering 18% of the Savijoki River (Finland) catchment area. The gypsum amendment in such fields resulted in approximately a four-fold increase in the mean sulfate concentration for a 2-month period, and a transient, early peak reaching approximately 220 mg/L. The sulfate concentration gradually decreased almost to the pregypsum level after 3 years. Laboratory experiments with Unio crassus mussels and gypsum-spiked river water showed significant effects on foot movement activity, which was more intense with the highest sulfate concentration (1100 mg/L) than with the control. Survival of the glochidia after 24 and 48 h of exposure was not significantly affected by sulfate concentrations up to 1000 mg/L, nor was the length growth of the moss Fontinalis antipyretica affected. The field studies on benthic algal biomass accrual, mussel and fish density, and Salmo trutta embryo survival did not show gypsum amendment effects. Gypsum treatment did not raise the sulfate concentrations even to a level just close to critical for the biota studied. However, because the effects of sulfate are dependent on both the spatial and the temporal contexts, we advocate water quality and biota monitoring with proper temporal and spatial control in rivers within gypsum treatment areas.