Long-term rise in riverine dissolved organic carbon concentration is predicted by electrolyte solubility theory.

The riverine dissolved organic carbon (DOC) flux is of similar magnitude to the terrestrial sink for atmospheric CO2, but the factors controlling it remain poorly determined and are largely absent from Earth system models (ESMs). Here, we show, for a range of European headwater catchments, that electrolyte solubility theory explains how declining precipitation ionic strength (IS) has increased the dissolution of thermally moderated pools of soluble soil organic matter (OM), while hydrological conditions govern the proportion of this OM entering the aquatic system. Solubility will continue to rise exponentially with declining IS until pollutant ion deposition fully flattens out under clean air policies. Future DOC export will increasingly depend on rates of warming and any directional changes to the intensity and seasonality of precipitation and marine ion deposition. Our findings provide a firm foundation for incorporating the processes dominating change in this component of the global carbon cycle in ESMs.

Dynamic Modeling and Target Loads of Sulfur and Nitrogen for Surface Waters in Finland, Norway, Sweden, and the United Kingdom.

The target load concept is an extension of the critical load concept of air pollution inputs to ecosystems. The advantage of target loads over critical loads is that one can define the deposition and the point in time (target year) when the critical (chemical) limit is no longer violated. This information on the timing of recovery requires dynamic modeling. Using a well-documented dynamic model, target loads for acidic deposition were determined for 848 surface waters across Finland, Norway, Sweden, and the United Kingdom for the target year 2050. In the majority of sites ( n = 675), the critical ANC-limit was predicted to be achieved by 2050; however, for 127 sites, target loads were determined. In addition, 46 sites were infeasible, i.e., even a reduction of anthropogenic deposition to zero would not achieve the limit by 2050. The average maximum target load for sulfur was 38% lower than the respective critical load across the study lakes ( n = 127). Target loads on a large regional scale can inform effects-based emission reduction policies; the current assessment suggests that reductions beyond the Gothenburg Protocol are required to ensure surface water recovery from acidification by 2050.

Abating N in Nordic agriculture - Policy, measures and way forward.

During the past twenty years, the Nordic countries (Denmark, Sweden, Finland and Norway) have introduced a range of measures to reduce losses of nitrogen (N) to air and to aquatic environment by leaching and runoff. However, the agricultural sector is still an important N source to the environment, and projections indicate relatively small emission reductions in the coming years. The four Nordic countries have different priorities and strategies regarding agricultural N flows and mitigation measures, and therefore they are facing different challenges and barriers. In Norway farm subsidies are used to encourage measures, but these are mainly focused on phosphorus (P). In contrast, Denmark targets N and uses control regulations to reduce losses. In Sweden and Finland, both voluntary actions combined with subsidies help to mitigate both N and P. The aim of this study was to compare the present situation pertaining to agricultural N in the Nordic countries as well as to provide recommendations for policy instruments to achieve cost effective abatement of reactive N from agriculture in the Nordic countries, and to provide guidance to other countries. To further reduce N losses from agriculture, the four countries will have to continue to take different routes. In particular, some countries will need new actions if 2020 and 2030 National Emissions Ceilings Directive (NECD) targets are to be met. Many options are possible, including voluntary action, regulation, taxation and subsidies, but the difficulty is finding the right balance between these policy options for each country. The governments in the Nordic countries should put more attention to the NECD and consult with relevant stakeholders, researchers and farmer's associations on which measures to prioritize to achieve these goals on time. It is important to pick remaining low hanging fruits through use of the most cost effective mitigation measures. We suggest that N application rate and its timing should be in accordance with the crop need and carrying capacity of environmental recipients. Also, the choice of application technology can further reduce the risk of N losses into air and waters. This may require more region-specific solutions and knowledge-based support with tailored information in combination with further targeted subsidies or regulations.

Experimental addition of nitrogen to a whole forest ecosystem at Gårdsjön, Sweden (NITREX): Nitrate leaching during 26 years of treatment.

Chronic high deposition of nitrogen (N) to forest ecosystems can lead to increased leaching of inorganic N to surface waters, enhancing acidification and eutrophication. For 26 years nitrogen has been added as ammonium nitrate (NH4NO3) at 40 kg N ha-1 yr-1 to a whole forested catchment ecosystem at Gårdsjön, Sweden, to experimentally simulate the transition from a N-limited to N-rich state. Over the first 10 years of treatment there was an increasing amount of nitrate (NO3-) and to a lesser extent ammonium (NH4+) lost in runoff, but then N leaching stabilised, and for the subsequent 16 years the fraction of N added lost in runoff remained at 9%. NO3- concentrations in runoff were low in the summer during the first years of treatment, but now are high throughout the year. High frequency sampling showed that peaks in NO3- concentrations generally occurred with high discharge, and were enhanced if high discharge coincided with occasions of N addition. Approximately 50% of the added N has gone to the soil. The added N is equivalent to 140 years of ambient N deposition. At current ambient levels of N deposition there thus appears to be no immediate risk of N saturation at this coniferous forest ecosystem, and by inference to other such N-limited forests in Scandinavia.

Consequences of intensive forest harvesting on the recovery of Swedish lakes from acidification and on critical load exceedances.

Across much of the northern hemisphere, lakes are at risk of re-acidification due to incomplete recovery from historical acidification and pressures associated with more intensive forest biomass harvesting. Critical load (CL) calculations aimed at estimating the amount of pollutants an ecosystem can receive without suffering adverse consequences are dependent on these factors. Here, we present a modelling study of the potential effects of intensified forest harvesting on re-acidification of a set of 3239 Swedish lakes based on scenarios with varying intensities of forest biomass harvest and acid deposition. There is some evidence that forestry would have caused a certain level of acidification even if deposition remained at 1860 levels. We show that all plausible harvest scenarios delay recovery due to increased rates of base cation removal. Scenario results were used to estimate critical loads for the entire population of lakes in Sweden. The forestry intensity included in critical load calculations is a political decision. After scaling calculations to the national level, it was apparent that a high but plausible forest harvest intensity would lead to an increase in the area of CL exceedances and that even after significant reductions in forest harvest intensity, there would still be areas with CL exceedances. Our results show that forest harvest intensity and regional environmental change must be carefully considered in future CL calculations.

Assessing recovery from acidification of European surface waters in the year 2010: evaluation of projections made with the MAGIC model in 1995.

In 1999 we used the MAGIC (Model of Acidification of Groundwater In Catchments) model to project acidification of acid-sensitive European surface waters in the year 2010, given implementation of the Gothenburg Protocol to the Convention on Long-Range Transboundary Air Pollution (LRTAP). A total of 202 sites in 10 regions in Europe were studied. These forecasts can now be compared with measurements for the year 2010, to give a "ground truth" evaluation of the model. The prerequisite for this test is that the actual sulfur and nitrogen deposition decreased from 1995 to 2010 by the same amount as that used to drive the model forecasts; this was largely the case for sulfur, but less so for nitrogen, and the simulated surface water [NO3(-)] reflected this difference. For most of the sites, predicted surface water recovery from acidification for the year 2010 is very close to the actual recovery observed from measured data, as recovery is predominantly driven by reductions in sulfur deposition. Overall these results show that MAGIC successfully predicts future water chemistry given known changes in acid deposition.

Assessing anthropogenic impact on boreal lakes with historical fish species distribution data and hydrogeochemical modeling.

Quantifying the effects of human activity on the natural environment is dependent on credible estimates of reference conditions to define the state of the environment before the onset of adverse human impacts. In Europe, emission controls that aimed at restoring ecological status were based on hindcasts from process-based models or paleolimnological reconstructions. For instance, 1860 is used in Europe as the target for restoration from acidification concerning biological and chemical parameters. A more practical problem is that the historical states of ecosystems and their function cannot be observed directly. Therefore, we (i) compare estimates of acidification based on long-term observations of roach (Rutilus rutilus) populations with hindcast pH from the hydrogeochemical model MAGIC; (ii) discuss policy implications and possible scope for use of long-term archival data for assessing human impacts on the natural environment and (iii) present a novel conceptual model for interpreting the importance of physico-chemical and ecological deviations from reference conditions. Of the 85 lakes studied, 78 were coherently classified by both methods. In 1980, 28 lakes were classified as acidified with the MAGIC model, however, roach was present in 14 of these. In 2010, MAGIC predicted chemical recovery in 50% of the lakes, however roach only recolonized in five lakes after 1990, showing a lag between chemical and biological recovery. Our study is the first study of its kind to use long-term archival biological data in concert with hydrogeochemical modeling for regional assessments of anthropogenic acidification. Based on our results, we show how the conceptual model can be used to understand and prioritize management of physico-chemical and ecological effects of anthropogenic stressors on surface water quality.

Modeling past and future acidification of Swedish lakes.

Decades of acid deposition have caused acidification of lakes in Sweden. Here we use data for 3000 lakes to run the acidification model MAGIC and estimate historical and future acidification. The results indicate that beginning in about 1920 a progressively larger number of lakes in Sweden fell into the category of "not naturally acidified" (∆pH > 0.4). The peak in acidification was reached about 1985; since then many lakes have recovered in response to lower levels of acid deposition. Further recovery from acidification will occur by the year 2030 given implementation of agreed legislation for emissions of sulphur (S) and nitrogen (N) in Europe. But the number of catchments with soils being depleted in base cations will increase slightly. MAGIC-reconstructed history of acidification of lakes in Sweden agrees well with information on fish populations. Future acidification of Swedish lakes can be influenced by climate change as well as changes in forest harvest practices.

Riparian zone influence on stream water dissolved organic carbon concentrations at the Swedish integrated monitoring sites.

Short-term variability in stream water dissolved organic carbon (DOC) concentrations is controlled by hydrology, climate and atmospheric deposition. Using the Riparian flow-concentration Integration Model (RIM), we evaluated factors controlling stream water DOC in the Swedish Integrated Monitoring (IM) catchments by separating out hydrological effects on stream DOC dynamics. Model residuals were correlated with climate and deposition-related drivers. DOC was most strongly correlated to water flow in the northern catchment (Gammtratten). The southern Aneboda and Kindla catchments had pronounced seasonal DOC signals, which correlated weakly to flow. DOC concentrations at Gårdsjön increased, potentially in response to declining acid deposition. Soil temperature correlated strongly with model residuals at all sites. Incorporating soil temperature in RIM improved model performance substantially (20-62% lower median absolute error). According to the simulations, the RIM conceptualization of riparian processes explains between 36% (Kindla) and 61% (Aneboda) of the DOC dynamics at the IM sites.

Nitrogen leaching and acidification during 19 years of NH4NO3 additions to a coniferous-forested catchment at Gårdsjön, Sweden (NITREX).

The role of nitrogen (N) in acidification of soil and water has become relatively more important as the deposition of sulphur has decreased. Starting in 1991, we have conducted a whole-catchment experiment with N addition at Gårdsjön, Sweden, to investigate the risk of N saturation. We have added 41 kg N ha(-1) yr(-1) as NH(4)NO(3) to the ambient 9 kg N ha(-1) yr(-1) in fortnightly doses by means of sprinkling system. The fraction of input N lost to runoff has increased from 0% to 10%. Increased concentrations of NO(3) in runoff partially offset the decreasing concentrations of SO(4) and slowed ecosystem recovery from acid deposition. From 1990-2002, about 5% of the total N input went to runoff, 44% to biomass, and the remaining 51% to soil. The soil N pool increased by 5%. N deposition enhanced carbon (C) sequestration at a mean C/N ratio of 42-59 g g(-1).

A comparison of MAGIC and paleolimnological predictions of preindustrial pH for 55 Swedish lakes.

Two fundamentally different approaches to define reference conditions for acidification assessments are hydrogeochemical modeling and paleolimnological reconstructions. Both methods have been applied to calculate the preindustrial chemistry for 55 Swedish lakes in two independent studies. This paper investigates whether these methods give similar reconstructions of the preindustrial pH for these lakes. Special focus has been attached to the importance of total organic carbon concentrations and CO2 partial pressure (pCO2) in the conversion from ANC to pH in the hydrogeochemical modeling. With a uniform pCO2 value for all the lakes of 0.63 matm, the mean absolute difference between pH from the hydrogeochemical model and the paleolimnological pH was +0.23 units (mean absolute difference 0.36 units). If instead a lake specific preindustrial pCO2 is assumed, equal to contemporary pCO2, the mean difference in the predicted preindustrial pH between the two methods was reduced to +0.03 units (mean absolute difference 0.22 units). Statistical analyses indicated that with a lake specific pCO2, the difference between the reconstructions is smaller than 0.13 pH-units at a 95% level of significance. The results of this study build confidence in the reliability of both methods, providing that lake-specific estimates of pC02 are used.

Mineralization of organic sulfur delays recovery from anthropogenic acidification.

While SO4(2-) concentrations in runoff are decreasing in many catchments in Europe, present day S output still exceeds the S input for most forested catchments in Europe and North America. Here we report that a large part of the observed SO4(2-) in the runoff at a large-scale catchment study site (the Gårdsjön roof experiment in southwestern Sweden) originates from the organic S pool in the O horizon. Budget estimates comparing soil S pools showed reductions in the S pool of 57 mmol of S m(-2) in the O horizon and 26 mmol of SO4(2-) m(-2) in the mineral Bs horizon after excluding anthropogenic deposition for four years. There was an increase of about 1% per hundred in the delta34S(SO4), value of the mineral soil SO4(2-) between 1990 and 1995 (average and 95% confidence interval of 6.2 +/- 0.6 and 7.7 +/- 0.6% per hundred, respectively), but the delta34S(SO4) values in the E horizon are still much lower than the sprinkler water input of +19.7% per hundred, although the horizon has only a small extractable SO4(2-) pool. After nine years (1991-2000) of artificially supplying S inputs comparable with those amounts supplied by preindustrial rain, the amount of S in runoff still exceeded the input by 30%. This extra 30% corresponds to a loss of 3 mmol of S m(-2) year(-1), compared to the soil S organic O horizon pool of 1098 mmol m(-2) in 1990, suggesting that recovery is delayed for decades, at least.

Modeling recovery of Swedish ecosystems from acidification.

Dynamic models complement existing time series of observations and static critical load calculations by simulating past and future development of chemistry in forest and lake ecosystems. They are used for dynamic assessment of the acidification and to produce target load functions, that describe what combinations of nitrogen and sulfur emission reductions are needed to achieve a chemical or biological criterion in a given target year. The Swedish approach has been to apply the dynamic acidification models MAGIC, to 133 lakes unaffected by agriculture and SAFE, to 645 productive forest sites. While the long-term goal is to protect 95% of the area, implementation of the Gothenburg protocol will protect approximately 75% of forest soils in the long term. After 2030, recovery will be very slow and involve only a limited geographical area. If there had been no emission reductions after 1980, 87% of the forest area would have unwanted soil status in the long term. In 1990, approximately 17% of all Swedish lakes unaffected by agriculture received an acidifying deposition above critical load. This fraction will decrease to 10% in 2010 after implementation of the Gothenburg protocol. The acidified lakes of Sweden will recover faster than the soils. According to the MAGIC model the median pre-industrial ANC of 107 microeq L(-1) in acid sensitive lakes decreased to about 60 microeq L(-1) at the peak of the acidification (1975-1990) and increases to 80 microeq L(-1) by 2010. Further increases were small, only 2 microeq L(-1) between 2010 and 2040. Protecting 95% of the lakes will require further emission reductions below the Gothenburg protocol levels. More than 7000 lakes are limed regularly in Sweden and it is unlikely that this practice can be discontinued in the near future without adverse effects on lake chemistry and biology.

Terrestrial ecosystem recovery--modelling the effects of reduced acidic inputs and increased inputs of sea-salts induced by global change.

The reduced emissions of acidifying sulfur and nitrogen in Europe since the late 1970s will be further reduced when the Gothenburg protocol is fully implemented by 2010. Here we address the consequences for the recovery of acidified terrestrial ecosystems using the acidification model MAGIC applied to 3 large-scale "clean rain" experiments, the so-called roof experiments at Risdalsheia, Norway; Gårdsjön, Sweden, and Klosterhede, Denmark. Implementation of the Gothenburg protocol will initiate recovery of the soils at all 3 sites by rebuilding base saturation. The rate of recovery is small and base saturation increases less than 5% over the next 30 years. A climate-induced increase in storm severity will increase the sea-salt input to the ecosystems. This will provide additional base cations to the soils and more than double the rate of the recovery, but also lead to strong acid pulses following high sea-salt inputs as the deposited base cations exchange with the acidity stored in the soil. Future recovery of soils and runoff at acidified catchments will thus depend on the amount and rate of reduction of acid deposition, and in the case of systems near the coast, the frequency and intensity of sea-salt episodes as well.

Recovery from acidification in central Europe--observed and predicted changes of soil and streamwater chemistry in the Lysina catchment, Czech Republic.

The geochemical model MAGIC was applied to estimate streamwater and soil chemistry between 1851 and 2030 at the Lysina catchment, an acid-sensitive granitic catchment covered by planted Norway spruce monoculture in the western Czech Republic. The total deposition of sulfur to the catchment was 164 meq m(-2) in 1991, but had declined to 52 meq m(-2) by 2000. Although SO2 emissions in the region declined by 90% compared to the 1980s, acidification recovery was small within the period 1990-2000. Stream pH increased only slightly (from 3.92 to 4.07), although SO4 concentration declined sharply from 568 microeq l(-1) (1990) to 232 microeq l(-1) (2000). Organic acids played an important role in streamwater buffering. According to the MAGIC prediction using deposition measured in 1999-2000, streamwater pH will increase to 4.3 and soil base saturation will increase to 6.2% by 2030 (from 5.7% in 2002). Pre-industrial pH was estimated to be 5.5 and soil base saturation 24.7%. The loss of base cations (Ca, Mg, Na, K) was caused predominantly by atmospheric acidity, but intensive forestry was responsible for approximately one third of the net base cation loss via accumulation in harvested biomass. Severely damaged sites, under continued pressure from forestry, will not return to a good environmental status in the near future (if ever) when the acid deposition input is only partially reduced.