Long-Term Changes in Aluminum Fractions of Drainage Waters in Two Forest Catchments with Contrasting Lithology

Aluminum (Al) chemistry was studied in soils and waters of two catchments covered by spruce (Picea abies) monocultures in the Czech Republic that represent geochemical end-members of terrestrial and aquatic sensitivity to acidic deposition. The acid-sensitive Lysina catchment, underlain by granite, was compared to the acid-resistant Pluhův Bor catchment on serpentine. Organically-bound Al was the largest pool of reactive soil Al at both sites. Very high median total Al (Alt) concentrations (40 μmol L−1) and inorganic monomeric Al (Ali) concentrations (27 μmol L−1) were observed in acidic (pH 4.0) stream water at Lysina in the 1990s and these concentrations decreased to 32 μmol L−1 (Alt) and 13 μmol L−1 (Ali) in the 2000s. The potentially toxic Ali fraction decreased in response to long-term decreases in acidic deposition, but Ali remained the largest fraction. However, the organic monomeric (Alo) and particulate (Alp) fractions increased in the 2000s at Lysina. In contrast to Lysina, marked increases of Alt concentrations in circum-neutral waters at Pluhův Bor were observed in the 2000s in comparison with the 1990s. These increases were entirely due to the Alp fraction, which increased more than 3-fold in stream water and up to 8-fold in soil water in the A horizon. Increase of Alp coincided with dissolved organic carbon (DOC) increases. Acidification recovery may have increased the content of colloidal Al though the coagulation of monomeric Al

Changes in soil dissolved organic carbon affect reconstructed history and projected future trends in surface water acidification

Preindustrial (1850s) and future (2060) streamwater chemistry of an anthropogenically acidified small catchment was estimated using the MAGIC model for three different scenarios for dissolved organic carbon (DOC) concentrations and sources. The highest modeled pH = 5.7 for 1850s as well as for 2060 (pH = 4.4) was simulated given the assumption that streamwater DOC concentration was constant at the 1993 level. A scenario accounting for an increase of DOC as an inverse function of ionic strength (IS) of soilwater and streamwater resulted in much lower preindustrial (pH = 4.9) and future recovery to (pH = 4.1) if the stream riparian zone was assumed to be the only DOC source. If upland soilwater (where significant DOC increase was observed at −5 and −15 cm) was also included, DOC was partly neutralized within the soil and higher preindustrial pH = 5.3 and future pH = 4.2 were estimated. The observed DOC stream flux was 2–4 times higher than the potential carbon production of the riparian zone, implying that this is unlikely to be the sole DOC source. Modeling based on the assumption that stream DOC changes are solely attributable to changes in the riparian zone appears likely to underestimate preindustrial pH

Dissolved and gaseous nitrogen losses in forests controlled by soil nutrient stoichiometry

Global chronic nitrogen (N) deposition to forests can alleviate ecosystem N limitation, with potentially wide ranging consequences for biodiversity, carbon sequestration, soil and surface water quality, and greenhouse gas emissions. However, the ability to predict these consequences requires improved quantification of hard-to-measure N fluxes, particularly N gas loss and soil N retention. Here we combine a unique set of long-term catchment N budgets in the central Europe with ecosystem 15N data to reveal fundamental controls over dissolved and gaseous N fluxes in temperate forests. Stream leaching losses of dissolved N corresponded with nutrient stoichiometry of the forest floor, with stream N losses increasing as ecosystems progress towards phosphorus limitation, while soil N storage increased with oxalate extractable iron and aluminium content. Our estimates of soil gaseous losses based on 15N stocks averaged 2.5 ± 2.2 kg N ha−1 yr−1 and comprised 20% ± 14% of total N deposition. Gaseous N losses increased with forest floor N:P ratio and with dissolved N losses. Our relationship between gaseous and dissolved N losses was also able to explain previous 15N-based N loss rates measured in tropical and subtropical catchments, suggesting a generalisable response driven by nitrate (NO3−) abundance and in which the relative importance of dissolved N over gaseous N losses tended to increase with increasing NO3− export. Applying this relationship globally, we extrapolated current gaseous N loss flux from forests to be 8.9 Tg N yr−1, which represent 39% of current N deposition to forests worldwide

Predicting sulphur and nitrogen deposition using a simple statistical method

Data from 32 long-term (1994–2012) monitoring sites were used to assess temporal development and spatial variability of sulphur (S) and inorganic nitrogen (N) concentrations in bulk precipitation, and S in throughfall, for the Czech Republic. Despite large variance in absolute S and N concentration/deposition among sites, temporal coherence using standardised data (Z score) was demonstrated. Overall significant declines of SO4 concentration in bulk and throughfall precipitation, as well as NO3 and NH4 concentration in bulk precipitation, were observed. Median Z score values of bulk SO4, NO3 and NH4 and throughfall SO4 derived from observations and the respective emission rates of SO2, NOx and NH3 in the Czech Republic and Slovakia showed highly significant (p < 0.001) relationships. Using linear regression models, Z score values were calculated for the whole period 1900–2012 and then back-transformed to give estimates of concentration for the individual sites. Uncertainty associated with the concentration calculations was estimated as 20% for SO4 bulk precipitation, 22% for throughfall SO4, 18% for bulk NO3 and 28% for bulk NH4. The application of the method suggested that it is effective in the long-term reconstruction and prediction of S and N deposition at a variety of sites. Multiple regression modelling was used to extrapolate site characteristics (mean precipitation chemistry and its standard deviation) from monitored to unmonitored sites. Spatially distributed temporal development of S and N depositions were calculated since 1900. The method allows spatio-temporal estimation of the acid deposition in regions with extensive monitoring of precipitation chemistry

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

Long-term changes (1990–2015) in the atmospheric deposition and runoff water chemistry of sulphate, inorganic nitrogen and acidity for forested catchments in Europe in relation to changes in emissions and hydrometeorological conditions

The international Long-Term Ecological Research Network (ILTER) encompasses hundreds of long-term research/monitoring sites located in a wide array of ecosystems that can help us understand environmental change across the globe. We evaluated long-term trends (1990–2015) for bulk deposition, throughfall and runoff water chemistry and fluxes, and climatic variables in 25 forested catchments in Europe belonging to the UNECE International Cooperative Programme on Integrated Monitoring of Air Pollution Effects on Ecosystems (ICP IM). Many of the IM sites form part of the monitoring infrastructures of this larger ILTER network. Trends were evaluated for monthly concentrations of non-marine (anthropogenic fraction, denoted as x) sulphate (xSO4) and base cations x(Ca + Mg), hydrogen ion (H+), inorganic N (NO3 and NH4) and ANC (Acid Neutralising Capacity) and their respective fluxes into and out of the catchments and for monthly precipitation, runoff and air temperature. A significant decrease of xSO4 deposition resulted in decreases in concentrations and fluxes of xSO4 in runoff, being significant at 90% and 60% of the sites, respectively. Bulk deposition of NO3 and NH4 decreased significantly at 60–80% (concentrations) and 40–60% (fluxes) of the sites. Concentrations and fluxes of NO3 in runoff decreased at 73% and 63% of the sites, respectively, and NO3 concentrations decreased significantly at 50% of the sites. Thus, the LTER/ICP IM network confirms the positive effects of the emission reductions in Europe. Air temperature increased significantly at 61% of the sites, while trends for precipitation and runoff were rarely significant. The site-specific variation of xSO4 concentrations in runoff was most strongly explained by deposition. Climatic variables and deposition explained the variation of inorganic N concentrations in runoff at single sites poorly, and as yet there are no clear signs of a consistent deposition-driven or climate-driven increase in inorganic N exports in the catchments.Long-term changes (1990–2015) in the atmospheric deposition and runoff water chemistry of sulphate, inorganic nitrogen and acidity for forested catchments in Europe in relation to changes in emissions and hydrometeorological conditionsacceptedVersio

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

Modelling study of soil C, N and pH response to air pollution and climate change using European LTER site observations

Current climate warming is expected to continue in coming decades, whereas high N deposition may stabilize, in contrast to the clear decrease in S deposition. These pressures have distinctive regional patterns and their resulting impact on soil conditions is modified by local site characteristics. We have applied the VSD+ soil dynamic model to study impacts of deposition and climate change on soil properties, using MetHyd and GrowUp as pre-processors to provide input to VSD+. The single-layer soil model VSD+ accounts for processes of organic C and N turnover, as well as charge and mass balances of elements, cation exchange and base cation weathering. We calibrated VSD+ at 26 ecosystem study sites throughout Europe using observed conditions, and simulated key soil properties: soil solution pH (pH), soil base saturation (BS) and soil organic carbon and nitrogen ratio (C:N) under projected deposition of N and S, and climate warming until 2100. The sites are forested, located in the Mediterranean, forested alpine, Atlantic, continental and boreal regions. They represent the long-term ecological research (LTER) Europe network, including sites of the ICP Forests and ICP Integrated Monitoring (IM) programmes under the UNECE Convention on Long-range Transboundary Air Pollution (LRTAP), providing high quality long-term data on ecosystem response. Simulated future soil conditions improved under projected decrease in deposition and current climate conditions: higher pH, BS and C:N at 21, 16 and 12 of the sites, respectively. When climate change was included in the scenario analysis, the variability of the results increased. Climate warming resulted in higher simulated pH in most cases, and higher BS and C:N in roughly half of the cases. Especially the increase in C:N was more marked with climate warming. The study illustrates the value of LTER sites for applying models to predict soil responses to multiple environmental changes