Experimental simulation of the effects of extreme climatic events on major ions, acidity and dissolved organic carbon leaching from a forested catchment, Gårdsjön, Sweden

Climate change is predicted to lead to an increase in extreme rainfall and, in coastal areas, sea-salt deposition events. The impacts of these two climatic extremes on stream hydrochemistry were separately evaluated via a novel watering manipulation at the Gårdsjön experimental catchment, SW Sweden. In summer 2004, a 2000 m² hillslope draining to a defined stream reach was brought to a high-flow hydrological steady state for a 9 day period by sustained addition of ‘clean’ water using a distributed sprinkler system. Marine ions were then added, to generate a realistic ‘sea salt’ episode. A remarkably well constrained hydrological response was observed, such that a simple two-compartment mixing model could reasonably well reproduce observed conservative tracer (chloride, Cl) measurements, and 78% of added water was recovered in runoff. Stream base cation concentrations and acidity responded predictably to clean water and sea-salt addition, with the former leading to an increase in pH and acid neutralising capacity, and the latter to episodic acidification through hydrogen ion and aluminium displacement from soil exchange sites by marine base cations. Anion responses were less predictable: water addition caused a flush of nitrate, but this was apparently independent of rainfall composition. Sulphate remained near-constant during clean water addition but declined sharply during sea-salt addition, indicative of a strong, pH-dependent solubility control on leaching, presumably adsorption/desorption in the mineral soil. Most strikingly, dissolved organic carbon (DOC) concentrations were stable during clean water addition but varied dramatically in response to sea-salt addition, exhibiting a strong negative correlation with Cl concentrations in water draining the organic soil. These observations provide a robust experimental verification of the hypothesis that deposition chemistry, through its influence on acidity and/or ionic strength, has a major influence on DOC leaching to surface waters.     

Hydrological and biological processes modulate carbon,nitrogen and phosphorus flux from the St. Lawrence River to its estuary (Quebec,Canada)

Changes in atmospheric deposition, stream water chemistry, and solute fluxes were assessed across 15 small forested catchments. Dramatic changes in atmospheric deposition have occurred over the last three decades, including a 70% reduction in sulphur (S) deposition. These changes in atmospheric inputs have been associated with expected changes in levels of acidity, sulphate and base cations in streams. Soil retention of S appeared to partially explain rates of chemical recovery. In addition to these changes in acid–base chemistry we also observed unexpected changes in nitrogen (N) biogeochemistry and nutrient stoichiometry of stream water, including decreased stream N concentrations. Among all catchments the average flux of dissolved inorganic nitrogen (DIN) was best predicted by average runoff, soil chemistry (forest floor C/N) and levels of acid deposition (both S and N). The rate of change in stream DIN flux, however, was much more closely correlated with reductions in rates of S deposition rather than those of DIN. Unlike DIN fluxes, the average concentrations as well as the rates of decline in streamwater nitrate (NO₃) concentration over time were tightly linked to stream dissolved organic carbon/dissolved organic nitrogen ratios DOC/DON and DON/TP rather than catchment characteristics. Declines in phosphorus adsorption with increasing soil pH appear to contribute to the relationship between C, N, and P in our study catchments. Our observations suggest that catchment P availability and its alteration due to environmental changes (e.g. acidification) might have profound effects on N cycling and catchment N retention that have been largely unrecognized.     

Ion flux from precipitation to peat soil in spruce forest–<Emphasis Type="Italic">Sphagnum</Emphasis> bog communities in the Ochiishi district,eastern Hokkaido,Japan

To evaluate the contribution of proton flux from precipitation on peat acidification in mire ecosystems, we estimated ion fluxes to peat soils from bulk deposition in Sphagnum-dominated bogs and from throughfall plus stem flow in spruce forests in three cool-temperate ombrogenous mires in the Ochiishi district, northeastern Japan. We tested the hypothesis that proton fluxes from the atmosphere to peat soils are affected by vegetation types, leading to the consequent difference in soil acidity. The proton flux in bulk deposition was higher than that in throughfall plus stem flow, but the concentration of H⁺ in the peat surface water in Sphagnum bogs was lower than that in spruce forests. The inverse relationship between proton flux and soil water acidity means that the soil water acidity could not be explained quantitatively by proton flux from the atmosphere to the peat surface. The ion fluxes of sea-salt components were dependent on the distance from the coast to the mires. This means that the sea-salt accumulation in the peat surface soil can be directly attributed to the high flux of sea-salt from precipitation. The flux of sea-salts deposited on the mires positively correlated with the H⁺ concentration of the peat surface water in each community, implying that the acidity of peat surface water depends on the cation fluxes from precipitation.     

Acidity controls on dissolved organic carbon mobility in organic soils

Dissolved organic carbon (DOC) concentrations in surface waters have increased across much of Europe and North America, with implications for the terrestrial carbon balance, aquatic ecosystem functioning, water treatment costs and human health. Over the past decade, many hypotheses have been put forward to explain this phenomenon, from changing climate and land management to eutrophication and acid deposition. Resolution of this debate has been hindered by a reliance on correlative analyses of time series data, and a lack of robust experimental testing of proposed mechanisms. In a 4 year, four‐site replicated field experiment involving both acidifying and deacidifying treatments, we tested the hypothesis that DOC leaching was previously suppressed by high levels of soil acidity in peat and organo‐mineral soils, and therefore that observed DOC increases a consequence of decreasing soil acidity. We observed a consistent, positive relationship between DOC and acidity change at all sites. Responses were described by similar hyperbolic relationships between standardized changes in DOC and hydrogen ion concentrations at all sites, suggesting potentially general applicability. These relationships explained a substantial proportion of observed changes in peak DOC concentrations in nearby monitoring streams, and application to a UK‐wide upland soil pH dataset suggests that recovery from acidification alone could have led to soil solution DOC increases in the range 46–126% by habitat type since 1978. Our findings raise the possibility that changing soil acidity may have wider impacts on ecosystem carbon balances. Decreasing sulphur deposition may be accelerating terrestrial carbon loss, and returning surface waters to a natural, high‐DOC condition.     

Processes controlling DOC in pore water during simulated drought cycles in six different UK peats

The effect of episodic drought on dissolved organic carbon (DOC) dynamics in peatlands has been the subject of considerable debate, as decomposition and DOC production is thought to increase under aerobic conditions, yet decreased DOC concentrations have been observed during drought periods. Decreased DOC solubility due to drought-induced acidification driven by sulphur (S) redox reactions has been proposed as a causal mechanism; however evidence is based on a limited number of studies carried out at a few sites. To test this hypothesis on a range of different peats, we carried out controlled drought simulation experiments on peat cores collected from six sites across Great Britain. Our data show a concurrent increase in sulphate (SO₄) and a decrease in DOC across all sites during simulated water table draw-down, although the magnitude of the relationship between SO₄ and DOC differed between sites. Instead, we found a consistent relationship across all sites between DOC decrease and acidification measured by the pore water acid neutralising capacity (ANC). ANC provided a more consistent measure of drought-induced acidification than SO₄ alone because it accounts for differences in base cation and acid anions concentrations between sites. Rewetting resulted in rapid DOC increases without a concurrent increase in soil respiration, suggesting DOC changes were primarily controlled by soil acidity not soil biota. These results highlight the need for an integrated analysis of hydrologically driven chemical and biological processes in peatlands to improve our understanding and ability to predict the interaction between atmospheric pollution and changing climatic conditions from plot to regional and global scales.     

Fine-scale temporal characterization of trends in soil water dissolved organic carbon and potential drivers

Long-term monitoring of surface water quality has shown increasing concentrations of dissolved organic carbon (DOC) across a large part of the Northern Hemisphere. Several drivers have been implicated including climate change, land management change, nitrogen and sulphur deposition and CO₂ enrichment. Analysis of stream water data, supported by evidence from laboratory studies, indicates that an effect of declining sulphur deposition on catchment soil chemistry is likely to be the primary mechanism, but there are relatively few long term soil water chemistry records in the UK with which to investigate this, and other, hypotheses directly. In this paper, we assess temporal relationships between soil solution chemistry and parameters that have been argued to regulate DOC production and, using a unique set of co-located measurements of weather and bulk deposition and soil solution chemistry provided by the UK Environmental Change Network and the Intensive Forest Monitoring Level II Network. We used statistical non-linear trend analysis to investigate these relationships at 5 forested and 4 non-forested sites from 1993 to 2011. Most trends in soil solution DOC concentration were found to be non-linear. Significant increases in DOC occurred mostly prior to 2005. The magnitude and sign of the trends was associated qualitatively with changes in acid deposition, the presence/absence of a forest canopy, soil depth and soil properties. The strongest increases in DOC were seen in acidic forest soils and were most clearly linked to declining anthropogenic acid deposition, while DOC trends at some sites with westerly locations appeared to have been influenced by shorter-term hydrological variation. The results indicate that widespread DOC increases in surface waters observed elsewhere, are most likely dominated by enhanced mobilization of DOC in surficial organic horizons, rather than changes in the soil water chemistry of deeper horizons. While trends in DOC concentrations in surface horizons have flattened out in recent years, further increases may be expected as soil chemistry continues to adjust to declining inputs of acidity.     

Does elevated nitrogen deposition or ecosystem recovery from acidification drive increased dissolved organic carbon loss from upland soil? A review of evidence from field nitrogen addition experiments

Dissolved organic carbon (DOC) concentrations have risen in upland waters across large areas of Europe and North America. Two proposed drivers of these increases are (1) deposition of atmospheric pollutant nitrogen (N) with consequent effects on plant and decomposer carbon dynamics, and (2) soil recovery from acidification associated with decreasing sulphur deposition. Examination of 12 European and North American field N addition experiments showed inconsistent (positive, neutral, and negative) responses of DOC to N addition. However, responses were linked to the form of N added and to resulting changes in soil acidity. Sodium nitrate additions consistently increased DOC, whereas ammonium salts additions usually decreased DOC. Leachate chemistry was used to calculate an index of “ANC forcing” of the effect of fertilization on the acid-base balance, which showed that DOC increased in response to all de-acidifying N additions, and decreased in response to all but three acidifying N additions. Exceptions occurred at two sites where N additions caused tree mortality, and one experiment located on an older, unglaciated soil with high anion adsorption capacity. We conclude that collectively these experiments do not provide clear support for the role of N deposition as the sole driver of rising DOC, but are largely consistent with an acidity-change mechanism. It is however possible that the unintended effect of acidity change on DOC mobility masks genuine effects of experimental N enrichment on DOC production and degradation. We suggest that there is a need, more generally, for interpretation of N manipulation experiments to take account of the effects that experimentally-induced changes in acidity, rather than elevated N per se, may have on ecosystem biogeochemistry.     

Nitrogen deposition contributes to soil acidification in tropical ecosystems

Elevated anthropogenic nitrogen (N) deposition has greatly altered terrestrial ecosystem functioning, threatening ecosystem health via acidification and eutrophication in temperate and boreal forests across the northern hemisphere. However, response of forest soil acidification to N deposition has been less studied in humid tropics compared to other forest types. This study was designed to explore impacts of long‐term N deposition on soil acidification processes in tropical forests. We have established a long‐term N‐deposition experiment in an N‐rich lowland tropical forest of Southern China since 2002 with N addition as NH₄NO₃ of 0, 50, 100 and 150 kg N ha^?1 yr^?1. We measured soil acidification status and element leaching in soil drainage solution after 6‐year N addition. Results showed that our study site has been experiencing serious soil acidification and was quite acid‐sensitive showing high acidification (pH_(H2O)<4.0), negative water‐extracted acid neutralizing capacity (ANC) and low base saturation (BS,< 8%) throughout soil profiles. Long‐term N addition significantly accelerated soil acidification, leading to depleted base cations and decreased BS, and further lowered ANC. However, N addition did not alter exchangeable Al³⁺, but increased cation exchange capacity (CEC). Nitrogen addition‐induced increase in SOC is suggested to contribute to both higher CEC and lower pH. We further found that increased N addition greatly decreased soil solution pH at 20 cm depth, but not at 40 cm. Furthermore, there was no evidence that Al³⁺ was leaching out from the deeper soils. These unique responses in tropical climate likely resulted from: exchangeable H⁺ dominating changes of soil cation pool, an exhausted base cation pool, N‐addition stimulating SOC production, and N saturation. Our results suggest that long‐term N addition can contribute measurably to soil acidification, and that shortage of Ca and Mg should receive more attention than soil exchangeable Al in tropical forests with elevated N deposition in the future.     

The biogeochemistry of two forested catchments in the Black Forest and the eastern Ore Mountains (Germany)

The biogeochemical input-output fluxes of two forested catchments with contrasting levels of atmospheric deposition were investigated in Germany. This paper focuses on the effects of recent changes in atmospheric inputs on the chemical composition in the soil solution and stream. The catchment 'Schluchsee' (Black Forest; SW Germany) is characterized by relatively low atmospheric inputs whereas 'Rotherdbach' (Ore Mountains; E Germany) received significant amounts of acid deposition (mainly originating from SO₂ emissions) until recent years. Both sites reveal decreases in H⁺ and S deposition during the 1990s. This pattern is typical when compared to trends in Europe. In response to the reduced S deposition, soil solution and streamwater SO₄ ^2– concentrations decreased significantly. A net release of SO₄ ^2– (output > input) was observed at both sites due to the release of S previously stored in the soil. The level of N deposition was more or less constant at both sites. At Schluchsee, NO₃ ^– concentration in streamwater remained more or less unchanged, whereas a decrease at Rotherdbach was observed. A recovery from acidification was found in seepage water as indicated by increasing acid neutralizing capacity (ANC). Streamwater ANC increased only in the permanently acidified Rotherdbach. No change of ANC was observed in the Schluchsee stream, which was characterized by episodic acidification during high-flow conditions. Nevertheless, the key factor controlling the recovery from surface water acidification was the type, amount and distribution of stored S pools in the ecosystem. Thus, time series analysis of long-term data of input-output chemistry can be a valuable instrument in order to improve the understanding of linked terrestrial-aquatic systems and give useful clues for modeling efforts.     

Factors controlling soil water and stream water aluminum concentrations after a clearcut in a forested watershed with calcium-poor soils

The 24 ha Dry Creek watershed in the Catskill Mountains of southeastern New York State USA was clearcut during the winter of 1996–1997. The interactions among acidity, nitrate (NO₃⁻), aluminum (Al), and calcium (Ca²⁺) in streamwater, soil water, and groundwater were evaluated to determine how they affected the speciation, solubility, and concentrations of Al after the harvest. Watershed soils were characterized by low base saturation, high exchangeable Al concentrations, and low exchangeable base cation concentrations prior to the harvest. Mean streamwater NO₃⁻ concentration was about 20 μmol l⁻¹ for the 3 years before the harvest, increased sharply after the harvest, and peaked at 1,309 μmol l⁻¹ about 5 months after the harvest. Nitrate and inorganic monomeric aluminum (Al_im) export increased by 4−fold during the first year after the harvest. Al_im mobilization is of concern because it is toxic to some fish species and can inhibit the uptake of Ca²⁺ by tree roots. Organic complexation appeared to control Al solubility in the O horizon while ion exchange and possibly equilibrium with imogolite appeared to control Al solubility in the B horizon. Al_im and NO₃⁻ concentrations were strongly correlated in B-horizon soil water after the clearcut (r ² = 0.96), especially at NO₃⁻ concentrations greater than 100 μmol l⁻¹. Groundwater entering the stream from perennial springs contained high concentrations of base cations and low concentrations of NO₃⁻ which mixed with acidic, high Al_im soil water and decreased the concentration of Al_im in streamwater after the harvest. Five years after the harvest soil water NO₃⁻ concentrations had dropped below preharvest levels as the demand for nitrogen by regenerating vegetation increased, but groundwater NO₃⁻ concentrations remained elevated because groundwater has a longer residence time. As a result streamwater NO₃⁻ concentrations had not fallen below preharvest levels, even during the growing season, 5 years after the harvest because of the contribution of groundwater to the stream. Streamwater NO₃⁻ and Al_im concentrations increased more than reported in previous forest harvesting studies and the recovery was slower likely because the watershed has experienced several decades of acid deposition that has depleted initially base-poor soils of exchangeable base cations and caused long-term acidification of the soil.     

Alternative explanations for rising dissolved organic carbon export from organic soils

Since 1988, there has been, on average, a 91% increase in dissolved organic carbon (DOC) concentrations of UK lakes and streams in the Acid Waters Monitoring Network (AWMN). Similar DOC increases have been observed in surface waters across much of Europe and North America. Much of the debate about the causes of rising DOC has, as in other studies relating to the carbon cycle, focused on factors related to climate change. Data from our peat‐core experiments support an influence of climate on DOC, notably an increase in production with temperature under aerobic, and to a lesser extent anaerobic, conditions. However, we argue that climatic factors may not be the dominant drivers of DOC change. DOC solubility is suppressed by high soil water acidity and ionic strength, both of which have decreased as a result of declining sulphur deposition since the 1980s, augmented during the 1990s in the United Kingdom by a cyclical decline in sea‐salt deposition. Our observational and experimental data demonstrate a clear, inverse and quantitatively important link between DOC and sulphate concentrations in soil solution. Statistical analysis of 11 AWMN lakes suggests that rising temperature, declining sulphur deposition and changing sea‐salt loading can account for the majority of the observed DOC trend. This combination of evidence points to the changing chemical composition of atmospheric deposition, particularly the substantial reduction in anthropogenic sulphur emissions during the last 20 years, as a key cause of rising DOC. The implications of rising DOC export for the carbon cycle will be very different if linked primarily to decreasing acid deposition, rather than to changes in climate, suggesting that these systems may be recovering rather than destabilising.     

Influence of drought-induced acidification on the mobility of dissolved organic carbon in peat soils

A strong relationship between dissolved organic carbon (DOC) and sulphate (SO₄^2?) dynamics under drought conditions has been revealed from analysis of a 10‐year time series (1993–2002). Soil solution from a blanket peat at 10 cm depth and stream water were collected at biweekly and weekly intervals, respectively, by the Environmental Change Network at Moor House‐Upper Teesdale National Nature Reserve in the North Pennine uplands of Britain. DOC concentrations in soil solution and stream water were closely coupled, displaying a strong seasonal cycle with lowest concentrations in early spring and highest in late summer/early autumn. Soil solution DOC correlated strongly with seasonal variations in soil temperature at the same depth 4‐weeks prior to sampling. Deviation from this relationship was seen, however, in years with significant water table drawdown (>?25 cm), such that DOC concentrations were up to 60% lower than expected. Periods of drought also resulted in the release of SO₄^2?, because of the oxidation of inorganic/organic sulphur stored in the peat, which was accompanied by a decrease in pH and increase in ionic strength. As both pH and ionic strength are known to control the solubility of DOC, inclusion of a function to account for DOC suppression because of drought‐induced acidification accounted for more of the variability of DOC in soil solution (R²=0.81) than temperature alone (R²=0.58). This statistical model of peat soil solution DOC at 10 cm depth was extended to reproduce 74% of the variation in stream DOC over this period. Analysis of annual budgets showed that the soil was the main source of SO₄^2? during droughts, while atmospheric deposition was the main source in other years. Mass balance calculations also showed that most of the DOC originated from the peat. The DOC flux was also lower in the drought years of 1994 and 1995, reflecting low DOC concentrations in soil and stream water. The analysis presented in this paper suggests that lower concentrations of DOC in both soil and stream waters during drought years can be explained in terms of drought‐induced acidification. As future climate change scenarios suggest an increase in the magnitude and frequency of drought events, these results imply potential for a related increase in DOC suppression by episodic acidification.     

The influence of soil frost on the quality of dissolved organic carbon in a boreal forest soil: combining field and laboratory experiments

Riparian soils exert a major control on stream water dissolved organic carbon (DOC) in northern latitudes. As the winter climate in northern regions is predicted to be particularly affected by climate change, we tested the sensitivity of DOC formation to winter conditions in riparian soils using an 8?year field-scale soil frost manipulation experiment in northern Sweden. In conjunction with the field experiment, we also carried out a laboratory experiment based on three levels of four winter climatic factors: frost intensity, soil water content, frost duration and frequency of freeze–thaw cycles. We evaluated changes in lability of DOC in soil solution from lysimeter samples taken at different depths (10–80?cm) as well as from DOC extracted from soils in the laboratory, using carbon-specific ultraviolet absorbance at 254?nm (sUVA₂₅₄). In the field, significantly more labile DOC was observed during the spring and summer from upper horizons of frost-exposed soils, when compared to controls. In addition, the amount of labile DOC was positively correlated with frost duration at a soil depth of 10?cm. In the laboratory, frost intensity was the factor that had the greatest positive influence on DOC lability; it also reduced the C:N ratio which may indicate a microbial origin of the DOC. The laboratory experiment also demonstrated significant interactions between some of the applied climatic factors, such as frost intensity interacting with water content. In combination, field and laboratory experiments demonstrate that winter soil conditions have profound effects on DOC-concentration and quality during subsequent seasons.     

Changes in the land mollusc fauna and soil chemistry in an inland district in southern Sweden

The land mollusc fauna and some abiotic soil variables were investigated at 20 forest sites SW of Vaxjo, southern Sweden, in 1964-66 and again in 1987-88 to evaluate possible effects of soil acidification, base cation leaching and nitrogen deposition The number of snail individuals decreased on average by 60% in herb-rich deciduous forests and by 80% in spruce and herb-poor oak forests Nesovitrea petronella, N hammonis, Euconulus fulvus, Vertigo substriata, Cochlicopa lubrica and Clausilia bidentata were most affected The calcium content in litter and surface layer of soil had decreased on average by 31%
The snail number decrease is negatively correlated to base saturation In the lower range of calcium content the change is in good accordance with a significant regression line of abundance on calcium from 1964–66
The snail abundance is positively correlated to base saturation, to soil moisture and probably also to nitrogen content
The soil chemistry and the snail fauna of the coniferous forest sites are so severely affected that a continued acidification and base cation leaching might lead to extinction of the snail fauna in this kind of forest Problems, possibilities and use of results from retrospective studies on the soil fauna are discussed     

Assessing the short-term response of stream diatoms to acidity using inter-basin transplantations and chemical diffusing substrates

1. Acid‐base status has major effects on diatoms, but there is little information on their short‐term response to changing acidity. This is despite the use of diatoms as bioindicators in streams where acid episodes are important during rainstorms (hours to days) or snowmelt (days to weeks). In the Llyn Brianne experimental catchments (Wales, UK), we attempted to mimic the effects of short‐term acidification by (i) reciprocally transplanting diatoms between two streams of contrasting acidity and (ii) using acid‐diffusing substrates. 2. Diatom diversity decreased rapidly on substrata transplanted from the circumneutral into the acidic stream, and increased in the reciprocal transplantation. Changes in dominant taxa occurred within three days in the acidic stream because of the rapid growth of Eunotia exigua, and by nine days in the circumneutral stream because of the proliferation of Achnanthidium minutissimum. Transplants were near indistinguishable from ambient assemblages by day 12. 3. There were no effects of enclosures on assemblage composition, but diatoms responded more rapidly to altered chemistry in enclosures with coarse mesh (26 × 50 mm) than finer mesh (320 μm). 4. Chemical diffusing substrates comprised terracotta tiles attached to dosing reservoirs that created locally acid (using H₂SO₄) or metal‐rich conditions (using MnSO₄) in the circumneutral stream over 26 days. Diatom responses were compared with reference substrates dosed with deionised or circumneutral stream water, and we also assessed whether effects were moderated by macroinvertebrate grazers. 5. Surface pH was lower by 1–2 pH units on acid‐dosed substrates than on reference tiles or in surrounding streamwater. Grazed assemblages on acid‐dosed substrates differed significantly from ungrazed reference assemblages, acquiring significantly greater relative abundance of Eunotia spp. However, the magnitude of response was less than in the between‐stream transplantations either because (i) metal exposure and base cation concentrations differed between the transplants and dosing substrates or (ii) diatom response to reduced pH on the diffusing substrates was restricted by the scarcity of acidobiontic diatoms in the circumneutral stream. Similar filter, founder or dominance effects might also affect diatom responses to real acid episodes. 6. These data show that diatom assemblages can respond rapidly and directly to changes in acid‐base status, but short‐term acidification might affect diatoms more rapidly than subsequent recovery. Because the experimental methods used were imperfect representations of episodic effects, diatom response to real acid events requires further field evaluation.     

Increased temperature sensitivity of net DOC production from ombrotrophic peat due to water table draw-down

The production and release of dissolved organic carbon (DOC) from peat soils is thought to be sensitive to changes in climate, specifically changes in temperature and rainfall. However, little is known about the actual rates of net DOC production in response to temperature and water table draw‐down, particularly in comparison to carbon dioxide (CO₂) fluxes. To explore these relationships, we carried out a laboratory experiment on intact peat soil cores under controlled temperature and water table conditions to determine the impact and interaction of each of these climatic factors on net DOC production. We found a significant interaction (P < 0.001) between temperature, water table draw‐down and net DOC production across the whole soil core (0 to −55 cm depth). This corresponded to an increase in the Q₁₀ (i.e. rise in the rate of net DOC production over a 10 °C range) from 1.84 under high water tables and anaerobic conditions to 3.53 under water table draw‐down and aerobic conditions between −10 and − 40 cm depth. However, increases in net DOC production were only seen after water tables recovered to the surface as secondary changes in soil water chemistry driven by sulphur redox reactions decreased DOC solubility, and therefore DOC concentrations, during periods of water table draw‐down. Furthermore, net microbial consumption of DOC was also apparent at − 1 cm depth and was an additional cause of declining DOC concentrations during dry periods. Therefore, although increased temperature and decreased rainfall could have a significant effect on net DOC release from peatlands, these climatic effects could be masked by other factors controlling the biological consumption of DOC in addition to soil water chemistry and DOC solubility. These findings highlight both the sensitivity of DOC release from ombrotrophic peat to episodic changes in water table draw‐down, and the need to disentangle complex and interacting controls on DOC dynamics to fully understand the impact of environmental change on this system.     

Acid rain recovery may help to mitigate the impacts of climate change on thermally sensitive fish in lakes across eastern North America

From the 1970s to 1990s, more stringent air quality regulations were implemented across North America and Europe to reduce chemical emissions that contribute to acid rain. Surface water pH slowly increased during the following decades, but biological recovery lagged behind chemical recovery. Fortunately, this situation is changing. In the past few years, northeastern US fish populations have begun to recover in lakes that were historically incapable of sustaining wild fish due to acidic conditions. As lake ecosystems across the eastern United States recover from acid deposition, the stress to the most susceptible populations of native coldwater fish appears to be shifting from acidification effects to thermal impacts associated with changing climate. Extreme summer temperature events – which are expected to occur with increasing frequency in the coming century – can stress and ultimately kill native coldwater fish in lakes where thermal stratification is absent or highly limited. Based on data from northeastern North America, we argue that recovery from acid deposition has the potential to improve the resilience of coldwater fish populations in some lakes to impacts of climate change. This will occur as the amount of dissolved organic carbon (DOC) in the water increases with increasing lake pH. Increased DOC will reduce water clarity and lead to shallower and more persistent lake thermoclines that can provide larger areas of coldwater thermal refuge habitat. Recovery from acidification will not eliminate the threat of climate change to coldwater fish, but secondary effects of acid recovery may improve the resistance of coldwater fish populations in lakes to the effects of elevated summer temperatures in historically acidified ecosystems. This analysis highlights the importance of considering the legacy of past ecosystem impacts and how recovery or persistence of those effects may interact with climate change impacts on biota in the coming decades.     

Contrasting responses of two Sitka spruce forest plots in Ireland to reductions in sulphur emissions: results of 20 years of monitoring

Long-term trends in ion concentrations of bulk precipitation, throughfall, forest floor leachate (humus water) and shallow and deep soil water were assessed at two Sitka spruce (Picea sitchensis) stands—one on an Atlantic peat bog in the west of Ireland (Cloosh), the other on the east coast on a peaty podzol (Roundwood). Deposition at Cloosh was dominated by marine ions (sodium, [Na⁺], chloride [Cl^?], and magnesium [Mg²⁺]), whereas bulk precipitation and throughfall at Roundwood was characterized by inputs of non-marine sulphate (nmSO₄ ^2?), acidity and inorganic nitrogen (NH₄ ⁺, NO₃ ^?). Significant declines in concentrations of nmSO₄ ^2? and acidity in bulk precipitation and throughfall were observed at both sites. The decline in throughfall nmSO₄ ^2? was significantly related to reductions in European sulphur dioxide (SO₂) emissions. At Roundwood, SO₄ ^2? declined significantly in humus, shallow and deep soil water. In deep soil water this was accompanied by a long-term increase in pH and a reduction in total aluminum (Al_tot). The recovery from acidification was delayed by high concentrations of NO₃ ^?, which strongly influenced acidity and Al_tot concentrations. At Cloosh, there was a significant decline in SO₄ ^2? in humus water but long-term trends were not evident in shallow or deep soil water; SO₄ ^2? concentrations at these depths fluctuated in response to drought-events. Marine ions strongly influenced soil water chemistry at both sites; at Cloosh soil water acidity was strongly related to Na⁺ and Cl^?, while at Roundwood, Na⁺, Cl^? and Mg²⁺ influenced Al_tot concentrations. Dissolved organic carbon increased significantly in humus and soil water at Roundwood, where it was associated with declining acidity. Soil water at both sites was influenced by a combination of anthropogenic sulphur (S) and nitrogen (N) deposition, drought and sea-salt events. The study highlights the value of long-term monitoring in assessing the response of forest soils to S and N deposition against a background of climate influences on soil water through drought and sea-salt events.     

Watershed- and plot-scale tests of the mobile anion concept

Anion fluxes from a forest soil are usually correlated with those of base cations (BC). Declines in base cation deposition or long-term depletion from the soil may change these relationships. We used multiple regression to identify biogeochemical variables predicting annual volume-weighted concentrations of BC in streamwater draining a forested watershed, and analysis of variance to compare the effects of Ca and Cl inputs on BC fluxes out of soil horizons in irrigated plots. For the watershed, anion concentrations in streamwater predicted BC export most precisely (R ²=0.84). The best two-variable model (adjustedR ²=0.91) also included BC concentration in bulk deposition. Consistent with predictions from equations governing exchange chemistry, the proportion of charge contributed by Ca²⁺ increased with increasing total anion concentration, while that of Na⁺ decreased. At the plot scale, Cl^– concentrations in treatment solutions had a stronger effect (p=0.06) on BC concentration in Oa-horizon solutions than did Ca²⁺ concentrations (p=0.33). In individual horizons of individual plots, BC and total ion concentrations were correlated, but cation composition was not consistent within horizons from different plots. This study detected no evidence of longterm cation depletion in the soils controlling streamwater, but did detect extremely base-poor plots. Because acid deposition affects surface horizons first, streamwater chemistry may not be an adequate way to assess nutrient supply of forest soils.Abbreviations AD anion deficit - BC base cations - HBEF Hubbard Brook Experimental Forest     

The effects of dissolved organic carbon,acidity and seasonality on metal geochemistry within a forested catchment on the Precambrian Shield,central Ontario,Canada

Metal pollution, in combination with other environmental stressors such as acid deposition and climate change, may disturb metal biogeochemical cycles. To investigate the influence of dissolved organic carbon, acidity and seasonality on metal geochemistry, this study has described concentrations of 19 metals as they pass through an acidified forested catchment on the Precambrian Shield in south-central Ontario, Canada. Metal, dissolved organic carbon (DOC) and sulphate (SO₄ ²⁻) concentrations fluctuate throughout the catchment compartments as the water passes through and interacts with vegetation, soils and bedrock. Relationships among metals, DOC and SO₄ ²⁻ are most pronounced in compartments where DOC and SO₄ ²⁻ exhibit high variability, namely in the throughfall, organic horizon soil water, and wetland-draining stream. Metal, DOC and SO₄ ²⁻ concentrations varied seasonally in the streams, and temporal coherence occurred among metal, DOC and SO₄ ²⁻ concentrations in the organic horizon soil water and the wetland-draining stream (PC1). In the wetland-draining stream, the highest DOC, Cr, Cu, Fe, Pb, and V concentrations occur in the summer, whereas concentrations of SO₄ ²⁻ and most other metals peak in the fall after a period of drought. Despite the rural location, provincial water quality objectives for surface water were exceeded for many metals when the peak fall values occurred.