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International audience; The knowledge of the sources of base cations in stream water is a prerequisite to assess potential effects of changing environmental conditions such as changing rainfall, weathering or groundwater flows on cation export with stream water. This study use stable Mg isotopes to identify potential sources in the well-studied catchment of Krycklan located on gneissic bedrock covered by quaternary sediments in Sweden. Samples were collected from open filed rain, throughfall, stream, soil, rock and litterfall. The δ26Mg values of these samples was determined and the contributions of different sources to Mg fluxes in the stream were determined from the variation of the Mg isotope and Sr / Mg ratios.The results show an overall variation of 1.10‰ between all samples. In addition, Magnesium isotope ratios varied little in the streamwater and in soil solution, except during snowmelt periods during which a large portion of the annual runoff occurs. Magnesium in the streamwater is explained as a mixture of three pools (open field rain, soil solution and groundwater) with the latter two influenced by catchment processes. Outside the snowmelt period, Mg in streamwater mainly derived from the groundwater, assumed to be mineral weathering signature in this catchment, with a contribution ranging from 12 to 63% to Mg fluxes. Open field rain dominates Mg fluxes in streamwater during spring flood (0 to 78%) and may contribute significantly during larger summer and autumn rainfall events. Soil solution input to streamwater range from 16 to 59% of Mg fluxes in streamwater. Our results demonstrate that δ26Mg values together with Mg concentrations and Sr/Mg ratios can be used to constrain the Mg sources of stream water and quantify weathering release rates.

Peat stored in large wetlands plays an important role in the carbon cycle and strongly influences water quality of terrestrial surface water bodies. At the same time, peat is also stored in the direct vicinity of many boreal forest streams. From this strategic position, peat can receive and chemically reset hillslope water before it reaches the stream network. Yet, in contrast to large wetlands, only little spatial information is available on the lateral extent of near-stream peat and even less about its vertical variation. Here, we present field data on peat depth and lateral extent collected from approximately 200 transects (with 12 soil profiles taken per transect) distributed across the entire stream network of the Krycklan boreal catchment in Northern Sweden. This soil profile data revealed a considerable heterogeneity of peat and organic horizon thicknesses. By combining the field data with morphological and geological maps, we show how parent material, stream order and local topography influence near stream peat structures. Furthermore, we discuss potential consequences on surface water quality by linking the detailed peat data set to estimates of lateral, shallow groundwater inflows derived from hydrometric measurements and digital terrain analysis.

The study evaluates the biogeochemical model ForSAFE-2D, designed to simulate water and chemical transport from the forest to the stream, by simulating the hydrology and the transport of the chemical tracer chloride (Cl−) along a forest hillslope in Northern Sweden. The simulated Cl− exports were in balance with the simulated inputs but measurements suggested a net release of Cl− from the catchment. Underestimated deposition inputs (deposition peaks and possibly dry deposition) were probably and partially responsible for this mismatch. However, we could not exclude that other soil biogeochemical processes omitted in ForSAFE-2D could also contribute to Cl− exports from the catchment. The study showed that ForSAFE-2D is a promising tool to better understand the factors that regulate the chemical export from the forest to the stream. The results also confirmed that there are limitations in using Cl− as a tracer in forest ecosystems.

Using a 15 year stream record from a northern boreal catchment, we demonstrate that the inter-annual variation in dissolved organic carbon (DOC) concentrations during snowmelt was related to discharge, winter climate and previous DOC export. A short and intense snowmelt gave higher stream water DOC concentrations, as did long winters, while a high previous DOC export during the antecedent summer and autumn resulted in lower concentrations during the following spring. By removing the effect of discharge we could detect that the length of winter affected the modeled soil water DOC concentrations during the following snowmelt period, which in turn affected the concentrations in the stream. Winter climate explained more of the stream water DOC variations than previous DOC export during the antecedent summer and autumn.

Forest biofuel is a main provider of energy in Sweden and the market is expected to grow even further in the future. Removal of logging residues via harvest can lead to short-term acidification but the long-term effects are largely unknown. The objectives of this study were to 1) model the long-term effect of whole-tree harvest (WTH) on soil and stream water acidity and 2) perform sensitivity analyses by varying the amounts of logging residues, calcium (Ca 2 + ) concentrations in tree biomass and site productivity in nine alternate scenarios. Data from three Swedish forested catchments and the Model of Acidification of Groundwater in Catchments (MAGIC) were used to simulate changes in forest soil exchangeable Ca 2 + pools and stream water acid neutralizing capacity (ANC) at Gammtratten, Kindla and Aneboda. Large depletions in soil Ca 2 + supply and a reversal of the positive trend in stream ANC were predicted for all three sites after WTH. However, the magnitude of impact on stream ANC varied depending on site and the concentration of mobile strong acid anions. Contrary to common beliefs, the largest decrease in modelled ANC was observed at the well-buffered site Gammtratten. The effects at Kindla and Aneboda were much more limited and not large enough to offset the general recovery from acidification. Varying the tree biomass Ca 2 + concentrations exerted the largest impact on modelled outcome. Site productivity was the second most important variable whereas changing biomass amounts left on site only marginally affected the results. The outcome from the sensitivity analyses pointed in the same direction of change as in the base scenario, except for Kindla where soil Ca 2 + pools were predicted to be replenished under a given set of input data. The reliability of modelled outcome would increase by using site-specific Ca 2 + concentrations in tree biomass and field determined identification of site productivity.

In this study we present data from a seven-year time series from 15 nested streams within a 68 km(2) catchment, covering a pH gradient of almost three units. We demonstrate that the two landscape t ...

The riparian zone is the narrow strip of land, which lines lakes and watercourses. In the boreal region the riparian zone of headwaters often tends to be -wetland-like with high concentrations of organic matter, low pH and more or less reducing conditions. This means that riparian soils in many respects are different from the podzols and other types of mineral soils that dominate the boreal landscape. In this study a large number of major and trace elements (Al, As, B, Ba, Ca, Cd, Cl, Co, Cr, Cs, Cu, Fe, K, La, Li, Mg, Mn, Na, Ni, Pb, Rb, Se, Si, Sr, Th, Ti, U, V, Zn, Zr) and other parameters such as sulphate, total organic carbon (TOC) and pH were analysed in groundwater and soil water in a boreal hillslope. The objective was to investigate how the chemistry changes as the groundwater passes through the riparian zone and enters the stream. Most of the investigated elements displayed substantially higher (up to 60 times) concentrations in the riparian soils than in the uphill mineral soils. There were also examples of nearly uniform concentrations throughout the transect (e.g. Na and Si), but in only a few cases were lower concentrations observed in the riparian zone (e.g. K, Mg and Ca). The degree of enrichment in the riparian soils could be linked to the affinity for organic matter, indicating that the pattern with strongly elevated concentrations in riparian soils is typical for organophilic elements. However, the elevated concentrations of many elements in the riparian zone could not be linked to increased uptake in biota (bilberry leaves and spruce shoots). In summary, the results confirmed that the riparian zone plays a central role for regulating the stream water quality and the transfer of a wide range of elements from terrestrial to aquatic ecosystems. Hence, riparian soils are essential for understanding the fate of nutrients, pollutants and other substances in the boreal landscape.

Riparian zones (RZ) are a major factor controlling water chemistry in forest streams. Base cations' (BC) concentrations, fluxes, and cycling in the RZ merit attention because a changing climate and increased forest harvesting could have negative consequences, including re-acidification, for boreal surface waters. We present a two-year study of BC and silica (Si) flow-weighted concentrations from 13 RZ and 14 streams in different landscape elements of a boreal catchment in northern Sweden. The spatial variation in BC and Si dynamics in both RZ and streams was explained by differences in landscape element type, with highest concentrations in silty sediments and lowest concentrations in peat-dominated wetland areas. Temporal stability in BC and Si concentrations in riparian soil water, remarkably stable Mg/Ca ratios, and homogeneous mineralogy suggest that patterns found in the RZ are a result of a distinct mineralogical upslope signal in groundwater. Stream water Mg/Ca ratios indicate that the signal is subsequently maintained in the streams. Flow-weighted concentrations of Ca, Mg, and Na in headwater streams were represented by the corresponding concentrations in the RZ, which were estimated using the Riparian Flow-Concentration Integration Model (RIM) approach. Stream and RZ flow-weighted concentrations differed for K and Si, suggesting a stronger biogeochemical influence on these elements, including K recirculation by vegetation and retention of Si within the RZ. Potential increases in groundwater levels linked to forest harvesting or changes in precipitation regimes would tend to reduce BC concentrations from RZ to streams, potentially leading to episodic acidification.

Surface water concentrations of dissolved organic carbon ([DOC]) are changing throughout the northern hemisphere due to changes in climate, land use and acid deposition. However, the relative importance of these drivers is unclear. Here, we use the Integrated Catchments model for Carbon (INCA-C) to simulate long-term (1996-2008) streamwater [DOC] at the four Swedish integrated monitoring (IM) sites. These are unmanaged headwater catchments with old-growth forests and no major changes in land use. Daily, seasonal and long-term variations in streamwater [DOC] driven by runoff, seasonal temperature and atmospheric sulfate (SO₄(2-)) deposition were observed at all sites. Using INCA-C, it was possible to reproduce observed patterns of variability in streamwater [DOC] at the four IM sites. Runoff was found to be the main short-term control on [DOC]. Seasonal patterns in [DOC] were controlled primarily by soil temperature. Measured SO₄(2-) deposition explained some of the long-term [DOC] variability at all sites.

We bring together three decades of research from a boreal catchment to facilitate an improved mechanistic understanding of surface water dissolved organic carbon (DOC) regulation across multiple scales. The Krycklan Catchment Study encompasses 15 monitored nested research catchments, ranging from 3 to 6900 ha in size, as well as a set of monitored transects of forested and wetland soils. We show that in small homogenous catchments, hydrological functioning provides a first order control on the temporal variability of stream water DOC. In larger, more heterogeneous catchments, stream water DOC dynamics are regulated by the combined effect of hydrological mechanisms and the proportion of major landscape elements, such as wetland and forested areas. As a consequence, streams with heterogeneous catchments undergo a temporal switch in the DOC source. In a typical boreal catchment covered by 10-20% wetlands, DOC originates predominantly from wetland sources during low flow conditions. During high flow, the major source of DOC is from forested areas of the catchment. We demonstrate that by connecting knowledge about DOC sources in the landscape with detailed hydrological process understanding, an improved representation of stream water DOC regulation can be provided. The purpose of this study is to serve as a framework for appreciating the role of regulating mechanisms, connectivity and scaling for understanding the pattern and dynamics of surface water DOC across complex landscapes. The results from this study suggest that the sensitivity of stream water DOC in the boreal landscape ultimately depends on changes within individual landscape elements, the proportion and connectivity of these affected landscape elements, and how these changes are propagated downstream.

The fate of hydrophobic organic compounds (HOCs) in soils and waters in a northern boreal catchment was explored through the development of a chemical fate model in a well-characterised catchment system dominated by two land types: forest and mire. Input was based solely on atmospheric deposition, dominated by accumulation in the winter snowpack. Release from soils was governed by the HOC concentration in soil, the soil organic carbon fraction and soil-water DOC content. The modelled export of selected HOCs in surface waters ranged between 11 and 250 ng day(-1) during the snow covered period, compared to 200 and 9600 ng/d during snow-melt; highlighting the importance of the snow pack as a source of these chemicals. The predicted levels of HOCs in surface water were in reasonable agreement to a limited set of measured values, although the model tended to over predict concentrations of HOCs for the forested sub-catchment, by over an order of magnitude in the case of hexachlorobenzene and PCB 180. This possibly reflects both the heterogeneity of the forest soils and the complicated and changing hydrology experienced between the different seasons.

This paper defines landscape-scale patterns in the character of natural organic matter (NOM) and tests for relationships to catchment soil, vegetation and topography. The drainage network of a boreal catchment, subcatchment size 0.12–78 km2, in Northern Sweden was sampled in August 2002 during a period of stable low water flow. The NOM was characterized with UV/Vis spectroscopy, fluorescence, XAD-8 fractionation (%humic substances), gel permeation chromatography (apparent molecular weight), and elemental composition (C:N). The largest spatial variation was found for C:N, absorbance ratio, and specific visible absorptivity. The lowest variation was in fluorescence index, %humic substances and molecular retention time. But the variation in total organic carbon (TOC), iron and aluminium concentration was more than twice that of C:N. Between headwater and downstream sites no significant changes were distinguished in the NOM character. At stream reaches, junctions and lakes little change (

Summary Two different but complementary modelling approaches for reproducing the observed dynamics of total organic carbon (TOC) in a boreal stream are presented. One is based on a regression analysis, while the other is based on riparian soil conditions using a convolution of flow and concentration. Both approaches are relatively simple to establish and help to identify gaps in the process understanding of the TOC transport from soils to catchments runoff. The largest part of the temporal variation of stream TOC concentrations (4–46 mg L−1) in a forested headwater stream in the boreal zone in northern Sweden may be described using a four-parameter regression equation that has runoff and transformed air temperature as sole input variables. Runoff is assumed to be a proxy for soil wetness conditions and changing flow pathways which in turn caused most of the stream TOC variation. Temperature explained a significant part of the observed inter-annual variability. Long-term riparian hydrochemistry in soil solutions within 4 m of the stream also captures a surprisingly large part of the observed variation of stream TOC and highlights the importance of riparian soils. The riparian zone was used to reproduce stream TOC with the help of a convolution model based on flow and average riparian chemistry as input variables. There is a significant effect of wetting of the riparian soil that translates into a memory effect for subsequent episodes and thus contributes to controlling stream TOC concentrations. Situations with high flow introduce a large amount of variability into stream water TOC that may be related to memory effects, rapid groundwater fluctuations and other processes not identified so far. Two different climate scenarios for the region based on the IPCC scenarios were applied to the regression equation to test what effect the expected increase in precipitation and temperature and resulting changes in runoff would have on stream TOC concentrations assuming that the soil conditions remain unchanged. Both scenarios resulted in a mean increase of stream TOC concentrations of between 1.5 and 2.5 mg L−1 during the snow free season, which amounts to approximately 15% more TOC export compared to present conditions. Wetter and warmer conditions in the late autumn led to a difference of monthly average TOC of up to 5 mg L−1, suggesting that stream TOC may be particularly susceptible to climate variability during this season.

Criteria are needed for distinguishing naturally acid water from that acidified by air pollution, especially in the organic-rich waters of northern Sweden. The Steady-State Water Chemistry Model (SSWC) was augmented to include organic acidity so that it could predict pre-industrial pH in organic-rich waters. The resulting model predictions of pre-industrial ANC and pH were then tested against diatom predictions of pre-industrial pH and alkalinity in 58 lakes from N. Sweden (after alkalinity was converted to ANC using the CBALK method). The SSWC Model's predictions of pre-industrial lake pH in N. Sweden did not correspond well with the diatom predictions, even when accounting for the uncertainty in the diatom model. This was due to the SSWC's sensitivity to short-term fluctuations in contemporary water chemistry. Thus the SSWC Model is not suitable for judging the acidification of individual lakes in areas such as northern Sweden where the degree of chronic acidification is small, or without a good average value of contemporary water chemistry. These results should be considered when assessing the accuracy of critical loads calculated using SSWC.

Low-order boreal streams are particularly sensitive interfaces where dissolved organic matter (DOM) is transported from soils to inland waters. Disentangling the relative influence of key environmental factors suspected to influence stream water DOM composition is highly relevant to predicting the reactivity and fate of terrestrial DOM entering inland waters. Here we examined changes to DOM composition using absorbance and fluorescence, from 17 boreal streams ranging from first to fourth orders, over 14 months, including the rarely studied winter season, and two snowmelt periods (n = 836). We also analyzed soil pore water samples from three forest soil lysimeters to a depth of 70 cm (n = 60). Of five identified fluorescing parallel factor analysis components, two (C4 and C5) expressed a clear mire wetland or forest signature, providing distinct molecular markers of dominant land cover. In fact, land cover alone explained 49% of the variability in DOM composition. In contrast, seasonal fluctuations in hydrology only contributed to minor shifts (8%) in the composition of stream water DOM, while in-stream transformations to DOM composition were undetectable. These findings suggest that low-order boreal streams act as a passive pipe, since in-stream processing of DOM is restricted by short water residence times (6 h to 2 days). In addition, we demonstrated the sensitivity of optical approaches to distinguish between key terrestrial sources of DOM in the boreal landscape. By distinguishing the proportional leverage of key environmental controls on headwater stream DOM composition, we are better equipped to predict where and when key DOM transformations occur in the aquatic conduit.

Inorganic aluminum (Al) concentrations are critical for defining the biological effects of acidification. The landscape's role in controlling the spatial variability of Al and its speciation has received only limited attention. We analyzed the speciation of stream Al at 14 sites within a 68 km2 boreal catchment during spring snowmelt, a period of episodic acidity. Three factors that influenced Al at these sites were landscape type (specifically the proportion of wetland areas), stream pH, and dissolved organic carbon (DOC). Forested catchment sites underlain by mineral soils had higher total Al concentrations and greater inorganic Al proportions than catchments with larger wetland areas, despite significantly higher pH. We suggest that this difference results from source limitation of Al in the peat wetlands. The control of Al solubilitywas dominated by organic complexes, with the organic carrying capacity exceeding Al in the majority of samples. When assessing the inorganic phase, only four percent of the samples were oversaturated with regards to commonly forming secondary Al minerals, with no samples showing supersaturation higher than 10 times with respect to any given solid phase. Inorganic Al rarely exceeded biological thresholds, except for short periods during peak flow in forested areas, despite two-thirds of the streams having minimum pH values below 4.9. Streams with a high percentage of wetland area were associated with lower Al:DOC ratios. The Al:DOC ratios were quite stable in each stream before, during, and after snowmelt, with the exception of isolated spikes in the Al:DOC ratio associated with particulate Al at a downstream site during high flow.

We have combined a long-term hydrochemistry model (MAGIC) with a model that predicts short-term transient changes in hydrochemistry (pBDM) during hydrological events in order to improve the temporal resolution of retrospective analyses and future predictions of streamwater acidification. The model has been applied to a heavily impacted catchment in the Czech Republic. Spring flood acid-neutralizing capacity (ANC), pH, and inorganic monomeric aluminum (Al i n+ ) were simulated for the years of 1860, 1900, 1930, 1950, 1965, and 1985, measured in 1999, and predicted for 2030 using two different emission control scenarios. If the emission reduction according to the current legislation scenario is implemented, the model predicts that the spring flood pH, ANC, and Al i n+ will recover close to the level of the 1950s by 2030. This will occur despite the annual average chemistry being far from having recovered to that level. The results suggest that the recovery of spring flood events is faster then the recovery of annual average chemistry and that much of what is won by further emission reduction will not be fully realized on an annual time scale.

Total organic carbon (TOC) concentrations from seven boreal catchments in northern Sweden were monitored between June 1996 and May 1998 to examine spatial and temporal variations in streamwater TOC export and its relationship with catchment characteristics. The annual average export of TOC ranged between 36 and 76 kg ha–1 yr–1 and correlated positively with the areal extent of wetlands (r2 = 0.72; p = 0.03). The daily output of TOC was 5–11 times higher during the spring than during any other season. In total, the four week long spring period contributed between 50% and 68% of the annual TOC export from the seven catchments. The relative importance of the spring snow melt period for the annual TOC export, however, correlated negatively with the percentage of wetlands (r2 = 0.83; p

Resolving the Double Paradox of rapidly mobilized old water with highly variable responses in runoff chemistry

Natural organic matter (NOM) from stream and soil water in a humic-rich headwater catchment in northern Sweden (initial total organic carbon (TOC) concentrations 10-40 mg C L-1) was rapidly degrade ...

Inland waters transport large amounts of dissolved organic matter (DOM) from terrestrial environments to the oceans, but DOM also reacts en route, with substantial water column losses by mineralization and sedimentation. For DOM transformations along the aquatic continuum, lakes play an important role as they retain waters in the landscape allowing for more time to alter DOM. We know DOM losses are significant at the global scale, yet little is known about how the reactivity of DOM varies across landscapes and climates. DOM reactivity is inherently linked to its chemical composition. We used fluorescence spectroscopy to explore DOM quality from 560 lakes distributed across Sweden and encompassed a wide climatic gradient typical of the boreal ecozone. Six fluorescence components were identified using parallel factor analysis (PARAFAC). The intensity and relative abundance of these components were analyzed in relation to lake chemistry, catchment, and climate characteristics. Land cover, particularly the percentage of water in the catchment, was a primary factor explaining variability in PARAFAC components. Likewise, lake water retention time influenced DOM quality. These results suggest that processes occurring in upstream water bodies, in addition to the lake itself, have a dominant influence on DOM quality. PARAFAC components with longer emission wavelengths, or red-shifted components, were most reactive. In contrast, protein-like components were most persistent within lakes. Generalized characteristics of PARAFAC components based on emission wavelength could ease future interpretation of fluorescence spectra. An important secondary influence on DOM quality was mean annual temperature, which ranged between � 6.2 and +7.5 °C. These results suggest that DOM reactivity depends more heavily on the duration of time taken to pass through the landscape, rather than temperature. Projected increases in runoff in the boreal region may force lake DOM toward a higher overall amount and proportion of humic-like substances.

The recent browning (increase in color) of surface waters across much of the northern hemisphere has important implications for light climate, ecosystem functioning, and drinking water treatability. Using log-linear regressions and long-term (6–21 years) data from 112 Swedish watercourses, we identified temporal and spatial patterns in browning-related parameters [iron, absorbance, and total organic carbon (TOC)]. Flow variability and lakes in the catchment were major influences on all parameters. Co-variation between seasonal, discharge-related, and trend effects on iron, TOC, and absorbance were dependent on pH, landscape position, catchment size, latitude, and dominant land cover. Large agriculture-dominated catchments had significantly larger trends in iron, TOC, and water color than small forest catchments. Our results suggest that while similarities exist, no single mechanism can explain the observed browning but show that multiple mechanisms related to land cover, climate, and acidification history are responsible for the ongoing browning of surface waters. Electronic supplementary material The online version of this article (doi:10.1007/s13280-014-0560-5) contains supplementary material, which is available to authorized users.

In northern regions, spring snowmelt generally results in an episodic decline of surface water pH. Natural organic acids may be an important factor in this type of pH change. We studied the variations in the acid/base character of aquatic organic acids during spring snowmelt in 1997 at Svartberget, a stream rich in total organic carbon (TOC) that is located in the boreal zone of northern Sweden. Snowmelt at Svartberget was accompanied by a drop in stream pH of up to 1.8 pH units, as well as the dilution of base cation and strong acid anion concentrations. Aluminum and TOC increased or decreased during snowmelt, depending on the sampling site within the 50-ha catchment. Although there were distinct differences in pH, TOC, and major inorganic ions in the runoff from three subcatchments, there was very little variation in the acid/base character of TOC. Thus organic acids in the Svartberget catchment share a common set of acid/base properties despite markedly different subcatchment drainage patterns, vegetation, and soils. The dissociation behavior of organic acids at Svartberget could be described with high precision (R2 = 0.91, p < 0.001, and n = 115) by a triprotic acid analog model (pKa1 = 2.5, pKa2 = 4.0, and pKa3 = 5.8), together with the measured site density of organic acids (8.6±0.8 μeq (mg TOC)−1). A Gaussian pKa distribution (μ = 4.20 and σ = 1.43) predicted organic acid dissociation with similar precision (R2 = 0.91, p < 0.001, and n = 94). Variations in site density among the tributary streams could largely be explained by aluminum complexation. Sites with lower measured site densities had greater concentrations of organically bound Al. Thus Al binding reduces the potential release or neutralization of H+ by organic acids.

Episodic pH decline associated with spring flood runoff in a typical headwater stream in the boreal forest of northern Sweden is driven almost exclusively by natural processes. Despite a drastic decline in acid neutralisation capacity (ANC), a 75-fold increase in hydrogen ion concentration and an associated increase in inorganic monomeric aluminium fractions, anthropogenic deposition (the strong acids SO42− and NO3− associated with anthropogenic deposition) made only a minor contribution (5–8%) to the ANC and pH decline during the spring flood of 1997. Instead the ANC decline from 60 μeq. l−1 during winter baseflow to −26 μeq. l−1 at peak flow, as well as the associated pH decline from approximately 6.4–4.6 was, according to an episodic acidification model, driven almost exclusively by organic acids originating from the soil and dilution by low ionic strength snowmelt water. The natural component of ANC and pH decline during spring flood, such as that reported here, has important implications for the aquatic ecology of the boreal zone in general, and for the Swedish liming program in particular, since government subsidies are used to keep pH above 6.0 throughout spring flood, in the belief that this is the natural pH level prior to the appearance of acid rain in Europe.

Forest riparian zones are a major in control of surface water quality. Base cation (BC) concentrations, fluxes, and cycling in the riparian zone merit attention because of increasing concern of negative consequences for re-acidification of surface waters from future climate and forest harvesting scenarios. We present a two-year study of BC and silica (Si) flow-weighted concentrations from 13 riparian zones and 14 streams in a boreal catchment in northern Sweden. The Riparian Flow-Concentration Integration Model (RIM) was used to estimate riparian zone flow-weighted concentrations and tested to predict the stream flow-weighted concentrations. Spatial variation in BC and Si concentrations as well as in flow-weighted concentrations was related to differences in Quaternary deposits, with the largest contribution from lower lying silty sediments and the lowest contribution from wetland areas higher up in the catchment. Temporal stability in the concentrations of most elements, a remarkably stable Mg / Ca ratio in the soil water and a homogeneous mineralogy suggest that the stable patterns found in the riparian zones are a result of distinct mineralogical upslope groundwater signals integrating the chemical signals of biological and chemical weathering. Stream water Mg / Ca ratio indicates that the signal is subsequently maintained in the streams. RIM gave good predictions of Ca, Mg, and Na flow-weighted concentrations in headwater streams. The difficulty in modelling K and Si suggests a stronger biogeochemical influence on these elements. The observed chemical dilution effect with flow in the streams was related to variation in groundwater levels and element concentration profiles in the riparian zones. This study provides a first step toward specific investigations of the vulnerability of riparian zones to changes induced by forest management or climate change, with focus on BC or other compounds.

The boreal landscape is a complex, spatio-temporally varying mosaic of forest and mire landscape elements that control surface water hydrology and chemistry. Here, we assess long-term water quality time series from three nested headwater streams draining upland forest (C2), peat/mire (C4) and mixed (C7) (forest and mire) catchments. Acid deposition in this region is low and is further declining. Temporal trends in weather and runoff (1981–2008), dissolved organic carbon concentration [DOC] (1993–2010) and other water quality parameters (1987–2011) were assessed. There was no significant annual trend in precipitation or runoff. However, runoff increased in March and declined in May. This suggested an earlier snowmelt regime in recent years. Significant monotonic increasing trends in air temperature and length of growing season suggested a decrease in snowfall and less spring runoff. Stream [DOC] was positively correlated with some trace metals (copper, iron and zinc) and negatively with several other chemical parameters (e.g. sulfate, conductivity, calcium). Both sulfate and conductivity showed declining trends, while a significant increase was observed in pH during winter and spring. Calcium and magnesium showed monotonic decreasing trends. The declining trajectories of stream base cation and sulfate concentrations during other times of the year were not accompanied by changes in pH and alkalinity. These results indicate subtle effects of recovery from acidification. Water temperature increased significantly both annually and in most months. A simultaneous monotonic increase in iron (Fe) and [DOC] in autumn suggests co-transport of Fe-DOC in the form of organometallic complexes. A monotonic increase in UV absorbance in most months without co-occurring changes in DOC trend suggests a shift in DOC quality to a more humic-rich type. The observed increase in soil solution [DOC] and subtle trends in stream [DOC] suggest that climate rather than recovery from acidification is the dominant driver of DOC trends in the Svartberget catchment.

Four river basins in southern Sweden, with catchment sizes from 0.3 to 127 km2 (median 1.9), were sampled in October~2007. The 243 samples were analysed for 26 trace elements (Ag, As, Au, Ba, Be, Bi, Cd, Co, Cr, Cu, Ga, Ge, In, La, Li, Mo, Ni, Pb, Sb, Se, Sn, Tl, Ti, U, V and Zn) to identify spatial patterns within drainage networks. The range and median of each element were defined for different stream orders, and relationships to catchment characteristics, including deposition history, were explored. The sampling design made it possible to compare the differences along 40 stream reaches, above and below 53 stream junctions with 107 tributaries and between the 77 inlets and outlets of 36 lakes. The largest concentration differences (at reaches, junctions and lakes) were observed for lakes, with outlets usually having lower concentration compared to the inlets for As, Ba, Be, Bi, Cd, Co, Cr, Ga, Ge, Ni, Pb, Sn, Ti, Tl, U, V and Zn. Significantly lower concentrations were observed for Cd and Co when comparing headwaters with downstream sites in each catchment. Common factor analysis (FA) revealed that As, Bi, Cr, Ga, Ge, Tl and V co-vary positively with Al, Fe and total organic carbon (TOC) and negatively with La, Li and pH. The strong removal of a large number of trace elements when passing through lakes is evident though in the FA, where lake surface coverage plots opposite to many of those elements. Forest volume does not respond in a similar systematic fashion and, surprisingly, the amount of wetland does not relate strongly to either Fe or TOC at any of the rivers. A better understanding of the quantitative removal of organic carbon and iron will aid in understanding trace element fluxes from landscapes rich in organic matter and iron.

Long term data series (1996–2009) for eleven acidic, headwater streams (

[1] Large spatial and temporal variations in stream total organic carbon (TOC) concentration and export occurred during an 11-year observation period (1993–2003) in a boreal headwater catchment. TOC flux and concentration patterns from mire- and forest-dominated subcatchments differed (mean annual flux 8.2 g m−2 a−1 versus 5.8 g m−2 a−1). Temporal variations in stream TOC concentrations in both landscape types were primarily driven by variations in streamflow, with the mire stream generally diluting by half with increased runoff during spring flood and TOC from the forested landscape increasing during runoff peaks irrespective of season. Average TOC concentration in the mire stream in the snow-free season increased with increased seasonal precipitation from around 20 to 40 mg L−1 but then dropped to around 35 mg L−1 during very wet years. Average snow-free season TOC concentration at the forested site remained stable when summer precipitation was below average but then increased from 10 to around 25 mg L−1 during exceptionally wet years. For both the forested subcatchment and the whole catchment, TOC concentrations increased during the warm summer months during wet years, but no such increase occurred during dry years. Interannual variations in TOC flux were primarily driven by variations during the snow-free period. Wet years decreased the relative TOC export from the mire and favored the relative export of TOC from areas dominated by forest, an observation that also held true on a larger scale when similar landscape types were considered. Predicted climate change in rainfall and temperature patterns will affect the amount and character of TOC exported downstream from boreal landscapes with a mix of forest and mire.

Krycklan is a 68 km2 catchment in northern Sweden, where hydrological, hydrochemical and biogeochemical research has been carried out for more than 30 years. Hence, the area has a well developed sampling infrastructure and long time-series, which has lead to a good understanding of the hydrological processes. During two years uranium activities in streams from 10 sub-catchments in the area were followed, which has resulted in more than 400 measurements. The material was then analyzed from a geostatistical perspective, and it could be shown the forest and wetland percentage was the single most important factor for explaining the spatial and temporal variability in uranium transport within the catchment.

[1] Aluminum (Al) transfer from soils to surface waters is a crucial determinant of aquatic biodiversity in acidified and/or naturally acid surface waters. Defining how landscapes and acid deposition influence Al export depends on our understanding of the mobilization of Al within catchments. This paper documents the evolution of Al chemistry in water during its transport through a hillslope by using soil water chemistry combined with hydrometric data. Al levels moving laterally from upslope mineral soils were low (

soil during the spring. The approximately sixtyfold increase in runoff, from 0.13 mm d � 1 to 8 mm d � 1 , was generated by a 30–40 cm rise of the groundwater level. The total runoff during the snowmelt period from late April to late May was 134 mm, of which 75% was preevent water. Mass balance calculations based on hydrometric and isotopic data independently, both using upscaling of a hillslope transect to the entire 13-ha catchment, provided similar results of both water storage changes and the amount of event water that was left in the catchment after the snowmelt. In general, groundwater levels and runoff were strongly correlated, but different functional relationships were observed for frozen and unfrozen soil conditions. Although runoff generation in the catchment generally could be explained by the transmissivity feedback concept, the results suggest that there is a temporal variability in the flow pathways during the spring controlled by soil frost during early snowmelt. INDEX TERMS: 1860 Hydrology: Runoff and streamflow; 1836 Hydrology: Hydrologic budget (1655); 1821 Hydrology: Floods; 1823 Hydrology: Frozen ground; KEYWORDS: hydrograph separation, oxygen 18, snowmelt, spring flood, boreal, northern Sweden, transmissivity feedback

Long-term (1987–2012) water quality monitoring in 36 acid-sensitive Swedish lakes shows slow recovery from historic acidification. Overall, strong acid anion concentrations declined, primarily as a result of declines in sulfate. Chloride is now the dominant anion in many acid-sensitive lakes. Base cation concentrations have declined less rapidly than strong acid anion concentrations, leading to an increase in charge balance acid neutralizing capacity. In many lakes, modeled organic acidity is now approximately equal to inorganic acidity. The observed trends in water chemistry suggest lakes may not return to reference conditions. Despite declines in acid deposition, many of these lakes are still acidified. Base cation concentrations continue to decline and alkalinity shows only small increases. A changing climate may further delay recovery by increasing dissolved organic carbon concentrations and sea-salt episodes. More intensive forest harvesting may also hamper recovery by reducing the supply of soil base cations.

The quantitative distinction of the natural and anthropogenic components of episodic pH decline is important but problematic. This paper presents the Boreal Dilution Model as a means of separating the natural effects of acid neutralizing capacity (ANC) dilution and organic acids from those of acid deposition on stream pH during spring flood or other flow episodes in areas that are not chronically acidified. Key model assumptions are that base flow ANC reflects preindustrial ANC, that the contemporary dissolved organic carbon is natural, and that dilution of base cations during spring flood is a measure of natural ANC dilution. The model could help elucidate the natural variation of spring flood chemistry, as well as the response to changes in acidification pressures. An example of the model's application to one catchment is presented. This example, together with the correlation between winter SO42− deposition and modeled anthropogenic ANC depression during spring flood in some 27 episodes from 18 catchments, is presented to assess the model's plausibility.

The riparian zone, the last few metres of soil through which water flows before entering a gaining stream, has been identified as a first order control on key aspects of stream water chemistry dynamics. We propose that the distribution of lateral flow of water across the vertical profile of soil water chemistry in the riparian zone provides a conceptual explanation of how this control functions in catchments where matrix flow predominates. This paper presents a mathematical implementation of this concept as well as the model assumptions. We also present an analytical solution, which provides a physical basis for the commonly used power-law flow-load equation. This approach quantifies the concept of riparian control on stream-water chemistry providing a basis for testing the concept of riparian control. By backward calculation of soil-water-chemistry profiles, and comparing those with observed profiles we demonstrate that the simple juxtaposition of the vertical profiles of water flux and soil water chemistry provides a plausible explanation for observed variations in stream water chemistry of several major stream components such as Total Organic Carbon (TOC), magnesium, calcium and chloride. The "static" implementation of the model structure presented here provides a basis for further development to account for seasonal influences and hydrological hysteresis in the representation of hyporheic, riparian, and hillslope processes.