Organic and minerogenic acidity in Finnish rivers in relation to land use and deposition

The role of organic and minerogenic acidity in controlling pH levels in Finnish rivers was studied by measuring total organic carbon (TOC) and non-marine sulphate (*SO(4)) concentrations in river water of the main river basins and their sub-basins. The basins are located along a latitudinal gradient (60 degrees N to 69 degrees N) and cover 297,322 km(2), 88% of the total area of Finland. The basins are predominately covered by coniferous forests and peatlands, and are located in areas with low sulphate deposition (80-430 mg S m(-2) a(-1)). The proportion of the basin covered by forests on mineral soils ranges from 29 to 64% and the proportion of peatlands from 3 to 60%. The percentage of peatland is highest in northern Finland (28-60%), whereas the proportion of forests on mineral soils increases towards the south. The majority of the agricultural land is located in southern and western Finland. *SO(4) concentrations were positively correlated with the proportion of agricultural land in the basin. Moreover, the percentage of peatlands had a positive correlation with the concentrations of TOC and organic anion. High peatland proportion and high TOC and organic anion concentrations decreased pH values in the river water, whereas no correlation between *SO(4) concentrations and pH was observed. The average organic anion concentration exceeded the average *SO(4) concentration in river water in 17 basins out of the 86 studied basins. The organic anion-dominated areas were situated in northern basins, reflecting the high extent of peatlands in these areas. *SO(4) dominated in southern Finland and in western coastal areas, where the extent of agricultural land, acid sulphate soils and the deposition of sulphate is highest.     

Dissolved and particulate nutrient export from rural catchments: a case study from Luxembourg

Nutrient enrichment of freshwaters continues to be one of the most serious problems facing the management of surface waters. Effective remediation/conservation measures require accurate qualitative and quantitative knowledge of nutrient sources, transport mechanisms, transformations and annual dynamics of different nitrogen (N) and phosphorus (P) forms. In this paper, nitrate (NO3-N), soluble reactive phosphorus (SRP) and total phosphorus (TP) concentrations and loads are presented for two adjacent rural basins of 306 km2 and 424 km2, and for five sub-basins differing in size (between 1 km2 and 33 km2), land use (extent of forest cover between 20% and 93%) and household pressure (from 0 to 40 people/km2) with the aim of studying the influence of land use and catchment size on nutrient exports. The studied catchments are all situated on Devonian schistous substrates in the Ardennes region (Belgium-Luxembourg), and therefore have similar hydrological regimes. As the study period could not be the same for all basins, annual export coefficients were corrected with the 25 years normalized discharge of the Sure River: two regression analyses (for dry and humid periods) relating monthly nutrient loads to monthly runoff were used to determine correction factors to be applied to each parameter and each basin. This procedure allows for the comparing annual export coefficients from basins sampled in different years. Results show a marked seasonal response and a large variability of NO3-N export loads between forested (4 kg N ha-1 year-1), agricultural (27-33 kg N ha-1 year-1) and mixed catchments (17-22 kg N ha-1 year-1). For SRP and TP, no significant agricultural impact was found. Land and bank erosion control the total P massflow in the studied catchments (0.4-1.3 kg P ha-1 year-1), which is mostly in a particulate form, detached and transported during storm events. Soluble reactive P fluxes ranged between 10% and 30% of the TP mass, depending on the importance of point sources in the basins studied. No relation was found between the size of the basins and the export of nitrate, SRP or TP. Nutrient export, specially for NO3-N and TP, shows significant inter-annual variations, closely linked to inter-annual discharge variations. Flow and load frequency data analysis confirm this association for all the basins on an annual basis. Seasonal or storm specific fluxes strongly deviate from their annual values.     

Organic and inorganic carbon concentrations and fluxes from managed and unmanaged boreal first-order catchments

Seasonal and between stream variation (catchment dependent variation) in losses of organic and inorganic carbon via downstream transport and outgassing of CO₂ into the atmosphere were studied in 11 small boreal catchments situated in close proximity to each other. Of these catchments four were undrained peatland rich catchments, four drained peatland rich catchments and three managed mineral soil-dominated catchments. Downstream export of total inorganic carbon (TIC) varied between 870 and 1400 kg km^− 2 a^− 1 and was rather consistent between the catchments, except in the case of the mineral soil-dominated catchment Kangaslampi, where export was only 420 kg km^− 2 a^− 1. The export of total organic carbon (TOC) varied between 2300 and 14,800 kg km^− 2 a^− 1 and was highest in peatland rich catchments. Peatland drainage decreased TIC and TOC concentrations in the long term, but did not affect lateral carbon export due to increased runoff from the catchments. Partial pressure of CO₂ in streams was the highest in undrained peatland rich catchments, but the outgassing of CO₂ into the atmosphere was also high from drained peatlands due to the higher discharge rate and long ditch networks. In mineral soil-dominated catchments both downstream export of carbon and emission into the atmosphere were low. TOC exports were compared in two climatically different years (2003 and 2007). The results indicate that climate change might alter the timing of the TOC export from the catchments, the importance of the spring ice melt diminishing and both snow cover and snow free period export increasing.     

Trends in hydrometeorological conditions and stream water organic carbon in boreal forested catchments

Temporal trends in stream water total organic carbon (TOC) concentration and export were studied in 8 forested headwater catchments situated in eastern Finland. The Seasonal Kendall test was conducted to identify the trends and a mixed model regression analysis was used to describe how catchment characteristics and hydrometeorological variables (e.g. precipitation, air and stream water temperatures, and atmospheric deposition) related to the variation in the concentration and export of stream water TOC. The 8 catchments varied in size from 29 to 494 ha and in the proportion of peatland they contained, from 8 to 70%. Runoff and TOC concentration were monitored for 15-29 years (1979-2006). Trends and variation in TOC levels were analysed from annual and seasonal time series. Mean annual TOC concentration increased significantly in seven of the eight catchments. The trends were the strongest in spring and most apparent during the last decade of the study period. The slopes of the trends were generally smaller than the variation in TOC concentration between years and seasons and between catchments. The annual TOC export showed no clear trends and values were largely determined by the temporal variability in runoff. Annual runoff showed a decreasing trend in two of the eight catchments. Mean annual air and stream water temperatures showed increasing trends, most clearly seen in the summer and autumn series. According to our modeling results, stream water temperature, precipitation and peatland percentage were the most important variables explaining annual and most seasonal TOC concentrations. The atmospheric deposition of SO₄, NH₄, and NO₃ decreased significantly over the study period, but no significant link with TOC concentration was found. Precipitation was the main hydrometeorological driver of the TOC export. We concluded that stream water TOC concentrations and exports are mainly driven by catchment characteristics and hydrometeorological factors rather than trends in atmospheric acid deposition.     

Stream water hydrochemistry as an indicator of carbon flow paths in Finnish peatland catchments during a spring snowmelt event

Extreme hydrological events are known to contribute significantly to total annual carbon export, the largest of which in Arctic and boreal catchments is spring snowmelt. Whilst previous work has quantified the export of carbon during snowmelt, the source of the carbon remains unclear. Here we use cation hydrochemistry to trace the primary flowpaths which govern the export of carbon during the snowmelt period; specifically we aim to examine the importance of snowpack meltwater to catchment carbon export. The study was carried out in two forested peatland (drained and undrained) catchments in Eastern Finland. Both catchments were characterised by base-poor stream water chemistry, with cation concentrations generally decreasing in response to increasing discharge. Streamflow during the snowmelt period was best described as a mixture of three sources: pre-event water, snowpack meltwater and a third dilute component we attribute to the upper snow layer which was chemically similar to recent precipitation. Over the study period, pre-event water contributed 32% and 43% of the total stream runoff in Välipuro (undrained) and Suopuro (drained), respectively. The results also suggest a greater near-surface throughflow component in Suopuro, the drained catchment, prior to snowmelt. CO₂ and DOC concentrations correlated positively with cation concentrations in both catchments indicating a common, peat/groundwater flowpath. CH₄ concentrations were significantly higher in the drained catchment and appeared to be transported in near-surface throughflow. Meltwater from the snowpack represented an important source of stream water CO₂ in both catchments, contributing up to 49% of total downstream CO₂ export during the study period. We conclude that the snowpack represents a potentially important, and often overlooked, transient carbon store in boreal snow-covered catchments.     

Impact of forest ditching on nutrient loadings of a small stream--a paired catchment study in Kronoby,W. Finland

The effect of ditching of boreal forest land (W. Finland) on P and N dynamics and export was assessed using a paired catchment approach (response stream + control stream) for a 4-year study period. After the ditching operations, there was a small but significant increase in the NH4+ export, but no significant changes in the concentrations and loads of total reactive P, total non-reactive P, total organic N and NO3-. In both streams, the reactive P fraction largely followed the Fe concentrations. High input to output ratios, and thus, high retention was a typical feature of the inorganic N compounds. Total organic N and the TOC/TON ratio were positively correlated with the total organic carbon.     

Climate driven release of carbon and mercury from permafrost mires increases mercury loading to sub-arctic lakes

In sub-arctic and arctic regions mercury is an element of concern for both wildlife and humans. Over thousands of years large amounts of atmospherically deposited mercury, both from natural and anthropogenic sources, have been sequestered together with carbon in northern peatlands. Many of these peatlands are currently underlain by permafrost, which controls mire stability and hydrology. With the ongoing climate change there is concern that permafrost thawing will turn large areas of these northern peatlands from carbon/mercury-sinks into much wetter carbon/mercury-sources. Here we can show that such a change in mire structure in the sub-arctic Stordalen mire in northern Sweden actually is responsible for an increased export of mercury to the adjacent lake Inre Harrsjön. We also show that sediment mercury accumulation rates during a warm period in the pre-industrial past were higher than in the 1970s when atmospheric input peaked, indicating that in areas with permafrost, climate can have an effect on mercury loading to lakes as large as anthropogenic emissions. Thawing of permafrost and the subsequent export of carbon is a widespread phenomenon, and the projection is that it will increase even more in the near future. Together with our observations from Stordalen, this makes northern peatlands into a substantial source of mercury, at risk of being released into sensitive arctic freshwater and marine systems.     

Export of dissolved organic matter in relation to land use along a European climatic gradient

The terrestrial export of dissolved organic matter (DOM) is associated with climate, vegetation and land use, and thus is under the influence of climatic variability and human interference with terrestrial ecosystems, their soils and hydrological cycles. We present a data-set including catchments from four areas covering the major climate and land use gradients within Europe: a forested boreal zone (Finland), a temperate agricultural area (Denmark), a wet and temperate mountain region in Wales, and a warm Mediterranean catchment draining into the Gulf of Lyon. In all study areas, DOC (dissolved organic carbon) was a major fraction of DOM, with much lower proportions of DON (dissolved organic nitrogen) and DOP (dissolved organic phosphorus). A south-north gradient with highest DOC concentrations and export in the northernmost catchments was recorded: DOC concentrations and loads were highest in Finland and lowest in France. These relationships indicate that DOC concentrations/export are controlled by several factors including wetland and forest cover, precipitation and hydrological processes. DON concentrations and loads were highest in the Danish catchments and lowest in the French catchments. In Wales and Finland, DON concentrations increased with the increasing proportion of agricultural land in the catchment, whereas in Denmark and France no such relationship was found. DOP concentrations and loads were low compared to DOC and DON. The highest DOP concentrations and loads were recorded in catchments with a high extent of agricultural land, large urban areas or a high population density, reflecting the influence of human impact on DOP loads.     

Past and future trends in nutrients export by rivers to the coastal waters of China

We analyzed the past and future trends in river export of dissolved and particulate nitrogen (N), phosphorus (P) and carbon (C) to the coastal waters of China, for sixteen rivers, as calculated by the Global NEWS models (Nutrient Export from WaterSheds). Between 1970 and 2000, the dissolved N and P export increased significantly, while export of other nutrients changed less. We analyzed the future trends (2000-2050) for the Millennium Ecosystem Assessment (MEA) scenarios. In general, the largest increases of dissolved nutrients export are projected for the Global Orchestration scenario, assuming a globalized world and a reactive approach toward environmental management. Future trends in river export of nutrients vary largely among basins, nutrient forms and scenarios. We calculate both increasing and decreasing trends between 2000 and 2050. We also identify the sources contributing to the nutrient export. For selected river basins we present results for alternative scenarios, which are based on the Global Orchestration scenario, but assume more environmental management. This illustrates how the NEWS models can be useful in regional analyses for decision making.     

Historical storage budgets of organic carbon, nutrient and contaminant elements in saltmarsh sediments: biogeochemical context for managed realignment, Humber Estuary, UK

Biogeochemical data from Welwick marsh (Humber Estuary, UK), an actively accreting saltmarsh, provides a decadal-centennial-scale natural analogue for likely future biogeochemical storage effects of managed realignment sites accreting either intertidal muds or saltmarsh. Marsh topographic profiles and progradation history from aerial photographs were combined with (137)Cs and niobium contamination history to establish and verify chronology and sediment mass accumulation. These data, combined with down-core measurements of particulate organic carbon (C(org)), organic nitrogen (N(org)), particle reactive phosphorus and selected contaminant metal (Zn, Pb, Cu, As and Nb) contents were then used to calculate sediment and chemical storage terms and to quantify changes in these over time. These data are used to help predict likely future biogeochemical storage changes at managed realignment sites in the estuary. The net effect of returning some 26 km(2) of reclaimed land to intertidal environments now (about 25% of the maximum possible realignment storage identified for the estuary) could result in the storage of some 40,000 tonnes a(-1) of sediment which would also bury about 800 tonnes a(-1) of C(org) and 40 tonnes a(-1) of N(org). Particulate contaminant P burial would be around 25 tonnes a(-1) along with approximately 6 tonnes a(-1) contaminant Zn, 3 tonnes a(-1) contaminant Pb, and approximately 1 tonnes a(-1) contaminant As and Cu. The study also shows that reclamation activities in the outer estuary since the mid-1700s has prevented, in total, the deposition of about 10 million tonnes of sediment, along with 320,000 tonnes of C(org) and 16,000 tonnes of N(org). The study provides a mid-1990s baseline against which future measurements at the site can determine changes in burial fluxes and improvement or deterioration in contaminant metal contents of the sediments. The data are directly relevant for local managed realignment sites but also broadly indicative for sites generally on the European North Sea Coast.     

Faecal indicator organism concentrations and catchment export coefficients in the UK

Characterisation of faecal indicator organism (FIO) concentrations and export coefficients for catchments with particular combinations of land use and under specific climatic regimes is critical in developing models to predict daily loads and apportion sources of the microbial parameters used to regulate water quality. Accordingly, this paper presents a synthesis of FIO concentration and export coefficient data for the summer bathing season, with some comparative winter data, for 205 river/stream sampling points widely distributed across mainland UK. In terms of both geometric mean (GM) FIO concentrations and export coefficients (expressed as cfu km(-2) h(-1)), the results reveal (1) statistically significant elevations at high flow compared with base flow, with concentrations typically increasing by more than an order of magnitude and export coefficients by about two orders; (2) significantly higher values in summer than in winter under high-flow conditions; and (3) extremely wide variability between the catchments (e.g. four orders of magnitude range for GM faecal coliform concentrations), which closely reflects land use-with urban areas and improved pastures identified as key FIO sources. Generally, these two most polluting land uses are concentrated in lowland areas where runoff (m3 km(-2) h(-1)) is low compared with upland areas, which in the UK are dominated by rough grazing and forestry. Consequently, contrasts in export coefficients between land use types are less than for FIO concentrations. The GMs reported for most land use categories are based on 13 sites and exhibit quite narrow confidence intervals. They may therefore be applied with some confidence to other catchments in the UK and similar geographical regions elsewhere. Examples are presented to illustrate how the results can be used to estimate daily summer base- and high-flow FIO loads for catchments with different land use types, and to assess the likely effectiveness of certain strategies for reducing FIO pollutant loadings in areas with extensive areas of lowland improved pasture.     

Nitrogen and phosphorus dynamics of a re-wetted shallow-flooded peatland

Minerotrophic peatlands play an important role in the regulation of water quality and quantity but due to drainage and agricultural land use most of these systems have lost this function. In Central Europe, many re-wetting projects have been implemented to restore wetlands for multifunctional purposes during the last years. The Pohnsdorfer Stauung (Northern Germany) is a eutrophic fen which was used for intensive agriculture for 40 years. The peatland is divided in two subareas by a small stream. In the scope of re-wetting measures, one subarea (westpolder) was flooded by blockading the main drainage ditch in 1996/97, a second subarea (eastpolder) was re-connected to the stream by an inlet and outlet in 2001. Nitrogen and phosphorus dynamics were investigated in the surface water of these systems over a 5-year (westpolder) and 3-year (eastpolder) period, and balances were calculated. In both polders high dynamics of nitrogen and phosphate concentrations were observed in the surface water. Nitrate peaked in the winter months, whereas ammonium, phosphate and organically bound nitrogen (N(org)) revealed highest values during summer. Daily balances for the eastpolder and annual balances for both polders were calculated. In both polders nitrate was retained but phosphate and N(org) were exported. Differences of the nutrient dynamics and the absolute and relative balances between the polders were due to the different hydrology: the eastpolder received a high nitrate load by the stream, in the westpolder nutrient loads are low and internal nutrient cycles are dominating. During the summer months, high ammonium concentrations, oxygen depletion, and phosphate release occur in the warm, stagnant water of both polders. Normally, high phosphate and ammonium concentrations did not coincided with discharge phases from the polders. However, in August 2002 after heavy rainfall high phosphorus and ammonium discharge was observed. One important factor influencing the detected nutrient dynamics and balances is the change from a drained and fertilized peatland to a flooded wetland in only a few years. We conclude that continuous water flow and stable water levels are desired for flooded peatlands to prevent high concentrations of ammonium and phosphate and to utilize the potential for nitrate retention. In degenerated peatlands, flooding should only be regarded as an easy technological solution in order to conserve the peat mineralization, and to form the foundation for the further development of the peatland to a more efficient nutrient retaining system.     

Climate-change impacts on hydrology and nutrients in a Danish lowland river basin

The Mike 11-TRANS modelling system was applied to the lowland Gjern river basin in Denmark to assess climate-change impacts on hydrology and nitrogen retention processes in watercourses, lakes and riparian wetlands. Nutrient losses from land to surface waters were assessed using statistical models incorporating the effect of changed hydrology. Climate-change was predicted by the ECHAM4/OPYC General Circulation Model (IPCC A2 scenario) dynamically downscaled by the Danish HIRHAM regional climate model (25 km grid) for two time slices: 1961-1990 (control) and 2071-2100 (scenario). HIRHAM predicts an increase in mean annual precipitation of 47 mm (5%) and an increase in mean annual air temperature of 3.2 degrees C (43%). The HIRHAM predictions were used as external forcings to the rainfall-runoff model NAM, which was set up and run for 6 subcatchments within and for the entire, Gjern river basin. Mean annual runoff from the river basin increases 27 mm (7.5%, p<0.05) when comparing the scenario to the control. Larger changes, however, were found regarding the extremes; runoff during the wettest year in the 30-year period increased by 58 mm (12.3%). The seasonal pattern is expected to change with significantly higher runoff during winter. Summer runoff is expected to increase in predominantly groundwater fed streams and decrease in streams with a low base-flow index. The modelled change in the seasonal hydrological pattern is most pronounced in first- or second-order streams draining loamy catchments, which currently have a low base-flow during the summer period. Reductions of 40-70% in summer runoff are predicted for this stream type. A statistical nutrient loss model was developed for simulating the impact of changed hydrology on diffuse nutrient losses (i.e. losses from land to surface waters) and applied to the river basin. The simulated mean annual changes in TN loads in a loamy and a sandy subcatchment were, respectively, +2.3 kg N ha(-1) (8.5%) and +1.6 kg N ha(-1) (6.9%). The rainfall-runoff model and the nutrient loss model were chained with Mike 11-TRANS to simulate the combined effects of climate-change on hydrology, nutrient losses and nitrogen retention processes at the scale of the river basin. The mean annual TN export from the river basin increased from the control to the scenario period by 7.7%. Even though an increase in nitrogen retention in the river system of 4.2% was simulated in the scenario period, an increased in-stream TN export resulted because of the simulated increase in the diffuse TN transfer from the land to the surface-waters.     

Impact of selected agricultural management options on the reduction of nitrogen loads in three representative meso scale catchments in Central Germany

Nitrogen inputs into surface waters from diffuse sources are still unduly high and the assessment of mitigation measures is associated with large uncertainties. The objective of this paper is to investigate selected agricultural management scenarios on nitrogen loads and to assess the impact of differing catchment characteristics in central Germany. A new modelling approach, which simulates spatially distributed N-transport and transformation processes in soil and groundwater, was applied to three meso scale catchments with strongly deviating climate, soil and topography conditions. The approach uses the integrated modelling framework JAMS to link an agro-ecosystem, a rainfall-runoff and a groundwater nitrogen transport model. Different agricultural management measures with deviating levels of acceptance were analysed in the three study catchments.N-leaching rates in all three catchments varied with soil type, the lowest leaching rates being obtained for loess soil catchment (18.5 kg nitrate N ha^− 1 yr^− 1) and the highest for the sandy soils catchment (41.2 kg nitrate N ha^− 1 yr^− 1). The simulated baseflow nitrogen concentrations varied between the catchments from 1 to 6 mg N l^− 1, reflecting the nitrogen reduction capacity of the subsurfaces. The management scenarios showed that the highest N leaching reduction could be achieved by good site-adapted agricultural management options. Nitrogen retention in the subsurface did not alter the ranking of the management scenarios calculated as losses from the soil zone. The reduction effect depended strongly on site specific conditions, especially climate, soil variety and the regional formation of the crop rotations.     

The combined effect of geology, phosphate sources and runoff on phosphate export from drainage basins

A large degree of uncertainty is usually associated with phosphate loads estimated by means of export coefficients. Methods of reducing this uncertainty were investigated. Soluble and total phosphate export coefficients were calculated for 7 South African catchments over periods covering 3–5 years. Spatial variance in the export coefficients could largely be accounted for if catchments were grouped according to their geological characteristics; those in the upper Limpopo River drainage basin having igneous and those in the Vaal River drainage basin having sedimentary geological formations. A secondary, but nonetheless important factor contributing to the spatial variance of export coefficients was whether or not a particular catchment contained mainly point or mainly non-point sources. After catchments were grouped according to these two factors, 74–99% of temporal variance of export coefficients could be explained by fitting linear regression equations to phosphate export vs runoff.The possible link between the bio-availability of particulate phosphorus and catchment geology is discussed. The significance of such a link, with regard to phosphate load estimates and making projections of future trophic status, is emphasised.     

A long-term view of nutrient transfers through the Seine river continuum

A model (the Riverstrahler model) is used to describe nutrient transfer and transformation at the scale of the whole drainage network of the Seine based on information concerning the basic mechanisms governing N, P and Si inputs to the drainage network and in-stream transformation and retention. It was used to calculate the budget of these nutrients through the whole river continuum from land to sea. With the help of historical documents, the constraints used as forcing function in this model were reconstructed to express the changing conditions of land-use and urban population over the last five hundred years. The corresponding scenarios were run for different hydrological regimes including dry, mean and wet conditions. The results were validated on the long-term series of nutrient measurements spanning more than a century available at some stations on the Seine, upstream and downstream of the city of Paris. The model was also used to explore past and future trends in nutrient loading, retention and delivery to the coastal zone, in response to human management of the terrestrial watershed. Beside the initial pristine state, used as an idealized reference state (with N, P and Si delivered fluxes of about 45-110 kg N km(-2) yr(-1), 2-5 kg P km(-2) yr(-1), 510-1325 kg Si km(-2) yr(-1)), four periods were distinguished. The first one is that of the traditional cottage economy which prevailed, with quite a constant total population, until the end of the 18th century. N, P and Si fluxes were about 235-750 kg N km(-2) yr(-1), 15-60 kg P km(-2) yr(-1) and 425-1280 kg Si km(-2) yr(-1), depending on hydrological conditions. The second period, from the beginning of the 19th century to about the 1950's, corresponded to rapid increase in the total and urban population with a corresponding increase of point sources of N and P. From 1950 onwards, modern farming practices resulted in a dramatic increase in diffuse sources of nitrogen and to a lesser extent phosphorus: riverine N and P export reached 1320-2800 kg N km(-2) yr(-1), and 310-340 kg P km(-2) yr(-1): silica export remained fairly constant at around 410-1260 kg Si km(-2) yr(-1) depending on the hydrological conditions. In the 1990's, the fourth period is represented by a stabilized population and improved wastewater treatment, when the export of phosphorus is reduced to values as low as 40-60 kg P km(-2) yr(-1), but without as effective a reduction of nitrogen export. This represents an unprecedented situation for the marine coastal system, i.e. a shift from nitrogen to phosphorus limitation, as nitrogen is still delivered far in excess of the amount of silica available for diatom blooms.     

Modelling Pb, Zn and As transfer from terrestrial to aquatic ecosystems during the ice-free season in three Pyrenean catchments

Long-range atmospheric trace element contamination affecting natural systems has occurred since early historical times in the Northern Hemisphere. In relatively remote sites, soils are the largest reservoir of these airborne contaminants. Trace elements stored in soils can later be remobilised and thus soils are a potential delayed, long-lasting source of contamination for the aquatic ecosystems. Here we measured the atmospheric deposition and in-lake fluxes in order to model the transfer of Pb, Zn and As from terrestrial to aquatic ecosystems during the snow- and ice-free season in three mountain catchments in the Central Pyrenees. According to the model, there was a net export of Pb and As from the catchments. We postulate that accumulated anthropogenic Pb contamination and the weathering of As-rich rocks are the most likely sources. In contrast, Zn was largely retained in the catchment. For Pb and As, the terrestrial inputs were > 91% and for Zn were ~ 71% of the total inputs to the lakes. Nearly all Pb entering the lakes was retained in the sediments whereas 5-38% of As and Zn was lost through the outflow. We were unable to adjust the model for Zn for one of the lakes. The uptake by macrophytes could be a considerable sink for Zn, which was not considered in our transport model.     

The fate of experimentally deposited nitrogen in mesocosms from two Canadian peatlands

In large regions of Europe and North America, peatlands have been exposed to elevated rates of atmospheric nitrogen (N) deposition. We investigated the fate of experimentally added N (NH(4)(15)NO3) at two different N loads (1.2 and 4.7 g N m(-2) yr(-1)) and water tables (1 and 32 cm) in intact cores from two peatlands, located in Central and Eastern Canada. The sites receive an estimated total N load of 0.6 g m(-2) a(-1) and 1.5 g m(-2) yr(-1), excluding nitrogen fixation. In all treatments, experimentally added nitrate (NO(3-)) was fully (96-99%) and ammonium (NH(4+)) mostly (81-97%) retained by the plant cover, mainly consisting of Sphagnum mosses, or in the unsaturated zone below. However, on average only 48% of the (15)N were recovered from the plant cover, and substantial amounts were found in depth layers of 2-6 cm (21-46%) and 8-12 cm (1.4-10.8%) below the moss surface. The amount of (15)N retained also significantly decreased with a lower water table from 56+/-9% to 40+/-10%. These findings document a substantial mobility of N, particularly during water table drawdown. Analysis of (15)N by a sequential diffusion procedure revealed a transfer of (15)N from NO(3-) into NH(4+) and dissolved organic N (DON), but the contents of (15)N in these pools accounted for less than 1% of the total N, natural background subtracted. The mass flux of dissolved (15)N into the peat was small compared to the total mass flux of (15)N. The accumulation of (15)N in the bulk peat must have been caused by a mechanism that was not investigated, possibly by transport of particulate organic N.     

The relative contribution of sewage and diffuse phosphorus sources in the River Avon catchment, southern England: implications for nutrient management

In order to effectively manage nutrient river load reductions and target remediation strategies, it is important to determine the relative contributions of diffuse and point sources across the river catchment. This study used a geographical information system (GIS) to apply phosphorus (P) export coefficients (obtained from the literature) to 58 water quality monitoring sites across a large, urbanised, mixed land use catchment, typical of southern lowland England (the River Avon, Warwickshire, UK). These coefficients were used to estimate the annual P load at each monitoring site, and also the relative contribution of point source (from sewage treatment works (STW)) and diffuse input (from both livestock and agricultural land use). The estimated annual P loads showed very close agreement (r2=0.98) with the measured total phosphorus (TP) loads. Sites with the highest proportion of P derived from STW had the highest TP concentrations and loads, and also had greater variations between seasons, with elevated P concentrations occurring during the summer months. The GIS model was re-run to determine the effect of an 80% reduction in P output from STW serving over 10,000 people, thereby assessing the effect of implementing the European Union's Urban Waste Water Treatment Directive (UWWTD). The exported TP load was reduced by 52%, but the sites with the highest TP concentrations were still those with the highest proportion of P derived from STW. The GIS model was re-run to estimate the impact of 80% P reductions at a further 11 STW of varying sizes. This reduced the total TP load by only 29 tonnes year-1, but greatly reduced the P concentrations in many highly nutrient contaminated tributaries. The number of sites with P concentrations greater than 1 mg l-1 was cut from 15 (before UWWTD implementation) to 2. These findings suggest that after UWWTD implementation, resources should focus on introducing tertiary sewage treatment at the remaining large STW, before targeting diffuse inputs. This conclusion is also likely to apply to other lowland river catchments in southern England, most of which have similar population densities to the River Avon.     

Chemical composition of arctic snow: concentration levels and regional distribution of major elements

At the end of the northern winter 1996/1997, 21 snow samples were collected from 17 arctic localities in Norway, Sweden, Finland, Svalbard, Russia, Alaska, Canada, Greenland and Iceland. Major element concentrations of the filtered (0.45 mum) melted snow indicate that most samples are consistent with a diluted seawater composition. Deviations from this behaviour indicate additional SO(4)(2-) and Cl(-) relative to seawater, suggesting a minor contribution from (probably local) coal combustion emissions (Alaska, Finland, Sweden, Svalbard). The samples with the highest Na and Cl(-) content (Canada, Russia) also have higher Na/SO(4)(2-) and Cl(-)/SO(4)(2-) ratios than seawater, suggesting a slight contamination from (probably local) deicing activities. Local soil or rock dust inputs in the snow are indicated by 'excess' Ca contents (Alaska, Svalbard, Greenland, Sweden). No overall relationship was found between pH (range: 4.6-6.1) and total or non-seasalt SO(4)(2-) (NSS), suggesting that acidification due to long-range transport of SO(2) pollution is not operating on an arctic-wide scale. In a few samples (Alaska, Finland, Sweden, Svalbard), a significant proportion (>50%) of SO(4)(2-) is non-marine in origin. Sources for this non-marine SO(4)(2-) need not all be found in long-range atmospheric transport and more likely sources are local industry (Finland, Sweden), road traffic (Alaska) or minor snow-scooting traffic (one Svalbard locality). A few samples from northern Europe show a relatively weak trend of decreasing pH with increasing NO(3)(-).