Stream Water Concentrations Research Articles

Effect on nitrate concentration in stream water of agricultural practices in small catchments in Brittany: II. Temporal variations and mixing processes

Abstract. In catchments with impervious bedrock, the nitrate concentrations in streamwater often show marked seasonal and small inter-annual variations. The inter-annual trends are usually attributed to changes in nitrogen inputs, due to changes in land use or in nitrogen deposition whereas seasonal patterns are explained in terms of availability of soil nitrate for leaching and of seasonality of nitrogen biotransformations. The companion paper showed that inter-annual variations of nitrogen in streamwater are not directly related to the variations of land use. The aim of this study is to describe nitrate concentration variations in a set of very small adjacent catchments, and to discuss the origin of the inter-annual and seasonal trends. Data from four catchments at the Kerbernez site (South Western Brittany, France) were used in this study. Nitrate concentrations in streamwater were monitored for eight years (1992 to 1999) at the outlet of the catchments. They exhibit contrasting inter-annual and seasonal patterns. An extensive survey of agricultural practices during this period allowed assessment of the amount of nitrogen available for leaching. The discharges measured since 1997 show similar specific fluxes but very different seasonal dynamics between the catchments. A simple, lumped linear store model is proposed as an initial explanation of the differences in discharge and nitrate concentration patterns between the catchments. The base flow at the outlet of each catchment is considered as a mixture of water from two linear reservoirs with different time constants. Each reservoir comprises two water stores, one mobile contributing to discharge, the other, immobile, where nitrate moves only by diffusion. The storm flow, which accounts for less than 10% of the annual flux, is not considered here. Six parameters were adjusted for each catchment to fit the observed data: the proportion of deep losses of water, the proportion of the two reservoirs and the size and initial concentration of the two immobile stores. The model simulates the discharge and nitrate concentration dynamics well. It suggests that the groundwater store plays a very important role in the control of nitrate concentration in streamwater, and that the pattern of the seasonal variation of nitrate concentration may result from the long term evolution of nitrogen losses by leaching. Keywords: nitrate, diffuse pollution, groundwater, seasonal variations, agricultural catchment, simulation model

Modelling flow and nitrate transport in groundwater for the prediction of water travel times and of consequences of land use evolution on water quality

AbstractA two‐dimensional model representing flow and nitrate transport in groundwater was developed and applied to a hillslope of the Kervidy catchment. The objective of the modelling was: (1) to characterize better the flow and nitrate transport in the groundwater and to determine the characteristic times of the system; (2) to explore the consequences of changes in nitrate leaching to groundwater on nitrate concentration in stream water. The finite‐difference code MODFLOW was used to simulate the distribution of hydraulic head within the groundwater. Nitrate transport was described by the convection equation solved using MT3D. MODPATH was also used to analyse flow paths and travel times in the groundwater. Four units were considered in the model: (i) the plough layer, (ii) the soil, (iii) the weathered shale and (iv) the fissured shale. Autotrophic denitrification in the shale and partly in the weathered shale was represented, as well as heterotrophic denitrification in the upper horizon of bottom land. A steady‐state average flow was assumed with a spatially uniform groundwater recharge of 2 mm day−1, corresponding to the winter mean daily recharge observed in the Kervidy catchment. Nitrate recharge rate was fixed at 100 mg l−1, which is equivalent to a nitrogen flux of 165 kg ha−1 year−1. Six scenarios of nitrate leaching changes were analysed with the model. The first two correspond to spatially uniform decreases of the nitrate recharge rate to 80 and 60 mg l−1, respectively. In the other four scenarios, nitrate recharge rate was spatially distributed along the hillslope so that the average nitrogen flux remained equal to 165 kg ha−1 year−1. Simulated hydraulic heads were similar to observed values along the hillslope, except for the summit. The transport model reproduced the spatial pattern of nitrate concentrations observed in the weathered shale groundwater, a deviation appearing only in the nearest piezometer to the stream. Travel times within the groundwater appeared to be highly variable, from a few days up to 3 years. Scenario analysis showed that a significant decrease of stream nitrate concentration can be expected following a global decrease in nitrate leaching along the hillslope. However, the fall could be very gradual in time. Copyright © 2002 John Wiley & Sons, Ltd.

Evaluating impact of land use and N budgets on stream water quality in Hokkaido, Japan

This study was conducted to evaluate the impact of land use system and N loadings to the environment estimated from N budgets on quality of stream water in Hokkaido, Japan. A case study was carried out in three towns of southern Hokkaido, which are Shiraoi, Yakumo, and Shizunai, characterized by intensive poultry farming (IPF), dairy cattle farming (DCF), and race horse farming (RHF), respectively. The estimation of N budgets using an N flow model indicated that the highest disposal N (880 Mg N yr−1) was generated in the IPF town and it resulted in 250 kg ha−1yr−1 surplus N in croplands. The disposal N was much lower in the DCF and the RHF town (102 and 71 Mg N yr−1, respectively) than that of the IPF town. Cropland surplus N in DCF town was 31 kg N ha−1yr−1, whereas RHF town had negative N balance. The linear regression analysis indicated that NO3-N concentration in stream water was significantly correlated with the proportion of upland field in drainage basins. The regression slopes varied among the towns, and it was the highest for IPF (0.040), intermediate for DCF (0.023) and the lowest for RHF town (0.006). The multiple regression analysis showed that regression slopes were significantly correlated (R 2= 0.77 at 5% level) with livestock disposal N and cropland surplus N. Therefore, we assumed that these regression lines were the baselines for non-point source pollution, and the regression slopes were determined to act as impact factors of stream water quality. However, two sampling sites in the IPF area were scattered above the baseline. This fact strongly suggests that the area was affected by point source pollution.

Yields of Dissolved Organic C, N, and P. from Three High-Elevation Catchments, Colorado Front Range, U.S.A.

Ecosystem dynamics in high-elevation watersheds are extremely sensitive to changes in chemical, energy, and water fluxes. Here we report information on yields of dissolved organic C, N, and P for the 1999 snowmelt runoff season from three high-elevation catchments in the Colorado Front Range, U.S.A.: Green Lake 4 (GL4) and Albion townsite (ALB) on North Boulder Creek and the Saddle Stream (SS), a tributary catchment dominated by alpine tundra. Dissolved organic carbon (DOC) concentrations in stream waters ranged from <1 to 10 mg C L-1, with the highest values occurring at the SS site. Dissolved organic nitrogen (DON) concentrations ranged from below detection limits to 0.28 mg N L-1 and were again highest at the tundra-dominatedsite. Dissolved organic phosphorus (DOP) concentrations were at or near detection limits throughout the season in all three catchments indicating a strong terrestrial retention of P. OnlyDOC showed a significant relationship to discharge. Yields of DOC in the three catchments ranged from 10.6 to 11.8 kg C ha-1 while yields of DON and DOP ranged from 0.32 to 0.41 and 0.02 to 0.08 kg ha-1, respectively. The relatively highyield of organic N and P relative to C from the highest elevationsite (GL4) was somewhat surprising and points to either: (1) a source of dissolved organic material (DOM) in the upper reaches of the catchment that is enriched in these nutrients or (2) theselective uptake and processing of organic N and P downstream ofthe sampling site. Additionally, seasonal changes in the relativeimportance of DOM precursor materials appear to result in changesin the N content of DOM at both the GL4 and ALB sites.

Mercury Concentrations in Stream and River Water: An Analytical Framework Applied to Minnesota and Wisconsin (USA)

The total concentration of all mercuryspecies in water, [THg]w, is a key water qualitymeasure. This paper proposes an analytical framework forthe analysis, interpretation and eventual projection ofstream (and river) [THg]w. Mercury (Hg) isconceptualized as being distributed among four carriergroups in water: suspended mineral particles, particulateorganic carbon, dissolved organic carbon, and inorganiccomplexes and ions. The conceptual understanding is used asa statistical analytical framework and turned into aquantitative model for Minnesota and Wisconsin based on some1000 data cases from 18 streams (watershed area: 9 ha–115500km2). The resultant model yields a coefficient ofdetermination of 92% for [THg]w of the fitting datasubset, or 94% for the evaluation subset. Its coefficientshave well defined physical meanings, and are generallyconsistent with independent field measurements from the sameregion or elsewhere. The model provides a comprehensive andquantitative view of the Hg contents of the carriers: thecontents increase with the proportion of watershed area aswetlands or as forests, rise drastically and then fallprecipitously during spring snowmelt, and otherwise peak inthe growing season and reach a minimum in the presence ofsnowpack. The model further reveals that dissolved Hg tendsto increase with emission-related wet sulfate depositionacross the data region.

Catchment characteristics controlling the mobilization and potential toxicity of aluminium fractions in the catchment of the River Dee, northeast Scotland

Elevated streamwater concentrations of aluminium have been associated with the onset of acidification, both by natural and anthropogenic means. This has important implications for river water quality. Concentrations of total, labile-inorganic and non-labile-organic fractions of aluminium were determined across the River Dee catchment, northeast Scotland. Fifty-nine subcatchments, chosen to reflect the variety of soils, parent materials and land use patterns across this major river system were sampled bi-weekly for 1 year. The distribution of aluminium was closely linked to factors of parent material and organic soil cover. Strong spatial and temporal relationships were observed between pH and all fractions of aluminium. Significant episodic peaks in aluminium occurred, these being especially pronounced when a storm event followed a period of dry weather. A weathering rate index utilizing the Na dominance of base cations was found to be a predictor of potential streamwater toxicity implied through Ca/inorganic aluminium ratios. It was demonstrated that Al was mobilized from acid headwater streams, whilst concentrations in the main stem remained much lower.

Synoptic Survey of Surface Water Isotopes and Nutrient Concentrations, Páramo High-Elevation Region, Antisana Ecological Reserve, Ecuador

Here we provide baseline information on water isotopes and nutrient concentrations for channelized streams and wetlands from a páramo ecosystem in Antisana Ecological Reserve, Ecuador. Water samples were collected from wetland areas and compared to the nearby Rio Tumiguina. Stream water samples were also collected downstream from glacial source areas for 7 km (Rio Tumiguina) and 10 km (Rio Antisana). Water samples from the gauging station on the Rio Tumiguina (n = 4) and nearby wetlands (n = 4) showed significant differences for some nutrients and little difference for other nutrients. Nitrate (NO3-N) concentrations were below 14 μg L−1 (1 μmol L−1) at both sites and not significantly different. Concentrations of ammonium (NH4-N) in both stream water and wetlands were much higher than NO3-N concentrations. For example, NH4-N concentrations in stream water of 195 μg L−1 (14 μmol L−1) were 17 times that of NO3-N concentrations. In contrast to NO3-N and NH4-N, there was a significant difference (P < 0.001) between concentrations of soluble reactive phosphate (SRP), with concentrations of SRP in the Rio Tumiguina of about 263 μg L−1 (8.2 μmol L−1) and below detection limits in wetlands. Dissolved organic carbon (DOC) concentrations in the Rio Tumiguina of 0.4 mg L−1 were quite low compared to the 23 mg L−1 of DOC from the páramo wetlands. At both stream transects, the δ18O values decreased from glacial signatures of about – 17± near the glacial terminus to – 13± at distances of 7 to 10 km. Nitrate concentrations were at or below detection limits at all sampling sites. Ammonium concentrations were higher than NO3-N concentrations in all samples. Concentrations of dissolved organic phosphorus (DOP) were almost as high as dissolved organic carbon (DOC) near the glacial outlets. Concentrations of dissolved organic nitrogen (DON) and DOC were near detection limits near the glacial outlets and then increased downstream.

Trends in nitrogen deposition and leaching in acid-sensitive streams in Europe

Abstract. Long-term records of nitrogen in deposition and streamwater were analysed at 30 sites covering major acid sensitive regions in Europe. Large regions of Europe have received high inputs of inorganic nitrogen for the past 20 - 30 years, with an approximate 20% decline in central and northern Europe during the late 1990s. Nitrate concentrations in streamwaters are related to the amount of N deposition. All sites with less than 10 kgN ha-1 yr-1 deposition have low concentrations of nitrate in streamwater, whereas all sites receiving &gt; 25 kgN ha-1 yr-1 have elevated concentrations. Very few of the sites exhibit significant trends in nitrate concentrations; similar analyses on other datasets also show few significant trends. Nitrogen saturation is thus a process requiring many decades, at least at levels of N deposition typical for Europe. Declines in nitrate concentrations at a few sites may reflect recent declines in N deposition. The overall lack of significant trends in nitrate concentrations in streams in Europe may be the result of two opposing factors. Continued high deposition of nitrogen (above the 10 kgN ha-1 yr-1 threshold) should tend to increase N saturation and give increased nitrate concentrations in run-off, whereas the decline in N deposition over the past 5 – 10 years in large parts of Europe should give decreased nitrate concentrations in run-off. Short and long-term variations in climate affect nitrate concentrations in streamwater and, thus, contribute "noise" which masks long-term trends. Empirical data for geographic pattern and long-term trends in response of surface waters to changes in N deposition set the premises for predicting future contributions of nitrate to acidification of soils and surface waters. Quantification of processes governing nitrogen retention and loss in semi-natural terrestrial ecosystems is a scientific challenge of increasing importance. Keywords: Europe, acid deposition, nitrogen, saturation, recovery, water

Seasonality, water quality trends and biological responses in four streams in the Cairngorm Mountains, Scotland

Abstract. The chemical composition and invertebrate communities found in four streams in the Cairngorms, Scotland, were monitored between 1985-1997. Stream waters were mildly acidic (mean pH ca. 6.5), with low alkalinity (mean acid neutralising capacity varying from 35-117 meq l-1) and low ionic strength. Subtle differences in the chemistry of each stream were reflected in their invertebrate faunas. Strong seasonality in water chemistry occurred, with the most acid, low alkalinity waters observed during the winter and early spring. This was particularly marked during snowmelt between January and April. In contrast, summer flows were usually groundwater dominated and characterised by higher alkalinity and higher concentrations of most other weathering-derived solutes. Seasonality was also clear in the invertebrate data, with Canonical Correspondence Analysis (CCA) separating seasonal samples along axes related to water temperature and discharge characteristics. Inter-annual hydrological and chemical differences were marked, particularly with respect to the winter period. Invertebrate communities found in each of the streams also varied from year to year, with spring communities significantly more variable (P&lt;0.01) than other seasons (quantified using Euclidean distance on CCA ordinations). Hydrochemical trends over the study period were analysed using a seasonal Kendall test, LOcally WEighted Scatterplot Smoothing (LOWESS) and graphical techniques. These indicated that a reduction in sulphate concentrations in stream water is occurring, consistent with declining levels of atmospheric deposition. This may be matched by increases in pH and declining calcium concentrations, though available evidence is inconclusive. Other parameters, such as chloride, total organic carbon and zinc, reveal somewhat random patterns, probably reflecting irregular variations in climatic factors and/or atmospheric deposition. Previous studies have shown that the stream invertebrate communities have remained stable over this period (i.e. no significant linear trends) and show no evidence of acid-related impoverishment. Thus, over longer timescales invertebrates in these streams appear robust to the short-term (seasonal and inter-annual) environmental variability and long-term (decadal) chemical changes identified. Keywords: hydrochemistry, hydrology, trends, macroinvertebrates, uplands, Cairngorms, acidification

Are there signs of acidification reversal in freshwaters of the low mountain ranges in Germany?

Abstract. The reversal of freshwater acidification in the low mountain ranges of Germany is of public, political and scientific concern, because these regions are near natural ecosystems and function as an important drinking water supply. The aim of this study was to evaluate the status and trends of acidification reversal after two decades of reduced anthropogenic deposition in selected freshwaters of the low mountain ranges in the Harz, the Fichtelgebirge, the Bavarian Forest, the Spessart and the Black Forest. In response to decreased sulphate deposition, seven out of nine streams investigated had significantly decreasing sulphate concentrations (all trends were calculated with the Seasonal Kendall Test). The decrease in sulphate concentration was only minor, however, due to the release of previously stored soil sulphur. No increase was found in pH and acid neutralising capacity (defined by Reuss and Johnson, 1986). Aluminum concentrations in the streams did not decrease. Thus, no major acidification reversal can currently be noted in spite of two decades of decreased acid deposition. Nevertheless, the first signs of improvement in water quality were detected as there was a decrease in the level and frequency of extreme values of pH, acid neutralising capacity and aluminium concentrations in streams. With respect to nitrogen, no change was determined for either nitrate or ammonium concentrations in precipitation or stream water. Base cation fluxes indicate increasing net loss of base cations from all ecosystems investigated, which could be interpreted as an increase in soil acidification. The latter was due to a combination of continued high anion leaching and significant reduction of base cation deposition. No major improvement was noted in biological recovery, however, initial signs of recovery were detectable as there was re-occurrence of some single macroinvertebrate species which were formerly extinct. The results of this study have important implications for water authorities, forest managers and policy makers: the delay in acidification reversal suggests a need for ongoing intensive amelioration of waters, a careful selection of management tools to guarantee sustainable management of forests and the reduction of nitrogen deposition to prevent further acidification of soils and waters. Keywords: freshwater, acidification reversal, drinking water supply, forested catchments, Germany

Mechanism of nitrate loss from a forested catchment following a small-scale, natural disturbance

In Matsu-zawa catchment, central Japan, nitrate concentrations in stream water increased following a small-scale, natural disturbance involving an outbreak of pine wilt disease that affected ~25% of the forested catchment. To clarify nutrient dynamics in soils and their relationship with stream water nitrate, we investigated soil nitrogen dynamics and soil water chemistry in disturbed and undisturbed, water-unsaturated and -saturated plots. The highest values for nitrification rate, nitrate concentration in soil solution, and nitrate exported from the root zone were observed for the disturbed plot. The ratio of nitrification to mineralization in surface soil of the disturbed plot dramatically increased from 1989 (pre-disturbance) to 1997. Root zone leachate from the disturbed area showed gradually increasing groundwater nitrate concentrations in the temporarily saturated zone during lateral, matrix flow. The catchment's deep soils and associated hydrologic processes limited the degree of plant uptake of the nitrate generated in the disturbed area. It was inferred that the persistent high levels of nitrate observed in the stream water resulted largely from the stable high nitrate concentrations observed in the saturated groundwater of this catchment. Stream water nitrate loads discharged following the disturbance were about 16 times greater than prior to it.

Seasonal and event-scale variations in solute chemistry for four Sierra Nevada catchments

Hydrobiogeochemical processes controlling stream water chemistry were examined in four small (<5 km 2) catchments having contrasting bedrock lithologies in the western Sierra Nevada foothills of California. The Mediterranean climate with its cool/wet and hot/dry cycle produces strong seasonal patterns in hydrological, biological and geochemical processes. Stream water solutes fall into three general groups according to seasonal fluctuation in concentration: strong, rainy season minimum–dry season maximum (Cl −, SO 4 2−, base cations); weak, rainy season minimum–dry season maximum (Si); and rainy season maximum–dry season minimum (NO 3 − and K +). Solute dynamics in soil solutions and stream water suggest that mixing of drainage waters from bedrock and soil sources regulate stream water solute concentrations. Patterns are further altered by the leaching of solutes accumulated in the soil over the summer period of desiccation and the temporal discoupling of nutrient cycles that occurs due to differences in the timing between vegetation growth (late spring) and leaching (early winter). Solute concentrations are remarkably similar between watersheds with varying bedrock types, with the exception of nitrate, sulfate and bicarbonate. Three watersheds have nitrogen-bearing metasedimentary bedrock that contributes to elevated nitrate concentrations in stream waters. Watersheds whose bedrock includes mineralized veins of sulfide and carbonate minerals similarly have greater sulfate and bicarbonate concentrations in stream water. Hydrobiogeochemical processes are highly dynamic at the seasonal and storm-event temporal scales and spatially complex at the watershed scale making management of stream water chemical composition, such as nitrate concentrations, very challenging.

Carbon dioxide and methane evasion from a temperate peatland stream

Peatland streams potentially represent important conduits for the exchange of gaseous carbon between the terrestrial ecosystem and the atmosphere. We investigated how gaseous evasion of carbon from the stream surface compared with downstream carbon transport at three locations on a Scottish headwater stream. Carbon dioxide was consistently above atmospheric saturation in the stream, with mean concentrations of 159.1, 81.8, and 29.5 µmol L−1 at the lower, middle, and upper sites, respectively (i.e., 7.6, 3.9, and 1.2 times in excess of atmospheric equilibrium concentrations). Methane concentrations in stream water were much lower but showed a similar pattern. Rates of gaseous evasion from the stream surface to the atmosphere, determined experimentally using direct measurement of dissolved gas concentrations in conjunction with coinjection of conservative solute and volatile gas tracers, also declined downstream. Combined stream losses of all forms of carbon from the entire catchment (i.e., degassing from the stream surface and exports downstream) totaled 54,140 kg C yr−1. Evasion of carbon dioxide from the stream surface accounted for 34% of this total, compared to 57% lost as dissolved organic carbon via export downstream. When expressed per unit area of watershed, the gaseous C evasion from the stream represents a loss of 14.1 g C m−2 yr−1, which equals 28–70% of the estimated net carbon accumulation rate for such peatlands. This study shows that gaseous carbon loss from the surface of temperate headwater streams can be both spatially variable and significant in terms of rates of net annual land surface‐atmosphere exchange at the catchment scale.

Accumulation of Al, Mn, Fe, Cu, Zn, Cd and Pb by the bryophyte Scapania undulata in three upland waters of different pH

Measurements were made of the contents of Al, Mn, Fe, Cu, Zn, Cd and Pb in Scapania undulata in three streams (D2, D5, D11) in the English Lake District. The stream waters had average pH values of 5.35 (D2), 5.81 (D5) and 7.26 (D11), the main differences in other major chemical components being in Mg, Al, Ca and alkalinity. There was generally more metal accumulation in the older parts of the plants, but this was not significant in all cases. Extents of accumulation varied with stream pH and dissolved metal concentration. For Al, accumulation was greatest in streams D2 and D5. Mn accumulated most in D5 and Fe was without preference. Cu, Zn and Cd accumulated mostly in the plants in stream D11 and Pb accumulated more in D5 and D11. In terms of enrichment factors (amount of metal in the plants divided by stream water concentration) the sequence was Zn<Cd<Cu<Mn<Pb<Al<Fe. Laboratory experiments supported the findings of the field data, providing evidence that uptake increases with pH at constant total metal concentration. The results are interpreted qualitatively in terms of the chemical speciation of the metals in the stream water and competition between metal ions and protons at the plant–water interface. It is suggested that Al, Cu, Zn, Cd and Pb behave according to chemical complexation, whereas redox processes and/or colloidal interactions may be significant for Mn and Fe.

Control of nitrogen export from watersheds by headwater streams.

A comparative (15)N-tracer study of nitrogen dynamics in headwater streams from biomes throughout North America demonstrates that streams exert control over nutrient exports to rivers, lakes, and estuaries. The most rapid uptake and transformation of inorganic nitrogen occurred in the smallest streams. Ammonium entering these streams was removed from the water within a few tens to hundreds of meters. Nitrate was also removed from stream water but traveled a distance 5 to 10 times as long, on average, as ammonium. Despite low ammonium concentration in stream water, nitrification rates were high, indicating that small streams are potentially important sources of atmospheric nitrous oxide. During seasons of high biological activity, the reaches of headwater streams typically export downstream less than half of the input of dissolved inorganic nitrogen from their watersheds.

Control of cation concentrations in stream waters by surface soil processes in an Amazonian watershed.

The chemical composition of ground waters and stream waters is thought to be determined primarily by weathering of parent rock. In relatively young soils such as those occurring in most temperate ecosystems, dissolution of primary minerals by carbonic acid is the predominant weathering pathway that liberates Ca2+, Mg2+ and K+ and generates alkalinity in the hydrosphere. But control of water chemistry in old and highly weathered soils that have lost reservoirs of primary minerals (a common feature of many tropical soils) is less well understood. Here we present soil and water chemistry data from a 10,000-hectare watershed on highly weathered soil in the Brazilian Amazon. Streamwater cation concentrations and alkalinity are positively correlated to each other and to streamwater discharge, suggesting that cations and bicarbonate are mainly flushed from surface soil layers by rainfall rather than being the products of deep soil weathering carried by groundwater flow. These patterns contrast with the seasonal patterns widely recognized in temperate ecosystems with less strongly weathered soils. In this particular watershed, partial forest clearing and burning 30 years previously enriched the soils in cations and so may have increased the observed wet season leaching of cations. Nevertheless, annual inputs and outputs of cations from the watershed are low and nearly balanced, and thus soil cations from forest burning will remain available for forest regrowth over the next few decades. Our observations suggest that increased root and microbial respiration during the wet season generates CO2 that drives cation-bicarbonate leaching, resulting in a biologically mediated process of surface soil exchange controlling the streamwater inputs of cations and alkalinity from these highly weathered soils.

Modeling transport of dissolved silica in a forested headwater catchment: Implications for defining the hydrochemical response of observed flow pathways

Groundwater, subsurface stormflow, and overland flow components of discharge, derived from a hydrological model that was applied to a forested headwater catchment in north central Virginia, were used with measured stream water and lysimeter concentrations of dissolved silica to investigate the hydrochemical behavior of the catchment. Concentrations in base flow, taken to be a reflection of groundwater, vary with discharge, an observation in conflict with the typical assumption of constant concentration used in end‐member mixing analyses. This observed flow dependence was modeled by considering the concentration in groundwater to be related to the saturation deficit in this zone. A positive correlation between the average groundwater saturation deficit and base flow dissolved silica concentrations is consistent with batch experiments and petrographic analysis of regolith core samples, which both indicate an increase in silica available for dissolution with depth in the groundwater zone. In the absence of subsurface storm flow zone sampling during rainfall events a constant concentration was assumed for this zone. Concentration‐discharge (C‐Q) paths in the stream were used to evaluate the modeled stream silica concentrations. An inconsistency in the direction of the modeled C‐Q rotations suggests that the storm flow zone dissolved silica concentration may also vary with time, because of the “flushing” of high‐concentration, preevent soil water on the rising limb of the storm hydrograph. For this catchment in Virginia the assumption of a constant concentration for subsurface storm flow, as well as for base flow, appears to be invalid.

THE LONG-TERM EFFECTS OF LAND-USE HISTORY ON NITROGEN CYCLING IN NORTHERN HARDWOOD FORESTS

Nearly all northeastern U.S. forests have been disturbed by wind, logging, fire, or agriculture over the past several centuries. These disturbances may have long-term impacts on forest carbon and nitrogen cycling, affecting forests' vulnerability to N saturation and their future capacity to store C. We evaluated the long-term (80–110 yr) effects of logging and fire on aboveground biomass, foliar N (%), soil C and N pools, net N mineralization and nitrification, and NO3− leaching in northern hardwood forests in the White Mountain National Forest, New Hampshire. Historical land-use maps were used to identify five areas each containing previously logged, burned, and relatively undisturbed (old-growth) forests. Aboveground biomass averaged 192 Mg/ha on the historically disturbed sites and 261 Mg/ha on the old-growth sites, and species dominance shifted from early- successional and mid-successional species (Betula papyrifera and Acer rubrum) to late-successional species (Fagus grandifolia and particularly A. saccharum). Forest floors in the old-growth stands had less organic matter and lower C:N ratios than those in historically burned or logged sites. Estimated net N mineralization did not vary by land-use history (113 kg·ha−1·yr−1); mean (± 1 se) nitrification rates at old-growth sites (63 ± 4.3 kg·ha−1·yr−1) doubled those at burned (34 ± 4.4 kg·ha−1·yr−1) and logged (29 ± 4.7 kg·ha−1·yr−1) sites. Across all plots, nitrification increased as forest floor C:N ratio decreased, and NO3− concentrations in streamwater increased with nitrification. These results indicate that forest N cycling is affected by century-old disturbances. The increased nitrification at the old-growth sites may have resulted from excess N accumulation relative to C accumulation in forest soils, due in part to low productivity of old-aged forests and chronic N deposition.

Temporal variability of nitrate concentration in a schist aquifer and transfer to surface waters

Nitrate concentrations monitored for 2.5 a in the stream water and groundwater of a small catchment, 86.5% of which is devoted to intensive agriculture, show temporal variations with a maximum during winter (as much as 200 mg l −1 in groundwater and 100 mg l −1 in stream water) and a minimum at the end of summer/beginning of autumn. Variations were also observed in the stream water and shallow groundwater after rainfall. The processes involved to explain these variations, determined mainly from NO 3 − Cl −, SO 4 2−, piezometric and streamflow data, are: (a) variability of the relative contributions to stream water and shallow groundwater by upward fluxes of deeper groundwater which, as demonstrated previously, is denitrified mainly as a result of reaction with pyrite. (b) Denitrification of shallow groundwater during summer with organic matter acting as the electron donor. (c) Dilution by rain water. Nitrate concentrations in both stream water and shallow groundwater depend on the amount of precipitation, with an increased contribution from deep denitrified groundwater during dry periods. The temporal variations in NO 3 − concentration observed several metres below the water table are related to the preferential and rapid movement of NO 3 −-polluted water through fractures and large fissures, which has been estimated at 1 m day −1. Nitrate pollution in the catchment, because of the interaction with pyrite, also increases the net chemical weathering rate to values exceeding the world average.

Elevational Patterns of Acid Deposition into a Forest and Nitrogen Saturation on Mt. Oyama, Japan

Virgin fir trees have been dying on Mt. Oyama, which is located in the southwestern part of Kanto Plain, although the frequency of death seems to be reducing recently. We report elevational patterns of acid deposition in precipitation and throughfall under fir and cedar canopies and nitrogen saturation in the forest ecosystem on Mt. Oyama. The deposition fluxes of major inorganic ions in precipitation were nearly constant regardless of elevation except for hydrogen and ammonium ions, whereas the deposition fluxes of all major inorganic ions in throughfall among cedar increased. The 5-year average of annual nitrate deposition in precipitation from 1994 to 1998 showed 19.3–23.5 kg ha-1 yr-1 (annual inorganic total N deposition: 9.6–10.7 kgN ha-1 yr-1) at four sites ranging in elevation from 500 to 1252 m, whereas the deposition in both cedar and fir throughfall was over 6 times greater than that in precipitation. The average soil surface nitrate concentration in 1998 was 140 μg g-1 (the range: 21.1-429 μg g-1, n=80) and the 7-year average of nitrate concentration in stream water from 1992 to 1998 was 4.81 mg L-1 (the range: 2.38–20.6 mg L-1, n=317). Our results indicate that nitrogen saturation is occurring in the forest ecosystem because of high N deposition, probably via acid fog, on Mt. Oyama.