Travel time controls the magnitude of nitrate discharge in groundwater bypassing the riparian zone to a stream on Virginia's coastal plain

Groundwater that bypasses the riparian zone by travelling along deep flow paths may deliver high concentrations of fertilizer‐derived NO₃^? to streams, or it may be impacted by the NO₃^? removal process of denitrification in streambed sediments. In a study of a small agricultural catchment on the Atlantic coastal plain of Virginia's eastern shore, we used seepage meters deployed in the streambed to measure specific discharge of groundwater and its solute concentrations for various locations and dates. We used values of Cl^? concentration to discriminate between bypass water recharged distal to the stream and that contained high NO₃^? but low Cl^? concentrations and riparian‐influenced water recharged proximal to the stream that contained low NO₃^? and high Cl^? concentrations. The travel time required for bypass water to transit the 30‐cm‐thick, microbially active denitrifying zone in the streambed determined the extent of NO₃^? removal, and hydraulic conductivity determined travel time through the streambed sediments. At all travel times greater than 2 days, NO₃^? removal was virtually complete. Comparison of the timescales for reaction and transport through the streambed sediments in this system confirmed that the predominant control on nitrate flux was travel time rather than denitrification rate coefficients. We conclude that extensive denitrification can occur in groundwater that bypasses the riparian zone, but a residence time in biologically active streambed sediments sufficient to remove a large fraction of the NO₃^? is only achieved in relatively low‐conductivity porous media. Instead of viewing them as separate, the streambed and riparian zone should be considered an integrated NO₃^? removal unit. Copyright © 2011 John Wiley & Sons, Ltd.     

Response of surface water chemistry to reduced levels of acid precipitation: comparison of trends in two regions of New York,USA

In light of recent reductions in sulphur (S) and nitrogen (N) emissions mandated by Title IV of the Clean Air Act Amendments of 1990, temporal trends and trend coherence in precipitation (1984–2001 and 1992–2001) and surface water chemistry (1992–2001) were determined in two of the most acid‐sensitive regions of North America, i.e. the Catskill and Adirondack Mountains of New York. Precipitation chemistry data from six sites located near these regions showed decreasing sulphate (SO₄^2?), nitrate (NO₃^?), and base cation (C_B) concentrations and increasing pH during 1984–2001, but few significant trends during 1992–2001. Data from five Catskill streams and 12 Adirondack lakes showed decreasing trends in SO₄^2? concentrations at all sites, and decreasing trends in NO₃^?, C_B, and H⁺ concentrations and increasing trends in dissolved organic carbon at most sites. In contrast, acid‐neutralizing capacity (ANC) increased significantly at only about half the Adirondack lakes and in one of the Catskill streams. Flow correction prior to trend analysis did not change any trend directions and had little effect on SO₄^2? trends, but it caused several significant non‐flow‐corrected trends in NO₃^? and ANC to become non‐significant, suggesting that trend results for flow‐sensitive constituents are affected by flow‐related climate variation. SO₄^2? concentrations showed high temporal coherence in precipitation, surface waters, and in precipitation–surface water comparisons, reflecting a strong link between S emissions, precipitation SO₄^2? concentrations, and the processes that affect S cycling within these regions. NO₃^? and H⁺ concentrations and ANC generally showed weak coherence, especially in surface waters and in precipitation–surface water comparisons, indicating that variation in local‐scale processes driven by factors such as climate are affecting trends in acid–base chemistry in these two regions. Copyright © 2005 John Wiley & Sons, Ltd.     

Hydrochemical behaviour of dissolved nitrogen and carbon in a headwater stream of the Canadian Shield: relevance of antecedent soil moisture conditions

This paper examines the impact of contrasting antecedent soil moisture conditions on the hydrochemical response, here the changes in dissolved nitrogen (NO₃^?, NH₄⁺ and dissolved organic nitrogen (DON)) and dissolved organic carbon (DOC) concentrations, of a first‐order stream during hydrological events. The study was performed in the Hermine, a 5 ha forested watershed of the Canadian Shield. It focused on a series of eight precipitation events (spring, summer and fall) sampled every 2 or 3 h and showing contrasted antecedent moisture conditions. The partition of the eight events between two groups (dry or wet) of antecedent moisture conditions was conducted using a principal component analysis (PCA). The partition was controlled (first axis explained 86% of the variability) by the antecedent streamflow, the streamflow to precipitation ratio Q/P and by the antecedent groundwater depth. The mean H⁺, NO₃^?, NH₄⁺, total dissolved nitrogen and DOC concentrations and electrical conductivity values in the stream were significantly higher following dry antecedent conditions than after wetter conditions had prevailed in the Hermine, although the temporal variability was high (17 to 138%). At the event scale, a significantly higher proportion of the changes in DON, NO₃^?, and DOC concentrations in the stream was explained by temporal variations in discharge compared with the seasonal and annual scales. Two of the key hydrochemical features of the dry events were the synchronous changes in DOC and flow and the frequent negative relationships between discharge and NO₃^?. The DON concentrations were much less responsive than DOC to changes in discharge, whereas NH was not in phase with streamflow. During wet events, the synchronicity between streamflow and DON or NO₃^? was higher than during dry events and discharge and NO₃^? were generally positively linked. Based on these observations, the hydrological behaviour of the Hermine is conceptually compatible with a two‐component model of shallow (DON and DOC rich; variable NO₃^?) and deep (DON and DOC poor; variable NO₃^?) subsurface flow. The high NO₃^? and DOC levels measured at the early stages of dry events reflected the contribution from NO₃^?‐rich groundwaters. The contribution of rapid surface flow on water‐repellent soil materials located close to the stream channel is hypothesized to explain the DOC levels. An understanding of the complex interactions between antecedent soil moisture conditions, the presence of soil nutrients available for leaching and the dynamics of soil water flow paths during storms is essential to explain the fluxes of dissolved nitrogen and carbon in streams of forested watersheds. Copyright © 2007 John Wiley & Sons, Ltd.     

Chemical Composition of Dew Resulting from Radiative Cooling at a Semi-arid Site in Agra, India

Dew samples were collected between October 2007 and February 2008 from a suburban site in Agra. pH, conductivity, major inorganic ions (F^?, Cl^?, NO ₃ ^? , SO ₄ ^2? , Na⁺, K⁺, Ca²⁺, Mg²⁺, and NH ₄ ⁺ ), and some trace metals (Cr, Sn, Zn, Pb, Cd, Ni, Mn, Fe, Si, Al, V, and Cu) were determined to study the chemistry of dew water. The mean pH was 7.3, and the samples exhibited high ionic concentrations. Dew chemistry suggested both natural and anthropogenic influences, with acidity being neutralized by atmospheric ammonia and soil constituents. Ion deposition flux varied from 0.25 to 3.0?neq?m^?2?s^?1, with maximum values for Ca²⁺ followed by NH ₄ ⁺ , Mg²⁺, SO ₄ ^2? , Cl^?, NO ₃ ^? , Na⁺, K⁺, and F^?. Concentrations of trace metals varied from 0.13 to 48?μg?l^?1 with maximum concentrations of Si and minimum concentration of Cd. Correlation analysis suggested their contributions from both crustal and anthropogenic sources.     

Photochemistry of Ions at D-region Altitudes of the Ionosphere: A Review

The current state of knowledge of the D-region ion photochemistry is reviewed. Equations determining production rates of electrons and positive ions by photoionization of atmospheric neutral species are presented and briefly discussed. Considerable attention is given to the progress in the chemistry of O⁺(⁴S), O⁺(²D), O⁺(²P), N⁺, N₂ ⁺, O₂ ⁺, NO⁺, N₄ ⁺, O₄ ⁺, NO⁺(N₂), NO⁺(CO₂), NO⁺(CO₂)₂, NO⁺(H₂O) _n for n = 1–3, NO⁺(H₂O)(N₂), NO⁺(H₂O)₂(N₂), NO⁺(H₂O)(CO₂), NO⁺(H₂O)₂(CO₂), O₂ ⁺(H₂O), H₃O⁺(OH), H⁺(H₂O) _n for n = 1–8, O^?, O₂ ^?, O₃ ^?, O₄ ^?, OH^?, CO₃ ^?, CO₄ ^?, NO₂ ^?, NO₃ ^?, ONOO^?, Cl^?, Cl^?(H₂O), Cl^?(CO₂), HCO₃ ^?, CO₃ ^?(H₂O), CO₃ ^?(H₂O)₂, NO₃ ^?(H₂O), NO₃ ^?(H₂O)₂, OH^?(H₂O), and OH^?(H₂O)₂ ions. The analysis of the D-region rocket ion mass spectrometer measurements shows that, among these ions, O₂ ⁺, NO⁺, NO⁺(H₂O), and H⁺(H₂O) _n for n = 1–7 can make the main contribution to the total positive ion number density, and O^?, O₂ ^?, Cl^?, OH^?(H₂O), CO₃ ^?, HCO₃ ^?, NO₃ ^?, ONOO^?, CO₄ ^?, NO₃ ^?(H₂O), NO₃ ^?(H₂O)₂, and ³⁵Cl^?(CO₂) ions can be responsible for the main contribution to the total negative ion number density. Photodetachment of electrons from O^?, Cl^?, O₂ ^?, O₃ ^?, OH^?, NO₂ ^?, and NO₃ ^?, dissociative electron photodetachment of O₄ ^? and OH^?(H₂O), and photodissociation of O₃ ^?, O₄ ^?, CO₃ ^?, CO₄ ^?, ONOO^?, HCO₃ ^?, CO₃ ^?(H₂O), NO₃ ^?(H₂O), O₂ ⁺(H₂O), O₄ ⁺, N₄ ⁺, NO⁺(H₂O), NO⁺(H₂O)₂, H⁺(H₂O) _n for n = 2–4, NO⁺(N₂), and NO⁺(CO₂) are studied, and the photodetachment and photodissociation rate coefficients are calculated using the current state of knowledge on the cross sections of these processes and fluxes of solar radiation.     

Influence of Atmospheric Solar Radiation Absorption on Photodestruction of Ions at D-Region Altitudes of the Ionosphere

The influence of atmospheric solar radiation absorption on the photodetachment, dissociative photodetachment, and photodissociation rate coefficients (photodestruction rate coefficients) of O^?, Cl^?, O₂ ^?, O₃ ^?, OH^?, NO₂ ^?, NO₃ ^?, O₄ ^?, OH^?(H₂O), CO₃ ^?, CO₄ ^?, ONOO^?, HCO₃ ^?, CO₃ ^?(H₂O), NO₃ ^?(H₂O), O₂ ⁺(H₂O), O₄ ⁺, N₄ ⁺, NO⁺(H₂O), NO⁺(H₂O)₂, H⁺(H₂O) _n for n = 2–4, NO⁺(N₂), and NO⁺(CO₂) at D-region altitudes of the ionosphere is studied. A numerical one-dimensional time-dependent neutral atmospheric composition model has been developed to estimate this influence. The model simulations are carried out for the geomagnetically quiet time period of 15 October 1998 at moderate solar activity over the Boulder ozonesonde. If the solar zenith angle is not more than 90° then the strongest influence of atmospheric solar radiation absorption on photodestruction of ions is found for photodissociation of CO₄ ^? ions when CO₃ ^? ions are formed. It follows from the calculations that decreases in the photodestruction rate coefficients of ions under consideration caused by this influence are less than 2 % at 70 km altitude and above this altitude if the solar zenith angle does not exceed 90°.     

Pollutant Concentrations in Mountain River Waters in the Upper Baksan Area (Prielbrus’e National Park) and Their Seasonal Variations

Materials of expedition studies in 2013 in the Prielbrus’e National Park were used to analyze the concentrations of a wide range of pollutants (SO₄^2-, Cl^?, Na⁺, K⁺, F^?, Mn, Cu, Zn, Pb, Cr, Ni, NO₃^-, NH₄⁺) in the water of mountain rivers forming the main artery of the region, the Baksan R. The analyzed data characterize seasonal variations in pollutant concentrations at seven sampling sections and their dynamics along the river down to the 35th km from the source in different seasons.     

Transport of nitrogen in soil water following the application of animal manures to sloping grassland

Abstract

A field experiment was conducted on a sloping grassland soil in southwest England to investigate the downslope transport of nitrogen in soil water following the application of cattle manure, slurry and inorganic fertilizer. Transport of nitrogen (N) species was monitored on hydrologically isolated plots. Manure (50 t ha^?1), slurry (50 m³ ha^?1) and fertilizer (250 kg N ha^?1) were applied in February/March 1992. Subsurface water movement, by both matrix and preferential flow, was the dominant flow route during the experiment. Subsurface and surface nutrient flow pathways were monitored by analysing soil water and surface runoff for NO₃-N, NH₄-N and total N. Subsurface flow chemistry was dominated by NO₃-N, with concentrations usually between 2 and 5 mg NO₃ ?N dm^?3. Differences between fertilizer and manure treatments and the untreated control were not significant. Significantly elevated NO₃-N concentrations were observed in soil water in the buffer zone, indicating the importance of a buffer zone at least 10 m wide between manure spreading zones and an adjacent water course.     

Hydrological flowpaths and nitrate removal rates within a riparian floodplain along a fourth‐order stream in Brittany (France)

Three main reservoirs were identified that contribute to the shallow subsurface flow regime of a valley drained by a fourth‐order stream in Brittany (western France). (i) An upland flow that supplied a wetland area, mainly during the high‐water period. It has high N‐NO₃^? and average Cl^? concentrations. (ii) A deep confined aquifer characterized by low nitrate and low chloride concentrations that supplied the floodplain via flow upwelling. (iii) An unconfined aquifer under the riparian zone with high Cl^? and low N‐NO₃^? concentrations where biological processes removed groundwater nitrate. This aquifer collected the upland flow and supplied a relict channel that controlled drainage from the whole riparian zone. Patterns of N‐NO₃^? and Cl^? concentrations along riparian transects, together with calculated high nitrate removal, indicate that removal occurred mainly at the hillslope–riparian zone interface (i.e. first few metres of wetland), whereas dilution occurred in lower parts of the transects, especially during low‐water periods and at the beginning of recharge periods. Stream flow was modelled as a mixture of water from the three reservoirs. An estimation of these contributions revealed that the deep aquifer contribution to stream flow averaged 37% throughout the study period, while the contribution of the unconfined reservoir below the riparian zone and hillslope flow was more variable (from ca 6 to 85%) relative to rainfall events and the level of the riparian water table. At the entire riparian zone scale, NO₃^? removal (probably from denitrification) appeared most effective in winter, despite higher estimated upland NO₃^? fluxes entering the riparian zone during this period. Copyright © 2003 John Wiley & Sons, Ltd.     

Wetland nitrogen dynamics in an Adirondack forested watershed

Wetlands often form the transition zone between upland soils and watershed streams, however, stream–wetland interactions and hydrobiogeochemical processes are poorly understood. We measured changes in stream nitrogen (N) through one riparian wetland and one beaver meadow in the Archer Creek watershed in the Adirondack Mountains of New York State, USA from 1 March to 31 July 1996. In the riparian wetland we also measured changes in groundwater N. Groundwater N changed significantly from tension lysimeters at the edge of the peatland to piezometer nests within the peatland. Mean N concentrations at the peatland perimeter were 1·5, 0·5 and 18·6 µmol L^?1 for NH₄⁺, NO₃^? and DON (dissolved organic nitrogen), respectively, whereas peatland groundwater N concentration was 56·9, 1·5 and 31·6 µmol L^?1 for NH₄⁺, NO₃^? and DON, respectively. The mean concentrations of stream water N species at the inlet to the wetlands were 1·5, 10·1 and 16·9 µmol L^?1 for NH₄⁺, NO₃^? and DON, respectively and 1·6, 28·1 and 8·4 µmol L^?1 at the wetland outlet. Although groundwater total dissolved N (TDN) concentrations changed more than stream water TDN through the wetlands, hydrological cross‐sections for the peatland showed that wetland groundwater contributed minimally to stream flow during the study period. Therefore, surface water N chemistry was affected more by in‐stream N transformations than by groundwater N transformations because the in‐stream changes, although small, affected a much greater volume of water. Stream water N input–output budgets indicated that the riparian peatland retained 0·16 mol N ha^?1 day^?1 of total dissolved N and the beaver meadow retained 0·26 mol N ha^?1 day^?1 during the study period. Nitrate dominated surface water TDN flux from the wetlands during the spring whereas DON dominated during the summer. This study demonstrates that although groundwater N changed significantly in the riparian peatland, those changes were not reflected in the stream. Consequently, although in‐stream changes of N concentrations were less marked than those in groundwater, they had a greater effect on stream water chemistry—because wetland groundwater contributed minimally to stream flow. Copyright © 2004 John Wiley & Sons, Ltd.     

Variation in nitrate uptake and denitrification rates across a salinity gradient in Mediterranean semiarid streams

Streams are significant locations for nitrate (NO₃ ^?) processing within landscapes. This is especially important in dry climates given the limited water availability for biological processes elsewhere. In arid and semiarid regions, many streams are naturally saline. Elevated salinity can constrain the structure and function of aquatic organisms, which is expected to increase worldwide being associated to global warming. We investigated whole-reach NO₃ ^? uptake and denitrification in nine semiarid streams of variable water salinity (i.e. from freshwater to hyposaline) to test if NO₃ ^? processing would decrease with increasing salinity. We used pulse additions and Tracer Addition for Spiraling Curve Characterization (TASCC) to measure whole-reach uptake of added NO₃ ^?, and the acetylene block technique to measure sediment denitrification. TASCC results showed that only five of nine streams were able to retain added NO₃ ^?. Of these five retentive streams, four were saline; however, salinity did not control significantly the variation in whole-reach NO₃ ^? uptake observed across streams. Other measured environmental variables such as streambed NH₄ ⁺ and organic carbon availability were better at explaining this variation. Denitrification was detected in all streams except one and its variation across streams was also independent of salinity. Although denitrification rates tended to be high, their contribution to whole-reach NO₃ ^? uptake was insignificant (≤2.16 %). Alternative pathways, heterotrophic assimilation and/or dissimilatory NO₃ ^? reduction to NH₄ ⁺, were probably responsible for most whole-reach NO₃ ^? uptake. Together, our results highlight that the function of streams in controlling external NO₃ ^? inputs is highly variable and salinity does not apparently constrain this role.     

Influences of watershed landscape composition and configuration on lake‐water quality in the Yangtze River basin of China

Lake‐water quality is highly dependent on the landscape characteristics in its respective watershed. In this study, we investigated the relationships between lake‐water quality and landscape composition and configuration within the watershed in the Yangtze River basin of China. Water quality variables, including pH, electrical conductivity (EC), dissolved oxygen (DO), Secchi depth (SD), NO₂^?, NO₃^?, NH₄⁺, TN, TP, chemical oxygen demand (COD_Mn), chlorophyll‐a (Chl‐a), and trophic state index (TSI), were collected from 16 lakes during the period of 2001–2003. Landscape composition (i.e. the percentage of vegetation, agriculture, water, urban, and bare land) and landscape configuration metrics, including number of patches (NP), patch density (PD), largest patch index (LPI), edge density (ED), mean patch area (MPA), mean shape index (MSI), contagion (CONTAG), patch cohesion index (COHESION), Shannon's diversity index (SHDI), and aggregation index (AI), were calculated for each lake's watershed. Results revealed that the percentage of agriculture was negatively related to NO₂^?, TN, TP, Chl‐a concentrations, and TSI, while the percentage of urban was significantly correlated with EC, NH₄⁺, and COD_Mn concentrations. Among landscape‐level configuration metrics, only ED showed significant relationships with TN, TP concentrations, and TSI. However, at the class level, the PD, LPI, ED, and AI of agriculture and urban land uses were significantly correlated with two or more water quality variables. This study suggests that, for a given total area, large and clustered agricultural or urban patches in the watershed may have a greater impact on lake‐water quality than small and scattered ones. Copyright © 2011 John Wiley & Sons, Ltd.     

Impact of Hurricane Irene and Tropical Storm Lee on riparian zone hydrology and biogeochemistry

Although riparian zones are well known to reduce nitrogen (N) and phosphorus (P) runoff to streams, they also have the potential to affect greenhouse gas (CO₂, N₂O, and CH₄) fluxes to the atmosphere. Following large storms, soil biogeochemical conditions often become more reduced, especially in oxbow depressions and side channels, which can lead to hot moments of greenhouse gas production. Here, we investigate the impact of the remnants of Hurricane Irene and Tropical Storm Lee on riparian zone hydrology (water table: WT), and biogeochemistry (oxidation‐reduction potential [ORP], dissolved oxygen [DO], NO₃^?, PO₄^3?, CO₂, N₂O, CH₄). Results indicate that large storms have the potential to reset WT levels for weeks to months. Overbank flooding at our site following Irene and Lee led to the infiltration of well‐oxygenated water at depth (higher DO and ORP) while promoting the development of anoxic conditions within soil aggregates near the soil surface (increased N₂O and CH₄ fluxes). A short‐term increase in CO₂ emission was observed following Irene at our site where aerobic respiration was water‐limited. Over a 2‐year period, an oxbow depression exhibited higher WT, higher N₂O and CH₄ fluxes (hot moment), higher CO₂ fluxes (seasonal), and lower NO₃^? concentrations (seasonal) than the rest of the riparian zone. However, neither Irene, nor Lee, nor the oxbow depression significantly impacted PO₄^3?. Dissolved organic carbon, ORP, and DO data illustrate the time‐lag (>20 years) between the creation of an oxbow depression and the development of reducing conditions despite clear differences in riparian zone and oxbow WT dynamics.     

The solute budget of a forest catchment and solute fluxes within a Pinus radiata and a secondary native forest site,southern Chile

Solute concentrations and fluxes in rainfall, throughfall and stemflow in two forest types, and stream flow in a 90 ha catchment in southern Chile (39°44′S, 73°10′W) were measured. Bulk precipitation pH was 6·1 and conductivity was low. Cation concentrations in rainfall were low (0·58 mg Ca²⁺ l^?1, 0·13 mg K⁺ l^?1, 0·11 mg Mg²⁺ l^?1 and <0·08 mg NH₄–N l^?1), except for sodium (1·10 mg l^?1). Unexpected high levels of nitrate deposition in rainfall (mean concentration 0·38 mg NO₃–N l^?1, total flux 6·3 kg NO₃–N ha^?1) were measured. Concentrations of soluble phosphorous in bulk precipitation and stream flow were below detection limits (<0·09 mg l^?1) for all events. Stream‐flow pH was 6·3 and conductivity was 28·3 μs. Stream‐water chemistry was also dominated by sodium (2·70 mg l^?1) followed by Ca, Mg and K (1·31, 0·70 and 0·36 mg l^?1). The solute budget indicated a net loss of 3·8 kg Na⁺ ha^?1 year^?1, 5·4 kg Mg²⁺ ha^?1 year^?1, 1·5 kg Ca²⁺ ha^?1 year^?1 and 0·9 kg K⁺ ha^?1 year^?1, while 4·9 kg NO₃–N ha^?1 year^?1 was retained by the ecosystem. Stream water is not suitable for domestic use owing to high manganese and, especially, iron concentrations. Throughfall and stemflow chemistry at a pine stand (Pinus radiata D. Don) and a native forest site (Siempreverde type), both located within the catchment, were compared. Nitrate fluxes within both forest sites were similar (1·3 kg NO₃–N ha^?1 year^?1 as throughfall). Cation fluxes in net rainfall (throughfall plus stemflow) at the pine stand generally were higher (34·8 kg Na⁺ ha^?1 year^?1, 21·5 kg K⁺ ha^?1 year^?1, 5·1 kg Mg²⁺ ha^?1 year^?1) compared with the secondary native forest site (24·7 kg Na⁺ ha^?1 year^?1, 18·9 kg K⁺ ha^?1 year^?1 and 4·4 kg Mg²⁺ ha^?1 year^?1). However, calcium deposition beneath the native forest stand was higher (15·9 kg Ca²⁺ ha^?1 year^?1) compared with the pine stand (12·6 kg Ca²⁺ ha^?1 year^?1). Copyright © 2002 John Wiley & Sons, Ltd.     

Nitrogen compounds in the surface and subsurface waters of Karelia

Materials of long-term studies of the concentration and distribution of N forms (NH₄⁺, NO₃⁻, NO₂⁻, N_org) in precipitation, surface water and groundwater are generalized. Precipitation was found to be the main source of N compounds input into these waters. The effect of anthropogenic factors is local and does not influence the concentration and distribution of N forms in most water bodies that serve as wastewater recipients. The N forms dominating in precipitation are NO₃⁻ and N H₄⁺; N_org dominates in most surface water bodies, and NO₃⁻ dominates in groundwater. The median concentrations of N_tot in clear surface and subsurface waters are similar. The obtained characteristics of the concentrations and distribution of N forms in natural waters of Karelia can be used for other water bodies in the humid zone.     

Controls on surface water chemistry in two lake‐watersheds in the Adirondack region of New York: differences in nitrogen solute sources and sinks

The southwestern Adirondack region of New York receives among the highest rates of atmospheric nitrogen (N) deposition in the USA. Atmospheric N deposition to sensitive ecosystems, like the Adirondacks, may increase the acidification of soils through losses of exchangeable nutrient cations, and the acidification of surface waters associated with enhanced mobility of nitrate (NO₃^?). However, watershed attributes, including surficial terrestrial characteristics, in‐lake processing, and geological settings, have been found to complicate the relationships between atmospheric N deposition and N drainage losses. We studied two lake‐watersheds in the southwestern Adirondacks, Grass Pond and Constable Pond, which are located in close proximity (～26 km) and receive similarly high N deposition, but have contrasting watershed attributes (e.g. wetland area, geological settings). Since the difference in the influence of N deposition was minimal, we were able to examine both within‐ and between‐watershed influences of land cover, the contribution of glacial till groundwater inputs, and in‐lake processes on surface water chemistry with particular emphasis on N solutes and dissolved organic carbon (DOC). Monthly samples at seven inlets and one outlet of each lake were collected from May to October in 1999 and 2000. The concentrations of NO₃^? were high at the Grass Pond inlets, especially at two inlets, and NO₃^? was the major N solute at the Grass Pond inlets. The concentrations of likely weathering products (i.e. dissolved Si, Ca²⁺, Mg²⁺, Na⁺) as well as acid neutralizing capacity and pH values, were also particularly high at those two Grass Pond inlets, suggesting a large contribution of groundwater inputs. Dissolved organic N (DON) was the major N solute at the Constable Pond inlets. The higher concentrations of DON and DOC at the Constable Pond inlets were attributed to a large wetland area in the watershed. The DOC/DON ratios were also higher at the Constable Pond inlets, possibly due to a larger proportion of coniferous forest area. Although DON and DOC were strongly related, the stronger relationship of the proportion of wetland area with DOC suggests that additional factors regulate DON. The aggregated representation of watershed physical features (i.e. elevation, watershed area, mean topographic index, hypsometric‐analysis index) was not clearly related to the lake N and DOC chemistry. Despite distinctive differences in inlet N chemistry, NO₃^? and DON concentrations at the outlets of the two lakes were similar. The lower DOC/DON ratios at the lake outlets and at the inlets having upstream ponds suggest the importance of N processing and organic N sources within the lakes. Although an inverse relationship between NO₃^? and DOC/DON has been suggested to be indicative of a N deposition gradient, the existence of this relationship for sites that receive similar atmospheric N deposition suggest that the relationship between NO₃^? and the DOC/DON ratio is derived from environmental and physical factors. Our results suggest that, despite similar wet N deposition at the two watershed sites, N solutes entering lakes were strongly affected by hydrology associated with groundwater contribution and the presence of wetlands, whereas N solutes leaving lakes were strongly influenced by in‐lake processing. Copyright © 2006 John Wiley & Sons, Ltd.     

Dynamics of stream nitrate sources and flow pathways during stormflows on urban,forest and agricultural watersheds in central Pennsylvania,USA

Understanding the influence of storm events on nitrate (NO₃^?) dynamics is important for efficiently managing NO₃^? pollution. In this study, five sites representing a downstream progression of forested uplands underlain by resistant sandstone to karst lowlands with agricultural, urban and mixed land‐use were established in Spring Creek, a 201 km² mixed land‐use watershed in central Pennsylvania, USA. At each site, stream water was monitored during six storm events in 2005 to assess changes in stable isotopes of NO₃^? (δ¹⁵N‐NO₃^? and δ¹⁸O‐NO₃^?) and water (δ¹⁸O‐H₂O) from baseflow to peakflow. Peakflow fractions of event NO₃^? and event water were then computed using two‐component mixing models to elucidate NO₃^? flow pathway differences among the five sites. For the forested upland site, storm size appeared to affect NO₃^? sources and flow pathways. During small storms (<35 mm rainfall), greater event NO₃^? fractions than event water fractions indicated the prevalence of atmospheric NO₃^? source contributions at peakflow. During larger storms (>35 mm rainfall), event NO₃^? fractions were less than event water fractions at peakflow suggesting that NO₃^? was flushed from stored sources via shallow subsurface flow pathways. For the urbanized site, wash‐off of atmospheric NO₃^? was an important NO₃^? source at peakflow, especially during short‐duration storms where event water contributions indicated the prevalence of overland flow. In the karst lowlands, very low fractions of event water and even lower fractions of event NO₃^? at peakflow suggested the dominance of ground water flow pathways during storms. These ground water flow pathways likely flushed stored NO₃^? sources into the stream, while deep soils in the karst lowlands also may have promoted NO₃^? assimilation. The results of this study illustrated how NO₃^? isotopes and δ¹⁸O‐H₂O could be combined to show key differences in water and NO₃^? delivery between forested uplands, karst valleys and fully urbanized watersheds. Copyright © 2009 John Wiley & Sons, Ltd.     

Factors controlling the acid‐neutralizing capacity of Japanese cedar forest watersheds in stands of various ages and topographic characteristics

Acid‐neutralizing capacity (ANC) is an important index for streamwater acidification caused by external factors (i.e. chronic acid deposition) and internal factors such as soil acidification due to nitrification. In this study, the influence of forest clear‐cutting and subsequent regrowth on internal acidification was investigated in central Japan, where stream pH (near 7·0) and ANC (above 0·1 meq L^?1) are high. pH, the concentrations of major cations (Na⁺, K⁺, Mg²⁺ and Ca²⁺), major anions (NO₃^?, Cl^? and SO₄^2?) and dissolved silica (Si), and ANC were measured in 33 watersheds of various stand ages, during 2002 to 2004. Only NO₃^? concentration decreased with stand age, whereas pH, ANC, and concentrations of the sum of base cations (BC) and Si were negatively correlated with the minimum elevation of the watershed. The correlation between the BC/Si ratio and minimum elevation suggested that factors contributing to acid neutralization changed at 1100 m above sea level. In watersheds at lower elevations (?1100 m), the relatively high contribution of soil water with longer soil contact times should result in higher ANC, and cation exchange reactions should be the dominant process for acid neutralization due to deposition of colluvial soils on the lower slope. In contrast, in higher‐elevation watersheds (≥1100 m), weathered residual soils are thin and the small contribution of deeper groundwater results in lower ANC. These results suggest that the local acid sensitivity is determined by the hydrological and geomorphologic factors generated by steep topography. Copyright © 2008 John Wiley & Sons, Ltd.     

Natural Attenuation of Perchlorate in Denitrified Groundwater

Monitoring of a well‐defined septic system groundwater plume and groundwater discharging to two urban streams located in southern Ontario, Canada, provided evidence of natural attenuation of background low level (ng/L) perchlorate (ClO₄^?) under denitrifying conditions in the field. The septic system site at Long Point contains ClO₄^? from a mix of waste water, atmospheric deposition, and periodic use of fireworks, while the nitrate plume indicates active denitrification. Plume nitrate (NO₃^?‐N) concentrations of up to 103 mg/L declined with depth and downgradient of the tile bed due to denitrification and anammox activity, and the plume was almost completely denitrified beyond 35 m from the tile bed. The ClO₄^? natural attenuation occurs at the site only when NO₃^?‐N concentrations are <0.3 mg/L, after which ClO₄^? concentrations decline abruptly from 187 ± 202 to 11 ± 15 ng/L. A similar pattern between NO₃^?‐N and ClO₄^? was found in groundwater discharging to the two urban streams. These findings suggest that natural attenuation (i.e., biodegradation) of ClO₄^? may be commonplace in denitrified aquifers with appropriate electron donors present, and thus, should be considered as a remediation option for ClO₄^? contaminated groundwater.     

Impact of septic tank systems on local groundwater quality and water supply in the Pearl River Delta,China: case study

Located at southern coast of China, the Pearl River Delta (PRD) is facing serious water problems in both quantity and quality after its rapid urbanization in the last decade. Most remarkably, the local groundwater, that was used to be the source of drinking water before the urbanization was polluted due to poor management of the septic tanks. In order to study the effects of suburban development on local groundwater flow and water quality in the PRD region, Fengcun of Guangzhou has been chosen as the study area. In Fengcun, drinking water was groundwater before the 1990s, but now piped reservoir water is used by each family because the groundwater has been polluted. This study clarifies the source and process of the groundwater pollution from septic tanks using isotopic and geochemical characteristics, especially nitrate (NO₃^?) concentrations. Water samples were collected from the wells and ponds in Fengcun in March and July 2005 and in July 2006. Based on the pe–pH diagram, NO₃^? and ammonium of groundwater are from the effect of human activities, rather than from nitrification and ammonification of N₂. NO₃^? pollution of groundwater is from point sources, and NO₃^? concentrations decrease from northeast to southwest. Groundwater is polluted rapidly by the leakage of septic tanks. NO₃^? concentrations of pollution sources were lower than 20 mg l^?1 in March 2005, but had increased to about 120 mg l^?1 in July 2006. This implies that groundwater protection should be strengthened in rural areas of the PRD. Copyright © 2007 John Wiley & Sons, Ltd.