Soil NO3− storage from oasis development in deserts: Implications for the prevention and control of groundwater pollution

The sources and storage of soil NO₃⁻ in the western Tengger Desert, Northwest China, were explored using water chemistry analysis and stable isotope techniques. In line with the expansion and development of oases, part of the desert has been transformed into cultivated land and artificial forest land. The mean soil NO₃⁻ contents found in areas of cultivated land and artificial forest were 123.06 mg kg⁻¹ and 1.26 mg kg⁻¹, far higher and slightly lower than the background desert soil values, respectively. The δ¹⁵N-NO₃⁻ and δ¹⁸O-NO₃⁻ values in cultivated soils ranged from 1.00 to 11.81 ‰, and from −1.85 to 8.99 ‰, respectively, and the mean mNO₃⁻/Cl⁻ value in cultivated soils was 2.3. These figures would appear to demonstrate that the rapid increase in the nitrate content in soils is principally due to the use of nitrogen fertilizer. Such increases in soil NO₃⁻ storage is likely to promote the leaching of nitrogen into the groundwater where coarsely textured soils exist, the pollution of water sources used for irrigation water, and extreme precipitation events. The δ¹⁵N-NO₃⁻ and δ¹⁸O-NO₃⁻ values in groundwater ranged from 3.72 to 6.54 ‰, and from −0.19 to 12.06 ‰, respectively, mainly reflecting the nitrification of soil nitrogen. These values appeared similar to those measured in the soil water in adjacent areas of cultivated land and vegetated desert, indicating that the groundwater has been affected by both natural and artificial NO₃⁻. Artificial afforestation of desert regions would therefore seem to be a useful way of reducing the threat posed by anthropogenic sources to the circulation of NO₃⁻-N within arid regions, as well as promoting wind sheltering and sand fixation. This study explored the NO₃⁻ storage and groundwater quality responses to oasis development in arid areas in an attempt to provide effective information for local agricultural organizations and agricultural nitrogen management models.     

Tracing groundwater nitrate sources in the Dakar suburban area: an isotopic multi‐tracer approach

The Dakar region is a mega city with multiple contaminant sources from urban expansion as well as industrial and agricultural activities. The major part of the region is underlain by unconfined sandy aquifer, which is vulnerable to contaminants derived from human land use. At present, the contaminated groundwater which extends over a large area in the suburban zone of Thiaroye poses a threat to the future of this valuable resource, and more specifically, a health threat. This study focuses on nitrate pollution occurrences and associated processes using nitrate isotope data (¹⁵N_NO3, ¹⁸O_NO3) combined with environmental isotopic tracers (¹⁸O, ²H, and ³H). Samples from 36 wells were collected to determine the level, distribution, and sources of contamination in relation to land use. Results indicate that shallow groundwater in the urbanized area of Thiaroye shows distinct evidence of surface contamination with nitrate as much as 300 mg/l NO₃^?. In rural area not serviced by water supply distribution network, much higher NO₃^? contents were found in few wells due to household and livestock feedlots. In most groundwater samples δ¹⁵N values ranged from + 10 to + 22‰, indicative of predominantly human and animal wastes. This was confirmed by environmental isotope data which suggest a mixture of polluted recharge waters. By using the dual δ¹⁵N vs δ¹⁸O as well as δ¹⁵N vs NO₃^? approach, denitrification may occur to some extent but it is blurred by mixing with new infiltrated nitrates and cycling derived from continuous leaky septic system. Results suggest that nitrate contamination of the aquifer is a consequence of unregulated urbanisation (homemade latrines), continuing contaminant transfer in shallow water depth where aerobic conditions prevail. Copyright © 2011 John Wiley & Sons, Ltd.     

Geologic controls on the chemical behaviour of nitrate in riverside alluvial aquifers,Korea

To investigate the origin and behaviour of nitrate in alluvial aquifers adjacent to Nakdong River, Korea, we chose two representative sites (Wolha and Yongdang) having similar land‐use characteristics but different geology. A total of 96 shallow groundwater samples were collected from irrigation and domestic wells tapping alluvial aquifers. About 63% of the samples analysed had nitrate concentrations that exceeded the Korean drinking water limit (44·3 mg l^?1 NO₃^?), and about 35% of the samples had nitrate concentrations that exceeded the Korean groundwater quality standard for agricultural use (88·6 mg l^?1 NO₃^?). Based on nitrogen isotope analysis, two major nitrate sources were identified: synthetic fertilizer (about 4‰ δ¹⁵N) applied to farmland, and animal manure and sewage (15–20‰ δ¹⁵N) originating from upstream residential areas. Shallow groundwater in the farmland generally had higher nitrate concentrations than those in residential areas, due to the influence of synthetic fertilizer. Nitrate concentrations at both study sites were highest near the water table and then progressively decreased with depth. Nitrate concentrations are also closely related to the geologic characteristics of the aquifer. In Yongdang, denitrification is important in regulating nitrate chemistry because of the availability of organic carbon from a silt layer (about 20 m thick) below a thin, sandy surface aquifer. In Wolha, however, conservative mixing between farmland‐recharged water and water coming from a village is suggested as the dominant process. Mixing ratios estimated based on the nitrate concentrations and the δ¹⁵N values indicate that water originating from the village affects the nitrate chemistry of the shallow groundwater underneath the farmland to a large extent. Copyright © 2003 John Wiley & Sons, Ltd.     

Collocation of hydrological and biological attenuation of nitrate in an urban stream

The hydrologic and biogeochemical processes that control nutrient export in urban streams are not well understood. Attenuation can occur by tributary dilution, groundwater discharge, and biological processing both in the water column and the hyporheic zone. A wastewater treatment plant on Pennypack Creek, an urban stream near Philadelphia, PA, provided high nitrate concentrations for analysis of downstream attenuation processes. Longitudinal sampling for an 8‐km reach revealed decreases in nitrate concentration of 2 mg l^?1 at high flow and 4.5 mg l^?1 during low flow. During high flow, δ¹⁵N‐NO₃ increased from 9.5 to 10.5‰ and during low flow increased from 10.1 to 11.1‰. Two reaches were sampled at fine spatial intervals (approximately 200 m) to better identify attenuation processes. Mixing analysis indicated that groundwater discharge and biological processing both control nitrate concentration and isotope signatures. However, fine‐scaled sampling did not reveal spatially discrete zones; instead, these processes were occurring simultaneously. While both processes attenuate nitrate, they have opposite isotope signatures, which may have muted changes in δ¹⁵N‐NO₃. At high flow, a decrease in Cl/NO₃ ratios helped distinguish groundwater discharge occurring along both finely sampled reaches. At low flow, biological processing seemed to be occurring more extensively, but the δ¹⁵N‐NO₃ signature was not consistent with either a single process or a sequential combination of groundwater dilution and biological nitrate attenuation. The collocation of processes makes it more difficult to assess biological processing hot spots and predict how urbanization and subsequent stream restoration influence nitrate attenuation. Copyright © 2016 John Wiley & Sons, Ltd.     

Isotopic signature of nitrate in river waters of the lower Mississippi and its distributary,the Atchafalaya

Periodic summer hypoxia occurring in the Northern Gulf of Mexico has been attributed to large nutrient inputs, especially nitrate‐nitrogen, from the Mississippi–Atchafalaya River system. The 2008 Gulf Hypoxia Action Plan calls for river corridor wetland restoration to reduce nitrate loads, but it is largely unknown how effective riverine wetland systems in the lower Mississippi River are for nitrate removal. We carried out an intensive isotope study to address this question by comparing nitrate isotopic signatures of the well‐channelized Mississippi River with those of the Atchafalaya River, which has extensive floodplains and backwater swamps. We investigated changes in δ¹⁵N_NO3 and δ¹⁸O_NO3 for water samples collected biweekly to monthly over a 2‐year period at the Atchafalaya River outlets (Morgan City and Wax Lake) and on the Mississippi River at Baton Rouge. In addition, in situ water quality parameters including temperature, dissolved oxygen and pH were recorded for each sampling date. Waters from both rivers showed moderately high nitrate concentration (>1 mg l^?1) and undetectable (< 0.01 mg l^?1) nitrite throughout the study period. The Mississippi River had slightly, but significantly higher (p=0.01) mean nitrate concentrations (1.5 mg l^?1) and higher δ¹⁵N_NO3 (7.7‰) than the Atchafalaya (1.1 mg l^?1, 7.0‰); while no difference in δ¹⁸O_NO3 (4.6‰) was found between the rivers. Flux‐weighted mean isotope values were overall lower than mean values for both the Mississippi and Atchafalaya Rivers, with a greater difference between the two rivers (7.4‰ versus 6.5‰, respectively). River flooding and hurricane storm surge also appeared to affect nitrate isotopic values. The lack of large difference in isotopic values between the Atchafalaya and Mississippi Rivers suggests that the majority of nitrate is transported through the Atchafalaya River with relatively little processing, and that riverine floodplains and wetlands are not effective sinks for nitrate, as previously assumed, because of insufficient residence time and well‐oxygenated river waters. Copyright © 2012 John Wiley & Sons, Ltd.     

Evaluation of nitrate levels in groundwater under agricultural fields in two pilot areas in central Chile: A hydrogeological and geochemical approach

The aim of this study is to evaluate the impact of the application of industrial fertilizers and liquid swine manure in groundwater in two pilot agricultural areas, San Pedro and Pichidegua, which have been under long‐term historic use of fertilizers. A comprehensive hydrogeological investigation was carried out to define the geology and the groundwater flow system. Chemical and isotopic tools were used to evaluate the distribution and behavior of the nitrate in the groundwater. The isotopic tools included δ¹⁸O, δ²H, and ³H, which provide information about the origin and residence time of the groundwater; δ¹⁵N‐NO₃^? and δ¹⁸O‐NO₃^?, which provide information about nitrate sources and processes that can affect nitrate along the groundwater flow system. The application rate of liquid manure and other fertilizers all together with land uses was also evaluated. The hydrogeological investigation identified the presence of a confined aquifer underneath a thick low‐permeability aquitard, whose extension covers most of the two study areas. The nitrate concentration data, excepting a few points in zones located near recharge areas in the upper part of the basins and lower areas at the valley outlets (San Pedro), showed nitrate concentration below 10 mgN/L at the regional scale. The isotope data for nitrate showed no influence of the liquid swine manure in the groundwater at the regional scale, except for the high part of the basins and the outlet of the San Pedro valley, which are areas fertilized by manure. This data showed that the regional aquifer on both pilot study areas is protected by the thick low‐permeability aquitard, which is playing an important role on nitrate attenuation. Evidence of denitrification was also found on both shallow and deep groundwater in the Pichidegua site. This study showed that a comprehensive hydrogeological characterization complemented by chemical and isotope data is key for understanding nitrate distribution and concentration in aquifers from areas with intensive agriculture activities.     

Spatial and temporal variations in surface water nitrate concentrations in a mixed land use catchment under humid temperate climatic conditions

Streamwater nitrate (NO^―₃) concentrations along the main stream and at the outlet of several subcatchments within the 114\3 km² Zwalm watershed in Flanders, Belgium, have been monitored regularly since 1991. Land use within the Zwalm catchment is predominantly agricultural, with forested regions in the south and urban concentrations in the north‐east of the catchment. Streamwater NO^―₃ concentrations increased with increases in stream discharge rates, but in general, discharge rate explained only about 30% of the variation in NO^―₃ concentrations. The low R² values were attributed to the observed anticlockwise hysteresis in the NO^―₃ concentration – discharge relationship and to differences in NO^―₃ concentrations between both seasonal flow and various flow regimes, with winter flow explaining 51% of the variation in NO^―₃ concentrations, whereas summer flow explained only 28% of the variation. A hypothesis was formulated in which flow regime accounts for the seasonal variation in NO^―₃ export, postulating that the catchment seasonally alternates between two hydrological stages. The first stage occurs during wet winter periods, when the catchment drains as a single source area, whereas the second stage occurs during dry summer periods, when the groundwater store disconnects into separate subcatchments. This causes NO^―₃ concentration peaks to be more delayed during summer storm events compared with winter storm events. Regarding flow regimes, differences between high and low flow conditions and between increasing and stable/decreasing flow were not as pronounced a differences between seasons. In contrast to the estimation of NO^―₃ concentrations, discharge was a strong predictor (R²= 0\71) of the NO^―₃ flux within the tributaries of the Zwalm catchment. The NO^―₃ concentrations in the main stream increased with decreasing elevation, whereas the seasonal concentration patterns along the main channel were similar to those observed at the outlet. NO^―₃ concentrations varied considerably among catchments and showed a high variability over time, although in general, the variation in NO^―₃ concentration was higher between catchments than within catchments. The impact of land use is clearly reflected in the streamwater NO^―₃ concentrations, although NO^―₃ concentration patterns were also affected by topography and, to a lesser extent, by soil type. A gradual increase in NO^―₃ concentrations at the outlet of the Zwalm catchment could be observed throughout the 1991 – 1998 study period, providing evidence for the general trends of increase in Flanders, which are attributed to the intensification of agricultural activities. Copyright © 2000 John Wiley & Sons, Ltd.     

The impact of stream-groundwater exchange on seasonal nitrate loads in an urban stream

Urbanization negatively impacts water quality in streams by reducing stream-groundwater interactions, which can reduce a stream's capacity to naturally attenuate nitrate. Meadowbrook Creek, a first order urban stream in Syracuse, New York, has an inverse urbanization gradient, with heavily urbanized headwaters that are disconnected from the floodplain and downstream reaches that have intact riparian floodplains and connection to riparian aquifers. This system allows assessment of how stream-groundwater interactions in urban streams impact the net sources and sinks of nitrate at the reach scale. We used continuous (15-min) streamflow measurements and weekly grab samples at three gauging stations positioned longitudinally along the creek to develop continuous nitrate load estimates at the inlet and outlet of two contrasting reaches. Nitrate load estimates were determined using a USGS linear regression model, RLOADEST, and differences between loads at the inlet and outlet of contrasting reaches were used to quantify nitrate sink and source behaviour year-round. We observed a nitrate load of 1.4 × 10⁴ kg NO₃⁻ per water year, on average, at the outlet of the urbanized reach while the nitrate load at the outlet of the downstream, connected reach was 1.0 × 10⁴ kg NO₃⁻ per water year, on average. We found the more heavily urbanized, hydrologically-disconnected reach was a net source of nitrate regardless of season. In contrast, stream-groundwater exchange caused the hydrologically connected reach to be both a source and sink for nitrate, depending on time of year. Both reaches alter nitrate source and sink behaviour at various spatiotemporal scales. Groundwater connection in the downstream, connected reach reduces annual nitrate loads and provides more opportunities for sources and sinks of nitrate year-round than the hydrologically disconnected stream reach. Mechanisms include groundwater discharge into the stream with variable nitrate concentrations, surface-water groundwater interactions that foster denitrification, and stream load loss to surrounding near-stream aquifers. This study emphasizes how loads are important in understanding how stream-groundwater interactions impact reach scale nitrate export in urban streams.     

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.     

Seasonal fluxes and sediment routing in tropical catchments affected by nickel mining

An important gap in the management of land erosion in mining-affected areas is the understanding of the entire sediment routing system and the links between sources and storage at the catchment scale. In this study, we examine sediment delivery and its seasonality in the nickel mining-affected Santa Cruz and Pamalabawan catchments in the Philippines. We monitored discharge, suspended sediment concentrations and suspended sediment loads across 13 sub-catchments with contrasting degrees of mining influence from June 2018 to July 2019. First, we show the importance of the size of the area that has been physically disturbed within our sub-catchments, with as little as 10–22% of relative disturbance area being enough to generate four-fold to eight-fold increase in the sediment yield relative to less disturbed and pristine areas. We found that sub-catchments with > 10% disturbance exhibit the highest sediment yields (15.5 ± 44.7 t km⁻² d⁻¹) compared with sub-catchments with < 10% disturbance (3.6 ± 17.7 t km⁻² d⁻¹) and undisturbed catchments (2.0 ± 5.7 t km⁻² d⁻¹). We also show that sediment flushing predominantly occurs in the most disturbed sub-catchments at the onset of the wet season. A small number of flood events transports the bulk of the sediment, with hysteresis effects being most pronounced in disturbed areas. Lastly, we show that floodplain sediment recycling exerts a key control on sediment delivery at both reach and catchment scales, with the relative contribution of floodplain sources to the sediment budget becoming dominant in the latter stages of the wet season- up to 89% of the total sediment export per storm event. This study highlights the importance of both degree of disturbance and sediment pathways in controlling sediment transport in mining-disturbed areas, and that considering the entire sediment routing system including intermediate stores is crucial to optimizing existing and future measures against siltation and potential contamination of trace metals and metalloids downstream of mining areas.     

Land-use dominates climate controls on nitrogen and phosphorus export from managed and natural Nordic headwater catchments

Agricultural, forestry-impacted and natural catchments are all vectors of nutrient loading in the Nordic countries. Here, we present concentrations and fluxes of total nitrogen (totN) and phosphorus (totP) from 69 Nordic headwater catchments (Denmark: 12, Finland:18, Norway:17, Sweden:22) between 2000 and 2018. Catchments span the range of Nordic climatic and environmental conditions and include natural sites and sites impacted by agricultural and forest management. Concentrations and fluxes of totN and totP were highest in agricultural catchments, intermediate in forestry-impacted and lowest in natural catchments, and were positively related %agricultural land cover and summer temperature. Summer temperature may be a proxy for terrestrial productivity, while %agricultural land cover might be a proxy for catchment nutrient inputs. A regional trend analysis showed significant declines in N concentrations and export across agricultural (−15 μg totN L⁻¹ year⁻¹) and natural (−0.4 μg NO₃-N L⁻¹ year⁻¹) catchments, but individual sites displayed few long-term trends in concentrations (totN: 22%, totP: 25%) or export (totN: 6%, totP: 9%). Forestry-impacted sites had a significant decline in totP (−0.1 μg P L⁻¹ year⁻¹). A small but significant increase in totP fluxes (+0.4 kg P km⁻² year⁻¹) from agricultural catchments was found, and countries showed contrasting patterns. Trends in annual concentrations and fluxes of totP and totN could not be explained in a straightforward way by changes in runoff or climate. Explanations for the totN decline include national mitigation measures in agriculture international policy to reduced air pollution and, possibly, large-scale increases in forest growth. Mitigation to reduce phosphorus appears to be more challenging than for nitrogen. If the green shift entails intensification of agricultural and forest production, new challenges for protection of water quality will emerge possible exacerbated by climate change. Further analysis of headwater totN and totP export should include seasonal trends, aquatic nutrient species and a focus on catchment nutrient inputs.     

Contrasting carbon export dynamics of human impacted and pristine tropical catchments in response to a short‐lived discharge event

Utilising newly available instrumentation, the carbon balance in two small tropical catchments was measured during two discharge events at high temporal resolution. Catchments share similar climatic conditions, but differ in land use with one draining a pristine rainforest catchment, the other a fully cleared and cultivated catchment. The necessity of high resolution sampling in small catchments was illustrated in each catchment, where significant chemical changes occurred in the space of a few hours or less. Dissolved and particulate carbon transport dominated carbon export from the rainforest catchment during high flow, but was surpassed by degassing of CO₂ less than 4 h after the discharge peak. In contrast, particulate organic carbon dominated export from the cleared catchment, in all flow conditions with CO₂ evasion accounting for 5–23% of total carbon flux. Stable isotopes of dissolved inorganic carbon (DIC) in the ephemeral rainforest catchment decreased quickly from ~1.5 ‰ to ~ ?16 ‰ in 5 h from the flood beginning. A two‐point mixing model revealed that in the initial pulse, over 90% of the DIC was of rainwater origin, decreasing to below 30% in low flow. In the cultivated catchment, δ¹³C_DIC values varied significantly less (?11.0 to ?12.2 ‰) but revealed a complex interaction between surface runoff and groundwater sources, with groundwater DIC becoming proportionally more important in high flow, due to activation of macropores downstream. This work adds to an increasing body of work that recognises the importance of rapid, short‐lived hydrological events in low‐order catchments to global carbon dynamics. Copyright © 2013 John Wiley & Sons, Ltd.     

δ53Cr values of catchment runoff exhibit seasonality regardless of bedrock Cr concentrations: Role of periodically changing chromium export fluxes

One pre-requisite for the construction of a global chromium isotope mass balance is detailed understanding of Cr isotope systematics in the critical zone where redox-processes can modify the isotope signature of geogenic Cr input into the hydrosphere. A Cr isotope inventory of bedrock, soil, and runoff was performed in a Central European headwater catchment underlain by amphibolite, situated in the vicinity of two previously studied catchments underlain by different bedrock types (serpentinite and leucogranite). Fresh bedrock in the amphibolite catchment NAZ contained ~300 mg/kg Cr, serpentinite at PLB contained ~800 mg/kg Cr, and leucogranite at LYS contained ~2 mg/kg Cr. Monthly hydrochemical monitoring at all three sites revealed higher Cr(VI) export fluxes in winter than in summer. NAZ was characterized by a distinct seasonality in the δ⁵³Cr values, with minima during winter/spring snowmelts (−0.35‰) and maxima during dry summers (0.40‰). Similar seasonality in δ⁵³Cr values had been reported from PLB and LYS. Bedrock at all three sites had similar Cr isotope composition close to −0.10‰, a value indistinguishable from the δ⁵³Cr value of bulk silicate Earth (BSE). Positive mean δ⁵³Cr value of NAZ runoff indicated Cr-isotope fractionations during weathering of geogenic Cr(III), combined with adsorption of the resulting Cr(VI) on soil particles during pedogenesis. However, the mass-weighted mean δ⁵³Cr of NAZ runoff was lower (−0.08‰), indistinguishable from the Cr isotope signature of bedrock. The same pattern of lower mass-weighted mean δ⁵³Cr values of runoff, compared to arithmetic mean δ⁵³Cr values of runoff, were observed also at PLB and LYS. We suggest that elevated Cr runoff fluxes in winter remove some of the residual isotopically light Cr that accumulated in the soil during summer. Seasonality in runoff δ⁵³Cr values appears to be a relatively widespread phenomenon, de-coupled from Cr availability for chemical weathering.     

Impacts of land-use changes on watershed discharge and water quality in a large intensive agricultural area in Thailand

The objectives of this research were to evaluate the effect of land-use change on streamflow, sediment and water quality data along the Lower Yom River, Thailand, covering an intensively agricultural area of 14 613.6 km², and to assess the relative impact of point and non-point sources of pollution from multiple-land-use watersheds. Long-term calibration and validation of the SWAT (Soil and Water Assessment Tool) model was performed on data for 2000–2013. Land-use change led to a 13–49% increase in runoff in the basin and resulted in 37–427% increased sediment yield. The amount of NO₃-N load doubled in the upper and middle parts of the study area, while the increase in PO₄^3– ranged from 37 to 377%, reflecting the increase in agricultural lands and urban areas. It is concluded that the changed land use is closely associated with the quantity of runoff, sediment yield and the NO₃-N and PO₄^3– concentrations.     

Sources and transport of nitrate constrained by the isotopic technique in a karst catchment: an example from Southwest China

The concentration and isotopic composition of nitrate were analyzed to improve an understanding of nitrate sources and transformation processes in a typical karstic agricultural field in the Houzhai catchment, Guizhou Province, Southwest China. The results revealed that no distinct spatial pattern of content and isotopic composition of nitrate exists in this karst catchment. Nitrate in surface stream (SFS) had slightly lighter isotopic composition and lower concentration compared with nitrate in subterranean stream (STS) during the dry season. Concentrations of SFS nitrate increased to concentrations similar to those of STS during the wet season. The isotopic values indicated that nitrate were mainly impacted by manure sources during the dry season and influenced by a mix of chemical fertilizer and manure during the wet season. The denitrification rates were roughly estimated based on the isotopic compositions of nitrate after considering volatilization and ignoring assimilation. The calculated result showed that approximately one fifth of nitrate load was removed by denitrification in the catchment. Annual nitrate flux from the outlets accounted for 14.2% of applied total fertilizers used in the catchment, approximately 85% of total transported flux from the catchment in the wet season. Furthermore, chemical weathering processes were enhanced by using nitrogen fertilizer because liberated protons and enhanced HCO₃^? flux were produced through by nitrification. Copyright © 2014 John Wiley & Sons, Ltd.     

Variable nitrate concentration–discharge relationships in a forested watershed

The relationship between solute concentrations and discharge can inform an integrated understanding of hydrological and biogeochemical processes at watershed scales. Recent work from multiple catchments has shown that there is typically little variation in concentration relative to large variations in discharge. This pattern has been described as chemostatic behavior. Pond Branch, a forested headwater catchment in Maryland, has been monitored for stream nitrate (NO₃^?) concentrations at weekly intervals for 14 years. In the growing season and autumn of 2011 a high‐frequency optical NO₃^? sensor was used to supplement the long‐term weekly data. In this watershed, long‐term weekly data show that NO₃^? concentrations decrease with increasing discharge whereas 6 months of 15‐minute sensor observed concentrations reveal a more chemostatic behavior. High‐frequency NO₃^? concentrations from the sensor collected during different storm events reveal variable concentration–discharge patterns highlighting the importance of high resolution data and ecohydrological drivers in controlling solute export for biologically reactive solutes such as NO₃^?.     

Time-series of δ26Mg values in a headwater catchment reveal decreasing magnesium isotope variability from precipitation to runoff

Data on temporal variability in Mg isotope ratios of atmospheric deposition and runoff are critical for decreasing the uncertainty associated with construction of isotope mass balances in headwater catchments, and statistical evaluation of isotope differences among Mg pools and fluxes. Such evaluations, in turn, are needed to distinguish between biotic and abiotic contributions to Mg²⁺ in catchment runoff. We report the first annual time-series of δ²⁶Mg values simultaneously determined for rainfall, canopy throughfall, soil water and runoff. The studied 55-ha catchment, situated in western Czech Republic, is underlain by Mg-rich amphibolite and covered by mature spruce stands. Between 1970 and 1996, the site received extremely high amounts of acid deposition and fly ash form nearby coal-burning power plants. The δ²⁶Mg values of open-area precipitation (median of −0.79‰) at our study site were statistically indistinguishable from the δ²⁶Mg values of throughfall (−0.73‰), but significantly different from the δ²⁶Mg values of soil water (−0.55‰) and runoff (−0.55‰). The range of δ²⁶Mg values during the observation period decreased in the order: open-area precipitation (0.57‰) > throughfall (0.27‰) > runoff (0.21‰) > soil water (0.16‰). The decreasing variability in δ²⁶Mg values of Mg²⁺ from precipitation to soil water and runoff reflected an increasing homogenization of atmospheric Mg in the catchment and its mixing with geogenic Mg. In addition to atmospheric Mg, runoff also contained Mg mobilized from the three major solid Mg pools, bedrock (δ²⁶Mg of −0.32‰), soil (−0.28‰), and vegetation (−0.31‰). The drought of summer 2019 did not affect the nearly constant δ²⁶Mg value of runoff. Collectively, our data show that within-catchment processes buffer the Mg isotope variability of the atmospheric input.     

Using stable isotopes of surface water and groundwater to quantify moisture sources across the Yellow River source region

Characterization of stable isotope compositions (δ²H and δ¹⁸O) of surface water and groundwater in a catchment is critical for refining moisture sources and establishing modern isotope–elevation relationships for paleoelevation reconstructions. There is no consensus on the moisture sources of precipitation in the Yellow River source region during summer season. This study presents δ²H and δ¹⁸O data from 111 water samples collected from tributaries, mainstream, lakes, and groundwater across the Yellow River source region during summertime. Measured δ¹⁸O values of the tributaries range from ?13.5‰ to ?5.8‰ with an average of ?11.0‰. Measured δ¹⁸O values of the groundwater samples range from ?12.7‰ to ?10.5‰ with an average of ?11.9‰. The δ¹⁸O data of tributary waters display a northward increase of 1.66‰ per degree latitude. The δ¹⁸O data and d‐excess values imply that moisture sources of the Yellow River source region during summertime are mainly from the mixing of the Indian Summer Monsoon and the Westerlies, local water recycling, and subcloud evaporation. Analysis of tributary δ¹⁸O data from the Yellow River source region and streamwater and precipitation δ¹⁸O data from its surrounding areas leads to a best‐fit second‐order polynomial relationship between δ¹⁸O and elevation over a 4,600 m elevation range. A δ¹⁸O elevation gradient of ?1.6‰/km is also established using these data, and the gradient is in consistence with the δ¹⁸O elevation gradient of north and eastern plateau. Such relationships can be used for paleoelevation reconstructions in the Yellow River source region.