High Atmospheric Nitrate Inputs and Nitrogen Turnover in Semi-arid Urban Catchments

The influx of atmospheric nitrogen to soils and surfaces in arid environments is of growing concern due to increased N emissions and N usage associated with urbanization. Atmospheric nitrogen inputs to the critical zone can occur as wet (rain or snow) or dry (dust or aerosols) deposition, and can lead to eutrophication, soil acidification, and groundwater contamination through leaching of excess nitrate. The objective of this research was to use the δ¹⁵N, δ¹⁸O, and Δ¹⁷O values of atmospheric nitrate (NO₃ ^?) (precipitation and aerosols) and NO₃ ^? in runoff to assess the importance of N deposition and turnover in semi-arid urban watersheds. Data show that the fractions of atmospheric NO₃ ^? exported from all the urban catchments, throughout the study period, were substantially higher than in nearly all other ecosystems studied with mean atmospheric contributions of 38% (min 0% and max 82%). These results suggest that catchment and stream channel imperviousness enhance atmospheric NO₃ ^? export due to inefficient N cycling and retention. In contrast, catchment and stream channel perviousness allow for enhanced N processing and therefore reduced atmospheric NO₃ ^? export. Overall high fractions of atmospheric NO₃ ^? were primarily attributed to slow N turn over in arid/semi-arid ecosystems. A relatively high fraction of nitrification NO₃ ^? (~30%) was found in runoff from a nearly completely impervious watershed (91%). This was attributed to nitrification of atmospheric NH₄ ⁺ in dry-deposited dust, suggesting that N nitrifiers have adapted to urban micro niches. Gross nitrification rates based on NO₃ ^? Δ¹⁷O values ranged from a low 3.04 ± 2 kg NO₃-N km^?2 day^?1 in highly impervious catchments to a high of 10.15 ± 1 kg NO₃-N km^?2 day^?1 in the low density urban catchment. These low gross nitrification rates were attributed to low soil C:N ratios that control gross autotrophic nitrification by regulating gross NH₄ ⁺ production rates.     

Using a nitrogen and oxygen isotopic approach to identify nitrate sources and cycling in the Wei River of northwestern China

The Wei River is the largest tributary of the Yellow River in China. To understand the sources and cycling of nitrate in the Wei River, we determined the concentrations and nitrogen and oxygen isotopic values of nitrate from water samples. Our results revealed that NO₃^?-N dominated the inorganic N and ranged from 0.1 to 8.8 mg/L (averaging 3.3 mg/L). Although this NO₃^?-N concentration does not exceed the World Health Organization's drinking water standard of 10 mg/L, the NO₃^?-N content of most water samples exceeded 3 mg/L, indicating poor water quality. The NO₃^?-N concentrations and δ¹⁵N-NO₃^? values demonstrate that there are significant differences in the spatial distribution of nitrogen between the tributaries and the main stream of the Wei River. In addition, a negative linear relationship (r² = 0.63) between NO₃^?-N concentrations and δ¹⁸O-NO₃^? values suggests mixing between two distinct sources (fertilizer and manure or sewage). Furthermore, we infer that the main source of nitrate is not manure or sewage itself, but rather the nitrification of NH₄⁺ in manure and sewage. Finally, no obvious denitrification processes were observed. These results expand our understanding of sewage as a major source of nitrate to the Wei River, emphasizing the role of nitrification.     

Assimilation and nitrification in pelagic waters: insights using dual nitrate stable isotopes (δ<Superscript>15</Superscript>N, δ<Superscript>18</Superscript>O) in a shallow lake

Nitrate dual stable isotopes (δ¹⁵N and δ¹⁸O of NO₃ ^?) have proven to be a powerful technique to elucidate nitrogen (N) cycling pathways in aquatic systems. We applied this technique for the first time in the pelagic zone of a small temperate meso-eutrophic lake to identify the dominant N cycling pathways, and their spatial and temporal variability. We measured the lake NO₃ ^? δ¹⁵N and δ¹⁸O signatures over an annual cycle and compared them to that of the watershed. Both δ¹⁵N and δ¹⁸O of NO₃ ^? in the lake increased during summer relative to the inputs. Relationships between lake NO₃ ^? isotopic composition and concentrations were different across thermal strata with an apparent isotope effect in the epilimnion of ¹⁵ε_epi = 4.6‰ and ¹⁸ε_epi = 10.9‰. We found a strong deviation of the lake NO₃ ^? δ¹⁸O and δ¹⁵N from the expected 1:1 line for assimilation (slope = 1.73) suggesting that nitrification was co-occurring. We estimated that nitrification could support between 5 and 30% of nitrate-based production during the growing season, but was negligible in early spring and fall, and probably more dominant under ice. We showed that the technique is promising to study N processes at the ecosystem scale in shallow lakes, particularly during winter. Our results suggest that recycled NO₃ ^? could support primary productivity and influence phytoplankton composition in the surface waters of small lakes.     

Assessing Nitrogen-Saturation in a Seasonally Dry Chaparral Watershed: Limitations of Traditional Indicators of N-Saturation

To evaluate nitrogen (N) saturation in xeric environments, we measured hydrologic N losses, soil N pools, and microbial processes, and developed an N-budget for a chaparral catchment (Sierra Nevada, California) exposed to atmospheric N inputs of approximately 8.5 kg N ha^?1 y^?1. Dual-isotopic techniques were used to trace the sources and processes controlling nitrate (NO₃ ^?) losses. The majority of N inputs occurred as ammonium. At the onset of the wet season (November to April), we observed elevated streamwater NO₃ ^? concentrations (up to 520 µmol l^?1), concomitant with the period of highest gaseous N-loss (up to 500 ng N m^?2 s^?1) and suggesting N-saturation. Stream NO₃ ^? δ¹⁵N and δ¹⁸O and soil N measurements indicate that nitrification controlled NO₃ ^? losses and that less than 1% of the loss was of atmospheric origin. During the late wet season, stream NO₃ ^? concentrations decreased (to <2 µmol l^?1) as did gaseous N emissions, together suggesting conditions no longer indicative of N-saturation. We propose that chaparral catchments are temporarily N-saturated at ≤8.5 kg N ha^?1 y^?1, but that N-saturation may be difficult to reach in ecosystems that inherently leak N, thereby confounding the application of N-saturation indicators and annual N-budgets. We propose that activation of N sinks during the typically rainy winter growing season should be incorporated into the assessment of ecosystem response to N deposition. Specifically, the N-saturation status of chaparral may be better assessed by how rapidly catchments transition from N-loss to N-retention.     

Modest Gaseous Nitrogen Losses Point to Conservative Nitrogen Cycling in a Lowland Tropical Forest Watershed

Primary tropical rainforests are generally considered to be relatively nitrogen (N) rich, with characteristically large hydrologic and gaseous losses of inorganic N. However, emerging evidence suggests that some tropical ecosystems can exhibit tight N cycling, with low biologically available losses. In this study, we combined isotopic data with a well-characterized watershed N mass balance to close the N budget and characterize gaseous N losses at the ecosystem scale in a lowland tropical rainforest on the Osa Peninsula in southwestern Costa Rica. We measured δ¹⁵N and δ¹⁸O of nitrate (NO₃ ^?) in precipitation, surface, shallow and deep soil lysimeters and stream water biweekly for 1 year. Enrichment of both isotopes indicates that denitrification occurs predominantly as NO₃ ^? moves from surface soil down to 15 cm depth or laterally to stream water, with little further processing in deeper soil. Two different isotopic modeling approaches suggested that the gaseous fraction comprises 14 or 32% of total N loss (2.7 or 7.5 kg N ha^?1 y^?1), though estimates are sensitive to selection of isotopic fractionation values. Gas loss estimates using the mass balance approach (3.2 kg N ha^?1 y^?1) fall within this range and include N₂O losses of 0.9 kg N ha^?1 y^?1. Overall, gaseous and soluble hydrologic N losses comprise a modest proportion (~ 25%) of the total N inputs to this ecosystem. By contrast, relatively large, episodic hydrologic losses of non-biologically available particulate N balance the majority of N inputs and may contribute to maintaining conservative N cycling in this lowland tropical forest. Similar patterns of N cycling may occur in other tropical forests with similar state factor combinations—high rainfall, steep topography, relatively fertile soils—such as the western arc of the Amazon Basin and much of IndoMalaysia, but this hypothesis remains untested.     

Isotopic evidence for the occurrence of biological nitrification and nitrogen deposition processing in forest canopies

This study examines the role of tree canopies in processing atmospheric nitrogen (N_dep) for four forests in the United Kingdom subjected to different N_dep: Scots pine and beech stands under high N_dep (HN, 13–19 kg N ha^?1 yr^?1), compared to Scots pine and beech stands under low N_dep (LN, 9 kg N ha^?1 yr^?1). Changes of NO₃‐N and NH₄‐N concentrations in rainfall (RF) and throughfall (TF) together with a quadruple isotope approach, which combines δ¹⁸O, Δ¹⁷O and δ¹⁵N in NO₃^? and δ¹⁵N in NH₄⁺, were used to assess N transformations by the canopies. Generally, HN sites showed higher NH₄‐N and NO₃‐N concentrations in RF compared to the LN sites. Similar values of δ¹⁵N‐NO₃^? and δ¹⁸O in RF suggested similar source of atmospheric NO₃^? (i.e. local traffic), while more positive values for δ¹⁵N‐NH₄⁺ at HN compared to LN likely reflected the contribution of dry NH_x deposition from intensive local farming. The isotopic signatures of the N‐forms changed after interacting with tree canopies. Indeed, ¹⁵N‐enriched NH₄⁺ in TF compared to RF at all sites suggested that canopies played an important role in buffering dry N_dep also at the low N_dep site. Using two independent methods, based on δ¹⁸O and Δ¹⁷O, we quantified for the first time the proportion of NO₃^? in TF, which derived from nitrification occurring in tree canopies at the HN site. Specifically, for Scots pine, all the considered isotope approaches detected biological nitrification. By contrast for the beech, only using the mixing model with Δ¹⁷O, we were able to depict the occurrence of nitrification within canopies. Our study suggests that tree canopies play an active role in the N cycling within forest ecosystems. Processing of N_dep within canopies should not be neglected and needs further exploration, with the combination of multiple isotope tracers, with particular reference to Δ¹⁷O.     

Identification of nitrogen sources and transformations within karst springs using isotope tracers of nitrogen

Isotope analyses of nitrate and algae were used to gain better understanding of sources of nitrate to Florida’s karst springs and processes affecting nitrate in the Floridan aquifer at multiple scales. In wet years, δ¹⁵N and δ¹⁸O of nitrate ranged from +3 to +9‰ in headwater springs in north Florida, indicating nitrification of soil ammonium as the dominant source. With below normal rainfall, the δ¹⁵N and δ¹⁸O of nitrate were higher in almost all springs (reaching +20.2 and +15.3‰, respectively) and were negatively correlated with dissolved oxygen. In springs with values of δ¹⁵N-NO₃ and δ¹⁸O-NO₃ greater than +10‰, nitrate concentrations declined 40–50% in dry years and variations in the δ¹⁵N and δ¹⁸O of nitrate were consistent with the effects of denitrification. Modeling of the aquifer as a closed system yielded in situ fractionation caused by denitrification of 9 and 18‰ for Δ¹⁸O and Δ¹⁵N, respectively. We observed no strong evidence for local sources of nitrate along spring runs; concentrations declined downstream (0.42–3.3?μmol-NO₃ L^?1 per km) and the isotopic dynamics of algae and nitrate indicated a closed system. Correlation between the δ¹⁵N composition of nitrate and algae was observed at regional and spring-run scales, but the relationship was complicated by varying isotopic fractionation factors associated with nitrate uptake (Δ ranged from 2 to 13‰). Our study demonstrates that nitrate inputs to Florida’s springs are derived predominantly from non-point sources and that denitrification is detectable in aquifer waters with relatively long residence time (i.e., matrix flow).     

Multiyear dual nitrate isotope signatures suggest that N‐saturated subtropical forested catchments can act as robust N sinks

In forests of the humid subtropics of China, chronically elevated nitrogen (N) deposition, predominantly as ammonium (NH₄⁺), causes significant nitrate (NO₃^?) leaching from well‐drained acid forest soils on hill slopes (HS), whereas significant retention of NO₃^? occurs in near‐stream environments (groundwater discharge zones, GDZ). To aid our understanding of N transformations on the catchment level, we studied spatial and temporal variabilities of concentration and natural abundance (δ¹⁵N and δ¹⁸O) of nitrate (NO₃^?) in soil pore water along a hydrological continuum in the N‐saturated Tieshanping (TSP) catchment, southwest China. Our data show that effective removal of atmogenic NH₄⁺ and production of NO₃^? in soils on HS were associated with a significant decrease in δ¹⁵N‐NO₃^?, suggesting efficient nitrification despite low soil pH. The concentration of NO₃^? declined sharply along the hydrological flow path in the GDZ. This decline was associated with a significant increase in both δ¹⁵N and δ¹⁸O of residual NO₃^?, providing evidence that the GDZ acts as an N sink due to denitrification. The observed apparent ¹⁵N enrichment factor (ε) of NO₃^? of about ?5‰ in the GDZ is similar to values previously reported for efficient denitrification in riparian and groundwater systems. Episode studies in the summers of 2009, 2010 and 2013 revealed that the spatial pattern of δ¹⁵N and δ¹⁸O‐NO₃^? in soil water was remarkably similar from year to year. The importance of denitrification as a major N sink was also seen at the catchment scale, as largest δ¹⁵N‐NO₃^? values in stream water were observed at lowest discharge, confirming the importance of the relatively small GDZ for N removal under base flow conditions. This study, explicitly recognizing hydrologically connected landscape elements, reveals an overlooked but robust N sink in N‐saturated, subtropical forests with important implications for regional N budgets.     

Indirect N2O emissions from shallow groundwater in an agricultural catchment (Seine Basin, France)

Production and accumulation of nitrous oxide (N₂O), a major greenhouse gas, in shallow groundwater might contribute to indirect N₂O emissions to the atmosphere (e.g., when groundwater flows into a stream or a river). The Intergovernmental Panel on Climate Change (IPCC) has attributed an emission factor (EF_5g) for N₂O, associated with nitrate leaching in groundwater and drainage ditches—0.0025 (corresponding to 0.25% of N leached which is emitted as N₂O)—although this is the subject of considerable uncertainty. We investigated and quantified the transport and fate of nitrate (NO₃ ^?) and dissolved nitrous oxide from crop fields to groundwater and surface water over a 2-year period (monitoring from April 2008 to April 2010) in a transect from a plateau to the river with three piezometers. In groundwater, nitrate concentrations ranged from 1.0 to 22.7 mg NO₃ ^?–N l^?1 (from 2.8 to 37.5 mg NO₃ ^?–N l^?1 in the river) and dissolved N₂O from 0.2 to 101.0 μg N₂O–N l^?1 (and from 0.2 to 2.9 μg N₂O–N l^?1 in the river). From these measurements, we estimated an emission factor of EF_5g = 0.0026 (similar to the value currently used by the IPCC) and an annual indirect N₂O flux from groundwater of 0.035 kg N₂O–N ha^?1 year^?1, i.e., 1.8% of the previously measured direct N₂O flux from agricultural soils.     

Identifying drivers of leaf water and cellulose stable isotope enrichment in <Emphasis Type="Italic">Eucalyptus</Emphasis> in northern Australia

Several previous studies have investigated the use of the stable hydrogen and oxygen isotope compositions in plant materials as indicators of palaeoclimate. However, accurate interpretation relies on a detailed understanding of both physiological and environmental drivers of the variations in isotopic enrichments that occur in leaf water and associated organic compounds. To progress this aim we measured δ¹⁸O and δ²H values in eucalypt leaf and stem water and δ¹⁸O values in leaf cellulose, along with the isotopic compositions of water vapour, across a north-eastern Australian aridity gradient. Here we compare observed leaf water enrichment, along with previously published enrichment data from a similar north Australian transect, to Craig–Gordon-modelled predictions of leaf water isotopic enrichment. Our investigation of model parameters shows that observed ¹⁸O enrichment across the aridity gradients is dominated by the relationship between atmospheric and internal leaf water vapour pressure while ²H enrichment is driven mainly by variation in the water vapour—source water isotopic disequilibrium. During exceptionally dry and hot conditions (RH < 21%, T > 37 °C) we observed strong deviations from Craig–Gordon predicted isotope enrichments caused by partial stomatal closure. The atmospheric–leaf vapour pressure relationship is also a strong predictor of the observed leaf cellulose δ¹⁸O values across one aridity gradient. Our finding supports a wider applicability of leaf cellulose δ¹⁸O composition as a climate proxy for atmospheric humidity conditions during the leaf growing season than previously documented.     

Nitrification and denitrification in a midwestern stream containing high nitrate: in situ assessment using tracers in dome-shaped incubation chambers

The extent to which in-stream processes alter or remove nutrient loads in agriculturally impacted streams is critically important to watershed function and the delivery of those loads to coastal waters. In this study, patch-scale rates of in-stream benthic processes were determined using large volume, open-bottom benthic incubation chambers in a nitrate-rich, first to third order stream draining an area dominated by tile-drained row-crop fields. The chambers were fitted with sampling/mixing ports, a volume compensation bladder, and porewater samplers. Incubations were conducted with added tracers (NaBr and either ¹⁵N[NO₃ ^?], ¹⁵N[NO₂ ^?], or ¹⁵N[NH₄ ⁺]) for 24–44 h intervals and reaction rates were determined from changes in concentrations and isotopic compositions of nitrate, nitrite, ammonium and nitrogen gas. Overall, nitrate loss rates (220–3,560 μmol N m^?2 h^?1) greatly exceeded corresponding denitrification rates (34–212 μmol N m^?2 h^?1) and both of these rates were correlated with nitrate concentrations (90–1,330 μM), which could be readily manipulated with addition experiments. Chamber estimates closely matched whole-stream rates of denitrification and nitrate loss using ¹⁵N. Chamber incubations with acetylene indicated that coupled nitrification/denitrification was not a major source of N₂ production at ambient nitrate concentrations (175 μM), but acetylene was not effective for assessing denitrification at higher nitrate concentrations (1,330 μM). Ammonium uptake rates greatly exceeded nitrification rates, which were relatively low even with added ammonium (3.5 μmol N m^?2 h^?1), though incubations with nitrite demonstrated that oxidation to nitrate exceeded reduction to nitrogen gas in the surface sediments by fivefold to tenfold. The chamber results confirmed earlier studies that denitrification was a substantial nitrate sink in this stream, but they also indicated that dissolved inorganic nitrogen (DIN) turnover rates greatly exceeded the rates of permanent nitrogen removal via denitrification.     

The importance of denitrification for N2O emissions from an N-saturated forest in SW China: results from in situ 15N labeling experiments

Long-term elevated atmogenic deposition (~5 g m^?2 year^?1) of reactive nitrogen (N) causes N saturation in forests of subtropical China which may lead to high nitrous oxide (N₂O) emissions. Recently, we found high N₂O emission rates (up to 1,730 μg N₂O–N m^?2 h^?1) during summer on well-drained acidic acrisols (pH = 4.0) along a hill slope in the forested Tieshanping catchment, Chongqing, southwest China. Here, we present results from an in situ ¹⁵N–NO₃ ^? labeling experiment to assess the contribution of nitrification and denitrification to N₂O emissions in these soils. Two loads of 99 at.% K¹⁵NO₃ (equivalent to 0.2 and 1.0 g N m^?2) were applied as a single dose to replicated plots at two positions along the hill slope (at top and bottom, respectively) during monsoonal summer. During a 6-day period after label application, we found that 71–100 % of the emitted N₂O was derived from the labeled NO₃ ^? pool irrespective of slope position. Based on this, we assume that denitrification is the dominant process of N₂O formation in these forest soils. Within 6 days after label addition, the fraction of the added ¹⁵N–NO₃ ^? emitted as ¹⁵N–N₂O was highest at the low-N addition plots (0.2 g N m^?2), amounting to 1.3 % at the top position of the hill slope and to 3.2 % at the bottom position, respectively. Our data illustrate the large potential of acid forest soils in subtropical China to form N₂O from excess NO₃ ^? most likely through denitrification.     

Dominance of biologically produced nitrate in upland waters of Great Britain indicated by stable isotopes

Atmospheric deposition of nitrogen (N) compounds is the major source of anthropogenic N to most upland ecosystems, where leaching of nitrate (NO ₃ ^? ) into surface waters contributes to eutrophication and acidification as well as indicating an excess of N in the terrestrial catchment ecosystems. Natural abundance stable isotopes ratios, ¹⁵N/¹⁴N and ¹⁸O/¹⁶O (the “dual isotope” technique) have previously been used in biogeochemical studies of alpine and forested ecosystems to demonstrate that most of the NO ₃ ^? in upland surface waters has been microbially produced. Here we present an application of the technique to four moorland catchments in the British uplands including a comparison of lakes and their stream inflows at two sites. The NO ₃ ^? concentrations of bulk deposition and surface waters at three sites are very similar. While noting the constraints imposed by uncertainty in the precise δ¹⁸O value for microbial NO ₃ ^? , however, we estimate that 79–98% of the annual mean NO ₃ ^? has been microbially produced. Direct leaching of atmospheric NO ₃ ^? is a minor component of catchment NO ₃ ^? export, although greater than in many similar studies in forested watersheds. A greater proportion of atmospheric NO ₃ ^? is seen in the two lake sites relative to their inflow streams, demonstrating the importance of direct NO ₃ ^? deposition to lake surfaces in catchments where terrestrial ecosystems intercept a large proportion of deposited N. The dominance of microbial sources of NO ₃ ^? in upland waters suggests that reduced and oxidised N deposition may have similar implications in terms of contributing to NO ₃ ^? leaching.     

An in-depth look into a tropical lowland forest soil: nitrogen-addition effects on the contents of N2O, CO2 and CH4 and N2O isotopic signatures down to 2-m depth

Atmospheric nitrogen (N) deposition is rapidly increasing in tropical regions. We investigated how a decade of experimental N addition (125 kg N ha^?1 year^?1) to a seasonal lowland forest affected depth distribution and contents of soil nitrous oxide (N₂O), carbon dioxide (CO₂) and methane (CH₄), as well as natural abundance isotopic signatures of N₂O, nitrate (NO₃ ^?) and ammonium (NH₄ ⁺). In the control plots during dry season, we deduced limited N₂O production by denitrification in the topsoil (0.05–0.40 m) as indicated by: ambient N₂O concentrations and ambient ¹⁵N-N₂O signatures, low water-filled pore space (35–60%), and similar ¹⁵N signatures of N₂O and NO₃ ^?. In the subsoil (0.40–2.00 m), we detected evidence of N₂O reduction to N₂ during upward diffusion, indicating denitrification activity. During wet season, we found that N₂O at 0.05–2.00 m was mainly produced by denitrification with substantial further reduction to N₂, as indicated by: lighter ¹⁵N-N₂O than ¹⁵N-NO₃ ^? throughout the profile, and increasing N₂O concentrations with simultaneously decreasing ¹⁵N-N₂O enrichment with depth. These interpretations were supported by an isotopomer map and by a positive correlation between ¹⁸O-N₂O and ¹⁵N-N₂O site preferences. Long-term N addition did not affect dry-season soil N₂O-N contents, doubled wet-season soil N₂O-N contents, did not affect ¹⁵N signatures of NO₃ ^?, and reduced wet-season ¹⁵N signatures of N₂O compared to the control plots. These suggest that the increased NO₃ ^? concentrations have stimulated N₂O production and decreased N₂O-to-N₂ reduction. Soil CO₂-C contents did not differ between treatments, implying that N addition essentially did not influence soil C cycling. The pronounced seasonality in soil respiration was largely attributable to enhanced topsoil respiration as indicated by a wet-season increase in the topsoil CO₂-C contents. The N-addition plots showed reduced dry-season soil CH₄-C contents and threshold CH₄ concentrations were reached at a shallower depth compared to the control plots, revealing an N-induced stimulation of methanotrophic activity. However, the net soil CH₄ uptake rates remained similar between treatments possibly because diffusive CH₄ supply from the atmosphere largely limited CH₄ oxidation.     

Influence of bioturbation on denitrification and dissimilatory nitrate reduction to ammonium (DNRA) in freshwater sediments

Intensive agriculture leads to increased nitrogen fluxes (mostly as nitrate, NO₃ ^?) to aquatic ecosystems, which in turn creates ecological problems, including eutrophication and associated harmful algal blooms. These problems have focused scientific attention on understanding the controls on nitrate reduction processes such as denitrification and dissimilatory nitrate reduction to ammonium (DNRA). Our objective was to determine the effects of nutrient-tolerant bioturbating invertebrates (tubificid oligochaetes) on nitrogen cycling processes, specifically coupled nitrification–denitrification, net denitrification, DNRA, and biogeochemical fluxes (O₂, NO₃ ^?, NH₄ ⁺, CO₂, N₂O, and CH₄) in freshwater sediments. A mesocosm experiment determined how tubificid density and increasing NO₃ ^? concentrations (using N¹⁵ isotope tracing) interact to affect N cycling processes. At the lowest NO₃ ^? concentration and in the absence of bioturbation, the relative importance of denitrification to DNRA was similar (i.e., 49.6 and 50.4 ± 8.1 %, respectively). Increasing NO₃ ^? concentrations in the control cores (without fauna) stimulated denitrification, but did not enhance DNRA, which significantly altered the relative importance of denitrification compared to DNRA (94.6 vs. 5.4 ± 0.9 %, respectively). The presence of tubificid oligochaetes enhanced O₂, NO₃ ^?, NH₄ ⁺ fluxes, greenhouse gas production, and N cycling processes. The relative importance of denitrification to DNRA shifted towards favoring denitrification with both the increase in NO₃ ^? concentrations and the increase of bioturbation activity. Our study highlights that understanding the interactions between nutrient-tolerant bioturbating species and nitrate contamination is important for determining the nitrogen removal capacity of eutrophic freshwater ecosystems.     

N2O and CH4 Emissions,and NO3 − Leaching on a Crop-Yield Basis from a Subtropical Rain-fed Wheat–Maize Rotation in Response to Different Types of Nitrogen Fertilizer

Guaranteeing high crop yields while reducing environmental impacts of nitrogen fertilizer use due to associated losses of N₂O emissions and nitrate (NO₃ ^?) leaching is a key challenge in the context of sustainable intensification of crop production. However, few field data sets are available that explore the effect of different forms of N management on yields as well as on N losses in the form of N₂O or NO₃ ^?. Here we report on a large-scale field lysimeter (8 × 4 m²) experiment, which was designed to determine soil CH₄ and N₂O emissions, NO₃ ^? leaching losses and crop yields from a subtropical rain-fed wheat–maize rotation in the Sichuan Basin, one of the most intensively used agricultural regions in China. One control and three different fertilizer treatments with the same total rate of N application (280 kg N ha^?1 y^?1) were included: NF: control (no fertilizer); NPK: synthetic N fertilizer; OMNPK: synthetic N fertilizer plus pig manure; RSDNPK: synthetic N fertilizer plus crop residues. As compared to the standard NPK treatment, annual NO₃ ^? leaching losses for OMNPK and RSDNPK treatments were decreased by 36 and 22%, respectively (P < 0.05). Similarly, crop yield-scaled NO₃ ^? leaching for NPK treatment was higher than those for either OMNPK or RSDNPK treatments (P < 0.05). Direct N₂O emissions for RSDNPK treatment were decreased as compared with NPK and OMNPK treatments (P < 0.05). Furthermore, the yield-scaled GWP (global warming potential) was lower for the treatments where either pig manure or crop residues were incorporated as compared to the standard NPK treatment (P < 0.05). Our study indicates that it is possible to reduce the negative environmental impact of NO₃ ^? leaching and N₂O emissions without compromising crop productivity. Yield-scaled NO₃ ^? leaching, similar to the yield-scaled GWP, represents another valuable-integrated metric to address the dual goals of reducing nitrogen pollution and maintaining crop grain yield for a given agricultural system.     

Nitrous oxide emissions and nitrate leaching from a rain-fed wheat-maize rotation in the Sichuan Basin, China

Aims

A 3-year field experiment (October 2004–October 2007) was conducted to quantify N₂O fluxes and determine the regulating factors from rain-fed, N fertilized wheat-maize rotation in the Sichuan Basin, China.

Methods

Static chamber-GC techniques were used to measure soil N₂O fluxes in three treatments (three replicates per treatment): CK (no fertilizer); N150 (300 kg N fertilizer ha^?1 yr^?1 or 150 kg N?ha^?1 per crop); N250 (500 kg N fertilizer ha^?1 yr^?1 kg or 250 kg N?ha^?1 per crop). Nitrate (NO ₃ ^? ) leaching losses were measured at nearby sites using free-drained lysimeters.

Results

The annual N₂O fluxes from the N fertilized treatments were in the range of 1.9 to 6.7 kg N?ha^?1 yr^?1 corresponding to an N₂O emission factor ranging from 0.12 % to 1.06 % (mean value: 0.61 %). The relationship between monthly soil N₂O fluxes and NO ₃ ^- leaching losses can be described by a significant exponential decaying function.

Conclusions

The N₂O emission factor obtained in our study was somewhat lower than the current IPCC default emission factor (1 %). Nitrate leaching, through removal of topsoil NO ₃ ^? , is an underrated regulating factor of soil N₂O fluxes from cropland, especially in the regions where high NO ₃ ^- leaching losses occur.     

Dual N and O isotopes of nitrate in natural plants: first insights into individual variability and organ-specific patterns

Nitrate (NO₃ ^?) is an important form of nitrogen (N) available to plants. The measurements of NO₃ ^? concentration [NO₃ ^?] and isotopes (δ¹⁵N and δ¹⁸O) in plants provide unique insights into ecosystem NO₃ ^? availability and plant NO₃ ^? dynamics. This work investigated the variability of these parameters in individuals of a broadleaved (Aucuba japonica) plant and a coniferous (Platycladus orientalis) plant, and explored the applicability of tissue NO₃ ^? isotopes for deciphering plant NO₃ ^? utilization mechanisms. The NO₃ ^? in washed leaves showed concentration and isotopic ratios that were much lower than that in unwashed leaves, indicating a low contribution of atmospheric NO₃ ^? to NO₃ ^? in leaves. Current leaves showed higher [NO₃ ^?] and isotopic ratios than mature leaves. Moreover, higher leaf [NO₃ ^?] and isotopic enrichments (relative to soil NO₃ ^?) were found under higher soil NO₃ ^? availability for A. japonica. In contrast, leaves of P. orientalis showed low [NO₃ ^?] and negligible isotopic enrichments despite high soil NO₃ ^?. Higher [NO₃ ^?] was found in both fine and coarse roots of the P. orientalis plant, but significant isotopic enrichment was found only in coarse roots. These results reflect that the NO₃ ^? accumulation and isotopic effects decreased with leaf age, but increased with soil NO₃ ^? supply. Leaves are therefore identified as a location of NO₃ ^? reduction for A. japonica, while P. orientalis did not assimilate NO₃ ^? in leaves but in coarse roots. This work provided the first organ-specific information on NO₃ ^? isotopes in plant individuals, which will stimulate further studies of NO₃ ^? dynamics in a broader spectrum of plant ecosystems.     

Nitrogen biogeochemistry of a mature Scots pine forest subjected to high nitrogen loads

Nitrogen (N) biogeochemistry of a mature Scots pine (Pinus sylvestris L.) stand subjected to an average total atmospheric N deposition of 48 kg ha^?1 year^?1 was studied during the period 1992–2007. The annual amount of dissolved inorganic nitrogen (DIN) in throughfall (TF) averaged 34 kg ha^?1 year^?1 over the 16-year monitoring period. The throughfall fluxes contained also considerable amounts of dissolved organic nitrogen (DON) (5–8.5 kg N ha^?1 year^?1), which should be incorporated in the estimate of N flux using throughfall collectors. Throughfall DIN fluxes declined at a rate of ?0.9 kg N ha^?1 year^?1, mainly due to the decreasing TF fluxes of ammonium (NH₄), which accounted for 70% to TF DIN. The decrease in TF DIN was accompanied by a decrease in DIN leaching in the seepage water (?1.6 kg N ha^?1 year^?1), which occurred exclusively as nitrate (NO₃ ^?). Nitrate losses in the leachate of the forest floor (LFH) equalled the TF NO₃ ^? delivered to the LFH-layer. On the contrary, about half of the TF NH₄ ⁺ was retained within the LFH-layer. Approximately 60% of the TF DIN fluxes were leached indicating that N inputs were far in excess of the N requirements of the forest. For DON, losses were only substantial from the LFH-layer, but no DON was leached in the seepage water. Despite the high N losses through nitrate leaching and NO _x emission, the forest was still accumulating N, especially in the aggrading LFH-layer. The forest stand, on the contrary, was found to be a poor N sink.     

Small differences in ombrotrophy control regional-scale variation in methane cycling among <Emphasis Type="Italic">Sphagnum</Emphasis>-dominated peatlands

Across northern Alberta, Canada, bogs experience periodic wildfire and, in the Fort McMurray region, are exposed to increasing atmospheric N deposition related to oil sands development. As the fire return interval shortens and/or growing season temperatures increase, the regional peatland CO₂–C sink across northern Alberta will likely decrease, but the magnitude of the decrease could be diminished if increasing atmospheric N deposition alters N cycling in a way that stimulates post-fire successional development in bogs. We quantified net ammonification, nitrification, and dissolved organic N (DON) production in surface peat along a post-fire chronosequence of five bogs where we also experimentally manipulated N deposition (no water controls plus 0, 10, and 20 kg N ha^?1 yr^?1 simulated deposition, as NH₄NO₃). Initial KCl-extractable NH₄⁺–N, NO₃^?–N and DON averaged 176?±?6, 54?±?0.2, and 3580?±?40 ng N cm^?3, respectively, with no consistent changes as a function of time since fire and no consistent effects of experimental N addition. Net ammonification, nitrification, and DON production averaged 3.8?±?0.3, 1.6?±?0.2, and 14.3?±?2.0 ng N cm^?3 d^?1, also with no consistent changes as a function of time since fire and no consistent effects of experimental N addition. Our hypothesis that N mineralization would be stimulated after fire because root death would create a pulse of labile soil organic C was not supported, most likely because ericaceous plant roots typically are not killed in boreal bog wildfires. The absence of any N mineralization response to experimental N addition is most likely a result of rapid immobilization of added NH₄⁺–N and NO₃^?–N in peat with a wide C:N ratio. In these boreal bogs, belowground N cycling is likely characterized by large DON pools that turn over relatively slowly and small DIN pools that turn over relatively rapidly. For Alberta bogs that have persisted at historically low N deposition values and begin to receive higher N deposition related to anthropogenic activities, peat N mineralization processes may be largely unaffected until the peat C:N ratio reaches a point that no longer favors immobilization of NH₄⁺–N and NO₃^?–N.