N2O Saturation Research Articles

Distributions of N2O concentration and sea-to-air flux in the western Tropical North Pacific: Influences of eddies and typhoons

Marine systems are active regions for producing and emitting nitrous oxide (N2O), a potent greenhouse gas. In October 2018, samples were collected in the western tropical North Pacific (WTNP) to study the distributions, emissions, and influencing factors of N2O. The N2O concentrations in surface seawater showed little variation, ranging from 6.2 to 7.9 nmol L−1 (corresponding to N2O saturation range of 104–125%), with an average of 6.7 ± 0.6 nmol L−1. The vertical N2O distribution is a mirror image of dissolved oxygen (DO), increasing with depth from the surface to a maximum in the vicinity of the DO minimum. The sea-to-air fluxes of N2O ranged from 0.1 to 7.5 μmol m−2 d−1, with an average of 1.7 ± 2.2 μmol m−2 d−1, indicating that the WTNP was a net source of N2O to the atmosphere. Nitrification is the main process for N2O production. The presence of the Mindanao Eddy noticeably changes the vertical profiles of N2O in the water column, allowing the N2O-rich deep water to reach the subsurface layers, but has little effect on the surface N2O concentration. After Typhoon “Yutu” passed through, N2O concentrations in surface and subsurface water increased dramatically. The surface concentration increased by about 20%, and the sea-to-air flux of N2O increased by about 56%. Despite the short duration of the typhoon, its effect on N2O distribution and sea-to-air flux was more pronounced than that of eddies.

Dissolved Nitrous Oxide and Hydroxylamine in the Northern South China Sea in Summer

AbstractNitrous oxide (N2O) is a potent greenhouse gas and a strong ozone‐depleting substance. Ocean is an important natural source of atmospheric N2O, which has attracted increasing attention recently as to understand the biogeochemical cycles of nitrogen in marine systems. Nitrification is one of the major N2O production pathways during which N2O is produced as a side product and hydroxylamine (NH2OH) is produced as an obligate intermediate. However, few studies have reported the NH2OH variability in natural seawater and its relationship between N2O remains ambiguous. In summer 2022, spatial distribution and influencing factors of N2O and NH2OH in the northern South China Sea (SCS) were investigated. Dissolved N2O varied from 5.79 to 34.80 nmol L−1 in water column and generally increased with water depth above 800 m. N2O was correlated with dissolved oxygen and nitrate, inferring that N2O was mainly produced via nitrification. NH2OH varied from below detection limit to 3.91 nmol L−1. The adoption of multiple standard additions can largely reduce the bias in NH2OH measurement. Structural equation modeling showed that NH2OH has a potential effect favoring excessive N2O. Surface N2O saturation ranged between 102% and 278%, indicating that the northern SCS was a net source of atmospheric N2O in summer.

Relationships among the climate-relevant gases during the Southern Ocean bloom season

The ocean plays an essential role in regulating the sources and sinks of climate-relevant gases, like CO2, N2O and dimethyl sulfide (DMS), thus influencing global climate change. Although the Southern Ocean is known to be a strong carbon sink, a significant DMS source and possibly a large source of N2O, our understanding of the interaction among these climate-relevant gases and their potential impacts on climate change is still insufficient in the Southern Ocean. Herein, we analyzed parameters, including surface water pCO2, dissolved inorganic carbon (DIC), alkalinity (TA), DMS and N2O in the water column, collected during the austral summer of 2015–2016 in the 32nd Chinese Antarctic Research Expedition (CHINARE) at the tip of Antarctic Peninsula. A positive correlation between DMS and pCO2 (indicated by deficit of DIC, ∆DIC, refer to values in 100 m) was observed in waters above 75 m, whereas no correlation between N2O saturation anomaly (SA) and DMS, ∆DIC was found. In the area with stable stratification with phytoplankton bloom, significant DMS source and strong CO2 uptake with weak N2O emission were observed. Conversely, strong mixing or upwelling area was shown to be a strong marine CO2 source and significant N2O release with weak DMS source.

Seasonal patterns and key chemical predictors of dissolved greenhouse gases in small prairie pothole ponds

Shallow ponds can provide ideal conditions for production of greenhouse gases (GHGs) carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O), and thus are important to include in global and regional GHG budgets. The Canadian Prairie Pothole Region contains millions of shallow natural ponds, and we investigated GHG dynamics in 145 ponds across the region. Ponds were consistently supersaturated with CH4, often supersaturated with CO2 (57% occurrence), and often undersaturated with N2O (65% occurrence). Spring measurements showed higher N2O saturation ( p = 0.0037) than summer, while summer had higher CH4 ( p < 0.001) and CO2 ( p = 0.023) saturation than spring. Ponds exhibited large physicochemical variation, yet sulfate concentration and pH were strong predictors of dissolved CH4 and CO2, respectively. No predictor was identified for N2O. The link between sulfate and CH4 has important implications as dissolved CH4 in low sulfate (<178 mg L−1) systems was much more responsive to changes in temperature. This research fills an important knowledge gap about the GHG dynamics of prairie pothole ponds and the role of water chemistry for diffuse GHG release. Our work can also be used in ongoing efforts to describe ecosystem services (or disservices) assigned to ponds in this agriculture-dominated region.

Impacts of vertical mixing and ice-melt on N2O and CH4 concentrations in the Canadian Arctic Ocean

The sources and sinks of methane (CH4) and nitrous oxide (N2O) in the Arctic Ocean are subject to significant uncertainty, due to a combination of high spatial and temporal variability, and limited observations over relevant scales. To address this, an underway ship-board system was developed to simultaneously and continuously measure surface water CH4 and N2O concentrations in the Canadian Arctic Ocean, providing high-resolution data over a range of hydrographic regimes. Across our survey region during late summer, 2021, CH4 and N2O saturation ranged from 94% to 231% and 96%–120%, respectively. Localized CH4 and N2O maxima were observed along the cruise track, including high concentrations over the continental shelf of eastern Baffin Island, and in some waters influenced by sea ice cover or recent glacier retreat. We use our high-resolution data to examine the relationship between N2O and CH4 concentrations and a variety of oceanographic variables, demonstrating both positive correlations with salinity, which reflects the likely influence of vertical mixing, and negative correlations with salinity, indicative of ice-melt and freshwater inputs. These results build upon previous discrete CH4 and N2O observations in the Canadian Arctic, providing new information on the fine-scale distribution of these gases, and the potential underlying biogeochemical factors driving their variability. Results from our work have implications for understanding the biogeochemical cycling of Arctic Ocean CH4 and N2O under a rapidly warming climate.

Seasonal variability of nitrous oxide concentrations and emissions in a temperate estuary

Abstract. Nitrous oxide (N2O) is a greenhouse gas, with a global warming potential 298 times that of carbon dioxide. Estuaries can be sources of N2O, but their emission estimates have significant uncertainties due to limited data availability and high spatiotemporal variability. We investigated the spatial and seasonal variability of dissolved N2O and its emissions along the Elbe Estuary (Germany), a well-mixed temperate estuary with high nutrient loading from agriculture. During nine research cruises performed between 2017 and 2022, we measured dissolved N2O concentrations, as well as dissolved nutrient and oxygen concentrations along the estuary, and calculated N2O saturations, flux densities, and emissions. We found that the estuary was a year-round source of N2O, with the highest emissions in winter when dissolved inorganic nitrogen (DIN) loads and wind speeds are high. However, in spring and summer, N2O saturations and emissions did not decrease alongside lower riverine nitrogen loads, suggesting that estuarine in situ N2O production is an important source of N2O. We identified two hotspot areas of N2O production: the Port of Hamburg, a major port region, and the mesohaline estuary near the maximum turbidity zone (MTZ). N2O production was fueled by the decomposition of riverine organic matter in the Hamburg Port and by marine organic matter in the MTZ. A comparison with previous measurements in the Elbe Estuary revealed that N2O saturation did not decrease alongside the decrease in DIN concentrations after a significant improvement of water quality in the 1990s that allowed for phytoplankton growth to re-establish in the river and estuary. The overarching control of phytoplankton growth on organic matter and, subsequently, on N2O production highlights the fact that eutrophication and elevated agricultural nutrient input can increase N2O emissions in estuaries.

Nitrous Oxide Dynamics in the Siberian Arctic Ocean and Vulnerability to Climate Change

AbstractNitrous oxide (N2O) is a strong greenhouse gas and stratospheric ozone‐depleting substance. Around 20% of global emissions stem from the ocean, but current estimates and future projections are uncertain due to poor spatial coverage over large areas and limited understanding of drivers of N2O dynamics. Here, we focus on the extensive and particularly data‐lean Arctic Ocean shelves north of Siberia that experience rapid warming and increasing input of land‐derived nitrogen with permafrost thaw. We combine water column N2O measurements from two expeditions with on‐board incubation of intact sediment cores to assess N2O dynamics and the impact of land‐derived nitrogen. Elevated nitrogen concentrations in water column and sediments were observed near large river mouths. Concentrations of N2O were only weakly correlated with dissolved nitrogen and turbidity, reflecting particulate matter from rivers and coastal erosion, and correlations varied between river plumes. Surface water N2O concentrations were on average close to equilibrium with the atmosphere, but varied widely (N2O saturation 38%–180%), indicating strong local N2O sources and sinks. Water column N2O profiles and low sediment‐water N2O fluxes do not support strong sedimentary sources or sinks. We suggest that N2O dynamics in the region are influenced by water column N2O consumption under aerobic conditions or in anoxic microsites of particles, and possibly also by water column N2O production. Changes in biogeochemical and physical conditions will likely alter N2O dynamics in the Siberian Arctic Ocean over the coming decades, in addition to reduced N2O solubility in a warmer ocean.

NosZ–II–type N2O-reducing bacteria play dominant roles in determining the release potential of N2O from sediments in the Pearl River Estuary, China

The microbial reduction of N2O serves as a “gatekeeper” for N2O emissions, determining the flux of N2O release into the atmosphere. Estuaries are active regions for N2O emissions, but the microbial functions of N2O-reducing bacteria in estuarine ecosystems are not well understood. In this study, the 15N isotope tracer method, qPCR, and high-throughput sequencing were used to analyze N2O production, reduction, and emission processes in surface sediments of the Pearl River Estuary. The 15N isotope tracer experiment showed that the N2O production rates declined and the N2O reduction potential (Rr, the ratio of N2O reduction rates to N2O production rates) increased from upstream to downstream of the Pearl River Estuary, leading to a corresponding decrease of the N2O emission rates from upstream to downstream. The gene abundance ratio of nosZ/nir gradually increased from upstream to downstream and was negatively correlated with the water N2O saturation. The gene abundance of nosZ II was significantly higher than that of nosZ I in the estuary, and the nosZ II/nosZ I abundance ratio was positively correlated with N2O reduction potential. Furthermore, the community composition of NosZ-I- and NosZ–II–type N2O-reducing bacteria shifted from upstream to downstream. NosZ–II–type N2O-reducing bacteria, especially Myxococcales, Thiotrichales, and Gemmatimonadetes species, contributed to the high N2O reduction potential in the downstream. Our results suggest that NosZ–II–type N2O-reducing bacteria play a dominant role in determining the release potential of N2O from sediments in the Pearl River Estuary. This study provides a new insight into the function of microbial N2O reduction in estuarine ecosystems.

Deoxygenation turns the coastal Red Sea lagoons into sources of nitrous oxide

Direct measurements of dissolved N2O concentrations, fluxes and saturation percentages undertaken for the first time in two coastal lagoons — Al-Shabab and Al-Arbaeen, along the east coast of the Red Sea, revealed the region as a significant source of N2O to the atmosphere. The exacerbated dissolved inorganic nitrogen (DIN) from various anthropogenic sources led to substantial oxygen depletion in both the lagoons, which turned to bottom anoxia at Al-Arbaeen lagoon during the spring season. We assume that the accumulation of N2O is caused by nitrifier-denitrification in the hypoxic/anoxic boundaries. In fact, the results indicated that oxygen-depleted bottom waters favoured denitrification when the oxygenated surface waters recorded nitrification signals. Overall, the N2O concentration ranged from 109.4 to 788.6 nM (40.6–325.6 nM) in spring and 58.7 to 209.8 nM (35.8–89.9 nM) in winter in the Al-Arbaeen (Al-Shabab) lagoon. The N2O flux ranged from 647.1 to 1763.2 μmol m−2 day−1 (85.9 to 160.2 μmol m−2 day−1) and 112.5 to 150.8 μmol m−2 day−1 (76.1 to 88.7 μmol m−2 day−1) in the spring and winter respectively, in the Al-Arbaeen (Al-Shabab) lagoons. The ongoing developmental activities may worsen the current situation of hypoxia and associated biogeochemical feedbacks; therefore, the present results underline the need for continuous monitoring of both lagoons to restrict more severe oxygen depletion in future.

Spatial and temporal variations of dissolved CO2, CH4 and N2O in Lakes Edward and George (East Africa)

We report dissolved CO2, CH4 and N2O concentrations in two large East African lakes, Edward (surface area 2,325 km2, average depth of 37 m) and George (surface area 273 km2, average depth of 2 m). Lake George showed modest seasonal and spatial variations, and lower partial pressure of CO2 (pCO2) (26 ± 16 ppm, mean ± standard deviation), CH4 (234 ± 208 nmol/L) and N2O saturation levels (%N2O) (80 ± 9 %) than Lake Edward (404 ± 145 ppm, 357 ± 483 nmol/L, 139 ± 222 %). Surface waters in both lakes were over-saturated in CH4, and Lake George was under-saturated in CO2 while Lake Edward was slightly over-saturated in CO2. This difference was related to higher phytoplankton biomass in Lake George than Lake Edward, with average chlorophyll-a concentrations of 177 ± 125 and 18 ± 25 µg/L, respectively. Permanent high cyanobacterial biomass in Lake George led to uniform dissolved CO2, CH4 and N2O concentrations. In surface waters of Lake Edward, spatial variations of pCO2, CH4 and N2O were related to bottom depth, and locally (in particular in Katwe Bay) also related to the inputs of water from Lake George via the Kazinga Channel, a 40-km natural channel connecting the lakes. Short-term mixing events related to storms increased CO2, CH4 and N2O content in surface waters, in particular for CH4 and N2O. This indicates that mixing events in response to storms can create ‘hot moments’ for CH4 and N2O emissions to the atmosphere in tropical lakes, given the weaker vertical density gradients compared to higher latitude systems.

Catchment properties as predictors of greenhouse gas concentrations across a gradient of boreal lakes

Boreal lakes are the most abundant lakes on Earth. Changes in acid rain deposition, climate, and catchment land use have increased lateral fluxes of terrestrial dissolved organic matter (DOM), resulting in a widespread browning of boreal freshwaters. This browning affects the aqueous communities and ecosystem processes, and boost emissions of the greenhouse gases (GHG) CH4, CO2, and N2O. In this study, we predicted biotic saturation of GHGs in boreal lakes by using a set of chemical, hydrological, climate, and land use parameters. For this purpose, concentrations of GHGs and nutrients (organic C, -P, and -N) were determined in surface water samples from 73 lakes in south-eastern Norway covering wide ranges in DOM and nutrient concentrations, as well as catchment properties and land use. The spatial variation in saturation of each GHG is related to explanatory variables. Catchment characteristics (hydrological and climate parameters) such as lake size and summer precipitation, as well as NDVI, were key determinants when fitting GAM models for CH4 and CO2 saturation (explaining 71 and 54%, respectively), while summer precipitation and land use data were the best predictors for the N2O saturation, explaining almost 50% of deviance. Our results suggest that lake size, precipitation, and terrestrial primary production in the watershed control the saturation of GHG in boreal lakes. These predictions based on the 73-lake dataset was validated against an independent dataset from 46 lakes in the same region. Together, this provides an improved understanding of drivers and spatial variation in GHG saturation in boreal lakes across wide gradients of lake and catchment properties. The assessment highlights the need to incorporate multiple explanatory parameters in prediction models of GHGs for extrapolation across the boreal biome.

Low nitrous oxide concentration and spatial microbial community transition across an urban river affected by treated sewage

Urban rivers receive used water derived from anthropogenic activities and are a crucial source of the potent greenhouse gas nitrous oxide (N2O). However, considerable uncertainties still exist regarding the variation and mechanisms of N2O production in response to the discharge of treated sewage from municipal wastewater treatment plants (WWTPs). This study investigated N2O concentrations and microbial processes responsible for nitrogen conversion upstream and downstream of WWTPs along the Tama River flowing through Tokyo, Japan. We evaluated the effect of treated sewage on dissolved N2O concentrations and inherent N2O consumption activities in the river sediments. In summer and winter, the mean dissolved N2O concentrations were 0.67 µg-N L−1 and 0.82 µg-N L−1, respectively. Although the dissolved N2O was supersaturated (mean 288.7% in summer, mean 240.7% in winter) in the river, the N2O emission factors (EF5r, 0.013%–0.025%) were significantly lower than those in other urban rivers and the Intergovernmental Panel on Climate Change default value (0.25%). The nitrate (NO3−) concentration in the Tama River increased downstream of the WWTPs discharge sites, and it was the main nitrogen constituent. An increasing trend of NO3− concentration was observed from upstream to downstream, along with an increase in the N2O consumption potential of the river sediment. A multiple regression model showed that NO3− is the crucial factor influencing N2O saturation. The diversity in the upstream microbial communities was greater than that in the downstream ones, indicating the involvement of treated sewage discharge in shaping the microbial communities. Functional gene quantification for N2O production and consumption suggested that nirK-type denitrifiers likely contributed to N2O production. Structural equation models (SEMs) revealed that treated sewage discharged from WWTPs increased the NO3− loading from upstream to downstream in the river, inducing changes in the microbial communities and enhancing the N2O consumption activities. Collectively, aerobic conditions limited denitrification and in turn facilitated nitrification, leading to low N2O emissions even despite high NO3− loadings in the Tama River. Our findings unravel an overestimation of the N2O emission potential in an urban oxygen-rich river affected by treated sewage discharge.

Diffusive Fluxes and Controls of N2O from Coastal Rivers in Tianjin City

Rivers are an important emission source of greenhouse gases. To explore the spatial characteristics and influencing factors of N2O emission from the coastal rivers in Tianjin City, six rivers into the Bohai Sea from different land-use types were selected, and the N2O concentrations, saturation, and diffusive fluxes were measured using the headspace-gas chromatography method. The N2O concentration was in supersaturation, and the rivers were the source of atmospheric N2O. The average concentration, saturation, and diffusive fluxes of N2O were (23.85±15.20) nmol·L-1, (309.71±197.38)%, and (27.04±16.46) μmol·(m2·d)-1, with the ranges of 12.70-115.69 nmol·L-1, 164%-1502%, and 9.17-244.79 μmol·(m2·d)-1, respectively. The N2O concentrations and diffusive fluxes of the rivers presented great spatial heterogeneity, with the sewage river (Huangdipai River)>urban river (Haihe River main stream, Jiyun River)>suburban river (Duliujian River, Yongding Xinhe River)>agricultural river (Chaobai Xinhe River). The N2O concentration and diffusion fluxes were significantly correlated with salinity, nutrients, and carbon sources. NO3--N and TP contributed greatly to the diffusive flux differences. N2O production and emission greatly related to the nitrogen cycle process in the Tianjin River, and different forms of nitrogen variously contributed to N2O diffusive fluxes. The salinity gradient had the opposite effect on the N2O emission in urban rivers and drainage rivers. The N2O diffusive fluxes of the sewage river in Tianjin were significantly higher than that of other river types. In the future, due to the development of urbanization and the expansion of urban land, more management measures should focus on the hotspots such as the downstream of wastewater treatment plants of sewage rivers, the estuaries of urban rivers, and the residential gathering areas of suburban rivers to reduce N2O emission.

N2O emission and its influencing factors in subtropical streams, China

BackgroundRivers and streams are one of the primary sources of nitrous oxide (N2O) which is an important greenhouse gas with great global warming potential. Yet, over the past century, human activities have dramatically increased reactive nitrogen loadings into and consequently led to increased N2O emission from the river ecosystems. Here, we carried out a study in two subtropical rivers, i.e., Jinshui River and Qi River with slight and intense human disturbance in their respective catchments in China. The study intended to explore spatial variability and seasonality in N2O emissions, and the relative importance of physicochemical variables, nitrification and denitrification potentials, and functional genes abundance influencing N2O emissions.ResultsN2O concentration, N2O saturation, and N2O flux of Jinshui River peaked in high flow season. N2O concentration, N2O saturations, and N2O flux in Qi River and downstream of Jinshui River were significantly higher than that in other areas in normal and low flow seasons. N2O concentration was positively correlated with water temperature, water NO3−, and DOC, negatively correlated with water NH4+ and DOC/NO3− (the ratio of dissolved organic carbon to NO3− in water), and positively correlated with potential nitrification rate in high flow season, but not correlated with functional genes abundance. Both rivers had lower N2O saturation and flux than many freshwater systems, and their EFr-5 (N2O emission factor for river) was lower than the recommended values of IPCC.ConclusionsWhile the two rivers were moderate sources of N2O and N2O emissions in river systems were normally elevated in the summer, areas with intense human disturbance had higher N2O concentration, N2O saturations, and N2O flux than those with slight human disturbance. Physicochemical variables were good indicators of N2O emissions in the river ecosystems.

Restored riverine wetlands in a headwater stream can simultaneously behave as sinks of N2O and hotspots of CH4 production

Wetlands can improve water quality, but they are also recognized as important sources of greenhouse gases (GHG) such as nitrous oxide (N2O) and methane (CH4). Emissions of these gases from wetland ecosystems, especially those in headwaters, are poorly understood. Here, we determined monthly concentrations of dissolved N2O and CH4 in a headwater stream of the Taihu Lake basin of China that contains both wetland and non-wetland reaches. Daily GHG dynamics in the wetland reach were also investigated. Riverine N2O and CH4 concentrations generally varied within 10–30 nmol L−1 and 0.1–1.5 μmol L−1, respectively. CH4 saturation levels in the wetland reach were about seven times higher than those in the non-wetland reach, but there was no difference in N2O saturation. In the wetland reach, saturation levels of CH4 peaked in July, coincident with a dip in N2O saturation to levels below its saturated solubility. This underscores that hotspots of CH4 production and sinks for N2O can occur occasionally in wetlands in mid-summer, when vegetative growth and microbial activities are high. Diurnal measurements indicated that CH4 saturation in water flows passing through the wetlands from midnight through the early morning can surge to levels 10 times higher than those detected at other times of the day. Simultaneously, saturation levels of N2O decreased by 75%, indicating a net consumption of N2O. Changes in nutrient supply determined by upstream inflows, as well as dissolved oxygen, pH, and other environmental factors mediated by the wetlands, correlate with the differentiated behavior of N2O and CH4 production in wetlands. Additional work will be necessary to confirm the roles of these factors in regulating GHG emissions in riverine wetlands.

Submarine groundwater discharge drives nitrous oxide source/sink dynamics in a metropolitan estuary

AbstractCoastal waterways can be significant sources of the potent greenhouse gas nitrous oxide (N2O) due to nitrogen inputs and eutrophication. Here, we quantify groundwater derived N2O inputs and atmospheric emissions within a modified urban embayment (Sydney Harbour, Australia). Overall, we found low N2O saturation (91–171%) and air–water fluxes (−2.2 to 24.6 μmol m−2 d−1). Concentrations were highest in upstream brackish areas and a commercial/industrial subembayment. Dissolved inorganic nitrogen concentrations were low and inversely correlated to N2O throughout the harbor. N2O surface water dynamics were apparently driven by saline submarine groundwater discharge, as quantified by the radioisotope tracer radon‐222. Groundwater discharge was highest within the embayments and mangrove‐lined upper estuary. While groundwater was a net N2O source to surface waters, two upstream sub‐embayments featured groundwater N2O concentrations lower than surface water, suggesting a sink driven by surface waters recirculating in intertidal sediments. Surface‐water N2O was undersaturated within one upstream embayment, likely due to N2O consumption within sediments. Contrastingly, the downstream embayments featured higher groundwater N2O and accounted for 45% ± 21% of the groundwater N2O flux. Sydney Harbour was a net source of N2O to the atmosphere (mean 0.6 ± 0.3 μmol m−2 d−1) with larger N2O fluxes occurring from relatively small areas. N2O emissions (expressed in CO2 equilivents) were equivalent to 17% of CO2 emission estimates from previous studies. The low N2O emissions in Sydney Harbour contrast with other modified estuaries which often emit higher N2O fluxes due to larger nitrogen inputs.

Nitrogen and oxygen isotopomeric constraints on the sources of nitrous oxide and the role of submarine groundwater discharge in a temperate eutrophic salt‐wedge estuary

AbstractEstuaries have been identified as sources of nitrous oxide (N2O) emissions to the atmosphere but questions remain as to which production pathway(s) govern the oversaturation of N2O observed in most estuaries worldwide. Here, we use a suite of nitrate and N2O isotopes, as well as the 15N site preference signatures of N2O to assess (1) the relative importance of different N2O production pathways in a eutrophic groundwater‐impacted salt‐wedge estuary and the aquifers underlying the estuary and (2) the influence of groundwater input on the overall N2O saturation in the estuary. This is one of the few studies to examine the effect of groundwater–surface water interaction on N2O cycling using N2O isotopes. The site preference values of N2O in the deep aquifer below the estuary were distinctive (83‰ ± 25‰) and were much higher than in either surface water (21‰ ± 6‰) or shallow groundwater (44‰ ± 8‰), suggesting the influence of multiple biotic and/or abiotic processes which proceed through multiple cycles, and/or the occurrence of a yet unidentified N2O production pathway. Isotope endmember considerations revealed that nitrifier‐denitrification was the major N2O production pathway within the shallow aquifer whereas within the estuarine water column, N2O saturation was governed by chemodenitrification and discharge of N2O‐laden submarine groundwater. Our study not only emphasizes the substantial, yet often underappreciated role of submarine groundwater discharge in estuarine N2O budgets, but also highlights the need to reevaluate the importance of the noncanonical denitrification pathways (i.e., chemodenitrification and nitrifier‐denitrification) in controlling the overall N2O production from estuarine and groundwater environments.

Surface nitrous oxide (N2O) concentrations and fluxes from different rivers draining contrasting landscapes: Spatio-temporal variability, controls, and implications based on IPCC emission factor

Increasing indirect nitrous oxide (N2O) emission from river networks as a result of enhanced human activities on landscapes has become a global issue, as N2O has been widely recognized as an important ozone-depleting greenhouse gas. However, indirect N2O emissions from different rivers, particularly for those that drain completely different landscapes, are poorly understood. Here, we investigated the spatial-temporal variability of N2O emissions among the different rivers in the Chaohu Lake Basin of Eastern China. Our results showed that river reaches in urban watersheds are the hotspots of N2O production, with a mean N2O concentration of ∼410 nmol L−1, which is 9–18 times greater than those mainly draining forested (23 nmol L−1), agricultural (42 nmol L−1) and mixed (45 nmol L−1) landscapes. Riverine dissolved N2O was generally supersaturated with respect to the atmosphere. Such N2O saturation can best be explained by nitrogen availability, except for those in the forested watersheds, where dissolved oxygen is thought to be the primary predictor. The estimated N2O fluxes in urban rivers reached ∼471 μmol m−2 d−1, a value of ∼22, 13, and 11 times that in forested, agricultural and mixed watersheds, respectively. Averaged riverine N2O emission factors (EF5r) of the forested, agricultural, urban and mixed watersheds were 0.066%, 0.12%, 0.95% and 0.16%, respectively, showing different deviations from the default EF5r that released by IPCC in 2019. This points to a need for more field measurements with wider spatial coverage and finer frequency to further refine the EF5r and to better reveal the mechanisms behind indirect N2O emissions as influenced by watershed landscapes.

Land use drives nitrous oxide dynamics in estuaries on regional and global scales

AbstractUrban and agricultural development of coastal catchments is known to increase dissolved nitrogen inputs into estuaries; however, much less is known about how land use influences the production of the powerful greenhouse gas nitrous oxide (N2O). Here, we assess dissolved N2O dynamics in four nearby estuaries across a regional land use gradient and summarize the literature to put the observations into global perspective. During summer dry conditions, N2O saturation ranged from 131.4% ± 45.0% in the most pristine system (28% modified) to 198.6% ± 52.3% within the most modified urban system (91% modified). The N2O saturation in the wetter winter campaign was higher and more variable than the summer dry campaign (range 84.7–677.7%) likely due to direct transport of N2O into the estuaries from catchment runoff and/or produced through denitrification fueled by high nitrate inputs. During both seasons, N2O was lowest in areas adjacent to fringing mangroves and highest in upstream fresh/saltwater mixing areas. Coupling our results with previously published N2O data from 50 estuarine systems worldwide revealed that estuarine N2O increases concomitantly with catchment modification, dissolved inorganic nitrogen availability, and decreasing oxygen concentrations. Based on these results, a 1% increase in anthropogenic modification to global catchments (i.e., agricultural development and/or urbanization) may increase estuarine N2O saturation by 2.6% ± 1.2%. These findings indicate that future estuarine N2O emissions are likely to increase as anthropogenic modification of coastal catchments intensifies.

Nitrous oxide in the Great Lakes: insights from two trophic extremes

Freshwaters are a significant yet understudied component of the global nitrous oxide (N2O) budget. Despite the potential importance of the Laurentian Great Lakes in the freshwater N2O budget, studies have been extremely limited to date. This study evaluated the production pathways, concentrations, and atmospheric emissions of N2O across the two trophic extremes of the Great Lakes: the deep oligotrophic waters of Lake Superior and shallow eutrophic zones of western Lake Erie. Production pathways via denitrification and nitrification were evaluated through stable isotope analysis, and atmospheric emissions were determined from surface concentrations and wind speed. Across all sites and dates, N2O saturation ranged from 98 to 129% in Lake Superior and 93 to 676% in Sandusky Bay, Lake Erie, indicating these lakes are net sources of N2O to the atmosphere. Isotopic site preference values (SP) suggest a mix of production pathways, with nitrification dominating most time periods and denitrification occurring under conditions of high nutrient availability and microbial activity. N2O atmospheric emissions were strong but highly variable in Lake Erie, and emissions in Lake Superior were consistently low (− 0.26 to 33.03 and − 0.14 to 1.41 μmol N m−2 day−1, respectively). Our findings highlight two paradigms of N2O production and emissions: low, wind-driven rates in deep oligotrophic zones and temporally dynamic rates driven by N loading in shallow eutrophic zones. Offshore regions likely make up the majority of the N2O budget for the Great Lakes, yet nearshore regions have a greater capacity for increased N2O emissions in the face of increased nutrient loading.