From sink to source: high inter-annual variability in the carbon budget of a Southern African wetland.

We report on three years of continuous monitoring of carbon dioxide (CO2) and methane (CH4) emissions in two contrasting wetland areas of the Okavango Delta, Botswana: a perennial swamp and a seasonal floodplain. The hydrographic zones of the Okavango Delta possess distinct attributes (e.g. vegetation zonation, hydrology) which dictate their respective greenhouse gas (GHG) temporal emission patterns and magnitude. The perennial swamp was a net source of carbon (expressed in CO2-eq units), while the seasonal swamp was a sink in 2018. Despite differences in vegetation types and lifecycles, the net CO2 uptake was comparable at the two sites studied in 2018/2020 (-894.2 ± 127.4 g m-2 yr-1 at the perennial swamp, average of the 2018 and 2020 budgets, and -1024.5 ± 134.7 g m-2 yr-1 at the seasonal floodplain). The annual budgets of CH4 were however a factor of three larger at the permanent swamp in 2018 compared to the seasonal floodplain. Both ecosystems were sensitive to drought, which switched these sinks of atmospheric CO2 into sources in 2019. This phenomenon was particularly strong at the seasonal floodplain (net annual loss of CO2 of 1572.4 ± 158.1 g m-2), due to a sharp decrease in gross primary productivity. Similarly, drought caused CH4 emissions at the seasonal floodplain to decrease by a factor of 4 in 2019 compared to the previous year, but emissions from the perennial swamp were unaffected. Our study demonstrates that complex and divergent processes can coexist within the same landscape, and that meteorological anomalies can significantly perturb the balance of the individual terms of the GHG budget. Seasonal floodplains are particularly sensitive to drought, which exacerbate carbon losses to the atmosphere, and it is crucial to improve our understanding of the role played by such wetlands in order to better forecast how their emissions might evolve in a changing climate. Studying such hydro-ecosystems, particularly in the data-poor tropics, and how natural stressors such as drought affect them, can also inform on the potential impacts of man-made perturbations (e.g. construction of hydro-electric dams) and how these might be mitigated. Given the contrasting effects of drought on the CO2 and CH4 flux terms, it is crucial to evaluate an ecosystem's complete carbon budget instead of treating these GHGs in isolation. This article is part of a discussion meeting issue 'Rising methane: is warming feeding warming? (part 2)'.

δ13C methane source signatures from tropical wetland and rice field emissions.

The atmospheric methane (CH4) burden is rising sharply, but the causes are still not well understood. One factor of uncertainty is the importance of tropical CH4 emissions into the global mix. Isotopic signatures of major sources remain poorly constrained, despite their usefulness in constraining the global methane budget. Here, a collection of new δ13CCH4 signatures is presented for a range of tropical wetlands and rice fields determined from air samples collected during campaigns from 2016 to 2020. Long-term monitoring of δ13CCH4 in ambient air has been conducted at the Chacaltaya observatory, Bolivia and Southern Botswana. Both long-term records are dominated by biogenic CH4 sources, with isotopic signatures expected from wetland sources. From the longer-term Bolivian record, a seasonal isotopic shift is observed corresponding to wetland extent suggesting that there is input of relatively isotopically light CH4 to the atmosphere during periods of reduced wetland extent. This new data expands the geographical extent and range of measurements of tropical wetland and rice δ13CCH4 sources and hints at significant seasonal variation in tropical wetland δ13CCH4 signatures which may be important to capture in future global and regional models. This article is part of a discussion meeting issue 'Rising methane: is warming feeding warming? (part 2)'.

The uncertain climate footprint of wetlands under human pressure.

Significant climate risks are associated with a positive carbon-temperature feedback in northern latitude carbon-rich ecosystems, making an accurate analysis of human impacts on the net greenhouse gas balance of wetlands a priority. Here, we provide a coherent assessment of the climate footprint of a network of wetland sites based on simultaneous and quasi-continuous ecosystem observations of CO2 and CH4 fluxes. Experimental areas are located both in natural and in managed wetlands and cover a wide range of climatic regions, ecosystem types, and management practices. Based on direct observations we predict that sustained CH4 emissions in natural ecosystems are in the long term (i.e., several centuries) typically offset by CO2 uptake, although with large spatiotemporal variability. Using a space-for-time analogy across ecological and climatic gradients, we represent the chronosequence from natural to managed conditions to quantify the "cost" of CH4 emissions for the benefit of net carbon sequestration. With a sustained pulse-response radiative forcing model, we found a significant increase in atmospheric forcing due to land management, in particular for wetland converted to cropland. Our results quantify the role of human activities on the climate footprint of northern wetlands and call for development of active mitigation strategies for managed wetlands and new guidelines of the Intergovernmental Panel on Climate Change (IPCC) accounting for both sustained CH4 emissions and cumulative CO2 exchange.

Urban landscapes and legacy industry provide hotspots for riverine greenhouse gases: A source-to-sea study of the River Clyde.

There is growing global concern that greenhouse gas (GHG) emissions from water bodies are increasing because of interactions between nutrient levels and climate warming. This paper investigates key land-cover, seasonal and hydrological controls of GHGs by comparison of the semi-natural, agricultural and urban environments in a detailed source-to-sea study of the River Clyde, Scotland. Riverine GHG concentrations were consistently oversaturated with respect to the atmosphere. High riverine concentrations of methane (CH4) were primarily associated with point source inflows from urban wastewater treatment, abandoned coal mines and lakes, with CH4-C concentrations between 0.1 - 44 µg l-1. Concentrations of carbon dioxide (CO2) and nitrous oxide (N2O) were mainly driven by nitrogen concentrations, dominated by diffuse agricultural inputs in the upper catchment and supplemented by point source inputs from urban wastewater in the lower urban catchment, with CO2-C concentrations between 0.1 - 2.6 mg l-1 and N2O-N concentrations between 0.3 - 3.4 µg l-1. A significant and disproportionate increase in all GHGs occurred in the lower urban riverine environment in the summer, compared to the semi-natural environment, where GHG concentrations were higher in winter. This increase and change in GHG seasonal patterns points to anthropogenic impacts on microbial communities. The loss of total dissolved carbon, to the estuary is approximately 48.4 ± 3.6 Gg C yr-1, with the annual inorganic carbon export approximately double that of organic carbon and four times that of CO2, with CH4 accounting for 0.03%, with the anthropogenic impact of disused coal mines accelerating DIC loss. The annual loss of total dissolved nitrogen to the estuary is approximately 4.03 ± 0.38 Gg N yr-1 of which N2O represents 0.06%. This study improves our understanding of riverine GHG generation and dynamics which can contribute to our knowledge of their release to the atmosphere. It identifies where action could support reductions in aquatic GHG generation and emission.

Photocatalytic fixation of NOx in soils.

Nitrogen oxides (NOx = NO + NO2) are important atmospheric pollutants that are directly harmful to human health. Recently in urban and industrial areas, synthetic materials have been developed and deployed to photocatalytically oxidize NOx to nitrate (NO3-) in order to improve air quality. We show that the natural presence of small amounts (≤5%) of titanium oxides, such as anatase and rutile, can also drive NOx oxidation to nitrate in soils under UV-visible irradiation. The NO uptake coefficients ranged between 0.1 × 10-6 for sandy soils to 6.4 × 10-5 in the case of tropical clay soils; the latter comparable in efficiency to current industrial man-made catalysts. This photocatalytic N-fixation mechanism offers a new strategy for NOx mitigation from the atmosphere by transforming it into nitrate, and simultaneously provides an energy efficient source of essential fertilizer to agriculture.

Leveraging research infrastructure co-location to evaluate constraints on terrestrial carbon cycling in northern European forests.

Integrated long-term, in-situ observations are needed to document ongoing environmental change, to "ground-truth" remote sensing and model outputs and to predict future Earth system behaviour. The scientific and societal value of in-situ observations increases with site representativeness, temporal duration, number of parameters measured and comparability within and across sites. Research Infrastructures (RIs) can support harmonised, cross-site data collection, curation and publication. Integrating RI networks through site co-location and standardised observation methods can help answers three questions about the terrestrial carbon sink: (i) What are present and future carbon sequestration rates in northern European forests? (ii) How are these rates controlled? (iii) Why do the observed patterns exist? Here, we present a conceptual model for RI co-location and highlight potential insights into the terrestrial carbon sink achievable when long-term in-situ Earth observation sites participate in multiple RI networks (e.g., ICOS and eLTER). Finally, we offer recommendations to promote RI co-location.

Bulk phosphorous deposition at four typical land use sites in Southwest China.

Whilst ongoing increases in the deposition of atmospheric nitrogen (N) in China have attracted a lot of attention, to date there has been little research on phosphorus (P) deposition. In this study, we quantified inorganic P (PO43-), dissolved organic P (DOP) and total P (TP) in bulk deposition at four sites in the Sichuan Basin, Southwest China. Chengdu (CD), Shifang (SF), Yanting (YT), and Gongga (GG). They represent the land use categories urban, suburban, agricultural and forest, respectively, during 2008-2018 at CD and YT, 2015-2018 at SF, and 2007-2014 at GG. Annual average TP concentrations (deposition rates) were 0.07 (0.61), 0.49 (3.22), 0.17 (1.07) and 0.01 (0.20) mg L-1 (kg ha-1 yr-1), at CD, SF, YT and GG, respectively. The TP concentrations at YT and GG showed significant increasing trends over the years, with very little change at CD and a decline at SF because of the implementation of environmental control measures. Average PO43- to DOP ratios were 0.65, 0.95, 0.82 and 0.81 at CD, SF, YT and GG, respectively, indicating that DOP accounts for a higher proportion at the urban site, and dominated by combustion sources. Bulk P deposition showed higher deposition rates in summer and lower in winter. These results highlight the importance of long term monitoring in detecting spatial and temporal changing trends of the chemical composition, so as to implement effective policies to eliminate air pollution, especially for Southwest China, where there is limited research on atmospheric P deposition.

Soil carbon storage is related to tree functional composition in naturally regenerating tropical forests.

Regenerating tropical forests are increasingly important for their role in the global carbon cycle. Carbon stocks in above-ground biomass can recover to old-growth forest levels within 60-100 years. However, more than half of all carbon in tropical forests is stored below-ground, and our understanding of carbon storage in soils during tropical forest recovery is limited.Importantly, soil carbon accumulation does not necessarily reflect patterns in above-ground biomass carbon accrual during secondary forest succession, and factors related to past land use, species composition and soil characteristics may influence soil carbon storage during forest regrowth.Using tree census data and a measure of tree community shade tolerance (species-specific light response values), we assessed the relationship between soil organic carbon stocks and tree functional groups during secondary succession along a chronosequence of 40- to 120-year-old naturally regenerating secondary forest and old-growth tropical forest stands in Panama.While previous studies found no evidence for increasing soil C storage with secondary forest age, we found a strong relationship between tree functional composition and soil carbon stocks at 0-10 cm depth, whereby carbon stocks increased with the relative influence of light-demanding tree species. Light demanding trees had higher leaf nitrogen but lower leaf density than shade-tolerant trees, suggesting that rapid decomposition of nutrient-rich plant material in forests with a higher proportion of light-demanding species results in greater accumulation of carbon in the surface layer of soils. Synthesis. We propose that soil carbon storage in secondary tropical forests is more strongly linked to tree functional composition than forest age, and that the persistence of long-lived pioneer trees could enhance soil carbon storage as forests age. Considering shifts in tree functional groups could improve estimates of carbon sequestration potential for climate change mitigation by tropical forest regrowth. Read the free Plain Language Summary for this article on the Journal blog.

Los bosques tropicales en regeneración son cada vez más importantes por su papel en el ciclo global del carbono. Las reservas de carbono en la biomasa aérea pueden recuperarse hasta los niveles de los bosques maduros en un plazo de 60 a 100 años. Sin embargo, más de la mitad de todo el carbono en los bosques tropicales se almacena bajo tierra, y nuestra comprensión del almacenamiento de carbono en los suelos durante la recuperación de los bosques tropicales es limitada.Es importante señalar que la acumulación de carbono en el suelo no refleja necesariamente los patrones de acumulación de carbono en la biomasa aérea durante la sucesión de bosques secundarios y los factores relacionados con el uso pasado del terreno, la composición de especies y las características del suelo pueden influir en el almacenamiento de carbono en el suelo durante la regeneración del bosque.Usando datos del censo de árboles y una medida de la tolerancia a la sombra de la comunidad de árboles (valores de respuesta a la luz específicos de la especie), evaluamos la relación entre las reservas de carbono orgánico del suelo y los grupos funcionales de los árboles durante la sucesión secundaria a lo largo de una cronosecuencia de 40 a 120 años bosques secundarios de regeneración natural y rodales de bosques tropicales primarios en Panamá.Mientras que estudios previos no encontraron evidencia de un aumento del almacenamiento de C en el suelo con la edad del bosque secundario, encontramos una fuerte relación entre la composición funcional de los árboles y las reservas de carbono del suelo a 0­10 cm de profundidad, por lo que las reservas de carbono aumentaron con la influencia relativa de especies de árboles que demanda de luz. Los árboles que requieren luz tenían más nitrógeno en las hojas pero menor densidad de hojas que los árboles tolerantes a la sombra, lo que sugiere que la descomposición rápida del material vegetal rico en nutrientes en los bosques con una mayor proporción de especies que requieren luz da como resultado una mayor acumulación de carbono en la capa superficial de los suelos. Síntesis. Proponemos que el almacenamiento de carbono en el suelo en los bosques tropicales secundarios está más fuertemente relacionado con la composición funcional de los árboles que con la edad del bosque, y que la persistencia de árboles pioneros de larga vida podría mejorar el almacenamiento de carbono en el suelo a medida que los bosques envejecen. La consideración de los cambios en los grupos funcionales de los árboles podría mejorar las estimaciones del potencial de secuestro de carbono para la mitigación del cambio climático mediante la regeneración de los bosques tropicales.

Phenology is the dominant control of methane emissions in a tropical non-forested wetland.

Tropical wetlands are a significant source of atmospheric methane (CH4), but their importance to the global CH4 budget is uncertain due to a paucity of direct observations. Net wetland emissions result from complex interactions and co-variation between microbial production and oxidation in the soil, and transport to the atmosphere. Here we show that phenology is the overarching control of net CH4 emissions to the atmosphere from a permanent, vegetated tropical swamp in the Okavango Delta, Botswana, and we find that vegetative processes modulate net CH4 emissions at sub-daily to inter-annual timescales. Without considering the role played by papyrus on regulating the efflux of CH4 to the atmosphere, the annual budget for the entire Okavango Delta, would be under- or over-estimated by a factor of two. Our measurements demonstrate the importance of including vegetative processes such as phenological cycles into wetlands emission budgets of CH4.

Monoterpenes from tropical forest and oil palm plantation floor in Malaysian Borneo/Sabah: emission and composition.

Regional estimates of VOC fluxes focus largely on emissions from the canopy and omit potential contributions from the forest floor including soil, litter and understorey vegetation. Here, we measured monoterpene emissions every 2 months over 2 years from logged tropical forest and oil palm plantation floor in Malaysian Borneo using static flux chambers. The main emitted monoterpenes were α-pinene, ß-pinene and d-limonene. The amount of litter present was the strongest indicator for higher monoterpene fluxes. Mean α-pinene fluxes were around 2.5-3.5 µg C m-2 h-1 from the forest floor with occasional fluxes exceeding 100 µg C m-2 h-1. Fluxes from the oil palm plantation, where hardly any litter was present, were lower (on average 0.5-2.9 µg C m-2 h-1) and only higher when litter was present. All other measured monoterpenes were emitted at lower rates. No seasonal trends could be identified for all monoterpenes and mean fluxes from both forest and plantation floor were ~ 100 times smaller than canopy emission rates reported in the literature. Occasional spikes of higher emissions from the forest floor, however, warrant further investigation in terms of underlying processes and their contribution to regional scale atmospheric fluxes.

Nitrous oxide emission factors of mineral fertilisers in the UK and Ireland: A Bayesian analysis of 20 years of experimental data.

In this study, we analysed datasets of N2O emission factors (EFs) from 21 separate studies carried out on arable and managed grasslands across the UK and Ireland over the past 20 years. A total of 641 separate events were collated from 40 experimental field sites. Individual EFs ranged over an order of magnitude (0-12% of applied N) for each fertiliser type, following a log-normal distribution in all cases. Our study shows that a Bayesian approach can provide a robust statistical method that is capable of performing uncertainty analysis on log-normal distributed data in a more defensible manner than conventional statistical methods allow. This method allowed for a national scale comparison of EFs between the most commonly applied mineral fertilisers based solely on previously published data (UK and Ireland in this case). The study shows that ammonium nitrate (AN) and Calcium ammonium nitrate (CAN) are the largest emitting fertiliser types by mass across the British Isles (temperate climate zone), with EFs of 1.1 (1.0-1.2) % and 1.0 (0.7-1.3) % for all recorded events, respectively; however, emissions from AN applications were significantly lower for applications to arable fields (0.6%) than to grasslands (1.3%). EFs associated with urea (CO(NH2)2) were significantly lower than AN for grasslands with an EF of 0.6 (0.5-0.7) %, but slightly higher for arable fields with an EF of 0.7 (0.4-1.4) %. The study highlights the potential effectiveness of microbial inhibitors at reducing emissions of N2O from mineral fertilisers, with Dicyandiamide (DCD) treated AN reducing emissions by approximately 28% and urea treated with either DCD or N-(n)-butyl) thiophosphorictriamide (NBTP) reducing emissions by approximately 40%. Although limited by a relatively small sample size (n = 11), urea treated with both DCD and NBPT appeared to have the lowest EF of all treatments at 0.13 (0.08-0.21) %, highlighting the potential to significantly reduce N2O emissions at regional scales if applied instead of conventional nitrogen fertilisers.

Differential Ecosystem Function Stability of Ammonia-Oxidizing Archaea and Bacteria following Short-Term Environmental Perturbation.

Rapidly expanding conversion of tropical forests to oil palm plantations in Southeast Asia leads to soil acidification following intensive nitrogen fertilization. Changes in soil pH are predicted to have an impact on archaeal ammonia-oxidizing archaea (AOA), ammonia-oxidizing bacteria (AOB), and complete (comammox) ammonia oxidizers and, consequently, on nitrification. It is therefore critical to determine whether the predicted effects of pH on ammonia oxidizers and nitrification activity apply in tropical soils subjected to various degrees of anthropogenic activity. This was investigated by experimental manipulation of pH in soil microcosms from a land-use gradient (forest, riparian, and oil palm soils). The nitrification rate was greater in forest soils with native neutral pH than in converted acidic oil palm soils. Ammonia oxidizer activity decreased following acidification of the forest soils but increased after liming of the oil palm soils, leading to a trend of a reversed net nitrification rate after pH modification. AOA and AOB nitrification activity was dependent on pH, but AOB were more sensitive to pH modification than AOA, which demonstrates a greater stability of AOA than AOB under conditions of short-term perturbation. In addition, these results predict AOB to be a good bioindicator of nitrification response following pH perturbation during land-use conversion. AOB and/or comammox species were active in all soils along the land-use gradient, even, unexpectedly, under acidic conditions, suggesting their adaptation to native acidic or acidified soils. The present study therefore provided evidence for limited stability of soil ammonia oxidizer activity following intensive anthropogenic activities, which likely aggravates the vulnerability of nitrogen cycle processes to environmental disturbance.IMPORTANCE Physiological and ecological studies have provided evidence for pH-driven niche specialization of ammonia oxidizers in terrestrial ecosystems. However, the functional stability of ammonia oxidizers following pH change has not been investigated, despite its importance in understanding the maintenance of ecosystem processes following environmental perturbation. This is particularly true after anthropogenic perturbation, such as the conversion of tropical forest to oil palm plantations. This study demonstrated a great impact of land-use conversion on nitrification, which is linked to changes in soil pH due to common agricultural practices (intensive fertilization). In addition, the different communities of ammonia oxidizers were differently affected by short-term pH perturbations, with implications for future land-use conversions but also for increased knowledge of associated global nitrous oxide emissions and current climate change concerns.

Global Research Alliance N2 O chamber methodology guidelines: Considerations for automated flux measurement.

Nitrous oxide (N2 O) emissions are highly episodic in response to nitrogen additions and changes in soil moisture. Automated gas sampling provides the necessary high temporal frequency to capture these emission events in real time, ensuring the development of accurate N2 O inventories and effective mitigation strategies to reduce global warming. This paper outlines the design and operational considerations of automated chamber systems including chamber design and deployment, frequency of gas sampling, and options in terms of the analysis of gas samples. The basic hardware and software requirements for automated chambers are described, including the major challenges and obstacles in their implementation and operation in a wide range of environments. Detailed descriptions are provided of automated systems that have been deployed to assess the impacts of agronomy on the emissions of N2 O and other significant greenhouse gases. This information will assist researchers across the world in the successful deployment and operation of automated N2 O chamber systems.

Photochemical emission and fixation of NOX gases in soils.

Gaseous nitrogen oxides (NOx), which result from the combustion of fossil fuels, volcanic eruptions, forest fires, and biological reactions in soils, not only affect air quality and the atmospheric concentration of ozone, but also contribute to global warming and acid rain. Soil NOx emissions have been largely ascribed to soil microbiological processes; but there is no proof of abiotic catalytic activity affecting soil NO emissions. We provide evidence of gas exchange in soils involving emissions of NOx by photochemical reactions, and their counterpart fixation through photocatalytic reactions under UV-visible irradiation. The catalytic activity promoting NOx capture as nitrate varied widely amongst different soil types, from low in quartzitic sandy soils to high in iron oxide and TiO2 rich soils. Clay soils with significant amounts of smectite also exhibited high rates of NOx sequestration and fixed amounts of N comparable to that of NO (nitric oxide) losses through biotic reactions. In these soils, a flux of 100 µg NNO m-2 h-1, as usually found in most ecosystems, could be reduced by these photochemical reactions by more than 60%. This mechanism of N fixation provides new insight into the nitrogen cycle and may inspire alternative strategies to reduce NO emissions from soils.

Ambient concentrations and deposition rates of selected reactive nitrogen species and their contribution to PM2.5 aerosols at three locations with contrasting land use in southwest China.

The fast economic development of southwest China has resulted in significant increases in the concentrations of reactive nitrogen (Nr) in the atmosphere. In this study, an urban (Chengdu, CD), suburban (Shifang, SF) and agriculture (Yanting, YT) - dominated location in the Sichuan Province, southwest China, were selected to investigate the atmospheric composition of Nr, their concentrations and deposition rates. We measured Nr concentrations in precipitation (NH4+, NO3- and organic N (DON)), the gas phase (NH3 and NO2), and the aerosol particles (PM2.5), and calculated their fluxes over a two year period (2014-2016). Total annual N deposition rates were 49.2, 44.7 and 19.8 kg N ha-1 yr-1 at CD, SF and YT, respectively. Ammonia concentrations were larger at the urban and suburban sites than the agricultural site (12.2, 14.9, and 4.9 µg N m-3 at CD, SF and YT, respectively). This is consistent with the multitude of larger sources of NH3, including city garbage, livestock and traffic, in the urban and suburban areas. Monthly NO2 concentrations were lower in warmer compared to the colder months, but seasonal differences were insignificant. Daily PM2.5 concentrations ranged from 7.7 to 236.0, 5.0-210.4 and 4.2-128.4 µg m-3 at CD, SF and YT, respectively, and showed significant correlations with fine particulate NH4+ and NO3- concentrations. Ratios of reduced to oxidized N were in the range of 1.6-2.7. This implies that the control of reduced Nr especially in urban environments is needed to improve local air quality.

Bulk deposition of organic and inorganic nitrogen in southwest China from 2008 to 2013.

China is regarded as one of the nitrogen deposition hotspots in the world. Measurements to-date have focused mainly on the North China Plain, ignoring the fact that atmospheric chemical and physical properties vary across the country and that there may be other hotspots regions that should be investigated. For this reason we have conducted a six year study, measuring the bulk deposition of reduced (NH4-N), oxidized (NO3-N), and dissolved organic nitrogen (DON) at three contrasting sites in the Sichuan province, southwest China. The study sites were a high altitude forest in the Gongga Mountains (GG), an agriculture dominated region in Yanting (YT) and an urban site in the mega city Chengdu (CD). The annual average bulk deposition fluxes of total dissolved nitrogen (TDN) were 7.4, 23.1 and 36.6 kg N ha-1 yr-1 at GG, YT and CD sites, respectively, during the study period 2008 to 2013. The contributions of NH4-N, NO3-N and DON to the TDN were in the range of 48.4-57.8%, 28.8-43.7%, and 8.0-15.6%, respectively. DON bulk deposition was mainly dominated by agricultural activities. TDN bulk deposition fluxes showed increasing trends at the agricultural and urban sites from 2008 to 2013, but there was little change at the remote forest (GG) site. While reduced N dominated bulk N deposition at all the three sites, its contribution showed a decreasing trend, suggesting a gradual increase in the importance of oxidized N. These results reveal the value of long term monitoring in detecting changes in the atmospheric chemical composition of this rapidly changing region, and their inclusion in the policy debate regarding which sources should be controlled in order to reduce the long term impacts of N deposition, especially for southwest China, where there are few measurements of N deposition.

A modeling study on mitigation of N2O emissions and NO3 leaching at different agricultural sites across Europe using LandscapeDNDC.

The identification of site-specific agricultural management practices in order to maximize yield while minimizing environmental nitrogen losses remains in the center of environmental pollution research. Here, we used the biogeochemical model LandscapeDNDC to explore different agricultural practices with regard to their potential to reduce soil N2O emissions and NO3 leaching while maintaining yields. In a first step, the model was tested against observations of N2O emissions, NO3 leaching, soil micrometeorology as well as crop growth for eight European cropland and grassland sites. Across sites, LandscapeDNDC predicts very well mean N2O emissions (r(2)=0.99) and simulates the magnitude and general temporal dynamics of soil inorganic nitrogen pools. For the assessment of site-specific mitigation potentials of environmental nitrogen losses a Monte Carlo optimization technique considering different agricultural management options (i.e., timing of planting, harvest and fertilization, amount of applied fertilizer as well as residue management) was used. The identified optimized field management practices reduce N2O emissions and NO3 leaching from croplands on average by 21% and 31%, respectively. Likewise, average reductions of 55% for N2O emissions and 16% for NO3 leaching are estimated for grasslands. For mitigating environmental loss - while maintaining yield levels - it was most important to reduce fertilizer application rates by in average 10%. Our analyses indicate that yield scaled N2O emissions and NO3 leaching indicate possible improvements of nitrogen use efficiencies in European farming systems. Moreover, the applied optimization approach can be used also in a prognostic way to predict optimal timings and fertilization options (rates and splitting) upon accurate weather forecasts combined with the knowledge of modeled soil nutrient availability and plant nitrogen demand.

The global nitrogen cycle in the twenty-first century.

Global nitrogen fixation contributes 413 Tg of reactive nitrogen (Nr) to terrestrial and marine ecosystems annually of which anthropogenic activities are responsible for half, 210 Tg N. The majority of the transformations of anthropogenic Nr are on land (240 Tg N yr(-1)) within soils and vegetation where reduced Nr contributes most of the input through the use of fertilizer nitrogen in agriculture. Leakages from the use of fertilizer Nr contribute to nitrate (NO3(-)) in drainage waters from agricultural land and emissions of trace Nr compounds to the atmosphere. Emissions, mainly of ammonia (NH3) from land together with combustion related emissions of nitrogen oxides (NOx), contribute 100 Tg N yr(-1) to the atmosphere, which are transported between countries and processed within the atmosphere, generating secondary pollutants, including ozone and other photochemical oxidants and aerosols, especially ammonium nitrate (NH4NO3) and ammonium sulfate (NH4)2SO4. Leaching and riverine transport of NO3 contribute 40-70 Tg N yr(-1) to coastal waters and the open ocean, which together with the 30 Tg input to oceans from atmospheric deposition combine with marine biological nitrogen fixation (140 Tg N yr(-1)) to double the ocean processing of Nr. Some of the marine Nr is buried in sediments, the remainder being denitrified back to the atmosphere as N2 or N2O. The marine processing is of a similar magnitude to that in terrestrial soils and vegetation, but has a larger fraction of natural origin. The lifetime of Nr in the atmosphere, with the exception of N2O, is only a few weeks, while in terrestrial ecosystems, with the exception of peatlands (where it can be 10(2)-10(3) years), the lifetime is a few decades. In the ocean, the lifetime of Nr is less well known but seems to be longer than in terrestrial ecosystems and may represent an important long-term source of N2O that will respond very slowly to control measures on the sources of Nr from which it is produced.