Abiotic release of nitrous acid (HONO) in equilibrium with soil nitrite (NO 2 - ) was suggested as an important contributor to the missing source of atmospheric HONO and hydroxyl radicals (OH). The ...role of total soil-derived HONO in the biogeochemical and atmospheric nitrogen cycles, however, has remained unknown. In laboratory experiments, we found that for nonacidic soils from arid and arable areas, reactive nitrogen emitted as HONO is comparable with emissions of nitric oxide (NO). We show that ammonia-oxidizing bacteria can directly release HONO in quantities larger than expected from the acid-base and Henry's law equilibria of the aqueous phase in soil. This component of the nitrogen cycle constitutes an additional loss term for fixed nitrogen in soils and a source for reactive nitrogen in the atmosphere.
Quantifying the nitrous oxide (N₂O) and nitric oxide (NO) fluxes emitted from croplands remains a major challenge. Field measurements in different climates, soil and agricultural conditions are still ...scarce and emissions are generally assessed from a small number of measurements. In this study, we report continuously measured N₂O and NO fluxes with a high temporal resolution over a 2-year crop sequence of barley and maize in northern France. Measurements were carried out using 6 automatic chambers at a rate of 16 mean flux measurements per day. Additional laboratory measurements on soil cores were conducted to study the response of NO and N₂O emissions to environmental conditions. The detection limit of the chamber setup was found to be 3ngNm⁻² s⁻¹ for N₂O and 0.1ngNm⁻² s⁻¹ for NO. Nitrous oxide fluxes were higher than the threshold 37% of the time, while they were 72% of the time for NO fluxes. The cumulated annual NO and N₂O emissions were 1.7kgN₂O-Nha⁻¹ and 0.5kgNO-Nha⁻¹ in 2007, but 2.9kgN₂O-Nha⁻¹ and 0.7kgNO-Nha⁻¹ in 2008. These inter-annual differences were largely related to crop types and to their respective management practices. The forms, amounts and timing of nitrogen applications and the mineralization of organic matter by incorporation of crop residues were found to be the main factor controlling the emissions peaks. The inter-annual variability was also due to different weather conditions encountered in 2007 and 2008. In 2007, the fractioned N inputs applied on barley (54kgha⁻¹ in March and in April) did not generate N₂O emissions peaks because of the low rainfall during the spring. However, the significant rainfall observed in the summer and fall of 2007, promoted rapid decomposition of barley residues which caused high levels of N₂O emissions. In 2008, the application of dairy cattle slurry and mineral fertilizer before the emergence of maize (107kgNmin ha⁻¹ or 130kgNtot ha⁻¹ in all) coincided with large rainfalls promoting both NO and N₂O emissions, which remained high until early summer. Laboratory measurements corroborated the field observations: NO fluxes were maximum at a water-filled pore space (WFPS) of around 27% while N₂O fluxes were optimal at 68% WFPS, with a maximum potentially 14 times larger than for NO.
Animal manure is considered a valuable organic fertilizer due to its important nutrient content enhancing soil fertility and plant growth in agriculture. Besides its beneficial role as fertilizer, ...animal manure represents a significant source of volatile organic compounds (VOCs), playing a significant role in atmospheric chemistry. Understanding the composition of VOCs Understanding VOCs from animal manure is crucial for assessing their environmental impact, as they can cause air pollution, odors, and harm to human health and ecosystems. Laboratory studies enhance field measurements by providing a precise inventory of manure emissions, addressing gaps in existing literature. Both approaches complement each other in advancing our understanding of manure emissions. In this context, we conducted an experimental study involving various animal manures (cow, horse, sheep, and goat) taken from a farm in Grignon (near Paris, France). We employed atmospheric simulation chambers within a controlled laboratory environment. The analysis of VOCs involved the combination of Proton Transfer Reaction-Quadrupole ion guide-Time-of-Flight Mass Spectrometry (PTR-QiTOF-MS) and Thermal Desorption-Gas Chromatography-Mass Spectrometry (TD-GC-MS). Using PTR-QiTOF-MS, 368 compounds were detected and quantified within the manure samples. The complementary analysis by TD-GC-MS enhanced our identification of VOCs. Our findings revealed various chemical groups of VOCs, including oxygenated compounds (e.g., ethanol, cresol, acetaldehyde, etc.), nitrogenated compounds (ammonia, trimethylamine, etc.), sulfur compounds (methanethiol, dimethyl sulfide, etc.), aromatic compounds (phenols and indoles), terpenes (isoprene, D-limonene, etc.) and halogenated compounds. Cow manure exhibited the highest VOC emission fluxes, followed by goat, sheep, and horse manures. Notably, oxygenated VOCs were dominant contributors to total VOC emission fluxes in all samples. Statistical analysis highlighted the distinct nature of cow manure emissions, characterized by oxygenated compounds and nitrogenated compounds. In addition, goat manure was isolated from the other samples with high emissions of compounds having both oxygen and nitrogen atoms in their molecular formulas (e.g., CH3NO2). The experimental dataset obtained in this study provides an inventory reference for both VOCs and their emission fluxes in animal manures. Furthermore, it highlights odorant compounds and VOCs that serve as atmospheric aerosol precursor. Future studies can explore the effectiveness of various manure treatment methods to promote sustainable agriculture practices.
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•In-depth analysis of gas-phase emissions from four animal manure samples.•Laboratory chamber study of manures using online and offline techniques.•Detailed inventory of 368 volatile organic compounds with their emission fluxes.•Predominance of oxygenated compounds in all manure samples.•Detecting indoles, dimethyl sulfide, cresol as odorant compounds in all samples.
The recycling of organic waste products (e.g. sewage sludge, SS) is currently being promoted as a substitute for mineral fertilizers for agricultural lands. The spreading of SS allows the recycling ...of the nutrients and organic matter it contains. SS contains various pollutants such as volatile organic compounds (VOCs) that adversely affect the ecosystem and human health through ozone production and serve as critical precursors of atmospheric secondary organic aerosols. There are very few studies quantifying the gaseous compounds emitted from SS, and those studies primarily address their odorant properties for identifying suitable odour abatement techniques. There is an urgent need for more comprehensive quantitative information on VOCs emitted from SS as aerosol precursors. In this context, an experimental study was performed on SS samples taken from a wastewater treatment plant located in France. Undigested SS (UDSS), digested SS (DSS) and SS with 30% and 60% dryness were collected from different stages of treatment sequence and analyzed using atmospheric simulation chambers coupled to proton-transfer-reaction quadrupole ion-guide time-of-flight mass spectrometer. Our study revealed that SS samples emitted a large spectrum of VOCs. 380 compounds were detected, quantified and classified into different chemical groups. The VOC emissions increased with the increase in the dryness of the sample; the highest being in SS 60%, followed by SS 30%, UDSS and DSS. OVOCs were dominant in SS 60%. The statistical analysis showed that the anaerobic digestion and the dewatering to 60% of dryness decreased the emissions of sulphuric compounds. Aromatic compounds and indoles (e.g. skatole) were emitted significantly from the UDSS. Some of these VOCs can serve as precursor gases for atmospheric aerosol formation. The experimental dataset obtained in this study provides an accurate inventory reference for the VOC emissions from SS samples and shows the impacts of the treatment on emission characteristics of VOCs.
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•380 VOCs have been detected and quantified in sewage sludge.•Total VOC emissions increase as the dry and organic matter contents increase.•Anaerobic digestion and dewatering reduce the sulphuric compound emissions.•Aromatic compounds and skatole are highly emitted from the undigested sludge.•OVOCs are dominant in SS 60%.
Atmospheric ammonia (NH3) dominates global emissions of total reactive nitrogen (Nr), while emissions from agricultural production systems contribute about two-thirds of global NH3 emissions; the ...remaining third emanates from oceans, natural vegetation, humans, wild animals and biomass burning. On land, NH3 emitted from the various sources eventually returns to the biosphere by dry deposition to sink areas, predominantly semi-natural vegetation, and by wet and dry deposition as ammonium (NH4+) to all surfaces. However, the land/atmosphere exchange of gaseous NH3 is in fact bi-directional over unfertilized as well as fertilized ecosystems, with periods and areas of emission and deposition alternating in time (diurnal, seasonal) and space (patchwork landscapes). The exchange is controlled by a range of environmental factors, including meteorology, surface layer turbulence, thermodynamics, air and surface heterogeneous-phase chemistry, canopy geometry, plant development stage, leaf age, organic matter decomposition, soil microbial turnover, and, in agricultural systems, by fertilizer application rate, fertilizer type, soil type, crop type, and agricultural management practices. We review the range of processes controlling NH3 emission and uptake in the different parts of the soil-canopy-atmosphere continuum, with NH3 emission potentials defined at the substrate and leaf levels by different NH4+ / H+ ratios (Γ). Surface/atmosphere exchange models for NH3 are necessary to compute the temporal and spatial patterns of emissions and deposition at the soil, plant, field, landscape, regional and global scales, in order to assess the multiple environmental impacts of airborne and deposited NH3 and NH4+. Models of soil/vegetation/atmosphere NH3 exchange are reviewed from the substrate and leaf scales to the global scale. They range from simple steady-state, "big leaf" canopy resistance models, to dynamic, multi-layer, multi-process, multi-chemical species schemes. Their level of complexity depends on their purpose, the spatial scale at which they are applied, the current level of parameterization, and the availability of the input data they require. State-of-the-art solutions for determining the emission/sink Γ potentials through the soil/canopy system include coupled, interactive chemical transport models (CTM) and soil/ecosystem modelling at the regional scale. However, it remains a matter for debate to what extent realistic options for future regional and global models should be based on process-based mechanistic versus empirical and regression-type models. Further discussion is needed on the extent and timescale by which new approaches can be used, such as integration with ecosystem models and satellite observations.
We analysed the biogenic volatile organic compound (BVOC)
emissions from rapeseed leaf litter and their potential to create secondary
organic aerosols (SOAs) under three different conditions, i.e., ...(i) in the
presence of UV light irradiation, (ii) in the presence of ozone, and (iii) with
both ozone and UV light. These experiments were performed in a controlled
atmospheric simulation chamber containing leaf litter samples, where BVOC
and aerosol number concentrations were measured for 6 d. Our results
show that BVOC emission profiles were affected by UV light irradiation which
increased the summed BVOC emissions compared to the experiment with solely
O3. Furthermore, the diversity of emitted VOCs from the rapeseed litter
also increased in the presence of UV light irradiation. SOA formation was
observed when leaf litter was exposed to both UV light and O3,
indicating a potential contribution to particle formation or growth at local
scales. To our knowledge, this study investigates, for the first time, the
effect of UV irradiation and O3 exposure on both VOC emissions and SOA
formation for leaf litter samples. A detailed discussion about the processes
behind the biological production of the most important VOC is proposed.
The CANOPEE project aims to better understand the biosphere–atmosphere exchanges of biogenic volatile organic compounds (BVOCs) in the case of Mediterranean ecosystems and the impact of in-canopy ...processes on the atmospheric chemical composition above the canopy. Based on an intensive field campaign, the objective of our work was to determine the chemical composition of the air inside a canopy as well as the net fluxes of reactive species between the canopy and the boundary layer. Measurements were carried out during spring 2012 at the field site of the Oak Observatory of the Observatoire de Haute Provence (O3HP) located in the southeast of France. The site is a forest ecosystem dominated by downy oak, Quercus pubescens Willd., a typical Mediterranean species which features large isoprene emission rates. Mixing ratios of isoprene, its degradation products methylvinylketone (MVK) and methacrolein (MACR) and several other oxygenated VOC (OxVOC) were measured above the canopy using an online proton transfer reaction mass spectrometer (PTR-MS), and fluxes were calculated by the disjunct eddy covariance approach. The O3HP site was found to be a very significant source of isoprene emissions, with daily maximum ambient concentrations ranging between 2–16 ppbv inside and 2–5 ppbv just above the top of the forest canopy. Significant isoprene fluxes were observed only during daytime, following diurnal cycles with midday net emission fluxes from the canopy ranging between 2.0 and 9.7 mg m−2 h1. Net isoprene normalized flux (at 30 °C, 1000 μmol quanta m−2 s−1) was estimated at 7.4 mg m−2 h−1. Evidence of direct emission of methanol was also found exhibiting maximum daytime fluxes ranging between 0.2 and 0.6 mg m−2 h−1, whereas flux values for monoterpenes and others OxVOC such as acetone and acetaldehyde were below the detection limit. The MVK+MACR-to-isoprene ratio provided useful information on the oxidation of isoprene, and is in agreement with recent findings proposing weak production yields of MVK and MACR, in remote forest regions where the NOx concentrations are low. In-canopy chemical oxidation of isoprene was found to be weak and did not seem to have a significant impact on isoprene concentrations and fluxes above the canopy.
The EMEP/EEA guidebook 2009 for agricultural emission inventories reports an average ammonia (NH3) emission factor (EF) by volatilisation of 55% of the applied total ammoniacal nitrogen (TAN) content ...for cattle slurry, and 35% losses for pig slurry, irrespective of the type of surface or slurry characteristics such as dry matter content and pH. In this review article, we compiled over 350 measurements of EFs published between 1991 and 2011. The standard slurry application technique during the early years of this period, when a large number of measurements were made, was spreading by splash plate, and as a result reference EFs given in many European inventories are predominantly based on this technique. However, slurry application practices have evolved since then, while there has also been a shift in measurement techniques and investigated plot sizes. We therefore classified the available measurements according to the flux measurement technique or measurement plot size and year of measurement. Medium size plots (usually circles between 20 to 50 m radius) generally yielded the highest EFs. The most commonly used measurement setups at this scale were based on the Integrated Horizontal Flux method (IHF or the ZINST method (a simplified IHF method)). Several empirical models were published in the years 1993 to 2003 predicting NH3 EFs as a function of meteorology and slurry characteristics (Menzi et al., 1998; Søgaard et al., 2002). More recent measurements show substantially lower EFs which calls for new measurement series in order to validate the various measurement approaches against each other and to derive revised inputs for inclusion into emission inventories.
Identifying the contributions of chemistry and transport to observed ozone pollution using regional‐to‐global models relies on accurate representation of ozone dry deposition. We use a recently ...developed configuration of the NOAA GFDL chemistry‐climate model – in which the atmosphere and land are coupled through dry deposition—to investigate the influence of ozone dry deposition on ozone pollution over northern midlatitudes. In our model, deposition pathways are tied to dynamic terrestrial processes, such as photosynthesis and water cycling through the canopy and soil. Small increases in winter deposition due to more process‐based representation of snow and deposition to surfaces reduce hemispheric‐scale ozone throughout the lower troposphere by 5–12 ppb, improving agreement with observations relative to a simulation with the standard configuration for ozone dry deposition. Declining snow cover by the end of the 21st‐century tempers the previously identified influence of rising methane on winter ozone. Dynamic dry deposition changes summer surface ozone by −4 to +7 ppb. While previous studies emphasize the importance of uptake by plant stomata, new diagnostic tracking of depositional pathways reveals a widespread impact of nonstomatal deposition on ozone pollution. Daily variability in both stomatal and nonstomatal deposition contribute to daily variability in ozone pollution. Twenty‐first century changes in summer deposition result from a balance among changes in individual pathways, reflecting differing responses to both high carbon dioxide (through plant physiology versus biomass accumulation) and water availability. Our findings highlight a need for constraints on the processes driving ozone dry deposition to test representation in regional‐to‐global models.
Growing urbanization leads to microclimate perturbations and in particular to higher temperatures inside the city as compared to its rural surroundings, a phenomenon known as the urban heat island. ...Although it exists at several scales, this study focused only on the urban canopy layer, where inhabitants live. A bibliometric study was performed to describe and understand the relationships between strategies of urban greening and canopy layer urban heat island modification in terms of air quality and microclimate. Science mapping of 506 bibliographical resources was performed through co-word and co-citation analysis. A subset of forty-four articles related to microclimate and air quality modelling was extracted and synthesized. This analysis showed scientific papers were polarized into microclimate or air quality studies without strong links between both, implying small collaboration between these fields. There is need for studies coupling microclimate and air pollution modelling to assess vegetation’s impacts at city scale.
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