Ozone-depleting Greenhouse Gas Research Articles

Effect of microbial growth and electron competition on nitrous oxide source and sink function of hyporheic zones

The hyporheic zones (HZs) are key sites of the production of nitrous oxide (N2O), a potent ozone-depleting greenhouse gas. Denitrification is the primary process of N2O production in HZs, including four reduction steps (NO3−→NO2−→NO→N2O→N2). Electron competition occurs between the four reduction steps and can significantly impact the production of N2O. However, denitrification was typically considered as simplified two step reactions for investigating the release of N2O, neglecting the electron competition among the four-step reactions. Moreover, the N2O production/consumption patterns are regulated by both hydraulic and biogeochemical conditions in HZs. Dynamic microbial growth cannot only mediate the biogeochemical reactions, but also change hydraulic properties spatiotemporally by bioclogging. But microbial growth is rarely considered for investigating N2O dynamics of HZs. To assess these effects on hyporheic N2O dynamics and source-sink function, we establish a novel numerical model of N2O dynamics of HZs, coupling porous flow, reactive transport, electron competition, microbial growth and bioclogging. The results show that the weak electron competitiveness of N2O reductase results in a less allocation of electrons to the N2O reduction process, particularly in situations with limited carbon sources, thus increasing the release of N2O into the rives. Microbial growth significantly influences N2O release from HZs into rivers, increasing by more than two orders of magnitude on average compared to the model neglecting microbial dynamics. In contrast to the classical knowledges that HZs in coarse sediments tending to short residence time cannot act as sources of N2O, dynamic microbial growth obviously increases the potential for N2O release from HZs in coarse sediments to the rivers. The global Monte Carlo regional sensitivity analyses indicate that microbial biomass is the most critical factor determined the hyporheic source-sink function for N2O, followed by carbon oxidation rate and residence time. These are significantly different from previous knowledge that the residence time and oxygen/nitrogen uptake rate are the most sensitive parameters, which may lead to misunderstanding of the key controlling factors of N2O release from HZs. In addition, we propose a new Damköhler number (DaO2∗) of dissolved oxygen by multiplying the classical DaO2 with a dimensionless microbial modification factor for identifying N2O source-sink function of HZs, with DaO2∗ < 1 for N2O sink, while DaO2∗ > 1 for N2O source.

Seasonality of nitrous oxide emissions at six full-scale wastewater treatment plants.

Nitrous oxide (N2O) is an ozone-depleting greenhouse gas that contributes significantly to the carbon footprint of a wastewater treatment plant (WWTP). Plant-specific measurement campaigns are required to reliably quantify the emission level that has been found to significantly vary between WWTPs. In this study, the N2O emissions were quantified from five full-scale WWTPs during 4-19-day measurement campaigns conducted under both cold period conditions (water temperature below 12 °C) and warm period conditions (water temperature from 12 to 20 °C). The measurement data were studied alongside long-term monitoring data from a sixth WWTP. The calculated emission factors (EFs) varied from near 0 to 1.8% relative to the influent total nitrogen load. The results confirmed a significant seasonality of N2O emissions as well as a notable variation between WWTPs in the emission level, which a single fixed EF cannot represent. Wastewater temperature was one explanatory factor for the emission seasonality. Both low and high emissions were measured from denitrifying-nitrifying activated sludge (AS) processes, while the emissions from only nitrifying AS processes were consistently high. Nitrite (NO2-) at the end of the aerobic zones of the AS process was linked to the variability in N2O emissions during the cold period.

Shifts in the high-resolution spatial distribution of dissolved N2O and the underlying microbial communities and processes in the Pearl River Estuary.

Estuaries are significant sources of the ozone-depleting greenhouse gas N2O. However, owing to large spatial heterogeneity and discrete measurements, N2O emissions from estuaries are considerably uncertain. Microbial processes are disputed in terms of the dominant N2O production under severe human disturbance. Herein, combining real-time and high-resolution measurements with bioinformatics analysis, we accurately mapped the consecutive two-dimensional N2O distribution in the Pearl River Estuary (PRE), China, and revealed its underlying microbial mechanisms. Both the horizontal and vertical distributions of N2O concentrations varied greatly at fine scales. Supersaturated N2O concentrations (9.1 to 132.2nmol/L) in the surface water decreased along the estuarine salinity gradient, with several emission hotspots scattering upstream. The vertical N2O distribution showed marked differences from complete mixing upstream to incomplete mixing downstream, with constant or changeable concentrations with increasing depth. Furthermore, spatially varied denitrifying and nitrifying microorganisms controlled the N2O production and distribution in the PRE, with denitrification playing the dominant role. The nirK-type and nirS-type denitrifying bacteria were the primary producers of N2O in the water and sediment columns, respectively. In addition, substrate concentration (NO3- and DOC) regulated N2O production by affecting key microbial processes, while physical influences (water-mass mixing and salt wedges) reshaped N2O distribution. With these information, a conceptual model of estuarine N2O production and distribution was constructed to generalize the possible biochemical processes under environmental constraints, which could provide insights into the N2O biogeochemical cycle and emission mitigation from a mechanistic perspective.

Are Microalgae New Players in Nitrous Oxide Emissions from Eutrophic Aquatic Environments?

Anthropogenic activities cause the introduction of nitrogen (N) into aquatic environments where these N inputs drive the biological synthesis of nitrous oxide (N2O), a potent and ozone-depleting greenhouse gas. To assess the significance of N2O emissions to climate change, the Intergovernmental Panel on Climate Change (IPCC) estimates indirect N2O emissions from rivers, lakes, and estuaries by multiplying the amounts of N received by these ecosystems with specific emission factors. Interestingly, the IPCC recently increased the N2O emission factor associated with wastewater discharge into “nutrient-impacted (eutrophic) aquatic receiving environments” nearly four times based on experimental evidence of high N2O emissions from N-receiving eutrophic ecosystems. As microalgae can produce N2O, these organisms may contribute to the N2O emissions frequently reported in eutrophic aquatic bodies. If that is the case, estimating N2O emissions solely based on nitrogen inputs to water bodies might lead to inaccurate N2O budgeting as microalgae growth is often limited by phosphorus in these environments. Establishing the significance of microalgal N2O synthesis in eutrophic environments is, therefore, critical and may lead to considerable changes on how to budget and mitigate N2O emissions and eutrophication.

Cell density dependent restriction of N2O reductase in denitrifying Pseudomonas spp., a potential driver of N2O emissions in natural systems.

Denitrification is a major biological source and sink for the ozone-depleting greenhouse gas N2. Thus, the respiratory physiology of denitrifiers and the mechanisms determining their propensity for accumulation of N-oxides are of fundamental interest. Here, we report a pervasive positive correlation between cell density and N2O accumulation in Pseudomonas aeruginosa and P. fluorescens F113. We show that this was a result of quorum sensing by comparing the P. aeruginosa PAO1-UW wild type to a rhlI/lasI knockout mutant able to sense, but not synthesize the N-acyl-homoserine lactones (AHL) of the Rhl and Las circuits. Neither the transcription of nosZ (encoding N2O reductase, N2OR) nor the abundance of peptides of known relevance to denitrification could explain the restriction of N2O reduction in AHL-affected cultures. However, a protein shown to be involved in synthesis and repair of iron-sulphur (Fe-S) centers under NO stress, CyaY, was significantly downregulated in the AHL producing wild type. This hints to a possible route of N2OR-suppression via compromised Fe-S centers in the ancillary protein NosR. While the exact mechanism remains obscure, it appears that quorum sensing driven restriction of N2OR activity is common. Thus, given its ubiquity among prokaryotes, and the potential for cross-species and -strain effects, quorum sensing is plausibly a driver of N2O emissions in a range of systems.

Restoring wetlands on intensive agricultural lands modifies nitrogen cycling microbial communities and reduces N2O production potential

The concentration of nitrous oxide (N2O), an ozone-depleting greenhouse gas, is rapidly increasing in the atmosphere. Most atmospheric N2O originates in terrestrial ecosystems, of which the majority can be attributed to microbial cycling of nitrogen in agricultural soils. Here, we demonstrate how the abundance of nitrogen cycling genes vary across intensively managed agricultural fields and adjacent restored wetlands in the Sacramento-San Joaquin Delta in California, USA. We found that the abundances of nirS and nirK genes were highest at the intensively managed organic-rich cornfield and significantly outnumber any other gene abundances, suggesting very high N2O production potential. The quantity of nitrogen transforming genes, particularly those responsible for denitrification, nitrification and DNRA, were highest in the agricultural sites, whereas nitrogen fixation and ANAMMOX was strongly associated with the wetland sites. Although the abundance of nosZ genes was also high at the agricultural sites, the ratio of nosZ genes to nir genes was significantly higher in wetland sites indicating that these sites could act as a sink of N2O. These findings suggest that wetland restoration could be a promising natural climate solution not only for carbon sequestration but also for reduced N2O emissions.

Revisiting the involvement of ammonia oxidizers and denitrifiers in nitrous oxide emission from cropland soils

Nitrous oxide (N2O), an ozone-depleting greenhouse gas, is generally produced by soil microbes, particularly NH3 oxidizers and denitrifiers, and emitted in large quantities after N fertilizer application in croplands. N2O can be produced via multiple processes, and reduced, with the involvement of more diverse microbes with different physiological constraints than previously thought; therefore, there is a lack of consensus on the production processes and microbes involved under different agricultural practices. In this study, multiple approaches were applied, including N2O isotopocule analyses, microbial gene transcript measurements, and selective inhibition assays, to revisit the involvement of NH3 oxidizers and denitrifiers, including the previously-overlooked taxa, in N2O emission from a cropland, and address the biological and environmental factors controlling the N2O production processes. Then, we synthesized the results from those approaches and revealed that the overlooked denitrifying bacteria and fungi were more involved in N2O production than the long-studied ones. We also demonstrated that the N2O production processes and soil microbes involved were different based on fertilization practices (plowing or surface application) and fertilization types (manure or urea). In particular, we identified the following intensified activities: (1) N2O production by overlooked denitrifying fungi after manure fertilization onto soil surface; (2) N2O production by overlooked denitrifying bacteria and N2O reduction by long-studied N2O-reducing bacteria after manure fertilization into the plowed layer; and (3) N2O production by NH3-oxidizing bacteria and overlooked denitrifying bacteria and fungi when urea fertilization was applied into the plowed layer. We finally propose the conceptual scheme of N flow after fertilization based on distinct physiological constraints among the diverse NH3 oxidizers and denitrifiers, which will help us understand the environmental context-dependent N2O emission processes.

N2O decomposition properties of Ru catalysts supported on various oxide materials and SnO2

Nitrous oxide (N2O) is a stratospheric ozone depleting greenhouse gas that has global warming potential. As the catalytic decomposition of N2O is one of the most promising techniques for N2O emissions abatement, in this study, for this purpose the properties of Ru supported on various oxide materials were investigated under excess O2 conditions, and the identities of the N2O adsorption species on the catalysts were confirmed. To clarify the correlation between the catalytic properties and N2O decomposition activity, the supported Ru catalysts were characterised by means of powder X-ray diffraction, X-ray fluorescence measurements, energy-dispersive X-ray mapping and several gas sorption techniques. The results showed that the redox properties for Ru (RuO2) at low temperature are closely associated with N2O decomposition activity. The local structures, optimal Ru loading and N2O adsorption species of the novel Ru/SnO2 catalysts were studied and they showed high activity for N2O decomposition.

Effects of support materials and Ir loading on catalytic N2O decomposition properties

N2O is a stratospheric ozone-depleting greenhouse gas with a global warming potential. The catalytic decomposition of N2O is one of the most promising and economical techniques to reduce the amount of the gas in the atmosphere. In the present study, the effects of support materials and Ir loading on the catalytic N2O decomposition properties were comprehensively investigated. The decomposition activity is closely associated with the Ir dispersion which is estimated using pulsed CO chemisorption. In addition, NO-TPD profiles and in situ FTIR spectra revealed a correlation between the adsorption properties of N2O/NOx and the catalytic N2O decomposition activity.

Hydroxylamine Complexes of Cytochrome c': Influence of Heme Iron Redox State on Kinetic and Spectroscopic Properties.

Hydroxylamine (NH2OH or HA) is a redox-active nitrogen oxide that occurs as a toxic intermediate in the oxidation of ammonium by nitrifying and methanotrophic bacteria. Within ammonium containing environments, HA is generated by ammonia monooxygenase (nitrifiers) or methane monooxygenase (methanotrophs). Subsequent oxidation of HA is catalyzed by heme proteins, including cytochromes P460 and multiheme hydroxylamine oxidoreductases, the former contributing to emissions of N2O, an ozone-depleting greenhouse gas. A heme-HA complex is also a proposed intermediate in the reduction of nitrite to ammonia by cytochrome c nitrite reductase. Despite the importance of heme-HA complexes within the biogeochemical nitrogen cycle, fundamental aspects of their coordination chemistry remain unknown, including the effect of the Fe redox state on heme-HA affinity, kinetics, and spectroscopy. Using stopped-flow UV-vis and resonance Raman spectroscopy, we investigated HA complexes of the L16G distal pocket variant of Alcaligenes xylosoxidans cytochrome c'-α (L16G AxCP-α), a pentacoordinate c-type cytochrome that we show binds HA in its Fe(III) (Kd ∼ 2.5 mM) and Fe(II) (Kd = 0.0345 mM) states. The ∼70-fold higher HA affinity of the Fe(II) state is due mostly to its lower koff value (0.0994 s-1 vs 11 s-1), whereas kon values for Fe(II) (2880 M-1 s-1) and Fe(III) (4300 M-1 s-1) redox states are relatively similar. A comparison of the HA and imidazole affinities of L16G AxCP-α was also used to predict the influence of Fe redox state on HA binding to other proteins. Although HA complexes of L16G AxCP-α decompose via redox reactions, the lifetime of the Fe(II)HA complex was prolonged in the presence of excess reductant. Spectroscopic parameters determined for the Fe(II)HA complex include the N-O stretching vibration of the NH2OH ligand, ν(N-O) = 906 cm-1. Overall, the kinetic trends and spectroscopic benchmarks from this study provide a foundation for future investigations of heme-HA reaction mechanisms.

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.

Spatial Variability and Factors Influencing the Air-Sea N2O Flux in the Bering Sea, Chukchi Sea and Chukchi Abyssal Plain

The concentrations of the ozone-depleting greenhouse gas nitrous oxide (N2O) in the upper 300 m of the Subarctic and Arctic Oceans determined during the 5th Chinese National Arctic Research Expedition were studied. The surface water samples revealed that the study area could be divided into three regions according to the distribution of dissolved N2O in the surface water, namely, the Aleutian Basin (52° N–60° N), continental shelf (60° N–73° N) and Canadian Basin (north of 73° N), with N2O in the surface water in equilibrium, oversaturated and undersaturated relative to the atmosphere, respectively. The influences of physical and chemical processes, such as eddy diffusion and sedimentary emissions, beneath the surface layer are discussed. The results of a flux evaluation show that the Aleutian Basin may be a weak N2O source of approximately 0.46 ± 0.1 μmol·m−2·d−1, and the continental shelf acts as a strong N2O source of approximately 8.2 ± 1.4 μmol·m−2·d−1. By contrast, the Chukchi Abyssal Plain (CAP) of the Canadian Basin is at least a temporal N2O sink with a strength of approximately −10.2 ± 1.4 μmol·m−2·d−1.

Influence of oxygen availability on the activities of ammonia-oxidizing archaea.

Recent studies point to the importance of oxygen (O2 ) in controlling the distribution and activity of marine ammonia-oxidizing archaea (AOA), one of the most abundant prokaryotes in the ocean. The AOA are associated with regions of low O2 tension in oceanic oxygen minimum zones (OMZs), and O2 availability is suggested to influence their production of the ozone-depleting greenhouse gas nitrous oxide (N2 O). We show that marine AOA available in pure culture sustain high ammonia oxidation activity at low μM O2 concentrations, characteristic of suboxic regions of OMZs (<10 µM O2 ), and that atmospheric concentrations of O2 may inhibit the growth of some environmental populations. We quantify the increasing N2 O production by marine AOA with decreasing O2 tensions, consistent with the plausibility of an AOA contribution to the accumulation of N2 O at the oxic-anoxic redox boundaries of OMZs. Variable sensitivity to peroxide also suggests that endogenous or exogenous reactive oxygen species are of importance in determining the environmental distribution of some populations.

Genome-Wide Discovery of Putative sRNAs in Paracoccus denitrificans Expressed under Nitrous Oxide Emitting Conditions.

Nitrous oxide (N2O) is a stable, ozone depleting greenhouse gas. Emissions of N2O into the atmosphere continue to rise, primarily due to the use of nitrogen-containing fertilizers by soil denitrifying microbes. It is clear more effective mitigation strategies are required to reduce emissions. One way to help develop future mitigation strategies is to address the currently poor understanding of transcriptional regulation of the enzymes used to produce and consume N2O. With this ultimate aim in mind we performed RNA-seq on a model soil denitrifier, Paracoccus denitrificans, cultured anaerobically under high N2O and low N2O emitting conditions, and aerobically under zero N2O emitting conditions to identify small RNAs (sRNAs) with potential regulatory functions transcribed under these conditions. sRNAs are short (∼40–500 nucleotides) non-coding RNAs that regulate a wide range of activities in many bacteria. Hundred and sixty seven sRNAs were identified throughout the P. denitrificans genome which are either present in intergenic regions or located antisense to ORFs. Furthermore, many of these sRNAs are differentially expressed under high N2O and low N2O emitting conditions respectively, suggesting they may play a role in production or reduction of N2O. Expression of 16 of these sRNAs have been confirmed by RT-PCR. Ninety percent of the sRNAs are predicted to form secondary structures. Predicted targets include transporters and a number of transcriptional regulators. A number of sRNAs were conserved in other members of the α-proteobacteria. Better understanding of the sRNA factors which contribute to expression of the machinery required to reduce N2O will, in turn, help to inform strategies for mitigation of N2O emissions.

U.S. carbon tetrachloride emissions exceed expectations

Atmospheric emissions of carbon tetrachloride—a restricted ozone-depleting greenhouse gas—are on average 4 gigagrams per year in the U.S., as much as two orders of magnitude higher than expected on...

Determining Roles of Accessory Genes in Denitrification by Mutant Fitness Analyses.

Enzymes of the denitrification pathway play an important role in the global nitrogen cycle, including release of nitrous oxide, an ozone-depleting greenhouse gas. In addition, nitric oxide reductase, maturation factors, and proteins associated with nitric oxide detoxification are used by pathogens to combat nitric oxide release by host immune systems. While the core reductases that catalyze the conversion of nitrate to dinitrogen are well understood at a mechanistic level, there are many peripheral proteins required for denitrification whose basic function is unclear. A bar-coded transposon DNA library from Pseudomonas stutzeri strain RCH2 was grown under denitrifying conditions, using nitrate or nitrite as an electron acceptor, and also under molybdenum limitation conditions, with nitrate as the electron acceptor. Analysis of sequencing results from these growths yielded gene fitness data for 3,307 of the 4,265 protein-encoding genes present in strain RCH2. The insights presented here contribute to our understanding of how peripheral proteins contribute to a fully functioning denitrification pathway. We propose a new low-affinity molybdate transporter, OatABC, and show that differential regulation is observed for two MoaA homologs involved in molybdenum cofactor biosynthesis. We also propose that NnrS may function as a membrane-bound NO sensor. The dominant HemN paralog involved in heme biosynthesis is identified, and a CheR homolog is proposed to function in nitrate chemotaxis. In addition, new insights are provided into nitrite reductase redundancy, nitric oxide reductase maturation, nitrous oxide reductase maturation, and regulation.

Introduction to the special issue on ozone layer protection and climate change: the extraordinary experience of building the Montreal Protocol, lessons learned, and hopes for future climate change efforts

This special issue on Ozone Layer Protection and Climate Change reflects the leadership of the Association of Environmental Studies and Sciences (AESS) in drawing interdisciplinary attention to important environmental issues. The authors are scientists, diplomats, regulatory authorities, environmental activists, and scholars who are intimately involved in actions that protect the stratospheric ozone layer and climate. This issue provides new information and insightful analytic summaries of critical issues in the protection of the atmospheric environment and is also an urgent appeal to professors and students to place atmospheric protection prominently in thinking, research, teaching, and professional activities related to “sustainable development.” The authors describe and document the bold steps taken by individual and institutional leaders involved in the Montreal Protocol to thwart catastrophic ozone layer destruction, which incidentally, albeit on a sound scientific basis, addressed climate change. Because of strong leadership, effective networking, and concepts such the “precautionary principle” and “start and strengthen,” the Montreal Protocol is considered to be the most successful global environmental treaty. For example, thanks to innovative approaches adopted by both industry and government, the Montreal Protocol has already replaced about 85 % of ozone-depleting greenhouse gases with low global warming potential alternatives and increased product energy efficiency. But hardwork is needed to overcome the important challenges that remain, such as the phasedown of the 15 % of alternatives that are high global warming potential hydrofluorocarbons. Scientists, government officials, scholars, and business people must push for higher standards to achieve the combined goals of reducing both ozone-depleting substances and greenhouse gases.

One-pot room-temperature conversion of cyclohexane to adipic acid by ozone and UV light.

Nitric acid oxidation of cyclohexane accounts for ~95% of the worldwide adipic acid production and is also responsible for ~5 to 8% of the annual worldwide anthropogenic emission of the ozone-depleting greenhouse gas nitrous oxide (N2O). Here we report a N2O-free process for adipic acid synthesis. Treatment of neat cyclohexane, cyclohexanol, or cyclohexanone with ozone at room temperature and 1 atmosphere of pressure affords adipic acid as a solid precipitate. Addition of acidic water or exposure to ultraviolet (UV) light irradiation (or a combination of both) dramatically enhances the oxidative conversion of cyclohexane to adipic acid.

Aqueous N2O Reduction with H2 Over Pd-Based Catalyst: Mechanistic Insights From Experiment and Simulation

Nitrous Oxide (N2O), an ozone depleting greenhouse gas, is an observed intermediate in aqueous nitrate/nitrite reduction mediated by both natural microbial and synthetic laboratory catalysts. Because of our interest in catalytic nitrate/nitrite remediation, we have endeavored to develop a detailed concordant experimental/theoretical picture of N2O reduction with H2 over a Pd catalyst in an aqueous environment. We use batch experiments in H2 excess and limiting conditions to examine the reduction kinetics. We use density functional theory (DFT) to model the elementary steps in N2O reduction on model Pd(100), Pd(110), Pd(111) and Pd(211) facets and including the influence of adsorbed O, H, and of H2O. Both experiments and theory agree that hydrogen is necessary for removal of adsorbed oxygen from the catalyst surface. The dissociation of N2O to N2(g) and O(ads) is facile and in the absence of H proceeds until the catalyst is O-covered. Water itself is proposed to facilitate the hydrogenation of surface O by transferring absorbed hydrogen to Pd-absorbed O and OH. We measure an apparent activation energy of 41.4 kJ/mol (0.43 eV) for N2O reduction in the presence of excess H2, a value that is within 0.1 eV of the barriers determined theoretically.