Nitrous Oxide (N2O): The Dominant Ozone-Depleting Substance Emitted in the 21st Century
02 Oct 2009-Science (American Association for the Advancement of Science)-Vol. 326, Iss: 5949, pp 123-125
TL;DR: In this paper, the ozone depletion potential-weighted anthropogenic emissions of N2O with those of other ozone-depleting substances were compared, and it was shown that N 2O emission currently is the single most important ozone-destroying emission and is expected to remain the largest throughout the 21st century.
Abstract: By comparing the ozone depletion potential-weighted anthropogenic emissions of N2O with those of other ozone-depleting substances, we show that N2O emission currently is the single most important ozone-depleting emission and is expected to remain the largest throughout the 21st century. N2O is unregulated by the Montreal Protocol. Limiting future N2O emissions would enhance the recovery of the ozone layer from its depleted state and would also reduce the anthropogenic forcing of the climate system, representing a win-win for both ozone and climate.
Citations
More filters
TL;DR: Humans must modify their behavior or risk causing irreversible changes to life on Earth, as the damage done by humans to the nitrogen economy of the planet will persist for decades, possibly centuries, if active intervention and careful management strategies are not initiated.
Abstract: Atmospheric reactions and slow geological processes controlled Earth's earliest nitrogen cycle, and by ~2.7 billion years ago, a linked suite of microbial processes evolved to form the modern nitrogen cycle with robust natural feedbacks and controls. Over the past century, however, the development of new agricultural practices to satisfy a growing global demand for food has drastically disrupted the nitrogen cycle. This has led to extensive eutrophication of fresh waters and coastal zones as well as increased inventories of the potent greenhouse gas nitrous oxide (N(2)O). Microbial processes will ultimately restore balance to the nitrogen cycle, but the damage done by humans to the nitrogen economy of the planet will persist for decades, possibly centuries, if active intervention and careful management strategies are not initiated.
1,882 citations
TL;DR: Improved process understanding, building on the increased use of isotope tracing techniques and metagenomics, needs to go along with improvements in measurement techniques for N2O (and N2) emission in order to obtain robust field and laboratory datasets for different ecosystem types.
Abstract: Although it is well established that soils are the dominating source for atmospheric nitrous oxide (N2O), we are still struggling to fully understand the complexity of the underlying microbial production and consumption processes and the links to biotic (e.g. inter- and intraspecies competition, food webs, plant–microbe interaction) and abiotic (e.g. soil climate, physics and chemistry) factors. Recent work shows that a better understanding of the composition and diversity of the microbial community across a variety of soils in different climates and under different land use, as well as plant–microbe interactions in the rhizosphere, may provide a key to better understand the variability of N2O fluxes at the soil–atmosphere interface. Moreover, recent insights into the regulation of the reduction of N2O to dinitrogen (N2) have increased our understanding of N2O exchange. This improved process understanding, building on the increased use of isotope tracing techniques and metagenomics, needs to go along with improvements in measurement techniques for N2O (and N2) emission in order to obtain robust field and laboratory datasets for different ecosystem types. Advances in both fields are currently used to improve process descriptions in biogeochemical models, which may eventually be used not only to test our current process understanding from the microsite to the field level, but also used as tools for up-scaling emissions to landscapes and regions and to explore feedbacks of soil N2O emissions to changes in environmental conditions, land management and land use.
1,871 citations
TL;DR: This Review summarizes the current understanding of the microbial nitrogen-cycling network, including novel processes, their underlying biochemical pathways, the involved microorganisms, their environmental importance and industrial applications.
Abstract: Nitrogen is an essential component of all living organisms and the main nutrient limiting life on our planet By far, the largest inventory of freely accessible nitrogen is atmospheric dinitrogen, but most organisms rely on more bioavailable forms of nitrogen, such as ammonium and nitrate, for growth The availability of these substrates depends on diverse nitrogen-transforming reactions that are carried out by complex networks of metabolically versatile microorganisms In this Review, we summarize our current understanding of the microbial nitrogen-cycling network, including novel processes, their underlying biochemical pathways, the involved microorganisms, their environmental importance and industrial applications
1,794 citations
TL;DR: This review presents in depth discussions of all these classes of Cu enzymes and the correlations within and among these classes, as well as the present understanding of the enzymology, kinetics, geometric structures, electronic structures and the reaction mechanisms these have elucidated.
Abstract: Based on its generally accessible I/II redox couple and bioavailability, copper plays a wide variety of roles in nature that mostly involve electron transfer (ET), O2 binding, activation and reduction, NO2− and N2O reduction and substrate activation. Copper sites that perform ET are the mononuclear blue Cu site that has a highly covalent CuII-S(Cys) bond and the binuclear CuA site that has a Cu2S(Cys)2 core with a Cu-Cu bond that keeps the site delocalized (Cu(1.5)2) in its oxidized state. In contrast to inorganic Cu complexes, these metalloprotein sites transfer electrons rapidly often over long distances, as has been previously reviewed.1–4 Blue Cu and CuA sites will only be considered here in their relation to intramolecular ET in multi-center enzymes. The focus of this review is on the Cu enzymes (Figure 1). Many are involved in O2 activation and reduction, which has mostly been thought to involve at least two electrons to overcome spin forbiddenness and the low potential of the one electron reduction to superoxide (Figure 2).5,6 Since the Cu(III) redox state has not been observed in biology, this requires either more than one Cu center or one copper and an additional redox active organic cofactor. The latter is formed in a biogenesis reaction of a residue (Tyr) that is also Cu catalyzed in the first turnover of the protein. Recently, however, there have been a number of enzymes suggested to utilize one Cu to activate O2 by 1e− reduction to form a Cu(II)-O2•− intermediate (an innersphere redox process) and it is important to understand the active site requirements to drive this reaction. The oxidases that catalyze the 4e−reduction of O2 to H2O are unique in that they effectively perform this reaction in one step indicating that the free energy barrier for the second two-electron reduction of the peroxide product of the first two-electron step is very low. In nature this requires either a trinuclear Cu cluster (in the multicopper oxidases) or a Cu/Tyr/Heme Fe cluster (in the cytochrome oxidases). The former accomplishes this with almost no overpotential maximizing its ability to oxidize substrates and its utility in biofuel cells, while the latter class of enzymes uses the excess energy to pump protons for ATP synthesis. In bacterial denitrification, a mononuclear Cu center catalyzes the 1e- reduction of nitrite to NO while a unique µ4S2−Cu4 cluster catalyzes the reduction of N2O to N2 and H2O, a 2e− process yet requiring 4Cu’s. Finally there are now several classes of enzymes that utilize an oxidized Cu(II) center to activate a covalently bound substrate to react with O2.
Figure 1
Copper active sites in biology.
Figure 2
Latimer Diagram for Oxygen Reduction at pH = 7.0 Adapted from References 5 and 6.
This review presents in depth discussions of all these classes of Cu enzymes and the correlations within and among these classes. For each class we review our present understanding of the enzymology, kinetics, geometric structures, electronic structures and the reaction mechanisms these have elucidated. While the emphasis here is on the enzymology, model studies have significantly contributed to our understanding of O2 activation by a number of Cu enzymes and are included in appropriate subsections of this review. In general we will consider how the covalency of a Cu(II)–substrate bond can activate the substrate for its spin forbidden reaction with O2, how in binuclear Cu enzymes the exchange coupling between Cu’s overcomes the spin forbiddenness of O2 binding and controls electron transfer to O2 to direct catalysis either to perform two e− electrophilic aromatic substitution or 1e− H-atom abstraction, the type of oxygen intermediate that is required for H-atom abstraction from the strong C-H bond of methane (104 kcal/mol) and how the trinuclear Cu cluster and the Cu/Tyr/Heme Fe cluster achieve their very low barriers for the reductive cleavage of the O-O bond.
Much of the insight available into these mechanisms in Cu biochemistry has come from the application of a wide range of spectroscopies and the correlation of spectroscopic results to electronic structure calculations. Thus we start with a tutorial on the different spectroscopic methods utilized to study mononuclear and multinuclear Cu enzymes and their correlations to different levels of electronic structure calculations.
1,181 citations
TL;DR: Curbing nitrogen emissions is a central environmental challenge for the twenty-first century, argue Mark Sutton and his colleagues.
Abstract: Curbing nitrogen emissions is a central environmental challenge for the twenty-first century, argue Mark Sutton and his colleagues.
993 citations
References
More filters
01 Jan 2007
TL;DR: The first volume of the IPCC's Fourth Assessment Report as mentioned in this paper was published in 2007 and covers several topics including the extensive range of observations now available for the atmosphere and surface, changes in sea level, assesses the paleoclimatic perspective, climate change causes both natural and anthropogenic, and climate models for projections of global climate.
Abstract: This report is the first volume of the IPCC's Fourth Assessment Report. It covers several topics including the extensive range of observations now available for the atmosphere and surface, changes in sea level, assesses the paleoclimatic perspective, climate change causes both natural and anthropogenic, and climate models for projections of global climate.
32,826 citations
Book•
03 Oct 2000
TL;DR: IPCC Special Report on Emissions Scenarios as mentioned in this paper provides an overview of the scenario literature and the scenario driving forces, as well as a summary of the discussions and recommendations.
Abstract: IPCC Special Report on Emissions Scenarios Contents: Foreword Preface Summary for policymakers Technical Summary Chapter 1: Background and Overview Chapter 2: An Overview of the Scenario Literature Chapter 3: Scenario Driving Forces Chapter 4: An Overview of Scenarios Chapter 5: Emission Scenarios Chapter 6: Summary Discussions and Recommendations
3,304 citations
TL;DR: In this paper, the probable importance of NO and NO2 in controlling the ozone concentrations and production rates in the stratosphere is pointed out and some processes which may lead to production of nitric acid are discussed.
Abstract: The probable importance of NO and NO2 in controlling the ozone concentrations and production rates in the stratosphere is pointed out. Observations on and determinations of nitric acid concentrations in the stratosphere by Murcray et al. (1968) and Rhine et al. (1969) support the high NO and NO2 concentrations indicated by Bates/Hays (1967). Some processes which may lead to production of nitric acid are discussed. The importance of O (1S), possibly produced in the ozone photolysis below 2340 A, on the ozone photochemistry is mentioned.
1,452 citations
01 Jan 2007
TL;DR: In this paper, the authors present a collection of essays by Terry Barker, Igor Bashmakov, Lenny Bernstein, Jean Bogner, Peter Bosch, Rutu Dave, Ogunlade Davidson, Brian Fisher, Michael Grubb, Sujata Gupta, Kirsten Halsnaes, BertJan Heij, Boubacarraoui, Shigeki Kobayashi, Mark Levine, Daniel Martino, Omar Masera Cerutti, Bert Metz, Leo Meyer, Gert-Jan Nabuurs, Adil Najam
Abstract: Drafting authors: Terry Barker, Igor Bashmakov, Lenny Bernstein, Jean Bogner, Peter Bosch, Rutu Dave, Ogunlade Davidson, Brian Fisher, Michael Grubb, Sujata Gupta, Kirsten Halsnaes, BertJan Heij, Suzana Kahn Ribeiro, Shigeki Kobayashi, Mark Levine, Daniel Martino, Omar Masera Cerutti, Bert Metz, Leo Meyer, Gert-Jan Nabuurs, Adil Najam, Nebojsa Nakicenovic, Hans Holger Rogner, Joyashree Roy, Jayant Sathaye, Robert Schock, Priyaradshi Shukla, Ralph Sims, Pete Smith, Rob Swart, Dennis Tirpak, Diana Urge-Vorsatz, Zhou Dadi
1,409 citations