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1.
The global budget of N(2)O shows a significant imbalance between the known rate of destruction in the stratosphere and the estimated rates of natural and anthropogenic production in soils and the ocean. Measurements of the (15)N/(14)N and (18)O/(16)O ratios in two major tropospheric sources of N(2)O, tropical rain forest soils and fertilized soils, show that soil N(2)O from a tropical rain forest in Costa Rica and from sugar-cane fields in Maui is strongly depleted in both (15)N and (18)O relative to mean tropospheric N(2)O. A major source of heavy N(2)O, enriched in both (15)N and (18)O, must therefore be present to balance the light N(2)O from soils. One such source is the back-mixing flux of N(2)O from the stratosphere, which is enriched in (15)N and (18)O by photolysis and chemistry. However these return fluxes of (15)N and (18)O are so great that a large oceanic flux of N(2)O is required to balance the heavy isotope-enriched stratospheric flux. All these effects will be reflected in climatically related isotopic variations in trapped N(2)O in polar ice cores. 相似文献
2.
Nitrous oxide is a greenhouse gas that also plays a role in the cycling of stratospheric ozone. Air samples from the lower stratosphere exhibit 15N/14N and 18O/16O enrichment in nitrous oxide, which can be accounted for with a simple model describing an irreversible destruction process. The observed enrichments are quite large and incompatible with those determined for the main stratospheric nitrous oxide loss processes of photolysis and reaction with excited atomic oxygen. Thus, although no stratospheric source needs to be invoked, the data indicate that present understanding of stratospheric nitrous oxide chemistry is incomplete. 相似文献
3.
The ocean is an important global source of nitrous oxide (N(2)O), a greenhouse gas that contributes to stratospheric ozone destruction. Bacterial nitrification and denitrification are thought to be the primary sources of marine N(2)O, but the isotopic signatures of N(2)O produced by these processes are not consistent with the marine contribution to the global N(2)O budget. Based on enrichment cultures, we report that archaeal ammonia oxidation also produces N(2)O. Natural-abundance stable isotope measurements indicate that the produced N(2)O had bulk δ(15)N and δ(18)O values higher than observed for ammonia-oxidizing bacteria but similar to the δ(15)N and δ(18)O values attributed to the oceanic N(2)O source to the atmosphere. Our results suggest that ammonia-oxidizing archaea may be largely responsible for the oceanic N(2)O source. 相似文献
4.
氧化亚氮(N2O)是主要的温室气体之一,并且对平流层臭氧层分解起到重要作用。土壤中N2O的产生和排放过程复杂多样,对其进行精准溯源与过程区分有助于制定减排策略。稳定同位素自然丰度技术利用N2O的同位素值δ15Nbulk(N2O中15N在整体水平上的同位素特征值)、δ18O(N2O中18O在整体水平上的同位素特征值)以及δ15Nsp(N2O分子内15N的位点特异性同位素值),可以示踪N2O来源、指示N2O产生的微生物作用途径,在N2O转化过程溯源中已取得重要进展。而同位素分馏效应是稳定同位素自然丰度技术应用的理论基础,其中微生物过程及其导致的同位素分馏是需要重点关注的问题。本研究概述了同位素分馏效应在N2O的产生、排放过程中的研究进展及其主要影响因素,梳理了同位素特征值δ15Nbulk、δ18O和δ15Nsp在分析N2O来源的研究进展,并且提出了影响准确区分过程的因素。因素包括单一产生路径的同位素特征值范围广、不同产生路径的同位素特征值范围的重叠、反应底物同位素组成的变化以及与N2O还原相关的分馏因子的可变性等问题。明确了今后需加强δ15Nsp等N2O同位素特征值分馏效应的测定,利用组合同位素特征值及先进手段进行全面的N2O溯源研究。图2参80 相似文献
5.
Arpigny C Jehin E Manfroid J Hutsemékers D Schulz R Stüwe JA Zucconi JM Ilyin I 《Science (New York, N.Y.)》2003,301(5639):1522-1524
High-resolution spectra of the CN B2 summation operator +-X2 summation operator + (0,0) band at 390 nanometers yield isotopic ratios for comets C/1995 O1 (Hale-Bopp) and C/2000 WM1 (LINEAR) as follows: 165 +/- 40 and 115 +/- 20 for 12C/13C, 140 +/- 35 and 140 +/- 30 for 14N/15N. Our N isotopic measurements are lower than the terrestrial 14N/15N = 272 and the ratio for Hale-Bopp from measurements of HCN, the presumed parent species of CN. This isotopic anomaly suggests the existence of other parent(s) of CN, with an even lower N isotopic ratio. Organic compounds like those found in interplanetary dust particles are good candidates. 相似文献
6.
GI Gellene 《Science (New York, N.Y.)》1996,274(5291):1344-1346
Application of a theory of nuclear symmetry-based reaction restrictions to the O2 + O --> O3 reaction provides a potential explanation for the symmetry-induced isotopic enrichment observed for laboratory and atmospherically produced O3. Within this theory, the rate of formation of O3 from collisions of O and isotopically homonuclear O2 depends on whether the O2 molecule is in an f (allowed) or an e (restricted) parity label state. The restriction can be relaxed by various potential energy surface coupling terms, and the assumption that approximately 78 percent of the restricted O2(e) levels produce O3 with the same efficiency as the allowed O2(f) levels can account for laboratory-observed isotopic fractionation. In particular, the theory explains the special enhanced formation of the completely asymmetric isotopomer 16O17O18O. 相似文献
7.
Nitrous oxide in the earth's atmosphere contributes to catalytic stratospheric ozone destruction and is also a greenhouse gas component. A precise budgetary accounting of N(2)O sources has remained elusive, and there is an apparent lack of source identification. One source of N(2)O is as a by-product in the manufacture of nylon, specifically in the preparation of adipic acid. Characterization of the reaction N(2)O stoichiometry and its isotopic composition with a simulated industrial adipic acid synthesis indicates that because of high rates of global adipic acid production, this N(2)O may account for approximately 10 percent of the increase observed for atmospheric N(2)O. 相似文献
8.
Wiechert U Halliday AN Lee DC Snyder GA Taylor LA Rumble D 《Science (New York, N.Y.)》2001,294(5541):345-348
We have determined the abundances of 16O, 17O, and 18O in 31 lunar samples from Apollo missions 11, 12, 15, 16, and 17 using a high-precision laser fluorination technique. All oxygen isotope compositions plot within +/-0.016 per mil (2 standard deviations) on a single mass-dependent fractionation line that is identical to the terrestrial fractionation line within uncertainties. This observation is consistent with the Giant Impact model, provided that the proto-Earth and the smaller impactor planet (named Theia) formed from an identical mix of components. The similarity between the proto-Earth and Theia is consistent with formation at about the same heliocentric distance. The three oxygen isotopes (delta17O) provide no evidence that isotopic heterogeneity on the Moon was created by lunar impacts. 相似文献
9.
本研究优化了采用反硝化细菌法同时测定土壤浸提液中硝酸盐氮氧同位素组成的方法。在已有研究结果的基础上,通过采用5000~8000 r·min-1的转速离心、高纯氮气吹扫1 h、减少加样量及改造仪器自动进样器等措施对已发表方法进行了优化。对国际标准样品USGS34的分析表明,0.1~0.8μg NO-3-N样品量即可以得到较稳定、准确的测定值和校正值;同一时间内制备的硝酸盐δ15N的SD介于0.05‰~0.09‰之间,δ18O的SD介于0.28‰~0.48‰之间;在三个月之内δ15N和δ18O的测定值基本一致,表明该方法具有较好的准确度、精密度和稳定性。通过研究浸提剂、保存条件以及加热对测定土壤浸提液中硝酸盐氮氧同位素组成的影响,结果表明:常用的去离子水、KCl、Ca Cl2可能都含有微量的硝酸盐,随着加样量增大,浸提剂中含有的硝酸盐可能就会影响δ15N和δ18O的测定;对于土壤硝酸盐的浸提液,冷冻保存效果较好,保证了土壤硝酸盐氮氧同位素的准确性和稳定性;尽管加热对硝酸盐标准样品USGS34和IAEA-NO3的δ15N没有显著影响,但δ18O显著升高,说明加热易引起氧同位素分馏;而土壤硝酸盐浸提液样品加热前后的δ15N和δ18O的测定值没有显著变化,因此为避免产生氧同位素分馏和节省测试时间,建议同时测定土壤浸提液硝酸盐δ15N和δ18O时直接和反硝化细菌反应。应用本方法对不同肥料处理田间土壤浸提液硝酸盐的氮氧同位素组成进行了测定。 相似文献
10.
Atmospheric gases trapped in polar ice at the firn to ice transition layer are enriched in heavy isotopes (nitrogen-15 and oxygen-18) and in heavy gases (O(2)/N(2) and Ar/N(2) ratios) relative to the free atmosphere. The maximum enrichments observed follow patterns predicted for gravitational equilibrium at the base of the firn layer, as calculated from the depth to the transition layer and the temperature in the firn. Gas ratios exhibit both positive and negative enrichments relative to air: the negative enrichments of heavy gases are consistent with observed artifacts of vacuum stripping of gases from fractured ice and with the relative values of molecular diameters that govern capillary transport. These two models for isotopic and elemental fractionation provide a basis for understanding the initial enrichments of carbon-13 and oxygen-18 in trapped CO(2), CH(4), and O(2) in ice cores, which must be known in order to decipher ancient atmospheric isotopic ratios. 相似文献
11.
Experimental evidence is presented which demonstrates a chemically produced, mass-independent isotopic fractionation of oxygen. The effect is thought to result from self-shielding by the major isotopic species (16)O(2), but other possible mechanisms such as molecular symmetry cannot be ruled out. In a three-isotope plot, the experimentally produced fractionation line is essentially equal in slope to the observed carbonaceous chondrite mixing line. The implications for the early history of the solar system are discussed. 相似文献
12.
Nitrogen-15: microbiological alteration of abundance 总被引：4，自引：0，他引：4
The abundance of N(15) relative to N(14) is significantly altered during experiments in vitro in which nitrate and nitrite are microbiologically reduced to nitrogen gas. In all studies to date, N(14)O(3)-and N(14)O(2)-species have been preferentially reduced. This selectivity has a complex dependence on conditions in the medium. The results are not only relevant to natural variations in N(15) relative to N(14) but should be seriously considered during N(15) tracer studies in soils. 相似文献
13.
Molina MJ Zhang R Wooldridge PJ McMahon JR Kim JE Chang HY Beyer KD 《Science (New York, N.Y.)》1993,261(5127):1418-1423
Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO(3) hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H(2)SO(4)/H(2)O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO(3) vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO(3) and H(2)O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H(2)SO(4) solutions and on solid H(2)SO(4) hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles. 相似文献
14.
Miller RL Suits AG Houston PL Toumi R Mack JA Wodtke AM 《Science (New York, N.Y.)》1994,265(5180):1831-1838
Highly vibrationally excited O(2)(X(3)sigmag(-), v >/= 26) has been observed from the photodissociation of ozone (O(3)), and the quantum yield for this reaction has been determined for excitation at 226 nanometers. This observation may help to address the "ozone deficit" problem, or why the previously predicted stratospheric O(3) concentration is less than that observed. Recent kinetic studies have suggested that O(2)(X(3)sigmag(-), v >/= 26) can react rapidly with O(2) to form O(3) + O and have led to speculation that, if produced in the photodissociation of O(3), this species might be involved in resolving the discrepancy. The sequence O(3) + hv --> O(2)(X(3)sigmag(-), v >/= 26) + O; O(2)(X(3)sigmag(-), v >/= 26) + O(2) --> O(3) + O (where hv is a photon) would be an autocatalytic mechanism for production of odd oxygen. A two-dimensional atmospheric model has been used to evaluate the importance of this new mechanism. The new mechanism can completely account for the tropical O(3) deficit at an altitude of 43 kilometers, but it does not completely account for the deficit at higher altitudes. The mechanism also provides for isotopic fractionation and may contribute to an explanation for the anomalously high concentration of heavy O(3) in the stratosphere. 相似文献
15.
Mount GH Solomon S Sanders RW Jakoubek RO Schmeltekopf AL 《Science (New York, N.Y.)》1988,242(4878):555-558
Scattered sunlight and direct light from the moon was used in two wavelength ranges to measure the total column abundances of stratospheric ozone(O(3)) and nitrogen dioxide (NO(2)) at Thule, Greenland (76.5 degrees N), during the period from 29 January to 16 February 1988. The observed O(3) column varied between about 325 and 400 Dobson units, and the lower values were observed when the center of the Arctic polar vortex was closest to Thule. This gradient probably indicates that O(3) levels decrease due to dynamical processes near the center of the Arctic vortex and should be considered in attempts to derive trends in O(3) levels. The observed NO(2) levels were also lowest in the center of the Arctic vortex and were sometimes as low as 5 x 10(14) molecules per square centimeter, which is even less than comparable values measured during Antarctic spring, suggesting that significant heterogeneous photochemistry takes place during the Arctic winter as it does in the Antarctic. 相似文献
16.
Marty B Chaussidon M Wiens RC Jurewicz AJ Burnett DS 《Science (New York, N.Y.)》2011,332(6037):1533-1536
The Genesis mission sampled solar wind ions to document the elemental and isotopic compositions of the Sun and, by inference, of the protosolar nebula. Nitrogen was a key target element because the extent and origin of its isotopic variations in solar system materials remain unknown. Isotopic analysis of a Genesis Solar Wind Concentrator target material shows that implanted solar wind nitrogen has a (15)N/(14)N ratio of 2.18 ± 0.02 × 10(-3) (that is, ≈40% poorer in (15)N relative to terrestrial atmosphere). The (15)N/(14)N ratio of the protosolar nebula was 2.27 ± 0.03 × 10(-3), which is the lowest (15)N/(14)N ratio known for solar system objects. This result demonstrates the extreme nitrogen isotopic heterogeneity of the nascent solar system and accounts for the (15)N-depleted components observed in solar system reservoirs. 相似文献
17.
Demore WB 《Science (New York, N.Y.)》1973,180(4087):735-737
Chain decomposition of ozone by hydroxyl and hydroperoxyl radicals has been observed. The rate constant at 3000 degrees K for OH + O(3)-->HO(2) + O(2) is 8 x 10(-14) cubic centimeters per second. The rate constant for HO(2) + O(3)--> OH + 2O(2), is 3 x 10(-15) cubic centimeters per second. These results have implications concerning stratospheric ozone. 相似文献
18.
Laboratory studies show that the reaction of short-lived O2(B3Sigmau) molecules (lifetime approximately 10 picoseconds) with N2 and the photodissociation of the N2:O2 dimer produce NOx in the stratosphere at a rate comparable to the oxidation of N2O by O(1D). This finding implies the existence of unidentified NOX sinks in the stratosphere. The NO2 observed in this experiment is isotopically heavy with a large 15N/14N enhancement. However, photodissociation of this NO2 unexpectedly produced NO molecules with a low 15N/14N ratio. The diurnal odd-nitrogen cycle in the stratosphere will be marked by a complex isotope signature that will be imprinted on the halogen and HOX catalytic cycles. 相似文献
19.
MJ Prather 《Science (New York, N.Y.)》1998,279(5355):1339-1341
Nitrous oxide (N2O) is one of the top three greenhouse gases whose emissions may be brought under control through the Framework Convention on Climate Change. Current understanding of its global budget, including the balance of natural and anthropogenic sources, is largely based on the atmospheric losses calculated with chemical models. A representative one-dimensional model used here describes the photochemical coupling between N2O and stratospheric ozone (O3), which can easily be decomposed into its natural modes. The primary, longest lived mode describes most of the atmospheric perturbation due to anthropogenic N2O sources, and this pattern may be observable. The photolytic link between O3 and N2O is identified as the mechanism causing this mode to decay 10 to 15 percent more rapidly than the N2O mean atmospheric lifetime, affecting the inference of anthropogenic sources. 相似文献
20.
KA Boering SC Wofsy BC Daube HR Schneider M Loewenstein JR Podolske TJ Conway 《Science (New York, N.Y.)》1996,274(5291):1340-1343
Measurements of stratospheric carbon dioxide (CO2) and nitrous oxide (N2O) concentrations were analyzed to investigate stratospheric transport rates. Temporal variations in tropospheric CO2 were observed to propagate into the stratosphere, showing that tropospheric air enters the lower tropical stratosphere continuously, ascends, and is transported rapidly (in less than 1 month) to both hemispheres. The mean age A of stratospheric air determined from CO2 data is approximately 5 years in the mid-stratosphere. The mean age is mathematically equivalent to a conserved tracer analogous to exhaust from stratospheric aircraft. Comparison of values for A from models and observations indicates that current model simulations likely underestimate pollutant concentrations from proposed stratospheric aircraft by 25 to 100 percent. 相似文献