In situ stratospheric measurements of CH4, (C-13)H4, N2O, and OC(O-18) using the BLISS tunable diode laser spectrometer

NASA Technical Reports Server (NTRS)

Webster, Christopher R.; May, Randy D.

1992-01-01

Simultaneous in situ measurements of stratospheric CH4, (C-13)H4, N2O, OC(O-18), pressure, and temperature have been made from Palestine, Texas (32 deg N) in September 1988 with the JPL Balloon-borne Laser In Situ Sensor. Measurements of CH4 and N2O in the altitude range 30-35 km agree well with other measurements, except for an anomalously high value for the N2O at 31 km. Measurements of CH4 support earlier observations of fold in the vertical profile. A ratio for stratospheric (C-13)H4/CH4 of 0.0105 +/- 0.0010 implies an enrichment of delta(C-13) = -45 +/- 92 parts per thousand over the PDB value, in agreement with previous measurements in the troposphere. A large mixing ratio of 1.9 +/- 0.2 ppmv for OC(O-18) is measured, corresponding to an enrichment of delta(O-18) = 280 +/- 50 parts per thousand for the (O-18) isotopic species over the SMOW value.

Greenhouse gas budget (CO2, CH4 and N2O) of intensively managed grassland following restoration.

PubMed

Merbold, Lutz; Eugster, Werner; Stieger, Jacqueline; Zahniser, Mark; Nelson, David; Buchmann, Nina

2014-06-01

The first full greenhouse gas (GHG) flux budget of an intensively managed grassland in Switzerland (Chamau) is presented. The three major trace gases, carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) were measured with the eddy covariance (EC) technique. For CO2 concentrations, an open-path infrared gas analyzer was used, while N2O and CH4 concentrations were measured with a recently developed continuous-wave quantum cascade laser absorption spectrometer (QCLAS). We investigated the magnitude of these trace gas emissions after grassland restoration, including ploughing, harrowing, sowing, and fertilization with inorganic and organic fertilizers in 2012. Large peaks of N2O fluxes (20-50 nmol m(-2) s(-1) compared with a <5 nmol m(-2) s(-1) background) were observed during thawing of the soil after the winter period and after mineral fertilizer application followed by re-sowing in the beginning of the summer season. Nitrous oxide (N2O) fluxes were controlled by nitrogen input, plant productivity, soil water content and temperature. Management activities led to increased variations of N2O fluxes up to 14 days after the management event as compared with background fluxes measured during periods without management (<5 nmol m(-2) s(-1)). Fluxes of CO2 remained small until full plant development in early summer 2012. In contrast, methane emissions showed only minor variations over time. The annual GHG flux budget was dominated by N2O (48% contribution) and CO2 emissions (44%). CH4 flux contribution to the annual budget was only minor (8%). We conclude that recently developed multi-species QCLAS in an EC system open new opportunities to determine the temporal variation of N2O and CH4 fluxes, which further allow to quantify annual emissions. With respect to grassland restoration, our study emphasizes the key role of N2O and CO2 losses after ploughing, changing a permanent grassland from a carbon sink to a significant carbon source. © 2014 John Wiley & Sons Ltd.

Infrared spectroscopy of solid normal hydrogen doped with CH3F and O2 at 4.2 K: CH3F:O2 complex and CH3F migration

NASA Astrophysics Data System (ADS)

Abouaf-Marguin, L.; Vasserot, A.-M.

2011-04-01

Double doping of solid normal hydrogen with CH3F and O2 at about 4.2 K gives evidence of (ortho-H2)n:CH3F clusters and of O2:CH3F complex formation. FTIR analysis of the time evolution of the spectra in the region of the v3 C-F stretching mode indicates that these clusters behave very differently from (ortho-H2)n:H2O clusters. The main point is the observed migration of CH3F molecules in solid para-H2 at 4.2 K which differs from that of H2O under identical experimental conditions. This is confirmed by an increase over time of the integrated intensity of the CH3F:O2 complex with a rate constant K = 2.7(2) . 10-4 s-1.

The Regulation of CH4 and N2O fluxes by Wetlands at Landscape Level

NASA Astrophysics Data System (ADS)

Soosaar, K.; Maddison, M.; Salm, J. O.; Järveoja, J.; Hansen, R.; Mander, Ü.

2012-04-01

The world's wetlands, despite being only about 5% of the terrestrial landscape, are currently significant net sinks of more than 1 Pg yr-1 of carbon (Mitsch et al 2012). At landscape level wetlands and riparian zones are important regulators of nutrient transport (Zedler 2003). However, they can be also significant hot spots of greenhouse gas (GHG) emissions (Teiter&Mander 2005). Swedish experience shows that the nationally planned wetland creation (12,000 ha) could make a significant contribution to the targeted reduction of N fluxes (up to 27% of the Swedish environmental objective), at an environmental risk equalling 0.04% of the national anthropogenic GHG emission (Thiere et al 2011). Only few studies consider the potential GHG emission throughout both natural and created wetlands. The main objective of this study was to clarify the potential of various wetland ecosystem and riparian zones of northern rural landscapes in regulation of GHG emissions. Monthly-based measurements of GHG emissions using closed chamber method were performed from October 2007 to October 2011 in 47 study sites in Estonia. The study sites cover various wetlands and riparian forests as well as reference areas on automorphic soils. In general, wetlands' drainage was the most significant disturbance factor influencing GHG fluxes, causing significant increase of N2O emission as well as decreasing CH4 emission. However, we also observed significantly high CH4 flux from drained peatlands. In most of the soils with ground/soil water levels deeper than 30 cm from the surface, a significant decrease of CH4 fluxes were detected. The highest CH4 emissions (up to 5060 kg CH4-C ha-1 yr-1) were detected from drained fen grasslands. In the case of N2O, no clear differences were found between colder and warmer periods. Relatively higher N2O fluxes were measured from the drained fen grassland, the fertilized arable land, the riparian forest on automorphic soil, and the drained transition fen forest

Stratospheric N2O5, CH4, and N2O profiles from IR solar occultation spectra

NASA Technical Reports Server (NTRS)

Camy-Peyret, C.; Flaud, J.-M.; Perrin, A.; Rinsland, C. P.; Goldman, A.; Murcray, F. J.

1993-01-01

Stratospheric volume mixing ratio profiles of N2O5, CH4, and N2O have been retrieved from a set of 0.052/cm resolution (FWHM) solar occultation spectra recorded at sunrise during a balloon flight from Aire sur l'Adour, France (44 N latitude) on 12 October 1990. The N2O5 results have been derived from measurements of the integrated absorption by the 1246/cm band. Assuming a total intensity of 4.32 x 10 exp -17 cm/molecule/sq cm independent of temperature, the retrieved N2O5 volume mixing ratios in ppbv, interpolated to 2 km height spacings, are 1.64 +/- 0.49 at 37.5 km, 1.92 +/- 0.56 at 35.5 km, 2.06 +/- 0.47 at 33.5 km, 1.95 +/- 0.42 at 31.5 km, 1.60 +/- 0.33 at 29.5 km, 1.26 +/- 0.28 at 27.5 km, and 0.85 +/- 0.20 at 25.5 km. Error bars indicate the estimated 1-sigma uncertainty including the error in the total band intensity. The retrieved profiles are compared with previous measurements and photochemical model results.

[Emission of CH4, N2O and NH3 from vegetable field applied with animal manure composts].

PubMed

Wan, He-Feng; Zhao, Chen-Yang; Zhong, Jia; Ge, Zhen; Wei, Yuan-Song; Zheng, Jia-Xi; Wu, Yu-Long; Han, Sheng-Hui; Zheng, Bo-Fu; Li, Hong-Mei

2014-03-01

Greenhouse gas (GHG) emission from vegetable land is of great concern recently because agriculture land is one of the major sources contributing to global GHG emission. In this study, an experiment of Lactuca sativa L. land applied with different animal manure composts was carried out in a greenhouse vegetable land located in the surburb of Beijing to monitor the emission of GHG (CH4 and N2O) and ammonia in situ, and to analyze the affecting factors of GHG and ammonia emission. Results showed that the emission factors (EFs) of CH4 from Treatment NRM, RM and CF were 0.2%, 0.027% and 0.004%, respectively,the EFs of N2O from these three treatments were 0.18%, 0.63% and 0.74%, respectively, and the EFs of ammonia were 2.00%, 3.98% and 2.53%, respectively. CH4 emission flux was significantly affected by soil temperature and humidity, while N2O emission flux was related to soil temperature, surface temperature and humidity. The emission fluxes of CH4, N2O and NH3 were significantly affected by soil moisture, but there was little relation between CH4, N2O and NH3 emissions and the ambient temperature in the greenhouse.

Subtask 1.22 - Microbial Cycling of CH4, CO2, and N2O in a Wetlands Environment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dingyi Ye; Bethany Kurz; Marc Kurz

Soil microbial metabolic activities play an important role in determining CO{sub 2}, CH{sub 4}, and N{sub 2}O fluxes from terrestrial ecosystems. To verify and evaluate CO{sub 2} sequestration potential by wetland restoration in the Prairie Pothole Region (PPR), as well as to address concern over restoration effects on CH{sub 4} and N{sub 2}O emissions, laboratory and in situ microcosm studies on microbial cycling of CO{sub 2}, CH{sub 4}, and N{sub 2}O were initiated. In addition, to evaluate the feasibility of the use of remote sensing to detect soil gas flux from wetlands, a remote-sensing investigation was also conducted. Results ofmore » the laboratory microcosm study unequivocally proved that restoration of PPR wetlands does sequester atmospheric CO{sub 2}. Under the experimental conditions, the simulated restored wetlands did not promote neither N{sub 2}O nor CH{sub 4} fluxes. Application of ammonia enhanced both N{sub 2}O and CH{sub 4} emission, indicating that restoration of PPR wetlands may reduce both N{sub 2}O and CH{sub 4} emission by cutting N-fertilizer input. Enhancement of CO{sub 2} emission by the N-fertilizer was observed, and this observation revealed an overlooked fact that application of N-fertilizer may potentially increase CO{sub 2} emission. In addition, the CO{sub 2} results also demonstrate that wetland restoration sequesters atmospheric carbon not only by turning soil conditions from aerobic to anoxic, but also by cutting N-fertilizer input that may enhance CO{sub 2} flux. The investigation on microbial community structure and population dynamics showed that under the experimental conditions restoration of the PPR wetlands would not dramatically increase population sizes of those microorganisms that produce N{sub 2}O and CH{sub 4}. Results of the in situ study proved that restoration of the PPR wetland significantly reduced CO{sub 2} flux. Ammonia enhanced the greenhouse gas emission and linearly correlated to the CO{sub 2} flux within

Long-term measurements of atmospheric trace gases (CO2, CH4, N2O, SF6, CO, H2), O2, and δ13CH4 isotopes at Weybourne Atmospheric Observatory, UK: past, present and future

NASA Astrophysics Data System (ADS)

Manning, Andrew C.; Forster, Grant L.; Oram, David E.; Reeves, Claire E.; Pickers, Penelope A.; Barningham, S. Thomas; Sturges, William T.; Bandy, Brian; Nisbet, Euan G.; Lowry, David; Fisher, Rebecca; Fleming, Zoe

2016-04-01

The Weybourne Atmospheric Observatory (WAO) is situated on the north Norfolk Coast (52.95°N, 1.13°E) in the United Kingdom and is run by the University of East Anglia (UEA), with support from the UK National Centre for Atmospheric Science (NCAS). In 2016, the WAO became a UK-ICOS (Integrated Carbon Observing System) monitoring station. Since 2008, we have been collecting high-precision long-term in situ measurements of atmospheric carbon dioxide (CO2), oxygen (O2), carbon monoxide (CO) and molecular hydrogen (H2), as well as regular bag sampling for δ13CH4. In early 2013, the measurement of atmospheric methane (CH4) commenced, and nitrous oxide (N2O) and sulphur hexafluoride (SF6) began in 2014. We summarise the CO2, O2, CH4, N2O, SF6, CO, H2 and δ13CH4 measurements made to date and highlight some key features observed (e.g. seasonal cycles, long-term trends, pollution events and deposition events). We summarise how the long-term measurements fit into other broader projects which have helped to support the long term time-series at WAO over the years, and highlight how we contribute to broader global atmospheric observation networks.

Stratospheric N2O5, CH4, and N2O Profiles from IR Solar Occultation Spectra

NASA Technical Reports Server (NTRS)

Peyeret, C. Camy; Flaud, J.-M.; Perrin, A.; Rinsland, C. P.; Goldman, A.; Murcray, F. J.

1993-01-01

Stratospheric volume mixing ratio profiles of N2O5, CH4, and N2O have been retrieved from a set of 0.052/ cm resolution (FWHM) solar occultation spectra recorded at sunrise during a balloon flight from Aire sur I'Adour, France (44 deg N latitude) on 12 October 1990. The N2O5 results have been derived from measurements of the integrated absorption by the 1246/ cm band. Assuming a total intensity of 4.32 x 10(exp 17)cm(exp -1) molecule sq cm(exp -2) independent of temperature, the retrieved N2O5 volume mixing ratios in ppbv (parts per billion by volume, 10(exp -9)), interpolated to 2 km height spacings, are 1.64 +/- 0.49 at 37.5 km, 1.92 +/- 0.56 at 35.5 km, 2.06 +/- 0.47 at 33.5 km, 1.95 +/- 0.42 at 31.5 km, 1.60 +/- 0.33 at 29.5 km, 1.26 +/- 0.28 at 27.5 km, and 0.85 +/- 0.20 at 25.5 km. Error bars indicate the estimated I-sigma uncertainty including the error in the total band intensity (+/- 20% has been assumed). The retrieved profiles are compared with previous measurements and photochemical model results.

N2O and CH4 emissions from N-fertilized rice paddy soil can be mitigated by wood vinegar application at an appropriate rate

NASA Astrophysics Data System (ADS)

Sun, Haijun; Feng, Yanfang; Ji, Yang; Shi, Weiming; Yang, Linzhang; Xing, Baoshan

2018-07-01

To understand the impacts of wood vinegar (WV), a by-product of biochar production, on N2O and CH4 emissions and their total global warming potential (GWPt) from N-fertilized rice paddy soil, a soil column experiment was conducted using three treatments: 240 kg urea-N ha-1 accompanied with 0, 5, and 10 t WV ha-1, respectively. Results showed that N2O and CH4 emission flux patterns were dominated by water regime of rice growth cycle, which was independent with WV application. The total N2O, CH4 emission loads and GWPt over rice season of three N received treatments were 6.41-8.85 kg ha-1, 127.7-405.0 kg ha-1, and 5.24-12.03 t CO2-e ha-1, respectively. Rice seasonal N2O and CH4 emissions were synchronously mitigated by 22.4% and 36.4%, respectively, when WV was applied at 5 t ha-1. Consequently, 5 t ha-1 WV treatment reduced 31.5% of GWPt compared with the urea treatment. In addition, 10 t ha-1 WV treatment exerted a more positive effect on suppressing N2O with 27.6% reduction. However, it increased GWPt by 57.2% because its CH4 emission load was increased by 101.8%. In conclusion, WV amendment applied at an appropriate rate (5 t ha-1) or combination with other CH4 control technologies were suggested to reduce both N2O and CH4 emissions and thereby the GWPt in N-fertilized rice paddy soil.

Annual Greenhouse Gas (CO2, CH4, and N2O) Fluxes Via Ebullition from a Temperate Emergent Wetland

NASA Astrophysics Data System (ADS)

Mcnicol, G.; Sturtevant, C. S.; Knox, S. H.; Baldocchi, D. D.; Silver, W. L.

2014-12-01

Quantifying wetland greenhouse gas exchange is necessary to evaluate their potential for mitigating climate change via carbon sequestration. However measuring greenhouse gas fluxes of carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) in wetlands is difficult due to high spatial and temporal variability, and multiple transport pathways of emission. Transport of biogenic soil gas via highly sporadic ebullition (bubbling) events is often ignored or quantified poorly in wetland greenhouse gas budgets, but can rapidly release large volumes of gas to the atmosphere. To quantify a robust annual ebullition flux we measured rates continuously for a year (2013-2014) using custom-built chambers deployed in a restored emergent wetland located in the Sacramento-San Joaquin Delta, CA. We combined ebullition flux rates with observations of gas concentrations to estimate annual ebullition emissions of CO2, CH4, and N2O and compare flux rates to whole-ecosystem exchange of CO2 and CH4 measured simultaneously by eddy covariance.Mean ebullition flux rates were 18.3 ± 5.6 L m-2 yr-1. Ebullition CH4 concentrations were very high and ranged from 23-76 % with a mean of 47 ± 2.9 %; CO2 concentrations were lower and ranged from 0.7-6.6 % with a mean of 2.8 ± 0.3 %; N2O concentrations were below atmospheric concentrations and ranged from 130-389 ppb(v) with a mean of 257 ± 13 ppb(v). We calculated well-constrained annual ebullition fluxes of: 6.2 ± 1.9 g CH4 m-2 yr-1, 1.0 ± 0.3 g CO2 m-2 yr-1 and 9.3 ± 2.8 mg N2O m-2 yr-1. Methane emissions via ebullition were very large, representing 15-25 % of total wetland CH4 emissions measured at this site, whereas ebullition released only relatively small quantities of CO2 and N2O. Our results demonstrate that large releases of CH4 via ebullition from open water surfaces can be a significant component of restored wetland greenhouse gas budgets.

Simulated nitrogen deposition reduces CH4 uptake and increases N2O emission from a subtropical plantation forest soil in southern China.

PubMed

Wang, Yongsheng; Cheng, Shulan; Fang, Huajun; Yu, Guirui; Xu, Minjie; Dang, Xusheng; Li, Linsen; Wang, Lei

2014-01-01

To date, few studies are conducted to quantify the effects of reduced ammonium (NH4+) and oxidized nitrate (NO3-) on soil CH4 uptake and N2O emission in the subtropical forests. In this study, NH4Cl and NaNO3 fertilizers were applied at three rates: 0, 40 and 120 kg N ha(-1) yr(-1). Soil CH4 and N2O fluxes were determined twice a week using the static chamber technique and gas chromatography. Soil temperature and moisture were simultaneously measured. Soil dissolved N concentration in 0-20 cm depth was measured weekly to examine the regulation to soil CH4 and N2O fluxes. Our results showed that one year of N addition did not affect soil temperature, soil moisture, soil total dissolved N (TDN) and NH4+-N concentrations, but high levels of applied NH4Cl and NaNO3 fertilizers significantly increased soil NO3(-)-N concentration by 124% and 157%, respectively. Nitrogen addition tended to inhibit soil CH4 uptake, but significantly promoted soil N2O emission by 403% to 762%. Furthermore, NH4+-N fertilizer application had a stronger inhibition to soil CH4 uptake and a stronger promotion to soil N2O emission than NO3(-)-N application. Also, both soil CH4 and N2O fluxes were driven by soil temperature and moisture, but soil inorganic N availability was a key integrator of soil CH4 uptake and N2O emission. These results suggest that the subtropical plantation soil sensitively responses to atmospheric N deposition, and inorganic N rather than organic N is the regulator to soil CH4 uptake and N2O emission.

Integrated measurements and modeling of CO2, CH4, and N2O fluxes using soil microsite frequency distributions

NASA Astrophysics Data System (ADS)

Davidson, Eric; Sihi, Debjani; Savage, Kathleen

2017-04-01

Soil fluxes of greenhouse gases (GHGs) play a significant role as biotic feedbacks to climate change. Production and consumption of carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) are affected by complex interactions of temperature, moisture, and substrate supply, which are further complicated by spatial heterogeneity of the soil matrix. Models of belowground processes of these GHGs should be internally consistent with respect to the biophysical processes of gaseous production, consumption, and transport within the soil, including the contrasting effects of oxygen (O2) as either substrate or inhibitor. We installed automated chambers to simultaneously measure soil fluxes of CO2 (using LiCor-IRGA), CH4, and N2O (using Aerodyne quantum cascade laser) along soil moisture gradients at the Howland Forest in Maine, USA. Measured fluxes of these GHGs were used to develop and validate a merged model. While originally intended for aerobic respiration, the core structure of the Dual Arrhenius and Michaelis-Menten (DAMM) model was modified by adding M-M and Arrhenius functions for each GHG production and consumption process, and then using the same diffusion functions for each GHG and for O2. The area under a soil chamber was partitioned according to a log-normal probability distribution function, where only a small fraction of microsites had high available-C. The probability distribution of soil C leads to a simulated distribution of heterotrophic respiration, which translates to a distribution of O2 consumption among microsites. Linking microsite consumption of O2 with a diffusion model generates microsite concentrations of O2, which then determine the distribution of microsite production and consumption of CH4 and N2O, and subsequently their microsite concentrations using the same diffusion function. At many moisture values, there are some microsites of production and some of consumption for each gas, and the resulting simulated microsite concentrations of CH4

Biogenic CH4 and N2O emissions overwhelm land CO2 sink in Asia: Toward a full GHG budget

NASA Astrophysics Data System (ADS)

Tian, H.

2017-12-01

The recent global assessment indicates the terrestrial biosphere as a net source of greenhouse gases to the atmosphere (Tian et al Nature 2016). The fluxes of greenhouse gases (GHG) vary by region. Both TD and BU approaches indicate that human-caused biogenic fluxes of CO2, CH4 and N2O in the biosphere of Southern Asia led to a large net climate warming effect, because the 100-year cumulative effects of CH4 and N2O emissions together exceed that of the terrestrial CO2 sink. Southern Asia has about 90% of the global rice fields and represents more than 60% of the world's nitrogen fertilizer consumption, with 64%-81% of CH4 emissions and 36%-52% of N2O emissions derived from the agriculture and waste sectors. Given the large footprint of agriculture in Southern Asia, improved fertilizer use efficiency, rice management and animal diets could substantially reduce global agricultural N2O and CH4 emissions. This study highlights the importance of including all three major GHGs in regional climate impact assessments, mitigation option and climate policy development.

Automated CO2, CH4 and N2O Fluxes from Tree Stems and Soils: Magnitudes, Temporal Patterns and Drivers

NASA Astrophysics Data System (ADS)

Barba, J.; Poyatos, R.; Vargas, R.

2017-12-01

The emissions of the main greenhouse gases (GHG; CO2, CH4 and N2O) through tree stems are still an uncertain component of the total GHG balance of forests. Despite that stem CO2 emissions have been studied for several decades, it is still unclear the drivers and spatiotemporal patterns of CH4 and N2O stem emissions. Additionally, it is unknown how stem emissions could be related to soil physiological processes or environmental conditions. We measured CO2, CH4 and N2O emissions hourly from April to July 2017 at two different heights (75 [LStem] and 150cm [HStem]) of bitternut hickory (Carya cordiformis) trees and adjacent soil locations in a forested area in the Mid Atlantic of the USA. We designed an automated system to continuously measure the three greenhouse gases (GHG) in stems and soils. Stem and soil CO2 emissions showed similar seasonal patterns with an average of 6.56±0.09 (soil), 3.72±0.05 (LStem) and 2.47±0.04 µmols m-2 s-1 (HStem) (mean±95% CI). Soil temperature controlled CO2 fluxes at both daily and seasonal scales (R2>0.5 for all cases), but there was no clear effect of soil moisture. The stems were a clear CH4 source with emissions decreasing with height (0.35±0.02 and 0.25±0.01 nmols m-2 s-1 for LStem and HStem, respectively) with no apparent seasonal pattern, and no clear relationship with environmental drivers (e.g., temperature, moisture). In contrast, soil was a CH4 sink throughout the experiment (-0.55±0.02 nmols m-2 s-1) and its seasonal pattern responded to moisture changes. Despite soil and stem N2O emissions did not show a seasonal pattern or apparent dependency on temperature or moisture, they showed net N2O emissions with a decrease in emissions with stem height (0.29±0.05 for soil, 0.38±0.06 for LStem and 0.28±0.05 nmols m-2 s-1 for HStem). The three GHG emissions decreased with stem height at similar rates (33%, 28% and 27% for CO2, CH4 and N2O, respectively). These results suggest that the gases were not produced in the stem

CO 2 uptake is offset by CH 4 and N 2O emissions in a poplar short-rotation coppice

DOE PAGES

Zenone, Terenzio; Zona, Donatella; Gelfand, Ilya; ...

2015-04-18

The need for renewable energy sources will lead to a considerable expansion in the planting of dedicated fast-growing biomass crops across Europe. These are commonly cultivated as short-rotation coppice (SRC), and currently poplar ( Populus spp.) is the most widely planted. In this study, we report the greenhouse gas (GHG) fluxes of carbon dioxide (CO 2), methane (CH 4) and nitrous oxide (N 2O) measured using eddy covariance technique in an SRC plantation for bioenergy production. Measurements were made during the period 2010–2013, that is, during the first two rotations of the SRC. The overall GHG balance of the 4more » years of the study was an emission of 1.90 (±1.37) Mg CO 2eq ha -1; this indicated that soil trace gas emissions offset the CO 2 uptake by the plantation. CH 4 and N 2O contributed almost equally to offset the CO 2 uptake of -5.28 (±0.67) Mg CO2eq ha -1 with an overall emission of 3.56 (±0.35) Mg CO 2eq ha -1 of N 2O and of 3.53 (±0.85) Mg CO 2eq ha-1 of CH 4. N 2O emissions mostly occurred during one single peak a few months after the site was converted to SRC; this peak comprised 44% of the total N 2O loss during the two rotations. Accurately capturing emission events proved to be critical for deriving correct estimates of the GHG balance. The nitrogen (N) content of the soil and the water table depth were the two drivers that best explained the variability in N 2O and CH 4, respectively. Here, this study underlines the importance of the ‘non-CO 2 GHGs’ on the overall balance. Further long-term investigations of soil trace gas emissions should monitor the N content and the mineralization rate of the soil, as well as the microbial community, as drivers of the trace gas emissions.« less

Effects of Different Vegetation Zones on CH4 and N2O Emissions in Coastal Wetlands: A Model Case Study

PubMed Central

Liu, Yuhong; Wang, Lixin; Bao, Shumei; Liu, Huamin; Yu, Junbao; Wang, Yu; Shao, Hongbo; Ouyang, Yan; An, Shuqing

2014-01-01

The coastal wetland ecosystems are important in the global carbon and nitrogen cycle and global climate change. For higher fragility of coastal wetlands induced by human activities, the roles of coastal wetland ecosystems in CH4 and N2O emissions are becoming more important. This study used a DNDC model to simulate current and future CH4 and N2O emissions of coastal wetlands in four sites along the latitude in China. The simulation results showed that different vegetation zones, including bare beach, Spartina beach, and Phragmites beach, produced different emissions of CH4 and N2O in the same latitude region. Correlation analysis indicated that vegetation types, water level, temperature, and soil organic carbon content are the main factors affecting emissions of CH4 and N2O in coastal wetlands. PMID:24892044

Isotopomer analysis of production and consumption mechanisms of N2O and CH4 in an advanced wastewater treatment system.

PubMed

Toyoda, Sakae; Suzuki, Yuuri; Hattori, Shohei; Yamada, Keita; Fujii, Ayako; Yoshida, Naohiro; Kouno, Rina; Murayama, Kouki; Shiomi, Hiroshi

2011-02-01

Wastewater treatment processes are believed to be anthropogenic sources of nitrous oxide (N(2)O) and methane (CH(4)). However, few studies have examined the mechanisms and controlling factors in production of these greenhouse gases in complex bacterial systems. To elucidate production and consumption mechanisms of N(2)O and CH(4) in microbial consortia during wastewater treatment and to characterize human waste sources, we measured their concentrations and isotopomer ratios (elemental isotope ratios and site-specific N isotope ratios in asymmetric molecules of NNO) in water and gas samples collected by an advanced treatment system in Tokyo. Although the estimated emissions of N(2)O and CH(4) from the system were found to be lower than those from the typical treatment systems reported before, water in biological reaction tanks was supersaturated with both gases. The concentration of N(2)O, produced mainly by nitrifier-denitrification as indicated by isotopomer ratios, was highest in the oxic tank (ca. 4000% saturation). The dissolved CH(4) concentration was highest in in-flow water (ca. 3000% saturation). It decreased gradually during treatment. Its carbon isotope ratio indicated that the decrease resulted from bacterial CH(4) oxidation and that microbial CH(4) production can occur in anaerobic and settling tanks.

Straw enhanced CO2 and CH4 but decreased N2O emissions from flooded paddy soils: Changes in microbial community compositions

NASA Astrophysics Data System (ADS)

Wang, Ning; Yu, Jian-Guang; Zhao, Ya-Hui; Chang, Zhi-Zhou; Shi, Xiao-Xia; Ma, Lena Q.; Li, Hong-Bo

2018-02-01

To explore microbial mechanisms of straw-induced changes in CO2, CH4, and N2O emissions from paddy field, wheat straw was amended to two paddy soils from Taizhou (TZ) and Yixing (YX), China for 60 d under flooded condition. Illumia sequencing was used to characterize shift in bacterial community compositions. Compared to control, 1-5% straw amendment significantly elevated CO2 and CH4 emissions with higher increase at higher application rates, mainly due to increased soil DOC concentrations. In contrast, straw amendment decreased N2O emission. Considering CO2, CH4, and N2O emissions as a whole, an overall increase in global warming potential was observed with straw amendment. Total CO2 and CH4 emissions from straw-amended soils were significantly higher for YX than TZ soil, suggesting that straw-induced greenhouse gas emissions depended on soil characteristics. The abundance of C-turnover bacteria Firmicutes increased from 28-41% to 54-77% with straw amendment, thereby increasing CO2 and CH4 emissions. However, straw amendment reduced the abundance of denitrifying bacteria Proteobacteria from 18% to 7.2-13% or increased the abundance of N2O reducing bacteria Clostridium from 7.6-11% to 13-30%, thereby decreasing N2O emission. The results suggested straw amendment strongly influenced greenhouse gas emissions via alerting soil properties and bacterial community compositions. Future field application is needed to ascertain the effects of straw return on greenhouse gas emissions.

Electronic spectroscopy and photodissociation dynamics of Co(2+)-methanol clusters: Co2+ (CH3OH)n (n = 4-7).

PubMed

Thompson, Christopher J; Faherty, Kieron P; Stringer, Kay L; Metz, Ricardo B

2005-03-07

Solvated cluster ions Co2+ (CH3OH)n (n = 4-7) have been produced by electrospray and studied using photofragment spectroscopy. There are notable differences between the photodissociation spectra of these complexes and the analogous water complexes. Co2+ (CH3OH)6 absorbs significantly more strongly than Co2+ (H2O)6. The photodissociation spectra of Co2+ (CH3OH)n (n = 4, 5 and 6) are very similar, which suggests that they share the Co2+ (CH3OH)4 chromophore, with additional solvent molecules in the second shell. In contrast, our earlier studies indicate that Co2+ (H2O)6 is six coordinate, and its spectrum is significantly different from that of Co2+ (H2O)4. The larger clusters Co2+ (CH3OH)n (n = 5-7) dissociate by simple loss of one or more solvent molecules. Larger clusters tend to lose more solvent molecules, especially at higher photon energies. As with the corresponding water cluster, Co2+ (CH3OH)4 photodissociates by proton transfer through a salt-bridge intermediate. This is accompanied by a modest kinetic energy release of 170 kJ mol(-1) and occurs with a lifetime of 145 ns.

X-ray diffraction analysis of 4- and 4'-substituted C n H2 n + 1O-C6H3(OH)-CH=N-C6H4-C m H2 m + 1 ( n/ m = 2/1 and 3/4) salicylideneanilines

NASA Astrophysics Data System (ADS)

Kuz'mina, L. G.; Navasardyan, M. A.; Mikhailov, A. A.

2017-11-01

X-ray diffraction study of two crystalline modifications of C2H5O-C6H3(OH)-CH=N-C6H4-CH3 ( 1a, sp. gr. P21/ n, and 1b, sp. gr. C2/c) and C3H7O-C6H3(OH)-CH=N-C6H4-C4H9 ( 2, sp. gr. P212121) has been performed. The 1a crystal structure contains two independent molecules. The molecules are conformationally nonrigid with respect to the mutual rotation of benzene rings; the dihedral angles between their planes are 29.19° and 26.00° in the independent molecules of 1a, 18.72° in the molecule of 1b, and 50.35° in the molecule of 2. The crystal packing of the compounds is discussed.

Factors Related with CH4 and N2O Emissions from a Paddy Field: Clues for Management implications

PubMed Central

Wang, Chun; Lai, Derrick Y. F.; Sardans, Jordi; Wang, Weiqi; Zeng, Congsheng; Peñuelas, Josep

2017-01-01

Paddy fields are major sources of global atmospheric greenhouse gases, including methane (CH4) and nitrous oxide (N2O). The different phases previous to emission (production, transport, diffusion, dissolution in pore water and ebullition) despite well-established have rarely been measured in field conditions. We examined them and their relationships with temperature, soil traits and plant biomass in a paddy field in Fujian, southeastern China. CH4 emission was positively correlated with CH4 production, plant-mediated transport, ebullition, diffusion, and concentration of dissolved CH4 in porewater and negatively correlated with sulfate concentration, suggesting the potential use of sulfate fertilizers to mitigate CH4 release. Air temperature and humidity, plant stem biomass, and concentrations of soil sulfate, available N, and DOC together accounted for 92% of the variance in CH4 emission, and Eh, pH, and the concentrations of available N and Fe3+, leaf biomass, and air temperature 95% of the N2O emission. Given the positive correlations between CH4 emission and DOC content and plant biomass, reduce the addition of a carbon substrate such as straw and the development of smaller but higher yielding rice genotypes could be viable options for reducing the release of greenhouse gases from paddy fields to the atmosphere. PMID:28081161

Occurrence of greenhouse gases (CO2, N2O and CH4) in groundwater of the Walloon Region (Belgium).

NASA Astrophysics Data System (ADS)

Jurado, Anna; Borges, Alberto V.; Pujades, Estanislao; Hakoun, Vivien; Knöller, Kay; Brouyère, Serge

2017-04-01

Greenhouse gases (GHGs) are an environmental problem because their concentrations in the atmosphere have continuously risen since the industrial revolution. They can be indirectly transferred to the atmosphere through groundwater discharge into surface water bodies such as rivers. However, their occurrence is poorly evaluated in groundwater. The aim of this work is to identify the hydrogeological contexts (e.g., chalk and limestone aquifers) and the most conductive conditions for the generation of GHGs in groundwater at a regional scale. To this end, carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) concentrations, major and minor elements and environmental isotopes were monitored in several groundwater bodies of the Walloon Region (Belgium) from September 2014 to June 2016. The concentrations of GHGs in groundwater ranged from 1769 to 100519 ppm for the partial pressure of CO2 and from 0 to 1064 nmol/L and 1 to 37062 nmol/L for CH4 and N2O respectively. Overall, groundwater was supersaturated in GHGs with respect to atmospheric equilibrium, suggesting that groundwater contribute to the atmospheric GHGs budget. Prior inspection of the data suggested that N2O in groundwater can be produced by denitrification and nitrification. The most suitable conditions for the accumulation of N2O are promoted by intermediate dissolved oxygen concentrations (2.5-3 mg L-1) and the availability of nitrate (NO3-). These observations will be compared with the isotopes of NO3-. CH4 was less detected and at lower concentration than N2O, suggesting that groundwater redox conditions are not reducing enough to promoted the production of CH4. The results will be presented and discussed in detail in the presentation.

Aerial Photography Estimation of CH4 and N2O Emissions from Adelie Penguins During 1983-2012 in Victoria Land, Antarctic

NASA Astrophysics Data System (ADS)

He, H.; Li, X.; Cheng, X.

2016-12-01

Sea animals are the "bio-indicators" of the climate change in the Antarctic. The abundant nutrient components in their excreta such as carbon (C) and nitrogen (N) promote the emissions of greenhouse gases (GHGs) including methane (CH4) and nitrous oxide (N2O). Adélie Penguins are important sea animals, their colonies therefore become the potential "hotspots" of the GHGs emissions. Some field observations have been carried out to study the penguin excreta on CH4 and N2O emissions in the Antarctic peninsula. However, due to the lacking of the penguin population data, the total emissions of GHGs have not been estimated at regional scale. This study aimed to extract penguin information from two period aerial photographs respectively in 1983 and 2012 using object-oriented method in Victoria Land, Antarctic, and then estimate the Adélie penguin populations on Inexpressible Island combined with the shadow analysis. Meanwhile, a GHGs model was developed to estimate CH4 and N2O emissions from Adelie penguins based on the CH4 and N2O fluxes of penguin guanos, the number of penguins, and the fresh weight of penguin guanos and so on. The results indicated that object-oriented method was effective in penguin information extraction from high-resolution images, and there were 17120 and 21183 Adélie penguins respectively in 1983 and 2012, respectively. The main reasons for the increase in penguin populations from 1983 to 2012 might be explained from physical environment and biological environment, such as the rising temperatures and reduced Antarctic toothfishes. And the total CH4 and N2O emissions from penguins on Inexpressible Island during breeding season were 246 kg CH4 and 2.67 kg N2O in 1983, and 304 kg CH4 and 3.31 kg N2O in 2012. Our study aimed to provide important reference value for the estimation of GHG budget in Antarctic.

CW EC-QCL-based sensor for simultaneous detection of H 2O, HDO, N 2O and CH 4 using multi-pass absorption spectroscopy

DOE PAGES

Yu, Yajun; Sanchez, Nancy P.; Griffin, Robert J.; ...

2016-05-03

A sensor system based on a continuous wave, external-cavity quantum-cascade laser (CW EC-QCL) was demonstrated for simultaneous detection of atmospheric H 2O, HDO, N 2O and CH 4 using a compact, dense pattern multi-pass gas cell with an effective path-length of 57.6 m. The EC-QCL with a mode-hop-free spectral range of 1225-1285 cm -1 operating at similar to 7.8 mu m was scanned covering four neighboring absorption lines, for H 2O at 1281.161 cm -1, HDO at 1281.455 cm -1, N 2O at 1281.53 cm -1 and CH 4 at 1281.61 cm -1. A first-harmonic-normalized wavelength modulation spectroscopy with second-harmonicmore » detection (WMS-2f/1f) strategy was employed for data processing. An Allan-Werle deviation analysis indicated that minimum detection limits of 1.77 ppmv for H 2O, 3.92 ppbv for HDO, 1.43 ppbv for N 2O, and 2.2 ppbv for CH 4 were achieved with integration times of 50-s, 50-s, 100-s and 129-s, respectively. In conclusion, experimental measurements of ambient air are also reported.« less

Reactions of CH3SH and CH3SSCH3 with gas-phase hydrated radical anions (H2O)n(•-), CO2(•-)(H2O)n, and O2(•-)(H2O)n.

PubMed

Höckendorf, Robert F; Hao, Qiang; Sun, Zheng; Fox-Beyer, Brigitte S; Cao, Yali; Balaj, O Petru; Bondybey, Vladimir E; Siu, Chi-Kit; Beyer, Martin K

2012-04-19

The chemistry of (H(2)O)(n)(•-), CO(2)(•-)(H(2)O)(n), and O(2)(•-)(H(2)O)(n) with small sulfur-containing molecules was studied in the gas phase by Fourier transform ion cyclotron resonance mass spectrometry. With hydrated electrons and hydrated carbon dioxide radical anions, two reactions with relevance for biological radiation damage were observed, cleavage of the disulfide bond of CH(3)SSCH(3) and activation of the thiol group of CH(3)SH. No reactions were observed with CH(3)SCH(3). The hydrated superoxide radical anion, usually viewed as major source of oxidative stress, did not react with any of the compounds. Nanocalorimetry and quantum chemical calculations give a consistent picture of the reaction mechanism. The results indicate that the conversion of e(-) and CO(2)(•-) to O(2)(•-) deactivates highly reactive species and may actually reduce oxidative stress. For reactions of (H(2)O)(n)(•-) with CH(3)SH as well as CO(2)(•-)(H(2)O)(n) with CH(3)SSCH(3), the reaction products in the gas phase are different from those reported in the literature from pulse radiolysis studies. This observation is rationalized with the reduced cage effect in reactions of gas-phase clusters. © 2012 American Chemical Society

Experimental study and detailed modeling of toluene degradation in a low-pressure stoichiometric premixed CH4/O2/N2 flame.

PubMed

Bakali, A El; Dupont, L; Lefort, B; Lamoureux, N; Pauwels, J F; Montero, M

2007-05-17

Temperature and mole fraction profiles have been measured in laminar stoichiometric premixed CH4/O2/N2 and CH4/1.5%C6H5CH3/O2/N2 flames at low pressure (0.0519 bar) by using thermocouple, molecular beam/mass spectrometry (MB/MS), and gas chromatography/mass spectrometry (GC/MS) techniques. The present study completes our previous work performed on the thermal degradation of benzene in CH4/O2/N2 operating at similar conditions. Mole fraction profiles of reactants, final products, and reactive and stable intermediate species have been analyzed. The main intermediate aromatic species analyzed in the methane-toluene flame were benzene, phenol, ethylbenzene, benzylalcohol, styrene, and benzaldehyde. These new experimental results have been modeled with our previous model including submechanisms for aromatics (benzene up to p-xylene) and aliphatic (C1 up to C7) oxidation. Good agreement has been observed for the main species analyzed. The main reaction paths governing the degradation of toluene in the methane flame were identified, and it occurs mainly via the formation of benzene (C6H5CH3 + H = C6H6 + CH3) and benzyl radical (C6H5CH3 + H = C6H5CH2 + H2). Due to the abundance of methyl radicals, it was observed that recombination of benzyl and methyl is responsible for main monosubstitute aromatic species analyzed in the methane-toluene flame. The oxidation of these substitute species led to cyclopentadienyl radical as observed in a methane-benzene flame.

Beyond the Methanogenic Black-Box: Greenhouse Gas Fluxes (CO2, CH4, N2O) as Evidence for Wetlands as Dynamic Redox Systems

NASA Astrophysics Data System (ADS)

Mcnicol, G.; Knox, S. H.; Sturtevant, C. S.; Baldocchi, D. D.; Silver, W. L.

2015-12-01

Seminal wetland research in the 1990s demonstrated that annual methane (CH4) fluxes scaled positively with ecosystem production across distinctive wetlands globally. This relationship implies a model of flooded wetland ecosystems as 'methanogenic black-boxes'; poised at a low redox state, and tending to release a fixed fraction of incoming annual productivity as CH4. In contrast, recent studies have reported high ratios of carbon dioxide (CO2) to CH4 emissions, and are adding to a body of evidence suggesting wetlands can vary more widely in their redox state. To explore this apparent incongruence we used principles of redox thermodynamics and laboratory experiments to develop predictions of wetland greenhouse gas (GHG) fluxes under different redox regimes. We then used a field study to test the hypothesis that ecosystem seasonality in gross primary productivity (GPP) and temperature would drive changes in GHG emissions, mediated by a dynamic - as opposed to static - redox regime. We estimated wetland GHG emissions from an emergent marsh in the Sacramento Delta, CA from March 2014-2015. We measured CO2, CH4 and N2O emissions via diffusion and ebullition with manual sampling, and whole-ecosystem fluxes of CO2 and CH4 using eddy-covariance. Ebullition and diffusive CH4 fluxes were strongly seasonal, with minimum rates (0.86 and 0.35 mg C-CH­­4 m-2 yr-1, respectively) during winter, and maximum rates (1.3 and 1.8 g C-CH­­4 m-2 yr-1, respectively) during the summer growing season. In contrast, winter diffusive CO2 fluxes (494 g C-CO2 m-2 yr-1) and fall bubble CO2 concentrations (1.49%) were highest, despite being seasons of lower GPP, temperature, and CH4 flux. Further, diffusive and ebullition fluxes of N2O showed zero net flux only during spring and summer months, whereas the wetland was a significant source of N2O during winter (81.2 ± 24.4 mg N-N2O m-2 yr-1). These seasonal flux dynamics contradict a 'methanogenic black box' model of wetland redox, which

Crystal and molecular structure of the first dibino non-geminal macrocyclic dicyclophosphazene, & {;N 3P 3Cl 4[HN(CH 2) 3O(CH 2) 2O(CH 2) 3NH]&}; 2

NASA Astrophysics Data System (ADS)

Enjalbert, Renée; Galy, Jean; Sournies, François; Labarre, Jean-François

1990-04-01

Reaction of N 3P 3Cl 6 with the 4,7-dioxadecane-1,10-diamine (coded as 3O2O3) using an Et 2O/Na 2CO 3 water interface process leads to the DIBINO non-geminal 30-membered macrocyclic dicyclophosphazene &{;N 3P 3Cl 4[HN(CH 2) 3O(CH 2) 2O(CH 2) 3NH]&}; 2. This 30-crown-ether-like architecture crystallizes in the triclinic system, P1, a=9.019(6), b=9.224(5), c=11.542(8) Å, α=94.87(4), β=95.97(4), γ=99.68(3)°, V=936(1) Å 3, Dx=1.599 Mg m -3, R=0.049 for 2862 unique reflections and 199 variable parameters. The structure exhibits a spatial arrangement of two N 3P 3Cl 4 with two [HN(CH 2) 3O(CH 2) 3O(CH 2) 3NH] as bridges on different P atoms of N 3P 3 rings. Moreover, the two N 3P 3 rings are trans to the average plane of the 30-membered macrocycle ("chair" conformation).

Greenhouse gas fluxes (CO2, CH4, N2O) of a short-rotation poplar plantation after conversion from agriculture

NASA Astrophysics Data System (ADS)

Zona, D.; Janssens, I.; Aubinet, M.; Ceulemans, R.

2012-12-01

The increasing demand for renewable energy may lead to the conversion of millions of hectares into bioenergy plantations with a possible substantial transitory carbon (C) loss. Here we report on the greenhouse gas fluxes (CO2, CH4, and N2O) measured using eddy covariance of a short-rotation bioenergy poplar plantation converted from agricultural fields. The first six months after the establishment of the plantation (June-Dec 2010) presented substantial CO2, CH4, and N2O emissions (a total of 5.36 ± 0.52 Mg CO2eq ha-1 in terms of CO2 equivalents). Nitrous oxide loss mostly occurred during a week-long peak emission after an unusually large rainfall. This week-long N2O emission represented 52% of the entire N2O loss during one and an half years of measurements. As most of the N2O loss occurred in just this week-long period, accurately capturing these emission events are critical to accurate estimates of the GHG balance of bioenergy. While initial establishment (Jun-Dec 2010) of the plantation resulted in a net CO2 loss into the atmosphere (2.76 ± 0.16 Mg CO2eq ha-1), in the second year (2011) the plantation presented a substantial net CO2 uptake (-4.82 ± 0.47 Mg CO2eq ha-1). During the entire measurement period, CH4 was a source to the atmosphere (0.63 ± 0.05 Mg CO2eq ha-1 in 2010, and 0.49 ± 0.05 Mg CO2eq ha-1 in 2011), and was controlled by water table depth. Importantly, over the entire measurement period, the sum of the CH4 and N2O losses was almost double (3.51 ± 0.52 Mg CO2eq ha-1) than the magnitude of net CO2 uptake (-2.06 ± 0.50 Mg CO2eq ha-1). As water availability was an important control on the GHG emission of the plantation, expected climate change and altered rainfall pattern could increase the negative environmental impacts of bioenergy.

Fluxes of CO2, CH4 and N2O at two European beech forests: linking soil gas production profiles with soil and stem fluxes

NASA Astrophysics Data System (ADS)

Maier, Martin; Machacova, Katerina; Halaburt, Ellen; Haddad, Sally; Urban, Otmar; Lang, Friederike

2016-04-01

Soil and plant surfaces are known to exchange greenhouse gases with the atmosphere. Some gases like nitrous oxide (N2O) and methane (CH4) can be produced and re-consumed in different soil depths and soil compartments, so that elevated concentrations of CH4 or N2O in the soil do not necessarily mean a net efflux from the soil into the atmosphere. Soil aeration, and thus the oxygen status can underlay a large spatial variability within the soil on the plot and profile scale, but also within soil aggregates. Thus, conditions suitable for production and consumption of CH4 and N2O can vary on different scales in the soil. Plant surfaces can also emit or take up CH4 and N2O, and these fluxes can significantly contribute to the net ecosystem exchange. Since roots usually have large intercellular spaces or aerenchyma they may represent preferential transport ways for soil gases, linking possibly elevated soil gas concentrations in the subsoil in a "shortcut" to the atmosphere. We tested the hypothesis that the spatial variability of the soil-atmosphere fluxes of CO2, CH4 and N2O is caused by the heterogeneity in soil properties. Therefore, we measured soil-atmosphere gas fluxes, soil gas concentrations and soil diffusivity profiles and did a small scale field assessment of soil profiles on the measurments plots. We further tried to link vertical profiles of soil gas concentrations and diffusivity to derive the production and consumption profiles, and to link these profiles to the stem-atmosphere flux rates of individual trees. Measurements were conducted in two mountain beech forests with different geographical and climatic conditions (White Carpathians, Czech Republic; Black Forest, Germany). Gas fluxes at stem and soil levels were measured simultaneously using static chamber systems and chromatographic and continuous laser analyses. Monitoring simultaneously vertical soil gas profiles allowed to assess the within-soil gas fluxes, and thus to localize the production and

A comparison of CH4, N2O and CO2 emissions from three different cover types in a municipal solid waste landfill.

PubMed

Wang, Xiaojun; Jia, Mingsheng; Lin, Xiangyu; Xu, Ying; Ye, Xin; Kao, Chih Ming; Chen, Shaohua

2017-04-01

High-density polyethylene (HDPE) membranes are commonly used as a cover component in sanitary landfills, although only limited evaluations of its effect on greenhouse gas (GHG) emissions have been completed. In this study, field GHG emission were investigated at the Dongbu landfill, using three different cover systems: HDPE covering; no covering, on the working face; and a novel material-Oreezyme Waste Cover (OWC) material as a trial material. Results showed that the HDPE membrane achieved a high CH 4 retention, 99.8% (CH 4 mean flux of 12 mg C m -2 h -1 ) compared with the air-permeable OWC surface (CH4 mean flux of 5933 mg C m -2 h -1 ) of the same landfill age. Fresh waste at the working face emitted a large fraction of N 2 O, with average fluxes of 10 mg N m -2 h -2 , while N 2 O emissions were small at both the HDPE and the OWC sections. At the OWC section, CH 4 emissions were elevated under high air temperatures but decreased as landfill age increased. N 2 O emissions from the working face had a significant negative correlation with air temperature, with peak values in winter. A massive presence of CO 2 was observed at both the working face and the OWC sections. Most importantly, the annual GHG emissions were 4.9 Gg yr -1 in CO 2 equivalents for the landfill site, of which the OWC-covered section contributed the most CH 4 (41.9%), while the working face contributed the most N 2 O (97.2%). HDPE membrane is therefore, a recommended cover material for GHG control. Monitoring of GHG emissions at three different cover types in a municipal solid waste landfill during a 1-year period showed that the working face was a hotspot of N 2 O, which should draw attention. High CH 4 fluxes occurred on the permeable surface covering a 1- to 2-year-old landfill. In contrast, the high-density polyethylene (HDPE) membrane achieved high CH 4 retention, and therefore is a recommended cover material for GHG control.

Ozone perturbations by enhanced levels of CFCs, N2O, and CH4 A two-dimensional diabatic circulation study including uncertainty estimates

NASA Technical Reports Server (NTRS)

Isaksen, I. S. A.; Stordal, F.

1986-01-01

Observations made over the last few years suggest that the tropospheric concentrations of N2O, CH4, and O3 are increasing. Increases in the concentration of chlorofluorocarbons (CFCs) have been observed for some time. The present study is concerned with combined scenarios of future releases of N2O, CH4, and CFCs, which can affect the height profiles of ozone, while changes in latitudinal gradients of ozone may also be expected. Ozone perturbation calculations performed in the two-dimensional transport-chemistry model described by Stordal et al. (1985) are also presented, and the effects of increased levels of CFCs, N2O, and CH4 are examined. It is found that CH4 may be the most important ozone-perturbing trace species in connection with future tropospheric climatic impacts. A substantial increase in the tropospheric abundancy of CH4 could lead to large future ozone enhancements throughout the troposphere and lower stratosphere at middle and low latitudes.

Emissions of CH4 and N2O under Different Tillage Systems from Double-Cropped Paddy Fields in Southern China

PubMed Central

Zhang, Hai-Lin; Bai, Xiao-Lin; Xue, Jian-Fu; Chen, Zhong-Du; Tang, Hai-Ming; Chen, Fu

2013-01-01

Understanding greenhouse gases (GHG) emissions is becoming increasingly important with the climate change. Most previous studies have focused on the assessment of soil organic carbon (SOC) sequestration potential and GHG emissions from agriculture. However, specific experiments assessing tillage impacts on GHG emission from double-cropped paddy fields in Southern China are relatively scarce. Therefore, the objective of this study was to assess the effects of tillage systems on methane (CH4) and nitrous oxide (N2O) emission in a double rice (Oryza sativa L.) cropping system. The experiment was established in 2005 in Hunan Province, China. Three tillage treatments were laid out in a randomized complete block design: conventional tillage (CT), rotary tillage (RT) and no-till (NT). Fluxes of CH4 from different tillage treatments followed a similar trend during the two years, with a single peak emission for the early rice season and a double peak emission for the late rice season. Compared with other treatments, NT significantly reduced CH4 emission among the rice growing seasons (P<0.05). However, much higher variations in N2O emission were observed across the rice growing seasons due to the vulnerability of N2O to external influences. The amount of CH4 emission in paddy fields was much higher relative to N2O emission. Conversion of CT to NT significantly reduced the cumulative CH4 emission for both rice seasons compared with other treatments (P<0.05). The mean value of global warming potentials (GWPs) of CH4 and N2O emissions over 100 years was in the order of NT

Emissions of CH4 and N2O under different tillage systems from double-cropped paddy fields in Southern China.

PubMed

Zhang, Hai-Lin; Bai, Xiao-Lin; Xue, Jian-Fu; Chen, Zhong-Du; Tang, Hai-Ming; Chen, Fu

2013-01-01

Understanding greenhouse gases (GHG) emissions is becoming increasingly important with the climate change. Most previous studies have focused on the assessment of soil organic carbon (SOC) sequestration potential and GHG emissions from agriculture. However, specific experiments assessing tillage impacts on GHG emission from double-cropped paddy fields in Southern China are relatively scarce. Therefore, the objective of this study was to assess the effects of tillage systems on methane (CH4) and nitrous oxide (N2O) emission in a double rice (Oryza sativa L.) cropping system. The experiment was established in 2005 in Hunan Province, China. Three tillage treatments were laid out in a randomized complete block design: conventional tillage (CT), rotary tillage (RT) and no-till (NT). Fluxes of CH4 from different tillage treatments followed a similar trend during the two years, with a single peak emission for the early rice season and a double peak emission for the late rice season. Compared with other treatments, NT significantly reduced CH4 emission among the rice growing seasons (P<0.05). However, much higher variations in N2O emission were observed across the rice growing seasons due to the vulnerability of N2O to external influences. The amount of CH4 emission in paddy fields was much higher relative to N2O emission. Conversion of CT to NT significantly reduced the cumulative CH4 emission for both rice seasons compared with other treatments (P<0.05). The mean value of global warming potentials (GWPs) of CH4 and N2O emissions over 100 years was in the order of NT

Mitigating effects of ex situ application of rice straw on CH4 and N2O emissions from paddy-upland coexisting system

PubMed Central

Wang, Wei; Wu, Xiaohong; Chen, Anlei; Xie, Xiaoli; Wang, Yunqiu; Yin, Chunmei

2016-01-01

The in situ application of rice straw enhances CH4 emissions by a large margin. The ex situ application of rice straw in uplands, however, may mitigate total global warming potential (GWP) of CH4 and N2O emissions from paddy-upland coexisting systems. To evaluate the efficiency of this practice, two field trials were conducted in rice-rice-fallow and maize-rape cropping systems, respectively. Year-round measurements of CH4 and N2O emissions were conducted to evaluate the system-scaled GWP. The results showed that CH4 accounted for more than 98% of GWP in paddy. Straw removal from paddy decreased 44.7% (302.1 kg ha−1 yr−1) of CH4 emissions and 51.2% (0.31 kg ha−1 yr−1) of N2O emissions, thus decreased 44.8% (7693 kg CO2-eqv ha−1 yr−1) of annual GWP. N2O accounted for almost 100% of GWP in upland. Straw application in upland had insignificant effects on CH4 and N2O emissions, which increased GWP only by 91 kg CO2-eqv ha−1 yr−1. So, the transfer of straw from paddy to upland could decrease GWP by 7602 kg CO2-eqv ha−1 yr−1. Moreover, straw retention during late rice season contributed to 88.2% of annual GWP increment. It is recommended to transfer early rice straw to upland considering GWP mitigation, nutrient recycling and labor cost. PMID:27869209

Mitigating effects of ex situ application of rice straw on CH4 and N2O emissions from paddy-upland coexisting system

NASA Astrophysics Data System (ADS)

Wang, Wei; Wu, Xiaohong; Chen, Anlei; Xie, Xiaoli; Wang, Yunqiu; Yin, Chunmei

2016-11-01

The in situ application of rice straw enhances CH4 emissions by a large margin. The ex situ application of rice straw in uplands, however, may mitigate total global warming potential (GWP) of CH4 and N2O emissions from paddy-upland coexisting systems. To evaluate the efficiency of this practice, two field trials were conducted in rice-rice-fallow and maize-rape cropping systems, respectively. Year-round measurements of CH4 and N2O emissions were conducted to evaluate the system-scaled GWP. The results showed that CH4 accounted for more than 98% of GWP in paddy. Straw removal from paddy decreased 44.7% (302.1 kg ha-1 yr-1) of CH4 emissions and 51.2% (0.31 kg ha-1 yr-1) of N2O emissions, thus decreased 44.8% (7693 kg CO2-eqv ha-1 yr-1) of annual GWP. N2O accounted for almost 100% of GWP in upland. Straw application in upland had insignificant effects on CH4 and N2O emissions, which increased GWP only by 91 kg CO2-eqv ha-1 yr-1. So, the transfer of straw from paddy to upland could decrease GWP by 7602 kg CO2-eqv ha-1 yr-1. Moreover, straw retention during late rice season contributed to 88.2% of annual GWP increment. It is recommended to transfer early rice straw to upland considering GWP mitigation, nutrient recycling and labor cost.

Continuous multi-plot measurements of CO2, CH4, N2O and H2O in a managed boreal forest - The importance of accounting for all greenhouse gases

NASA Astrophysics Data System (ADS)

Vestin, P.; Mölder, M.; Sundqvist, E.; Båth, A.; Lehner, I.; Weslien, P.; Klemedtsson, L.; Lindroth, A.

2015-12-01

In order to assess the effects of different management practices on the exchange of greenhouse gases (GHG), it is desirable to perform repeated and parallel measurements on both experimental and control plots. Here we demonstrate how a system system combining eddy covariance and gradient techniques can be used to perform this assessment in a managed forest ecosystem.The net effects of clear-cutting and stump harvesting on GHG fluxes were studied at the ICOS site Norunda, Sweden. Micrometeorological measurements (i.e., flux-gradient measurements in 3 m tall towers) allowed for quantification of CO2, CH4 and H2O fluxes (from May 2010) as well as N2O and H2O fluxes (from June 2011) at two stump harvested plots and two control plots. There was one wetter and one drier plot of each treatment. Air was continuously sampled at two heights in the towers and gas concentrations were analyzed for CH4, CO2, H2O (LGR DLT-100, Los Gatos Research) and N2O, H2O (QCL Mini Monitor, Aerodyne Research). Friction velocities and sensible heat fluxes were measured by sonic anemometers (Gill Windmaster, Gill Instruments Ltd). Automatic chamber measurements (CO2, CH4, H2O) were carried out in the adjacent forest stand and at the clear-cut during 2010.Average CO2 emissions for the first year ranged between 14.4-20.2 ton CO2 ha-1 yr-1. The clear-cut became waterlogged after harvest and a comparison of flux-gradient data and chamber data (from the adjacent forest stand) indicated a switch from a weak CH4 sink to a significant source at all plots. The CH4 emissions ranged between 0.8-4.5 ton CO2-eq. ha-1 yr-1. N2O emissions ranged between 0.4-2.6 ton CO2-eq. ha-1 yr-1. Enhanced N2O emission on the drier stump harvested plot was the only clear treatment effect on GHG fluxes that was observed. Mean CH4 and N2O emissions for the first year of measurements amounted up to 29% and 20% of the mean annual CO2 emissions, respectively. This highlights the importance of including all GHGs

Selective photocatalytic reduction of CO2 by H2O/H2 to CH4 and CH3OH over Cu-promoted In2O3/TiO2 nanocatalyst

NASA Astrophysics Data System (ADS)

Tahir, Muhammad; Tahir, Beenish; Saidina Amin, Nor Aishah; Alias, Hajar

2016-12-01

Photocatalytic CO2 reduction by H2O and/or H2 reductant to selective fuels over Cu-promoted In2O3/TiO2 photocatalyst has been investigated. The samples, prepared via a simple and direct sol-gel method, were characterized by XRD, SEM, TEM, XPS, N2 adsorption-desorption, UV-vis diffuse reflectance, Raman and PL spectroscopy. Cu and In loaded into TiO2, oxidized as Cu2+ and In3+, promoted efficient separation of photo-generated electron/hole pairs (e-/h+). The results indicate that the reduction rate of CO2 by H2O to CH4 approached to 181 μmol g-1 h-1 using 0.5% Cu-3% In2O3/TiO2 catalyst, a 1.53 fold higher than the production rate over the 3% In2O3/TiO2 and 5 times the amount produced over the pure TiO2. In addition, Cu was found to promote efficient production of CH3OH and yield rate reached to 68 μmol g-1 h-1 over 1% Cu-3% In2O3/TiO2 catalyst. This improvement was attributed to charge transfer property and suppressed recombination rate by Cu-metal. More importantly, H2 reductant was less favorable for CH4 production, yet a significant amount of CH4 and CH3OH were obtained using a mixture of H2O/H2 reductant. Therefore, Cu-loaded In2O3/TiO2 catalyst has shown to be capable for methanol production, whereas product selectivity was greatly depending on the amount of Cu-loading and the type of reductant. A photocatalytic reaction mechanism was proposed to understand the experimental results over the Cu-loaded In2O3/TiO2 catalyst.

CH4 and N2O emissions from China's beef feedlots with ad libitum and restricted feeding in fall and spring seasons.

PubMed

Lin, Zhi; Liao, Wenhua; Yang, Yuanyuan; Gao, Zhiling; Ma, Wenqi; Wang, Dianwu; Cao, Yufeng; Li, Jianguo; Cai, Zhenjiang

2015-04-01

Accurately quantifying methane (CH4) and nitrous oxide (N2O) emissions from beef operations in China is necessary to evaluate the contribution of beef cattle to greenhouse gas budgets at the national and global level. Methane and N2O emissions from two intensive beef feedlots in the North China Plain, one with a restricted feeding strategy and high manure collection frequency and the other with an ad libitum feeding strategy and low manure collection frequency, were quantified in the fall and spring seasons using an inverse dispersion technique. The diel pattern of CH4 from the beef feedlot with an ad libitum feed strategy (single peak during a day) differed from that under a restricted feeding condition (multiple peaks during a day), but little difference in the diel pattern of N2O emissions between two feeding strategies was observed. The two-season average CH4 emission rates of the two intensive feedlots were 230 and 198gCH4animal(-1)d(-1) and accounted for 6.7% and 6.8% of the gross energy intake, respectively, indicating little impact of the feeding strategy and manure collection frequency on the CH4 conversion factor at the feedlot level. However, the average N2O emission rates (21.2g N2Oanimal(-1)d(-1)) and conversion factor (8.5%) of the feedlot with low manure collection frequency were approximately 131% and 174% greater, respectively, than the feedlot under high frequency conditions, which had a N2O emission rate and conversion factor of 9.2g N2Oanimal(-1)d(-1) and 3.1%, respectively, indicating that increasing manure collection frequency played an important role in reducing N2O emissions from beef feedlots. In addition, comparison indicated that China's beef and dairy cattle in feedlots appeared to have similar CH4 conversion factors. Copyright © 2015 Elsevier Inc. All rights reserved.

Measurements and Modeling of Nitric Oxide Formation in Counterflow, Premixed CH4/O2/N2 Flames

NASA Technical Reports Server (NTRS)

Thomsen, D. Douglas; Laurendeau, Normand M.

2000-01-01

Laser-induced fluorescence (LIF) measurements of NO concentration in a variety of CH4/O2/N2 flames are used to evaluate the chemical kinetics of NO formation. The analysis begins with previous measurements in flat, laminar, premixed CH4/O2/N2 flames stabilized on a water-cooled McKenna burner at pressures ranging from 1 to 14.6 atm, equivalence ratios from 0.5 to 1.6, and volumetric nitrogen/oxygen dilution ratios of 2.2, 3.1 and 3.76. These measured results are compared to predictions to determine the capabilities and limitations of the comprehensive kinetic mechanism developed by the Gas Research Institute (GRI), version 2.11. The model is shown to predict well the qualitative trends of NO formation in lean-premixed flames, while quantitatively underpredicting NO concentration by 30-50%. For rich flames, the model is unable to even qualitatively match the experimental results. These flames were found to be limited by low temperatures and an inability to separate the flame from the burner surface. In response to these limitations, a counterflow burner was designed for use in opposed premixed flame studies. A new LIF calibration technique was developed and applied to obtain quantitative measurements of NO concentration in laminar, counterflow premixed, CH4/O2/N2 flames at pressures ranging from 1 to 5.1 atm, equivalence ratios of 0.6 to 1.5, and an N2/O2 dilution ratio of 3.76. The counterflow premixed flame measurements are combined with measurements in burner-stabilized premixed flames and counterflow diffusion flames to build a comprehensive database for analysis of the GRI kinetic mechanism. Pathways, quantitative reaction path and sensitivity analyses are applied to the GRI mechanism for these flame conditions. The prompt NO mechanism is found to severely underpredict the amount of NO formed in rich premixed and nitrogen-diluted diffusion flames. This underprediction is traced to uncertainties in the CH kinetics as well as in the nitrogen oxidation chemistry

Influence of aeration on CH4, N2O and NH3 emissions during aerobic composting of a chicken manure and high C/N waste mixture.

PubMed

Shen, Yujun; Ren, Limei; Li, Guoxue; Chen, Tongbin; Guo, Rui

2011-01-01

Co-composting of chicken manure, straw and dry grasses was investigated in a forced aeration system to estimate the effect of aeration rates on NH(3), CH(4) and N(2)O emissions and compost quality. Continuous measurements of gas emissions were carried out and detailed gas emission patterns were obtained using an intermittent-aeration of 30 min on/30 min off at rates of 0.01 (A1), 0.1 (A2) and 0.2 (A3) m(3)min(-1)m(-3). Concentrations of CH(4) and N(2)O at the low aeration rate (A1) were significantly greater than those at the other two rates, but there was no significant difference between the A2 and A3 treatments. CH(4) and N(2)O emissions for this mixture could be controlled when the composting process was aerobic and ammonia emissions were reduced at a lower aeration rate. Comparison of CH(4), N(2)O, NH(3) emissions and compost quality showed that the aeration rate of the A2 treatment was superior to the other two aeration rates. Copyright © 2010 Elsevier Ltd. All rights reserved.

Intramolecular chalcogen-tin interactions in [(o-MeE-C6H4)CH2]2SnPh2-nCln; E = S, O, CH2, n = 0, 1, 2 and intermolecular chlorine-tin interactions in the meta and para-methoxy isomers

PubMed Central

Vargas-Pineda, Diana Gabriela; Guardado, Tanya; Cervantes-Lee, Francisco; Metta-Magana, Alejandro J.

2010-01-01

Organotin(IV) compounds of the type [(o-MeE-C6H4)CH2]2SnPh2-nCln were synthesized, E = O, n = 0 (1), n = 1 (2), n = 2 (3), E = S, n = 0 (4), n = 1 (5), n = 2 (6) and E = CH2, n = 0 (7), n = 1 (8), n = 2 (9). The dichloro compounds 3 and 6 have been investigated by single crystal X-ray diffraction and exhibit bi-capped tetrahedral geometry at the tin atom as a consequence of significant intramolecular Sn⋯O (3) and Sn⋯S (6) secondary bonding, in monomolecular units. Compound 3 when crystallized from a hexane/thf solvent mixture shows two different conformers, 3′ and 3″, in the crystal structure, 3′ has two equivalent Sn⋯O interactions, while 3″ has two non-equivalent Sn⋯O interactions. Upon recrystallization of 3 from hexane only a single structural form is observed, 3′. The Sn⋯E distances in 3′, 3″, and 6 are 71.3; 73.5, 72.9; and 76.3% of the ΣvdW radii, respectively. The meta and para-substituted isomers of 3 (10, 11) exhibit a distortion at the tin atom due to self-association via intermolecular Sn⋯Cl interactions resulting in polymeric structures. 119Sn NMR spectroscopy suggests that the intramolecular Sn⋯E interactions persist in solution for the dichloride compounds 3 and 6. PMID:20047301

Drainage and tillage practices in the winter fallow season mitigate CH4 and N2O emissions from a double-rice field in China

NASA Astrophysics Data System (ADS)

Zhang, Guangbin; Yu, Haiyang; Fan, Xianfang; Yang, Yuting; Ma, Jing; Xu, Hua

2016-09-01

Traditional land management (no tillage, no drainage, NTND) during the winter fallow season results in substantial CH4 and N2O emissions from double-rice fields in China. A field experiment was conducted to investigate the effects of drainage and tillage during the winter fallow season on CH4 and N2O emissions and to develop mitigation options. The experiment had four treatments: NTND, NTD (drainage but no tillage), TND (tillage but no drainage), and TD (both drainage and tillage). The study was conducted from 2010 to 2014 in a Chinese double-rice field. During winter, total precipitation and mean daily temperature significantly affected CH4 emission. Compared to NTND, drainage and tillage decreased annual CH4 emissions in early- and late-rice seasons by 54 and 33 kg CH4 ha-1 yr-1, respectively. Drainage and tillage increased N2O emissions in the winter fallow season but reduced it in early- and late-rice seasons, resulting in no annual change in N2O emission. Global warming potentials of CH4 and N2O emissions were decreased by 1.49 and 0.92 t CO2 eq. ha-1 yr-1, respectively, and were reduced more by combining drainage with tillage, providing a mitigation potential of 1.96 t CO2 eq. ha-1 yr-1. A low total C content and high C / N ratio in rice residues showed that tillage in the winter fallow season reduced CH4 and N2O emissions in both early- and late-rice seasons. Drainage and tillage significantly decreased the abundance of methanogens in paddy soil, and this may explain the decrease of CH4 emissions. Greenhouse gas intensity was significantly decreased by drainage and tillage separately, and the reduction was greater by combining drainage with tillage, resulting in a reduction of 0.17 t CO2 eq. t-1. The results indicate that drainage combined with tillage during the winter fallow season is an effective strategy for mitigating greenhouse gas releases from double-rice fields.

Kinetics of OH- and Cl-initiated oxidation of CH2dbnd CHC(O)O(CH2)2CH3 and CH2dbnd CHCH2C(O)O(CH2)2CH3 and fate of the alkoxy radicals formed

NASA Astrophysics Data System (ADS)

Rivela, Cynthia; Blanco, María B.; Teruel, Mariano A.

2016-05-01

Rate coefficients of the reactions of OH and Cl radicals with vinyl and allyl butyrate were determined for the first time at 298 K and 1 atm using the relative method to be (in cm3 molecule-1 s-1): k1(OH + CH2dbnd CHC(O)O(CH2)2CH3) = (2.61 ± 0.31) × 10-11, k2(Cl + CH2dbnd CHC(O)O(CH2)2CH3) = (2.48 ± 0.89) × 10-10, k3(OH + CH2dbnd CHCH2C(O)O(CH2)2CH3) = (2.89 ± 0.31) × 10-11, and k4(Cl + CH2dbnd CHCH2C(O)O(CH2)2CH3) = (2.25 ± 0.96) × 10-10. Reactivity trends and atmospheric lifetimes of esters are presented. Additionally, a product study shown butyric acid and polifunctional products for the reactions of vinyl and allyl butyrate, respectively and general mechanism is proposed.

Growing season CH4 and N2O fluxes from a subarctic landscape in northern Finland; from chamber to landscape scale

NASA Astrophysics Data System (ADS)

Dinsmore, Kerry J.; Drewer, Julia; Levy, Peter E.; George, Charles; Lohila, Annalea; Aurela, Mika; Skiba, Ute M.

2017-02-01

Subarctic and boreal emissions of CH4 are important contributors to the atmospheric greenhouse gas (GHG) balance and subsequently the global radiative forcing. Whilst N2O emissions may be lower, the much greater radiative forcing they produce justifies their inclusion in GHG studies. In addition to the quantification of flux magnitude, it is essential that we understand the drivers of emissions to be able to accurately predict climate-driven changes and potential feedback mechanisms. Hence this study aims to increase our understanding of what drives fluxes of CH4 and N2O in a subarctic forest/wetland landscape during peak summer conditions and into the shoulder season, exploring both spatial and temporal variability, and uses satellite-derived spectral data to extrapolate from chamber-scale fluxes to a 2 km × 2 km landscape area.From static chamber measurements made during summer and autumn campaigns in 2012 in the Sodankylä region of northern Finland, we concluded that wetlands represent a significant source of CH4 (3.35 ± 0.44 mg C m-2 h-1 during the summer campaign and 0.62 ± 0.09 mg C m-2 h-1 during the autumn campaign), whilst the surrounding forests represent a small sink (-0.06 ± < 0.01 mg C m-2 h-1 during the summer campaign and -0.03 ± < 0.01 mg C m-2 h-1 during the autumn campaign). N2O fluxes were near-zero across both ecosystems.We found a weak negative relationship between CH4 emissions and water table depth in the wetland, with emissions decreasing as the water table approached and flooded the soil surface and a positive relationship between CH4 emissions and the presence of Sphagnum mosses. Temperature was also an important driver of CH4 with emissions increasing to a peak at approximately 12 °C. Little could be determined about the drivers of N2O emissions given the small magnitude of the fluxes.A multiple regression modelling approach was used to describe CH4 emissions based on spectral data from PLEIADES PA1 satellite imagery across a 2 km

Impact of the heatwave in 2003 on the summer CH4 and N2O budget of a spruce forest ecosystem: A four-year comparison

NASA Astrophysics Data System (ADS)

Lamers, M.; Fiedler, S.; Jungkunst, H. F.; Stahr, K.; Streck, T.

2009-04-01

Both CH4 and N2O reduction and oxidation are highly sensitive to variation in soil moisture. Significant changes of net CH4 and total N2O fluxes from soils can therefore be expected to accompany redistribution for precipitation in the course of climate change where more extreme events are predicted for the future. The extreme summer drought in 2003 offered the unique opportunity to study the impact of such events on the emission of greenhouse gases, such as methane or nitrous oxide, under field conditions. The main objective of the present study was to evaluate the impact of the summer drought in 2003 on the net methane and nitrous oxide budget of a spruce forest ecosystem (South-West Germany) with large variation in soil drainage. During the summers of 2000-2004 we measured net CH4 and N2O fluxes (bi)-weekly using the closed-chamber technique for six different soil types ranging from well-aerated Cambisols to poorly drained Gleysols and a wet Histosol. With regard to CH4 the extreme summer draught (1) did not elevate net CH4-sink function of soils, but (2) highly reduced net CH4-source strength and (3) reversed the net CH4 source of the investigated catchment into a sink. In all four summers investigated, net ecosystem exchange of CH4 was found only in the hydromorphic soils but not in the dominant well-aerated soils. This highlighted the key role of hydromorphic soils for the investigated pedodiverse system. With regard to N2O the summer draught in 2003 significantly reduced N2O emissions at least for the Humic Gleysol and the Sapric Histosol and hence markedly reduced the net N2O source strength of the investigated ecosystem.

CH{sub 4} and N{sub 2}O emissions from China’s beef feedlots with ad libitum and restricted feeding in fall and spring seasons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Zhi; Liao, Wenhua; Yang, Yuanyuan

Accurately quantifying methane (CH{sub 4}) and nitrous oxide (N{sub 2}O) emissions from beef operations in China is necessary to evaluate the contribution of beef cattle to greenhouse gas budgets at the national and global level. Methane and N{sub 2}O emissions from two intensive beef feedlots in the North China Plain, one with a restricted feeding strategy and high manure collection frequency and the other with an ad libitum feeding strategy and low manure collection frequency, were quantified in the fall and spring seasons using an inverse dispersion technique. The diel pattern of CH{sub 4} from the beef feedlot with anmore » ad libitum feed strategy (single peak during a day) differed from that under a restricted feeding condition (multiple peaks during a day), but little difference in the diel pattern of N{sub 2}O emissions between two feeding strategies was observed. The two-season average CH{sub 4} emission rates of the two intensive feedlots were 230 and 198 g CH{sub 4} animal{sup −1} d{sup −1} and accounted for 6.7% and 6.8% of the gross energy intake, respectively, indicating little impact of the feeding strategy and manure collection frequency on the CH{sub 4} conversion factor at the feedlot level. However, the average N{sub 2}O emission rates (21.2 g N{sub 2}O animal{sup −1} d{sup −1}) and conversion factor (8.5%) of the feedlot with low manure collection frequency were approximately 131% and 174% greater, respectively, than the feedlot under high frequency conditions, which had a N{sub 2}O emission rate and conversion factor of 9.2 g N{sub 2}O animal{sup −1} d{sup −1} and 3.1%, respectively, indicating that increasing manure collection frequency played an important role in reducing N{sub 2}O emissions from beef feedlots. In addition, comparison indicated that China’s beef and dairy cattle in feedlots appeared to have similar CH{sub 4} conversion factors. - Highlights: • CH{sub 4} and N{sub 2}O emissions from China’s beef feedlots

Simulating CH4 and N2O emissions from direct-seeded rice systems using the DeNitrification DeComposition (DNDC) model

NASA Astrophysics Data System (ADS)

Simmonds, M.; Li, C.; Lee, J.; Six, J.; Van Kessel, C.; Linquist, B.

2015-12-01

Process-based modeling of CH4 and N2O emissions from rice fields is a practical tool for conducting greenhouse gas inventories and estimating mitigation potentials of alternative practices at the scales of management and policy-making. However, few studies have evaluated site-level model performance in side-by-side field trials of various management practices during both the growing season and fallow periods. We empirically evaluated the DeNitrification-DeComposition (DNDC) model for estimating CH4 and N2O fluxes in California rice systems under varying management (N fertilizer application rate, type of seeding system, fallow period straw and water management), soil environments, and weather conditions. Five and nine site-year combinations were used for calibration and validation, respectively. The model was parameterized for two cultivars, M206 and Koshihikari, and able to simulate 30% and 78% of the measured variation in yields, respectively. A major strength of DNDC was in estimating general site-level seasonal CH4 emissions (R2 = 0.85). However, a major limitation was in simulating finer resolution of differences in CH4 emissions (or lack thereof) among side-by-side management treatments (range of 0.2-465% relative absolute deviation). Additionally, DNDC did not satisfactorily simulate fallow period CH4 emissions, or seasonal and fallow period N2O emissions across all sites with the exception of a few cases. Specifically, simulated CH4 emissions were oversensitive to fertilizer N rates, but lacked sensitivity to the type of seeding system and prior fallow period straw management. Additionally, N2O emissions were oversensitive to fertilizer N rates and field drainage. Sensitivity analysis showed that CH4 emissions were highly sensitive to changes in the root to total plant biomass ratio. Overall, uncertainty in model predictions was attributed to uncertainty in both the input parameters due to in-field spatiotemporal variability of soil properties, and in the

Responses of CH(4), CO(2) and N(2)O fluxes to increasing nitrogen deposition in alpine grassland of the Tianshan Mountains.

PubMed

Li, Kaihui; Gong, Yanming; Song, Wei; He, Guixiang; Hu, Yukun; Tian, Changyan; Liu, Xuejun

2012-06-01

To assess the effects of nitrogen (N) deposition on greenhouse gas (GHG) fluxes in alpine grassland of the Tianshan Mountains in central Asia, CH(4), CO(2) and N(2)O fluxes were measured from June 2010 to May 2011. Nitrogen deposition tended to significantly increase CH(4) uptake, CO(2) and N(2)O emissions at sites receiving N addition compared with those at site without N addition during the growing season, but no significant differences were found for all sites outside the growing season. Air temperature, soil temperature and water content were the important factors that influence CO(2) and N(2)O emissions at year-round scale, indicating that increased temperature and precipitation in the future will exert greater impacts on CO(2) and N(2)O emissions in the alpine grassland. In addition, plant coverage in July was also positively correlated with CO(2) and N(2)O emissions under elevated N deposition rates. The present study will deepen our understanding of N deposition impacts on GHG balance in the alpine grassland ecosystem, and help us assess the global N effects, parameterize Earth System models and inform decision makers. Copyright © 2012 Elsevier Ltd. All rights reserved.

Photo-induced CO2 reduction by CH4/H2O to fuels over Cu-modified g-C3N4 nanorods under simulated solar energy

NASA Astrophysics Data System (ADS)

Tahir, Beenish; Tahir, Muhammad; Amin, Nor Aishah Saidina

2017-10-01

Copper modified polymeric graphitic carbon nitride (Cu/g-C3N4) nanorods for photo-induced CO2 conversion with methane (CH4) and water (H2O) as reducing system under simulated solar energy has been investigated. The nanocatalysts, synthesized by pyrolysis and sonication, were characterized by XRD, FTIR, Raman analysis, XPS, SEM, N2 adsorption-desorption and PL spectroscopy. The presence of Cu2+ ions over the g-C3N4 structure inhibited charge carriers recombination process. The results indicated that photo-activity and selectivity of Cu/g-C3N4 photo-catalyst for CO2 reduction greatly dependent on the type of CO2-reduction system. CO2 was efficiently converted to CH4 and CH3OH with traces of C2H4 and C2H6 hydrocarbons in the CO2-water system. The yield of the main product, CH4 over 3 wt.% Cu/g-C3N4 was 109 μmole g-cata.-1 h-1 under visible light irradiation, significantly higher than the pure g-C3N4 catalyst (60 μmole/g.cat). In photo-induced CO2-CH4 reaction, CO and H2 were detected as the main products with smaller amount of hydrocarbons. The highest efficiency was detected over 3 wt.%Cu-loading of g-C3N4 and at optimal CH4/CO2 feed ratio of 1.0. The maximum yield of CO and H2 detected were 142 and 76 μmole g-catal.-1 h-1, respectively at selectivity 66.6% and 32.5%, respectively. Significantly enhanced CO2/CH4 reduction over Cu/g-C3N4 was attributed to its polymeric structure with efficient charge transfer property and inhibited charges recombination rate. A proposed photo-induced reaction mechanism, corroborated with the experimental data, was also deliberated.

40 CFR Table Aa-2 to Subpart Aa of... - Kraft Lime Kiln and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 22 2012-07-01 2012-07-01 false Kraft Lime Kiln and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O AA Table AA-2 to Subpart AA of Part 98 Protection of Environment... and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O Fuel Fossil fuel-based emissions...

40 CFR Table Aa-2 to Subpart Aa of... - Kraft Lime Kiln and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 21 2011-07-01 2011-07-01 false Kraft Lime Kiln and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O AA Table AA-2 to Subpart AA of Part 98 Protection of Environment... and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O Fuel Fossil fuel-based emissions...

40 CFR Table Aa-2 to Subpart Aa of... - Kraft Lime Kiln and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 22 2013-07-01 2013-07-01 false Kraft Lime Kiln and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O AA Table AA-2 to Subpart AA of Part 98 Protection of Environment... and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O Fuel Fossil fuel-based emissions...

Effects of the herbicides prosulfuron and metolachlor on fluxes of CO2, N2O, and CH4 in a fertilized Colorado grassland soil

USGS Publications Warehouse

Kinney, C.A.; Mosier, A.R.; Ferrer, I.; Furlong, E.T.; Mandernack, K.W.

2004-01-01

The effect that pesticides have on trace gas production and consumption in agricultural soils is often overlooked. Independent field and laboratory experiments were used to measure the effects that the commonly used herbicides prosulfuron and metolachlor have on trace gas fluxes (CO2, N2O, and CH4) from fertilized soil of the Colorado shortgrass steppe. Separate sample plots (1 m2) on tilled and no-till soil at the sites included the following treatments: 1) a control without fertilizer or herbicide, 2) a fertilized (NH4NO3 equivalent to 244 kg ha-1) control without herbicide, 3) and fertilized plots amended with an herbicide (prosulfuron equivalent to 0.46 kg ha-1 57% by weight active ingredient or metolachlor equivalent to 5.7 L ha-1, 82.4% by weight active ingredient). During an initial study of one year duration, measurement of gas exchange revealed that prosulfuron-amendment stimulated N2O emissions and CH4 consumption by as much as 1600% and 1300% during a single measurement, respectively. During a second set of flux measurements beginning in August 2001, more frequent weekly measurements were made during a twelve week period. From this second study an increased N2O efflux and CH4 uptake occurred after a 7-week lag period that persisted for about 5 weeks. These changes in gas flux amounted to an overall increase of 41% and 30% for N2O emission and CH4 consumption, respectively. The co-occurrence of stimulated N2O and CH4 fluxes suggests a similar cause that is related to prosulfuron degradation. Evidence suggested that prosulfuron degradation stimulated microbial activity responsible for trace gas flux. Ultimately, prosulfuron-amendment led to an ???50% reduction in the global warming potential from N2O and CH4 fluxes at this field site, which is equivalent to a reduction of the global warming potential of 0.18 mols CO2 m-2 d-1 from these gases. Metolachlor application did not significantly affect the trace gas fluxes measured. These results demonstrate the

Fluxes of N2O and CH4 from forest and grassland lysimeter soils in response to simulated climate change

NASA Astrophysics Data System (ADS)

Weymann, Daniel; Brueggemann, Nicolas; Puetz, Thomas; Vereecken, Harry

2015-04-01

Central Europe is expected to be exposed to altered temperature and hydrological conditions, which will affect the vulnerability of nitrogen and carbon cycling in soils and thus production and fluxes of climate relevant trace gases. However, knowledge of the response of greenhouse gas fluxes to climate change is limited so far, but will be an important basis for future climate projections. Here we present preliminary results of an ongoing lysimeter field study which aims to assess the impact of simulated climate change on N2O and CH4 fluxes from a forest and a fertilized grassland soil. The lysimeters are part of the Germany-wide research infrastructure TERENO, which investigates feedbacks of climate change to the pedosphere on a long-term scale. Lysimeters (A = 1m2) were established in 2010 at high elevated sites (HE, 500 and 600 m.a.s.l.) and subsequently transferred along an altitudinal gradient to a low elevated site (LE, 100 m.a.s.l.) within the Eifel / Lower Rhine Valley Observatory in Western Germany, thereby resulting in a temperature increase of 2.3 K whereas precipitation decreased by 160 mm during the present study period. Systematic monitoring of soil-atmosphere exchange of N2O and CH4 based on weekly manual closed chamber measurements at HE and LE sites has started in August 2013. Furthermore, we routinely determine dissolved N2O and CH4 concentrations in the seepage water using a headspace equilibration technique and record water discharge in order to quantify leaching losses of both greenhouse gases. Cumulative N2O fluxes clearly responded to simulated climate change conditions and increased by 250 % and 600 % for the forest and the grassland soil, respectively. This difference between the HE and LE sites was mainly caused by an exceptionally heavy precipitation event in July 2014 which turned the LE site sustainably to a consistently higher emission level. Nonetheless, emissions remained rather small and ranged between 20 and 40 μg m-2 h-1. In

EMISSIONS AND COST ESTIMATES FOR GLOBALLY SIGNIFICANT ANTHROPOGENIC COMBUSTION SOURCES OF NOX, N2O, CH4, CO AND CO2

EPA Science Inventory

The report discusses the development of emission factors for CO2, CO, CH4, NOx, and N2O for about 80 globally significant combustion sources in seven source categories: utility, industrial, fuel production, transportation, residential, commercial, and kilns/ovens/dryers. ecause o...

Geographic Inventory Framework (GiF) for estimating N2O and CH4 emissions from agriculture in the province of Alberta, Canada

NASA Astrophysics Data System (ADS)

Dimitrov, D. D.; Wang, J.

2016-12-01

A Geographic Information Framework (GiF) has been created to estimate and map agricultural N2O and CH4 emissions of the province of Alberta, Canada. The GiF consists of a modelling component, a GIS component, and application software to communicate between the model, database and census data. For compatibility, GiF follows the IPCC Tier 1 method and contains census data for animal populations, crop areas, and farms for the main IPCC animal and plant types (dairy cows, cattle cows, pigs, sheep, poultry, other animals, grasses, legumes, other crops), and estimated N2O and CH4 emissions from manure management, enteric fermentation, direct soil emissions (with applied manure, synthetic fertilizer, crop residue degradation, biological fixation) and indirect soil emissions (with atmospheric deposition and leaching). Methane emissions from enteric fermentation (609.24 Gg) prevailed over those from manure (44.99 Gg), and nitrous oxide emission from manure (22.01 Gg) prevailed over those from soil (17.73 Gg), with cattle cows emitting most N2O and CH4, followed by plant N2O emissions, and pigs and dairy cows CH4 emissions. The GIS maps showed discernible pattern of N2O and CH4 emissions increasing from North and West to the central Alberta and then slightly declining to South and East, which could be useful to address various mitigation strategies. The framework allows easy replacement of Tier 1 emission factors by Tire 2 or 3 ones from process-based models. Future applying of the latter will allow accounting for CO2 source/sink strength of agricultural ecosystems, hence their complete GHG balance affected by soil, water, and climate.

Experimental warming of a mountain tundra increases soil CO2 effluxes and enhances CH4 and N2O uptake at Changbai Mountain, China

PubMed Central

Zhou, Yumei; Hagedorn, Frank; Zhou, Chunliang; Jiang, Xiaojie; Wang, Xiuxiu; Li, Mai-He

2016-01-01

Climatic warming is expected to particularly alter greenhouse gas (GHG) emissions from soils in cold ecosystems such as tundra. We used 1 m2 open-top chambers (OTCs) during three growing seasons to examine how warming (+0.8–1.2 °C) affects the fluxes of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) from alpine tundra soils. Results showed that OTC warming increased soil CO2 efflux by 141% in the first growing season and by 45% in the second and third growing season. The mean CH4 flux of the three growing seasons was −27.6 and −16.7 μg CH4-C m−2h−1 in the warmed and control treatment, respectively. Fluxes of N2O switched between net uptake and emission. Warming didn’t significantly affect N2O emission during the first and the second growing season, but stimulated N2O uptake in the third growing season. The global warming potential of GHG was clearly dominated by soil CO2 effluxes (>99%) and was increased by the OTC warming. In conclusion, soil temperature is the main controlling factor for soil respiration in this tundra. Climate warming will lead to higher soil CO2 emissions but also to an enhanced CH4 uptake with an overall increase of the global warming potential for tundra. PMID:26880107

Sub-arctic Wetland Greenhouse Gases (CO2, CH4 & N2O) Emissions are Driven by Interactions of Environmental Controls and Herbivore Grazers

NASA Astrophysics Data System (ADS)

Kelsey, K.; Leffler, A. J.; Beard, K. H.; Choi, R. T.; Welker, J. M.

2015-12-01

Climate change is increasing temperatures, altering precipitation regimes and causing earlier growing seasons, particularly at northern latitudes. Such changes in local environmental conditions have the potential to affect biogeochemical cycling including the exchange of greenhouses gases between the atmosphere and the terrestrial biosphere. In addition to the effects of these environmental controls, animals such as migratory geese also influence biogeochemical cycles through grazing, trampling and delivering nutrient-rich fecal matter. In this work we aimed to quantify how local environmental conditions and the presence of grazing interact as drivers of emissions of three key greenhouse gases, CO2, CH4 and N2O, in coastal wetlands of the Yukon Kuskokwim Delta. We explored the magnitude of emissions across gradients of soil temperature and water table depth, and across vegetation types related to the presence of grazing, ranging from no vegetation through grazed and ungrazed vegetation. We also investigated emissions from grazed areas using experimental manipulations of the timing of grazing and advancement of the growing season. We found that local environmental conditions and use by grazers exert interacting controls on emissions of CO2, CH4 and N2O. Emissions of CO2 and CH4 were positively related to soil temperature and CH4 emissions were inversely related to water table depth, but the relationship varied by vegetation type. Net emissions of CO2 were greatest in ungrazed vegetation types (6.62 umols CO2 m-2 sec-1; p=0.0007) whereas CH4 emissions were greatest in the grazed vegetation (122.56 nmols CH4 m-2 sec-1; p=0.037). Flux of N2O was less than 1 nmol N2O m-2 sec-1 across all landscape positions under typical grazing and temperature conditions, but emissions were stimulated to over 10 nmols m-2 sec-1 when grazing occurred early relative to a typical season. Our results indicate that environmental conditions and the presence of migratory herbivores are both

Affect of dairy cow manure, urine, and slurry on N<2>O, CO<2>, and CH<4> emissions from Pasture

NASA Astrophysics Data System (ADS)

Dorich, C.; Varner, R. K.; Contosta, A.; Li, C.

2012-12-01

Agriculture is responsible for roughly 25% of total anthropogenic emission of greenhouse gases (GHG) globally. These agricultural emissions are primarily in the form of methane (CH<4>) and nitrous oxide (N<2>O) where they account for roughly 40 and 80 percent of anthropogenic emissions of their gas, respectively. Measuring and modeling of these gases has remained difficult however as management varies between farms and N<2>O fluxes have been difficult to link to climate and site conditions. Most of these N<2>O fluxes occur during soil freeze-thaw and wetting-drying cycles as well as fertilizer addition moments, all of which are difficult to measure and harder yet to model. Thus the N<2>O flux remains poorly understood and may be underestimated in literature. This provides a problem in agriculture emissions as N use efficiency has been suggested as a proxy for farm scale emissions. On a farm scale these large fluxes of N<2>O from soil "hot moments" can account for up to 60% of the total GHG emissions and thus it is essential to capture the full flux. At the University of New Hampshire Agriculture Experiment Station's (NHAES) organic dairy farm a manure fertilizer experiment was conducted. Manure, urine, and slurry from the UNH dairy farms were collected, analyzed, and applied to pasture plots in May 2012 in order to examine N<2>O flux hot moments. Sites were measured at least bi-weekly with manual static flux chambers taken with soil temperature and moisture along with measurements for soil inorganic N, soil C:N, plant biomass and C:N, and soil pH. Gas samples were analyzed for CO<2>, CH<4>, and N<2>O. Emissions were compared with other fluxes from the farm ecosystem including; corn silage, free stall bedding, composting and solid manure, and a manure slurry tank.

Distribution of dissolved green-house gases (CO2, CH4, N2O) in Lakes Edward and George: Results from the first field cruise of the HIPE project

NASA Astrophysics Data System (ADS)

Borges, Alberto V.; Morana, Cédric D. T.; Lambert, Thibault; Okello, William; Bouillon, Steven

2017-04-01

Inland waters (streams, rivers, lakes, reservoirs) are quantitatively important components of the global budgets of atmospheric emissions of long-lived greenhouse gases (GHGs) (CO2, CH4, N2O). Available data indicate that a very large fraction of CO2 and CH4 emissions from rivers and reservoirs occurs at tropical latitudes. Data on GHGs at tropical latitudes from lakes however are much more scarse, and the relative importance of emissions, in particular in Africa, remains to be determined. Large tropical lakes are net autotrophic (hence potentially sinks for atmospheric CO2) due generally low dissolved organic carbon concentrations, seasonally near constant light and temperature conditions, and generally deep water columns favourable for export of organic matter to depth. This sharply contrasts with their much better documented temperate and boreal counterparts, usually considered as CO2 sources to the atmosphere sustained by net heterotrophy. Here, we report a data-set of dissolved CO2, CH4, N2O obtained in October 2016 in Lakes Edward and George and adjacent streams and crater lakes in the frame of Belgian Science Policy (BELSPO) HIPE (Human impacts on ecosystem health and resources of Lake Edward, http://www.co2.ulg.ac.be/hipe/) project. Lake George and part of Lake Edward were sinks for atmospheric CO2 and N2O due to high primary production and denitrification in sediments, respectively, and modest sources of CH4 to the atmosphere. Sampled rivers and streams were oversaturated in CO2 and CH4 and close to atmospheric equilibrium with regards to N2O. Spatial variations within rivers and streams were related to elevation and vegetation characteristics on the catchments (savannah versus forest). Levels of CO2, CH4, and N2O were within the range of those we reported in other African rivers. Crater lakes acted as sinks for atmospheric CO2 and N2O but were extremely over-saturated in CH4, due to intense primary production sustained by cyanobacteria. These CH4 levels

CLAES CH4, N2O and CCL2F2 (F12) global data. [Cryogenic Array Etalon Spectrometer

NASA Technical Reports Server (NTRS)

Kumer, J. B.; Mergenthaler, J. L.; Roche, A. E.

1993-01-01

Zonal mean comparisons of CH4 (for altitude regions above the 1.35 ppmv contour), of N2O (above the 210 ppbv contour), and of F12 (above the 360 pptv contour) with UARS prelaunch climatology and with recent models shows reasonable agreement, and some interesting differences in the details of equatorial uplift and descent near the winter poles, including apparent north-south differences. Prominent features such as the double peaked uplift structure in the April-May SAMS data are clearly evident in all three CLAES tracers. Contours of SAMS CH4 and N2O occur mostly at higher pressures than in the CLAES data, presumably due in part to increased tropospheric content of these gases, and/or perhaps some dynamic difference associated with the 15 years time difference between the data sets. The CLAES F12 are the first long time base global data sets. These show more tropical uplift than climatology or models. This might suggest a somewhat shorter lifetime of F12 in the stratosphere than is currently accepted.

Effects of the fungicides mancozeb and chlorothalonil on fluxes of CO2, N2O, and CH4 in a fertilized Colorado grassland soil

USGS Publications Warehouse

Kinney, C.A.; Mosier, A.R.; Ferrer, I.; Furlong, E.T.; Mandernack, K.W.

2004-01-01

Management of agricultural soil plays an important role in present and future atmospheric concentrations of the greenhouse gases carbon dioxide (CO2), nitrous oxide (N2O), and methane (CH4). Pesticides are used as management tools in crop production, but little is known about their effects on soil-atmosphere exchange of CO2, N2O, and CH4. Field studies described in this paper determined the effect of two commonly used fungicides, mancozeb and chlorothalonil, on trace gas exchange. Separate experimental plots, 1 m2, were established in nitrogen fertilized no-tilled native grassland and tilled soils with and without fungicide application. Two studies were conducted. The first study was initiated in June 1999 and lasted for 1 year with monthly flux measurements from tilled and no-till soils. The second study commenced in August 2001 with twelve weekly measurements from tilled soils only. From both studies mancozeb suppressed emissions of CO2 and N2O in the tilled soil by an average of 28% and 47%, respectively. This suppression corresponded with efficacy periods of 14-29 and 56-77 days, respectively. From the no-till soils mancozeb decreased CO2 and N2O emissions by 33% and 80% for periods of 29 and 94 days, respectively. Mancozeb inhibited CH4 consumption in the first study by 46% and 71% in the tilled and no-till soil for periods of 8 and 29 days, respectively, but had no effect in the second study. From both studies chlorothalonil initially suppressed CO2 and N2O emissions and enhanced CH4 uptake in the tilled soil by an average of 37%, 40%, and 115%, respectively. These effects corresponded with efficacy periods of 14-29, 21-56, and 1-14 days, respectively. In the no-till soil chlorothalonil inhibited CO2 and N2O emissions and enhanced CH4 uptake by 29%, 48%, and 86% for periods of 29, 56, and 56 days, respectively. Following the initial period of suppression, chlorothalonil subsequently enhanced N2O emissions in the tilled soil by an average of 51% and in the no

A neutral molecular-based layered magnet [Fe(C2O4)(CH3OH)]n exhibiting magnetic ordering at TN approximately 23 K.

PubMed

Zhang, Bin; Zhang, Yan; Zhang, Jinbiao; Li, Junchao; Zhu, Daoben

2008-10-07

Solvothermal synthesis of FeCl(2).4H2O and H2C2O(4).2H2O in methanol at 120 degrees C yielded yellow plate-like crystals of [Fe(C2O4)(CH3OH)]n. Each iron atom is in a distorted octahedral environment, being bonded to four oxygen atoms from two bisbidentate oxalate anions, one O atom of a chelating oxalate anion and one O atom from a methanol molecule as an oxalate group bridging ligand in a five-coordination mode. The neutral layer of [Fe(C2O4)(CH3OH)]n with a [4,4] net along the ac plane. There is no interaction between layers. A long range magnetic ordering with spin canting at TN approximately 23 K was observed and confirmed by AC susceptibility measurements.

New family of lanthanide-based inorganic-organic hybrid frameworks: Ln2(OH)4[O3S(CH2)nSO3]·2H2O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4) and their derivatives.

PubMed

Liang, Jianbo; Ma, Renzhi; Ebina, Yasuo; Geng, Fengxia; Sasaki, Takayoshi

2013-02-18

We report the synthesis and structure characterization of a new family of lanthanide-based inorganic-organic hybrid frameworks, Ln(2)(OH)(4)[O(3)S(CH(2))(n)SO(3)]·2H(2)O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4), and their oxide derivatives. Highly crystallized samples were synthesized by homogeneous precipitation of Ln(3+) ions from a solution containing α,ω-organodisulfonate salts promoted by slow hydrolysis of hexamethylenetetramine. The crystal structure solved from powder X-ray diffraction data revealed that this material comprises two-dimensional cationic lanthanide hydroxide {[Ln(OH)(2)(H(2)O)](+)}(∞) layers, which are cross-linked by α,ω-organodisulfonate ligands into a three-dimensional pillared framework. This hybrid framework can be regarded as a derivative of UCl(3)-type Ln(OH)(3) involving penetration of organic chains into two {LnO(9)} polyhedra. Substitutional modification of the lanthanide coordination promotes a 2D arrangement of the {LnO(9)} polyhedra. A new hybrid oxide, Ln(2)O(2)[O(3)S(CH(2))(n)SO(3)], which is supposed to consist of alternating {[Ln(2)O(2)](2+)}(∞) layers and α,ω-organodisulfonate ligands, can be derived from the hydroxide form upon dehydration/dehydroxylation. These hybrid frameworks provide new opportunities to engineer the interlayer chemistry of layered structures and achieve advanced functionalities coupled with the advantages of lanthanide elements.

Soil CO2 CH4 and N2O fluxes from an afforested lowland raised peatbog in Scotland: implications for drainage and restoration

NASA Astrophysics Data System (ADS)

Yamulki, S.; Anderson, R.; Peace, A.; Morison, J. I. L.

2013-02-01

The effect of tree (lodgepole pine) planting with and without intensive drainage on soil greenhouse gas (GHG) fluxes was assessed after 45 yr at a raised peatbog in West Flanders Moss, central Scotland. Fluxes of CO2 CH4 and N2O from the soil were monitored over a 2-yr period every 2 to 4 weeks using the static opaque chamber method in a randomised experimental block trial with the following treatments: drained and planted (DP), undrained and planted (uDP), undrained and unplanted (uDuP) and for reference also from an adjoining near-pristine area of bog at East Flanders Moss (n-pris). There was a strong seasonal pattern in both CO2 and CH4 effluxes which were significantly higher in late spring and summer months because of warmer temperatures. Effluxes of N2O were low and no significant differences were observed between the treatments. Annual CH4 emissions increased with the proximity of the water table to the soil surface across treatments in the order: DP < uDP < uDuP < n-pris with mean annual effluxes over the 2-yr monitoring period of 0.15, 0.64, 7.70 and 22.63 g CH4 m-2 yr-1, respectively. For CO2, effluxes increased in the order uDP < DP< n-pris < uDuP, with mean annual effluxes of 1.23, 1.66, 1.82 and 2.55 kg CO2 m-2 yr-1, respectively. CO2 effluxes dominated the total net GHG emission, calculated using the global warming potential (GWP) of the three GHGs for each treatment (76-98%), and only in the n-pris site was CH4 a substantial contribution (23%). Based on soil effluxes only, the near pristine (n-pris) peatbog had 43% higher total net GHG emission compared with the DP treatment because of high CH4 effluxes and the DP treatment had 33% higher total net emission compared with the uDP because drainage increased CO2 effluxes. Restoration is likely to increase CH4 emissions, but reduce CO2 effluxes. Our study suggests that if estimates of CO2 uptake by vegetation from similar peatbog sites were included, the total net GHG emission of restored peatbog would

Synthesis of Fe3O4@SiO2@OSi(CH2)3NHRN(CH2PPh2)2PdCl2 type nanocomposite complexes: Highly efficient and magnetically-recoverable catalysts in vitamin K3 synthesis.

PubMed

Uruş, Serhan

2016-12-15

The synthesis of aminomethylphosphine-metal complexes have opened a new perspective to the catalytic applications of organic compounds. Magnetic Fe3O4 nano-core was synthesized using the closed quartz tube with Teflon cover and microwaved 200°C for 1h with power controlled instrument set to max. 600W. Novel nano-composite supported; Fe3O4@SiO2(CH2)3NHArN(CH2PPh2)2 and Fe3O4@SiO2(CH2)3N(CH2PPh2)2 type bis(diphenylphosphinomethyl)amino ligands and their Pd(II) complexes have been synthesized and characterized with FT-IR, SEM, EDX, TEM, UV-Visible, XRD and TG/DTA techniques. All the complexes were used as heterogeneous catalysts in the oxidation of 2-methyl naphthalene (2MN) to 2-methyl-1, 4-naphthoquinone (vitamin K3, menadione, 2MNQ) in the presence of hydrogen peroxide and acetic acid. Selectivity reached about 55-60% with a conversion of 90-96% using the nano-magnetite supported aminomethylphosphine-Pd(II) complexes. The complexes were very active in three times in the catalytic recycling experiments in five catalytic cycles. Copyright © 2016 Elsevier Ltd. All rights reserved.

Tree species influence soil-atmosphere fluxes of the greenhouse gases CO2, CH4 and N2O

NASA Astrophysics Data System (ADS)

Steffens, Christina; Vesterdal, Lars; Pfeiffer, Eva-Maria

2016-04-01

In the temperate zone, forests are the greatest terrestrial sink for atmospheric CO2, and tree species affect soil C stocks and soil CO2 emissions. When considering the total greenhouse gas (GHG) balance of the forest soil, the relevant GHGs CH4 and N2O should also be considered as they have a higher global warming potential than CO2. The presented data are first results from a field study in a common garden site in Denmark where tree species with ectomycorrhizal colonization (beech - Fagus sylvatica, oak - Quercus robur) and with arbuscular mycorrhizal colonization (maple - Acer pseudoplatanus, ash - Fraxinus excelsior) have been planted in monocultures in adjacent blocks of about 0.25 ha in the year 1973 on former arable land. The soil-atmosphere fluxes of all three gases were measured every second week since August 2015. The hypothesis is that the total GHG efflux from forest soil would differ between species, and that these differences could be related to the type of mycorrhizal association and leaf litter quality. Preliminary results (August to December 2015) indicate that tree species influence the fluxes (converted to CO2-eq) of the three GHGs. Total soil CO2 efflux was in the low end of the range reported for temperate broadleaved forests but similar to the measurements at the same site approximately ten years ago. It was highest under oak (9.6±2.4 g CO2 m-2 d-1) and lowest under maple (5.2±1.6 g CO2 m-2 d-1). In contrast, soil under oak was a small but significant sink for CH4(-0.005±0.003 g CO2-eq m-2 d-1), while there were almost no detectable CH4 fluxes in maple. Emissions of N2O were highest under beech (0.6±0.6 g CO2-eq m-2 d-1) and oak (0.2±0.09 g CO2-eq m-2 d-1) and lowest under ash (0.03±0.04 g CO2-eq m-2 d-1). In the total GHG balance, soil CH4 uptake was negligible (≤0.1% of total emissions). Emissions of N2O (converted to CO2-eq) contributed <1% (ash) to 8% (beech) to total GHG emissions. Summing up all GHG emissions, the tree species

SAPO-34 Membranes for N-2/CH4 separation: Preparation, characterization, separation performance and economic evaluation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, SG; Zong, ZW; Zhou, SJ

2015-08-01

SAPO-34 membranes were synthesized by several routes towards N-2/CH4 separation. Membrane synthesis parameters including water content in the gel, crystallization time, support pore size, and aluminum source were investigated. High performance N-2-selective membranes were obtained on 100-nm-pore alumina tubes by using Al(i-C3H7O)(3) as aluminum source with a crystallization time of 6 h. These membranes separated N-2 from CH, with N-2 permeance as high as 500 GPU with separation selectivity of 8 at 24 degrees C. for a 50/50 N-2/CH4 mixture. Nitrogen and CH, adsorption isotherms were measured on SAPO-34 crystals. The N-2 and CH, heats of adsorption were 11 andmore » 15 kJ/mol, respectively, which lead to a preferential adsorption of CE-H-4 over N-2 in the N-2/CH4 mixture. Despite this, the SAPO-34 membranes were selective for N-2 over CH4 in the mixture because N-2 diffuses much faster than CH4 and differences in diffusivity played a more critical role than the competitive adsorption. Preliminary economic evaluation indicates that the required N-2/CH4 selectivity would be 15 in order to maintain a CH4 loss below 10%. For small nitrogen-contaminated gas wells, our current SAPO-34 membranes have potential to compete with the benchmark technology cryogenic distillation for N-2 rejection. (C) 2015 Elsevier B.V. All rights reserved,« less

Synthesis, structure and reactivity of rare-earth metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2.

PubMed

Yang, Jingying; Xie, Zuowei

2015-04-14

Rare-earth metallacarborane alkyls can be stabilized by the incorporation of a functional sidearm into both π and σ ligands. Reaction of [Me3NH][7,8-O(CH2)2-7,8-C2B9H10] with one equiv. of Ln(CH2C6H4-o-NMe2)3 gave metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2 (Ln = Y (), Gd (), Er ()) via alkane elimination. They represent the first examples of rare-earth metallacarborane alkyls. Treatment of with RN[double bond, length as m-dash]C[double bond, length as m-dash]NR (R = Cy, (i)Pr) or 2-benzoylpyridine afforded the corresponding mono-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[η(2)-(RN)2C(CH2C6H4-o-NMe2)](DME) (R = Cy (), (i)Pr ()) or [η(1):η(5)-O(CH2)2C2B9H9]Y[C5H4NC(Ph)(CH2C6H4-o-NMe2)O](THF)2 (), respectively. Complex also reacted with ArNCO or ArNC (Ar = 2,6-diisopropylphenyl, 2,6-dimethylphenyl) to give di-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[OC([double bond, length as m-dash]NC6H3Me2)N(C6H3Me2)C(CH2C6H4-o-NMe2)O](THF)2 () or [η(1):η(5)-O(CH2)2C2B9H9]Y[C([double bond, length as m-dash]NC6H3(i)Pr2)C([double bond, length as m-dash]NC6H3(i)Pr2)(CH2C6H4-o-NMe2)](DME) (). These results showed that the reactivity pattern of the Ln-C σ bond in rare-earth metallacarborane alkyls was dependent on the nature of the unsaturated organic molecules. New complexes were characterized by various spectroscopic techniques and elemental analysis. Some were further confirmed by single-crystal X-ray analysis.

Effect of air composition (N2, O2, Ar, and H2O) on CO2 and CH4 measurement by wavelength-scanned cavity ring-down spectroscopy: calibration and measurement strategy

NASA Astrophysics Data System (ADS)

Nara, H.; Tanimoto, H.; Tohjima, Y.; Mukai, H.; Nojiri, Y.; Katsumata, K.; Rella, C. W.

2012-11-01

We examined potential interferences from water vapor and atmospheric background gases (N2, O2, and Ar), and biases by isotopologues of target species, on accurate measurement of atmospheric CO2 and CH4 by means of wavelength-scanned cavity ring-down spectroscopy (WS-CRDS). Changes of the background gas mole fractions in the sample air substantially impacted the CO2 and CH4 measurements: variation of CO2 and CH4 due to relative increase of each background gas increased as Ar < O2 < N2, suggesting similar relation for the pressure-broadening effects (PBEs) among the background gas. The pressure-broadening coefficients due to variations in O2 and Ar for CO2 and CH4 are empirically determined from these experimental results. Calculated PBEs using the pressure-broadening coefficients are linearly correlated with the differences between the mole fractions of O2 and Ar and their ambient abundances. Although the PBEs calculation showed that impact of natural variation of O2 is negligible on the CO2 and CH4 measurements, significant bias was inferred for the measurement of synthetic standard gases. For gas standards balanced with purified air, the PBEs were estimated to be marginal (up to 0.05 ppm for CO2 and 0.01 ppb for CH4) although the PBEs were substantial (up to 0.87 ppm for CO2 and 1.4 ppb for CH4) for standards balanced with synthetic air. For isotopic biases on CO2 measurements, we compared experimental results and theoretical calculations, which showed excellent agreement within their uncertainty. We derived instrument-specific water correction functions empirically for three WS-CRDS instruments (Picarro EnviroSense 3000i, G-1301, and G-2301), and evaluated the transferability of the water correction function from G-1301 among these instruments. Although the transferability was not proven, no significant difference was found in the water vapor correction function for the investigated WS-CRDS instruments as well as the instruments reported in the past studies

A new metal-organic framework for separation of C2H2/CH4 and CO2/CH4 at room temperature

NASA Astrophysics Data System (ADS)

Duan, Xing; Zhou, You; Lv, Ran; Yu, Ben; Chen, Haodong; Ji, Zhenguo; Cui, Yuanjing; Yang, Yu; Qian, Guodong

2018-04-01

A 3D microporous metal-organic framework with open Cu2+ sites and suitable pore space, [Cu2(L)(H2O)2]·(H2O)4(DMF)8 (ZJU-15, H4L = 5,5‧-(9H-carbazole-2,7-diyl)diisophthalic acid; DMF = N,N-dimethylformamide; ZJU = Zhejiang University), has been constructed and characterized. The activated ZJU-15a has three different types of cages and exhibits BET surface area of 1660 m2 g-1, and can separate gas mixture of C2H2/CH4 and CO2/CH4 at room temperature.

Comparison of the frequencies of NH3, CO2, H2O, N2O, CO, and CH4 as infrared calibration standards

NASA Technical Reports Server (NTRS)

Brown, L. R.; Toth, R. A.

1985-01-01

The absolute accuracies of infrared calibration standards for the line positions have been investigated using a 0.0056-kayser-resolution (unapodized) Fourier-transform spectrum recorded from 550 to 5000 kayser. The spectrum has been obtained using a multicell arrangement containing the various molecular species. Detailed comoparisons reveal that standards for CO2, CH4, and N2O obtained from laser research and NH3 from Fourier-transform spectrometer research are consistent within the accuracies of the present data (+ or 0.0001 kayser). However, certain N2O, H2O, and CO values in the 1100-to 2300 kayser region are systematically high by 0.0001 to 0.0004 kayser. Correction factors for the H2O and CO standards are obtained to bring these into agreement with the laser values. In addition, corrected values for the 2nu-2 and nu-1 bands of N2O at 9 microns are reported.

Diurnal variation of CO2, CH4, and N2O emission fluxes continuously monitored in-situ in three environmental habitats in a subtropical estuarine wetland.

PubMed

Yang, Wen-Bin; Yuan, Chung-Shin; Tong, Chuan; Yang, Pin; Yang, Lei; Huang, Bang-Qin

2017-06-15

Wetlands play a crucial role in modulating atmospheric concentrations of greenhouse gases (GHGs) such as carbon dioxide (CO 2 ), methane (CH 4 ), and nitrous oxide (N 2 O). The key factors controlling GHG emission from subtropical estuarine wetlands were investigated in this study, which continuously monitored the uptake/emission of GHGs (CO 2 , CH 4 , and N 2 O) by/from a subtropical estuarine wetland located in the Minjiang estuary in the coastal region of southeastern China. A self-designed floating chamber was used to collect air samples on-site at three environmental habitats (Phragmites australis marsh, mudflats, and river water). The CO 2 , CH 4 , and N 2 O concentrations were then measured using an automated nondispersive infrared analyzer. The magnitudes of the CO 2 and N 2 O emission fluxes at the three habitats were ordered as river water>P. australis>mudflats. P. australis emitted GHGs through photosynthesis and respiration processes. Emissions of CH 4 from P. australis and the mudflats were revealed to be slightly higher than those from the river water. The total GHG emission fluxes at the three environmental habitats were quite similar (4.68-4.78gm -2 h -1 ). However, when the total carbon dioxide equivalent fluxes (CO 2 -e) were considered, the river water was discovered to emit the most CO 2 -e compared with P. australis and the mudflats. Based on its potential to increase global warming, N 2 O was the main contributor to the total GHG emission, with that emitted from the river water being the most considerable. Tidal water carried onto the marsh had its own GHG content and thus has acted as a source or sink of GHGs. However, water quality had a large effect on GHG emissions from the river water whereas the tidal water height did not. Both high salinity and large amounts of sulfates in the wetlands explicitly inhibited the activity of CH 4 -producing bacteria, particularly at nighttime. Copyright © 2017 Elsevier Ltd. All rights reserved.

Molecular simulation of CH4/CO2/H2O competitive adsorption on low rank coal vitrinite.

PubMed

Yu, Song; Bo, Jiang; Wu, Li

2017-07-21

The competitive adsorptions of CH 4 /CO 2 /H 2 O on coal vitrinite (DV-8, C 214 H 180 O 24 N 2 ) were computed based on density function theory (DFT) and grand canonical Monte Carlo (GCMC). The adsorption process reaches the saturation state after adsorbing 17 CH 4 s, 22 CO 2 s, and 35 H 2 Os per C 214 H 180 O 24 N 2 respectively. The optimal configurations of CH 4 -vitrinite, CO 2 -vitrinite, and H 2 O-vitrinite respectively manifest as aromatic 1 /T 2 /rT 3 (1 adsorption location, 2 adsorption sites and T here represents sites above the carbon atom and the heteroatom, 3 adsorption orientation and rT here means the orientations of three hydrogen atoms pointing to vitrinite), aromatic/T/v (v represents the orientations perpendicular to the plane of vitrinite), and aromatic/rV/T (rV represents an oxygen atom pointing to the vitrinite surface). The GCMC results show that high temperature is not conducive to the vitrinite's adsorption of adsorbates and the adsorption capacity order is H 2 O > CO 2 > CH 4 (263-363 K) in the one-component, binary, and ternary adsorbate systems. The optimal configurations of vitrinite are similar to graphite/graphene, while ΔE is significantly lower than graphite/graphene. Simulation data are in good agreement with the experimental results.

Emissions of N2O, CH4 and CO2 from tropical forest soils

NASA Technical Reports Server (NTRS)

Keller, Michael; Kaplan, Warren A.; Wofsy, Steven C.

1986-01-01

Emissions of nitrous oxide, methane, and carbon dioxide were measured at diverse locations in tropical forests of Brazil, Ecuador, and Puerto Rico using a static open chamber technique. Mean fluxes to the atmosphere were 1.7 x 10 to the 10th, -0.7 x 10 to the 10th, and 1.5 x 10 to the 14th molecules/sq cm per s for N2O, CH4, and CO2, respectively. The data indicate that tropical forests contribute a significant fraction of the global source for atmospheric N2O, about 40 percent of the current source, and possibly 75 percent of the preindustrial source. Methane is consumed by soils on average, but the sink is an insignificant part (less than 5 percent) of the atmospheric cycle for the gas. Emissions of CO2 from forest soils are higher at equatorial sites than at middle or high latitudes, as expected from ecological considerations. Soils emit CO2 at rates more than twice as large as the rate of carbon infall in litter; hence much of the emitted CO2 must arise from root metabolism.

Climate change reduces the net sink of CH4 and N2O in a semiarid grassland

USDA-ARS?s Scientific Manuscript database

Methane (CH4) and nitrous oxide (N2O) are potent greenhouse gases; their concentrations in the atmosphere have increased because of human activity. Soils are important sources and sinks of both gases where their production and consumption are largely regulated by biological processes. Climate change...

Distinct transport properties of O2 and CH4 across a carbon nanotube

NASA Astrophysics Data System (ADS)

Meng, Xianwen; Wang, Yu; Zhao, Yanjiao; Huang, Jiping

2013-04-01

It is of fundamental importance to investigate either O2 or CH4 molecules across nanochannels in many areas such as breathing or separation. Thus, many researches have focused on such a single type of molecules across nanochannels. However, O2 and CH4 can often appear together and crucially affect human life, say, in a mine. On the basis of molecular dynamics simulations, here we attempt to investigate the mixture of O2 and CH4, in order to identify their different transport properties in a nanochannel. We take a single-walled carbon nanotube (SWCNT) as a model nanochannel, and find that their transport properties are distinctly different. As the concentration of O2 increases up to a high value of 0.8, it is always faster for CH4 molecules to transport across the SWCNT, and the total number of gas molecules transporting across the SWCNT is decreased. Meanwhile, CH4 molecules are always dominant in the SWCNT, and the total number of O2 or CH4 inside the SWCNT is a constant. By calculating the van der Waals interaction between the SWCNT and O2 or CH4, we find that the net interaction between CH4 and the SWCNT is much stronger. Our findings may offer some hints on how to separate CH4 from O2, and/or store CH4 efficiently.

Effects of elevated ozone concentration on CH4 and N2O emission from paddy soil under fully open-air field conditions.

PubMed

Tang, Haoye; Liu, Gang; Zhu, Jianguo; Kobayashi, Kazuhiko

2015-04-01

We investigated the effects of elevated ozone concentration (E-O3) on CH4 and N2O emission from paddies with two rice cultivars: an inbred Indica cultivar Yangdao 6 (YD6) and a hybrid one II-you 084 (IIY084), under fully open-air field conditions in China. A mean 26.7% enhancement of ozone concentration above the ambient level (A-O3) significantly reduced CH4 emission at tillering and flowering stages leading to a reduction of seasonal integral CH4 emission by 29.6% on average across the two cultivars. The reduced CH4 emission is associated with O3-induced reduction in the whole-plant biomass (-13.2%), root biomass (-34.7%), and maximum tiller number (-10.3%), all of which curbed the carbon supply for belowground CH4 production and its release from submerged soil to atmosphere. Although no significant difference was detected between the cultivars in the CH4 emission response to E-O3, a larger decrease in CH4 emission with IIY084 (-33.2%) than that with YD6 (-7.0%) was observed at tillering stage, which may be due to the larger reduction in tiller number in IIY084 by E-O3. Additionally, E-O3 reduced seasonal mean NOx flux by 5.7% and 11.8% with IIY084 and YD6, respectively, but the effects were not significant statistically. We found that the relative response of CH4 emission to E-O3 was not significantly different from those reported in open-top chamber experiments. This study has thus confirmed that increasing ozone concentration would mitigate the global warming potential of CH4 and suggested consideration of the feedback mechanism between ozone and its precursor emission into the projection of future ozone effects on terrestrial ecosystem. © 2014 John Wiley & Sons Ltd.

Highly efficient alkane oxidation catalyzed by [Mn(V)(N)(CN)4](2-). Evidence for [Mn(VII)(N)(O)(CN)4](2-) as an active intermediate.

PubMed

Ma, Li; Pan, Yi; Man, Wai-Lun; Kwong, Hoi-Ki; Lam, William W Y; Chen, Gui; Lau, Kai-Chung; Lau, Tai-Chu

2014-05-28

The oxidation of various alkanes catalyzed by [Mn(V)(N)(CN)4](2-) using various terminal oxidants at room temperature has been investigated. Excellent yields of alcohols and ketones (>95%) are obtained using H2O2 as oxidant and CF3CH2OH as solvent. Good yields (>80%) are also obtained using (NH4)2[Ce(NO3)6] in CF3CH2OH/H2O. Kinetic isotope effects (KIEs) are determined by using an equimolar mixture of cyclohexane (c-C6H12) and cyclohexane-d12 (c-C6D12) as substrate. The KIEs are 3.1 ± 0.3 and 3.6 ± 0.2 for oxidation by H2O2 and Ce(IV), respectively. On the other hand, the rate constants for the formation of products using c-C6H12 or c-C6D12 as single substrate are the same. These results are consistent with initial rate-limiting formation of an active intermediate between [Mn(N)(CN)4](2-) and H2O2 or Ce(IV), followed by H-atom abstraction from cyclohexane by the active intermediate. When PhCH2C(CH3)2OOH (MPPH) is used as oxidant for the oxidation of c-C6H12, the major products are c-C6H11OH, c-C6H10O, and PhCH2C(CH3)2OH (MPPOH), suggesting heterolytic cleavage of MPPH to generate a Mn═O intermediate. In the reaction of H2O2 with [Mn(N)(CN)4](2-) in CF3CH2OH, a peak at m/z 628.1 was observed in the electrospray ionization mass spectrometry, which is assigned to the solvated manganese nitrido oxo species, (PPh4)[Mn(N)(O)(CN)4](-)·CF3CH2OH. On the basis of the experimental results the proposed mechanism for catalytic alkane oxidation by [Mn(V)(N)(CN)4](2-)/ROOH involves initial rate-limiting O-atom transfer from ROOH to [Mn(N)(CN)4](2-) to generate a manganese(VII) nitrido oxo active species, [Mn(VII)(N)(O)(CN)4](2-), which then oxidizes alkanes (R'H) via a H-atom abstraction/O-rebound mechanism. The proposed mechanism is also supported by density functional theory calculations.

Differences in CH4 and N2O emissions between rice nurseries in Chinese major rice cropping areas

NASA Astrophysics Data System (ADS)

Zhang, Yi; Li, Zhijie; Feng, Jinfei; Zhang, Xin; Jiang, Yu; Chen, Jin; Zhang, Mingqian; Deng, Aixing; Zhang, Weijian

2014-10-01

Studies on greenhouse gas (GHG) emissions from paddy field have primarily focused on the post-transplanting period, however, recent researches raise new concerns about GHGs emission from rice nursery. In this study, CH4 and N2O fluxes were determined from different nurseries under major rice cropping systems in China. The tested nurseries included flooded nursery (FN), moist nursery (MN) and dry nursery (DN). Methane emissions from FN were significantly higher than those from MN and DN under all the rice cropping systems. When comparing with FN, MN decreased total CH4 emissions by 74.2%, 72.1% and 49.6% under the rice-upland rotation cropping system (RUR), and the double rice cropping system for the early rice (EDR) and the late rice (LDR), respectively. DN decreased CH4 emissions by 99.2%, 92.0%, 99.0% and 78.6% compared to FN under the single rice cropping system (SR), RUR, EDR and LDR, respectively. When comparing with FN, MN and DN increased N2O emissions by 58.1-134.1% and 28.2-332.7%, respectively. Ultimately, compared with FN across the cropping systems, MN and DN decreased net global warming potentials (GWPs) of CH4 and N2O by 33-68% and 43-86%, respectively. The mitigating effect of MN and DN on total GWPs varied greatly across the systems, ranging from 30.8% in the LDR to 86.5% in the SR. Chinese actual emission from rice nurseries was reduced to 956.66 × 103 t CO2 eq from the theoretical estimate of 2242.59 × 103 t CO2 eq if under the flooded nursery scenario in 2012. Taking into account the large rice nursery area (2032.52 × 103 ha) in China, the results of this study clearly indicate the importance to estimate and mitigate GHGs emission from flooded rice nursery. Being effective to reduce GHG emissions and increase rice yield, dry nursery technique is a promising candidate for climate smart rice cropping.

[Effects of Water and Nitrogenous Fertilizer Coupling on CH4 and N2O Emission from Double-Season Rice Paddy Field].

PubMed

Fu, Zhi-qiang; Long, Pan; Liu, Yi-yi; Zhong, Juan; Long, Wen-fei

2015-09-01

To provide support for the efficient use of water and fertilizer technology to double-season rice cultivation, water and fertilizer coupling mode was applied in this research, including two irrigation methods and four N levels. The irrigation methods were flood irrigation and intermittent irrigation, while four N levels were high-N, middle-N, low-N and none-N. Field experiment was conducted to study the effect of water and fertilizer coupling mode on CH4 and N2O emission. The results showed that the accumulated CH4 emissions were significantly reduced by intermittent irrigation, in comparison with flood irrigation, the reduction in early rice season were from 13. 18 kg.hm-2 to 87. 90 kg.hm-2, and were from 74. 48 kg.hm-2 to 131. 07 kg.hm-2 in late rice season, with a rate of 24. 4% -67. 4% and 42. 5% -65. 5% respectively; whereas the accumulated N20 emissions were increased, the increment were from 0. 03 kg.hm-2 to 0. 24 kg.hm-2 in early rice season and from 0. 35 kg.hm-2 to 1. 53 kg.hm-2 in late rice season when compared flood irrigation, increased by 6.2% -18. 3% and 40.2% - 80.9% respectively. On the whole, intermittent irrigation reduces the warming potential of greenhouse gases (GWP), which were decreased by 18. 8% to 58. 6% in early rice season and by 34. 4% to 60. 1% in late rice season, and the reduction of total GWP were from 2 388 to 4 151 kg. hm-2 (CO2 eq), with a rate of 41% -54% . Through correlation analysis it found that CH4 emissions from soil were significantly related with soil solution Eh and solution CH4 concentration. In comparison with the flood irrigation, the application of intermittent irrigation in double-season rice cultivation was conducive to CH4 reduction, though the increase came in N2O, but the GWPs were significantly reduced. Comprehensively, intermittent irrigation matching with middle-N is more benefit to double-season rice cultivation.

Fluxes of the greenhouse gases (CO2, CH4 and N2O) above a short-rotation poplar plantation after conversion from agricultural land

NASA Astrophysics Data System (ADS)

Zona, Donatella; Ceulemans, Reinhart

2013-04-01

The increasing demand for renewable energy may lead to the conversion of millions of hectares into bioenergy plantations with a possible substantial transitory carbon (C) loss. In this study we report on the greenhouse gas fluxes (CO2, CH4, and N2O) measured using eddy covariance of a short-rotation bioenergy poplar plantation converted from agricultural fields. During the first six months after the establishment of the plantation (June-Dec 2010) there were substantial CO2, CH4, and N2O emissions (a total of 5.36 ± 0.52 Mg CO2eq ha-1 in terms of CO2 equivalents). Nitrous oxide loss mostly occurred during a week-long peak emission after an unusually large rainfall. This week-long N2O emission represented 52% of the entire N2O loss during one and an half years of measurements. As most of the N2O loss occurred in just this week-long period, accurately capturing these emission events are critical to accurate estimates of the GHG balance of bioenergy. While initial establishment (Jun-Dec 2010) of the plantation resulted in a net CO2 loss into the atmosphere (2.76 ± 0.16 Mg CO2eq ha-1), in the second year (2011) there was substantial net CO2 uptake (-3.51 ± 0.56 Mg CO2eq ha-1). During the entire measurement period, CH4 was a source to the atmosphere (0.63 ± 0.05 Mg CO2eq ha-1 in 2010, and 0.49 ± 0.05 Mg CO2eq ha-1 in 2011), and was controlled by water table depth. Importantly, over the entire measurement period, the sum of the CH4 and N2O losses was much higher (3.51 ± 0.52 Mg CO2eq ha-1) than the net CO2 uptake (-0.76 ± 0.58 Mg CO2eq ha-1). As water availability was an important control on the GHG emission of the plantation, expected climate change and altered rainfall pattern could increase the negative environmental impacts of bioenergy.

Laboratory-scale measurements of N2O and CH4 emissions from hybrid poplars (Populus deltoides x Populus nigra).

PubMed

McBain, M C; Warland, J S; McBride, R A; Wagner-Riddle, C

2004-12-01

The purpose of this study was to determine whether or not young hybrid poplar (Populus deltoides x Populus nigra) could transport landfill biogas internally from the root zone to the atmosphere, thereby acting as conduits for landfill gas release. Fluxes of methane (CH4) and nitrous oxide (N2O) from the seedlings to the atmosphere were measured under controlled conditions using dynamic flux chambers and a tunable diode laser trace gas analyser (TDLTGA). Nitrous oxide was emitted from the seedlings, but only when extremely high soil N2O concentrations were applied to the root zone. In contrast, no detectable emissions of CH4 were measured in a similar experimental trial. Visible plant morphological responses, characteristic of flood-tolerant trees attempting to cope with the negative effects of soil hypoxia, were observed during the CH4 experiments. Leaf chlorosis, leaf abscission and adventitious roots were all visible plant responses. In addition, seedling survival was observed to be highest in the biogas 'hot spot' areas of a local municipal solid waste landfill involved in this study. Based on the available literature, these observations suggest that CH4 can be transported internally by Populus deltoides x Populus nigra seedlings in trace amounts, although future research is required to fully test this hypothesis.

40 CFR Table C-2 to Subpart C - Default CH4 and N2O Emission Factors for Various Types of Fuel

Code of Federal Regulations, 2012 CFR

2012-07-01

... for Various Types of Fuel C Table C-2 to Subpart C Protection of Environment ENVIRONMENTAL PROTECTION... Combustion Sources Pt. 98, Subpt. C, Table C-2 Table C-2 to Subpart C—Default CH4 and N2O Emission Factors... factor (kg N2O/mmBtu) Coal and Coke (All fuel types in Table C-1) 1.1 × 10−02 1.6 × 10−03 Natural Gas 1.0...

40 CFR Table C-2 to Subpart C - Default CH4 and N2O Emission Factors for Various Types of Fuel

Code of Federal Regulations, 2011 CFR

2011-07-01

... for Various Types of Fuel C Table C-2 to Subpart C Protection of Environment ENVIRONMENTAL PROTECTION... Combustion Sources Pt. 98, Subpt. C, Table C-2 Table C-2 to Subpart C—Default CH4 and N2O Emission Factors... factor (kg N2O/mmBtu) Coal and Coke (All fuel types in Table C-1) 1.1 × 10−02 1.6 × 10−03 Natural Gas 1.0...

Exotic Spartina alterniflora invasion alters ecosystem-atmosphere exchange of CH4 and N2O and carbon sequestration in a coastal salt marsh in China.

PubMed

Yuan, Junji; Ding, Weixin; Liu, Deyan; Kang, Hojeong; Freeman, Chris; Xiang, Jian; Lin, Yongxin

2015-04-01

Coastal salt marshes are sensitive to global climate change and may play an important role in mitigating global warming. To evaluate the impacts of Spartina alterniflora invasion on global warming potential (GWP) in Chinese coastal areas, we measured CH4 and N2O fluxes and soil organic carbon sequestration rates along a transect of coastal wetlands in Jiangsu province, China, including open water; bare tidal flat; and invasive S. alterniflora, native Suaeda salsa, and Phragmites australis marshes. Annual CH4 emissions were estimated as 2.81, 4.16, 4.88, 10.79, and 16.98 kg CH4 ha(-1) for open water, bare tidal flat, and P. australis, S. salsa, and S. alterniflora marshes, respectively, indicating that S. alterniflora invasion increased CH4 emissions by 57-505%. In contrast, negative N2O fluxes were found to be significantly and negatively correlated (P < 0.001) with net ecosystem CO2 exchange during the growing season in S. alterniflora and P. australis marshes. Annual N2O emissions were 0.24, 0.38, and 0.56 kg N2O ha(-1) in open water, bare tidal flat and S. salsa marsh, respectively, compared with -0.51 kg N2O ha(-1) for S. alterniflora marsh and -0.25 kg N2O ha(-1) for P. australis marsh. The carbon sequestration rate of S. alterniflora marsh amounted to 3.16 Mg C ha(-1) yr(-1) in the top 100 cm soil profile, a value that was 2.63- to 8.78-fold higher than in native plant marshes. The estimated GWP was 1.78, -0.60, -4.09, and -1.14 Mg CO2 eq ha(-1) yr(-1) in open water, bare tidal flat, P. australis marsh and S. salsa marsh, respectively, but dropped to -11.30 Mg CO2 eq ha(-1) yr(-1) in S. alterniflora marsh. Our results indicate that although S. alterniflora invasion stimulates CH4 emissions, it can efficiently mitigate increases in atmospheric CO2 and N2O along the coast of China. © 2014 John Wiley & Sons Ltd.

Pasture age effects on N[sub 2]O, NO and CH[sub 4] emissions in the Atlantic Lowlands of Costa Rica

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keller, M.; Reiners, W.A.; Veldkamp, E.

A study conducted in Brazil indicated that N[sub 2]O emissions increased following forest conversion to pasture. Our first study in Costa Rica indicated the reverse. To explore this contradiction, we measured N[sub 2]O, NO, and CH[sub 4] emissions in a chronosequence of 8 sites comprising forest and derive pastures of ayes 2 to 25 years, all on the same soil type in the Atlantic Lowlands of Costa Rica. We found large differences through the chronosequence in the fluxes of these three gases. Flux changes were related to changes in available nitrogen, organic matter, moisture content, and bulk density in themore » soil. N[sub 2]O emissions from the 2-year pasture were much greater than from the forest. Emissions declined with pasture age so that 25-year pasture had much smaller emissions than the forest. NO emissions from young pastures were similar to forest emissions, then declined sharply with pasture age. Forest soils consumed CH[sub 4]. Pasture soils mainly produced CH[sub 4]. Prediction of the effects of land use change on trace gas fluxes in the tropics will require an assessment of the history and soil condition of individual land units.« less

CW EC-QCL-based sensor for simultaneous detection of H₂O, HDO, N₂O and CH₄ using multi-pass absorption spectroscopy.

PubMed

Yu, Yajun; Sanchez, Nancy P; Griffin, Robert J; Tittel, Frank K

2016-05-16

A sensor system based on a continuous wave, external-cavity quantum-cascade laser (CW EC-QCL) was demonstrated for simultaneous detection of atmospheric H₂O, HDO, N₂O and CH₄ using a compact, dense pattern multi-pass gas cell with an effective path-length of 57.6 m. The EC-QCL with a mode-hop-free spectral range of 1225-1285 cm^-1 operating at ~7.8 µm was scanned covering four neighboring absorption lines, for H₂O at 1281.161 cm^-1, HDO at 1281.455 cm^-1, N₂O at 1281.53 cm^-1 and CH₄ at 1281.61 cm^-1. A first-harmonic-normalized wavelength modulation spectroscopy with second-harmonic detection (WMS-2f/1f) strategy was employed for data processing. An Allan-Werle deviation analysis indicated that minimum detection limits of 1.77 ppmv for H₂O, 3.92 ppbv for HDO, 1.43 ppbv for N₂O, and 2.2 ppbv for CH₄ were achieved with integration times of 50-s, 50-s, 100-s and 129-s, respectively. Experimental measurements of ambient air are also reported.

Vertical Transport Rates in the Stratosphere in 1993 from Observations of CO2, N2O and CH4

NASA Technical Reports Server (NTRS)

Wofsy, Steven C.; Boering, Kristie A.; Daube, Bruce C., Jr.; McElroy, Michael B.; Loewenstein, Max; Podolske, James R.; Elkins, James W.; Dutton, Geoffrey S.; Fahey, David W.

1994-01-01

Measurements of CO2, N2O and CH4 are analyzed to define hemispheric average vertical exchange rates in the lower stratosphere from November 1992 to October 1993. Effective vertical diffusion coefficients were small in summer, less than or equal to 1 m(exp 2)/sec at altitudes below 25 km; values were similar near the tropopause in winter, but increased markedly with altitude. The analysis suggests possibly longer residence times for exhaust from stratospheric aircraft, and more efficient transport from 20 km to the middle stratosphere, than predicted by many current models. Seasonally-resolved measurements of stratospheric CO2 and N2O provide significant new constraints on rates for global-scale vertical transport.

Seasonal, inter-annual and decadal changes of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) in the Scheldt estuary (Belgium, The Netherlands)

NASA Astrophysics Data System (ADS)

Borges, Alberto V.; Middelburg, Jack J. B.; Chou, Lei; Kromkamp, Jacco; Houtekamer, Marco; Harlay, Jérôme

2014-05-01

We carried out monthly cruises to study the seasonal and spatial variations of the partial pressure of carbon dioxide CO2 (pCO2), methane (CH4) and nitrous oxide (N2O) concentrations in the Scheldt estuary, a strongly human impacted system located in Belgium and the Netherlands. This survey was initiated in 2008 for pCO2, and from 2009 onwards for methane (CH4) and nitrous oxide (N2O). In the lower estuary, pCO2 strongly decreased and oxygen saturation level (%O2) strongly increased during the spring phytoplankton bloom. In the upper estuary, two yearly maxima of pCO2 coinciding with minima of %O2 occurred in spring and fall due to enhanced nitrification and/or net heterotrophy. In the upper estuary, pCO2 decreased in winter due to lower temperature (affecting solubility and inhibiting biological activity). pCO2 also decreased in summer due to increase in primary production and decrease of net heterotrophy. In the upper estuary, maxima of CH4 were observed in winter due to enhanced river inputs (high discharge) while in the lower estuary higher CH4 was observed in summer. This was probably due to inputs of CH4 from inter-tidal areas at the mouth of estuary that increased in summer due to higher temperatures and higher organic matter availability. N2O also showed higher values during winter in the upper estuary, but in summer N2O was low in the lower estuary due to decreased solubility due to higher temperature. During winter 2009, extremely high N2O values were observed in the upper estuary, up to 3257 nM (23738% saturation). This was related to the problems encountered by the Brussels North waste water treatment plant (WWTP) in late 2009. One of the collectors of the station was shut down in 25 November 2009, and by 8 December 2009, the whole WWTP was shut down and the waste-water was delivered directly to the Rupel. Extremely high N2O values were observed in the upper estuary on 7 December 2009, and abnormally high N2O values (compared to other years) persisted

Axial zero-field splitting in mononuclear Co(ii) 2-N substituted N-confused porphyrin: Co(2-NC3H5-21-Y-CH2C6H4CH3-NCTPP)Cl (Y = o, m, p) and Co(2-NC3H5-21-CH2C6H5-NCTPP)Cl.

PubMed

Lai, Ya-Yuan; Chang, Yu-Chang; Chen, Jyh-Horung; Wang, Shin-Shin; Tung, Jo-Yu

2016-03-21

The inner C-benzyl- and C-o-xylyl (or m-xylyl, p-xylyl)-substituted cobalt(ii) complexes of a 2-N-substituted N-confused porphyrin were synthesized from the reaction of 2-NC3H5NCTPPH (1) and CoCl2·6H2O in toluene (or o-xylene, m-xylene, p-xylene). The crystal structures of diamagnetic chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-hydrogen-21-carbaporphyrinato-N,N',N'')zinc(ii) [Zn(2-NC3H5-21-H-NCTPP)Cl; 3 ] and paramagnetic chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-benzyl-21-carbaporphyrinato-N,N',N'')cobalt(ii) [Co(2-NC3H5-21-CH2C6H5NCTPP)Cl; 7], and chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-Y-xylyl-21-carbaporphyrinato-N,N',N'')cobalt(ii) [Co(2-NC3H5-21-Y-CH2C6H4CH3NCTPP)Cl] [Y = o (8), m (9), p (10)] were determined. The coordination sphere around the Zn(2+) (or Co(2+)) ion in 3 (or 7-10) is a distorted tetrahedron (DT). The free energy of activation at the coalescence temperature Tc for the exchange of phenyl ortho protons o-H (26) with o-H (22) in 3 in a CDCl3 solvent is found to be ΔG = 61.4 kJ mol(-1) through (1)H NMR temperature-dependent measurements. The axial zero-field splitting parameter |D| was found to vary from 35.6 cm(-1) in 7 (or 30.7 cm(-1) in 8) to 42.0 cm(-1) in 9 and 46.9 cm(-1) in 10 through paramagnetic susceptibility measurements. The magnitude of |D| can be related to the coordination sphere at the cobalt sites.

40 CFR Table C-2 to Subpart C of... - Default CH4 and N2O Emission Factors for Various Types of Fuel

Code of Federal Regulations, 2013 CFR

2013-07-01

... for Various Types of Fuel C Table C-2 to Subpart C of Part 98 Protection of Environment ENVIRONMENTAL... Fuel Combustion Sources Pt. 98, Subpt. C, Table C-2 Table C-2 to Subpart C of Part 98—Default CH4 and...) Default N2O emission factor (kg N2O/mmBtu) Coal and Coke (All fuel types in Table C-1) 1.1 × 10−02 1.6...

40 CFR Table C-2 to Subpart C of... - Default CH4 and N2O Emission Factors for Various Types of Fuel

Code of Federal Regulations, 2014 CFR

2014-07-01

... for Various Types of Fuel C Table C-2 to Subpart C of Part 98 Protection of Environment ENVIRONMENTAL... Fuel Combustion Sources Pt. 98, Subpt. C, Table C-2 Table C-2 to Subpart C of Part 98—Default CH4 and...) Default N2O emission factor (kg N2O/mmBtu) Coal and Coke (All fuel types in Table C-1) 1.1 × 10− 02 1.6...

Characterizing CH4, CO2 and N2O emission from barn feeding Tibetan sheep in Tibetan alpine pastoral area in cold season

NASA Astrophysics Data System (ADS)

Xu, Tianwei; Zhao, Na; Hu, Linyong; Xu, Shixiao; Liu, Hongjin; Ma, Li; Zhao, Xinquan

2017-05-01

Herein, methane (CH4), carbon dioxide (CO2) and nitrous oxide (N2O) emission from different aged barn feeding Tibetan sheep were characterized using a respiration chamber in combination with gas chromatograph method in cold season of 2013. This work was based on measuring the increase of gas concentration inside respiration chamber by the means of gas chromatograph. Results indicated that diurnal CH4 emission patterns for barn feeding Tibetan sheep were driven by feeding schedule, diurnal CO2 emission patterns were relatively stable with two slight emission peaks, diurnal N2O emission patterns were driven by the variation of temperature inside chamber. Diurnal CH4 emission rates were 17.65, 19.49 and 21.06 g sheep-1 d-1 for yearling, two-year and three-year barn feeding Tibetan sheep, account for 6.15%, 5.76% and 5.45% of their daily gross energy intakes, respectively. Diurnal CO2 emission rates were 526.88, 588.43 and 640.66 g sheep-1 d-1 for yearling, two-year and three-year barn feeding Tibetan sheep, respectively. Diurnal N2O emission rates were 1.64, 1.25 and 1.05 mg sheep-1 d-1 for yearling, two-year and three-year barn feeding Tibetan sheep, respectively. Three-year barn feeding Tibetan sheep released more CO2-eq on per unit BW and BW0.75 gain basis.

Impact of hydrochar on rice paddy CH4 and N2O emissions: A comparative study with pyrochar.

PubMed

Zhou, Beibei; Feng, Yanfang; Wang, Yueman; Yang, Linzhang; Xue, Lihong; Xing, Baoshan

2018-08-01

Hydrothermal carbonization (HTC) thermally converts wet biomasses to carbon materials, dramatically reducing energy use for drying and improving solid product yield compared to pyrolysis process. However, researches regarding agricultural usage of hydrochar (HC) are limited. In the present study, the influence of HC amendment on CH 4 and N 2 O emissions, as well as global warming potential (GWP) and greenhouse gas intensity (GHGI) were investigated. Additionally, pyrochar (PC) treatments as well as two char-free control treatments with (CKU) or without (CK) N fertilizer were also included for comparison. Chars were produced from wheat straw (WC) and saw dust (SC) and applied at different rates (0.5% and 3%, w/w). Both hydrochar and pyrochar decreased paddy CH 4 emissions when amended at a lower rate (0.5%) compared to CKU treatment, which was more obvious for pyrochar when applied at the rate of 3%. Contrarily, 3%-HC significantly stimulated CH 4 emissions, which were around 5 and 3 times higher than that of CKU for WC and SC, respectively. Furthermore, hydrochar showed the potential to decrease paddy N 2 O emissions (6.06-32.32%) at both application rates. However, N 2 O emissions with PC treatments varied depending on application rate (20.20-75.76%). GWP and GHGI values of 0.5%-HC and PC treatments were similar, 6.67-25.00% and 3.85-25.00% lower than those of CKU treatment, respectively. However, 3%-HC amendments led to significantly increased GWP and GHGI. This study suggested that application rate of hydrochar used in rice fields should be taken into serious consideration to fulfill its potential in GHGs mitigation and minimize environmental side effects. Copyright © 2018 Elsevier Ltd. All rights reserved.

Coupled effects of straw and nitrogen management on N2O and CH4 emissions of rainfed agriculture in Northwest China

NASA Astrophysics Data System (ADS)

Htun, Yin Min; Tong, Yanan; Gao, Pengcheng; Xiaotang, Ju

2017-05-01

Straw incorporation is a common agricultural practice, but the additional carbon source may increase greenhouse gas emissions by stimulating microbial activity in soil, particularly when straw is applied at the same time as nitrogen (N) fertilizer. We investigated the coupled effects of straw and N fertilizer on greenhouse gas emissions in a rainfed winter wheat-summer fallow system in Northwest China. Simultaneous applications of straw and N fertilizer increased N2O emissions by up to 88%, net greenhouse gas (NGHG) emission and net greenhouse gas intensity (NGHGI) by over 90%, and the N2O emission factor by over 2-fold. When straw was applied before N fertilizer, the emission factor (0.22%) decreased by approximately one-half compared with that for simultaneous applications (0.45%). In addition, early straw incorporation decreased N2O emissions, NGHG, and NGHGI by 35% (0.62 kg N2O-N ha-1 yr-1), 40% (242 kg CO2-eq ha-1 yr-1), and 38% (42 kg CO2-eq t-1 grain), respectively. We identified the period 30-35 days after N fertilization as a crucial period for evaluating the effectiveness of management practices on N2O emissions. The time between straw and fertilizer applications was negatively related to N2O emission (R2 = 0.8031; p < 0.01) but positively related to soil CH4 uptake (R2 = 0.7662; p < 0.01). Therefore, early straw incorporation can effectively mitigate greenhouse gas emissions by reducing N2O flux and increasing soil CH4 uptake without significantly decreasing grain yield.

Seasonal CH4 and N2O emissions and plant growth characteristics of several cultivars in direct seeded rice systems

NASA Astrophysics Data System (ADS)

Simmonds, M.; Anders, M. M.; Adviento-Borbe, M. A.; Van Kessel, C.; McClung, A.; Linquist, B.

2014-12-01

Understanding cultivar effects on field greenhouse gas (GHG) emissions in rice (Oryza sativa L.) systems is needed to improve the accuracy of predictive models used for estimating GHG emissions, and to determine to what extent choice of cultivar may have on GHG mitigation. We compared CH4 and N2O emissions, global warming potential (GWP = N2O + CH4), yield-scaled GWP (GWPY = GWP Mg-1 grain), and plant growth characteristics of 8 cultivars within 4 study sites in California and Arkansas. Seasonal CH4 emissions differed between cultivars by a factor of 2.1 and 1.3 at one California and one Arkansas site, respectively. Nitrous oxide emissions were negligible, comprised <10% of GWP, and were not different among cultivars. When sites and cultivars were pooled, and data were normalized to site averages, there was a positive correlation (r = 0.33) between root biomass at heading and seasonal CH4 emissions, but no correlation with shoot biomass at heading, or grain or straw biomass at maturity. Although differences in GWP and GWPY were observed, the consistency of some of the trends was variable across sites, indicating the importance of the genotype x environment interaction. While no high-yielding and low CH4-emitting cultivars were identified at the California sites, among the Southern varieties tested at the Arkansas site, the lowest emitting cultivar had the highest yield. This highlights the potential for breeding high-yielding varieties with low GWP, the ideal scenario to achieve low GWPY due to simultaneously mitigating GHG emissions and improving global food security.

Infrared photodissociation spectroscopy of H(+)(H2O)6·M(m) (M = Ne, Ar, Kr, Xe, H2, N2, and CH4): messenger-dependent balance between H3O(+) and H5O2(+) core isomers.

PubMed

Mizuse, Kenta; Fujii, Asuka

2011-04-21

Although messenger mediated spectroscopy is a widely-used technique to study gas phase ionic species, effects of messengers themselves are not necessarily clear. In this study, we report infrared photodissociation spectroscopy of H(+)(H(2)O)(6)·M(m) (M = Ne, Ar, Kr, Xe, H(2), N(2), and CH(4)) in the OH stretch region to investigate messenger(M)-dependent cluster structures of the H(+)(H(2)O)(6) moiety. The H(+)(H(2)O)(6), the protonated water hexamer, is the smallest system in which both the H(3)O(+) (Eigen) and H(5)O(2)(+) (Zundel) hydrated proton motifs coexist. All the spectra show narrower band widths reflecting reduced internal energy (lower vibrational temperature) in comparison with bare H(+)(H(2)O)(6). The Xe-, CH(4)-, and N(2)-mediated spectra show additional band features due to the relatively strong perturbation of the messenger. The observed band patterns in the Ar-, Kr-, Xe-, N(2)-, and CH(4)-mediated spectra are attributed mainly to the "Zundel" type isomer, which is more stable. On the other hand, the Ne- and H(2)-mediated spectra are accounted for by a mixture of the "Eigen" and "Zundel" types, like that of bare H(+)(H(2)O)(6). These results suggest that a messenger sometimes imposes unexpected isomer-selectivity even though it has been thought to be inert. Plausible origins of the isomer-selectivity are also discussed.

Synthesis, structure, and properties of nickel complexes with nitrilotris(methylenephosphonic acid) [Ni(H{sub 2}O)3N(CH2PO{sub 3}H){sub 3}] and Na{sub 4}[Ni(H{sub 2}O)N(CH{sub 2}PO{sub 3}){sub 3}] ∙ 11H{sub 2}O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Somov, N. V., E-mail: somov@phys.unn.ru; Chausov, F. F., E-mail: chaus@yandex.ru; Zakirova, R. M.

2016-03-15

Nitrilotris(methylenephosphonato)triaquanickel and tetrasodium nitrilotris(methylenephosphonato) aquanickelate undecahydrate were synthesized and characterized. The crystal of [Ni(H{sub 2}O){sub 3}N(CH{sub 2}PO{sub 3}H){sub 3}] is composed of linear coordination polymers and belongs to sp. gr. P2{sub 1}/c, Z = 4, a = 9.17120(10) Å, b = 16.05700(10) Å, c = 9.70890(10) Å, β = 115.830(2)°. The Ni atom is in an octahedral coordination formed by two oxygen atoms of one phosphonate ligand, one oxygen atom of another ligand molecule, and three water molecules in a meridional configuration. The crystal of Na{sub 4}[Ni(H{sub 2}O)N(CH{sub 2}PO{sub 3}){sub 3}] ∙ 11H{sub 2}O has an island dimeric chelate structuremore » and belongs to sp. gr. C2/c, Z = 8, a = 18.7152(2) Å, b = 12.05510(10) Å, c = 21.1266(2) Å, β = 104.4960(10)°. The Ni atom has a slightly distorted octahedral coordination involving one nitrogen atom and closes three five-membered N–C–P–O–Ni rings sharing the Ni–N bond.« less

Sensitivity of the boreal forest-mire ecotone CO2, CH4, and N2O global warming potential to rainy and dry weather

NASA Astrophysics Data System (ADS)

Ťupek, Boris; Minkkinen, Kari; Vesala, Timo; Nikinmaa, Eero

2015-04-01

In a mosaic of well drained forests and poorly drained mires of boreal landscape the weather events such as drought and rainy control greenhouse gas dynamics and ecosystem global warming potential (GWP). In forest-mire ecotone especially in ecosystems where CO2 sink is nearly balanced with CO2 source, it's fairly unknown whether the net warming effect of emissions of gases with strong radiative forcing (CH4 and N2O) could offset the net cooling effect of CO2 sequestration. We compared the net ecosystem CO2 exchange (NEE) estimated from the carbon sequestrations of forest stands and forest floor CO2 fluxes against CH4 and N2O fluxes of nine forest/mire site types along the soil moisture gradient in Finland. The ground water of nine sites changed between 10 m in upland forests and 0.1 m in mires, and weather during three years ranged between exceptionally wet and dry for the local climate. The NEE of upland forests was typically a sink of CO2, regardless the weather. Though, xeric pine forest was estimated to be a source of CO2 during wet and intermediate year and became a weak sink only in dry year. The NEE of forest-mire transitions ranged between a sink in dry year, while increased stand carbon sequestration could offset the reduced forest floor CO2 emission, and a source in wet year. The NEE of two sparsely forested mires strongly differed. The lawn type mire was balanced around zero and the hummock type mire was relatively strong NEE sink, regardless the weather. Generally, nearly zero N2O emission could not offset the cooling effect of net CH4 sink and net CO2 sink of upland forest and forest-mire transitions. However in sparsely forested mires, with N2O emission also nearly zero, the CH4 emission during wet and intermediate year played important role in turning the net cooling effect of NEE into a net warming. When evaluating GWP of boreal landscapes, undisturbed forest-mire transitions should be regarded as net cooling ecosystems instead of hotspots of net

Variations of atmospheric CH4, N2O and SF6 over Japan and the East China Sea

NASA Astrophysics Data System (ADS)

Ishijima, K.; Goto, D.; Ishidoya, S.; Yashiro, H.; Umezawa, T.; Sugawara, S.; Patra, P. K.; Muromachi, A.; Elkins, J. W.; Dutton, G. S.; Dlugokencky, E. J.; Morimoto, S.; Aoki, S.; Nakazawa, T.

2013-12-01

East Asia is one of the most important regions for anthropogenic sources of both short-lived air pollutants and long-lived greenhouse gases (GHGs). According to recent estimates from an emission database, China has become the largest emitter of long-lived GHGs. Since Japan and the East China Sea are located at the east end of Eurasia, atmospheric species emitted from the continent are transported over them throughout the year. Particularly in winter to spring, outflow of the emitted species is enhanced over the East China Sea due to the East Asian Monsoon. To monitor temporal and spatial variability of atmospheric GHGs in the East Asian region, we conducted systematic GHG observations during 2003-2012 from flask samples collected onboard four different commercial ferry boats, which connected between Wakkanai and Rishiri islands (WAK ; 45.4°N, 141.5°E), between Sakaiminato and Oki islands (OKI ; 35.8°N, 133.2°E), between Kagoshima and Okinawa islands (RYU ; 30.0°N, 130.0°E), and between Ishigaki and Hateruma islands (HTR ; 24.0°N, 124.0°E). Air samples were collected almost weekly, and they were sent to Tohoku University and analyzed for GHGs and related gases. In this study, we present analyses of observed CH4, N2O and SF6 concentrations in comparison with simulations by the Atmospheric general circulation model-based Chemistry Transport model (ACTM). The observed three species predictably show higher concentrations than those observed at Cape Kumukahi (KUM), which is a NOAA air sampling site located in the Central Pacific, reflecting strong outflow of the species from East Asia. Annual mean latitudinal gradients found from the four locations as well as decrease toward KUM are generally reproduced by the ACTM. This is mostly because of reasonable spatial distributions in GHG emissions given in the ACTM. The three species also show discernible seasonal cycles. ACTM simulates seasonal cycles of CH4 and SF6 relatively well, but not for N2O, suggesting

Vertical distribution of CH4 and N2O over the tropical site Hyderabad

NASA Technical Reports Server (NTRS)

Lal, Shyam; Subbaraya, B. H.; Fabian, Peter; Borchers, R.

1994-01-01

Vertical distribution profiles of N2O and CH4 have been measured from Hyderabad, India using a balloon-borne cryogenic air sampler. The samples have been analyzed using gas chromatographic techniques. Results for two balloon flights made in 1987 and 1990 show effects of tropical characteristics like higher tropopause and upwelling motion due to Hadley circulation. These profiles also exhibit perturbations around 25 km height, which are likely to be due to dynamical effects. A comparison with the SAMS data show that the SAMS values for both these gases are higher by a factor of about 1.5 to 2 around 30 km height.

[Effects of combined applications of pig manure and chemical fertilizers on CH4 and N2O emissions and their global warming potentials in paddy fields with double-rice cropping].

PubMed

Wang, Cong; Shen, Jian-Lin; Zheng, Liang; Liu, Jie-Yun; Qin, Hong-Ling; Li, Yong; Wu, Jin-Shui

2014-08-01

A field experiment was carried out to study the effects of combined applications of pig manure and chemical fertilizers on CH4 and N2O emissions, which were measured using the static chamber/gas chromatography method, and their global warming potentials in typical paddy fields with double-rice cropping in Hunan province. The results showed that the combined applications of pig manure and chemical fertilizers did not change the seasonal patterns of CH4 and N2O emissions from paddy soils, but significantly changed the magnitudes of CH4 and N2O fluxes in rice growing seasons as compared with sole application of chemical fertilizers. During the two rice growing seasons, the cumulative CH4 emissions for the pig manure and chemical nitrogen (N) fertilizer each contributing to 50% of the total applied N (1/2N + PM) treatment were higher than those for the treatments of no N fertilizer (ON), half amount of chemical N fertilizer (1/2N) and 100% chemical N fertilizer (N) by 54.83%, 33.85% and 43.30%, respectively (P < 0.05), whilst the cumulative N2O emissions for the 1/2N + PM treatment were decreased by 67.50% compared with N treatment, but increased by 129.43% and 119.23% compared with ON and 1/2N treatments, respectively (P < 0.05). CH4 was the dominant contributor to the global warming potential (GWP) in both rice growing seasons, which contributed more than 99% to the integrated GWP of CH4 and N2O emissions for all the four treatments. Both GWP and yield-scaled GWP for the treatment of 1/2N + PM were significantly higher than the other three treatments. The yield-scaled GWP for the treatment of 1/2N + PM was higher than those for the N, 1/2N and ON treatments by 58.21%, 26.82% and 20. 63%, respectively. Therefore, combined applications of pig manure and chemical fertilizers in paddy fields would increase the GWP of CH4 and N2O emissions during rice growing seasons and this effect should be considered in regional greenhouse gases emissions inventory.

Inter-seasonal and spatial distribution of ground-level greenhouse gases (CO2, CH4, N2O) over Nagpur in India and their management roadmap.

PubMed

Majumdar, Deepanjan; Rao, Padma; Maske, Nilam

2017-03-01

Ground-level concentrations of carbon dioxide (CO 2 ), methane (CH 4 ), and nitrous oxide (N 2 O) were monitored over three seasons, i.e., post-monsoon (September-October), winter (January-February), and summer (May-June) for 1 year during 2013-2014 in Nagpur City in India. The selected gases had moderate to high variation both spatially (residential, commercial, traffic intersections, residential cum commercial sites) and temporally (at 7:00, 13:00, 18:00, and 23:00 hours in all three seasons). Concentrations of gases were randomly distributed diurnally over city in all seasons, and there was no specific increasing or decreasing trend with time in a day. Average CO 2 and N 2 O concentrations in winter were higher over post-monsoon and summer while CH 4 had highest average concentration in summer. Observed concentrations of CO 2 were predominantly above global average of 400 ppmv while N 2 O and CH 4 concentrations frequently dropped down below global average of 327 ppbv and 1.8 ppmv, respectively. Two-tailed Student's t test indicated that post-monsoon CO 2 concentrations were statistically different from summer but not so from winter, while difference between summer and winter concentrations was statistically significant (P < 0.05). CH 4 concentrations in all seasons were statistically at par to each other. In case of N 2 O, concentrations in post-monsoon were statistically different from summer but not so from winter, while difference between summer and winter concentrations was statistically significant (P < 0.05). Average ground-level concentrations of the gases calculated for three seasons together were higher in commercial areas. Environmental management priorities vis a vis greenhouse gas emissions in the city are also discussed.

Permafrost collapse shifts alpine tundra to a carbon source but reduces N2O and CH4 release on the northern Qinghai-Tibetan Plateau

NASA Astrophysics Data System (ADS)

Mu, C. C.; Abbott, B. W.; Zhao, Q.; Su, H.; Wang, S. F.; Wu, Q. B.; Zhang, T. J.; Wu, X. D.

2017-09-01

Important unknowns remain about how abrupt permafrost collapse (thermokarst) affects carbon balance and greenhouse gas flux, limiting our ability to predict the magnitude and timing of the permafrost carbon feedback. We measured monthly, growing-season fluxes of CO2, CH4, and N2O at a large thermokarst feature in alpine tundra on the northern Qinghai-Tibetan Plateau (QTP). Thermokarst formation disrupted plant growth and soil hydrology, shifting the ecosystem from a growing-season carbon sink to a weak source but decreasing feature level CH4 and N2O flux. Temperature-corrected ecosystem respiration from decomposing permafrost soil was 2.7 to 9.5-fold higher than in similar features from Arctic and Boreal regions, suggesting that warmer and dryer conditions on the northern QTP could accelerate carbon decomposition following permafrost collapse. N2O flux was similar to the highest values reported for Arctic ecosystems and was 60% higher from exposed mineral soil on the feature floor, confirming Arctic observations of coupled nitrification and denitrification in collapsed soils. Q10 values for respiration were typically over 4, suggesting high-temperature sensitivity of thawed carbon. Taken together, these results suggest that QTP permafrost carbon in alpine tundra is highly vulnerable to mineralization following thaw, and that N2O production could be an important noncarbon permafrost climate feedback. Permafrost collapse altered soil hydrology, shifting the ecosystem from a carbon sink to carbon source but decreasing CH4 and N2O flux. Little to no vegetation recovery after stabilization suggests potentially large net carbon losses. High N2O flux compared to Arctic and Boreal systems suggests noncarbon permafrost climate feedback.

North American terrestrial CO 2 uptake largely offset by CH 4 and N 2O emissions: toward a full accounting of the greenhouse gas budget

DOE PAGES

Tian, Hanqin; Chen, Guangsheng; Lu, Chaoqun; ...

2014-03-14

The terrestrial ecosystems of North America have been identified as a sink of atmospheric CO 2 though there is no consensus on the magnitude. However, the emissions of non-CO 2 greenhouse gases (CH 4 and N 2O) may offset or even overturn the climate cooling effect induced by the CO 2 sink. Using a coupled biogeochemical model, in this study, we have estimated the combined global warming potentials (GWP) of CO 2, CH 4 and N 2O fluxes in North American terrestrial ecosystems and quantified the relative contributions of environmental factors to the GWP changes during 1979–2010. The uncertainty rangemore » for contemporary global warming potential has been quantified by synthesizing the existing estimates from inventory, forward modeling, and inverse modeling approaches. Our “best estimate” of net GWP for CO 2, CH 4 and N 2O fluxes was₋0.50 ± 0.27 Pg CO 2 eq/year (1 Pg=1015 g) in North American terrestrial ecosystems during 2001–2010. The emissions of CH 4 and N 2O from terrestrial ecosystems had offset about two thirds (73% ± 14%) of the land CO 2 sink in the North American continent, showing large differences across the three countries, with offset ratios of 57% ± 8% in US, 83% ± 17 % in Canada and 329% ± 119 % in Mexico. Climate change and elevated tropospheric ozone concentration have contributed the most to GWP increase, while elevated atmospheric CO 2 concentration have contributed the most to GWP reduction. Extreme drought events over certain periods could result in a positive GWP. By integrating the existing estimates, we have found a wide range of uncertainty for the combined GWP. In conclusion, from both climate change science and policy perspectives, it is necessary to integrate ground and satellite observations with models for a more accurate accounting of these three greenhouse gases in North America.« less

Drivers of small scale variability in soil-atmosphere fluxes of CH4, N2O and CO2 in a forest soil

NASA Astrophysics Data System (ADS)

Maier, Martin; Nicolai, Clara; Wheeler, Denis; Lang, Friedeike; Paulus, Sinikka

2016-04-01

Soil-atmosphere fluxes of CH4, N2O and CO2 can vary on different spatial scales, on large scales between ecosystems but also within apparently homogenous sites. While CO2 and CH4 consumption is rather evenly distibuted in well aerated soils, the production of N2O and CH4 seems to occur at hot spots that can be associated with anoxic or suboxic conditions. Small-scale variability in soil properties is well-known from field soil assesment, affecting also soil aeration and thus theoretically, greenhouse gas fluxes. In many cases different plant species are associated with different soil conditions and vegetation mapping should therefor combined with soil mapping. Our research objective was explaining the small scale variability of greenhouse gas fluxes in an apparently homogeneous 50 years old Scots Pine stand in a former riparian flood plain.We combined greenhouse gas measurements and soil physical lab measurments with field soil assessment and vegetation mapping. Measurements were conducted with at 60 points at a plot of 30 X 30 m at the Hartheim monitoring site (SW Germany). For greenhouse gas measurements a non-steady state chamber system and laser analyser, and a photoacoustic analyser were used. Our study shows that the well aerated site was a substantial sink for atmospheric CH4 (-2.4 nmol/m² s) and also a for N2O (-0.4 nmol/m² s), but less pronounced, whereas CO2 production was a magnitude larger (2.6 μmol/m² s). The spatial variability of the CH4 consumption of the soils could be explained by the variability of the soil gas diffusivity (measured in situ + using soil cores). Deviations of this clear trend were only observed at points where decomposing woody debris was directly under the litter layer. Soil texture ranged from gravel, coarse sand, fine sand to pure silt, with coarser texture having higher soil gas diffusivity. Changes in texture were rather abrupt at some positions or gradual at other positions, and were well reflected in the vegetation

[Effect of carbon substrate concentration on N2, N2O, NO, CO2, and CH4 emissions from a paddy soil in anaerobic condition].

PubMed

Chen, Nuo; Liao, Ting-ting; Wang, Rui; Zheng, Xun-hua; Hu, Rong-gui; Butterbach-Bahl, Klaus

2014-09-01

Understanding the effects of carbon and nitrogen substrates concentrations on the emissions of denitrification gases including nitrogen (N2) , nitrous oxide (N2O) and nitric oxide (NO), carbon dioxide (CO2) and methane (CH4) from anaerobic paddy soils is believed to be helpful for development of greenhouse gas mitigation strategies. Moreover, understanding the quantitative dependence of denitrification products compositions on carbon substrate concentration could provide some key parameters or parameterization scheme for developing process-oriented model(s) of nitrogen transformation. Using a silt loam soil collected from a paddy field, we investigated the influence of carbon substrate concentration on the emissions of the denitrification gases, CO2 and CH4 from anaerobically incubated soils by setting two treatments: control (CK) with initial soil nitrate and dissolved organic carbon (DOC) concentrations of ~ 50 mg.kg-1 and -28 mg kg-1 , respectively; and DOC added (C + ) with initial soil nitrate and DOC concentrations of ~50 mg.kg-1 and ~300 mg.kg-1 , respectively. The emissions of denitrification gases, CO2 and CH4, as well as concentrations of carbon and nitrogen substrates for each treatment were dynamically measured, using the gas-flow-soil-core technique and a paralleling substrate monitoring system. The results showed that CH4 emission was not observed in CK treatment while observed in C treatment. Aggregate emission of greenhouse gases for C + treatment was significantly higher comparing with the CK treatment (P <0. 01). The mass fractions of NO, N20 and N2 emissions in total nitrogen gases emissions were approximately 9% , 35% and 56% for CK treatment, respectively; and approximately 31% , 50% and 19% for C+ treatment, respectively, with significant differences between these two treatments (P < 0.01). The results indicated that carbon substrate concentrations can significantly change the composition of nitrogen gas emissions. The results also implicated

Effects of N loading rate on CH4 and N2O emissions during cultivation and fallow periods from forage rice fields fertilized with liquid cattle waste.

PubMed

Riya, S; Zhou, S; Kobara, Y; Sagehashi, M; Terada, A; Hosomi, M

2015-09-15

The use of liquid cattle waste (LCW) as a fertilizer for forage rice is important for material recycling because it can promote biomass production, and reduce the use of chemical fertilizer. Meanwhile, increase in emission of greenhouse gases (GHGs), especially CH4 and N2O would be concerned. We conducted a field study to determine the optimum loading rate of LCW as N to promote forage rice growth with lower GHG emissions. The LCW was applied to forage rice fields, N100, N250, N500, and N750, at four different N loading rates of 107, 258, 522, and 786 kg N ha(-1), respectively, including 50 kg N ha(-1) of basal chemical fertilizer. The above-ground biomass yields increased 14.6-18.5 t ha(-1) with increases in N loading rates. During the cultivation period, both the CH4 and N2O fluxes increased with increases in LCW loading rates. In the treatments of N100, N250, N500, and N750, the cumulative CH4 emissions during the entire period, including cultivation and fallow period were 29.6, 18.1, 54.4, and 67.5 kg C ha(-1), respectively, whereas those of N2O were -0.15, -0.02, 1.49, and 5.82 kg N ha(-1), respectively. Considering the greenhouse gas emissions and above-ground biomass, the yield-scaled CO2-equivalents (CO2-eqs) were 66.3, 35.9, 161, and 272 kg CO2 t(-1) for N100, N250, N500, and N750, respectively. These results suggest that N250 is the most appropriate LCW loading rate for promoting forage rice production with lower GHG emissions. Copyright © 2015 Elsevier Ltd. All rights reserved.

The Structure of Titan’s N2 and CH4 Coronae

NASA Astrophysics Data System (ADS)

Jiang, Fayu; Cui, Jun; Xu, Jiyao

2017-12-01

In this study, we analyze the structures of Titan’s N2 and CH4 coronae using a large data set acquired by the Ion Neutral Mass Spectrometer (INMS) instrument on board Cassini. The N2 and CH4 densities measured from the exobase up to 2000 km imply a mean exobase temperature of 146 K and 143 K, respectively, which is lower than the mean upper atmospheric temperature by 4 and 7 K. This indicates that on average, Titan possesses a subthermal rather than suprathermal corona. A careful examination reveals that the variability in corona structure is not very likely to be solar driven. Within the framework of the collisionless kinetic model, we investigate how the CH4 energy distribution near the exobase could be constrained if strong CH4 escape occurs on Titan. Several functional forms for the CH4 energy distribution are attempted, assuming two representative CH4 escape rates of 1.2× {10}25 s-1 and 2.2× {10}27 s-1. We find that the double Maxwellian and power-law distributions can reproduce the shape of the CH4 corona structure as well as the imposed CH4 escape rate. In both cases, the escape rate is contributed by a suprathermal CH4 population on the high-energy tail, with a number fraction below 5% and a characteristic energy of 0.1-0.6 eV per suprathermal CH4 molecule. The coexistence of the subthermal CH4 corona revealed by the INMS data and substantial CH4 escape suggested by some previous works could be reconciled by a significant departure in the exobase CH4 energy distribution from ideal Maxwellian that enhances escape and causes a noticeable redistribution of the corona structure.

Highly Permeable AlPO-18 Membranes for N 2 /CH 4 Separation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zong, Zhaowang; Elsaidi, Sameh K.; Thallapally, Praveen K.

Herein we demonstrate that AlPO-18 membranes can separate N2/CH4 gas mixtures at unprecedented N2 permeances. The best membranes separated N2/CH4 mixtures with N2 permeances as high as 3076 GPU and separation selectivities as high as 4.6. Gas mixture separation data, N2 and CH4 adsorption isotherms, ideal adsorbed solution theory (IAST), and breakthrough experiments were collected to understand the separation mechanisms. Competitive adsorption and differences in diffusivities were identified as the prevailing separation mechanisms. Differences in diffusivity played a more dominant role than the competitive adsorption, and led to nitrogen selective membranes.

Synthesis, spectral and antifungal analysis of diaryldithiophosphates of mono- and dibutyltin(IV): x-ray structure of [{(3,5-CH3)2C6H3O)2PS2}2Sn(nBu)2].

PubMed

Syed, Atiya; Khajuria, Ruchi; Kumar, Sandeep; Jassal, Amanpreet Kaur; Hundal, Maninder S; Pandey, Sushil K

2014-01-01

Diaryldithiophosphate complexes of mono- and dibutyltin(IV) corresponding to [(ArO)(2)PS(2)(n)Sn(nBu)xCl(4-x-n)] (Ar = o-CH(3)C(6)H(4), m-CH(3)C(6)H(4), p-CH(3)C(6)H(4), 4-Cl-3-CH(3)C(6)H(3), (3,5-CH(3))(2)C(6)H(3); n = 1, 2 for x = 1 and n = 2 for x = 2) were successfully isolated and characterized by elemental analyses, IR, multinuclear NMR ((1)H, (13)C, (31)P and (119)Sn) spectroscopy and X-ray analysis. The thermal properties of the complex [(3,5-CH(3))(2)C(6)H(3)O(2)PS(2)](2)Sn(nBu)(2) (12) have been examined by combined DTA/ DTG thermal analyses. Single crystal X-ray analysis of [(3,5-CH(3))(2)C(6)H(3)O(2)PS(2)](2)S(n)(nBu)(2) (12) revealed that two diaryldithiophosphate ions are coordinated to tin atom in an anisobidentate fashion through the sulfur atoms of each dithiophosphate moiety leading to distorted skew-trapezoidal bipyramidal geometry. The antifungal activity depicts that these complexes are active against fungus Penicillium chrysogenium.

Spatial variability of greenhouse gases emissions (CO2, CH4, N2O) in a tropical hydroelectric reservoir flooding primary forest (Petit Saut Reservoir, French Guiana)

NASA Astrophysics Data System (ADS)

Cailleaud, Emilie; Guérin, Frédéric; Bouillon, Steven; Sarrazin, Max; Serça, Dominique

2014-05-01

At the Petit Saut Reservoir (PSR, French Guiana, South America), vertical profiles were performed at 5 stations in the open waters (OW) and 6 stations in two shallow flooded forest (FF) areas between April 2012 and September 2013. Measurements included physico-chemical parameters, ammonium, nitrate and dissolved greenhouse gas (CO2, CH4, N2O) concentrations, dissolved and particulate organic carbon (DOC, POC) and nitrogen (PN), δ13C-POC and δ15N-PN . The diffusive fluxes were calculated from surface concentrations. The aim of this study was to estimate the spatial variations of greenhouse gas emissions at a dentrical hydroelectric reservoir located in the tropics and flooding primary forest. Twenty years after impoundment, the water column of the PSR is permanently and tightly stratified thermally in the FF whereas in the OW, the thermal gradients are not as stable. The different hydrodynamical behaviours between the two different zones have significant consequences on the biogeochemistry: oxygen barely diffuses down to the hypolimnion in the FF whereas destratification occurs sporadically during the rainy season in the OW. Although we found the same range of POC in the FF and the OW (2.5-29 μmol L-1) and 20% more DOC at the bottom of OW than in the FF (229-878 μmol L-1), CO2 and CH4 concentrations were always significantly higher in the FF (CO2: 11-1412 μmol L-1, CH4: 0.001-1015 μmol L-1) than in the OW. On average, the CO2 concentrations were 30-40% higher in the FF than in the OW and the CH4 concentrations were three times higher in the FF than in the OW. The δ13C-POC and C:N values did not suggest substantial differences in the sources of OM between the FF and OW. At all stations, POC at the bottom has an isotopic signature slightly lighter than the terrestrial OM in the surrounding forest whereas the isotopic signature of surface POM would result from phytoplankton and methanotrophs. The vertical profiles of nitrogen compounds reveal that the main

Reflected shock tube studies of high-temperature rate constants for OH + CH4 --> CH3 + H2O and CH3 + NO2 --> CH3O + NO.

PubMed

Srinivasan, N K; Su, M-C; Sutherland, J W; Michael, J V

2005-03-10

The reflected shock tube technique with multipass absorption spectrometric detection of OH radicals at 308 nm has been used to study the reactions OH + CH(4) --> CH(3) + H(2)O and CH(3) + NO(2) --> CH(3)O + NO. Over the temperature range 840-2025 K, the rate constants for the first reaction can be represented by the Arrhenius expression k = (9.52 +/- 1.62) x 10(-11) exp[(-4134 +/- 222 K)/T] cm(3) molecule(-1) s(-1). Since this reaction is important in both combustion and atmospheric chemistry, there have been many prior investigations with a variety of techniques. The present results extend the temperature range by 500 K and have been combined with the most accurate earlier studies to derive an evaluation over the extended temperature range 195-2025 K. A three-parameter expression describes the rate behavior over this temperature range, k = (1.66 x 10(-18))T(2.182) exp[(-1231 K)/T] cm(3) molecule(-1) s(-1). Previous theoretical studies are discussed, and the present evaluation is compared to earlier theoretical estimates. Since CH(3) radicals are a product of the reaction and could cause secondary perturbations in rate constant determinations, the second reaction was studied by OH radical production from the fast reactions CH(3)O --> CH(2)O + H and H + NO(2) --> OH + NO. The measured rate constant is 2.26 x 10(-11) cm(3) molecule(-1) s(-1) and is not dependent on temperature from 233 to 1700 K within experimental error.

Formation of a nanobubble and its effect on the structural ordering of water in a CH4-N2-CO2-H2O mixture.

PubMed

Kaur, Surinder Pal; Sujith, K S; Ramachandran, C N

2018-04-04

The replacement of methane (CH4) from its hydrate by a mixture of nitrogen (N2) and carbon dioxide (CO2) involves the dissociation of methane hydrate leading to the formation of a CH4-N2-CO2-H2O mixture that can significantly influence the subsequent steps of the replacement process. In the present work, we study the evolution of dissolved gas molecules in this mixture by applying classical molecular dynamics simulations. Our study shows that a higher CO2 : N2 ratio in the mixture enhances the formation of nanobubbles composed of N2, CH4 and CO2 molecules. To understand how the CO2 : N2 ratio affects nanobubble nucleation, the distribution of molecules in the bubble formed is examined. It is observed that unlike N2 and CH4, the density of CO2 in the bubble reaches a maximum at the surface of the bubble. The accumulation of CO2 molecules at the surface makes the bubble more stable by decreasing the excess pressure inside the bubble as well as surface tension at its interface with water. It is found that a frequent exchange of gas molecules takes place between the bubble and the surrounding liquid and an increase in concentration of CO2 in the mixture leads to a decrease in the number of such exchanges. The effect of nanobubbles on the structural ordering of water molecules is examined by determining the number of water rings formed per unit volume in the mixture. The role of nanobubbles in water structuring is correlated to the dynamic nature of the bubble arising from the exchange of gas molecules between the bubble and the liquid.

Endohedral complexes of fullerene-like silica molecules with H2O, CH4, and CH3NH2 molecules

NASA Astrophysics Data System (ADS)

Filonenko, O. V.; Lobanov, V. V.

2013-07-01

The possibility of formation of (SiO2)60@H2O, (SiO2)60@CH4, and (SiO2)60@CH3NH2 endohedral complexes was studied by the density functional (DFT) method (B3LYP exchange correlation functional, 6-31G** basis). The penetration of these molecules into the cavity of fullerene-like silica molecules is hindered by high activation barriers, which ensures the stability of the complexes formed during the synthesis of these molecules.

In Situ Measurements of N2O and CH4 During SOLVE on the ER-2 Using a New Tunable Diode Laser Instrument

NASA Technical Reports Server (NTRS)

Jost, Hansjurg

2002-01-01

This report is the final report for Cooperative Agreement NCC2-1105: 'In Situ Measurements of N2O and CH4 during SOLVE on the ER-2 using a new tunable diode laser instrument.' The tasks outlined in the proposal are listed below with a brief comment. The publications and the conference presentations are listed. Finally the important publications are attached. The Cooperative Agreement made possible a research effort to produce high precision and high accuracy in situ measurements of methane and nitrous oxide on the ER-2 during the SOLVE field campaign and to analyze these measurements. These measurements of CH4 and N2O were of utmost importance to studies of the ozone losses in the Arctic winter and spring. The concentrations measured over a large spatial and temporal range allowed the separation of the dynamical and chemical ozone loss. The most important results of the SOLVE program were contained in two scientific papers. This Cooperative Agreement allowed the participation of the Argus instrument in the program and the analysis of the data.

The development and evaluation of airborne in situ N2O and CH4 sampling using a quantum cascade laser absorption spectrometer (QCLAS)

NASA Astrophysics Data System (ADS)

Pitt, J. R.; Le Breton, M.; Allen, G.; Percival, C. J.; Gallagher, M. W.; Bauguitte, S. J.-B.; O'Shea, S. J.; Muller, J. B. A.; Zahniser, M. S.; Pyle, J.; Palmer, P. I.

2016-01-01

Spectroscopic measurements of atmospheric N2O and CH4 mole fractions were made on board the FAAM (Facility for Airborne Atmospheric Measurements) large atmospheric research aircraft. We present details of the mid-infrared quantum cascade laser absorption spectrometer (QCLAS, Aerodyne Research Inc., USA) employed, including its configuration for airborne sampling, and evaluate its performance over 17 flights conducted during summer 2014. Two different methods of correcting for the influence of water vapour on the spectroscopic retrievals are compared and evaluated. A new in-flight calibration procedure to account for the observed sensitivity of the instrument to ambient pressure changes is described, and its impact on instrument performance is assessed. Test flight data linking this sensitivity to changes in cabin pressure are presented. Total 1σ uncertainties of 2.47 ppb for CH4 and 0.54 ppb for N2O are derived. We report a mean difference in 1 Hz CH4 mole fraction of 2.05 ppb (1σ = 5.85 ppb) between in-flight measurements made using the QCLAS and simultaneous measurements using a previously characterised Fast Greenhouse Gas Analyser (FGGA, Los Gatos Research, USA). Finally, a potential case study for the estimation of a regional N2O flux using a mass balance technique is identified, and the method for calculating such an estimate is outlined.

Surface modification of layered perovskite Sr2TiO4 for improved CO2 photoreduction with H2O to CH4.

PubMed

Kwak, Byeong Sub; Do, Jeong Yeon; Park, No-Kuk; Kang, Misook

2017-11-27

Layered perovskite Sr 2 TiO 4 photocatalyst was synthesized by using sol-gel method with citric acid. In order to increase the surface area of layered perovskite Sr 2 TiO 4 , and thus to improve its photocatalytic activity for CO 2 reduction, its surface was modified via hydrogen treatment or exfoliation. The physical and chemical properties of the prepared catalysts were characterized by X-ray diffraction, high-resolution transmission electron microscopy, elemental mapping analysis, energy-dispersive X-ray spectroscopy, N 2 adsorption-desorption, UV-Vis spectroscopy, X-ray photoelectron spectroscopy, photoluminescence, and electrophoretic light scattering. CO 2 photoreduction was performed in a closed reactor under 6 W/cm 2 UV irradiation. The gaseous products were analyzed using a gas chromatograph equipped with flame ionization and thermal conductivity detectors. The exfoliated Sr 2 TiO 4 catalyst (E-Sr 2 TiO 4 ) exhibited a narrow band gap, a large surface area, and high dispersion. Owing to these advantageous properties, E-Sr 2 TiO 4 photocatalyst showed an excellent catalytic performance for CO 2 photoreduction reaction. The rate of CH 4 production from the photoreduction of CO 2 with H 2 O using E-Sr 2 TiO 4 was about 3431.77 μmol/g cat after 8 h.

Photodissociation of the CH3Cl/+/ and N2O/+/ cations.

NASA Technical Reports Server (NTRS)

Dunbar, R. C.

1971-01-01

Use of the ion cyclotron resonance (icr) technique to observe the photodissociation of the cations CH3Cl(+) and N2O(+) in the gas phase. Ions were trapped in the icr cell for periods of the order of seconds, which permitted the photodissociation process to be observed with wavelength-selected light. A cyclotron resonance ejection technique was employed to show that CH3Cl(+) ions were being dissociated rather than the CH3ClH(+) ions which were also present. The photodissociation cross section for N2O(+) was found to be without strong wavelength dependence between 4000 and 6500 A. The cross section for CH3Cl(+) showed a large peak at 3150 A. Possible assignments of this peak are considered, and it is suggested that a photodissociation occurs through an ion excitation involving a change in occupation of the bonding or antibonding orbitals of the C-Cl bond.

Geographic Distribution of N2, CH4, CO2, and H2O Ices on Triton from Near-IR Spectroscopic Monitoring

NASA Astrophysics Data System (ADS)

Grundy, W. M.; Young, L. A.; Young, E. F.; Buie, M. W.; Spencer, J. R.

2004-11-01

We present new 0.8 to 2.4 μ m spectral observations of Neptune's satellite Triton, obtained at IRTF\\slash SpeX between 2001 and 2004 as part of an ongoing search for time-variable phenomena associated with Triton's seasonal volatile transport processes, and also perhaps with reported shorter-term "reddening" events. The ability to detect spectral changes on these time scales depends critically on accurate characterization of any cyclic variations resulting from Triton's 5.877 day rotation period. We will report on our observations of periodic variations of Triton's near-IR absorption bands of N2, CH4, and H2O ices, but not of CO2 ice, in this initial stage of our Triton monitoring program. The observed variations (or lack thereof) give an indication of how these four ice species are distributed in longitude. The most heterogeneously distributed ice is N2, which shows nearly twice as much absorption on Triton's Neptune-facing hemisphere as on the anti-Neptune hemisphere. Comparison with Voyager-era, visual wavelength imaging of Triton's surface suggest that the observed N2 ice is concentrated on low-latitude regions of Triton's polar cap, which are predominantly located on the Neptune-facing hemisphere. Non-volatile H2O ice seems to be slightly concentrated on Triton's leading hemisphere. Despite being highly diluted in N2 ice, the longitudinal distribution of Triton's CH4 ice differs from that of Triton's N2 ice, being slightly concentrated on Triton's trailing hemisphere. Triton's CO2 ice shows the least longitudinal variation, suggesting that it is either very uniformly distributed or that it is confined to high latitudes. This work was supported by NASA's Planetary Astronomy and Planetary Geology &\\ Geophysics programs, and by NSF's Planetary Astronomy program. \\hangindent=0.3truein Grundy, W.M., and L.A. Young (2004) Near infrared spectral monitoring of Triton with IRTF\\slash SpeX I: Establishing a baseline. Icarus (in press).

Using Mid-IR Cavity Ring-Down Spectrometry to Simultaneously Measure N2o, CO2, and CH4 Fluxes: Responses to Ammonium Nitrate Additions in Salt Marshes

NASA Astrophysics Data System (ADS)

Brannon, E.; Moseman-Valtierra, S.; Tang, J.; Chen, X.; Martin, R.; Garate, M.

2014-12-01

Greenhouse gas emissions from salt marshes, especially of nitrous oxide (N2O), are a central interest because anthropogenic nutrient loads may substantially alter net climatic forcing of these globally significant ecosystems. In a series of lab and field experiments, a new cavity ring down spectrometer (CRDS, Picarro G2508) that uses mid-infrared (mid-IR) frequencies to measure N2O was compared to a near-IR gas analyzer (LGR N2O/CO analyzer). The Picarro G2508 reports N2O as well as CO2 and CH4 concentrations roughly every second at the parts per billion level. Responses of N2O fluxes to experimental ammonium nitrate additions in marsh mesocosms and marsh plots in situ were compared among these analyzers, along with minimum detectable N2O fluxes. At fluxes above 150 μmol N2O m-2 d-1, the Picarro G2508 and LGR analyzers performed similarly in both mesocosm and field plots that had been enriched with ammonium nitrate, however there were significantly lower minimum detectable N2O fluxes (about 1 order of magnitude) for the LGR than for the Picarro. A gas chromatograph (Shimadzu GC 2014) was also used to test calibration of the G2508. These experiments suggest that mid-IR CRDS technology offers a new tool for simultaneous analyses of N2O along with CO2 and CH4, which fills an important need for quantifying the net climatic forcing of ecosystems. However based on relatively high minimum N2O detection levels of the CRDS, it may work best in highly eutrophic environments.

Measurements of CH4, N2O, CO, H2O and O3 in the middle atmosphere by the ATMOS experiment on Spacelab 3

NASA Technical Reports Server (NTRS)

Gunson, M. R.; Farmer, C. B.; Norton, R. H.; Zander, R.; Rinsland, C. P.; Shaw, J. H.; Gao, Bo-Cai

1989-01-01

The volume mixing ratios of five minor gases (CH4, N2O, CO, H2O, and O3) were retrieved through the middle atmosphere from the analysis of 0.01/cm resolution infrared solar occultation spectra recorded near 28 N and 48 S latitudes with the ATMOS (Atmospheric Trace Molecule Spectroscopy) instrument, flown on board Spacelab 3. The results, which constitute the first simultaneous observations of continuous profiles through the middle atmosphere for these gases, are in general agreement with reported measurements from ground, balloon and satellite-based instruments for the same seasons. In detail, the vertical profiles of these gases show the effects of the upper and middle atmospheric transport patterns dominant during the season of these observations. The profiles inferred at different longitudes around 28 N suggest a near-uniform zonal distribution of these gases. Although based on fewer observations, the sunrise occultation measurements point to a larger variability in the vertical distribution of these gases at 48 S.

The development and evaluation of airborne in situ N2O and CH4 sampling using a Quantum Cascade Laser Absorption Spectrometer (QCLAS)

NASA Astrophysics Data System (ADS)

Pitt, Joseph; Le Breton, Michael; Allen, Grant; Percival, Carl; Gallagher, Martin; Bauguitte, Stephane; O'Shea, Sebastian; Muller, Jennifer; Zahniser, Mark; Pyle, John; Palmer, Paul

2016-04-01

Spectroscopic measurements of atmospheric N2O and CH4 mole fractions were made on board the FAAM (Facility for Airborne Atmospheric Measurements) large Atmospheric Research Aircraft. We evaluate the performance of the mid-IR continuous wave Aerodyne Research Inc. Quantum Cascade Laser Absorption Spectrometer (QCLAS) employed over 17 flights conducted during summer 2014. Two different methods of correcting for the influence of water vapour on the spectroscopic retrievals are compared and evaluated. Test flight data demonstrating the sensitivity of the instrument to changes in cabin pressure is presented, and a new in-flight calibration procedure to account for this issue is described and assessed. Total 1σ uncertainties of 1.81 ppb for CH4 and 0.35 ppb for N2O are derived. We report a mean difference in 1 Hz CH4 mole fraction of 2.05 ppb (1σ = 5.85 ppb) between in-flight measurements made using the QCLAS and simultaneous measurements using a previously characterised Los Gatos Research Fast Greenhouse Gas Analyser (FGGA).

The development and evaluation of airborne in situ N2O and CH4 sampling using a Quantum Cascade Laser Absorption Spectrometer (QCLAS)

NASA Astrophysics Data System (ADS)

Pitt, J. R.; Le Breton, M. R.; Allen, G.; Percival, C.; Gallagher, M. W.; Bauguitte, S.; O'Shea, S.; Muller, J.; Zahniser, M. S.; Pyle, J. A.; Palmer, P. I.

2015-12-01

Spectroscopic measurements of atmospheric N2O and CH4 mole fractions were made on board the FAAM (Facility for Airborne Atmospheric Measurements) large Atmospheric Research Aircraft. We evaluate the performance of the mid-IR continuous wave Aerodyne Research Inc. Quantum Cascade Laser Absorption Spectrometer (QCLAS) employed over 17 flights conducted during summer 2014. Two different methods of correcting for the influence of water vapour on the spectroscopic retrievals are compared and evaluated. Test flight data demonstrating the sensitivity of the instrument to changes in cabin pressure is presented, and a new in-flight calibration procedure to account for this issue is described and assessed. Total 1σ uncertainties of 1.81 ppb for CH4 and 0.35 ppb for N2O are derived. We report a mean difference in 1 Hz CH4 mole fraction of 2.05 ppb (1σ = 5.85 ppb) between in-flight measurements made using the QCLAS and simultaneous measurements using a previously characterised Los Gatos Research Fast Greenhouse Gas Analyser (FGGA).

New High-Frequency Measurements of CH4, N2O and SF6 from a High-Altitude Station in the Eastern Himalayas of India and Derived Emissions Estimates

NASA Astrophysics Data System (ADS)

Ganesan, A. L.; Chatterjee, A.; Salameh, P.; Harth, C. M.; Rigby, M.; Manning, A. J.; Hall, B. D.; Ghosh, S. K.; Muhle, J.; Meredith, L. K.; Mandal, T. K.; Weiss, R. F.; Prinn, R. G.

2012-12-01

We present new in situ measurements from a station in Darjeeling, India (27.03°N, 88.26°E, 2200 m above sea level). These measurements comprise the first high-frequency dataset of methane (CH4), nitrous oxide (N2O) and sulfur hexafluoride (SF6) collected in India. Measurements are made with a gas chromatographic system, using a flame ionization detector (GC-FID) for CH4 and an electron capture detector (GC-ECD) for N2O and SF6. Measurements have been linked to calibration scales used in the Advanced Global Atmospheric Gases Experiment (AGAGE, Tohoku University for CH4 and Scripps institution of Oceanography 1998 and 2005, for N2O and SF6, respectively). Preliminary results show a significant diurnal cycle for CH4, consistent with upslope flows bringing local emissions from the town and valley to the site during the day and downslope flows bringing cleaner air at night. This nighttime decrease in mixing ratio could be attributed to a variety of factors, including reduced local emissions or sampling of cleaner, free tropospheric air from aloft. Underlying this local signal is a much larger regional influence, which is driven by the large-scale meteorology that governs which upwind regions contribute to the measured mole fractions at the site. We also investigate local influences on N2O and SF6, which are much smaller than CH4 or negligible, because of their comparatively weaker nearby sources. We present emissions estimates for India using the high-resolution UK Met Office Lagrangian particle dispersion model, the Numerical Atmospheric dispersion Modeling Environment (NAME). Air histories generated using NAME reveal that the site regularly intercepts air from important rice-growing and biomass burning regions of Northern India. This unique dataset allows further constraints to be placed on "top-down" estimates of emissions from these CH4 sources. Further constraints will also be possible for regional agricultural sources of N2O and South-Asian SF6, both of which

The development and evaluation of airborne in situ N2O and CH4 sampling using a Quantum Cascade Laser Absorption Spectrometer (QCLAS)

NASA Astrophysics Data System (ADS)

Pitt, J. R.; Le Breton, M.; Allen, G.; Percival, C. J.; Gallagher, M. W.; Bauguitte, S. J.-B.; O'Shea, S. J.; Muller, J. B. A.; Zahniser, M. S.; Pyle, J.; Palmer, P. I.

2015-08-01

Spectroscopic measurements of atmospheric N2O and CH4 mole fractions were made on board the FAAM (Facility for Airborne Atmospheric Measurements) large Atmospheric Research Aircraft. We present details of the mid-IR Aerodyne Research Inc. Quantum Cascade Laser Absorption Spectrometer (QCLAS) employed, including its configuration for airborne sampling, and evaluate its performance over 17 flights conducted during summer 2014. Two different methods of correcting for the influence of water vapour on the spectroscopic retrievals are compared and evaluated. A new in-flight calibration procedure to account for the observed sensitivity of the instrument to ambient pressure changes is described, and its impact on instrument performance is assessed. Test flight data linking this sensitivity to changes in cabin pressure is presented. Total 1σ uncertainties of 1.81 ppb for CH4 and 0.35 ppb for N2O are derived. We report a mean difference in 1 Hz CH4 mole fraction of 2.05 ppb (1σ = 5.85 ppb) between in-flight measurements made using the QCLAS and simultaneous measurements using a previously characterised Los Gatos Research Fast Greenhouse Gas Analyser (FGGA). Finally, a potential case study for the estimation of a regional N2O flux using a mass balance technique is identified, and the method for calculating such an estimate is outlined.

40 CFR Table Aa-2 to Subpart Aa of... - Kraft Lime Kiln and Calciner Emissions Factors for CH4 and N2O

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 21 2014-07-01 2014-07-01 false Kraft Lime Kiln and Calciner Emissions Factors for CH4 and N2O AA Table AA-2 to Subpart AA of Part 98 Protection of Environment ENVIRONMENTAL... Manufacturing Pt. 98, Subpt. AA, Table AA -2 Table AA-2 to Subpart AA of Part 98—Kraft Lime Kiln and Calciner...

Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria

USGS Publications Warehouse

Circone, S.; Kirby, S.H.; Stern, L.A.

2006-01-01

Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H 2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within ??2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol-1 K-1 for 1/n CH4??H 2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled. ?? 2006 American Chemical Society.

Evaluation of the airborne quantum cascade laser spectrometer (QCLS) measurements of the carbon and greenhouse gas suite - CO2, CH4, N2O, and CO - during the CalNex and HIPPO campaigns

NASA Astrophysics Data System (ADS)

Santoni, G. W.; Daube, B. C.; Kort, E. A.; Jiménez, R.; Park, S.; Pittman, J. V.; Gottlieb, E.; Xiang, B.; Zahniser, M. S.; Nelson, D. D.; McManus, J. B.; Peischl, J.; Ryerson, T. B.; Holloway, J. S.; Andrews, A. E.; Sweeney, C.; Hall, B.; Hintsa, E. J.; Moore, F. L.; Elkins, J. W.; Hurst, D. F.; Stephens, B. B.; Bent, J.; Wofsy, S. C.

2014-06-01

We present an evaluation of aircraft observations of the carbon and greenhouse gases CO2, CH4, N2O, and CO using a direct-absorption pulsed quantum cascade laser spectrometer (QCLS) operated during the HIPPO and CalNex airborne experiments. The QCLS made continuous 1 Hz measurements with 1σ Allan precisions of 20, 0.5, 0.09, and 0.15 ppb for CO2, CH4, N2O, and CO, respectively, over > 500 flight hours on 79 research flights. The QCLS measurements are compared to two vacuum ultraviolet (VUV) CO instruments (CalNex and HIPPO), a cavity ring-down spectrometer (CRDS) measuring CO2 and CH4 (CalNex), two broadband non-dispersive infrared (NDIR) spectrometers measuring CO2 (HIPPO), two onboard gas chromatographs measuring a variety of chemical species including CH4, N2O, and CO (HIPPO), and various flask-based measurements of all four species. QCLS measurements are tied to NOAA and WMO standards using an in-flight calibration system, and mean differences when compared to NOAA CCG flask data over the 59 HIPPO research flights were 100, 1, 1, and 2 ppb for CO2, CH4, N2O, and CO, respectively. The details of the end-to-end calibration procedures and the data quality assurance and quality control (QA/QC) are presented. Specifically, we discuss our practices for the traceability of standards given uncertainties in calibration cylinders, isotopic and surface effects for the long-lived greenhouse gas tracers, interpolation techniques for in-flight calibrations, and the effects of instrument linearity on retrieved mole fractions.

Soil CO2, CH4 and N2O effluxes and concentrations in soil profiles down to 15.5m depth in eucalypt plantations under contrasted rainfall regimes

NASA Astrophysics Data System (ADS)

Germon, A.; Nouvellon, Y.; Christophe, J.; Chapuis-Lardy, L.; Robin, A.; Rosolem, C. A.; Gonçalves, J. L. D. M.; Guerrini, I. A.; Laclau, J. P.

2017-12-01

Silvicultural practices in planted forests affect the fluxes of greenhouse gases at the soil surface and the major factors driving greenhouse gas production in forest soils (substrate supply, temperature, water content,…) vary with soil depth. Our study aimed to assess the consequences of drought on the temporal variability of CO2, CH4 and N2O fluxes throughout very deep soil profiles in Eucalyptus grandis plantations 3 months before the harvest then in coppice, the first 18 months after clear-cutting. Two treatments were compared: one with 37% of throughfall excluded by plastic sheets (TE), and one without rainfall exclusion (WE). Measurements of soil CO2 efflux were made every two weeks for 30 months using a closed-path Li8100 system in both treatment. Every two weeks for 21 months, CO2, CH4 and N2O surface effluxes were measured using the closed-chamber method and concentrations in the soil were measured at 7 depths down to 15.5 m in both TE and WE. At most measurement dates, soil CO2 efflux were significantly higher in TE than in WE. Across the two treatments and the measurement dates, CO2 concentrations increased from 4446 ± 2188 ppm at 10 cm deep to 15622 ± 3523 ppm at 15.5 m, CH4 concentrations increased from 0.41 ± 0.17 ppm at 10 cm deep to 0.77 ± 0.24 ppm at 15.5 m and N2O concentrations remained roughly constant and were on average 478 ± 55 ppb between soil surface and 15.5 m deep. CO2 and N2O concentrations were on average 20.7 and 7.6% lower in TE than in WE, respectively, across the sampling depths. However, CH4 concentrations in TE were on average 44.4% higher than in WE, throughout the soil profile. Those results suggest that extended drought periods might reduce the production of CO2 and N2O but increase the accumulation of CH4 in eucalypt plantations established in deep tropical soils. Very deep tropical soils cover huge areas worldwide and improving our understanding of the spatiotemporal dynamics of gas concentrations in deep soil layers

Seasonal changes of CO(2), CH(4) and N(2)O fluxes in relation to land-use change in tropical peatlands located in coastal area of South Kalimantan.

PubMed

Inubushi, K; Furukawa, Y; Hadi, A; Purnomo, E; Tsuruta, H

2003-07-01

Tropical peatland could be a source of greenhouse gases emission because it contains large amounts of soil carbon and nitrogen. However these emissions are strongly influenced by soil moisture conditions. Tropical climate is characterized typically by wet and dry seasons. Seasonal changes in the emission of carbon dioxide (CO(2)), methane (CH(4)) and nitrous oxide (N(2)O) were investigated over a year at three sites (secondary forest, paddy field and upland field) in the tropical peatland in South Kalimantan, Indonesia. The amount of these gases emitted from the fields varied widely according to the seasonal pattern of precipitation, especially methane emission rates were positively correlated with precipitation. Converting from secondary forest peatland to paddy field tended to increase annual emissions of CO(2) and CH(4) to the atmosphere (from 1.2 to 1.5 kg CO(2)-C m(-2)y(-1) and from 1.2 to 1.9 g CH(4)-C m(-2)y(-1)), while changing land-use from secondary forest to upland tended to decrease these gases emissions (from 1.2 to 1.0 kg CO(2)-C m(-2)y(-1) and from 1.2 to 0.6 g CH(4)-C m(-2)y(-1)), but no clear trend was observed for N(2)O which kept negative value as annual rates at three sites.

Energetics of the O-H bond and of intramolecular hydrogen bonding in HOC6H4C(O)Y (Y = H, CH3, CH2CH=CH2, C[triple bond]CH, CH2F, NH2, NHCH3, NO2, OH, OCH3, OCN, CN, F, Cl, SH, and SCH3) compounds.

PubMed

Bernardes, Carlos E S; Minas da Piedade, Manuel E

2008-10-09

The energetics of the phenolic O-H bond in a series of 2- and 4-HOC 6H 4C(O)Y (Y = H, CH3, CH 2CH=CH2, C[triple bond]CH, CH2F, NH2, NHCH 3, NO2, OH, OCH3, OCN, CN, F, Cl, SH, and SCH3) compounds and of the intramolecular O...H hydrogen bond in 2-HOC 6H 4C(O)Y, was investigated by using a combination of experimental and theoretical methods. The standard molar enthalpies of formation of 2-hydroxybenzaldehyde (2HBA), 4-hydroxybenzaldehyde (4HBA), 2'-hydroxyacetophenone (2HAP), 2-hydroxybenzamide (2HBM), and 4-hydroxybenzamide (4HBM), at 298.15 K, were determined by micro- or macrocombustion calorimetry. The corresponding enthalpies of vaporization or sublimation were also measured by Calvet drop-calorimetry and Knudsen effusion measurements. The combination of the obtained experimental data led to Delta f H m (o)(2HBA, g) = -238.3 +/- 2.5 kJ.mol (-1), DeltafHm(o)(4HBA, g) = -220.3 +/- 2.0 kJ.mol(-1), Delta f H m (o)(2HAP, g) = -291.8 +/- 2.1 kJ.mol(-1), DeltafHm(o)(2HBM, g) = -304.8 +/- 1.5 kJ.mol (-1), and DeltafHm(o) (4HBM, g) = -278.4 +/- 2.4 kJ.mol (-1). These values, were used to assess the predictions of the B3LYP/6-31G(d,p), B3LYP/6-311+G(d,p), B3LYP/aug-cc-pVDZ, B3P86/6-31G(d,p), B3P86/6-311+G(d,p), B3P86/aug-cc-pVDZ, and CBS-QB3 methods, for the enthalpies of a series of isodesmic gas phase reactions. In general, the CBS-QB3 method was able to reproduce the experimental enthalpies of reaction within their uncertainties. The B3LYP/6-311+G(d,p) method, with a slightly poorer accuracy than the CBS-QB3 approach, achieved the best performance of the tested DFT models. It was further used to analyze the trends of the intramolecular O...H hydrogen bond in 2-HOC 6H 4C(O)Y evaluated by the ortho-para method and to compare the energetics of the phenolic O-H bond in 2- and 4-HOC 6H 4C(O)Y compounds. It was concluded that the O-H bond "strength" is systematically larger for 2-hydroxybenzoyl than for the corresponding 4-hydroxybenzoyl isomers mainly due to the presence of

Impacts of feedlot floor condition, deposition frequency, and inhibitors on N2O and CH4 emissions from feedlot dung and urine patches.

PubMed

Liao, Wenhua; Liu, Chunjing; Gao, Zhiling

2018-04-09

Patches of dung and urine are major contributors to the feedlot gas emissions. This study investigated the impacts of dung deposition frequency (partly reflecting animal stocking density of a feedlot), dairy feedlot floor conditions (old floor indicated with the presence of consolidated manure pad [CMP] vs. new floor with the absence of consolidated manure pad [CMPn]), and application of dicyandiamide (DCD) and hydroquinone (HQ) on nitrous oxide (N 2 O) and methane (CH 4 ) emissions from patches in the laboratory, and the integrative impacts were expressed in terms of global warming potential (CO 2 -equivalent). Dung deposition frequency, feedlot floor condition, and application of inhibitors showed inverse impacts on N 2 O and CH 4 emissions from patches. Greenhouse gas (GHG) emissions from the dung, urine, and dung+urine patches on the CMP feedlot surface were approximately 7.48, 87.35, and 7.10 times those on the CMPn feedlot surface (P < 0.05). Meanwhile, GHG emissions from CMP and CMPn feedlot surfaces under high deposition frequency condition were approximately 10 and 1.7 times those under low-frequency condition. Moreover, application of HQ slightly reduced the GHG emission from urine patches, by 14.9% (P > 0.05), while applying DCD or DCD+HQ significantly reduced the GHG, by 60.3% and 65.0%, respectively (P < 0.05). Overall, it is necessary to include feedlot management such as animal stocking density and feedlot floor condition to the process of determining emission factors for feedlots. In the future, field measurements to quantitatively evaluate the relative contribution of nitrification and denitrification to the N 2 O emissions of feedlot surfaces are highly required for effective N 2 O control. This study shows that feedlot CH 4 and N 2 O emissions inversely respond to the dicyandiamide (DCD) application. Applying DCD significantly reduces GHG emissions of feedlot urine patches. Feedlot floor condition and stocking density strongly impact

Synthesis,and structural characterization of [(CH3(C5H4N))Ga(SCH2(CO)O)]-[(4-MepyH)]+, a novel Ga(III) five coordinate complex.

NASA Technical Reports Server (NTRS)

Banger, Kulbinder K.; Duraj, Stan A.; Fanwic, Phillp E.; Hepp, Aloysius F.; Martuch, Robert A.

2003-01-01

The synthesis and structural characterization of a novel ionic Ga(III) five coordinate complex [{CH3(C5H4N)}Ga(SCH2(CO)O)2]-[(4-MepyH)]+, (4-Mepy = CH3(C5H5N)) from the reaction between Ga2Cl4 with sodium mercapto-acetic acid in 4-methylpyridine is described. Under basic reaction conditions the mercapto ligand is found to behave as a 2e- bidentate ligand. Single crystal X-ray diffraction studies show the complex to have a distorted square pyramidal geometry with the [(-SCH2(CO)CO-)] ligands in a trans conformation. The compound crystallizes in the P2(sub 1)/c (No. 14) space group with a = 7.7413(6) A, b = 16.744(2) A, c = 14.459(2) A, V = 1987.1(6) A(sup 3), R(F) = 0.032 and R(sub w) = 0.038.

[Effects of biochar application three-years ago on global warming potentials of CH4 and N2O in a rice-wheat rotation system.

PubMed

Wu, Zhen; Dong, Yu Bing; Xiong, Zheng Qin

2018-01-01

To evaluate the long-term effects of biochar amendment on greenhouse gas emissions (GHGs), a field experiment was conducted to examine the effects of 3-year field-aged biochar (B 3 ) and fresh biochar (B 0 ) on global warming potential (GWP) and greenhouse gas intensity (GHGI) of methane (CH 4 ) and nitrous oxide (N 2 O) in a typical rice-wheat rotation system. Four treatments were established as control without nitrogen fertilizer (CK), urea without biochar (N), urea with fresh biochar amended in 2015 (NB 0 ), and urea with 3-year field-aged biochar amended in 2012 (NB 3 ). Results showed that both the NB 0 and NB 3 treatments obviously increased soil pH, soil organic carbon (SOC), total nitrogen (TN) and influenced the potential activity of functional microorganisms related to GHGs compared to the N treatment. Relative to the N treatment, the NB 3 treatment significantly improved crop yield by 14.1% while reduced the CH 4 and N 2 O emissions by 9.0% and 34.0%, respectively. In addition, the NB 0 treatment significantly improved crop yield by 9.3%, while reduced the N 2 O emission by 38.6% though increased the CH 4 emissions by 4.7% relative to the N treatment. Moreover, both the NB 0 and NB 3 treatments could significantly reduce both GWP and GHGI, with NB 3 being more effective in simultaneously mitigating the GHGs emissions and enhancing crop yield. Since field-aged biochar showed obvious effects on GHGs mitigation and carbon sequestration after 3 years, biochar incorporations had long-term effect on GHGs mitigation and crop production in the rice-wheat rotation system.

Conformational and spectroscopic study of xanthogen ethyl formates, ROC(S)SC(O)OCH2CH3. Isolation of CH3CH2OC(O)SH

NASA Astrophysics Data System (ADS)

Juncal, Luciana C.; Cozzarín, Melina V.; Romano, Rosana M.

2015-03-01

ROC(S)SC(O)OCH2CH3, with R = CH3sbnd , (CH3)2CHsbnd and CH3(CH2)2sbnd , were obtained through the reaction between potassium xanthate salts, ROC(S)SK, and ethyl chloroformate, ClC(O)OCH2CH3. The liquid compounds were identified and characterized by 1H and 13C NMR and mass spectrometry. The conformations adopted by the molecules were studied by DFT methods. 6 conformers were theoretically predicted for R = CH3sbnd and (CH3)2CHsbnd , while the conformational flexibility of the n-propyl substituent increases the total number of feasible rotamers to 21. For the three molecules, the conformers can be associated in 3 groups, being the most stable the AS forms - the Cdbnd S double bond anti (A) with respect to the Csbnd S single bond and the Ssbnd C single bond syn (S) with respect to the Cdbnd O double bond - followed by AA and SS conformers. The vibrational spectra were interpreted in terms of the predicted conformational equilibrium, presenting the ν(Cdbnd O) spectral region signals corresponding to the three groups of conformers. A moderated pre-resonance Raman enhancement of the ν(Cdbnd S) vibrational mode of CH3(CH2)2OC(S)SC(O)OCH2CH3 was detected, when the excitation radiation approaches the energy of a n → π∗ electronic transition associated with the Cdbnd S chromophore. UV-visible spectra in different solvents were measured and interpreted in terms of TD-DFT calculations. The unknown molecule CH3CH2OC(O)SH was isolated by the UV-visible photolysis of CH3OC(S)SC(O)OCH2CH3 isolated in Ar matrix, and also obtained as a side-product of the reaction between potassium xanthate salts, ROC(S)SK, and ethyl chloroformate, ClC(O)OCH2CH3.

Simultaneous measurement of stratospheric O3, H2O, CH4, and N2O profiles from infrared limb thermal emissions

NASA Technical Reports Server (NTRS)

Abbas, M. M.; Glenn, M. J.; Kunde, V. G.; Brasunas, J.; Conrath, B. J.; Maguire, W. C.; Herman, J. R.

1987-01-01

Thermal emission measurements of the earth's stratospheric limb were made with a cryogenically cooled high-resolution Michelson interferometer on a balloon flight launched from Palestine, TX, on Nov. 6, 1984. Infrared spectra for complete limb sequences were obtained over portions of the 700-1940/cm range with an unapodized spectral resolution of 0.03/cm for tangent heights varying from 13 to 39 km. The observed data from 1125 to 1425/cm have been analyzed for simultaneous measurement of O3, H2O, CH4, and N2O profiles. The analysis employs line-by-line and layer-by-layer radiative-transfer calculations, including curvature and refraction effects. The optimum use of geometric and spectral effects is made to obtain sharply peaked weighting functions. Contributions from stratospheric aerosol are included by measuring the light extinction within the window regions of the observed spectra. The retrieved constituent profiles are compared with measurements made with a variety of techniques by other groups. The comparison shows good agreement with the published data for all gases, indicating the capability of retrieving trace gas profiles from high-resolution thermal emission limb measurements.

Permafrost collapse shifts alpine tundra to a carbon source but reduces N2O and CH4 release on the northern Qinghai-Tibetan Plateau

NASA Astrophysics Data System (ADS)

Mu, C.

2017-12-01

Important unknowns remain about how abrupt permafrost collapse (thermokarst) affects carbon balance and greenhouse gas flux, limiting our ability to predict the magnitude and timing of the permafrost carbon feedback. We measured monthly, growing-season fluxes of CO2, CH4, and N2O at a large thermokarst feature in alpine tundra on the northern Qinghai-Tibetan Plateau (QTP). Thermokarst formation disrupted plant growth and soil hydrology, shifting the ecosystem from a growing-season carbon sink to a weak source, but decreasing feature-level CH4 and N2O flux. Temperature-corrected ecosystem respiration from decomposing permafrost soil was 2.7 to 9.5-fold higher than in similar features from Arctic and Boreal regions, suggesting that warmer and dryer conditions on the northern QTP could accelerate carbon decomposition following permafrost collapse. N2O flux was similar to the highest values reported for Arctic ecosystems, and was 60% higher from exposed mineral soil on the feature floor, confirming Arctic observations of coupled nitrification and denitrification in collapsed soils. Q10 values for respiration were typically over 4, suggesting high temperature sensitivity of thawed carbon. Taken together, these results suggest that QTP permafrost carbon in alpine tundra is highly vulnerable to mineralization following thaw, and that N2O production could be an important non-carbon permafrost climate feedback.

Experimental binding energies for the metal complexes [Mg(CH3OH)n](2+), [Ca(CH3OH)n](2+), and [Sr(CH3OH)n](2+) for n in the range 4-20.

PubMed

Bruzzi, E; Stace, A J

2014-10-09

A supersonic source of clusters has been used to prepare neutral complexes of methanol in association with an alkaline earth metal atom. From these complexes the following metal-containing dications have been generated through electron ionization: [Mg(CH3OH)n](2+), [Ca(CH3OH)n](2+), and [Sr(CH3OH)n](2+), and for n in the range 4-20, kinetic energy release measurements following the evaporation of a single molecule have been undertaken using a high resolution mass spectrometer. Using finite heat bath theory, these data have been transformed into binding energies for individual methanol molecules attached to each of the three cluster systems. In the larger complexes (n > 6) the results exhibit a consistent trend, whereby the experimental binding energy data for all three metal ions are similar, suggesting that the magnitude of the charge rather than charge density influences the strength of the interaction. From a comparison with data recorded previously for (CH3OH)nH(+) it is found that the 2+ charge on a metal ion has an effect on the binding energy of molecules in complexes containing up to 20 solvent molecules. The results recorded for [Ca(CH3OH)n](2+) show evidence of a very marked transition between n = 6 and 7, which is thought to coincide with the completion of a primary solvation shell and the onset of molecules starting to occupy a second and most probably a third shell.

Experimental measurements of vapor-liquid equilibria of the H2O + CO2 + CH4 ternary system

USGS Publications Warehouse

Qin, J.; Rosenbauer, R.J.; Duan, Zhenhao

2008-01-01

Reported are the experimental measurements on vapor-liquid equilibria in the H2O + CO2 + CH4 ternary system at temperatures from (324 to 375) K and pressures from (10 to 50) MPa. The results indicate that the CH4 solubility in the ternary mixture is about 10 % to 40 % more than that calculated by interpolation from the Henry's law constants of the binary system, H2O + CH4, and the solubility of CO2 is 6 % to 20 % more than what is calculated by the interpolation from the Henry's law constants of the binary mixture, H 2O + CO2. ?? 2008 American Chemical Society.

The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO2(N3)2, MO2(N3)2⋅2 CH3CN, (bipy)MO2(N3)2, and [MO2(N3)4](2-) (M=Mo, W).

PubMed

Haiges, Ralf; Skotnitzki, Juri; Fang, Zongtang; Dixon, David A; Christe, Karl O

2015-08-10

Molybdenum(VI) and tungsten(VI) dioxodiazide, MO2(N3)2 (M=Mo, W), were prepared through fluoride-azide exchange reactions between MO2F2 and Me3SiN3 in SO2 solution. In acetonitrile solution, the fluoride-azide exchange resulted in the isolation of the adducts MO2(N3)2⋅2 CH3CN. The subsequent reaction of MO2(N3)2 with 2,2'-bipyridine (bipy) gave the bipyridine adducts (bipy)MO2(N3)2. The hydrolysis of (bipy)MoO2(N3)2 resulted in the formation and isolation of [(bipy)MoO2N3]2O. The tetraazido anions [MO2(N3)4](2-) were obtained by the reaction of MO2(N3)2 with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO2(N3)2, (bipy)WO2(N3)2, [PPh4]2[MoO2(N3)4], [PPh4]2[WO2(N3)4], and [(bipy)MoO2N3]2O by their X-ray crystal structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Subsoil methanogenesis as source of stem CH4 emission in upland forest trees: preferential CH4 transport via the root system?

NASA Astrophysics Data System (ADS)

Maier, M.; Machacova, K.; Urban, O.; Friederike, L.

2016-12-01

Quantifying and understanding green house gas fluxes in natural soil-plant-atmosphere systems are crucial to predicting global climate change. Wetland species or trees at waterlogged sites are known to emit large amounts of CH4. Yet upland forest soils are regarded as CH4 sinks and tree species like upland European beech (Fagus sylvatica, L.) are assumed not to emit CH4. We studied the soil-atmosphere and stem-atmosphere fluxes of CH4, and soil gas profiles at two upland beech forest sites in Central Europe. Soil was a net CH4 sink at both. Unusually there was one beech tree with substantial CH4 emissions that were higher than the CH4 sink of the soil. The soil gas profile at this tree indicated CH4 production at a soil depth >0.3 m, despite the net uptake of CH4 observed at the soil surface adjacent to the tree. Field soil assessment showed strong redoximorphic color patterns in the adjacent soil. We think that there is a transport link between the soil and stem via the root system representing a preferential transport mechanism for CH4 despite the fact that beech roots usually do not bear aerenchyma. The gas transport process , either via dissolved CH4 in the xylem water or in the root gas phase, is not yet clear. The observed CH4 stem emissions represent an important CH4flux in this ecosystem, und thus should be considered in future research. AcknowledgementThis research was financially supported by the Czech Academy of Sciences and the German Academic Exchange Service within the project "Methane (CH4) and nitrous oxide (N2O) emissions from Fagus sylvatica trees" (DAAD-15-03), National Programme for Sustainability I (LO1415) and project DFG (MA 5826/2-1). We would like to thank Marek Jakubik, Katerina Svobodova, Sinikka Paulus, Ellen Halaburt and Sally Haddad for technical support.

Predicting Coupled Emissions of N2O, CO2 and CH4 from Arable Fields in Ireland Using the ECOSSE Model

NASA Astrophysics Data System (ADS)

Khalil, M. I.; Smith, J.; Abdalla, M.; O'Brien, P.; Smith, P.; Müller, C.

2011-12-01

Agriculture and associated land-use changes contribute a significant portion to global greenhouse gas (GHG) emissions; mainly as N2O, CO2 and CH4. Improved modelling of soil processes will greatly enhance the value of national inventories, both in terms of more accurate reporting and better mitigation policy options. In Ireland, Agriculture and Land Use, Land Use Change and Forestry, is currently a priority research focus, aimed at reducing uncertainty in estimates of GHG emissions and sinks. The ECOSSE model has several advantages, including limited meteorological and soil data requirements, compared to other models. It can simulate the impacts of land-use, management and climate change on C and N emissions and stocks for both mineral and organic soils at field and national scales. In this study, ECOSSE has been used to predict GHG emissions and SOC changes in arable lands cropped with spring barley receiving different rates of N application. The simulated outputs are evaluated against measured data available from a two-year field study. The modelled responses of N2O fluxes are found to be consistent with the measured values. The bias in the total difference between measured values and the corresponding modelled N2O fluxes was large due to the impact of a few unexpected measurements. In the fertilized fields, significant correlation between modelled and measured N2O fluxes was observed, with correlation coefficients of 0.54-0.60 and root mean square errors of 18.6-20.8 g N ha-1 d-1. The measured seasonal (crop growth period) N2O losses (integrated) were 0.41 and 0.50% of the N applied at rates of 70-79 and 140-159 kg ha-1, respectively. As a further comparison, the simulated values for the dates when measurements were taken were similarly integrated. The corresponding simulated seasonal N2O losses were 0.69 and 1.11% of the added N, suggesting an overestimation by 70-123% of the measured values. However, this could be due to missed emissions associated with the

Integral and differential cross section measurements at low collision energies for the N2++CH4/CD4 reactions

NASA Astrophysics Data System (ADS)

Nicolas, Christophe; Torrents, Raquel; Gerlich, Dieter

2003-02-01

Absolute integral cross sections are measured in the collision energy range between 0.1 to 3.5 eV for the N2++CH4 and N2++CD4 reactions using the universal guided ion beam apparatus. The reaction branching ratio, CX3+:CX2+:N2X+ (X=H or D), is found to be 0.86:0.09:0.05 and 0.88:0.07:0.05 for the N2++CH4 and N2++CD4 reactions, respectively. The CH3+/CH2+ ratio is constant over the whole collision energy range and very similar to the one obtained for the almost isoenergetic Ar++CH4 reaction. Axial velocity distributions of the product ions are measured by time of flight at collision energies between 0.1 and 3.5 eV. The results provide direct insight into the reaction dynamics. The dissociative charge transfer channels, leading to CH3+ and CH2+ product ions, occur via an electron jump combined with some exchange of momentum between the colliding partners. The H (D) transfer leading to N2H+ can be described as a direct process, similar to a spectator stripping mechanism. Various isotope effects are observed, the dominant being that the cross sections for reaction with CH4 are up to 20% bigger than the corresponding ones for CD4.

Reactivity of chemisorbed oxygen atoms and their catalytic consequences during CH4-O2 catalysis on supported Pt clusters.

PubMed

Chin, Ya-Huei Cathy; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

2011-10-12

Kinetic and isotopic data and density functional theory treatments provide evidence for the elementary steps and the active site requirements involved in the four distinct kinetic regimes observed during CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants on Pt clusters. These four regimes exhibit distinct rate equations because of the involvement of different kinetically relevant steps, predominant adsorbed species, and rate and equilibrium constants for different elementary steps. Transitions among regimes occur as chemisorbed oxygen (O*) coverages change on Pt clusters. O* coverages are given, in turn, by a virtual O(2) pressure, which represents the pressure that would give the prevalent steady-state O* coverages if their adsorption-desorption equilibrium was maintained. The virtual O(2) pressure acts as a surrogate for oxygen chemical potentials at catalytic surfaces and reflects the kinetic coupling between C-H and O═O activation steps. O* coverages and virtual pressures depend on O(2) pressure when O(2) activation is equilibrated and on O(2)/CH(4) ratios when this step becomes irreversible as a result of fast scavenging of O* by CH(4)-derived intermediates. In three of these kinetic regimes, C-H bond activation is the sole kinetically relevant step, but occurs on different active sites, which evolve from oxygen-oxygen (O*-O*), to oxygen-oxygen vacancy (O*-*), and to vacancy-vacancy (*-*) site pairs as O* coverages decrease. On O*-saturated cluster surfaces, O*-O* site pairs activate C-H bonds in CH(4) via homolytic hydrogen abstraction steps that form CH(3) groups with significant radical character and weak interactions with the surface at the transition state. In this regime, rates depend linearly on CH(4) pressure but are independent of O(2) pressure. The observed normal CH(4)/CD(4) kinetic isotope effects are consistent with the kinetic-relevance of C-H bond activation; identical (16)O(2)-(18)O(2) isotopic exchange rates in the presence or

Structure of complexes of nitrilo tris methylene phosphonic acid with copper, [CuN(CH{sub 2}PO{sub 3}){sub 3}(H{sub 2}O){sub 3}] and Na{sub 4}[CuN(CH{sub 2}PO{sub 3}){sub 3}]{sub 2} · 19H{sub 2}O, as bactericides and inhibitors of scaling and corrosion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Somov, N. V., E-mail: somov@phys.unn.ru; Chausov, F. F., E-mail: chaus@uni.udm.ru

2015-03-15

Nitrilotris methylene phosphonate triaqua copper and octasodium bis(nitrilotris methylene phosphonate cuprate(II)) nonadecahydrate have been synthesized and investigated. [CuN(CH{sub 2}PO{sub 3}){sub 3}(H{sub 2}O){sub 3}] is crystallized in the sp. gr. P2{sub 1}/c, Z = 4, a = 9.2506(2) Å, b = 15.9815(2) Å, c = 9.5474(2) Å, β = 113.697(2)°. The copper atom is coordinated by oxygen atoms in the configuration of elongated octahedron; the ligand (of bridge type) links neighboring copper atoms. Na{sub 8}[CuN(CH{sub 2}PO{sub 3}){sub 3}]{sub 2} · 19H{sub 2}O is crystallized in the sp. gr. P2{sub 1}/c, Z = 2, a = 11.24550(10) Å, b = 17.38980(10) Å,more » c = 13.5852(2) Å, β = 127.8120(10)°. This complex is chelating; the copper atom closes three five-membered N-C-P-O-Cu cycles with a shared Cu-N bond. Copper is coordinated in a distorted trigonal-bipyramidal configuration.« less

Potential for negative emissions of greenhouse gases (CO2, CH4 and N2O) through coastal peatland re-establishment: Novel insights from high frequency flux data at meter and kilometer scales

NASA Astrophysics Data System (ADS)

Windham-Myers, Lisamarie; Bergamaschi, Brian; Anderson, Frank; Knox, Sara; Miller, Robin; Fujii, Roger

2018-04-01

High productivity temperate wetlands that accrete peat via belowground biomass (peatlands) may be managed for climate mitigation benefits due to their global distribution and notably negative emissions of atmospheric carbon dioxide (CO2) through rapid storage of carbon (C) in anoxic soils. Net emissions of additional greenhouse gases (GHG)—methane (CH4) and nitrous oxide (N2O)—are more difficult to predict and monitor due to fine-scale temporal and spatial variability, but can potentially reverse the climate mitigation benefits resulting from CO2 uptake. To support management decisions and modeling, we collected continuous 96 hour high frequency GHG flux data for CO2, CH4 and N2O at multiple scales—static chambers (1 Hz) and eddy covariance (10 Hz)—during peak productivity in a well-studied, impounded coastal peatland in California’s Sacramento Delta with high annual rates of C fluxes, sequestering 2065 ± 150 g CO2 m‑2 y‑1 and emitting 64.5 ± 2.4 g CH4 m‑2 y‑1. Chambers (n = 6) showed strong spatial variability along a hydrologic gradient from inlet to interior plots. Daily (24 hour) net CO2 uptake (NEE) was highest near inlet locations and fell dramatically along the flowpath (‑25 to ‑3.8 to +2.64 g CO2 m‑2 d‑1). In contrast, daily net CH4 flux increased along the flowpath (0.39 to 0.62 to 0.88 g CH4 m‑2 d‑1), such that sites of high daily CO2 uptake were sites of low CH4 emission. Distributed, continuous chamber data exposed five novel insights, and at least two important datagaps for wetland GHG management, including: (1) increasing dominance of CH4 ebullition fluxes (15%–32% of total) along the flowpath and (2) net negative N2O flux across all sites as measured during a 4 day period of peak biomass (‑1.7 mg N2O m‑2 d‑1 0.51 g CO2 eq m‑2 d‑1). The net negative emissions of re-established peat-accreting wetlands are notably high, but may be poorly estimated by

The Effects of Flame Structure on Extinction of CH4-O2-N2 Diffusion Flames

NASA Technical Reports Server (NTRS)

Du, J.; Axelbaum, R. L.; Gokoglu, S. (Technical Monitor)

1996-01-01

The effects of flame structure on the extinction limits of CH4-O2-N2 counterflow diffusion flames were investigated experimentally and numerically by varying the stoichiometric mixture fraction Z(sub st), Z(sub st) was varied by varying free-stream concentrations, while the adiabatic flame temperature T(sub ad) was held fixed by maintaining a fixed amount of nitrogen at the flame. Z(sub st) was varied between 0.055 (methane-air flame) and 0.78 (diluted- methane-oxygen flame). The experimental results yielded an extinction strain rate K(sub ext) of 375/s for the methane-air flame, increasing monotonically to 1042/s for the diluted-methane-oxygen flame. Numerical results with a 58-step Cl mechanism yielded 494/s and 1488/s, respectively. The increase in K(sub ext) with Z(sub st) for a fixed T(sub ad) is explained by the shift in the O2 profile toward the region of maximum temperature and the subsequent increase in rates for chain-branching reactions. The flame temperature at extinction reached a minimum at Z(sub st) = 0.65, where it was 200 C lower than that of the methane-air flame. This significant increase in resistance to extinction is seen to correspond to the condition in which the OH and O production zones are centered on the location of maximum temperature.

Impact of raw pig slurry and pig farming practices on physicochemical parameters and on atmospheric N2O and CH 4 emissions of tropical soils, Uvéa Island (South Pacific).

PubMed

Roth, E; Gunkel-Grillon, P; Joly, L; Thomas, X; Decarpenterie, T; Mappe-Fogaing, I; Laporte-Magoni, C; Dumelié, N; Durry, G

2014-09-01

Emissions of CH4 and N2O related to private pig farming under a tropical climate in Uvéa Island were studied in this paper. Physicochemical soil parameters such as nitrate, nitrite, ammonium, Kjeldahl nitrogen, total organic carbon, pH and moisture were measured. Gaseous soil emissions as well as physicochemical parameters were compared in two private pig farming strategies encountered on this island on two different soils (calcareous and ferralitic) in order to determine the best pig farming management: in small concrete pens or in large land pens. Ammonium levels were higher in control areas while nitrate and nitrite levels were higher in soils with pig slurry inputs, indicating that nitrification was the predominant process related to N2O emissions. Nitrate contents in soils near concrete pens were important (≥ 55 μg N/g) and can thus be a threat for the groundwater. For both pig farming strategies, N2O and CH4 fluxes can reach high levels up to 1 mg N/m(2)/h and 1 mg C/m(2)/h, respectively. CH4 emissions near concrete pens were very high (≥ 10.4 mg C/m(2)/h). Former land pens converted into agricultural land recover low N2O emission rates (≤ 0.03 mg N/m(2)/h), and methane uptake dominates. N2O emissions were related to nitrate content whereas CH4 emissions were found to be moisture dependent. As a result relating to the physicochemical parameters as well as to the gaseous emissions, we demonstrate that pig farming in large land pens is the best strategy for sustainable family pig breeding in Uvéa Islands and therefore in similar small tropical islands.

Mercury-Bridged Cobaltacarborane Complexes Containing B-Hg-B Three-Center Bonds. Synthesis and Structure of mu, mu’-((n5-C5R5)Co(CH3)2C2B3H4)Hg, mu-(n(5)-C5R5)Co(CH3)2C2B3H4)HgCl, (R=H, CH3) and Related Compounds.