Production of N2O,CH4, and CO2 from soils in the tropical savanna during the dry season

Emissions of N₂O, CH₄, and CO₂ from soils at two sites in the tropical savanna of central Venezuela were determined during the dry season in February 1987. Measured arithmetic mean fluxes of N₂O, CH₄, and CO₂ from undisturbed soil plots to the atmosphere were 2.5×10⁹, 4.3×10¹⁰, and 3.0×10¹³ molecules cm^-2 s^-1, respectively. These fluxes were not significantly affected by burning the grass layer. Emissions of N₂O increased fourfold after simulated rainfall, suggesting that production of N₂O in savanna soils during the rainy season may be an important source for atmospheric N₂O. The CH₄ flux measurements indicate that these savanna soils were not a sink, but a small source, for atmospheric methane. Fluxes of CO₂ from savanna soils increased ninefold two hours after simulated rainfall, and remained three times higher than normal after 16 hours. More research is needed to clarify the significance of savannas in the global cycles of N₂O, CH₄, CO₂, and other trace gases, especially during the rainy season.     

Trace gas measurements at the monitoring station cape point,South Africa,between 1978 and 1988

Since 1978, a measuring station has been operated at Cape Point (34°21 S, 18°29 E). In this article, results of measurements of CO, CFCl₃, CCl₄, O₃, N₂O and CH₄ are presented as monthly means and analyzed with respect to long-term trends and seasonal variations. For CO and CH₄, very similar seasonal variations have been observed, indicating strong interrelations between these two gases. For CO and O₃, no significant changes of the mean annual concentrations can be established for the observation periods of 10 and 5 years, respectively. The measurements yield a growth rate of 9.1 pptv yr^-1 for CFCl₃ (1980–1987) and 0.6 ppbv yr^-1 for N₂O (1983–1987). The concentration increases of CH₄ (10.3 ppbv yr^-1 for 1983–1987) and of CCl₄ (2.1 pptv yr^-1 for 1980–1988) are analyzed for temporal changes during the last years.Presented at the Second Conference on Baseline Observations in Atmospheric Chemistry (SABOAC II) in Melbourne, Australia, November 1988.     

GHOST – A Novel Airborne Gas Chromatograph for In Situ Measurements of Long-Lived Tracers in the Lower Stratosphere: Method and Applications

A novel fully-automated airborne gas chromatograph for in situmeasurements of long-lived stratospheric tracers hasbeen developed, combining the high selectivity of a megabore PLOTcapillary column with recently developed sampling and separationtechniques. The Gas cHromatograph for theObservation of Stratospheric Tracers (GHOST)has been successfully operated during three STREAM campaigns(Stratosphere TRoposphere Experiment byAirborne Measurement) onboard a Cessna Citation IIaircraft in two different modes: Either N₂O andCF₂Cl₂(CFC-12) or CFC-12 and CFCl₃ (CFC-11) have been measuredsimultaneously, with a time resolution of 2 min for both modes.Under flight conditions the instrument precision (1) forthese species is better than 0.9%, and the accuracy(1) is better than 2.0% of the tropospheric values ofall measured compounds. The detection limits (3) arebelow 28 ppb for N₂O, 14 ppt for CFC-12, and 8 ppt forCFC-11, respectively, i.e., well below 10 % of the troposphericvalues of all measured compounds. Post-mission optimization of thechromatographic separation showed a possible enhancement of thetime resolution by up to a factor of 2, associated with acomparable increase in precision and detection limit. As test ofactual performance of GHOST results from an in-flight N₂Ointercomparison with a tunable diode laser absorptionspectrometer (TDLAS) are presented. They yield an excellentagreement between both instruments. Furthermore, on the basis ofthe hitherto most extensive set of upper tropospheric and lowerstratospheric data, the relative stratospheric N₂2O lifetime isre-assessed. When referenced to the WMO reference CFC-11 lifetimeof 45 ± 7 years an N₂O lifetime of 91 ± 15 yearsis derived, a value substantially smaller than the WMO referencelifetime of 120 years. Moreover, this value implies astratospheric N₂O sink strength of 16.3 ± 2.7 Tg (N)yr^–1 which is 30% larger than previous estimates.     

漂浮通量箱法和扩散模型法测定内陆水体CH_4和N_2O排放通量的初步比较研究

采用漂浮通量箱法和扩散模型法同步地观测了模拟内陆水体在不同条件下的CH4和N2O的水-气交换通量,旨在比较两类方法取得结果的异同。结果显示:这两类方法所测得的绝大多数CH4排放通量都与水中溶解氧呈显著线性负相关(显著性系数P0.001)。同时N2O排放通量与表层水温及水中铵态氮、硝态氮、溶解碳和溶解氧的关系可用包含所有上述水环境因素的Arrhenius动力学方程来表达,这些因素可以共同解释86%~90%的N2O通量变化(P0.0001),且不同方法测定的N2O通量的表观活化能和对表层水温的敏感系数分别介于47~59 kJ mol-1和1.92~2.27之间;扩散模型法所获得的CH4和N2O通量分别是箱法测定值的13%~175%和15%~240%,差异程度因模型而异;不同模型取得通量间相差20%~1200%,平均相差2.3倍。上述结果表明:仅用一种模型方法来取得CH4或N2O排放通量易形成较大偏差;不同扩散模型法和箱法测定的通量在反映CH4和N2O排放的内在规律方面具有一致性,但它们对真实气体通量的测量是否都存在不同程度的系统误差,尚需进一步研究。     

Emission of nitrous oxide from temperate forest soils into the atmosphere

N₂O emission rates were measured during a 13-month period from July 1981 till August 1982 with a frequency of once every two weeks at six different forest sites in the vicinity of Mainz, Germany. The sites were selected on the basis of soil types typical for many of the Central European forest ecosystems. The individual N₂O emission rates showed a high degree of temporal and spatial variabilities which, however, were not significantly correlated to variabilities in soil moisture content or soil temperatures. However, the N₂O emission rates followed a general seasonal trend with relatively high values during spring and fall. These maxima coincided with relatively high soil moisture contents, but may also have been influenced by the leaf fall in autumn. In addition, there was a brief episode of relatively high N₂O emission rates immediately after thawing of the winter snow. The individual N₂O emission rates measured during the whole season ranged between 1 and 92 g N₂O-N m^–2 h^–1. The average values were in the range of 3–11 g N₂O-N m^–2 h^–1 and those with a 50% probability were in the range of 2–8 g N₂O-N m^–2 h^–1. The total source strength of temperate forest soils for atmospheric N₂O may be in the range of 0.7–1.5 Tg N yr^–1.     

Assessment of Major Pools and Fluxes of Carbon in Indian Forests

The major pools including phytomass, soil, litter, and fluxes of carbon (C)due to litterfall and landuse changes were estimated for Indian forests. Basedon growing stock-volume approach at the state and district levels, the Indianforest phytomass was estimated in the range of 3.8–4.3 PgC. The totalsoil organic pool in the top 1m depth was estimated as 6.8 PgC, usingestimated soil organic carbon densities and Remote Sensing (RS) based area byforest types. Based on 122 published Indian studies and RS-based forest area,the total litterfall carbon flux was estimated as 208.8 MgCha^–1 yr^–1.The cumulative net carbon flux (1880–1996) from Indian forests(1880–1996) due to landuse changes (deforestation, afforestation andphytomass degradation) was estimated as 5.4 PgC, using a simple book-keepingapproach. The mean annual net C flux due to landuse changes during1985–1996 was estimated as 9.0 TgC yr^–1. For the recentperiod, the Indian forests are nationally a small source with some regionsacting as small sinks of carbon as well. The improved quantification of poolsand fluxes related to forest carbon cycle is important for understanding thecontribution of Indian forests to net carbon emissions as well as theirpotential for carbon sequestration in the context of the Kyoto protocol.     

Nitrous oxide emissions from fertilized and unfertilized soils in a subtropical region (Andalusia,Spain)

Field measurements of N₂O emission rates were carried out from August until October 1982 in a subtropical region in Europe, i.e. in Andalusia, Spain. The measurements were performed by using an automatic sampling and analysis technique allowing the semi-continuous determination of N₂O emission rates. The N₂O emission rates were positively correlated to the soil surface temperature and exhibited a diurnal rhythm with maximum rates in the afternoon and minimum rates in the early morning with average values of 1 g N₂O–N/m²/h for the grass lawn and 15 g N₂O–N/m²/h for cultivated land. Application of urea and ammonium nitrate resulted in elevated N₂O emission rates when compared to the unfertilized control. The loss of fertilizer-nitrogen as N₂O was 0.18% for urea and 0.04% for NH₄NO₃ which compares very well with data obtained in a temperate climate (Germany). The total source strength of fertilizer-derived N₂O is estimated to be 0.01–2.2 Tg N₂O–N per year. The N₂O flux from unfertilized natural soils may be as high as 4.5 Tg N₂O–N, indicating that the N₂O emission from soils contributes significantly to the global N₂O budget.     

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

Stratospheric volume mixing ratio profiles of N₂O₅, CH₄, and N₂O have been retrieved from a set of 0.052 cm^–1 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^–1 band. Assuming a total intensity of 4.32×10^–17 cm^–1/molecule cm^–2 independent of temperature, the retrieved N₂O₅ volume mixing ratios in ppbv (parts per billion by volume, 10^–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 1- 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.Laboratoire associé aux Universités Pierre et Marie Curie et Paris Sud.     

Sink Potential of Canadian Agricultural Soils

Net greenhouse gas (GHG) emissions from Canadian crop and livestock production were estimated for 1990, 1996 and 2001 and projected to 2008. Net emissions were also estimated for three scenarios (low (L), medium (M) and high (H)) of adoption of sink enhancing practices above the projected 2008 level. Carbon sequestration estimates were based on four sink-enhancing activities: conversion from conventional to zero tillage (ZT), reduced frequency of summerfallow (SF), the conversion of cropland to permanent cover crops (PC), and improved grazing land management (GM). GHG emissions were estimated with the Canadian Economic and Emissions Model for Agriculture (CEEMA). CEEMA estimates levels of production activities within the Canadian agriculture sector and calculates the emissions and removals associated with those levels of activities. The estimates indicate a decline in net emissions from 54 Tg CO₂–Eq yr^–1 in1990 to 52 Tg CO₂–Eq yr^–1 in 2008. Adoption of thesink-enhancing practices above the level projected for 2008 resulted in further declines in emissions to 48 Tg CO₂–Eq yr^–1 (L), 42 TgCO₂–Eq yr^–1 (M) or 36 Tg CO₂–Eq yr^–1 (H). Among thesink-enhancing practices, the conversion from conventional tillage to ZT provided the largest C sequestration potential and net reduction in GHG emissions among the scenarios. Although rates of C sequestration were generally higher for conversion of cropland to PC and adoption of improved GM, those scenarios involved smaller areas of land and therefore less C sequestration. Also, increased areas of PC were associated with an increase in livestock numbers and CH₄ and N₂O emissions from enteric fermentation andmanure, which partially offset the carbon sink. The CEEMA estimates indicate that soil C sinks are a viable option for achieving the UNFCCC objective of protecting and enhancing GHG sinks and reservoirs as a means of reducing GHG emissions (UNFCCC, 1992).     

The Influence of Advection on the Short Term CO 2 -Budget in and Above a Forest Canopy

An experimental micrometeorological set-up was established at the CARBOEURO-FLUX site in Tharandt, Germany, to measure all relevant variables for the calculation of the vertical and horizontal advective fluxes of carbon dioxide. The set-up includes two auxiliary towers to measure horizontal and vertical CO₂ and H₂O gradients through the canopy, and to make ultrasonic wind measurements in the trunk space. In combination with the long-term flux tower an approximately even-sided prism with a typical side-length of 50 m was established. It is shown that under stable (nighttime) conditions the mean advective fluxes have magnitudes on the same order as the daily eddy covariance (EC) flux, which implies that they play a significant, but not yet fully understood, role in the carbon budget equation. The two advective fluxes are opposite and seem to cancel each other at night (at least for these measurements). During the day, vertical advection tends to zero, while horizontal advection is still present implying a flow of CO₂ out of the control volume. From our measurements, a mean daily gain of 2.2 gC m^–2 d^–1 for the horizontal advection and a mean daily loss of 2.5 gC m^–2d^–1 for the vertical advection is calculated for a period of 20 days. However the large scatter of the advective fluxes has to be further investigated. It is not clear yet whether the large variability is natural or due to measurement errors and conceptual deficiencies of the experiment. Similar results are found in the few comparable studies.     

Estimated N2O and CO2 Emissions as Influenced by Agricultural Practices in Canada

The Denitrification-Decompostion (DNDC) model was used to estimate the impact of change in management practices on N₂O emissions in seven major soil regions in Canada, for the period 1970 to 2029. Conversion of cultivated land to permanent grassland would result in the greatest reduction in N₂O emissions, particularly in eastern Canada wherethe model estimated about 60% less N₂O emissions for thisconversion. About 33% less N₂O emissions were predicted for a changefrom conventional tillage to no-tillage in western Canada, however, a slight increase in N₂O emissions was predicted for eastern Canada. GreaterN₂O emissions in eastern Canada associated with the adoption of no-tillage were attributed to higher soil moisture causing denitrification, whereas the lower emissions in western Canada were attributed to less decomposition of soil organic matter in no-till versus conventional tilled soil. Elimination of summer fallow in a crop rotation resulted in a 9% decrease in N₂O emissions, with substantial emissions occurringduring the wetter fallow years when N had accumulated. Increasing N-fertilizer application rates by 50% increased average emissions by 32%,while a 50% decrease of N-fertilizer application decreased emissions by16%. In general, a small increase in N₂O emissions was predicted when N-fertilizer was applied in the fall rather than in the spring. Previous research on CO₂ emissions with the CENTURY model (Smith et al.,2001) allowed the quantification of the combined change in N₂O andCO₂ emissions in CO₂ equivalents for a wide range of managementpractices in the seven major soil regions in Canada. The management practices that have the greatest potential to reduce the combined N₂O andCO₂ emissions are conversion from conventional tillage to permanent grassland, reduced tillage, and reduction of summer fallow. The estimated net greenhouse gas (GHG) emission reduction when changing from cultivated land to permanent grassland ranged from 0.97 (Brown Chernozem) to 4.24 MgCO₂ equiv. ha^–1 y^–1 (BlackChernozem) for the seven soil regions examined. When changing from conventional tillage to no-tillage the net GHG emission reduction ranged from 0.33 (Brown Chernozem) to 0.80 Mg CO₂ equiv. ha^–1 y^–1 (Dark GrayLuvisol). Elimination of fallow in the crop rotation lead to an estimated net GHG emission reduction of 0.43 (Brown Chernozem) to 0.80 Mg CO₂ equiv.ha^–1 y^–1 (Dark Brown Chernozem). The addition of 50% more or 50% less N-fertilizer both resulted in slight increases in combined CO₂ and N₂O emissions. There was a tradeoff in GHG flux with greaterN₂O emissions and a comparable increase in carbon storage when 50% more N-fertilizer was added. The results from this work indicate that conversion of cultivated land to grassland, the conversion from conventional tillage to no-tillage, and the reduction of summerallow in crop rotations could substantially increase C sequestration and decrease net GHG emissions. Based on these results a simple scaling-up scenario to derive the possible impacts on Canada's Kyoto commitment has been calculated.     

Potential Soil C Sequestration on U.S. Agricultural Soils

Soil carbon sequestration has been suggested as a means to help mitigate atmospheric CO₂ increases, however there is limited knowledge aboutthe magnitude of the mitigation potential. Field studies across the U.S. provide information on soil C stock changes that result from changes in agricultural management. However, data from such studies are not readily extrapolated to changes at a national scale because soils, climate, and management regimes vary locally and regionally. We used a modified version of the Intergovernmental Panel on Climate Change (IPCC) soil organic C inventory method, together with the National Resources Inventory (NRI) and other data, to estimate agricultural soil C sequestration potential in the conterminous U.S. The IPCC method estimates soil C stock changes associated with changes in land use and/or land management practices. In the U.S., the NRI provides a detailed record of land use and management activities on agricultural land that can be used to implement the IPCC method. We analyzed potential soil C storage from increased adoption of no-till, decreased fallow operations, conversion of highly erodible land to grassland, and increased use of cover crops in annual cropping systems. The results represent potentials that do not explicitly consider the economic feasibility of proposed agricultural production changes, but provide an indication of the biophysical potential of soil C sequestration as a guide to policy makers. Our analysis suggests that U.S. cropland soils have the potential to increase sequestered soil C by an additional 60–70 Tg (10¹²g) C yr^{– 1}, over present rates of 17 Tg C yr^–1(estimated using the IPCC method), with widespread adoption of soil C sequestering management practices. Adoption of no-till on all currently annually cropped area (129Mha) would increase soil C sequestration by 47 Tg C yr^–1. Alternatively, use of no-till on 50% of annual cropland, with reduced tillage practices on the other 50%, would sequester less – about37 Tg C yr^–1. Elimination of summer fallow practices and conversionof highly erodible cropland to perennial grass cover could sequester around 20 and 28Tg C yr^–1, respectively. The soil C sequestration potentialfrom including a winter cover crop on annual cropping systems was estimated at 40Tg C yr^–1. All rates were estimated for a fifteen-yearprojection period, and annual rates of soil C accumulations would be expected to decrease substantially over longer time periods. The total sequestration potential we have estimated for the projection period (83 Tg C yr^–1) represents about 5% of 1999total U.S. CO₂ emissions or nearly double estimated CO₂ emissionsfrom agricultural production (43 Tg C yr^–1). For purposes ofstabilizing or reducing CO₂ emissions, e.g., by 7% of 1990 levels asoriginally called for in the Kyoto Protocol, total potential soil C sequestration would represent 15% of that reduction level from projected 2008 emissions(2008 total greenhouse gas emissions less 93% of 1990 greenhouse gasemissions). Thus, our analysis suggests that agricultural soil C sequestration could play a meaningful, but not predominant, role in helping mitigate greenhouse gas increases.     

Rate constants for the reactions of the NO3 radical with HCOOH/HCOO− and CH3COOH/CH3COO− in aqueous solution between 278 and 328 K

The kinetics of the aqueous phase reactions of NO₃ radicals with HCOOH/HCOO^– and CH₃COOH/CH₃COO^– have been investigated using a laser photolysis/long-path laser absorption technique. NO₃ was produced via excimer laser photolysis of peroxodisulfate anions (S₂O ₈ ^2– ) at 351 nm followed by the reactions of sulfate radicals (SO ₄ ^– ) with excess nitrate. The time-resolved detection of NO₃ was achieved by long-path laser absorption at 632.8 nm. For the reactions of NO₃ with formic acid (1) and formate (2) rate coefficients ofk ₁=(3.3±1.0)×10⁵ l mol^–1 s^–1 andk ₂=(5.0±0.4)×10⁷ l mol^–1 s^–1 were found atT=298 K andI=0.19 mol/l. The following Arrhenius expressions were derived:k ₁(T)=(3.4±0.3)×10¹⁰ exp[–(3400±600)/T] l mol^–1 s^–1 andk ₂(T)=(8.2±0.8)×10¹⁰ exp[–(2200±700)/T] l mol^–1 s^–1. The rate coefficients for the reactions of NO₃ with acetic acid (3) and acetate (4) atT=298 K andI=0.19 mol/l were determined as:k ₃=(1.3±0.3)×10⁴ l mol^–1 s^–1 andk ₄=(2.3±0.4)×10⁶ l mol^–1 s^–1. The temperature dependences for these reactions are described by:k ₃(T)=(4.9±0.5)×10⁹ exp[–(3800±700)/T] l mol^–1 s^–1 andk ₄(T)=(1.0±0.2)×10¹² exp[–(3800±1200)/T] l mol^–1 s^–1. The differences in reactivity of the anions HCOO^– and CH₃COO^– compared to their corresponding acids HCOOH and CH₃COOH are explained by the higher reactivity of NO₃ in charge transfer processes compared to H atom abstraction. From a comparison of NO₃ reactions with various droplets constituents it is concluded that the reaction of NO₃ with HCOO^– may present a dominant loss reaction of NO₃ in atmospheric droplets.     

Eddy correlation measurements of CO2, latent heat,and sensible heat fluxes over a crop surface

Eddy correlation equipment was used to measure mass and energy fluxes over a soybean crop. A rapid response CO₂ sensor, a drag anemometer, a Lyman-alpha hygrometer and a fine wire thermocouple were used to sense the fluctuating quantities.Diurnal fluxes of sensible heat, latent heat and CO₂ were calculated from these data. Energy budget closure was obtained by summing the sensible and latent heat fluxes determined by eddy correlation which balanced the sum of net radiation and soil heat flux. Peak daytime CO₂ fluxes were near 1.0 mg m^–2 (ground area) s^–1.The eddy correlation technique was also employed in this study to measure nocturnal CO₂ fluxes caused by respiration from plants, soil, and roots. These CO₂ fluxes ranged from - 0.1 to - 0.25 mg m^–2s^–1.From the data collected over mature soybeans, a relationship between CO₂ flux and photosynthetically active radiation (PAR) was developed. The crop did not appear to be light-saturated at PAR flux densities < 1800 Ei m^–2 s^–1. The light compensation point was found to be about 160 Ei m^–2 s^–1.Published as Paper No. 7402, Journal Series, Nebraska Agricultural Experiment Station. The work reported here was conducted under Nebraska Agricultural Experiment Station Project 27-003 and Regional Research Project 11–33.Post-doctoral Research Associate, Professor and Professor, respectively. Center for Agricultural Meteorology and Climatology, Institute of Agriculture and Natural Resources, University of Nebraska, Lincoln, NE 68583-0728.     

Mass transfer at the air/water interface: Mass accommodation coefficients of SO2, HNO3, NO2 and NH3

We present here experimental determinations of mass accommodation coefficients using a low pressure tube reactor in which monodispersed droplets, generated by a vibrating orifice, are brought into contact with known amounts of trace gases. The uptake of the gases and the accommodation coefficient are determined by chemical analysis of the aqueous phase.We report in this article measurements of _exp=(6.0±0.8)×10^–2 at 298 K and with a total pressure of 38 Torr for SO₂, (5.0±1.0)×10^–2 at 297 K and total pressure of 52 Torr for HNO₃, (1.5±0.6)×10^–3 at 298 K and total pressure of 50 Torr for NO₂, (2.4±1.0)×10^–2 at 290 K and total pressure of 70 Torr for NH₃.These values are corrected for mass transport limitations in the gas phase leading to =(1.3±0.1)×10^–1 (298 K) for SO₂, (1.1±0.1)×10^–1 (298 K) for HNO₃, (9.7±0.9)×10^–2 (290 K) for NH₃, (1.5±0.8)×10^–3 (298 K) for NO₂ but this last value should not be considered as the true value of for NO₂ because of possible chemical interferences.Results are discussed in terms of experimental conditions which determine the presence of limitations on the mass transport rates of gaseous species into an aqueous phase, which permits the correction of the experimental values.     

Factors Influencing the Atmospheric Depositional Fluxes of Stable Pb, 210Pb, and 7Be into Chesapeake Bay

Atmospheric depositional fluxes of ⁷Be and²¹⁰Pb (bulk) and stable Pb (wet) were measuredsimultaneously for one year (from September 1995–August 1996) atStillpond, Maryland on the uppereastern shore of the Chesapeake Bay. The annual total(bulk) depositional fluxes of ²¹⁰Pb and ⁷Bewere 0.78 and 13 dpm cm^-2, respectively, andagree well with other previously reported results atnearby locations such as Norfolk, VA and Lewes, DE. The wet depositional flux of stable Pb (58 ng cm^-2 yr^-1)was also similar to thatmeasured at other Chesapeake sites during 1990–1991(55 ng cm^-2 yr^-1, for both Wye and Elms,Maryland). This suggests that a constant Pb flux hasbeen reached since the mandatory use of unleadedgasoline was instituted. The concentrations of⁷Be, ²¹⁰Pb, and to a lesser extent stable Pbwere diluted exponentially by precipitation, based onconcentrations versus precipitation plots. Due tohigher enrichment of ²¹⁰Pb in the lowertroposphere, the dilution effect was largest on²¹⁰Pb (i.e., controlled mainly by below-cloudscavenging processes), and thus its depositional fluxincrease is negligible as precipitation amountincreases. A good correlation between the amount ofprecipitation and total depositional flux of ⁷Beand stable Pb, which are more enriched in the uppertroposphere, suggests that precipitation amount isimportant in controlling their fluxes (i.e.,controlled by both below-cloud scavenging and in-cloudcondensation processes). Based on ⁷Be versus²¹⁰Pb plots, it appears that ⁷Be, relativeto ²¹⁰Pb, is less efficiently scavenged bysnowfall. Our results suggest that in addition toprecipitation amounts, marine air-mass transport orsnowfall may be important factors in controlling theseasonal variability of the fallout fluxes of tracemetals in coastal areas.     

FTIR studies of reactions between the nitrate radical and haloethenes

Products and mechanisms for the gas-phase reactions of NO₃ radicals with CH₂=CHCl, CH₂=CCl₂, CHCl=CCl₂,cis-CHCl=CHCl andtrans-CHCl=CHCl in air have been studied. The experiments were carried out at 295±2 K and 740±5 Torr in a 480-L Teflon-coated reaction chamber and at 295±2 K and 760±5 Torr in a 250-L stainless steel reactor. NO₃ was generated by the thermal dissociation of N₂O₅. Experiments with¹⁵NO₃ and CD₂CDCl have also been performed. The initially formed nitrate peroxynitrates decay into carbonyl compounds, nitrates, HCl and ClNO₂. In adidtion, there are indications of nitrooxy acid chlorides being produced. The reactions with CH₂=CCl₂ and CHCl=CCl₂ are more complex due to release of chlorine atoms which eventually lead to formation of chloroacid chlorides.A general reaction mechanism is proposed and the observed concentration-time profiles of reactants and products are simulated for each compound. The rate constants for the initial step of NO₃ addition to the chloroethenes are determined as: (2.6±0.5, 9.4±0.9, 2.0±0.4 and 1.4±0.4) × 10^–16 cm³ molecule^–1 s^–1 for CH₂=CHCl, CH₂=CCl₂, CHCl=CCl₂ andcis-CHCl=CHCl, respectively.     

锡林浩特草原CO2通量特征及其影响因素分析

利用锡林浩特国家气候观象台开路涡度相关系统、辐射土壤观测系统,测得的长期连续通量观测数据,对锡林浩特草原2009—2011年期间的CO₂通量观测特征进行了分析。结果表明:CO₂通量存在明显的年际、季节和日变化特征。3 a中NEE年际变率达到200 g·m^-2,季节变率最大达到460 g·m^-2,日变化幅度生长季最大达到0.25 mg·m^-2·s^-1。通过不同时间尺度碳通量与温度、水分、辐射等环境因子的分析,认为CO₂通量日变化主要受温度和光合有效辐射影响,而季节变化和年变化主要受降水和土壤含水量的影响。降水强度及时间分布是制约牧草CO₂吸收的关键因素,大于15%的土壤含水量有利于促进牧草生长。     

Upper Water Column Nitrous Oxide Distributions in the Northeast Subarctic Pacific Ocean

This is the first study to investigate the magnitude and distribution of N₂O concentrations along the Line P oceanographic transect in the Northeast (NE) subarctic Pacific Ocean. Concentrations of N₂O were measured from the surface to 600 m depth at five stations between 126°W and 145°W. Although nitrification within the mixed layer may produce some N₂O, we conclude that mixing and diffusion processes, which vertically transport N₂O upwards from below the mixed layer, are the primary sources of N₂O to the surface waters of the NE subarctic Pacific Ocean. Below the mixed layer, nitrification appears to be the dominant source of N₂O, and based on correlations of excess N₂O (ΔN₂O) versus apparent oxygen utilization and NO₃ ^? concentrations, we estimated that the N₂O yield from nitrification was approximately 0.028 to 0.040%. The longitudinal distributions of N₂O concentrations below the mixed layer were variable and we consider the potential role that different transiting water masses may play in contributing to this variability. Finally, we estimated that the regional average sea-to-air N₂O flux was 4.37 mol of N₂O km^?2 d^?1, a value which is approximately four times that of the global average seawater-to-air flux rate. Our N₂O yield estimates are within the range of those expected under oxic conditions, leading us to conclude that decreasing dissolved O₂ concentrations in the NE subarctic Pacific Ocean, and the water masses that influence this region, over the past 50 years have yet to produce a substantial increase in N₂O production. Given the expectation that dissolved O₂ concentrations in the subarctic Pacific Ocean will continue to decrease during this century, this study has provided an important baseline from which future studies will be able to track changes in seawater N₂O concentrations and fluxes to the atmosphere.

[Traduit par la rédaction] La présente étude est la première à s'intéresser à la valeur et à la distribution des concentrations de N₂O le long du transect océanographique de la ligne P dans le Pacifique Nord-Est subarctique. Les concentrations de N₂O ont été mesurées de la surface jusqu’à une profondeur de 600 m à cinq stations entre 126°O et 145°O. Bien que la nitrification à l'intérieur de la couche de mélange puisse produire du N₂O, nous concluons que le mélange et les processus de diffusion, qui transportent verticalement le N₂O vers le haut à partir d'en dessous de la couche de mélange, sont les sources principales de N₂O pour les eaux de surface du Pacifique Nord-Est subarctique. En dessous de la couche mélange, la nitrification semble être la principale source de N₂O, et d'après les corrélations de l'excès de N₂O (ΔN₂O) par rapport à l'utilisation apparente d'oxygène et aux concentrations de NO₃ ^?, nous avons estimé que le rendement en N₂O de la nitrification était approximativement de 0,028 à 0,040%. Les distributions longitudinales des concentrations de N₂O en dessous de la couche de mélange étaient variables et nous considérons le rôle possible que des différentes masses d'eau transitoires peuvent avoir à jouer dans cette variabilité. Finalement, nous avons estimé que la moyenne régionale du flux mer–air de N₂O était de 4,37 moles de N₂O km^?2 j^?1, une valeur qui est environ quatre fois celle du taux planétaire moyen du flux eau de mer–air. Nos estimations du rendement en N₂O sont de l'ordre de celles attendues dans des conditions oxyques, ce qui nous amène à conclure que la diminution des concentrations d'oxygène dissout dans le Pacifique Nord–Est subarctique, et dans les masses d'eau qui influencent cette région, au cours des cinquante dernières années ont encore à produire une augmentation substantielle de production de N₂O. Étant donné qu'on s'attend à ce que les concentrations d'oxygène dissout dans le Pacifique subarctique continuent à diminuer durant le présent siècle, cette étude a fourni une importante base de référence à partir de laquelle de futures études pourront suivre les changements dans les concentrations de N₂O dans l'eau de mer et dans ses flux vers l'atmosphère.     

Estimation of Nocturnal Area Fluxes of Carbon Cycle Gases in Saint Petersburg Suburbs

Carbon dioxide, methane, and carbon monoxide are the carbon cycle gases, the data on their emissions are needed when monitoring air pollution and developing methods for reducing anthropogenic emissions to the atmosphere and for climate forecasting. The estimates of nocturnal area fluxes for CO₂, CH₄, and CO presented for a suburb of Saint Petersburg (Peterhof) are obtained using the box model and continuous observations of concentration of these gases. The mean values of CH₄, CO₂, and CO fluxes estimated for Peterhof for 2014–2015 are 44 ± 27, 6100 ± 4000, and 90 ± 100 t/(km² year), respectively. The intensity of the CO area flux has pronounced seasonal variations characterized by the maximum of ~(160 ± 120) t/(km² year) in November—February and by the minimum of ~(30 ± 20) t/(km² year) in June-July. The analysis of the ratio of CO/CO₂ fluxes identified the main types of anthropogenic sources typical of Peterhof: motor transport, natural gas combustion, and the use of wood stoves for the heating of private low-rise buildings (in the cold season).