Practical applicability of high frequency correction theories to CO<Subscript>2</Subscript> flux measured by a closed-path system

The theoretical correction of CO₂ fluxes for high frequency attenuation in closed-path systems was re-summarized and its applicability examined using both measurements obtained at an Asiaflux forest site and empirical transfer functions used in previous studies. For our measurement system, the theoretical transfer function was applicable to high frequency correction, even when condensation occurred in the sampling line. Further, in respect to some measurement systems described in previous studies, it was found that the theoretical function was potentially applicable along with the empirical functions used. Meanwhile, in some systems significant errors could not be resolved by re-estimation of the theories. In these systems, because of undefined buffering effects, the actual response lag time decided by the maximum covariance method or by measurement of the system response time using tracer gas was significantly different from the lag time calculated from the tube dimensions and the measured flow rate. If the average flow rate calculated by the actual lag time was used to determine the theoretical function, the theoretical function became closer to, and sometimes agreed with, the empirical function. Any remaining deviation from each function might be associated with pressure fluctuations, but this problem was unable to be examined here. The results suggested that an empirical formulation for each site is considered applicable rather than a theoretical approach, although the theories are being developed to practical application.     

Estimates of anthropogenic CO<Subscript>2</Subscript> uptake in a global ocean model

A global ocean general circulation model (L30T63) is employed to study the uptake and distribution of anthropogenic CO₂ in the ocean. A subgrid-scale mixing scheme called GM90 is used in the model. There are two main GM90 parameters including isopycnal diffusivity and skew (thickness) diffusivity. Sensitivities of the ocean circulation and the redistribution of dissolved anthropogenic CO₂ to these two parameters are examined. Two runs estimate the global oceanic anthropogenic CO₂ uptake to be 1.64 and 1.73 Pg C yr^-1 for the 1990s, and that the global ocean contained 86.8 and 92.7 Pg C of anthropogenic CO₂ at the end of 1994, respectively. Both the total inventory and uptake from our model are smaller than the data-based estimates. In this presentation, the vertical distributions of anthropogenic CO₂ at three meridional sections are discussed and compared with the available data-based estimates. The inventory in the individual basins is also calculated. Use of large isopycnal diffusivity can generally improve the simulated results, including the exchange flux, the vertical distribution patterns, inventory, storage, etc. In terms of comparison of the vertical distributions and column inventory, we find that the total inventory in the Pacific Ocean obtained from our model is in good agreement with the data-based estimate, but a large difference exists in the Atlantic Ocean, particularly in the South Atlantic. The main reasons are weak vertical mixing and that our model generates small exchange fluxes of anthropogenic CO₂ in the Southern Ocean. Improvement in the simulation of the vertical transport and sea ice in the Southern Ocean is important in future work.     

Consequences of Uncertainties in CO<Subscript>2</Subscript> Density for Estimating Net Ecosystem CO<Subscript>2</Subscript> Exchange by Open-path Eddy Covariance

Errors in the estimation of CO₂ surface exchange by open-path eddy covariance, introduced during the removal of density terms [Webb et al. Quart J Roy Meteorol Soc 106:85–100, (1980) - WPL], can happen both because of errors in energy fluxes [Liu et al. Boundary-Layer Meteorol 120:65–85, (2006)] but also because of inaccuracies in other terms included in the density corrections, most notably due to measurements of absolute CO₂ density (ρ _c ). Equations are derived to examine the propagation of all errors through the WPL algorithm. For an open-path eddy covariance system operating in the Sierra de Gádor in south-east Spain, examples are presented of the inability of an unattended, open-path infrared gas analyzer (IRGA) to reliably report ρ _c and the need for additional instrumentation to determine calibration corrections. A sensitivity analysis shows that relatively large and systematic errors in net ecosystem exchange (NEE) can result from uncertainties in ρ _c in a semi-arid climate with large sensible heat fluxes (H _s ) and (wet) mineral deposition. When ρ_c is underestimated by 5% due to lens contamination, this implies a 13% overestimation of monthly CO₂ uptake.     

Multi-Phase Chemistry of C<Subscript>2</Subscript> and C<Subscript>3</Subscript> Organic Compounds in the Marine Atmosphere

A box model is used to explore the detailed chemistry of C₂ and C₃ organic compounds in the marine troposphere by tracing the individual reaction paths resulting from the oxidation of ethane, ethene, acetylene, propane, propene and acetic acid. The mechanisms include chemical reactions in the gas phase and in the aqueous phase of clouds and aerosol particles at cloud level under conditions resembling those in the northern hemisphere. Organic hydroperoxides are found to be important intermediate products, with subsequent reactions leading partly to the formation of mixed hydroxy or carbonyl hydroperoxides that are readily absorbed into cloud water, where they contribute significantly to the formation of multifunctional organic compounds and organic acids. Organic hydroperoxides add little to the oxidation of sulfur dioxide dissolved in the aqueous phase, which is dominated by H₂O₂. Next to acetaldehyde and acetone, glycol aldehyde, glyoxal, methyl glyoxal and hydroxy propanone are prominent oxidation products in the gas and the aqueous phase. Acetaldehyde is not efficiently converted to acetic acid in clouds; the major local sources of acetic acid are gas-phase reactions. Other acids produced include hydroperoxy acetic, glycolic, glyoxylic, oxalic, pyruvic, and lactic acid. The mechanism of Schuchmann et al. (1985), which derives glycolic and glyoxylic acid from the oxidation of acetate, is found unimportant in the marine atmosphere. The principal precursors of glyoxylic acid are glyoxal and glycolic acid. The former derives mainly from acetylene and ethene, the latter from glycolaldehyde, also an oxidation product of ethene. The oxidation of glyoxylic acid leads to oxalic acid, which accumulates and is predicted to reach steady state concentrations in the range 30–90 ng m⁻³. This is greater, yet of the same magnitude, than the concentrations observed over the remote Pacific Ocean.     

On the relationship between the eddy covariance,the turbulent flux,and surface exchange for a trace gas such as CO<Subscript>2</Subscript>

In the context of CO₂ surface exchange estimation, an analysis combining the basic principles of diffusion and scalar conservation shows that the mixing ratio is the appropriate variable both for defining the (eddy covariance) turbulent flux and also for expressing the relationship between the turbulent flux and surface exchange in boundary-layer budget equations. Other scalar intensity variables sometimes chosen, both the CO₂ density and molar fraction, are susceptible to the influence of surface exchange of heat and water vapour. The application of a hypsometric analysis to the boundary-layer “control volume” below the tower measurement height reveals flaws in previously applied approaches: (a) incompressibility cannot be assumed to simplify mass conservation (the budget in terms of CO₂ density); (b) compressibility alone makes the analysis of mass conservation vulnerable to uncertainties associated with resultant non-zero vertical velocities too small to measure or model over real terrain; and (c) the WPL (Webb et al. (1980) Quart J Roy Meteorol Soc 106:85–100) “zero dry air flux” assumption is invalidated except at the surface boundary. Nevertheless, the definition and removal of the WPL terms do not hinge upon this last assumption, and so the turbulent CO₂ flux can be accurately determined by eddy covariance using gas analysers of either open- or closed-path design. An appendix discusses the necessary assumptions and appropriate interpretations for deriving the WPL terms.     

太平洋海气CO2通量对气候事件的响应

应用一个嵌套了海洋生物地球化学循环的太平洋环流碳循环模式,分析了1960～2000年太平洋不同海区海气碳通量随时间的变化。模拟结果显示,赤道太平洋为大气CO₂的排放区,南、北太平洋(南、北纬15°至模式计算区域南、北边界)为吸收区。3个海区海气碳通量随时间均存在显著的波动,其中赤道太平洋海气碳通量年际波动最显著。3个海区海气碳通量年际波动对气候事件的响应并不一致,在El Niño年赤道太平洋冷舌的强度和总溶解无机碳(DIC)的浓度以及输出生产力均会受到上升流减弱的影响而降低,La Niña年这些海气碳通量控制要素的分布情况则正好相反,但在南北太平洋副热带以及高纬度海区,El Niño和La Niña对这些要素带来的影响却并不一定相反,对输出生产力的影响甚至是一致的。以海表温度(SST)为例考察海气碳通量与物理场之间的关系表明,在赤道太平洋上升流对DIC的影响是控制海气碳通量变化的主要因素,而在其他海区,尤其是副热带海区,由于垂直运动的年际变化较小,且生物生产力水平较低,SST的波动对海气碳通量年际变化的影响更加重要。     

An Alternative Approach for CO2 Flux Correction Caused by Heat and Water Vapour Transfer

Energy and CO₂ fluxes are commonly measured above plant canopies using an eddy covariance system that consists of a three-dimensional sonic anemometer and an H₂O/CO₂ infrared gas analyzer. By assuming that the dry air is conserved and inducing mean vertical velocity, Webb et al. (Quart. J. Roy. Meteorol. Soc. 106, 85-100, 1980) obtained two equations to account for density effects due to heat and water vapour transfer on H₂O/CO₂ fluxes. In this paper, directly starting with physical consideration of air-parcel expansion/compression, we derive two alternative equations to correct for these effects that do not require the assumption that dry air is conserved and the use of the mean vertical velocity. We then applied these equations to eddy flux observations from a black spruce forest in interior Alaska during the summer of 2002. In this ecosystem, the equations developed here led to increased estimates of CO₂ uptake by the vegetation during the day (up to about 20%), and decreased estimates of CO₂ respiration by the ecosystem during the night (approximately 4%) as compared with estimates obtained using the Webb et al. approach.     

Comparative Measurements Of Co2flux Over A Forest Using Closed-Path And Open-Path Co2analysers

An eddy covariance system using a closed-path CO₂analyser was constructed for long-term CO₂flux measurements above a forest, and its total frequency response was valuated experimentally. The amplitude and phase responses of the system wereexamined through a preliminary test, in which a prescribed pattern of CO₂fluctuation was input to the system. The result showed that the amplitude of the output from the system was attenuated as frequency increased, with a half-power frequency of 0.3 Hz. The phase was delayed by the air sampling through a long tube, but the delay in phase decreased asfrequency increased. We then presented a new technique for the correction of flux loss due to the inadequate system response for the eddy covariance measurements of CO₂ flux. Using the present system and the correction technique, diurnal variations in CO₂ flux were measured over a temperate deciduous forest on three days in 1997. The results were compared with the CO₂fluxes measured with a fast response open-path gas analyser. The CO₂fluxes from the closed-path system agreed with those from the open-path system after the Webb, Pearman and Leuning correction was made for the latter. In the present test over a forest, the contribution of the frequency-response correction to the CO₂fluxes was small and its averaged percentage was only 3%in the daytime. However, the percentage would likely increase, if the system were applied to a shorter vegetation site where high frequency components are more important. The comparison confirmed that we can obtain correct measurements of CO₂flux using the present closed-path system and the correction technique.     

Influence of leaf water potential on diurnal changes in CO2 and water vapour fluxes

Mass and energy fluxes between the atmosphere and vegetation are driven by meteorological variables, and controlled by plant water status, which may change more markedly diurnally than soil water. We tested the hypothesis that integration of dynamic changes in leaf water potential may improve the simulation of CO₂ and water fluxes over a wheat canopy. Simulation of leaf water potential was integrated into a comprehensive model (the ChinaAgrosys) of heat, water and CO₂ fluxes and crop growth. Photosynthesis from individual leaves was integrated to the canopy by taking into consideration the attenuation of radiation when penetrating the canopy. Transpiration was calculated with the Shuttleworth-Wallace model in which canopy resistance was taken as a link between energy balance and physiological regulation. A revised version of the Ball-Woodrow-Berry stomatal model was applied to produce a new canopy resistance model, which was validated against measured CO₂ and water vapour fluxes over winter wheat fields in Yucheng (36°57′ N, 116°36′ E, 28 m above sea level) in the North China Plain during 1997, 2001 and 2004. Leaf water potential played an important role in causing stomatal conductance to fall at midday, which caused diurnal changes in photosynthesis and transpiration. Changes in soil water potential were less important. Inclusion of the dynamics of leaf water potential can improve the precision of the simulation of CO₂ and water vapour fluxes, especially in the afternoon under water stress conditions.     

Effects of an Urban Park and Residential Area on the Atmospheric CO2 Concentration and Flux in Seoul, Korea

The CO₂ concentrations and fluxes over an urban forest site (Namsan) and an urban residential region (Boramae) in Seoul, Korea, during the non-growing season (2–4 March 2011), the growing season (10–12 June 2011), and the late-growing season (22–24 September 2011) were analyzed. The CO₂ concentrations of two sites showed nearly the same diurnal variation, with a maximum value occurring during the night and a minimum value occurring during daytime, as well as the same seasonal variation, with a maximum value during the non-growing season (early spring) and a minimum value during the growing season (summer). The CO₂ flux over the urban forest did not show any typical diurnal variation during the non-growing season, but did show diurnal variation with a small positive value during the night and a large negative value during daytime in the growing and late-growing seasons due to photosynthesis in the urban forest. The CO₂ flux over the urban residential region showed a positive daily mean value for all periods, with large values during the non-growing season and small values during the growing season, and it also showed diurnal variation with two maxima at 0600–1000 LST and 1800–2400 LST, and two minima at 0300-0600 LST and 1100-1500 LST, and was strongly correlated with the use of liquefied natural gas for cooking and heating by surrounding houses.     

On the Significance of the Webb Correction to Fluxes

For establishing correct mass or energy balances at the Earth's surface, detailed and correct measurements of air constituent fluxes are needed. Flux measurements obtained from the eddy covariance technique have to pass several corrections of different relevance in order to give correct flux data. One of these corrections, the Webb correction, is analysed herein from latent heat flux and CO₂ flux data recorded during two field experiments. The significance of this correction for the latent heat flux data varies with the air humidity and the Bowen ratio. The correction changes the latent heat flux values only a little, but significantly (by 2 to 3%). For other air constituents (like CO₂), the Webb correction is much more important (20 to 30% of the flux).     

Products and Mechanism of the NO<Subscript>3</Subscript> Reaction with Thiophene

Products of the gas-phase reaction of the NO₃ radical with thiophene have been investigated using different experimental systems. On the one hand, experiments have been conducted in our laboratory using two different methods, a Teflon static reactor coupled to a gas chromatograph combined with mass-spectrometry (GC-MS) and a discharge flow tube with direct MS spectroscopic detection. A qualitative analysis in these cases indicates that possible products for the reaction of thiophene+NO₃ at room temperature include: sulphur dioxide, acetic and formic acids, a short-chain aldehyde, 2-nitrothiophene and 3-nitrothiophene. On the other hand, quantitative experiments have been performed in the European Photoreactor (EUPHORE) in Valencia, Spain. In this case, the major products were: HNO₃ (≈80%), nitrothiophenes (≈30%), SO₂ (≈20%), propanal (3%) and a fraction of particles (≈10%). The results obtained indicate that at least 70% of the reaction of NO₃ with thiophene proceeds by an H-abstraction process at room temperature. The mechanism of the reaction studied is proposed on the basis of experimental results.     

Uptake and Storage of Anthropogenic CO2 in the Pacific Ocean Estimated Using Two Modeling Approaches

A basin-wide ocean general circulation model(OGCM) of the Pacific Ocean is employed to estimate the uptake and storage of anthropogenic CO 2 using two different simulation approaches.The simulation(named BIO) makes use of a carbon model with biological processes and full thermodynamic equations to calculate surface water partial pressure of CO 2,whereas the other simulation(named PTB) makes use of a perturbation approach to calculate surface water partial pressure of anthropogenic CO 2.The results from the two simulations agree well with the estimates based on observation data in most important aspects of the vertical distribution as well as the total inventory of anthropogenic carbon.The storage of anthropogenic carbon from BIO is closer to the observation-based estimate than that from PTB.The Revelle factor in 1994 obtained in BIO is generally larger than that obtained in PTB in the whole Pacific,except for the subtropical South Pacific.This,to large extent,leads to the difference in the surface anthropogenic CO 2 concentration between the two runs.The relative difference in the annual uptake between the two runs is almost constant during the integration processes after 1850.This is probably not caused by dissolved inorganic carbon(DIC),but rather by a factor independent of time.In both runs,the rate of change in anthropogenic CO 2 fluxes with time is consistent with the rate of change in the growth rate of atmospheric partial pressure of CO 2.     

Satellite Measurements of Tropospheric Column O<Subscript>3</Subscript> and NO<Subscript>2</Subscript> in Eastern and Southeastern Asia: Comparison with a Global Model (MOZART-2)

Satellite measurements of tropospheric column O₃ and NO₂ in eastern and southeastern Asia are analyzed to study the spatial and seasonal characteristics of pollution in these regions. Tropospheric column O₃ is derived from differential measurements of total column ozone from Total Ozone Mapping Spectrometer (TOMS), and stratospheric column ozone from the Microwave Limb Sounder (MLS) instrument on the Upper Atmosphere Research Satellite (UARS). The tropospheric column NO₂ is measured by Global Ozone Monitoring Experiment (GOME). A global chemical and transport model (Model of Ozone and Related Chemical Tracers, version 2; MOZART-2) is applied to analyze and interpret the satellite measurements. The study, which is based on spring, summer, and fall months of 1997 shows generally good agreement between the model and satellite data with respect to seasonal and spatial characteristics of O₃ and NO₂ fields. The analysis of the model results show that the industrial emission of NO_x (NO + NO₂) contributes about 50%–80% to tropospheric column NO₂ in eastern Asia and about 20%–50% in southeastern Asia. The contribution of industrial emission of NO_x to tropospheric column O₃ ranges from 10% to 30% in eastern Asia. Biomass burning and lightning NO_x emissions have a small effect on tropospheric O₃ in central and eastern Asia, but they have a significant impact in southeastern Asia. The varying effects of NO_x on tropospheric column ozone are attributed to differences in relative abundance of volatile organic compounds (VOCs) with respect to total nitrogen in the two regions.     

Reductions of PM<Subscript>2.5</Subscript> in Beijing-Tianjin-Hebei urban agglomerations during the 2008 Olympic Games

The Atmospheric Environmental Monitoring Network successfully undertook the task of monitoring the atmospheric quality of Beijing and its surrounding area during the 2008 Olympics.The results of this monitoring show that high concentrations of PM2.5 pollution exhibited a regional pattern during the monitoring period(1 June-30 October 2008).The PM2.5 mass concentrations were 53 μg m 3,66 μg m 3,and 82 μg m 3 at the background site,in Beijing,and in the Beijing-Tianjin-Hebei urban agglomerations,respectively.The PM2.5 levels were lowest during the 2008 Olympic Games(8-24 August):35 μg m 3 at the background site,42 μg m 3 in Beijing and 57 μg m 3 in the region.These levels represent decreases of 49%,48%,and 56%,respectively,compared to the prophase mean concentration before the Olympic Games.Emission control measures contributed 62%-82% of the declines observed in Beijing,and meteorological conditions represented 18%-38%.The concentration of fine particles met the goals set for a "Green Olympics."     

Consequences of Incomplete Surface Energy Balance Closure for CO2 Fluxes from Open-Path CO2/H2O Infrared Gas Analysers

We present an approach for assessing the impact of systematic biases in measured energy fluxes on CO₂ flux estimates obtained from open-path eddy-covariance systems. In our analysis, we present equations to analyse the propagation of errors through the Webb, Pearman, and Leuning (WPL) algorithm [Quart. J. Roy. Meteorol. Soc. 106, 85–100, 1980] that is widely used to account for density fluctuations on CO₂ flux measurements. Our results suggest that incomplete energy balance closure does not necessarily lead to an underestimation of CO₂ fluxes despite the existence of surface energy imbalance; either an overestimation or underestimation of CO₂ fluxes is possible depending on local atmospheric conditions and measurement errors in the sensible heat, latent heat, and CO₂ fluxes. We use open-path eddy-covariance fluxes measured over a black spruce forest in interior Alaska to explore several energy imbalance scenarios and their consequences for CO₂ fluxes.     

The correct form of the Webb,Pearman and Leuning equation for eddy fluxes of trace gases in steady and non-steady state,horizontally homogeneous flows

The original density corrections proposed by Webb et al. [Webb EK, Pearman GI, Leuning R (1980) Quart J Roy Meteorol Soc 106:85–100] for calculating the eddy fluxes of trace gases are shown to be correct for both steady and non-steady state, horizontally homogeneous flows. The revised theory replaces the original assumption of zero vertical flux of dry air with the requirement of no sources or sinks of dry air in the layer below the height of measurement.     

厌氧条件下土壤反硝化气体(N2、N2O、NO)和CO2排放——氦环境培养—气体同步直接测定法的应用初探

反硝化过程是维系闭合氮循环所必需的氮素形态转化环节。土壤反硝化过程速率及产物比的直接测定是研究氮循环过程机理的基础,但却是一个难题。为解决此难题,德国卡尔斯鲁厄技术研究所与中国科学院大气物理研究所最近合作新建了一套通过氦环境培养-气体同步直接测定土壤反硝化气体--氮气（N2）、氧化亚氮（N2O）、一氧化氮（NO）和二氧化碳（CO2）排放的系统和与之配套的三阶段培养方法。为检验该新建系统和配套方法测定土壤反硝化过程的准确性和可靠性,以华北地区广泛分布的盐碱地农田土壤（采自山西运城）为研究对象开展实验室培养试验,在初始可溶性有机碳（DOC）供应比较充足约300 mgC kg–1干土（d.s.）的条件下,测试了不同初始土壤硝态氮含量水平（10、100 mgN kg–1d.s.左右,分别表示为10N和100N）的反硝化气体和CO2排放过程。结果显示：100N的反硝化速率（定义为N2、N2O 和NO 排放速率之和）显著高于10N 处理（统计检验显著水平p＜0.01）;两个处理的反硝化产物均以N2为主（质量比分别占77%和75%）,产物的NO/N2O摩尔比分别为1.2和1.5,N2O/N2摩尔比均为0.19;土壤反硝化气体动态排放速率及相关指标的测定结果表明,培养土壤中消失的硝态氮被回收81%～87%,培养前后的氮平衡率达92%～95%。因此,该新建方法测定土壤反硝化速率和产物比的结果具有很好的可靠性,为定量研究土壤反硝化过程提供了有效的直接测定手段。研究中检测到的土壤反硝化产物NO/N2O摩尔比大于1,不同于以往用液体培养基纯培养反硝化细菌得出的NO/N2O摩尔比远小于1的结论。这意味着,不能用NO/N2O摩尔比小于1与否来推断土壤排放的N2O和NO是主要来源于反硝化作用还是硝化作用。