箱法在草地温室气体通量野外实验观测中的应用研究

利用静态箱法采样,配以气相色谱仪法分析对草地N2O、CH4和CO2温室气体通量进行了较系统的现场测量,同时对箱体内外温度进行同步观测。在对野外原位观测实验数据进行定量分析的基础上,论证了静态箱法对草原土壤-植被系统的N2O、CH4和CO2通量测量的适用性和科学性,讨论了实验结果的可靠性。     

华东稻田CH4和N2O排放

稻田CH4和N2O排放的季节变化规律完全不同，两者的排放通量随土壤水分条件变化而互为消长，但它们的日变化形式则比较一致。晴天时的CH4和N2O排放日变化规律明显，主要表现为下午单峰模态，有时CH4排放夜间出现一个次峰。CH4和N2O排放总量因肥料类型而不同，堆肥加尿素处理比NH4HCO3处理少排放N2O 30%，多排放CH4 12%。     

生长旺盛期呼伦贝尔草甸草原生态系统呼吸与CH_4吸收通量的日变化研究

利用静态箱法于2011年结实期和2012年开花期与结实期分别对不同人类活动(自由放牧和刈割)影响下的呼伦贝尔草甸草原及相应的封育草原的CH4通量和植物土壤系统呼吸作用排放的CO2通量进行野外定位观测研究。结果表明:呼伦贝尔草甸草原(放牧和刈割及其对应的封育样地)均表现为CH4的汇,3个观测时期汇强的变化范围为:-23.98±6.40~-95.96±28.57μg Cm-2 h-1。呼伦贝尔草甸草原CH4通量的日变化对温度的响应较为复杂。不同时期呼伦贝尔草甸草原的植物土壤系统呼吸速率的日变化存在差异,水分和温度的共同影响造成2012年结实期日均CO2排放量低于2011年结实期。放牧对呼伦贝尔草甸草原CH4吸收通量的日变化模式的影响较小,但在2011年结实期和2012年开花期促进了CH4日均通量(促进幅度12.05%~93.35%),2012年结实期放牧降低了CH4日均通量(降低幅度23.32%~30.43%);刈割降低CH4吸收日均通量11.55%~60.62%。呼伦贝尔草甸草原日均累计碳排放量中CH4所占比例为0.35%~2.62%,而放牧和刈割行为对呼伦贝尔草甸草原的日均累计碳排放的影响结果在不同物候期以及不同植被群落类型均有不同。     

浙江临安水稻田甲烷排放通量的观测研究

1990年7—9月，在浙江临安（30°14＇N，119°42＇E），利用微气象学（梯度廓线）法及箱式技术对水稻田CH4排放通量进行了同步观测，取得了中稻整个生长期内的CH4排放资料。文章仅对箱式技术的观测结果作了介绍与分析。观测发现在整个灌溉期内，稻田CH4释放率为3.67—16.14 mg/m2·h，均值为10.58 mg/m2·h。CH4排放的季节变化明显，日变化也同样很明显。另外还发现，CH4排放通量与水（地）温及其他气象因素，如强风、阴雨等有关。与梯度廓线法的观测结果不同，箱式观测到的CH4排放通     

小麦秸秆还田量对晋南地区裸地土壤—大气间甲烷、二氧化碳、氧化亚氮和一氧化氮交换的影响

采用静态暗箱采样—气相色谱/化学发光分析相结合的方法,对晋南地区盐碱地不同小麦秸秆还田量裸地土壤夏、秋季(2008年6～10月)的甲烷(CH4)、二氧化碳(CO2)、氧化亚氮(N2O)和一氧化氮(NO)交换通量进行了原位观测。结果表明:观测期内,秸秆全还田(FS)、秸秆一半还田(HS)和秸秆不还田(NS)处理土壤—大气间CH4、CO2、N2O和NO平均交换通量分别为-0.8±2.7、-1.4±2.3、-6.5±1.8μg(C).m-2.h-1(CH4),267.1±23.1、212.0±17.8、188.5±13.6mg(C).m-2.h-1(CO2),20.7±3.0、16.3±2.3、14.7±1.7μg(N).m-2.h-1(N2O),3.9±0.5、3.4±0.5、3.0±0.4μg(N).m-2.h-1(NO)。交换通量表现出明显的季节变化趋势,灌溉、降雨和温度变化是影响该趋势的主要因素。相对于NS处理,FS和HS处理降低了累积CH4吸收量(66%和59%),增加了累积CO2(42%和12%)、N2O(41%和9%)和NO(30%和13%)排放量,因此,秸秆还田促进了农田土壤总的温室气体排放。计算得到FS和HS处理小麦秸秆的CO2、N2O、NO排放系数分别为73.4%±1.6%和43.3%±1.0%(CO2)、0.37%±0.01%和0.17%±0.00%(N2O)、0.06%±0.00%和0.05%±0.00%(NO),FS处理的排放系数显著高于HS处理,且均低于同一实验地种植玉米、施肥农田的小麦秸秆排放系数(N2O和NO排放系数分别为2.32%和0.42%)。可见,在采用排放因子方法估算还田秸秆CO2、N2O和NO排放量时,应考虑秸秆还田量、农作物种植和施肥因素的影响。     

华东稻麦轮作农田CH4、N2O和NO排放特征

利用同步自动观测系统对华东稻麦轮作农田的CH4、N2O和NO排放进行了长期连续观测,分析了这3种气体排放的季节特征及决定因素,结果表明,华东稻麦轮作农田的CH4、N2O和NO排放具有完全不同的季节变化形式。CH4的排放发生在水稻生长期,其他阶段排放不明显,土壤水分状况是决定整个轮作周期内CH4排放变化的主要因素。N2O排放具有"冬季无,水田少,旱地多"的季节变化特点,尤其以旱地阶段的排放为主,土壤水分状况和温度共同决定着N2O排放的季节变化形式。NO排放具有"冬季无,水田很少,春季旱地多于秋季旱地"的季节分布特点,轮作周期内97.3%±0.6%的NO排放都发生在除冬季以外的旱地阶段,NO排放的季节变化形式由土壤水分状况和温度共同决定。大多数情况下稻田CH4和N2O排放呈互为消长的关系,但在烤田期间,二者却有时甚至同时出现高排放。在N2O日平均排放通量小于5 mg.m-2.h-1时,稻麦轮作农田的N2O和NO排放呈明显的互为消长关系,但大于5 mg.m-2.h-1时,N2O排放很强,同时NO排放也很强。     

种植不同作物对农田N2O和CH4排放的影响及其驱动因子

以种植玉米(Zea mays)、大豆(Glycine max)和水稻(Oryza sativa)的农田生态系统为研究对象,于2003年6~10月系统观测了N2O和CH4的排放、土壤温度和湿度以及相关的生物学因子。玉米和水稻分别施化肥氮300 kg.hm-2,大豆未施氮肥。研究结果表明,作物类型对农田N2O和CH4排放具有显著的影响。土壤-玉米系统、土壤-大豆系统和土壤-水稻系统的N2O季节性平均排放通量分别为620.5±57.6、338.0±7.5和238.8±13.6μg.m-2.h-1(N2O)。种植作物促进了农田生态系统的N2O排放,玉米地土壤和裸地土壤的N2O平均排放通量分别为364.2±11.7和163.7±10.5μg.m-2.h-1(N2O)。土壤-玉米系统、土壤-水稻系统、玉米地土壤和裸地土壤N2O排放受土壤温度的影响,与土壤湿度无显著统计相关,但受土壤温度和水分的综合影响。土壤-大豆系统N2O排放随作物绿叶干重的增加而指数增加,与土壤温度和水分条件无统计相关,由大豆作物自身氮代谢所产生的N2O-N季节总量约为6.2 kg.hm-2(N)。土壤-水稻系统CH4平均排放通量为1.7±0.1 mg.m-2.h-1(CH4),烤田抑制了稻田CH4的排放。烤田前影响稻田CH4排放的主要因素是水稻生物量,烤田后的浅水灌溉及湿润灌溉阶段的CH4排放与土壤温度和水稻生物量无关。本研究未观测到旱作农田有吸收CH4的现象。     

半干旱草原温室气体排放/吸收与环境因子的关系研究

静态箱一气相色谱法对内蒙古半干旱草原连续两年的实验观测研究结果表明,内蒙古草原是大气CO2和N2O的排放源,而是CH4的汇.在植物生长不同季节,草原生态系统排放/吸收温室气体CO2,CH4和N2O的日变化形式各有不同,其中在植物生长旺季日变化形式最具特征.3种温室气体的季节排放/吸收高峰主要出现在土壤湿度较大的春融和降雨较为集中时期.所有草原植物生长季节CO2净排放日变化形式均为白天出现排放低值,夜间出现排放高值.较高的温度有利于CO2排放,地上生物量决定着光合吸收CO2量值的高低.影响半干旱草原吸收CH4和排放N2O日变化形式的关键是土壤含水量和供氧状况,日温变化则主要影响日变化强度.吸收CH4和排放N2O的季节变化与土壤湿度季节变化分别呈线性反、正相关,相关系数均在0.4～0.6之间.自由放牧使CO2、N2O和CH4交换速率日较差降低,同时使N2O和CH4年度排放/吸收量减少和CO2年度排放量增加.     

半干旱草原温室气体排放/吸收与环境因子的关系研究

静态箱—气相色谱法对内蒙古半干旱草原连续两年的实验观测研究结果表明，内蒙古草原是大气CO2和N2O的排放源，和CH4的汇。在植物生长不同季节，草原生态系统排放／吸收温室气体CO2、CH4和N2O的日变化形式各有不同，其中在植物生长旺季日变化形式最具特征。三种温室气体的季节排放／吸收高峰主要出现在土壤湿度较大的春融期和降雨较为集中时期。对所有草原植物生长季节，CO2净排放日变化形式均为白天出现排放低值，夜间出现排放高值。较高的温度有利于CO2排放，地上生物量决定着光合吸收CO2量值的高低。影响半干旱草原吸收CH4和排放N2O日变化形式的关键是土壤台水量和供氧状况，日温变化则主要影响日变化强度。吸收CH4和排放N2O的季节变化与土壤湿度季节变化分别呈线性反、正相关，相关系数均在0．4-0．6之间。自由放牧使CO2、N2O和CH4交换速率日较差降低，同时使N2O和CH4年度排放／吸收量减少和CO2年度排放量增加。     

清远地区晚稻田甲烷排放的实验

根据2003年清远地区晚稻田甲烷(CH4)排放的实验观测资料,分析了该地区晚稻田生长期间CH4排放的变化规律,对影响排放的相关因子进行了分析。结果表明:晚稻田CH4排放的变化规律基本为3峰型,整个生长期间平均排放通量为6.09 mg.m-2.h-1。不同稻种之间的CH4排放通量差别不是很大,种植的2个水稻品种"金优99"和"七丝尖"相差1.08 mg.m-2.h-1。水位和土壤氧化还原电位对CH4排放通量有明显的影响。     

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.     

Influence of the surface microlayer on the flux of nonconservative trace gases (CO,H2, CH4, N2O) across the ocean-atmosphere interface

Gas exchange experiments were conducted in the tropical Atlantic Ocean during a ship expedition with FS Meteor using a small rubber raft. The temporal change of the mixing ratios of CO, H₂, CH₄ and N₂O in the headspace of a floating glass box and the concentrations of these gases in the water phase were measured to determine their transfer velocities across the ocean-atmosphere interface. The ocean acted as a sink for these gases when the water was undersaturated with respect to the mixing ratio in the headspace. The transfer velocities were different for the individual gases and showed still large differences even when normalized for diffusivity. Applying the laminar film model, film thicknesses of 20 to 70 m were calculated for the observed flux rates of the different gas species. When the water was supersaturated with respect to atmospheric CO, H₂, CH₄ and N₂O, the transfer velocities of the emission process were smaller than those determined for the deposition process. In case of H₂ and CH₄, emission was even not calculable although, based on the observed gradient, the laminar film model predicted significant fluxes at the air-sea interface. The results are interpreted by destruction processes active within the surface microlayer.     

CH4和N2O的辐射强迫与全球增温潜能

CH₄和N₂O作为主要温室气体,自工业革命以来排放量急剧增加,已经被列入《京都议定书》要求控制它们的排放。本文利用高光谱分辨率的辐射传输模式,计算了CH₄、N₂O在晴空大气和有云大气条件下的瞬时辐射效率和平流层调整的辐射效率,以及它们的全球增温潜能(GWP)和全球温变潜能(GTP),并根据模式结果拟合了CH₄和N₂O的辐射强迫的简单计算公式。本文的研究表明:CH₄和N₂O在有云大气下的平流层调整的辐射效率分别为4.142×10-4 W m-2 ppb-1和3.125×10-3 W m-2 ppb-1 (1ppb=10-9),经大气寿命调整后的辐射效率分别为3.732×10-4 W m-2 ppb-1和2.987×10-3 W m-2 ppb-1,与IPCC(2007)的相应结果高度一致。CH₄和N₂O 100年的全球增温潜能GWP分别为16和266;100年的脉冲排放的全球温变潜能GTPP分别为0.24和233;持续排放的全球温变潜能GTPS分别为18和268。它们在未来全球变暖和气候变化中,影响仅次于CO₂,仍然起着非常关键的作用。     

The heterogeneous formation of N2O over bulk condensed phases in the presence of SO2 at high humidities

In view of the uncertainty of the origin of the secular increase of N₂O, we studied heterogeneous processes that contribute to formation of N₂O in an environment that comes as close as possible to exhaust conditions containing NO and SO₂, among other constituents. The N₂O formation was followed using electron capture gas chromatography (ECD-GC). The other reactants and intermediates (SO₂, NO, NO₂ and HONO) were monitored using gas phase UV-VIS absorption spectroscopy. Experiments were conducted at 298 and 368 K as well as at dry and high humidity (approaching 100% rh) conditions. There is a significant heterogeneous rate of N ₂ O formation at conditions that mimic an exhaust plume from combustion processes.The simultaneous presence of NO, SO₂, O₂ in the gas phase and condensed phase water, either in the bulk liquid or adsorbed state has been confirmed to be necessary for the production of significant levels of N₂O. The stoichiometry of the overall reaction is: 2 NO+SO₂+H₂O N₂O+H₂SO₄. The maximum rate of N₂O formation occurred at the beginning of the reaction and scales with the surface area of the condensed phase and is independent of its volume. A significant rate of N₂O formation at 368 K at 100% rh was also observed in the absence of a bulk substrate. The diffusion of both gas and liquid phase reactants is not rate limiting as the reaction kenetics is dominated by the rate ofN₂O formation under the experimental conditions used in this work. The simultaneous presence of high humidity (90–100% rh at 368 K) and bulk condensed phase results in the maximum rate and final yield of N₂O approaching 60% and 100% conversion after one hour in the presence of amorphous carbon and fly-ash, respectively.Work performed in partial fulfillment of the requirements of Dr ès Sciences at EPFL.     

Catalysed self-cleaning of air on the earth's surface

Generally, it is assumed that UV-light, high temperature or reactive molecules like O₃ and OH are needed to activate gas reactions in air. In consequence, the catalytic activity on natural materials such as sand and soil on the earth's surface is assumed to be insignificant. We have measured O₂-dissociation rates on natural quartz sand at 40˚C and compared these with O₂-dissociation rates near 500˚C on materials with well-known catalytic activity. In terms of probabilities for dissociation of impinging O₂-molecules the measured rates are in the 10⁻¹²–10⁻⁴ range. We have also measured dissociation rates of H₂ and N₂, water-formation from H₂ and O₂ mixtures, exchange of N between N₂, NO _x and a breakdown of HNO₃, NO₂ and CH₄ on natural quartz sand at 40˚C. The measured rates together with an effective global land area have been used to estimate the impact of thermodynamically driven reactions on the earth's surface on the global atmospheric budgets of H₂, NO₂ and CH₄. The experimental data on natural quartz sand together with data from equilibrium calculations of air suggest that an expected increase in anthropogenic supply of air pollutants, such as NO _x or other “reactive” nitrogen compounds, hydrogen and methane, will be counter-acted by catalysis on the earth's surface. On the other hand, at Polar Regions and boreal forests where the “reactive” nitrogen concentration is below equilibrium, the same catalytic effect activates formation of bio-available nitrogen compounds from N₂, O₂ and H₂O.     

Products and mechanisms of the gas phase reactions of NO3 with CH3SCH3, CD3SCD3, CH3SH and CH3SSCH3

Products and mechanisms of the reaction between the nitrate radical (NO₃) and three of the most abundant reduced organic sulphur compounds in the atmosphere (CH₃SCH₃, CH₃SH and CH₃SSCH₃), have been studied in a 480 L reaction chamber using in situ FT-IR and ion chromatography as analytical techniques. In the three reactions, methanesulphonic acid was found to be the most abundant sulphur containing product. In addition the stable products SO₂, H₂SO₄, CH₂O, and CH₃ONO₂ were identified and quantified and thionitric acid-S-methyl ester (CH₃SNO₂) was observed in the i.r. spectrum from all of the three reactions. Deuterated dimethylsulphide (CD₃SCD₃) showed an isotope effect on the reaction Deuterated dimethylsulphide (CD₃SCD₃) showed an isotope effect on the reaction rate constant (k_H/k_D) of 3.8±0.6, indicating that hydrogen abstraction is the first step in the NO₃+CH₃SCH₃ reaction, probably after the formation of an inital adduct.Based on the products and intermediates identified, reaction mechanisms are proposed for the three reactions.     

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。     

Nitrous Oxide Flux Estimates for South-Eastern Australia

Nitrous oxide (N₂O) fluxes for south-easternAustralia have been estimated using a combination ofthe in situ N₂O and radon (Rn) measurementsmade at the Cape Grim Baseline Air Pollution Station,in north-west Tasmania. The average N₂O fluxesfrom the south-eastern mainland of Australia and fromTasmania over the nine years of record analysed (1985–1993) have beenfound to be 130 ± 30 kgN km^-2yr^-1 and 160 ± 45 kgN km^-2yr^-1respectively. These fluxes are larger than expectedand a significant dependence of the flux on rainfallis observed, with greater fluxes in the spring (October–December) andduring periods of positive SouthernOscillation Index. A large flux (1,300 ± 500kgN km^-2 yr^-1) from a nearby island (KingIsland) was also estimated from the data record,indicating a strong source, although the small size ofthe island means that it is not a significant sourcefor Australia.     

我国甲烷排放情景分析:IPAC模型结果

近期发布的IPCC第六次评估报告再次强调了短寿命期温室气体减排对温升减缓的作用。甲烷是最重要的短寿命期非CO₂温室气体。在各国提出各自新的减排目标之后,针对甲烷减排的行动方案也越来越多。甲烷减排正在成为下一阶段各国和全球合作的重点领域之一。本文在我国碳减排目标下的能源转型基础上,结合其他非能源活动的减排排放源的减排技术选择基础上,利用IPAC模型对未来甲烷的排放情景进行了分析。在模型设定的两个情景分析基础之上,研究发现,到2050年的能源转型可明显减少能源活动的甲烷排放,和2015年相比能源活动的排放可减少67％。和其他行业相比,能源部门的甲烷减排具有更好的协同性。如果考虑进一步减排甲烷,则需要在考虑其他大气污染物减排的基础上,可通过实现天然气的进一步减排来实现。同时其他部门的甲烷减排也具有很大潜力,低甲烷排放情景可以实现到2050年将甲烷排放减少到1 494万吨,和2015年相比全范围排放可减排58％。