大气CH4中的碳稳定同位素组成的PreCon-GC/C-IRMS系统测定

利用预浓缩装置-气相色谱/燃烧-同位素比值质谱仪（PreCon-GC/C-IRMS）联用系统,建立了就采样、浓缩和在线质谱分析大气CH4中稳定碳同位素组成的测定方法。通过多组试验对比,分析并讨论了利用PreCon-GC/C-IRMS联用技术测定大气CH4中碳稳定同位素比值的试验条件、系统线性、稳定性及准确度和精密度等。结果表明,在本方法条件下,当离子流强度在1.0 V～20 V时,系统线性良好（斜率S=0.04 ‰/V）,在4.0 V～15 V内其线性（斜率S=0.03 ‰/V）优于总体线性;系统测量稳定性可靠,δ13C值的测定结果的S.D＜0.3 ‰,最大偏差＜0.5 ‰,回收率达99.99%,准确度和精度均符合分析与研究要求。利用该系统对室内和室外草坪地空气中CH4的碳稳定同位素组成做了初步测试,其碳同位素的平均值分别为-31.358 ‰和-33.085 ‰,且相同地点区域空气中CH4的δ13C值,在1 d内和不同日期间的变化均在0.5 ‰以内,重现性良好。     

同位素异位体溯源土壤N2O的方法、技术和展望

土壤是N₂O的重要排放来源之一。土壤中N₂O产生途径众多、受多种因素调控，深入分析土壤N₂O产生途径才能采取针对性的减排策略。稳定同位素技术已广泛用于研究土壤N₂O排放，N₂O同位素异位体法是近年来新兴的研究方法。该研究方法通过测定土壤N₂O的同位素组成(δ¹⁵NSPN₂O、δ¹⁸ON₂O和δ¹⁵N^bulkN₂O)分析N₂O排放贡献，因无需添加标记物、对土壤系统干扰小、成本低，适合在野外田间研究N₂O排放，是15N标记方法的有力补充。本文详细介绍了N₂O同位素异位体法的原理、质谱测定方法、定量分析方法、影响该方法的因素及其应用前景。     

N2O产生法测定土壤无机态氮15N丰度

用化学方法分别将土壤中微量的铵、硝酸盐和亚硝酸盐转化为N2O气体,然后用带自动预浓缩装置的同位素比值质谱仪测定N2O中的15N丰度.N2O中的15N丰度测量值完全符合铵、硝酸盐和亚硝酸盐的15N参考值.方法快速、简单和准确,不受空气氮的污染.特别是方法的检测限很低,每批次样品中只需含5～ 20μg N.它将有助于土壤氮素的矿化作用、硝化作用和反硝化作用的研究.     

稻田CH4和N2O排放对大气CO2浓度升高响应的研究进展

大气CO₂浓度升高是全球气候变化的主要驱动力,可直接或间接影响陆地生态系统碳氮循环。阐明稻田生态系统CH₄和N₂O排放对大气CO₂浓度升高的响应及其机制,是农业生产应对全球气候变化的重要组成部分。本文综述了国内外不同大气CO₂浓度升高模拟技术平台条件下稻田CH₄和N₂O排放的响应规律,进一步讨论分析了大气CO₂浓度升高影响CH₄和N₂O排放的相关机制,并展望了今后稻田CH₄和N₂O排放对大气CO₂浓度升高响应的主要研究方向,以期为应对全球气候变化提供理论依据和技术支撑。     

大气CH_4中碳稳定同位素组成的PreCon-GC/C-IRMS系统测定

利用预浓缩装置-气相色谱,燃烧-同位素比值质谱仪(PreCon-GC/C-IRMS)联用系统,建立了就采样、浓缩和在线质谱分析大气CH_4中稳定碳同位素组成的测定方法.通过多组试验对比,分析并讨论了利用PreCon-GC/C-IRMS联用技术测定大气CH_4中碳稳定同位素比值的试验条件、系统线性、稳定性及准确度和精密度等.结果表明,在本研究方法条件下,当离子流强度在1.0～20 V时,系统线性良好(斜率S=0.04%./V),在4.0～15 V内其线性(斜率S=0.03%./V)优于总体线性;系统测量稳定性可靠,δ~(13)C值的测定结果的S.D<0.3‰,最大偏差<0.5‰,回收率达99.99%,准确度和精度均符合分析与研究要求.利用该系统对室内和室外草坪地空气中CH_4的碳稳定同位素组成做初步测试,其碳同位素的平均值分别为-31.358‰和-33.085%.,且相同地点区域空气中CH_4的δ~(13)C值,在1d内和不同日期间的变化均在0.5‰以内,重现性良好.     

反硝化细菌法测定土壤NO2--15N丰度的方法优化

NO₂^-是土壤中多个氮转化过程的关键中间产物,具有浓度低、转化快的特点。反硝化细菌法与质谱技术相结合,已广泛用于NO₃^-或NO₂^-的¹⁵N同位素分析。本文旨在优化现有Stenotrophomonas nitritireducens反硝化细菌法的培养和反应条件,实现对土壤浸提液中NO₂^--¹⁵N丰度的专一、快速、准确测定。结果表明,使用种子液好氧摇培与单菌落微氧培养对NO₂^-样品的¹⁵N同位素测定无显著差异,种子液可保证不同批次菌体的稳定性,好氧培养可将培养时间从7～8d缩短至12～15h。高纯N₂或He气吹扫0.5h均能有效去除O₂和空白杂质氮,但N₂吹扫成本更低。转移N₂O气体至干燥气瓶,不影响测定结果的准确性和精密...     

有机物对红外光谱技术测定植物叶片和茎秆水δ18O和δD的影响

植物叶片、茎秆和土壤水δ18O和δD是研究土壤植被大气系统生态水文循环过程的重要示踪剂。与传统的稳定同位素质谱(IRMS)技术相比,稳定同位素红外光谱(IRIS)技术具有测量速度快、运行成本低等优势,将促进稳定同位素生态学的发展。但是利用低温真空蒸馏抽提技术获得的植物叶片和茎秆水中含有甲醇和乙醇类有机污染物,造成δ18O和δD的IRIS测量值偏离IRMS测量值(2.64±0.43)‰和(3.6±0.8)‰,超过了仪器精度。本研究利用纯水混入不同浓度的色谱纯甲醇或乙醇,结合Los Gatos公司的光谱分析软件确定甲醇(NB)和乙醇(BB)类物质污染程度的光谱度量值,建立了δ18O和δD的光谱污染校正方法。研究表明,同一台分析仪建立的校正曲线无明显的时间漂移;不同分析仪建立的校正曲线存在显著差异;IRIS校正值与IRMS测量值的交叉验证表明,IRIS测定冬小麦和夏玉米叶片和茎秆水的δ18O和δD可以被准确地校正,与IRMS的差值分别为(0.11±0.12)‰和(0.7±0.4)‰。     

大气CO2和O3浓度升高对水稻'汕优63'叶片光合作用的影响

大气CO2浓度升高使水稻光合作用增强,而地表O3浓度增加则相反,但人们对大气CO2和O3浓度同时升高情景下水稻光合作用的响应和适应知之甚少。本文利用新型的自然光气体熏蒸平台,以杂交籼稻‘汕优63’为供试材料,设置室内对照(CK,大气本底浓度,实时模拟室外环境)、高浓度CO2(CO2本底浓度+200μmol·mol-1)、高浓度O3(O3本底浓度的1.6倍)、高浓度CO2+O3 4个处理,于拔节期、抽穗期和灌浆期测定稻叶的主要光合参数。整个布气期间,CO2和O3浓度平均的控制目标完成比(TAR)分别为1.04和1.00。与CK相比,CO2处理使拔节、抽穗和灌浆期净光合速率(Pn)分别增加15%、11%和28%,O3处理使对应生育期Pn分别降低32%、32%和88%,CO2+O3处理对拔节期和抽穗期Pn无显著影响,但成熟期Pn平均下降48%。CO2处理使拔节和抽穗期叶片气孔导度(Gs)和蒸腾速率(Tr)显著下降,但灌浆期无显著变化;O3处理对各期Gs和Tr的影响明显大于CO2处理,且以灌浆期的降幅最大;CO2+O3处理叶片Gs和Tr的降幅总体上明显低于单独的O3处理。CO2处理或CO2+O3处理叶片胞间CO2浓度(Ci)明显增加,而O3处理叶片Ci的变化相对较小。CO2处理使各期水分利用效率(WUE)增加,而O3处理则呈相反趋势,特别是生长后期。CO2+O3处理叶片拔节期和抽穗期WUE平均增加约15%,但灌浆期因O3的累积伤害,WUE不升反降。以上结果表明,大气CO2浓度升高将使杂交稻‘汕优63’叶片光合能力增强,但地表同步升高的O3浓度则使光合能力削弱并表现出明显的累积伤害,大气CO2和O3浓度同时升高可缓解O3胁迫对‘汕优63’光合作用的负效应。     

农田土壤主要温室气体(CO2、CH4、N2O)的源/汇强度及其温室效应研究进展

气候变化是当今全球面临的重大挑战, 人类社会生产生活引起的温室气体排放是全球气候变暖的主要原因。大气中CO₂、CH₄ 和N₂O 是最重要的温室气体, 对温室效应的贡献率占了近80%。据估计, 大气中每年有5%~20%的CO₂、15%~30%的CH₄、80%~90%的N₂O 来源于土壤, 而农田土壤是温室气体的重要排放源。本文重点阐述了农田土壤温室气体产生、排放或吸收机理及其影响因素, 指出土地利用方式和农业生产力水平等人为控制因素通过影响土壤和作物生长条件来影响农田土壤温室气体产生与排放或吸收。所以, 我们可以从人类活动对农田生态系统的影响着手, 通过改善农业生产方式和作物生长条件来探索温室气体减排措施, 达到固碳/氮增汇的目的。对国内外关于农田温室气体排放的源/汇强度及其综合温室效应评估的最新研究进展进行了综述, 指出正确估算与评价农田土壤温室气体的源/汇强度及其对大气中主要温室气体浓度变化的贡献, 有助于为温室气体减排以及减少气候变化预测的不确定性提供理论依据。     

高CO2浓度和遮荫对小麦叶片光能利用特性及产量构成因子的影响

CO2和光能是植物光合作用的动力和底物,它们的变化必然引起植物光合特性和生长的变化。研究大气CO2浓度和光强变化对植物光合生理的影响,有利于认识作物对全球生态变化的生理响应机制。试验以高大气CO2浓度和遮荫为处理手段,通过测定小麦(Triticum aestivum)旗叶的光合气体交换参数、光强光合速率响应曲线和产量构成因子,分析光强光能利用效率之间的关系,研究高大气CO2浓度(760μmol.mol 1)和遮荫对小麦叶片光合特性及产量构成因子的影响。结果表明,高大气CO2浓度下,小麦叶片的净光合速率(Pn)增加;同时最大净光合速率(Pnmax)、光饱和点(LSP)、光补偿点(LCP)显著升高;遮荫处理使小麦叶片的Pnmax、LSP、LCP降低。正常光照下大气CO2浓度升高使小麦叶片呼吸速率(Rd)显著下降,遮荫后大气CO2浓度升高对Rd无显著影响。大气CO2浓度升高能显著提高小麦叶片表观量子效率(AQY),而遮荫对AQY的影响因大气CO2浓度而异,高大气CO2浓度下遮荫使AQY显著提高,正常大气CO2浓度下遮荫则使AQY明显下降。高大气CO2浓度下遮荫使小麦株高、穗长增加,而穗粒数、单株穗粒重、千粒重减小。受光合特性的变化和光强限制,高大气CO2浓度下遮荫使小麦叶片呼吸增强,导致Pn下降,不利于干物质积累和籽粒产量的形成。     

水分类型对土壤排放的温室气体组成和综合温室效应的影响

实验室研究表明,土壤排放出的温室气体（ＣＯ２、ＣＨ４和Ｎ２Ｏ）组成及总理显著地受土壤水分类型和施用秸秆的影响。连续淹水条件下,土壤仅排放微理的Ｎ２Ｏ,但排放出大量的Ｃ睡Ｃ敢条件下,土壤不排放Ｃ上键合的但排放出大量的Ｎ２Ｏ;虽然淹水的土壤排水促进Ｎ２Ｏ排放,但显著抑制ＣＨ４的排放,淹水好气交替处理的土壤其排放的ＣＯ２、ＣＨ４和Ｎ２Ｏ均在好气和连续淹水之间。根据各种温室产生温室效应的相对潜力,计算土壤     

Emission of CO2, CH4 and N2O from lakeshore soils in an Antarctic dry valley

We measured soil profile concentrations and emission of CO₂, CH₄ and N₂O from soils along a lakeshore in Garwood Valley, Antarctica, to assess the extent and biogeochemical significance of biogenic gas emission to C and N cycling processes. Simultaneous emission of all three gases from the same site indicated that aerobic and anaerobic processes occurred in different layers or different parts of each soil profile. The day and location of high gas concentrations in the soil profile corresponded to those having high gas emission, but the pattern of concentration with depth in the soil profile was not consistent across sites. That the highest gas concentrations were not always in the deepest soil layer suggests either limited production or gas diffusion in the deeper layers. Emission of CO₂ was as high as 47 μmol m⁻² min⁻¹ and was strongly related to soil temperature. Soil respiration differed significantly according to location on the lakeshore, suggesting that factors other than environmental variables, such as the amount and availability of O₂ and nutrients, play an important role in C mineralization processes in these soils. High surface emission (maximum: 15 μmol m⁻² min⁻¹) and profile gas concentration (maximum: 5780 μL L⁻¹) of CH₄ were at levels comparable to those in resource-rich temperate ecosystems, indicating an active indigenous population of methanogenic organisms. Emission of N₂O was low and highly variable, but the presence of this gas and NO₃ in some of the soils suggest that denitrification and nitrification occur there. No significant relationships between N₂O emission and environmental variables were found. It appears that considerable C and N turnover occurs in the lakeshore soils, and accurate accounting will require measurements of aerobic and anaerobic mineralization. The production and emission of biogenic gases confirm the importance of these soils as hotspots of biological activity in the dry valleys and probable reservoirs of biological diversity.     

13C标记技术在土壤和植物营养研究中的应用

过去研究有机物在土壤中的周转通常采用14C标记技术 ,但由于人们对其放射性的关注 ,进入 80年代以来研究者趋于使用稳定性同位素13C标记技术。虽然13C标记技术相对来说还较年轻 ,但从已有有限的研究资料来看其优越性已经显示出来。一是在一定的条件下可以利用自然丰度分异较大的天然材料作为标记材料 ,既可以省去标记的时间和费用 ,又可以做到真正的原位研究 ;二是利用13C和15N加富标记技术 ,结合核磁共振测定 ,不仅可以研究有机物分解的动态变化 ,还可以追踪有机物在周转过程中C、N组分化学结构的变化 ,能为揭示土壤养分循环和腐殖质形成机理提供更多的信息。本文根据已收集到的部分资料 ,对13C标记技术在土壤和植物营养中的应用情况作一简要综述 ,并在此基础上讨论了13C加富标记技术在研究植物光合作用、光合产物的去向以及标记秸杆在土壤中的分解等方面的应用及其注意点 ,旨在能为国内开展这方面的工作提供十分有用的参考     

Emissions of CO2, CH4 and N2O from Southern European peatlands

Peatlands play an important role in emissions of the greenhouse gases CO₂, CH₄ and N₂O, which are produced during mineralization of the peat organic matter. To examine the influence of soil type (fen, bog soil) and environmental factors (temperature, groundwater level), emission of CO₂, CH₄ and N₂O and soil temperature and groundwater level were measured weekly or biweekly in loco over a one-year period at four sites located in Ljubljana Marsh, Slovenia using the static chamber technique. The study involved two fen and two bog soils differing in organic carbon and nitrogen content, pH, bulk density, water holding capacity and groundwater level. The lowest CO₂ fluxes occurred during the winter, fluxes of N₂O were highest during summer and early spring (February, March) and fluxes of CH₄ were highest during autumn. The temporal variation in CO₂ fluxes could be explained by seasonal temperature variations, whereas CH₄ and N₂O fluxes could be correlated to groundwater level and soil carbon content. The experimental sites were net sources of measured greenhouse gases except for the drained bog site, which was a net sink of CH₄. The mean fluxes of CO₂ ranged between 139 mg m⁻² h⁻¹ in the undrained bog and 206 mg m⁻² h⁻¹ in the drained fen; mean fluxes of CH₄ were between −0.04 mg m⁻² h⁻¹ in the drained bog and 0.05 mg m⁻² h⁻¹ in the drained fen; and mean fluxes of N₂O were between 0.43 mg m⁻² h⁻¹ in the drained fen and 1.03 mg m⁻² h⁻¹ in the drained bog. These results indicate that the examined peatlands emit similar amounts of CO₂ and CH₄ to peatlands in Central and Northern Europe and significantly higher amounts of N₂O.     

Fluxes of CO2, CH4 and N2O from drained organic soils in deciduous forests

We examined net greenhouse gas exchange at the soil surface in deciduous forests on soils with high organic contents. Fluxes of CO₂, CH₄ and N₂O were measured using dark static chambers for two consecutive years in three different forest types; (i) a drained and medium productivity site dominated by birch, (ii) a drained and highly productive site dominated by alder and (iii) an undrained and highly productive site dominated by alder. Although the drained sites had shallow mean groundwater tables (15 and 18 cm, respectively) their average annual rates of forest floor CO₂ release were almost twice as high compared to the undrained site (1.9±0.4 and 1.7±0.3, compared to 1.0±0.2 kg CO₂ m⁻² yr⁻¹). The average annual CH₄ emission was almost 10 times larger at the undrained site (7.6±3.1 compared to 0.9±0.5 g CH₄ m⁻² yr⁻¹ for the two drained sites). The average annual N₂O emissions at the undrained site (0.1±0.05 g N₂O m⁻² yr⁻¹) were lower than at the drained sites, and the emissions were almost five times higher at the drained alder site than at the drained birch site (0.9±0.35 compared to 0.2±0.11 g N₂O m⁻² yr⁻¹). The temporal variation in forest floor CO₂ release could be explained to a large extent by differences in groundwater table and air temperature, but little of the variation in the CH₄ and N₂O fluxes could be explained by these variables. The measured soil variables were only significant to explain for the within-site spatial variation in CH₄ and N₂O fluxes at the undrained swamp, and dark forest floor CO₂ release was not explained by these variables at any site. The between-site spatial variation was attributed to variations in drainage, groundwater level position, productivity and tree species for all three gases. The results indicate that N₂O emissions are of greater importance for the net greenhouse gas exchange at deciduous drained forest sites than at coniferous drained forest sites.     

Membrane probe array: Technique development and observation of CO2 and CH4 diurnal oscillations in peat profile

The purpose of this study was to monitor the dynamics of gases such as CO₂ and CH₄ in a soil profile with sufficient temporal resolution to observe possible diurnal variations. A computer-controlled device called a membrane probes array (MPA) was developed that consisted of 9-12 individual membrane probes installed at various soil depths. Each probe was made of a stainless steel pipe with a 1 mm orifice covered with a silicone membrane. Soil gases diffuse through the membrane at a rate proportional to the ambient soil gas concentration. To measure diffusion rates, the probes are flushed with N₂ one-by-one at regular time intervals and accumulated gas is detected as a spike with IR and FID analyzers. The longer the period between flushings the higher the gas accumulation and the lower the detection limit for a particular soil gas. The developed MPA agreed well with conventional manual gas sampling in West-Siberian mesotrophic fen. In peat cores with intact Carex-Sphagnum vegetation incubated under constant temperature, water level and artificial light:dark (14:10) cycles, regular diurnal oscillations of soil CO₂ and CH₄ occurred in the upper part of the peat core down to 19 cm. Gas content in the top layer (3 cm) grew during the light phase, and returned back during the dark phase. In layers further down in the soil, the same events were observed but with progressively increased time delay and lower amplitude. The obtained data agreed with the hypothesis that diurnal variations in soil CO₂ and CH₄ content are caused by periodic changes in intensity of root exudation that provide a major C- and energy source for soil microorganisms including methanogens. At a soil depth of 23 cm, where the peak of gas bubbles occurred, the signal for both gases became chaotic and not related to the light:dark cycle.     

基于动物组织器官中稳定性同位素组成变化的溯源研究进展

稳定性同位素分析技术是一种用于研究动物产地来源和生活史的有效技术,也是一项新兴的食品追溯技术.本文综述了国内外关于动物组织器官中稳定性同位素组成特征,组织器官同位素的平衡时间,以及饲料、饮水、地域和贮藏加工过程对同位素组成影响的最新研究进展,旨在为动物源性食品产地和动物生活史的溯源研究提供理论参考.     

气候变化和大气CO2上升条件下土壤有机碳的动力学研究

Considering that even contaminated soils are a potential resource for agricultural production, it is essential to develop a set of cropping systems to allow a safe and sustainable agriculture on contaminated lands while avoiding any transfer of toxic trace elements to the food chain. In this review, three main strategies, i.e., phytoexclusion, phytostabilization, and phytoextraction, are proposed to establish cropping systems for production of edible and non-edible plants, and for extraction of elements for industrial use. For safe production of food crops, the selection of low-accumulating plants/cultivars and the application of soil amendments are of vital importance. Phytostabilization using non-food energy and fiber plants can provide additional renewable energy sources and economic benefit with minimum cost of agricultural measures. Phytoextracting trace elements (e.g., As, Cd, Ni, and Zn) using hyperaccumulator species is more suitable for slightly and moderately polluted sites, and phytomining of Ni from serpentine soils has shown a great potential to extract Ni-containing bio-ores of economic interests. We conclude that appropriate combinations of soil types, plant species/cultivars, and agronomic practices can restrict trace metal transfer to the food chain and/or extract energy and metals of industrial use and allow safe agricultural activities.     

浮萍对福州平原稻田CH4和N2O排放的影响分析

浮萍是稻田中常见的漂浮在水面的水生植物,具有固氮作用,但是,浮萍对稻田温室气体排放的影响尚不明确.以位于湿润亚热带的福州平原稻田为研究对象,探讨浮萍对该区域稻田CH4和N2O排放的影响,为科学评价、准确编制我国水稻田温室气体排放清单提供基础数据.研究结果表明,观测期内,有萍小区和无萍小区CH4排放范围分别为0.19～26.50 mg·m-2·h-1和1.02～28.02 mg·m-2·h-1,平均值分别为9.28 mg·m-2·h-1和11.66 mg·m-2·h-1,有萍小区CH4排放低于无萍小区(P＜0.01),有萍小区CH4排放高峰比无萍小区约提前1周,高峰期后排放迅速降低;有萍小区和无萍小区N2O排放范围分别为-50.11～201.82 μg·m-2·h-1和-28.93～54.42μg·m-2·h-1,平均值分别为40.29 μg·m-2·h-1和11.93 μg·m-2·h-1,有萍小区N2O排放高于无萍小区(P＜0.05).稻田排干后,N2O排放迅速上升,2个小区N2O排放呈现出相似的规律.有萍小区和无萍小区的CH4与N2O排放的影响因子有所不同.综合考虑CH4和N2O两种温室气体,CH4仍是稻田温室效应产生的主要贡献者,浮萍可降低位于沿海区域的福州平原稻田综合温室效应的17.3％.     

Evidence of biogenic greigite (ferrimagnetic Fe3S4) in soil

The occurrence of greigite (Fe₃S₄) in soils is reported for the first time. It forms irregularly-shaped aggregations within plant cells in the Gr₂ horizon of a gley soil developed from colluvial material. Greigite was identified by X-ray diffraction and magnetic measurements and was investigated by optical and transmission electron microscopy. Biogenic formation is proposed, based on the elongated shape of single greigite crystals, and sulphur isotope analyses, which showed a depletion in ³⁴S relative to the soil-water sulphate. The cell-edge length of 0.98639±0.00003 nm is significantly smaller than values reported for sedimentary greigite. The mean coherence length of 27 nm agrees with TEM observations and indicates that the single greigite crystals lie in the superparamagnetic region. However, the fine aggregates show magnetically single-domain behaviour. Greigite is the only carrier of a stable magnetic remanence in the soil profile studied.