Impact of water table depth on forest soil methane turnover in laboratory soil cores deduced from natural abundance and tracer 13C stable isotope experiments

We investigated turnover of methane (CH4) in soils from a poorly drained UK forest. In situ, this forest exhibited a negligible soil-atmosphere CH4 flux, whereas adjacent grassland plots were sources of CH4. We hypothesised that the forest plots exhibited reduced anaerobic CH4 production through water-table draw down. Consequently, we exposed soil cores from under oak to high and low water-table conditions in the laboratory. Methane fluxes increased significantly in the high water-table (1925+/-1702 mug CH4 m(-2) h(-1)) compared to the low one (-3.5+/-6.8 microg CH4 m(-2) h(-1)). Natural abundance delta13C values of CH4 showed a strong depletion in high water-table cores (-56.7+/-2.9 per thousand) compared to methane in ambient air (-46.0 per thousand) indicative of methanogenic processes. The delta13C values of CH4 from low water-table cores (delta13C-46.8+/-0.2 per thousand) was similar to ambient air and suggested little alteration of headspace CH4 by the soil microbial community. In order to assess the CH4 oxidizing activity of the two treatments conclusively, a 13CH4 spike was added to the cores and 13CO2 production was measured as the by-product of CH4 oxidation. 13CH4 oxidation rates were 57.5 (+/-12.7) and 0.5 (+/-0.1) microg CH4 m(-2) h(-1) for high and low water-tables, respectively. These data show that the lower water-table hydrology treatment impacted methanogenic processes without stimulating methanotrophy.     

不同温度下乙醇电氧化过程的原位红外光谱研究

直接乙醇燃料电池因其优异的性能备受关注。乙醇的电催化氧化并非简单的燃烧,涉及多种催化反应过程。乙醇的C-C键断裂选择性低,以及乙醇氧化中间产物C1分子由于没有及时氧化离开催化剂表面而造成的催化剂中毒,是制约其应用的瓶颈问题。电化学原位红外光谱是在电化学反应的同时,原位采集反应物种特定官能团的振动信息,可在分子水平揭示反应过程,推测反应机理。不同温度条件下乙醇电氧化过程的研究,有助于合理的设计高性能乙醇燃料电池催化剂。选用高性能的PtRh/RGO催化剂,结合同位素示踪法和电化学原位红外光谱技术,研究了不同温度下乙醇的电氧化过程。循环伏安研究表明,乙醇电氧化性能及其C-C键断裂的程度为PtRh/RGO (45℃)>PtRh/RGO (25℃)>商业Pt/C。电化学原位红外光谱从分子水平跟踪了乙醇的电氧化过程,观察到随着电位的增加, CO2, CO,-CH3,-C-O特征峰的强度逐渐增加。CO2和CH3COOH分别归属于乙醇完全氧化和不完全氧化的终产物,因此红外光谱中两种物质特征峰积分面积的比值[CO2]/[CH3COOH]可做为CO2选择性的量度。用来定量标定CH3COOH的特征峰是位于1 280 cm-1的-C-O振动峰,但对于PtRh/RGO催化剂的红外光谱而言,它的乙酸特征峰振动峰位1 280 cm-1附近出现1 214 cm-1甲醇衍生物的振动峰,通过一种反射红外光谱与标样透射红外光谱差减扣除叠加峰方法,定量计算了叠加峰中1 280 cm-1特征峰的积分强度,从而计算出PtRh/RGO的CO2选择性。结果表明对比25℃时, 45℃下PtRh/RGO具有更高的选择性, 0.3 V时提高48.1%, 0.5和0.6 V时略有提高, 0.4 V时降低,这可能是乙醇中β-C和水中OH竞争吸附所致。在两种反应温度条件下, CO2选择性都在电位高于0.4 V时呈现下降趋势。为了进一步研究CO2来源于α-C或β-C的完全氧化,使用同位素标记的13CH312CH2OH做为探针分子,通过电化学原位红外光谱研究了25和45℃下PtRh/RGO电极上乙醇电氧化过程。结果表明,β-C完全氧化为CO2的起始电位与温度无关,都为0.3 V。通过用13CO2/12CO2积分面积的比值定量分析,发现45℃下,该比值在电位0.3~0.5 V时相比于25℃下分别增加0.11, 0.18和0.22,表明随着温度或电位的增加,β-C完全氧化的选择性增加。     

Factors influencing stable isotope ratios in CH4 and CO2 within subenvironments of freshwater wetlands: implications for delta-signatures of emissions

Much uncertainty still exists regarding spatial and temporal variability of stable isotope ratios (13C/12C and D/H) in different CH4-emission sources. Such variability is especially prevalent in freshwater wetlands where a range of processes can influence stable isotope compositions, resulting in variations of up to approximately 50% for delta13C-CH4 and approximately 50% for deltaD-CH4 values. Within a temperate-zone bog and marsh situated in southwestern Ontario, Canada, gas bubbles in pond sediments exhibit only minor seasonal and spatial variation in delta13C-CH4, deltaD-CH4 and delta13C-CO2 values. In pond sediments, CO2 appears to be the main source of carbon during methanogenesis either directly via CO2 reduction or indirectly through dissimilation of autotrophic acetate. In contrast, CH4 production occurs primarily via acetate fermentation at shallow depths in peat soils adjacent to ponds at each wetland. At greater depths within soils, sigmaCO2 and H2O increasingly exert an influence on delta13C- and deltaD-CH4 values. Secondary alteration processes (e.g., methanotrophy or diffusive transport) are unlikely to be responsible for depth-related changes in stable isotope values of CH4. Recent models that attempt to predict deltaD-CH4 values in freshwater environments from D/H ratios in local precipitation do not adequately account for such changes with depth. Subenvironments (i.e., soil-forming and open water areas) in wetlands should be considered separately with respect to stable isotope signatures in CH4 emission models.     

Biodegradability screening of soil amendments through coupling of wavelength-scanned cavity ring-down spectroscopy to multiple dynamic chambers

A system was developed for the automatic measurements of 13CO? efflux to determine biodegradation of extra carbon amendments to soils. The system combines wavelength-scanned cavity ring down laser spectroscopy (WS-CRDS) with the open-dynamic chamber (ODC) method. The WS-CRDS instrument and a batch of 24 ODC are coupled via microprocessor-controlled valves. Determination of the biodegradation requires a known δ13C value and the applied mass of the carbon compounds, and the biodegradation is calculated based on the 13CO? mixing ratio (ppm) sampled from the headspace of the chambers. The WS-CRDS system provided accurate detection based on parallel samples of three standard gases (13CO? of 2, 11 and 22 ppm) that were measured simultaneously by isotope ratio mass spectrometry (linear regression R2 = 0.99). Repeated checking with the same standards showed that the WS-CRDS system showed no drift over seven months.The applicability of the ODC was checked against the closed static chamber (CSC) method using the rapid biodegradation of cane sugar-δ13C-labeled through C4 photosynthesis. There was no significant difference between the results from 7-min ODC and 120-min CSC measurements. Further, a test using samples of either cane sugar (C4) or beetroot sugar (C3) mixed into standard soil proved the target functionality of the system, which is to identify the biodegradation of carbon sources with significantly different isotopic signatures.     

Short-term sequestration of slurry-derived carbon into particle size fractions of a temperate grassland soil

Surface application of animal wastes in intensive grassland systems has caused growing environmental problems during the last decade and, therefore, increasing public and scientific concern. In the present study we examined if the natural abundance 13C stable isotope tracer techniques could be used to investigate a poorly defined aspect of waste application, i.e. incorporation of slurry-derived C and its distribution in soil organic matter (SOM) fractions with different turnover times of a pasture soil. C3 and C4 slurries (delta13C(V-PDB) = -30.7/1000 and -21.3/1000, respectively) from cows fed either on a maize (C4) or perennial ryegrass (C3) diet were applied to a C3 soil with a delta13C value of (-30.0+/-0.2)/1000. The cattle slurry was applied at 50 m3 ha(-1). Coarse sand, fine sand, silt, clay and fine clay were isolated from bulk soil samples (0-2 cm depth), freeze-dried and ground prior to total organic C (TOC) using elemental analysis and 13C natural abundance analysis by isotope-ratio mass spectrometry. The stable isotope tracer technique did allow to quantify the short-term sequestration of slurry-derived C in particle-size fractions of the grassland soil. Slurry-derived carbon was sequestered in various amounts in the five particle-size fractions, but most of it was sequestered in the coarse sand fraction during the two week experiment. The preferential input into the coarse sand fraction suggests that only the larger particulate slurry-derived materials were trapped into the soil during the experimental period. Less than 40% of the applied slurry-derived C was sequestered into the soil, suggesting a potential for large losses into the wider environment. The practice of surface spreading of slurry to temperate grassland soils is clearly not efficient, and improvements in slurry application methods, such as incorporation directly into the soil, should therefore be encouraged.     

Continuous field measurements of delta(13)C-CO(2) and trace gases by FTIR spectroscopy

Continuous analysis of the (13)C/(12)C ratio of atmospheric CO(2) (delta(13)C-CO(2)) is a powerful tool to quantify CO(2) flux strengths of the two major ecosystem processes assimilation and respiration. Traditional laboratory techniques such as isotope ratio mass spectrometry (IRMS) in combination with flask sampling are subject to technical limitations that do not allow to fully characterising variations of atmospheric delta(13)C-CO(2) at all relevant timescales. In our study, we demonstrate the strength of Fourier transform infrared (FTIR) spectroscopy in combination with a PLS-based calibration strategy for online analysis of delta(13)C-CO(2) in ambient air. The ability of the instrument to measure delta(13)C-CO(2) was tested on a grassland field-site and compared with standard laboratory-based IRMS measurements made on field-collected flask samples. Both methods were in excellent agreement, with an average difference of 0.4 per thousand (n=81). Simultaneously, other important trace gases such as CO, N(2)O and CH(4) were analysed by FTIR spectroscopy.     

Estimation of pathways of the production of greenhouse gases in the tropical swamp forest in Thailand by stable isotope investigation

Dynamics of greenhouse gases (N(2)O and CH(4)) with the dry-wet cycle along with the variation of oxidation-reduction boundaries were investigated in the tropical wetland in monsoon Asia. It was clarified that the production of N(2)O and CH(4) was closely related to the development of a redox boundary in the Bang Nara River systems. An intermittent increase in N(2)O was observed at the beginning of the rainy season, when a large amount of easily decomposable organic matter was introduced into the river. After 10 days, when dissolved oxygen was consumed completely at the middle reaches, the emission of CH(4) became maximal due to the possible occurrence of denitrification. The distribution of stable isotope ratios in N(2)O clearly demonstrated that nitrification is the major process for its production. Furthermore, the production of N(2)O in this study area was found to vary in time and space with changes in the redox boundary along the water flow.     

卤素对于燃烧中CO氧化和NO生成的影响

卤族元素在燃烧时会影响CO的氧化和NO的生成。本文通过化学平衡方法分析了H2O和HCl对于CO氧化的协同效应,在非均匀布风流化床中进行了PVC塑料与煤或半焦的混烧试验,测量了CO和CH4的排放特性,从而从理论上和实验上证明了HCl对CO氧化的抑制作用。并给出了今后研究的方向和问题。     

AC等离子体辅助CH4低温氧化的分子激发作用

本文采用实验测量和数值模拟结合的方法,对AC放电下He/CH4/O2混合气中激发态对甲烷裂解和低温氧化的动力学贡献进行研究。基于HP-Mech,增加反应物的放电机理以及激发态参与的化学反应及其驰豫反应,建立CH4低温氧化机理。采用化学反应动力学求解器CHEMKIN中的两段式Plasma-PSR模型模拟放电过程及化学反应过程。该动力学模型能较好地预测反应物的消耗和主要产物的生成,反应路径分析表明激发态物质CH4(v),O2(v),O2(a^1△g)等通过链式反应CH4(v)+OH→CH3+H2O,O2(v)+H→OH+O,O2(a^1△g)+H→OH+O促进活性自由基和产物的生成。     

电荷调控下Ti3C2O2和V2CO2吸附CH4的第一性原理计算

本文采用第一性原理计算首先研究了Ti3C2O2和V2CO2与CH4气体分子之间的相互作用,发现Ti3C2O2和V2CO2对CH4的吸附较弱属于物理吸附,不适宜用作探测CH4。在此基础上研究了电荷调控下CH4气体分子与Ti3C2O2和V2CO2之间的相互作用。结果表明：随着体系电荷态的增加,Ti3C2O2和V2CO2对CH4气体分子的吸附作用逐渐增加变为化学吸附。当体系电荷态大于或等于-2时,CH4气体分子在Ti3C2O2和V2CO2表面可以被有效捕获。撤去电荷后,Ti3C2O2、V2CO2与CH4气体分子之间的吸附恢复至物理吸附,CH4气体分子易脱附。因此,通过调控Ti3C2O2和V2CO2的电荷态,可以简单地实现CH4的捕获与释放。Ti3C2O2和V2CO2有望成为CH4探测或捕获材料。     

Extensive browsing by a conventional grazer? Stable carbon isotope analysis reveals extraordinary dietary flexibility among Sanga cattle of North Central Namibia

Intraspecies dietary flexibility, such as variable consumption of graze vs. browse in herbivores, has received scant attention on a spatial scale despite growing evidence of substantial variability within and among populations, especially in bovids. Here, we report on extraordinary differences in cattle diet among two communal pasture areas across seasons in northern Namibia: King Nehale (KN, open grassland) and Okongo (OK, dense woodland). Percentage C₃ browse and C₄ grass consumption was determined from δ¹³C values of dung samples, using a Bayesian stable-isotope mixing model (SIAR – stable isotope analysis in R). During the wet and early dry season, KN cattle consumed 11 and 19% browse, respectively, and the OK cattle consumed 84% browse. At the end of the dry season, the browse intake of KN cattle increased to 33% while that of OK cattle decreased to 55%. Vegetation structure influenced the graze/browse consumption strongly in both areas. A better understanding of this extraordinary dietary flexibility is imperative as anthropogenically driven habitat change is projected to lead to the extinction of perceived grazing specialists.     

基于第一性原理计算H_2S、CO_2、CH_4在Fe-MoS_2上的吸附性能

在高含硫气藏开发中,伴随着CH_4的采出,H_2S和CO_2也不可避免的被采出.这两种气体会产生管道腐蚀和气体中毒等诸多不利影响.为了解决这一现实需要,从研究较为广泛的MoS_2材料入手,考虑了其掺杂结构中的吸附性能的变化,相关计算原理基于密度泛函数理论.主要计算了一种吸附式掺杂过渡金属原子Fe在MoS_2上的结构,同时也计算了H_2S,CO_2,CH_4气体在其表面的吸附能,电荷转移,电子密度差等相关参数.结果表明,CH_4对这种材料表现出不敏感的特性,而CO_2、H_2S均表现出吸附的性质,预测这种材料可能作为一种可使用的吸附材料,或是开发作为一种新型的气体预警材料.     

Determination of (13)C/(12)C-Ratios in Rumen Produced Methane and CO(2) of Cows, Sheep and Camels

Abstract Naturally produced methane shows different δ(13)C-values with respect to its origin, e.g., geological or biological. Methane-production of ruminants is considered to be the dominant source from the animal kingdom. Isotopic values of rumen methane-given in literature-range between -80‰ and -50‰ and are related to feed composition and also sampling techniques. Keeping cows, camels and sheep under identical feed conditions and sampling rumen gases via implanted fistulae we compared δ(PDB) (13)C-values of methane and CO(2) between the species. Referring to mean values obtained from 4 or 5 samples at different times of 11 animals (n = 47) we calculated δ(PDB) (13)C-medians resulting in small but not significant differences within and significant differences between the species for CO(2) and methane. The δ(PDB) (13)C-differences between methane and CO(2) were statistically equal within and also between the species. Therefore a linear regression of methane values on CO(2) is appropriate and leads to: δ(PDB) (13)C(methane)‰ = 1,57 * δ(PDB) (13)C(CO(2))‰-47‰ with a correlation coefficient of r = 0,87.     

FTIR监测北京地区CO2和CH4及其变化分析

近几十年来,温室效应导致地表温度明显上升,其所引起的全球气候变迁问题越来越受到人们的关注.CO2和CH4是大气中主要的两种人为温室气体,对它们进行连续的测量,获取它们长时间变化情况对大气环境科学具有重要的意义.目前国内监测这两种气体的主要手段是气相色谱方法.鉴于傅里叶变换红外光谱技术的优点,使用开放式长光程FTIR系统在北京地区对这两种气体进行了监测.该系统直接测量开放光路中的环境气体的大气吸收光谱,并使用非线性最小二乘方法进行光谱分析,获取待测组分的浓度信息.在实验部分给出了2005年9月4日到2005年9月10日6天中的北京地区CO2及CH4的测量结果,并对两者的变化趋势和相关性进行了分析.     

CH_4-CO_2二元系低温分离方案的可行性探讨

通过对CH4-CO2二元系进行相图分析,得出低温分离脱除CO2的两种方案,一是气液分离,一是气固分离。采用闪蒸分离的方法来研究气液分离方案的可行性,利用HYSYS软件对二元系进行了闪蒸分离的计算分析,结果表明闪蒸分离难以同时保证较高的甲烷回收率和甲烷纯度,从而证明了气液分离方案不可行。根据气固相平衡计算得出了CH4-CO2二元系中CO2的结霜温度图,据图分析了气固分离方法的可行性,结果表明凝华分离方案可以达到带压液化天然气流程的要求,因而是可行的。     

Isotope Effects in the Spectra of Hydrogen-Bonded Complexes. Experimental and Theoretical Study of an IR Absorption Spectrum of the (12CH3) $$_{2}^{{13}}$$ CO…HF Complex

Optics and Spectroscopy - IR absorption spectra of mixtures (12CH3) $$_{2}^{{13}}$$ CO/HF and free (12CH3) $$_{2}^{{13}}$$ CO molecules are recorded in the region of 4000−800 cm−1 with...     

二甲醚HCCI燃烧高温反应动力学分析

应用单区燃烧模型对二甲醚均质压燃燃烧的化学反应动力学过程进行了数值模拟研究。通过分析在内燃机压燃燃烧边界条件下二甲醚高温氧化反应过程中的关键基元反应速度、关键中间产物以及自由基的浓度随曲轴转角的变化,得到了二甲醚燃烧氧化的高温反应途经。结果表明,二甲醚均质压燃燃烧具有明显的两阶段放热特性,即低温反应放热和高温反应放热。高温反应阶段又可分为蓝焰反应阶段和热焰反应阶段,其中蓝焰反应阶段是甲醛氧化成CO的过程,热焰反应主要是CO氧化成CO2的过程。二甲醚氧化产物之一甲酸(HOCHO)在蓝焰反应阶段分解生成CO2。     

Kinetic studies on the CO oxidation over platinum by means of carbon 13 tracer

The kinetics of the CO oxidation over polycrystalline platinum was investigated with a transient isotope tracer method. Transient CO₂ production was generated by a dosage of various gas mixtures of ¹²CO and O₂ to the surface precovered by various ratios of ¹³CO to ¹²CO. The initial ratio of ¹³CO₂ to ¹²CO₂ in the CO₂ produced transiently equaled that of ¹³CO to ¹²CO in the CO preadsorbed for all the conditions studied; CO must be chemisorbed before being oxidized, i.e. a Langmuir-Hinshelwood mechanism is operative. The ratio of ¹³CO₂ to ¹²CO₂ in CO₂ decreased more rapid than the average ratio of ¹³CO(a) to ¹²CO(a) in CO(a). This apparent inhomogeneity in the reactivity of CO(a) was explained in terms of the boundary reaction model, in which the reaction took place predominantly outside or near the boundary of the CO(a) island.     

CO_2置换CH_4水合物实验研究进展

全面总结了目前CO2置换CH4水合物中CH4实验研究进展。首先从水合物结构角度出发讨论置换的可能性及置换效率;而后分别从热力学和动力学角度探讨置换反应机理;最后设计并优化了实验系统。作者认为探明置换内在机理是未来置换法开采水合物能源技术发展的关键。     

空气CH4浓度变化及其与CO的相关性

CH4是一种重要的温室气体,在空气中的含量仅次于CO2.化合物之间的相关性在化合物的浓度测量和估算等方面都有重要的意义.通过分辨率为1 cm-1的长开放光路傅里叶变换红外光谱仪测量采样路径内的北京西四环高速公路附近空气CH4和CO透过率光谱,进行非线性最小二乘光谱拟合,计算出待测组分浓度.北京秋季空气CH4浓度变化趋势几乎一样.白天的浓度变化趋势表明城市中人为活动对CH4的排放影响极大,尤其是机动车尾气的排放,而晚上浓度主要是近地面的积累.2005年9月4日到2005年9月10日的连续浓度变化表明北京秋季每天CH4和CO浓度变化趋势相同,它们的浓度变化具有一定的相关性.