不纯碳酸盐碳氧同位素组成的在线分析

利用 GV IsoPrime(R)Ⅱ型稳定同位素质谱仪测量不纯碳酸盐样品的碳氧同位素组成,这些样品是用国家碳酸盐碳氧同位素一级标准物质 GBW04406与去除了碳酸盐的沉积物混合配制而成的, CaCO3含量在 2%～ 90%之间.结果显示 ,δ 13C内部精度为 0.002‰～ 0.005‰ (1σ ),δ 18O内部精度为 0.003‰～ 0.009‰ (1σ ),与测量所得的纯 CaCO3国际国内标准物质结果的内部精度范围一致,且外部精度达到仪器的指标要求,同时 ,不同 CaCO3含量样品的δ 13C和δ 18O的测量值 (测量平均值:δ 13C =-10.932‰± 0.021‰,δ 18O=-12.483‰± 0.054‰; 1σ )也在误差允许范围之内与 GBW04406推荐值 (δ 13C=-10.85‰± 0.05‰, δ 18O =-12.40‰± 0.15‰ ; 1σ )一致.可见碳酸盐的含量并不影响其碳氧同位素组成的分析结果,所以在线分析不纯碳酸盐的碳氧同位素组成是可行的,在线分析不纯碳酸盐样品的碳氧同位素组成之前应先对样品中碳酸盐含量进行大致估计,根据碳酸盐含量高低来确定样品用量以达到最佳分析效果.     

硅酸盐岩石中微量碳酸盐的碳氧同位素分析及其应用

硅酸盐岩石中总是或多或少地含有一些微量碳酸盐 ,但是至今尚未对其碳氧同位素地球化学开展研究。本文建立了对硅酸盐岩中微量碳酸盐的碳氧同位素分析方法 ,并以大别山双河地区两种片麻岩为例 ,讨论了其地球化学应用。对比实验证明 ,微量法可以将碳含量检出限降低至 2 2 0 μg。大别山双河两种片麻岩中微量碳酸盐的碳氧同位素测量发现 ,黑云母副片麻岩与花岗质正片麻岩具有明显不同的特征。副片麻岩的碳含量较高 ,δ1 3 C值为 - 4.5‰～ 0‰ ,指示其原岩为正常海相沉积环境 ,并与邻近大理岩的原岩沉积环境不同。正片麻岩的碳含量较低 ,δ1 3 C值为 - 2 3.4‰～ - 2 .1‰ ,反映出地表有机碳对岩浆岩原岩的混染。两种片麻岩中碳酸盐与硅酸盐全岩之间的氧同位素分馏既有处于平衡状态 ,也有处于不平衡状态。     

硅酸盐岩中微量碳酸盐的碳氧同位素分析及其地球化学应用

硅酸盐岩中总是或多或少地含有一些微量碳酸盐，但是至今尚未对其碳氧同位素地球化学开展研究。本文建立了对硅酸盐岩中微量碳酸盐的碳氧同位素分析方法，并以大别山双河地区两种片麻岩为例，讨论了其地球化学应用。通过对比实验证明，微量法通常可将碳含量检出限降低至5μg/g。对大别山双河两种片麻岩中微量碳酸盐的碳氧同位素测量发现，黑云母副片麻与花岗质正片麻岩具有明显不同的特征。副片麻岩的碳含量较高，δ^13值为－4．5‰－0‰，批示其原岩为正常海相沉积环境，并与邻近大理岩原岩的灰岩沉积环境不同。正片麻岩的碳含量较低，δ^13值为－23．4‰－－2．1‰，反映出地表有机碳对岩浆岩原岩的混染。两种片麻岩中碳酸盐与硅酸盐全岩之间的氧同位素分馏既仍处于平衡状态，也有处于不平衡状态。不平衡分馏指示其受到过后期退变质流体的影响。不过，变质岩中微量碳酸盐的碳含量和碳机位素比值分析能够对原岩类型提供有效的区别。     

元素分析仪-同位素比值质谱仪测定海洋沉积物有机碳稳定同位素方法初探

初步建立了利用元素分析仪-同位素比值质谱仪(EA-IRMS)联用技术测定海洋沉积物中有机碳稳定同位素的方法。标定了标准工作参考气CO2(δ13CvsPDB为-32.053‰);验证了仪器的稳定性,标准偏差为0.009‰;当离子流强度范围为0.4～8.7 V时,总体线性为0.0337‰/V,小于仪器线性指标0.06‰/V的要求;同时测定了国家标准物质GBW 04408、国际标准物质Urea和海洋沉积物样品M01的精密度和准确度,标准偏差在0.04‰～0.13‰范围内;并在三家实验室进行了测量比对实验,标准偏差小于0.20‰,满足地质样品再现性0.5‰的要求。所选样品区域δ13Corg范围为-25.29‰～-22.30‰,表明该海域总有机碳是陆源和海源两种来源的混合物。     

元素分析仪-同位素比值质谱测量碳氮同位素比值最佳反应温度和进样量的确定

沉积有机质的碳氮稳定同位素值是进行古气候、古环境及生态系统研究不可或缺的主要研究手段,目前碳氮同位素主要利用元素分析仪-同位素比值质谱(EA-IRMS)系统来测定。EA-IRMS测定过程中的反应温度及样品进样量直接影响反应物在测试中的燃烧程度,从而影响测试数据的精度。本文利用EA-IRMS技术,以标准样品为参考,在不同转化温度下测试碳氮同位素值,研究保证测试精度的最佳反应温度条件;同时,通过分析不同含氮量样品的检测限,明确了样品含氮量与最低检测限之间的关系,确定了精确测定氮同位素值的最低进样量。结果表明:反应温度对测试精度有显著影响,在碳同位素测定时,将反应温度设定为900℃或以上时测试精度均能达到±0.2‰;氮同位素测定时,反应温度须设定为950℃时测试精度才能达到±0.3‰。实验得出样品含氮量与检测限之间的线性相关性为R2=0.873,开展氮同位素测定时可根据此关系来判断和控制进样量。     

中国东南部花岗岩的碳含量和同位素比值

本文应用ＥＡ－ＭＳ连续技术（将元素分析仪（ＥＡ）与气体质谱仪（ＭＳ）连接起来,进行硅酸盐岩石微量碳的含量和同位素比值测定）首次测定了中国东南部花岗岩及其部分磷灰石的全碳含量和同位素组成,结果发现,这些花岗岩的碳含量和同位素组成分布较宽（碳含量为０．０４％～０．７９％,δ＾１３Ｃ值为－７．５‰～－３７．０‰）。磷灰石与全岩的δ＾１３Ｃ呈正相关关系,指示自花岗岩浆上升到结晶以来未受到同化混染或热液蚀变     

岩石中碳同位素比值的EA—MS测定及其地球化学应用

将元素分析仪与气体质谱仪连接起来,能够进行硅酸盐岩石微量碳的含量和同位素比值测定。本文介绍了笔者建立这－ＥＡ－ＭＳ连续技术对天然岩石样品方法中全碳的含量和同位素组成,结果发现这些岩石普遍含有较高的轻碳。     

Kiel Ⅳ-IRMS双路在线分析微量碳酸盐的碳氧同位素

石笋能重建百年、十年的气候事件,为达到空间高分辨率,对微量碳酸盐的检测提出了更高要求,传统磷酸酸解法的样品用量大(约10 mg)已经无法满足微量样品的分析,而激光探针质谱分析方法需对检测结果进行校正。本文采用KielⅣ-IRMS双路在线分析技术对微量碳酸盐样品的碳、氧同位素进行检测研究其可行性,并以GBW 04405和NBS 19为例研究了不同样品量的碳酸盐标准样品在不同反应时间对同位素分馏的影响。结果表明,由于标准样品所需的反应时间不同,从而导致同位素分馏值的差异。对样品量为4~85μg的标准样品GBW 04405进行检测,δ13C、δ18O测量值分别为0.574‰±0.027‰、-8.519‰±0.065‰,与推荐值0.57‰±0.03‰、-8.49‰±0.14‰基本一致,表明该方法能够满足微量碳酸盐测试的要求。将KielⅣ-IRMS双路在线分析技术与GasbenchⅡ-IRMS检测方法进行对比,对于标准样品GBW 04405,KielⅣ-IRMS所用样品量约为50μg,δ13C、δ18O测量值分别为0.576‰±0.012‰、-8.501‰±0.050‰,GasbenchⅡ-IRMS所用样品量约为140μg,δ13C、δ18O测量值分别为0.569‰±0.034‰、-8.590‰±0.099‰。表明KielⅣ-IRMS方法相比于GasbenchⅡ-IRMS方法所需样品量少,精度高,结果重现性好,该方法在碳酸盐样品的应用上能达到空间高分辨率。     

有机化学物质碳氮稳定同位素系列标准物质研制

实验室和研究人员所使用的碳、氮同位素标准物质一般由国际原子能机构(IAEA)获得,然而近年来,随着碳氮同位素在实验室质量监控、方法评价、仪器校准等方面的广泛应用,市场需求量不断增加, IAEA研制的碳、氮同位素标准物质的种类与数量逐渐不能满足科学研究快速发展的需求。我国急需研制适应当今分析技术水平的有机质碳氮同位素国家标准物质用以进行质量监控、方法评价、仪器校准。为保证量值传递精度,本文研制了4个有机化学物质的碳氮稳定同位素标准物质,其中3个为尿素样品,1个为L-谷氨酸。经检验4种标准物质的均匀性通过F值检验,标准物质的δ~(13)C和δ~(15)N值经过一年的稳定性检验,特征量值变化在测量方法允许的不确定度范围内,由此判定δ~(13)C和δ~(15)N值稳定性良好。由包括研制单位实验室在内的12家实验室协同定值,采用高温燃烧-气体同位素质谱法测定了δ~(13)C和δ~(15)N值,系列标准物质δ~(13)C和δ~(15)N认定值区间呈梯度分布,δ~(13)C值为-40‰～0‰,δ~(15)N值为-10‰～30‰,涵盖了我国天然样品中有机质碳氮稳定同位素组成范围;研制的系列标准物质δ~(13)C的定值扩展不确定度不大于0.08‰,δ~(15)N的定值扩展不确定度不大于0.09‰,定值水平与国际标准物质相当。该系列标准物质已被国家质检总局批准为国家一级标准物质,批准号为GBW04494～GBW04497。可被用于地质、生态、环境等多种样品δ~(13)C和δ~(15)N比值测定时的分析监控、仪器校准、方法评价、质量保证和质量监控。     

连续流同位素质谱测定水中溶解无机碳含量和碳同位素组成的方法研究

用连续流同位素质谱对水样中溶解无机碳含量和碳同位素组成的测量方法进行了研究,使用德国Finnigan公司DeltaPlusXP同位素质谱仪和GasBenchⅡ在线制样装置对实验室制备的四个实验室标准进行了反应流程、平衡时间、信号强度、数据精度、标准稳定性等检测,结果显示平衡时间大于4h检测信号达到稳定,同时发现44CO2信号强度和水样中溶解无机碳(DIC)浓度具有很好的相关性,因此可以利用信号强度来计算原样品中的DIC浓度。在四个实验室标准中,由NaHCO3配置的标准具有非常好的稳定性和精度,可以作为测试的工作标准。本方法测量水样中溶解无机碳的δ13C分析精度为0.1‰。本方法可以广泛应用于自然界各种水体中溶解无机碳(DIC)含量及其稳定碳同位素组成的分析。     

兰州市冬季气溶胶吸光特性研究——黑碳与棕色碳的区分及特征分析

为研究兰州市冬季亚微米气溶胶的吸光特性,利用2014年1月10日至2月4日黑碳仪（AE31）和高分辨率飞行时间质谱仪（HR-ToF-AMS）观测资料,对气溶胶的吸光特性进行了分析。首先根据黑碳气溶胶（BC）和棕色碳气溶胶（BrC）的光学特性差异对二者进行区分,然后分析两者的吸光特性。结果表明：观测期间亚微米气溶胶中黑碳和有机物的平均浓度分别为3.7 μg·m^-3和29.3 μg·m^-3。随着亚微米气溶胶浓度的增加,黑碳和棕色碳吸收系数均增加,但棕色碳吸收系数增加得更快。黑碳和棕色碳在550 nm处的平均吸收系数分别为（9.9±5.9）Mm^-1和（51.0±28.1）Mm^-1。棕色碳的Angstrom指数为4.4。另外,采用正定矩阵因子解析模型（PMF）将棕色碳的来源划分为六种（碳氢类有机气溶胶（HOA）、烹饪类有机气溶胶（COA）、生物质燃烧（BBOA）、燃煤排放（CCOA）、半挥发低氧化程度有机气溶胶（SV-OOA）和低挥发高氧化程度有机气溶胶（LV-OOA））,并通过多元线性回归方法计算了各来源的吸光贡献,其中BBOA和CCOA对棕色碳吸光系数的贡献为41.5%,其次是SV-OOA（32.8%）、LV-OOA（14.2%）、HOA（7.8%）和COA（3.8%）,说明一次和二次有机气溶胶均为兰州地区棕色碳的重要来源。     

The detailed palaeoecology of a mid‐Wisconsinan interstadial (ca. 32 000 14C a BP) vegetation surface from interior Alaska

We present a multi‐proxy reconstruction from a well‐preserved vegetation surface (ca. 32 000 ¹⁴C a BP) from the Fox Permafrost tunnel near Fairbanks, Alaska. A thick litter layer of plant material on the vegetation surface is consistent with the vegetation lacking evidence of disturbance. Plant macrofossils and graminoid cuticle analysis show the presence of a graminoid assemblage consistent with phytolith data. The pollen data indicate that trees were not local to the site and that Artemisia sp. was present in the region. The insect and bryophyte reconstructions are consistent with the vascular plant reconstruction, indicating the site was at least periodically wet. δ¹³C values from the graminoids present show a large range encompassing both the wet and dry range displayed by modern graminoids in Alaska. Sequential δ¹³C analyses conducted along the length of leaves attached to the vegetation surface indicate a seasonal shift towards relatively higher water use efficiency. The lower water use efficiency earlier in the growing season may have stemmed from the use of winter season meltwater by plants at the site – a scenario consistent with the site's cryostratigraphy. Our multi‐proxy reconstruction contributes to the limited palaeoecological data available for graminoid‐dominated vegetation present in Eastern Beringia and particularly the interior of Alaska during the mid‐Wisconsinan interstadial. Copyright © 2011 John Wiley & Sons, Ltd.     

内陆水体溶解无机碳同位素研究进展及展望

碳是陆地生态系统中最重要的生命元素,能够在各个圈层之间相互转换和运移。碳循环作为地球各圈层相互连接的纽带,被认为是地表系统最重要的元素地球化学循环。碳在水体中主要以溶解性有机碳（dissolved organic carbon,简称DOC）和溶解性无机碳（dissolved inorganic carbon,简称DIC）形式存在。内陆水体（包括河水、地下水、湖水和水库等）尽管只占陆地表面1%,但它们在碳循环过程中发挥了重要作用。其DIC浓度(CDIC)和DIC同位素组成(δ13CDIC)可以为碳循环研究提供线索,因此成为近年来国际研究的热点之一。本文系统总结了全球内陆水体DIC同位素的研究进展。DIC同位素具有广泛的地质应用,不同碳源具有独特的同位素特征。因此,DIC同位素被用于定性和定量地示踪碳源,指示碳循环过程以及确定河水补给端元。     

Stable Carbon Isotopic Composition of Black Carbon in Surface Soil as a Proxy for Reconstructing Vegetation on the Northern Slope of the Qinling Mountains

Because of the unique geographical location and important ecological effect of the Qinling Mountains,reconstruction of its vegetation and climate needs comprehensive research.We need to consider a multiple-proxy approach to gain more information on recovering the paleovegetation and climate in the Qinling Mountains.Black carbon(BC)is produced by the incomplete combustion of vegetation and fossil fuels,and is a good proxy,recording paleoenvironmental information.However,in the Qinling Mountains,what are the characteristics of the BC,and whether BC stable carbon isotope(δ~(13)C_(BC))can be used as a new proxy to study ancient vegetation,still need further study.In order to establish a sound basis for studying paleoenvironmental by BC proxy in the Qinling Mountains,we carried out systematic and detailed study on modern process of BC on the northern slope of the mountains.We analyzed stable carbon isotopes and carbon concentration of organic carbon(%SOC,δ~(13)C_(SOC))and BC(%BC,δ~(13)C_(BC)),and identified the pollen assemblages from systematically sampled surface soil.The results show that the calculated ratio of C_4 plants in the vegetation(%C_4)based on theδ~(13)C_(SOC)data reflects a similar distribution of C_4 plants in the surface vegetation and the pollen assemblage.Theδ~(13)C_(BC)values have a strong positive correlation withδ~(13)C_(SOC)values,and their difference(△~(13)C_(SOC-BC))is in the low range.These data indicate thatδ~(13)C_(BC)andδ~(13)C_(SOC)have very similar characteristics.Surface soilδ~(13)C_(BC)values can indicate surface vegetation as effectively asδ~(13)C_(SOC)values,and theδ~(13)C_(BC)proxy can be used effectively in paleovegetational research in the northern slope of Qinling Mountains.     

Bicarbonate Daily Variations in a Karst River: the Carbon Sink Effect of Subaquatic Vegetation Photosynthesis

Using the Guancun River, an underground stream-fed river, in Rong’an County of Guangxi, China as a case study, the daily biochemical cycle was examined in this paper based on the data collected a weeklong via high resolution data logger monitoring and high-frequency sampling. Furthermore, the loss of inorganic carbon along its flow path was estimated. Results show that chemical components of the groundwater input are quite stable, showing little change extent; while all of the chemical parameters from two downstream monitoring stations show diel variation over the monitoring period, suggesting that plant activity in the river has a strong influence on water chemistry of the river. The comparison of the input fluxes from the groundwater with the output fluxes of HCO3? estimated at the downstream monitoring station during the high-frequency sampling period shows a strong decrease of HCO3?, indicating that the river is losing inorganic carbon along its flow path. The loss is estimated to be about 1,152 mmol/day/m of HCO3? which represent about 94.9 kg/day of inorganic carbon along the 1,350 m section of the Guancun River. It means that HCO3? entering the river from karst underground stream was either consumed by plants or trapped in the authigenic calcite and thus constitutes a natural sink of carbon for the Guancun karst system.     

松嫩平原耕层土壤固碳潜力估算

提高土壤碳收集能力对减缓全球温室效应具有重要意义。利用松嫩平原南部第二次土壤普查及多目标区域地球化学调查获取的两期表层土壤有机碳数据,根据近20年来各土壤类型不同土地利用方式土壤有机碳量变化趋势,估算了松嫩平原南部各土壤类型、各用地方式下土壤碳源、汇潜力。由估算得出,如果目前的土地利用方式、气候条件、耕作方式、种植技术不变,松嫩平原耕地土壤0~20 cm土层的固碳潜力为-1.229Tg碳,各土壤类型的林地土壤固碳潜力绝大多数为正值,说明林业用地为碳汇区,固碳潜力合计为3.169Tg碳,而天然牧草地绝大多数的固碳潜力为负值,固碳潜力合计为-2.235Tg碳,为碳源区,本次研究估算得出,松嫩平原总体的固碳潜力为-0.917Tg碳。     

是“岩溶碳汇”还是“岩溶碳通量”?

大气碳收支不平衡问题是全球碳循环研究的核心问题之一,决定了人类活动导致的气候变化速度和程度。在过去50年,陆地和海洋作为全球碳循环的主要汇呈增加趋势,而岩溶作用(CaMg(CO_3)_2+2CO_2+2H_2O  Ca~(2+)+Mg~(2+)+4 HCO_3~-)则通过与岩石圈、水圈、大气圈(层)的密切联系成为联系陆地和海洋碳库的纽带。尽管岩溶作用在水循环和生物圈的作用下,每年可产生约8亿t的碳通量,使岩溶作用过程成为全球碳循环的一个重要环节。但在目前研究技术手段和认识水平的条件下,将岩溶作用这一可逆过程直接认定为岩溶碳汇有不妥之处。因此,在没有涉及生物固碳效应的前提下,应当将岩溶作用参与的碳循环表述为岩溶碳通量。     

Pioneering assessment of carbon stocks in polder soils developed in inter-dune landscapes in a semiarid climate,Lake Chad

In semiarid Sahelian region, the dynamics of soil organic carbon (SOC) and water are key to sustainable land management. This work focuses on the behaviour of carbon. A total of 33 soil profiles in four polders, ranging from 10 to 65 years in age, were sampled, analysed (0–1 m), and matched with marsh soil profiles in recent sediments considered as reference (t₀) for carbon stocks determination. SOC and soil inorganic carbon (SIC) stocks show a spatial variability between polders. SOC stocks were t₀ 200 ± 0.8; t₆₀ 183 ± 34; and t₆₅ 189 ± 1.1 MgC·ha^?1, whereas the SIC stocks were negligible. These results show the highest stocks of soil carbon observed for this climatic region. The SOC stocks were also calculated for the equivalent soil mass at a defined depth (0–0.3 m); the corrected calculation of SOC stocks (S_corr) for 2450 Mg·ha^?1 of equivalent soil mass is t₀ 64 ± 1.9, t₆₀ 59 ± 9.8, and t₆₅ 53 ± 2.2 MgC·ha^?1; the stocks decrease by ?7.8% and ?17.2% from t₀ to t₆₀ and t₆₅. Carbon was inherited from the pre-existing·marsh and the polders have conserved high stock values.     

Interlaboratory study of a method for determining nonvolatile organic carbon in aquifer materials

The organic carbon fraction in aquifer materials exerts a major influence on the subsurface mobilities of organic and organic-associated contaminants. The spatial distribution of total organic carbon (TOC) in aquifer materials must be determined before the transport of hydrophobic organic pollutants in aquifers can be modeled accurately. Previous interlaboratory studies showed that it is difficult to measure TOC concentrations <0.1% in aquifer materials, when total inorganic carbon (TIC) concentrations are >1%. We have tested a new analytical method designed to improve the accuracy and precision of nonvolatile TOC quantitation in geologic materials that also contain carbonate minerals. Four authentic aquifer materials and one NIST standard reference material were selected as test materials for a blind collaborative study. Nonvolatile TOC in these materials ranged from 0.05 to 1.4%, while TIC ranged from 0.46 to 12.6%. Sample replicates were digested with sulfurous acid, dried at 40°C, and then combusted at 950°C using LECO or UIC instruments. For the three test materials that contained >2% TIC, incomplete acidification resulted in a systematic positive bias of TOC values reported by five of the six laboratories that used the test method. Participants did not have enough time to become proficient with the new method before they analyzed the test materials. A seventh laboratory successfully used an alternative method that analyzed separate liquid and solid fractions of the acidified sample residues.     

人为土壤有机碳的分布特征及其固定意义

文章在分析不同类型的人为土壤形成过程及其特点的基础上研究了人为土壤有机碳含量、分布年龄与同位素组成特征。结果表明,人为土壤中有机碳的含量分布不同于起源土壤或者相应的非人为土壤,主要体现在有机碳含量降低的缓慢和不规则性以及有机碳含量的相对富集。通过计算证明人为土壤的有机碳密度高于相邻土壤或起源土壤。放射性碳测定表明人为土壤中的有机碳年龄较老,说明了有机碳在这些土壤中存在的相对稳定性。土壤有机碳的稳定同位素组成分析表明,土壤中深层的有机碳与现代有机碳来源不同,也表明了土壤中有机碳的稳定存在。文章还分析了人为土壤中有机碳富集和稳定的可能机制,包括物理、化学和生物学机制,认为就有机碳的固定而言,人为土壤是一种具有最佳管理方式的可持续利用的土壤资源